Progress in Energy and Combustion Science 62 (2017) 33
86

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review

2XTagedPD1 XShurong
XD Wanga,*, 4XD3 XGongxin
XD Daia, 6XD5 XHaiping
XD Yangb, 8XD7 XZhongyang
XD Luoa
a
TagedP State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
b
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China

TAGEDPA R T I C L E I N F O TAGEDPA B S T R A C T

Article History: The past decades have seen increasing interest in developing pyrolysis pathways to produce biofuels and
Received 7 March 2017 bio-based chemicals from lignocellulosic biomass. Pyrolysis is a key stage in other thermochemical conver-
Accepted 25 May 2017 sion processes, such as combustion and gasification. Understanding the reaction mechanisms of biomass
Available online xxx
pyrolysis will facilitate the process optimization and reactor design of commercial-scale biorefineries. How-
ever, the multiscale complexity of the biomass structures and reactions involved in pyrolysis make it chal-
TagedPKeywords:
lenging to elucidate the mechanism. This article provides a broad review of the state-of-art biomass
Biomass
pyrolysis research. Considering the complexity of the biomass structure, the pyrolysis characteristics of its
Pyrolysis mechanism
Components
three major individual components (cellulose, hemicellulose and lignin) are discussed in detail. Recently
Kinetics developed experimental technologies, such as Py-GC
MS/FID, TG-MS/TG-FTIR, in situ spectroscopy, 2D-
Selective catalysis PCIS, isotopic labeling method, in situ EPR and PIMS have been employed for biomass pyrolysis research,
Pretreatment including online monitoring of the evolution of key intermediate products and the qualitative and quantita-
tive measurement of the pyrolysis products. Based on experimental results, many macroscopic kinetic
modeling methods with comprehensive mechanism schemes, such as the distributed activation energy
model (DAEM), isoconversional method, detailed lumped kinetic model, kinetic Monte Carlo model, have
been developed to simulate the mass loss behavior during biomass pyrolysis and to predict the resulting
product distribution. Combined with molecular simulations of the elemental reaction routes, an in-depth
understanding of the biomass pyrolysis mechanism may be obtained. Aiming to further improve the quality
of pyrolysis products, the effects of various catalytic methods and feedstock pretreatment technologies on
the pyrolysis behavior are also reviewed. At last, a brief conclusion for the challenge and perspectives of bio-
mass pyrolysis is provided.
© 2017 Elsevier Ltd. All rights reserved

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2. Multiscale complexity of lignocellulosic biomass and its pyrolysis behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.1. Composition of lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2. Cellulose structure and pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.3. Hemicellulose structure and pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.4. Lignin structure and pyrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.5. Extractives and inorganic minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.6. Pyrolysis behavior of whole biomass and the interactions of the three main biomass components. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3. Latest experimental methods to unravel the biomass pyrolysis mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.1. Pyrolysis product analysis by Py
GC
MS/FID. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.2. Pyrolysis product analysis by TG-FTIR and TG-MS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.3. Biomass pyrolysis behavior determined by characterizing the reaction process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.4. Formation pathways of pyrolysis products revealed by isotopic labeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.5. Biomass pyrolysis behavior unraveled by characterizing intermediate product. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4. Macroscopic kinetic modeling for biomass pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.1. Macroscopic kinetic models for mass loss simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.1.1. Distributed activation energy model (DAEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

*
Corresponding author.
E-mail address: srwang@zju.edu.cn (S. Wang).

http://dx.doi.org/10.1016/j.pecs.2017.05.004
0360-1285/© 2017 Elsevier Ltd. All rights reserved.
34 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86

4.1.2. Isoconversional method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

4.2. Macroscopic kinetic models for pyrolysis product prediction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.2.1. Detailed lumped kinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2.2. Chemical percolation devolatilization model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.2.3. Kinetic Monte Carlo (KMC) model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5. Molecular simulation of the pyrolysis pathways of biomass and bio-based model compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.1. Cellulose pyrolysis mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.1.1. The elementary pathways for the pyrolysis of glucose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.1.2. The pyrolysis pathways of model compounds including b¡1,4-glycosidic bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5.2. Hemicellulose pyrolysis mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.3. Lignin pyrolysis mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
6. Catalytic pyrolysis of biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.1. Chemical reaction paths in biomass catalytic pyrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.2. In situ and ex situ catalytic pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
6.3. Catalytic effect of inorganic minerals on pyrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
6.4. Catalytic pyrolysis by metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
6.5. Catalytic pyrolysis by zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
7. The effect of pretreatment on biomass pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
7.1. Physical pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.1.1. Grinding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.1.2. Densification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.2. Chemical pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.2.1. Acid & alkali pretreatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.2.2. Hydrothermal pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.2.3. Steam explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.2.4. Ammonia fiber expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.3. Thermal pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.3.1. Drying. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.3.2. Torrefaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7.4. Biological pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
8. Challenge and perspectives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
9. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

1. Introduction cTagedP onditions. Fast pyrolysis of biomass at rapid heating rates and short
hot vapor residence times (< 1 s) produces liquid with yield up to
TagedPConsumption of fossil fuels worldwide has increased tremen- 75 wt.% [12,13]. The pyrolysis liquid, which is normally called bio-
dously in last few decades, which leads to several environmental oil, can be further upgraded to transportation fuels and value-added
issues, including greenhouse gas emissions and deteriorating air chemicals. The char and gaseous products can be combusted to pro-
quality caused by pollutants such as SOx, NOx and fine particulate vide energy for the pyrolysis reaction or heat/power generation [12].
matter. Moreover, the fluctuation of fossil fuel prices and the deple- Many potential agricultural and environmental applications of
tion of fossil resources have shadowed the global economy. The pro- char are also being explored to enhance the value chain of the
duction of carbon-neutral and low-emission fuels from renewable pyrolysis process [12,14]. Techno-economic analysis showed that
resources, such as biomass, is of growing importance in the gradual transportation fuel production from biomass via pyrolysis-based
substitution of conventional fossils. Biomass is biological material pathways had economic advantages over other conversion path-
from living, or recently living organisms produced directly or indi- ways, such as gasification and biochemical pathways [15
18].
rectly by photosynthesis, most often plants or plant-derived materi- Due to the huge demand for liquid transport fuels, biomass
als [1
3]. Biomass resources are widely available in nature. It is pyrolysis technology will attract increasing interest from both
estimated that the global biomass production is approximately 100 academia and industry [19].
billion tons per year [4]. As the only renewable carbonaceous TagedPBiomass slow pyrolysis, particularly wood carbonization and dis-
resource, biomass has the potential to produce heat, electricity, fuel, tillation, has been used by humans for more than a thousand years.
chemicals, and other products [5,6]. The International Energy Agency Nevertheless, the pioneering studies on biomass pyrolysis were initi-
(IEA) suggests that bioenergy has the potential to provide 10% of the ated in 19th century [20]. The effect of the reaction conditions on the
world's primary energy supply by 2035, and biofuels can replace up yields of the solid, liquid and gas pyrolysis products was first
to 27% of world transportation fuel by 2050 [7]. reported in 1875 by Gruner [21]. However, little progress was made
TagedPBiomass can be converted into fuels and chemicals through bio- until the 1980s. During this stage, the kinetics of biomass/cellulose
chemical or thermochemical processes. Digestion (anaerobic and pyrolysis received significant attention. In 1956, Stamm [22]
aerobic) and fermentation are typical biochemical processes used to reported the kinetics of wood and cellulose thermal degradation and
produce methane and alcohols [8,9]. The main thermochemical pro- suggested that thermal degradation followed a first-order reaction
cesses include pyrolysis, gasification, combustion, hydrothermal liq- model. In 1970, Roberts [23] reviewed the pyrolysis kinetics of bio-
uefaction and hydrothermal carbonization [10,11]. Among these mass and related substances. The results showed that pyrolysis may
thermochemical pathways, pyrolysis, the thermal decomposition of proceed through different reaction routes. In 1979, the classic Broi-
organics in the absence of oxygen, has been extensively developed do
Shafizadeh (B‒S) model for cellulose pyrolysis based on the for-
as a promising platform to produce fuels and chemicals from various mation of char, volatiles and gas via different pathways was
types of biomass. Pyrolysis produces char, liquid and gas products, proposed [24]. These findings provide some fundamentals for fur-
the distribution of which strongly depends on the reaction ther development of biomass pyrolysis technology.
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPSince the 1980s, a growing body of research has focused on bio-
mass fast pyrolysis for liquid production due to the oil crisis. A num-
ber of research units in Europe and America conducted biomass fast
pyrolysis in the period 1980
2000 [25
27], focusing on the devel-
opment of various reactors for biomass fast pyrolysis. Those reactor
technologies include the bubbling fluidized bed, circulating fluidized
bed, transported bed, ablative reactor and rotating cone reactor
[26,28]. Meanwhile, the effect of the reaction conditions was investi-
gated to optimize the fast pyrolysis process and to maximize the bio-
oil yield. Modified kinetic reaction models were also proposed in the
same period [29
35]. Additionally, possible formation mechanisms
of typical pyrolysis products were proposed [36
41].
TagedPBiomass pyrolysis has received considerably more attention from
the academic field in the past decade. The number of scientific jour-
nal papers published per year on this topic increased from less than
200 in 2005 to more than 1800 in 2016, based on the statistical
result from Web of Science. The research is currently focused on
revealing the reaction mechanisms of pyrolysis and the develop-
ment of novel pyrolysis-based pathways to produce transportation
fuels. Advanced experimental technologies, such as spatiotempo-
rally resolved diffuse reflectance in situ spectroscopy of particles
(STR-DRiSP) [42], electron paramagnetic resonance (EPR) [43], and
photoionization mass spectrometry (PIMS) [44], have emerged and
have been used to detect reaction intermediates during pyrolysis,
improving the understanding of biomass pyrolysis chemistry. Addi-
tionally, advanced kinetic methods (the detailed lumped kinetic
model [45], chemical percolation devolatilization model [46] and
kinetic Monte Carlo model [47]) and molecular simulation methods
(density functional theory [48] and Car
Parrinello molecular
dynamics [49]) were developed to elucidate the biomass pyrolysis
mechanism. During the past decade, various technologies, such as
catalytic pyrolysis, have also been developed to improve the quality
of bio-oil, making it more compatible with the current petroleum
industry [50,51]. Pretreatment of biomass feedstock to remove or
modify the undesired functional groups and/or structures in the bio-
mass matrix has been explored as a way to improve the conversion
efficiency. Considerable pretreatment achievements have been
reported, such as torrefaction [52,53], steam explosion [54,55], acid/
alkali pretreatment [56] and biological pretreatment [57].
TagedPMany review papers in the field of biomass pyrolysis have been
published, focusing on only one aspect of biomass pyrolysis, such as
the reaction process [58
60], reaction mechanism [61
63], pyroly-
sis kinetics [64
67], catalytic pyrolysis [68
71] and effects of pre-
treatment [72,73]. This work provides a broad review of the state-
of-the-art advances in multiple aspects of biomass pyrolysis
research and development. The complexity of the biomass structure
is one of the challenges in elucidating biomass pyrolysis behavior.
Therefore, the biomass structure and the correlated pyrolysis behav-
ior are reviewed in Section 2. To gain deep insight into the biomass
pyrolysis behavior, some advanced experimental technologies have
been developed and are covered in Section 3. In Sections 4 and 5,
macroscopic kinetic modeling and microscopic pyrolysis pathways
based on molecular simulations of biomass pyrolysis are reviewed,
respectively. Section 6 coverts biomass catalytic pyrolysis, including
the catalytic reaction chemistry and the effects of various types of
catalysts. Section 7 reviews biomass pretreatment methods, includ-
ing torrefaction, acid/alkali pretreatment and steam explosion.
Future research and opportunities are then outlined in Section 8.
2. Multiscale complexity of lignocellulosic biomass and its
pyrolysis behavior
2.1. Composition of lignocellulosic biomass
TagedPLignocellulosic biomass is the most abundant non-edible bio-
mass, mainly composed of forestry and agricultural wastes, such as
35
TagedP oodchips and rice straw [74,75]. Woody biomass can be classified
w
into two broad categories, softwood and hardwood [76]. Softwood
originates from conifers and gymnosperm trees, including evergreen
species, such as fir, pine, cedar, hemlock, spruce and cypress [77].
Softwood grows faster and is less dense than hardwood. Hardwood
comes from angiosperm plants, most of which are deciduous. Wil-
low, poplar, oak, cottonwood and aspen are typical examples of
hardwood [77]. The cell structure of hardwood is more complex
than that of softwood, containing large water-conducting pores or
vessels that are surrounded by narrow fibrous cells [78,79]. Agricul-
tural residues include rice and wheat straw, corn stover, corn stalks,
and sugarcane bagasse. These agricultural residues are annual grass
lignocelluloses. Perennial bioenergy grasses, such as miscanthus and
switchgrass, are also important grass lignocelluloses [80,81].
TagedPLignocellulosic biomass is composed of three major components,
cellulose, hemicellulose and lignin, with a small amount of extrac-
tives and ash. As illustrated in Fig. 1, the three major components
are unevenly distributed in the cell wall as skeleton, linking material
and hard solids, respectively. Cellulose macromolecules regularly
gather to form tough microfibers that function as the skeleton mate-
rial of the cell wall, and the inner space is packed with amorphous
hemicellulose and lignin linking material [82]. Cellulose connects
with hemicellulose or lignin molecules mainly through hydrogen
bonds, while the connections between hemicellulose and lignin
include both hydrogen and covalent bonds [83,84]. Carbohydrates
and lignin link tightly together in lignin-carbohydrate complexes,
which results in residual carbohydrate or lignin fragments in
extracted lignin or hemicellulose samples.
TagedPThe contents of cellulose, hemicellulose and lignin in biomass
vary significantly, depending on the type of biomass. The cellulose
content can reach 40
60%, the hemicellulose content is 15
30%,
and the lignin content is approximately 10
25% (as shown in
Table 1). In addition to the three major components, a small fraction
of extractives and inorganic ash also exist in biomass as nonstruc-
tural components that do not constitute the cell walls or cell layers.
Wood biomass contains much higher amounts of the three main
components (»90%), while agricultural and herbaceous biomass
contain more extractives and ash.
2.2. Cellulose structure and pyrolysis
TagedPCellulose, a linear macromolecular polysaccharide that consists
of a long-chain of glucose units linked by b¡1,4-glycosidic bonds, is
the most abundant organic polysaccharide on the planet. Woody
biomass contains approximately 45% cellulose, while the content of
Fig. 1. Cellulose, hemicellulose and lignin in plant cells (reprinted from Wang et al.
[82] with permission of De Gruyter).
36 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86

Table 1 TagedP lycosidic bonds can easily bind to the hydroxyl group at the C6
g
Chemical compositions of various biomass types. position of the glucose residue, leading to the formation of LG. Fur-
Cellulose Hemicellulose Lignin Extractive Ash ans, such as HMF, were mainly formed from the stepwise dehydra-
tion of monosaccharide units, so the yield of HMF decreased as DP
Softwood biomass
increased. Furthermore, a higher DP can affect the thermal weight
P.armandii Franch 48.4 17.8 24.1 9.5 0.2
[85] loss behavior of cellulose. Wang et al. [85] found that the tempera-
Pine [86] 46.9 20.3 27.3 5.1 0.3 ture corresponding to the maximum mass loss rate for the extracted
Spruce [86] 45.6 20.0 28.2 5.9 0.3 cellulose in TG analysis was higher than that for microcrystalline cel-
Spruce [87] 43.0 29.4 27.6 1.7 0.6
lulose, which was attributed to the higher molecular mass of the
Fir [88] 45 22 30 2.6 0.5
Japanese cedar [89] 38.6 23.1 33.8 4 0.3
extracted cellulose.
Eastern Red cedar 40.3 17.9 35.9 5.6 0.3 TagedPThe glucopyranosyl monomers in cellulose are in the b configura-
[90] tion. The anomeric carbons result in a stretched chain conformation,
Hardwood biomass which facilitates the linking of these chains into flat sheets via hydro-
Alder [86] 45.5 20.6 23.3 9.8 0.7
gen bonds [94,99]. There are three hydrogen bonds, of which two are
Aspen [86] 52.7 21.7 19.5 5.7 0.3
Willow [86] 41.7 16.7 29.3 9.7 2.5 intramolecular hydrogen bonds and one is an intermolecular hydro-
Poplar [88] 49 24 20 5.9 1 gen bond, per glucosyl unit in raw cellulose. The packing of numerous
Cherry wood [88] 46 29 18 6.3 0.5 cellulose flat sheets forms crystalline fibrils. It is believed that the
Beech [88] 45 33 20 2 0.2 interactions between sheets are mostly through van der Waals forces,
Beech [87] 44.2 33.5 21.8 2.6 0.5
Japanese beech [89] 43.9 28.4 24.0 3 0.6
which contribute significantly to the stabilization of cellulose fibrils.
On the basis of the arrangement pattern of chain molecules, the cellu-
Herbaceous and agricultural biomass
Rice straw [91] 37 16.5 13.6 13.1 19.8 lose ultrastructure can be classified into crystalline and amorphous
Rice straw [89] 34.53 18.42 20.22 10.11 13.31 regions. The cellulose molecular arrangement is uniform and ordered
Rice husk [89] 37.00 23.43 24.77 3.19 17.27 in the crystalline region and is loose and disordered in 9XD X the amorphous
Wheat straw [89] 37.55 18.22 20.24 4.05 3.74 region. However, there is no obvious separation between the two
Corn straw [91] 42.7 23.2 17.5 9.8 6.8
Corn leaves [89] 26.93 13.27 15.18 22.01 10.95
regions [94,99]. The cellulose crystalline region has better thermal
Corn cob [89] 34.61 15.24 18.16 10.60 3.53 stability than the amorphous region due to its packed cellulose struc-
Bamboo [89] 39.80 19.49 20.81 6.77 1.21 ture [99,100]. In addition, intramolecular hydrogen bonds may stabi-
Miscanthus [89] 34.4 25.4 22.8 11.9 5.5 lize the cellulose molecules and inhibit thermal expansion along the
Switchgrass [92] 40
45 31
35 6
12 5
11 5
6
cellulose chains, improving the thermal stability of the lignocellulosic
Hazelnut shell [87] 25.2 28.2 42.1 3.1 1.4
fiber [99]. The glass transition temperature (Tg) of amorphous cellu-
lose has been reported between 243 and 307 °C [101], and the mini-
mum temperature for the decomposition of cellulose crystals is
TagedPcellulose in cotton, flax and chemical pulp can reach 80
95% [93]. greater than 300 °C [102]. During the pyrolysis process, the amor-
According to the X-ray diffraction pattern of cellulose crystals, the phous region degrades firstly, and the crystalline region must absorb
crystallographic repeating units are two anhydroglucose units linked substantial heat to break the hydrogen bond network prior to decom-
with a helical axis, and the left and right anhydroglucose rotate position of the crystal structure [103]. After the reaction water
around each other by 180° along the helical axis [94]. Therefore, cel- evolves at the initial temperature of 200 °C, cellulose undergoes the
lobiose, rather than glucose, is the basic unit of cellulose polymer. cleavage of intra- and intermolecular hydrogen bonds below 300 °C.
TagedPThe chemical formula of cellulose is often denoted as (C6H10O5)n, Subsequent dehydration is the dominant reaction among intramolec-
where n is the degree of polymerization (DP). The average DP for ular H-bonds, where cleavage of the O2
HO6 intramolecular
woody fiber is at least 9000
10,000 and possibly as high as 15,000 hydrogen bonds, O6H
O3 intermolecular hydrogen bonds and
[77]. The glycosidic bonds linking the glucose units in cellulose are pyran ring CH first occurs, followed by cleavage of O3
HO5 intra-
not strong and tend to cleave under acid or high-temperature condi- molecular hydrogen bonds [104].
tions. Therefore, the cellulose structure degrades sharply during the TagedPThe relative amount of crystalline material in cellulose can be
initial stages of fast pyrolysis with the reduction of DP due to the evaluated using a parameter termed the crystallinity index, which is
cleavage of glycosidic bonds. Cleavage of b¡1,4-glycosidic bonds obtained by performing XRD analysis. The crystallinity index for
contributes largely to the formation of furans and levoglucosan (LG) microcrystalline cellulose is approximately 80% and is 30
60% for
[95]. In addition, DP also has an important impact on the pyrolysis biomass fibers. Crystallite size is another important parameter
behavior of cellulose. Mettler et al. [96] analyzed the pyrolysis prod- related to the cellulose crystal structure, referring to the smallest
uct distributions of cellulose and six glycosyl oligomers with DP in single crystal in powder form. Increasing crystallite size always
the range of 1 to 6. Their results showed that the seven glucose- results in increased crystallinity index due to the decreasing crystal-
based carbohydrates generated almost the same product categories, lite surface corresponding to the amorphous region [99,105]. Both
but with varied quantity. LG, 5-hydroxymethylfurfural (HMF), furfu- the crystallinity index and crystallite size have a significant effect on
ral, methylglyoxal, hydroxyacetaldehyde (HAA) and acetic acid were the cellulose pyrolysis behavior, which has been extensively investi-
the major products of the pyrolysis of glucose-based carbohydrates. gated in recent years. Kim et al. [105] performed thermal degrada-
Glucose-based carbohydrates with a higher DP corresponded to a tion of three native cellulose samples, with different crystallinity
higher yield of LG, while the yields of other products changed signifi- indices and crystallite sizes. They observed that the initial thermal
cantly with varying DP. Zhou et al. [97] also investigated the pyroly- decomposition temperature and peak temperature in the DTA and
sis of four cellulosic model compounds (glucose, cellobiose, DTG curves shifted to higher values as the crystallinity index and
maltohexaose and cellulose) at 500 °C in a micro-pyrolyzer. With crystallite size increased. This effect was closely related to heat
increasing DP, the LG yield increased from 8.10% to 54.50%, which transfer during the thermal decomposition of cellulose. Poletto et al.
indicated a significant correlation between the formation of LG and [106,107] reported that larger cellulose crystallite size is more ther-
the cleavage of glycosidic bonds. Patwardhan et al. [98] confirmed mally stable. Trache et al. [108] further noted that the correlation
that the formation of LG and other pyrans was directly correlated between the heat of decomposition and the crystalline index could
with the DP of a sample, and a higher DP favored the formation of be attributed to the difficulty of the heterolytic cleavage of the glyco-
pyrans. They proposed that the cations formed from the cleavage of sidic bonds along the ordered chains, leading to the requirement of
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPhigh energy in decomposition of high degree of molecular ordering.
It has been speculated that crystalline cellulose results in greater LG
formation, while amorphous cellulose contributes more to the for-
mation of char and gas. Amorphous cellulose is also believed to pro-
duce more furfural and HMF in the temperature range of 200
300 °
C [36,109]. Recently, Wang et al. [110] carefully investigated the
effect of cellulose crystallinity on the thermal kinetics and product
distribution by performing the pyrolysis of control cellulose and
ball-milled cellulose samples, whose crystallinity indices were 60.5%
and 6.5%, respectively. The thermogravimetric analyses showed that
the samples with lower crystallinity started to degrade at lower tem-
peratures, exhibiting sharper DTG curves and lower thermal degra-
dation activation energies. In addition, these two cellulose samples
showed significant differences in product formation. High levels of
amorphous cellulose produced high LG yields at low temperatures,
whereas the higher crystallinity sample produced higher yields of
anhydrosugars at high temperatures. Meanwhile, samples with
lower crystallinity produced more of the larger furanic compounds
(HMF, 5-methylfurfural, and furfural), which were assumed to form
through an acid-catalyzed ring contraction mechanism and consecu-
tive water-elimination steps. They also found that crystallinity did
not impact the fragmentation reactions that formed lighter organic
molecules. The major difference in the product formation pathways
of the two cellulose samples might be attributed to the formation of
a liquid intermediate in the ball-milled samples but not in the con-
trol samples, in which the inter-ring dehydration and cross-linking
reactions are favored [110,111].
TagedPIn addition to the crystallinity index and crystallite size, crystal-
line allomorph is another key parameter of the cellulose crystal
structure. Hydroxyl groups in cellulose macromolecules form large
amounts of intra- and intermolecular hydrogen bonds, which pro-
duce various ordered crystalline arrangements, resulting in the for-
mation of different crystalline allomorphs [112]. Several crystalline
allomorphs are recognized by their characteristic XRD patterns and
solid-state 13C NMR spectra [112]. Celluloses I, II, and III are typical
allomorphs. Their molecular models are shown in Fig. 2. Cellulose I,
the native form of cellulose in plant cell walls, is the most abundant
in nature. Other forms of cellulose can be generated from cellulose I
through various treatments. Cellulose I has two-dimensional intra-
layer hydrogen-bonding networks. It is a mixture of two distinct
crystalline configurations, cellulose Ia and cellulose Ib, where the
former corresponds to a triclinic crystal with one chain and the latter
exhibits a monoclinic crystal containing two chains [113
115]. The
relative amounts of celluloses Ia and Ib depend on the source of the
cellulose. Cellulose Ia is dominant in lower plants, while Ib mainly
exists in higher plants. For instance, cellulose Ia is the main form in
algae and bacteria, accounting for more than 60 wt.% of the cellulose,
while the cellulose Ib content in higher plants, such as cotton, can
reach 80 wt.% [115]. In addition, cellulose Ib can gradually transform
Fig. 2. Molecular models of cellulose allomorphs (reprinted from Mukarakate et al.
[117] with permission of American chemical society).
37
iTagedP nto cellulose Ia under thermal conditions [116]. Cellulose II can be
generated from cellulose I through two distinct processes, regenera-
tion (solubilization and subsequent recrystallization) and merceriza-
tion (alkali treatment), which give rise to antiparallel sheets with a
three-dimensional network of intralayer and interlayer hydrogen
bonding [94,112]. Cellulose I (natural cellulose) and cellulose II
(regenerated cellulose or mercerized cellulose) are commonly avail-
able and often selected as representatives of cellulose. Cellulose III
can be generated from cellulose I or cellulose II through treatment
with anhydrous ammonia, which is a reversible reaction [117,118].
Detailed reviews of cellulose crystalline allomorphs are available
elsewhere [94,112,119].
TagedPThe type of crystalline allomorph may also have a considerable
influence on cellulose pyrolysis. However, relatively limited atten-
tion has been given to this topic. Watanabe et al. [120,121]
found that the scission of hydrogen bonds in cellulose Ia mainly
occurred at 40
100 °C and was completed below 180 °C, while the
band intensities of intrachain hydrogen bonds (O3
H3O5 and
O2
H2O6) in cellulose Ib decreased remarkably at 220 °C. Agarwal
et al. [122] simulated the structural transformation of cellulose Ib
and found that the structural transition was initiated by the scission
of O2
H2O6 intrachain hydrogen bonds by converting to interchain
hydrogen bonds. Intrachain hydrogen bonds were dominant in the
low-temperature structure (27
152 °C), while interchain hydrogen
bonds were dominant in high-temperature structure (152
277 °C).
Zhang et al. [123] compared the pyrolysis products of cellulose I, cel-
lulose II and amorphous cellulose. Cellulose I mainly formed furfural
and 1,4;3,6-dianhydro-alpha-D-glucopyranose in the liquid prod-
ucts, while the major products of cellulose II and amorphous cellu-
lose were furfural and HMF. In addition, cellulose II and amorphous
cellulose favored the removal of oxygen in the form of CO2. Recently,
Mukarakate et al. [117] conducted a systemic investigation of the
influence of crystalline allomorphs (cellulose I, II, and III) and crystal-
linity (low, mediate and high) on cellulose pyrolysis. The results
showed that the pyrolysis products from cellulose I and cellulose II
varied dramatically as the crystallinity changed. For cellulose I, the
selectivity of the major product, LG, decreased as the crystallinity
decreased. Only the most highly crystalline cellulose II samples pro-
duced vapors dominated by LG, while cellulose III showed a similar
product distribution, regardless of relative crystallinity. Meanwhile,
the cellulose samples producing primarily LG, including cellulose I
and II at high crystallinity and cellulose III at all three crystallinity
levels, had the highest onset of mass loss temperatures and the low-
est char yields. They also observed that cellulose III samples dis-
played an obvious molten phase transition regardless of relative
crystallinity, while the high-crystallinity cellulose I appeared to vol-
atilize without substantial phase transition.
2.3. Hemicellulose structure and pyrolysis
TagedPIn contrast to cellulose, hemicellulose is composed of short-chain
heteropolysaccharides and presents an amorphous and branched
structure. Although the shape of the polysaccharide chain is similar
to that of cellulose, the degree of polymerization of hemicellulose is
only approximately 200 on average [124]. The monosaccharide units
constituting hemicellulose include mainly hexoses (glucose, man-
nose, and galactose) and pentoses (xylose and arabinose), as well as
some other low-content saccharides (rhamnose and fructose). In
addition, there are some uronic acids (4-O-methyl-d-glucuronic
acid, d-glucuronic acid, and d-galacturonic acid) and acetyl groups
in the hemicellulose structure. The structure of these building
blocks are shown in Fig. 3, and their contents in hemicellulose are
summarized in Table 2. In general, these building blocks constitute
polysaccharides, such as glucuronoxylan, galactoglucomannan, ara-
binoglucuronoxylan, xylanglucose, xyloglucan and arabinoxylan,
which further constitute hemicellulose. The content of hemicellulose
38 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86

Fig. 3. Chemical structure of hemicellulose building blocks.

TagedPand the species of polysaccharides greatly depend on the sources of
biomass. Hardwood, softwood, and herbaceous plants have hemicel-
lulose contents of 10
15%, 18
23% and 20
25%, respectively. The
polysaccharides in hardwood hemicellulose include glucuronoxylan,
xyloglucan and glucomannan, while softwood hemicellulose is pri-
marily composed of xyloglucan, arabinoglucuronoxylan and galacto-
glucomannan, and the herbaceous hemicellulose primarily consists
of glucuronoarabionxylan and xyloglucan [61,125,126].
TagedPAs shown in Table 2, monosaccharides are the primary building
blocks (functional groups) of hemicellulose, with a small amount of
uronic acids and acetyl groups. The pyrolysis behavior of hemicellu-
lose is highly reflected by the characteristics of those building blocks
in the thermal conversion process. Investigation of pyrolysis of those
monosaccharides can provide insight and implications for the pyrol-
ysis chemistry of hemicellulose. Ra €isa
€nen et al. [135] revealed that
the product distributions from the pyrolysis of xylose, arabinose,
mannose and galactose were similar in quality but different in quan-
tity. Furans, ketones and anhydrosugars were the major products,
with furfural the most abundant. The pyrolysis of xylose and arabi-
nose generated more small molecular compounds than that of man-
nose. The pyrolysis of hexose (mannose and galactose) also
produced HMF, which was not a typical product obtained from
xylose and arabinose. Gardiner et al. [136] pyrolyzed mannose and
galactose in a vacuum environment, and found that the main
TagedP roducts of mannose pyrolysis were 1,6-anhydro-b-D-mannopyra-
p
nose and 1,4:3,6-dianhydro-D-mannopyranose, whereas those from
galactose pyrolysis were 1,6-anhydro-b-D-galactopyranose and
HMF. Wang et al. [137] found that mannose, galactose, and arabinose
had similar thermal behavior for the formation of many products,
including acetic acid and furfural. They suggested that all the mono-
saccharide units in hemicellulose could be easily ring-opened and
cracked, resulting in the formation of 1-hydroxy-2-propanone, fura-
none, and other small molecular compounds. The pyrolysis of uronic
acids and acetyl groups mainly contribute to the formation of CO2,
formic acids, and acetic acids [127,137
139].
TagedPD10X X
Different types of hemicellulose polysaccharides show distinct
chemical properties, including sugar composition, backbone struc-
ture, glycoside linkage type, composition and distribution of side-
chain functional groups, degree of acetylation (DA), and degree of
polymerization. For example, glucuronoxylan, known as O-acetyl-4-
O-methylglucuronoxylan, is the most abundant hemicellulose poly-
saccharide in hardwood, accounting for 15
30%. It mainly consists
of b-D-xylose backbones with b¡1,4-glycosidic bond. Most of the
xylose residues contain an acetyl group at C-2 or C-3, and glucurono-
syl and 4-O-methylglucuronosyl residues attach to the backbones
through a¡1,2-glycosidic bonds. The DP of glucuronoxylan is
approximately 200 for hardwood hemicellulose. Galactogluco-
mannan is a typical polysaccharide in softwood hemicellulose,

Table 2
Monomeric composition of hemicellulose.

