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Oil-to-Chemicals: Technological Approaches and Advanced Process Configurations

Multi-Client Study Presentation (Study Completed December 2017)

December 2017

THE CATALYST GROUP RESOURCES™

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Gwynedd Office Park ● P.O. Box 680 ● Spring House, PA 19477 ● Phone: 215-628-4447 ● Fax: 215-628-2267 E-mail: [email protected] ● Web Site: www.catalystgrp.com

Oil-to-Chemicals: Technological Approaches and

Advanced Process Configurations

STUDY COMPLETED! I. INTRODUCTION

This TCGR multi-client study was completed in December 2017. The study’s scope, and specific contents (as depicted in the TofC on pages 11-19) reflect the inputs from a group of “charter” subscribers who indicated their priorities for coverage, areas to be expanded/ deepened and focal points for emphasis in opportunity identification. These are leading industrial integrated refiners and petrochemical producers and users.

There is a need for an objective assessment and detailed technological analysis of the activities directed towards oil-to-chemicals pursuits. It is clear that among the leading positions/approaches developed to date, notably by ExxonMobil and Saudi Aramco/SABIC, the full breadth of the potential need may not be addressed because each user will require a unique solution. Therefore it would be useful to evaluate the olefins and/or aromatic needs of chemical plants in reverse order, back towards the intake of crude oil using different existing and new technologies that may prove more economical at smaller scale than the massive CAPEX schemes currently being proposed by licensors, as solutions. Beyond these leading activities, numerous independent technology developers like UOP/Honeywell, Axens, CB&I and other majors are working towards combinations of technologies which can achieve a similar objective. TCGR’s assessment, entitled “Oil-to-Chemicals: Technological Approaches and Advanced Process Configurations,” takes an end-market based approach, using numerous subscriber-defined process configurations, with the objective of documenting the available technologies, plus those in development (including the needed combinations) to maximize the return on conversion based on product slate (chemicals/petrochemicals and specialty/intermediates). Such optimization is required if such practices are expected to be competitive with low-cost thermal cracker routes as well as increasingly large aromatics complexes based on scale. The results provide practitioners, developers and prospective partners/evaluators, especially the major global chemical (olefins, aromatics) producers, with the tools needed to evaluate technology options in specific case study applications, via mixing and matching unique solutions, in order to determine viability in practice or worthiness of further investment. II. BACKGROUND The movement towards the production of chemicals and petrochemicals such as olefins and aromatics directly from crude oil, as opposed to via thermal cracking of naphtha/ethane (for olefins) and via traditional refining reforming (for aromatics), is being driven by numerous

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factors, the most important of which is the imbalance between demand for oil-derived liquid fuels (diesel, gasoline) and the more rapid growth in markets for petrochemicals like olefins (ethylene, propylene), aromatics (BTX) and specialty intermediate streams like C4s and higher olefins. The imbalance has made the idea of using crude as a direct feedstock more appealing for integrated producers of fuels and chemicals as well as direct chemical companies.

Figure 1. The Imbalance between Growth for Oil-derived Fuels (Diesel, Gasoline) vs. Petrochemicals/Chemicals (Olefins, BTX, etc.) is Driving Crude-to-Chemicals Considerations

Sources: OPEC 2016, IEA 2016, IHS 2016, Platts 2016, and TCGR 2016

The technologies for these novel, and important, chemical/petrochemical production processes are being pursued by industry leaders like ExxonMobil and Saudi Aramco/SABIC, but also affect the competitiveness of peer participants, i.e. all chemical producers, as well as EPCs, process licensors and technology developers like CB&I, Axens, UOP/Honeywell. Added to this are traditional routes being potentially made uncompetitive, such as naphtha cracking, and there is strong, widespread and urgent interest in approaches to, and justification for, these opportunities/threats. Depending on the crude oil feedstock, the avoidance of refinery fuels production and using specialty hydrocracking (HC) processes to naphtha or via fluid catalytic cracking (FCC) to olefins or BTX could provide lower costs than participating in the current/historical refinery value chain. As an example, CP Chem’s Aromax™ can provide BTX from olefins and the resid FCC unit could be more inexpensively tailored towards C2= and C3= olefins production, rather than the more costly and less selective steam cracking of naphtha.

