Abstract

Process Economics Program Report 261

METHANOL TO OLEFINS
(November 2007)

Ethylene and propylene are by far the two largest volume chemicals produced by the
petrochemicals industry. In 2006 about 110 million metric tons of ethylene and 70 million metric
tons of propylene were produced worldwide. Global demand for light olefins (ethylene and
propylene) is expected to grow at an annual rate of 5% for propylene and 4% for ethylene. Today
the majority of light olefins are produced by the petrochemicals industry either from pyrolysis
(steam cracking) of naphtha or from fluid catalytic cracking (FCC) of naphtha. The recent
dramatic increase in oil prices is reviving a strong interest in the production of light olefins from
non-petroleum source among which low-cost methanol may play a significant role.
Because of the wide variety of feedstock sources and projected massive new capacity
additions in the near future, methanol has promise as an economical, non-petroleum source for
the production of light olefins. At present, the technologies for producing light olefins from
methanol appear ready for commercialization.
In this report, we evaluate one of the most promising new applications for low-cost methanol:
the catalytic conversion of methanol to light olefins. We develop and present conceptual designs
and preliminary economics of the two processes currently available for licensethe UOP/Hydro
MTO (methanol-to-olefins) technology based on the MTO-100 silicoaluminophosphate synthetic
molecular sieve based catalyst, and Lurgis MTP (methanol-to-propylene) process based on
MTPROP, a proprietary ZSM-5 type of catalyst supplied from Sd-Chemie.

SRI Consulting PEP Report 261

 R eport No. 261

ME T HA NOL T O OL E F INS

by V IC T OR WA N

November 2007

A private report by the

P R OC E S S E C ONOMIC S P R OG R A M

SR I Menlo P ark, C alifornia 94025

 SRIC agrees to assign professionally qualified personnel to the preparation of the
Process Economics Programs 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
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harmless from any liability to any third party resulting directly or indirectly from the Clients 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

GLOSSARY........................................................................................................................ x

1 INTRODUCTION ........................................................................................................ 1-1

2 SUMMARY ................................................................................................................. 2-1

GENERAL ASPECTS................................................................................................. 2-1

TECHNOLOGY ASPECTS......................................................................................... 2-2

Commercial Methanol to Olefins Technology ........................................................... 2-2

Analysis of Patents ..................................................................................................... 2-2

Process Design .......................................................................................................... 2-3

PROCESS ECONOMICS........................................................................................... 2-4

Methanol to Ethylene and Propylene ......................................................................... 2-4

Methanol to Propylene................................................................................................ 2-4

CONCLUSIONS ......................................................................................................... 2-6

3 INDUSTRY STATUS.................................................................................................. 3-1

ETHYLENE INDUSTRY ............................................................................................. 3-1

Ethylene Feedstock Considerations........................................................................... 3-4

Ethylene End Uses ..................................................................................................... 3-5

Ethylene Supply and Demand .................................................................................... 3-7

Ethylene Prices........................................................................................................... 3-8

PROPYLENE INDUSTRY .......................................................................................... 3-8

Propylene Transportation and Storage ...................................................................... 3-11

Propylene End Uses................................................................................................... 3-11

Supply and Demand of Propylene.............................................................................. 3-13

Propylene Prices ........................................................................................................ 3-14

Production of Primary Propylene................................................................................ 3-16

Propylene from Ethylene Plants ................................................................................. 3-18

Propylene from Refineries .......................................................................................... 3-19

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 CONTENTS (Continued)

Production of Secondary Propylene........................................................................... 3-20

Propane Dehydrogenation.......................................................................................... 3-21

Metathesis .................................................................................................................. 3-23

Methanol to Propylene................................................................................................ 3-26

METHANOL TO OLEFINS ......................................................................................... 3-28

Olefin Cracking ........................................................................................................... 3-29

R&D Activities by ExxonMobil .................................................................................... 3-30

DMTO Technology ..................................................................................................... 3-30

METHANOL AS FEEDSTOCK................................................................................... 3-31

Regional Capacity Trends .......................................................................................... 3-32

Methanol Prices .......................................................................................................... 3-35

