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Use of agricultural biogas

for electrical power generation


with fuel cells

Dr. Doris Schmack


FAL workshop Biomass fermentation as basis
for high quality fuel for fuel cell applications
fundamentals and special aspects
25.-27.02.2004

The Project
Aims:
Screening of different gas cleaning technologies
Cleaning of agricultural biogas up to fuel cell quality
Operation of a molten carbonate fuel cell with cleaned
biogas
Project timeframe: 2002-02-01 to 2003-11-30

Project partners:

Funded by:

Under the scientific


supervision of:

Introduction
Conventional CHP

Fuel Cells

Electrical Efficiency

35 %

50 %

Waste Heat

80 C

400 C

Noise Emissions

strong

little

NOx
SO2

little

state-of-the-art

under development

Pollutants

Development Status

Overview
Fuel cells
Gas cleaning target
Biogas composition
Specifications of fuel cells
Gas cleaning
Technologies
Experiments
Results
Gas cleaning concepts
Operation of the laboratory fuel cell
Summary and perspective

Overview
Fuel cells
Gas cleaning target
Biogas composition
Specifications of fuel cells
Gas cleaning
Technologies
Experiments
Results
Gas cleaning concepts
Operation of the laboratory fuel cell
Summary and perspective

Fuel cell types

high temperature
fuel cells

low temperature
fuel cells

Anode
Alkaline FC (AFC)

Cathode

H2
H2O

Polymer Electrolyte FC
H2
(PEFC)
Phosphoric acid FC (PAFC)

O2
OH-

H2O
O2

H+

H2O

Molten Carbonate FC
(MCFC)

H2
CO2
H2O

CO3

Solid Oxide FC (SOFC)

H2
H2O

O2-

2-

room temp.

O2
CO2
O2

30-80 C
180-220 C
650 C

1000 C

Fuel cells:
General aspects
CH4

Reforming of biogas necessary:


CH4 + 2 H2O CO2 + 4 H2
CH4 +
H2O CO + 3 H2
CO +
H2O CO2 +
H2

reforming reaction
Shift reaction

Reforming at high temperatures.


Low temperature FC: external reforming.
S compounds

harmful to Ni catalysts in reformer


must always be removed!

CO2

dilution effects
worse kinetics
lower cell voltage

Fuel cells:
Individual aspects
AFC

pH sensitive
CO2 harmful (both in fuel and oxidizer)
Operation on pure H2/O2

PAFC

CO2 < 3 Vol%


Separation of CO2 necessary

PEFC

competing adsorption on anode catalyst


CO from reforming harmful
high standards for shift reaction

MCFC

operating temperature approx. 650C


high quality heat available
CO2 is reactant
higher cell voltage
higher overall efficiency

Reactions in MCFC

Catalyst

CH4 + 2 H2O CO2 + 4 H2

Anode / Catalyst

H2O
CO2

H2 +

CO3--

H2O + CO22 + 2 e-

Matrix w/ electrolyte CO3--

Reforming
reaction

Anode reaction
2 e-

CH4, H2O

Cathode / Catalyst

CO22 + O2 + 2 e- CO3--

O2

Cathode reaction

off gas

MTU CFC laboratory stack

Stack with 10 single cells


Operating temperature 650 C
Maximal power 300 Watt
Biogas consumption < 3 l/min

Overview
Fuel cells
Gas cleaning target
Biogas composition
Specifications of fuel cells
Gas cleaning
Technologies
Experiments
Results
Gas cleaning concepts
Operation of the laboratory fuel cell
Summary and perspective

Biogas composition
in Haimhausen

Major components

Minor components

CH4

50-60 %

H 2S

< 1000 ppm

CO2

35-40 %

COS

< 1,5 ppm

H 2O

TD < 25 C

NH3

< 50 ppm

O2

<2%

Siloxanes

n. d.

N2

<5%

Halogenated
Hydrocarbons

n. d.

