Abstract Process Economics Program Report 195A ADVANCES IN FLUID CATALYTIC CRACKING (November 2005)

Recent emphasis in fluid catalytic cracking is on maximum light olefins production, gasoline sulfur reduction and compliance with FCCU NOx and SOx emissions requirements. New cracking catalysts and additives for the reduction of NOx, SOx and gasoline sulfur continue to significantly improve FCCU operation. New hardware designs offer improved unit operation and efficiency. Areas of recent new hardware design improvements include the standpipe inlet, third stage cyclones, spent catalyst distributor and catalyst stripping. Wet gas scrubbers or selective catalytic reduction may now be required in some cases to meet emissions requirements. This report provides an overview of FCC developments in catalyst, process and hardware technologies since PEP Report 195, Advances in Fluid Catalytic Cracking, issued in 1991. The report then develops process economics for cracking the most common type of FCC feedstock, vacuum gas oil. PEP Report 228, Refinery Residue Upgrading, issued in 2000 reviews the special issues and technology of Residual Fluid Catalytic Cracking (RFCC) and develops process economics for cracking a residual feedstock. Since the refinery production of light olefins such as propylene offers refiners in some regions, especially Asia and Western Europe, an opportunity for profit, the process economics of maximum light olefins FCC from VGO are developed.

Air emissions (SOX, NOX) from FCCUs and the reduction of FCC gasoline sulfur are major environmental issues discussed. Professionals and managers involved in the energy industry who manage, research, develop, plan, operate, design plants or manage investments in the petroleum refining and allied industries could benefit from the information contained in this report.

PEP’05 RHN R eport No. 195A

ADVANC E S IN FL UID C ATAL YTIC C R AC K ING

by R ichard H. Niels en

November 2005

A private report by the

P R OC E S S E C ONOMIC S P R OG R AM

S R I Menlo P ark, C alifornia 94025 SRIC agrees to assign professionally qualified personnel to the preparation of the Process Economics Program’s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither SRIC nor its employees will assume any liability for the special or consequential damages arising from the Client’s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client’s use of the reports or other deliverables produced by SRIC pursuant to this agreement

For detailed marketing data and information, the reader is referred to one of the SRI Consulting programs specializing in marketing research. THE CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS PROGRAM covers major hydrocarbons and their derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico. CONTENTS

1 INTRODUCTION ...... 1-1

2 CONCLUSIONS ...... 2-1

3 SUMMARY ...... 3-1

COMMERCIAL ASPECTS ...... 3-1

TECHNICAL ASPECTS ...... 3-2

ECONOMICS ASPECTS...... 3-4

4 INDUSTRY STATUS...... 4-1

ROLE OF CATALYTIC CRACKING...... 4-2

FIXED SOURCE EMMISIONS REGULATIONS...... 4-3

Particulates...... 4-4

SOx ...... 4-5

NOx ...... 4-5

CO ...... 4-5

PRODUCT SPECIFICATIONS...... 4-6

Gasoline...... 4-6

Diesel...... 4-9

Propylene, Propane, Ethylene and Ethane ...... 4-11

SUPPLY AND DEMAND ...... 4-15

Motor Fuels...... 4-15

Propylene...... 4-19

INSTALLED CATALYTIC CRACKING CAPACITY...... 4-21

NEW CONSTRUCTION ...... 4-44

5 GENERAL PROCESS REVIEW ...... 5-1

FEEDSTOCK...... 5-1

PRODUCTS...... 5-8

iii CONTENTS (Continued)

Gasoline...... 5-9

CHEMISTRY...... 5-12

Cracking Mechanisms ...... 5-13 Alkene Cracking Mechanism...... 5-13 Alkane Cracking Mechanism...... 5-15 Carbenium Ion Mechanisms...... 5-15 Coke and Catalyst Decay...... 5-19 Carbonium Ion Mechanisms...... 5-23 Dichotomies...... 5-23 Sulfur Compound Cracking Mechanism...... 5-25 Coke Combustion...... 5-29

NOx Formation Mechanism ...... 5-30

Cracking Kinetics...... 5-33

FCC GASOLINE SULFUR REDUCTION...... 5-36

Feedstock Hydrodesulfurization ...... 5-37

Gasoline End Point Reduction ...... 5-38

Co-processing C5-C6s...... 5-38

Post Treatment ...... 5-39

CATALYSIS ...... 5-40

Adsorption and Diffusion ...... 5-41

Catalyst Attrition...... 5-42

Commercial FCC Catalysts ...... 5-43 Gasoline Sulfur Reduction...... 5-46 Maximum Light Olefins ...... 5-46 Maximum Middle Distillates...... 5-47

