Chemical Engineering Journal 176177 (2011) 286290

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Chemical Engineering Journal

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

Hydrogen production via synthetic gas by biomass/oil partial oxidation

J. Hanika a, , J. Lederer b , V. Tukac c , V. Vesely a , D. Kovc b
a

Institute of Chemical Process Fundamentals, Czech Academy of Sciences, v.v.i., 165 02 Prague 6, Czech Republic
VUANCH, a.s., Revolucn 84, 400 01 st n. Labem, Czech Republic
c
Institute of Chemical Technology Prague, Technick 5, 166 28 Prague 6, Czech Republic
b

a r t i c l e

i n f o

Article history:
Received 29 November 2010
Received in revised form 9 June 2011
Accepted 17 June 2011
Keywords:
Hydrogen
Biomass
Partial oxidation
Meal rape

a b s t r a c t
Comparison of pilot plant partial oxidation of meal rape and hydrocarbon oil mixture with process simulation using equilibrium reactor model by process simulator Aspen Plus resulted in a good agreement.
The application of representative compounds method for simulation of such complex mixture was found
as a useful tool for optimal process conditions prediction. Based on this procedure the ratio feed to both
oxygen and steam were proposed for prediction of good experimental parameters for good process yield
of hydrogen. It was stated that key parameter lambda (or analogously oxygen to feed ratio) controlling
the partial oxidation process in optimal regime should be in the interval 0.60.8, i.e. under reduction
conditions.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays hydrogen demand caused by deep fuel rening and
the other sustainable processes leads to utilization of new raw
materials. According to EU Regulations legislative rules till horizon
2020 suppose elimination of CO2 emissions in 20% and increase of
bio-components in fuels on level 20% in comparison to the present
situation. Simultaneously, extensive biodiesel production creates
great amount of biomass wastes transcendent over feeding potential of farm animals. One of potentially useful process of hydrogen
production from renewable natural sources via synthetic gas seems
to be partial oxidation (POX) and gasication of biomass material
like meal rape from rape oil and/or bio-diesel production [1].
A motivation for research and development sector is based on
intention to intensify hydrogen production. This product is without
any doubt promising commodity for energy accumulation. Sustain of hydrogen production is necessary for deep hydrorening
of engine fuels. On the other hand there is an opportunity for
utilization of biomass waste resulted from fuels bio-components
production. These aspects can be merged together by application
of waste partial oxidation (POX) e.g. meal rape in form of suspension in high boiling hydrocarbons from crude oil distillation.
A decrease of oxygen and water steam demand in feed for POX
process is expected in this variant.

Corresponding author.
E-mail addresses: hanika@icpf.cas.cz (J. Hanika), jaromir.lederer@vuanch.cz

(J. Lederer), vratislav.tukac@vscht.cz (V. Tukac), vesely@icpf.cas.cz (V. Vesely).

1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.06.050

This paper demonstrates a possibility of common partial oxidation of hydrocarbon visbreaking rest and meal rape which is bio
waste from fuels bio components production. The other goal of this
work was to develop simulation model of experimental POX reactor
working with rape meal and fuel oil mixture.
1.1. Meal rape characterization
Differences in elemental contents and other properties of meal
rape and high boiling hydrocarbon mixture forming vis-breaking
rest is given in Table 1. The important difference between both feed
materials is as follows: meal rape contains only one half of carbon,
but much more oxygen, water, and inorganic components (forming
ash after its burning) of that level corresponding to hydrocarbon
oil. The Table 1 brings also specic combustion heat of both raw
materials. The higher oxygen content of meal rape suppresses its
value as a fuel.
Distribution of residence time of biomass particles in the reactor
affects results due to different rate of consecutive reaction steps:
pyrolysis, water gas shift and steam reforming reactions. The following processes can be observed depending on temperature:
Thermal evaporation and dissociation of volatile components
(473553 K).
Hydrocarbons formation/release (553773 K).
Cracking of biomass structure (773973 K).
Gasication of non-volatile components soot reacts with oxygen and steam (9731173 K).
Thermodynamic equilibrium preferential hydrogen and carbon
monoxide formation (temperature above 1573 K).

