the potential of water-gas shift membrane reactors for ctx...

The potential of water-gas shift membrane

reactors for CtX and flexible poly-generation

processes

7th International Freiberg/Inner Mongolia Conference

on IGCC & XtL Technologies, Coal Conversion and Syngas

9 June 2015, Inner Mongolia, China

Alexander Buttler, Hartmut Spliethoff

Institute for Energy Systems, Technical Universtiy of Munich

Structure

Transition of the German Energy System

• Actual challenge of volatile renewable feed-in

• Future demand of flexible power plants and resulting requirements

The potential of IGCC poly-generation plants in a changing energy system

Water-gas shift membrane reactor

• Theory

• Flexible poly-generation concept

Modelling and analysis

• Modelling appraoch and boundary conditions

• Concept evaluation

7th international Freiberg/Inner Mongolia Conference on IGCC&XtL Technologies, Alexander Buttler09.06.15 2

Transformation of the German energy system

7th international Freiberg/Inner Mongolia Conference on IGCC&XtL Technologies, Alexander Buttler

Installed capacity of wind and PV

0

20

40

60

80

100

120

140

160

1995 2000 2005 2010 2015 2020 2025 2030 2035 2040 2045 2050

Pow

er

[GW

]

Solar Wind Offshore Wind Onshore

Peak net load

Installed Wind and PV power will exceed

peak load next year

09.06.15 3

Actual challenge of volatile renewable feed-in


Impact of wind and PV on the residual load

82,587,0 85,8

81,2 80,983,9

73,2 72,976,3

39,2 39,1 38,7

19,5 20,518,2

11,6 12,5 10,6

0

10

20

30

40

50

60

70

80

90

2014 2013 2012

Tite

l

Load Max

Res1 Max

Res2 Max

Load Min

Res1 Min

Res2 Min

0

10

20

30

40

50

60

70

80

90

0 1000 2000 3000 4000 5000 6000 7000 8000

Po

wer

[GW

]

hours per year

Biomass, hydro Wind+PV Load Res2 Res1

Strong lowering of minimal residual load

Little decrease of residual peak load

09.06.15 4



Inflexibilities of the conventional power plants - negative electricity prices

0

10

20

30

40

50

60

70

80

Jan. März Mai Juli Sept. Nov.

nuclear Lignite Hard coal Gas OilNet power [GW]

12,17,5

19,6

9,2

20,9

21,4

3,5

1,0

Max Min

79,9

23,6

March May July-80

-60

-40

-20

0

20

40

60

80

100

0 10 20 30 40 50 60 70 80

Da

y-A

he

ad

Sp

ot m

ark

et p

rice

[€

/MW

h]

Residual load [GW]

Data 2014

ø 32,6 €/MWh

Min. -65 €/MWh

Max. 88 €/MWh

Minimum net output of conventional power

plants lies far above minimum residual load

Source: Own illustrations based on eex.com and eex-transparency.com

09.06.15 5

The potential of IGCC poly-generation plants in a changing

energy system


Gasifier island

Gas cleaning

CCPP

Synthesis unit Electrolysis

unit

Power Production Synfuel Production

100%

0%

Base load demand

(nuclear power phase-

out)

Medium load

demand

Peak load

demand and

energy storage

IGCC allows a very flexible adaption

to the future requirements

09.06.15 6



Theory

Large scale concept

Feed

Membrane tubes

Source: Melin (2004)

Hydrogen flux across the membrane:

With

P…Permeability

δ...Membrane thickness

T…Temperature

pH2…partial pressure

AM…Membrane area

09.06.15 7



Concept and advantages of a flexible WGS-MR-poly-generation plant

WGSGF CCPP

MeOH/SNG

AGR

steam

CO2 to pipeline

HGCUGF CCPP

MeOH/SNG

WGS-MR

steam

CO2 to pipeline

Advantages of MR-concept:

+ Low steam demand for CO-shift

+ Reduced gas temperature cycling

+ variable split of gas streams with

adjusted composition for gas turbine or

synthesis plant

BC…Base Case (Water quench,

Rectisol)

MR…Membrane Reactor (Gas quench,

hot gas clean up)

BC

MR

09.06.15 8

.

.

.

O2

CO2 to pipeline

To synfuel plantH2, CO, CO2; SN=opt.

To gas turbine (N2+H2)

N2 from ASU

Clean gas

steam

H2

H2

H2

H2

H2

H2

Expansion in turbine

Sweep gas

Ret

enta

te

Permeate

Catalytic combustion

Number of WGS-MR for synfuel plant NSYN

Number of WGS-MR for CCPP NCCPP



Detailed poly-generation concept

Splitter for adjustment of optimal gas composition for synthesis plant

𝑛𝑆𝑤𝑒𝑒𝑝

𝑛𝐶=

𝑌∙ 𝑛𝐶,𝐻2+𝑌∙𝑋 ∙𝑛𝐶,𝐻2𝑆𝑁+𝑌∙𝑋 ∙ 𝑛𝐶,𝐶𝑂+ 𝑀−1 ∙𝑛𝐶,𝐻2

With

C…Clean gas

Y…H2-yield

X…CO-conversion

SN…stochiometric number

…….(=H2/CO=2.05)

For MeOH:

For given syngas composition 𝑛𝑆𝑤𝑒𝑒𝑝

𝑛𝐶:

