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I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 1286– 1294

Available at www.sciencedirect.com

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

Innovative concepts for hydrogen production processes

based on coal gasification with CO2 capture

Calin-Cristian Cormos, Fred Starr, Evangelos Tzimas, Stathis Peteves

European Commission, DG Joint Research Centre, Institute for Energy, P.O. Box 2, 1755 ZG Petten, The Netherlands

ar t ic l e i n f o abs tra ct

Article history: This paper investigates the technical aspects of innovative hydrogen production concepts
Received 15 June 2007 based on coal gasification with CO2 capture. More specifically, it focuses on the technical
Received in revised form evaluation and the assessment of performance of a number of plant configurations
28 October 2007 based on standard entrained-flow gasification processes (dry feed and slurry feed
Accepted 19 December 2007 types) producing hydrogen at pipeline pressure, which incorporate improvements for
Available online 11 February 2008 increasing hydrogen purity and pressure. The dry feed type of entrained-flow gasifier is
currently considered to be the most efficient means of producing hydrogen from coal.
Keywords:
The main shortcomings are relatively low hydrogen purity due to the need of using
Hydrogen production
nitrogen as a transport gas for the coal and a pressure limitation of this type of design. The
Coal gasification
purity issue can be solved by using captured CO2 to transport the coal in the gasifier.
CO2 capture
The pressure limitation can be overcome by using in-plant compression of the raw
H2 pressure and purity
syngas. Simulations, made using commercial process flow modelling packages (ChemCAD),
show that these changes can be made without compromising plant efficiency;
on the contrary, the efficiency slightly increases because of the better thermal integration
of the plant.
& 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction Among these feedstock types, in the near and medium

term future, coal is likely to play a key role for large-scale
The introduction of hydrogen in the energy system as an hydrogen production, as required for the deployment
energy carrier complementary to electricity is exciting much of the hydrogen economy [3–5]. Coal-fuelled production
interest in Europe, as this offers significant advantages processes are likely to be based on entrained-flow gasification
including reduction of greenhouse gas emissions at the point as this also permits the capture of CO2 whereby it can be
of end use, enhancement of the security of energy supply and stored in geological reservoirs or used for enhanced oil
improvement of economic competitiveness. Hydrogen can be recovery (EOR) or enhanced coal bed methane recovery
produced from different feedstocks, such as natural gas, oil (ECBM) [6–8].
derived products, coal and water [1,2]. At the present time, A condition for the successful penetration of hydrogen in
most of the hydrogen produced uses natural gas as feedstock. the energy system is the ability to supply it from the
Usually the hydrogen is used in the chemical and petrochemi- production facility at high pressure and purity. High pressure
cal sectors, e.g. for ammonia and methanol synthesis, will ensure its long distance transmission and distribution to
hydrogenation, hydrocracking and hydrodesulphurization the consumers via pipelines with the minimum additional
processes. effort for recompressing the gas along the pipeline [9]. Ideally,