Methanol Shipping...................................................................................................... 3-36

4 UOP/HYDRO MTO PROCESS .................................................................................. 4-1

INTRODUCTION ........................................................................................................ 4-1

COMMERCIAL DEVELOPMENTS ............................................................................ 4-1

Recent Advancements in UOP/Hydro MTO Technology ........................................... 4-3

TECHNOLOGY REVIEW ........................................................................................... 4-4

MTO Catalyst Development ....................................................................................... 4-4

MTO Reactor Design Consideration .......................................................................... 4-6

Fluidization Regimes ............................................................................................ 4-6
Fast-fluidized Bed MTO Reactor .......................................................................... 4-7
Effect of Reaction Temperature and Water as Diluent......................................... 4-9
Effect of Space Velocity........................................................................................ 4-10
Influence of Coke Deposition ............................................................................... 4-10
UOP/Hydro MTO Reaction Conditions................................................................. 4-10
MTO Reaction Mechanism................................................................................... 4-11

MTO Process Chemistry and Kinetics........................................................................ 4-12

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 CONTENTS (Continued)

Kinetic Models based on ZSM-5 .......................................................................... 4-12

Kinetic Models based on SAPO-34 ...................................................................... 4-12

Product Recovery ....................................................................................................... 4-15

METHANOL TO OLEFINS BY THE UOP/HYDRO PROCESS ................................. 4-15

Process Description.................................................................................................... 4-16

Section 100 - Methanol Conversion ..................................................................... 4-16
Section 200 - Product Separation ........................................................................ 4-17

Process Discussion .................................................................................................... 4-29

COST ESTIMATES .................................................................................................... 4-32

Comparison With Other Technologies ....................................................................... 4-43

MTO Applications ....................................................................................................... 4-43

5 METHANOL TO PROPYLENE BY THE LURGI MTP PROCESS ............................ 5-1

INTRODUCTION ........................................................................................................ 5-1

COMMERICAL DEVELOPMENTS ............................................................................ 5-2

TECHNOLOGY REVIEW ........................................................................................... 5-3

ZSM-5 Catalyst ........................................................................................................... 5-4

Reactor Design and Operation................................................................................... 5-5

Product Recovery ....................................................................................................... 5-6

PROCESS DESCRIPTION ........................................................................................ 5-7

Section 100 - Methanol Conversion ........................................................................... 5-7

Section 200 - Propylene Recovery............................................................................. 5-8

PROCESS DISCUSSION........................................................................................... 5-18

PROCESS ECONOMICS........................................................................................... 5-20

LURGI MTP PROCESS APPLICATIONS .................................................................. 5-28

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

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

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 CONTENTS (Concluded)

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

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

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 FIGURES

3.1 U.S Market Prices for Ethylene ............................................................................. 3-8

3.2 U.S. Market Prices for Propylene .......................................................................... 3-15

3.3 U.S. Polymer-Grade Propylene to Ethylene Production and Price Ratios............ 3-16

3.4 Block Diagram of Methanol-to-Propylene Process ............................................... 3-27

3.5 Block Diagram of Coal-to-Propylene Process....................................................... 3-28

3.6 Schematic the UOP/Hydro MTO Process ............................................................. 3-30

3.7 SChematic of the DMTO Process ......................................................................... 3-31

4.1 Reaction Network from MTO Over SAPO-34........................................................ 4-13

4.2 Methanol to Olefins by the UOP/Hydro Process

Flow Diagram ........................................................................................................ D-3

4.3 The UOP/Hydro MTO Process with a DME Recovery Block ................................ 4-30

4.4 Methanol to Olefins by the UOP/Hydro Process

Effect of Plant Capacity on Investment Cost ......................................................... 4-36

4.5 Methanol to Olefins by the UOP/Hydro Process

Effect of Methanol Price and Plant Capacity of Ethylene Product Value .............. 4-39

4.6 Methanol to Olefins by the UOP/Hydro Process

Historical Pre-tax Return on Investment (ROI)...................................................... 4-40

4.7 Methanol to Olefins by the UOP/Hydro Process

Production Economics at Historical Ethylene and Propylene Prices .................... 4-41

