GTL-Case Nov 10 Lovraj Workshop-1

GTL: A CASE STUDY FOR 6000 BPD GTL PLANT
R. N. MAITI, AJAY N. DESHPANDE R&D DIVISION

24 - 25th November, 2010 LOVRAJ KUMAR MEMORIAL TRUST ANNUAL WORKSHOP NEW DELHI
Delivering excellence through people
24/11/2010 Slide Number- 1 of 38
OVERVIEW
Introduction
Key technical components in GTL plant with FT route
Design Configuration of 6000 BPD GTL Plant Conversions & Thermal efficiencies Broad specifications of key equipments Conclusions
GTL: A case study for 6000BPD GTL Plant 24/11/2010 Slide Number - 2 of 38
Engineers India Ltd Delivering excellence through people
GTL IN GAS ECONOMY
GTL

GTL technology converts C1 fraction of natural gas to hydrocarbon liquids CH4 is chemically very stable components and requires significant amount of energy and sophisticated catalyst systems GTL is residue free, sulphur free Products of GTL Naphtha; Diesel; High value Wax; High quality lube base oils Not as substitute for piped natural gas/LNG/crude But as a unique feedstock for high quality fuels and lubes
Basic Gas to Liquids Process

Air Natural Gas
Sulfur
Air Separation
O2
Gas Processing
Methane
(+Ethane)
LPGs Propane/Butane Condensate C5+ LPG Naphtha Diesel

Jet / Kerosene Base Oil / Lubricants Solvents ( n parrafins) Specialty Waxes
Ethane
Synthesis CO Fischer Synthetic Product Gas Refining H2 Tropsch Crude

Steam Steam & Water
Utilities =
Water, Steam & Power
Optional Products
Offsites =
Flares, Controls, Bldgs.
THREE STEP PROCESS
Syn Gas Generation: Steam Methane Reforming/partial oxidation to produce syn gas (a mixture of hydrogen and CO in the ratio of 2:1 molar) Fischer Tropsch Synthesis: Syn gas synthesis to produce liquid hydrocarbons Downstream processing (Tail gas treatment, Hydrocracking of liquid products)
Step 1- Synthesis Gas Generation Natural Synthesis Gas Synthesis Gas Generation Gas + yCO xH2
- Steam Methane Reforming (SMR) - Partial Oxidation (POX) - Autothermal Reforming (ATR) 800oC CO + 3H2, endothermic 206 CatalytickJ/mol Available Technology
SMR : CH4 + H2O
900-1400oC CO + 2H2, exothermic 38 NonPOX : CH4 + kJ/mol 1/2O2 catalytic Same as POX but catalytic & uses air instead of oxygen
REACTIONS OCCURRING IN SYN GAS REACTOR

Reaction Mechanism Reaction chemistry Steam Reforming Partial Oxidation Water Gas Shift reaction CO2 Reforming Carbon Deposition Carbon Conversion Carbon Deposition CH4 + H2O CO + 3 H2 2CH4 + O2 2CO + 4 H2 CO + H2O CO2 + H2 Hydrogen to CO Heat of Reaction, ratio, Molar KJ/mol (20) 3 2 -206.1 38.0 41.15 -247.3 -74.82 1 -131.3 173.3
CH4 + CO2 2CO + 2 H2 1 CH4 2H2 + C C + H2O CO + H2 2CO CO2 + C
SYN GAS REACTORS

Processes Steam Methane Reforming (SMR) Partial Oxidation (POX) Autothermal (SMR + POX) Typical H2/CO ratio, molar >2.5 1.5 - 2.0 1.5 - 2.7 Oxygen Requirement (Kg/Kg of NG) Nil 1.0 - 1.2 0.3 0.5
STEP 2 : F-T SYNTHESIS CONVERSION Synthesis Gas F-T aliphatic HC,mainly nReactor paraffins) n (-CH2-) xH2+yCO Catalysts
- Cobalt - Iron - Fixed bed - Fluidized bed (Circulating / Fixed) CO hydrogenation Slurry + 180- nCO bed 2nH2 350oC 20-35 Water gas shift CO + bar H2O Methanation Ltd Delivering excellence through people CO + Engineers India 3H2
Syncrude (Long chain
Available Technology
(-CH2-)n + nH2O
-152 kJ/mol
H2
+ CO2
-41 kJ/mol H2O + CH4 -206 kJ/mol

