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Integrated processes for converting coal to chemicals and fuelsManinder Jit Singh
Haldor Topsøe
Coal Syngas conditioning
Coal gasification
Sulfuric acid SNG
Ammonia
Methanol
DME
Formaldehyde
Gasoline
Converting coal to chemicals and fuels
Integrated production
Maximize utilization of H2 and CO2
• Combined production• Hydrogen, TREMPTM
• Ammonia, urea, methanol
• TIGAS
• Minimizing sulfur emissions• Sulfur removal unit
• Commercial grade sulfuric acid
• Integrated steam system• Overall benefit on energy efficiency
Process steps in an integrated CTX plant
Sulfuric acidAir
Coal Syngas
Steam
Steam
N2
CO2
MeOH
DME product
MeOH product
Urea product
NH3 product
O2
NH3
Gasifier Finalpurification
NH3synthesis
WSA™
Ureasynthesis
MeOHsynthesis
DMEsynthesis
ASU
Sour shift Acid gasremoval
H2S
Typical Topsoe sour shift section
Features of sour shift catalyst SSK-10
• Active at low temperatures• Allows high CO conversion at low steam/dry gas
• High selectivity at low steam to dry gas ratio• Methanation reaction is limited
• Proprietary kinetics for the CH4 formation• Sour shift can be designed for minimum S/DG ratio
• No risk of temperature run away
• Specialised guard catalyst• Dust protection
• Carbonyl protection
Sulfur removal downstream the sour shift
• Both H2S and COS will typically be present
• Sour shift will hydrolyze the COS to equilibrium
• Methanol plants with by-pass across the shift section• Possibility to install hydrolysis reactor on the by-pass stream
• CKA-3 catalyst from Topsoe• Selective hydrolysis of COS to equilibrium
• No change in the H2/CO ratio
• HTZ-31 promoted absorbent from Topsoe• Remove equilibrium COS before the synthesis units
What to do with H2S?
H2S
Sulfuric acid
Claus plantSulfur
Uses of sulfuric acid
Sulfuric acid plant
WSA Plant
What is WSA?
Wet gas Sulfuric Acid
A catalytic process for purification of sulfur- containing streams while producing concentrated sulfuric acid
Sulfuricacid
Cleaned gas
Energy (HP Steam)
SH2SRSHCOSCS2SO2SO3H2SO4
H2S gas
SO2 converter
Acid cooler
Product acid
Combustion air
Stack gas
Blower
WSAcondenser
Interbedcooler
GascoolerCombust
or
Air
Blower
BFW Steamdrum
WHB
CW
Superheated steam
Value addition by WSA!CAPEX & Environment:• More than 99.9% of the sulfur content can be recovered
• Without need of tail gas treatment unit
• Simple lay-out• Relatively few components and small plot space gives low investment
OPEX:• Excellent heat management
• Producing large amount of valuable HP superheated steam
• Sulfur is recovered as concentrated sulfuric acid of commercial grade• Valuable product of extensive use in India
• Ease of operation• High plant availability (no fouling S-condensers/catalyst or HC and NH3 feed issues)
• No waste products or chemicals added• Minimal impact on OSBL utilities
Comparison WSA vs. ClausProduction
Production figures WSA Claus + TGTU$/t tph $/yr tph $/yr
Sulfuric acid 32 3.56 978,939 - -Sulfur 100 - - 1.16 999,974HP steam 17 9.50 1,388,965 - -LP steam 13 - - 2.70 301,874
Total production value 2,367,903 1,301,848
= 0
1,388,964$ = USD
Comparison WSA vs. ClausConsumption
Consumption figures WSA Claus + TGTU
unit $/unit tph/kWh $/yr tph/kWh $/yr
Fuel gas t 130 - - 0.23 257,152Oxygen t 47 - - 0.56 226,363HP steam t 17 - - 1.33 194,455BFW t 0.34 11.2 32,750 3.70 10,819CW t 0.03 30.8 7,947 - -El. Power kWh 0.08 205 141,047 400 275,213
$ = USD
Total consumption cost 181,744 964,002
Net production income 2,186,160 337,846Sulfuic acid at zero value 1,207,221
WSA references
21
3
4
1
2
6
1
13
1415
11 5
49 10
3
56
7
8
1
2
45
6
8 9
5
6
2
3
5
2
1
3
7
8
12
4
3
74
2
19
9
10
Oil refining
Coking
Gasification
Metallurgy
Viscose
Sundry applications
18
4
1
7
3
17
16
118
9
20
10
11
13
12
10
5
11
17
15
12
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2322
12
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16
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15 1619 18
6
14
13
17
2021
19 1822
7
28
20
23
8
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13
31
23
2825 2726
30
6
2532
33
2424
21
34
2931
9
30 35
14
26
36
3738
2829
Acid production :4 – 1,140 MTPD130+ references30 within gasification Korean Western Power
