CME 312 Final Paper

The Impact of a Mild Sub-Critical Hydrothermal Carbonization Pretreatment on

Umbila Wood. A Mass and Energy Balance Perspective
(988 WORDS)
What is the volatile matter? In table 1, why carbon wt%s
are huge different between fixed carbon(PROXIMATE) and
carbon (ULTIMATE) in untreated sample (U0)?
Please verify the values in Table 4 and 6.
Henry Ho, Kevin J. Lee, Jian Lin
Introduction
The article, The Impact of a Mild Sub-Critical Hydrothermal Carbonization
Pretreatment on Umbila Wood. A Mass and Energy Balance Perspective by Carlos Alberto
Cuvilas and et al, mainly focuses on the study of pretreatment of biomass through hydrothermal
carbonization (HTC), and its effect on biomass conversion as a source of energy. Biomass is
organic matter, mainly plant matter, which can be converted into fuel, and used as energy.
Unlike natural gases, biomasses are renewable resources, meaning that it can be
replenished naturally over time. However, it is also difficult to handle, transport, store, and use as
a result of its low homogeneity and energy density.1 As a result, it can lead to problems in energy
conversion units like deposition, sintering, agglomeration, fouling, and corrosion.1 In order for
biomass to satisfy requirements for thermochemical conversion processes and units, it requires
chemical pretreatments like fermentation or pyrolysis. HTC is a thermochemical process
(pyrolysis) in which dehydration, polymerization, and decarboxylation reactions of biomass in
the presence of water, high temperature, and high pressure is used to increase carbon content. It
transforms lignocellulosic biomass to a carbon rich materials like bio char. The study that was
conducted mainly used tropical woody biomass. The study also looks at the effect of the HTC
reaction treatment with respect to mass and energy balance by taking into consideration of the
proportion of solid, liquid and gaseous products.
The study, obtained and used Pterocarpus angolensis or umbila trees as the biomass
medium,.1 The experiment looks at HTC treatments in water and dilute acid. A 1000 mL
autoclave was used to carbonize 80 gr biomass in 800 mL 0.1M H2SO4 dilute acid solution or
800 mL water at 180 2 degrees celsius.1 The pretreatment conditions are shown in Table 7:

From the table one would see the different conditions for each treatment.
As a result, the
increase of carbon content
from HTC through water and
acid treatments is shown in
Table 1. The subgroup U0
represents untreated biomass
as a control for comparison.
The volatile content (not
specified) in the solid
decreased especially in acid
treatments.1 There is a
significant increase of
carbon content by weight
percentage in both HTC
treatment conditions, but is
more significant in acid
compared to water. The increase of severity or time from 150 to 350 minutes of
both treatment process also influences the increase of carbon content. The table shows a large
discrepancy between proximate and ultimate analysis with respect to carbon % weight.
Proximate analysiss parameters include sulfur, moisture, volatile matter, ash, and fixed carbon,
while ultimate analysiss parameters are dependent on quantitative analysis of various elements
present in the coal sample. The individual carbon atoms are the same in both analysis, but are
presented in different ways, thus the discrepancy in % weight.
Mass Balance
Treatment of biomass by HTC leads to the production of biochar, a carbon rich solid
fraction, as well as hydrogen, carbon dioxide, carbon monoxide,and many other compounds. The
concentrations of each compound at the end of the reaction depends on the conditions of the
treatment as well as the severity of the treatment.

From this graph one can see the changes in mass from the four different treatment
conditions.These mass values were acquired while observing the experiment. Thus in order to
verify them, one would have to conduct the experiment themselves. From these values, we can
see that the law of mass balance (mass in = mass out) was conserved. Note that while the water
treatment produced a higher mass yield, the acid treatment actually improved the quality of the
biomass, since the acid treatment produced more CO2 via combustion.
Energy Balance (Henry Ho)
A formula described by Yan et al. is used to calculate the energy balance:
Enthalpy of formation for biomass is determined using the enthalpy change due to
combustion (Hc) of the biomass solids, Eq.4:
x y
x
CHxOy + (1+ 4 2 O2 CO2+ 2 H2O

(4)

where CHxOy is the chemical formula of the biomass, with the x and y values determined from
the ultimate analysis of the biomass.
Hc was obtained through combustion in a bomb calorimeter (Parr 6300) and
mathematically can be obtained as follows:
Hc = Hf(prod) Hf(reactants)

(5)

Hf(reactants) = Hf(prod) - Hc

(6)

Consequently:

The heat of reaction was determined by the difference of the enthalpies of formation of
the products and reactants in all treatment conditions considered in this study. Several
assumptions were made in these calculations, such as the gas was solely made up of CO2 and that
the reference condition for the enthalpy calculations was 25 C.

Table 5 displays the changes in empirical chemical formulas due to carbonization and the
effect carbonization has on the energy released due to formation and combustion of said raw
biomasses to desired feedstock. Both water and diluted acid treatment increased the energy
released, with the diluted acid producing superior results, and longer applications of either
treatments showed improvements as well.

Table 6 displays the enthalpy prior and the enthalpy succeeding the process. These energy
values were acquired while observing the experiment. Thus, in order to verify them, one would
have to conduct the experiment themselves. It is evident that all treatments lead to the discharge
of energy, i.e., positive energy balances, and, thus, energy is not conserved. Once again, diluted
acid treatments on biomasses developed better results than the biomasses with water treatments
and longer treatments produced improved results than their respective treatments, i.e., the
biomass that received 350 minutes of diluted acid treatment produced better results than the
biomass that received 150 minutes of diluted acid treatment.
From the study, conclusions were drawn upon the data and laws of mass and energy
balance. By looking at this experiment with Mass and Energy balance, one would find that the
quality of biomass was improved by the acid treatment but quantity decreased. In conclusion,
this study has highlighted the relevance of mass and energy balance in a real world setting.

Citations (Footnotes):
1

Cuvilas, Carlos Alberto, Efthymios Kantarelis, and Yang Weihong. "The Impact Of A Mild SubCritical Hydrothermal Carbonization Pretreatment On Umbila Wood. A Mass And Energy
Balance Perspective." Energies (19961073) 8.3 (2015): 2165-2175. Academic Search
Complete. Web. 12 May 2015.