J. Hanika et al. / Chemical Engineering Journal 176177 (2011) 286290

287

Table 1
Comparison of meal rape and waste hydrocarbon oil properties.
Element/parameter (wt%)

VBR waste

Meal rape

C
H
O
N
S
P
Na
K
Cl
Ash (%)
Wetness (%)
Combustion heat (MJ/kg)

86.25
9.29
0.66
0.779
3.02
0
0
0
0
0.0009
0
39.2

43
6.6
20
1.1
0.6
1.4
0.05
1.3
0.3
7.1
10
20

Fig. 2. Co-annular jet burner (internal jet: steamoxygen; external jet:

biomassoil).

less than 1. It could be mentioned that for thermal pyrolysis is

typical value of lambda parameter equal to zero.
Fig. 1. Pilot plant gasication reactor.

Main products of POX carbon monoxide, carbon dioxide and

hydrogen are accompanied by sulphur and nitrogen compounds
which are necessary to remove or transform by interrelated process units, e.g., Clauss process and catalytic water gas shift process
to produce elemental sulphur and hydrogen, respectively. Finally,
produced hydrogen has petrochemical grade quality. Its application in the fuel cells is in general limited by the presence of minor
impurities.
1.2. Character of partial oxidation regime
Burning processes are usually characterized by parameter
lambda as a molar ratio of oxygen in the feed to theoretical amount
of oxygen necessary to burn carboneous compounds in the feed. It
is evident, that oxidation regime is typical by lambda value greater
than 1, in this case carbon dioxide and water are formed predominantly. On the other hand, hydrogen and carbon monoxide are
formed under reduction conditions characterized by lambda value

2. Experimental
Experimental pilot plant unit for partial oxidation was constructed in UNIPETROL RPA Co., Litvinov. The unit key component
is represented by gasication reactor (see Fig. 1), equipped by
co-annular feeding jet burner (see Fig. 2), and water quench and
tubular heat cooler/exchanger. Pilot POX reactor of I.D. 0.3 m and
overall length 2 m was equipped by 5 3 kW electrical heating to
reach pseudo adiabatic regime at temperature about 1200 C. Suspension of dry biomass in mineral oil (feed rate 1.53.0 kg/h) was
partially combusted in oxygenwater steam atmosphere (oxygen
ow rate 23 kg/h and steam feed rate 1.25 kg/h) to produce carbon
monoxide, carbon dioxide and hydrogen as main gaseous components in the reaction product.
Gas chromatography with mass detection was used to analyze
gaseous products. Results were treated by statistical verication to
evaluate overall mass balance. Soot collected in water stream were
separated by ltration, dried at 105 C and determined gravimetrically.

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J. Hanika et al. / Chemical Engineering Journal 176177 (2011) 286290

200
99,6
0,05
202
BIOMASS

99,6
1,03

BATCHER

RAWMAT

200
99,6

0
101,3

0,66

EVAPORAT

0,98

120
99,6

STEAM
OIL

25

OXYGEN

105

Q=495

99,6

99,6
WATER

2,14

BURNER

GASFEED

3,83

0,66
REACTOR
25
8,50

1200

Q=-4222

99,6

99,6

PRODUCT
QUENCH

3,83

WATERC
89
PRODQ
EXCHANG
Q=-2595

99,6

50

12,33

99,6
2,83

50
VENTGAS

99,6
12,33

Temperature (C)

50

Pressure (kPa)

GLSEP

PRODC

Mass Flow Rate (kg/hr)

Duty (Watt)

Q=0

99,6
9,50
LIQUID

Fig. 3. Aspen Plus owchart of basic part of pilot POX unit.