Corresponding author. Tel.: +31 224 565001; fax: +31 224 565630.
E-mail addresses: [email protected], [email protected] (C.-C. Cormos).
0360-3199/$ - see front matter & 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2007.12.048
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the hydrogen transmission pressure should be similar to that  99% (vol.) oxygen purity is used instead of 95% as gasifier
of natural gas, i.e. 60–70 bar [10]. oxidant.
A second key aspect is that of the purity of hydrogen
produced by the gasification plant. It is expected that Clearly, all these modifications could penalize a dry feed
hydrogen will be produced at a purity of 99.99% (vol.), to be design. Hence, it is important to asses any reduction in
suitable for proton exchange membrane (PEM) fuel cell performance compared to the standard type of dry feed
applications for the transport sector, which could represent gasifier, and if there is a difference to see whether the
the first large-scale utilization of hydrogen. To take advantage efficiency margin of this modified dry feed design is main-
of economies of scale, it is reasonable to assume that such tained over the slurry feed system. As noted above, the CO2
highly pure hydrogen will be produced centrally, rather than which is needed to transport the coal will be taken from the
being purified at the point of end use, when the demand of stream of captured CO2 .
hydrogen will be significant. All systems analysed in the paper produce hydrogen only,
but the ancillary power for the air separation unit (ASU) and
other plant equipment is generated on site using a combined
2. Shortcomings of current designs of cycle gas turbine (CCGT), to whose steam is integrated with
entrained-flow gasifiers that coming from gasifier process steam boilers. The elec-
tricity for the ancillaries is produced by steam turbines
There are, basically, two ways in which coal is transported and gas turbines, the later being supplied with hydrogen plus
into an entrained-flow gasifier: (i) via water slurry (slurry feed the tail gas from PSA. To summarize, although the plant
gasifier), and (ii) via a gas, typically nitrogen (dry feed gasifier). requires a medium CCGT, all the electricity is consumed
For the slurry feed gasifier, the need to bring water by the plant and the plant has no net power output. In
in the slurry up to gasifier temperatures results in some of all plant configurations, the coal input was maintained the
the coal having to be combusted, producing CO2 , same (equivalent to 550 MWth based on coal lower heating
as this reaction provides much more energy than the reaction value—LHV).
of coal with oxygen to produce CO. The effect of this
is to reduce the amount of hydrogen that can be produced,
since the CO can subsequently react with steam to form
hydrogen in a shift reactor located downstream of the gasifier 3. Basic outline of innovation and
[11–14]. methodology
Despite this disadvantage in terms of hydrogen yield, the
hydrogen that is produced from slurry feed gasifiers contains 3.1. Plant configuration with in-plant compression
less nitrogen than dry feed gasifiers, since the latter utilizes
nitrogen to transport the coal into the gasifier. The level of In a conventional entrained-flow gasifier, used for the
nitrogen contamination of the hydrogen could be reduced production of hydrogen, the hot raw syngas from the gasifier
even more, if the purity of the oxygen fed to the gasifier is is cooled down to a suitable temperature using quench gas,
increased from the typical level of 95% to 99% (vol.). Nitrogen water quench or a radiant boiler, depending on the gasifica-
contamination is important since its presence requires a tion process [11–16]. The raw syngas is then cleaned of
more rigorous treatment of the produced raw hydrogen and particulates and passed through a series of CO shift con-
this implies an actual loss of hydrogen. verters, where CO in the raw syngas reacts with steam to
Increased oxygen purity could also be beneficial to the dry produce hydrogen and carbon dioxide [13]. The H2 S and CO2
feed gasifiers. However, a more significant difference to the are then removed in an acid gas removal system [16–19]. The
level of nitrogen contamination in these gasifiers can be made hydrogen, if necessary, is further purified in a PSA unit.
by replacing the nitrogen by carbon dioxide as a transport gas. In the innovative concept presented here, to overcome the
This gas can be subsequently removed by the acid gas pressure limitation associated with dry feed gasifiers, an in-
removal (AGR) and pressure swing adsorption (PSA) systems plant compressor is positioned after the gas quench and
much more easily than nitrogen. There is also no problem before shift conversion (see Fig. 1). The temperature and the
with the supply of carbon dioxide since it can be taken from pressure of the syngas at this point are 150 1C and 35 bar,
the pipeline that is used to transport this gas, which has been respectively. After the compression, the temperature and the
captured downstream, to the storage site. pressure of the gas are raised to 250–270 1C and 72 bar,
Regarding the pressure, only slurry feed gasifiers are able to respectively.
produce hydrogen at sufficiently high pressure (60–70 bar) An advantage of this configuration is that the heat
[13]. Dry feed gasifiers, in contrast, are currently limited to generated during compression is used to promote the shift
30–40 bar [12,13]. It is therefore proposed in this paper to reaction and to raise steam, this having a positive influence
compress the syngas at a suitable point in the plant so that on the overall plant efficiency. The gas is dry at the inlet of the
the outlet pressure can be increased. in-plant compressor; hence, steam must be added to the
The aim of this paper is to analyse an innovative modifica- syngas at the compressor outlet to promote the shift reaction.
tion of a dry feed gasifier in which: For the capture of CO2 , a physical solvent ðSelexols Þ was
considered. The decision to use a physical solvent was based
 Carbon dioxide is used as a coal transport gas. on the advantages that this kind of solvent has over chemical
 In-plant compression is used to boost the syngas pressure. solvents (e.g. methyldiethanolamine—MDEA), the advantages
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Quench Gas Table 1 – Coal properties

Blower

In-plant Proximate analysis (wt%)

