Converting Power into Chemicals and Fuels E-Book

Martin Bajus

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 1222

Veröffentlichungsjahr: 2023

Beschreibung

CONVERTING POWER INTO CHEMICALS AND FUELS Understand the pivotal role that the petrochemical industry will play in the energy transition by integrating renewable or low-carbon alternatives Power into Chemicals and Fuels stresses the versatility of hydrogen as an enabler of the renewable energy system, an energy vector that can be transported and stored, and a fuel for the transportation sector, heating of buildings and providing heat and feedstock to industry. It can reduce both carbon and local emissions, increase energy security and strengthen the economy, as well as support the deployment of renewable power generation such as wind, solar, nuclear and hydro. With a focus on power-to-X technologies, this book discusses the production of basic petrochemicals in such a way as to minimize the carbon footprint and develop procedures that save energy or use energy from renewable sources. Various different power-to-X system configurations are introduced with discussions on their performance, environmental impact, and cost. Technologies for sustainable hydrogen production are covered, focusing on water electrolysis using renewable energy as well as consideration of the remaining challenges for large scale production and integration with other technologies. Power into Chemicals and Fuels readers will also find: * Discussion of recent advances in power-into-x technologies for the production of ethylene, propylene, formic acid, and more * Coverage of every stage in the power-into-x process, from power generation to upgrading the final product * Thermodynamic, technoeconomic, and life cycle assessment analyses of each major process Power into Chemicals and Fuels is a valuable resource for scientists and engineers working in the petrochemicals and hydrocarbons industries, as well as for all industry professionals in these and related fields.

Leseprobe

Converting Power into Chemicals and Fuels

Power-to-X Technology for a Sustainable Future

Martin Bajus

This edition first published 2023

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Library of Congress Cataloging-in-Publication Data

Names: Bajus, Martin, 1943- author. | John Wiley & Sons, publisher.

Title: Converting power into chemicals and fuels : power-to-X technology for a sustainable future / Martin Bajus.

Description: [Hokoben, NJ]: Wiley, [2023] | Publication place and date from CIP data view.

Identifiers: LCCN 2023017550 | ISBN 9781394184293 (hardback) | ISBN 9781394184262 (pdf) | ISBN 9781394185764 (epub) | ISBN 9781394185771 (ebook)

Subjects: LCSH: Energy storage. | Energy conversion. | Renewable energy sources.

Classification: LCC TK2980 .B35 2023 | DDC 621.31/26–dc23/eng/20230501

LC record available at https://lccn.loc.gov/2023017550

Cover Image: © Kittikorn Nimitpara/Moment/Getty

Cover Design: Wiley

Set in 9.5/12.5pt STIXTwoText by Integra Software Services Pvt. Ltd., Pondicherry, India

To my loving wife Máriaand grandchildren,Rebeka, Kristina, Sorayah,Jakub and David

Contents

Cover

Title Page

Copyright Page

Dedication

About the Book

Preface

Acknowledgments

General Literature

Nomenclature

Abbreviations and Acronyms

1 Power-to-Chemical Technology

1.1 Introduction

1.2 Power-to-Chemical Engineering

1.2.1 Carbon Dioxide Thermodynamics

1.2.2 Carbon Dioxide Aromatization Thermodynamics

1.2.3 Reaction Mechanism of Carbon Dioxide Methanation

1.2.4 Water Electrolysis Thermodynamics

1.2.5 Methane Pyrolysis Reaction Thermodynamic Consideration

1.2.5.1 The Carbon-Hydrogen System

1.2.6 Reaction Kinetics and Mechanism

1.2.7 Thermal Mechanism of Methane Pyrolysis into a Sustainable Hydrogen

1.2.8 Catalytic Mechanism Splitting of Methane into a Sustainable Hydrogen

1.2.9 Conversion of Methane over Metal Catalysts into a Sustainable Hydrogen

1.2.9.1 Nickel Catalysts

1.2.9.2 Iron Catalysts

1.2.9.3 Regeneration of Metal Catalysts

1.2.10 Conversion of Methane over Carbon Catalysts into Clean Hydrogen

1.2.10.1 Activity of Carbon Catalysts

1.2.10.2 Stability and Deactivation of Carbon Catalysts

1.2.10.3 Regeneration of Carbon Catalysts

1.2.10.4 Co-Feeding to Extend the Lifetime of Carbon Catalysts

1.2.11 Reactors

1.2.11.1 Conversion, Selectivity and Yields

1.2.11.2 Modelling Approach of the Structured Catalytic Reactors

1.2.11.3 Reactor Concept for Catalytic Carbon Dioxide Methanation

1.2.11.4 Monolithic Reactors

1.2.11.5 Mass Transfer in the Honeycomb and Slurry Bubble Column Reactor

1.2.11.6 Heat Transfer in Honeycomb and Slurry Bubble Column Reactors

1.2.11.7 Process Design

1.2.11.8 Comparison and Outlook

1.3 Potential Steps Towards Sustainable Hydrocarbon Technology: Vision and Trends

1.3.1 Technology Readiness Levels

1.3.2 A Vision for the Oil Refinery of 2030

1.3.3 The Transition from Fuels to Chemicals

1.3.3.1 Crude Oil to Chemicals Investments

1.3.3.2 Available Crude-to-Chemicals Routes

1.3.4 Business Trends: Petrochemicals 2025

1.3.4.1 Asia-Pacific

1.3.4.2 Middle East

1.3.4.3 United States

1.4 Digital Transformation

1.4.1 Benefits of Digital Transformation

1.4.2 A New Workforce and Workplace

1.4.3 Technology Investment

1.4.4 The Greening of the Downstream Industry

1.4.4.1 Sustainable Alkylation Technology

1.4.4.2 Ecofriendly Catalyst

1.5 RAM Modelling

1.5.1 RAM1 Site Model

1.5.2 RAM2 Plant Models

1.5.3 RAM3 Models

1.5.4 RAM Modelling Benefit

1.6 Conclusions

Further Reading

2 The Green Shift in Power-to-Chemical Technology and Power-to-Chemical Engineering: A Framework for a Sustainable Future

