- CO2/CH4 Separation -

UBE’s Membrane Modules

CONFIDENTIAL

Recovery of N2 from Dehumidification Dehydration from Separation H2 from Separation CO2

compressed air of compressed air aqueous organic hydrocarbons from hydrocarbons
vapor

N2 Air Dryer Dehydration H2 CO2

Fire and explosion Instrument Air Bio-Ethanol H2 Recovery on Hydrocarbon

protection for oil and Medical Equipment i-Propanol Oil Refinery (Methane)
gas well injection, Dry Box etc. Ketones etc. and Chemical Enrichment from
Blanket for tank, tire Plants Landfill Gas,
filling etc. Biogas, and Natural
Gas
2
History of UBE’s Membrane Business

・ 1978 Started R&D Work

・ 1981 Jointed MITI’s C1 Project (National Projects)
・ 1983 Field Tests at Ammonia Plant
・ 1985 Organized Membrane Dept.
・ 1986 Supply First Hydrogen Recovery Unit
・ 1989 First Membranes for CO2 & Dryer
・ 1992 First Membrane for N2/O2 Separation
・ 1993 New Membranes for H2 & CO2
・ 1999 Started EtOH Dehydration Commercial Plant
・ 2006 Expansion of Business mainly with N2/O2
Separator & Ethanol Dehydration Membrane
Permeation Rate

High Permeation H2O

H2 He

Permeation Rate
CO2
H2S
O2
Ar
CO
N2
CH4
C2H6

Low Permeation C3+ (Hydrocarbon)

Natural Gas treatment in Japan Enhanced Oil Recovery (EOR) in Turkey

Landfill gas treatment in Germany

Application Examples
- Environmental Application -
(CO2/CH4 Separation from Biogas)
 Module Structure - CO2 Separation

Off Gas
(Permeate Gas)
Compressed Product Gas
Biogas (Non-Permeate
(Feed Gas) Gas)

CO2 Rich Gas

Compressed Product Gas

Biogas (Non-Permeate
(Feed Gas) Gas)
CH4 Rich Gas

Polyimide Hollow Fiber

Environmental Application

(CO2/CH4 Separation from Biogas)

Methane Fermenter

Methane Fermentation Gas

(CH4: 60%,CO2: 40%)

Livestock Dung

Ovoid Shape CO2/CH4 Module

Digestion Tank

UBE Membrane Module

Purified CH4
）
(CH4: >95%）
Household Sewage Main Application
- Alternative Natural Gas
Pipe Line Gas
Natural Gas Vehicle
Power Generator

CH4 is one of important greenhouse gases that have

to be reduced, but it is 20 times more effective than
Landfill Gas
CO2. CH4 should be separated and purified for
effective utilization.
Durability against Contaminants

Water / Humidity: Liquid water should be avoided

and less than 80 RH%
Small Particles: As few as possible, less than 0.01 µm
Residual Oil: < 0.01mg/Nm3 (< 0.008 ppm w/w)
Hydrocarbons: < 0.013mg/Nm3 (< 0.01 ppm w/w)
H2S: < 3 vol%
NH3 & Amines: < 100 vppm
Acid: Should be avoided
Aromatics: As low as possible
Alcohol: Good
 Environmental Application

Typical Process Flow for Methane Separation

Methane
Fermenter
Gas Cleaning

Compressor After Mist Oil Carbon Dust Heater

Cooler Filter Filter Bed Filter
Landfill Gas

UBE Membrane Module

Feed Gas Product Gas
(Non-Permeate Gas)
Off Gas Methane Rich Gas
(Permeate Gas)
 CONFIDENTIAL

Application Examples
- Environmental Application -
(CO2/CH4 Separation from Biogas)

11
Purification of Methane from Bio Gas
CONFIDENTIAL

A. One Membrane and One Compressor

UBE Membrane Module

Feed Gas Product Gas
CH4: 60.0% CH4: 95.0 vol%
Off Gas
CO2: 40.0% Recovery: 76%

Material Balance
CH4 Composition, Vol%
Flow
Recovery (1) (2) (3) (4) (5) (6)
Pattern
(%) Feed CH4 Rich CO2 Rich 2nd Feed Recycle
CO2 40.0 40.0 5.0 71.9
A 76
CH4 60.0 40.0 95.0 28.1
CO2 40.0 40.0 4.8 76.4 9.5 35.0
B 81
CH4 60.0 40.0 95.2 23.6 90.5 65.0
CO2 40.0 40.0 4.3 94.9 71.0 40.0
C 97
CH4 60.0 40.0 95.7 5.1 29.0 60.0
Ref.) N. Tanihara and M. Hayashi, Maku (Membrane), 35, 37 (2010).
12
 Purification of Methane from Bio Gas
CONFIDENTIAL