165°C Compressor
39 bar Moisture 8.9
Ash 13
Volatiles 31.2
1550°C 800°C 150°C 250°C
39 bar Fixed carbon 46.9
39 bar 35 bar 72 bar Steam
Ultimate analysis dry base (wt%)
Carbon 70.47
Hydrogen 4.9
Shift
Converter Nitrogen 1.4
Gasifier
Sulphur 1
Steam Oxygen 7.86
Coal
To Acid Gas Ash 14.37
Removal
Oxygen Heating values (MJ/kg)
Slag Heat Higher heating value (HHV) 29.24
Exchanger Lower heating value (LHV) 28.13

Air Air
Separation
Unit

Nitrogen (Case 3) and carbon dioxide (Case 4). All these cases were
simulated using the ChemCAD software package [20].
Fig. 1 – Plant configuration for dry feed gasification with The information required by the modelling work of these
syngas in-plant compression. case studies was derived from internal studies [21–24]
and from the literature [13,15,25–35]. The coal properties
(proximate and ultimate analysis, higher heating value—HHV
and lower heating value—LHV) used to evaluate all the cases
of which increase with the CO2 partial pressure in the syngas
studied in this paper are presented in Table 1.
[13,17].
Main input data and assumptions used for modelling and
simulation of the hydrogen production processes based on
3.2. Hydrogen purification aspects coal gasification (either slurry feed or dry feed gasifiers) are
presented in Table 2.
To obtain a high level of hydrogen purity (99.99 vol%), a PSA
system is used [13,15]. As the level of nitrogen in the syngas
increases, the loss of hydrogen in the tail gas also increases. 4. Main plant items and model parameters
Hence, to minimize this loss the oxygen purity to the gasifier
is set at 99% (vol.) in all the cases analysed in this paper. As This section provides a brief description of each major
noted, there is a contrast to most gasification processes where component of technology used in all four cases studied in
the oxygen level is 95% (vol.). Also, as noted earlier, another this paper.
way to minimize the hydrogen loss in the tail gas is to use
captured CO2 as a coal transport gas.
4.1. Coal gasification

3.3. Methodology and input data The coal gasification takes place in oxygen blown entrained-
flow gasifier in two different situations: a coal–water slurry
Four plant configurations have been analysed in this paper: feed gasifier operated at 75 bar and a dry coal feed gasifier
operated at 40 bar.
 Case 1: Slurry feed gasifier with water quench. For the slurry feed gasifier, the coal–water slurry and
 Case 2: Dry feed gasifier with gas quench. oxygen are fed through an injector located at the top of the
 Case 3: Dry feed gasifier with in-plant compression and gasifier. The coal gasification process takes place at slagging
nitrogen as coal transport gas. temperatures (1300–1500 1C). The configuration assumes the
 Case 4: Dry feed gasifier with in-plant compression and full water quench of the hot gases leaving the gasifier. The
carbon dioxide as coal transport gas. raw syngas leaves the quench chamber at 200–300 1C and it is
saturated with wet steam. This will provide sufficient steam
The first two case studies are conventional gasification for the CO conversion process in the shift reactor.
technologies. These are a slurry fed gasifier with water For a dry coal feed gasifier, the coal is transported to the
quench (Case 1) and a dry feed gasifier with nitrogen as coal gasifier as a dense phase in nitrogen (or other transport gas
transport gas (Case 2). The next two case studies are like CO2 Þ and is then mixed with oxygen and steam. The
innovative concepts, where a dry feed gasifier is combined gasification temperature is around 1500–1600 1C. The hot raw
with in-plant compression. In addition, the effects of using syngas leaving the gasifier is quenched with cooled syngas
two different transport gases are assessed, namely, nitrogen which is recirculated from further down the plant. This gas
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Table 2 – Input data and model assumptions Table 2. (continued )

