novel co2 separation technology using msm-1 zeolite...

JOGMEC Techno Forum 2014

Novel CO2 Separation Technology

Using MSM-1 Zeolite Membrane

November 27th, 2014

B-2 : R&D of JOGMEC and Japanese Companies (2)

Kenichi Kawazuishi

Chiyoda Corporation

(CO2 Separation From Natural Gas)

All Right Reserved. CHIYODA Corporation and

Mitsubishi Chemical Corporation 2014

1

- In order to develop the gas fields containing high CO2, it is necessary to remove

CO2 efficiently with lower cost.

-Zeolite membrane has a very superior performance for CO2 separation. Applying

zeolite membrane to the separation of the natural gases which have high CO2

concentration, it can be expected to reduce drastically both CAPEX and OPEX.

- We can accelerate the efficient development of the natural gas fields which

contain high concentration of CO2 especially in South-East Asia region.

- Namely, it can be expected to contribute toward obtaining natural gas concessions

and improving the energy security of our country.

-Besides, the separated CO2 will be utilized for the CO2-EOR and the fracturing

media for shale oil and gas field developments.

Aims



2

Source: Foster Wheeler, “New Challenges and Solutions in Designing Large Sour Gas Projects”

World’s Conventional Sour Gas Reserves



3

Mitsubishi Chemical Corporation

- has been developing very superior zeolite

membrane for CO2 separation

- focuses to the development of natural resources

⇒ look for a partner to commercialize

Chiyoda Corporation

-has recognized Mitsubishi’s superior technology,

which is suitable/applicable to energy

saving/environmentally friendly

- is at rather near position to gas/oil producing

countries, as a global engineering contractor.

Joint-development

＝ be able to provide efficient and compact

technology of CO2 separation

Needs (Gas Producing Countries)

＝ want to develop the gas fields having high

CO2, economically and efficiently

Seeds

(Japanese Companies)

JOGMEC Technical Solution Project




Mitsubishi Chemical Corporation

-Is able to obtain the business

chances, as the supplier of

membrane/ membrane modules

-License this technology

Chiyoda Corporation

-Is able to obtain the business

chances, as an engineering

contractor, using this technology

-License this technology


＝ be able to provide efficient and compact

technology of CO2 separation

Needs (Gas Producing Countries)

＝ want to develop the gas fields having high

CO2, economically and efficiently

Seeds

(Japanese Companies)



5

Motivation



Membrane Separation System can promote not only the

gas field development which includes high CO2

concentration, but also the CO2-EOR/CO2 fracturing.

Gas Field

Development

CO2

Concentration

Large Low

Small, OffshoreFuture

Now

Scaleof Gas Field

Demand for

Natural Gas・It will continue to grow

Gas

Treatment

Technology

(CO2 Removal)

Size of CO2 Removal Plant

High Large

CompactLowMembrane

AGR

OPEX

※ AGR (Acid Gas Removal)

:Acid Gas Component in the raw natural gas are removed by chemical absorption.

※

High, Sour gas

6

Characteristics of MSM-1

The size of MSM-1 pores

is suitable for the

separation of CO2 from

Natural Gas (CH4).

Separation

Kinetic Diameter (nm)

Kinetic Diameter MSM-1: Mitsubishi high-Silica Membrane -1

Published applications for patent: JP2012-66242 etc.

Pore Size (MSM-1)

0.30 0.35 0.40

difference: 0.05 nm

CO2

CH4

○

×

CHA type zeoliteAll Right Reserved. CHIYODA Corporation and


7

Driving force

Pressure difference

between membrane

outside and inside.

Characteristics of MSM-1

Image of membrane Structure

Zeolite Membrane

CO2/ CH4CH4

Porous substrate (Alumina tube etc.)

CO2

High pressure

Atmospheric

pressure

Photo of Zeolite Membrane



8

Polymer

Membrane

Zeolite Membrane

DDR SAPO MSM-1

CO2 Permeance

CO2 Separation

Factor

Stability Thermal

Water

Chemical

Excellent Good Fair

Insufficient

Separation

Large membrane

area is required.

Low

Stability

Improved

Separation

Small Membrane

area

Good

Stability

※1 DDR: Deca-Dodecasil 3R

※2 SAPO: Silico-Alumino-Phosphate

※2※1

Advantages of MSM-1 (General)



9

0

50

100

150

200

250

300

350

400

0.0E+00 5.0E-07 1.0E-06 1.5E-06 2.0E-06 2.5E-06 3.0E-06

CO

2/C

H4

Separ

atio

n f

acto

r

CO2 permeance [mol/(Pa・s・m2)]

MSM-1

DDR membrane

(JP2004-105942)

Polymer

membrane

SAPO membrane

(US8302782)

MSM-1 shows superior separation performance of both CO2

permeance and CO2/CH4 separation factor.