Gas cleaning targets

raw biogas
Haimhausen

specification
MTU

H2O

rH

up to 100 %

< 60 %

H2S

ppmV

norm. <300
max. 1000

< 0,1

COS ppmV

< 1,5

< 0,1

NH3

ppmV

< 50

< 400

HCl

ppmV

n. d.

< 0,1

O2

Vol.%

<4

Note
condensation,
corrosion, protection of
activated carbon
elimination by
conventional
technologies
most conventional
technologies fail

no cleaning necessary

Sulfur compounds
... contaminate the MCFC reforming catalyst

Sulfur compounds in the biogas in Haimhausen:


H2S

approx. 50-100 ppmV, peaks 300-1500 ppmV


strong periodic changes
easy to remove with many technologies

COS

approx. 0.3-1.5 ppmV (in Haimhausen)


little variation with time
most established technologies fail

Higher sulfur compounds not analyzed

COS
New in biogas context
Detection by own GC analyses
Concentration (up to 1.5 ppmV) high enough to poison
catalyst
Problem: Conventional technologies fail
most activated carbons
iron oxides

But:
Low concentration
use of expensive adsorbents possible

Overview
Fuel cells
Gas cleaning target
Biogas composition
Specifications of fuel cells
Gas cleaning
Technologies
Experiments
Results
Gas cleaning concepts
Operation of the laboratory fuel cell
Summary and perspective

Gas cleaning technologies


H2S

COS

CO2

Biolog. Desulfurization

Activated carbon

Iron oxide/hydroxide

Iron complexes

Tenside scrubbing

Amine process

PSA
Water scrubbing

Membrane separation

Gas cooling

other

Glycol dehydration
Selexol

H2O

Gas cleaning:
Analytical equipment

Biogas analyzer SSM 6000


CH4, CO2, O2 and H2S
Gas chromatograph GC 3800
trace analysis of H2S and COS
Humidity sensor GMH 3350
H2O
Laboratory methods
NH3

Biological desulfurization
Oxidation of H2S to elemental sulfur by
sulfur bacteria after addition of air/oxygen

very effective at high H2S concentrations


cleaning down to approx. 50 ppmV
simple technology, minimal investment und operating
costs
State-of-the-art at
most current plants

Other H2S cleaning steps


can start at 50-100 ppmV

Desulfurization with
activated carbon
Effective elimination of H2S down to <0.1 ppmV
Simple setup, low investment costs
Operating costs depend on
H2S content in raw biogas
Drawbacks:
not regenerable
Problems with high
concentrations
sensitive to humidity
Prior gas drying (specially in summer)
Very suited as secondary cleaning step
State-of-the-art (several suppliers)

Activated carbon:
Elimination of H2S
H2S Rohgas
100

H2S Reingas

ppm

10

0,1

0,01
16.06. 17.06. 18.06. 19.06. 20.06. 21.06. 22.06. 23.06. 24.06.

Activated carbon:
Elimination of COS
1

AK 1

nach Reinigung

0,8
COS [ppm]

COS [ppm]

0,8

vor Reinigung

0,6
0,4

0
12:00

12:14

12:28

nach Reinigung

0,6
0,4

12:43

12:57

13:12

0
12:57

13:26

AK 3

nach Reinigung

0,6
0,4
0,2
0
13:12

13:26

13:55

14:24

vor Reinigung

AK 4

0,8
COS [ppm]

COS [ppm]

AK 2

0,2

0,2

0,8

vor Reinigung

14:52

15:21

15:50

vor Reinigung
nach Reinigung

0,6
0,4
0,2

14:24

15:36

16:48

0
06.08.

09.08.

12.08.

15.08.

18.08.

21.08.

Desulfurization with
iron oxides
Good elimination of H2S down to <0.5 ppm
Simple setup, low investment costs
Operating costs depend on raw gas,
lower than with activated carbon
Drawbacks:
big reaction volume
not regenerable
no elimination of COS
secondary cleaning step necessary
Suited for small and moderate H2S loads
State-of-the-art (often used in sewage works)

Desulfurization with
iron oxides
H2S Reingas

1000

H2S Rohgas

H2S [ppm]

100

10

0,1
30.01.