Hemicellulose Mannose Glucose Galactose Arabinose Xylose R Fructose Uronic acids

Hardwood
Eucalyptus saligna [127] 6.2 6.7 7.2 3.8 54.4

21.7
Fraxinus mandshurica [127] 8.0 2.7 7.0 3.2 62.7

23.6
Tamarix austromongolica [128]
1.9 8.1 3.8 73.6 1.6
11.1
Poplar [129] 2.2
9.3 3.5
7.2 1.9
2.8 0.9
1.3 78.7
88.8 1.6
2.2
8.4
12.3
Softwood
Pinus sylvestris [127] 29.9 22.9 9.4 8.0 18.4

11.5
Tsuga chinensis [127] 39.4 21.6 11.8 7.5 10.0

9.9
P.armandii Franch [85] 31.6 11.7 10.8 9.5 19.1

16.5
Pinus densiflora [130] 22.6 21.2 10.1 5.7 17.5 1.4 0.7 20.7
spruce wood [131] 49 19 19 5 <1 <1
7
Grass
rice straw [132] 5.1 5.0 7.5 8.3 61.0

13.1
corn stalk [132] 5.4 7.2 7.9 9.9 59.9

9.7
Wheat brain [133]
49 1 17 30

3
Corn cob [133]
43 2 7 43 1
4
Miscanthus [134] 0.2 1.1 1.2 11.1 86.2 0.2 0.01

 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPconstituting 10%
25% of the total. It has a chain skeleton structure
where b-D-glucose and b-D-mannose are linked by b¡1,4-glyco-
sidic bonds with a¡1,6-D-galactose residue in the side chain. The C-
2 and C-3 atoms in the main chain units are partially acetylated, and
the acetyl content is approximately 6%, with 3
4 hexose units corre-
sponding to one acetyl on average. Galactoglucomannan has a DP of
approximately 40
100 in softwood. Arabinoglucuronoxylan is a rep-
resentative hemicellulose polysaccharide in non-wood biomass
(mainly agricultural biomass) and also exists in softwood in small
amounts. It mainly consists of a linear b¡1,4-D-xylose skeleton
structure with a¡1,2-glycosidic bonds linking 4-O-methyl-a-D-
pyran glucuronic acid and a¡1,3-glycosidic bonds linking a-L-arabi-
nofuranose. The DP of arabinoglucuronoxylan in non-wood biomass
ranges from 50
185. More information about the structural charac-
teristics of hemicellulose polysaccharides is reviewed in references
[61,124,126].
TagedPCompared to simple monosaccharides, the structures of hemicel-
lulose polysaccharides are much more complicated, which may lead
to obvious differences in their pyrolysis behaviors. For example, the
pyrolysis of xylan firstly encountered the rupture of glycosidic bonds
to form intermediate units that mainly included various anhydrosu-
gars and xylopyranosyl cation, and then the evolution of these inter-
mediates may involve different reaction pathways [61,140]. In
contrast, the pyrolysis of monosaccharide xylose does not undergo
this depolymerization step. In addition, some branch linkages in the
xylan chain may be broken in the pyrolysis process to form specific
products such as acetic acid, formed from the cleavage of O-acetyl
groups. Wang et al. [137] compared the pyrolysis of xylan and
monosaccharides (arabinose, mannose and galactose). They found
that temperature corresponding to the maximum weight loss rate
for xylan (283 °C) was obviously lower than that for monosacchar-
ides (over 330 °C), and the char yield from xylan (26.5%) was much
more than that from monosaccharides (less than 20%). Shafizadeh
et al. [141] also observed the difference in the product distribution
from pyrolysis of xylan and monosaccharides, and they suggested
that this was due to the glycosyl units, formed by the cleavage of gly-
cosidic bonds of xylan, can condense randomly to tarry products or
degrade to a variety of volatile compounds. Therefore, the pyrolysis
of hemicellulose polysaccharides can provide more insights into
hemicellulose pyrolysis behavior. Werner et al. [142] investigated
the thermal decomposition behavior of several hemicellulose poly-
saccharides (b-glucan, arabinogalactan, arabinoxylan, galacto-
mannan, glucomannan, xyloglucan, and xylan). The polysaccharides
exhibited different mass loss rate characteristics, wherein glucan-
based polysaccharides were the thermally most stable and xylan
was the least stable. In addition, the formation of anhydrosugar was
closely correlated with the monosaccharide composition of the poly-
saccharides. Generally, pentoses formed 1,4-anhydropentoses and
hexoses formed 1,6-anhydrohexoses. For instance, glucans, mannans
and galactans mainly formed the anhydrosugars 1,6-anhydro-b-d-
glucopyranose (LG), 1,6-anhydro-b-d-mannopyranose (levomanno-
san) and 1,6-anhydro-b-d-galactopyranose (levogalactosan), respec-
tively, while polysaccharides containing arabinose and xylose
mainly formed 1,4-anhydro-arabinofuranose (arabinosan) and 1,4-
anhydro-b-d-xylopyranose (xylosan), respectively [142]. Moreover,
these anhydrosugar intermediates may contribute to the differences
in stability among the polysaccharides during decomposition since
LG (six carbon atoms) is more stable than arabinosan (five carbon
atoms) and xylosan (five carbon atoms) [142]. Pentosan more easily
formed char than glucan D1X X during thermal decomposition [85,142].
The proposed explanation is that the scission of glucans generally
yields a glucosyl cation with a free primary hydroxyl group at C-6,
which favors the formation of a stable 1,6-anhydride that can con-
vert into volatile LG [143]. On the other hand, the decomposition of
xylan is most likely to yield a xylopyranosyl cation, which tends to
polymerize to char because it cannot be stabilized by the formation
39
TagedPof uronicanhydride via intramolecular dehydroxy reaction due to
the absence of a hydroxymethyl group, contrast to the glycosyl cat-
ion [143]. Compared to other hemicellulose polysaccharides, the
pyrolysis of xylan yields more CO2, which may result from the high
content of glucuronic acid units and O-acetyl groups in the xylan
structure, because the decarboxylation of COOH groups, cracking
and reforming of CHO and COOH groups, and decarboxylation of O-
acetyl groups yield CO2 [139,144,145].
TagedPThe pyrolysis of hemicellulose extracted/isolated from biomass
may provide greater insight into the pyrolysis mechanism of native
hemicellulose compared to simple polysaccharides or monosacchar-
ides. The extraction of hemicellulose from biomass has been studied
for decades, and many extraction methods have been developed,
such as hot alkali, alkaline peroxide, steam explosion (autohydroly-
sis), microwave heat fractionation, organosolv, wet oxidation, ozo-
nolysis, enzymatic hydrolysis, dilute-acid hydrolysis, and
(pressurized) hot-water extraction [61,124]. However, no extraction
methods have been reported to extract all hemicellulose polysac-
charides from biomass because hemicellulose is prone to be decom-
posed. Alkali-extracted hemicelluloses are commonly used as model
compounds for hemicellulose [85,138,139,146]. This alkali-extracted
hemicellulose preserves the original structure of hemicellulose with
a high degree of polymerization [85]. Therefore, it may contribute to
the high yield of char during thermal decomposition [85]. On the
other hand, alkali extraction removes the acetyl groups of native
hemicelluloses, which decreases the formation of acids. Recently,
Wang et al. [127,132] extracted hemicellulose from softwood
(Pinus sylvestris and Tsuga chinensis), hardwood (Eucalyptus
saligna and Fraxinus mandshurica) and agricultural waste (rice
straw and corn straw) biomass using a neutral solvent, DMSO, which
minimally damaged the hemicellulose structure and preserved the
acetyl groups and other side or branching groups. The softwood
hemicelluloses (PSH and TCH) were composed of D-galacto-D-
gluco-D-mannan and L-arabino-4-O-methyl-D-glucurono-D-xylan.
The hardwood hemicelluloses (ESH and FMH) were mainly com-
posed of 4-O-methyl-D-glucurono-D-xylan and had high contents of
O-acetyl and uronic acid units, while the straw hemicelluloses (CSH
and RSH) were composed of L-arabino-4-O-methyl-D-glucurono-D-
xylan. Correspondingly, the major monosaccharide was hexose in
the softwood hemicellulose and xylose in the hardwood and straw
hemicellulose. Softwood hemicellulose pyrolysis had a higher peak
temperature (approximately 310 °C) than hardwood and straw
hemicellulose pyrolysis (274 °C for ESH, 286 °C for FMH, 291 °C for
CSH and 286 °C for RSH). Moreover, the softwood hemicellulose
exhibited a higher activation energy (approximately 160 kJ/mol)
than the hardwood and straw hemicellulose (approximately 150 kJ/
mol). This might result from the higher thermal stability of hexose
units than pentose units in the form of a b¡1,4-glucosidic bonded
polymer. Hardwood hemicelluloses yielded more char (approxi-
mately 33 wt.%) than softwood and straw hemicelluloses
(25
30 wt.%). Additionally, the char yields of these hemicelluloses
were higher than that of the simple polysaccharide xylan (approxi-
mately 24%), which indicated that the char yield of hemicellulose
was correlated with the monosaccharide compositions and struc-
tural diversity. The hemicellulose with higher content of pentose
and side branches had a higher char yield, since hemicellulose with
well-preserved branches and better structural diversity could pro-
duce multiple types of macromolecular radicals through the cleav-
age of glycosidic bonds, and these macromolecular radicals were
likely to undergo polymerization to form char [127]. The pyrolysis
products from hardwood and straw hemicelluloses had high con-
tents of acids and furfural, and were rich in five-carbon compounds,
while those from softwood hemicelluloses mainly contained six-car-
bon compounds, such as HMF and anhydrosugars. The molecular
weight of hemicellulose extracted by neutral solvent is lower than
that extracted by alkali solution, indicating that only part of the
40 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPpolysaccharides are extracted. Thus, to gain a comprehensive under-
standing of the pyrolysis behavior of hemicellulose, it is worth to
integrate the investigation of pyrolysis of various hemicelluloses
extracted using different methods.
2.4. Lignin structure and pyrolysis
TagedPIn contrast to the carbohydrates structure of cellulose and hemi-
cellulose, lignin has an aromatic matrix that adds strength and rigid-
ity to the cell walls. The lignin content varies among species of
biomass and even among morphological parts of a plant. For exam-
ple, softwood lignin accounts for 25
35% of the total plant mass,
while hardwood and grass lignin account for 20
25% and 10
15%,
respectively. Lignin is mainly an amorphous tridimensional polymer
composed of three basic units, namely p-coumaryl (4-hydroxycin-
namyl), coniferyl (3-methoxy 4-hydroxycinnamyl) and sinapyl (3,5-
dimethoxy 4-hydroxycinnamyl) alcohols, which are also known as
p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) units (Fig. 4),
respectively [147
149]. The main difference in the three basic units
is the number of methoxyl groups attached to an aromatic ring. The
H, G and S units have none, one and two methoxyl groups, respec-
tively. These basic units contain a phenyl group and a propyl side
chain; therefore, the typical aromatic unit in lignin is called a phe-
nylpropane unit (ppu). The proportion of H/G/S units in lignin largely
depends on the biomass species. As shown in Table 3, softwood lig-
nin has a high content of guaiacyl units, hardwood lignin presents a
mixture of guaiacyl and syringyl units, and grass lignin contains a
mixture of all three units [147
149]. According to the abundance of
the three basic units, lignin can be classified as type-G (softwood lig-
nin), type-G-S (hardwood lignin) and type-H-G-S (grass lignin).
These units form the lignin matrix through various linkages, and dif-
ferent functional groups attach to the propyl side chain, leading to
extremely complicated lignin structures.
TagedPThe linkages of basic lignin units are complex and can be divided
into three classes: ether bonds, carbon-carbon bonds and ester
bonds. Ether bonds are the most prevalent in lignin, accounting for
60
70% of the total linkages, while carbon-carbon bonds account for
30
40%. The content of ester bonds in the lignin structure is low and
mainly exist in herbaceous plants. Ether bonds are mainly present as
linkages between a phenylpropane side chain and a benzene ring
(b-O-4, a-O-4, g -O-4), between benzene rings (4-O-5) and between
phenylpropane side chains (a-O-b0 , a-O-g 0 ), while carbon-carbon
bonds primarily contain 5
5, b¡1, and b¡5 linkages, as well as
Fig. 4. Basic units of lignin polymer.
Table 3
The content of the basic units in different lignins [148].
Basic unit Softwood lignin Hardwood lignin Grass lignin
Syringyl unit (S) 0 ¡ 1% 50 ¡ 75% 25 ¡ 50%
Guaiacyl unit (G) 90 ¡ 95% 25 ¡ 50% 25 ¡ 50%
p-hydroxyphenyl unit (H) 0.5 ¡ 3.4% Trace 10 ¡ 25%
sTagedP ome b¡6, a¡6, a-b0 , etc. [78,125,150,151]. Representative struc-
tures of these linkages are shown in Fig. 5. The contents of these
linkages vary among biomass lignins. The typical proportions are
summarized in Table 4. b-O-4 is the most frequent linkage in lignin
and its content in softwood and hardwood lignin is 43
50% and
50
65%, respectively, which is much higher than that of other ether
bonds. The 5
5 linkage is the main carbon-carbon linkage in both
softwood and hardwood lignin, and softwood lignin contains more
b¡5 and 5
5 linkages than hardwood lignin because the C5 posi-
tions of G-type units are available for coupling whereas those in S
units are substituted by methoxyl groups. Therefore, softwood has a
higher condensation degree than hardwood lignin. In addition, the
steric effect of the methoxy groups on the aromatic rings of the S
units may lead to more linear structural forms in the hardwood lig-
nin matrix than in the softwood lignin matrix. The various linkage
patterns in different lignins significantly influence their pyrolysis
behavior. Generally, ether linkages, such as a-ether and b-ether, are
easily cleaved to form phenolic products. In particular, a-O-4 and
b-O-4 are the weakest among all linkages and can be thermally
cleaved at 200
250 °C [62,152]. In contrast, carbon-carbon linkages
such as b¡1 and b¡5 have relatively low reactivity, and the cleavage
of linkages combining the carbon atoms in different aromatic rings,
such as 5
5, is difficult. Therefore, the thermal degradation of lignin
shows a broader peak in its DTG curves compared to cellulose and
hemicellulose due to the successive cleavage of linkages as the reac-
tion temperature increases. Moreover, hardwood lignin exhibits
obviously weaker thermal stability, due to its high b-O-4 content
and low 5
5 content than softwood lignin [153,154]. The higher
condensation degree of softwood lignin also contributes to greater
char yield compared to hardwood lignin [153,154]. The reactivity of
the linkages is also influenced by the substituted functional groups
(phenolic hydroxyl group and methoxyl group). Kawamoto et al.
[155] investigated the reactivity of dimers with different linkages
(a-O-4, b-O-4, b¡1, and 5
5), and found that the reactivity of
dimers followed the order: a-O-4 (phenolic and non-phenolic (with
methoxyl group)), b-O-4 (phenolic) > b-O-4 (non-phenolic), b¡1
(phenolic and non-phenolic) > 5
5 (phenolic and non-phenolic),
and the phenolic type was more reactive than the non-phenolic type
for compounds with the same linkage.
TagedPLignin also contains various oxygenated functional groups,
including methoxyl, hydroxyl, carboxyl and carbonyl groups, etc.,
which significantly affect the reactivity of lignin. The number of
methoxyl groups in softwood (92
96/ppu) is lower than that in
hardwood (132
146/ppu), in accordance with the H/G/S composi-
tion of lignin [148]. The content of methoxyl groups in lignin is cor-
related with the formation of lignin pyrolysis char. For type-G and
type-H lignin, the C3 and/or C5 position in the aromatic ring do not
contain methoxyl groups, which enables condensation, in contrast
to the same positions in type-S lignin [153,154,156,157]. Further-
more, methoxyl groups may decompose into small molecular radi-
cals, which further stabilize the large-molecule fragments produced
during lignin pyrolysis and prevent their polymerization to char.
Table 4
Linkage quantities in different lignins
(Number/100 ppu) [148].
Linkage Softwood Hardwood
b-O-4 43
50 50
65
b¡5 9
12 4
6
a-O-4 6
8 4
8
b-b’ 2
4 3
7
5
5 10
25 4
10
4-O-5 4 6
7
b¡1 3
7 5
7
others 16 7
8
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 5. Various linkages in the lignin structure.
TagedPTherefore, the lignins with high methoxyl group contents produce
less char during the pyrolysis process. The evolution of methoxyl
groups during lignin pyrolysis also affected the product distribution
[154,157
160]. The decomposition of methoxyl groups could lead
to transformation of type-S phenols to type-G phenols and even to
monophenols or catechols, and this transformation was enhanced at
high reaction temperatures. Therefore, with increasing reaction tem-
perature from 400 to 800 °C, the formation of type-S phenols
decreased while that of type-H phenols increased and that of type-G
phenols reached a maximum at 600 °C [158]. The decomposition of
methoxyl groups also release small molecular compounds such as
methane and methanol [154,161
163]. Hydroxyl groups are another
important functional group in lignin, including aliphatic, guaiacyl
phenolic, syringyl phenolic and p-hydroxyphenyl hydroxyl groups.
The aliphatic hydroxyl is typically the dominant hydroxyl in lignin.
In lignin pyrolysis, it is easy to remove the aliphatic hydroxyl group
from the side chains through dehydration at low temperature, lead-
ing to the formation of an unsaturated side chain structure. Conse-
quently, phenols with unsaturated side chains, such as 4-
propenylguaiacol, 4-vinylguaiacol and 4-propenylsyringol, are com-
mon lignin products [138,154,157
159,161,162,164,165]. The
hydroxyl groups in the side chains significantly affect the reactivity
of the linkages because hydroxyl groups at the Ca or Cg position act
as hydrogen donors during pyrolysis [166,167]. The distribution of
phenolic hydroxyl groups varies in different biomass types. Soft-
wood mainly contains guaiacyl phenolic hydroxyl groups with a
minor amount of p-hydroxyphenyl and almost no syringyl phenolic
hydroxyl groups. In contrast to softwood, the hydroxyl group con-
tent in hardwood lignin follows the order of aliphatic > guaiacyl
phenolic » syringyl phenolic > p-hydroxyphenyl. Grass lignin has a
higher content of p-hydroxyphenyl than wood lignin. The distribu-
tions of these phenolic hydroxyl groups are correlated with the type
41
TagedP f lignin and the final phenolic products of pyrolysis
o
[138,154,157
159,161,162,164,165]. There are also other types of
oxygenated groups, such as carboxyl and carbonyl groups, in the lig-
nin structure. These groups may decompose to small-molecule
chemicals, such as CO2, CO and formaldehyde, or remain in the side
chains of phenols [154,161
163,166,167].
TagedPIt remains challenging to isolate native lignin from biomass
because of the complexity of the lignin structure and the linkages
between lignin and other components in plants. In the past decades,
many methods have been proposed to isolate lignin, including the
Klason method, Kraft process, Bjö rkman process, organosolv process
and sulfite pulping process, etc. [147,148,168]. These methods alter
the physical and chemical properties of native lignin to some degree.
The milled wood lignin isolated by the Bjö rkman process is sug-
gested to be representative of native lignin because the structure is
well preserved by using neutral solvent extraction [156,157]. The
pyrolysis behavior of various lignins isolated using different meth-
ods has been intensively investigated [82,149,169], and the main
pyrolysis characteristics are correlated with the distribution of the
linkages and the functional groups as indicated above.
2.5. Extractives and inorganic minerals
TagedPIn addition to the three major components, there are small
amounts of extractives in biomass. They do not constitute cell walls
or cell layers but are nonstructural components. Extractives can be
extracted by nonpolar solvents (such as toluene and hexane) or polar
solvents (such as water, methylene chloride and alcohol). The
extractives in lignocellulosic biomass mainly include waxes, fats,
resins, tannins, sugars, starches, pigments, etc. These components
can be classified into three groups: aliphatic compounds (mainly
fats and waxes), terpenes and terpenoids, and phenolic compounds
42 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedP[170
172], the amounts of which strongly depend on the type of
biomass and the location on the plant [172
174]. Due to the rela-
tively low content of extractives in biomass compared to the three
major components, their influence on biomass pyrolysis is some-
times ignored. However, they indeed affect the pyrolysis behavior
and the properties of bio-oil, especially when pyrolyzing extrac-
tives-rich biomass [175
177].
TagedPThe decomposition of extractives may occur in the same temper-
ature range as that of the natural polymers that make up the cell
walls of plants. However, most extractive compositions are ther-
mally unstable, leading to a peak at low temperature in DTG curves.
The temperature corresponding to the maximum thermal weight
loss rate for extractives is approximately 205 °C, in contrast to that
of 270 °C, 327 °C and greater than 327 °C for hemicellulose, cellulose
and lignin, respectively [178]. Guo et al. [179] found that the activa-
tion energy for raw Mongolian pine and Manchurian ash pyrolysis
was 104.37 and 85.07 kJ/mol, respectively, and they increased to
119.38 and 109.15 kJ/mol after removing the extractives. This sug-
gested that the presence of extractives improved the activity of the
components and promoted the decomposition of structural com-
pounds. In addition to the thermal decomposition behavior, the
presence of extractives resulted in a different final product distribu-
tion. Increasing the extractive content in the initial biomass
improved the yield of liquids and lowered the yield of char and gas
[176]. Guo et al. [179] observed that biomass with the extractives
removed yielded pyrolysis products at a lower temperature com-
pared to raw biomass. The extractive-free biomass also produced
more water, CO2, CO, and aldehydes, and less acids and alkanes,
compared to the raw biomass. Wang et al. [180] found that higher
extractives contents could increase the sugar, especially LG, and
furan contents in the bio-oil. Furthermore, extractives yield addi-
tional products which may influence the product distribution of the
whole biomass sample [181]. Extractive-derived products, including
fatty acids, hydroxy fatty acids, resin acids, triglycerides and sterols,
contribute to a separate upper phase of bio-oil, which is attributed
to their low oxygen content and high viscosity [172,182].
TagedPBiomass also contains a very small amount of inorganic minerals,
which are primarily composed of potassium, calcium, sodium, mag-
nesium, silicon, phosphorus, sulfur, chlorine, etc.. Traces of alumi-
num, titanium, vanadium, manganese, iron, cobalt, nickel, copper,
zinc, molybdenum, and other heavy metals may also be present in
biomass [183
185]. The content and distribution of those minerals
in biomass vary in different biomass. Woody biomass typically con-
tains a much lower quantity of inorganics than agricultural residues
[82,185]. As shown in Table 5, SiO2, CaO and K2O are the dominant
components of ash, CaO is the major component of wood biomass
ash, and SiO2 is the major component of herbaceous and agricultural
biomass. Most inorganic minerals are retained in the char during
pyrolysis. Despite the small amount, the inorganic minerals in bio-
mass may exert significant influence on pyrolysis. The catalytic
effect of those inorganics on biomass pyrolysis will be discussed in
Section 6.
2.6. Pyrolysis behavior of whole biomass and the interactions of the
three main biomass components
TagedPThe pyrolysis behavior of whole biomass is closely related to the
proportion and the form of three major components. Greenhalf et al.
Table 5
Chemical ash composition of biomass based on high-temperature ash analyses (normalized to 100%), wt.% [185].
SiO2 CaO K2 O
Wood and woody biomass 22.22 43.03 10.75
Herbaceous and agricultural biomass 33.39 14.86 26.65
[TagedP 186] performed a comparative study of straw, perennial grasses
and hardwoods pyrolysis, and found that the hardwoods had lower
maximum thermal decomposition rates which occurred at higher
temperatures due to the higher lignin content. Qu et al. [91] found
that peanut straw pyrolysis produced larger content of carbohy-
drates for the higher content of cellulose than corn stalk, while
bio-oil from corn stalk pyrolysis contained more aldehydes due
to the higher content of hemicellulose. Butler et al. [187] com-
pared the pyrolysis product distribution of spruce, salix, miscan-
thus and wheat straw. It was found that the relative portions of
lignin derived products were consistent with the expected lignin
structure, namely a relatively high content of guaiacol products
from guaiacyl units for spruce, syringol products from syringyl
units for salix, and lignin-derived phenols from p-hydroxyphenyl
units for miscanthus. Besides, spruce with the lowest hemicellu-
lose content produced the smallest yield of acetic acid, which
was mainly from the dissociation of O-acetyl group in hemicellu-
lose. Biagini et al. [188] found that the release behaviors of the
typical volatiles determined by TG-FTIR during pyrolysis of
whole biomass could be simulated via the integration of the
individual release behaviors of cellulose, hemicellulose, and lig-
nin. It seemed that the interactions of the biomass components
could be ignored. This was also found by some other researchers
[38,189,190].
TagedPHowever, the interactions of the three main biomass components
do exist and have a great influence on biomass pyrolysis behavior
[191
196]. Hosoya et al. [193] found that the presence of lignin
remarkably suppressed the tendency of thermal polymerization and
carbonization of the macromolecular products, such as levoglucosan
from cellulose pyrolysis. It promoted the degradation of cellulose to
small molecular products. In addition, the presence of cellulose sup-
pressed char formation from lignin, while enhanced the conversion
of lignin to phenols. According to the different release behavior of
synthetic biomass samples based on three-component mixtures
obtained by TG-FTIR, Liu et al. [194] proposed that the presence of
lignin decreased the formation of 2-furaldehyde and CHO containing
compounds in hemicellulose pyrolysis, while the presence of hemi-
cellulose remarkably decreased the yield of LG, and largely enhanced
the formation of HAA in cellulose pyrolysis. Wang et al. [195] found
that the hemicellulose-cellulose interaction had a positive influence
on the formation of 2,5-diethoxytetrahydrofuran, and a negative
effect on the formation of altrose and LG. The presence of cellulose
promoted the formation of hemicellulose-derived acetic acid and 2-
furaldehyde, while the presence of lignin showed an inhibitory
effect. The interaction between hemicellulose and lignin enhanced
the formation of lignin-derived phenols and inhibited the formation
of hydrocarbons. Based on the quantitative comparisons of pyrolysis
products from native mixture, physical mixture, and superposition
of individual biomass components, Zhang et al. [196] proposed that
there was no significant interaction between cellulose and hemicel-
lulose, while the interaction between cellulose and lignin in herba-
ceous biomass was significant, as indicated by the yield increase
of low-molecular-weight compounds and furans, and the yield
decrease of LG.
TagedPAlthough great efforts have been made to investigate the interac-
tions of the three main biomass components, the detailed interac-
tion mechanism is still not very clear. This hindered the better
understanding of pyrolysis behavior of whole biomass.
P2O5 Al2O3 MgO Fe2O3 SO3 Na2O TiO2
3.48 5.09 6.07 3.44 2.78 2.85 0.29
6.48 3.66 5.62 3.26 3.61 2.29 0.18
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
3. Latest experimental methods to unravel the biomass pyrolysis
mechanism
TagedPResearch and development of biomass pyrolysis in the 20th cen-
tury mainly focused on maximizing the bio-oil yield and improving
the quality of the target products (Dbio-oil, 12X X gas or char) by optimizing
the operating conditions and reactor configurations [67]. The most
common experimental method is to perform applied pyrolysis in
reactors and to characterize the collected products. Several types of
reactors including fixed bed [197], fluidized bed [198], ablative
[199], rotating cone [200], circulating fluidized bed [201], and vac-
uum [202], have been investigated extensively for applied pyrolysis
studies. Although progress has been made to optimize process and
reactor scale-up, empirical studies have limitation to elucidate the
reaction mechanism. Recently, research focus has shifted to funda-
mental studies to understand the pyrolysis reaction chemistry, with
the help of advanced instrumentation.
TagedPThermogravimetric (TG) analysis has been widely used in analyti-
cal biomass pyrolysis research. It determines the mass loss process
with temperature D13X X change and is often applied for macroscopic
kinetic modelling. According to the heating programs used in col-
lecting data, the TG analysis can be divided into isothermal process
[203] and non-isothermal process [204]. Considering the relatively
low heating rate of TG D14X X analyzer, biomass has been significantly
decomposed before it reaches the required temperature during iso-
thermal analysis, making the ideal isothermal conditions challenging
in TG research [205]. Thus, the non-isothermal method is frequently
used. These two heating methods can also be combined into a single
process named stepwise heating [206]. Based on TG analysis, many
kinetic models for biomass pyrolysis have been proposed [67]. How-
ever, due to the limitations of the analytical technology, the pyroly-
sis products are roughly categorized into char, tar and gases. Limited
information can be obtained from TG studies regarding the reaction
intermediates, reaction pathways, etc.
TagedPAn in-depth understanding of pyrolysis mechanism requires
more detailed information about the pyrolysis process, including
quantification of the pyrolysis products, evolution process of the
reactants and products, and determination of the reaction inter-
mediates. To achieve these goals, several advanced experimental
technologies, including Py
GC
MS/FID, TG-MS/TG-FTIR, reaction
process analysis technology (in situ spectroscopy, 2D-PCIS), isotopic
labeling and intermediate product analysis technology (in situ EPR,
PIMS), have been developed and applied to biomass pyrolysis
research. This section covers the advances in these research areas.
3.1. Pyrolysis product analysis by Py
GC
MS/FID
TagedPA micro-pyrolyzer combined with gas chromatography (GC),
mass spectrometry (MS), and flame ionization detection (FID)
(Py
GC
MS/FID) is a powerful tool to quantitatively investigate the
product distribution from biomass pyrolysis with great convenience.
The pyrolytic vapors generated in the micropyrolyzer are directly
transported into the GC
MS/FID for characterization without con-
densation. The pyrolysis vapors may be qualitatively determined by
a MS detector after separation by GC and then quantified by FID or
another type of detector. Compared with the several seconds of resi-
dence time in conventional laboratory-scale reactors, the residence
time of volatiles in a micro-pyrolyzer can be as short as 15
20 ms
[207]. The short residence time sustainably inhibits secondary reac-
tions, making the micro-pyrolyzer ideal for investigating the pri-
mary reactions of biomass pyrolysis.
TagedPWith the help of Py
GC
MS/FID, the product distributions of the
primary pyrolysis of three major components in biomass were stud-
ied systematically [98,139,208,209]. Patwardhan et al. [98] quanti-
fied fifteen main products from the pyrolysis of glucose-based
carbohydrates, including glucose, cellobiose, maltose, maltohexaose,
43
cTagedP ellulose, curdlan, waxy maize starch and dextran. LG was the major
pyrolysis product for all saccharides, especially cellulose (59 wt.%).
The orientation or the position of the glycosidic linkages had little
effect on the product distribution except the 1,6-linked polysaccha-
ride, which produced a remarkably lower yield of LG. By comparing
the product distributions of cellulose pyrolyzed at temperatures
ranging from 350 to 600 °C, it was observed that cellulose mainly
produced anhydrosugars at lower pyrolysis temperature (less than
400 °C), whereas LG (48 wt.%) and formic acid (28 wt.%) were the
major products at 600 °C [208]. The primary product distributions of
hemicellulose and lignin pyrolyzed at 500 °C were determined by
Patwardhan et al. [139,209]. The condensable volatiles were mea-
sured by Py
GC
MS/FID, and the yields of gases including CO and
CO2 were determined using a De Jaye gas analyzer connected to GC.
The final quantified products accounted for 84.3% and 84.5% of the
overall products according to the mass balances for hemicellulose
and lignin, respectively. The yields of the primary pyrolysis products
of hemicellulose isolated from switchgrass via alkaline extraction
decreased in the order of CO2, formic acid, char, dianhydro xylopyra-
nose, xylose, anhydroxylopyranose, acetol, CO and 2-furaldehyde
[139], while the primary pyrolysis products of lignin were mono-
meric phenolic compounds, among which phenol, 4-vinyl phenol, 2-
methoxy-4-vinyl phenol, and 2,6-dimethoxy phenol were the major
products [209]. During pyrolysis of hemicellulose and lignin, the
high pyrolysis temperature promoted the formation of low-molecu-
lar-weight species and inhibited char formation [139,209]. The
dehydration products from hemicellulose including 2-furaldehyde,
dianhydro xylopyranose and anhydroxylopyranose achieved their
highest yields at 350
450 °C [139]. The yield of alkylated phenols
from lignin increased with temperature, whereas that of methoxy-
lated phenols reached a maximum at 600 °C [209].
TagedPThe determination of the product distribution by Py
GC
MS/FID
is crucial to understanding the pyrolysis mechanism. This informa-
tion provides insight into the primary reactions [196,210]. It can also
help to reveal secondary reactions [207,211]. Choi et al. [210] per-
formed a quantitative mole balance of the reaction species during
the pyrolysis of seven lignin model compounds (five b-O-4 and two
a-O-4 linked molecules) and a trimer lignin model compound with
b-O-4 and a-O-4 linkages in Py
GC
MS/FID, and concluded that
concerted retro
ene fragmentation and homolytic dissociation
were the initial reactions for b-O-4 compounds and a-O-4 com-
pounds, respectively. According to the differenceD15X Xbetween the prod-
uct distributions from primary pyrolysis in a micro-pyrolyzer and
that involving both primary and secondary reactions in a fluidized
bed reactor, Patwardhan et al. [207] proposed that the major second-
ary reactions of cellulose were oligomerization of LG and decompo-
sition of primary products such as HMF, anhydro xylopyranose and
2-furaldehyde. Butler et al. [211] found that compounds including
lignin-derived monomers with vinyl groups, furan and pyran com-
pounds were more likely to undergo secondary reactions than other
products during pyrolysis of complete biomass. The micro-pyrolyzer
can also be used to study the secondary reactions of pyrolysis by
changing reaction conditions, including the sample weight, particle
size, and morphology of biomass samples. Zhang et al. [212] system-
atically evaluated the primary and secondary reactions during cellu-
lose fast pyrolysis by Py
GC
MS/FID. They found that the char from
cellulose pyrolysis could catalyze the secondary reactions including
secondary char and gas formation from volatile products and
decomposition/dehydration of LG into low-molecular-weight prod-
ucts, furans, and dehydrated pyranose.
TagedPOne improvement of Py
GC
MS/FID is to integrate a thermal
conductivity detector (TCD, which is used to measure non-condens-
able gas) together (Py
GC
MS/FID/TCD), as shown in Fig. 6
[213,214]. Py
GC
MS/FID/TCD can quantify the composition of tar,
char and non-condensable gases simultaneously. However, these
analytical technologies can only analyze a small fraction of pyrolysis
44 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 6. Schematic diagram of Py
GC
MS/FID/TCD (reprinted from Wang et al. [214]
with permission of Elsevier).
TagedPproducts due to the insufficient resolution and the inability to detect
isomers in traditional GC
MS [215]. One promising solution is com-
prehensive two-dimensional gas chromatography (GC £ GC) coupled
with time-of-flight mass spectrometry (TOF-MS) (GC £ GC-TOFMS).
GC £ GC uses a nonpolar column for the first dimension to distin-
guish compounds with similar chemical structures and a polar col-
umn for the second dimension. GC £ GC-TOFMS can identify much
more chemicals during biomass pyrolysis than traditional GC
MS. A
study by Tessarolo et al. [216] showed that the number of chemicals
identified by GC £ GC-TOFMS was 4
7 times as many as those iden-
tified by GC
MS. Combined with FID, GC £ GC-TOFMS (GC £ GC-
TOFMS/FID) can also be used for the quantitative analysis of pyroly-
sis products [217]. However, the existing GC £ GC-TOFMS studies
are mainly focused on the chemical characterization of bio-oils
[215,216,218
220], its application in analytical pyrolysis studies is
limited.
3.2. Pyrolysis product analysis by TG-FTIR and TG-MS
TagedPOne drawback of Py
GC
MS/FID is that it only allows non-con-
tinuous analysis. It cannot be applied to obtain information about
the evolution characteristics with time or temperature. To solve this
problem, TG coupled with Fourier transformed infrared spectros-
copy (TG-FTIR) and TG coupled with mass spectrometry (TG-MS)
were developed. These two technologies can monitor the devolatili-
zation of biomass, that is, record the mass loss process and identify
the major volatile species and their corresponding release tempera-
ture range.
TagedPTG-FTIR obtains information about the functional groups of
volatiles, from which specific species are identified. The com-
monly detected pyrolysis products include non-condensable
gases, such as CO, CO2 and CH4, and condensable volatiles, such
as H2O, methanol, acids and phenols [127,144,163,221
224]. A
typical FTIR spectrum of gas products is shown in Fig. 7. Based
on TG-FTIR analysis, the behaviors of gas products evolving from
the pyrolysis of cellulose, hemicellulose and lignin have been
determined. Yang et al. [144] found that the release of CO2
(2363 cm¡1) from hemicellulose mainly occurred at low tempera-
ture (< 500 °C), while that from lignin occurred at high tempera-
ture (> 500 °C). The release of CO (2167 cm¡1) from
hemicellulose occurred over the whole temperature range, while
that from lignin mainly occurred at temperatures higher than
600 °C. Cellulose produced a relatively smaller amount of CO2
and CO. Lignin showed the highest yield of CH4 (3017 cm¡1)
because of its highest O
CH3 content. The release of organic
compounds with CHO (1730 cm¡1) and C
O
C (1167 cm¡1)
Fig. 7. Typical FTIR spectrum of gas products from biomass pyrolysis (hemicellulose)
(reprinted from Yang et al. [144] with permission of Elsevier).
TagedPmainly occurred at low temperatures from the pyrolysis of hemi-
cellulose (200
400 °C) and cellulose (300
450 °C), while the
release from lignin was negligible. Liu et al. [163] found that the
pyrolysis process of lignin can be divided into two stages. CO2,
H2O, CO, formaldehyde, alcohols and phenols were intensively
released in the first primary stage (166
274 °C) with maximum
yields at approximately 223 °C, while CO2, CO and CH4 were the
main gaseous products in the second stage (351
481 °C), which
reached a peak at approximately 423 °C.
TagedPAfter comparison of the volatile release behavior during pyrolysis
of hemicellulose isolated from hardwood and softwood, Wang et al.
[127] found that there were additional shoulder peaks in the H2O
evolution curves for softwood hemicelluloses, which was ascribed to
nonadjacent dehydration to yield anhydrosugars, which only
occurred in softwood hemicellulose. The absorbance intensities of
acids for hardwood hemicelluloses were much higher than those for
softwood hemicelluloses due to the higher contents of O-acetyl and
uronic acid units in hardwood hemicelluloses. They also investigated
the release behavior during pyrolysis of lignin from hardwood and
softwood [221]. Hardwood lignin released more methanol than soft-
wood lignin due to its higher methoxyl group content.
TagedPAnother important application of TG-FTIR is to monitor the emis-
sions of pollutants, such as SOx, NOx, and HCl, during biomass pyrol-
ysis [225
227]. Ren et al. [225] investigated the influences of the
heating rate, particle size and atmosphere on the N-selectivity to
HCN, NH3, NO and HNCO during wheat straw pyrolysis. The larger
particle size favored the formation of NH3 over HCN. A high heating
rate promoted the formation of NO and HNCO and inhibited the for-
mation of NH3 and HCN. The presence of O2 promoted the yields of
HCN and HNCO, while the use of CO2 reduced the formation of HCN
and suppressed the emission of HNCO. Proteins (amino acids) in the
biomass are the main source of N-containing species. There were
strong interactions between amino acids and other biomass compo-
nents. Ren et al. [227] found that hemicellulose inhibited N¡NH3
conversion, while lignin promoted NH3 formation from proline and
glutamic acid.
TagedPTG-FTIR cannot measure homodiatomic species, such as H2 [188].
Moreover, it's difficult to distinguish compounds with similar func-
tional groups, such as different light hydrocarbons. TG-MS measures
mass-to-charge ratio (m/z) of volatiles and can solve this problem.
However, due to the complicated composition of volatiles from bio-
mass pyrolysis, it's difficult to distinguish compounds with high
molecular weight via TG-MS. Thus, it is mainly applied to determine
the release behaviors of light gases, such as H2, CH4, H2O, C2H4, CO,
CO2 and NH3, during biomass pyrolysis [138,228
231].
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
3.3. Biomass pyrolysis behavior determined by characterizing the
reaction process
TagedPBoth Py-GC/MS/FID and TG-FTIR (TG-MS) focus on the final pyrol-
ysis products. The pyrolysis mechanism can be speculated based on
analysis of the pyrolysis products. However, they cannot provide
detailed information about the reaction process, which can reflect
pyrolysis reactions directly. In situ spectroscopy was developed for
this purpose.
TagedPIn situ FTIR is the most common in situ spectroscopy, and is used
to investigate the changes of surface functional groups of biomass
throughout the pyrolysis process [232
235]. Uchimiya et al. [232]
monitored the slow pyrolysis process of cottonseed hull (as shown
in Fig. 8). It was found that the signals for
OH and
CH2- disap-
peared after 70 min, while that of CHO started to appear after
50 min, then decreased and disappeared by 90 min after reaching
the maximum intensity near 65 min. Siengchum et al. [235] studied
the pyrolysis process of coconut shell by in situ FTIR. The peak inten-
sity of the O

