Flexibility in renewable fuel production from biomass the ... · A Fischer-Tropsch reactor converts...

Flexibility in renewable fuel production from biomass – the role of

electrolysis boosted Fischer-Tropsch synthesis

Felix Habermeyer DLR e.V. May 27th 2019

FlexCHX project has received funding from the European Union’s Horizon 2020 research and innovation Programme under Grant Agreement No 763919.

EUBCE • F. Habermeyer • 27.05.2019 • Lisbon • The role of Fischer-Tropsch synthesis in renewable fuel production from biomass DLR.de • Chart 2

A. FLEXCHX Process Concept

B. Fischer-Tropsch synthesis

C. Optimal FT process integration

3

Flexible combined

production of power, heat

and transport fuels from

renewable energy sources

FLEXCHX

FLEXCHX

Acronym: FLEXCHX

Funding scheme: RIA

Duration: 36M, March 2018 – February 2021

H2020 funding: 4 489 545 €

Coordinator: VTT

Consortium: VTT (Finland), Enerstena (Lithuania),

INERATEC (Germany), Deutsches Zentrum Fuer Luft - Und

Raumfahrt e.V., Germany-DLR (Germany), HELEN (Finland),

Kauno Energija (Lithuania), Lithuanian Energy Institute

(Lithuania), NESTE Engineering Solutions (Finland),

Johnson Matthey (UK) and Grönmark (Finland)

FlexCHX project has received funding from the

European Union’s Horizon 2020 research and innovation

Programme under Grant Agreement No 763919. EUBCE • F. Habermeyer • 27.05.2019 • Lisbon •

The role of Fischer-Tropsch synthesis in

renewable fuel production from biomass

High heat

demand

&

Low

renewable

electricity

availability

Seasonal solar irradiation and heating demand for a

typical Northern European country

[1]

[1] https://ilmatieteenlaitos.fi/energialaskennan-testivuodet-nyky as cited in Kurkela, E. (2017) Flexible combined production of power, heat and transport fuels from renewable energy sources. Project Proposal [2] Kurkela, E. (2017) Flexible combined production of power, heat and transport fuels from renewable energy sources. Project Proposal

The FLEXCHX process can respond to supply and demand on the energy

market


Low heat

demand

&

High

renewable

electricity

availability


[2]

[2]

Further information about the FLEXCHX project


CHP integration


Presenter Institution Date Time Session Reference

Esa Kurkela VTT Tuesday – 28.05 15:15-16:45 2BO.10.1

Flexible Hybrid Process for Combined Production of Heat, Power and Renewable Feedstock for Refineries

Nerijus Striugas LEI Wednesday – 29.05 8:30-10:00 2CV.2.16

Integration of Waste Heat Streams into Industrial CHPs or District Heating Units

All other public results are available at: http://www.flexchx.eu/downloads.htm





Process design to maximize the Fischer-Tropsch output


Process design parameters affecting the FT reactor

• FT productivity is determined by the inert content set by gasifier and reformer

• Air: Low operation costs – yet higher inert gas content

• Oxygen enriched air: High operation costs – yet lower inert gas content in the syngas

• Flowsheet adjustments to increase the FT performance

Air Oxygen enriched air

FT-Syncrude

Heat & Off-gas

Inerts

Syngas

Short recycle Long recycle

Second reactor stage


Liquid and solid hydrocarbons • Paraffines • Iso-Paraffines • Olefins • Alcohols • Acids

Unreacted educt

Hydrocarbon gases C1-C4

A Fischer-Tropsch reactor converts syngas to hydrocarbon chains


CO

H2

CO

CO

H2 H2

H2

Low temperature

Fischer-Tropsch

micro reactor

Syngas


Catalyst: Cobalt Temperature range: 220-240 °C

Pressure range: 10-40 bar

Performance indicators:

• Selectivity for higher chain lengths σC5+

• Carbon monoxide conversion ζCO: < 80 %

Typical input ratio

H2/CO: 2.1 [4]

Educt By-Product

CO H2

CH4

C4H10

Product

C5H12

C32H66

…

…

[3] Van Der Laan, G. P., & Beenackers, A. A. C. M. (1999). Kinetics and selectivity of the Fischer–Tropsch synthesis: a literature review. Catalysis Reviews, 41(3-4), 255-318. [4] Yang, J., Eiras, S. B., Myrstad, R., Venvik, H. J., Pfeifer, P., & Holmen, A. (2016). 12 Fischer-Tropsch Synthesis on Co-Based Catalysts in a Microchannel Reactor. Fischer-Tropsch Synthesis, Catalysts, and Catalysis: Advances and Applications, 142, 223.