Steam raising and power generation systems

Gasification process Steam levels
Gasification pressure: 75 bar (slurry feed gasifier)/40 bar (dry feed High pressure (HP)—104 bar
gasifier) Medium pressure (MP)—39 bar
Oxygen/coal ratio (kg/kg): 0.98 (slurry feed gasifier)/0.89 (dry feed Low pressure (LP)—4 bar
gasifier) Condensation pressure: 0.05 bar
Steam/coal ratio (kg/kg): 0 (slurry feed gasifier)/0.09 (dry feed Power consumption for heat rejection: 1% of the heat discharged
gasifier) Gas turbine efficiency: 35%
Coal concentration in the water slurry: 66 wt% Steam turbine efficiency: 85%
Nitrogen ðCO2 Þ/coal ratio (kg/kg): 0.09 (dry feed gasifier) Hydraulic efficiency of pumps: 75%
Oxygen purity fed to the gasifier: 99 vol%
ASU power consumption: 250 kWh/ton of oxygen
Pressure of O2 and N2 delivered by ASU: 2 bar
O2 pressure to gasifier: 85 bar (slurry feed gasifier)/48 bar (dry
feed gasifier)
quench gives a final temperature of 800–850 1C. After the
Carbon conversion: 99.99%
Gasifier pressure loss: 2.5% quench, the gas enters into syngas cooler boilers where high
Electric power for gasification auxiliary: 1% of input coal LHV and medium pressure steam is raised. A part of the raw
syngas is compressed and recycled to quench the hot gas and
Syngas quench and conditioning
the rest is mixed with steam and sent to the shift reactors. In
Quench type: water (slurry feed gasifier)/gas (dry feed gasifier)
Syngas temperature: 250  C ðwater quenchÞ=800  C (gas
the innovative concepts, presented in this paper, the syngas is
quench) compressed to 72 bar before it is mixed with the steam to
Quench gas ratio: 60% promote the shift reaction.
Quench gas and syngas compressor efficiency: 80%
Pressure loss for fly ash removal system: 5% 4.2. Air separation unit
Water–gas shift reactors
Catalyst type: sour shift catalyst (cobalt–molybdenum catalyst) The air separation unit is an independent unit that produces
CO conversion: 95–98% the oxygen needed for the gasification process by fractional
Steam/CO ratio: 1.8–2.7 distillation of liquid air [13]. The oxygen outlet pressure from
Catalyst temperature range: 250–500 1C
the ASU is close to atmospheric pressure and it is compressed
Number of catalytic beds: 2
prior to feeding it to the gasifier. It is assumed in the
Reactor type: adiabatic
Pressure loss: 1.5% per each catalytic bed modelling work that the oxygen purity is 99% O2 (vol.) and
the oxygen pressure at the ASU outlet is 2 bar. The oxygen
Acid gas removal system
purity is an important requirement as there is little point in
Solvent: Selexols (mixture of dimethyl ethers of polyethylene
using CO2 as a coal transport gas, if the oxygen contains
glycol)
much more than 1% nitrogen (vol.).
AGR structure: two stages (first H2 S removal/secondCO2 removal)
H2 S removal stage configuration: absorption
tower–flash–stripping tower 4.3. Water–gas shift conversion
CO2 removal configuration: absorption tower–flash
Absorption tower temperature: 25–35 1C The water–gas shift reaction is used to produce hydrogen and
Absorption pressure: 65–66 bar (for Case 3: 28–29 bar) CO2 by reacting the carbon monoxide in the syngas with
Pressure loss: 1.5% per each column
superheated steam. The shift reaction is exothermic and is
Number of flashing vessels for Selexol solvent regeneration: 4
used to raise extra steam for power production. The CO2
Pressure in the flash vessels: 20, 5, 2 and 1.05 bar
Overall CO2 removal yield: 95–97% (for Case 3: 93%) which is produced from the shift reaction is later captured.
Hydraulic efficiency of pumps: 75% For the case studies analysed in this paper, a sour shift of
CO (cobalt–molybdenum sulphur tolerant catalyst) was used
Claus plant and tail gas treatment
in all the models, since this does not require any purification
Oxygen—blown Claus plant
H2 S-rich gas composition to Claus plant: 420% H2 S (vol.) of the raw gas [1,15]. The shift catalyst also ensures the
Tail gas is recycled to H2 S absorption stage transformation of carbonyl sulphide (COS) into hydrogen
sulphide and carbon dioxide. It is assumed in the modelling
CO2 compressing stage
work that two catalytic beds are used and the CO conversion
Delivery pressure: 114 bar
Compressor efficiency: 85% is in the range of 95–98%.
Intercooler temperature: 35 1C
4.4. Acid gas removal system
Pressure swing adsorption
Hydrogen purification yield: 82–84%
Hydrogen purity: 99.99% H2 (vol.) The AGR systems analysed in this paper comprise separate
Pressure loss: 1.5% CO2 and H2 S removal units using a physical solvent
Tail gas pressure: 1.5 bar ðSelexols Þ. The H2 S is captured prior to CO2 capture and the
H2 S-rich gas is sent to a Claus plant for sulphur removal. The
Heat exchangers
Minimum DT for heat transfer: 10 1C gas leaving the first unit, which now is sulphur free, is sent to
Pressure loss: 1% the second unit for CO2 capture.
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The solvent is regenerated by flashing to four different Coal – water

