From CO to Energy: Carbon Capture in Cement Production and

Scientific Committee Meeting in Mons

News from 08/03/18 to 02/07/18 (~4 months)

« From CO2 to Energy:Carbon Capture in Cement Production and its Re-use »

02/07/18

University of Mons 2

Agenda of the meeting – 02/07/2018:

- Introduction : M. Schneider and P. Lybaert

- Status of the ECRA Chair: D. Thomas• General information• External communication activities & Future activities• Annual ECRA Chair activities report

- Scientific information-> News of the ECRA Chair PhD theses & Post-doc:• PhD Thesis of S. Mouhoubi and Post-doc works of L. Dubois• PhD Theses of N. Meunier and of R. Chauvywith discussions ECRA-UMONS

- Signing of the ECRA Chair prolongation (2019-2022): 15hDiscussion on the future ECRA Chair (phase III) scientific topics

- Future activities of the ECRA Chair: scientific event in 2019 ? Other ?

- Report on ECRA’s activities beyond the ECRA Chair - M. Schneider- Final remarks – closing

ECRA Chair « CO2 to Energy » - Scientific Meeting in Mons – 02/07/2018


STATUS OF THE ECRAChair@UMONS



ECRA Academic Chair TimelineCurrent status

24/04/13

Phase 1 (2013-2016):2 PhD theses + 1 Post-doc

Phase 2 (2016-2019)2 PhD theses (+ 1 Post-doc)

2013 2014 2015 2016 2017

PhD THESIS 1 – N. MEUNIER

PhD THESIS 2 – S. LARIBI

POST-DOC – L. DUBOIS

PhD THESIS 3 – R. CHAUVY

ECRA ACADEMIC CHAIR – 3 YEARS (1)

2018 2019

= today

ECRA ACADEMIC CHAIR – 3 YEARS (2)

PhD THESIS 4 – S. MOUHOUBI


L. DUBOIS

finalized

PhD THESIS 5


Annual meetings of PhD theses committees with internal (UMONS) and externalmembers:

- For R. Chauvy :→ took place on 31-05-2018→ was validated

- For S. Mouhoubi:→ took place on 19-06-2016→ was validated

Reports will be available soon on the ECRA Website / document section

PhD thesis committees


→ Finalisation of tasks and redaction of the PhD thesis manuscript→ Public thesis defence final date: 12 October 2018

→ All ECRA TAB members are all cordially invited to the public thesis defence

PhD thesis of N. Meunier


PhD Thesis 5: Optimization of a catalytic process for the CO2 purification

derived from an oxy-fuel combustion

→ Scientific content:

- Catalytic CO2 purification process (deNOx)

-> reducing NO (in N2) by oxidizing CO (in CO2)

- Optimization of operating conditions and innovative catalysts performances

- Challenge of oxidizing conditions (presence of O2) and presence of CO2 and H2O

(cause of deactivation)

- Innovative subject in accordance with ECRA interests for oxy-combustion

→ Collaboration with ULCO (Dunkerque) : 3-year PhD Thesis (« French » model)

→ Funding: 50% ECRA Chair-UMONS / 50% ULCO


New PhD thesis


New PhD thesis → selected candidate

Bachelor of Science in

Industrial Chemistry

Science in Industrial

Chemistry18 january 2010

Makerere University

(Ouganda)

Chemical Engineering Master of science in

Engineering4 october 2017

Norwegian University of

Science and Technology

(NTNU- Norway)

Moses MAWANGA(32 years-old)

→ The PhD thesis will start on the 1st of October or November



5th Annual report 2017-2018 sent in May 2018 (period May 2017 – April 2018)

Remarks ?? Approval ??


5th annual report


Future external communication activities (1)

DA2018 – 11th International Conference on Distillation and Absorption –

Florence (Italy) – September 2018

→ Simultaneous absorption of SO2 and CO2 from conventional and partial

oxy-fuel cement plant flue gases

S. Laribi, L. Dubois, G. De Weireld and D. Thomas

Short article (6 pages) accepted in

Chemical Engineering Transactions (vol.69, 2018)


ORAL communication

University of Mons 10ECRA Chair « CO2 to Energy » - Scientific Meeting in Mons – 02/07/2018

Future external communication activities (2) GHGT-14 - 14th International Conference on Greenhouse Gas Control

Technologies - October 21st - 25th 2018 – Melbourne (Australia)

3 abstracts accepted

→ Thermodynamic modelling of N,N-diethylethanolamine aqueous solutions as

a first step to the study of demixing mixture with N-Methyl-1,3-Propanediamine

for CO2 capture

S. Mouhoubi, L. Dubois, P. Loldrup Fosbøl, G. De Weireld and D. Thomas

ORAL communication

→ Optimization of the post-combustion CO2 capture process applied to cement

plant flue gases: parametric study with different solvents and configurations

combined with intercooling

L. Dubois and D. Thomas

ORAL communication

Possible submission of manuscripts in IJGGC

→ Techno-Economic and Environmental Assessment of the capture and

conversion of CO2 into methanol applied to the cement industry

Remi Chauvy, Nicolas Meunier, Diane Thomas, Guy De Weireld

POSTER communication

University of Mons 11ECRA Chair « CO2 to Energy » - Scientific Meeting in Mons – 02/07/2018

Future external communication activities (3)

* 8th International VDZ Congress takes place on 26 - 28 September 2018, in

Duesseldorf (Germany)

-> Conversion of CO2 - A Techno-economic Assessment

Remi Chauvy

* ECRA/CEMCAP/CLEANKER Workshop on 17 October 2018, in Brussels

-> Topic of “Carbon capture in cement production and its reuse”

with a strong focus on the reuse

Diane Thomas

* IEAGHG’s 2018 International Summer School, hosted by the Norwegian

CCS Research Centre at Trondheim (Norway), 24-30 June 2018

Seloua Mouhoubi

ORAL communication

ORAL communication


SCIENTIFIC INFORMATION



General framework of the ECRA Chair – PhD ThesesC

em

ent

ind

ust

ry

Oxy-fuelCO2 captureyCO2 > 70%

Partial oxy-fuelCO2 capture

35 < yCO2 < 70%

Post-combustionCO2 captureyCO2 < 35%

CO2 Catalytic Conversion into methanol

Other CO2 Conversion routes

Absorption-RegenerationProcess: conventional solvents

Air Products CO2 Purification Unit (CPU)

Modeling and Optimization

Modeling and Experiments(solvents screening)

Modeling and Experiments(effect of impuritieson catalytic process)

CryogenicUnit

DehydrationUnit

Sour Compress.

Unit

Pressure Swing Adsorption (PSA)Adsorption Process

= Sinda Laribi’s PhD Thesis

= Nicolas Meunier’s PhD Thesis

= Other works

Absorption-RegenerationProcess: demixing solvents

Modeling and Experiments

= Remi Chauvy’s PhD Thesis

= Seloua Mouhoubi’s PhD Thesis

Modeling and Technico-economic analysis

Absorption-RegenerationProcess: other configurations


= Lionel Dubois’s Post-Doc

Modeling and Experiments(materials screening)

CO2 Capture & Purification CO2 Conversion



Ce

men

tin

du

stry



35 < yCO2 < 70%









CryogenicUnit

DehydrationUnit

Sour Compress.

Unit




= Other works











MAB1 ProjectAbsorber modeling

2017-2018

MAB1 ProjectFormic acid productionConventional process

2017-2018

Works of undergraduate studentsin the framework of the ECRA Chair (2017-2018)


MAB1 ProjectFormic acid production

Electrochemical reduction2017-2018

Posters available


CO2 capture and purification

• PhD Thesis of S. Mouhoubi• Post-doc works of L. Dubois

CO2 conversion

• PhD Thesis of N. Meunier• PhD Thesis of R. Chauvy

News of the ECRA Chair theses/works


ECRA ACADEMIC CHAIR RESEARCH ACTIVITIES AT UMONS:

CO2 CAPTURE, PURIFICATION AND CONVERSIONModeling and simulation of post-combustion CO2 capture process using demixing solvents

applied to cement flue gases

ECRA Chair scientific meeting July the 2nd – Mons (Belgium)

Ir Seloua MOUHOUBI

PhD Student

Chemical & Biochemical Process Engineering Unit

[email protected]

University of Mons

General framework of the ECRA ChairC

em

ent

ind

ust

ry



35 < yCO2 < 70%









CryogenicUnit

DehydrationUnit

Sour Compress.

