High-Pressure Steam Reforming of Ethanol

Sheldon H.D. Lee, Rajesh Ahluwalia, and Shabbir Ahmed Argonne National Laboratory
Poster presented at 2005 Fuel Cell Seminar Palm Springs, CA, Nov. 13-17, 2005

Objective
Study the pressurized steam reforming of hydrated ethanol for H2 production for a refueling infrastructure
Study reforming equilibria and kinetics at elevated pressures Evaluate high-pressure reforming options, e.g. membrane reactors

Advantages
Ethanol fuel
Renewable liquid fuel Easy to transport High energy density (relative to compressed or liquefied gases) Environmentally more benign (compared with petroleum-derived fuels)

High-pressure steam reforming

More options for H2 purification technique (membrane separation, PSA, etc.) Energy cost saving for H2 compression

Process Challenges
Unfavorable H2 yield at thermodynamic equilibrium Higher tendency for coke formation Choice of material for high-temperature/ high-pressure operation

Approach
Study thermodynamic equilibria
Effects of temperature, pressure, and steam-to-C ratio Compare high-pressure reforming, compressing reformate, compressing high-purity hydrogen Evaluate purification options with high-pressure reformate Set up a micro-reactor test facility for experimental testing Use Chemcad to perform system modeling on efficiency and H2 yield associated with alternative process designs

Evaluate system options with respect to efficiency and cost

Establish reforming kinetics through experiments and models

Hydrogen

Air

SR Reformer

Membrane Separator

Burner

Exhaust

Heat Exchanger

Ethanol+Water

Approach

Use membrane-reformer to shift the thermodynamic equilibrium back towards higher H2 yield
Use GCTool to perform system modeling on efficiency and H2 yield associated with alternative process designs Conduct micro-reactor experiments to maximize H2 yield as a function of operating parameters: catalyst formulation, temperature, pressure, S/C molar ratio, and space velocity Characterize potential membrane materials for their effectiveness, stabilities, and selectivities

Background
Hydrogen compression represents a significant power loss
40 5-Stage Intercooled Compressor Compressor Efficiency: 70% Mechanical Efficiency: 97% Electric Motor Efficiency: 90%

35
Compression Loss / LHV (%)

31.5 30 27.5 25 23.5

FinalPressure: 6000 psi

21.3 20 19.8 18.5

15

10 1 2 3 4 5 6 7 8 9 10 Initial Pressure of Hydrogen, atm

Producing hydrogen at elevated pressures represents a significant improvement in process efficiency.

High pressure increases CH4 formation at the expense of H2 Ethanol steam reforming reaction: C2H5OH (l) + 3H2O(l) = 2CO2 + 6H2, H = +348 kJ Eq. (1)

80 70

Product, %-wet

60 50 40 30 20 10 0 0

C2H5OH + 3H2O Products T = 700C

H2O
Effect of pressure on the equilibrium product gas compositions from the steam reforming of ethanol.

CH4 H2 CO2 100 200 CO 300

Pressure, atm

Tendency to form carbonaceous deposits (coke) increases at higher pressures

COx Selectivity, % =
120

Mols of CO + CO2 Produced G-Atoms of C in Feed

X 100

COx Selectivity

100 80

S/C = 6, T = 700C

60 40 20 0 0 1000

COx

2000

3000

4000

5000

Pressure, psia
COx selectivity as a function of pressure

Potential remedies for adverse pressure effect

Remove H2 or CO2 to shift equilibrium High temperature and high S/C molar ratio in the feed increases H2 yield and reduces undesirable CH4
Product Yield, mol/(mol-EtOH)
S/C = 6, P = 2000 psia

Product Yield, mol/(mol-EtOH)

6 5 4 3 2

T = 700C, P = 2000 psia

3 2 2 1 1

H2

H2

CH4 CO2 CO

CO2
1

CO
0
600 700 800 900

CH4
1000

0
1 2 3 4 5 6

Temperature, C

S/C Ratio

Effect of temperature and steam-to-carbon ratio on the equilibrium product gas composition from the steam reforming of ethanol.