31.01.

01.02.

02.02.

03.02.

04.02.

Iron complexes
Contact with iron complex solutions in column
formation of elemental sulfur at presence of oxygen

cleaning down to approx. 5 ppmV H2S


low priced iron complexes available
regenerable, minimal operating costs
moderate investment costs

Drawbacks:
separation of sulfur, plugging
chemical stability
Commercial processes available (e. g. LO-CAT)

Iron complexes:
experiments
H2S Rohgas

1000

H2S Reingas

H2S [ppm]

100

10

1
12.12.

13.12.

14.12.

15.12.

16.12.

17.12.

18.12.

19.12.

Efficiency about 95 %
Suited for high H2S loads / bigger plants
Secondary cleaning step necessary for FC operation

Amine process
Selective removal of CO2 and/or H2S
Dependant on pressure and amine
Best amine for pure desulfurization: MDEA
Conventional design:
6-10 bars pressure
good cleaning performance
high costs at small plants
Aim:
unpressurized process, cost reduction
Question:
Still enough cleaning performance?

Unpressurized amine process:


experiments
1000

H2S - Rohgas

H2S - Reingas

H2S [ppm]

100

10

1
03.12.

04.12.

05.12.

efficiencies about 80 %
still relatively high investment costs
rich gas must be treated separately

06.12.

Membrane processes
Use of the selectivity of suited membranes for separation
of CO2, H2S and H2O
No regeneration of separation medium necessary
High operating, medium investment costs
Drawbacks:
high pressure (energy consumption)
selectivity vs. permeability
methane loss with permeate (up to 30 % of costs)
very expensive

Gas drying
Aims of gas drying:
avoid condensation (pipe plugging)
protection against corrosion
protection of other units like activated carbon
Possible processes:
gas cooling
electrical energy for cooling, icing up
Selexol
PSA/TSA (pressure/temperature swing adsorption)
high pressure high energy demand
Glycol dehydration with TEG

unpressurized, use of CHP/FC spill heat

Gas drying:
Glycol dehydration
Gas drying by contact with triethylene glycol (TEG)
9 Closed, low-maintenance system
9 Use of CHP/FC spill heat
low operating costs
9 Dewpoint reduction under 10 C
(single stage design)
9 reliable inhibition of
condensation
9 sufficient drying for
operation of activated carbon

Results
glycol dehydration
30

Taupunkt [C]
dewpoint
[C]

25
20

vor Trocknung
before
drying

15
10
5
0
09.05.03

nach Trocknung
after
drying

10.05.03

11.05.03

12.05.03

13.05.03

3 heat exchangers
higher investment costs
higher electrical energy demand
higher total costs than gas cooling

Gas cleaning concepts


1000

H2S [ppm]

100
10
1
0,1
50

150

500

plant
size
[m/h]

Overview
Fuel cells
Gas cleaning target
Biogas composition
Specifications of fuel cells
Gas cleaning
Technologies
Experiments
Results
Gas cleaning concepts
Operation of the laboratory fuel cell
Summary and perspective

Fuel cell operation

Overview
Fuel cells
Gas cleaning target
Biogas composition
Specifications of fuel cells
Gas cleaning
Technologies
Experiments
Results
Gas cleaning concepts
Operation of the laboratory fuel cell
Summary and perspective

Summary

Screening of gas cleaning technologies


Overview over possibilities and costs
Compliance with specifications of gas quality
Cost-effective gas cleaning possible
Multi level gas cleaning concept
Very promising fuel cell performance with biogas
Interruption of fuel cell operation very harmful for
MCFC

Perspective
Further examination of certain
gas cleaning technologies
Production of gas cleaning units
HotModule operation on biogas
Cost reduction - funding

Thank you!