Unit




= Other works











MOUHOUBI Seloua – ECRA Chair meeting – Mons – 02/07/2018 17

University of Mons MOUHOUBI Seloua – ECRA Chair meeting – Mons – 02/07/2018

Presentation outline

I. Introduction to demixing technology

II. Modeling methodology

III. DEEA-H2O-CO2 subsystem

IV. MAPA-H2O-CO2 subsystem

V. Conclusion and future works

18


I.1. Demixing process


Source: based on DEEA-MAPA process

Flue gas in

CO2

Treated gas

Rich liquid

Lean liquid

30-40% decrease of the regeneration energyLowering the rich solution flow rate to be regenerated

19


Tertiary amine Diamine

C4H12N2C6H15NO

I.2. Amine definition

+ High absorption capacity

+ Low regeneration energy

- Low CO2 reaction kinetics

+ High absorption capacity

- High regeneration energy

+ High CO2 reaction kinetics

20



Thermodynamics

Kinetics

Results Process

modelling using

Aspen Plus

- DEEA-H2O-CO2 subsystem

- MAPA-H2O-CO2 subsystem

Properties

Reactions

Properties

Models

DEEA-MAPA-H2O-CO2 system

II. Modeling methodology

21


III. Study of DEEA-H2O-CO2 system

22

➢Thermodynamic modeling

➢Kinetic modeling

➢Aspen Plus process modeling and simulation


➢ DEEA system main results

3

3.5

4

4.5

5

5.5

6

6.5

7

0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 0.01

Ere

g[G

J/t C

O2]

(L/G) [m3/m3]

3M DEEA3M MEA

Ereg = PboilerGCO2.reg

[GJ/h]

[tCO2/h]

23

Experimental validation using UMONS micro-pilot under progress

Absorber and stripper temperature profiles

Minimization of solvent specific regeneration energy


IV. Study of MAPA-H2O-CO2 system

24


➢ Reaction chemistry and characteristics

2𝐻2𝑂 ↔ 𝐻3𝑂+ + 𝑂𝐻− (1)

2𝐻2𝑂 + 𝐶𝑂2 ↔ 𝐻3𝑂+ +𝐻𝐶𝑂3

− (2)

𝐻𝐶𝑂3− + 𝐻2𝑂 ↔ 𝐻3𝑂

+ + 𝐶𝑂32− (3)

𝑀𝐴𝑃𝐴𝐻+ +𝐻2𝑂 ↔ 𝑀𝐴𝑃𝐴 + 𝐻3𝑂+ (4)

𝑀𝐴𝑃𝐴2𝐻+ + 𝐻2𝑂 ↔ 𝑀𝐴𝑃𝐴𝐻+ + 𝐻3𝑂+ (5)

𝑀𝐴𝑃𝐴 + 𝐻𝐶𝑂3− ↔ 𝑀𝐴𝑃𝐴𝐶𝑂𝑂− +𝐻2𝑂 (6)

Reaction number (1) (2) (3) (4) (5)

Parameters

A 132.899 231.465 216.049 -8.0939 -4.4414

B -13445.9 -12092.1 -12431.7 -6047.4 -5785.7

C -22.3773 -36.7816 -35.4819 - -

Parameter Unit MAPAH+ MAPA2H+ MAPACOO-

Charge Charge +1 +1 -1

Molecular weight g/mol 89.152 90.152 131.152

DHAQFM kJ/mol -176.392 -220.142 -577.52

DGAQFM kJ/mol 52.299 3.139 -255.71

PLXANT - -Aspen default

ions value

𝑙𝑛 𝐾 = 𝐴 +𝐵

𝑇+ 𝐶 𝑙𝑛 𝑇 + 𝐷 𝑇

MAPA-H2O-CO2 system equilibrium constant parameters in mole fraction basis

MAPAH+, MAPA2H+ and MAPACOO- parameters introduction in Aspen Plus

The equilibrium constant of reaction

(6) is calculated by Aspen Plus from

the standard Gibbs free energy change

of the reaction

IV.1. Thermodynamic modeling

Source: Monteiro et al., 2013 and Aronu et al., 2011

Source: Arshad et al., 2016

25


Molecule or

Electrolyte

Molecule or

Electrolyte

Molecule or

Electrolyte

Molecule or

Electrolyte

1 H2O H3O+ OH- 37 MAPA H3O

+ MAPACOO-

2 H3O+ OH- H2O 38 H3O+ MAPACOO- MAPA

3 H2O H3O+ CO3

2- 39 MAPA MAPAH+ OH-

4 H3O+ CO32- H2O 40 MAPAH+ OH- MAPA

5 H2O H3O+ HCO3

- 41 MAPA MAPAH+ HCO3-

6 H3O+ HCO3- H2O 42 MAPAH+ HCO3

- MAPA

7 CO2 H3O+ OH- 43 MAPA MAPAH+ CO3

2-

8 H3O+ OH- CO2 44 MAPAH+ CO32- MAPA

9 CO2 H3O+ CO3

2- 45 MAPA MAPAH+ MAPACOO-

10 H3O+ CO32- CO2 46 MAPAH+ MAPACOO- MAPA

11 CO2 H3O+ HCO3

- 47 MAPA MAPA2H+ OH-

12 H3O+ HCO3

- CO2 48 MAPA2H+ OH- MAPA

13 H2O H3O+ MAPACOO- 49 MAPA MAPA2H+ HCO3-

14 H3O+ MAPACOO- H2O 50 MAPA2H+ HCO3

- MAPA

15 H2O MAPAH+ OH- 51 MAPA MAPA2H+ CO32-

16 MAPAH+ OH- H2O 52 MAPA2H+ CO32- MAPA

17 H2O MAPAH+ HCO3- 53 MAPA MAPA2H+ MAPACOO-

18 MAPAH+ HCO3- H2O 54 MAPA2H+ MAPACOO- MAPA

19 H2O MAPAH+ CO32- 55 CO2 H3O

+ MAPACOO-

20 MAPAH+ CO32- H2O 56 H3O

+ MAPACOO- CO2

21 H2O MAPAH+ MAPACOO- 57 CO2 MAPAH+ OH-

22 MAPAH+ MAPACOO- H2O 58 MAPAH+ OH- CO2

23 H2O MAPA2H+ OH- 59 CO2 MAPAH+ HCO3-

24 MAPA2H+ OH- H2O 60 MAPAH+ HCO3- CO2

25 H2O MAPA2H+ HCO3- 61 CO2 MAPAH+ CO3

2-

26 MAPA2H+ HCO3- H2O 62 MAPAH+ CO32- CO2

27 H2O MAPA2H+ CO32- 63 CO2 MAPAH+ MAPACOO-

28 MAPA2H+ CO32- H2O 64 MAPAH+ MAPACOO- CO2

29 H2O MAPA2H+ MAPACOO- 65 CO2 MAPA2H+ OH-

30 MAPA2H+ MAPACOO- H2O 66 MAPA2H+ OH- CO2

31 MAPA H3O+ OH- 67 CO2 MAPA2H+ HCO3

-

32 H3O+ OH- MAPA 68 MAPA2H+ HCO3- CO2

33 MAPA H3O+ HCO3

- 69 CO2 MAPA2H+ CO32-

34 H3O+ HCO3

- MAPA 70 MAPA2H+ CO32- CO2

35 MAPA H3O+ CO32- 71 CO2 MAPA2H+ MAPACOO-

36 H3O+ CO3

2- MAPA 72 MAPA2H+ MAPACOO- CO2

➢ Regression of MAPA-H2O-CO2 system electrolyte-molecule pair parameters

Based on the speciation reported by

(Arshad et al., 2016):

