Fuel Vol. 75, No. 12, pp.

1449-1456, 1996

ELSEVIER

PII: SOO16-2361(96)00132-9

Copyright 0 1996 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0016-2361/96$15.00+0.00

Thermodynamic simulations of lignite-fired IGCC with in situ desulfurization and CO2 capture

Wim F. Elseviers, Tania Van Mierlo, Verelst

Martine

J. F. Van de Voorde

and Harry

Department of Chemical Engineering, Vrue Universiteit Brussels, Belgium (Received 18 April 1996; revised 73 June 1996)

Brussel, Pleinlaan 2, B- 1050

IGCC cycles running on Greek lignite with in situ desulfurization and CO2 capture were simulated using the ASPEN PLUS process simulator and compared with other power cycles. Dolomite was chosen as the material for in situ desulfurization. Considering the power produced and residual sulfur content of the offgas, an oxygen-blown gasifier operated at 1.8 MPa and 95OC, having a thermal efficiency of 38.9%, gives the best performance. The efficiency loss due to CO2 capture can be largely compensated using IGCC cycles.
Copyright 0 1996 Elsevier Science Ltd.
(Keywords: IGCC; CO* capture; simulation)

The application of oil- and gas-fired combustion turbine cycle systems has grown rapidly because of the lower cost, higher efficiencies and improved gas turbine reliability. Because of supply limitations and the increasing costs of conventional clean fuels such as oil and gas, the use of coal in combined cycles for electrical and thermal energy production is gaining interest. Integrated gasification combined cycles (IGCC) with high efficiencies and low emissions, due to integrated gas cleaning, are an attractive alternative for power production from solid fuels )2, as shown by several demonstration plants: Buggenum (The Netherlands)3, Reno (USA)4 and Puertollano (Spain) 16. Modern coal gasification technologies present a unique opportunity to combine the advantages of high-efficiency combinedcycle power generation with an environmentally friendly coal-based process. IGCC power stations are a major step forward in producing electricity at competitive prices while significantly reducing emissions through advances in low-NO, gas turbine combustion technology and intensive desulfurization processes. GASIFICATION BASICS

The prime reactions taking place in solid fuel gasification can be summarized as follows. The heat required for the endothermic Boudouard reaction C(s) +
CO2(g) = 2CO(,)>

AH298 = 283.1 kJ mol- (1)

and the reactions of the fixed carbon with steam C(s) + H2O(s) = CO(s) +
H2(4>

AH2s8 = 131.4kJmol- Cc,) +

2H20(,) = COz(,) + 2H2(g),

(2)

AH29s = 90.28 kJmol_ is delivered through partial combustion: C(s) +

@2(g) = CO(,),

(3)

AH2s8 = -110.6kJmoll (4)

C(s) +

02(g) =

C02(g)r

AH29s = -393.7 kJmol_ (5)

For a better understanding of the subsequent discussion of the simulation results, a short overview of gasification basic reactions, as used in this model, is given. Solid fuels with high moisture and relatively low fixed carbon contents are not suited for direct combustion. As an alternative, they can be converted to a combustible gas containing mainly H2 and CO in a gasification process. The gasification gas can be used for firing a gas turbine or for the production of several basic chemicals such as NH3 or acetic acid from synthesis gas after steam reforming.

If pure oxygen from a cryogenic air separation plant is used as oxidizing agent, the gas produced consists mainly of CO, C02, H2 and H20. N2 will be present if air is used instead of oxygen. The gas composition is determined through the equilibrium of the water gas shift reaction: CO(s) +
H20(,) = C02cg) + H2(g)>

AH29s = -41.10 kJmol_

(6)

The above-mentioned reactions are just a small selection of possible reactions, as upon pyrolysis a number of volatile components are also formed, resulting in small amounts of methane and ethane in the gas.

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As the gasification takes place in a reducing atmosphere, sulfur, nitrogen and chlorine species present in the solid fuel will be converted to H2S, NH3 and HCl respectively. H2S is in equilibrium with COS, as can be seen from Hz?,) + COW = COS(,) + J320(,), AZZ2s8= 33.39 kJ mol- (7)

Polish bituminous coal, with in situ desulfurization and off-gas CO2 capture, were simulated using the ASPEN PLUS process simulator. As simulation results for a similar run of the Buggenum power plant show very good agreement with the experimental data supplied, it can be concluded that ASPEN PLUS is a suitable and powerful tool for this kind of work7.
Fuel analysis