B. Two Membranes and One Compressor

Compressor 1st Stage
Product Gas
Feed Gas UBE Membrane Module
CH4: 95.2 vol%
CH4: 60.0%
Recovery: 81%
CO2: 40.0% Off Gas
UBE Membrane Module

2nd Stage

Material Balance
CH4 Composition, Vol%
Flow
Recovery (1) (2) (3) (4) (5) (6)
Pattern
(%) Feed CH4 Rich CO2 Rich 2nd Feed Recycle
CO2 40.0 40.0 5.0 71.9
A 76
CH4 60.0 40.0 95.0 28.1
CO2 40.0 40.0 4.8 76.4 9.5 35.0
B 81
CH4 60.0 40.0 95.2 23.6 90.5 65.0
CO2 40.0 40.0 4.3 94.9 71.0 40.0
C 97
CH4 60.0 40.0 95.7 5.1 29.0 60.0
Ref.) N. Tanihara and M. Hayashi, Maku (Membrane), 35, 37 (2010).
13
Purification of Methane from Bio Gas
CONFIDENTIAL

C. Two Membranes and Two Compressors

1st Stage Product Gas
Feed Gas UBE Membrane module CH4: 95.7 vol%
CH4: 60.0% Recovery: 97%
CO2: 40.0%

UBE Membrane module

2nd Stage
Compressor
Off Gas
Material Balance
CH4 Composition, Vol%
Flow
Recovery (1) (2) (3) (4) (5) (6)
Pattern
(%) Feed CH4 Rich CO2 Rich 2nd Feed Recycle
CO2 40.0 40.0 5.0 71.9
A 76
CH4 60.0 40.0 95.0 28.1
CO2 40.0 40.0 4.8 76.4 9.5 35.0
B 81
CH4 60.0 40.0 95.2 23.6 90.5 65.0
CO2 40.0 40.0 4.3 94.9 71.0 40.0
C 97
CH4 60.0 40.0 95.7 5.1 29.0 60.0
Ref.) N. Tanihara and M. Hayashi, Maku (Membrane), 35, 37 (2010).
14
 Purification of Methane from Bio Gas
CONFIDENTIAL

Combination with Cryogenic CO2 Recovery Unit

Compressor 1st Stage
Product Gas
Feed Gas UBE Membrane Module
CH4: 91.8 vol%
CH4: 60.0%
Recovery: 95.7%
CO2: 40.0% Off Gas
UBE Membrane Module
CH4: 80%
CO2: 20%
Cryogenic CO2 Recovery Unit 2nd Stage
(CO2 >90% is needed)

High Purity CO2 (>99.9 vol%)

Module
1st Stage CO-710F x 1 pc Material Balance
2nd Stage CO-710F x 4 pcs
Feed Gas Off Gas Product Gas

Flow Rate, Nm3/hr 600 292 393

Feed Gas Condition
Pressure, MPaG 1.00 0.00 0.88
Flow Rate: 600 Nm3/hr
Temperature, C˚ 50 50 50
Pressure: 1.00 MPaG
Composition, vol%
Composition
CH4 60.0 5.66 91.80
CH4: 60.0 vol%
CO2 40.0 94.34 8.20
CO2: 40.0 vol%
15
Job Record for UBE CO2 Membrane Unit

No. Application Location Pressure Capacity

1 Landfill Gas Germany 35 bar 200 Nm3/h
2 Landfill Gas Netherlands 32 bar 350 Nm3/h
3 Natural Gas Japan 68 bar 2,100 Nm3/h
4 Enhanced Oil Turkey 55 bar 1,500 Nm3/h
5 CO2 Rejection Germany 30 bar 30 Nm3/h
6 Landfill Gas Netherlands 32 bar 350 Nm3/h
7 Landfill Gas USA 75 bar 2,600 Nm3/h
8 Natural Gas Canada 85 bar 25,000 Nm3/h
9 Landfill Gas Netherlands 36 bar 350 Nm3/h
10 Synsesis Gas Japan 7 bar 2,100 Nm3/h
11 Natural Gas Italy 40 bar 3,100 Nm3/h
12 Natural Gas Australia 121 bar 20,000 Nm3/h
13 BioGas (Sewage Fermentation) Japan 7 bar 10 Nm3/h
14 BioGas (Livestock Dung Fermentation) Japan 9 bar 20 Nm3/h
15 Landfill Gas USA 13 bar 3,300 Nm3/h
16 BioGas Netherlands 7.5 bar 1,500 Nm3/h
17 BioGas Germany 8 bar 100 Nm3/h
18 BioGas Netherland 8 bar 5 Nm3/h
 Job Record for UBE CO2 Membrane Unit

Netherlands

Netherlands
Germany
Canada
Netherlands Germany
Germany
Netherlands
Italy Japan USA
Japan
USA
Turkey
Netherlands (Enhanced Oil)

Japan
(Syn. Gas) Japan

Natural Gas

Australia Biogas

Landfill Gas

Others
 End

Membrane Group