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In its completed multi-client study, entitled “Oil-to-Chemicals: Technological Approaches and Advanced Process Configurations,” TCGR takes a market-driven approach towards technology development, availability and implementation, to capture viable routes (including technology combinations) to allow the oil-to-chemicals practitioner to practice and profit from various feedstock conversion routes. The study’s breadth includes a range of crude oils (heavy to light) plus bio-crudes, as well as a range of product slates from propylene-focused to a mix of chemicals, including specialty/C4s. Included are three major market segments for chemicals/ petrochemicals from the processes: (1) olefins; (2) aromatics; and (3) specialty/intermediates (e.g., C4 and higher olefins). The emphasis is on economically viable or developing technological solutions for cost-effective chemical/petrochemical supply via direct oil-to-chemicals routes. Of particular interest to chemical producers is how from the end-product (e.g., BTX) can you back integrate into the best configuration for costs based on the crude oil type and are there attractive margins to consider these new configurations/combinations? III. THE NEED FOR THE STUDY

The documentation to date has been centered on ExxonMobil and Saudi Aramco/SABIC comparisons, each of which has its own internally-derived rationale for pursuing oil-to-chemicals, whether it is taking advantage of the imbalance in growth rates between chemicals/petrochemicals and fuels or the need to further add value to crude oil resources providing higher rates of returns on investments. In many cases, others in the chemicals/petrochemicals industries may have different needs for the output or preferred routes/relationships with technology licensors or developers to get there. In TCGR’s independent, detailed technological assessment, analytical and critical perspectives are taken, across alternative approaches, to ensure that both the benefits and costs are considered. It will also highlight the state of availability/development of the technologies, alone or in combination, so that a mix and match approach can be assessed.

Today, most have only seen the reports from various sources, including IHS Chemicals’ Process Economics Program (PEP) which explains and benchmarks ExxonMobil’s Singapore plant compared against Saudi Aramco’s patents. Others may be familiar with recent references such as SABIC’s presentation at the ME-TECH (Feb. 2017; Dubai) and/or CB&I’s presentation from the MERTC conference (Jan. 2017; Bahrain). Notably, there is the Corma paper “Crude to Chemicals: Light Olefins from Crude Oil” (Catal. Sci. Technol., 2017, 7,12-46) which provides a review of resid FCC upgrading but does not adequately appreciate resid hydrocracking (HC) or catalytic steam cracker (CSR) advances, although there is a brief review of Sinopec’s catalytic pyrolysis process (CPP).

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Figure 2. Refining Strategies to Maximize Light Olefins from Crude Oil

Source: Corma, 2017

Table 1

Main Processes Dedicated to Crude Oil Cracking with Circulating Solids, Operating Conditions, and Ethylene Yields (adapted from Matsunami et al., Hydrocarbon Process., 1970, 49(11), 121-26)

Source: Corma, 2017

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Key questions addressed in the study include how chemical companies can target this technology opportunity - from an olefins and aromatics/BTX chemical plant feedstock point of view - but enhance the olefins and/or BTX yields even higher through retrofit catalysts and known process technology incremental revamps?

What is needed is to document recent catalyst and process advances relevant to olefins and BTX chemical products that avoid the upfront investment in catalytic distillation units (CDUs) and vacuum distillation units (VDUs) and other parts of the refinery while maximizing BTX and olefin yields (primarily C3+ and C4+) beyond typical refinery economics and normal/known process configurations that have historically been optimized for fuels production.

Table 2 Analysis of Crude to Chemicals Complexes: Case Studies

Source: CB&I, 2017 IV. SCOPE AND METHODOLOGY Oil-to-chemicals routes for three (3) product groups, via numerous case study approaches, are addressed as follows: 1) olefins; 2) aromatics; and 3) specialty/intermediates (e.g., C4s and higher olefins) The study includes coverage addressing:

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• Upstream to the feedstock/oil source, in order to differentiate between pre-

treatment steps (if required)

- Heavy/sour crudes: S. America, Russia/Urals; Canadian tar sands; opportunity crudes

• Product slate via technology approach, i.e., %olefin by carbon (C2, C3, C4, etc.).

- Ethylene, propylene, C4 and higher olefins

• Implications on technology implementers, to assess economic/financial metrics (CAPEX, product costs, ROI, etc.)

- Steam cracker modifications, combinations/integrations, etc.

• Advancements in technology (catalysts, processes, combinations) yielding novel options for consideration/evaluation in retrofit

• Impacts on technology developers and users, to gauge readiness levels and timing of commercial impacts

- Practitioners, licensors, developers, etc.

• Potential end-market and competitor/supplier implications, indicating likely winners and losers

- Optimal crude/product combinations, integrated vs. independent suppliers, etc. The scope includes numerous process configurations, some of which are proposed by the study’s “charter” subscribers (i.e., those who committed to supporting it prior to formal launch), with consideration of the following:

• Modified steam crackers; catalytic steam cracking

• Gasoil/steam cracking, gasoil/HSFCC

• Resid FCC: Multiple riser systems, R2R, Milos (Shell), HSFCC (Axens)

• Hydrocracker/FCC; Flexicoking/FCC; FCC/Reforming

• H-Oil and slurry HC (IFP); LC Fining (Lummus/CB&I)

• Hydroconversion upgrader (GHU, Genoil)

• Ebullated bed – EST (Eni)

• Pyrolysis catalytic cracking (PCC)

• Deep catalytic cracking (DCC)

• Aromax (CP Chem), Cyclar (UOP/Honeywell), etc.