[3]

Higher mass flow leads to lower CO conversion and lower C5+ selectivity


40

45

50

55

60

65

70

75

80

85

90

6 8 10 12

ζ CO

[%

]

GHSV [N L/gcat/h]

80

81

82

83

84

85

86

87

88

6 8 10 12

σC

5+

[%

]

GHSV [N L/gcat/h]

T = 210 °C

p = 20 bar

H2 / CO =2.1

T = 210 °C

p = 20 bar

H2 / CO =2.1

Gas hourly space velocity (GHSV) – standard volume flow over catalyst mass

Influence of GHSV on CO-Conversion ζCO Influence of GHSV on C5+ selectivity σC5+


[4] [4]

[4] Yang, J., Eiras, S. B., Myrstad, R., Venvik, H. J., Pfeifer, P., & Holmen, A. (2016). 12 Fischer-Tropsch Synthesis on Co-Based Catalysts in a Microchannel Reactor. Fischer-Tropsch Synthesis, Catalysts, and Catalysis: Advances and

Applications, 142, 223.

[5] Hamelinck, C. N., Faaij, A. P., den Uil, H., & Boerrigter, H. (2004). Production of FT transportation fuels from biomass; technical options, process analysis and optimisation, and development potential. Energy, 29(11), 1743-1771.

[6] Yates, I. C., & Satterfield, C. N. (1991). Intrinsic kinetics of the Fischer-Tropsch synthesis on a cobalt catalyst. Energy & Fuels, 5(1), 168-173.

ζCO = 80 % limit

Fischer-Tropsch Model:

• Plug flow reactor

• Lumped kinetic model [5][6]

• Fitted to experimental data in literature [4]

• Reaction kinetic implemented in Aspen Plus





Short recycle

+ LeViness states that a recycle uses capital equipment more efficiently compared to a two-stage reactor [7]

- Accumulation of inert gas content

Long recycle

+ Reformation of hydrocarbon gases + Higher overall process efficiency than short recycle [8] - Higher investment costs

Second reactor stage

+ No accumulation of inert gases - Reactor inlet conditions for second stage harder to control

Different process integration methods increasing FT reactor performance

EUBCE • F. Habermeyer • 27.05.2019 • Lisbon • The role of Fischer-Tropsch synthesis in renewable fuel production from biomass DLR.de • Chart 11 FlexCHX project has received funding from the European Union’s Horizon 2020 research and innovation Programme under Grant Agreement No 763919.

[7] LeViness, S., Deshmukh, S. R., Richard, L. A., & Robota, H. J. (2014). Velocys Fischer–Tropsch synthesis technology—new advances on state-of-the-art. Topics in Catalysis, 57(6-9), 518-525. [8] Herz, G., Reichelt, E., & Jahn, M. (2018). Techno-economic analysis of a co-electrolysis-based synthesis process for the production of hydrocarbons. Applied Energy, 215, 309-320

With this FT model the effect of a recycle on the product yield C5+ can be

analyzed


Recycle Ratio r = [0-0.7]


Pure Syngas: CO, H2

Overall Syngas Conversion ζCO,oa

Product mass flow

𝑟 =𝑛 𝑟𝑒𝑐𝑦𝑙𝑒

𝑛 𝑜𝑓𝑓−𝑔𝑎𝑠

mcat GHSV

r 0

1

Simulation in Aspen Plus

A recycle decreases the overall product yield in favor of off-gas


0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Mas

s fl

ow

[kg

/s]

Recycle ratio [-]

Product

C10+

C5-9

Off-gas

• Setting the recycle ratio to 70 % lowers the

overall production by 0.1 kg/s

• Shift towards smaller chain lengths


With an increased recycle ratio C5+ selectivity and CO conversion are reduced


0.5

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

ζ CO

[-]

, σ

C5

+ [-]

Recycle ratio [-]

Per-pass CO conversion

Selectivity C5+

Overall CO Conversion

• The selectivity for higher chain

lengths deteriorates due to the

increasing mass flow over the catalyst

• The per-pass CO conversion drops

due to the same reason

• The overall CO conversion is reduced

by ~5 %

• With the recycle an overall CO-

conversion above 80 % can be

achieved without damaging the

catalyst

• Tradeoff overall conversion –

investment costs

T = 210 °C

p = 20 bar

H2/CO = 2.1

mcat. const.


Analyzing the tradeoff between overall conversion and investment costs for

short recycle and two stage operation

EUBCE • F. Habermeyer • 27.05.2019 • Lisbon • The role of Fischer-Tropsch synthesis in renewable fuel production from biomass DLR.de • Chart 15 FlexCHX project has received funding from the European Union’s Horizon 2020 research and innovation Programme under Grant Agreement No 763919.

