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INDUSTRIAL CHEMISTRY

IN THE 21ST CENTURY

STUDY GUIDE

BY

WOLFGANG H MEYER

Wolfgang H Meyer, Phd

543 Baansyfer Ave, Ruimsig, South Africa

Wolfgangh.meyer@gmail.com

Phone: +27822538156

Objective of the Course (36h)

The participants shall gain an understanding of the traditional industrial chemistry processes and

products and develop a holistic view on the choice of raw materials and processes on a global but

also region-specific level and its economic dependencies.

The influence of climate change on processes under investigation based on renewable feed stocks

and the relation of energy versus chemicals in connection with economic, political, socio-economic

and environmental considerations will be part of the conceptual learnings of this course. In

addition, learning objectives include the understanding of current global and local trends in the field

of both energy and chemicals.

The objectives of this course focus more on an understanding of the “why” i.e. the reasons for the

choices of materials, processes, location and the reasons for trends than the “how” i.e. details on

process-engineering or chemical fundamentals and principles which are normally covered in the

curricula of the respective disciplines in chemistry and engineering. The course includes such

principles when necessary for discussions about technical limitations of new processes.

© 2015

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CONTENTS

Introduction 1

1. Feedstocks – Energy and Chemicals 2

1.1 Types of Feedstocks 2

1.1.1 Crude Oil 3

1.1.2 Natural Gas 8

1.1.3 Coal 12

1.1.4 Biomass and Waste 16

1.2 Resources, Availability and Consumption 21

1.3 Greenhouse Gas Emissions 33

1.4 Summary 40

2. Primary Building Blocks of Chemical Products 41

2.1 Types of Final Products 41

2.2 Ethylene 43

2.3 Propene 48

2.4 Aromatics - BTX 51

2.5 Other Building Blocks 69

2.6 Summary 75

3. Secondary Building Blocks of Chemical Products 76

3.1 Bi functional Molecules for step-growth Polymers 76

3.2 Building blocks for oligomeric materials 86

4. Discussion of Selected Processes 87

4.1 Shell Higher Olefin Process (SHOP) 87

4.2 Paraffin dehydrogenation (Pacol Process) 89

5. Final Products 91

5.1 Plastics 91

5.2 Cross Sections of Selected Products 104

5.2.1 Tires 104

5.2.2 Laminated Products 106

5.2.3 Carpets 107

6. Green Chemistry 108

6.1 Definition and Examples 108

6.2 Processes Using Renewable Feedstocks 111

6.3 Biopolymers 126

6.4 Process Cost Comparisons 127

References 130

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LIST OF FIGURES

Figure 1 Sulfur content and API gravity for selected oil wells. 4

Figure 2 Crude oil location in and around the North Sea. 5

Figure 3 Molar composition of natural gas of different geographic origins. 8

Figure 4 Schematic geology of natural gas resources. 9

Figure 5 Workup of raw natural gas. 10

Figure 6 Products from Natural Gas. 10

Figure 7 Formation of coal from peat. 12

Figure 8 Infrastructure example of UCG at a coastline. 15

Figure 9 Structure of cellulose. 18

Figure 10 Example of hemicellulose structure. 19

Figure 11 Representative lignin fragment (left) and the three monomer units. 19

Figure 12 Proved oil reserves assessment over time (top) and oil consumption. 22

Figure 13 Proved crude oil reserves and consumption per region, 2013. 23

Figure 14 Split of proved oil reserves by region and country, 2013. 24

Figure 15 Averaged higher heating values for different biomass categories. 25

Figure 16 Proved fossil fuel reserves in billion toe, end 2013. 26

Figure 17 Production and local consumption of coal in mmtoe, 2013. 27

Figure 18 Regional coal production, 1980 – 2013. 27

Figure 19 Proved gas reserves, 1980 – 2013. 28

Figure 20 Location of shale gas and shale oil, assessed basins, 2013. 28