Air slurry
pressure levels (20, 5, 2 and 1.05 bar) and it is recycled back to
the absorption stage. CO2 is compressed to 114 bar and sent O2
Air Separation Unit &
through a pipeline to the storage site or it is used for different Gasification
O2 Compression
applications (e.g. EOR). It is assumed in the work presented in
this paper that the overall CO2 capture rate is in the range of
93–97%. The hydrogen level in the gas stream leaving AGR is Water Quench Slag
around 91–96% (vol.). O2

Water – Gas Shift

4.5. Pressure swing adsorption
Claus Plant & Acid Gas
Sulphur CO2
PSA operates on an isothermal cycle, adsorbing at high Tail Gas Treatment Removal
pressure and desorbing at low pressure. The main application
of PSA is for hydrogen purification. The hydrogen purity is Pressure Swing
high (99–99.9999 vol%) and the yield of the process lies Adsorption
between 80% and 92% depending on process conditions
Ancillary Combined Cycle
[1,13,15]. Power Gas Turbine
For the plant configurations analysed in this paper, the PSA Purified hydrogen
yield is extremely important because the tail gas (discharged
at 1.5 bar) is used together with a part of unpurified hydrogen Fig. 2 – Scheme of hydrogen production based on slurry feed
as a fuel gas in the CCGT. In all the scenarios presented in this gasification, shift conversion, CO2 and H2 S removal and H2
paper, the purity of the hydrogen that is exported from the purification.
plant is set at 99.99% (vol.) and the hydrogen outlet pressure is
set to 64 bar.
Coal &
Air Transport gas
4.6. Steam raising and power generation
Air Separation Unit & O2
Gasification Steam
O2 Compression
In the modelling work considered in this paper, it is assumed
that the steam generated in the plant has three pressure
Syngas Quench &
levels. These are high pressure steam (HP) at 104 bar, medium Slag
Cooling
pressure steam (MP) at 39 bar and low pressure steam (LP)
at 4 bar.
O2
Part of the steam generated in the plant is used to cover the Syngas Compression
(Cases 3-4 only)
heat requirements of the process (pre-heating of the feed
streams, steam for gasification, solvent regeneration process,
etc.), and the other part is used to produce the power needed Water – Gas Shift Steam
to run the plant equipment. Power is also generated in a CCGT
using the tail gas coming from hydrogen purification process Sulphur Claus Plant & Acid Gas
CO2
by PSA. The plant is assumed to be self-sufficient in terms of
Tail gas Treatment Removal
heat and power requirement (zero net power output).
The block diagrams of the hydrogen production plant based Pressure Swing
Adsorption
on coal gasification with CO2 capture are presented in Fig. 2
(slurry feed gasification process with water quench) and in Ancillary Combined Cycle
Fig. 3 (dry feed gasification process). Power Gas Turbine
H2 compression
(Case 2 only)

5. Results
Purified hydrogen
The modelling and simulation of all the cases analysed in this Fig. 3 – Scheme of hydrogen production based on dry feed
paper was done using a general chemical process simulator gasification, syngas compression (optional), shift
software (ChemCAD). The thermodynamic package used in conversion, CO2 and H2 S removal and H2 purification.
the simulations (based on a modified SRK model) was chosen
taking into account the chemical species present in the
system and the range of process parameters (e.g. pressure,
temperature). The simulation of the plant configurations 5.1. Raw syngas properties
yields all necessary process data (flows, composition,
temperatures, pressures, power generated and consumed) For the gasification processes assessed in this paper (coal–
that are needed to assess the overall performance of the water slurry feed and dry coal feed gasifiers), the main
processes. properties of the raw syngas are presented in Table 3.
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Table 3 – Properties of the raw syngas 5.3. Water–gas shift conversion

