"CO2 separation and Helium purification
with SEPURAN® membrane by EvonikIndustries"
2018. 2.13 第７回革新的CO2膜分離技術シンポジウム「エボニック製SEPURAN® 分離膜によるCO2分離およびヘリウム精製、水素分離」
ダイセル・エボニック(株) スペシャリティ製品営業部 須川
Evonik Fibres GmbH
Application Technology SEPURAN®
Olivier Zehnacker

1Outline

About Evonik and Fibres and Membranes
SEPURAN® Gas separation technology
SEPURAN® Green for biogas upgrading
SEPURAN® Green References
SEPURAN®® Noble
Noble inin NG
He application
SEPURANapplication
SEPURAN® Noble in H2 application2

Outline

About Evonik and Fibres and Membranes
SEPURAN® Gas separation technology
SEPURAN® Green for biogas upgrading
SEPURAN® Green References
SEPURAN®® Noble
Noble inin NG
He application
SEPURANapplication
SEPURAN® Noble in H2 application

3

About Evonik

4Our positioning

Evonik is the creative
industrial group from
Germany and one of theworld’s leading specialty
chemicals companies.
5

What we do
Living better with Evonikmore fuel saving

fluffier

more elastic

healthiermore effective

CAR TIRESTOWELS

MATTRESSESNUTRITION

TABLETSCountless products gain their special attributes through our creative power.

6

Who we areEvonik at a glance~1380%
Of turnover gained fromleading market positions

Billion Euro sales in 2016

Sites

>36,000 2.165
Employees in over 100 countries

7172

EBITDA 2016

billion Euro~500
R&D projects

Where we can be foundEvonik operates worldwide
Western Europe(incl. Germany)€ 5,534 M sales
23,919 employees
45 sites

North America€ 2,699 M sales
4,660 employees
39 sites

Essen

Eastern Europe

Asia-Pacific North€ 767 M sales
646 employees
11 sites€ 1,947 M sales
3,688 employees
30 sites

ViennaParsippany
Dubai
ShanghaiCentral & SouthAmerica€ 563 M sales
793 employees
15 sites

Sales in 20168

São Paulo

Middle East &Africa

Asia-Pacific South€ 403 M sales
194 employees
12 sites€ 818 M sales
1,746 employees
24 sites

SingaporeAn attractive company | a modern structure Evonik is one of the world’s leading specialty chemicals companies.
 The central elements of our strategy for sustained value creation are profitable growth, efficiency, and values.

 Around 80 percent of Evonik’s sales come from market-leading positions, which we are systematically expanding.
 We concentrate on high-growth megatrends, especially health, nutrition, resource efficiency, and globalization.

9Breakdown of Product Line Fibres, Membranes & Specialties
Fibres,Membranes & Specialties

Membranes

Sepuran Green

Sepuran Process Gases

Fibres & PI Specialties(incl. Evonik Fibres)

Sepuran Natural Gas

Medical Devices& Systems

OSN

London (UK)

SEPURAN® Product Family
10

DuraMem®
PuraMem®

Specialties

Evonik Fibres GmbH, Austria

11Efficient Gas Cleaning with Sepuran® Technology12

Outline

About Evonik and Fibres and Membranes
SEPURAN® Gas separation technology
SEPURAN® Green for biogas upgradingSEPURAN® Green References
SEPURAN®® Noble
Noble inin NG
He application
SEPURANapplication
SEPURAN® Noble in H2 application

13

We achieve high performances with our polymers
Performance Driven= Polymers from Evonik

our polyimide product family
exhibits market leading gas
separation properties= Semi finished products
from Evonik

PI
PAI

PPSU

High-performancepolymers

PEI

PMI

PEEK
FPs

PPA

LCP

PPS

PES

PA 1012

PMMI
PAR

PSU

PA4.6

Transp. PA

PA11

PA 1010

PPE

PBT

PET
PA6 / PA66

PC

Cost Driven

POM

14

PA612

PA 610PMMA

Engineeringpolymers

PA12PURABS

Commodity
polymersSANPPPS
PVCPE

amorphous

PE-LD

PE-HD

crystalline

EVONIK IMPACT ON FULL VALUE CHAIN LEADS TO SUPERIOR MEMBRANE PRODUCTS
Value chain of Evonik membrane business

Monomer

Polymer

Hollow Fibre

Evonik Business

15Membrane
Cartridge /ModuleOEM /Separation
Process

CustomerTechnology Support &Application Development

Excellent materials alone do not make a good membrane…
Polymer

Dope solution tailored tomembrane needs



Optimized polymer properties for
CO2/CH4 separation (selectivity) andN2 generation (productivity)

 Module & cartridge design tailored toapplication needs
 Potting formulations and processes
 Max out separation capacity

ModuleMembraneSpinning process scale upMinimized layer thickness

Yield optimization

 Optimized process lay-out Automated process control
 Benchmarking
 Hybrid systems

Process… but it all starts with the right material
16

Global presence with strong focus on regional Application Technology
Business MGMT and/or AT
Production and AT
NBD in progress

