Vince WhiteAir Products PLCHersham, UKwhitev@airproducts.com

THE SECOND APP OXY-FUEL CAPACITY BUILDING COURSE

Xijiao Hotel, Beijing, CHINA

15/16 March, 2010

ASU and CO2 Processing

Units for Oxyfuel CO2

Capture Plants

www.airproducts.com/CO2_capture

2

公司概况AP Introduction

■ 是世界领先的工业气体、特殊化工材料、设备

与技术服务供应商World leading industrial gases, special chemical

materials, equipment and technique service provider

■ 成立于1940年, 70年的成功历史Started in 1940, 70 years history

■ 2009年销售额为83亿美元. 2008年位列美国

财富500强第258位 In 2009 AP’s revenue was

US$8.3 billion, listing 258 in US Fortune 500

■ 获得全美化工行业”2009年最受赞赏公司” 第4

名, 是公司连续第十年获此殊荣the #4 most admired company within the chemicals

industry sector in 2009, being consistently on the “Most

Admired” list since 2000

3

公司概况AP Introduction

■ 在40多个国家运营并拥有300多套空分, 并且为客户销售、设计并建造了超过1200套空分>300 air separation plants owned and operated in over 40 countries; >1,200 plants sold, designed and built for customers globally

■ 已制造的深冷空分产能从1,500 Nm3/h到单套氧气105,000 Nm3/h, 深冷工艺设计可达到205,000Nm3/h Cryogenic offering spans from plants with a capability of 50T/D to single train facilities with oxygen production capacities beyond 7,000T/D

■ 是世界最大的氢气制造商, 每小时生产氢气238Nm3/h Worlds largest manufacturer of hydrogen at more than 2.38 mil. Nm3/H

■ 是世界最大的LNG换热器供应商,全球拥有超过70% 的市场份额 Worlds largest supplier of LNG Heat Exchangers (>70% of market)

4

空气产品(中国)China At a Glance

■ 1980 年代初期开始设备销售Entered market in early 1980’s with equipment

supply

■ 1987年首度投资中国First investment in 1987

■ 2008年销售额超过3亿美元US$350MM in sales (consolidated basis)

■ 总投资额超过6亿美元Over US$600MM Investments

■ 共有1800名员工Over 1800 employees

5

■ 在上海设立全球工程中心, 全球深冷设

备制造中心及亚洲技术中心Global engineering centre, global cryogenic

equipment manufacturing facility and Asia

technology centre near Shanghai

■ 能源炼化是主要的服务对象Tonnage gases is key focus and builds on #1

position in China market

■ 向中国提供第一家氢燃料加注站AP supplies China’s first Hydrogen Fuelling

Station

空气产品(中国)China At a Glance

6

Steam Boiler & Turbines

Coal

MWe

Flue Gas

Recycle

Oxygen

O2 Supply CO2 Transport

& Sequestration

Air Separation Units

Steam Boiler &Turbine

CO2 Purification & Compression

CO2 Transport & Sequestration

Oxyfuel Combustion Requires…

CO2 Purification

& Compression

7

Large Air Separation Units (ASUs)

8

空分装置运行流程Overview Of The Cryogenic Process

空气Air

热

氧Oxygen

主空压机与增压空气压缩Main and Boost Air Compression

空冷及预处理Air Cooling and Pretreatment

储罐Storage

深冷分离Separation

9

空分装置的设计制造能力Demonstrated Air Separation Capabilities

■ 技术基础 Technology base

– 深冷空气分离设备 Cryogenic air separation

■ 制氧量可达150,000 Nm3/h Up to 7,000 t/d

– 还可同时生产氮气，氩气和其他稀有气体 plus co-product nitrogen, argon, and other rare gases

■ 制氮仅根据需要来配置Nitrogen only configurations

– 非深冷空气分离设备Non cryogenic air separation

■ 最小为每天 58 Nm3/h From 2 t/d

■ 吸附法生产(PSA/VSA) Adsorption (PSA/VSA)

