CO2 as a resource in a circular economy

MSc Chemistry

Molecular Sciences

Literature Study

CO

2

in a circular economy

Methods of capture and utilisation of

the world’s most prominent green

house gas

by

Youri van Valen

11094176

December 2019

12 EC

October 2018 – December 2019

Supervisor/Examiner:

Examiner:

dr. J.C. (Chris) Slootweg

prof. dr. G.J.M. (Gert-Jan) Gruter

Table of Contents

1.2.1 Technical resource cycle 3

1.2.2 Biological resource cycle 3

1.3 CO2 IN A CIRCULAR ECONOMY 4

1.3.1 Carbon Capture and Storage vs Carbon Capture and Utilisation 5

1.3.2 CO2 is a resource 5

1.3.3 CO2 availability and emission sources 5

1.4 CHALLENGES IN IMPLEMENTATION OF THE CE:RELIANCE ON RENEWABLE ENERGY SOURCES 8

2 THEORY ON CO2 UTILISATION 10

2.1 THERMODYNAMICS 10

2.2 CHALLENGES IN CO2UTILISATION 12

2.3 CARBON CAPTURE AND SEPARATION SYSTEMS 12

2.3.1 Carbon capture systems 13

2.3.2 CO2 separation technologies 14

2.4 CHEMICAL AND BIOCHEMICAL CONVERSION OF CO2 21

2.4.1 Biochemical conversion 21

2.4.2 Chemical conversion 22

3 CREATING FUELS USING CO2 AS A FEEDSTOCK 23

3.1 DIRECT HYDROGENATION OF CO2 TO METHANOL. 23

3.1.1 Reaction mechanism 23

3.1.2 Catalyst 25

3.1.3 Mass and energy balance 26

3.1.4 George Olah renewable methanol plant 27

3.2 ELECTROCHEMICAL REDUCTION OF CO2 TO FORMATE/FORMIC ACID. 28

3.2.1 Reaction mechanism 28

3.2.2 Catalyst 29

3.2.3 Mass and energy balance 31

4 PREPARATION OF CHEMICALS USING CO2 32

4.1 POLYCARBONATES 32

4.1.1 Reaction Mechanism 32

4.1.2 Catalysts 34

4.2.1 Reaction mechanism 38

4.2.2 Catalyst 39

5 DISCUSSION AND CONCLUSIONS 40

6 ACKNOWLEGDEMENTS 41

1 Introduction

1.2 Resource Cycles

1.2.1 Technical resource cycle

1.3.1 Carbon Capture and Storage vs Carbon Capture and Utilisation

1.3.2 CO2 is a resource

Sector Percentage global CO2 emission

Electricity and Heat 49

Transport 20

Manufacturing and Construction 20

Residential, Commercial and Services 9

Others 2

Industrial Sector CO2 emission (Mt)

Ferrous and Non-Ferrous metals 2127

Chemicals 1159

Cement 1352.25

Other 3222.24

Indirect (electricity and heat) 5246.79

Landfill, Waste Incineration and others 32.50

Total 13139.78 Process CO2 emissions (Gt) Cement production 1.352 Chemicals production 0.477 Lime production 0.242 Coke ovens 0.134

Non-ferrous metal production 0.074

Iron and steel production 0.072

Ferroalloy production 0.061

Limestone and dolomite use 0.060

Solvent and other product use 0.049

Mineral production 0.042

Non-energy use of lubricants/waxes 0.024

1.4 Challenges in implementation of the CE: Reliance on renewable energy

sources

2 Theory on CO

utilisation

2.1 Thermodynamics

1.

○ □

2.2 Challenges in CO

Utilisation

2.3 Carbon capture and separation systems

2.3.1 Carbon capture systems

2.3.1.1 Post-combustion carbon capture

2.3.1.3 Oxy-fuel combustion

2.3.1.4 Direct air capture

2.3.2 CO2 separation technologies

2.4 Chemical and Biochemical conversion of CO

3 Creating fuels using CO

as a feedstock

3.1 Direct hydrogenation of CO

to methanol.

3.1.3 Mass and energy balance

Mass Balance (t/tMeOH)

CO2 In 1.460 H2O In 1.990 Air In 0.813 MeOH out 1 H2O out 0.768 O2 out 1.592

Flue gas out 0.905 CO2 used 1.280

Energy Balance (MWh/tMeOH) Electricity consumption 11.954 w/o electrolyser 0.177 Heating needs 0.439 Cooling needs 0.862 CDU Plant Conven-tional Plant Electricity (MWh/tMeOH) 11.945 0.147 Direct CO2 emissions (tCO2/tMeOH) 0.090 0.695 Indirect CO2 emissions (tCO2/tMeOH) 0.091 0.073 Inlet CO2 (tCO2/tMeOH) 1.460 0 Natural Gas Savings (tNG/yr) (0.6 tNG/tMeOH) 264702.72 0

3.2 Electrochemical reduction of CO

to formate/formic acid.

3.2.3 Mass and energy balance

Substance Molar Weight Moles per Mole HCOOH

Mass per tonne HCOOH In CO2 0.04401 kg/mol 1 956.12 kg H2O 0.01801528 kg/mol 1 391.38 Out HCOOH 0.04603 kg/mol 1 1000 kg O2 0.03200 kg/mol 0.5 347.59 kg

4 Preparation of chemicals using CO

4.1 Polycarbonates

4.1.2 Catalysts

4.1.2.1 Heterogeneous catalysts

4.2.2 Catalyst

Catalyst CO2 conv. (%) TOF(h-1)

MoCl5 0 NA TaCl5 19 1.6 NbCl5 36 3 ZrCl4 86 7.2 YCl3 91 7.6 ScCl3 95 8 YCl31 77 6.6

Substrate Reaction time (h) CO2 conversion (%) TOF (h-1)

Epichlorohydrin 5 92 1.6