Separation Performance



10

Conventional Technology - AGR, Polymer Membrane

AGR(Acid Gas Removal)

Polymer Membrane

Smaller Energy

Consumption than AGR

(1) Stability(Chemicals)/Life time

(2) Separation Factor

1 Step with AGR 2 Step with Recycle

CO2 Conc.:ca.2 mol%

(for Pipeline)

CO2 Conc.: several 10ppm

(for LNG Plant)

Absprber Regenerator

CO2(酸性ガス)

原油天然ガス

処理ガス

Cooling Water

Steam

AGR - Disadvantage

Large Energy

Consumption

Polymer Membrane –

Disadvantage

Feed NG

Treated Gas CO2

(Sour Gas)



11

MSM-1 has much higher CO2 Separation Factor than polymer

membrane.

It reduces CH4 (Hydrocarbon) loss, compared with conventional

polymer membrane system.

Separation Factor = 100

MSM-1

Polymer

Membrane

CO2 100

CH4 100 CO2 90

CH4 8.3

Separation

Factor Example

100～

Approx. 30

CO2 10

CH4 91.7

CO2 100

CH4 100 CO2 90

CH4 23.1

CO2 10

CH4 76.9


Reduce to 1/3

Methane Loss


… Reduce to 1/4


… Reduce to 1/5

Advantages of MSM-1 (Separation Factor)



12

AGR Reboiler Duty

CH4 Loss –

Polymer Membrane

CO2 Concentration in Natural Gas

high low

Reb

oil

er

Du

ty ,

CH

4 L

oss

(E

nerg

y C

osu

mp

tio

n, E

nerg

y L

oss)

(per

un

it a

mo

un

t o

f tr

eate

d N

G)

CH4 Loss –

MSM-1

- MSM-1 has very large advantages, especially when natural gas has high concentration of CO2.

- Combination of MSM-1 and AGR shows the smallest energy consumption/loss in the case of

CO2 removing from high CO2 to law CO2.

Advantages of MSM-1 (smallest energy consumption/loss)

・Compared with AGR, Membrane Separation System can reduce the Operational

Energy such as required energy for AGR and methane loss.

・Due to the high CO2 Separation factor, MSM-1 membrane

with AGR will achieve more than 60% Operational Energy

reduction compared with AGR-only system.

Typical Comparison of

Operational Energy

Advantages of MSM-1 (Operational Energy)

13

(CO2＜50ppm Case)

(*) (Operational Energy) = (Methane Loss)+(Heat Input to AGR)



14

0%

20%

40%

60%

80%

100%

120%

CAPE

X +

OPE

X(1

0yea

rs)

Membrane

AGR

AGR MSM-1 + AGR

CO240mol%

LNG Spec.

CO210mol%

LNG Spec.

CO240mol%

AG

R

AG

R

Sour Gas

250,000 Nm3/hr

CO2 40mol%

4.0 MPaG

Treated

Natural Gas

CO2 <50ppm

(LNG Spec.)

Membrane AGR

Permeate Gas

(CO2 Rich) CO2

MSM-1 shows quite large advantages on (CAPEX + OPEX), comparing with AGR.

⇒ We will continue to study on further cost reduction.

Confidential Advantages of MSM-1 (Cost Comparison)



15

Field Test

CO2

Natural Gas

Compressor 1

Flare

Compressor 2Membrane

Module

Permeate Gas (CO2)

Residue Gas

Field Test(1) ： Domestic Field, To confirm the performance of MSM-1 itself,

and to obtain engineering data for optimum design of membrane module, using

a medium scale module.

Field Test(2) ： Oversea’s Field, To confirm the performance and life of MSM-1

under the actual condition in existing natural gas treating facilities. The module

to be used will be commercial scale.

We are planning to conduct 2 Step Fields tests.

Conceptual Flow of Field Test(1)

Future Plan



16

Future Plan Confidential



2B CA

Commercial

Scale PlantModule Test/Field Test(1)

(Domestic Field)

Field Test(2)

(Oversea’s Field)

…Test Module

(Medium Scale)

Large Scale

Module Design

Scale Up

(CFD Study)

1 Series

(3 – 8 Modules in a Series)N Units

（Determined by Gas Treating Capacity)

N Units

1 Unit consists or around 10 Series)

Technology Development towards Commercialization

1,000 Nm3/h

(0.9 MMSCFD)20,000 Nm3/h

(18 MMSCFD)

17

Φ12mm×360mm 19elements Inside

Outside

Small Scale Model Module Confidential



18

Mt. Asama-yama

Thank You

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