Catalyst Additives ...... 5-47 Light Olefins (Propylene)...... 5-51

SOx ...... 5-54 CO ...... 5-56 iv CONTENTS (Continued)

NOx ...... 5-56 Gasoline Sulfur Reduction Additives...... 5-57 Bottoms Cracking ...... 5-58

6 CONVENTIONAL GAS OIL CRACKING ...... 6-1

PROCESS REVIEW...... 6-1 Feed Injection and Atomization ...... 6-3 Riser ...... 6-6

Riser Termination ...... 6-9 Spent Catalyst Stripper...... 6-11 Standpipes...... 6-15 Regenerator...... 6-17 Catalyst Coolers ...... 6-18 Oxygen Enrichment ...... 6-19 Third Stage Separator ...... 6-20 Power Generation...... 6-21 Electrostatic Precipitators...... 6-21 Developmental Hardware...... 6-22 Downflow Reactor...... 6-22 Coupled Riser-Downer Reactor...... 6-24 Dual Loop Riser ...... 6.26

Operating Conditions...... 6-26

Environmental...... 6-26

CO ...... 6-27

SOx...... 6-27 Lurgi EP-Absorber System ...... 6-29

Fluor SOx Cleanup Process...... 6-29 Dynawave® Froth Scrubber ...... 6-30 LABSORBTM Process ...... 6.30 ® CANSOLV SO2 Scrubbing System Technology ...... 6-32

NOx ...... 6-32

v CONTENTS (Continued)

DeNOx ...... 6-34 TM LoTOx Process ...... 6-34 Biological Process ...... 6-34

Particulates...... 6.35

Yields ...... 6.35

Modeling and Simulation (Control) ...... 6-36

PROCESS DESCRIPTION ...... 6.38

Section 100 – Cracking and Main Fractionation ...... 6-49

Section 200 – Vapor Recovery...... 6-51

PROCESS DISCUSSION...... 6-51

Feedstock ...... 6-52

Riser Reactor/Regenerator ...... 6-52

Main Fractionator and Vapor Recovery...... 6-53

Environment...... 6-54

COST ESTIMATES ...... 6-54

Investment Costs...... 6-54

Production Costs ...... 6-55

Profitability ...... 6-56

7 CATALYTIC CRACKING FOR MAXIMUM OLEFINS...... 7-1

PROCESS REVIEW...... 7-1

UOP PetroFCCSM ...... 7-1

Selected Component Cracking...... 7-2

MaxofinTM FCC Process...... 7-3

SuperflexSM Process...... 7-3

High Severity FCC...... 7-5

INDMAX Process...... 7-5

Deep Catalytic Cracking Process...... 7-6

vi CONTENTS (Continued)

