Hydrogen Production from Coal and Biomass Co-gasi ca-

tion Process with Carbon Capture and Storage

C.-C. Cormos, S. Agachi

This document appeared in

Detlef Stolten, Thomas Grube (Eds.):
18th World Hydrogen Energy Conference 2010 - WHEC 2010
Parallel Sessions Book 3: Hydrogen Production Technologies - Part 2
Proceedings of the WHEC, May 16.-21. 2010, Essen
Schriften des Forschungszentrums Jülich / Energy & Environment, Vol. 78-3
Institute of Energy Research - Fuel Cells (IEF-3)
Forschungszentrum Jülich GmbH, Zentralbibliothek, Verlag, 2010
ISBN: 978-3-89336-653-8
Proceedings WHEC2010 255

Hydrogen Production from Coal and Biomass

Co-gasification Process with Carbon Capture and Storage

Calin-Cristian Cormos, Serban Agachi, Babes-Bolyai University, Faculty of

Chemistry and Chemical Engineering, Cluj-Napoca, Romania

1 Introduction
Introduction of hydrogen in energy system as a new energy carrier complementary to
electricity and conventional fuels (e.g. natural gas, oil derived products, coal etc.) is raising
much interest, as this offers significant advantages including reduction of greenhouse gas
emissions at the point of end use, enhancement of the security of energy supply and
improvement of economic competitiveness. Hydrogen is used in chemical industry for
various processes, e.g. ammonia and methanol synthesis, hydrogenation, hydro-cracking
and hydro-desulphurization processes and it is currently produced from natural gas, oil
derived products and coal. Among these feedstock types, solid fuels (fossil sources like coal
and lignite but also renewable energy sources like biomass) are likely to play a key role using
gasification-based processes for large-scale hydrogen production, as required for the
development of the hydrogen economy.
By gasification process, a solid feedstock is partially oxidized with oxygen and steam to
produce syngas which can be used for conversion into different valuable compounds (e.g.
hydrogen, ammonia, synthetic fuels) or to generate power in a combined cycle gas turbine.
Integrated Gasification Combined Cycle (IGCC) is one of energy conversion processes
having the highest potential for carbon capture with low penalties in term of efficiency and
cost. In a modified IGCC scheme designed for carbon capture and storage, the syngas is
catalytically shifted to maximize hydrogen level and to concentrate carbon species in form of
carbon dioxide that can be later capture in a pre-combustion arrangement. After CO2 and
H2S capture in a double stage Acid Gas Removal (AGR) system, hydrogen-rich gas is used
in a combined cycle gas turbine (CCGT) for power generation and/or for production of
purified hydrogen stream which can be used in (petro)chemical industry or for transport
sector in hydrogen-fuelled fuel cells (PEM).
The paper assesses from technical point of view the hydrogen production through co-
gasification process of coal and biomass (e.g. sawdust, agricultural wastes, meat and bone
meal) simultaneous with carbon capture and storage (more than 90 % feedstock carbon
capture rate). The main aim of the paper is to describe the methodology to design and
evaluate the plant performances using critical factors like: fuel selection criteria, choice of
gasification reactor, heat and power integration, carbon capture and storage (CCS)
technologies, ancillary power generation, plant flexibility, methods to increase the plant
energy efficiency, hydrogen and carbon dioxide quality specifications considering the use of
hydrogen in transport sector (PEM fuel cells) and carbon dioxide storage in geological
formation or using for Enhanced Oil Recovery (EOR). The case studies were investigated in
256 Proceedings WHEC2010

detail by process flow modelling (using ChemCAD software package) and the most
promising plant concepts identified.

2 Plant Configuration of Hydrogen Production Based on Coal and Biomass

Co-gasification with CCS
A conventional Integrated Gasification Combined Cycle (IGCC) without carbon capture uses
syngas resulted from gasification (after removing ash and hydrogen sulphide) for power
production by burning in a gas turbine. The hot flue gases coming from gas turbine are used
to raise steam in Heat Recovery Steam Generator (HRSG), which by expansion in a steam
turbine generates extra electricity in addition to the one generates by the gas turbine. The
case studies investigated in this paper are producing only hydrogen, the electricity generated
by the gas and the steam turbines are used only to cover the plant ancillary demand.
Compared with conventional IGCC concept which is designed for power production only,
design modifications for hydrogen generation as well as introduction of carbon capture stage
using pre-combustion method like gas – liquid absorption (e.g. chemical or physical solvents)
involve some critical changes in the plant configuration. The conceptual layout of a modified
IGCC scheme for hydrogen production with simultaneous carbon capture is presented in
Figure 1 (as exemplification, a dry-feed gasifier with water quench was used e.g. Siemens
gasifier) [1].