-The amount of aqueous CO2(aq), OH-,

H3O+ and MAPAH+ is low so the

interactions involving one of these

species were neglected

-The interactions involving MAPA and

HCO3- at the same time were not

regressed

As a results 10 x 2 parameters were

regressed using about 219 equilibrium

data from Denmark University (DTU)

program


26


Parameter Molecule or Electrolyte Molecule or Electrolyte Value

C H2O MAPA2H+ HCO3- 6.4215

C MAPA2H+ HCO3- H2O -4.5447

C H2O MAPA2H+ CO32- 10.1484

C MAPA2H+ CO32- H2O -4.6924

C H2O MAPA2H+ MAPACOO- 17.1218

C MAPA2H+ MAPACOO- H2O -3.6546

C MAPA MAPA2H+ CO32- -9.6644

C MAPA2H+ CO32- MAPA 0.1786

C MAPA MAPA2H+ MAPACOO- 737.5282

C MAPA2H+ MAPACOO- MAPA 47.4818

D H2O MAPA2H+ HCO3- 324.0754

D MAPA2H+ HCO3- H2O 489.4839

D H2O MAPA2H+ CO32- 803.9712

D MAPA2H+ CO32- H2O -63.0466

D H2O MAPA2H+ MAPACOO- -368.5756

D MAPA2H+ MAPACOO- H2O -825.8831

D MAPA MAPA2H+ CO32- 2310.4849

D MAPA2H+ CO32- MAPA 3315.8692

D MAPA MAPA2H+ MAPACOO- 661.9211

D MAPA2H+ MAPACOO- MAPA 95.4655

➢ DEEA-H2O-CO2 system electrolyte-molecule pair regressed results

➢ Equilibrium calculations using a flash unit

The total pressure was varied within a range of 6 to 7000 kPa

Temperatures: 40, 60 and 120°CConcentration: 1M MAPA and 2M MAPA

𝜏𝑚,𝑐𝑎 = 𝐶𝑚,𝑐𝑎 +𝐷𝑚,𝑐𝑎

𝑇

𝜏𝑚,𝑐𝑎 = 𝐶𝑚,𝑐𝑎 +𝐷𝑚,𝑐𝑎

𝑇

Used data:

Concentration: 1M and 3M of MAPA

Temperature: 40, 60, 80 and 100°C


27

pCO2=Ptot yCO2

α𝐶𝑂2,,𝑟𝑖𝑐ℎ =𝐶𝐶𝑂2𝐶𝑎𝑚𝑖𝑛𝑒


0.1

1

10

100

1000

0 0.5 1 1.5 2

PC

O2

(kP

a)

α (mol CO2/mol MAPA)

2M MAPA

ENRTL Aspen Plus

40°C Arshad et al 2014


120°C Arshad et al 2014 1

10

100

1000

0 0.5 1 1.5 2

PT

ota

l(k

Pa)


2M MAPA




ENRTL Aspen Plus

0.1

1

10

100

1000

0 0.5 1 1.5 2 2.5

PC

O2

(kP

a)


1M MAPA




ENRTL Aspen Plus

1

10

100

1000

0 0.5 1 1.5 2 2.5

PT

ota

l(k

Pa)


1M MAPA




ENRTL Aspen Plus

➢ CO2 partial pressure and total pressure as function of the loading


28


Termolecular mechanism is a one step mechanism

CO2 absorption by aqueous MAPA solutions takes place mainly through the reactions of

carbamate formation.

𝑀𝐴𝑃𝐴 + 𝐶𝑂2 + 𝐵𝑘1,𝑘−1

𝑀𝐴𝑃𝐴𝐶𝑂𝑂− + 𝐵𝐻+

𝑀𝐴𝑃𝐴 + 𝐶𝑂2 +𝑀𝐴𝑃𝐴𝑘1𝑀𝐴𝑃𝐴,𝑘−1

𝑀𝐴𝑃𝐴

𝑀𝐴𝑃𝐴𝐶𝑂𝑂− +𝑀𝐴𝑃𝐴𝐻+

𝑀𝐴𝑃𝐴 + 𝐶𝑂2 +𝐻2𝑂𝑘1𝐻2𝑂,𝑘−1

𝐻2𝑂

𝑀𝐴𝑃𝐴𝐶𝑂𝑂− + 𝐻3𝑂+

−𝑟𝐶𝑂2.𝑀𝐴𝑃𝐴= ሺ𝑘1𝑀𝐴𝑃𝐴

𝑀𝐴𝑃𝐴 + 𝑘1𝐻2𝑂 𝐻2𝑂 ) 𝑀𝐴𝑃𝐴 𝐶𝑂2

Reaction constants of the two reactions separately:

Aspen Plus simulations are under progress

IV.2. Kinetic modeling

𝑘1𝑀𝐴𝑃𝐴ሺሺ )𝑚3𝑘𝑚𝑜𝑙−1 2 𝑠−1) = 1.6654 × 109ⅇ𝑥𝑝

−3359.6

𝑇

𝑘1𝐻2𝑂ሺሺ )𝑚3𝑘𝑚𝑜𝑙−1 2𝑠−1) = 4.777 × 105ⅇ𝑥𝑝

−1871

𝑇

29


V. Conclusion and future works

Bibliographic review

- Study of different phase change CO2

capture processes

- Focus on liquid biphasic solvents

Identification of the promising biphasic solvent:

DEEA+MAPA demixing mixtures

Interest of the non demixing mixtures

Aspen Plus process modeling and simulation

KineticsThermodynamics

Reactions set and kinetic constantsElectrolyte NRTL modeling



- DEEA-MAPA-H2O-CO2 system







(under progress)

30


Experimental section

- CO2 preliminary absorption performances tests on DEEA and MAPA and their mixture

- Aspen Plus modeling of the absorption-regeneration using micro pilot unit conditions and

experimental validation of the modeling of the two subsystems DEEA-H2O-CO2 and

MAPA-H2O-CO2 (under progress)

- Absorption-regeneration tests in micro pilot scale using non-demixing mixtures

- Adaptation of the micro pilot for the demixing mixtures

Global evaluation and optimization of the technology applied to cement flue gases

- Optimization of the mixture concentrations (demixing and non demixing mixtures) and

of the process operating conditions

- Optimization of the energetic gain, application to cement flue gases

- Global technico-economic evaluation of the technology

31

University of Mons 32MOUHOUBI Seloua – ECRA Chair meeting – Mons – 02/07/2018

2018 IEAGHG International Interdisciplinary Carbon

Dioxide Capture and Storage Summer School 24th–29th

June 2018 Trondheim Norway


Thank you for your attention

33

Dr Lionel DUBOIS

ECRA Academic Chair

Research & Scientific Coordinator


[email protected]

ECRA Chair Scientific Meeting 2nd July 2018 UMONS (Belgium)

ECRA ACADEMIC CHAIR RESEARCH ACTIVITIES AT UMONS:

CO2 CAPTURE, PURIFICATION AND CONVERSION

« Simulations of various configurations of the post-combustion CO2 capture process

applied to Brevik cement plant flue gas »


Absorption – Regeneration process

Conventional configuration:

Dr Lionel Dubois | ECRA Chair Scientific Committee Meeting | 02-07-2018

Electricityconsumption

Cooling demand

Heating demand

[Neveux, 2013]


Alternative process configurations:


Promoting absorptionthanks to temperature levels

adjustments

Promoting energy integration thanks to enhancement of the heat

exchanges between the fluids

Promoting heat recovery thanks to heat quality adjustments


University of Mons 37Dr Lionel Dubois | ECRA Chair Scientific Committee Meeting | 02-07-2018


RVC (Rich Vapor Compression)

LVC (Lean Vapor Compression)


CASTOR/CESAR pilot = referenceEuropean projectsAll data available

Brevik cement plant = ECRA referenceFirst European project for testing CO2

capture from cement industry

Gin = 4000 m³/hyCO2,in = 20.4 mol.%A = 90 mol.%Purity of produced CO2 = 98 mol.%

GCO2,regen = 1.5 t CO2/h

CO2 recovery flow

• Aspen Hysys V8.6• Acid gas package• Thermodynamic models: Peng-Robinson (gas) and e-NRTL (liquid)• Reactions sets included in the package (validated by literature)

General principles of the simulations

→ For different process configurations & solvents: with/without INTERCOOLING


Summary of the results WITHOUT intercooling:



➔ Lower Eregen with MDEA 10 wt.% + PZ 30 wt.%➔ LVC and RVC configurations leading to the minimum of Eregen

(heat recovery process modifications)


Intercooling & water-wash sections:



➔ All the details provided in two publications:

➔ “Comparison of various configurations of the absorption-regeneration process using different solvents for the post-combustion CO2 capture applied to cement plant flue gases”, L. Dubois and D. Thomas, IJGGC, Vol. 69, pp 20-35, 2018.