PRODUCT DISTRIBUTION
For further distribution of heavy cuts (C5+) into gasoline (C5 - C11), diesel (C11 - C18), wax (C19+) Shultz-Flory theory was used as given below
Where Wr+ is weight of product with carbon number greater than r-1, x = 5 and is the probability of chain growth.
SALIENT FEATURES OF F-T SYNTHESIS
Composition is a function of chain growth mechanism Product is a mixture of light & heavy hydrocarbons Composition depends on reaction temperature 180-250 deg C : Predominantly diesel & waxes 330-350 deg C : Predominantly gasoline & olefins Heat removal and control of temperature extremely critical. Heat typically recovered by boiling water in reactor tubes.
F-T CATALYSTS

Focused on achieving highest chain growth (>0.95) towards heavy waxes Comprise of primary metal (Co or Fe), secondary metal (Ru-Noble metal) & oxide promoter on alumina / silica support Co Catalyst Fe Catalyst Life Long Short Cost Expensive Low cost Syngas H2/CO 2.0 0.7 to 2.0 Products Lower MW High MW By products H2O H2O/CO2
F-T REACTORS
Fixed Bed Reactor (FB)

Multitubular design with catalyst packed in tubes Diameter limited by slow heat removal Good for heavy liquid & waxes
Fluidised Bed Reactor

Two types : Circulating Fluidised Bed (CFB) Fixed Fluidised Bed (FFB) Improved heat removal by circulating gas Suitable for gasoline ; Unsuitable for heavy waxes Reduced catalyst consumption in FFB
Slurry Reactor (MPSR)

Very high heat transfer rate High conversion per pass avoids recycle cost Higher catalyst activity with better selectivity as no hot spots Catalyst regeneration by continuous purge and feed
STEP 3 : PRODUCT REFINING Long chain waxy HC

(-CH2-)n
Product Refining
Hydroprocessing Section - Hydroisomerisation / hydrocracking of n-paraffins to iso-paraffins of

desired length & boiling range - Mild hydrocracking at 300-350 deg C & 30-50 bar - Reactivity increases with increasing number of paraffins - Maximum yield of middle distillates - Minimum yield of C4 & lighters
Naphtha,Kero , Diesel,Waxes
Distillation Section
Conventional distillation for product fractionation
Gas Processing & Wax Finishing as necessary

TAIL GAS
Efficient utilization of tail gas is must to improve economics

Fuel Gas Combustion LPG Recovery followed by Gas Combustion CO2 recovery followed by gas combustion CO2 recovery followed by adsorption for H2
GTL Block Flow Diagram

CO2 Recycle Air sep unit Amine treating FT synthesis H2 N2 CO2 Tail gas
O2
NG feed
SMR+ ATR
GTL Products Water treatment Export Steam
Steam Generation
CONCEPT STUDIES
BASIS

Tripura Gas composition is taken as the basis SMR+ATR simulations were carried out using FEM of Gibbs Energy algorithm in Aspen PLUS
Fixed bed FT reactor ( Reactor Model; in-house) Utilization of tail gas
GAS COMPOSITIONS
Composition H2 CH4 C2H6 C3H8 C4H10 N2 O2 CO CO2 H2O CO2
Mol% 97.53 1.97 0.12 0.02 0 0 0 0.36 0 0

SYN GAS GENERATION
FEM studies (using ASPEN RGIBBS reactor module) show that POX, Steam Reforming, and ATR reactors operate close to thermodynamic equilibrium. The model is used to determine steam and oxygen feed rates, and operating temperature and pressure required for obtaining syngas of required composition. Part of the Natural gas is reformed at high steam to carbon ratio with heat derived from hot syn gas from POX Partially reformed syn gas along with balance natural gas and oxygen is oxidised in second reactor at substoichiometric condition Syn gas from second reactor provides heat for reforming in first reactor
FT REACTOR
Multi tubular fixed bed reactor model Kinetics based on FE catalyst Once through type Intermittent removal of Water Optimum Tube diameter for better heat removal
FLOW SCHEME
FLOW SCHEME
OVERALL MATERIAL BALANCE