Figure: Layout of IGCC scheme for hydrogen production with carbon capture and storage
(CCS).
Proceedings WHEC2010 257

Main differences of this scheme compared with conventional IGCC scheme without carbon
capture are the following: introduction of catalytically conversion stage of CO (also called
water gas shift – WGS); a modified Acid Gas Removal (AGR) system which captures, in
addition of H2S as in the conventional technology, also CO2; the hydrogen purification stage
by Pressure Swing Absorption (PSA) for the stream to be delivered to external customers (H2
purity for export was set at 99.95 % vol. to be compatible with PEM fuel cells) and a
combined cycle gas turbine (CCGT) running on hydrogen-rich gas.
Hydrogen produced is intended to be used in PEM fuel cells for transport sector which imply
very strict quality specification (>99.95 % H2 and virtually no CO and H2S due to the
possibility of fuel cells poisoning) [2]. Also, a major factor which influences the ancillary
power consumption of the plant is the compression of captured carbon dioxide stream to
more than 100 bar before being sent to geological storage or utilized for Enhanced Oil
Recovery (EOR). This additional step gives a significant difference compared with
conventional IGCC scheme. The compression of carbon dioxide stream is requiring a
significant amount of energy which in the end will imply an energy penalty of the carbon
capture design. The captured CO2 stream will have to have very low concentration of water
(<500 ppm) and hydrogen sulphide (<100 ppm) as these components could give corrosion
problems along the pipeline network [3].

3 Modeling and Simulation of Hydrogen Production Scheme

In conventional IGCC process, a wide range of gasification reactors were and continue to be
used to convert coal or lignite into syngas with good energy efficiency. But for hydrogen
production with carbon capture, gasifier options are much more restricted because of this
design particularity. For instance, air-blown gasifiers are unsuitable, mainly because of the
nitrogen dilution which negatively influences the overall thermal balance of the plant and
hydrogen purification step. Considering all the criteria (described in literature [4]) to be taken
into account when choosing a gasifier for hydrogen production with carbon capture, it
appears that entrained-flow gasifiers are the most promising reactors for this plant concept.
Having that in mind, in the following paragraphs, the evaluation is geared mainly towards this
type of reactors. The commercial gasification reactors of this type include: Shell, Siemens,
GE Texaco, E-Gas etc.
As gasification reactor considered in modelling, as mentioned before the option was in favor
of entrained-flow type operating at high temperature (slagging conditions) which give a high
fuel conversion (~99 %). From different commercial gasification technologies available on the
market, Siemens gasifier (formerly known Future Energy) was chosen, the main factors for
consideration being dry feed design (which increases the energy efficiency compared with
slurry feed type) and water quench which ensures the optimal condition for shift conversion
(pre-condition for CO2 capture).
When discussing the fuel selection for IGCC plant, the approach used for conventional power
plants (steam plants) has to be changed radically. The coal used in steam plants is advised
to have low content of ash and sulphur (to reduce corrosion and SOx emissions), but most
important is that the ash has to have a relatively high melting point to prevent ash build up on
the boiler heat transfer area. When analyzing IGCC concept, one of the advantages of this
258 Proceedings WHEC2010

technology over the conventional power plant is the ability to use lower grade coals or
alternative fuels (e.g. biomass and solid wastes) most of them unable to be processes in a
conventional power plant because of high ash, sulphur and chlorine content and low ash
melting point. Processing lower grade coals or renewable energy sources has also an
important economic benefit because these fuels are presumed to be cheaper. This paper
investigates the possibility to blend the coal with various sources of biomass (e.g. sawdust,
agricultural waste) for hydrogen production based on an IGCC scheme. Table 1 presents the
composition and thermal characteristics of evaluated fuels.

Table 1: Feedstock composition and thermal properties.

Parameter Coal Sawdust Wheat Corn stalks MBM

straw
Proximate analysis (% wt.)
Moisture (a.r.) 8.10 10.00 10.00 8.00 1.90
Volatile matter (dry) 28.51 80.05 69.94 73.40 73.40
Ultimate analysis (% wt. dry)
Carbon 72.04 49.20 41.11 44.80 46.20
Hydrogen 4.08 5.99 5.20 5.39 6.70
Nitrogen 1.67 0.82 1.01 0.85 9.70
Oxygen 7.36 42.98 37.36 41.75 17.07
Sulphur 0.65 0.03 0.24 0.21 0.65
Chlorine 0.01 0.00 0.60 0.00 0.88
Ash 14.19 0.98 14.48 7.00 18.80
Calorific value (kJ/kg dry)
Gross (HHV) 28 704.40 19 436.40 16 091.57 17 206.46 21 163.74
Net (LHV) 27 803.29 18 113.45 14 943.10 16 016.02 19 683.98
Ash composition (% wt.)
SiO2 52.20 9.44 54.64 63.30 0.00
Al2O3 27.30 1.56 5.73 0.00 0.00
Fe2O3 5.10 1.88 6.16 4.70 2.90
CaO 6.40 62.00 5.02 0.60 66.28
MgO 2.10 2.18 2.45 4.80 0.00
TiO2 1.50 0.10 0.23 0.00 0.00
K2O 1.00 15.00 14.09 8.40 13.00
Na2O 0.30 0.61 2.16 0.50 17.82
SO3 2.40 2.72 3.03 7.20 0.00
P2O5 1.30 1.23 2.43 2.10 0.00
SrO 0.00 0.15 0.00 0.00 0.00