➔ “Optimization of the post-combustion CO2 capture process applied to cement plant flue gases: parametric study withdifferent solvents and configurations combined with intercooling”, L. Dubois and D. Thomas→ Submitted for a special issue in IJGGC related to GHGT-14 conference


Summary of the results WITH intercooling:



➔ Intercooling leads to supplementary energy savings➔Minimum of Eregen with MDEA+PZ + RVC + IC: 2.19 GJ/tCO2

→ Globally 35% Eregen savings in comparison with base case


Personal researches tasksNew Aspen Plus/Aspen HysysTM simulations:- Development of an optimized CO2 capture process for the application to cement flue gases:configurations combined with intercooling, water-wash, etc. and partial oxy-fuel conditions, optimization in terms of process, solvent and configuration to lower the capture costs.- Combination of separate PhD Theses results: e.g. technico-economic comparison between partial oxy-fuel using CO2 capture absorption-regeneration process & full oxy-fuel process with CO2 purification (Sour Compression Unit – SCU)→ Open to any specific demands from ECRA members

➔ Globally: broadening of the ECRA Chair & keeping the dynamic established since 2013

Projects development tasks - Technological watch for the establishment of new research projects- Contact establishment with different potential partners (Universities, Research Centres, etc.)- Answer to several project calls: “Win2Wal” (Walloon Region Project), “FNRS Project” (National Fund for Research), “Interreg Project” (Inter-regional Collaborations), etc.

Coordination & Support tasksPhD theses support, reports & publications, logistic support, international congress participation,

events organization, website management, networking activities, etc.

Research Coordinator tasks schedule

Dr Lionel DUBOIS

ECRA Academic Chair

Research & Scientific Coordinator


[email protected]

ECRA Chair Scientific Meeting 2nd July 2018 UMONS (Belgium)

Questions?

Thanks very much for your attention !

CO2 Capture & Conversion Process:Application to Power-to-Liquid

Ir Nicolas MEUNIER

PhD Student

Thermodynamics Unit

[email protected]

ECRA Chair scientific meeting 2nd July 2018 – UMONS (Mons)

University of Mons

Submitted Peer-Reviewed Article

45Ir MEUNIER N. | ECRA Chair Scientific Meeting – Mons – 02/07/2018

Submitted in Applied Energy

Innovation

➢ Integrated CO2 Capture & Conversion

➢ Combined techno-econo-environmental analysis of the process

Optimization

➢ Heat & water integrations

Short-term Solution

➢ Mature technologies to implement!

➢ Profitable process (in define regions)!

University of Mons

LiquidAnalysis

Experimental Installation


Gases mixture

Oven

Gas Analysis

Pressure Regulation

University of Mons

Experimental Study – Commercial Catalyst


• # experimental points: 27 (> 160 h)

• Temperatures: 190 < T < 300°C

• Pressure: 80 bar

• Inlet gas flow rate: 4.2 NL/min

• Overall methanol production: ~400 mL

University of Mons



Power-Law Model

𝑹𝑪𝑯𝟑𝑶𝑯 = 𝒌𝑪𝑯𝟑𝑶𝑯. 𝒆𝒙𝒑𝑬𝟏𝑹𝑻

. 𝒑𝑯𝟐

𝒎𝟏 . 𝒑𝑪𝑶𝟐𝒎𝟐

𝑹𝑪𝑶 = 𝒌𝑪𝑶. 𝒆𝒙𝒑𝑬𝟐𝑹𝑻

. 𝒑𝑯𝟐

𝒏𝟏 . 𝒑𝑪𝑶𝟐𝒏𝟐

✓ Very simple to deduct from experimental points

❖ Only applicable for the conditions of the experimental tests

❖ Does not explain the physical mechanisms occuring during the reactions!

• Langmuir-Hinshelwood-Hougen-Watson (LHHW) Model

✓ Applicable outside the experimental conditions

✓ Explain physical mechanisms occurring during the reactions

❖ Harder to implement!

University of Mons

0

0.001

0.002

0.003

0 0.001 0.002 0.003

Cal

cula

ted

R(C

H3

OH

) [m

ol/

s/kg

]

Experimental R(CH3OH) [mol/s/kg]



Power-Law Model

0

0.001

0.002

0.003

0.004

0 0.001 0.002 0.003

Cal

cula

ted

R(C

O)

[mo

l/s/

kg]

Experimental R(CO) [mol/s/kg]

+ 10%

- 10%

+ 10%

- 10%

+ 20%

➢ Good estimation of CH3OH productions• Mean relative error (MRE): 5.6 % (ECPM : 5%)

➢ Less good estimation of CO productions• Mean relative error (MRE): 15.1 % (ECPM : 10%)

University of Mons

Experimental Study – Homemade Catalyst


Shaping of the catalytic powder

Preparation Extrusion Cutting

(after drying)

University of Mons

Experimental Study – Homemade Catalyst


Shaping of the catalytic powder

❖ Improved recipe !

Attrition test (ASTM D4058-96)

30 min // 60 RPM

✓ Better resistance to attrition

✓ Only 9% loss with 30% bentonite

➢ Catalytic tests required!

0%

20%

40%

60%

80%

100%

0 10 20 30 40 50

Ben

ton

ite

con

ten

t (w

t%)

Attrition loss (%)

Recipe 1 Recipe 2

University of Mons

Next steps & Schedule


01/07/2018 31/07/2018 31/08/2018 30/09/2018 31/10/2018

Experiments - Homemade Cat.

Writing (Ch. 5)

Process Simulation

Writing (Ch. 6)

Supervisor - Reading & Corrections

Official thesis submission to the jury

Internal presentation

External presentation

University of Mons 53Ir CHAUVY R. | ECRA Chair Scientific Meeting – Mons – 02/07/2018

Perspectives

THESIS

All ECRA members are warmly welcome to attend the external auditionon 12th October 2018 – 15.30

CO2 Capture & Conversion Process:Application to Power-to-gas

Ir Remi CHAUVY

PhD Student

Thermodynamics Unit

[email protected]

ECRA Chair scientific meeting 2nd July 2018 – UMONS (Mons)

University of Mons

Technologies

Water electrolysis: converting power to H2 and O2 by dissociation of water (green H2)• Alkaline electrolysis (most mature)

• PEM electrolysis

• SOEC electrolysis (early stage of development)

Methanation: catalytic methanation

Gas upgrading

General background on power-to-gas

55Ir CHAUVY R. | ECRA Chair Scientific Meeting – Mons – 02/07/2018

University of Mons

Market

Gas injection into the natural gas grid

Power-to-methane: production of synthetic natural gas (SNG) with composition similar to natural gas

Mobility: H2 & SNG mobility fuel in H2 or CNG (compressed natural gas) vehicles: downstream market of grid injection

Catalytic methane: raw materials for chemicals etc.




