CarboTech Engineering GmbH

Intelligent Utilization of Biogas –

Upgrading and Adding to the Grid

Dr. Alfons Schulte-Schulze Berndt

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Content – presentation

General Guidelines for Sustainable Biogas Utilization

Route of Biogas Utilization
Why Upgrading Biogas to Natural Gas Quality
Conversion Route from Biomass to Heat and Power
Specification of Raw Biogas / Upgraded Biogas / Grid Quality
Processes for Biogas Upgrading
Principle of Biogas Upgrading by Means of Gas Scrubbing
Process Scheme Biogas Upgrading by Water Scrubbing System
Principle of Biogas Upgrading by Means of Pressure Swing Adsorption
Process Scheme Biogas Upgrading using PSA-Process
Comparison of Various Biogas Upgrading Systems
Principle of ZETECH4© - Zero Emission Technology
Energy Balance Sheet Biogas Upgrading
Plant Examples – Biogas Upgrading Plants
Conclusion

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 General Guidelines for Sustainable Biogas Utilization

Minimize energy and utilities input for biogas conversion into biomethane,
power and heat.

Maximize conversion efficiency factors.

Minimize losses of biomass and biogas.

Avoid methane emission to atmosphere.

Keep transport channels for biomass, biogas and biomethane short.

While converting biogas to power and heat utilize both energy streams
completely.

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Route of Biogas Utilization

biogas
tra
ion diti
vis ona
l
future

steam reforming methane gas motor /

H2-generation enrichment cogeneration plant

H2-purification

hydrogen natural gas substitute power / heat

"biomethane"
disadvantage:
lower heat utilization
low electrical effiency factor
industrial stationary vehicle
gas fuel cell fuel
vehicle feed into natural gas grid
fuel (highest efficiency factor)
Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Why Upgrading Biogas to Natural Gas Quality?

Precondition to get access to natural gas grid

Grid routes opens access to intelligent biogas utilization:

- decentralized cogeneration plants – total utilization of power and heat

- advantages biomethane versus biogas cogeneration

-- higher electrical efficiency
-- lower capital cost
-- lower service cost
-- longer lifetime

- industrial heat generation – high efficient and low emissions

- vehicle fueling station – CO2-neutral and environmental friendly

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Conversion Route from Biomass to Heat and Power

Biogas-Upgrading
Biogas-Generation

future biomass

biogas
Bio-natural
gas
5 – 9 bar

Decentralized Biogas Utilization Centralized Biogas Utilization

feeding natural gas
station grid gas engine power (1/3)
industry & households heat (2/3)

Disadvantage:
CNG-filling station low energy utilization factor, no
utilization of heat

HPCG-plant power Advantage:

heat complete utilization of heat and
power
Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Specification of Raw Biogas / Upgraded Biogas / Grid Quality

component symbole raw biogas biomethane DVGW260/grid quality

methane CH4 55 - 70 % > 97 % no minimum values

carbon dioxide CO2 30 - 45 % <1% <6%
nitrogen N2 <2% <2% no maximum values
oxygen O2 < 0,5 % < 0,5 % < 0,5 %
hydrogen sulfide H2 S < 500 ppm v < 5 mg/Nm3 < 5 mg/Nm3
hydrocarbons CxHy < 100 ppm v < 10 ppm v < condensation point
water H2O saturated < 0,03 g/m3 < condensation point
calorific value HS,M 6 - 7,5 kWh/m3 max. 11 kWh/m3 8,4 - 13,1 kWh/m3
wobbe index WS,M 6 - 11,5 kWh/m3 max. 14,5 kWh/m3 12,8 - 15,7 kWh/m3

Note: Biomethane has to match with gas quality in the grid at injection point.

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Processes for Biogas Upgrading

Major target: recover methane, remove impurities CO2, H2S, N2, O2, H2O and other

process general description

gas scrubbing CO2 is adsorbed by means of washing liquid

(e.g. water, amines, glycolethane etc.)
adsorption CO2 is bound at internal surfaces of adsorption
material (zeolithes, molesieves)
membrane process CO2 is separated due to different permeation rates
at membrane barriers
CO2-liquefaction phase separation of liquid CO2 and gaseous
methane at very low temperatures

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Processes for Biogas Upgrading

process description disadvantages advantages

1. gas scrubbing CO2 and H2S is absorbed • pre-purifying (H2S) and drying • high gas quality in case
by means of washing liquid process necessary no O2 & N2 in raw biogas
(e.g. water, amines, • continuous loss of washing •
3
for plants (> 2.000 m /h)
glycolethane etc.) liquid specific investment cost lower
• continuous disposal of washing
liquid
• use of chemicals or other liquids
• offgas heavily loaded with H2S and
washing liquid
• risk of bacterial contamination of
product gas
• enrichment of O2/N2 in product gas