H, C

OH, C

H, and CHO bands in the in situ IR spec-
tra increased between 200 and 400 °C, which indicated the
formation of carbonyl intermediate species. The intensity of CHO
and C

H bonds decreased between 400 and 500 °C, where CO and
CO2 were formed. This confirmed that CO and CO2 were mainly
formed from cracking of C

H and CHO bonds. In situ IR also
revealed that CH4 was yielded from breaking of C

C bond in
500
580 °C, and H2 was mainly produced from the breaking of C

H
bonds. Kirtania et al. [234] observed that the surface functional
groups disappeared completely by 550 °C when the heating rate was
low, while there was a delay in the release of functional groups at
high heating rate via in situ synchrotron IR. The delay at high heating
rate would result in more functional groups retained after pyrolysis,
and should be considered when the char was subsequently used in
thermochemical processing. One important application of in situ
FTIR is in catalysis to analyze the changes in functional groups
on the catalyst surface, which can provide important information
about the reaction mechanism of the catalytic process. Cheng
et al. [236] conducted an in situ FTIR study of furan-saturated
HZSM-5 to investigate the chemistry of furan (a model of cellu-
losic biomass) conversion into aromatics and olefins over HZSM-
5. Combined with TG-MS analysis, they found that furan poly-
merized on HZSM-5 to form oligomers at room temperature, and
the oligomer would undergo a series of reactions, including
Diels-Alder condensation, dehydration, decarbonylation, decar-
boxylation, alkylation and so on, to yield aromatics and olefins at
temperatures higher than 400 °C.
Fig. 8. In situ FTIR spectra collected during the slow pyrolysis of cottonseed hull (reprinted from Uchimiya et al. [232] with permission of Elsevier).
45
TagedPThere are additional in situ spectroscopy technologies, such as in
situ synchrotron X-ray diffraction [237], spatiotemporally resolved
diffuse reflectance in situ spectroscopy of particles (STR-DRiSP)
[238] and in situ 1H NMR spectroscopy [42,239]. In situ synchrotron
X-ray diffraction is used to investigate the degradation of crystallite
structures. Zickler et al. [237] studied the thermal decomposition of
crystallite cellulose from 300
360 °C. Fiber diffraction patterns
resulting from the crystal lattice of native cellulose arranged in ori-
ented microfibrils were collected as a function of heat treatment
time. Scherrer size, calculated using the equatorial and meridional
diffraction peaks, was used to analyze the changes in the cellulose
microfibril size. It was found that the thermal decomposition of crys-
talline cellulose in wood mainly occurred via a thermally activated
decrease in the fibril diameter with an approximate activation
energy of 112 kJ/mol, and might be accompanied by a random break-
ing of the fibrils into shorter pieces. STR-DRiSP (shown in Fig. 9), pro-
posed by Paulsen et al. [238], is a promising technology for better
understanding of fast pyrolysis transport and reaction kinetics. It
can measure biomass composition during fast pyrolysis with high
spatial (10 mm) and temporal (1 ms) resolution based on differences
in absorption between lignin/char and carbohydrates. Using this
technology, Paulsen et al. [238] obtained composition profiles as a
function of time and position for yellow poplar wood particles pyro-
lyzed at 500, 600, and 700 °C and proposed a comprehensive two-
dimensional reaction-transport model of a single particle, which
could achieve satisfactory simulation of these data. In situ 1H NMR
spectroscopy is mainly applied to study proton mobility during bio-
mass pyrolysis. Dufour et al. [42] performed a detailed investigation
of the pyrolysis of Miscanthus and its components. For lignin, the
mobile phase was formed at 150 °C, while its mass loss began at
200 °C. This proved the existence of a glass transition during lignin
pyrolysis. And the molecular mobility for cellulose was evidenced for
the first time even at a low heating rate. The differences between the
evolution of the mobile hydrogen fractions of synthetic Miscanthus
(blend of xylan+ fractioned cellulose and lignin) and those of native
and demineralized Miscanthus revealed strong interactions between
the polymers and their pyrolysis products. Cellulose reduced the
mobility of lignin and hemicellulose, and minerals reduced cellulose
mobility. They further carried out in situ rheology during the pyroly-
sis of Miscanthus, microgranular cellulose, ethanol organosolv lignin,
and xylan to reveal the viscoelastic behavior of the materials [239].
Combined with in situ 1H NMR analysis, they found that a viscous
and mobile material was formed during cellulose and xylan pyrolysis
by products at liquid phase. For lignin, a soft material and mobility
were first yielded by glass transition phase, then overlapped with
46 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 9. Schematic diagram of STR-DriSP (reprinted from Paulsen et al. [238] with permission of John Wiley and Sons).
TagedPcovalent bond scission, resulting in a completely mobile material. The
mobile liquid-like products were trapped inside elastic solid-like cav-
ities. Cellulose tended to impose its visco-elastic behaviors to the
polymer network during biomass pyrolysis.
TagedPGeneralized two-dimensional perturbation correlation infrared
spectroscopy (2D-PCIS), proposed by Noda et al. [240,241], was
developed based on the widely used 2D NMR technique and can be
used to decipher perturbation-induced (e.g., heat-treatment-tem-
perature) changes in specific bonds. It's a mathematic treatment of
infrared spectra collected at different temperatures. The basic idea
of 2D-PCIS spectroscopy has been discussed previously [240,242].
2D-PCIS spectra are usually displayed as schematic contour maps
characterized by autopeaks (on the diagonal) and cross peaks (in off-
diagonal positions), as shown in Fig. 10. Autopeaks only appear in
synchronous spectra with positive correlation values and represent
vibrations that are most susceptible to changes in the external per-
turbant. There are cross peaks in both synchronous and asynchro-
nous spectra with positive or negative correlation values, and they
are regarded as a measure of dissimilarity of change [243]. The
detailed interpretation of 2D-PCIS spectra, named Noda's rules, was
summarized by Harvey et al. [243]. The spectra for 2D-PCIS analysis
are usually collected by DRIFTS (diffuse reflectance infrared Fourier
transform spectroscopy) and are calculated using the 2D shige soft-
ware [243].
TagedP2D-PCIS analysis is mainly used to investigate the change in func-
tional groups during biomass char formation [243
246] and torre-
faction [242,247,248]. The 2D-PCIS results from Harvey et al. [243]
showed that the variation tendency of H-bonded, primary alcohol
Fig. 10. Synchronous (left) and asynchronous (right) spectra of 2D-PCIS analysis (red and blue areas indicate positive and negative values, respectively) (Reprinted from Ru et al.
[248] with permission of American chemical society).
TagedP roups was opposite to that of non-hydrogen bonded/free OH, and
g
the decrease in the former occurred before the increase in the latter.
This indicated defragmenting of the lignocellulose H-bonding net-
work to transform H-bonded, primary alcohol groups to free OH. In
addition, dehydrogenation/dehydroxylation of single-bonded meth-
ylene groups (R¡CHn) occurred to form double-bonded R=CHn func-
tional groups during char formation process. Chen et al. [246]
studied the char formation process during tobacco waste pyrolysis.
The auto-peaks in the 2D-PCIS spectra showed that the H bond in
R¡NH2, the C¡H bond in methyl or methylene, and the O¡C¡N¡H
stretch in R¡CO¡NH2 were the most susceptible to temperature
changes. The decomposition of protein and lignin resulted in a
decrease in the H bond in R¡NH2 and the C¡H bond in methyl or
methylene. The changes of R¡NH2 occurred after those of the intra-
and intermolecular H bonds in hemicellulose or cellulose and pre-
ceded that of the NH3+ group, which was formed when ¡NH2
adsorbed a proton (H+). This indicated that H in holocellulose first
transitioned to R¡NH2 in protein and then formed the NH3+ group.
3.4. Formation pathways of pyrolysis products revealed by isotopic
labeling
TagedPIsotopic labeling is another effective method to study the bio-
mass pyrolysis mechanism. It can determine the origin of specific
atoms within each of the pyrolysis products, and reflect the forma-
tion process of each pyrolysis product.
TagedPPaine et al. [249
252] investigated the reaction pathways of glu-
cose pyrolysis, using GC
MS to identify the products with 13C
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPisotopic labeling and to determine the extent of label from reactant
incorporation into the products and the location of the label. They
first studied the pyrolysis of glycerin, which contains abundant car-
bohydrate functionality. Its pyrolysis chemistry was quite relevant
to the reactions occurring at the reduced end of glucose [249]. With
2
13C1-glycerin and 1,3
13C2-glycerin as reactants, the dominant
product was acetaldehyde with a single label, and C-2 of glycerin
was retained in the methyl group or the aldehyde group of acetalde-
hyde. They concluded that glycerin mainly underwent two compet-
ing mechanisms to form acetaldehyde. One was a concerted cyclic
version of Grob fragmentation through an intermediate which was
hydrogen-bonded between 1-hydroxyl and 3-hydroxyl. This path
produced enol-acetaldehyde, formaldehyde and H2O simultaneously
and delivered the C-2 of glycerin to the carbonyl group of acetalde-
hyde. The other reaction pathway involved hydrogen-bonding
between adjacent hydroxyl groups and was an alkaline version of
the pinacol rearrangement followed by retro-aldol fragmentation of
the intermediate, the 3-oxopropoxide anion. This path delivered the
C-2 of glycerin to the methyl group of acetaldehyde.
TagedPBy applying these two mechanisms to the initiate breakage of the
six-carbon chain of D-glucose, the formation of C1 and C2 carbonyl
compounds [250], C3 and C4 carbonyl compounds and a cyclopente-
nedione isomer [251], and furans [252] from the pyrolysis of D-glu-
cose were further investigated. Approximate 70% of the
formaldehyde originated from C-6 in glucose by a direct single-step
Cyclic Grob fragmentation involving hydrogen bonding of the C-6
hydroxyl-hydrogen to the C-4 hydroxyl group. It could also be
formed via continuous dehydration of the intermediate D-fructose,
followed by cleavage of the C-6 hydroxymethyl at low pyrolysis tem-
perature. Fifty percent of the formic acid was derived from the C-1 of
glucose via a conformation change of glucose followed by pericyclic
1,3-dehydration to form formate ester and Norrish type II elimina-
tion of this formate ester. Acetaldehyde was most likely derived
from C-5/C-6 in glucose through a simple Grob fragmentation
involving the C-4 and C-6 hydroxyl groups, which was analogous to
the Grob process of the acetaldehyde formation from glycerin. HAA
originated from the pair-wise carbon in the glucose chain, with a
preference order of C1

C2 > C5

C6  C3

C4  (C2

C3 and
C4

C5). The principal pathway was the sequential thermal retro-
aldol fragmentation leading to three molecules of HAA from glucose.
Acetic acid was mainly formed from C-1 and C-2. The first step was
isomerization of open-chain D-glucose to open-chain D-fructose.
Then, open-chain D-fructose underwent a Cyclic Grob fragmentation
involving the hydroxyl groups at C-1 and C-3 to form ketene, which
was further hydrated to acetic acid [250]. The C3 products predomi-
nantly derived from the first three carbons or the last three carbons
of D-glucose as a result of single bond breakage between C-3 and C-
4. C4 species tended to originate from the last four carbons as a
result of bond breakage between C-2 and C-3 [251]. HMF and furfu-
ral were the main furan products. The formation of HMF proceeded
via carbonyl-migration of D-glucose to generate D-fructose, which
further underwent continuous dehydration. During this process, C-1
became the aldehyde group, and C-6 became the hydroxymethyl
substituent. The formation of furfural was more complicated. It
could be derived from the loss of formaldehyde by cyclic Grob frag-
mentation of the cyclic or chain conformations of D-glucose. Furfural
could also be produced via dissociation of the C-6 hydroxymethyl of
HMF [252].
3.5. Biomass pyrolysis behavior unraveled by characterizing
intermediate product
TagedPThe studies performed using the above analytical technologies
have shown the existence of homolytic cleavage reactions during
biomass pyrolysis, which will result in formation of free radicals
[210]. Free radicals are important intermediate products during
47
TagedP iomass pyrolysis and might also play an important role in subse-
b
quent reactions, such as condensed-phase polymerization [253].
Besides, the detection of free radicals provides direct experimental
evidence to verify the assuming reaction pathways for biomass
pyrolysis, such as the homolytic reactions and concerted reactions
for cleavage of the b-O-4 ether linkage in lignin [210].
TagedPElectron paramagnetic resonance (EPR) spectroscopy is the most
common technology to detect radicals. However, it is usually limited
in the ex situ measurement of chars [254,255] and bio-oil [253,256].
The radicals measured in char and bio-oil are different from the pri-
mary products of the pyrolysis process. In contrast to ex situ EPR, in
situ high-temperature EPR can directly monitor the radicals formed
during biomass pyrolysis [257
260]. Ba €hrle et al. [257] studied the
pyrolysis behavior of hardwood and softwood Klason lignin in the
temperature range of 350
550 °C by in situ high-temperature EPR.
The radical concentration remained at a constant low level when the
pyrolysis temperature did not exceed 300 °C and then increased
with rising temperature, with a sharp increase between 350 and
400 °C. Hardwood lignin always formed more radicals than softwood
lignin at temperatures from 350 to 450 °C because the linkages in
softwood lignin were more difficult to break than those in hardwood
lignin. However, the radical concentration of hardwood lignin
decreased with increasing time in the slow regime (after the initial
750 s) at 550 °C and became lower than that of softwood lignin as a
result of the dominant radical quenching reactions which only
occurred in hardwood lignin. The disproportionation of two semi-
quinone radicals to quinone and hydroquinone species was found to
be the most likely quenching reaction. The in situ high-temperature
EPR studies also showed that radical reactions during biomass pyrol-
ysis were significantly changed by the presence of catalysts
[259,260]. Zheng et al. [259] found that the addition of Na2CO3
enhanced the dehydration and cross-linking reactions during cellu-
lose pyrolysis, which decreased the number of H atoms in aromatic
moieties and hyperfine interactions between unpaired electrons and
protons, thus narrowing the EPR line of cellulose char. Ba €hrle et al.
[260] found that the addition of nonporous silica and zeolite cata-
lysts increased the radical concentration, possibly due to the stabiliz-
ing effect of the inorganic surface on the formed radicals. The effect
for zeolites was more significant than that for nonporous silica due
to their porous structure and higher surface area.
TagedPIn situ high-temperature EPR can only detect relatively stable
radicals in the solid residue, and cannot be used to monitor volatile
radicals [257]. To investigate gas-phase radicals in the thermal deg-
radation of biomass, the researchers at Louisiana State University
designed an isothermal flow reactor in conjunction with a coldfin-
ger-EPR, as shown in Fig. 11 [43]. The pyrolysis products carried by
N2/CO2 are condensed onto the coldfinger of the Dewar placed in the
Fig. 11. Cold finger assembly for low temperature matrix isolation EPR (reprinted
from Kibet et al. [43] with permission of American chemical society).
48 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPEPR cavity and cooled by liquid nitrogen from pyrolysis temperature
to 77 K. The CO2 carrier easily freezes to create an ideal matrix for
radical condensation, thus preserving the volatile radicals [261].
Kibet et al. [43] investigated lignin pyrolysis by this equipment and
confirmed the presence of volatile radicals, including phenoxy and
substituted phenoxy radicals derived from the phenolic linkages in
lignin. These radicals were the probable precursors for the formation
of phenolic compounds, including 2,6-dimethoxy phenoxy (syringyl
groups), 2-methoxy phenoxy (guaiacyl groups), and phenols (phe-
noxy groups).
TagedPHowever, EPR spectrum analysis is difficult and time-consuming,
especially for biomass pyrolysis, in which multiple radical species
exist. EPR can only identify some specific radicals. In addition, EPR
cannot detect other intermediate products, such as the primary
products of biomass pyrolysis. Recently, photoionization mass spec-
trometry (PIMS) has attracted increasing attention from researchers.
Compared with conventional “hard” electron ionization (EI) MS,
“soft” photoionization, which is obtained by means of an ultraviolet
(UV) or vacuum UV (VUV) light source, enables fragment-free or
fragment-minimal mass spectra of the pyrolysis products [262,263].
Thus, PIMS can detect reactive intermediates. In addition, it can
investigate the time/temperature evolution of products in pyrolysis
reactors and provide crucial information about biomass pyrolysis
mechanisms. Current PIMS techniques, which can be mainly classi-
fied into three types according to their ionization source, namely dis-
charge-lamp PIMS [264,265], laser-based VUV or resonance
enhanced multiphoton ionization (REMPI) PIMS [266] and synchro-
tron VUV¡PIMS [44,267
270], have been successfully applied to
biomass pyrolysis studies.
TagedPDischarge lamps are widely used for photoionization due to their
simplicity and low cost [262]. Le Brech et al. [265] investigated the
pyrolysis of different biomasses by VUV lamp PIMS combined with a
U-shape fixed bed reactor. Based on the evolution of the main
markers of volatiles from the pyrolysis of cellulose and lignin in real-
time, their detailed chemical pyrolysis mechanism was discussed.
For cellulose pyrolysis, LG could be formed through transglycosyla-
tion and the rupture of the glycosidic bond, while other oxygenated
compounds, such as 2-furanmethanol, were produced via ring open-
ing and dehydration. Lignin first underwent rupture of ethers (b-O-4
or a-O-4) and was transformed into intermediate char with release
of the phenolic and alkyl phenolic compounds. Then, cleavage of the
C

C bonds within and between the alkyl chains in the intermediate
Fig. 12. Schematic of the hyperthermal nozzle/REMPI PIMS system and the obtained mass spectra of the products of pyrolysis from PPE (reprinted from Jarvis et al. [266] with per-
mission of American chemical society).
cTagedP har occurred to form char and to release phenolic compounds with
short alkyl chains. VUV lamp PIMS can be combined with microflui-
dized bed reactors for online analysis of the volatiles produced dur-
ing biomass fast pyrolysis and to unravel the influence of the
biomass composition and of heat and mass transfers on the biomass
fast pyrolysis processes [264].
TagedPPhotoionization can also be performed using lasers. Jarvis et al.
[266] directly detected the products from the pyrolysis of 2-phe-
nethyl phenyl ether (PPE, a common lignin model component) via a
hyperthermal nozzle/REMPI PIMS system (as shown in Fig. 12a) to
study the importance of concerted and homolytic unimolecular
decomposition pathways for the cleavage of b-O-4 ether linkage.
The observation of phenoxy radical (m/z = 93, in Fig. 12b), cyclopen-
tadienyl radical (m/z = 65) and phenyl ethyl radical (m/z = 105) was
indicative of C

O homolysis of the PhCH2CH2

OPh bond, while the
detection of benzyl radical (m/z = 91) was an indication of C

C
homolysis of the PhCH2

CH2OPh bond. In addition, phenol (m/
z = 94) and styrene (m/z = 104) were detected, which suggested
pyrolysis of PPE by concerted reactions. Based on the intensity analy-
sis of the intermediate products, it was concluded that the concerted
reactions were dominant at lower temperatures (< 1000 °C), while
the C