Property Slurry feed Dry feed The shift reaction occurs in two catalytic reactors. The shifted
syngas compositions at the second shift reactor outlet are
Coal transport medium Water Nitrogen CO2 presented in Table 4. The high H2 O=CO ratio used in all cases
Pressure (bar) 75 40 40 (1.8–2.7) ensures a CO conversion around 96–98%.
Temperature ( 1C) 1369 1560 1551
The heat generated from the shift reaction is used to
Composition (vol%) raise medium pressure steam and low pressure steam. Part of
CO 42.24 61.56 63.63 the steam generated is used to cover the heat requirements
H2 25.33 26.54 25.62 of the process (pre-heating the feed streams, gasification,
CO2 10.61 2.62 3.63
solvent regeneration, etc.) and the other part is sent to CCGT
H2 O 20.81 4.58 5.93
and used to generate the power needed to run the ancillary
CH4 0.01 0 0
H2 S 0.26 0.31 0.31 equipment.
COS 0.02 0.03 0.03
N2 0.64 4.27 0.76
O2 0 0 0 5.4. Acid gas removal
Ar 0.08 0.09 0.09

After shift conversion, the syngas is cooled to ambient

temperature (20–30 1C) then the liquid water is removed and
the gas is sent to AGR system ðSelexols Þ for a separate capture
of CO2 and H2 S. The absorption temperature and pressure
Comparing the slurry feed gasifier with the dry feed
were in the range of 25–40 1C and 65–66 bar (except in Case 2
gasifiers, Table 3 reveals that in the case of the slurry gasifier,
where the absorption pressure is 28–29 bar). The gas compo-
the content of CO2 in the syngas is higher and the CO content
sitions after AGR system are presented in Table 5.
is lower than that of the dry feed gasifiers because part of the
carbon from the coal must be oxidized totally to CO2 to
provide the heat necessary to vaporize the water from the
slurry. As a consequence, the cold gas efficiency is lower than Table 4 – Gas composition after the shift converters
that for the dry coal feed gasifier (71% for slurry feed gasifier (second reactor outlet)
and 78–80% for dry feed gasifier).
One of the most important results is that in the Gas composition Case study
dry feed gasifier, although the substitution of the nitrogen (vol%)
by CO2 reduces the nitrogen content from 4.27% to 0.76%, 1 2 3 4
the CO and CO2 levels do not change significantly (see CO 0.6 0.54 0.64 0.65
Table 3). H2 34.23 43.86 45.41 45.72
CO2 26.67 31.83 32.89 34.29
H2 O 37.99 21.42 18.62 18.73
5.2. Raw syngas conditioning CH4 0 0 0 0
H2 S 0.14 0.17 0.17 0.17
For the slurry feed gasifier, the raw syngas is quenched down N2 0.33 2.14 2.23 0.4
with water to 240–250 1C, so that, after quenching, the syngas O2 0 0 0 0
Ar 0.04 0.04 0.04 0.04
has the right composition and temperature for promoting the
shift reaction.
For the dry feed gasifiers, the hot gas is quenched with
cold syngas to 800–850 1C and is then used to generate high
pressure and medium pressure steam. In the innovative Table 5 – Gas composition after the AGR system
concepts presented is this paper (Cases 3 and 4), after
cooling to 150 1C, the syngas is compressed to 72 bar.
Gas Case study
The temperature rise in the compression stage (outlet
composition
temperature 250–270 1C) is used to promote the shift (vol%)
conversion. The power needed to compress the syngas is 1 2 3 4
around 6.5 MW (less than 1.2% of the thermal energy of the
coal input) which is acceptable in the context of the net CO 0.89 0.82 0.97 0.93
H2 96.22 91.02 92.62 96.3
energy production of the plant.
CO2 1.82 3.77 1.8 1.8
The compression of the syngas can be done using
H2 O 0.05 0.1 0.05 0.05
a centrifugal compressor which would be of essentially CH4 0.01 0 0 0
the same type as used in high pressure pipeline networks. H2 S 0.01 0 0.01 0.01
The gas is then mixed with steam, in a ratio that is N2 0.9 4.21 4.46 0.82
suitable for shift conversion (for all cases before the shift O2 0 0 0 0
reaction, the steam content of the syngas is around Ar 0.1 0.08 0.09 0.09