• Others

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Table 3

Representative Advances in Oil-to Chemicals Technologies: Upping Olefins and BTXs Heavy Oil/Bitumen Canada Upgrading Technologies

• Pyrolysis Upgrading. − Ivanhoe HTL, piloted in CA − WESCO’s CJP Process − USP Process by Value Creation − CPP, Sinopec

• Slurry Hydrocracking. − ENI, EST Process. − HCAT, Heatwaters/HTI − HRH, Mobis − GHU, Genoil, perhaps slurry

modified − UOP, Uniflex, Fe based ex

PetroCanada − Chevron, Slurry HC.

FCC and Cracking Advances

• R2R Advances, TOTAL/S&W • Indmax, IOC • HSFCC, Aramco/Axens, including downstream dimerization • DCC Advances, Sinopec/S&W • Regular FCC, two riser e.g. Milos.

Cold (Sonic) Cracking

• Sonoprocess, Petrosonic • CCU, Pristec • CCC, Bayshore Petroleum

Novel Pipeline Processes (all to pilot or commercial)

• Gasolfin, InovaCat, naphtha to olefins/BTX swing fixed bed.

• Gasolin Equivalent, Chiyoda Corp, Japan • Maxene, UOP, naphtha/paraffins pretreat to

up olefins. • Olefin/Paraffin Membranes separations

− Permylene, Imtex − Optiperm, CMS, Compact Membrane

Systems − ECN, Amsterdam

• ACO Process, KBR/SK, naphtha to olefins

• Corrillo feedstock separation process • DSU Process, Molten Na separation

of metals and S • Shock Wave Reactor,

Hydrodynamics Inc. (vs. thermal cracker

• Cyclar Upgrades, UOP • Aromax Upgrades, CP Chem.

Source: TCGR, 2017

Via a market-driven approach documenting detailed technological assessments (including combinations) as determined by the industry’s leading participants as “charter” subscribers, TCGR’s study presents a state-of-the art assessment in oil-to-chemicals approaches to addressing the imbalance between olefin supply/demand in this uncertain but opportunistic period.

TCGR uses in-house and external resources, as well as expertise from within industry as well as our highly-regarded DIALOG GROUP ® in order to complete:

- Technology evaluations - Patent reviews and analyses - Representative economics - Market needs/drivers - Competitive implications (developers vs. users)

A refined/expanded Table of Contents is provided on pages 11-19 in order to depict the breadth and depth of the study as envisioned. References Corma 2017; Crude to Chemicals: Light Olefins from Crude Oil (Catal. Sci. Technol., 2017, 7,12-46) CB&I, 2017; Crude to Chemicals: Opportunities and Challenges of an Industry Game-Changer; MERTC, Bahrain IEA, 2016 IHS, 2016 OPEC, 2016 Platts, 2016

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V. QUALIFICATIONS The Catalyst Group Resources, a member of The Catalyst Group, works with clients to develop sustainable competitive advantage in technology-driven industries such as chemicals, refining, petrochemicals, polymers, specialty/fine chemicals, biotechnology, pharmaceuticals, and environmental protection. We provide concrete proven solutions based on our understanding of how technology impacts business. Using our in-depth knowledge of molecular structures, process systems, and commercial applications, we offer a unique combination of business solutions and technology skills through a range of client-focused services. Often working as a member of our clients' planning teams, we combine our knowledge of cutting-edge technology with commercial expertise to: • Define the business and commercial impacts of leading-edge technologies • Develop technology strategies that support business objectives. • Assess technology options through strategy development, including:

- Independent appraisals and valuations of technology/potential - Acquisition consulting, planning and due diligence

• Provide leading-edge financial methodology for shareholder value creation • Lead and/or manage client-sponsored R&D programs targeted through our opportunity

identification process. • Provide leading information and knowledge through:

- World-class seminars, conferences and courses - Timely technical publications

The client-confidential assignments conducted by The Catalyst Group include projects in: • Reinventing R&D pipelines • Technology alliances • Technology acquisition • Market strategy

We have built our consulting practice on long-term client relationships, dedication, and integrity. Our philosophy is clear and focused:

We Provide the "Catalysts" for Business Growth by Linking Technology and Leading-Edge Business Practices to Market Opportunities

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VI. DELIVERABLES AND PRICING This report is timely and strategically important to those industry participants and observers both monitoring and investing in the development and implementation of technologies for the conversion of oil-to-chemicals. TCGR’s report, based on technology evaluations, commercial/ market assessments and interviews with key players goes beyond public domain information. As a result, subscribers are requested to complete and sign the “Order Form and Secrecy Agreement” on the following page. The study, “Oil-to-Chemicals: Technological Approaches and Advanced Process Configurations” was completed in December, 2017. Post-production subscribers after December, 2017 $23,500 Oil–to–Chemicals: Technological Approaches and Advanced Process Configurations Report in PDF format, in addition to subscription price $1,000

* Charter subscribers (those who signed up for the study before its launch) had the opportunity to work with TCGR to further refine the scope of the report by nominating specific process/configuration content as well as delineating areas of particular interest for inclusion in the assessment.