O homolysis became more significant at high temperatures
(> 1000 °C). The C

C homolysis mechanism was minor at all tem-
peratures.
TagedPSynchrotron radiation is a great choice of PIMS ionization source
due to its properties, including high photon flux, high brilliance,
polarization, and pulsed time structure. In recent years, SVUV-PIMS
has been widely utilized in combustion chemistry [271]. SVUV-PIMS
has also been introduced to the in situ study of biomass pyrolysis
[44,267
270]. Zhou et al. [270] developed a facility which combined
thermogravimetry with SVUV-PIMS, and the evolution of the gas-
eous products of pine wood pyrolysis was detected online. Weng
et al. [44] investigated the pyrolysis process of polar in a pyrolysis
apparatus equipped with SVUV-PIMS (as shown in Fig. 13). It is
reported for the first time that over low temperature range, the
syringyl and guaiacyl subunits of lignin showed different trends of
intensities with increasing temperature. The intensities of the
syringyl subunits first increased and then decreased, while those of
the guaiacyl subunits decreased continuously. Dufour et al. [268]
investigated the pyrolysis behavior of the major biomass compo-
nents by SVUV-PIMS. HAA was detected at very minor yield from
cellulose pyrolysis, which confirmed it was a secondary product.
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 13. Schematic diagram of the biomass pyrolysis apparatus based on SVUV-PIMS
(reprinted from Weng et al. [44] with permission of Elsevier).
TagedPThey also identified a new major intermediate product of cellulose
pyrolysis (5-methyl-4-oxotetrahydrofuran-2-carbaldehyde or posi-
tion isomers), which could be a precursor of furanone-based species
during cellulose pyrolysis. Using SVUV-PIMS, He et al. [269] investi-
gated the reaction pathways of a-O-4 and b-O-4 ether linkage cleav-
age based on model compounds 4-(benzyloxy) phenol (BOP) and
guaiacylglycerol-b-guaiacyl ether (GGGE). For the a-O-4 compound
BOP, benzyl radical (m/z = 91, in Fig. 14a), p-semiquinone radical
(m/z = 109), toluene (m/z = 92), and bibenzyl (m/z = 182) were
detected, confirming the homolytic cleavage of the Ca¡O bond.
However, radicals were not detected during pyrolysis of the b-O-4
compound GGGE, as shown in Fig. 14b. Thus, they proposed that the
concerted reaction dominated in the temperature range investigated
for the b-O-4 model compound.
TagedPOne major challenge for PIMS is compound quantification. All
previous studies were semi-quantitative and could only determine
the relative intensities of the products. Quantification by adding an
internal standard to the pyrolysis gas outlet flow and by using an
adequate calibration might be a good choice [263]. In addition, PIMS
can be used to identify isomers by scanning photon energies, and
has been successfully applied in combustion science [271]. Thus, the
ionization energies for different biomass pyrolysis products need to
be determined in the future.
Fig. 14. Photoionization mass spectra of the pyrolysis products of BOP (a) and GGGE (b) at 500 °C (reprinted from He et al. [269] with permission of American chemical society).
49
4. Macroscopic kinetic modeling for biomass pyrolysis
TagedPMacroscopic kinetic modeling is often used to simulate the
thermo-degradation rates of feedstocks or to predict the formation
rates of products during biomass pyrolysis. It can provide valuable
information for reactor design and process optimization for biomass
pyrolysis [272]. With the development of kinetic theories and com-
puter technologies, several macroscopic kinetic modeling methods
with comprehensive mechanism schemes have been developed,
such as DAEM, isoconversional method, lumped kinetic model
involving the detailed evolution pathways of products, chemical per-
colation devolatilization model and kinetic Monte Carlo model.
Generally, these models and methods can be divided into two cate-
gories, one is to simulate the mass loss rate of biomass, and the other
is to simulate the product distribution after pyrolysis.
4.1. Macroscopic kinetic models for mass loss simulation
TagedPThe theories of macroscopic kinetic models are mainly developed
from those of homogeneous reaction kinetics. The difference is that
solid-phase conversion, a, is employed rather than the reactant con-
centration since pyrolysis is a thermally stimulated heterogeneous
reaction, as shown in Eq. (1). Arrhenius theory is also used to
describe the reaction rate k(T), as shown in Eq. (2), in which A and E
are the pre-exponential factor and the activation energy, respec-
tively. The calculated kinetic parameters are usually called the
apparent parameters to distinguish them from the intrinsic parame-
ters of a specific individual step [205].
da
¼ kðT Þf ðaÞ ð1Þ
dt


E
kðTÞ ¼ Aexp
ð2Þ
RT
TagedPThe premise of the precise simulation of the mass loss pro-
cess during pyrolysis is the calculation of accurate kinetic param-
eters, namely E, A, and the reaction model f(a). The most widely
used computation method is model-fitting methods, which
assume the reaction model, f(a) in advance and then forcibly fit
the experimental data to obtain the kinetic parameters. f(a),
which is frequently used in solid reactions, such as the reaction-
order model, nucleation and growth model and diffusion model,
was also introduced to kinetic studies of biomass pyrolysis
[273
275]. For isothermal processes, the solving method is sim-
ple since the conversion rate a is a function of time t. Non-
50 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86

TagedPisothermal processes usually adopt a constant D16Xheating

X rate b, TagedP4.1.1. Distributed activation energy model (DAEM)
and Eq. (1) can be rearranged as Eq. (3). Eq. (3) can be solved TagedPDAEM was originally developed to describe coal pyrolysis
directly using DTG data. It can also be solved using TG data by [284
286] and was then introduced to the kinetic study of biomass
integration methods, such as the Coats
Redfern method [276], pyrolysis [156,287
291]. DAEM assumes that pyrolysis occurs
through approximation of the temperature integral. through numerous independent parallel reactions with different
activation energies, and the activation energy distribution of these
da 1
¼ kðT Þf ðaÞ ð3Þ reactions can be described by a continuous function. Compared with
dT b
common model-fitting methods, DAEM can simulate mass loss
TagedPAs the main component of lignocellulosic biomass, cellulose across the overall conversion rate with a much higher fitting preci-
has received the majority of the attention in the kinetic study of sion. Essentially, DAEM is a model-fitting method, and the reaction
pyrolysis due to its simplicity and good repeatability in the model f(a) needs to be assumed in advance. The reaction-order
structures. The total process of cellulose pyrolysis can be well model is the most widely used f(a) [290], and the relevant DAEM
described by one stage [203,204,274,277
282]. However, the (nth-DAEM, where n is the reaction order) can be described by Eq.
kinetic parameters obtained from different studies vary signifi- (4).
cantly, due to the differences in the types of cellulose, experi- 8 2 3
mental conditions, computation processes and linear interval >
> Z1 ZT

>
> 6 A E 7
>
> exp4
exp
dT 5f ðEÞdE n ¼ 1
selection [66], as shown in Fig. 15. For hemicellulose and lignin, >
> b RT
>
>
the degree of fitting linearity of the TG data is generally poor < 0 T0
1
a ¼ ð4Þ
over a wide conversion rate, and the mass loss can be separated >
> 2 3 1
into different temperature regions. Ramiah [283] proposed that >
> Z1 Z T
 1
n
>
> 6 A E 7
the mass loss during xylan pyrolysis could be separated into two >
> 41
ð1
nÞ exp
dT 5 f ðEÞdE n 6¼ 1
>
> b
: RT
ranges: the first at 195‒225 °C with activation energy of 62.8 kJ/ 0 T0
mol and the second at 225‒330 °C with a higher activation
T he methods used to calculate the kinetic parameters of DAEM
agedPT
energy of 108.7 kJ/mol. Liu et al. [163] observed two major deg-
can be separated into two types: distribution-free and distribution-
radation stages during the pyrolysis of lignin isolated from fir
fitting methods. The distribution-free method first determines the
and birch according to two mass loss peaks in the DTG curves.
correlation between E and a using the isoconversional method. f(E)
The activation energies for these two mass loss stages in the
can be determined by differentiating the a versus E relationship. The
pyrolysis of fir lignin were 72.9 kJ/mol and 136.9 kJ/mol, while
Miura differential method and Miura-Maki integral method
those in the pyrolysis of birch lignin were 87.2 kJ/mol and
[292,293] are common distribution-free methods. The computation
141.7 kJ/mol.
procedure of these methods is easy. However, the fitting precision
TagedPHowever, linear fitting of the TG data can only be achieved within
and reliability of the obtained kinetic parameters are not satisfactory
a narrow conversion rate range in the kinetic parameters calculation
[287]. The distribution-fitting method assumes f(E) in advance, and
using the common model-fitting methods, and it is difficult to obtain
then forcibly simulates the TG data to obtain the parameters accord-
a satisfactory precision in the simulation of mass loss for the initial
ing to numerical methods, such as pattern research [157], genetic
and final pyrolysis stages. Besides, the obtained kinetic parameters
algorithm [294] and multistart algorithm [295]. These methods
might not be reliable and consistent as a result of the previous
achieve highly precise fitting, with fitting correlations (R2) typically
assumption of f(a). The goodness of data fit is not sufficient to prove
greater than 0.99. Therefore, the distribution-fitting method has
its validity since multiple reaction models can achieve the same fit-
become dominant. The problem is the kinetic compensation effect
ting precision [204]. Several kinetic models and methods, such as
(KCE), i.e., different sets of DAEM kinetic parameters can satisfy the
DAEM and isoconversional methods, have been developed to pro-
experimental data at a single heating rate with similar precision
duce a greater simulation accuracy.
[287]. A method involving nonlinear least squares optimization of
multiple heating rate data might be a good option to avoid this prob-
lem [272].
TagedPThe distribution of activation energies f(E) is crucial for DAEM.
The Gaussian distribution [156,290,296] centered at E0 with stan-
dard deviation s is the most widely used distribution, as shown in
Eq. (5). The drawback of this distribution is its inherent symmetry
[297], which is inconsistent with reality. To satisfy the asymmetry of
the real pyrolysis process, some other distributions, such as the Wei-
bull distribution [298], Fraser
Suzuki function [299] and logistic
function [300], have been proposed.
" #
1 ðE
E0 Þ2
f ðEÞ ¼ pffiffiffiffiffiffiffi exp
ð5Þ
s 2p 2s 2

TagedPThere are multiple forms of DAEM. Among them, DAEM with a

Fig. 15. Kinetic parameters for cellulose pyrolysis [203,204,274,277
282].
single distribution function is the basic form. It is usually applied to
the kinetic analysis of cellulose. The obtained mean activation
energy and standard deviation were 240.2 kJ/mol and 2.4 kJ/mol,
respectively, according to 1st-DAEM based on a single symmetric
Gaussian function [301]. To fit the asymmetry of the DTG curve, 1st-
DAEM based on a single logistic function was developed by Cai et al.
and the calculated mean activation energy was 258.6 kJ/mol [300].
DAEM with a single distribution has also been applied to the kinetic
analysis of hemicellulose and lignin [301]. The activation energies
and standard deviations were 179.8 kJ/mol and 10.8 kJ/mol for
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86 51

TagedPhemicellulose, and 165.1 kJ/mol and 19.3 kJ/mol for lignin, respec- Table 6
tively. However, the fitting precision was poor. The conversion rate Kinetic parameters of biomass pyrolysis by DG-DAEM.

curves of the DAEM with a single activation energy distribution Feedstock E0/kJ¢mol¡1 logA/s¡1 s /kJ¢mol¡1 c Ref.
show one peak [287], while there are always shoulder peaks in the
Xylan 114.5 8.4 22.8 0.60 [301]
DTG curves of hemicellulose and lignin. Therefore, it is impossible to
180.0 14.8 6.7 0.40
describe their entire pyrolysis process using this form of DAEM. The Lignin 159.6 11.7 10.4 0.42
pyrolysis process of biomass is much more complex than hemicellu- 174.2 11.8 27.4 0.58
lose and lignin. DAEM with a single distribution is also not suitable Hemicellulose from P. 174.3 15.0 3.0 0.75 [85]
armandii Franch 201.2 15.1 0.25
for the description of whole biomass pyrolysis.
Hemicellulose from 146.7 12.0 3.8 0.63 [127]
TagedPTwo previous studies [247,302] found that the parallel reactions Eucalyptus saligna 175.5 28.9 0.37
occurring during pyrolysis could be divided into two types with dif- Hemicellulose from 149.8 12.3 5.6 0.73
ferent activation energy distributions, namely degradation reaction Fraxinus mandshurica
to form volatiles and condensation reaction to yield char and gases. 179.0 30.1 0.27
Hemicellulose from 158.1 14.4 4.8 0.73
Therefore, it is reasonable to represent these two reactions with two
Pinus sylvestris 181.0 36.1 0.27
distribution functions, as shown in Eq. (6), where c1 and c2 are the Hemicellulose from 159.8 12.3 5.9 0.78
corresponding contributions of the degradation and condensation Tsuga chinensis 186.0 46.4 0.22
reactions to the devolatilization, respectively. Of the three main Hemicellulose from rice 149.0 12.0 7.1 0.63 [296]
components, the structures of hemicellulose and lignin are branched straw 193.1 41.3 0.37
Hemicellulose from 150.0 12.1 5.5 0.73
and complicated. During their pyrolysis, multiple fragments are pro- corn stalk 172.3 34.5 0.27
duced and randomly polymerized to form char. Therefore, the con- Milled wood lignin from 148.8 10.6 184.2 0.64 [156]
densation reaction plays an important role in the decomposition of lauan 14.7 35.4 0.36
hemicellulose and lignin. Thus, the DAEM with double Gaussian dis- Alkali lignin from Pinus 139.7 9.8 15.0 0.59 [157]
bungeana 166.0 36.3 0.41
tributions (DG-DAEM) is required for the kinetic studies of hemicel-
Klason lignin from Pinus 166.2 10.8 6.4 0.43
lulose and lignin. The obtained kinetic parameters are shown in bungeana 182.6 36.2 0.57
Table 6. Generally, the degradation reaction (first Gaussian region) Organosolv lignin from 151.0 10.0 8.7 0.60
shows lower activation energy with a narrow interval, while the Pinus bungeana 171.5 36.6 0.40
condensation reaction (second Gaussian region) displays higher acti- Milled wood lignin from 145.6 10.1 13.0 0.72
Pinus bungeana 188.2 31.5 0.28
vation energy with a wide interval [157,296], as shown in Fig. 16. In Wheat straw 167.0 12.6 4.8 0.50 [291]
addition, the contribution of the degradation reaction is always 231.5 17.0 35.0 0.22
higher than that of the condensation reaction, which indicates that Winter barley straw 167.0 13.0 4.8 0.41
the degradation reaction is dominant during pyrolysis [157,296]. 231.5 17.7 35.0 0.29
Oat straw 167.0 12.4 4.8 0.40
DG-DAEM can quantitatively characterize the differences in pyroly-
231.5 17.7 35.0 0.35
sis behavior using different feedstocks. Wang et al. [157] investi-
gated the pyrolysis kinetics of lignins isolated using various
methods. The activation energy for condensation reactions of alkali
lignin was lower than those of the other three isolated lignins, tTagedP o the pyrolysis of cellulose, while the second represented the pyrol-
namely Klason lignin, organosolv lignin and mill wood lignin, due to ysis of the rest of the biomass including hemicellulose, lignin, and
the catalytic effect of the alkali metal in alkali lignin. The weighing extractives.
factor corresponding to condensation reactions in the pyrolysis of
f ðEÞ ¼ c1 f1 ðEÞ þ c2 f2 ðEÞ ð6Þ
Klason lignin was the highest, which was in agreement with its high-
est char yield in the TG analysis. For cellulose, it is not necessary to TagedPAssuming the pyrolysis behavior of whole biomass as a sum of
use DG-DAEM since its char yield is so low that the condensation the decomposition of three major components, a model consisting
reaction can be neglected. DG-DAEM has also been introduced to the of three parallel DAEM reactions (see Eq. (7)) was proposed by Cai
kinetics of whole biomass pyrolysis. The kinetic parameters calcu- et al. [290] to describe the pyrolysis process of whole biomass. The
lated by Va rhegyi et al. [291] for biomass feedstocks are listed in three activation energy distributions, centered at 169.7
186.8,
Table 6. However, the meanings of these two Gaussian distributions 204.2
212.5 and 237.1
266.6 kJ/mol, for the different biomass feed-
are different. They proposed that the first distribution corresponded stocks were ascribed to the decomposition of hemicellulose,

Fig. 16. Activation energy distributions of DG-DAEM for the pyrolysis of hemicellulose (left) and lignin (right) (reprinted from Wang et al. [157, 296] with permission of Elsevier).
52 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86

TagedPcellulose and lignin, respectively. The values of the first two reac- TagedPThe integral methods originate from the various approximations
tions were close to those of hemicellulose and cellulose, while the of the temperature integral p(u), as shown in Eq. (10), where u = E/
activation energy of the third reaction was slightly higher than that RT. When the crude approximation of Doyle [305] is introduced for
of lignin. In addition, the biomass compositions calculated by fitting p(u), the Flynn-Wall-Ozawa (FWO) method [306,307] is obtained, as
the pyrolysis kinetics agreed with experimental data from other shown in Eq. (11).
studies. Chen et al. [228] applied this three parallel Gaussian reac- Z a Z Z
A T _E=RT AE 1
2
u
tion model to study the pyrolysis kinetics of pine sawdust, and the gðaÞ ¼ f ðaÞ
1 da ¼ e dT ¼ u e du
0 b 0 bR u
mean activation energies for the three pseudo-components were
AE
186.8, 197.5 and 203.9 kJ/mol. Ru et al. [248,303] proposed another ¼ pðuÞ ð10Þ
modified DAEM with three Gaussian functions. From the aforemen- bR
tioned analysis, it was demonstrated that satisfactory simulation of  
AE E 1
cellulose pyrolysis can be achieved by a DAEM with only one Gauss- lnb ¼ ln
5:331
1:052 ¢ ð11Þ
RgðaÞ R T
ian function, while a DAEM with two Gaussian functions is required
for the pyrolysis of hemicellulose and lignin. The mean activation TagedPThe precision of the FWO method is not satisfactory due to the
energies and standard deviations for the degradation reactions and crude temperature integral approximation. A more accurate approx-
condensation reactions of hemicellulose and lignin are similar but imation proposed by Frank
Kamenetskii [308] is therefore adopted,
they are different from those of cellulose pyrolysis. Hence, the bio- producing the Kissinger
Akahira
Sunose (KAS) method [309]
mass pyrolysis process was divided into three paths. The first path (sometimes called the generalized Kissinger method), as shown in
was the degradation reactions in the pyrolysis of hemicellulose and Eq. (12). Ea is easily calculated by linear regression analysis of Eqs.
lignin, the second path was the pyrolysis of cellulose, and the third (11) and (12). A further increase in the accuracy can be achieved by
path was the condensation reactions in the pyrolysis of hemicellu- numerical integration, such as the Vyazovkin method [310] and Vya-
lose and lignin. The mean activation energies obtained for these zovkin AIC (advanced isoconversional) method [311].

  
three paths were 164.0, 175.9 and 221.6 kJ/mol for fast growing pop- b AR 1 E 1
lar [248] and 174.8, 184.4 and 216.0 kJ/mol for Pinus bungeana [303], ln 2 ¼ ln þ ln
¢ ð12Þ
T E gðaÞ R T
respectively.
TagedPDifferential methods are more accurate than integral methods
f ðEÞ ¼ c1 f1 ðEÞ þ c2 f2 ðEÞ þ c3 f3 ðEÞ ð7Þ since there is no approximation for the former. However, impreci-
TagedPHowever, the assumed reaction-order model in the DAEM studies sion may be raised during the processes of obtaining DTG data, such
above might not be accurate. The given reaction model without pre- as the application of numerical differentiation to TG data and the
vious determination produces inaccurate kinetic parameters. smoothing process of the obtained noisy data [205]. Hence, it's not
Recently, Wang et al. [273] proposed a procedure combining the iso- accurate to conclude that the precision of differential methods is
conversional method and model-fitting method to determine the greater than that of integral methods. In fact, Starink [312] proved
reaction models of the three major components of biomass before that integral methods were more accurate than differential methods
calculating their kinetic parameters by DAEM. The decomposition of under certain circumstances.
cellulose followed the Avrami-Erofeev nucleation model, while TagedPIt is noteworthy to distinguish the KAS method from the widely
hemicellulose and lignin obeyed the reaction-order model. There- used Kissinger method [313]. The Kissinger method only focuses on
fore, they proposed that the modified DAEM based on the Avrami- the maximum reaction rate during pyrolysis, as shown in Eq. (13),

Erofeev nucleation model (Am-DAEM, where m is the Avrami where Tp is the corresponding temperature of the maximum reac-
factor) [273] was more suitable than nth-DAEM for cellulose pyroly- tion rate. The activation
energy can be easily calculated from the
sis, as shown in Eq. (8). The activation energy of cellulose was slope of the line of ln Tb2
against
T1p .However, to obtain an accurate
p
119.2 kJ/mol, which was much lower than the activation energy
activation energy, the plot of ln Tb2 against T1p must be a straight
obtained using the first-order reaction model. p

8 2 3m 9 line, which requires the value of ln[ ¡ f0 (ap)] to be constant. This can
Z1 >
< ZT A
 >
= only be achieved when f(a) is the first-order reaction model (f’ (a)
6 E 7
a ¼ 1
exp
4 exp
dT5 f ðEÞdE ð8Þ =¡1). Otherwise, the value of ln[f’ (a)] is dependent on ap, and it dif-
>
: b RT >
;
0 T0 fers between the curves of different heating rates. Therefore, the Kis-
singer method is not classified as an isoconversional method.
!

b AR 
 E 1
TagedP4.1.2. Isoconversional method ln 2 ¼ ln þ ln
f 0 ap
¢ ð13Þ
Tp E R Tp
TagedPCompared with model-fitting methods, isoconversional methods
don't require the prior assumption of f(a); thus, the calculated TagedPIsoconversional methods were recently introduced into the
kinetic parameters are more reliable and consistent [205]. The iso- kinetic analysis of biomass pyrolysis. The calculated kinetic parame-
conversional method can determine the activation energy directly ters are listed in Table 7. Among the three major components in bio-
from a series of TG data under different heating rates (at least 3). The mass, the activation energies of cellulose remain almost unchanged
core principle is that the reaction rate at a certain conversion rate is over a wide conversion range. This indicates that the decomposition
a function of temperature. The ICTAC Kinetics Committee recom- pathways are almost constant and that there are no parallel reac-
mends determining the Ea values for a wide range of a from 0.05 to tions during pyrolysis. In the pyrolysis of hemicellulose and lignin,
0.95 with a step no larger than 0.05 [205]. Isoconversional computa- the activation energies increase greatly with increasing a
tional methods can generally be divided into two categories: differ- [273,314,315]. It was noted by Vyazovkin et al. [316] that an increase
ential methods and integral methods. The most common differential of E with a indicated the existence of parallel reactions, while a
method is the Friedman method [304], as shown in Eq. (9). The acti- decrease indicated a reversible stage or a change of limiting stage.
vation  energy
 Ea at each given a can be obtained by linear regression Hence, parallel reactions exist during the pyrolysis of hemicellulose
of ln bdt da
versus 1/T. and lignin. The change tendency of the activation energies with a

 can be used to divide the stages of the devolatilization process. The
bda E 1
ln ¼ ln½Af ðaÞ
¢ ð9Þ pyrolysis processes of spruce glucomannan (SGM) and commercial
dt R T konjac glucomannan (KGM) were separated into three regions by
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86 53

Table 7 TagedP iffusion-Jander equation and the 0.35th-order reaction model were
d
Kinetic parameters of biomass pyrolysis by isoconversional methods. the most suitable f(a) for conversion rates of 0.12‒0.35 and 0.35‒
Feedstock Method Ea/ kJ¢mol¡1 a Ref. 0.75, respectively, for the pyrolysis of SGM. The 2D diffusion and
0.35th-order reaction models were the corresponding ones for KGM.
Microcrystalline KAS 150
169 0.10
0.80 [319]
This method was adopted by Wang et al. [273] to analyze the pyroly-
cellulose
Microcrystalline cellu- Friedman 190
192 0.10
0.90 [320] sis of the three major components of biomass and produced satisfac-
lose from Aldrich, tory results. A similar method employing the activation energy from
Cellulose powder Friedman 157.2
175.6 0.20
0.80 [321] isoconversional methods as a standard was used by Anca
Couce
FWO 158.9
168.1 0.20
0.70
et al. [323]. They employed KAS to verify the reliability of the reac-
Cotton fibers FWO 150.4 § 3.6 0.10
0.80 [322]
Spruce glucomannan Friedman 211.6
420.9 0.13
0.87 [314]
tion models used in the fitting routine, and found that nth-order
FWO 216.7
393.9 0.16
0.87 reaction model was more suitable than the first-order reaction
Commercial konjac Friedman 182.2
280.0 0.13
0.87 model during the kinetic analysis of biomass.
glucomannan FWO 163.3
238.4 0.16
0.87 TagedPThe master plots method is an alternative way to determine the
Kapok hemicellulose Friedman 74.3
173.4 0.19
0.50 [315]
reaction model. It only requires that the pyrolysis activation energy
FWO 97.2
120.1
Microcrystalline KAS 109.4 0.05
0.95 [273] is known in advance and does not vary significantly over the entire
cellulose conversion range [205]. Hence, the master plots method is always
Beechwood xylan 35.5
262.9 combined with isoconversional methods. The core principle is to
Organosolv lignin 83.0
187.1 convert experimental data into an experimental master plot and
Poplar wood KAS 105.0
209.9 0.05
0.70 [318]
FWO 107.9
209.5
compare it with the references, namely, theoretical master plots
Beech KAS 169.6
193.1 0.10
0.90 [323] drawn by assuming certain reaction models. The reaction model
Pine 127.1
162.5 with the best fit is selected as the most suitable [205,275,320]. Based
Rice straw Friedman 146.6
345.9 0.05
0.95 [275] on this method, Sa nchez
Jimenez et al. [320] proposed that the ran-
KAS 139.0
282.5
dom chain scission model [326], which assumed that the weight loss
FWO 141.2
280.8
Vyazovkin 139.6
290.6 of cellulose during pyrolysis was derived from the random cleavage
Vyazovkin AIC 142.6
266.6 of glycosidic bonds along the polymer chains, was more suitable for
Pinus elliottii FWO 179.6
210.3 0.10
0.80 [324] cellulose pyrolysis than other models, including the widely used
Eucalyptus grandis 184.9
229.7 Avrami
Erofeev model and first-order model. Mishra et al. [275]
Mezilaurus itauba 173.8
200.6
Dipteryx odorata 174.8
213.7
found that the pyrolysis of rice straw could be described by two suc-
cessive reactions, a diffusion reaction followed by a third-order rate
equation. Poletto et al. [324] investigated the pyrolysis kinetics of
four wood species and found that the wood degradation mechanism
followed by diffusion processes when a< 0.4 and random nucleation
TagedPMoriana et al. [314]: the first region occurred at 0.12 <a< 0.35 with with one nucleus in each particle when a> 0.5.
small variations in Ea; Ea remained constant in the second region of
0.35 <a< 0.75; in the third regions, a> 0.75, Ea increased rapidly. 4.2. Macroscopic kinetic models for pyrolysis product prediction
This division was confirmed by Wang et al. [273], with 0.05
0.30,
0.30
0.65 and 0.65
0.95 as the three regions. These three stages TagedPThe prediction of the pyrolysis product distribution is the other
corresponded the first shoulder peak, the major mass loss peak and important application of macroscopic kinetic models. Limited by the
the second shoulder peak in the hemicellulose DTG curves. With analytical technology, the detailed product distribution of biomass
regard to lignin, Ea increased continuously with increasing a. Its pyrolysis could not be easily and accurately determined. Thus, the
devolatilization process could be divided into two stages, with the products of biomass pyrolysis in the classic lumped kinetic models
boundary at a= 0.70, according to the different increase rates [273]. are roughly divided into three types: tar, char and gases. These mod-
Jankovic [317] determined the correlation of Ea and a by the KAS els assume that biomass is converted into these three products
and Friedman methods for the pyrolysis of Acetocell and Lignoboost through single-step or multistep reactions. During the model build-
lignins and observed that the entire process could be separated into ing process, the biomass structure is not characterized. Thus, these
three stages. The activation energies for the main degradation stage models do not include information about the reaction pathways and
(second stage) remained constant at 195.3 kJ/mol and 215.3 kJ/mol are black-box models. The application of lumped kinetic models in
from KAS method for Acetocell and Lignoboost lignins, respectively, cellulose pyrolysis has a long history, and the most famous example
while those from the Friedman method were slightly higher than is the Broido
Shafizadeh (B‒S) model [24], as shown in Fig. 17A. The
those from KAS method, with the values of 198.0 kJ/mol and B‒S model assumes that cellulose first decomposes into active cellu-
217.4 kJ/mol, respectively. The pyrolysis behavior of whole biomass lose. Then, active cellulose evolves through two competitive path-
is much more complicated than that of biomass components, and ways: one corresponding to the formation of tar and the other
there are also parallel reactions, as indicated by the continuous corresponding to the formation of char and gases. The activation
increase in Ea. For example, the activation energies increased from energy for active cellulose formation was 242.4 kJ/mol, and the cor-
107.9 to 209.5 kJ/mol over the a range of 0.05
0.70 for poplar wood responding values for the following parallel reactions were 153.1 kJ/
pyrolysis [318]. mol for tar formation and 197.9 kJ/mol for the production of char
TagedPIsoconversional methods can be used to determine the reliable and gases [24]. The B‒S model can achieve good results for the pre-
kinetic parameters for solid reactions when complemented by diction of experimental data and is widely accepted. Many other
model-fitting methods. Khawam and Flanagan [325] proposed such models have been developed for cellulose pyrolysis based on modifi-
a procedure. First, isoconversional methods were used to obtain the cation of the B‒S model, such as the models shown in Fig. 17B
D
activation energies as the evaluation criterion; then, model-fitting [35,327,328]. Although the intermediate product, active cellulose,
methods, such as the Coats
Redfern method, were used to calculate has been observed during the flash pyrolysis of cellulose [329,330],
E under different assumptions of f(a). The f(a) that produced the E there are some cellulose pyrolysis models that do not include the
value closest to the isoconversional result was selected as the most formation of active cellulose, such as the models shown in Fig. 17E
reasonable reaction model. Moriana et al. [314] applied this proce- [331] and F [332]. Generally, models with the formation of active cel-
dure to the kinetic analysis of SGM and KGM and found that the 3D lulose are more accurate than those without when describing
54 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 17. Early lumped kinetic models for biomass pyrolysis.
TagedPcellulose pyrolysis [204]. There are fewer lumped kinetic models for
the pyrolysis of hemicellulose and lignin due to their much more
complicated structures and pyrolysis pathways. Most of them are
developed based on the classical B‒S model (see Fig. 17G
J
[35,327]). There are also some models without active intermediates
for lignin pyrolysis, such as the model proposed by Adam et al.
[333], who proposed that the decomposition of lignin at low temper-
ature occurred through three parallel reactions leading to the forma-
tions of gases, tar and char, while secondary decomposition of tar
should be considered as the temperature increased [333].
TagedPThe aforementioned lumped kinetic models are pretty rough,
with little mechanistic information about biomass pyrolysis. They
can only be used to predict the total yields of char, tar and gases.
Recently, with the development of analytical technology, the precise
quantification of pyrolysis product distribution has been achieved.
This makes it possible to build kinetic models involving detailed evo-
lution pathways of specific compounds.
TagedP4.2.1. Detailed lumped kinetic model
TagedPThe detailed lumped kinetic model based on biomass structure
characterization, which has been successfully applied in the fields
including oxidation and combustion of hydrocarbon fuels and
hydrocarbon pyrolysis [334], has also been introduced into the
kinetic study of biomass pyrolysis. Compared with the classical
lTagedP umped kinetic models, the detailed lumped kinetic model is more
mechanistic and mainly focuses on three different aspects [45]: (i)
characterization of the biomass structure; (ii) biomass devolatiliza-
tion process, leading to the formation of permanent gases, condens-
able vapors (tars) and solid residue (char); and (iii) secondary gas
phase reactions of the released gases and tar. To simplify the model
construction, the ash in biomass is normally regarded as inert and
has no influence on biomass thermo-degradation. In addition,
although interactions among the biomass components have been
proved to exist [194,195,335], the interactions are not considered in
the model. Biomass pyrolysis is assumed to be a linear combination
of the pyrolysis of three biomass components according to their pro-
portions.
TagedPCellulose is a long-chain polymer consisting of glucose through
b¡1,4-glycosidic bonds and is represented by (C6H10O5)n. The pyrol-
ysis pathways of cellulose proposed by Ranzi et al. [45] are simple
and only focus on typical products, such as LG and HAA. The decom-
position of cellulose was initiated by depolymerization to form
active cellulose with an activation energy of 192.3 kJ/mol. Then, the
active cellulose evolved through two competitive pathways: a
chain-end depolymerization reaction leading to LG with 41.8 kJ/mol
and b-scission reactions inside the polymer chain with subsequent
molecular and radical reactions to yield other typical products,
including HAA, HMF, water, gases (CO2, CO, CH4), and char, with
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedP125.4 kJ/mol. Meanwhile, cellulose could also undergo cross-linking
reactions to form char and water directly (133.8 kJ/mol).
TagedPHemicellulose has a more complicated structure, with hexoses
and pentoses as the backbone units and substituent groups, such as
O-acetyl groups, as side branches. Hemicellulose is simplified as a
xylose polymer (C5H8O4)n [45,336]. Its decomposition was assumed
to start from the formation of two active intermediates, HCE1 and
HCE2, with 129.6 kJ/mol, as shown in Fig. 18. Then, the intermediate
HCE1 underwent two parallel reactions: path 1 to form neutral
xylose with an activation energy of 46.0 kJ/mol, and path 2 to form
tar, gases and char with an activation energy of 112.9 kJ/mol. HCE2
degraded to yield tar, char, gases and two pseudo-components, G
(CO2) and G(COH2), with 137.9 kJ/mol. These pseudo-components
were assumed to be limited in the condensed phase and solid matrix
and were further released to form the corresponding gaseous prod-
ucts, CO2 (100.3 kJ/mol) and CO + H2 (217.7 kJ/mol).
TagedPLignin is a complex polymer composed of three basic units, p-
hydroxyphenyl alcohol, guaiacyl alcohol and syringyl alcohol,
through various ether linkages and C