2.1 Introduction

2.2 Eco-Friendly Catalyst

2.2.1 Development of Catalysts Supported on Carbons for Carbon Dioxide Hydrogenation

2.2.2 Properties of Carbon Supports

2.3 Hydrogen

2.3.1 Different Colours and Costs of Hydrogen

2.3.1.1 Blue Hydrogen

2.3.1.2 Green Hydrogen

2.3.1.3 Grey Hydrogen

2.3.1.4 Pink Hydrogen

2.3.1.5 Yellow Hydrogen

2.3.1.6 Multi-Coloured Hydrogen

2.3.1.7 Hydrogen Cost

2.4 Alternative Feedstocks

2.4.1 Carbon Dioxide-Derived Chemicals

2.5 Alternative Power-to-X-Technology

2.5.1 Power-to-X-Technology to Produce Electrochemicals and Electrofuels

2.6 Partial Oxidation of Methane

2.7 Biorefining

2.8 Sustainable Production to Advance the Circular Economy

2.8.1 Introduction

2.8.2 Circular Economy

2.8.2.1 Sustainability

2.8.2.2 Scope

2.8.2.3 Background of the Circular Economy

2.8.2.3.1 Emergence of the Idea

2.8.2.3.2 Moving Away from the Linear Model

2.8.2.3.3 Towards the Circular Economy

2.8.3 Circular Business Models

2.8.4 Industries Adopting a Circular Economy

2.8.4.1 Minimizing Dependence on Fossil Fuels

2.8.4.2 Minimizing the Impact of Chemical Synthesis and Manufacturing

2.8.4.3 Future Research Needs in Developing a Circular Economy

2.9 New Chemical Technologies

2.9.1 Renewable Power

Further Reading

3 Storage Renewable Power-to-Chemicals

3.1 Introduction

3.2 Terminology

3.3 Energy Storage Systems

3.4 World Primary Energy Consumption

3.4.1 2019 Briefly

3.4.2 Energy in 2020

3.4.2.1 Not Just Green but Greening

3.4.2.2 For Energy, 2020 Was a Year Like No Other

3.4.2.3 Glasgow Climate Pact

3.4.2.4 Energy in 2020: What Happened and How Surprising Was It

3.4.2.5 How Should We Think About These Reductions

3.4.2.6 What Can We Learn from the COVID-induced Stress Test

3.4.2.7 Progress Since Paris – How Is the World Doing

3.5 Carbon Dioxide Emissions

3.5.1 Carbon Footprint

3.5.1.1 Climate-driven Warming

3.5.2 Carbon Emissions in 2020

3.6 Clean Fuels ‒ the Advancement to Zero Sulfur

3.7 Renewables in 2019

3.8 Hydroelectricity and Nuclear Energy

3.9 Conclusion

Further Reading

4 Carbon Capture, Utilization and Storage Technologies

4.1 Industrial Sources of Carbon Dioxide

4.2 Carbon Capture, Utilization and Storage Technologies

4.3 Carbon Dioxide Capture

4.4 Developing and Deploying CCUS Technology in the Oil and Gas Industry

4.5 Sustainable Steel/Chemicals Production: Capturing the Carbon in the Material Value Chain

4.5.1 Valorisation of Steel Mill Gases

4.5.2 Summary and Outlook

Further Reading

5 Integrated Refinery Petrochemical Complexes Including Power-to-X Technologies

5.1 Introduction

5.2 Synergies Between Refining and Petrochemical Assets

5.2.1 Reaching Maximum Added Value – Integrated Refining Schemes

5.2.1.1 Fluid Catalytic Cracking Alternates

5.2.1.2 Hydrocracking Alternates

5.2.2 Comparisons and Sensitivities to Product/Utility Pricing

5.2.3 Options for Further Increasing the Petrochemical Value Chain

5.3 Carbon Dioxide Emissions

5.3.1 Effect of a Carbon Dioxide Tax

5.3.2 Crude Oil Effects

5.4 Summary

5.5 Power- to-X Technology

5.6 The Role of Nuclear Power

5.6.1 Small Nuclear Power Reactors

5.6.2 Conclusion

Further Reading

6 Power-to-Hydrogen Technology

6.1 Introduction

6.2 Traditional and Developing Technologies for Hydrogen Production

6.3 Dry Reforming of Methane

6.4 Tri-reforming of Methane

6.5 Greenfield Technology Option → Low Carbon Emission Routes

6.5.1 Water Electrolysis

6.5.1.1 Alkaline Electrolysis

6.5.1.2 Polymer Electrolyte Membrane Electrolysis

6.5.1.3 Solid Oxide Electrolysis

6.5.2 Methane Pyrolysis

6.5.2.1 Process Concepts for Industrial Application

6.5.2.2 Perspectives of the Carbon Coproduct

6.5.3 Thermochemical Processes

6.5.4 Photocatalytic Processes

6.5.5 Biomass Electro-Reforming

6.5.6 Microorganisms

6.5.7 Hydrogen from Other Industrial Processes

6.5.8 Hydrogen Production Cost

6.5.9 Electrolysers

6.5.10 Carbon Footprint

6.6 Advances in Chemical Carriers for Hydrogen

6.6.1 Demand Drivers

6.6.2 Options for Hydrogen Deployment

6.6.3 Advances in Hydrogen Storage/Transport Technology

6.6.4 Global Supply Chain

6.6.5 Power-to-Gas Demo

6.6.5.1 Hydrogen Fuelling Stations

6.6.5.2 Pathway to Commercialization

6.6.5.3 Transportation Studies in North America

6.6.6 Future Applications

6.7 Ammonia Fuel Cells

6.7.1 Proton-Conducting Fuel Cells

6.7.2 Polymer Electrolyte Membrane Fuel Cells

6.7.3 Proton-conducting Solid Oxide Fuel Cells

6.7.4 Alkaline Fuel Cells

6.7.5 Direct Ammonia Solid Oxide Fuel Cell

6.7.6 Equilibrium Potential and Efficiency of the Ammonia-Fed SOFC

6.8 Conclusions

Further Reading

7 Power-to-Fuels

7.1 Introduction

7.2 Selection of Fuel Candidates