Downer Catalytic Pyrolysis...... 7-6

Stripper as Reactor...... 7-8

Other Naphtha Cracking Process...... 7-8

PROCESS DESCRIPTION ...... 7-9

Section 100 – Cracking and Main Fractionation ...... 7-23

Section 200 – Vapor Recovery...... 7-23

Section 300 – Propylene Recovery ...... 7-24

PROCESS DISCUSSION...... 7-24

Cracking and Fractionation ...... 7-25

Vapor Recovery Section...... 7-26

Propylene Recovery ...... 7-26

COST ESTIMATES ...... 7-27

Investment Costs...... 7-28

Production Costs ...... 7-29

Profitability ...... 7-29

Without ARU...... 7-29

Polymer Grade Ethylene and Propylene ...... 7-40

APPENDIX A: PATENT SUMMARY TABLES...... A-1

APPENDIX B: DESIGN AND COST BASES ...... B-1

APPENDIX C: CITED REFERENCES...... C-1

APPENDIX D: PATENT REFERENCES BY COMPANY...... D-1

APPENDIX E: PROCESS FLOW DIAGRAM...... E-1

vii ILLUSTRATIONS

4.1 World Residual Supply/Demand Balance ...... 4-2

4.2 FCC in the Fuel Refinery (Simplified)...... 4-3

4.3 Gasoline Supply ...... 4-16

4.4 Diesel Fuel Supply...... 4-17

4.5 US Motor Fuels Prices...... 4-18

4.6 Propylene Supply and Demand for Polymer and Chemical Grades...... 4-19

4.7 PEP Polymer Grade Propylene Value...... 4-20

4.8 US Petroleum Administration for Defense Districts...... 4-23

5.1 Alkybenzene Distribution in FCC Gasolines ...... 5-10

5.2 Distribution of Total Naphthalenes Tetralins and Indanes in Gasolines ...... 5-10

5.3 Chain Mechanism for Catalytic Cracking Proposed by Wojciechowski...... 5-17

5.4 Reaction Scheme for Cracking Sulfur Compounds ...... 5-26

5.5 Cracking Scheme of an Extra Heavy Gas Oil (Coke Formation not Represented)...... 5-27

5.6 Cracking Scheme of Extra Heavy Gas Oil (A) Hydorcarbons, (B) Sulfur Species ...... 5-28

5.7 Mechanism for the Reaction of N-Hexene and H2S...... 5-29

5.8 NOx and N2 Formation Mechanism ...... 5-31

6.1 UOP Fluid Catalytic Cracking Process...... 6-2

6.2 Nozzle Design ...... 6-5

6.3 Riser Core-Annulus Solids Flow...... 6-8

6.4 General Schematic of Riser Termination Device Evolution ...... 6-9

6.5 Stripper Designs ...... 6-13

6.6 UOP Third Stage Separator ...... 6-20

6.7 ECV® Wet Scrubbing System ...... 6.31

6.8 Conventional FCCU...... E-3

7.1 MaxofinTM FCCU...... 7-4

7.2 Cracking and Fractionation Section ...... E-7

viii ILLUSTRATIONS (Concluded)

7.3 UOP Aromatics Complex for Maximum Para-Xylene...... 7-24

ix TABLES

3.1 Summary of Cost Estimates for Conventional and Light Olefins FCCUS...... 3-5

4.1 Typical Flue Gas Particulate Concentration Limits ...... 4-5

4.2 Leading 2005-2006 Gasoline Specifications...... 4-7

4.3 European Gasoline Specifications ...... 4-7

4.4 Summary of Gasoline Sulfur Specifications ...... 4-8

4.5 US and European Diesel Fuel Specifications ...... 4-10

4.6 Typical Propylene Quality Specifications ...... 4-11

4.7 Typical Propylene Specifications...... 4-12

4.8 Propane Specifications...... 4-13

4.9 Polymer Grade Ethylene Specifications...... 4-14

4.10 Common High Purity Ethane Specifications ...... 4-15

4.11 Distribution of Demand for Motor Fuels...... 4-18

4.12 Catalytic Cracking Refineries – World Summary ...... 4-22

4.13 Catalytic Cracking Refineries – North American Summary ...... 4-22

4.14 Conversion Capacity of North American Catalytic Cracking Refineries ...... 4-24

4.15 Conversion Capacities of Catalytic Cracking Refineries Outside North America . 4-30

4.16 Average Catalytic Cracking Capacity in Catalytic Cracking Refineries ...... 4-42

4.17 Catalytic Cracking Refineries – Number Distribution of FCC Capacities...... 4-43

4.18 Catalytic Cracking Refineries – Volume Distribution of FCC Capacities ...... 4-43

4.19 Announced Catalytic Cracker Construction ...... 4-44

5.1 Mass-Spec Analysis of FCC Feedstock...... 5-2

5.2 Feedstock Guideline for Residual FCC...... 5-2

5.3 Hydrocarbon Type Classes ...... 5-3

5.4 Characterization of Fractions and Whole Typical FCC Feedstock ...... 5-4

5.5 NMR Analysis of a FCC Feedstock...... 5-5

5.6 Comparison of Estimated Yields ...... 5-5

5.7 Distribution of Types of Sulfur Compounds in FCC Feedstocks...... 5-6

x TABLES (Continued)