C bonds. A simplified method
is to consider lignin a mixture of three b-O-4 skeleton-based aro-
matic dimers, namely LIG-C (C15H14O4), LIG-O (C16H10O6(OCH3)4)
and LIG-H (C17H13O4(OCH3)5), which was proposed based on the
characterization of lignin structure, as shown in Fig. 19 [45]. During
pyrolysis, LIG-C first decomposed into gases, char, phenols and a
pseudo species, LIGCC with an activation energy of 202.7 kJ/mol. LIG-
H and LIG-O decomposed into acetone and LIGOH (156.8 kJ/mol), and
CO2 and LIGOH (106.6 kJ/mol), respectively. LIGCC could be further
converted into LIG and other products including phenols, gases,
xylose
HCE1
hemicellulose tar +gases + char
HCE2 tar +gases + char + G(CO2) + G(COH2)
Fig. 18. Scheme for pyrolysis of hemicellulose.
R OH
OH
O HO
O H3C
HO
OR H3CO
LIG-C
Fig. 19. Structures of LIG-C, LIG-O, and LIG-H (reprinted from Ranzi et al. [45]).
Fig. 20. Structures of LIG(F)-C, LIG(F)-O, and LIG(F)-H (adapted from Faravelli et al. [337] with permission of Elsevier).
55
TagedPchar, et al. (131.7 kJ/mol), while LIGOH was mainly transformed into
gases and LIG (208.2 kJ/mol). Then, the LIG could be further cracked
into phenols (C11H12O4, 50.2 kJ/mol) or char and gases (125.4 kJ/
mol). On the basis of this model, Faravelli et al. [337] developed a
more detailed one, and they used a different series of b-O-4 skele-
ton-based reference components, including LIG(F)-C (C17H17O5), LIG
(F)-O (C16H11O6(OCH3)4) and LIG(F)-H (C18H17O5(OCH3)4), as shown
in Fig. 20. LIG(F)-C without methoxyl groups was representative of
softwood lignin, while LIG(F)-O and LIG(F)-H were representative of
hardwood lignin. The compositions of these three reference compo-
nents in different lignin could be determined based on elemental
analysis results (mainly the H/C/O composition), and their depo-
lymerization was described systematically by the reference struc-
tures and functional groups. This model included 100 molecular and
radical species with 500 elementary and lumped reactions, and it
could accurately predict the degradation rates and the information
of the products released during lignin pyrolysis.
TagedPExtractives were once ignored during the characterization of the
biomass structure in the lumped kinetic model because of their low
contents [45,338,339]. However, due to the lack of extractives, the
characterization of some biomass cannot be achieved using a simple
mixture of the three main components according to their elemental
composition [340]. There are thousands of different extractives
which can be identified in biomass, and their compositions, struc-
tures and biological functions vary greatly. Therefore, the extractive
species have to be simplified in the model construction. Debiagi
et al. [340] classified extractives into two types, hydrophilic extrac-
tives and hydrophobic extractives, according to their water solubil-
ity. Hydrophobic extractives mainly included resins and
triglycerides and were represented by a new reference component,
TGL (C57H100O7). The hydrophilic extractives were mainly composed
of condensed tannins and were represented by TANN (C15H12O7), as
shown in Fig. 21. During pyrolysis, the decomposition of TGL was
simplified as a single-step reaction with the products of one acrolein
(C2H3CHO) and three free fatty acids (C18H32O2) with activation
energy of 191.0 kJ/mol. The degradation of TANN was described by
H3CO R R
H3CO
OH
O O
OCH3 OCH3
H3CO
OH OH
OCH3 H3CO OCH3
OR OR
LIG-O LIG-H
56 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
O
CH3
O OH
O O
CH3
CH3
TGL
Fig. 21. Structures of TGL and TANN (reprinted from Debiagi et al. [340] with permission of American chemical society).
TagedPtwo reactions in series: TANN first underwent fission of the hetero-
cyclic ring to form phenolic species and an intermediate ITANN
(C9H6O6) with 46.0 kJ/mol. The intermediate ITANN was further con-
verted into char, water and gases (25.5 kJ/mol). The introduction of
extractives into the detailed lumped kinetic model greatly extended
its application and more accurately simulated the entire pyrolysis
process [341].
TagedPThe detailed kinetic scheme developed by the Ranzi group is
highly simplified and can predict the overall yield of some products
in a limited number of reaction steps. Considering the severe
computational time limitations when simulating biomass pyrolysis
at the reactor scale [338], this model is appropriate. It can effectively
predict the pyrolysis behavior of biomass, not only at the particle
scale but also at the reactor scale. However, the rate coefficients in
this model provide no mechanistic information because of the forced
fitting to the thermogravimetric weight loss profiles. This leads to
limited application of the obtained kinetic parameters [342]. In addi-
tion, due to the significant simplification of the biomass structures
and their devolatilization process, this model is far away from the
real pyrolysis process and can predict few pyrolysis products.
Recently, Vinu and Broadbelt [342] developed a more detailed
kinetic model based on mechanistic steps for cellulose pyrolysis. The
pyrolysis of cellulose started from concerted reactions in the cellu-
lose chain, leading to the formation of LG and glucose. The cellulose
chain simultaneously evolved through a series of reactions, includ-
ing dehydration, retro Diels
Alder reactions, cleavage of glycosidic
bonds and hydrolysis, to form C2
C4 low-molecular-weight prod-
ucts (LMWPs). The formed glucose could further undergo compli-
cated concerted reactions to yield various C1
C6 organic
compounds, such as HAA, HMF, furfural, and LG. In addition, the C4
and C5 fragments could undergo tautomerization and retro-aldol
reactions to form many other LMWPs, and the dehydrated sugars
and C5 fragments could form char and light gases. This model pre-
cisely simulated the pyrolysis of cellulose, and the results well
matched the experimental data for the product distribution of cellu-
lose pyrolysis. However, mechanistic kinetic models for the pyrolysis
of hemicellulose and lignin are lacking and need to be developed in
the future.
TagedP4.2.2. Chemical percolation devolatilization model
TagedPThe chemical percolation devolatilization (CPD) model is another
promising model to predict typical product yields. It was developed
by Fletcher and coworkers [343
345] for the prediction of coal
devolatilization and was recently extended to predict the devolatili-
zation of biomass [346]. Similar to the detailed lumped kinetic
model, characterization of the biomass structure is the first step in
chemical percolation devolatilization modeling, and biomass is con-
sidered as a linear combination of cellulose, hemicellulose and
OH
O
OH O
O OH
OH
n
OH
TANN
lTagedP ignin. The difference is that the feedstock structure in the CPD
model is modeled as clusters, labile bridges and side chains rather
than pseudo-components, as in the detailed lumped kinetic model.
As proposed by Fletcher et al. [46], the clusters for lignin are aro-
matic rings, while those for cellulose and hemicellulose are fixed
anomeric carbon and attached hydrogen, as shown in Fig. 22. The
modelling of the biomass structure can be achieved via five chemical
structure parameters, including the molecular weight of the cluster,
molecular weight of the side chains, coordination number (i.e., the
number of attachments per cluster), initial fraction of intact bridges,
and initial fraction of char bridges. The first four parameters can be
determined directly from biomass structure characterization via
solid-state 13C NMR measurements while the fifth is empirically set
to 0. However, it's cost-prohibitive to measure the structural param-
eters for each biomass sample. It's a good idea to determine the
parameters for each biomass component and then calculate the
parameters for the whole biomass through compositional analysis.
The structures of hemicellulose and lignin from hardwood and soft-
wood are different [127,221]. During biomass pyrolysis, the labile
bridges between clusters are activated to form an intermediate, acti-
vated bridge. Then, the bridge intermediate can break into either
side chains, which are further converted into light gas components,
or form a stable char bridge with the release of light gases. The
chemical structure and kinetic parameters of the biomass compo-
nents were determined by Fletcher et al. [46]. Using these parame-
ters, Lewis et al. [347] studied the pyrolysis kinetics of sawdust.
They assumed that biomass pyrolysis occurred as a weighted aver-
age of the three major components. Further cracking of tar into light
gas was included in the CPD model. The results showed that this
model could accurately predict the devolatilization of three kinds of
sawdust from three different reactors (flat-flame burner, drop-tube,
and thermogravimetric analyzer).
TagedPKey advantages of the above mentioned CPD are the direct use of
measurable structural parameters and that the corresponding
kinetic networks are simple and easy to understand. One drawback
is that the products are limited to gases, tar and char, and minimal
Fig. 22. Cellulose molecule with clusters highlighted (reprinted from Fletcher et al.
[46] with permission of American chemical society).
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPinformation about the molecular descriptions of the tar and light gas
is provided.
TagedPHorton et al. [348] recently developed a molecular-level kinetic
model of biomass gasification based on the CPD model to predict the
yields of the final gaseous products. In their model, the biomass
structure characterization method was different from that of Fletcher
et al. [46]. The feedstock was represented by a set of molecules and
mole fractions. Since there are large polymeric structures in biomass,
the explicit composition of each polymer cannot be measured experi-
mentally. In this model, a composition model composed of a set of
probability distribution functions (PDFs) was used to describe the rel-
ative amount of molecular groups. For linear polymers, including cel-
lulose and hemicellulose (hemicellulose was considered as a xylose
polymer), the repeatable monosaccharide units were considered as
the cores, and the side chains and labile bridges were considered ter-
minal substituents and bridges between cores. A Flory distribution
was introduced to describe the probability of the polymers with dif-
ferent DP values. For the cross-linked polymer lignin, the Freuden-
berg model [349] was used to represent its structure, and five labile
bridges, five side chains and five clusters were determined based on
this model. Five PDFs were used to calculate the mole fractions of
individual molecules via the combined probabilities from each PDF.
The first three corresponded to the PDFs for the labile bridges, side
chains and clusters. The additional two PDFs (polymer size distribu-
tion and binding site distribution) were used to describe the relative
amounts of a molecule with n clusters and how many sites on each
cluster were filled by side chains. The optimization of the composi-
tional parameters for the three biomass components were performed
based on elemental analysis. Then, the biomass structure could be
determined through flexible combination of cellulose, hemicellulose
and lignin according to the elemental analysis results. After the
molecular-level modeling of the biomass structure, Horton et al. [46]
proposed detailed reaction chemistry, which defined the reaction
network from the molecular inputs to outputs with 1356 reactions
and 357 species. Using this model, they achieved satisfactory results
for six different biomass samples. Since pyrolysis is the initial step of
gasification, there is a potential to introduce this model into the
study of biomass pyrolysis with some modification.
TagedP4.2.3. Kinetic Monte Carlo (KMC) model
TagedPIn contrast to the lumped kinetic model and CPD model, kinetic
Monte Carlo (KMC) modeling is based on all possible reaction path-
ways specific to every species in the reaction system. KMC modeling
relates the macroscopic reaction rate to the microscopic rate via a
stochastic approach originally developed by Gillespie [350,351] and
predict the products evolution process. A KMC model involves solv-
ing a chemical master equation which is used to determine the prob-
abilistic population of a molecular species at a given future time. The
stochastic simulation algorithm proposed by Gillespie [350] is
applied to determine the time evolution of the species population
based on the executed reaction, as shown in Eq. (14)
(16). The prob-
ability, pr, for each reaction, r, is determined by its current reaction
rate, kr, and the sum of the rates of all possible n reactions. All of the
probabilities for each reaction in a reaction system constitute a reac-
tion probability distribution.
kr
pr ¼ Pn ð14Þ
i¼1 ki
T he reaction to be executed, m, is selected by a uniformly distrib-
agedPT
uted random number between zero and one, x1, according to the
reaction probability distribution. The detailed stochastic procedure
is described by Eq. (15) [351].
m
1
X m
X large number of molecular simulation studies have been performed
pi < x1 < pi ð15Þ
i¼1 i¼1
57
TagedPThe time step for execution of the selected reaction, t , is deter-
mined based on another random number between 0 and 1, x2, and
the sum of all possible reaction rates, as shown in Eq. (16) [351].


1 1
t ¼ Pn ln ð16Þ
i¼1 ki
x2
TagedPThe formulation of KMC models for biomass pyrolysis is really
difficult due to the complicated biomass structure and pyrolysis pro-
cess. In addition, the increase in the numbers of reactants and reac-
tion pathways will make the solution of a KMC model slower and
more computationally prohibitive [350]. Thus, the application of
KMC models in biomass pyrolysis is rare. Beste and Buchanan
[47,352] recently conducted KMC studies for the pyrolysis of b-O-4
lignin model compounds. The rate constants for each reaction in
their studies were calculated through transition state theory based
on density functional calculations. Employing the KMC model, they
simulated the radical chain propagation during the pyrolysis of phe-
nethyl phenyl ether (PPE) [47]. The calculated rate constants for
individual reaction compared well with experimental estimates, and
the predicted product distribution was qualitatively in agreement
with the experiment. They further investigated oxygen¡carbon and
carbon¡carbon shift reactions with subsequent b-scission of the
b-radical in the pyrolysis of b-O-4 lignin model compounds includ-
ing PPE and a-hydroxy PPE [352]. The mole fraction as a function of
time was obtained for some key products. The results showed that
only approximately 15% of b-radical conversion could be ascribed to
a carbon¡carbon shift for PPE and a-hydroxy PPE at 345 °C, while
the remaining 85% was due to an oxygen¡carbon shift because the
activation energies for the subsequent b-scission of the oxygen¡car-
bon shift products (virtually no barrier) were much lower than those
of the carbon¡carbon shift products (62.7 kJ/mol).
5. Molecular simulation of the pyrolysis pathways of biomass
and bio-based model compounds
TagedPThe development of a fundamental description of biomass pyrol-
ysis chemistry is beneficial to process optimization and feedstock
flexibility [353]. However, molecular-level insight into the pyrolysis
mechanism via experiments has been hindered due to the unavail-
ability of analytical technologies to monitor the detailed process of
biomass pyrolysis [49]. Currently, with the rapid advancement in
computational technology and computational chemistry, molecular
simulation, which can provide detailed information about each ele-
mentary step and the associated kinetic parameters, is attracting
increasing attention as an effective tool to probe pyrolysis chemistry
[354]. One challenge in molecular simulation is the limitation of the
modeled molecular size. It is computationally expensive and unprac-
tical to model the pyrolysis of large molecules. For example, it
required decades of CPU time to simulate the pyrolysis of one cellu-
lose polymer with a DP of 100 via Car
Parrinello molecular dynam-
ics (CPMD), as shown in Fig. 23 [353]. Thus, model compounds of
small size, such as 2,3,4-hydroxyl-butyraldehyde and 2,3,4-
hydroxyl-butyricacid [355], and glucose [356], are studied first to
determine their reaction mechanisms. The results can be further
applied to extrapolate the fundamental chemistry of biomass pyrol-
ysis.
5.1. Cellulose pyrolysis mechanism
TagedP5.1.1. The elementary pathways for the pyrolysis of glucose
TagedPUnderstanding the pyrolysis chemistry of glucose, the basic unit
of cellobiose, is helpful to understand cellulose pyrolysis [357]. A
and have made strides toward mapping the reaction networks
between glucose and the observed pyrolysis products.
58 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 23. CPU time of CPMD simulations with 200 processors operating in parallel
(reprinted from Mettler et al. [353] with permission of Royal society of chemistry).
TagedPLG is the most abundant pyrolysis product from glucose. LG can
exist in either the pyranose or furanose form, with larger yield of the
former [98]. Pyranose LG can be formed directly from the dehydra-
tion of the hydroxyl groups at C1 and C6. The dehydration process
can occur via two mechanisms, which can be distinguished accord-
ing to which hydroxyl group is removed. According to a study per-
formed by Seshadri and Westmoreland via a density functional
theory (DFT) study at the CBS-QB3 level [48], the activation energies
for the loss of C1 hydroxyl and C6 hydroxyl from boat b-D-glucose
were 222.4 kJ/mol and 309.3 kJ/mol, respectively. Thus, the loss of C1
hydroxyl is favored. The furanose form of LG is produced by dehy-
dration of glucofuranose, which is formed via tautomerization of
glucose. The formation of furanose LG is more difficult than that of
pyranose LG from inverted-chair b-D-glucose (193 kJ/mol) due to
the higher activation energy for the isomerization of glucose to glu-
cofuranose (209 kJ/mol) [48]. LG can also be yielded via water-
assisted bimolecular reactions, which is more favored due to its
lower activation energy (165.1 kJ/mol from inverted-chair b-d-
OH OH
O O
O HO
HO HO
HO OH HO
OH OH
Fig. 24. The most favorable pathway for the formation of LGO from b-d-glucose [363].
Fig. 25. Elementary reactions of b-d-glucose conversion to HMF (reprinted from Mayes et al. [357]).
TagedPglucose to LG) [48]. LG is thermally stable. A study conducted by
Zhang et al. [358,359] investigated the thermal dissociation of LG
through three decomposition mechanisms (C
O bond scission, C
C
bond scission, and LG dehydration) at the B3LYP/6
31 +G(D,P) level.
The preferred LG decomposition pathway was dehydration with the
removal of a hydrogen atom from C3 and a hydroxyl group from C2,
and the activation energy was 272.0 kJ/mol. Glucose can also pro-
duce other anhydrosugars, such as 3,4-anhydroaltrose from the
dehydration of hydroxyl groups at C3 and C4, followed by isomeriza-
tion. The corresponding activation energy was higher than that for
the formation of LG [360,361]. Levoglucosenone (LGO) is another
anhydrosugar product, which was considered to be formed from the
dehydration of LG in earlier studies [362]. However, a recent study
by Lu et al. [363] indicated that LG was probably not the essential
intermediate to produce LGO due to the high energy barrier
(306.3 kJ/mol). The most feasible reaction pathway for LGO from
b-D-glucose was 1,2-dehydration to yield an intermediate with a
carbon-carbon double bond, followed by dehydration via six-mem-
bered hydrogen transfer, enol-keto tautomerization and finally 4,5-
dehydration (as shown in Fig. 24). Enol
keto tautomerization, with
an overall energy barrier of 290.8 kJ/mol, was the rate-determining
step.
TagedPHMF is a characteristic product of glucose pyrolysis [98,360], and
can be used as a valuable platform chemical [364,365]. The reaction
mechanisms for the formation of HMF from glucose can be divided
into two types. One path does not include the formation of a fructose
intermediate and involves mainly ring opening, dehydration and
cyclization reactions, such as the reaction pathways proposed by
Wang et al. [360] (B3LYP/6
31 ++G(d,p), 1-3-7-8-9 in Fig. 25) and
Zhang et al. [356] (B3LYP/6
31G(d,p), 1-3-12-11-9 in Fig. 25). The
rate-determining steps for these two pathways were the dehydra-
tive cyclization steps, the corresponding activation energies of which
were 281.1 kJ/mol and 293.1 kJ/mol. The other path proceeds
through initial tautomerization to fructose via ring opening and
isomerization, such as the pathways proposed by Wang et al. [366]
(M06-2X/6
31G+(d,p), 1-3-4-5-6-8-9 in Fig. 25) with activation
energy of 313.5 kJ/mol. Since previous studies have been performed
O O O
O O
HO
OH
O O
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86 59

TagedPon various basis, the results from those studies cannot be compared
to determine which best describes HMF formation. Considering this
problem, Mayes et al. [357] adopted the same methodology (M06-
2X/6
311 +G(2df,p)) to investigate all possible conversion routes
from glucose to HMF, as shown in Fig. 25. In addition to the reaction
pathways proposed by other studies, they proposed a novel route
which bypassed the fructose intermediate and the open forms of the
monosaccharides. This path began with ring contraction from the
pyranose form of glucose to a furanose gemdiol (17), which was fol-
lowed by dehydration. The ring contraction reaction and direct
dehydration of b-D-glucose were difficult due to their high activation
energies of 318.9 kJ/mol and 304.3 kJ/mol, respectively. Thus, the
formation of HMF began with ring opening. Compared with the reac-
tion paths without a fructose intermediate, those with a fructose
intermediate were preferred and the most favored route was 1-3-4-
5-6-8-9 in Fig. 25 with activation energy of 255.8 kJ/mol.
TagedPIt was proposed that HMF could further evolve through elimina-
tion of hydroxymethyl group to form furfural [360]. However, the
activation energy for this reaction was 313.3 kJ/mol. Thus, HMF and
fTagedP urfural are more likely formed through competitive reactions rather
than sequential reactions during the pyrolysis of glucose. A study
carried out by Wang et al. [366] classified possible reaction path-
ways for the conversion from glucose to furfural into four types: for-
mation via a fructose intermediate, formation via a 3-deoxy-glucose
(3-DG) intermediate, pathways initiated by Grob fragmentation
which was proposed for glycerol pyrolysis [367], and pathways initi-
ated by 1,2-dehydration. The most kinetically favored pathways of
these four mechanisms are shown in Fig. 26. The formation of furfu-
ral was the most favored via the 3-DG intermediate, which further
underwent hydrogenation-cyclization, 1,2 dehydration between
C3

H and C4

OH and Grob fragmentation (Path 2). The activation
energy for this route was 236.6 kJ/mol. They also compared the reac-
tion routes for the formation of furfural from the C1

C5 fragment
and C2

C6 fragment. It was found that furfural was mostly derived
from the C1

C5 of glucose, with the aldehyde group formed at C1.
TagedPGlucose can also undergo fragmentation (ring scission) to form
HAA. Four mechanisms of HAA formation were proposed by Zhang
et al. [356], as shown in Fig. 27. The first two began with ring open-

Fig. 26. Elementary reactions of b-d-glucose conversion to furfural.

Fig. 27. Elementary reactions of b-d-glucose conversion to HAA(adapted from Zhang et al. [356] with permission of Elsevier).
60 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPing via direct breakage of the C1

O bond, followed by recombina-
tion of the fragments. The difference was the recombination pattern,
through which path 1 produced 1 HAA molecule and path 2 pro-
duced 3. In the last two paths, dehydration first occurred between
two adjacent hydroxyls. Path 3 underwent dehydration with the
removal of the hydroxyl at C3 and the H atom at C2, followed by ring
opening and cleavage of the C4

C5 bond to form HAA, whereas the
dehydration in path 4 removed the hydroxyl at C4 and the H atom at
C5, followed by ring opening and cleavage of the C2

C3 bond. The
direct dehydration of glucose required high activation energy
(291.1 kJ/mol for 2,3-dehydration and 305.3 kJ/mol for 4,5-dehydra-
tion), which hindered the formation of HAA via path 3 and path 4.
Compared with path 1, path 2 was preferred due to its lower activa-
tion energy of 258.9 kJ/mol. Lu et al. [368] summarized the potential
pathways of HAA formation into three mechanisms based on the
first-step reaction, namely “C

O bond scission-first mechanism”,
“C

C bond scission-first mechanism”, and “dehydration-first mech-
anism”, among which C

O bond scission was the most competitive
due to its relatively low energy barrier. It seemed that HAA was
more likely to be formed from C5

C6 than C1

C2 and C3


C4.
TagedP5.1.2. The pyrolysis pathways of model compounds including b¡1,4-
glycosidic bond
TagedPIt's not sufficient to extrapolate the pyrolysis mechanism of cellu-
lose based on glucose alone, since the important b¡1,4-glycosidic
bond is not included. Thus, model compounds with more compli-
cated glucose structures, such as cellobiose [363,369
373], cello-
triose [374,375] and a-cyclodextrin [49] are adopted as surrogates
for cellulose.
TagedPDue to the high yield of LG (up to 60 wt.%) from cellulose pyroly-
sis [98], its formation path is crucial for the cellulose pyrolysis mech-
anism. It is obvious that LG formation begins with cleavage of
glycosidic bond. However, the detailed cleavage mechanism is
unclear. Three are three mechanism: the homolytic (radical) mecha-
nism [224], the heterolytic (ionic) mechanism [376] and the con-
certed mechanism [370]. Zhang et al. [377] found that the bond
dissociation energy (BDE) for the homolytic reaction (331 kJ/mol)
was much lower than that for the heterolytic reaction (659 kJ/mol).
Thus, homolytic cleavage was preferred. The formed anhydroglucose
radical could evolve through a hydrogen-donor reaction to yield an
intermediate, which could be further transformed into LG and form-
aldehyde [377,378]. The energy barrier for LG formation was lower
than that of formaldehyde.
TagedPHowever, a study by Hosoya et al. [379] proved that the forma-
tion of LG more likely occurred through a concerted reaction than a
Fig. 28. Mechanism of the formation of LG during cellulose pyrolysis.
TagedP omolytic reaction or heterolytic reaction during decomposition of
h
methyl b-D-glucoside. They proposed that LG formation began with
a conformational change from 4C1 conformer to 1C4, followed by
intramolecular substitution at the anomeric carbon. Assary and Cur-
tiss [372] reported a two-step concerted mechanism for the forma-
tion of LG from cellobiose. Cleavage of the glycosidic bond occurred
first to form a glucose and an intermediate with a carbon-carbon
double bond, which would be converted to LG via hydrogen transfer.
Mayes and Broadbelt [370] performed a detailed study to unravel
the formation pathways of LG from cellulose. Methyl cellobiose was
used as the model compound, since the methyl group, added to O4
at the nonreducing end, could prevent the conformation of the
model molecule changing to a manner inconsistent with cellulose.
As indicated by the DFT results, the energy required for glycosidic
cleavage of methyl-cellobiose via the concerted mechanism
(225.3 kJ/mol) was much less than that required via the homolytic
mechanism (395.0 kJ/mol) and heterolytic mechanism (377.5 kJ/
mol). The reaction rate coefficient at 500 °C for concerted glycosidic
cleavage was at least 4 orders of magnitude larger than those for
ionic and radical scission. Thus, the concerted pathway was favored.
The proposed concerted mechanism for the formation of LG (LG-end
mechanism) during cellulose pyrolysis is shown in Fig. 28. The mid-
chain initial concerted cleavage of the glycosidic bond (225.3 kJ/mol)
produced a terminal LG-like end intermediate and a shorter cellulose
chain. Then, the LG-end intermediate evolved via depropagation
(244.5 kJ/mol) to form an LG molecule and another LG-end interme-
diate. LG can also be formed via reaction of the nonreducing end res-
idue of the LG-end intermediate (NR end mechanism) [380]. It was
proved by Hosoya et al. [380] using the MP4(SDQ) and DFT(M06-2X)
methods that LG-end mechanism was preferred than NR end mecha-
nism during cellulose pyrolysis. In addition, LG could be yielded via a
glucose intermediate formed by thermohydrolysis during cellulose
pyrolysis. However, the activation energy for the glucose intermedi-
ate mechanism (264 kJ/mol) was much higher than that for the LG-
end mechanism (195 kJ/mol) [381]. Hence, the LG-end mechanism
was more competitive.
TagedPThe studies discussed above are based on the assumption that
cellulose is composed of only one chain, ignoring the interchain
hydrogen bonds of real cellulose crystals. However, Hosoya et al.
[380] found that the reaction behavior of LG formation predicted
based on one-chain model, which was composed of a glucose hex-
amer, was far away from reality. The corresponding activation
enthalpy (158.8 kJ/mol) was remarkably underestimated compared
with the experimental value (200.6
250.8 kJ/mol). Thus, the effect
of the hydrogen bonding network must be considered. Accordingly,
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPthey proposed a two-chain model with two glucose hexamers,
which contained O6HO3 and O6HO2 interchain hydrogen
bonds. The corresponding activation enthalpy (234.1
259.2 kJ/mol)
was in good agreement with the experimental value. Further
research using a three-chain hexamer model showed that the degra-
dation of cellulose leading to LG formation occurred selectively on
the crystalline surface.
TagedPAssary and Curtiss [372] proposed that LG could further undergo
dehydration to form LGO during cellulose pyrolysis. However, as
indicated by Lu et al. [363], further dehydration of LG required over-
coming a high energy barrier; thus, it was difficult. Based on the
reaction pathway from glucose to LGO, they proposed a similar
mechanism for LGO formation from cellulose (shown in Fig. 29),
which included the formation of carbon-carbon double bonds, dehy-
dration via six-membered hydrogen transfer and enol-keto tauto-
merization reaction. The double bonds were more likely to form via
concerted cleavage of the b¡1,4-glycosidic bond rather than 1,2-
dehydration during cellulose pyrolysis. The depolymerization of cel-
lulose chains can also evolve through other reaction pathways with
the formation of different primary products, such as HAA and HMF.
Zhang et al. [369] compared ten pathways for the initial pyrolysis of
cellobiose at the M062X/6
31G+(d,g) level. They found that the
aforementioned concerted reaction mechanism to form LG was criti-
cal to reduce the degree of polymerization of cellulose with a low
energy barrier of 202.4 kJ/mol. This route was further promoted by
the presence of H+ cation. As for the thermohydrolytic cleavage of
the glycosidic bond to yield glucose and the one-step concerted
reaction to form HMF, they were not kinetically favored due to their
high energy barriers of 300.4 kJ/mol and 320.9 kJ/mol, respectively.
In addition, according to the thermodynamic analysis, the depo-
lymerization route of cellulose, with breaking of pyran ring to form
HAA, could be competitive when the temperature was high, in
agreement with the experiment results of Luo et al. [382]. Since
there are three free hydroxyls in each glucose residue of cellulose,
the dehydration reactions in the initial decomposition of cellulose
should be considered. Zhang et al. [375] used cellotriose as a model
compound and found that dehydration of C2