CO2 Recyl 840 TPD ASU/PSA O2 (95%) 362 TPD SMR +ATR NG 1947 TPD (1612+33 6) Steam 4639 TPD H2 191 TPD PSA Amine SG 7452 TPD Water 3071TPD FT I/II/III Three Phase Flash H/C Water 1394 TPD 1046 TPD
CO2 Purge 450 TPD Power Plant TG 454 TPD
Treating
CONVERSIONS
Conversion calculations NG Feed Basis Feed 67155 Product 43583 Conversion 64.9 Total NG Basis NG to Feed NG to fuel header Product Conversion
Kg/h Kg/h %
67155 13981 43583 53.7
Kg/h Kg/h Kg/h %
OVER ALL ENTHALPY BALANCE

Overall Enthalpy Balance Feed To Unit To SMR Products H/C Liquid Hydrogen Tail gas Loss with Flue Gas Loss with Syn gas Cooler Thermal Conversion
Q, mmkcal/h 725 151
436 228 111 38 45 60.1%

OVERALL GTL CHEMISTRY
(12+x) CH4 + (5.5 +2 x) O2 n C12 H26 + (11+2x) H2O + x CO2 With x = 0

Max theoretical energy efficiency : 78% Carbon conversion efficiency : 100% Thermal efficiency up to 60-65% Carbon conversion efficiency up to 77-83 %
With x = 2.4 - 3.6

CARBON BALANCE THROUGH REACTORS

Carbon Balance Feed Product Liquid Products Tail Gas CO2 vent Total 3072 682 427 4180
4183
kmol/h
kmol/h kmol/h kmol/h
CARBON DISTRIBUTION
CO2 Recyl ASU/PSA H2 O2 (95%) PSA SMR +ATR NG 120 Amine SG 100 Water FT I/II/III Three Phase Flash Water
CO2 Purge 10.2 Power Plant TG 16.3
Treating
Steam
H/C 73.5
ENTHALPY
CO2 Recyl ASU/PSA O2 (95%) H2 31.5 PSA SMR +ATR NG 100+20 Amine SG FT I/II/III Three Phase Flash Water
CO2 Purge Power Plant
TG
Treating
Steam
Water
H/C 60.1
UTILITY: HP STEAM DRIVEN COMPRESSORS

Compressors K-01 K-02 K-03 K-04 K-05 ng compressor syn gas compressor O2 compressor CO2 compressor air compressor 2109 KW 17900 KW 1160 KW 4240 KW 660 KW
UTILITIES: STEAM GENERATION/CONSUMPTION

HP Steam Consumption Reformer Compressors K-01 to K-05 Excess Steam for power generation MP steam Amine Absorber FT Feed Heaters Generation Flue Gas + ATR o/I Flue Gas + ATR o/I Press Temp (Deg (Kg/cm2.g) C) 193276 kg/hr 42 258 192056 kg/hr 42 450 97944 kg/hr 42 450
HP Steam
200000 kg/hr 290000 kg/hr
42 42
258 450
BROAD SPECIFICATION OF FT REACTORS

FT 40 mm ID tube, 12 m Reactors R-04 A/B/C FT Reactor-1 63 MMKcal/h, 12000 tubes, 4000 tubes/reactor
R-5 A/B FT Reactor-2 31 MMKcal/h, 5800 tubes, 2900/reactor R-06 FT Reactor-3 17 MMKcal/h, 4000 tubes
BROAD SPECIFICATION OF COMPRESSORS

Power, KW HP steam driven (steam @ 42 kg/cm2 g, 450 deg C) K-01 K-02 K-03 K-04 K-05 NG compressor syn gas compressor O2 compressor CO2 compressor Air compressor 2109 17900 1160 4240 6600 Back Press Condensing Back Press Back Press Back Press Turbine type
BROAD SPECIFICATION OF EXCHANGERS