CO2 captureSorbent

regeneration

Sorbent & CO2

Sorbent

CO2

Flue gas

Methanation

Electricity

Electrolysis

Power grid

CH4

SNG

Distribution

H2

H2

H2O

Power

Heat

Mobility

Chemicals

Power-to-Gas concept


Heat exchange


Mapping of pilot and demonstration projects of power-to-gas in Europe[1]

[1] ENEA Consulting (2016)


University of Mons

Thermodynamics

Kinetics

𝐶𝑂2 + 4𝐻2 ↔ 𝐶𝐻4 + 2𝐻2𝑂 ∆𝐻2980 = −165 𝑘𝐽/𝑚𝑜𝑙 CO2 methanation

𝐶𝑂2 + 𝐻2 ↔ 𝐶𝑂 + 𝐻2𝑂 ∆𝐻2980 = +41 𝑘𝐽/𝑚𝑜𝑙 RWGS

𝐶𝑂 + 3𝐻2 ↔ 𝐶𝐻4 + 𝐻2𝑂 ∆𝐻2980 = −206 𝑘𝐽/𝑚𝑜𝑙 CO methanation


𝑟1 =𝑘1

𝑝𝐻23.5 ×

𝑝𝐶𝐻4×𝑝𝐻2𝑂2 −

𝑝𝐻24 ×𝑝𝐶𝑂2

𝐾1

𝐷𝐸𝑁2

𝑟2 =𝑘2

𝑝𝐻2×

𝑝𝐶𝑂×𝑝𝐻2𝑂−𝑝𝐻2

×𝑝𝐶𝑂2𝐾2

𝐷𝐸𝑁2

𝑟3 =𝑘3

𝑝𝐻22.5 ×

𝑝𝐶𝐻4×𝑝𝐻2𝑂−𝑝𝐻23 ×𝑝𝐶𝑂

𝐾3

𝐷𝐸𝑁2

𝐷𝐸𝑁 = 1 + 𝐾𝐶𝑂𝑝𝐶𝑂 + 𝐾𝐻2𝑝𝐻2 + 𝐾𝐶𝐻4𝑝𝐶𝐻4 +𝐾𝐻2𝑂𝑝𝐻2𝑂

𝑝𝐻2

Simulation results using kinetics from Xu & Fromentcompared to equilibrium curve at 10 bar

CO2 to methane: Basics


22.1 million m3

SNG per year60 439 m3 SNG per

day

2 230 ton CO2 captured per day

2 475 ton CO2 emitted per day

Brevik (Norway)Cement Plant

3 000 ton Clinker per day

Ir CHAUVY R. | ECRA Chair Scientific Meeting – Mons – 02/07/2018

30 150 ton CH4 per year

826 ton CH4

per day

About 3 600 billion m3 NG produced &

consumed per year [2]

[2] https://www.bp.com/en/global/corporate/energy-economics/statistical-review-of-world-energy/natural-gas/natural-gas-consumption.html

CO2 to methane: Sizing the installation

https://www.bp.com/en/global/corporate/energy-economics/statistical-review-of-world-energy/natural-gas/natural-gas-consumption.html


CO2

H2

Raw SNG

water

R = 0.7

Simulations with Aspen Plus & Economics v9

Process flowsheet

Use of Peng-Robinson package for the calculations of gas thermodynamic propertiesH2:CO2 = 4Temperature intercooling: 350°CPressure: 10 bar

CH4 74.85

%molCO2 4.97

H2 19.89

H2O traces

2 271 tpd

416 tpd

918 tpd

1 856 tpd

T = 25°C

CO2 to methane: Process simulation

CO2 methanation system

University of Mons

Cascaded process: multiple adiabatic fixed-bed reactorsoperating in series using heat exchangers between each reactorto the next downstream reactor to cool the process gas

Need to optimize!


REA-1 REA-2 REA-3 REA-4

GHSV (h-1) 5 000 5 000 4 000 2 000

T (°C) 350 350 350 350

F (m3h-1) 131 889 35 140 32 605 31 339

𝒎𝒄𝒂𝒕 (ton) 163 43 50 97

𝒅𝑹 (m) 3.5 1.8 1.9 2.7

𝑳𝑹 (m) 12

𝑽𝒓 (m3) 115.6 30.8 35.7 68.7

Reactors specifications

CO2 to methane: Process simulation

University of Mons

• Grid injection: depends on rules & regulations of countries

SPECIFICATIONS

• Study case: Germany


DescriptionG 260, G 262 (gas quality)

Simulation Unit

HHV 30.2 – 47.2 30.7 MJ/m3

Wobbe Index 37.8 – 56.5 45.6 MJ/m3

Min. CH4 content90 (L-gas)95 (H-gas)

74.9 mol%

H2 content < 10 19.9 mol%

CO2 content < 6 5.0 mol%

H2O content Traces (ppm) 0.3 mol%

SNG quality restrictions in Germany

CO2 to methane: Gas injection into the natural gas grid


CO2

Simulations with Aspen Plus v9

2 271 tpd

416 tpd

H2


CO2, H2 recirculation

1 856 tpd

60 439 m3pd

SNG upgrading system

Raw SNG

SNG

water

SNG upgrading system (in progress): CO2, H2 removal

- MEA-based absorption-regeneration system- PSA (pressure-swing adsorption)- Membrane

CO2 to methane: Process simulation for gas injection

University of Mons

First evaluation tends to highlight a 100% reduction for stripper heat duty


H2

Simulations with Aspen Plus v9

2 271 tpd

416 tpd

CO2

60 439 m3pd

1 856 tpd

CO2 capture unitHigh potential Reduction for

Stripper Heat Duty

Cooling water


water

SNG

SNG upgrading system

CO2 to methane: Process integration – First outlook


• Process optimization

• Process integration (CO2 capture + CO2 conversion unit)

• Techno-economic analysis (H2 consumption)

• Scenarios analysis (various specifications for SNG etc.)

• Environmental analysis (LCA)

Propose environmentally friendly, integrated and optimizedCO2 conversion processes applied to the cement sector !

Perspectives


“Selecting emerging CO2 utilization products for short to mid-term deployment”,

Remi CHAUVY, Nicolas MEUNIER, Diane THOMAS, Guy DE WEIRELD (2018)

Articles submissions for Peer-review



Ir Remi CHAUVY

PhD Student

Thermodynamics Unit

[email protected]


Preparation presentation VDZ Congress


Context: • General background

• CCUS

• General Framework

PART 1: Identification and selection of CO2-based conversion pathways• Method

• Results

PART 2: Techno-economic assessment of CO2

• Application to methanol• Description of the process

• Simulation

• Performance indicators

• Economic indicators

• Application to methane

• Application to formic acid (main conclusions)

Q&ABackup slides : Environmental analysis

Proposals for the ECRA Chair prolongation @UMONS

Phase III - Period 2019-2022

Discussion on scientific topics

« From CO2 to Energy:Carbon Capture in Cement Production and its Re-use »

02/07/18

University of Mons 71ECRA Chair « CO2 to Energy » - Scientific Meeting at UMONS – 02/07/2018

✓ ECRA Chair Phase III

- Organization: the same as in previous phases:

✓ Professors for steering and efficient scientific supervision✓ 1 Post-Doc (50%) for researches coordination and post-doc works✓ 1 new joint-supervised PhD Thesis during 3 years

(50% @UMONS – 50% ULCO (Dunkerque, France))- 1 new PhD thesis 100% @UMONS during 4 years- 1 new PhD Thesis (50%) or post-doc ?

- Budget accorded:125 k€/year provided by ECRA during 3 years

- Global scientific content unchanged: Carbon Capture & Reuse for the application in the cement industry

2019-2022


Future of the ECRA ChairPhase 3 (2019-2022)

24/04/13

Phase 1 + Phase 2 (2013-2019):2 + 2 PhD theses + 1 Post-doc

Phase 3 (2019-2022)New PhD theses + 1 Post-doc (50% funding)

2013-2016 + 2016-2019 2019 2020

PhD THESIS 1 – N. MEUNIER

PhD THESIS 2 – S. LARIBI

POST-DOC - RESEARCH COORDINATOR – L. DUBOIS

ECRA ACADEMIC CHAIR – 6 YEARS (1) (2)

2021 2022

= today

ECRA ACADEMIC CHAIR – 3 YEARS (3) ?

PhD THESIS 4 – S. MOUHOUBI

PhD THESIS 3 – R. CHAUVY

ECRA Chair « CO2 to Energy » - Scientific Meeting at UMONS – 02/07/2018

PhD THESIS 5 – ULCO

PhD THESIS 6 – SUBJECT TO BE DEFINED

PhD THESIS 7 or POST-DOC ?