Due to their corrosive nature, these components will require special care in materials selection. However, upon combustion in the gas turbine, sulfur components will be converted to SO2 whereas NH3 will yield NO,, making a gas cleanup system necessary to comply with environmental emission regulations. The H2S content of the gas can be lowered using in situ desulfurization in the gasifier. If still lower H2S concentrations are desired, additional intensive desulfurization becomes necessary. As gasifier gas volume flows are much smaller than gas turbine exhaust gas flows, such cleaning preferably takes place between gasifier and gas turbine. In situ desulfurization can be carried out by injecting a sorbent into the gasifier. Mineral carbonates, such as limestone or dolomite, are already in use for this purpose. In general, for a metal carbonate MeCOs the following reactions take place upon injection in a pressurized gasifier operating at 900C. The metal carbonate can decompose up to a certain CO2 partial pressure through the calcination reaction: MeCOs(,) + MeO(,) + CO2(s) Kp = Ptot [CO21 The oxide can then be converted into the sulfide: MeO(,) + H&s) + MeS(,) + HzO(s) Kp = (10) (8) (9)

The lignite feed composition and calculated lower heating value (LHV) are shown in Table 1.
Process description

PW1/[HA

(11)

At higher CO2 partial pressures, calcination will not occur and desulfurization will be achieved through direct reaction with the carbonate: MeCOs(,) + HzS(,) + MeS(,) + HzO(,) + COZ(,) (12) Z$ = ~tot [CO,1[H201 /[H2Sl (13) Comparing Equations (11) and (13), it is clear that desulfurization with the calcined material is independent of pressure, while residual H2S will increase with pressure if no calcination occurs. It can also be seen that an increase in CO2 and Hz0 partial pressures will have a negative influence on residual H2S. COS can be removed according to MeC03(,) + COS(,) + MeS(,) + 2 COQ) MeOg) + COS(,) * MeS(,) + COQ) (14) (15)

The process flow diagram is represented in Figure 1. A flow of 20 kgs- (db) of Greek lignite containing 60 wt% moisture (db) is dried to 15 wt% moisture by indirect steam with vapour recompression and fed to the gasifier. Compressed oxygen (95 vol.% O2 and 5 vol.% Ar) from a cryogenic air separation plant or compressed air is used as oxidizing agent. The oxygen or air flow rate is regulated to obtain adiabatic gasification under welldefined operating conditions. Partial combustion of the fuel supplies the heat necessary for the endothermic gasification reactions. Steam is added in a steam/fuel ratio of 1 : 20 (w/w) to activate gasification reactions. Furthermore, recycled CO2 off-gas or steam can be added to obtain good fluidization, yielding a superficial velocity ranging between 10 and 30 times minimum fluidization velocity (u,r). A sorbent (dolomite, limestone or zinc carbonate) is added in an active-metal/ sulfur ratio of 2 : 1 for in situ desulfurization. A cyclone system removes entrained solid particles from the fuel gas. Cooling the gas to 500C in a ceramic heat exchanger with heat recovery allows the volatile alkali components to condense on the fly ash particles to be removed by ceramic candle filters. The solid-free gas is burnt in a gas turbine unit using the same oxidizing agent as in the gasifier, i.e. 95 vol.% 02-5 vol.% Ar or compressed air. CO2 off-gas is used as a moderator to regulate the gas turbine inlet temperature. Corrosion restrictions on the gas turbine impose a maximum allowable concentration of 1800 ppmv sulfur, even if sulfur is less problematic than the volatile alkali compounds. After expansion to atmospheric pressure, the exhaust gases are further cooled to atmospheric temperature in several heat exchangers through exchanging heat with water and steam to operate an optimized, three-pressure-level recuperative Rankine bottom cycle, which also produces the gasifier steam, Condensed water is neutralized with an alkaline solution. The off-gas, containing mainly CO2 and Ar, is compressed to 8 MPa in a four-stage compressor with
Table 1. Lignite composition Proximate analysis (wt% db) Moisture FC VM Ash 15.0 36.2 47.2 16.6 Ultimate analysis (wt% db) Ash C H N Cl S 0 16.6 47.2 4.68 1.27 0.20 0.99 29.1 Ash analysis (wt%) SiOz
Al203

COS can also be removed through the equilibrium with H2S (reaction 7). As can be seen from the reaction equilibria, it is clear that a change in the shift reaction equilibrium will have a strong influence on desulfurization performance. IGCC SIMULATIONS To evaluate process performance and economics, a number of IGCC cycles running on Greek lignite or

CaO MgO Fez03 SO3

26.57 14.01 33.10 1.26 7.99 17.07

LHV (MJ kg- )