7.2.1 Fuel Production Processes

7.3 Power-to-Methane Technology

7.3.1 Carbon Dioxide Electrochemical Reduction

7.3.2 Carbon Dioxide Hydrogenation

7.4 Power-to-Methanol

7.5 Power-to-Dimethyl Ether

7.6 Chemical Conversion Efficiency

7.6.1 Exergy

7.6.2 Exergy Efficiency

7.6.3 Economic and Environmental Evaluation

7.6.4 Fuel Assessment

7.6.5 Performance of Fuel Production Processes

7.6.6 Process Chain Evaluation

7.6.7 Fuel Cost

7.7 Well-to-Wheel Greenhouse Gas Emissions

7.7.1 Environmental Impact

7.7.2 Infrastructure

7.7.3 Efficiency

7.7.4 Energy/Power Density

7.7.5 Pollutant Emissions

7.8 Gasoline Electrofuels

7.9 Diesel Electrofuels

7.10 Electrofuels and/or Electrochemicals

7.10.1 Physico-Chemical Properties

7.10.1.1 Density

7.10.1.2 Tribological Properties

7.10.1.3 Combustion Characteristics

7.10.1.4 Combustion and Emissions

7.10.2 Diesel Engine Efficiency

7.10.3 Potential of Diesel Electrofuels

7.11 Maturity, TRL, Production and Electrolysis Costs

7.11.1 Summary

7.12 Power-to-Liquid Technology

7.12.1 Power-to-Jet Fuel

7.12.2 Power-to-Diesel

7.13 Conclusion and Outlook

Further Reading

8 Power-to-Light Alkenes

8.1 Oxidative Dehydrogenation

8.1.1 Carbon Dioxide as a Soft Oxidant for Catalytic Dehydrogenation

8.1.2 Carbon Dioxide: Oxidative Coupling of Methane

8.1.3 From Carbon Dioxide to Lower Olefins

8.1.4 Low-Carbon Production of Ethylene and Propylene

8.1.4.1 Energy Demand per Unit of Ethylene/Propylene Production via Methanol

8.1.4.2 Carbon Dioxide Reduction per Unit of Ethylene/Propylene Production

8.1.4.3 Economics of Low-Carbon Ethylene and Propylene Production

8.2 Life Cycle Assessment

8.2.1 Small-Scale Production of Ethylene

8.3 Polymerization Reaction

8.3.1 Carbon Dioxide-Based Polymers

8.3.1.1 Perspective and Practical Applications

Further Reading

9 Power-to-BTX Aromatics

9.1 Low-Carbon Production of Aromatics

9.1.1 Methanol to Aromatics Process

9.1.1.1 ZSM-5 Catalyst

9.1.1.2 Process Variables

9.1.1.3 Kinetic Modelling

9.1.1.4 Aromatics via Hydrogen-Based Methanol (TRL7)

9.1.1.5 Energy Demand per Unit of Low-Carbon BTX Production

9.1.1.6 Carbon Dioxide Reduction

9.1.1.7 Economics of Low-Carbon BTX Production

9.2 Production of p-Xylene from 2,5-Dimethylfuran and Ethylene

9.3 Carbon Dioxide Dehydrogenation of Ethylbenzene to Styrene

Further Reading

10 Power-to-C

1

Chemicals

10.1 Introduction

10.2 Carbon Dioxide Utilization into Chemical Technology

10.3 Mechanism of Conversion of Carbon Dioxide

10.4 Hydrogenation of Carbon Dioxide

10.4.1 Heterogeneous Hydrogenation

10.4.2 Homogeneous Hydrogenation

10.5 Electrochemical Conversion of Carbon Dioxide into Valuable Chemicals

10.5.1 Technologies Available for Carbon Dioxide Reduction

10.6 Electrochemical Technologies

10.6.1 Roles of Ionic Liquids on Electrochemical Carbon Dioxide Reduction Promotion

10.6.2 Ionic Liquids as Absorbent for Carbon Dioxide Capture

10.6.3 Classification of the Electrode Material

10.6.4 High Hydrogen Evolution Overvoltage Metal

10.6.5 Low Hydrogen Evolution Overvoltage Metals

10.6.6 Copper Electrodes

10.6.7 Other Electrodes for Carbon Dioxide Reduction

10.7 Power-to-Methanol Technology

10.7.1 Carbon Dioxide Electrochemical Reduction

10.7.2 Direct Carbon Dioxide Hydrogenation into Methanol

10.7.3 Low-Carbon Methanol Production

10.7.4 Energy Demand

10.8 Power-to-Formic Acid Technology

10.8.1 Carbon Dioxide Electrochemical Reduction

10.8.2 Carbon Dioxide Hydrogenation

10.9 Power-to-Formaldehyde Technology

10.9.1 Carbon Dioxide Electrochemical Reduction

10.9.2 Carbon Dioxide Hydrogenation

10.10 Selective Hydrogenation of Carbon Dioxide to Light Olefins

10.10.1 Introduction

10.10.2 Carbon Dioxide via FTS to Lower Olefins

10.10.3 Methane via FTS to Lower Olefins

10.10.4 Carbon Dioxide via FTS to Liquid

iso

-C

5

-C

13

-Alkanes

10.10.4.1 Power-to-Liquids

10.10.4.2 Energy Demand per Unit of Synthetic Fuel Production

10.10.4.3 Carbon Dioxide Reduction per Unit of Synthetic Fuel Production

10.10.4.4 Economics

10.10.4.5 Comparison of the Hydrogen-Based Low-Carbon Synthesis Routes

10.11 Electrochemical Reduction of Carbon Dioxide to Oxalic Acid

10.11.1 Process Design and Modelling

10.11.2 Carbon Dioxide Absorption in Propylene Carbonate

Further Reading

11 Power-to-Green Chemicals

11.1 Introduction

11.2 Biomethanol Production

11.2.1 Biomethanol Production Process

11.2.2 Energy and Feedstock Demand per Unit of Biomethanol Production

11.2.3 Carbon Dioxide Reduction per Unit of Biomethanol Production

11.2.4 Economics of Biomethanol Production

11.3 Bioethanol Production

11.3.1 Bioethanol Production Process