✓ 1 Joint-supervised 3 yearsPhD thesis (50%)

1 PhD Thesis 4 years (100%)

1 PhD Thesis (50%) or Post-doc


Phase 3 (2019-2022): PhD subjects proposals


- Innovative aspects must be included in order to be able to publish papers

- Both experimental and simulation /techno-economic /LCA aspects would be ideal for significant developments of the considered technology

- ECRA Chair is open for collaboration with other UMONS Departments and/or other Universities (e.g. for the PhD Thesis in collaboration with ULCO)

- Exploiting the experimental device established during the PhD Thesis of N. Meunier would be relevant

- For a supplementary research subject: combining CO2 capture AND CO2

utilization is an option to be envisaged

Key points for the PhD Thesis subjects definition


Phase 3 (2019-2022): PhD subjects proposals


SUBJECT-1: Study of the CO2 conversion into methanol: catalytic process innovation and optimization

SUBJECT-2: Study of the CO2 conversion into methane: catalytic process innovation and optimization

SUBJECT-3: Utilization of CO2 derived from the cement industry for the mineralization into carbonates (need to be more thoroughly discussed)

SUBJECT-4: Integrated CO2 capture & conversion process into carbonates using anionic exchange resins (innovative subject combining capture AND conversion)

SUBJECT-5: Study of the global CCU chain for the use of CO2 derived from the cement industry as feedstock for the chemical industry(need to be more thoroughly discussed)

+ Any other subject(s) proposal(s) from ECRA warmly welcomed !

100%@UMONS research subjects


SUBJECT-1: Study of the CO2 conversion into methanol:

catalytic process innovation and optimization

- Direct continuation of the PhD Thesis subject of N. Meunier

- Exploitation of the experimental device (CO2 to MeOH catalytic reactor)





SUBJECT-2: Study of the CO2 conversion into methane:

catalytic process innovation and optimization

- Same approach as for the PhD Thesis of N. Meunier

- Adaptation of the experimental device (CO2 to MeOH catalytic reactor) for methane




Reactor to be adapted for methane


SUBJECT-3: Utilization of CO2 derived from the cement industry

for the mineralization into carbonates

- Can potentially integrate both the capture and the conversion of CO2

- Possibility to investigate the direct use of raw cement flue gas and the reuse of cement

wastes into the mineralization process

- Development of an experimental device allowing to test the technology

(Rq: eventual needing supplementary budget for the experimental device funding)



or

CO2 recarbonation into precast elements during manufacturing


SUBJECT-4: Integrated CO2 capture & conversion process

into carbonates using anionic exchange resins

- Integrates both the capture AND the conversion of CO2

- Innovative technology for the solvent regeneration step OR complementary

to a conventional CO2 capture plant

- Development of an experimental device allowing to test the technology

- Possible collaboration with other UMONS Department (SMPC) for resin development

(Rq: possibility to use and adapt existing experimental devices)




SUBJECT-5: Study of the global CCU chain for the use of CO2

derived from the cement industry as feedstock for the chemical industry



PhD Thesis ?? CO2 conversion into Urea ?

Methanol to X ?

Post-doc works ?

Works (projects) for undergraduate students ?

- Direct continuation of the PhD Thesis subjects of R. Chauvy and partially N.

Meunier.

- Simulation of a global Chain: from a cement plant, to CO2 capture, conversion

and eventual further utilization of the low-carbon product.

- Thanks to the simulations, obtaining parameters for carrying out Life Cycle

Analyzes (LCA) and technico-economic comparisons.

- As optional task: exploitation of the CO2-to-methanol catalytic reactor established

during the PhD thesis of N. Meunier (Master thesis works on this subject will be

also envisaged).


SUBJECT-6: ????


From « Novel carbon capture and utilisation technologies »SAPEA - 2018



Third ECRA Chair Scientific Event in 2019/2020 ?

Proposals regarding the event

▪ Period: Second semester 2019 or first semester 2020?

▪ Location: at Mons (at UMONS or at Van der Valk Hotel if rooms assured)

▪ Duration: 2 days as previous ones but 2 days at Mons to increase the number

of presentations (no plant visit)?

▪ Speakers: combining industrial and academic presentations

(open for PhD students, Post-Doc, etc.) + posters (but limited number)?

▪ Conference thematics: Carbon Capture Utilization & Storage: priority to the

application to cement industry but open for other applications?

▪ Other ideas or proposals regarding this event?


ANNEXES

02/07/18


« Integrated CO2 capture & conversion processinto carbonates using anionic exchange resins »


CementPlant

Flue gas Post-combustion CO2 Capture CO2 compression

CO2 conversion

Flue gas Post-combustion CO2 Capture & Conversion

Solvent regeneration &CO2 Conversion into carbonates

Conventional CCU Chain:

Integrated Carbon Capture & Conversion Chain:

De-SOxDe-NOxDe-Dust

CO2 Capture by absorption

CO2 Capture by absorption

Solventregeneration

High energyconsumption!

Hydroxydefor resin

regeneration

yCO2 ≈ 15-30%

yCO2 ≈ 15-30%

Significant energyconsumption!

De-SOxDe-NOxDe-Dust

Treated Flue gas

Treated Flue gas

CO2

Final carbon-based productto be valorized

No significant thermal energy consumptionfor solvent regeneration & No CO2 compression!

Carbonates

CementPlant


➔ Potential ECRA Chair PhD Thesis subject?

Otherhydroxydes

will leadto other

carbonatesPossible collaboration with other UMONSdepartment (SMPC) for resin development

« Integrated CO2 capture & conversion processinto carbonates using anionic exchange resins »


Carbon Capture & Partial direct CO2 conversion

Anionic exchange resins

Hydroxydefor resin

regeneration

→ Carbonates formation in adequate quantity

Regeneratedsolvent

→ Less CO2 must be compressed and transported→ The liquid flow rate to be thermally regenerated ↓ → Econsumption ↓

A part of the CO2-loaded solventcan be regenerated by an

alternative process & leadingdirectly to the CO2 conversion

Compression & Transport


VDZ Congress Presentation Draft


Conversion of CO2: A techno-economic assessment

Remi CHAUVY

Nicolas MEUNIER, Seloua MOUHOUBI, Lionel DUBOIS, Diane THOMAS, Guy De WEIRELD

Faculty of Engineering (FPMs), UMONS, Mons, Belgium

27/09/2018

University of Mons 88Ir CHAUVY Remi | VDZ International Congress – 27/09/2018

Outline

Context: • General background

• CCUS

• General Framework

PART 1: Identification and selection of CO2-based conversion pathways• Method

• Results

PART 2: Techno-economic assessment of CO2

• Application to methanol• Description of the process

• Simulation

• Performance indicators

• Economic indicators

• Application to methane

• Application to formic acid (main conclusions)

Q&ABackup slides : Environmental analysis


Context: General background

Transport23%

Industry 19%

Residential6%

Services3%

Other* 7%

Industry 18%

Residential 11%

Services 8%

Other* 5%

Electricity and heat42%

Global anthropogenic CO2 emissions by sector (2017) [1]

Total: 37 GtCO2

* Other: agriculture/forestry, fishing, energy industries otherthan electricity and heat generation, and other emissions notspecified elsewhere

Industrial sector: 20 to 25% of total CO2 emissions

Cement sector: Largest non-combustion sourcesof industrial CO2

5 to 7% of total CO2 emissions 2/3 of released emissions comefrom the decarbonation step:unavoidable

[1] IEA, CO2 Emissions from fuel combustion Highlights, IEA (2017)

Ir CHAUVY Remi | VDZ International Congress – 27/09/2018

University of Mons

ConversionChemicals

Mineralization (Ex-situ mineral carbonation technology)

BiologicalElectrochemical reduction

etc.

SequestrationGeological storage

Saline aquifersDepleted oil and gas fieldsIn-situ mineral carbonation

technology

Capture and Storage (CCS)

Capture and Utilization (CCU)

Amine scrubbingMembrane

Pressure Swing Adsorption etc.