Figure 21 Shale gas basins in Europe and intentions for extraction, 2012. 29

Figure 22 Fossil fuel consumption split in million ktoe, 2013. 30

Figure 23 Map of woody biomass facilities, Southeastern US. 31

Figure 24 Historical and projected electricity generation by fuel type. 32

Figure 25 Global GHG emissions by gas, 1990 – 2010. 33

Figure 26 Global GHG emissions by sector, 1990 – 2010. 34

Figure 27 Global energy consumption by industrial sector, 2005. 35

Figure 28 Global GHG emissions by chemical compound, 2010. 36

Figure 29 Scenario dependent projected annual CO2 only emissions and global warming resulting from cumulative emissions and expected CO2 concentrations. 38

Figure 30 Mean annual CO2 concentration measured at Manau Loa, Hawaii, 1959 – 2014. 39

Figure 31 Representative catalytic cracking reactor and regeneration reactor. 44

Figure 32 Ethylene production capacity per region, 2012. 45

Figure 33 Global ethylene consumption capacity per product, 2012. 46

Figure 34 GHG emissions in CO2 equivalents per ton PE from various feedstocks. 47

Figure 35 Propene production technology split, %, 2015, estimate. 48

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Figure 36 Propene production capacity per region, 2012. 49

Figure 37 Global propene consumption capacity per product, 2012. 50

Figure 38 Feed composition (top) and product composition of aromatics fraction (bottom) from reforming of heavy naphtha (blue) and light naphtha (red). 52

Figure 39 Example of a flowsheet for reforming process targeting BTX. 54

Figure 40 Flow scheme of the Aromizing CCR Process by Axens. 55

Figure 41 Examples of composition of the aromatics fraction for different processes or sources including the once through aromatics yield if applicable. 56

Figure 42 Morphylane® Process by Uhde, here for benzene recovery (bottom). 58

Figure 43 Combination of different process in an aromatics complex. 59

Figure 44 Combination of UOP’s licensed processes in an aromatics complex. 61

Figure 45 BTX processes available for licensing in grassroots plants by Axens. 63

Figure 46 Global benzene production capacity split by technology, 2010. 66

Figure 47 Global benzene consumption capacity, 2012. 66

Figure 48 Global toluene consumption capacity, 2012. 67

Figure 49 Global p xylene consumption capacity, 2012. 67

Figure 50 Example of a separation scheme of a naphtha cracker C4 cut. 71

Figure 51 BASF butadiene extraction process. 72

Figure 52 Global butadiene consumption capacity, 2012. 73

Figure 53 Adipic acid from cyclohexane oxidation. 77

Figure 54 Hydrocyanation of butadiene to adiponitrile. 77

Figure 55 Hydrogenation of adiponitrile to hexamethylenediamine. 78

Figure 56 Synthesis of ε caprolactam. 79

Figure 57 Structure of Kevlar® and Nomex® including alignment via hydrogen bonding. 80

Figure 58 The molecular structure of bisphenol A. 81

Figure 59 Structures of bisphenol A, phosgene, diphenyl carbonate and polycarbonate. 83

Figure 60 Tetrabromo bisphenol A (left) and tetramethyl bisphenol A (right). 84

Figure 61 Representation of a bisphenol-A diglycidyl ether epoxy resin before curing. 84

Figure 62 Structure of triethylene tetramine. 85

Figure 63 Crosslinked epoxy resins. 85

Figure 64 Applications of ethylene glycol ethers and propylene glycol ethers. 86

Figure 65 Schulz Flory distribution. 87

Figure 66 Structure representation of thermoplastics, elastomers and thermosets. 92

Figure 67 Hexamine and Novolac. 92

Figure 68 Bakelite Resol structure. Only carbon bonded methylene bridging is shown. 93

Figure 69 Bakelite products. 93

Figure 70 Global and European plastics production, 2002 – 2013. 94

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Figure 71 European plastic demand by polymer type and application examples, 2013. 94