11.3.2 Energy and Feedstock Demand per Unit of Bioethanol Production

11.3.3 Carbon Dioxide Reduction per Unit of Bioethanol Production

11.3.4 Carbon Dioxide Reduction for (Partially) Replacing Gasoline with Bioethanol

11.3.5 Economics of Bioethanol Production

11.4 Bioethylene Production

11.4.1 Bioethylene Production Process

11.4.2 Energy and Feedstock Demand per Unit of Bioethylene Production

11.4.3 Carbon Dioxide Reduction per Unit of Bioethylene Production

11.4.4 Economics of Bioethylene Production

11.5 Biopropylene Production

11.5.1 Biopropylene Production Processes

11.5.2 Energy and Feedstock Demand per Unit of Biopropylene Production

11.5.3 Carbon Dioxide Reduction per Unit of Biopropylene Production

11.6 BTX Production from Biomass

11.6.1 BTX Production Process

11.6.2 Energy and Feedstock Demand per Unit of BTX Production from Biomass

11.6.3 Carbon Dioxide Emissions per Unit of BTX Production from Biomass

11.7 Comparison of the Biomass-Based Synthesis Routes

11.8 Biofuels

11.8.1 Biodiesel Production

11.8.2 Purification of Glycerol

11.8.3 Conversion of Glycerol into Valuable Products

11.8.3.1 Solketal Synthesis Process

11.8.3.2 Reaction Mechanism

11.8.3.3 Kinetics of Reaction

11.8.3.4 Catalyst Design

11.8.3.5 Batch Process

11.8.3.6 Continuous Process

11.8.4 Current Issues and Challenges

11.8.5 Future Recommendation

11.8.6 Conclusion

11.9 Higher Alcohols and Ether Biofuels

11.9.1 Fuel Production Routes and Sustainability

11.9.2 Lignin

11.9.3 Fuel Properties

11.9.4 Concluding Remarks

11.10 Biofuels in the World: Biogasoline and Biodiesel

Further Reading

12 Industrial Small Reactors

12.1 Introduction

12.2 Thermochemical Water Splitting

12.3 Small Modular Reactors

12.4 Nuclear Process Heat for Industry

12.4.1 High-temperature Reactors for Process Heat

12.4.2 Recovery of Oil from Tar Sands

12.4.3 Oil Refining

12.4.4 Coal and Its Liquefaction

12.4.5 Biomass-Based Ethanol Production

12.4.6 District Heating

12.5 Microchannel Reduction Cell

12.6 Conversion of Carbon Dioxide to Graphene

12.7 The Ammonia Synthesis Reactor-Development of Small-scale Plants

Further Reading

13 Recycling of Waste Plastics → Plastics Circularity

13.1 Introduction

13.2 Mechanism Aspects of Waste Plastic Pyrolysis

13.2.1 Polyethylene and Polypropylene

13.2.2 Polyethylene Terephthalate

13.2.3 Polyvinyl Chloride

13.2.4 Polystyrene

13.2.5 Poly (Methyl Methacrylate)

13.3 Kinetics

13.4 Catalysts

13.4.1 Zeolites

13.4.2 Fluid Catalytic Cracking Catalysts

13.5 Parameters Affecting Pyrolysis

13.5.1 Type of Plastic Feed

13.5.2 Temperature and Residence Time

13.5.3 Pressure

13.6 Type of Reactors

13.6.1 Rotary Kiln Reactor

13.6.2 Screw Feed (Auger) Reactor

13.6.3 Fluid Catalytic Cracking Reactor

13.6.4 Stirred-Tank Reactor

13.6.5 Plasma Pyrolysis Reactor

13.6.6 Batch Reactor

13.6.7 Fixed Bed Reactor

13.6.8 Fluidized Bed Reactor

13.6.9 Conical Spouted Bed Reactor

13.6.10 Microwave Reactor

13.6.11 Pyrolysis in Supercritical Water

13.7 Applications of Pyrolysis Products

13.7.1 Pyrolysis Gases → Hydrogen and Methane

13.7.2 Pyrolysis Oil → Aromatics and Diesel Fuels

13.7.3 Pyrolysis Char → Nanotubes

Further Reading

Index

End User License Agreement

List of Tables

CHAPTER 01

Table 1.1 Enthalpy and Gibbs free energy changes...

Table 1.2 Thermodynamic equilibrium potential of electrochemical carbon dioxide...

Table 1.3 Reactions involving carbon dioxide conversion into chemicals/fuels.

Table 1.4 Effect of temperature on the free energy of formation for reaction oc...

Table 1.5 Aromatization of carbon dioxide (all species in gas phase).

Table 1.6 Initial activity of nickel, iron and cobalt catalysts in the decompos...

Table 1.7 Determining factors of the activity and stability of carbon catalysts...

Table 1.8 Characteristics of chemical/petrochemical technology.

Table 1.9 Technology readiness levels, definitions, descriptions and supporting...

Table 1.10 Technology readiness level (TRL) of carbon capture and utilization in...

Table 1.11 Crude oil to chemicals investments (The Catalyst Group, 2019).

Table 1.12 Market share of new petrochemical project announcements by world regi...

Table 1.13 Catalyst consumption.

CHAPTER 02

Table 2.1 The development of environmentally friendly processes.

Table 2.2 Areas and industries adopting a circular economy.

CHAPTER 03

Table 3.1 Energy content and energy density at storage conditions.

Table 3.2 Energy required to revert carbon dioxide into a fuels.

Table 3.3 World consumption of energy in 2019, 2020 and 2021.

Table 3.4 World carbon dioxide emissions.

CHAPTER 04

Table 4.1 Large industrial carbon dioxide sources and key parameters.