18.62

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Combustion oxygen ----

Heat to rankine cycle _____,,,_,,,,,_,,,,,,__,-,-,-,

Fhidization CO, Figure 1 IGCC process flow diagram

intercooling to obtain a COz-rich gas, ready for safe disposal12. The transport of CO2 in normal high-tensile carbon steel pipelines requires a gas above dewpoint at any condition in the pipeline system. Practically, this means a dewpoint below -4C. SO2 concentration limits depend upon the CO2 off-gas application. If CO2 injection below ground into a depleted oil or gas reservoir or some other underground structure is applied, SO2 and O2 concentrations should be <l ppmv to avoid growth of biological species. If CO2 is to be injected into the sea at a suitable depth, SO2 and 02 concentrations can be as high as 1 vol.% as long as no water is present in the gas. Thus, off-gas residual SO2 level is determined by both gas turbine tolerances and CO2 off-gas destination. Simulation input Component physicochemical properties are calculated using the Redlich-Kwong-Soave equation of state. For pure water streams, ASME steam tables were used. For a correct calculation of the sour water formation, it was necessary to use the non-random two-liquid (NRTL) electrolyte property model. In the ASPEN PLUS simulations, coal is treated as a so-called non-conventional solid. Thermodynamic and physical parameters are derived from the proximate, ultimate and sulfur analyses. Since chemical reaction calculations are possible only for pure components, coal has to be converted into real chemical substances, i.e. its constituent elements. Coal mineral matter, or ash, is left as a nonconventional solid, as it can be considered inert for all gasification reactions. Table 2 lists the components used in the simulations. Coal properties were estimated using the IGT coal density model. For low-rank coal containing significant amounts of incompletely converted biomaterial, the Boie correlation (Equation 16) seems to give a better accuracy

than the Dulong correlation for the calculation of lower heating value (LHV) in MJ kg- (daf): LHV =35.17xc + 116.25~ - 11.10~~ + 6.28~~ + 10.47~s - 0.4396 (16)

where fuel elemental composition is expressed as mass fractions xi on a dry, ash-free basis. The chemical reactions in the gasifier and the gas turbine are assumed to reach thermodynamic equilibrium and concentrations are calculated using the Gibbs free energy minimization method. Compressors and gas turbine are calculated using rigorous polytropic laws with a polytropic efficiency of 88% (compressor) or 87% (turbine) and 99% mechanical efficiency. Condenser, heat exchanger and burner friction losses are calculated as respectively 2, 3 and 4% of the corresponding inlet pressure. A pressure drop of 5 kPa is used for the ceramic candle filter unit13. The pressure drop across the fluid bed gasifier was estimated at 13 kPa. The gasifier packed bed height is 0.5m. The calculated minimum fluidization velocity umf of 0.03 ms- at minimum fluidization voidage cmf = 0.56 (ref. 14) corresponds well with experimental values ranging from 0.011 to 0.038 m s- (ref. 15).

SIMULATION

RESULTS

Table 2 Phase Gas/liquid

Components in simulation Components 02, Nz, Ar, HZ, HzO, CH4, C02, CO, COS, H2S, NH?, HCN, HCl, Cl*, NO, NOz, S02, S2 C, S, SiOl, A&O,, Fe203, Fe& FeS2, CaO, CaCOs, CaS, CaS04, CaC&, MgO, MgC03, MgS, MgSO,, MgCl2, CaMg(C03)2 ash, coal

Lignite ga$cation Recuperative Rankine cycle. As further discussion of the results will deal with overall net efficiency of both IGCC top cycle and recuperative Rankine bottom cycle, optimization of the latter will be discussed first. A process flow diagram of the Rankine cycle is given in Figure 2. The proposed Rankine bottom cycle for optimization is a three-pressure-level cycle with reheating. Gasification steam is delivered at the desired pressure through a draw-off in the appropriate steam turbine. The following technological limitations were imposed on the simulation: turbine isentropic efficiencies of 87%, mechanical efficiencies of 99% ?? no condensation in high- and intermediate-pressure turbines (HPT, IPT) ?? condensation in low-pressure turbine (LPT) is
??

Solid Non-conventional

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G\

Figure 2 Recuperative Rankine cycle process flow diagram. HPT, high-pressure turbine; IPT, intermediate-pressure turbine; LPT, lowpressure turbine

Table 3 Level HP

Rankine cycle optimization results Pressure (MPa) 6.0 10.0 11.5 1.3 1.4 1.5 0.3 0.5 0.7 Power (MW) 89.06 90.57 91.93 Power (MW) 90.94 92.78 93.14 92.42 92.57 92.69 92.19 92.69 92.64