2. membrane process CO2 is separated due to • complex pre-purifying (H2S, water) • dry process
different permeation rates necessary • no chemicals
at a membrane • high process pressures necessary • low mechanical wear
• unstable long-term behavior /
performance loss
• low CH4-recovery
• high investment cost
• high energy demand
• high CH4-emission

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Processes for Biogas Upgrading

process description disadvantages advantages

3. adsorption CO2, higher CxHy, H2S, SI-, • high H2S in raw gas • high gas quality
Fl-, Cl-compounds, odors requires pre-cleaning • dry process
will be removed by
• no use of chemicals
activated carbon / carbon
molecular sieve • no process water demand
• no waste water
• durably and flexibly
• partial removal of N2 and O2
• moderate investment cost
• no bacterial contamination of offgas

4. CO2-liquefaction CO2 is liquified by high • complex pre-purifying necessary • very high gas quality
pressure and low • very high power cost • no chemicals
temperatures and
• high investment cost • no water
separated by rectification
column • enrichment of O2/N2 in product gas

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Principle of Biogas Upgrading by Means of Gas Scrubbing

greengas / washing liquid: - water

biomethan - glycolethane (Selexol)
- amine
- other
washing theoretical absorption capacity
liquid basis : biogas 55 % CH4, 43 % CO2, 2% N2/O2, H20-saturated, 20°C

14
CO2-polyglycol DME

absorbed gas quantity [ltr./Kg]

12

10

6
CO2-water
4
biogas washing liquid
2 CH4-polyglycol DME
CH4-water
0
CH4 / CO2 / N2 / O2 / H2O / H2S CO2 / CH4 / H2O / H2S
1 10 pressure [bar a]
regeneration absorption

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Process scheme Biogas Upgrading by Water Scrubbing System

waste gas
(CO2, CH4, H2S, O2, N2) biological
dryer desulphurization
waste gas
(H2S-free)

CO2 + H2S scrubbing column

water

1. stage depressurization

stripping column
nutrients
biomethane

(waste
water)
air

blower
compressor
Cooler
biogas

1. stage 2. stage
waste
recycle gas (CH4, CO2, H2S) water
pump
cooler

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Principle of Biogas Upgrading by Means of Pressure Swing Adsorption

gas molecules
CH4 greengas / biomethane
N2 / O2
H2O / H2S
CO2 adsorber

adsorption: gas pressure high

regeneration: gas pressure low

Carbon
Molecular PRESSURE SWING ADSORPTION
Sieve
("PSA")

biogas off gas

CH4 / CO2 / N2 / O2 / H2O / H2S CO2 / N2 / O2 / H2O / H2S

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Process Scheme Biogas Upgrading using PSA-Process

CH4-rich gas

purge gas

H2S-
removal CH4-
production

gas
conditioning
compression
biogas
waste
gas
condensate vacuum pump

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Comparison of Various Biogas Upgrading Systems
(for new biogas injection projects, > 500 m3/h, energy crops, remote locations)

Pressure
Priority Water Selexol Amine Swing Membrane
factor Attribute Scrubber Scrubber Scrubber Adsorption process

2 CH 4-enrichment high ++ high ++ high ++ high ++ low -

1 O 2-/N 2-enrichment yes - yes - yes - no + yes -
2 CH 4-losses medium +/- high -- low ++ medium +/- high --
1 Product gas dryer yes - (yes -) yes - no + no +
required
1 H 2S-precleaning yes - yes - yes - yes - yes -
required
1 Waste gas treatment yes - yes - yes - no + no +
required
2 Utility demand medium +/- high -- high -- medium +/- high --
(power, water, cooling-
water, chemicals)
Power demand, appr. kW kW kW kW kW
0,28 0,32 0,42 0,21 0,5
(stand-alone system) m 3 feedgas m 3 feedgas m 3 feedgas m 3 feedgas m 3 feedgas

1 Level of emission medium +/- low + medium +/- low + low +

(waste water, offgas,
waste)
1 Capital cost medium +/- medium +/- high - medium +/- high -
Final rating -2 -4 -3 +5 -5

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Principle of ZETECH4© - Zero Emission Technology (patented)
biogas generation biogas upgrading
biomethane

biomass
H2S-
removal

compressor
hot
water condensate

flue gas
CH4-containing off gas
boiler

Advantages - no methane losses

- no methane emission / no H2S-emission
- no energy loss
- highest energy conversion efficiency
- no cogeneration plant for heat generation at site required