Figure 72 European plastic demand by segment and polymer type, 2013. 95

Figure 73 Symbols of different plastics used on products. 95

Figure 74 Treatment of plastics waste in European countries, 2012. 96

Figure 75 PlasticsEurope’s view on the different treatments of plastics waste. 96

Figure 76 Commonly used flame retardants. 99

Figure 77 Melamine phosphate. 101

Figure 78 Chemical structure of TNPP. 101

Figure 79 Example of a commercial phosphite antioxidant. 102

Figure 80 Examples of commercial UV stabilizers. 102

Figure 81 Cross section of a radial tire. 105

Figure 82 Key data of DuPont’s 2nd generation ethanol plant in Nevada. 113

Figure 83 Biopolymers production in the EU in 2012 and forecast for 2016. 126

Figure 84 Cost comparison of routes to acrylic acid at indicated raw material prices. 127

Figure 85 Capital cost for ethanol, price and cash cost for (bio)ethylene. 128

Figure 86 GHG emissions as CO2E for PE production from various feedstocks. 129

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LIST OF SCHEMES

Scheme 1 Types of feedstock. 2

Scheme 2 Crude oil refinery targeting fuels products, sulphur removal omitted. 6

Scheme 3 Integration of a fuels and chemicals plant. 7

Scheme 4 Blockflow diagram of natural gas processing. 11

Scheme 5 Different classifications of coal and their uses. 13

Scheme 6 Blockflow diagram of the DCL process by Shenua. 15

Scheme 7 Principal conversion routes for biomass. 18

Scheme 8 Conversion examples of biomass components targeting fuels as products. 20

Scheme 9 Products from lignocellulose and its components. 20

Scheme 10 Petrochemical processes, feed to intermediates. 75

Scheme 11 Blockflow diagram of BPA production from Badger. 82

Scheme 12 Formation of polycarbonate using diphenyl carbonate. 83

Scheme 13 Example of obtaining a C14 chain length through isomerisation and metathesis of unwanted carbon ranges. 88

Scheme 14 Blockflow diagram of the Shell Higher Olefin Process (SHOP). 88

Scheme 15 From crude oil to kerosene to LAB, process by UOP. 89

Scheme 16 Process flow diagram from kerosene to n paraffin. 90

Scheme 17 Pacol process flow diagram. 90

Scheme 18 Traditional bleach process for lignin removal from wood. 109

Scheme 19 "Green" process for lignin removal from wood via polyoxometalate as a bleaching catalyst. 110

Scheme 20 Principal biomass conversion technology routes. 111

Scheme 21 Lanzatech’s syngas fermentation platform. 112

Scheme 22 Proesa™ technology as enabler for downstream chemicals from cellulose. 112

Scheme 23 Routes to acrylic acid from renewable feedstocks. 114

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LIST OF TABLES

Table 1 Composition range for coal types. 13

Table 2 Assessment of oil reserves by the US Energy Information Administration, 2013. 23

Table 3 Heat units equivalents and approximate energy equivalent of 1 toe. 24

Table 4 Proved coal reserves, top 11 countries, end 2013. 26

Table 5 Historical and projected US GHG emission baselines, by gas: 2000-2030, Mt CO2e. 36

Table 6 From product classes to building blocks. 41

Table 7 Ethylene and propene yield for various feeds in steam cracking. 43

Table 8 Ethylene feedstock distribution by region, 2002. 43

Table 9 Carbon footprints of PE production from renewable feedstocks. 47

Table 10 Examples of product distribution for MTO or MTP® processes. 49

Table 11 Trend of selectivity of cracker products by feed used. 52

Table 12 Feed and products of UOP’s Tatoray™ Process. 61

Table 13 Processes available for licensing for the production of aromatics. 64

Table 14 Styrene production processes available for licensing, 2010. 70

Table 15 Fillers for polymeric materials. 97

Table 16 Types of flame retardants. 98

Table 17 Antistatic additives. 103

Table 18 Structural elements of tires and used material. 104

Table 19 Use of resins in tires. 105

Table 20 Comparison of the two bleaching processes. 110

Table 21 Selected 2nd generation ethanol plants and key data. 113

Table 22 Selected chemicals and companies referencing the development state of the technology. 115