Table 4.2 Typical carbon dioxide sources and their respective stochiometric vol...

Table 4.3 Processes for acid gas removal.

CHAPTER 05

Table 5.1 Refining and petrochemical industry characteristics.

Table 5.2 Sensitivities: Internal rate of return variation with changes in petr...

Table 5.3 Specific carbon dioxide emissions for the various cofigurations.

Table 5.4 Carbon dioxide emissions for the various configurations with and with...

Table 5.5 Impact of a carbon dioxide tax on internal rate of return, with and w...

Table 5.6 Impact of crude oil type on internal rate of return. The configuratio...

Table 5.7 Nuclear hybrid energy systems for hydrogen production.

CHAPTER 06

Table 6.1 Energy efficiencies of different technologies for hydrogen production...

Table 6.2 Comparison between different processes for hydrogen production.

Table 6.3 Global market and price for potential carbon products.

Table 6.4 Carbon footprint of hydrogen production.

CHAPTER 07

Table 7.1 Definition of revolutionary energy and fuels for transportation, lear...

Table 7.2 Limitation of transportation fuels for personal vehicles.

Table 7.3 Basic hydrogen and methane properties.

Table 7.4 Summary of the Power-to-Methane plants current in operation and of th...

Table 7.5 Basic methanol properties.

Table 7.6 Comparison of performance of different processes.

Table 7.7 Results of the economic evaluation for the base case of the discussed...

Table 7.8 Well-to-wheel GHG emissions caused by the electro fuels. For the orga...

Table 7.9 Properties of diesel fuels.

Table 7.10 Overview of fuel evaluations: DME, OME, Fischer-Tropsch diesel.

CHAPTER 08

Table 8.1 Input-output information for small-scale experimental setup.

CHAPTER 09

Table 9.1 Hydrogenation of carbon dioxide to aromatics over Na-Fe hierarchical ...

Table 9.2 Product spectrum of methanol-to-aromatics over HZSM-5 catalyst.

CHAPTER 10

Table 10.1 Comparison of various methanol production processes from methane.

Table 10.2 Summary of electrochemical reduction of carbon dioxide on high hydrog...

Table 10.3 Summary of electrochemical reduction of carbon dioxide on low hydroge...

Table 10.4 Comparison of Faradaic efficiency of the products for copper electrod...

Table 10.5 Product formed at the surface of varies cathodes for electrochemical ...

Table 10.6 Summary of different electrocatalysts used for electrocatalytic reduc...

Table 10.7 Summary of some of the process simulations and techno-economy studies...

Table 10.8 Comparison of energy demand and carbon dioxide emissions for methanol...

Table 10.9 Carbon dioxide conversion () and product selectivity for carbon dioxi...

Table 10.10 Catalytic results of FTO catalysts.

Table 10.11 Characteristics of Sunfire’s synthetic diesel from pilot plant.

Table 10.12 Comparison of hydrogen based low-carbon synthesis routes.

CHAPTER 11

Table 11.1 Biomass availability in Europe (Mtoe).

Table 11.2 Comparison of biomass-based synthesis routes.

Table 11.3 Physico-chemical properties of diesel versus different mixtures of di...

Table 11.4 Fuel properties of higher n-alcohols di-n-alkyl ethers.

CHAPTER 12

Table 12.1 Nuclear process heat application.

CHAPTER 13

Table 13.1 Impact of plastic type on fuel properties and yields of pyrolysis oil...

List of Illustrations

CHAPTER 01

Figure 1.1 (A) The overall scheme of the carbon capture...

Figure 1.2 Thermodynamics of some carbon dioxide reactions.

Figure 1.3 Equilibrium conversion of carbon...

Figure 1.4 A) Gibbs free energy changes.CO2 + 3H2...

Figure 1.5 Potential energy diagram of one possible...

Figure 1.6 Reaction scheme of the kinetic model...

Figure 1.7 Equilibrium positions of stoichiometric...

Figure 1.8 Energy demand for water electrolysis...

Figure 1.9 The methane equilibrium: CH4 C + 2 H2....

Figure 1.10 Free energy of formation of hydrocarbons...

Figure 1.11 Enthalpy diagrams of (A) steam...

Figure 1.12 Hydrogen mole fraction (in the...

Figure 1.13 Temperature range of applicability...

Figure 1.14 Hydrogen mole fraction (in the gas...

Figure 1.15 Reaction mechanism of the noncatalytic...

Figure 1.16 Reaction mechanism of noncatalytic methane pyrolysis.

Figure 1.17 Reaction mechanisms proposed for...

Figure 1.18 Vapour‒liquid‒solid mechanism for the...

Figure 1.19 Schematic drawing of the honeycomb...

Figure 1.20 Mass transfer phenomena in the...

Figure 1.21 Heat transfer phenomena in the...

Figure 1.22 The decline of the oil consumed...

Figure 1.23 Crude-to-Chemicals concepts (IHS Markit, 2019).

Figure 1.24 Market share of new petrochemical...

CHAPTER 02

Figure 2.1 Target products of chemical carbon dioxide...

Figure 2.2 Mass flows within the chemical industry...

Figure 2.3 Linear versus circular economy.

Figure 2.4 Circular business models.

CHAPTER 03

Figure 3.1 Comparison between different energy...

Figure 3.2 Various Power-to-X technologies...

Figure 3.3 Power-to-Fuel, interlinking the...

Figure 3.4 World primary energy consumption in 2021 [EJ].

Figure 3.5 The rate of ocean warming around Australia.

CHAPTER 04

Figure 4.1 Carbon dioxide emissions for different sectors...

Figure 4.2 Carbon dioxide capture via carbonate looping.

Figure 4.3 Schematic representation of the carbon...

CHAPTER 05

Figure 5.1 Synergies possible between refining...

Figure 5.2 Zero gasoline refinery in electric vehicle era.

Figure 5.3 Process flow diagram for Uniflex™ slurry...

Figure 5.4 Integrated refining configuration based on crude...