■ 分离膜生产 Membrane

■ 工程经验 Experience

– 遍布全球 Worldwide presence

■ 自己拥有或是售出的空分装置超过2000套>2,000 air separation units owned or sold

■ 运行和维护的装置超过700套>700 units operated and maintained

10

0

20,000

40,000

60,000

80,000

100,000

120,000

140,000

1987 1993 1996 1996 2006 >2009

大型空分装置项目及机组扩大化Experience - Large ASU Projects and Train Scale-up

■ 空分装置规模上升受市场驱使 Market drives ASU scale-up

■ 已被证明规模有70%的上升 Proven 70% scale-up

■ 最高已超过14,500 Nm3/h Quoting 5000+ metric t/d today

Doha卡塔尔

Polk美国

佛罗里达州

Plaquemine美国

路易斯安那州

Escravos 尼日利亚

Rozenburg荷兰

A5000 / A7000

Buggenum荷兰

Beaumont美国

德克萨斯州

每日制氧量(N

m3/h

)M

etric

Nm

3/h O

2

投产年份 Startup Date

11

Distillation Technology

Structured Packing

- Lower pressure drop – saves up to 10% of air compressor power

- Better turndown

- Higher plant capacity

Sieve trays

- Shorter columns

12

Brazed aluminum plate fin exchangers

Cools air streams against product

streams to recover refrigeration

Ambient to cryogenic temperatures

Cryogenic Heat Exchange

Liquid Oxygen

“Condensed” Boost Air

Nitrogen

Main Air

Gaseous Oxygen

Boost Air

Nitrogen

Main Air

Main Heat Exchanger

13

Process Cycle Selection Criteria

Oxygen demand profile

- Purity

- Pressure

- Demand pattern, quantities, duration, frequency

Argon co-production required?

Power evaluation criteria

Capex sensitivity

Process integration philosophy

Utility constraints, e.g. steam availability & quality, water consumption

Operating constraints, e.g. availability, reliability, time to on stream, ramp rate.

14

■ 空分装置配套数量取决于客户的特定要求: Number of trains based on

customer’s specific requirements:

– 能耗和资金成本的对比Power vs. Capital costs

– 空分装置至现场的运输Transport of ASU(s) to site

– 减少施工/安装成本及风险Reducing construction / erection costs and risks

– 可操作性 Operability

– 大规模压缩一体化Compression integration at large scale

– 适合客户的使用模式Fit with customer’s use patterns

■ 降负荷操作/变负荷操作Turndown / ramping up

– 可靠性，包括备品备件管理Reliability, including spare parts handling

– 交货周期 Schedule

超大型空分一体化的发展VLASU Integration Challenges

15

LPGOX

Waste

Air 1

2 3

4

5

6

7 8

9

10 11

1213

14

15

16 17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

E101

K101 K102

K103

K104

C101 C102

C103

C104

C105

E102

E103

E104

Low Purity, Low Pressure Dual HP Column Cycle for Oxyfuel

16

计划外停车时间 1995 – 2008Outage Duration 1995 - 2008

优异的投产空分运营表现Unbeatable ASU On-Stream Performance

■ 未考虑备用情况下的在线率 On-stream availability not corrected for back-up

■ 10年平均在线率 是 98.4% 10 year onstream average - 98.4%

■ 72.4% 停车情况时间不超过24 hours 72.4%of outages have a duration of <24hrs

■ 运行可靠性帮助客户在一个更稳定的环境下生产运作 Reliability focused operations to help customer run processes in a more sustainable fashion

8 - 16 小时(hrs)

17.1%

< 8 小时(hrs)

38.2%

>24 小时(hrs)

27.6%

16 – 24 小时(hrs)

17.1%

17

Operability: Plant Ramping, Advanced Controls technology

Benefits of Advanced Control capabilities

- Lower power consumption

- Higher product recoveries

- Faster disturbance response and mitigation

- Faster response to changing product demands

- Higher multi-plant efficiency

ASU ramping capabilities

- 1%/min typical

- 2%/min achievable with advanced control

- 3%/min possible when “designed in”