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Energy Balance Sheet Biogas Upgrading

raw biogas green gas

flow: 400 Nm3/h flow: 260 Nm3/h
pressure: 1,05 bar a pressure: 5 bar a
CH4: 65 % CH4: > 96 %
CO2: 32 % CO2: <2%
O2/N2: <3% O2/N2: <2%
waste gas
H2S: 300 mg/Nm3 H2S: < 5 mg/Nm3
flow: 140 Nm3/h
_______________________ ________________________
pressure: 1 bar a
HS,n: 7,15 kWh/Nm3 HS,n : 10,56 kWh/Nm3
CH4: 7,5 %
CO2: > 88 %
electrical energy utilizable O2/N2: <4%
87 kW (incl. cool waste heat H2S: < 5 mg/Nm3
water re-cooling) 30 kW therm

energy input energy output

7,15 kWh/Nm3 ·400 Nm3/h + 87 kW 10,56 kWh/Nm3 · 260 Nm3/h + 30 kW
2.947 kW 2.775 kW
energetic efficiency I : 94,2 % (without using waste gas)

combustion of waste gas in hot water boilers for pasteurization & fermentation
additional energy output : 99 kW
energetic efficiency II : 97,5 %
Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Plant Examples - Biogas Upgrading Plants

Year Location Raw gas Raw gas Upgrading Utilization

input [Nm3/h] source system

fig. 1 2004 Stockholm / Sweden 600 sewage gas water scrubber vehicle fuel

fig. 2 2000 Stockholm / Sweden 2 x 350 sewage gas PSA vehicle fuel

fig. 3 2001 Frederikstad / Norway 150 sewage gas PSA vehicle fuel

fig. 4 2002 Braunschweig / Germany 2 manure / bio waste reformer / PSA H2-generation for fuel cell

fig. 5 2003 Galgenen / Switherland 70 bio waste Selexol scrubber vehicle fuel

fig. 6 2005 Luzern / Switzerland 140 sewage gas PSA gas grid / vehicle fuel

fig. 7 2006 Aachen / Germany 1.000 energy crops PSA feed to natural gas grid

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Plant Example - Biogas Upgrading Plants (fig. 1)

Stockholm / Sweden

600 Nm3/h raw gas – 400 Nm3/h product gas

purity: 97 + 1 vol.-% CH4

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Plant Example - Biogas Upgrading Plants (fig. 2)

Stockholm / Sweden

2 x 350 Nm3/h biogas – 2 x 200 Nm3/h product gas

purity: 97 + 1 vol.-% CH4

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Plant Example - Biogas Upgrading Plants (fig. 3)

Frederikstad / Norway

150 Nm3/h biogas – 100 Nm3/h product gas

purity: 97 + 1 vol.-% CH4

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Plant Example - Biogas Upgrading Plants (fig. 4)

Braunschweig / Germany

2 Nm3/h biogas – 2 Nm3/h product gas

purity: 99,999 vol.-% H2

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Plant Example - Biogas Upgrading Plants (fig. 5)

Galgenen / Switzerland

70 Nm3/h raw gas – 40 Nm3/h product gas

purity: 96 + 1 vol.-% CH4

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 References - Biogas Upgrading Plants (fig. 6)

Luzern / Switzerland

140 Nm3/h biogas – 87 Nm3/h product gas

purity: 97 + 1 vol.-% CH4

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 References - Biogas Upgrading Plants (fig. 7)

+ 3500

+ 3000

Ventilator

Biomass: energy crops

Biogas: 1.000 Nm3/h / 53 % CH4
Entschwefelung Speicherbehälter
Produktgas
Biomethane: 530 m3/h / 96 % CH4
Ventilator Utilization: feed to natural gas grid
Location: Kerpen / Germany
Customer: Aachen Municipality
Vakuum-

Vakuum-
pumpe 1

pumpe 2
Tür Öl- PSA-Ventilskid
Ad-
sorber
Commissioning: End of 2006

CTOP 1
WT - Skid

Speicher Kabeltrasse zum Kühlerskid - 400mm oder 250mm

E E SPS

400x400 3 2 1
Steuerl.-
komp.

Biogasverdichter
FU's Trockner

Tür Ventilator Tür Tür

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Conclusion

Efficient biogas utilization requires transport via natural gas grid.

Biogas upgrading is a must for accessing natural gas grid.

Decentralized cogeneration plant fired with biomethane enables nearly 100 %

utilization of the energy of biogas.

Biogas upgrading technology is well known, proven, efficient and requires low
energy input.

Combined with Zero Emission Technology© (ZETECH4©) zero methane losses

and zero methane emission can be ensured.

Biomethane injection to natural gas grid is well proven technology, so far since
more than 10 years only positive experiences.

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006
 Am Technologiepark 1
D – 45307 Essen, Germany

Tel. +49 (0)201 172-1915

Fax +49 (0)201 172-1382
e-mail an.info@carbotech.de

Intelligent Utilization of Biogas – Upgrading and Adding to the Grid Jonköping, May 2006