Figure 5.5 Internal rate of return vs. petrochemicals on crude.

Figure 5.6 Carbon dioxide emissions for case A0: Atmospheric...

Figure 5.7 Carbon dioxide emissions vs. petrochemical output.

Figure 5.8 Impact of a CO2 tax on IRR.

Figure 5.9 Various Power-to-X technologies.

CHAPTER 06

Figure 6.1 World energy consumption by energy...

Figure 6.2 Product costs and carbon dioxide...

Figure 6.3 Equilibrium conversion for methane...

Figure 6.4 Process concept for tri-reforming process.

Figure 6.5 Technologies for water electrolysis.

Figure 6.6 Potential reactor configurations for...

Figure 6.8 Schematic diagram of the ammonia-fed PC-SOFC.

CHAPTER 07

Figure 7.1 Hydrogen production via electrolysis...

Figure 7.2 Sensitivity analysis for the impact...

Figure 7.3 Sensitivity analysis for the impact...

Figure 7.4 Power to FT hydrocarbons process scheme.

CHAPTER 08

Figure 8.1 Catalytic performance in CO2...

Figure 8.2 Low-carbon process sequence to ethylene...

Figure 8.3 Propylene oxide-carbon dioxide copolymerization...

Figure 8.4 The reaction of dimethyl carbonate and bisphenol A.

Figure 8.5 The sustainable conversion pathway from...

CHAPTER 09

Figure 9.1 Low-carbon production of BTX via...

Figure 9.2 Reaction scheme production of p-xylene...

Figure 9.3 Flow diagrams of a commercial process...

CHAPTER 10

Figure 10.1 Carbon dioxide applications in...

Figure 10.2 Carbon cycle based on methanol...

Figure 10.3 CAMERE process diagram for methanol...

Figure 10.4 The CARNOL process.

Figure 10.5 Direct hydrogenation of carbon dioxide...

Figure 10.6 List of chemical compounds obtained...

Figure 10.7 Strategies for (a) carbon dioxide management...

Figure 10.8 ECR electrolytic cell.

Figure 10.9 Power-to-methanol scheme using renewable electricity.

Figure 10.10 Carbon dioxide hydrogenation to methanol...

Figure 10.11 Product yield and olefin selectivity...

Figure 10.12 Chain growth of Fe-K/MPC catalyst...

Figure 10.13 FTO catalysis performance plotting map.

Figure 10.14 (a) Effect of Pd loading amount on the...

Figure 10.15 Integrated process for carbon dioxide...

CHAPTER 11

Figure 11.1 Process scheme of methanol production...

Figure 11.2 Process scheme of bioethanol production.

Figure 11.3 Process scheme for bioethylene production.

Figure 11.4 Process scheme for BTX production...

Figure 11.5 Synthesis of biodiesel and glycerol by the...

Figure 11.6 Various processes for chemical conversion...

Figure 11.7 Ketalization reaction between glycerol and acetone.

Figure 11.8 Production pathway for the synthesis of higher...

CHAPTER 12

Figure 12.1 Integral molten salt reactor design intended...

Figure 12.2 Industrial nuclear cogeneration: temperature...

Figure 12.3 (a) Cold-wall axial flow converters...

CHAPTER 13

Figure 13.1 Chemical structures of synthetic polymers.

Figure 13.2 Mechanism of pyrolysis...

Figure 13.3 The mechanism of thermal...

Figure 13.4 The mechanism of pyrolysis of polyvinyl chloride.

Figure 13.5 Mechanistic pathways of...

Figure 13.6 The mechanism of pyrolysis of poly...

Figure 13.7 Design of a screw (auger) reactor.

Guide

Cover

Title Page

Copyright Page

Dedication

Table of Contents

About the Book

Preface

Acknowledgments

General Literature

Nomenclature

Abbreviations and Acronyms

Begin Reading

Index

End User License Agreement

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About the Book

The Converting Power into Chemicals and Fuels: Power-to-X Technology for a Sustainable Future concept covers the activities involved in taking surplus renewable electricity from wind, solar, water or nuclear energy and converting it into other energy carriers (the “X”) to be able to store the energy for later use and absorb energy fluctuations.

The first step in the process is to convert the renewable power into hydrogen by electrolysis (Power-to-Hydrogen). Hydrogen, the smallest molecule we know, does not emit carbon dioxide when burnt. It can be used immediately, or it can be stored in pressurised tanks and retrieved when supply is low.

There are several different utilisation pathways: feeding hydrogen into the gas network; displacing some of the carbon dioxide containing natural gas (Power-to-Gas); or through a methanation process with carbon dioxide converting the hydrogen into methane. The methane can be injected into the natural gas network replacing the fossil natural gas (also Power-to-Gas). The carbon dioxide source for the methanation process could therefore be biogas produced from biowaste in biogas plants or wastewater plants.

Other concepts include the production of methanol or ammonia to be used in fuel cells in cars and ships, or synthetic fuels to be used in conventional car and jet engines (Power-to-Liquids). This is all achieved through synthesis that involves hydrogen and a carbon dioxide source that could come from the process of converting waste into biogas.

The generated “green hydrogen” from renewable energies can also be used in fuel refining (hydrogenation) in conventional refineries as well as a basic chemical in many different industries (Power-to-Chemicals, Power-to-Plastics).

Finally, the stored hydrogen can also be converted back into electricity when required via fuel cells (Power-to-Power).

Preface

I have written this book at a time when the global oil consumption averages about 100 million barrels per day or two litres per person. At a price of $50–$130 per barrel, petroleum is one of the most affordable commercial liquid products ($0.3–$0.6/litre). Technological advances and efficiency improvements over the last century have enabled this level of scalability and affordability. However, largely because of the prevalent use of petroleum for energy, global carbon dioxide emissions have reached 100 million metric tons per day, averaging 13 kg per person in the world or 43 kg per person in the US The transition to alternative energy sources suggests that global oil consumption will peak soon, even though proven world oil and coal reserves are sufficient for another 50 and 100 years, respectively.