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Oil-to-Chemicals: Technological Approaches

and Advanced Process Configurations

CONTENTS

SECTION I. INTRODUCTION/BACKGROUND.................................................................... 1

A. INTRODUCTION ................................................................................................................ 1

B. BACKGROUND .................................................................................................................. 1

C. THE NEED FOR THE STUDY ........................................................................................... 3

D. THE STUDY TEAM ............................................................................................................ 5

E. GLOSSARY OF TERMS AND ABBREVIATIONS .......................................................... 6

F. REFERENCES ..................................................................................................................... 7

SECTION II. EXECUTIVE SUMMARY .................................................................................. 9

A. THE NEED FOR OIL-TO-CHEMICALS: OPPORTUNITY CRUDES,

MARKETS

AND DRIVERS .................................................................................................................. 10

B. OIL-TO-CHEMICALS: OLEFINS .................................................................................... 11

C. OIL-TO-CHEMICALS BEYOND THE STEAM CRACKER AND FCC: ON

PURPOSE OLEFINS AND AROMATICS ....................................................................... 12

D. OIL-TO-SPECIALTY/INTERMEDIATE STREAMS (C4 AND HIGHER

PRODUCTS) ...................................................................................................................... 13

E. COMPETITIVE AND STRATEGIC IMPLICATIONS .................................................... 14

F. REFERENCES ................................................................................................................... 15

SECTION III. THE NEED FOR OIL-TO-CHEMICALS: OPPORTUNITY

CRUDES, MARKETS AND DRIVERS ................................................................................... 17

A. OPPORTUNITY CRUDES AND CRUDE PRICE DIFFERENTIALS ............................ 19

B. THE MARKETS ................................................................................................................. 22

C. ADVANCES IN CRACKING AND UNCONVENTIONAL OLEFIN AND BTX

SWING PROCESSES ........................................................................................................ 24

1. TCGR’s Analysis and Brainstorming Sessions ............................................................ 27

2. Results of Brainstorming Sessions ............................................................................... 28

D. SUMMARY ........................................................................................................................ 29

E. REFERENCES ................................................................................................................... 30

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SECTION IV. OIL-TO-CHEMICALS: OLEFINS ................................................................. 31

A. EXXONMOBIL “OIL-TO-CHEMICALS” STEAM CRACKING PROCESS ................ 31

1. Background and Assumptions ......................................................................................... 31

2. Process Flow and Description ......................................................................................... 34

3. Estimated Economics ...................................................................................................... 37

4. Sensitivity Analysis ......................................................................................................... 40

5. Summary and Conclusions .............................................................................................. 45

B. SAUDI ARAMCO/SABIC “OIL-TO-CHEMICALS” APPROACH ................................ 47

C. FCC OLEFINS PRODUCTION OVERVIEW .................................................................. 48

1. Overview and Economic Pinch Points ............................................................................ 49

2. Licensed FCC Technology .............................................................................................. 52

3. Issues/Challenges............................................................................................................. 60

D. FCC MODIFIED FOR OLEFINS PRODUCTION ........................................................... 62

1. Sinopec DCC (Deep Catalytic Cracking) Process ........................................................... 62

2. Sinopec CPP (Catalytic Pyrolysis Process) ..................................................................... 67

3. Kellogg Brown and Root (KBR) Maxofin ...................................................................... 72

4. TechnipFMC and Axens ................................................................................................. 73

5. Aramco, KFUPM, Nippon, TechnipFMC, Axens: HS-FCC Process ............................. 76

6. UOP PetroFCC Process ................................................................................................... 78

7. Shell Global Solutions - MILOS ..................................................................................... 80

E. CRACKING TIGHT-OILS IN FCC UNITS ..................................................................... 81

F. ON-PURPOSE PROPYLENE PRODUCTION ................................................................ 84

1. Oleflex ............................................................................................................................. 85

2. Catofin/Catadiene Catalyst and Process Improvements (HGM) .................................... 87

3. Dow FCDh Process ......................................................................................................... 89

G. CONCLUSIONS................................................................................................................. 91

H. REFERENCES ................................................................................................................... 92