OH via pinacol rear-
rangement was the most likely mechanism. However, its energy bar-
rier was so high (264.2 kJ/mol) that it required high temperature.
TagedPThe breaking of the pyran ring is the key step in the formation of
small molecular products during cellulose pyrolysis. Zhang et al.
[374] classified the possible reaction pathways into four types,
Fig. 29. The most favorable pathway for the formation of LGO from cellulose [363].
61
TagedP amely direct breaking mechanism, Retro-Diels-Alder mechanism,
n
C6

OH assisted pinacol ring cleavage mechanism and Retro-Aldol
mechanism, and studied these mechanisms in detail based on cello-
triose. The results indicated that the breaking of pyran ring became
much easier after removal of a water molecule either by direct dehy-
dration or by Pinacol dehydration. Retro-Aldol mechanism (with
C3 =O formed) was favored, followed by Retro-Diels-Alder mecha-
nism (with C3 =C4 bond formed), C6

OH assisted pinacol ring cleav-
age mechanism and direct breaking mechanism.
TagedPMost of the above DFT studies were performed in gas phase with-
out consideration of the crucial condensed-phase environment. The
existence of intermediate liquid during biomass pyrolysis has been
proved [383]. Within the liquid phase, many reactions, such as depo-
lymerization, rearrangement and dehydration, take place before the
products are further converted to gas, char or aerosol [384]. These
reactions are different from those in the gas phase [385]. Thus, an
understanding of condensed-phase chemistry is needed. CPMD,
which is a multiscale method combining quantum mechanics and
molecular dynamics, is a good choice for this purpose. Mettler et al.
[49] carried out CPMD simulation to reveal the long-debated path-
ways of cellulose pyrolysis using a-cyclodextrin as a cellulose surro-
gate. The results showed that furans were formed from cellulose
directly without any small-molecule intermediates (e.g., glucose and
LG), as shown in Fig. 30. The formation of furans and light oxygen-
ates, such as HAA, was initiated by the homolytic cleavage of the gly-
cosidic bond rather than through an ionic mechanism or concerted
mechanism. However, this CPMD simulation was performed at very
high temperatures (1700 ¡ 1900 °C), so the obtained mechanisms
might not be applicable under typical pyrolysis conditions. Further,
Agarwal et al. [386] investigated the nascent decomposition pro-
cesses of cellulose at 327 and 600 °C using a simulation cell com-
posed of two unit cells of cellulose Ib periodically repeated in three
dimensions to represent the solid cellulose. Ring contraction of the
glucopyranose ring to a glucofuranose ring was the most favored
route compared with other possible reactions, including ring open-
ing, depolymerization and fragmentation, with the lowest free-
energy barrier (83.6 kJ/mol) at 327 °C. This process was crucial to the
formation of liquid intermediate cellulose from reversible active cel-
lulose at around 260 °C. At 600 °C, a precursor to LG (pre-LG) was
formed via a transition state stabilized by anchimeric assistance and
hydrogen bonding, with a corresponding free-energy barrier of
150.5 kJ/mol. The precursors to HMF and formic acid were also
62 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 30. Reaction pathways of a-cyclodextrin (cellulose) pyrolysis (reprinted from Mettler et al. [49] with permission of Royal society of chemistry).
TagedPobserved to be directly formed from cellulose, and their free-energy
barriers were higher than that of pre-LG, which indicated that the
formation of LG was the most kinetically favored process during cel-
lulose pyrolysis.
5.2. Hemicellulose pyrolysis mechanism
TagedPCompared with cellulose, there are fewer studies focused on the
molecular simulation of hemicellulose pyrolysis. Since the exact
structure of hemicellulose is not fully understood, the reported stud-
ies are mostly based on the monosaccharide units in hemicellulose
including xylose [387
389], arabinose [390], etc..
TagedPXylose, the basic building block of hemicellulose, is the most
common model compound used for molecular modeling of hemicel-
lulose pyrolysis. Wang et al. [137] found that ring opening by the
breakage of the C1
O bond to yield D-xylose was the most likely
reaction in the initial degradation of b-D-xylose, according to the
bond strength estimated through the Mayer bond order [391]. This
result was confirmed by other researchers by comparison with other
reaction routes, such as immediate ring-opening reaction through
the simultaneous cleavage of the C
O and C
C bonds and direct
dehydration reactions [388,389]. The formed d-xylose was an impor-
tant intermediate during the pyrolysis of b-d-xylose. It could be fur-
ther transformed to 4-hydroxydihydrofuran-2(3H)-one, 1-hydroxy-
2-propanone and furfural. The formation of furfural was more kineti-
cally favored than the others with the lowest energy barrier of
TagedP 07.4 kJ/mol [137]. It began with dehydration of C3

3
OH, followed
by dehydration of C4

OH and cyclization. There are many other
possible pathways for the conversion of D-xylose to furfural. A study
carried out by Wang et al. [388] has investigated them in detail. The
results showed that the most likely route was through an xylulose
intermediate from multiple hydrogen migration of D-xylose, which
would further undergo hydrogenation cyclization and dehydration
to form furfural, with an overall energy barrier of 259.8 kJ/mol (as
shown in Fig. 31). The open-ring D-xylose could also be converted to
small molecular products, such as acetaldehyde, acetone and HAA
[387]. A study by Lu et al. [368] indicated that the C1

C2 and C4

C5
segments were the main sources of HAA during b-D-xylose pyrolysis.
For the HAA from the C1

C2 segment, the most feasible pathway
was breakage of the C2

C3 bond of D-xylose via retro-aldol reaction
to form glyceraldehyde and 1,2-ethenediol, followed by tautomeri-
zation (as shown in Fig. 31). The HAA from the C4

C5 segment was
formed through retro-aldol reaction to break the C3

C4 bond of
xylulose. Arabinose is another pentose in hemicellulose. Similar to
b-d-xylose, its reaction pathways were most likely initiated through
ring opening via breakage of the C1
O bond [390]. Due to the lower
energy barrier (287.2 kJ/mol), the formation of furfural from arabi-
nose was easier than that from xylose. Compared with pentoses,
hexoses (galactose and mannose) are more likely to form HMF as a
result of the high energy barriers for the dissociation of the hydroxy-
methyl group (378.1 kJ/mol for galactose, 346.2 kJ/mol for mannose)
[137].
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 31. The most favorable pathways for the formation of furfural and HAA from b-d-xylose [368,388].
TagedPConsidering that there are abundant side branches, such as O-
acetyl groups, at the C2 and C3 positions of the monosaccharide resi-
dues in hemicellulose, O-acetyl-xylose with an O-acetyl group linked
to C2 might be a better model compound for hemicellulose
[137,368,392]. Wang et al. [137] found that the dissociation of the
O-acetyl group via cleavage of the C2
O oxygen-bridged bond to
yield acetic acid was kinetically favored due to its low energy barrier
of 226.2 kJ/mol in the initial decomposition of O-acetyl-xylose. Com-
pared with the high energy barriers of other routes for acetic acid
formation through further decomposition of ring-opened intermedi-
ates, this path is responsible for the release of acetic acid at low tem-
perature. The residual part of O-acetyl-xylose would further evolve
through similar paths to xylose, initiated by the ring-opening reac-
tion [392]. The O-acetyl branches could also be cracked into acetal-
dehyde. The DFT calculation results showed that the formation of
acetaldehyde was kinetically and thermodynamically more difficult
than that of acetic acid [368]. The unsaturated C2 =C3 bond formed
after scission of the O-acetyl groups hindered the formation of HAA
from C1

C2 in the following degradation reactions. Thus, unlike
xylose, HAA from O-acetyl-xylose was mainly derived from the
C4

C5 segment [368]. To obtain results that more closely resemble
the actual pyrolysis behavior of hemicellulose, Wang et al. [296]
adopted four xylosyl oligomers consisting of three b¡1,4-linked
xylose residues with O-acetyl groups at C2 and/or C3 as model com-
pounds. The Mayer bond order was used to judge the thermal
strength of each bond. The results indicated that the O-acetyl group
at C3 was more thermally stable than that at C2. They also investi-
gated the breakage of b¡1,4-glycosidic bonds, and found that C4

O’
’ was stronger than C1

O’ . Thus, the depolymerization of hemicel-
lulose was more likely to occur via breakage of C1

O’ . Additionally,
the existence of the O-acetyl group would further strengthen C4

O’
’ in the b¡1,4-glycosidic bonds.
Fig. 32. Mechanisms for the cleavage of the b-O-4 linkage.
63
5.3. Lignin pyrolysis mechanism
TagedPThe structure of lignin is more complicated than those of polysac-
charides including cellulose and hemicellulose. The linkages
between phenylpropane monomers, mainly ether linkages and C
C
bonds, play important roles during lignin pyrolysis. Thus, multiple
studies have been conducted to reveal the detailed cleavage mecha-
nism.
TagedPThe b-O-4 ether linkage is the dominant interunit linkage in lig-
nin, constituting 46
60% of the total linkages [149]. The proposed
mechanisms for the cleavage of the b-O-4 linkage can be separated
into two types, namely, homolysis mechanism and concerted mech-
anism. Homolysis reactions can occur between Cb-O and Ca-Cb, and
concerted reactions can be further divided into retro-ene fragmenta-
tion with a six-membered transition state and Maccoll elimination
involving a four-membered transition state, as shown in Fig. 32
[266]. Since homolysis reactions proceed via barrierless transition
states, the BDE can be used as the approximate activation energy
[266]. The activation energies for cleavage of the b-O-4 linkage in
phenethyl phenyl ether (PPE), the most simple b-O-4 dimer model
compound for lignin, followed by retro-ene reaction (220.7 kJ/mol)
< Maccoll reaction (251.2 kJ/mol) < Cb-O homolysis (253.3 kJ/mol)
< Ca-Cb homolysis (286.7 kJ/mol) [393]. Thus, with regard to unimo-
lecular reactions, concerted mechanisms were kinetically favored
[394]. Taking the temperature effect into account, using CBS-QB3
calculations, Jarvis et al. [266] reported that the concerted retro-ene
and Maccoll reactions dominated when temperatures were below
1000 °C, while Cb-O homolysis became significant at temperatures
above 1000 °C, as shown in Fig. 33a, which was further proved by
the direct detection of key intermediates via a hyperthermal nozzle/
REMPI PIMS system. Huang et al. [395] reported similar results using
a more complex dimer (1-phenyl-2-phenoxy-1,3-propanediol) at
64 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 33. Rate constants for the cleavage of the b-O-4 linkage under different temperatures, (a) for PPE (reprinted from Jarvis et al. [266] with permission of American chemical
society); (b) for DMPD (reprinted from Wang et al. [397] with permission of Elsevier). The Arrhenius type pre-factors for Cb-O homolysis (2 £ 1015 s¡1) and Ca-Cb homolysis
(4 £ 1015 s¡1) were estimated based on the experimental values from similar reactions in anisole [399] and ethylbenzene [400].
TagedPthe B3LYP/6
31G(d,p) level. Based on the calculation of activation
energies for homolytic cleavage and concerted breakage at different
temperatures, it was concluded that the concerted reaction was
dominant at low temperature, whereas homolysis dominated at
high temperature. However, different results were obtained using
other dimer model compounds [396
398]. Chen et al. [396] found
that Cb-O homolysis was the most favored at low pyrolysis tempera-
tures (300 °C), while Cb-O concerted decomposition would become
competitive at medium pyrolysis temperatures (500 °C) based on
DFT calculations combined with Py
GC/MS analysis of a synthetic
lignin dimer, 1-(4-methoxyphenyl)¡2-(2-methoxyphenoxy) etha-
nol. Wang et al. [397] performed a DFT study to investigate the initial
breakage of b-O-4 linkage in the dimer 1-(3,5-dimethoxyphenyl)¡2-
(2-methoxyphenoxy)propane-1,3-diol (DMPD). They reported that
the order of the reaction rates at medium temperature (550 °C) was
Cb-O homolysis > retro-ene reaction> Maccoll reaction > Ca-Cb
homolysis, while at high temperature, Ca-Cb homolysis was compet-
itive with retro-ene reaction, as shown in Fig. 33b.
TagedPFrom above studies, it can be concluded that the substituents sig-
nificantly influence the breakage behavior of the b-O-4 linkage
[401
406]. According to the comparison of BDEs for the homolytic
cleavage of Cb-O and Ca-Cb bonds in PPE and several oxygen-substi-
tuted derivatives, Beste and Buchanan [401] found that the existence
of hydroxy and methoxy substituents at the phenyl ring adjacent to
the ether oxygen substantially reduced the BDEs of the Cb-O bond,
while the effect of oxygen substituents at the phenyl ring on the
other side could be ignored. The BDEs of the Ca-Cb bond were mini-
mally influenced by the oxygen substituents located at either phenyl
ring. The number of oxygen substituents also matters [401,403]. An
additional methoxyl at the phenyl ring adjacent to the ether oxygen
further reduced the Cb-O BDE. The homolytic cleavage of the Caro-
matic-O bond was promoted by the methoxy substituent at the ortho
position in the phenyl ring close to the ether bond [405]. The sub-
stituents on the aliphatic carbons (PhCH(X)CH(Y)OPh) also have a
significant effect on the cleavage of b-O-4 linkage as well. Parthasar-
athi et al. [406] found that the compound showed lower BDEs for
the b-O-4 linkage when there was a carbonyl group at the Ca posi-
tion of the ether linkage and an aliphatic carbon at the Cb position.
Changes in the BDEs for the Cb-O and Ca-Cb bonds alter the a/b
homolysis selectivity of the b-O-4 model compounds, which is
defined as the selectivity between the competitive hydrogen
abstraction reactions at the a and b position of the ether linkage
caused by the chain carrying phenoxyl and benzyl radicals [407].
According to a study performed by Beste et al. [407], the
TagedPintroduction of oxygen substituents at the para position of the phe-
nethyl ring in PPE enhanced the total a/b selectivity, and the
increase resulting from methoxy was larger than that corresponding
to hydroxy. The reaction rates of the b-pathways of both radicals
decreased, and the change in the a-pathway rates followed an oppo-
site trend with the increase of phenoxyl radical. They further investi-
gated the effects of methoxyl substituents at the para-, ortho-, and
di-ortho- position of the phenyl ring adjacent to the ether oxygen
[408]. It was found that the substituents decelerated the rate of
hydrogen abstraction by the phenoxyl radical, while the effect on
benzyl abstraction was less homogeneous. The substituents slightly
increased the benzyl radical abstraction rate of the b hydrogen. The
abstraction rate of the a hydrogen was reduced by p- and o-
methoxyl and was enhanced by di-o-methoxyl. The hydroxyl sub-
stituent at the Ca position of the ether linkage influences the ener-
getic and entropic contributions to the rate constants of hydrogen
abstraction reactions, thus altering the a/b homolysis selectivity
[409]. It lowered the activation energy for a-hydrogen abstraction
while increased that for b-hydrogen abstraction. The prefactor for
the a-pathway decreased due to the occupation of the hydrogen
abstraction site by hydroxyl. As a result, the total a/b selectivity was
largely promoted by the existence of the a-hydroxyl.
TagedPThe a-O-4 ether linkage is another typical lignin linkage. It seems
that homolytic cleavage of a-O-4 ether linkage is energetically
favored since the formed two radicals are stable, due to the reso-
nance stabilization by the p bond adjacent to a single, unpaired elec-
tron [210]. Liu et al. [410] proposed that the pyrolysis of 4-
benzyloxyphenol, an a-O-4 lignin dimer, was initiated by the Ca-O
homolysis, with an activation energy of 164.9 kJ/mol. Based on a
more complicated a-O-4 dimer, 4-(2-hydroxy-1-(2-methoxyphe-
noxy)ethyl)phenol, Huang et al. [411] found that the activation
energy of Ca-O homolysis (177.4 kJ/mol) was lower than that of con-
certed breakage of Ca-O (186.5 kJ/mol). Homolytic cleavage of Ca-O
was the major pyrolysis reaction channel in the initial decomposi-
tion of the a-O-4 dimer. The breakage behaviors of carbon
carbon
linkages have also been studied. According to the theoretical study
of reaction pathways of the b¡1 dimer model compound, 1,2-p-
hydroxyphenyl-1,3-propanediol, Huang et al. [412] proposed that
the concerted cleavage of the Ca-Cb bond was dominant over the
homolysis mechanism at low temperature, while at high tempera-
ture, the homolysis reaction was kinetically favored. A study by Jiang
et al. [413] based on the b¡1-type lignin dimer 1,2-bis(3,5-dime-
thoxyphenyl)propane-1,3-diol using DFT and Py-GC/MS analysis
indicated that the concerted mechanism was mostly responsible for
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPthe initial decomposition of the b¡1 dimer. The decomposition of
fused ring structures, such as phenylcoumaran (b¡5 bond)
[414,415], dibenzodioxocins [416] and pinoresinol [417], is more
complicated. The concerted cleavage of the Ca-O bond (244.2 kJ/
mol) in the b¡5 linkage was much easier than that of the Ca-Cb
bond (405.1 kJ/mol) [414]. Ca-O homolysis was also kinetically
favored due to its lower BDEs [415]. Thus, the b¡5 unit preferred to
evolve through cleavage of the Ca-O bond. However, the detailed
breakage mechanism requires further investigation because the
above two studies were performed on various bases. During the ini-
tial ring opening of the dibenzodioxocin lignin model compound,
the homolytic cleavage of the Ca-O bond was the most likely with
lowest BDE of 191.4 kJ/mol compared with other reactions, such as
Cb-O homolysis (238.8 kJ/mol), Ca-Cb homolysis (300.9 kJ/mol) and
5
50 homolysis (477.6 kJ/mol) [416]. For the pinoresinol linkage,
homolytic cleavage of the Ca-O and Ca-Cb bonds showed consider-
ably lower BDEs than that of other bonds [417]. Based on the calcu-
lated BDEs of 65 lignin dimer model compounds connected by
various ether bonds and carbon-carbon bonds from a study by Par-
thasarathi et al. [406], it was concluded that the ether bond was eas-
ier to fragment than the C

C bond, and the ether bond in the a-O-4
linkage and the Ca-Cb bond in the b¡1 linkage were the weakest
linkages among the ether lignin linkages and C

C bond linkages,
respectively. The substituents at the arene ring and at the aliphatic
carbon atoms also affect the breakage behavior of these linkages.
The methoxyl groups on the adjacent arene ring in the di-ortho posi-
tions considerably weakened the ether linkages, while the BDEs of
C

C bonds were affected by hydrocarbon, methyl, and hydroxyl
group substitution at the aliphatic carbons in the linkage.
TagedPThe formed phenyl compounds after cleavage of the aryl linkages
can evolve through secondary reactions. In view of the non-
methoxylated monoaromatics, such as phenol and catechol, formed
during lignin pyrolysis, it can be deduced that the methoxyl in the
phenyl ring is further converted during pyrolysis. Using anisole as a
model compound for the evolution of methoxyl in lignin, it was
found that the BDE for the homolytic cleavage of O
CH3 (234.5 kJ/
mol) was much lower than that of Caromatic-O (373.6 kJ/mol) [418].
Based on the DFT study of the evolution of methoxyl in guaiacol,
Wang et al. [397] proved that homolytic demethylation leading to
catechol was favored compared with methoxyl dissociation to form
phenol via a homolysis mechanism or concerted mechanism. Similar
results were obtained by Wang et al. [419] where the homolytic
cleavage of the O
CH3 bond was dominant according to the theoret-
ical study of vanillin pyrolysis. However, when coupling a hydrogen
radical to the carbon atom in the phenyl ring at the methoxyl loca-
tion, the energy barrier of guaiacol demethoxylation reaction was
substantially lowered to 43.0 kJ/mol and became more favorable
than homolytic demethylation (199.7 kJ/mol) [420]. The methoxyl
group in guaiacol could also undergo radical-induced rearrangement
reaction to yield 2-hydroxybenzaldehyde [421]. However, the high
energy barrier of this route (335 kJ/mol) made it difficult for this
reaction to occur. For the formation of small molecular gases, includ-
ing CO, CO2, CH4 and HCHO, DFT studies revealed that they were
more likely to occur via a concerted mechanism than a homolysis
mechanism during lignin pyrolysis due to their relatively lower
energy barriers [421,422].
6. Catalytic pyrolysis of biomass
TagedPDue to the complexity of the biomass structure and various
pyrolysis reaction pathways, several hundred types of oxygenated
compounds with distinct properties are generated from biomass
pyrolysis. Those compounds in bio-oil include acids, ketones, alde-
hydes, phenols, and anhydrosugars [13,423,424]. The complexity of
bio-oil makes it challenging for further utilization as intermediate to
produce transportation fuels or biochemicals. Moreover, bio-oil has
65
TagedP igh oxygen, water and acids contents, which makes bio-oil incom-
h
patible with the petroleum infrastructure. Adding a catalyst into the
pyrolysis reaction has been investigated as a method to optimize the
distribution of pyrolysis products. By using an appropriate catalyst, a
specific reaction can be selectively enhanced, leading to the
increased production of desirable products, such as hydrocarbons
and anhydrosugars [70,71,425,426]. Since Rolin et al. [427] investi-
gated the effect of several inorganic salts on biomass pyrolysis in
1983, biomass catalytic pyrolysis has received increasing attention.
In the past decade, significant scientific progress has been achieved,
especially the development of advanced catalysts. Meanwhile, the
insights into the reaction chemistry of catalytic pyrolysis and the dif-
ferent catalytic configurations are expanding our knowledge of the
biomass catalytic pyrolysis. In this section, the chemistry of biomass
catalytic pyrolysis and the effect of catalytic configuration (in situ
and ex situ) will be introduced. The development of various catalysts,
including inorganic salts, metal oxides and zeolites, is also discussed.
6.1. Chemical reaction paths in biomass catalytic pyrolysis
TagedPFig. 34 summarizes the major chemical reaction pathways
involved in the biomass catalytic pyrolysis, including deoxygenation,
cracking, aromatization, ketonization, aldol condensation, hydro-
treating and reforming. These reactions may occur selectively,
depending on the catalyst and reaction conditions.
TagedPCatalytic deoxygenation is an efficient route to reduce the oxygen
content in bio-oil. Dehydration, decarboxylation and decarbonyla-
tion are typical deoxygenation reactions to remove oxygen in the
form of H2O, CO and CO2, respectively. The removal of oxygen in the
form of CO2 is more desirable because it has the highest deoxygen-
ation efficiency and can significantly improve the effective H/Ceff
ratio in bio-oil. On the other hand, the dehydration of sugars derived
from cellulose and hemicellulose can produce anhydrosugars, such
as LG, LGO, 1,4:3,6-dianhydro-a-d-glucopyranose (DGP) and 1-
hydroxy-3,6-dioxabicyclo[3.2.1]octan-2-one (LAC), and furans, such
as furfural and HMF. These products are value-added building blocks
that can be converted into many useful chemicals [428
430].
TagedPCatalytic cracking can convert large molecules and heavy organic
chemicals into small molecular products. Meanwhile, the catalytic
cracking of oxygenates also gives rise to the formation of aromatics
and olefins. A series of reactions are typically involved during the
catalytic cracking process, such as cleavage of C
C bonds, hydrogen
transfer, isomerization, aromatic side-chain scission and deoxygen-
ation [70,426]. During catalytic cracking, polyols can generate olefins
by repeated dehydration and hydrogen transfer, and further Diel-
s
Alder and condensation reactions of olefins and dehydrated inter-
mediates result in the formation of aromatics [431]. The catalytic
cracking of low-molecular-weight compounds, such as acids (acetic
acid, propanoic acid, etc.) and alcohols (methanol, t-butanol, etc.),
forms C1
C4 hydrocarbons with H2O, CO and CO2. Complicated lig-
nin-derived phenolic compounds can undergo cleavage of oxygen-
aromatic carbon bonds or oxygen
alkyl carbon bonds to form aro-
matic hydrocarbons or simple phenolic compounds [432].
TagedPAromatization is another main route to low-molecular-weight
oxygenates and olefins into aromatics. Under HZSM-5 catalysis,
acids, alcohols, aldehydes, esters, ethers and furans can be largely
converted to aromatic hydrocarbons as the major products [433].
This aromatization process is complicated and may be explained by
the hydrocarbon pool mechanism, which was first proposed by Kol-
boe and co-workers to illustrate the reaction of methanol to olefins
[434]. When intermediate oxygenates diffuse into the pore channels
of zeolite, they undergo a series of dehydration, decarboxylation,
decarbonylation, and oligomerization reactions to form a carboca-
tion hydrocarbon pool [434,435]. The hydrocarbon pool can be con-
verted into olefins, monocylic aromatics and polycyclic aromatics
under the catalysis of zeolites and some certain organic active
66 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86

Fig. 34. Schematic of the chemical reactions for biomass catalytic pyrolysis.

TagedPcenters, which are known as hydrocarbon pool intermediates and
can also act as co-catalysts [434,435].
TagedPIn addition, ketonization/aldol condensation is a promising route
for the conversion of the carboxylic and carbonyl components into
longer-chain intermediates that can be further upgraded into gaso-
line/ diesel substituted fuels [426,436]. Ketonization is a reaction
that converts two carboxylic acid molecules into a ketone, CO2 and
H2O. This reaction can simultaneously remove carboxyl groups and
achieve C¡C coupling without consuming external hydrogen,
thereby increasing the heating value and stability of the products.
Metal oxides and zeolites have been proved active for the ketoniza-
tion of carboxylic acids. However, the ketonization reaction mecha-
nism is complex, and ketene, beta-keto-acids, carboxylates, and acyl
carbonium ions are suggested to be the key intermediates [437,438].
Two aldehydes and/or ketones with at least one a-H can undergo
self- or cross-aldol condensation to form a new unsaturated alde-
hyde or ketone and H2O. This reaction can be efficiently catalyzed by
both Brønsted and Lewis acids [438,439]. Generally, the presence of
acids hinders the aldol condensation due to competitive adsorption
on the active sites, and a ketonization step is more favorable.
TagedPReforming and hydrodeoxygenation are regarded as efficient
routes for the off-line upgrading of bio-oil [440,441]. Steam reform-
ing of small oxygenates such as acetic acid and HAA can generate H2.
Hydrodeoxygenation can retain most of the carbon in the products
while removing oxygen in water under a certain hydrogen pressure
atmosphere.
TagedPGenerally, for the in situ configuration, the catalyst is mixed with
biomass feedstock prior to the reaction, and pyrolysis and catalytic
conversion of the pyrolysis vapor occur in one reactor. The in situ
configuration favors cracking of the pyrolytic fragments as soon as
they are released, while minimizing the repolymerization of primary
products from pyrolysis [442]. Biomass pyrolysis and catalytic con-
version occur at the same temperature in the in situ configuration,
which limits the temperature optimization for both reactions. In
addition, some inorganic minerals may accumulate on the catalyst,
leading to catalyst poisoning [69].
TagedPFor the ex situ configuration, biomass pyrolysis and catalytic con-
version are performed in two separate reactors under independent
operating conditions. Therefore, each step can be conducted under
unique optimal conditions, which benefits optimization of bio-oil
production [69]. Additionally, the char formed in the biomass pyrol-
ysis process can be easily separated out as a solid by-product prior
to catalytic conversion of the vapor. In certain instances, catalysts
such as inorganic salts are impregnated into the biomass feedstock