- Higher rates possible by using liquid oxygen backup

18

ITM Oxygen ProgramTargeting Reduction in the Cost of Oxygen by One-Third

Phase 1: Technical Feasibility (0.1 TPD O2)

Phase 2: Prototype Testing (1-5 TPD O2)

Phase 3: Intermediate Scale Testing (150 TPD O2)

Broad, multi-disciplinary team

© Air Products and Chemicals, Inc. 2009. All

Rights Reserved

SOFCo EFS

(McDermott)

GE Energy

19

Ion Transport Membranes (ITM) provide high-flux, high-purity Oxygen

Mixed-conducting ceramic

membranes (non-porous)

Operate around 800 - 900°C

At high temperature, the

crystalline structure

incorporates oxygen

ion vacancies

Oxygen ions diffuse

through vacancies

100% selective for O2

O2- electrons

compressed

air

oxygen

P‟

P‟‟O2

O2

O2- ½O2 + 2e-

½O2 + 2e- O2-

L

LP

PFluxO

O

O /ln''

2

'

22

© Air Products and Chemicals, Inc.

2009. All Rights Reserved

20

ITM Oxygen integrates well with power generation cycles

AIR

OXYGEN

FUEL

HEAT

EXCHANGE

ION

TRANSPORT

MEMBRANE

HRSG

STEAM

OXYGEN

BLOWER

ELECTRIC

POWER

OXYGEN

„AIR‟

Previous studies have shownITM Oxygen requires 30% less capital and 30-60% less energy

than a cryogenic oxygen plant

© Air Products and Chemicals, Inc.

2009. All Rights Reserved

21

ITM Oxygen commercial modules continue

to be tested in the 5 TPD Pilot Plant

Heater

Control Room

Heat Exchangers

Vacuum

Pumps

Make-up Streams

ITM Vessel

6 Independent

Product Trains

Flow Duct Installed

2 Modules Installed

ITM Vessel Internals

515 days operation

• Demonstrated

Purity

• Demonstrated

Flux

• Testing

Operations

• Demo‟d thermo-

cycling

© Air Products and Chemicals, Inc.

2009. All Rights Reserved

22

Next stage scale-up is in design: Intermediate-Scale Test Unit (ISTU)

Forward schedule envisions completion of construction in late 2010

Goals include:

- Produce 150 TPD oxygen from an ITM Oxygen system integrated with power co-production equipment

- Use fuel as primary energy input to the system

- Use commercial design concepts toward scale-up to the next test platform (~2000 TPD)

© Air Products and Chemicals, Inc.

2009. All Rights Reserved

23

ITM Oxygen vessel scaled to match cryogenic oxygen plant output

ITM Oxygen Enables a Step-change Reduction in the Cost of Oxygen

2500 TPD

Oxygen Plant

© Air Products and Chemicals, Inc.

2009. All Rights Reserved

24

Oxyfuel CO2 Purification

Purification requires:

- Cooling to remove water

- Compression to 30 bar: integrated SOx/NOx/Hg removal

- Low Temperature Purification

Low purity, bulk inerts removal

High purity, Oxygen removal

- Compression to pipeline pressure

Steam Boiler & Turbines

Coal

MWe

Flue Gas

Recycle

Oxygen

CO2 Purification

& Compression

O2 Supply CO2 Transport

& Sequestration

Oxyfuel combustion of coal produces a flue gas containing:

– CO2 + H2O– Any inerts from air

in leakage or oxygen impurities

– Oxidation products and impurities from the fuel (SOx, NOx, HCl, Hg, etc.)