17

SEPURAN® Product families
 Market leading selectivity

 Market leader in Biogas upgradingunits Long term stability Industry standard productivity

NGGreenSEPURAN®
 On site nitrogen generation

 He recovery from Source gas or
Diluted streams

 Purities from 95-99.5%
 Superior air-factor

 High productive modules

N2Noble H2 recovery

 H2/CO ratio adjustment
 CO concentration

18

MEMBRANES ARE OFTEN CHARACTERIZED BY THEIR SELECTIVITY AND PERMEABILITY

Permeate (pPermeate)

Feed (pFeed)
pFeed

pPerm

Transport mechanism
pFeed > pPerm
12
3

1

2

CO2

19

Diffusion through membrane
Desorption permeate side

3Flow

CH4

Sorption feed sidelMembrane thickness

Separation mechanism
Differences in flow across the membranelead to enrichment of the quicker component
in the permeate.

ILLUSTRATION OF A GAS SEPARATION PROCESS IN A HOLLOW FIBRE MEMBRANE

Selective layer on theoutside
H2O

Porous substructure formechanical support

20

HeH2CO2O2Ar

N2Relative permeation rates of various gases

CH4Outline

About Evonik and Fibres and Membranes
SEPURAN® Gas separation technology
SEPURAN® Green for biogas upgrading
SEPURAN® Green References
SEPURAN®® Noble
Noble inin NG
He application
SEPURANapplication
SEPURAN® Noble in H2 application

21

CO2 Separation from Biogas with Sepuran® Green22SEPURAN® Green for upgrading biogas
Evonik’s contribution to an efficient biomethane purification process

Biogas fromorganic waste

Filling station

Biogas from(liquid) manure

Combined heatand powerplantUpgrading

Biogas fromrenewable
resources

Natural gas grid

Biogas plant23

Gas separation

Distribution

Traditional technologies dominate the biomethane market in EU today

Main Biogas
UpgradingTechnologies

24

The membrane removes CO2 and dries the biogas at the same time
Process steps of biogas upgrading with SEPURAN® Green Membranes
Raw Biogas

Desulphurisation

Condensate
separation
Control Filter

FilterH2ORemoval
CO2RemovalCompressor

Biomethane25

Single stage process with SEPURAN ® Green
100 m3/h, 16 bara

48,3 m3/h, 16 bara

CH4

52,9%

CH497,1%

CO246,0%

CO2

2,2%

52,5 m3/h,1,0 baraAdvantages
 Few membrane modules requiredEspecially useful for fuel gas stations

Disadvantages
 Low methane yield


26

CH411,8%CO287,7%

Methane yield: 87,1%

Three step biogas upgrading process patent with
SEPURAN® Green is a game changer!
For the first time membrane technology could offer complete separation!

27

Evonik Process with SEPURAN® Green

Methane yield: 99.6%

JP特許取得済み(特許5858992)

28

低容量ｺﾝﾌﾟﾚｯｻ１個で対応可能（初期投資＆ﾗﾝﾆﾝｸﾞｺｽﾄの大幅削減が可能）Outline

About Evonik and Fibres and Membranes
SEPURAN® Gas separation technology
SEPURAN® Green for biogas upgrading
SEPURAN® Green References
SEPURAN®® Noble
Noble inin NG
He application
SEPURANapplication
SEPURAN® Noble in H2 application

29

Substrates are changing from crops to waste streams.
Organic
Waste
Pipeline
Injection

SewageSludgeAgricultural
Waste

Food &Beverages

Industrial
Rawmaterial

Landfill
Waste

Kitchen
Waste

Biogas
CH4 – CO2

Industrial
Processes

Energy CropsCNG
Fuel

Biomethane
CH4Greenhouseplants

LNG
Fuel

Dry IceIndustrialprocesses

Carbon dioxide
CO2HeatingPOME

Government Support

30

DENA | June 1st, 2017 | SEPURAN® Green

Industrial & private motivation•

Legal Framework & Standards•

Sustainability & GHG saving mind-set•

Tax benefits & incentives•

Promote „greener“ produced products as such•

Environmental restrictions•

Giving up convenience2017: > 140 Global references of upgrading plants supplied withSEPURAN® GreenSepuran® Green membrane can be used in small-,mid- and large scale installations.