SECTION V. OIL-TO-CHEMICALS BEYOND THE STEAM CRACKER AND

FCC:

ON PURPOSE OLEFINS AND AROMATICS ....................................................................... 95

A. REACTOR DESIGN/PROCESS ADVANCES ................................................................. 95

1. Radial Flow Reactors (RFR) for Catalytic Olefins Production ....................................... 95

2. Coolbrook RDR (RotoDynamicReactor) Process ......................................................... 104

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B. CATALYTIC DISTILLATION ....................................................................................... 108

1. Application of CD-Hydro in Advanced Olefin Separation ........................................... 109

C. OTHER NEW OLEFIN PROCESSES ............................................................................ 110

1. Advanced Catalytic Olefin Process (ACO) ................................................................... 110

2. Inovacat GASOLFIN Technology ................................................................................. 112

3. Chiyoda Fixed-Bed BTX/Olefins Swing Process ......................................................... 115

4. Asahi Kasei/TechnipFMC OMEGA Process ................................................................ 115

D. ON-PURPOSE AROMATICS PROCESSES .................................................................. 117

1. Aromax Technology ...................................................................................................... 117

2. Cyclar Technology by UOP .......................................................................................... 120

3. GTC GT-G2A and GT-BTX PluS® Processes ............................................................. 123

E. NEW SEPARATIONS PROCESSES .............................................................................. 124

1. UOP “MaxEne” Separation Technology ....................................................................... 124

2. Corrillo Separation Scheme ........................................................................................... 126

3. Membranes in Separations: Permylene from Imtex ...................................................... 127

4. Membranes in Separations: Optiperm from Compact Membrane Systems (CMS) ..... 132

F. SONO-CHEMICAL APPLICATIONS OF CONTROLLED FLOW CAVITIES .......... 136

G. CONCLUSIONS............................................................................................................... 136

H. REFERENCES ................................................................................................................. 137

SECTION VI. OIL-TO-SPECIALTY/INTERMEDIATE STREAMS (C4 AND

HIGHER PRODUCTS) ............................................................................................................ 141

A. HISTORICAL AND CURRENT APPROACHES .......................................................... 142

B. ADVANCEMENTS AND ENABLING TECHNOLOGIES ........................................... 146

1. Hydrogen Separation Membranes ................................................................................. 146

2. Pervaporation (PV) and Vapor Permeation (VP) .......................................................... 149

3. Ethers ............................................................................................................................. 152

C. REMAINING HURDLES (TECHNICAL, ECONOMIC)............................................... 155

D. ASSESSMENT ................................................................................................................. 157

E. REFERENCES ................................................................................................................. 158

SECTION VII. COMPETITIVE AND STRATEGIC IMPLICATIONS ........................... 159

A. PROSPECTS FOR ECONOMICALLY VIABLE OIL-TO-CHEMICALS (OTC) .............

ROUTES ........................................................................................................................... 162

1. Ethylene Production ...................................................................................................... 162

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2. Propylene Production .................................................................................................... 164

3. C4+ Value Added ........................................................................................................... 165

4. The Use of Lighter vs. Heavier Feedstocks in Oil-to-Chemicals (OtC) ....................... 166

B. NEW TECHNOLOGIES/MIXED SOLUTIONS............................................................. 167

C. POSSIBLE OIL-TO-CHEMICALS CONFIGURATIONS ............................................. 168

1. Chemicals only producer, focused on olefins and/or BTX ........................................... 168

2. Integrated chemicals producer, seeking to maximize site margins ............................... 169

3. Refinery only, seeking to maximize chemicals margins ............................................... 170

D. COMPETITIVE AND MARKET REACTIONS TO CHANGES ................................... 170

E. RECOMMENDATIONS AND CONCLUSIONS ........................................................... 171

F. REFERENCES ................................................................................................................. 172

FIGURES

Figure I-A-1 The Imbalance between Growth for Oil-derived Fuels (Diesel, Gasoline)

vs. Petrochemicals/Chemicals (Olefins, BTX, etc.) is Driving Crude-to-

Chemicals Considerations .................................................................................... 2

Figure I-C-1 Refining Strategies to Maximize Light Olefins from Crude Oil .......................... 4

Figure II-I Oil-to-Chemicals: Where is Added Value ......................................................... 10

Figure III-1 Lummus-SRT Cracking™ Flow Scheme (Meyers, 2005) ................................. 18

Figure III-2 Typical ISBL installed cost (Meyers, 2005) ...................................................... 18

Figure III-A-1 The Imbalance between Growth for Oil-derived Fuels (Diesel, Gasoline)

vs. Petrochemicals/Chemicals (Olefins, BTX, etc.) is Driving Crude-to-

Chemicals Considerations .................................................................................. 19