25

Air Products‟ Oxyfuel CO2 Capture Technology

Raw

Flue Gas

Product

CO2

Inerts Vent

[To Atmosphere]

Process

Condensate

Heat

Recovery

Sour

Compression

Condensate

Collection

TSA Unit

CO2 Compression

Auto-Refrigerated

Inerts ( +O2)

Removal Process

Boiler Steam

Cycle

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To Boiler]

26

Air Products‟ CO2 Purification and Compression Technology for Oxyfuel

SOx/NOx removed in compression system

- NO is oxidised to NO2 which oxidises SO2 to SO3

- The Lead Chamber Process

FGD and DeNOx systems

– Optimisation

– Elimination

Low NOx burners are not required for oxyfuelcombustion

Hg will also be removed, reacting with the nitric acid that is formed

Sour Compression

SOx, NOx, Hg

Removal

Auto-Refrigerated

Inerts Removal

Ar, N2, O2

Air Products‟

PRISM® Membrane

For enhanced

CO2 + O2 Recovery

Removal minimises compression and transportation costs.

Optional O2 removal for EOR-grade CO2

CO2 capture rate of 90% with CO2 purity >95%

CO2 capture rate depends on raw CO2 purity which depends on air ingress

Inerts vent stream is clean, at pressure and rich in CO2(~25%) and O2 (~20%)

Polymeric membrane unit –selective for CO2 and O2 – in vent stream will recycle CO2and O2 rich permeate stream to the boiler.

CO2 capture rate increases to >97% and ASU size/power reduced by ~5%

27

CO2 Compression and Purification System –Inerts removal and compression to 110 bar

Flue Gas

Expander

Aluminium plate/fin exchanger

Driers

Flue Gas

Heater

30 bar Raw CO2

Saturated 30°C

76% CO2 24% Inerts

CO2 product

110 bar

96% CO2

4% Inerts

-60°C dp

Flue Gas

Vent

1.1 bar

20°C

25% CO2

75% inerts-55°C

28

0.9

0.92

0.94

0.96

0.98

1

10 20 30 40 50 60

CO2

Purity Depends On Feed

Pressure

At -55°C

CO2

Composition

Feed Pressure, bar

29

CO2

Recovery Depends On

Feed Composition

At -55°C, 30 bar

Recovery

Feed Composition

0

0.2

0.4

0.6

0.8

1

0 0.2 0.4 0.6 0.8

30

CO2

Recovery Depends On

Feed Composition

At -55°C, 30 bar

Vent

CO2

Composition

Feed Composition

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

31

CO2 Purity and Recovery

-55°C is as cold as we can make the phase separation

CO2 purity depends on pressure

- At 30 bar and -55°C, CO2 purity is 95%

- Higher pressure gives lower purity CO2

CO2 recovery depends on pressure

- Lower pressure gives lower CO2 recovery

- At 15 bar and -55°C, CO2 recovery is 75%

- At 30 bar and -55°C, CO2 recovery is 90%

CO2 recovery depends on feed composition

- Increases from zero at 25mol% to 90% at 75mol%

- Reducing air ingress increases CO2 capture rate

32

CO2 Purity Issues

Basic Design

CaseEOR Case

H2O < 500 ppm < 50 ppm

CO2> 90% mol > 90% mol

SO2From H&MB < 50 ppm

NO From H&MB From H&MB

O2< 4% mol 100 ppm

Ar + N2 + O2< 4% mol < 4% mol

Regulations regarding onshore and offshore disposal are being drafted world-wide

Co-disposal of other wastes (NOx, SO2, Hg) is a sensitive issue

Important that the CO2 can be purified for disposal or EOR

Basic Design

CaseEOR Case

H2O < 500 ppm < 50 ppm

CO2> 90% mol > 90% mol

SO2From H&MB < 50 ppm

NO From H&MB From H&MB

O2< 4% mol 100 ppm

Ar + N2 + O2< 4% mol < 4% mol

33

NOx SO2 Reactions in the CO2Compression System

We realised that SO2, NOx and Hg can be removed in the CO2compression process, in the presence of water and oxygen.