52–60 vol%).
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For a dry feed gasifier using nitrogen as transport 5.5. Hydrogen purification
gas, the clean gas purity is much lower (92.62% H2 ) than in
the case where CO2 is used (96.3% H2 ), or when a slurry After gas clean-up, a PSA stage is used to purify the raw
gasifier is used (96.22%) because of the use of nitrogen as a hydrogen to 99.99% H2 (vol.). If the purity of the raw hydrogen
transport gas. (96–98% H2 vol.) is considered to be high enough for different
H2 S is removed from the syngas prior to CO2 capture applications (e.g. heat or power generation) the hydrogen
in a standard configuration (absorption tower–flash–stripper) purification stage by PSA can be omitted leading to significant
which removes almost 100% of the H2 S. The H2 S capital cost savings.
stream, which also contains about 65–75% CO2 (vol.), is then The PSA purification yields are 82–84% according to the
sent to a Claus plant. This needs to use oxygen instead operational specifications of the industrial units of this type
of air for combustion, to enable the H2 S to burn properly, [13,15]. The tail gas (delivered at 1.5 bar) and, as previously
since the stream is so heavily diluted with CO2 . After stated, part of raw hydrogen is burned in the CCGT to produce
combustion and separation of molten sulphur, the power needed to run the plant. For Cases 1, 3 and 4, the purified
cooled and dried stream, containing CO2 and a small hydrogen pressure after PSA is high enough for pipeline
amount of unreacted H2 S, is recycled back to the inlet of transportation (64 bar). For Case 2, the purified hydrogen has to
AGR system. be compressed after PSA to the same delivery pressure (64 bar).
After H2 S removal, in the first stage of AGR, the gas is
further processed in a second stage for CO2 removal in a 5.6. Plant efficiency
configuration that uses an absorption tower and four flash
vessels operated at different pressure levels (20, 5, 2 and All plant configurations analysed in the paper were designed
1.05 bar). The CO2 capture rate is around 96–97% (except Case to be self-sufficient in terms of heat and power. This means
2 when it is around 93–94% because of the lower operating that the power needed to run the plant (ASU, pumps,
pressure). The captured CO2 stream is compressed to 114 bar compressors, solvent regeneration, etc.) is generated on-site
and is then sent to the storage site or used for different in a combined cycle gas turbine and no extra (net) power is
applications like EOR. produced apart from the plant power demand.

Table 6 – Performance of the investigated plant configurations

Property Case study

1 2 3 4

Fuel input ðMWth Þ 550 550 550 550

Power generated ðMWe Þ

Gas turbine 25.15 25.24 25.51 25.32
Steam turbine 36.13 35.87 40.25 40.42

Power consumed ðMWe Þ

Air separation unit 17.92 16.29 16.3 16.29
O2 compressor 9.26 7.01 6.84 6.84
Gasification auxiliarya 5.5 5.5 5.5 5.5
Process pumpsb 0.34 0.5 0.52 0.52
Cooling water pumpsc 1.54 1.32 1.3 1.3
Syngas compressord 0 1.28 7.77 7.63
AGR ðSelexols Þ systeme 7.49 4.5 7.61 7.9
Purge gas compressor 3.31 4.22 4.01 3.35
CO2 compressor 15.92 16.65 15.91 16.41
H2 compressor 0 3.84 0 0

Net power output (MWe Þ 0 0 0 0

CO2 capture rate (%) 96.46 93.3 96.18 96.25
Hydrogen flow ðNm3 =hÞ 98 155 106 026 107 365 106 983
Hydrogen output ðMWth Þ 294.33 317.93 321.94 320.8
Plant efficiency (%) 53.51 57.8 58.53 58.32

a
1% of the feedstock energy (LHV), this includes coal handling and preparation.
b
Process and feed water pumps.
c
1% of the heat released to the ambience.
d
Both for gas quench compression and syngas compression.
e
Consumption of the AGR system including recycle compressor.
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I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 1286 – 1294 1293