Taean IGCC plantStart-up 2015
Mississippi Power CompanyKemper County IGCC plantStart-up 2015
Sasol Synfuels (Pty.) Ltd.Secunda, RSAStart-up 2009
Uncoupling India from LNG import- by utilisation of national coal resources for SNG
• India is the fourth largest LNG importer in the world
• Imports are expected to rise ~30% in 2015
• National coal reserves and pet coke is the key
Schematic TREMP™ layout (Topsoe RecycleEnergy Efficient Methanation Process)
Feed Inlet temp. down to 230°C
SNG
Sulphur guard Bulk methanation Trim methantion
High exit temp., typically 675°C
• Robust process
• Low operating cost
• Excellent catalysts
Special features of TREMP™
MCR catalyst developed for Topsoe TREMP™ methanation
• MCR Catalyst – the heart of the TREMP ™ unit
• High thermal stability, demonstrated up to 800°C
• Active at low temperature (300°C)
• High resistance to carbon formation
• High mechanical strength
• The catalyst is delivered prereduced
Industrial case – Coal to SNG
• Qinghua SNG plant• Two step desulfurization of raw syngas
• High surface HTZ-5 absorbent
• Copper-Zinc based ST-101 for final absorption
• Services rendered• Process and basic design
• Detailed engineering of high pressure equipment
• Supply of catalyst
• Assistance during commissioning and start-up
Customer Qinghua, China
Start up 2013
Capacity, SNG 172,000 Nm3/h
Industrial case – Coal to LNG
Huineng Coal Chemical Co. Ltd. , China• SNG to LNG requires high product purity• Reached 105% load
• Services rendered• Process and basic design
• Detailed engineering of high pressure equipment
• Supply of catalyst
• Assistance during commissioning and start-up
CustomerHuineng Coal Chemical Co.Ltd., China
Start up 2014
Capacity, SNG 50,000 Nm3/h
Topsoe synthesis loop
S-300Converter
Make-up gas
Boiler
BFWCW
Productammonia
NH3(l)
S-300Converter
Make-up gas
Boiler
BFW CW
Productammonia
NH3(l)
Special features of Topsoe ammonia loop
• Topsoe 3 bed ammonia converter• Well proven radial flow converter with about 50 references
• Easy to operate• Highly reliable
• High efficiency• No purge
• KM ammonia synthesis catalyst• High activity
• Small particles
• Optimized for lower beds
• Higher NH3 concentration
• Lower temperatures
• Favorable equilibrium
KM1
KM111
KM111
S-300
KM 111 – New Topsoe ammonia synthesis catalyst
Industrial case – Coal to ammonia
Customer ZhongyanKunshan, China
Start up 2015
Capacity 900 MTPD Ammonia
• Zhongyan Kunshan Co. Ltd ammonia plant• Single S-300 ammonia converter
• Bayonet u-tube loop boiler
• Services rendered• Process and basic design
• Detailed engineering of high pressure equipment
• Supply of proprietary equipment and catalyst
• Assistance during commissioning and start-up
Topsoe methanol synthesis loop
MK-151 Topsoe methanol synthesis catalyst
• The FENCE™ technology inhibits sintering• Cu crystals separated by picket fence of metal oxides• Very high activity• Long lasting stability• Low by-products formation
CuZnO Al2O3
Industrial case – Coal to methanol
Customer XianyangShaanxi, China
Start up 2010
Capacity 2000 MTPD Methanol
• Xianyang methanol plant• One step desulfurization of raw syngas
• Single boiling water methanol reactor
• Operating at 108% capacity
• 1% better carbon efficiency compared to design
• Services rendered• Process and basic design
• Detailed engineering of high pressure equipment
• Supply of proprietary equipment and catalyst
• Assistance during commissioning and start-up
Industrial case – Integrated process
Customer Tianfu Chemical, China
Start up 2009
Capacity
• 910 MTPD Ammonia
• 750 MTPD Methanol
• 550 MTPD DME
• Tianfu ammonia and DME plant• Single S-300 ammonia converter
• Single boiling water methanol reactor
• Single adiabatic DME
• Product flexibility
• Services rendered• Process and basic design
• Detailed engineering of high pressure equipment
• Supply of proprietary equipment and catalyst
• Assistance during commissioning and start-up
Conclusion
• Coal can be used to produce a variety of products • Added value to the plant owner
• Integration of the process units creates synergies • Improves overall energy efficiency
• Economy of scale
• Product diversity
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