SO2 is converted to Sulphuric Acid, NO2 converted to Nitric Acid:- NO + ½ O2 = NO2 (1) Slow- 2 NO2 = N2O4 (2) Fast- 2 NO2 + H2O = HNO2 + HNO3 (3) Slow- 3 HNO2 = HNO3 + 2 NO + H2O (4) Fast- NO2 + SO2 = NO + SO3 (5) Fast- SO3 + H2O = H2SO4 (6) Fast

Rate increases with Pressure to the 3rd power- only feasible at elevated pressure

Little Nitric Acid is formed until all the SO2 is converted

Pressure, reactor design and residence times, are important.

34

Air Products‟ CO2 Compression and Purification System: Removal of SO2, NOx and Hg

1.02 bar

30°C

67% CO2

8% H2O

25%

Inerts

SOx

NOx

30 bar to Driers

Saturated 30°C

76% CO2

24% Inerts

Dilute H2SO4

HNO3

Hg

SO2 removal: 100% NOx removal: 90-99%

BFW

Condensate

cw

15 bar

30 bar

Water

cwcw

Dilute HNO3

35

Can we improve on 90% CO2 Capture?

Driers

30 bar Raw CO2

Saturated 30°C

76% CO2 24% Inerts

Vent stream is at pressure and is CO2 (and O2) rich

36

Auto-Refrigerated Partial Condensation with CO2and O2 recovered to the boiler

Driers

30 bar Raw CO2

Saturated 30°C

76% CO2 24% Inerts

Membrane

To Boiler

37

Key Features of Air Products‟ Oxyfuel CO2Purification Technology

FGD and DeNOx systems are not required to meet tight CO2 purity specifications

- Co-disposal of SO2 with CO2 is not possible

- Compressing CO2 with NO + SO2 + O2 + Water will result in H2SO4 production

- Low NOx burners are not required for oxyfuelcombustion

Oxygen can be removed for EOR-grade CO2

No penalty if liquid CO2 is required

Capture of CO2 increased to 98% with CO2 membrane

- Also reduces ASU size (~5% reduction)

38

Chronicles of Air Products‟ Proprietary Oxyfuel CO2 Purification

Path to commercialisation

- Auto-refrigerated partial condensation for inerts removal considered prior art since 2004 (IEA GHG 2005/9 report)

- O2 removal shown to be feasible (January 2007 – IEA GHG 2nd Oxyfuel Network Meeting)

- Air Products give path to SOx/NOx removal in sour compression (June 2006 at GHGT8)

Now we are advancing from lab to

demonstration!

39

OXYCOAL-UK : Phase 1 : BERR 404 Oxyfuel Fundamentals

– WP1: Combustion Fundamentals

– WP2: Furnace Design & Operation

– WP3: Flue Gas Clean-up / Purification

– WP4: Generic Process Issues

40

160 kWth

oxy-coal rig

Cylinder fed

bench rig

London

Renfrew, Scotland

6 kWth

slip stream Batch P

ho

to co

urtesy o

f Do

osa

n B

ab

cock

Ph

oto

cou

rtesy of Im

peria

l Co

llege

Path to from Lab to Demo

41

AB

C

MFC

D

From NRTF

Flue Gas Cooler

Condensate

Separator

Compressor &

Receiver

Reactor

The effect of Pressure on SO2

and

NO Conversion (1 sl/min, 7 and 14 barg)

Inlet

After

Compressor &

ReceiverInlet

After

Compressor &

Receiver

(Point A) (Point C) (Point A) (Point C)

ppm SO2 900 20 98% 950 150 84%

ppm NOx 520 50 90% 390 120 68%

ConversionConversion

7 bar g14 bar g

Presented at the 9th International Conference on Greenhouse Gas Control Technologies (GHGT-9) “Purification of Oxyfuel-Derived

CO2”, Vince White, Laura Torrente-Murciano, David Sturgeon, and David Chadwick, Washington, D.C., November 2008

42

160 kWth

oxy-coal rig

Cylinder fed

bench rig

London

Renfrew, Scotland

6 kWth

slip stream Batch

DOE ProjectHost: Alstom,Windsor, CT

0.3 MWth

slip stream

15 MWth

oxy-coal

combustion unit

Ph

oto

cou

rtesy of D

oo

san

Ba

bco

ck

Ph

oto

cou

rtesy of Im

peria

l Co

llege

Ph

oto

cou

rtesy of A

lstom

Po

wer

Path to from Lab to Demo

43

DOE Project: Air Products’