In all plant configurations, the coal input was the same rate is around 93–94%. The explanation for this lower capture
ð550 MWth Þ; the thermal energy of the fuel input and the rate is the lower pressure of the AGR system (28–29 bar)
hydrogen output are expressed taking into consideration the compared with other cases (65–66 bar).
lower heating values (28.13 MJ/kg for coal and, respectively, In this paper, the decision was made to place the in-plant
10:795 MJ=Nm3 for hydrogen). The energy balances for all four compressor after the gasifier but before the shift converters. If
plant configurations analysed in this paper are presented in the compression was delayed until the syngas is transformed
Table 6. In calculating the efficiencies of the various cases, the to hydrogen, a multi stage centrifugal unit would be needed
assumption was made that all the power required by the because of the lower gas density. Furthermore, the heat
ancillary equipment (i.e ASU, AGR, CO2 compressor, pumps generated during the compression would be difficult to
and where fitted, the in-plant compressor) was supplied from integrate with the rest of the process and it would be only
the gas and steam turbines. Hence, the only net energy output suitable for producing LP steam.
from the plant was in the form of hydrogen; all the electricity Finally, it would appear that with improvements in oxygen
that was generated was consumed by the ancillaries. It purity and use of CO2 as coal transport gas, the hydrogen
follows that the overall efficiency of the plant was calculated produced by a dry feed gasifier could reach a fuel gas purity
considering the thermal energy of the hydrogen output around 96% (vol.) comparable with the hydrogen purity
divided by the thermal energy of the coal used as feedstock. delivered by a slurry feed gasifier. This relatively high purity
The results show that the innovative concepts (Cases 3 and 4) implies that the hydrogen purification stage will be done with
have a higher efficiency than conventional concepts (Cases 1 lower cost and minimum hydrogen loss. Furthermore, a
and 2). purity level of 96% would be perfectly acceptable for some
hydrogen end-use applications (e.g. heat or power genera-
tion). This would enable the PSA system to be removed, with
6. Discussion some benefit to plant output and efficiency, but giving a
marked reduction to capital costs.
The main objectives of the paper were to examine methods of
overcoming two basic shortcomings of dry feed gasifiers used
for hydrogen production with CO2 capture, namely, relatively
low outlet pressure and the low hydrogen purity. To overcome 7. Conclusions
these problems, in-plant compression of the syngas was
proposed as a means of increasing the hydrogen plant outlet The paper shows that the increase in hydrogen outlet
pressure. Hydrogen purity was enhanced by using carbon pressure and the production of very pure hydrogen
dioxide as coal transport gas and by increasing the oxygen (99.99 vol%) can be achieved in the least penalty in plant
purity required for gasification.
efficiency in the following ways:
Although it was not in the scope of this paper to make an
economic analysis of the analysed plant concepts, the view is
 The use of in-plant compression of the raw syngas, in a
that an in-plant compressor will not have a significant
dry feed gasifier, not only maintains, but actually improves
influence on the plant capital cost. It should be noted that a
on the efficiency advantage of this type of gasifier
higher syngas pressure will have a positive benefit on the
compared with the slurry feed design.
capital and operating costs required for the AGR (smaller
 The use of CO2 as a transport gas rather than nitrogen, in a
column sizes, lower solvent flow rates, etc.). But the like-
dry feed gasifier, does not compromise the efficiency of the
lihood of a cost penalty should disappear completely when
hydrogen production process or change significantly the
the in-plant compressor scheme is compared with the
raw gas composition.
alternative, in which a hydrogen compressor has to be used
 A combination of the two techniques actually raises the
at the exit of the plant to bring the hydrogen up to standard
gasifier efficiency compared to the conventional dry feed
pipeline pressures.
gasifier.
The results indicate that the efficiencies of dry feed
gasifiers with in-plant compression of the syngas (Cases 3
and 4) are better by about 5% points than that of the slurry Acknowledgements
feed gasifier (Case 1) mainly because of the higher cold gas
efficiency of the dry gasifier and the fact that the heat This work has been carried out within the multi-annual work
generated in the syngas compression stage is used to promote programme of the European Commission’s Joint Research
the shift reaction. Also, the performances of dry feed gasifiers Centre within the ‘‘Assessment of Energy Technologies and
with an in-plant compressor are better by 0.5–0.75% points Systems’’ Action. Any interpretations or opinions contained
than the conventional dry feed gasifier (Case 2). in this paper are those of the authors and do not necessarily
Regarding dry feed gasifiers with in-plant syngas compres- represent the view of the European Commission.
sion (Cases 3 and 4), the coal transport gases assessed in this
paper (nitrogen and carbon dioxide) do not have much effect R E F E R E N C E S
on the overall efficiency of the plant (less than 0.25% points).
The carbon capture rates in all plant configurations are in
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 ARTICLE IN PRESS
1294 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 1286 – 1294

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