[4] Yang, J., Eiras, S. B., Myrstad, R., Venvik, H. J., Pfeifer, P., & Holmen, A. (2016). 12 Fischer-Tropsch Synthesis on Co-Based Catalysts in a Microchannel Reactor. Fischer-Tropsch Synthesis, Catalysts, and Catalysis: Advances and Applications, 142, 223.

ζoa =

ζ

𝟏 − 𝒓(𝟏 − ζ)

ζoa = 1−(1− ζI)(1− ζII)

*Experimental operation point : GHSV 8.017 N L/(gcat h), p = 20 bar, T = 210 °C, ζ = 73.7 %, σC5+ = 86.2 % [6]

Short Recycle Two-stage operation

mcat GHSV

ζ =

73.7%

ζI =

73.7%

ζII =

73.7% ζoa =

93 % ζoa = 93 %

𝐧 𝐢𝐧

mcat GHSV 𝐧 𝐢𝐧

mcat GHSV

r = 80 %

*

Inerts

Syngas Inerts

Syngas

For high feed inert gas content the two-stage solution appears to be the

favorable option


0

0.5

1

1.5

2

2.5

3

0 10 20 30 40

Cat

alys

t m

ass

rati

o [

-]

Feed inert content [mol %]

Two-Stage

Recycle

𝐂𝐚𝐭𝐚𝐥𝐲𝐬𝐭 𝐦𝐚𝐬𝐬 𝐫𝐚𝐭𝐢𝐨 =𝐦𝐜𝐚𝐭,𝐭𝐰𝐨−𝐬𝐭𝐚𝐠𝐞/𝐫𝐞𝐜𝐲𝐜𝐥𝐞

𝐦𝐜𝐚𝐭,𝐨𝐧𝐜𝐞−𝐭𝐫𝐨𝐮𝐠𝐡

• A short recycle requires more catalyst to

attain the same overall CO conversion as a

two-stage reactor

• With increasing feed inert gas content this

difference widens

• A two-stage solution is favorable for high

inert gas contents

T = 210 °C

p = 20 bar

H2/CO = 2.1

GHSV. = 8.017 N L/(gcat h)


Conclusion

• The FLEXCHX project offers a flexible production of power, heat and fuel from biomass adapted to market

conditions

• To model a Fischer-Tropsch reactor a lumped kinetic approach is used and fitted to published experimental

data

• Two-stage operation and recycle can be used to attain carbon monoxide conversions above 80 %

• A two-staged FT reactor is favorable to a recycle solution at high feed inert gas contents

• A comprehensive techno-economic analysis as well as a life-cycle assessment will be performed in the

course of the project

• The FT model will be validated with the experimental data provided by project partners and deployed to find

an optimal operation strategy

• The long recycle will be compared to the other options


Outlook


References

[1] https://ilmatieteenlaitos.fi/energialaskennan-testivuodet-nyky as cited in Kurkela, E. (2017) Flexible combined production of power, heat and transport fuels from

renewable energy sources. Project Proposal

[2] Kurkela, E. (2017) Flexible combined production of power, heat and transport fuels from renewable energy sources. Project Proposal

[3] Van Der Laan, G. P., & Beenackers, A. A. C. M. (1999). Kinetics and selectivity of the Fischer–Tropsch synthesis: a literature review. Catalysis Reviews, 41(3-4),

255-318.

[4] Yang, J., Eiras, S. B., Myrstad, R., Venvik, H. J., Pfeifer, P., & Holmen, A. (2016). 12 Fischer-Tropsch Synthesis on Co-Based Catalysts in a Microchannel Reactor.

Fischer-Tropsch Synthesis, Catalysts, and Catalysis: Advances and Applications, 142, 223.

[5] Hamelinck, C. N., Faaij, A. P., den Uil, H., & Boerrigter, H. (2004). Production of FT transportation fuels from biomass; technical options, process analysis and

optimisation, and development potential. Energy, 29(11), 1743-1771.

[6] Yates, I. C., & Satterfield, C. N. (1991). Intrinsic kinetics of the Fischer-Tropsch synthesis on a cobalt catalyst. Energy & Fuels, 5(1), 168-173.

[7] LeViness, S., Deshmukh, S. R., Richard, L. A., & Robota, H. J. (2014). Velocys Fischer–Tropsch synthesis technology—new advances on state-of-the-art. Topics in

Catalysis, 57(6-9), 518-525.

[8] Herz, G., Reichelt, E., & Jahn, M. (2018). Techno-economic analysis of a co-electrolysis-based synthesis process for the production of hydrocarbons. Applied

Energy, 215, 309-320.


Flexibility in renewable fuel production from biomass – the role of

electrolysis boosted Fischer-Tropsch synthesis

Felix Habermeyer DLR e.V. May 27th 2019


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