6.2. In situ and ex situ catalytic pyrolysis

TagedPDepending on the contact method of the catalyst with pyrolytic

vapors, biomass catalytic pyrolysis can be divided into two differ-
ent configurations [69,442]. The configuration in which the catalyst
is mixed directly with the feedstock in the pyrolysis reactors is
referred to as in situ catalytic pyrolysis, while the configuration in
which the resulting pyrolytic vapor is transported to a separate cat-
alysts bed downstream is referred to as ex situ catalytic pyrolysis
[69,442]. Fig. 35 illustrates the two configurations of catalytic
Fig. 35. In situ and ex situ catalytic configurations.
pyrolysis.
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPby absorption or ion exchange, for which in situ catalytic pyrolysis is
more suitable than ex situ catalytic pyrolysis.
TagedPBoth in situ and ex situ catalytic pyrolysis can greatly improve the
quality of the pyrolysis vapor. Wang et al. [443] analyzed the in situ
and ex situ catalytic pyrolysis of hemicellulose monosaccharides and
found that in situ catalysis pyrolysis promoted the formation of fur-
ans and acids at low temperature due to enhanced dehydration,
retro-aldol fragmentation and Grob fragmentation. In contrast, ex
situ catalytic pyrolysis decreased the yields of furans and acids,
which may contribute to the enhanced dehydration, decarboxyl-
ation, and decarbonylation reactions when the volatiles pass
through the catalyst bed. Gu € ngo
€ r et al. [444] compared the effect of
the in situ and ex situ catalytic pyrolysis of pine bark using ReUS-Y.
Ex situ catalytic pyrolysis had better performance for maximizing
the bio-oil yield and oxygen removal at higher temperature. Yildiz
et al. [445] found that in situ catalytic pyrolysis was more attractive
because more aromatic hydrocarbons and less coke were produced.
However, higher catalyst loading is required to obtain high quality
bio-oil for in situ catalytic pyrolysis. Nguyen et al. [446] studied the
in situ and ex situ catalytic pyrolysis of woodchips over faujasite type
zeolites. Their results showed that ex situ catalytic pyrolysis exhib-
ited better deoxygenation performance for liquid production. This
might be attributed to the pre-heated catalyst reactor for ex situ
case, in contrast to the presence of a temperature gradient for cata-
lyst and biomass in situ case. Wang et al. [214] compared the in situ
and ex situ catalytic pyrolysis of poplar in a tandem microreactor
system over HZSM-5. They found that the carbon yield of olefins was
greater for ex situ than for in situ (17.4% vs. 5.4%), while in situ pro-
duced more aromatic hydrocarbons than ex situ (26.1% vs. 18.9%).
Additionally, a significantly higher yield of carbonaceous residues
was observed for the in situ case (31.3%) compared to that for the ex
situ (18.6%). Gamliel et al. [447] investigated these two configura-
tions for the catalytic pyrolysis of Miscanthus giganteus with HZSM-
5 in a Py-GC system. Ex situ catalytic pyrolysis yielded more perma-
nent gas and higher selectivity over aromatic, while in situ catalytic
pyrolysis produced a higher yield of bio-oil. Solid yields were similar
for the two configurations. They further compared the experimental
result from the micro-reactor (in situ and ex situ) with that from a
bench-scale spouted-bed reactor (in situ). The composition of bio-oil
obtained from the spouted bed was similar to that from the ex situ
microreactor, while the solid residue from the spouted-bed reactor
was comparable to coke/char formed from in-situ micro-reactor. Li
et al. [448] recently conducted a techno-economic and uncertainty
analysis of in situ and ex situ catalytic pyrolysis for biofuel produc-
tion. The economic estimation showed that the minimum fuel-sell-
ing price for in situ catalytic pyrolysis was lower than that for ex situ
catalytic pyrolysis, while ex situ catalysis had a lower techno-eco-
nomic uncertainty than in situ catalysis. Although some of the results
of the aforementioned studies are controversial, the reactor configu-
ration plays an important role in the development of catalytic pyrol-
ysis. Ex situ and in situ catalytic pyrolysis have their own advantages
and disadvantages. The type of feedstock, desired products, and
operating conditions should be considered when selecting the reac-
tor configuration for a specific study.
6.3. Catalytic effect of inorganic minerals on pyrolysis
TagedPBiomass itself contains inorganic minerals, such as K, Ca, Na, and
Mg. Depending on the type of biomass and harvesting method, the
total content of these species ranges from 0.5% to 15% of the biomass
[449]. These inorganic species affect the product distribution from
fast pyrolysis by altering the reaction pathways of biomass decom-
position. Despite the minimal amounts of these inorganic minerals,
they have a remarkable influence on fast pyrolysis [208].
TagedPAlkali and alkaline earth metals (AAEMs), such as K, Na, Mg and
Ca, are the most abundant inorganic ions in biomass and they show
67
TagedP otable catalytic effect on biomass pyrolysis. The presence of potas-
n
sium salts decreased the temperature corresponding to the maxi-
mum decomposition and the thermal decomposition activation
energy [450]. As for the product distribution, higher yields of gas,
water and char were achieved in biomass pyrolysis catalyzed by
potassium salts [451]. It was also found that potassium salts pro-
moted the depolymerization and fragmentation of biomass compo-
nents, which led to the formation of low-molecular-weight
components, 2(5H)-furanone, furfural and lignin-derived phenols
[452,453]. On the other hand, potassium salts were unfavorable for
the formation of carbonyl compounds and alcohol, but promoted the
formation of CO2, CO and H2O. These mainly resulted from the good
cracking performance of potassium ion, because the interaction of
the metal ions and the oxygenated groups favored certain ring con-
formations and enhanced the reactivity to cracking reactions [454].
In particular, the metal ion in conjunction with the hydroxyl and
aldehyde groups would form a metal ion-water complex and induceD17X X
dehydration reactions in biomass pyrolysis [453]. Similar to the
effect of KCl, the addition of NaCl to biomass accelerated the thermal
decomposition of carbohydrates to form low-molecular-weight
products, which resulted in a lower bio-oil yield [455]. LG formation
was significantly suppressed by NaCl due to the reduced decomposi-
tion of cellulose chains via end-chain initiation and depropagation
because sodium ions favored competing dehydration reactions
[456]. However, Zhao et al. [457] reported a conflicting result, where
the bio-oil yield from rice husk pyrolysis increased from 53.81 wt.%
to 57.61 wt.% with the addition of 3 wt.% NaCl. They also observed
decreased concentrations of organic acids, esters, ketones, guaiacols,
and aldehydes.
TagedPCompared to alkali metal ions (Na+ and K+), alkaline earth metal
ions (Mg2+ and Ca2+) are stronger Lewis acids, which enhance dehy-
dration reactions for sugar compounds. Liu et al. [458,459] investi-
gated the catalytic effects of NaCl, KCl, MgCl2, and CaCl2 on cellulose
pyrolysis. They reported that Mg2+ (MgCl2) and Ca2+ (CaCl2) had a
greater influence on the pyrolysis of carbohydrates than did Na+ and
K+. Patwardhan et al. [208] also reported that the inhibition of LG
formation in cellulose pyrolysis followed the order of K+ > Na+ > Ca2
+
> Mg2+. However, Eom et al. [460] observed a contradictory result
that the impregnation of MgCl2 on cellulose enhanced the yield of
LG. They ascribed this difference to the raw material and the salt
impregnation method. This explanation was confirmed by a recent
research in which Mg2+ decreased the yield of LG from powder cellu-
lose but had no significant impact on that from thin-film cellulose
[461]. Patwardhan et al. [208] pointed out that the presence of
MgCl2 and CaCl2 favored the formation of furan ring derivatives,
such as 2-furaldehyde, HMF and LGO. Mg2+ and Ca2+ had a less sig-
nificant catalytic effect on lignin pyrolysis, except suppressing the
formation of 3-methoxycatechol and slightly enhancing the forma-
tion of 4-vinylguaiacol. The presence of K+ was reported to increase
the yields of C6 lignin derivatives including phenol, guaiacol and
syringol [460].
TagedPIn addition to alkali and alkaline earth metals, transition metals
in biomass may have some catalytic effect. ZnCl2 is a typical Lewis
acid and is widely adopted in biomass catalytic pyrolysis. It can cata-
lyze the breakdown of C

C and C

O bonds, and is active in the deg-
radation pathways including dehydration, depolymerization and
ring-opening [462]. The addition of ZnCl2 reduced the maximum
degradation rate for the both hemicellulose and cellulose fractions,
and promoted the formation of char and gas at the expense of liquid
production [462,463]. Additionally, the furfural yield significantly
increased under the catalysis of ZnCl2. ZnCl2 catalyzed both the pri-
mary and secondary reactions during pyrolysis to yield more furfural
through dehydration of the pentosyl and glucosyl residues, and
anhydrosugars [462,464,465]. It was suggested that ZnCl2 may inter-
act chemically with the substrate and/or may be partly hydrolyzed
with the product water to produce HCl that further catalyze the
68 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPreaction process [464]. Moreover, the coordination of the glycosidic
oxygen with zinc in the hydrated form may easily cleave the glyco-
sidic linkages to form monosaccharide, which further convert to
anhydrosugar and furanic compound by acid-catalyzed dehydration
reaction [466]. ZnCl2 also can act as a dehydrating and cross-linking
agent, promoting the carbonization [464,467]. A furfural yield of
11.5 wt.% was obtained by performing the pyrolysis of corn stover
impregnated with 18.5 wt.% ZnCl2 [466], which suggested that ZnCl2
was an efficient catalyst for furfural production from biomass
[468,469]. ZnCl2 could also be used for the production of anhydrosu-
gars, such as LGO, DGP and LAC, by controlling the reaction condi-
tions [465]. Similarly, Fe3+ catalyzed the conversion of cellulose into
anhydrosuagrs. When Fe3+ was introduced into cellulose by absorp-
tion and ion exchange, the yields of LA and LGO could reach 44.8%
and 40.7%, respectively [470]. Fe3+ was also found to be more effi-
cient in the catalytic thermal cracking of alkali lignin, resulting in a
decrease in char yield and lower phenolic compound yield than Ca2+
and K+ [471]. Nickel nitrate had a similar impact to iron nitrate on
crystalline cellulose and lignin pyrolysis. For cellulose pyrolysis, iron
and nickel ions promoted dehydration and decarboxylation reac-
tions while inhibited depolymerization, leading to high yield of char.
For lignin pyrolysis, rearrangement of the aromatic rings was
favored, leading to a decrease in the aromatic compounds in the tar
fraction [472,473]. Particularly, nickel ion was more efficient in the
rearrangement of the aromatic rings, producing more hydrogen than
iron ion [472,473]. The copper ion also showed a notable impact on
biomass pyrolysis, which decreased the maximum mass loss tem-
perature and increased the activation energy for wood pyrolysis.
Meanwhile, acids, aldehydes, and phenols were reduced, while
ketones were increased due to the inhibitory effect on the pyrolysis
of cellulose and lignin, and the promoting effect on hemicellulose
pyrolysis [474]. Eibner et al. [475] recently investigated the catalytic
effects of Ce, Mn, Fe, Co, Ni, Cu and Zn on eucalyptus pyrolysis. These
metallic salts had catalytic effects on char, tar and gas production.
Mn, Ce and Zn led to higher char yield, whereas Ni resulted in lower
tar yield and higher gas yield. The anhydrosugar yield was also
affected. Specifically, the LAC yield decreased in the following order:
Zn > Co > Ni, Mn > Ce > Fe >> Cu.
TagedPIn addition to metal ions, anions also influenced the behavior of
biomass pyrolysis. For example, biomass impregnated with sulfate
salts had lower degradation rates and peak temperatures than sam-
ples impregnated with nitrate salts [476]. Patwardhan et al. [208]
found that the reduction of LG production followed the order of
Cl¡>NO3¡OH>CO32¡PO43¡ for cellulose pyrolysis catalyzed by
different calcium salts.
6.4. Catalytic pyrolysis by metal oxides
TagedPMetal oxides are widely used in industry as supports, promoters,
and active components in various heterogeneous catalytic reactions.
Most metal oxides and their mixtures have acid, base, or combined
properties due to lattice imperfections, such as electron holes, point
defects, dislocations, and planar defects. The surface acid-base prop-
erties of metal oxides potentially favor the catalytic pyrolysis of bio-
mass to form desirable products. The activity of various metal oxides
in biomass catalytic pyrolysis has been investigated, including acidic
metal oxides, base metal oxides and transition metal oxides. The dif-
ferent acid and base sites of the metal oxides alter the distribution of
bio-oil components, promoting or inhibiting the formation of certain
products.
TagedPAl2O3 and SiO2-Al2O3 are the most common acidic metal oxides
used in biomass catalytic pyrolysis. In general, acidic metal oxides
can promote the dehydration, decarbonylation and cracking of
organic molecules, reducing the oxygen content of bio-oil and con-
verting large organic molecules into smaller molecules. The presence
of Al2O3 reduced the yield of bio-oil from approximately 58 wt.% to
TagedP pproximately 40 wt.%, and promoted the formation of hydrocar-
a
bons and CO in the pyrolysis of beech wood. This catalytic effect was
enhanced by using higher surface area Al2O3 [477]. SiO2, with weak
acidity and medium porosity, showed good catalytic activity for
removing oxygenated compounds, such as acids, ketones, and alde-
hydes, while suppressing the formation of coke and polycyclic aro-
matics [478]. SiO2-Al2O3 exhibited performance similar to Al2O3, but
produced more heavy compounds [477]. Sulfonation of metal oxides
can improve the acidity of the catalyst and selectively catalyze the
formation of specific compounds. For instance, SO42¡/SnO2 was
active in the production of 5-methyl furfural, while SO42¡/TiO2 pro-
moted the formation of furfural from cellulose. The SO42¡/ZrO2 cata-
lyst favored the furan formation at the expense of LG, in contrast to
pure ZrO2, in cellulose pyrolysis [479]. In addition, SO42¡/ZrO2 effi-
ciently catalyzed the formation of LGO from cellulose pyrolysis, with
a yield of 7.79 wt.% of the feedstock and a content of 11.78% of the
liquids [480]. SO42¡/ZrO2 also had a low resistance to coke and
enhanced the formation of carbon oxides in the catalytic pyrolysis of
poplar wood [481]. Magnetic SO42¡/TiO2
Fe3O4 was effective to
selectively produce LGO, reaching high yields of 15.43 wt.% and
7.06 wt.% from cellulose and poplar wood, respectively, due to its
stronger acidity than SO42¡/TiO2 and pure TiO2 [482].
TagedPMagnesium oxide (MgO) and Calcium oxide (CaO), the typical
base metal oxides catalyst used for biomass catalytic pyrolysis, are
effective for deoxygenation via ketonization and aldol condensation
of acid and ketone compounds. Basic catalysts could also promote
fragmentation reactions, resulting in the formation of low-molecu-
lar-weight products [441]. The addition of MgO decreased the yield
of bio-oil but improved the quality of bio-oil in terms of calorific
value, hydrocarbon distribution and removal of oxygenated groups
[483]. Stefanidis et al. [436] investigated the catalytic effects of sev-
eral MgOs with different physicochemical properties on the pyroly-
sis of beech wood sawdust. All tested MgOs greatly decreased the
oxygen content and acidity of the bio-oil through the formation of
CO2 via ketonization and aldol condensation. The results showed
that MgO with larger surface area and porosity exhibited better cata-
lytic activity. Previous studies demonstrated the significant deox-
ygenation activity of CaO. For example, a liquid with a 21% reduction
in the oxygen content was produced in a fluidized bed reactor
through the catalytic pyrolysis of white pine [484]. CaO also favored
the formation of alkylated cyclopentenone, alkylated phenols and
polyaromatic hydrocarbons (PAH) while greatly reduced the forma-
tion of catechols, acids and anhydrosugars [485,486]. The mixture of
CaO and MgO showed good activity for reducing the oxygen content
and acidity of bio-oil at the expense of a lower yield of organic liquid
and higher yield of char [487].
TagedPIn addition to acidic and basic metal oxides, transition metal
oxides with unique acid-base properties have been widely investi-
gated for biomass catalytic pyrolysis, with various effects on the
product distribution. Phenols containing alkoxy groups were the
dominant products of the catalytic pyrolysis of lignin over transition
metal oxides [488]. Fe2O3 and MnO showed similar product distribu-
tions to non-catalytic pyrolysis, suggesting insignificant catalytic
effects. NiO yielded the largest amount of 2-methoxy phenol, and
CuO and MoO3 produced more vanillin, with selectivity greater than
30%. CoO was efficient for the production of 1,3-benzodioxole, ben-
zene and 3,4-dimethoxytoluene, as well as for the reduction of phe-
nol and phenol alkoxy [488]. Fe2O3 was also found to be active to
decompose tar and promote the formation of H2 and CO2, while
decreased the yield of CO due to water gas shift reaction [489]. Nair
et al. [490] analyzed the production of guaiacol and its derivatives
from the catalytic pyrolysis of alkali lignin over TiO2, CeO2 and ZrO2.
The yield of guaiacols followed the order of: sol gel TiO2
(36
37 wt.%) > ZrO2  CeO2 (»29 wt.%) > Aeroxide TiO2 (26 wt.%) >
non-catalytic (18 wt.%). Despite the high selectivity to guaiacols,
TiO2 produced a negligible amount of aromatic hydrocarbons due to
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPthe absence of strong Brønsted acid sites. Torri et al. [491] observed
that the catalytic pyrolysis of pine sawdust over MoO3, TiO2 and
WO3 led to a slight increase in both the bio-oil and non-volatile frac-
tion yields. WO3 substantially increased the volatile yield from 1.6%
to 3.6%, while ZnO did not affect the bio-oil yield but reduced the
HM yield from 22% to 15%. CuO slightly increased the bio-oil yield
from 47% to 49%, mainly through increasing the yield of the semi-
volatile fraction from 23% to 30% and decreasing the non-volatile
fraction yield from 22% to 16%.
TagedPCompared to microparticle metal oxides, nanoparticle metal
oxides exhibit superior activity during biomass catalytic pyrolysis
due to their much larger specific surface areas. A study on TGA sug-
gested that nano-NiO catalyst significantly affected the pyrolysis
process by decreasing the decomposition temperature, char yield,
and activation energy of the pyrolysis kinetics compared with
micro-NiO [492]. Fabbri et al. [493] investigated the influence of
nanopowder metal oxides (SiO2, Al2O3, MgO, TiSiO4 and Al2O3-TiO2)
on the production of chiral anhydrosugars from the catalytic pyroly-
sis of cellulose. All these nanopowders, with the exception of silicon
oxide, promoted the formation of anhydrosugars. Aluminium tita-
nate increased the total yield of anhydrosugars from 20% to 35%,
while silicon oxide reduced anhydrosugar production from 20% to
4%. Nanopowder aluminum titanate also favored the formation of
the chiral cyclic chemical hydroxylactone LAC [429]. In the catalytic
pyrolysis of poplar wood over nanocatalyst (MgO, CaO, TiO2, Fe2O3,
NiO and ZnO), CaO significantly decreased the levels of phenols and
anhydrosugars and eliminated the acids. ZnO only slightly altered
the pyrolysis products. The other four catalysts decreased the linear
aldehydes dramatically and increased the ketones and cyclopenta-
nones [486]. Recently, SnO2 nanoparticles were found to be active in
reducing the carbonyl content, improving tar stability, and promot-
ing char cracking reactions, which increased the yield of hydrogen
and low-molecular-weight hydrocarbons (C1-C4) [494].
TagedPTo improve the catalytic performance, metal oxides can be modi-
fied by impregnation with an active component or by preparing
binary metal oxides. In general, the synergistic effect between active
metal atoms can improve the activity for selectively producing desir-
able chemicals. The Fe(III)/CaO catalyst exhibited the capability to
transform heavy phenols to light phenols without methoxyl groups
and unsaturated CHC bonds on the side chain and greatly increased
the yields of furans and light and aromatic hydrocarbons at the
expense of undesirable acids, aldehydes and ketones [495,496]. Fe/
g -Al2O3 displayed good performance for H2 production from bio-
mass, composing 30
35% of the gaseous products stream, because
Fe2+ and Fe0, the activity center of Fe/g -Al2O3, catalyzed steam
reforming and the water-gas shift reaction [497]. Binary metal
oxides (MgAl, Mg2Al, Zn2Al) reduced the yield of anhydrosugars
more than mono-metal oxides, and the physical mixtures of metal
oxides behaved in a manner similar to the individual constituents.
Different ratios of metal atoms or species resulted in various product
distributions. MgAl produced the largest amount of furanic com-
pounds, while Zn2Al produced fewer low-molecular-weight prod-
ucts and more phenols and anhydrosugars than Mg2Al and MgAl
[498]. These results suggest that altering the ratio and identity of the
constituent metals is a feasible strategy to tune the reactivity of the
catalyst [498,499].
6.5. Catalytic pyrolysis by zeolites
T eolites, crystalline materials composed of SiO4 and [AlO4]¡ tet-
agedPZ
rahedra, are the most investigated solid acid catalysts for biomass
catalytic pyrolysis. The negative charge of [AlO4]¡ tetrahedra can be
compensated by a H+ cation, giving rise to Brønsted acid sites
[6,500]. Zeolites usually have multi-dimensional microporous struc-
tures, which permit the diffusion of small molecular reactants into
the internal acid sites in the zeolite structure. This microporous
69
sTagedP ystem shows another key feature of zeolites, known as shape selec-
tivity. Porous zeolites are classified into three main categories:
microporous (pore size < 2 nm), mesoporous (2
50 nm), and macro-
porous (> 50 nm) [71]. The microporous materials have been exten-
sively studied in the catalysis of fast pyrolysis of lignocellulosic
biomass in past decades due to their good deoxygenation perfor-
mance and shape selectivity for value-added hydrocarbons. In par-
ticular, ZSM-5 zeolite, especially the protonated form, HZSM-5, has
been demonstrated to be the most effective catalyst for aromatic
hydrocarbon production [501]. Mesoporous and macroporous
zeolites may not favor reactions for specific products due to the
high exposure of the active site to the substrate [71]. This section
focuses on biomass catalytic pyrolysis using HZSM-5. Reviews
regarding other types of zeolite are available in the references
[68,70,71,426,441,502,503].
TagedPDuring the biomass catalytic pyrolysis using HZSM-5, the pri-
mary pyrolysis vapor undergoes a series of reactions on both the sur-
face and pores of the catalysts, including cracking, deoxygenation,
decarboxylation, cyclization, aromatization, isomerization, alkyl-
ation, disproportionation, oligomerization, and polymerization
[504]. Although the detailed reaction mechanism is not clear, poten-
tial reaction pathways are illustrated in Fig. 36. Biomass pyrolysis
produced a wide range of oxygenates with distinct activities over
the HZMS-5 catalyst. It has been found that alcohols dehydrate rap-
idly to the corresponding olefins at low temperature (around 200 °C)
and are further converted into higher olefins and aromatics at higher
temperature (350 °C) [505]. Ketones and acids are less reactive than
alcohols. Dehydration of acetone forms i-butene, which evolves into
C5+ olefins and even C5+ paraffins and aromatics at temperatures
greater than 350 °C. Over HZSM-5, acetic acid gradually transforms
into paraffins and aromatics, with acetone as an intermediate [506].
Acetaldehyde and phenols show extremely low reactivity over
HZSM-5, with the formation of a large amount of coke in the catalyst
bed [505,506]. In addition, the deoxygenation of oxygenates with
various functional groups follows different deoxygenation pathways
over HZSM-5. Alcohols and phenols mainly eliminate oxygen as
H2O, whereas aldehydes, formates and carbohydrates primarily lose
oxygen in the form of CO and H2O, and carboxylic acids as CO2 and
H2O [6].
TagedPThe acidity and porosity of zeolites significantly affect the reac-
tion chemistry and product distribution in biomass catalytic pyroly-
sis [507,508]. An increase in overall acidity favors the formation of
unsubstituted aromatics (benzene, naphthalene, anthracene, etc.)
and polycyclic aromatic compounds (2-ring and 3-ring), while sup-
presses the formation of alkylated (substituted) aromatics (xylene,
dimethyl-naphthalene, and methyl-anthracene etc.) [509]. There-
fore, tuning the acidity of ZSM-5 could create a slate of upgraded
biomass pyrolysis products to meet the demands of a specific mar-
ket. The porosity of zeolites can influence both the reaction inter-
mediates and products by the constraint of the pore size. As shown
in Fig. 37, biomass catalytic pyrolysis using small-pore zeolites pro-
duces primarily CO, CO2 and coke. Large-pore zeolites produce high
coke yields and low aromatic and oxygenate yields. Only the zeolites

with medium pore sizes in the range of 5.2
5.9 A, especially ZSM-5,
produce moderate yields of desirable aromatic and olefinic hydro-
carbons [510,511].
TagedPDoping certain metal cations or oxides into zeolite has been
explored as a method to increase the yield of desired compounds
and to suppress coke formation by tuning the density and activity of
the active sites. Recently, various metal-modified ZSM-5 catalysts
have been tested for the catalytic pyrolysis of biomass. Veses et al.
[512] reported that modification of ZSM-5 with Mg, Ni, Cu, Ga and
Sn significantly improved the properties of the liquid, resulting in
lower viscosity and oxygen content. They also observed a decrease
in the formation of acidic compounds and furans, and an increased
hydrocarbon yields. Among the tested catalysts, Ni/ZSM-5 and Sn/
70 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86

Fig. 36. Reaction pathways for the catalytic pyrolysis of lignocellulosic biomass with HZSM-5 (reprinted from Wang et al. [504] with permission of Royal society of chemistry).

TagedPZSM-5 were the most promising alternative catalysts due to their
ability to increase hydrocarbon production while maintaining low
coke formation rates. Li et al. [513] investigated the effects of Fe/,
Zr/, and Co/HZSM-5 zeolites on the catalytic pyrolysis of sawdust.
Compared to HZSM-5, all three modified catalysts had a significant
effect on gas production by catalytic cracking and increased the
yield of coke. Fe/HZSM-5 and Zr/HZSM-5 improved the overall aro-
matic hydrocarbon contents in the bio-oil. Mullen et al. [514]
observed that Fe/ZSM-5 changed the chemical pathway to form
TagedP enzene and naphthalenes instead of p-xylene and other alkyl ben-
b
zenes. They found that the addition of Fe inhibited the formation of
phenol, which led to lower coke production. Ni/ and Co/ZSM-5 cata-
lysts showed a remarkable increase in aromatic hydrocarbons and
phenolic compounds [515,516]. The addition of Co significantly
increased the CO2 yield, which indicated an enhanced decarboxyl-
ation reaction [516]. Additionally, the Zn/ZSM-5 catalyst was active
in the catalytic cracking of biomass pyrolysis vapor to aromatic
hydrocarbons and had a lower yield of coke than ZSM-5 [517].

Fig. 37. Schematic of the zeolite pore diameter (dN) compared to the kinetic diameter of the feedstock, and oxygenate and hydrocarbon catalytic pyrolysis products (reprinted
from Jae et al. [511] with permission of Elsevier).
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPThe narrow micropores of ZSM-5 zeolites (pore sizes between 5.2