IPl

an efficiency increase of 0.6%. Gasification steam at 1.5 MPa is taken from the high-pressure turbine (HPT). Increasing the HPT exit pressure (IP level 1) to the gasifier pressure level also increases Rankine cycle net power production. If the gasifier is operated at other pressures, a similar conclusion can be drawn. The optimal IPT outlet pressure (IP level 2) lies between 0.5 and 0.6MPa. Since this would lead to LPT expansion ratios of 100 to 120, the IPT outlet pressure has to be kept at 0.3 MPa, causing a minor power reduction of -0.15%. Reheating the steam to 580C before expansion in the LPT gives best cycle performance. The available heat is distributed as shown in Table 4 over the various countercurrent heat exchangers and boilers, so that no condensation occurs in the IPT and maximum power is produced. As increasing thermal input in the intermediate pressure boiler will always lead to a lower power output, the recovered heat is best used in the high-pressure steam boiler. For gasifier operation at 1.5 MPa this results in a 37 MW thermal input for the intermediate-pressure boiler. Cycle overall eficiency calculations. Cycle total thermal input is 373 MW. Power output is delivered from the gas turbine and Rankine cycle. Fuel drying costs 4.3MW, and the COz removal cost includes both the production of 95 vol.% 02-5 vol.% Ar from a cryogenic air separation plant (22.1 MW) and the CO2 off-gas compression (13.1 MW). Recycle gas and oxygen compression are the remaining costs, which are proportional to their respective flow rates. Gas turbine operation. In the subsequent discussion, the gasifier is operated at 9OOC,except where mentioned differently. For gas turbine operation, inlet temperature and pressure ratio need to be determined. As expansion is always to atmospheric pressure, the process parameter determining the pressure ratio is the gasifier pressure. The maximum gas turbine inlet temperature is 12OOC, due to materials limitations. Optimum performance will be dictated by the combination of maximum power production and turbine outlet temperature above 680C the temperature needed for the production of steam at 580C. From Figure 3 it can be concluded that gas turbine inlet temperature should be as high as possible for maximum power production, i.e. 1200C. Power production increases by 1 MW for each 50 K increase in inlet temperature. It is evident that power production increases with gasifier pressure and thus pressure ratio, so that inlet pressure should also be as high as possible from the power production point of view. The total heat available for steam production is independent of the inlet temperature. It can be seen that at the maximum inlet temperature of 12OOC,the gasifier pressure has to be <2.8 MPa to comply with the

IP2

Steam temp. (C) 400 500 580

allowed, isentropic efficiency decreases by 1% for each 1% of liquid in the turbine outlet stream maximum pressure ratio for HPT and IPT 30, LPT 70 maximum steam temperature 580C (exchanger material limitations) maximum steam pressure 11.5 MPa minimum condenser pressure 5 kPa (35C dewpoint) heat exchanger pressure drop 3% of inlet pressure gas-liquid heat exchange requires minimum AT of 10 K at the pinch point gas-gas heat exchange requires minimum AT of 100 K at the pinch point. Heat from the gas turbine top cycle is available from two sources: ceramic heat exchanger after gasifier (hot side 900 to 500C) ?? heat recovery from gas turbine exhaust gases (hot side 780 to 65C)
??

Taking into account the technological limitations, optimal cycle parameters can be deduced from the results given in Table 3. Increasing the high-pressure (HP) level to the maximum allowable of 11.5 MPa yields

Table 4

Heat distribution in Rankine cycle Available from alkali removal cooling gas turbine exhaust gas cooling Distributed over intermediate-pressure steam reheater

Available heat 900 to 500C 780 to 130C

intermediate-pressure steam boiler high-pressure steam boiler intermediate-pressure steam reheater high-pressure water economizer intermediate-nressure economizer

130 to 65C

gas turbine exhaust gas cooling

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Figure 3 Influence of gasifier pressure and gas turbine inlet temperature on gas turbine performance. Gas turbine inlet temperature (C): a, 1000; b, 1100; c, 1200

Figure 4 Influence of gasifier pressure and temperature on cycle efficiency and SO2 emission. Gasifier temperature (C): a, 850; b, 900; c, 950

outlet temperature limit of 680C. However, the gasifier pressure will be further limited by environmental SO2 considerations, as will be shown below.
Fluidized bed loading capacity. Kinetic considerations impose a maximum fluidized bed loading capacity of 4000 kg h- m-* at 900C to maintain a gas space time of 1.0-l 5 s. Increasing the loading capacity will yield a smaller gasifier surface area for a given feed rate, but will reduce gas space time since gas superficial velocity is inversely proportional to gasifier surface area. Furthermore, lowering the desired superficial velocity for proper bed fluidization will increase gas space time at a given bed loading. Operating at a higher bed loading and a lower gas velocity will shift to a higher level the critical pressure at which extra C02/H20 fluidization gas has to be added. Gas residence time will thus be determined by the combination of gasifier loading capacity and the desired gas superficial velocity for proper bed fluidization. For combustion in the gas turbine, fuel gas LHV is an important parameter. It is calculated in MJkg- from composition, yi being the mass-fraction of component i:

Adding extra steam converts CO into HZ, giving a decrease in CO mass fraction. Because dilution effects and formation through reaction compensate each other, the H2 mass fraction remains nearly constant. This results in an overall LHV decrease when more steam is added. As total flow increases upon steam addition, CO2 addition for proper fluidization is necessary only at higher pressures at the same bed loading and desired gas velocity. Clearly, a higher bed loading and a lower gas velocity are preferable for both cycle overall efficiency and minimal SO2 concentration in the off-gas produced.
GasiJier operation. As concluded above, gasification will take place at a bed loading of 4000 kg h- m-* and 0.5 m s-l gas velocity. Under these circumstances, lignite gasification kinetics require temperatures >85OC. At 9OOC,gasification is -10 times faster16. Within this temperature range, gasifier operating conditions will be determined by cycle overall efficiency and SO2 emissions. Figure 4 shows cycle overall efficiency and SO2 concentration in the CO2 off-gas as functions of gasifier pressure and temperature. Cycle overall efficiency increases with pressure. At a fixed gasifier pressure, efficiency decreases with increasing reaction temperature, due to higher exergy losses between gasifier and alkali removal. SO2 concentration in the CO2 off-gas increases with pressure. If 250ppmv SO2 is accepted as a reasonable emission limit, optimal process parameters can be determined. At 900C and pressures ~1.8 MPa, SO2 emission is too high at all temperatures. Operation at 1.5MPa yields 196ppmv SO2 with 38.4% efficiency. Increasing the pressure to 1.8 MPa would increase efficiency to 39.0% with 399ppmv SO2 emission. However, increasing the gasifier temperature to 950C produces a CO2 off-gas containing only 217 ppmv SO*, while efficiency increases to 38.9%. This suggests the use of a somewhat higher gasification temperature, together with a higher inlet pressure of the gas turbine unit. Fluidization agent type. Gasifier operation at 900C requires the addition of CO2 or steam for a good fluidization at pressures > 1.5 MPa. The influence of this addition on process performance at 1.8 MPa can be seen in Table 6.

LHV = 10.lyco + 122.7~~~ + 50.6~~~~

(17)

As can be seen from Table 5, fuel gas LHV decreases rapidly when CO2 addition is required. The shift of the water gas equilibrium towards CO cannot compensate for the overall decrease in H2 and CO mass fractions due to the strong dilution effect: when additional fluidization gas is required, its flow rate is of the same order of magnitude as the flow rate of flue gas leaving the gasifier.

Table 5 Gasifier pressure (MPa)

Effect of bed loading and gas velocity on cycle performancea co2 to gasifier (kg s- ) Fuel gas LHV (MJ kg- ) (0.7 m s-i) 5.1 3.4 2.5 1.9 (0.5 m ss ) 10.1 10.2 7.9 5.8 Fuel gas flow (kg s- ) 55.2 78.8 102.2 125.6 29.8 29.6 37.5 49.9 SOr in ;;I%; 483 837 1147 1418 154 196 399 742 Efficiency W) 36.8 37.7 37.8 38.0 37.2 38.3 39.0 39.3

m2,20~ ia; 3 t h- m 23.1 1.5 46.2 1.8 68.7 2.1 91.2 (b) 4 t h- rne2, 15~ 1.2 0.0 1.5 0.0 1.8 7.3 2.1 19.0

a Steam 1 kg s- to gasifier

Steam gasification is superior to CO2 gasification from the efficiency point of view. Taking into account SO2 emission, CO2 gasification gives a slightly better performance. However, since at elevated pressures, where oxygen gasification is insufficient for proper fluidization,

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Table 6 Influence of fluidization gas type on process performance at 1.8 MPa and 900C Steam to gasifier (kg s-l)
0.0