By 2050, the world population is projected to increase by more than 20% from today’s 8 billion to 9.7 billion, and the global gross domestic product (GDP) is expected to more than double. Not only will energy demand grow, but the demand for infrastructure, housing, and consumer goods will also grow. All this demand growth will undoubtedly increase the consumption of raw materials and eventually lead to a material challenge for natural resources and environmental sustainability.

The good news is that the petroleum, gas and petrochemical industries have the technology and assets needed for offshore wind turbines, blue and green hydrogen production, and carbon dioxide capture and storage. They also have the refinery units and technology to produce renewable fuels. These industries are prepared for the journey to complete this crucial energy transition to a lower-carbon world. Lummus Technology introduced the industry´s first net-zero ethane cracker. They announced the launch of a major enhancement to their leading ethane feed steam cracker that can achieve zero carbon dioxide emissions from an ethylene plant.

Strengthening the development of science, chemical processes, and chemical technology in the field of electrochemicals or/and electrofuels also means strengthening the economy and energy independence. We will convert more parts of light hydrocarbons from crude oils and natural gas into petrochemicals with the rise and increased use of electric vehicles. Different analysis predict different changes to gasoline usage due to the electric vehicle evolution. To respond to this trend, national oil companies are adapting their product from hydrocarbons into petrochemicals. It is also possible to consider a zero-gasoline refinery where a refinery is dedicated to producing olefins, aromatics, and synthesis gas production for petrochemicals. Some refineries in Europe will reduce gasoline production and increase production of olefins and aromatics for petrochemicals. Petrochemical processes, hydrocarbon technologies and green engineering have paved the way for incorporation of electrochemical technologies into modern chemical industry.

Nowadays, it is difficult to imagine the global energetic matrix free of fossil transportation fuels, especially in developing economies. Despite this, recent forecasts and growing demand for petrochemicals, as well as the pressure to minimize the environmental impact produced by fossil fuels, creates a positive scenario and acts as a driving force for closer integration between refining and petrochemical assets. In some scenarios the zero fuels refineries grow in the middle term, especially in developed economies.

The focus of the closer integration between refining and petrochemical industries is to promote and take advantage of the opportunities existing between both downstream sectors to generate value to the whole crude oil production chain. The synergy between refining and petrochemical processes raises the availability of raw material for petrochemical plants and makes the supply of energy for these processes more reliable whilst at the same time ensuring a better refining margin to refiners due to the high added value of petrochemical intermediates when compared with transportation fuels. The development of crude-to-chemicals technologies reinforces the necessity of closer integration of refining and petrochemical assets by brownfield refineries aiming to face the new market that tends to be focused on petrochemicals against transportation fuels. It’s important to note the competitive advantage of the refiners from the Middle East who have easy access to light crude oils that can be easily applied in crude-to-chemicals refineries. Crude oil-to-chemicals refineries are based on deep conversion processes that require high capital spending, and this fact can put pressure on the refiners with restricted access to capital, again reinforcing the necessity to look for close integration with the petrochemical sector aiming to achieve competitiveness.

At the extreme end of the petrochemical integration trend there are the zero fuels refineries.It is still difficult to imagine the downstream market without transportation fuels, but it seems a serious trend and the players in the downstream sector need to consider the focus change in their strategic plans as opportunity or threat, mainly considering the pressure over the transportation fuels due to the decarbonization necessity and new technologies.

Due to large production of biodiesel and green diesel, there is the possibility of having an oversupply of diesel. If that occurs, diesel can be converted to chemicals. This is a strategy of research aiming to anticipate the oversupply of diesel, where steam cracking of green diesel created olefins and benzene, toluene, and xylenes. Waste materials are targeted as raw feedstocks for biodiesel production. Solid waste from agriculture mining waste are among the most studied materials. With this concept, there are possibilities to synergize a bio-based economy and circular economy. Hence, the adoption of 5R principles (reduce, reprocess, reuse, recycle, and recover) and the use of renewable resources has been consolidated in the daily life of citizens and regulates the actuation of every industrial activity according to the circular economy.

Decarbonization has left numerous challenges for C1-technology. After carbon dioxide capture, the next challenge is carbon dioxide utilisation. The most prospective carbon dioxide utilization will be carbon dioxide hydrogenation to methanol to produce methane (methanation) or methanol. Dry reforming of methane is an interesting application of carbon dioxide as a sustainable C1 source in current commercial processes. We showed in the first edition of Petrochemistry (2020: Wiley) the latest references on kinetics and thermodynamics of carbon dioxide reforming of methane to understand the mechanism of coke formation. The conversion of carbon dioxide to methane and methanol is a strategic topic as methane and methanol are applied as hydrogen storage.

Hydrogen is an ideal electrochemical and electrofuel of the future. One of the main challenges of hydrogen fuelled vehicles is the appropriate technology to produce hydrogen on board the vehicle. There is clear trend to produce hydrogen from carbon dioxide and methane, both of which are greenhouse gases. Numerous governments are promoting green hydrogen from water electrolysis. However, the production cost of green hydrogen is still significantly higher than hydrogen from natural gas. Currently, the cheapest production of hydrogen is still from catalytic reforming and steam pyrolysis of naphtha, producing hydrogen as a by-product.

Storage of hydrogen in porous nanomaterials has stimulated crowded research activity in metal-organic frameworks, hydrides, composites. Storage of hydrogen in liquid form such as blue ammonia has recently been commercialized. This will stimulate more research activities in the transformation of petrochemicals into fuel additive production over novel catalysts. The United States has successfully introduced gasoline blended with 10% ethanol (E10) and is developing 2-methyltetrahydrofuran as a fuel additive. Dicyclopentadiene is used as a feedstock to produce endo- or exotetrahydrodicyclopentadiene. A fuel with such properties as high energy density, lower viscosity, and lower freezing point is desirable to be used in missile-bearing jets at higher altitudes. High molecular weight alcohol and ether fuels with their advanced autoignition propensities and oxygenated molecular structures are promising future fuel candidates for compression-ignition engine application, because they can provide improved combustion efficiencies and reduced pollutant emissions.