System Modeling
Reformer efficiency achieves 89% at stoichiometric S/C (= 1.5), followed by a linear decline at higher S/C
, % = [LHV of H2 produced per Eq. (1) Heat of reaction of Eq.(1)] 100/[LHV of Ethanol] where = efficiency LHV = lower heating value
100

Theoretical Efficiency % (LHV)

80 60 40 20 0 1 2 3 4 5 6 7 8 9 10

Effect of S/C molar ratio on the efficiency of an ideal reformer

S/C Ratio

Simulated process efficiency approaches 70% at a S/C = 5

C2H5OH + xH2O(l) CO2, CO, H2, H2O(g), CH4, CnHm, Chemcad simulated process based on Steam-reformer at equilibrium Hydrogen separation with membrane
90% hydrogen recovery
equilibrium

Combustion of raffinate to generate heat Heat exchange to reformer feeds Exhaust at 200C Efficiency decreases with increasing S/C
100 90

Efficiency % of LHV

80 70 60 50 5 6

Ideal Reaction Simulated Process

7 8 9 10

Steam-to-C Ratio

The total moles of H2 recovered are insensitive to reforming pressure in a two-stage reforming/membrane separator system
35 H 2 Mols Total (Stage 1+2) H 2 Mols (Stage 1) 30 25 20 15 10 5 0 100 150 200 250 300 350 400 Two-Stage Reforming Reforming T = 800 o C H 2 Separation in Stage 1 = 90% S/C = 3.5 H 2 Pressure (Stage 1) H 2 Mols (Stage 2) H 2 Pressure (Stage 2) 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

Reforming Pressure (atm)

Effect of the system pressure on the efficiency of one- and two-stage reformer-separator systems

H2 Recovered per Mole of Ethanol

H2 Pressure (atm)

High-pressure ethanol steam-reforming experiments are conducted to maximize H2 yield with respect to temperature, pressure, S/C molar ratio, and space velocity

Micro-reactor test facility

Ethanol-Water Vaporizer TC

TC
Furnace

TC Ethanol-Water Mixture HPLC Pump TC Micro Reactor

Test conditions: 600o-700oC 20-1000 psig The ethanol-water mixture is prevaporized before entering the reactor Sud-Chemie Ni catalyst in granules

Cooler

Vent
Micro-GC Analyzer

Switching Valve
Back-Pressure Regulator Gas-Liquid Separator Waste Container

Chiller

Ethanol decomposition as a function of temperature

CO, CH4, CO2, C2H6, and C2H4 Gas Composition (N2-Free Base), % (dry)

1.0 1000 psig S/C = 20 0.8 1000 psig S/C = 12 1000 psig S/C = 20 500 psig S/C = 20

105

H2
Dehydrogenation occurred to form Acetaldehyde: C2H5OH = H2 + C2H4O

H2

0.6

0.4

TC5 = ~470oC Started Acetaldehyde decompostion C2H4O = CH4 + CO TC5 = ~440oC Started Ethanol dehydration C2H5OH = C2H4 + H2O

95

CO CH4
90

Ethylene Ethane CO2

85

0.2

CO
0.0 0

CH4
50 100

CO2
150 200 250 300 350 400

450

500

80 550

Time, min

Gas composition of vaporized ethanol/water mixture from vaporizer (Vaporizer temperatures = 390o - 490oC)

At vaporizer temp. < 490oC, ethanol decomposed < 12% for S/C = 12 & 20 and 1000 psig < 3% for S/C = 20 and 500 psig

H2 Gas Composition (N2-Free Base), % (dry)

100

Partially decomposed ethanol feed effectively reformed by Ni catalyst bed

4 Legend Feed rate BC- Before catalyst bed AC- After catalyst bed 6

H2 H2

H2

H2
5

CO, CH4, & CO2, Product Yields, mol/mol of C 2H5OH

4 0.70 g/m in BC 0.70 g/m in AC 0.50 g/m in AC 0.30 g/m in AC 0.30 g/m in BC 1.00 g/m in BC 1.00 g/m in AC

