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Process Design & Profitability Analysis of

Natural Gas to Liquid Fuels Using


Ion-Transport Membrane Technology
Doug Muth, Eve Rodriguez, Christopher Sales
Faculty Advisor: Dr. Stuart Churchill
Senior Design Project 2005

Gas-to-Liquids (GTL)
What is Gas-to-Liquids?
Conversion of natural gas to liquid fuels (e.g., diesel).
Natural Gas
SYNGAS
PRODUCTION
FISCHER-TROPSCH
SYNTHESIS
HYDROCRACKING
Diesel

Motivations for GTL


Transportation
Natural gas reserves are often too far from gas pipelines.
Transporting liquid or electricity is more feasible.

Environmental
US EPA regulations require reduction of sulfur content.
GTL naturally produces extra low-sulfur diesel.

High Fuel Quality


High cetane numbers for GTL diesel.
Low aromatic and olefin content.

Design Basis
GTL plant to be located in Ohio.
Minimum DCFRR of 12% required.
Evaluate ion-transport membrane
technology for syngas production.

GTL Conversion Strategies

Direct Conversion of CH4 to Methanol

Too difficult to control.


High activation energy required.
No suitable catalyst.

Indirect Conversion Via Synthesis Gas

Syngas converted to long-chain hydrocarbons by the


Fischer-Tropsch (FT) reaction.
Syngas production methods:
1. Steam reforming of methane.
2. Dry reforming of methane.
3. Partial oxidation of methane.

Production of Synthesis Gas


Steam reforming of methane.
CH4 + H2O CO + 3H2 (endothermic)

Dry reforming of methane.


CH4 + CO2 2CO + 2H2 (endothermic)

Partial oxidation of methane.*


CH4 + O2 CO + 2H2 (exothermic)
*

Optimal H2/CO ratio (2:1) for FT synthesis.

Partial Oxidation of Methane


Nearly pure O2 required for partial oxidation.
O2 Purification Methods
Cryogenic distillation of air.
Hundreds of equilibrium stages required.
High energy costs of refrigeration.
Substantial capital cost (insulation, compressors, etc).

New Alternative: Oxygen ion-transport membrane.


Potentially cheaper than cryogenic air separation plant.
Membrane not yet commercialized, cost not known.

Ion-Transport Membrane
CH 4 + 1/2 O2

CO + 2H

CH 4 + H O
2

CO + 3H 2
Oxygen
-Depleted
Air
Oxidizing
atmosphere

Syngas
Reducing
atmosphere
Reforming
Catalyst
Natural Gas
Steam

O 22e-

Oxygen
Reduction
Catalyst
Air

Membrane
Courtesy of Air Products, Inc.

Membrane provides O2 for syngas production.

Ion-Transport Membrane
Membrane material: non-porous mixed conducting metallic oxides.
Perovskites
LaxA1-xCoFe1-yO3-z

(La = Lanthanides, 0<x<1, A = Sr, Ba, or Ca, 0<y<1, z = number which renders the compound charge neutral)

Conducts O2- through membrane vacancies.


O2 partial pressure gradient creates electrochemical driving force.

Courtesy of Air Products, Inc.

GTL Process Overview


GTL process divided into four main parts:
1. Convert CH4 to CO/H2 with membrane reactor.
CH4 + 1/2O2 CO + 2H2

2. Convert CO/H2 to synthetic hydrocarbons (FischerTropsch).


nCO + 2nH2 (-CH2-)n + H2O

3. Hydrocrack synthetic hydrocarbons to fuels (mainly


diesel).
4. Separate hydrocracked product into standard oil fractions.

GTL Process Overview


Natural Gas
HP Steam

1.

Air

ITM Reactor
(Syngas
Production)

Turbine and
Generator

Syngas
Excess Electricity

2.

Fischer-Tropsch
Synthesis
H2

3.

Synthetic wax

Hydrocracking
Fuel Gas
Hydrocracked wax

4.

Heavy Gas Oil


Fractionation
Tower

Naphtha
Kerosene
Diesel

Key Equipment Details


ITM Reactor

Fischer-Tropsch
Reactor

Hydrocracker

Distillation

ITM Reactor Vessel


Function:

Convert methane into synthesis gas.

Design Details:

T = 1650oF, P = 300 psig


Horizontal shell/tube reactor.
45,000 ft2 membrane area required.
2900 membrane tubes (OD = 2 in, L = 30 ft).
Inconel Alloy for shell and tubes.
Shell packed with 39,300 lbs nickel/alumina catalyst.

CH4 + O2 CO + 2H2
CH4 + H2O CO + 3H2

Praxair ITM Reactor Model (2002)

Steam Reforming
Catalyst Bed
ITM Membrane

Gottzmann et al. (US Patent)

Praxair ITM Reactor Model (2003)


Syngas

Methane & Steam

Steam Reforming
Catalyst Bed

Halvorson et al. (US Patent)

ITM Membrane

Air

O2-depleted Air

Entire ITM Section

Key Equipment Details


ITM Reactor

Fischer-Tropsch
Reactor

Hydrocracker

Distillation

Fischer-Tropsch Reactor
Function:

Produce long-chain hydrocarbons from synthesis gas.