Sour Compression Process

Development Unit (PDU)

Focused on reactor parameters

– Pressure

– SOx Feed Levels

– Residence Time

44

DOE Project: Air Products‟ Sour Compression PDU

Initiate Testing of Reactor System

- Autumn, 2009

Evaluate Performance of Reactor Based Flue Gas

- Summer, 2010

45

30 MWth oxy-coal

pilot plant

160 kWth

oxy-coal rig

Cylinder fed

bench rig

London

Renfrew, Scotland

Schwarze Pumpe, Germany

1 MWth

slip stream

6 kWth

slip stream Batch

DOE ProjectHost: Alstom,Windsor, CT

0.3 MWth

slip stream

15 MWth

oxy-coal

combustion unit

Ph

oto

cou

rtesy of V

atten

fall

Ph

oto

cou

rtesy of D

oo

san

Ba

bco

ck

Ph

oto

cou

rtesy of Im

peria

l Co

llege

Ph

oto

cou

rtesy of A

lstom

Po

wer

Path to from Lab to Demo

46

47

Air Products‟ CO2 Purification Unit (CPU) Pilot Plant at Vattenfall‟s Schwarze Pumpe

Raw

Flue

Gas

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

48

Flue Gas Condenser in a more acidic environment

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

The raw flue gas feed can be taken from two

locations in the existing OxPP: upstream of the FGD

to maximise SO2 content and downstream of the

FGD to ensure that impurity carry over from the FGD

does not affect the rest of the downstream process

Raw

Flue

Gas

49

Sulphur and Nitrogen Oxidation and Acid Removal

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

The "warm" part of the Air

Products pilot plant will

demonstrate the SOx/NOx

removal process using 15 and

30 bar contacting columns

Raw

Flue

Gas

50

Corrosion issues

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

With the acid streams that are formed

throughout the process the design of the

pilot plant must pay particular attention to

corrosion. We will take the opportunity to

test other materials.

Raw

Flue

Gas

51

Performance of TSA adsorbents

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

We will be monitoring the

behaviour of the TSA

Raw

Flue

Gas

52

Mercury behaviour and distribution in the process

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

We need to understand: how much mercury exists,

in what form, and at which locations in the process.

A guard bed downstream of the dryers will remove

elemental Hg to prevent attack on the Aluminium

heat exchangers.

Raw

Flue

Gas

53

CO2 VLE

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

Confirm vapour/liquid

equilibrium of the

CO2/Ar/N2/O2 stream that is

flashed to remove inerts from

the process and purified in the

distillation column.

Raw

Flue

Gas

54

CO2 Freeze-out

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

Performance depends on how tightly the main heat

exchanger can be pinched. We need to understand

the implications of operating so close to the triple

point of CO2: does solid CO2 form and what is the

consequence?

Raw

Flue

Gas

55

Membrane Performance

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

The performance the Air

Products PRISM® membrane

will be monitored since this is a

new application for this type of

membrane.

Raw

Flue

Gas

56

Flexibility

CO2 Returned

To OxPP

Inerts Vent

[To OxPP]

Process

Condensate

Sour

Compression

Condensate

Collection

TSA UnitMercury

Removal

Auto-Refrigerated

Inerts +O2

Removal Process

Air Products

PRISM®

Membrane

O2 and CO2 Rich

[To OxPP]

We can blend N2 and CO2 into the feed to simulate

higher or lower air ingress. This could also be used to

understand system dynamics by introducing a spike of

N2 or CO2 into the feed.