CO2 capture and purification

BiomassAquaculture

De-watering: whole algaeConversion: bio char; biogas, syngas; bio crude oil

Fractionation: lipids; proteins; carbohydrates

Inorganic MaterialsCarbonation

bicarbonates; carbonate aggregates; carbonate cements; other materials and chemicals

Fuels and organic chemicalsBiotic synthesis

Neat fuels and blend stocks; commodity, specialty and fine chemicals; emerging biochemical

Abiotic synthesis Carbon insertion: commodity, specialty and fine

chemicalsCarbon coupling: C2 basic chemicals

C1 reforming: CO, syngas; C1 basic chemicals

Working fluidsServices

Enhanced resource recovery: crude oil; Natural gas; Coalbed methane; ground/waste water;

geothermal energy

Utilization

4

CCUS global chain map

Context: Carbon Capture & Utilization (CCUS)



PhD Theses

Cement industry



35 < yCO2 < 70%


CO2 CatalyticConversion

into methanol

Other CO2

Conversion routes






CryogenicUnit

DehydrationUnit

Sour Compression

Unit


= Sinda Laribi’s work

= Nicolas Meunier’s work

Legend:

= Master Thesis in progress



= Remi Chauvy’s work

= Seloua Mouhoubi’s work




= Lionel Dubois’s work


ECRA Academic Chair FrameworkCO2 Capture & Purification CO2 Conversion



Process Modelling (PSE)Aspen Plus

Life cycle Inventory

Environmental burdens

Excel / Aspen Economics (PSE)

CAPEX & OPEX

Multi objective optimization

LCA

Identification of the CO2-based conversion pathways

Methodological selection based on severalcriteria & indicators

Validation

Objective:Proposition of several environmentally friendly,

integrated and optimized CO2 conversion processes

Ide

nti

fica

tio

n a

nd

se

lect

ion

of

CO

2-b

ase

d c

on

vers

ion

pat

hw

ays

Pro

cess

mo

de

llin

g an

d

op

tim

izat

ion

General framework



PART 1Identification and selection of CO2-based

conversion pathways



Identification of the CO2 conversion routesLiterature review, data, properties etc.

STEP 1 : Reduction of the panelReduction of the panel of CO2 conversion routes

STEP 2 : Semi-quantitative analysisSelection based on technical, economic, environmental aspects as well as marketconsiderations

Simulation of the processUse of adequate simulation software

STEP 3 : Uncertainty analysisPartially quantification of uncertainty due to input data, approximations andassumptions to assess the robustness of the model

Are the selected routes validated?

No

Yes

General framework

Development of original framework


University of Mons

STEP 1: Reduction of the panel

95

Results and discussion

Technology Readiness Level for main CO2-based products (non-exhaustive)

CO2-BASED

COMPOUNDCO2-CONVERSION PROCESS

Calcium carbonate Mineral carbonation

Dimethyl carbonate Organic synthesis

Ethanol Microbial process

Formic acid Electrochemical reduction

Methane Hydrogenation

Methanol Hydrogenation

Microalgae Biological process

Polycarbonates Organic synthesis

Salicylic acid Organic synthesis

Sodium carbonates Mineral carbonation

Syngas Dry reforming

Urea Organic synthesis

TRL 7-9

TRL 4-6

TRL 1-3

Shortlist of CO2 conversion options for short to mid-term deployment



Ranking list of the selected CO2-based compounds for short to mid-term deployment

STEP 2 & 3: Semi-quantitative and uncertainty analysis


Results and discussion


CO2-based compound

CO2-conversion process Score

Urea Organic synthesis *****Methanol Hydrogenation ****Microalgae Biological process ****Methane Hydrogenation ***Calcium carbonates

Mineral carbonation ***

Ethanol Microbial process **Sodium carbonates Mineral carbonation **Syngas Dry reforming *

CO2-based compound

CO2-conversion process Score

Polycarbonates Organic synthesis *****Salicylic acid Organic synthesis ***Dimethyl carbonate

Organic synthesis ***

Formic acid CO2 Electroreduction *

Low unit price but significant market volume

High unit price but low market volume

Concluding remarks



Concluding remarks

Highlights:

• CO2 utilization: Growing interests in research and development

• Key challenge: Identify the most suitable CO2 utilization options to be implemented in the near short to mid-term future, while generating emissions reductions and producing useful CO2-based products

• Methodological selection based on various comparison factors (maturity, technical, economic and market considerations as well as environmental aspects) to justify choices

• Methodology development to be less questionable & reproducible

• Endorsement by Uncertainty analysis to assess the robustness of the results

• Lack of rigorous information regarding the processes, transparency, consistency

• Lack of economic and environmental assessments regarding CCU processes



PART 2Techno-economic assessment of CO2

conversion pathways



Market: 80 Mton (2017), 450 €/ton

Development of a “Methanol economy” ▪ Energy storage▪ Ground transportation fuel ▪ Raw material for synthetic hydrocarbons and

their products29%

9%

10%10%

10%

4%

10%

5%

3%2%

2%

6%

Application to methanol

Methanol utilizationMethanol market[1]

[1] http://zeep.com/market-opportunities/


Tjeldbergodden (Norway)Methanol Plant

550 000 ton methanol per year

1 500 ton methanol per day

2 230 ton CO2 captured per day

2 475 ton CO2 emitted per day

Brevik (Norway)Cement Plant

3000 ton Clinker per day

0.8% of the GlobalMethanol Market

CO2 to methanol: Industril sizing of the installation



Methanol synthesis

Cement plant Production of

hydrogen CO2 capture

Pre-treated Flue gas

Emissionswater / air / solid wastes

Clinker Methanol

Infrastructure &

Raw materials

OxygenPurified flue gas

System boundary

Carbon free electricityElectricity WaterSteamElectricity Steam

Water

Conceptual Flow Sheet of the CO2 Capture & Conversion Processes

CO2 to methanol: Conceptual flow sheet



Absorption Block

Regeneration Block

CO2(to Conversion)

TreatedGas

H2O

MEASimulations with

Aspen Plus & Economics v9

Post-Combustion CO2 Capture Process

Absorber Stripper

CO2 98.0

%molH2O 1.98

N2 0.02

Flue gasto treat

N2 64.67

%mol

CO2 20.36

O2 8.56

H2O 6.2

Impurities 0.21

Integration

Loop

1 bar 2 bar

CO2 to methanol: CO2 capture process



Catalytic Block

Separation Block

Integration

Loop

CO2(from Stripper)

Purge

CH3OH

H2O

Inerts

Simulations withAspen Plus & Economics v9

Adapted CO2 Conversion Process (Methanol)

H2(from Electro.)

To

Stripper

To

Stripper

Reactor

Distill.

CO2 98.0

%molH2O 1.98

N2 0.02

80 bar - 240°C

1 bar

CO2 to methanol: Conversion process


𝐶𝑂 + 2 𝐻2 ↔ 𝐶𝐻3𝑂𝐻

𝐶𝑂2 + 𝐻2 ↔ 𝐶𝑂 + 𝐻2𝑂 (RWGS)

𝐶𝑂2 + 3 𝐻2 ↔ 𝐶𝐻3𝑂𝐻 + 𝐻2𝑂


CO2 Capture Process Methanol Conversion Process

0% AdditionalReboiler Duty

877 tpdWater

Main technological Indicators of the CO2 Capture & Conversion Processes

2475 tpdCO2

247 tpdCO2

93 MWth

10 MWel

7 MWel

3 MWel

0.4 MWel

1506 tpdCH3OH

2228 tpdCO2

WaterElectrolysis

300 tpd H2

2450 tpd O2

22 tpd H2O


CO2 to methanol: Integration


27% Reduction forStripper Heat Duty

(25 MW)

100% Recirculation For Water Make-up

(22 tpd)

2.5% of Produced Water

0% AdditionalReboiler Duty

855 tpdWater68 MWthCO2 Capture Process Methanol Conversion Process

Main technological Indicators of the CO2 Capture & Conversion Processes

CO2 to methanol: Integration



Methanol synthesis





Clinker Methanol

Infrastructure & Raw materials



Excess water

1000 kg

1479 kg CO2

203 kg H2

1626 kg

165 kg CO2

1987 kg

1830 kg

11 MWh

0 GJ0.33

MWh2.6 GJ

0.01MWh

1644 kg CO2

1.4 GJ

568 kg

14 kg water

Technological metrics of the CO2 capture and conversion units normalized to the production of one-ton methanol

CO2 to methanol: Global Chain



Summary of the Project Capital Costs for CO2 Capture & Conversion processes

Costs of Equipment Purchase & Installationfor CO2 Capture & Conversion processes

37.0 M€ Equipment Purchase & Installation

0 4 8 12 16 20

Purchased Equipment

Other

Contingencies

Piping

Electrical

Contract Fee

Total Costs (M€)