Figure III-A-2 Change in global liquid fuels production since January 2016 ........................... 20

Figure III-A-3 Spot crude oil price differentials (light vs. heavy) ............................................. 21

Figure III-A-4 Density and sulfur content of selected crude oils .............................................. 21

Figure III-B-1 Ethylene, Methanol and Propylene Expanding at a Rapid Pace ........................ 22

Figure III-B-2 Regional Benzene Consumption by Derivative ................................................. 23

Figure III-B-3 World Paraxylene Supply-Demand 2011-2017 ................................................. 23

Figure III-B-4 Ethane cash cost advantage is significant and sustainable ................................. 24

Figure III-C-1 Refining strategies to maximize light olefins from crude oil (Corma,

2017) .................................................................................................................. 25

Figure III-C-2 Envisioned Process Configuration ..................................................................... 29

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Figure IV-A-1 Process Flow diagram, with Flash Drum (US7588737) .................................... 34

Figure IV-A-2 Condensing Coils with Flash Drum (US7767170) ............................................ 35

Figure IV-A-3 Heat Recovery from the Flash Drum (US8158840) .......................................... 36

Figure IV-A-4 Bottom Recycle Stream (US8435386)............................................................... 36

Figure IV-A-5 Crude Price Sensitivity for Greenfield Plant ..................................................... 43

Figure IV-A-6 Fuel Gas Price Sensitivity for Greenfield Plant ................................................. 44

Figure IV-A-7 Propylene Price Sensitivity for Greenfield Plant ............................................... 44

Figure IV-A-8 Capital Cost Sensitivity for Retrofit Plant ......................................................... 45

Figure IV-C-1 Orthoflow FCC converter (Meyers, 2004)......................................................... 54

Figure IV-C-2 Vapor recovery unit (Meyers, 2004) .................................................................. 56

Figure IV-C-3 SSW IFP RFCC unit process diagram (Meyers, 2004) ..................................... 57

Figure IV-C-4 Side-by-side regenerator RFCC revamp design (Meyers, 2004) ....................... 58

Figure IV-D-1 DCC Thai Petrochemical Industries (SSW, 2007) ............................................ 63

Figure IV-D-2 Block flow diagram of a typical DCC unit for olefins production and

recovery (Dharia, et al., 2004) ........................................................................... 66

Figure IV-D-3 CPP commercial prototype (SSW, 2007) .......................................................... 68

Figure IV-D-4 CPP pyrolysis gas purification and separation project (SSW, 2007)................. 69

Figure IV-D-5 Typical yields range for ethylene and propylene for RIPP/SSW DCC

and

CPP processes (SSW, 2007) .............................................................................. 70

Figure IV-D-6 The scheme of crude to petrochemicals (Wang et al., 2006) ............................. 71

Figure IV-D-7 Variation for Propylene from Resid – R2P ........................................................ 74

Figure IV-D-8 Technip FMC/Axens Single Regenerator Design.............................................. 76

Figure IV-D-9 HS-FCC Retrofit to 2 Stage Regenerator........................................................... 78

Figure IV-D-10 Shell Milos Distillate + Olefins ......................................................................... 80

Figure IV-F-1 Oleflex process flow (Meyers, 2005) ................................................................. 86

Figure IV-F-2 Cyclic operation of a Catofin and Catadiene dehydrogenation reactor ............. 89

Figure IV-F-3 Propane conversion over Catofin PS catalyst with and without HGM at

the same pilot plant conditions .......................................................................... 89

Figure IV-F-4 The Dow Catalytic Dehydrogenation Process is a Platform Reactor

Technology ........................................................................................................ 90

Figure IV-F-5 Current Commercial PDH Technologies and Dow Fluidized Catalytic

Dehydrogenation (FCDh) .................................................................................. 91

Figure V-A-1 New catalytic route to lower olefins .................................................................. 95

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Figure V-A-2 Conceptual reactor scheme................................................................................. 96

Figure V-A-3 Gibbs Free energy of formation of hydrogen ..................................................... 97

Figure V-A-4 Thermodynamics for paraffins to olefins ........................................................... 98

Figure V-A-5 Commercial equipment for high throughput catalyst testing ............................. 99

Figure V-A-6 Thin film concept ............................................................................................... 99

Figure V-A-7 Rotor of Coolbrook’s RotoDynamic Reactor (RDR) Process ......................... 105

Figure V-A-8 Operational Comparison: Thermal Cracking to RDR ...................................... 106

Figure V-B-1 Catalytic Distillation Reactor with Internal ..................................................... 108

Figure V-B-2 Tentative new technology separation scheme .................................................. 109

Figure V-C-1 Advanced Catalytic Olefin production (ACO) ................................................ 111

Figure V-C-2 Process Flow: Advanced Catalytic Olefin Process (ACO) .............................. 111