MeOH: 0.43

SNG: 0.30 (𝑆𝑁= 𝑛𝐻2 − 𝑛𝐶𝑂2 𝑛𝐶𝑂 − 𝑛𝐶𝑂2

= 3)

Variable product ratio:

synthesis product/electricity ~ Nsyn/NCCPP

09.06.15 9

Modeling approach and boundary conditions


Gasifier Island and Gas Cleaning Combined Cycle Power Plant

Membrane Reactor

Ebsilon®Professional

All models validated with industrial

data [Kunze(2012), Buttler(2013)]

09.06.15 10

Main boundary conditions

Gasifier island

• Entrained flow gasifier with syngas cooler

• Fuel Input: 1000 MWth Hard Coal

• Temperature/Pressure: 1400 °C/40 bar

• Carbon Conversion: 98.5 %

• Cryogenic ASU: 0.273 kWh/kg O2

• Rectisol power demand: 0.04-0.06 kWh/kgCO2

• CO2 pressure: 110 bar

Combined Cycle Power Block

• Fuel Gas LHV: 8000 kJ/kg

• Gas turbine: TIT 1300 °C/ 0/0.5-1 load

• 3-pressure HRSG: 130/40/5 bar

Membrane reactor

• Pd/Cu

• H2O/CO 1.6

• H2-yield 94 %

• CO-conversion 98 %

Synthesis plants

• SNG: 3-stage adiabatic fixed bed process 600/450/300 °C, 0/0.5-1 load

• MeOH: LPMEOH isothermal 250 °C, 50 bar


37.739.4

42.245.1

52.8

65.461.2

0%

10%

20%

30%

40%

50%

60%

70%

0

100

200

300

400

500

600

700

BCIGCC

BC-SNGIGCC

MRIGCC

MRIGCC-100%SNG-20%*

MRIGCC-50%SNG-60%*

MRSNG

BCSNG

Effi

cien

cy

MW

Net power

SNG production (LHV)

Concept evaluation


SNG – WGS-MR-poly-generation-process

CO2-sequ.: 91.6% 69.1% >98%


Rectisol)


hot gas clean up)

BC-SNG IGCC…Base Case IGCC

configuration, gas composition adjusted

for SNG-synthesis plant

*values referred to gas turbine load or

synthesis plant load respectively

Electric power must-run of 88 GW (MR SNG)

Reduced SNG-production compared to base case

Poly-generation

09.06.15 12

Concept evaluation


Methanol – WGS-MR-poly-generation-process

CO2-sequ.: 91.6% 69.1% >98%


Rectisol)


hot gas clean up)

*values referred to gas turbine load or

synthesis plant load respectively37.7

42.244.1

50.4

62.4

58.1

0%

10%

20%

30%

40%

50%

60%

70%

0

100

200

300

400

500

600

700

BCIGCC

MRIGCC

MRIGCC-100%

MeOH-20%*

MRIGCC-50%

MeOH-60%*

MRMeOH

BCMeOH

Effi

cien

cy

MW

Net power

MeOH production (LHV)

Poly-generation

Electric power must-run of 30 GW (MR MeOH)

Slightly increased MeOH-production compared to base case

09.06.15 13

Summary

IGCC concept allows flexible adaption to future requirements in a changing energy system

WGS membrane reactor has the potential to improve the

• Efficiency (about 4 %-points)

• Flexibility (production of several product gas streams with different gas composition)

MeOH is identified as a better option compared to SNG

• Higher sweep gas stream (lower membrane area)

• Lower electric power must-run

• High value follow-up products (MtG, Methanol-to-Propylene)

Outlook:

• Economic evaluation

• Sensitivity analysis of the membrane area


The potential of water-gas shift membrane reactors for

CtX and flexible poly-generation processes

Thank you for your attentation!

7th International Freiberg/Inner Mongolia Conference

on IGCC & XtL Technologies, Coal Conversion and Syngas

9 June 2015, Inner Mongolia, China

Dipl.-Ing. Alexander Buttler

Institute for Energy Systems, Technical University of Munich

[email protected]

80

50

76

60

45

30

20

9390

75

27,3

35

50

65

80

0

20

40

60

80

100

120

1990 2000 2010 2020 2030 2040 2050

per

cen

tage

%

PEV relativ zu 2008 THG relativ zu 1990

Bruttostromverbrauch relativ zu 2008 EE-Anteil am BSV

Transformation of the German energy system


Time schedule of the energy concept of the German government

Goals Energy Concept 2010

Primary energy consumption compared to 2008

Gross electricity consumption compared to 2008

Greenhous gas emissions compared to 1990

Share of renewable energy generation on GEC

09.06.15 16



Negative electricity prices

1 10

2820

2 1 2 1

15

71

1215

5664 64

0

10

20

30

40

50

60

70

80

2005 2006 2007 2008 2009 2010 2011 2012 2013 2014

Nu

mb

er o

f h

ou

rs [

-]

price = 0 price <0

Source: own calculations based on eex.com

Phelix day-ahead spot market price

-80

-60

-40

-20

0

20

40

60

80

100

0 10 20 30 40 50 60 70 80

Da

y-A

he

ad

Sp

ot m

ark

et p

rice

[€

/MW

h]

Residual load [GW]

Data 2014

ø 32,6 €/MWh

Min. -65 €/MWh

Max. 88 €/MWh

09.06.15 17

the potential of water-gas shift membrane reactors for ctx...

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