5.8 Distribution of Nitrogen Compounds in One European FCCU Feedstock...... 5-7

5.9 Nitrogen Compounds in Feedstock and 450°F+(232°C+) Liquid Products ...... 5-8

5.10 Distribution of Sulfur in FCC Products...... 5-9

5.11 Approximate Gasoline Olefin Content by Hydrocarbon Boiling Range...... 5-9

5.12 Boiling Range of Sulfur Compounds in FCC Gasoline (Summary)...... 5-11

5.13 Major Gasoline Sulfur Compounds Normal Boiling Point and Hydrocarbon Boiling Range ...... 5-12

5.14 Summary of Carbon Skeletal Parameters of Coke Determined by 13C-NMR Spectra...... 5-20

5.15 Dichotomies in Catalytic Cracking...... 5-24

5.16 NOx Formation...... 5-32

5.17 Sulfur Species in Light Gasoline (IBP-160°F, IBP-71°C) ...... 5-39

3 5.18 Adsorption Equilibrium Constants (CM /GCAT) ...... 5-41

5.19 Selected Commercial FCC Catalysts...... 5-44

5.20 Preliminary Results of UMFCC Process for Middle Distillates...... 5-47

5.21 FCC Catalyst Additives Market – 2002 ...... 5-48

5.22 Selected Solid Additives for FCC ...... 5-49

5.23 Expected LPG Olefins Yield for 3% Level of Engelhard’s Maximum Olefins Additive...... 5-54

5.24 Variables Affecting SOx Emissions and Additive Performance...... 5-55

6.1 Improvement in FCCU Performance as Feed Nozzles Improved...... 6-3

6.2 Gas-Solid Fluidization Flow Regimes...... 6-7

6.3 Yield Shift Between Riser Exit and Vapor Line ...... 6-9

6.4 Riser Termination Considerations...... 6-10

6.5 Benefits of Improved Stripping ...... 6-12

6.6 Catalyst Flux Rates and Velocities for Disc and Donut and Structured Packing Strippers...... 6-14

6.7 Effect of Stripping Stream Flow Rate on at the Top and Bottom ...... 6-15

6.8 Yield Improvement from Increasing Catalyst Circulation Rate...... 6-16

xi TABLES (Continued)

6.9 Regenerator Oxygen Enrichment...... 6-19

6.10 Product Yields from Downer and Riser Reactors at Constant Conversion...... 6-23

6.11 Product Yields from Downer and Riser Reactors at Constant Coke Make...... 6-24

6.12 High Accessibility Catalyst Improves Downer Bottoms Conversion ...... 6-24

6.13 Comparison of Coupling, Riser and Downer Reactors’ Yields...... 6-25

6.14 Advantages and Disadvantages of Common Wet Scrubbing Agents...... 6-28

6.15 FCCU SCR Conditions...... 6-33

6.16 Maximization for Gasoline Compared to Maximum Diesel Fuel Resid Cracking.. 6-36

6.17 Vacuum Gas Oil Fluid Catalytic Cracking Design Bases and Assumptions...... 6-39

6.18 Vacuum Gas Oil Fluid Catalytic Cracking Product Yields and Properties...... 6-41

6.19 Conventional FCCU Stream Flows...... 6-42

6.20 Conventional FCCU Major Equipment ...... 6-45

6.21 Conventional FCCU Utilities Summary...... 6-48

6.22 Distillation of Fresh Feed and Liquid Products...... 6-52

6.23 Conventional FCCU Total Capital Investment...... 6-57

6.24 Conventional FCCU Capital Investment by Section...... 6-58

6.25 Conventional FCCU Production Costs ...... 6-59

7.1 Selected Component Cracking Yields...... 7-2

7.2 HS-FCC Compared to Conventional FCC ...... 7-5

7.3 Downer Catalytic Pyrolysis Yields Compared to DCC-1 Yields...... 7-7

7.4 Light Olefins Fluid Catalytic Cracking Design Bases and Assumptions...... 7-10

xii TABLES (Concluded)

7.5 Light Olefins Fluid Catalytic Cracking Product Yields and Properties...... 7-12

7.6 Light Olefins FCC – Dilute Ethylene Stream Flows...... 7-14

7.7 Light Olefins FCC – Dilute Ethylene Major Equipment ...... 7-19

7.8 Light Olefins FCC – Dilute Ethylene Utilities Summary...... 7-22

7.9 Aromatic Recovery Unit Yields...... 7-27

7.10 Light Olefins FCCU – Dilute Ethylene Total Capital Investment...... 7-31

7.11 Light Olefins FCCU – Dilute Ethylene Capital Investment by Section...... 7-32

7.12 Light Olefins FCCU – Dilute Ethylene Production Costs ...... 7-33

7.13 Light Olefins FCCU – Without ARU Total Capital Investment...... 7-35

7.14 Light Olefins FCCU – Without ARU Capital Investment by Section...... 7-36

7.15 Light Olefins FCCU – Without ARU Utilities Summary...... 7-37

7.16 Light Olefins FCCU – Without ARU Production Costs ...... 7-38

7.17 Light Olefins FCCU – Polymer Grade Ethylene Major Equipment ...... 7-41

7.18 Light Olefins FCCU – Polymer Grade Ethylene Total Capital Investment...... 7-44

7.19 Light Olefins FCCU – Polymer Grade Ethylene Capital Investment by Section...... 7-45

7.20 Light Olefins FCCU – Polymer Grade Ethylene Utilities Summary...... 7-46

7.21 Light Olefins FCCU – Polymer Grade Ethylene Production Costs ...... 7-47

xiii