CO2 Conversion CO2 Capture

60.4 M€ Global CAPEXProject Investment

0 2 4 6 8 10 12

Exchangers

Compressors

Reactor

Columns

Flash tanks

Total Costs (M€)

CO2 Conversion CO2 Capture

Due to 2 – 80 bar CO2 Compression

17.6 M€ for CO2 Capture (29 %)42.8 M€ for CO2 Conversion (71 %)


CO2 to methanol: Economic indicator

CAPEX32%

30%

19%

17%

2%

Exchangers

Compressors

Reactor

Columns

Flash tanks


Operating expenses related to the CO2 Capture & Conversion Processes

Electricity 70 €/MWh

Catalysts 10 €/kg

Steam 30 €/MWh

Electrolyser Power

53.8 MWh/ton H2

H2 Production 3765 €/ton H2

CH3OH Selling 450 €/ton CH3OH

O2 Selling 13.5 €/ton O2

CO2 Tax 5.0 €/ton CO2

Cost Assumptions for the Cost Estimations of Operational Expenses

-800 -600 -400 -200 0 200 400 600

Methanol selling

O2 selling

CO2 credit tax

Hydrogen Production

CO2 Capture

CO2 Conversion

Amortized CAPEX

TOTAL

Operational Expenses (€/ton methanol)

-600 -400 -200 0 200 400

Methanol selling

O2 selling

CO2 credit tax

Hydrogen Production

CO2 Capture

CO2 Conversion

Amortized CAPEX

TOTAL

Operational Expenses (€/ton captured CO2)

O2 Selling: 15 €/ton CO2

CO2 Credit Tax: 5 €/ton CO2

O2 Selling: 22 €/ton CH3OHCO2 Credit Tax: 7 €/ton CH3OH

CO2 Capture: 33 €/ton CH3OHCO2 Conversion: 24 €/ton CH3OH

CAPEX: 11 €/ton CH3OH

CO2 Capture: 22 €/ton CO2

CO2 Conversion: 16 €/ton CO2

CAPEX: 7 €/ton CO2



OPEX

University of Mons

-500

-400

-300

-200

-100

0

100

200

300

20 30 40 50 60 70 80

Eco

no

mic

bal

ance

(€

/to

n M

eth

ano

l)

Electricity Price (€/MWh)

110

Influence of the Electricity Priceon the CO2 Capture & Conversion Business Case

-600 -400 -200 0 200 400 600

Methanol selling

O2 selling

CO2 credit tax

Hydrogen Production

CO2 Capture

CO2 Conversion

Amortized CAPEX

TOTAL

Operational Expenses (€/ton methanol)

Normal Profit Pointof the CO2 Capture & Conversion Business Case

Normal Profit Pointat 39 €/MWh



Hydrogen consideration


CO2 to methanol: Alternative

CO2 capture unit: Alternative configuration

• CAPEX• OPEX• (2-3 slides in total)


Application to methaneApplication to Formic acid (main conclusions)

• Methane• Formic acid• Present the main conclusions


27/09/2018

Remi CHAUVY

Nicolas MEUNIER, Seloua MOUHOUBI, Lionel DUBOIS, Diane THOMAS, Guy De WEIRELD

Faculty of Engineering (FPMs), UMONS, Mons, Belgium


ADDITIONAL SLIDES

Ir CHAUVY Remi | CAT Scientific Meeting – 31/05/2018


Mass balance and direct CO2 emissions for production of 1 ton of cement


Precalciner

KilnGrinding &

mixing

50 kg additives

1 000 kg Cement CEM1

950 kg clinker

29 kg petroleum coke1 140 kg CaCO3

310 kg others76 kg coal

950 kg Calcined

raw meal

950 kg CO2

91 kg CO2

243 kg CO2 (fuel, precalciner)502 kg CO2 (calcination)

836 kg CO2 (total)


Evaluation of the 3E criteria


Environmental, health and safety Performance

Engineering Performance Economic Performance


PART 3CO2 to methanol: Environmental analysis



Methanol synthesis





Clinker Methanol

Infrastructure & Raw materials



Excess water

1000 kg

1479 kg CO2

203 kg H2

1626 kg

165 kg CO2

1987 kg

1830 kg

11 MWh

0 GJ0.33

MWh2.6 GJ

0.01MWh

1644 kg CO2

1.4 GJ

568 kg

14 kg water

Technological metrics of the CO2 capture and conversion units normalized to the production of one-ton methanol

CO2 to methanol: Global Chain


System boundary

System boundaries: Gate-to-gate LCA approach


Post combustion CO2 capture unit from fluegas using MEA

- MEA solvent supply and emissions

- Utilities supply: electricity & steam

- Infrastructures: construction + transportof materials

• System boundaries: Gate-to-gate LCA approach

- Infrastructures: decommissioning

- Transport: Considered on-site

CO2 conversion unit

- Hydrogen supply: H2 from wind-basedwater electrolysis

- Catalyst supply

- Utilities supply: electricity & steam

- Infrastructures: construction +transport of materials

In system boundaries:

Out of system boundaries:

LCA of the global chain



• Impacts considered:• Global warming (GWP) • Fossil resource depletion (FDP)• Terrestrial acidification (TAP) • Fresh water eutrophication (FEP)• Human toxicity (HTP)• Water depletion (WDP) • Metal (mineral) depletion (MDP)

• ReCiPe method (H)

• Inventory analysis: • Results from Aspen modelling• EcoInvent database• Use of SimaPro

LCA of the global chain



Integration CO2 capture and conversion units (CCUS)

0%

20%

40%

60%

80%

100%

FDP MDP WDP HTP FEP TAP GWP

Treated gas MEA Electricity Heat (Steam)

Feed H2 Catalyst use Water Infrastructure

Without integration between the 2 units

Ab. Impacts

FDP Fossil Depletion

MDP Metal Depletion

WDP Water Depletion

HTP Human Toxicity

FEP Fresh water Eutrophication

TAP Terrestrial Acidification

GWP Global Warming

LCA of the CCUS global chain

Hydrogen production maincontributor to most impactcategoriesHigh energy penalty especiallydue to the compression of H2 andCO2 inlets to reach the workingpressure of 80 bar



Comparison between the environmental impacts of the conventional production and the CO2-based alternative methanol

Ab. Impacts


MDP Metal Depletion

WDP Water Depletion

HTP Human Toxicity



GWP Global Warming


0100200300400500600700800900

1 000

FDP(kg oil eq)

MDP x 0.1(kg Fe eq)

WDP x0.01(m3)

HTP(kg 1.4-DB

eq)

FEP x 10E-3

(kg P eq)

TAP x 0.01(kg SO2

eq)

Tota

l im

pac

t (p

er t

on

met

han

ol)

Conventional production CO2-based methanol

-1 500

-1 000

-500

0

500

1 000

GW

P (

kgC

O2e

q p

er t

on

m

eth

ano

l)

Conventional

production

CO2-based methanol

H2 productionCO2 conversion unit (excluding H2 production)

CO2 capture unit

CO2 inlet

Highlights:

• CO2-based methanol demonstrates lower emissions (except for WDP)

• GHG sink (?)



Comparison between the environmental impacts of the conventional production and the CO2-based alternative methanol


-800

-400

0

400

800

1 200

1 600

Tota

l im

pac

t (p

er t

on

met

han

ol)

FDP (kg oil eq) MDP x 0.1 (kg Fe eq) WDP x 0.01 (m3) HTP (kg 1.4-DB eq)

FEP x 10E-3 (kg P eq) TAP x 0.01 (kg SO2 eq) GWP (kg CO2 eq)

Ab. Impacts


MDP Metal Depletion

WDP Water Depletion

HTP Human Toxicity



GWP Global Warming

Mix ENSTO-E Germany France Iceland

Conv. CO2-based Conv. CO2-based Conv.CO2-based

Conv.CO2-based

Highlights:

• Location electricity mix• Influence on WDP• GWP = – 617 to – 317

kgCO2eq per ton methanol


Documents

From CO to Energy: Carbon Capture in Cement Production and