CO2 CO2 CO2 H2 CO2 H2 CH4 CO

150 200 250 300 350 400

H2 Product Yields, mol/mol of C 2H5OH

H2
1

CO2

CH4 CO

CH4

CH4 CO

Product yields as a function of time

Feed: S/C =20 Catalyst bed temp. = 620o-650oC Pressure = 1000 psig

0 0
0.1 Legend Feed rate BC- Before catalyst bed AC- After catalyst bed 0.70 g/m in BC 0.70 g/m in AC 0.50 g/m in AC

50

100

0 450

Time, min

Product Yield, mol/mol of C 2H5OH

0.08

0.30 g/m in AC

0.30 g/m in BC

1.00 g/m in BC

1.00 g/m in AC

0.06

Ethane
0.04

Ethane Ethane

Ethylene
0.02

Ethylene

0 0 50 100 150 200 250 300 350 400 450

Time, min

The catalyst bed converted the decomposition products into reformate Twice the CH4 50% less CO, and undetectable ethane and ethylene 100% carbon conversion was achieved

3 times more H2 and CO2

Ni catalyst slowly degraded with time

4.0 3.5

CO, CH4, & CO2, Product Yields, mol/mol of C 2H5OH

3.0 2.5 2.0 1.5 1.0 t = 50 2.37 t = 350 1.89

CO2
0.5 0.0 0

0.77 0.48 0.19 50 100 150 200 250 300 0.56 0.39 0.21 350 400

CH4 CO

Product yields and carbon conversion as a function of time Feed: S/C =12 GHSV = 85,600 h-1 Catalyst bed temp. = 630o-660oC Pressure = 1000 psig
400

120

Time, min

100

Gaseous Carbon Conversion, %

t = 50 80 76.1

t = 350

60

63.2

40

20

0 0 50 100 150 200 250 300 350

Time, min.

Ni catalyst has been known* to deactivate as a result of coke formation The condensate collected from the test contained 4.53% ethanol,

0.84% acetaldehyde, and 0.06% acetic acid

*Agus Haryanto, Sandun Fernando, Naveen Murali, and Sushil Adhikari, Current Status of Hydrogen Production Techniques by Steam Reforming of Ethanol: A Review, Energy & Fuel, 2005, 19, 2098-2106

Effect of pressure on product gas composition

80

Product Composition, % (dry)

60

Feed: S/C = 12 Temp. = 650oC GHSV = 85,600 h-1

P = < 20 psig P = 1000 psig

40

20

0 H2 CO CH4 CO2 Ethylene Ethane

Effect of pressure on product gas composition agrees with equilibrium

predicted trend

Effect of gas hourly space velocity on product yields

1.0 6

0.9

H2
0.8

Avg. CO & CH4 Product Yields, mol/mol

0.7

0.6

Feed: S/C = 20 Temp. = 620o-650oC P = 1000 psig

CH4

0.5

0.4

0.3

CO2

0.2

CO
0.1 Ethane & Ethylene 0 20,000 40,000 60,000 GHSV, h -1 80,000 100,000 120,000

0.0

0 140,000

Increasing GHSV decreases H2, CO2, and CO yields,

but increases CH4 yield

Avg. H2 & CO2 Product Yields, mol/mol

Conclusions
Steam reforming of ethanol at elevated pressures can lead to better process efficiencies. Elevated pressure process presents challenges in unfavorable thermodynamic equilibrium, tendency for coke formation, and material choice. Homogeneous decomposition of ethanol occurred at temperatures close to boiling point of ethanol-water solution at pressure. High pressure increases CH4 formation at the expense of H2 yield

Future Work
Study kinetics and define operating parameters for maximizing H2 yield Evaluate system designs that take advantage of pressurized steam reforming

Acknowledgements
This work is supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen, Fuel Cells, & Infrastructure Technologies Program

The submitted manuscript has been created by the University of Chicago as Operator of Argonne National Laboratory (Argonne) under Contract No. W-31-109-ENG-38 with the U.S. Department of Energy. The U.S. Government retains for itself, and others acting on its behalf, a paid-up, nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government.

Argonne National Laboratory is managed by The University of Chicago for the U.S. Department of Energy