Table 23 BioFuels Digest list of companies/projects close to or already commercialised. 116

Table 24 Emissions per t PE from various feedstocks. 128

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Selection of Slides

Course Overview

Feedstocks

Chemical building blocks

basic and intermediates

Chemical processes

Green chemistry

Availability

Amounts

Consumption and forecast

How are they produced?

What are they used for?

Are there any alternatives based on renewables?

Selection of two processes will be discussed

State of technology aspects of technology selection

Details of the block flow diagram

Renewables for energy or chemicals or food?

What has been developed, what has survived, trends?

How to evaluate sustainability?

WH Meyer 2

What is the intention of the course?

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Crude Oil

WH Meyer 17

Oil recovery techniques

In the early days and still today

Gas: CO2, associated NG

Production costs increase. Onlyviable above certain oil price.

R&D !!!

Source: SBC Energy Institute 2014

WH Meyer 19

Crude OilComposition of hydrodesulfurized kerosene, CAS No. 64742-81-0

n-CC5/6 = n-alkane substituted cyclopentane and cyclohexane; iso-N = iso-naphthenes; diN = di-naphthenes;

mono-A = mono-aromatics; N-mono-A = naphthenic-mono-aromatics;

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Natural Gas

WH Meyer 24

Shale gas basins May 2013

Natural Gas

WH Meyer 33

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Coal

WH Meyer 40

Underground coal gasificationhttps://vimeo.com/61863096http://www.abc.net.au/news/2015-08-10/this-is-the-massive-gas-project-thats-become-a/6686928

Proved Reserves of Fossil Feedstock, end 2013

WH Meyer 48

Relation to energy density

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Crude Oil: Trends

WH Meyer 58

Unattended operations for marginal fieldshttp://www.abtoilandgas.com/solutions/production-buoy/

WH Meyer 77

Building Blocks of Chemical Products

Final product end-use chemicals building blocks1st tier building

blocks

Fibres Clothing

Carpets

Nylons

Polyesters

polyacrylates

polyacrylonitrile

Diamines, Diacids

Aminoacids

Dialcohols, diacids

Hydroxyl acids

Acrylic esters

Benzene

propene

Plastics, resins

(thermoplastic

and

thermosetting)

Containers

Household products and

appliances

Car parts

Building materials

Polyethylene

Polypropylene

Polystyrene

PET

Bakelite

ABS

PVC

polycarbonates

polyamides

polyimides

Ethylene

Propene

1-Hexene

1-Octene

Styrene

Terephthalic acid

Ethylene oxide

Propylene oxide

Formaldehyde

Hydroxyl aromatics

Ethylene

Propene

BTX

methanol

Rubbers Tyres

Door stoppers

Household products and

appliances

BR

SBR

SAN

EPDM

IR

Butadiene

Isoprene

Styrene

propene

Butadiene

Isoprene

propene

BTX

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WH Meyer 71

Greenhouse Gas and Global Warming

Temperature change for different emission scenarios

ppm CO2, 2015: 400(Manau Loa, Hawaii)

IPCC, 2014 (Intergovernmental Panel on Climate Change)

WH Meyer 129

Green Chemistry

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WH Meyer 153

Green Chemistry – Biopolymers, EU, 2012, 2016

WH Meyer 157

Green Chemistry Bioisoprene

Amyris: GM yeasts for conversion of sugar to isoprenoids

isoprene (C5) various C10

farnesene (C15)

sugar source

anti-malaria drug