and 5.9 A) enable the selective production of aromatics. However,
the narrow pores do not allow the large-molecule oxygenated chem-
icals to enter the active sites inside the catalyst to be converted into
desirable products, which may lead to coke formation on the catalyst
surface via polymerization. Moreover, the micropore system results
in diffusion limitations for the products, which may further lead to
coke formation and lower yield of desirable products. Although mac-
roporous and mesoporous materials are alternatives to the HZSM-5
catalyst for producing large-molecule chemicals, the size selectivity
may be compromised. Recently, hierarchical (mesoporous) zeolites
coupling a secondary level of porosity to the intrinsic zeolitic micro-
pores showed promising potential in the catalytic pyrolysis process.
As shown in Fig. 38, the hierarchically structured porosity facilitates
diffusion inside the zeolite crystal and enables the access of large
molecules to the active sites [518]. The introduction of auxiliary
mesoporosity into hierarchical ZSM-5 zeolites showed promising
selectivity benefits during the deoxygenation of pyrolysis vapor. Par-
ticularly, the increased formation of aromatics and the decrease in
oxygenates over the hierarchical ZSM-5 zeolites were shown to cor-
relate with the increased number of accessible Brønsted acid sites at
the mesopore surface [519]. Additionally, the increased formation of
aromatics was due to the alternation of the reaction pathway from
primary dehydration to preferential decarbonylation over the bulk
material due to the hierarchical structure [519]. Due to the promis-
ing potential of hierarchical zeolites, further modification by loading
metal starts to attract more attentions. Kim et al. [520] developed
hierarchical Zn/ZSM-5 catalyst for the aromatization of 2-methyl-2-
butene and found coking was greatly suppressed. Neumann et al.
[50] also observed the decrease of coke formation over cerium-
incorporated hierarchical HZSM-5 catalysts in the pyrolysis of glu-
cose. However, the product selectivity shifted from aromatics to
oxygenated chemicals due to the reduced acidity caused by cerium
incorporation. More recently, Veses et al. [51] found that Sn/, Cu/,
Ni/, and Mg/hierarchical structured ZSM-5 zeolites can promote
deoxygenation reactions, and incorporation of Mg cations created
Lewis acid sites, resulting in the marked promotion of ketonization
reactions of acids with aldehydes to produce ketones.
TagedPCatalyst deactivation is one challenging issue for biomass cata-
lytic pyrolysis using zeolite. The complex deactivation process is
affected by many factors, including the composition of the feedstock,
reaction conditions, and the properties of zeolites. In particular, the
strong external acid sites of HZSM-5 are responsible for coke forma-
tion by polymerization of large-molecule oxygenates on the catalyst
Fig. 38. Schematic representation of the access and transport/diffusion limitations in
conventional and hierarchical zeolites. The orange spheres represent molecules that
suffer from single-file diffusion. The secondary porosityenhances the number of pore
mouths to diffuse in and out of, as well as the diffusion properties within the pores
(indicated by the green spheres). The red dots represent bulky molecules which can
only react on pore mouths. (reprinted from Ennaert et al. [518]). (For interpretation
of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
71
sTagedP urface. Surface passivation by lowering the strong external acid
sites while retaining the internal acid sites has been proven to be a
useful strategy for decreasing the coke yield. Chemical liquid deposi-
tion (CLD) is a common external surface modification method that
can change the pore-opening size and reduce the amount of acid
sites on the surface of a catalyst [521]. Zhang et al. [522] performed
catalytic conversion of furan over ZSM-5 modified with 3-triethoxy-
silylpropylamine via CLD. The coke yield decreased from 44.1% for
the original ZSM-5 to 26.7% with the modified ZSM-5. The modified
ZSM-5 also produced higher yields of aromatics (24.5%) and olefins
(16.5%) than the original ZSM-5 catalyst (18.8% aromatics and 9.8%
olefins). Pre-coking on the surface of zeolites was proposed as
another effective way to suppress the coke yield. Zhang et al. [523]
found that spent HZSM-5 zeolites could minimize the coke yield and
favor the formation of target products with higher hydrocarbon con-
tents and lower oxygen contents than fresh zeolites. Wang et al.
[524] modified HZSM-5 zeolites by pre-coking via methanol-to-ole-
fins reactions, which decreased the strong external acid sites and
specific surface area of the zeolites, with the pre-coked percentage
increasing from 0% to 5.4%. Correspondingly, the coke yields
decreased gradually with increasing pre-coked percentage, whereas
the hydrocarbon yields first increased and then decreased, with a
maximum value of 53.47%. Zhang et al. [525] recently investigated
MgO-modified HZSM-5 in the conversion of bio-oil derived furan.
MgO deposition reduced the total acid sites (both weak acid sites
and strong acid sites) and external acid sites of HZSM-5, and the car-
bon yields of coke decreased first and then increased gradually as
the MgO deposition amount increased, while that of aromatics,
C2
C5 olefins, total chemicals, CO2 and CO first increased and then
decreased slightly.
TagedPDuring the catalytic pyrolysis process, most of the inorganic min-
erals present in the feedstock are retained in the bio-char. However,
a small fraction may vaporize with the pyrolysis vapor and deposit
on the catalyst, deteriorating the catalytic performance or even
resulting in catalyst deactivation. The issue has recently drawn
attention. Wang et al. [526] investigated the effect of alkali and alka-
line earth metals on biomass ex situ catalytic pyrolysis over zeolite
catalyst. Even trace amounts of AAEMs dramatically reduced the
yields of hydrocarbons in the order: K+ > Na+ > Ca2+ > Mg2+. A simi-
lar result was observed by Mahadevan et al. [527], who performed in
situ catalytic pyrolysis of pine wood over HZSM-5 and found that
AAEMs influenced the product distribution by decreasing the yields
of desired aromatic hydrocarbons and olefins and increasing the
yields of thermally derived char and non-condensable gases. Yildiz
et al. [528] further showed that even an ash concentration of 3 wt.%
relative to the feedstock or 0.002 wt.% relative to the bed material
(HZSM-5 catalyst) was sufficient to alter the distribution and compo-
sition of the pyrolysis products. The addition of ash reduced the
yields of both the organics and coke and increased the yields of
water and non-condensable gases. It is a good idea to leach the bio-
mass feedstock or to remove the char from the catalyst before the
regeneration step to overcome the drawbacks of biomass ash in cat-
alytic fast pyrolysis. Despite these results, further studies on the
effects of inorganic salts in biomass catalytic pyrolysis are important
to reveal the interactions among the pyrolysis vapor, inorganic salts
and catalyst and the their effect on the lifetime of the catalyst.
7. The effect of pretreatment on biomass pyrolysis
TagedPThe low bulk density, high oxygen content, and high alkali metal
content of raw lignocellulosic biomass are critical challenges in bio-
mass pyrolysis. Different types of biomass, even the same type of
biomass collected from different parts of a plant, present diverse
morphological structures and physicochemical characteristics.
The irregularity and differences in biomass feedstock can
adversely affect the biomass conversion efficiency [529]. Biomass
72 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPpretreatment can improve its quality by removing or modifying the
undesired functional groups and structures of the biomass, benefit-
ting biomass conversion and optimizing pyrolysis product forma-
tion. There are many biomass pretreatment technologies currently
under development, which can be classified into four categories
[530,531]: physical pretreatment (including grinding and densifica-
tion), chemical pretreatment (including acid and alkali pretreat-
ment, hydrothermal pretreatment, steam explosion and ammonia
fiber expansion), thermal pretreatment (including drying and torre-
faction) and biological pretreatment. All the pretreatment methods
greatly influence the behavior of biomass pyrolysis.
7.1. Physical pretreatment
TagedP7.1.1. Grinding
TagedPThe object of grinding is to reduce the particle size of the biomass
feedstock and to decrease the degree of polymerization and crystal-
linity of lignocellulose [530]. A reduction in particle size greatly
affects the biomass pyrolysis process. Shen et al. [532] found that
the bio-oil yields decreased as the average biomass particle size
increased from 0.3 to approximately 1.5 mm. They proposed that the
actual heating rates for biomass decreased with increasing particle
size, which resulted in the decreased yield of lignin-derived oligom-
ers, which was the main contribution to the reduced bio-oil yield. In
addition, partial destruction of the biomass cellular structure during
grinding was favorable to bio-oil production. They reported that the
yields of the light bio-oil fractions increased and those of the heavy
bio-oil fractions decreased with increasing particle size. Asadullah
et al. [533] noted the particle size influenced the char structure to a
greater extent for high heating rate pyrolysis (> 1000 °C/s) than for
slow heating rate pyrolysis (0.17 °C/s). However, biomass is difficult
to grind since it is fibrous. The grinding process contributes a high
fraction of the total operating cost in the biomass conversion process
[534]. This cost could be reduced by adopting torrefaction before
grinding [535].
TagedP7.1.2. Densification
TagedPBiomass densification (also called pelletization) is a process
applying a mechanical force to compact biomass residue or waste
(sawdust, shavings, chips or slabs) into uniformly sized solid par-
ticles such as pellets, briquettes and logs [536]. The biomass proper-
ties, including the moisture content, unit bulk density, durability
index, hardness, and energy content are changed by densification
[537,538]. Generally, biomass after densification has a lower mois-
ture content, higher density and hardness, and higher energy con-
tent, thus facilitating storage and handling, reducing the
transportation cost, and promoting the economical processing of
biomass conversion [536,537,539
541]. The altered biomass prop-
erties after densification influence the following pyrolysis behavior
and product distribution [542]. The pellet size and bulk density of
biomass affect the heat and mass transfer efficiency during pyrolysis
[543,544]. Rezaei et al. [545] found that a high density of wood pel-
lets resulted in a low rate of volatiles release from pellets and low
rate of heat diffusion inside the pellets. Pauilauskas et al. [546] found
an obvious difference in the radial direction of wood pellet pyrolysis,
and the temperature of center part had a 5
10 min delay during the
increasing temperature period. Zeng et al. [547] investigated the
solar pyrolysis of beech wood pellets and found that pelletization
increased the residence time of tar and enhanced the secondary
cracking into gaseous products.
7.2. Chemical pretreatment
TagedP7.2.1. Acid & alkali pretreatment
TagedPBiomass contains a small amount of minerals, typically in the
form of carbonates, sulfates, phosphates, and chlorides. These
TagedP inerals significantly influence the pyrolysis behavior, and might
m
have an unpredictable influence on the pyrolysis products. In addi-
tion, the potassium and sodium retained in the bio-char after bio-
mass pyrolysis reduces the melting temperature of the ash and
causes problems in the char combustor [548]. The soluble inorganic
species in bio-oil might increase its corrosivity and pollution poten-
tial and lead to unfavorable viscosity effects, aging rate, and filter
plugging [72]. Acid pretreatment, usually using dilute hydrochloric
acid or sulfuric acid, is a common method for removing minerals
from biomass. After acid pretreatment, biomass had a lower pore
volume and surface area and higher average pore diameter and
energy density [549,550]. The removal of minerals also enhanced
bio-oil production. Brown et al. [551] reported that the bio-oil yield
increased from 19% to 27% after acid pretreatment.
TagedPSimultaneously, acid treatment dissolved most of the hemicellu-
lose, greatly reducing the contents of hydroxy acids, aldehydes and
ketones in the bio-oil [552]. Gray et al. [553] conducted fast pyrolysis
of wood after acid treatment and found that the yields of low-molec-
ular-weight compounds, especially acetic acid and formic acid, were
significantly reduced. Brown et al. [551] pretreated corn stalks with
nitric acid and sulfuric acid, and the yields of formic acid and acetic
acid from pyrolysis were reduced by more than 80%, while the yield
of HAA was decreased by 50%. However, the simple subsequent
washing cannot completely remove the acid from the pore structure
of the biomass after acid pretreatment. Some of the acid remains in
the biomass and participates in the biomass pyrolysis [554]. These
acid ions also play a catalytic role in pyrolysis. Under the catalytic
effect of the acid ions, cellulose is primarily converted to anhydrosu-
gars, which is one cause of the reduction in the carboxylic acid and
ketone products [555].
TagedPAlkali pretreatment uses alkaline solutions, such as NaOH, Ca
(OH)2 and ammonia, to partially remove lignin and hemicellulose
[556]. It is performed at low temperature over a relatively long time
and with a high concentration of the base [557]. However, some
alkali is converted to irrecoverable salts or incorporated as salts into
the biomass during alkali pretreatment [558]. As a result, the ash
content can increase significantly. Wang et al. [56] found that the
ash content increased from 0.39% for untreated pinewood to 2.49%
for 0.5% NaOH-pretreated feedstock, which resulted in a lower bio-
oil yield and higher char yield. The residual alkali catalyzed dehydra-
tion reactions and resulted in an almost twofold increase in water
content in the bio-oil. The removal of some acidic groups, such as
the acetyl and uronic acid groups on hemicelluloses, during alkali
pretreatment led to a higher pH value for bio-oil. The concentrations
of furfural and HMF from hemicellulose and the phenolic com-
pounds from lignin decreased due to the removal of some hemicellu-
lose and lignin.
TagedP7.2.2. Hydrothermal pretreatment
TagedPHydrothermal pretreatment is usually performed at tempera-
tures of 180
260 °C with gauge pressure up to 4.69 MPa [536]. It is
also called wet torrefaction or hydrothermal carbonization since it is
usually used to obtain biomass feedstock with increased stability,
and carbon and energy contents [72]. After hydrothermal pretreat-
ment, the biomass can retain 80
95% of the original energy content
and 55
90% of the original mass [559]. The aqueous chemicals
formed by hydrothermal pretreatment mainly included acetic acid,
pentoses and hexoses from hemicellulose, furfural and HMF from
the dehydration of pentoses (xylose) and hexoses (glucose), and few
phenolic components [560]. Liu et al. [561] found that the main dif-
ference between the FTIR spectra of raw biomass and hydrother-
mally pretreated biomass was the peak ascribed to b-glycosidic
bond, which decreased significantly after pretreatment. Considering
the relatively high decomposition temperature of cellulose, it could
be concluded that only a portion of the cellulose was degraded,
while nearly all the hemicellulose decomposed during hydrothermal
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPpretreatment. The pyrolysis product distribution changed corre-
spondingly. Stephanidis et al. [560] found that the pretreated bio-
mass showed similar C/H and C/O ratios and less ash than those of
the untreated biomass. Hydrothermal pretreatment led to the pro-
duction of a substantial amount of sugars, mainly LG, with a concom-
itant reduction in carboxylic acids, ketones and phenols in the bio-
oil. Chang et al. [562] observed a significant increase in LG content in
bio-oils at the cost of decreased ketone and acids content after
hydrothermal pretreatment.
TagedP7.2.3. Steam explosion
TagedPSteam explosion pretreatment is an instantaneous pressure relief
process under high-temperature (180»240 °C) and high-pressure
steam conditions. The quality of biomass is improved by the pre-
treatment. Biswas et al. [563] found that the ash and alkali metal
contents in biomass were reduced after steam explosion pretreat-
ment, which was mainly ascribed to the release of mineral matters
into soluble liquid after the disruption of biomass structure. Further-
more, steam explosion pretreatment also enhanced the carbon con-
tent and decreased the oxygen content, thus increasing calorific
value of biomass feedstock. Moreover, the pellet density, impact
resistance, and abrasive resistance of the pellets were also improved
by steam explosion. Ding et al. [564] found that after steam explo-
sion pretreatment, samples showed significantly reduced hygro-
scopicity and improved dimensional stability. The equilibrium
moisture content decreased by 46% for pine and 61% for eucalypt
after steam explosion [565].
TagedPSteam explosion also changed the structure and pyrolysis behav-
ior of the biomass. During steam explosion, lignin depolymerized
into low-molecular-weight products and condensed with other deg-
radation products. It also partially degraded hemicellulose and pro-
moted its thermal decomposition [72]. Biswas et al. [54] found that
steam explosion caused depolymerization of hemicellulose and
shifted the hemicellulose decomposition region to the low-tempera-
ture range. The reactivity of lignin increased after steam explosion,
while the severe conditions reduced the lignin reactivity due to con-
densation and repolymerization. Xu et al. [566] observed that steam
explosion pretreatment of wool fiber residue was beneficial to the
formation of char after pyrolysis and ascribed the result to the
removal of loose substances in biomass during steam explosion.
Wang et al. [56] studied the change in the composition distribution
of biomass after steam explosion and found that all the hemicellu-
lose degraded during the pretreatment process, which led to a
decrease in the typical pyrolysis products in the bio-oil from hemi-
cellulose, such as acids, furfural and HMF. Meanwhile, the concen-
trations of LG and other anhydrosugars in the produced bio-oil were
enhanced.
TagedP7.2.4. Ammonia fiber expansion
TagedPAmmonia fiber expansion is a pretreatment technology that is
used to treat biomass with anhydrous ammonia at high pressure
(»2 MPa) and moderate temperature (60
120 °C) followed by rapid
decompression [567]. During ammonia fiber expansion pretreat-
ment, hemicellulose is degraded into oligomeric sugars and is deace-
tylated, while lignin reacts with aqueous ammonia, causing
depolymerization of the lignin and cleavage of the lignin-carbohy-
drate linkages. Decrystallization of cellulose also occurs [558,568].
Vijay et al. [569] investigated the effect of ammonia fiber expansion
pretreatment on the structure and pyrolysis behavior of corn stover,
prairie cord grass, and switchgrass. They found that the bio-char
obtained from these feedstocks after pretreatment exhibited
increased bulk and particle density compared to the untreated feed-
stocks, and no change was observed for the bio-oil. The research of
the influence of ammonia fiber expansion pretreatment on biomass
pyrolysis is limited; further investigation is needed.
73
7.3. Thermal pretreatment
TagedP7.3.1. Drying
TagedPBiomass collected from the source almost contains a considerable
amount of water. Sawdust for instance contains up to 60% moisture
[570]. Excessive moisture in biomass would re-condense in pyrolysis
liquid product (bio-oil). Although higher moisture content of bio-
mass might lead to higher liquid yield of biomass pyrolysis [571],
but moisture mainly contributed to aqueous phase, and it will dilute
the bio-oil and degrade the bio-oil quality [572]. Drying is a thermo-
physical process to remove the water in biomass via hot air or flue
gas that mainly occurs between ambient temperature and 150 °C. In
brief, when biomass is dried at temperatures between 50 and 100 °C,
biomass particles shrink and their porosity is reduced. The structure
can be reverted after rewetting. When dried at 120 to 150 °C, the lig-
nin in biomass softens and begins to flow, especially under pressure
[72].
TagedPDue to the removal of water in advance, biomass drying prior to
pyrolysis can increase the energy efficiency of the pyrolysis process
and the quality of the bio-oil. Drying techniques include natural dry-
ing, hot-air drying and microwave drying. Chen et al. [573] analyzed
the influence of drying on biomass property and the devolatilization
process, and find that moisture has no influence on the components
and chemical structure of straw. However, it caused grain size of
dried samples decreased and small cracks appeared on the surface.
Consequently, it contributes to better heat and mass transfer for bio-
mass pyrolysis and thereby increased pyrolysis rates, hence the yield
of volatile matters. Wang et al. [574] compared the influence of con-
ventional drying with microwave drying, and found that drying rate
of microwave was more than 5 times faster than that of the hot-air
drying rate. After drying with microwave, the yields of solid char
and liquid oil increased at the price of gas yield diminishing. Further-
more, low water and higher large molecular liquid species showed
for liquid oil. As the pore structure of the raw material was improved
by microwave drying, which favored the evolution of volatile matter,
but inhibited the secondary cracking reactions of bio-oil vapor,
thereby enhancing bio-oil production.
TagedP7.3.2. Torrefaction
TagedPTorrefaction, also known as mild-pyrolysis, is an easily performed
pretreatment process that occurs at 200 °C to 300 °C under an inert
atmosphere at low heating rates [575,576]. During torrefaction, bio-
mass is dried, simultaneously, a large amount of CO (»20%) and CO2
(»80%) and a small amount of volatile organics are released [577].
The volume of the original material can be reduced by 30% to 70%,
and over 90% of the original energy is preserved in the torrefied bio-
mass, as shown in Fig. 39 [578,579]. Biomass after torrefaction has
the following properties: (1) Higher heating value or energy density.
For example, the HHV of torrefied fast growing poplar increases
remarkably from 17.2 MJ/kg for raw biomass to 20.8 MJ/kg for torre-
fied biomass at 300 °C [248] because the biomass after torrefaction
has more C

C and C

H bonds, which have greater ability to release
energy than the O

H and C

O bonds in the raw biomass [580]. (2)
Lower atomic O/C and H/C ratios. The higher torrefaction tempera-
ture and residence time decrease the O/C and H/C ratios, making the
torrefied product similar to coal, as shown in Fig. 40 [535,581
583].
(3) Higher hydrophobicity or water-resistivity. It can help to stop
biomass from fungal degrading, thus reducing storage difficulty
[584]. (4) Improved grindability. Torrefaction can not only reduce
the specific energy required for grinding but also decrease the mean
particle size of the ground biomass [585]. (5) More uniform biomass
properties, which are attractive for process optimization, control
and standardization of the biomass energy production chain [586].
TagedPTorrefaction alters the biomass composition distribution. Gener-
ally, the degradation of hemicellulose occurs at temperatures above
200 °C, with lignin decomposing slowly in the background from
74 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 39. Torrefaction of biomass materials.
TagedPapproximately 160 °C to 900 °C [587,588], while cellulose decompo-
sition occurs from 200 °C to 400 °C. Thus, the decomposition of
hemicellulose is the dominant reaction during biomass torrefaction
[248,303,589]. Ru et al. [248] performed compositional analysis of
the raw and torrefied fast growing poplar according to the Van Soest
method. It was found that the content of hemicellulose decreased
from 22.1% for the raw biomass to 4.6% for the biomass torrefied at
300 °C, while that of cellulose decreased slightly from 55.0% to
43.7%. The lignin content increased by 34.1%. They further investi-
gated the change in the composition distribution of softwood bio-
mass Pinus bungeana after torrefaction and obtained a similar result
[303]. Chen et al. [589] observed that the mass of hemicellulose
reduced by 52.6% after torrefaction at 275 °C for 1 h, a much greater
reduction than that of cellulose and lignin.
TagedPThe chemical structures of biomass are also changed by torrefac-
tion. According to 2D-PCIS analysis, Ru et al. [248] found that the
dehydration of hydroxyls, dissociation of O-acetyl branches, and
breakage of ether linkages were the main reactions during torrefac-
tion. Chen et al. [242] concluded that the dissociation of O-acetyls
and dehydration of hydroxyls in hemicellulose occurred during bio-
mass torrefaction, and the removal of hydroxyls generated carboxyls
and conjugated ketones. Based on the quantitative result from CP/
MAS 13C NMR, Wen et al. [590] found that the cleavage of aryl-ether
bonds (b-O-4) and p-coumaric ester in lignin occurred during the
torrefaction of bamboo under mild conditions. Severe treatments of
bamboo (275 °C and 300 °C) caused almost complete disappearance
of b-O-4, b-b, and b¡5 linkages. Wang et al. [303] observed that the
ordered crystalline structure of cellulose was destroyed and the aryl
ether linkages and C4-propyl chains in lignin were dissociated
2.0
beech wood and miscanthus
wheat straw T
er
igh
cotton stalk
1.6 H pyrolysis products, such as acids, furans, and alicyclic ketones, were
corn stalk
coal
1.2 Peat
Lignite
tr
er
H/C
ng
0.8 Lo
Bituminous coal
0.4
Anthracite
0.0
0.0 0.2 0.4 0.6 0.8
O/C
Fig. 40. Van-Krevelen diagram for coal, charcoal, raw and various torrefied biomass
torrefaction temperatures (Tt) and residence times (tr) [535,581
583].
TagedP uring torrefaction. To suppress the interference from the overlap
d
between the structural signals of cellulose, hemicellulose and lignin,
individual components were studied to clarify the structural
changes. Wang et al. [591] found that the crystallinity of cellulose
increased slightly at first and then decreased sharply with increasing
temperature during cellulose torrefaction, which was attributed to
the competitive degradation between the crystalline region and
amorphous regions. Wang et al. [247] further proposed that the
dehydration of hydroxyls and the dissociation of branches were the
main reactions at low temperatures during hemicellulose torrefac-
tion, while depolymerization and fragmentation of monosaccharide
residues occurred at high temperature. Neupane et al. [53] observed
that torrefaction caused cleavage of aryl ether linkages and deme-
thoxylation of lignin.
TagedPThe changes in physicochemical characteristics during torrefac-
tion influence the behavior of biomass pyrolysis. Zheng et al. [592]
found that the water and acetic acid contents in bio-oil decreased at
elevated torrefaction temperature, while the aromaticity, higher
heating value, and density of the bio-oil increased. Wang et al. [303]
analyzed the influence of torrefaction on softwood pyrolysis. They
found that the yield of acetic acid significantly decreased with the
reduction of HMF and LG after torrefaction as a result of the depo-
lymerization of carbohydrates during torrefaction, and more guaia-
col and catechol and less phenols with C4-propyl groups were
formed due to the dissociation of propyl branches and the demethyl-
ation of methoxyls in lignin. Chen et al. [535] found that torrefaction
had a significant influence on the formation of solid char and gas.
They found that torrefaction enhanced the yield of solid char and
decreased the yield of liquid oil and biogas, with greater amounts of
H2 and CH4 in the biogas. When considering the influence of torre-
faction on each component, it was found that torrefaction led
increased furfural, alicyclic ketones and anhydrosugars at the cost of
decreased HMF for cellulose [591], while the yields of the typical
all reduced after hemicellulose torrefaction [247]. Torrefaction of lig-
nin increased the selectivity for phenolic compounds and decreased
the selectivity for furan compounds [53].
TagedPTorrefaction has become an important pretreatment step in bio-
mass thermochemical conversion. Two-staged biomass pyrolysis
consisting of torrefaction and subsequent fast pyrolysis or catalytic
fast pyrolysis was proposed to obtain chemicals and high-quality
bio-oil (as Fig. 41). Bergman et al. [593] suggested that by combining
torrefaction with compression molding, the economy of the thermal
conversion of biomass could be increased by 30%¡70%. The combi-
nation of torrefaction and catalytic pyrolysis favors the production
of aromatics. Chen et al. [594] found that the combination of torre-
faction and catalytic pyrolysis enhanced the formation of aromatic
hydrocarbons significantly at the cost of bio-oil yield. Neupane et al.
[53] found that catalytic fast pyrolysis of torrefied biomass led to a
 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
Fig. 41. Flow sheet of a two-staged biomass pyrolysis system.
TagedPhigher carbon yield of aromatic hydrocarbons. Adhikari et al. [595]
also concluded that torrefaction favored high aromatic hydrocarbon
production from the catalytic pyrolysis of lignin. However, some
studies produced the opposite results. Mahadevan et al. [596] con-
cluded that a high torrefaction temperature resulted in a significant
yield loss of aromatic hydrocarbons during in situ catalytic fast
pyrolysis. Zheng et al. [597] observed that torrefaction had little
impact on the product distributions from the catalytic fast pyrolysis
of cellulose.
7.4. Biological pretreatment
TagedPCompared with other pretreatment technologies, biological pre-
treatment is more environmentally friendly. It uses various types of
rot fungi to degrade some components of the biomass with no
requirement for high energy and makes it easier for the sample to
participate in the pyrolysis reaction, increasing the energy efficiency
of the overall process [598]. During biological pretreatment, micro-
organisms such as brown-, white-, and soft-rot fungi have been used
to degrade the lignin and hemicellulose in biomass [568].
TagedPWhite-rot fungi are the most important lignin-degrading bacteria
in nature, and their extracellular oxidase can effectively degrade lig-
nin into H2O and CO2. Yang et al. [599] investigated the pyrolysis of
corn stover after white-rot fungi pretreatment. During biological
pretreatment, the structure of lignin was destroyed and the crystal-
linity of cellulose was lowered, which made the structure of corn
stover simple, incompact and more suitable for pyrolysis. Biological
pretreatment also accelerated the thermal degradation of biomass
and lowered the activation energy and operating temperature, mak-
ing pyrolysis more efficient and energy-saving. In addition, the sul-
fur content was decreased by up to 46.15% by biological
pretreatment, which led to a significant reduction in the emission of
pollutant gases such as SOx. Zeng et al. [600] found that white-rot
fungus had substantial lignin-degrading ability, whereas brown-rot
fungus preferentially degraded the amorphous regions of cellulose.
Biological pretreatment promoted the thermal decomposition of
corn stover. Brown-rot fungus treatment increased the yield of bio-
oil from 32.7 to 50.8%, and white-rot fungus treatment increased the
yield from 16.8% to 26.8%. However, the rate of biological pretreat-
ment process is far too low for industrial application. Combination
with other pretreatment technologies is usually required [601].
TagedPAs a necessary step in the early stage of pyrolysis, biomass pre-
treatment technology attracted increasing concern. Different pre-
treatment methods changed the chemical composition and
structure of biomass to different extent. Comparison with variant
pretreatment methods, it can be known that acid, alkali treatment,
steam explosion and ammonia fiber explosion showed similar influ-
ence for biomass, as partial hemicellulose solved with solvent, at the
same time, some lignin degraded to lower polymers. Hence it is easy
for cellulose to degradation with more anhydrosugars and furans
formed [602]. However, the pretreatment technology is mainly used
for hydrolysis, but not pyrolysis, the influence on biomass pyrolysis
75
TagedP rocess still need more works. Torrefaction is low temperature
p
pyrolysis. Extra oxygen is removed with hemicellulose cracking dur-
ing 200
300 °C, leading to lower oxygen contents in biomass pyroly-
sis oil and gaseous product. Recently, it has been developed fast and
is often combined with pyrolysis process as the primary stage with
flue gas heating [603]. Hydrothermal treatment is a kind of wet tor-
refaction, and its influence on biomass feedstock and pyrolysis pro-
cess is similar to that of torrefaction. However, it is not typically
considered a pretreatment for pyrolysis because typically a signifi-
cant fraction of the biomass is carbonized while in contact with hot
compressed water [72].
8. Challenge and perspectives
TagedPAlthough the mechanism of biomass pyrolysis has been inten-
sively investigated, there are still a lot of challenges. To obtain break-
throughs and unravel the intrinsic complexity of the biomass
pyrolysis network, continued efforts are suggested to focus on the
following issues.
(TagedP 1) Convenient methods to extract, alter or synthesize specific
structural fragments of biomass. Extensive work is needed to
reveal the correlation between the biomass structure and the
pyrolysis reaction. The introduction of multiscale biomass frag-
ments with some typical functional groups as model compounds
will be of great assistance to comprehensively decouple the
complexity of the pyrolysis reaction network. The methods for
the directional synthesis of oligomers with specific linkages and
functional groups are necessary to better understand the evolu-
tion of the typical structures of biomass. To acquire more com-
plete pyrolysis information, extraction methods with minimal
damage to the biomass components need to be developed, and
systematic control experiments based on the extracted compo-
nents are recommended.
TagedP(2) Rapid and reliable qualitative and quantitative technologies to
characterize pyrolysis-derived compounds. Only a small portion
of products can be detected by the widely used GC
MS due to
insufficient resolution. Although GC £ GC-TOFMS/FID provides a
promising alternative to expand the information about the prod-
uct distribution, online quantification of vaporous products is
vital to building a more comprehensive homogeneous kinetic
model. The existing technologies (TG-FTIR and TG-MS) are based
on TG analyzer and cannot provide sufficient heating rates to
simulate the real fast pyrolysis process. Limited by the equipped
analytical apparatus, they can only characterize the evolution of
a small fraction of pyrolysis products and the quantification is
limited. SVUV-PIMS, which was developed in recent years,
shows great promise to achieve this goal. It can be used to detect
the important intermediate products, such as free radicals, for
which the current knowledge is limited. Whereas, large molecu-
lar organics debris from biomass pyrolysis is still a problem, as it
is very easy to block the gas line of PIMS, hence in-situ measure
76 S. Wang et al. / Progress in Energy and Combustion Science 62 (2017) 33
86
TagedPinstrument for large molecular intermediates and products is
necessary for biomass pyrolysis mechanism exploration.
TagedP(3) Determination of reliable and consistent macroscopic kinetic
parameters and the development of a comprehensive kinetic
mechanism model for biomass pyrolysis. The computational
simulation of biomass pyrolysis with respect to heat and mass
transfer requires a more uniform and reliable solid kinetic
model. This requires a previous determination of the true f(a).
The relatively accurate E calculated by isoconversional methods
is a good option to assess the most suitable f(a) from the cur-
rently available reaction models. Then DAEM based on the
determined f(a) is recommended to be derived for further calcu-
lation of other kinetic parameters through numerical computa-
tion. With the advancement of molecular simulation, a reliable
comprehensive mechanism model, including the formation
pathways of intermediates for cellulose pyrolysis, has been pro-
posed and can achieve precise prediction of the product distri-
bution. However, due to the insufficient understanding of their
chemical structures and reaction pathways, computational sim-
ulations of the pyrolysis of hemicellulose and lignin are still
missing and need to be addressed in the future. It is of great
importance to build a comprehensive kinetic mechanism model
by bridging macroscopic kinetics and microscopic kinetics, in
which the component interactions and the catalytic effects of
inorganic minerals are also considered. The built kinetic mecha-
nism model can be further used to better predict the evolution
process of typical products in real reactors after considering
heat and mass transfer.
TagedP(4) Molecular simulation of the pyrolysis reaction to reflect the real
biomass conversion process. Limited by the computing capabil-
ity, current simulations based on density functional theory and
transition state theory focus on small molecular scale com-
pounds. There is no satisfactory method to address the pyrolysis
of structural fragment compounds with more than a thousand
atoms or the catalytic reaction of medium-sized compounds on
catalyst surface. The molecular dynamics method has shown
good performance when simulating the pyrolysis of cellulose,
which has a large-scale periodic structure. The cluster model
method was developed to simulate catalytic pyrolysis on zeolite.
In the future, the advanced QM/MM (Quantum Mechanics/
Molecular Mechanics) method may be potential for simulating
the key reaction pathways during the pyrolysis of large-mole-
cule compounds.
TagedP(5) Improvement of catalytic pyrolysis. To improve the catalytic
performance with higher selectivity of desirable products and
lower coke generation, the development of an advanced catalyst
system is still an important issue in future research on biomass
catalytic pyrolysis. Catalyst acidity/basicity, porosity, hydrother-
mal stability, and resistance to deactivation are key property
that needs to be taken into account. Meanwhile, further research
is needed to explore the fundamental reaction mechanisms of
reactants on active sites, and the accumulation of inorganic min-
erals released from biomass on catalysts.
TagedP(6) Coordination of biomass pyrolysis with the pretreatment of
feedstock and the postprocessing of pyrolysis products. The
optimization of various pretreatment technologies, such as tor-
refaction and biological pretreatment, is suggested to be consid-
ered to further enhance biomass pyrolysis. Besides that, in order
to improve the directional upgrading efficiency of pyrolysis
products, such as bio-oil and bio-char, pyrolysis parameters and
catalysis system are suggested to be optimized synergistically
for the purpose of pyrolysis products application, including the
production of advanced liquid fuels like aromatic/aliphatic
hydrocarbons, or value-added chemicals like anhydrosugars, or
bio-chars with some special properties. The synergistic
TagedP ptimization will largely decrease the difficulties in the upgrad-
o
ing of pyrolysis products.
9. Conclusion
TagedPThe state-of-the-art biomass pyrolysis research has been
reviewed in this work. Thermochemical characteristics of three
major components of biomass, namely cellulose, hemicellulose and
lignin, the correlations between the pyrolysis behavior and the dis-
tribution of the component building blocks and functional groups
are first discussed. The DP and crystal morphology of cellulose, the
polysaccharide and side branch of hemicellulose, and the basic units
and ether linkages of lignin are the main factors that influence the
biomass pyrolysis behaviors including reaction kinetics, evolution of
intermediates and final product distribution. The biomass pyrolysis
research using advanced experimental technologies emerged in
recent years to quantify the pyrolysis product distribution, monitor
the reaction process, and determine the key intermediate products
are reviewed followingly. An emphasis is placed on the newly deter-
mined pyrolysis behavior by these technologies. The applications of
theoretical modeling methods, including new macroscopic kinetic
modeling and molecular simulation, to reveal biomass pyrolysis
mechanism are also discussed. The new macroscopic kinetic model-
ing shows great promise to achieve highly accurate mass loss simu-
lation and to predict pyrolysis product distributions. The molecular
simulation provides valuable information about the microscopic
pyrolysis pathways of biomass macromolecules. The catalytic con-
version of biomass is also covered in this review. The production of
advanced biofuels, such as aromatic/aliphatic hydrocarbons, and
value-added chemicals such as anhydrosugars and furans, by cata-
lytic pyrolysis is discussed. Besides, the correlation between the
changes in the biomass physico-chemical characteristics by various
pretreatment processes and the resulting pyrolysis behavior are
briefly reviewed. The challenge and perspectives for the study of bio-
mass pyrolysis are also outlined in the end of the review.
Acknowledgments
TagedPThe authors are grateful for the financial support from the
National Natural Science Foundation of China (51621005, 51336008,
51622604, 51476142, 51276166, 50676085, 50476057, 50176046,
and 51661145011) and the National Basic Research Program of
China (2013CB228100).
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