CO2 to gasifier (kg s- ) 8.9 6.1 4.5 2.3 0.0

SO2 in CO2 offgas @pmv) 319 399 417 434 448

Overall efficiency W) 38.8 39.0 39.1 39.3 39.5

1.0 2.0 3.0 4.0

SO2 levels will nearly always require an intensive cold desulfurization unit, steam gasification is preferable to CO* gasification because of the strong efficiency increase. Air gasification. Because the use of air as oxidizing agent introduces a large amount of nitrogen in the gasifier, steam or CO2 addition for good fluidization will be necessary only at much higher pressures. Power production is 183.0MW at 1.5 MPa and drops to 173.5 MW at 1.8 MPa, indicating a lower pressure level for air-blown gasification. Process off-gas consists mainly of CO2 and NZ, C02-N2 separation using an off-line DEA absorber-stripper unit will produce a COz-rich gas ready for safe disposal, if required. DEA solvent regeneration costs amount to 100.3 MW (2.94 MJ kg- C0217, which can be withdrawn from the gas turbine cycle heat recovery, decreasing Rankine cycle power production by 38.7 MW. Off-gas compression to 8 MPa requires only 11.8 MW, due to the absence of Ar. Cycle overall efficiency is 35.5% with CO2 capture. Without CO2 capture, cycle overall efficiency is 49.0%. In situ desulfurization through sorbent injection. In situ desulfurization is effected by injecting dolomite (CaMg(CO&), limestone (CaCO& magnesium carbonate (MgC03) or zinc carbonate (ZnC03) into the gasifier. Figure 5 shows the influence of pressure and sorbent material on residual H2S in the gasifier off-gas. Possible desulfurization properties of the ash constituents are not taken into account. It can be seen that without desulfurization, under the specified operating conditions, residual H2S levels are in the region of 4000 ppmv. At pressures > 1.6 MPa, where COz addition is required to maintain 0.5 m s-l gas velocity, the concentration drops due to the dilution effect, although the total amount of sulfur in the fuel gas remains the same. Magnesium carbonate shows no desulfurization prop-

4500 4000 3500 3000

, 900

2500
2000

erties and must be rejected as an in situ sorbent. A slight decrease in residual H2S level is entirely due to the dilution through CO2 formation during calcination. Magnesium sulfide is not formed at all. Dolomite, which can be considered as a mixture of dolomite and limestone, behaves about the same as limestone, showing that its desulfurization capacity can be entirely attributed to the presence of a CaCOs phase. Zinc carbonate shows a very good desulfurization behaviour over the entire pressure range studied. Residual H2S levels and sulfur removal percentages at 1.5 MPa and 900C for each sorbent are listed in Table 7. Although ZnC03 clearly gives the best performance, it must be rejected for in situ desulfurization because ZnO, formed upon calcination at high temperatures, is easily reduced to the volatile zinc metal in the reducing gasifier atmosphere, giving Zn concentrations in the vapour phase in excess of the gas turbine tolerance limit of 2ppmv Zn. As limestone and dolomite show nearly the same behaviour, either material would be suitable. However, taking into account desulfurization kinetics, dolomite has a better performance, because of its more porous structure due to the MgCOs calcination, resulting in 100% Ca-sorbent usage, contrasted with 20% for limestone. With dolomite injection, the residual H2S concentration increases gradually from 1.O to 1.6 MPa and more strongly at higher pressures, as can be seen from Figure 5. At 1.OMPa total pressure and under the given gasification conditions, the CO2 partial pressure corresponds to the equilibrium for the calcination reaction. As the residual H2S level decreases as CO2 partial pressure approaches calcination reaction equilibrium for both calcining and non-calcining regions, it is clear that this point gives the best desulfurization performance g>20. At pressures >0.8 MPa, calcination no longer occurs and the residual H2S level increases with pressure. Since at pressures <1.4 MPa no additional gas is required for good bed fluidization, only small changes in the water gas shift equilibrium occur, due to the lower CO2 release from the calcination reaction. CO2 off-gas recycle to the gasifier for proper fluidization at higher pressures has a much stronger effect on the water gas shift equilibrium. CO2 and H20 partial pressures increase, resulting in a rapidly increasing residual H2S level. Extra steam addition increases the flue gas flow rate, making CO2 fluidization gas addition necessary only at higher pressures. Nevertheless, this advantage cannot compensate for the direct influence on desulfurization equilibria, as can be seen from Table 8. Initially, a metal:sulfur ratio of 2 : 1 was chosen for the desulfurization simulations. The influence of Ca/S ratio for dolomite desulfurization is shown in Table 9. From a thermodynamic point of view, a stoichiometric Ca/S ratio gives the best results. Increasing Ca/S ratio releases excess C02, which influences the water gas shift
Table 7 Desulfurization performance different sorbent materials at 1.5 MPa and 900C for H# in gasifier off-gas (ppmv) 4105 4058 124 112 49

_~

_._b

.-e--c

-*-d

500 0 0

*,*+*=") C.*.*.*,.*,.*..~.*~~~.~ )_*_C...~__,_~_*_*_~...~_...*__.~---~'~-~-~-'-~-'-' 5 10 15 20 25

100 0

Sorbent None MgCO3 Dolomite Limestone ZnCOl

Gaslfler

~r~rmur~

[bar]

Figure 5 Influence of gasifier pressure and sorbent material on desulfurization performance. Sorbent material: a, none; b, MgCOS; c, CaC03; d, dolomite; e, Z&O,