Exchangers E-01 E-02 E-03A E-03B E-04 E-05 E-06 E-07 E-08 E-09 E-10 E-11 RG Boiler Economiser DM water Heater Syn gas Cooler Feed to Reactor FT-1 FT-1 o/I and syn gas exchanger FT-1 product cooler FT-2 feed heater FT-2 O/I and syn gas exchanger FT-2 Product cooler FT-3 feed heater FT-3 product cooler Q, mmKcal/h 147 45 24 54 10.57 4.45 25.6 4.42 3.16 13.6 3.02 10.5
CONCLUSIONS
The various technical components of GTL plant through FT route for natural gas utilization are presented Conceptual design configuration of 6000 BPD GTL plant provided Recycle of CO2 and utilization of Tail gas scheme incorporated for better economy Mass conversion is found to be 64.9% Thermal conversion was found to be 60.1% for H/C liquids and 75.8% considering H2 production
CONCLUSIONS
HP steam(@450 0C, 42 ata) and excess H2 is for export or integration with refinery. GTL is very expensive process. An attempt is made to provide the Facts and Figures of a semi-commercial size GTL plant.
Thank You
rn.maiti@eil.co.in
www.engineersindia.com
Economics for a 7100 BPD GTL Plant at Numaligarh

Case
Installed Cost Annual Expenditure Natural Gas Natural Gas Natural Gas @ Rs @ Rs @ Rs 0.6/SCM* 1.7/SCM 3.0/SCM 350 Feed Stock 13.2 Others 15.9 131.2 350 37.5 19.8 131.2 17 350 66.2 24.3 131.2 8
Annual Revenue
Internal Rate of Return, % 23

* ~ 0.5 US $/Million BTU
In Million US Dollars
Product distribution
C5-12=28% C13-18=22.6% C18+=49.6%
Free Energy Minimization Studies
ASPEN Plus RGIBBS reactor model used

Chemical and phase equilibrium composition can be calculated Approach used is Gibbs free energy minimization (FEM) of the system subject to atom balance constraints Reaction stoichiometry need not be specified
However, with reaction stoichiometry defined, approach to equilibrium can be specified
Conclusions from FEM Studies POX, Steam Reforming, and ATR reactors operate close to thermodynamic equilibrium. ASPEN RGIBBS reactor module can be used for predicting the equilibrium outlet composition for SMR, POX and ATR. The model can be used to determine steam and oxygen feed rates, and operating temperature and pressure required for obtaining syngas of required composition. Design of individual systems such as burner, reactor size, feed distributor, catalyst bed etc is to be decided by specialized group
SYN gas generation
ASPEN RGIBBS reactor module can be used for predicting the equilibrium outlet composition for SMR, POX and ATR POX, Steam Reforming, and ATR reactors operate close to thermodynamic equilibrium. Part of the Natural gas is reformed at high steam to carbon ratio with heat derived from hot syn gas from POX Partially reformed syn gas along with balance natural gas and oxygen is oxidised in second reactor at substoichiometric condition Syn gas from second reactor provides heat for reforming in first reactor
Studies with actual case
Part of the Natural gas is reformed at high steam to carbon ratio with heat derived from hot syn gas from POX Partially reformed syn gas along with balance natural gas and oxygen is oxidised in second reactor at substoichiometric condition Syn gas from second reactor provides heat for reforming in first reactor
Methane Autothermal reforming
Performance Indices
Conversion (H2+CO):- 94%

Conversion H2: Conversion CO:
96.1% 89.9%
C5+ g/NM3 of (H2+CO) converted:- 190 C5+ conversion based on NG= 61% Recycle compressor eliminated for FT reactor
Procedure Validation (POX)

Simulation of Shell Gasification Process (SGP) Data for Natural Gas Feedstock
Parameter Steam/C O2/C CO2/C Case-1 0.176 0.638 0.35 Shell Aspen Shell Case-2 0.176 0.642 Nil Aspen Shell Case-3 0.655 0.684 Nil Aspen
H2/CO 1.6 1.64 1.83 H2 mol% dry 57.46 58.8 61.88 CO 35.83 35.8 33.75 CO2 5.45 4.6 3.1 Engineers India Ltd Delivering excellence through people CH4 1.0 0.64 1.0
1.93 2.0 2.17 63.6 61.71 63.7 33.0 30.85 29.4 2.8 A case6.16for 6000BPD GTL Plant 6.28 GTL: study 24/11/2010 0.4 1.0 Slide Number - 49 of 38 0.37
Procedure Validation (Primary/Secondary Reformer)