Figure V-C-3 Inovacat GASOLFIN process .......................................................................... 113

Figure V-C-4 OMEGA Block Flow Diagram ........................................................................ 116

Figure V-C-5 Typical Yield of OMEGA Process Using C4 raffinate-1 as Feedstock............ 116

Figure V-D-1 Aromax technology by CP Chem .................................................................... 118

Figure V-D-2 Aromax yield composition in %wt................................................................... 119

Figure V-D-3 Diagram of Cyclar process ............................................................................... 120

Figure V-D-4 Benzene plus mixed xylenes from C3/C4s ........................................................ 121

Figure V-D-5 Applying “Cyclar” + “Tatoray” technology..................................................... 121

Figure V-D-6 FCC Gasoline Desulfurization Technology – GT-BTX PluS .......................... 123

Figure V-D-7 Gas to Aromatics – GT-G2A ........................................................................... 124

Figure V-E-1 “MaxEne” process flow diagram ..................................................................... 125

Figure V-E-2 Comparing two pretreatment schemes ............................................................. 127

Figure V-E-3 Ag containing membrane systems.................................................................... 129

Figure V-E-4 Ethylene recovery - distillation vs membrane .................................................. 130

Figure V-E-5 “Permylene” application for 1-butene recovery ............................................... 131

Figure V-E-6 “Optiperm” data for Propene/Propane separation ............................................ 133

Figure V-E-7 Propene recovery system with “Optiperm” ...................................................... 134

Figure V-E-8 PP reactor purge flowheet ................................................................................ 135

Figure VI-A-1 Block flow diagram of process routes for the separation and conversion

of C4 hydrocarbons .......................................................................................... 142

Figure VI-A-2 Process value chain analysis of FCC C4 (top figure, 5A) and SC C4

(bottom figure, 5B) .......................................................................................... 144

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Figure VI-A-3 Margin/value-added chain based on crude SC C4 feedstock ........................... 145

Figure VI-A-4 Margin/value-added chain of the process based on FCC feedstock, Case

2........................................................................................................................ 145

Figure VI-B-1 Hydrogen membrane system: Air Liquide MEDALTM ................................... 147

Figure VI-B-2 Hydrogen membrane system: GENERON ...................................................... 147

Figure VI-B-3 PRISM Membrane separators contain thousands of hollow fibers .................. 147

Figure VI-B-4 CSIRO membrane to recover H2 from ammonia as a new route of

hydrogen transportation ................................................................................... 148

Figure VI-B-5 Membrane Pervatech Energy save (25%-75%) ............................................... 150

Figure VI-B-6 ECN membrane ................................................................................................ 150

Figure VI-B-7 GFT scheme methanol/organic solvent separations ........................................ 151

Figure VI-B-8 The solvent dehydrating “SolvSep solution” (MTR) relies on a robust

zeolite membrane have pore of 2.9Å able to reduce the content of water

of organic solvents from 15wt% down to 0.1-1wt% range ............................. 151

Figure VI-C-1 Projected growth of α-olefins. ......................................................................... 156

Figure VI-C-2 Ethane to ethylene fuel cell. ............................................................................. 157

Figure VII-1 Chemicals demand expands with rising incomes ............................................. 160

Figure VII-2 Chemicals demand favors oil and gas .............................................................. 160

Figure VII-3 Ethylene cash cost comparision ....................................................................... 161

Figure VII-4 Methane to Ethylene: Siluria Direct C1 Conversion ........................................ 161

Figure VII-5 North America propylene production .............................................................. 162

Figure VII-B-1 Announced Crude to Chemicals Complexes ................................................... 167

Figure VII-C-1 Envisioned Process Configuration ................................................................... 169

Figure VII-C-2 Conceptional Catalytic Olefin Production Process Steps ................................ 169

TABLES

Table I-C-1 Crude to Chemicals Complexes: Selected Case Studies...................................... 5

Table II-D-1 Oil-to-Chemicals: Comparison Between Configurations .................................. 14

Table II-E-1 OtC SWOT Analysis.......................................................................................... 15

Table III-C-1 FCC related processes for petrochemicals and related technology ................... 26

Table III-C-2 TCGR Brainstorm Process for Review .............................................................. 27

Table IV-A-1 Example Crudes and Condensates ..................................................................... 32

Table IV-A-2 OSO Condensate Assay Data............................................................................. 33

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Table IV-A-3 Economic Basis (Crude: 50$/bbl, Natural Gas: 6$/MM Btu) ........................... 37

Table IV-A-4 Retrofit Economics – Base Case ........................................................................ 38

Table IV-A-5 Greenfield Economics – Base Case ................................................................... 39

Table IV-A-6 Retrofit Economics – Sensitivity Analysis ........................................................ 41