5.1 Lurgi MTP Process Carbon Product Yields, wt%.................................................. 5-5

5.2 Methanol to Propylene by the Lurgi MTP Process

Flow Diagram ........................................................................................................ D-7

5.3 Methanol to Propylene by the Lurgi MTP Process

Effect of Plant Capacity on Investment Cost ......................................................... 5-24

5.4 Methanol to Propylene by the Lurgi MTP Process

Effect on Methanol Price on Production Cost and Product Value......................... 5-27

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 TABLES

2.1 Comparative Economics for Production of Propylene

Economic Summary .............................................................................................. 2-5

3.1 Polymer Grade Ethylene Specifications ................................................................ 3-3

3.2 Global Ethylene Feedstock Consumption in 2006 ................................................ 3-5

3.3 World Capacity for Ethylene by Region................................................................. 3-7

3.4 Typical Propylene Quality Specifications .............................................................. 3-10

3.5 Typical Polymer Grade Propoylene Specifications ............................................... 3-10

3.6 Propylene Supply/Demand Summary for 2006..................................................... 3-14

3.7 Yields of Co-Product Propylene from Ethylene Production .................................. 3-18

3.8 Change in Expected Propylene Feedstock Utilization .......................................... 3-20

3.9 Producers of Propylene from Propane by Dehydrogenation ................................ 3-22

3.10 Producers of Propylene from Ethylene/Butylene Metathesis................................ 3-24

3.11 Historical and Projected World Methanol Capacity, Production and

Consumption by Region ........................................................................................ 3-34

3.12 U.S. Prices and Unit Sales Values for Methanol................................................... 3-35

4.2 Methanol to Olefins by the UOP/Hydro Process

Design Bases and Assumptions............................................................................ 4-19

4.3 Methanol to Olefins by the UOP/Hydro Process

Stream Flows......................................................................................................... 4-20

4.4 Methanol to Olefins by the UOP/Hydro Process

Major Equipment ................................................................................................... 4-25

4.5 Methanol to Olefins by the UOP/Hydro Process

Utilities Summary................................................................................................... 4-28

4.6 Yields from UOP/Hydro Process MTO Conversion Zone ..................................... 4-31

4.7 Methanol to Olefins by the UOP/Hydro Process

Total Capital Investment........................................................................................ 4-34

4.8 Methanol to Olefins by the UOP/Hydro Process

Capital Investment by Section ............................................................................... 4-35

4.9 Methanol to Olefins by the UOP/Hydro Process

Production Costs ................................................................................................... 4-37

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 TABLES (Concluded)

4.10 Methanol to Olefins by the UOP/Hydro Process

Production Costs ................................................................................................... 4-42

5.1 Methanol to Propylene by the Lurgi MTP Process

Design Bases and Assumptions............................................................................ 5-9

5.2 Methanol to Propylene by the Lurgi MTP Process

Stream Flow .......................................................................................................... 5-10

5.3 Methanol to Propylene by the Lurgi MTP Process

Major Equipment ................................................................................................... 5-15

5.4 Methanol to Propylene by the Lurgi MTP Process

Utilities Summary................................................................................................... 5-17

5.5 Methanol to Propylene by the Lurgi MTP Process

Total Capital Investment........................................................................................ 5-22

5.6 Methanol to Propylene by the Lurgi MTP Process

Capital Investment by Section ............................................................................... 5-23

5.7 Methanol to Propylene by the Lurgi MTP Process

Production Costs ................................................................................................... 5-25

A.1 Conversion of Methanol to Olefins Sapo Catalysts and Reaction Conditions

Patent Summary.................................................................................................... A-3

A.2 Conversion of Methanol to Olefins Zeolite Catalysts and Reaction Conditions

Patent Summary.................................................................................................... A-20

A.3 Conversion of Methanol to Olefins Reactor Design and Operation

Patent Summary.................................................................................................... A-25

A.4 Conversion of Methanol to Olefins Product Recovery

Patent Summary.................................................................................................... A-34

A.5 Conversion of Methanol to Olefins Other Catalysts/Process Integration

Patent Summary.................................................................................................... A-41

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