3. Process simulation
glycine + 0.5O2 2CO + 2.5H2 + NO
Two different approaches were used to develop mathematical
models of pilot plant partial oxidation reactor. The rst method
consists in formulation of steady state balancing models created
using process simulator Aspen-Plus [3]. Pseudohomogeneous CSTR
reactor model was used to t both reaction kinetics and chemical
equilibrium on experimental data.
Complex chemical composition of the feed was solved by
concept of representative chemical compounds resulting in the
same elemental composition as the original raw material mixture. Instead of detailed rape meal composition [2,7], e.g., cellulose,
lignin, proteins and phospholipids forming waste biomass similar
compounds glucose, vanillin, n-butyl-stearate, methionine and
tri-ethyl-phosphate were applied for process simulation. For these
compounds all necessary physicochemical data were available in
the Aspen Plus software database.
A choice of representative chemical compounds is not very
important in case of isothermal chemical equilibrium reactor
model. But, in case adiabatic reactor model application the adiabatic temperature value cannot be calculated without exact
knowledge of reaction enthalpy of individual reactions proceeding
inside the reaction space.
Typical partial oxidation reactions of representative compounds
are given by the following stoichiometric equations:
glucose + 3O2 6CO + 6H2
vanilline + 2.5O2 8CO + 4H2

methionine + 3O2 5CO + 5.5H2 + NO + SO2

triethylphosphate + 2.25O2 6CO + 7.5H2 + 0.25P4 O10
butylstearate + 10O2 22CO + 22H2
In Fig. 3 simplied owchart of main part of pilot partial oxidation
unit formulated in Aspen Plus is presented. Simulation model incorporates biomass, hydrocarbon oil, water and oxygen input streams
to the equilibrium reactor combined with water quench of ue gas
at the outlet of the reactor. Model of apparatus incorporate heat
exchangers and phase separator as well. Chemical and phase equilibrium calculated by minimization of Gibbs function method were
supposed for model solution. PengRobinson equation of state with
BostonMathias alpha function was used to describe real behaviour
of gases [4,5].
4. Results and discussion
4.1. Parameters of partial oxidation
The simulated results of chemical equilibrium for 10% content
of biomass meal rape in mineral hydrocarbon oil were used
for identication of starting experimental conditions. Adiabatic

J. Hanika et al. / Chemical Engineering Journal 176177 (2011) 286290

0.45
0.4

Simulaon

y(H2)

% vol.
40
35
30
25
20
15
10
5
0
CO2 CO C

289

Test
CH4 O2 H2 N2 NO NO2 H2S C2H4
POX Products

0.4-5%
0.5-5%
0.55-5%
0.4-10%
0.5-10%
0.55-10%

0.35
0.3
0.25

Fig. 4. Partial oxidation of 5% meal rape in oil simulation versus experiment.

Oxygensteam atmosphere; mean temperature 1210 C.

0.2

0.4

temperature rise exceeds 800 K and prospected product composition was very promising in this case.
Hydrogen production in syngas mixture depends both on oxygen and water steam ratio to biomass and hydrocarbon oil mixture,
temperature eld and also ow characteristics and internal mixing in the reactor. Typical simulation result for meal rape waste to
hydrocarbon oil (1/10, wt/wt) in the feed mixture during partial
oxidation was as follows:

0.6

0.8
1
O2/Feed, kg/kg

1.2

Fig. 5. Simulated hydrogen molar ratio in the product versus feed composition.
Oxygen to feed wt. ratio; 0.40.55 steam to feed wt. ratio; 510% meal rape in oil;
mean temperature 1210 C.

carbon monoxide volume fraction: 0.358;

molar ratio of CO/CO2 of product: 8.08.
Experimental tests with feed composition changed from pure
high boiling hydrocarbon oil to 5 wt% and 10 wt% biomass in oil produced following hydrogen and carbon monoxide content in product

adiabatic temperature of product: 1038 C;

hydrogen volume fraction: 0.487;
5

rel. concentration [% vol.]

4,5

CO/CO2
H2/CO2
CH4
EV-CO/CO2
EV-H2/CO2
EV-CH4

4
3,5
3
2,5
2
1,5
1
0,5
0

0,2

0,4

0,6

0,8

1,2

1,4

Lambda
Fig. 6. Product composition versus gasication regime. Temperature 1200 C; experiments with pure oil and (EV) with 8% meal rape content in hydrocarbon oil, respectively.

Fig. 7. Non-converted carbon in product versus gasication regime of different runs. Temperature 11501200 C, experiment label, oil rape meal content and weight
proportion of steam to oil feed: E-II (0 wt%, 0.66 kg/kg), E-III (5 wt%, 0.66 kg/kg), E-IV (0 wt%, 0.66 kg/kg), and E-V (8 wt%, 0.49 kg/kg).