Parameter Steam/C O2/C Case1(P=9.5bar) Case2 (P=16.0bar) 2.226 0.2923 Kellogg % Conv H2/CO 99.12 3.564 Aspen 99.73 3.57 4.0 0.239 Kellogg 99.04 4.86 Aspen 99.75 4.72 Case3 (POX) Nil 0.665 Texaco Aspen >99.9 1.745 >99.9 1.659
Procedure Validation (ATR)

Simulation of Haldor Topsoe (HT) Data
Parameter Steam/C O2/C CO2/C HT Temp, C H2/CO H2+CO* CH4+CO2* 1000 2.34 Case-A 0.6 0.58 0.01 Aspen 1020 2.3 HT 1021 2.16 93.4 6.5 Case-B 0.36 0.57 0.01 Aspen 1022 2.15 93.6 6.2 HT 1065 2.02 95.7 4.2 Case-C 0.21 0.59 0.01 Aspen 1100 1.96 95.4 4.4 HT 1031 1.83 91.3 8.6 Case-D 0.51 0.62 0.19 Aspen 1025 1.8 91.5 8.3
Engineers India * Mol % dry Ltd Delivering excellence through people
REACTOR MODEL: FT Reaction

CO + 1 1 CH 1 + H 1 HO O R H 12 2 1 1 / mol 2 = 1kJ
(1 )
CO + 1 1 CH 1+ H 1 H O R H 12 2 1 1 / mol 2 = 1 kJ
(1 )
CO + H 1 CO1+ H 1 O R H 11 1 1kJ / mol 1= 1
(1 )
REACTOR MODEL: Rate equation

Total rate of CO conversion
n mCO = rCO ,i = rCO , FT + rCO , M + rCO , S cat
E A , FT RT
rCO , FT = ko , FT e
1 cH 1111H 1O c + .
cCO
rCO , M = k M ( T ) cH 1 = ko , M e rCO , S = k S ( T ) cH 1 = ko , S e

E A ,M RT
cH 1
E A ,M RT
cH 1 O
REACTOR MODEL: Mass, Momentum and energy balance

Continuty equation for CO
CO u S CZ B rCO ,i ( z ) = 1
(1 )
(1 )
Energy Balance equation u S Ct C p

T Z
U + B rCO ,i ( z ) ( R Hi ) + 1 ( T Tcool ) = 1 D
where
1 U
1 hi
1 Di + ho Do + hmt
Momentum balance equation

P Z
f p G 1( 1 )
1 1 f rp 1 1 221 .221 1
(1 )
fp =
11 1 Re p
+1 1 .1
Process Integration Issues
Large energy streams for syn gas generation and syn gas synthesis The process can be configured to maximize on power/hydrogen/Steam for export Efficient utilisation of tail gas is must to improve economics
Four options were studied
Utilisation of Fuel Gas

(Option-1 Fuel Gas Combustion)
Fuel Gas 2407 TPD
Air Gas Combustion CO2 to vent CO2 2560 TPD
CO 169 TPD CO2 1923 H2 89 N2 74 H/C 144 H2O 8
Power/Steam
Gas to combustion has very low calorific value (1930 Kcal/kg) May require a support fuel
Utilisation of Fuel Gas

(Option-II LPG Recovery followed by Gas Combustion)
Fuel Gas 2407 TPD
Air Gas CO 6% Mol Combustion

CO2 43.6% H2 44.4%
LPG CO 169 TPD Recovery

CO2 1923 H2 89 N2 74 H/C 144 H2O 8
CO2 to vent CO2 2200 TPD
LPG 78 TPD
N2 2.6% H/C 2.9% H2O 0.5%
Power/Steam
Gas to combustion has very low calorific value (1600 Kcal/kg) may require a support fuel Additional recovery of LPG
Utilisation of Fuel Gas (Option-III CO2 recovery followed by gas combustion)

Fuel Gas 2407 TPD
Air CO2 Recovery by DEA CO2 1923 TPD Gas CO 9.8% Mol Combustion
H2 72.6% N2 4.3% H/C 12.6% H2O 0.7%
CO2
Power/Steam
Gas to combustion has high calorific value (9600 Kcal/kg) Size of gas turbine is drastically reduced
Utilisation of Fuel Gas (Option-IV CO2 recovery followed by Adsorption)