Converting Power into Chemicals and Fuels seeks to elucidate the pivotal role of petrochemical processes in actively pursuing the transition from fossil fuel scenarios to more sustainable energy supply systems. The transformation of energy systems into a sustainable future will be impossible without chemical energy conversion. As energy cannot be created, we always deal with conversion processes. Many of them involve molecular or solid energy carriers, thus it is evident that chemical technology is at the centre of the energy challenge. Chemical science can control the energetic costof the conversion of energy carriers.

The global demand for hydrocarbons – as petrochemical feedstock, as fuels for transport and for other uses – is expected to increase until at least 2040. These products have an unrivalled energy density and are easy to transport, making them an ideal means to carry and store energy. While alternatives are being developed for some of their current uses (e.g., in passenger cars, where electrification is expected to play a major role), hydrocarbons remain difficult to replace in heavy-duty and marine transport, in aviation and as a feedstock for petrochemical technology.

It is therefore of great importance for the energy and technological value chain that carbon emissions of hydrocarbon technologies be progressively reduced. The petrochemical and refining technology is well placed to evolve its business model with this objective, by increasingly using combinations of new feedstocks – such as captured carbon dioxide, waste, and biomass, in very efficient manufacturing. It can also expand its use of surplus renewable electricity and hydrogen on-site and further exploit synergies with other industries in integrated clusters. The flexibility and resilience of the hydrocarbon technology infrastructures, including those for the distribution of products, will allow this transformation to occur at a comparatively low cost and provide immediate benefits in term of carbon dioxide reduction. COP26 concluded in November 2021 in Glasgow (with nearly 200 countries agreeing the Glasgow Climate Pact to keep the rise in average global temperature at 1.5°C alive and finalise the outstanding elements of the Paris Agreement.

The petrochemical and refining technologies are already engaged in low-carbon transition, through investment in R&D projects and the early deployment of new technologies. These technologies, which have already been proven at different technology readiness levels (High-TRL 9), need to be implemented at scale. Innovative solutions will allow the use of new feedstocks and will cut greenhouse gas (GHG) emissions from refineries and from the use of their products. In the process, the European Union will develop and reinforce its global leadership in low-carbon technologies, which will be exported around the world where they are needed. Examples include the conversion of refineries to bio-refineries, the development of sustainable hydrogen and biofuels produced from surplus renewable electricity. These are just the tip of the iceberg of the chemical industry’s extensive R&D.

In addition to a reduction in carbon dioxide emissions, the European Union energy strategy addresses air quality and the transition to a more to a circular economy. This implies maintaining the value of products, materials and resources in the economy for as long as possible and minimising the generation of waste. The petrochemical and refining technologies are deeply embedded in these important areas, with innovations and initiatives that aim to improve air quality and minimise waste – or, when possible, re-use it.

Power-to-X denotes methods for converting renewable energy into liquids or gases, which can be stored, distributed, or converted to valuable products. Furthermore, Power-to-X can provide grid stability in connection with fluctuating electricity from renewable sources. One of the essential steps in determining the feasibility of a Power-to-X system for the market is the thermodynamic, techno-economic, and environmental assessment through mathematical modelling and simulation. In this book we present different Power-to-X system configurations with their performance, environmental impact, and cost. We provide an introduction to various Power-to-X processes including all the stages from the power generation to the upgrading of the final product (X), followed by several key system-level Power-to-X studies, which consist of thermodynamic, techno-economic, and life cycle assessment analyses.

The Power-to-X chemical technology hydrogen pillar is as follows:

Hydrogen Pillar–Electrochemicals → Power-to-e-Chemicals and Electrofuels → Power-to-e-Fuels.

– These include hydrogen → Power-to-Hydrogen production through water electrolysis as a means of storing surplus renewable electricity in chemical bonds.

– Hydrogen can be used for transportation in fuel cell vehicles (FCV), but can also be react with carbon dioxide to form other fuels → Power-to-Fuels

– We present a technical, environmental, and economic comparison of direct hydrogen use in fuel cells, and production of methane → Power-to-Methane methanol → Power-to-Methanol; and dimethyl ether → Power-to-DME for use in internal combustion engines for light-duty vehicle applications.

– With respect to their suitability as diesel fuels for the transport sector, the Power-to-Fuels products: dimethyl ether → Power-to-DME; oxymethylene dimethyl ether → Power-to-OME3-5; and n-alkanes → Power-to-FTdiesel.

Power-to-Chemical-technologies and Power-to-Fuel-processes thus pave the way for the integration of surplus renewable energies in the petrochemical and transport sector. Electrofuel technologies could first be introduced to enhance the carbon today´s fuels derive from biomass and wastes. Approximately 7% of global oil demand will be replaced by electric vehicle (EV) even though the real growth of electric vehicle s depends on numerous factors such as the price of a battery, subsidy from government, and the availability of rare-earth and lithium elements.

The integration of carbon dioxide via methanol and methane would require comparably low research development effort and would allow use of large parts of the existing petrochemical infrastructure and hydrocarbon technology. The designed chemical models include carbon capture and utilization (CCU) technologies for the direct conversion of carbon dioxide into olefins, BTX aromatics, carbon monoxide and hydrogen, ethylene oxide, and styrene. These electrochemical technologies are currently at early research and development stages with TRLs below seven.

The bottom-up model of the chemical technology yields future production pathways to produce the 20 large-volume chemicals: acrylonitrile, ammonia, benzene, caprolactam, cumene, ethylene, ethylene glycol, ethylene oxide, methanol, mixed xylenes, phenol, polyethylene, polypropylene, propylene, propylene oxide, p-xylene, styrene, terephthalic acid, toluene, and vinyl chloride. Production pathways are represented by more than 160 processes based on engineering-level data. Thereby, flows of energy and materials are determined in detail throughout entire supply.

Acknowledgments

Many thanks to my wife Mária for supporting my efforts in bringing together these concepts in the form of a book and also for her direct participation in the generation of graphics.

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