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MITSUBISHI

MITSUBISHI
SYNTHESIS
SYNTHESIS GAS
GAS PROCESS
PROCESS
FOR
FOR CO
CO22 EMISSION
EMISSION FREE
FREE
GTL
GTL PLANT
PLANT
CO
CO22 EMISSION
EMISSION in
in GTL
GTL PLANT
PLANT
࿽ In GTL Plant about 70% of carbon in natural
gas is converted in diesel oil and kerosene,
30% of carbon is emitted into atmosphere as
CO2.
࿽ CO 2 mitigation
70,000 BBL/D merit
Plant in GTL Plant.
• Product value ... 70,000 BBL/D × 25 US$/BBL
= 1.75 Million US$/D
• CO2 Emission Debit
... 13,700 Ton/D × 20 US$/T
= 0.274 Million US$/D
࿽ If CO2 emitted into atmosphere is mitigated,
about 15% of commercial value can be enjoyed.
PARTIAL
PARTIAL OXYDATION
OXYDATION V.S.STEAM
V.S.STEAM REFORMING
REFORMING
• GTL Process Developer Believe
1) Partial Oxidation process only can adjust CO & H2 ratio (1:2) for FT synthesis
2) Partial Oxidation process may increase 1 train capacity to enjoy scale of economy
(1 train capacity is limited by FT reactor and oxygen plant)

• Chemical Reaction
 Steam Reforming : CH4 + H2O  CO + 3H2

 Partial Oxidation : CH4 + H2O  CO + 3H2


H2 + 1/2O2  H20 (Excess H2 Combustion by O2)
CH4 + 1/2O2  CO + 2H2

 Steam Reforming with : 3CH4 + 3H2O  3CO + 9H2


CO2 Addition CO2 + H2  CO + H2O (Reverse CO Shift Reaction)
3CH4+2H2O +CO2  4CO + 8H2

• CO2 Addition to Steam Reforming Process


1) Adjust CO & H2 ratio for FT synthesis
2) CO2 can be available from steam reformer flue gas
3) Steam reforming process dominate synthesis gas process for methanol and ammonia because:
 Economy
 Reliability
4) Oxygen plant is expensive
5) CO2 addition steam reforming is proven oxo gas process
FEATURES
FEATURES OF
OF MHI
MHI SYNTHESIS
SYNTHESIS
GAS
GAS PROCESS
PROCESS
• Combination of Commercial Proven
Technologies
(Steam Reforming, CO2 Recovery from Flue Gas)
• Oxygen Plant is not Needed for Synthesis Gas
Production
• Steam Reforming with Flue Gas CO2 Recovery is
more Economical than Natural Gas Oxidation
Process
• Reduction of CO2 Emission from GTL Process and
Higher NG Conversion Efficiency
• CO2 Emission Free GTL Process Can be Achieved
by whole Flue Gas CO2 Recovery, Partially
Injected into the Process and Remained CO2 for
Disposal
PROCESS
PROCESS
• Supply CO2 Recovered from Steam Reformer Flue Gas
into the Process
• Adjust to Optimum H2 : CO Mole Ratio

GTL Synthesis  Patent Pending 4 Items


Purge Gas
Off Gas Recycle
(CO2, H2, CO)

CO2
Compressor
*1
CO2, Disposal
Steam

CO2
Reformer Removal

Natural Gas
Steam
Steam TO GTL Synthesis
H2 : CO ≈ 2:1

*1: CO2 emission free process


CARBON
CARBON BALANCE
BALANCE OF
OF
CO
CO22 EMISSION
EMISSION FREE
FREE GTL
GTL PROCESS
PROCESS
CO2 Emission
C : 4%

Fuel
 Gas
C:100% Note
Steam CO2 CO2 Disposal
Steam C :19%
Recovery
Reformer

Off Gas CO2

FT Hydro
Synthesis Cracking
FT Oil Aquifer or
C : 77% Oil Field

Note : 90% CO2 recovery base


TYPICAL
TYPICAL EXAMPLE
EXAMPLE OF
OF
CO
CO22 EMISSION
EMISSION FREE
FREE GTL
GTL PROCESS
PROCESS
CO2 to Pipeline for Disposal
1820 T/D

Steam

Reformer

 Gas
CO2
WHB Recovery
180MMSCFD
3500 T/D

Steam

Reformer
H2 : CO = 2.33 : 1
Hydrocracking Product
FT 20,000 BBL/D.
Synthesis
WHB

Off Gas Recycle

CO2 : 4150 T/D


EXAMPLE
EXAMPLE OF
OF PERFORMANCE
PERFORMANCE
FOR
FOR SYNTHESIS
SYNTHESIS PROCESS(20,000
PROCESS(20,000 BBL/D
BBL/D GTL)
GTL)
• Natural Gas Composition • Synthesis Gas H2:C0 Ratio
H2:CO = 2.33 : 1
CH4 91.51 (Mol%)
C2H6 3.20
C3H8 0.26 • Synthesis Gas Composition for
n C4H10 0.01 FT Synthesis
i C4H10 0.01
CO2 0.87 H2 57.50 (Mol%)
N2 4.14 CO 24.68
Total 100.00 CH4 4.05
N2 1.03
• Process Natural Gas Flow Rate
CO2 12.08
(Process Gas and Fuel)
H2 O 0.66
201,600 Nm3/H
Total 100.00
• Steam/Hydrocarbon Molecular
Ratio 2.0 • Synthesis Gas Flow Rate for FT
• Steam Reformer Heat Duty Synthesis
475.5 Gcal/H 769,000 Nm3/H
MHI
MHI EXPERIENCES
EXPERIENCES
SYNTHESIS GAS PROCESS FLUE GAS CO2 RECOVERY PROCESS

• Methanol Plant ··· 10 Units • Urea Production ··· 1 Unit


(Including World Largest • Liquefied CO2 Production
Synthesis Gas Plant) ··· 1 Unit
• Ammonia Plant ··· 33 Units

(Methanol Plant in Saudi Arabia)


(Flue Gas CO2 Recovery Plant in Malaysia)