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J. Hanika et al. / Chemical Engineering Journal 176177 (2011) 286290

production of methane was observed. On the other hand, increasing the lambda parameter value (above 1) the hydrogen production
tends to zero value. Similar conclusion follows also from data presented in Fig. 7. There non-converted carbon in product versus
gasication regime of different runs is presented. The trends of this
dependence are very similar to the previous Fig. 6.
The dependence of hydrogen to carbon dioxide ratio on lambda
parameter was investigated in experiments for different meal rape
concentration in the feed (08 wt%). The effect of meal rape content in the feed does not inuence the hydrogen production as
illustrated in Fig. 8.
5. Conclusion
Fig. 8. Hydrogen to carbon dioxide ratio versus gasication regime. Temperature
1200 C; parameter: content of meal rape in feed (wt%).

stream (rest CO2 and cca 1% CH4 ): 33.4, 35.5, 33.9 vol.% of H2 and
30.4, 31.8, 31.6 vol.% of CO, respectively.
Simplied model of one CSTR with the same reaction time of
all reaction steps was used for simulation of equilibrium reactions.
Qualitative agreement of experimental results with process simulation using Aspen Plus simulator has been reached in this study
see Fig. 4. The deviation between model and experimental results
is not so serious from the chemical engineering data scale-up point
of view.
Almost the similar content of carbon oxides and nearly the same
hydrogen concentration veries results of simulation balance. But,
the higher value of carbon dioxide concentration in the product
implies the fact that presumptions of both ideal mixing in reactor and/or complete chemical equilibrium are not totally fullled.
Possible way to overcome mentioned nonidealities is to modify
the simulation model to compute apparent equilibrium temperature corresponding to t experimental ue gas composition [6].
The resulting temperature approach was found (its lower value cca
500 C). In this case both carbon oxide and methane concentration
in product were affected as well.
Based on process simulation the optimal oxygen to feed ratio
(cca 0.8 kg/kg) with respect to hydrogen production was found, see
Fig. 5. There was also observed small effect of both steam mass ratio
(0.40.55) and meal rape (510%) in the feed.
4.2. Effect of partial oxidation regime
Partial oxidation regime can be characterised by similar lambda
parameter used e.g. in characterization of car engine regime.
Lambda is the dimensionless ratio of actual quantities of oxygen
into the reactor should amount to, in theory, the quantity of oxygen
required for combustion of carbon in the fuel to CO2 and hydrogen
to water. Where fuel (biomass) contains oxygen, then this oxygen is
considered a reactive and reduces the theoretical quantity of oxygen. If the fuel contains moisture, its oxygen does not count. The
effect of small content of nitrogen and sulphur in the feed on oxygen
demand was neglected.
Regime of partial oxidation of the complex feed strongly inuenced the product composition. Fig. 6 illustrates the effect of
lambda parameter on different product components ratio in the
product stream. This is experimental evidence of necessity to operate the process under the reduction conditions for lambda value
interval 0.60.8. In case of more reduction regime the dominant

Comparison of pilot plant partial oxidation of meal rape and

hydrocarbon oil mixture with process simulation using equilibrium reactor model by process simulator Aspen Plus resulted in
a good agreement. The application of representative compounds
method for simulation of such complex mixture was found as a
useful tool for optimal process conditions prediction. Based on this
procedure the ratio feed to both oxygen and steam were proposed
for prediction of good experimental parameters for good process
yield of hydrogen. It was stated that key process parameter lambda
(or analogously oxygen to feed ratio) controlling the partial oxidation process in optimal regime should be in the interval 0.60.8,
i.e. under reduction conditions. For lower values of this parameter massive methane formation was observed at temperature cca
1200 C.
Experimental tests in pilot unit were in good agreement with
the optimum components mass ratio used in plant POX unit which
is as follows:
Feed:oxygen:steam = 1:1:0.5. The advantage of co-gasication of
bio-waste and hydrocarbon oil mixture using suspension of 10 wt%
meal rape in the feed could be observed in
- higher hydrogen production in cca 2.5% rel. and
- lower oxygen and steam process demand in cca 5% rel.
Acknowledgement
Grant of the Czech Ministry of Industry and Trade No. MPO 2A2TP1/024 is gratefully acknowledged.
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