It can be noticed from Table 1 that all alternative fuels investigated in the present paper
(sawdust, agricultural wastes and meat and bone meal - MBM) have significant increased
Proceedings WHEC2010 259

content of modifier oxides (calcium, magnesium, sodium and potassium oxides) and lower
silica and alumina content which means low slag viscosity temperatures [5]. These
alternative fuels could be added to the coal to reduce the slag viscosity in a blending ratio (up
to 20 – 30 % wt. alternative fuels) which does not change significantly reactor characteristics
and performances compared with operating only on coal. At the same time, blending coal
with these alternative fuels offers good option to find a useful way of recover the energy
content of these materials in condition of reducing consumption of non-renewable energy
sources (coal).
The plant concepts for hydrogen production with carbon capture and storage based on coal
with or without addition of sawdust, wheat straw (WS), corn stalks (CS) and meat and bone
meal (MBM) were modeled and simulated to quantify the overall plant performance
indicators. Five case studies were investigated thoroughly in this paper (for all five cases, the
feedstock thermal energy was 1000 MW):
ƒ Case 1 – Coal only as feedstock;
ƒ Case 2 – Coal with addition of sawdust (80 / 20 % wt. blending ratio);
ƒ Case 3 – Coal with addition of wheat straw (80 / 20 % wt. blending ratio);
ƒ Case 4 – Coal with addition of corn stalks (80 / 20 % wt. blending ratio);
ƒ Case 5 – Coal with addition of meat and bone meal (80 / 20 % wt. blending ratio).

4 Results and Discussions

Hydrogen and electricity co-production schemes were modeled and simulated using process
flow modelling software (ChemCAD). As thermodynamic package used in all simulations,
Soave-Redlich-Kwong (SRK) model was chosen considering the chemical species present
and process operating conditions (pressure, temperature etc.). Simulation of plant
configurations yields all necessary process data (mass and molar flows, composition,
temperatures, pressures, power generated and consumed) that are needed to assess the
overall performance of the processes.
In all cases, the plant models were optimized by performing heat and power integration
analysis (using pinch technique) of the combined cycle block (CCGT) for maximization of
energy efficiency. Steam generated in gasification island (HP steam from gasifier cooling
wall) and syngas conditioning line (HP and LP steam) was integrated in the steam cycle of
the combined cycle gas turbine. After process optimization by heat and power integration
studies, the overall plant performance indicators were calculated.
An overview of the main plant indicators for all four investigated case studies is presented in
Table 2 (the electricity production was limited only to cover the plant ancillary demand).
260 Proceedings WHEC2010

Table 2: Overall plant performance indicators.

Main Plant Data Units Case 1 Case 2 Case 3 Case 4 Case 5

Solid fuel flowrate (a.r.) kg/h 141994 153230 157044 155235 149159
Coal / Sawdust / WS / CS / MJ/kg
25.353 / 16.057 / 13.204 / 14.539 / 19.263
MBM LHV (a.r)
Feedstock thermal energy – MWth
1000.00 1000.00 1000.00 1000.00 1000.00
LHV (A)

Thermal energy of the syngas MWth

801.00 793.30 788.04 795.00 825.20
(B)
Cold gas efficiency (B/A * 100) % 80.10 79.33 78.80 79.50 82.52
Thermal energy of syngas exit MWth
711.83 706.43 700.39 706.79 736.73
AGR (C)
Syngas treatment efficiency %
88.86 89.05 88.87 88.91 89.28
(C/B *100)

Gas turbine output MWe 56.42 56.12 56.66 56.17 57.81

Steam turbine output MWe 33.28 33.62 34.43 34.12 33.91
Gross electric power output (D) MWe 86.70 89.74 91.09 90.29 91.72
Hydrogen output – LHV (E) MWth 571.24 566.83 559.84 567.00 592.97