Raw

Flue

Gas

57

Challenges

Optimisation of SOx, NOx, & Hg removal

Reaction kinetics / equilibrium

Fouling / impurities effects

Materials of construction

Byproduct streams – H2SO4, HNO3, Hg species,…

Burners must be demonstrated with flue gas recycle

Minimisation of parasitic power for O2 supply and CO2compression / purification

• PDU

• CPU Pilot Plant

Boiler OEMs

Reference Plants

Design

FEED Studies

58

Timeline to Commercialisation

2009

2020

20102011

20122013

20142015

20162017

20182019

Nov 2010

Oct 2011

2010

2012

Oct 2009

Sep 2010

Oct 2009

Sep 2010

Nov 2010

Oct 2011

2010

2012

2015

2015

Demonstration Plant Onstream

(50-300MWe)

59

Summary

There is a major new industry requirement for ASUs from fossil-fuel fired power generation

ASUs have changed a great deal in the past 15 years

- New cycles

- Structured packing for distillation

- More power efficient

Single train sizes over 5000 tonne/day

CO2 Purification Units (CPU) being developed to purify raw CO2

60

It is about more than just O2…

Air Products has APPLICATION EXPERIENCE

- Large oxygen/air separation equipment to all type of applications and industries (Power, Gasification, Metals, Refining / Petrochemicals, etc.)

Air Products has INTEGRATION EXPERIENCE

- Air separation plants in all integration modes

- Oxygen supply control system

Load following, start-up shutdown, peak-shaving

- MAC heat recovery

- Off-gas oxygen recovery for boiler blended to LASU O2

- Standalone, nitrogen integrated, and air/nitrogen integrated (IGCC)

Air Products has MEGA-TRAIN EXPERIENCE

- Operating very large single train air separation plants since 1997 in Rozenburg, The Netherlands (3250 t/d); also installed a 2x3500 t/d unit in Qatar

Air Products demonstrates RELIABILITY

- First company to supply high-reliability tonnage oxygen for power projects without oxygen backup

Air Products provides OTHER GAS PRODUCTS

- Broad industrial gas industry experience creates synergies with H2, CO, and CO2

markets

61

Disclaimer

Neither Air Products and Chemicals, Inc. nor any of its contractors or subcontractors nor the United States Department of Energy, nor any person acting on behalf of either:

1. Makes any warranty or representation, express or implied, with respect to the accuracy, completeness, or usefulness of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately owned rights; or

2. Assumes any liabilities with respect to the use of, or for damages resulting from the use of, any information, apparatus, method, or process disclosed in this report.

Reference herein to any specific commercial products, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Department of Energy. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Department of Energy.

The authors gratefully acknowledge the contributions by the members of the ITM Oxygen team at Air Products, Siemens, Ceramatec, GE Energy Gasification, DOE, EPRI, Concepts NREC, NovelEdge, SOFCo EFS, EltronResearch, Penn State University, and Univ. of Pennsylvania.

This technology development has been supported in part by the U.S. Department of Energy under Contract No. FC26-98FT40343. The U.S. Government reserves for itself and others acting on its behalf a royalty-free, nonexclusive, irrevocable, worldwide license for Governmental purposes to publish, distribute, translate, duplicate, exhibit and perform this copyrighted paper.

Acknowledgement

62

A significant portion of this report was prepared by Air Products and Chemicals, Inc. pursuant to a Cooperative Agreement partially funded by the United States Department of Energy, and neither Air Products and Chemicals, Inc. nor any of its contractors or subcontractors nor the United States Department of Energy, nor any person acting on behalf of either:

1. Makes any warranty or representation, express or implied, with respect to the accuracy, completeness, or usefulness of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately owned rights; or

2. Assumes any liabilities with respect to the use of, or for damages resulting from the use of, any information, apparatus, method, or process disclosed in this report. Reference herein to any specific commercial products, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Department of Energy. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Department of Energy.

This paper was written with support of the U.S. Department of Energy‟s National Energy Technology Laboratory under Contract No. DE-NT0005309. The Government reserves for itself and others acting on its behalf a royalty-free, nonexclusive, irrevocable, worldwide license for Governmental purposes to publish, distribute, translate, duplicate, exhibit and perform this copyrighted paper.

Disclaimer

Acknowledgment: DOE/NETL

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