Design Details:

T = 400oF, P = 400 psig


Slurry volume of 3400 ft3.
276,000 lbs cobalt/ruthenium catalyst required.
Synthesis gas bubbled through bottom.
13 ft diameter ensures proper gas superficial velocity.
Dynamic settler separates molten wax from catalyst
particles.
Stainless steel construction.

nCO + 2nH2 (-CH2-)n + H2O

Fischer-Tropsch Products
Anderson-Schulz-Flory Distribution
M{n} = (1 - ) n-1
W{n} = n (1 - )2 n-1
For Co/Ru, = 0.94
Mole Fraction M{n}

Weight Fraction W{n}

Diesel

Entire Fischer-Tropsch Section

Key Equipment Details


ITM Reactor

Fischer-Tropsch
Reactor

Hydrocracker

Distillation

Hydrocracker Reactor
Function:

Cracks and isomerizes long-chains to shorter chains.

Design Details:

Molten wax trickles down from top.


Hydrogen-rich stream fed through bottom.
T = 725oF, P = 675 psig
Height = 27 ft, ID = 9 ft
30,000 lbs catalyst bed (0.6% Pt on alumina).
H2/Wax = 0.105 kgH2 / kgwax

WHSV = 2 kgwax / hour - kgcat.


Stainless steel construction.

Modeling the Hydrocracker


From Hydrocracking Kinetic Model
(developed by Pellegrini et al).
Lumped hydrocarbon groups
Hydrocracking reaction pathways
Cracking and isomerization occur.

Modeling the Hydrocracker


From Hydrocracking Kinetic Model
(developed by Pellegrini et al).

MW drops along reactor length.


Longer chains crack more quickly.
Isomerization improves cold properties.

Entire Hydrocracker Section

Key Equipment Details


ITM Reactor

Fischer-Tropsch
Reactor

Hydrocracker

Distillation

Fractionation Tower
Function:

Separates HC effluent into standard oil fractions.

Design Details:

P = 10 psig, Tcondenser = 100oF, Tbottoms = 725oF


Feed preheated to 725oF and fed on bottom stage.
Steam injected on bottom stage (0.5 lb / bbl bottoms)
16 Koch Flexitrays.
6 ft tray diameter, 2 ft spacing 40 ft height
Diesel drawn off at tray 12.
Kerosene drawn off at tray 8.
Naphtha & Fuel Gas in overhead.
Heavy Gas Oil recycled to hydrocracker
Sidedraws eliminate need for multiple towers.

Entire Fractionation Tower Section

Auxiliary Units

Process Summary
Raw Materials

Products

Natural Gas 1.95 MM SCFH

Diesel
Kerosene
Naphtha
HGO
Electricity

2,700 bbl/day
1,800 bbl/day
200 bbl/day
90 bbl/day
10,500 kW

US Proven Natural Gas Reserves (2003)


For a 15 year plant life, required puddle
size for plant is 0.263 trillion standard
cubic feet (TSCF).
1.126 trillion SCF available in Ohio.
U.S. Total: 189 TSCF

Profitability Analysis

Membrane price unknown.


Determine maximum membrane cost that still allows profitability.
Criterion: minimum IRR of 12%

Variable Cost Summary

Natural gas price trumps other variable costs of operation.

Assumed Product Prices

Diesel Fuel
Kerosene
Naphtha
HGO
Electricity

$1.82/gal*
$1.24/gal
$1.00/gal
70/gal
6/kW-hr

Source: US DOE

*Assumed 15% higher than typical diesel due to low-sulfur and high
cetane number.

Membrane Cost Tolerability


Membrane costs that give IRR = 12%
NG cost cannot exceed $6/MSCF.

PROBLEM:
Analysis assume no price correlation
between liquid fuels and natural gas!

Energy Price Correlation


Hydrocarbon prices historically show correlation.

Energy Price Correlation


Regression Analysis
R = 0.85
Diesel changes 16/gal for every $1/MSCF change in NG.
1.800
1.600

Actual
Predicted

Diesel Price ($/gal)

1.400
1.200
1.000
0.800
0.600
0.400
0.200
0.000
0

Natural Gas Price ($/MSCF)

New Membrane Cost Tolerability


Shallower slope less dependence on NG price.
Maximum tolerable NG cost increases to $12.5/MSCF.

Without price correlation

With price correlation

Sample Cash Flow


Assume NG costs $5/MSCF
Assume $5 million membrane investment.
NPV @ 12% is $59 million.

Why not just burn it?


Alternative: Burn the natural gas across a gas turbine to create
electricity.
Using data from 2001 senior design project Combined-Cycle Power
Generation by Beaver, Matamoros, and Prokopec.
290 MW possibility @ 57% total efficiency.
Total BM cost of plant: $150 million ($22.6 million + membrane)
Annual sales: $145 million ($68 million)
Total annual costs: $120 million ($38 million)
NPV @ 12% is -$118 million ($59 million)
IRR is only 2.7%

Not a competitive alternative!

Conclusions
Profitability is weakly dependent upon natural gas
cost.
ITM/GTL profitable at any NG price below $12.5/MSCF.
Current NG prices well-below this limit ($6/MSCF).

Membrane price unlikely to be a prohibitive factor.


NG price of $5/MSCF $26 million max membrane cost
allowed ($572/ft2).
BM Cost of plant without membrane is approx. $22.6
million.

Power plant unlikely to be competitive alternative.

Recommendations
Confirm ITM O2 flux rate
Flux rate of 10 cm3/cm2-min assumed for design.
Current research report values from 0.1 to 20 cm3/cm2-min.
Required membrane area strongly dependent on O2 flux
rate.

Determine ITM stability and durability.


Investigate low-sulfur, high cetane diesel price.
Recommend ITM/GTL plant construction
once membrane is commercialized.

Acknowledgements
Professor Leonard Fabiano
Dr. Stuart Churchill
Industrial Consultants
Gary Sawyer
Peter Schmeidler
Adam Brostow
William Retallick
David Kolesar
Henry Sandler
John Wismer

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