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Table 8 Effect of steam addition on desulfurization performance using dolomite at 900C 1.5 Gasifier pressure (MPa) Hz0 to gasifier (kg s- ) HIS in gasifier off-gas (ppmv) 124 153 210 HzS in gasifier off-gas (ppmv) 839 869 919 2.5

co2 to gasifier (kg s- ) 0 0 0

co* to gasifier (kg s- ) 33.8 31.6 27.4

1
2 4

80 i

Table 9

Influence of Ca/S ratio for dolomite desulfurization HzS + COS in off-gas (ppmv) 2123 419 121 125 129 146

Ca/S molar ratio 0.5 0.9 1.0 1.5 2.0 4.0

Figure 6 Influence of gasifier pressure and dolomite addition on in situ desulfurization using coal ash: a, ash only (Ca/S = 3.1); b, ash + 1 kg s- dolomite (Ca/S = 3.5); c, ash + 2.28 kg ss dolomite (Ca/S = 5.1)

in situ sorbent addition will be necessary, reducing operating costs and solid waste disposal problems. Table 10 gives an Comparison of lignite-jired cycles. overview of the cycles studied, all fed with 20 kgs- Greek lignite, having a 373 MW thermal input. Dolomite is used in a Ca : S ratio of 2 : 1 for in situ desulfurization. Taking into account both efficiency and SO2 emission, a higher bed loading (4000 kg h- mh2) and a lower gas velocity (15~~) result in an optimum performance for 02-CO2 gasification at 950C and 1.8 MPa. The use of steam as gasification and fluidization agent increases efficiency, but since SO2 emission levels also increase, an additional desulfurization unit between gasifier and burner becomes necessary. Because cold desulfurization inevitably leads to high exergy losses, thermal efficiency will be much lower. Operating costs will increase as well. Quantitatively, it is clear that CO2 capture decreases air gasification cycle efficiency from 49.0 to 35.3%, resulting in a 3.6% drop in efficiency compared with 38.9% for the optimal C02-O2 combined cycle. Considering the optimal C02-O2 gasification and air gasification without CO2 capture overall efficiencies, it can be concluded that the cost of zero CO2 emission amounts to 10.1% thermal efficiency. Bituminous coal gasljication

equilibrium. However, using 100% sorbent excess has only a small influence. Taking into account incomplete sorbent utilization and poor behaviour at sub-stoichiometric conditions, 100% excess of in situ sorbent material seems acceptable to obtain realistic simulation results. In situ desulfurization by coal ash. Desulfurization occurs at elevated temperatures through reaction of metal oxides or carbonates with H$S. From the coal composition in Table 1 it is clear that coal mineral matter, or ash, may also have desulfurization capacity, because of the presence of CaO and Fe20,. CaO as such is already present in the ash in a Ca : S ratio of -3 : 1, which is substantially sufficient for proper desulfurization. Figure 6 shows residual sulfur (HzS + COS) levels for in situ ash desulfurization with and without extra dolomite addition. It can be seen that desulfurization efficiency decreases upon sorbent addition, due to the CO2 release from calcination. Heat required for heating the cold sorbent to the operating conditions is produced through a slight increase in partial combustion of the coal, producing additional CO2 as well as HZ0 through the water gas shift equilibrium, lowering desulfurization efficiency. Residual levels for ash-only desulfurization are somewhat lower than for dolomite-only desulfurization. If ash participates in desulfurization in practice, no

Similar simulations were made using Polish bituminous coal. The conclusions are mainly the same, indicating that the simulation model can be used for various coal types. For bituminous coal, CO2 or steam addition is necessary not only for proper fluidization but also for a complete adiabatic gasification at 1200C. At 1.5 MPa and using dolomite for in situ desulfurization,

Table 10 Overview of performance parameters of lignite-fired cycles studied Process parameters

P (MPa)

Process performance Remarks Power (MW) 140.6 142.7 145.0 146.6 152.1 132.5 183.0 Efficiency (%) 37.1 38.3 38.9 39.3 40.8 35.3 49.0 SO2 in COz off-gas (ppmv) 837 196 217 742 989 <lOO not applicable

T (C) 900 900 950 900 900 900 900

02-co*
02

1.5 1.5 1.8 2.1 2.1 1.5 1.5

3 t hh m-*, 0.7 m s-l 4 t h- m- , 0.5 m s -I 4 t h-i m- . 0.5 m s-l 4 t h- m-*, 0.5 m s-i 4 t h- m-*, 0.5 m s- ditto, DEA CO2 capture ditto, no CO2 capture

02-co* oz-co* 02-Hz0 Air Air

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W. F. Elseviers et al.