Table IV-A-7 Greenfield Economics – Sensitivity Analysis.................................................... 42

Table IV-A-8 Representative Economics: Steam Cracking of Ethane .................................... 46

Table IV-A-9 Representative Economics: Steam Cracking of Naphtha .................................. 47

Table IV-C-1 Typical Cracking Yields .................................................................................... 52

Table IV-C-2 Heavy-Feed Processing Capabilities of Various Heat Rejection Systems ........ 59

Table IV-C-3 Investment Cost of Incremental Propylene ........................................................ 61

Table IV-D-1 Licensed DCC Units .......................................................................................... 64

Table IV-D-2 Typical Operating Parameters for a DCC Unit Compared with FCC

and Steam Cracking Units ................................................................................. 65

Table IV-D-3 DCC Light Olefin Yields ................................................................................... 67

Table IV-D-4 CPP - Main Operating Parameters ..................................................................... 68

Table IV-D-5 CPP - Product Distribution and Olefin Yields ................................................... 69

Table IV-D-6 Key Economic Data for a CPP Integrated Olefins Plant ................................... 71

Table IV-D-7 KBR Modified FCC for Max Olefins ................................................................ 72

Table IV-D-8 Maxofin Olefin Yields ....................................................................................... 73

Table IV-D-9 Grassroots High Propylene FCC Units .............................................................. 75

Table IV-D-10 Comparison of DCC and Metathesis on Olefins................................................ 75

Table IV-D-11 Effect of recycling spent catalyst to the feed riser ............................................. 79

Table IV-E-1 Cracking Results at 970°F (wt%) LTO vs VGO ............................................... 81

Table IV-E-2 Yields of Utica Crude Oil and Fractions ............................................................ 82

Table IV-E-3 Testing Utica ATB (650°F plus) ........................................................................ 82

Table IV-E-4 Cracking Utica Shale ......................................................................................... 83

Table IV-E-5 Inferred yields, Utica shale ................................................................................ 83

Table IV-E-6 FCC products yields comparison: projected results for a 40,000 bpd unit

(5760 tpd) at 77% gas oil conversion (values in tpd) ........................................ 84

Table IV-F-1 Main Sources of Propylene ................................................................................ 85

Table IV-F-2 Oleflex Economics ............................................................................................. 87

Table IV-F-3 Properties of catalyst samples taken from the same commercial plant

show the improvement in stability of the latest generation catalyst .................. 88

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Table V-A-1 Conventional steam cracking economics ......................................................... 102

Table V-A-2 Economics for the RFR for making olefins ..................................................... 103

Table V-A-3 Comparing conventional steam cracking with new RFR for olefins ............... 104

Table V-A-4 Comparison of Thermal Cracking to RDR ...................................................... 106

Table V-A-5 Comparison of Business Potential: Naphtha Cracking vs. RDR ..................... 107

Table V-C-1 Commercial Status of ACO ............................................................................. 110

Table V-C-2 Typical Yield Selectivities: FCC full range naphtha ....................................... 113

Table V-C-3 Economics of GASOLFIN process .................................................................. 114

Table V-C-4 Comparison of catalytic performance of different MFI-type zeolites ............. 115

Table V-C-5 OMEGA Increases Operating Margin ............................................................. 117

Table V-D-1 Aromax economics .......................................................................................... 119

Table V-D-2 Cyclar Product Distribution ............................................................................. 122

Table V-D-3 Cyclar economics ............................................................................................. 122

Table V-E-1 Impact on Olefin Yields ................................................................................... 126

Table V-E-2 Impact on Aromatic Yields .............................................................................. 126

Table V-E-3 Overall MaxEne Economic Impact .................................................................. 126

Table V-E-4 Comparison of 1-Butene Separation Benefits................................................. 131

Table V-E-5 Economics of distillation and membranes ....................................................... 132

Table V-E-6 Feed impurities for Olefin-Paraffin membranes .............................................. 134

Table V-E-7 Preliminary Economics .................................................................................... 135

Table VI-1 Typical composition of SC C4, FCC C4 and field butane feedstock ................ 141

Table VI-B-1 Catalyst Performance Comparison in the Production of MTBE ..................... 153

Table VII-A-1 Comparison of Olefin Production Processes: Oil-to-Chemicals and

Others ............................................................................................................... 163

Table VII-A-2 Propylene Sources (% of Total) ....................................................................... 164

Table VII-A-3 Investment Cost of Incremental Propylene ...................................................... 165

Table VII-A-4 Comparison of On-Purpose Propylene Processes ............................................ 165

Table VII-D-1 Oil-to-Chemicals (OtC) SWOT Analysis ........................................................ 170

(study completed december 2017) - catalystgrp.com chemical products that avoid the upfront...

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