Fuel Gas 2407 TPD
CO2 Recovery
CO 9.8% Mol H2 72.6% N2 4.3%
PSA
H2 to Export
CO2 1923 TPD to vent
H/C 12.6% H2O 0.7%
Low Pressure Gas to CO boiler/ Flare
Additional hydrogen is recovered; reduces steam injection to POX CO2 vented out separately
Partial Oxidation
CH4 + 1/2 O2 CO + 2 H2 Combustion chamber at high temperature (12001500C); no catalyst Three process sections: Burner section where combustion occurs (with oxygen to avoid presence of nitrogennitrogen is desirable only when making ammonia) Heat recovery section Carbon black removal section: first by water scrubbing, Then, extraction by naphtha from the sludge GTL: A case study for 6000BPD GTL Plant
EIL NEW DELHI
24/11/2010 Slide Number - 60 of 38
Steam Methane Reforming

CH4 + H2O CO + 3 H2 Carried out in the presence of catalystusually nickel dispersed on alumina support Operating conditions: 850 - 940C, 30 Kg/cm2 Tubular, packed reactors with heat recovery from flue gases using feed preheating or steam production in waste heat boilers Combination of steam reforming with partial oxidation uses the heat produced from partial oxidation to provide heat for steam reforming; resulting combination is autothermal Gases from partial oxidation burner are mixed with steam and sent to the steam reformer
EIL NEW DELHI

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GTL: A CASE STUDY FOR 6000 BPD GTL PLANT

R. N. MAITI, AJAY N. DESHPANDE R&D DIVISION

Delivering excellence through people

24/11/2010 Slide Number- 1 of 38

Key technical components in GTL plant with FT route

Engineers India Ltd Delivering excellence through people

GTL IN GAS ECONOMY

Engineers India Ltd Delivering excellence through people

Basic Gas to Liquids Process

LPGs Propane/Butane Condensate C5+ LPG Naphtha Diesel

Synthesis CO Fischer Synthetic Product Gas Refining H2 Tropsch Crude

THREE STEP PROCESS

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SMR : CH4 + H2O

REACTIONS OCCURRING IN SYN GAS REACTOR

CH4 + CO2 2CO + 2 H2 1 CH4 2H2 + C C + H2O CO + H2 2CO CO2 + C

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SYN GAS REACTORS

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Syncrude (Long chain

-41 kJ/mol H2O + CH4 -206 kJ/mol

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SALIENT FEATURES OF F-T SYNTHESIS

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Fluidised Bed Reactor

Slurry Reactor (MPSR)

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STEP 3 : PRODUCT REFINING Long chain waxy HC

Hydroprocessing Section - Hydroisomerisation / hydrocracking of n-paraffins to iso-paraffins of

Conventional distillation for product fractionation

Gas Processing & Wax Finishing as necessary

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GTL Block Flow Diagram

GTL Products Water treatment Export Steam

Fixed bed FT reactor ( Reactor Model; in-house) Utilization of tail gas

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Mol% 97.53 1.97 0.12 0.02 0 0 0 0.36 0 0

SYN GAS GENERATION

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Engineers India Ltd Delivering excellence through people

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OVERALL MATERIAL BALANCE

CO2 Purge 450 TPD Power Plant TG 454 TPD

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67155 13981 43583 53.7

Kg/h Kg/h Kg/h %

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OVER ALL ENTHALPY BALANCE

Q, mmkcal/h 725 151

436 228 111 38 45 60.1%

OVERALL GTL CHEMISTRY

(12+x) CH4 + (5.5 +2 x) O2 n C12 H26 + (11+2x) H2O + x CO2 With x = 0

With x = 2.4 - 3.6

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CARBON BALANCE THROUGH REACTORS

kmol/h kmol/h kmol/h

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CO2 Purge 10.2 Power Plant TG 16.3

CO2 Purge Power Plant

UTILITY: HP STEAM DRIVEN COMPRESSORS

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UTILITIES: STEAM GENERATION/CONSUMPTION