H.$ residual levels of 60-70ppmv are obtained, which increase to 120-140ppmv for operation at 2.1 MPa. Residual sulfur is minimal when either pure steam or pure carbon dioxide is used as the gasification medium, while mixed steam-carbon dioxide gasification always decreases the in situ sulfur removal efficiency. Steam or carbon dioxide does not seem to have a large influence on the global power production when optimizing both the gas turbine and the bottom steam cycle, although steam gasification leads to somewhat higher efficiencies (+0.3%). Thermal efficiencies of 41.2 and 42.7% are obtained at 1.5 and 2.1 MPa gasification pressure respectively for pure steam gasification. CONCLUSIONS Several IGCC-type gasification cycles running on Greek lignite or Polish bituminous coal with in situ desulfurization and COz capture have been simulated. Simulation results are similar for both coal types. IGCC top cycle gives the best performance when the gas turbine is operated at its maximum allowable temperature of 1200C. Using an optimized three-pressure-level Rankine bottom cycle, the optimum cycle thermal efficiency is 38.9% for a lignite-fired gasifier operated at 950C and 1.8 MPa. Using dolomite as in situ desulfurization sorbent, an SO2 residual level of 217ppmv in the COz off-gas can be achieved. However, when the coal ash contains enough active material, desulfurization sorbent injection may not be necessary. The use of steam as fluidization agent increases efficiency at the cost of higher SOz concentration. When zero CO2 emission is required, it can be concluded that the costs of the CO2 removal can largely be compensated by the use of an integrated cycle.

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Willeboer, W. In Proceedings of TOTEM, Veldhoven, The Netherlands, 28-30 September, 1994 Gottlicher, G. and Pruschek, R. In Proceedings of Cycle Development Workshop, Essen, 15 December, 1994 Vernon, J. L. and Jones, T. Sulfur and Coal , IEACR/57, IEA Coal Research, London, 1993, p. 45 Parkinson. G. and Fouhv. K. Chem. E~P.. NY. 1996. (3). 37 Sendin, II:, Schelberg, W, Gunster, WYand Bernal; id. Mod. Power Syst: Gasif. Syst. 1993,6, 41 Sendin, U., Diirrfeld, R. and Karg, J. In Proceedings of the Conference on New Power Generation Technology, San Francisco, 25-27 October, 1995 Verelst, H., Van Mierlo, T., Van de Voorde, M., Elseviers, W. and Maniatis, K. In Proceedings of the Joule II Final Meeting, Florence, 27-28 November, 1995 Hulkkonen, S., Aijiijna, M. and Holappa, J. IGTI, ASME COGEN-TURBO 8, 1993, p. 61 Kurkela, E., Stahlberg, P., Laatikainen, J. and Simell, P. In Final Seminar of the JALO Program, Dipoli Congress Centre, Espoo, Finland, 3-4 December, 1992 Fantom, I. R. In Gas Cleaning at High Temperatures (Eds) R. Clife and J. P. K. Seville), Blackie, London, 1993, pp. 541-555 Benson, H. E. In Chemistry of Coal Utilization , Second Supp. Vol. (Ed. M. A. Elliott), Wiley, New York, 1981, Ch. 25 Skovholt, 0. In Proceedings of the International Energy Agency carbon Dioxide Disposal Symposium (Ed. P. W. F. Riemer), Pergamon Press, Oxford, 1993, pp. 1095-1100 Bumard, G. K., Leitch, A. J., Stringer, J., Clark, R. K. and Holbrow, P. In Gas Cleaning at High Temperatures (Eds R. Clift and J. P. K. Seville). Blackie. London. 1993. DD.88-110 Johnson, J. L. In Chemistry of Coal Utilization Secbhd Suppl. Vol. (Ed. M. A. Elliott), Wiley, New York, 1981, Ch. 23 Sakerallopoulos, G. P. JOULE II Cycle Development Project: Coal Gasification Power Cycles Development Project, Contrast PL920567, Part B , Progress Report for the Second Project Coordination Meeting, Athens, September 1993 Sjostriim, K. and Liliedahl, T. In Combined Cycle Project: COz Mitigation Throueh CO,/Steam/Areon Gas Turbine Cvcles and CO&team/Argon Gas&cation , Second Intermediate Report, EC Joule II Project Contract JOU2-CT92-0128, 1994 Van Mierlo, T. and Verelst, H. In Proceedings of the Second International Conference on Combustion Technologies for a Clean Environment, Vol. II, 1993, p. 38.1 Fenouil, L. A. and Lynn, S. Ind. Eng. Chem. Res. 1995,34,2343 Kurkela, E., Hepola, J., Stahlberg, P. and Lappi, M. In Proceedings of the International Symposium on Energy and Environment, No. 25, 1991, pp. 267-276 Liliedahl, T., Sjostrom, K. and Wiktorsson, L. P. Fuel 1992,71, 197

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ACKNOWLEDGEMENTS This work has been funded by the Commission of the European Communities, DG XII, JOULE II programme under contract PL 920567. T. Van Mierlo is presently VUB-OZR research assistant.

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