* not all installations are displayed here yet

And 60+ more plants already…
31

EnviTec-Biogas GmbH, Saerbeck DE – “Minhe-Project” in China

Penglai, Shandong Provence, China

EnviThan Container, Gasholder

Client:Biogas:Shandong Minhe BiologicalSci-tech Co. Ltd.
Chicken Manure

Upgrading: 2 x 1,000 Nm³/h Biomethane
Methane:32

97,0 Vol% CH4

Operator and membrane container

Operating Pressure:

16,0 bar

Process:

3-stage membrane

Downstream:

CNG – bottle trailer
filling plant distribution at public
CNG stations

Yesco ES, Seoul City SK – City Gas Project in South Korea

Seoul City, Seoul, South Korea

Yesco’s upgrading “Mefin”

Client:Yesco, ES, City Gas Seoul

Operating Pressure:

9,8 barBiogas:Sewage sludge from WWTP

Process:

3-stage membrane

Downstream:

Gas grid injection tosupply privatehouseholds &industry

Upgrading: 1,500 Nm³/h Biogas
Methane:33

SEPURAN® Green piped in a rack

97,5 Vol% CH4

Tecno Project Industriale, Curno IT – “Montello-Project” in Italy

Montello, Region Bergamo, Italy

Montello Waste Treatment Plant

Client:Montello

Operating Pressure:

16,0 bar

Biogas:Municipal Waste

Process:

3-stage membrane

Downstream:

CNG & gas grid
injection CO2liquefaction sold torespective industry

Upgrading: 5 x 1,250 Nm³/h Biogas
Methane:34

Disgester – 5 new ones installed

97,0 Vol% CH4

Hipotech, Hokkaido Japan – 1st reference in Japan

Hokkaido, Japan

Upgrading unit and storage

Client:Hipotech/Tomoe

Operating Pressure:

10,0 bar

Biogas:Food Waste

Process:
membrane

3-stage

Downstream:

CNG - distribution

Upgrading: 10 Nm³/h Biogas
Methane:35

3-stage membrane unit

99,0 Vol% CH4

Outline

About Evonik and Fibres and Membranes
SEPURAN® Gas separation technology
SEPURAN® Green for biogas upgrading
SEPURAN® Green References
SEPURAN®® Noble
Noble inin NG
He application
SEPURANapplication
SEPURAN® Noble in H2 application

36

Helium Purification from Natural Gas with Sepuran® Noble37

Helium applications

 Helium upgrading and purificationfrom natural gas source Helium recovery from end user applications
 MRI’s Electronics
 Leak detection
 Lifting/ballooning Optical fibers

38

Conventional Helium upgrading and purification process
Natural Gas
0.4% He

39

Cryogenic
distillation

Crude Helium
50-70% HeHe
Purifying

Helium
99.99% He*Picture taken from www.praxair.com

Conventional Helium upgrading and purification process
Natural Gas
0.4% He

40

Cryogenic
SEPURAN®
Nobledistillation

Crude Helium
50-70% HeHe
SEPURAN®
NoblePurifying

Helium
99.99% He*Picture taken from www.praxair.com

Example: Upgrading of pretreated He to Crude He Low He containing Feed gas can be upgradedto crude He in one compression step.

Feed:
He0.4%
N2 16.1%
CH4 83.3%

Mixer

 Calculations are based on 20 bar(a).

RecycleEvonik membrane cascade for
Helium upgrading

ProductHe > 60%
41VentHe < 0.05%

 The He recovery is > 95%.

Membrane state of the art was:A Helium containing fuel gas can be upgraded in one
step from 0.4% He to 10% He. The He recovery is62% (at 25 bara)

Helium upgrading and purification process – first large scale reference

Source: The Linde Group42

Example: Upgrading of Crude He to pure He

Feed:
16 bar(a)He 50%
N2 46%
CH4 3%

H21%

SEPURAN®
Noble

Product:
1 bar(a)He 90.2%
N27.7%
CH4 0.3%
H21.8%Off gas:16 bar(a)He 0.7%
N2 93.0%
CH4 6.3%
H20.1%

 Crude He with only 50% can be upgraded to more than 90% in a one stage process.
 The He recovery is > 99%.
 This gas can go into the further processing to reach high purity He (Grade A).

43

Helium recovery in optical fiber industry with SEPURAN® Noble

44

From Nextrom website
http://www.rosendahlnextrom.com/fiber-optics/helium-recovery/

Outline

About Evonik and Fibres and Membranes
SEPURAN® Gas separation technology
SEPURAN® Green for biogas upgrading
SEPURAN® Green References
SEPURAN®® Noble
Noble inin NG
He application
SEPURANapplication
SEPURAN® Noble in H2 application45

H2 & CO2 Separation from e.g. Biomass Gasification with Sepuran® Noble46

To close the CO2 cycle, Crude Gas upgrading is the key step

Use forTransportation

CO2 in the airElectricity
Heating
CO2 fixed asbiomasse.g. pure CH4
Biomass
Gasification
Crude Gas
H2, CO2, CO, CH4

H2 & CO2 Separation from Biomass Gasification with Sepuran® Noble

Biomass

Biomass
Gasification

Crude Gas:
CH4
CO2H2COSEPURAN®
Noble

H2 rich gas
CO2

 High recovery of CO & CH4 due to high membrane selectivity
 Separation of CO2 & H2 for recycle from CO & CH448

CO & CH4
Further uses as- Fuel- Feedstock- ….

Sepuran® Membranes for yourseparation applications

49

Sepuran® Membranes for your separation applications

Evonik wants to become a leading supplier for Membrane applications

Evonik produces membranes with backward integration to tune chemistry

Evonik shows an increase number of references for Membrane applications

Membranes are an effective way for CO2 Separation50