ASU consumption + O2 MWe

38.32 38.32 39.05 38.45 36.77
compression
Gasification island power MWe
6.92 7.02 7.02 6.97 7.18
consumption
AGR + CO2 drying & MWe
34.35 34.42 35.05 34.94 37.27
compression
H2 compression MWe 7.69 7.60 7.56 7.57 7.97
Power island power MWe
2.42 2.38 2.41 2.36 2.53
consumption
Total ancillary power MWe
89.70 89.74 91.09 90.29 91.72
consumption (F)
Net electric power output (G = MWe
0.00 0.00 0.00 0.00 0.00
D - F)

Hydrogen efficiency (E/A * 100) % 57.12 56.68 55.98 56.70 59.29

Carbon capture rate % 92.35 92.83 93.64 93.25 92.24
CO2 specific emissions kg/MWh
45.63 44.99 42.19 43.99 45.34
(fossil+renewable)
CO2 specific emissions (fossil) kg/MWh 45.63 38.54 37.01 38.06 38.71

As can be noticed from Table 2, in term of hydrogen production all case studies produce
about 560 - 590 MWth (based on hydrogen LHV) with an efficiency in range of 56 – 59 %.
Proceedings WHEC2010 261

Regarding the plant overall hydrogen efficiency, for cases 2 to 4 there is little to be
differentiated among them (less than 0.7 % in term of overall hydrogen efficiency of the plant)
and they are comparable with case 1 (coal only). Case 5 (coal blended with MBM) is more
efficient with about 2.15 – 3.3 % compared with rest of the cases. This increase of plant
efficiency can be explained by the cumulative effect of optimizing gasifier performances
(lowering slag viscosity comparing with case 1 – coal only) and improved calorific value of
alternative fuel used to be blended with coal, in this case MBM (comparing with cases
2 to 4).
Also, it can be noticed the fact that coal to alternative fuels blending ratio does not influence
significantly the plant performance (comparing case 1 vs. cases 2 to 5). Specific CO2
emissions (fossil and renewable) are in the range of 42 – 45 kg/MWh with about 92 – 93 %
carbon capture rate. When counting only the fossil specific CO2 emissions, the cases 2 to 5
are performing better than case 1 (only fossil). IGCC technology has also other benefits from
environmental point of view: very low SOx and NOx emissions, possibility to process lower
grade coals or other types of solid fuels (as evaluated in this paper) which are difficult to
handle by conventional energy conversion process (e.g. steam plant).

5 Conclusions
The paper assesses the technical aspects of hydrogen production scheme with carbon
capture based on a modified IGCC plant design. The aim was to develop a set of criteria that
can be used to select the most appropriate gasification concepts for hydrogen and electricity
co-production plant with carbon capture and storage and then to quantify the overall energy
efficiency of the plant. A particular attention was devoted to the fuel selection (e.g. fuel
blending) for both optimization of the gasifier performance and promote the usage of non-
fossil fuels (various biomass sorts).
The most promising plant concepts for hydrogen production with carbon capture are all
based on entrained-flow gasifiers. For one case of entrained-flow gasifier reactor (Siemens)
with various feedstock (coal only or coal blended with various biomass sorts) different case
studies were presented in detail for assessing the main plant performance indicators (e.g.
hydrogen output; plant ancillary demand; hydrogen efficiency, specific CO2 emissions etc.).

Acknowledgements
This work was supported by Romanian National University Research Council (CNCSIS-
UEFISCSU), project number PNII – IDEI code 2455: “Innovative systems for poly-generation
of energy vectors with carbon dioxide capture and storage based on co-gasification
processes of coal and renewable energy sources (biomass) or solid waste”.

References
[1] Cormos, C.C., Starr, F., Tzimas, E., Peteves, S., 2008. Innovative concepts for
hydrogen production processes based on coal gasification with CO2 capture. Int. J.
Hydrogen Energy 33, 1284-1294
[2] Besancon, B. M., Hasanov, V., Imbault-Lastapis, R., Benesch, R., Barrio, M., Mølnvik,
M. J., 2009. Hydrogen quality from decarbonized fossil fuels to fuel cells. Int. J.
Hydrogen Energy 34, 2350-2360
262 Proceedings WHEC2010

[3] De Visser, E., Hendriks, C., Barrio, M., Mølnvik, M.J., De Koeijer, G., Liljemark, S., Le
Gallo, Y., 2008. Dynamis CO2 quality recommendations. Int. J. Greenhouse Gas
Control 2, 478-484
[4] Cormos, C.C., Starr, F., Tzimas, E., Peteves, S., Brown, A., 2007. Gasifier concepts for
hydrogen and electricity co-production with CO2 capture. 3-rd International Conference
on Clean Coal Technologies, Italy
[5] Cormos, C.C., 2009. Assessment of hydrogen and electricity co-production schemes
based on gasification process with carbon capture and storage. Int. J. Hydrogen
Energy 34, 6065-6077