© SRI Consulting PEP Report 217

PEP Report 217

BIO-BASED POLYOLS

By

Gregory Bohlmann

(October 2007)

ABSTRACT

Polyols are polymer products with an extended carbon chain and multiple reactive func-tional groups. Many vegetable-based oils have structures that lend themselves well as a base for these products, leading to the production of bio-based polyols. Naturally occurring varia-tions in composition can be dealt with using a variety of process strategies. In the United States, several different processes have been developed for converting soybean oil into poly-ols for flexible polyurethane foams. Urethane Soy Systems Company produces a family of polyols made by auto oxidation, also known as blown soybean oil. Cargill Industrial BioPro-ducts has developed polyols made by ring opening oligomerization of epoxidized soybean oil. Dow Chemical Company is developing soy-based polyols that are made in four main steps from soybean oil: (1) methanolysis, (2) hydroformylation, (3) hydrogenation and (4) polymeriza-tion.

Bio-derived materials such as soy-based polyols can offer significant advantages over conventional polyols in regard to sustainability, reduction of petroleum dependence and poten-tial lower cost. They also are often characterized by higher thermal stability and less sensitivity to hydrolysis. But an important issue for soy-based polyols is the growing biodiesel market. Growing biodiesel demand significantly drove up soybean oil prices in 2007. A question that arises is how the process economics of soy-based polyols are impacted and whether these new bio-derived materials can remain competitive with conventional polyols. In this report, PEP presents process designs and associated cost estimates for bio-based poyols made by auto oxidation, ring opening oligomerization and hydroformylation. In general, technology develop-ment is still in the semi-commercial stage with only one commercial scale facility in the United States. The general conclusions are summarized below:

• Until 2006, price increases for conventional polyols helped to stimulate interest in bio-based polyols. However, rising demand for biodiesel has driven up natural oil prices and subsequent costs of bio-based polyols. Producers back integrated to the produc-tion of natural oils will have an advantage in this environment.

• Production of soy-based polyols by auto oxidation or ring-opening oligomerization are relatively simple processes without complicated unit operations. However, production by hydroformylation is a complicated multi-step process with more demanding capital requirements.

R eport No. 217

B IO-B A S E D P OL Y OL S

by G R E G OR Y B OHL MA NN

Oc tober 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 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.

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CONTENTS

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

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

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

MARKET ASPECTS................................................................................................... 2-2

TECHNICAL ASPECTS ............................................................................................. 2-3

Soybean Processing................................................................................................... 2-3

Blown Soybean Oil ..................................................................................................... 2-4

Soy-Based Polyols by Ring-Opening Oligomerization............................................... 2-4

Soy-Based Polyols by Hydroformylation .................................................................... 2-5

ECONOMIC ASPECTS .............................................................................................. 2-6

CONCLUSIONS ......................................................................................................... 2-7

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

BIO-BASED POLYOLS MARKET STATUS............................................................... 3-2

BIO-BASED POLYOLS PRODUCERS ...................................................................... 3-4

BIO-BASED POLYOLS PRICES................................................................................ 3-6

4 CHEMISTRY AND PROPERTIES ............................................................................. 4-1

CHEMISTRY............................................................................................................... 4-1

Epoxidized Oils ........................................................................................................... 4-3

Esterification And Hydroformylation ........................................................................... 4-6

PROPERTIES............................................................................................................. 4-8

5 OILSEED PROCESSING........................................................................................... 5-1

PROCESS OVERVIEW.............................................................................................. 5-1

Dehulling..................................................................................................................... 5-3

Grinding, Rolling or Flaking ........................................................................................ 5-3

Cooking....................................................................................................................... 5-4

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CONTENTS (Continued)

Expelling ..................................................................................................................... 5-4

Extraction.................................................................................................................... 5-5

Meal Desolventizing and Finishing............................................................................. 5-7

Distillation ................................................................................................................... 5-7

Oil Compositions ........................................................................................................ 5-8

COMMERCIAL CRUSHING CAPACITY.................................................................... 5-8

PROCESS DESCRIPTION ........................................................................................ 5-10

Seed Preparation........................................................................................................ 5-11

Solvent Extration ........................................................................................................ 5-11

PROCESS DISCUSSION........................................................................................... 5-16

Selection of Extractor ................................................................................................. 5-16

Soybean Oil Yield ....................................................................................................... 5-16

Waste Treatment ........................................................................................................ 5-17

Materials of Construction............................................................................................ 5-17

CAPITAL AND PRODUCTION COSTS ..................................................................... 5-18

DISCUSSION OF CAPITAL COST AND PRODUCT VALUE.................................... 5-18

6 BLOWN SOYBEAN OIL ............................................................................................ 6-1

PRODUCT SPECIFICATIONS................................................................................... 6-1

PROCESS DESCRIPTION ........................................................................................ 6-3

PROCESS DISCUSSION........................................................................................... 6-9

Selection of Design Patent ......................................................................................... 6-9

On-Stream Factor....................................................................................................... 6-9

Waste Treatment ........................................................................................................ 6-10

CAPITAL AND PRODUCTION COSTS ..................................................................... 6-10

DISCUSSION OF PRODUCTION COSTS ................................................................ 6-10

7 POLYOLS BY RING-OPENING OLIGOMERIZATION ............................................. 7-1

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CONTENTS (Continued)

TYPICAL PROPERTIES ............................................................................................ 7-2

PROCESS DESCRIPTION ........................................................................................ 7-3

PROCESS DISCUSSION........................................................................................... 7-8

Selection of Design Patent ......................................................................................... 7-8

On-Steam Factor ........................................................................................................ 7-8

Waste Treatment ........................................................................................................ 7-9

CAPITAL AND PRODUCTION COSTS ..................................................................... 7-9

DISCUSSION OF PRODUCTION COSTS ................................................................ 7-9

8 POLYOLS BY HYDROFORMYLATION.................................................................... 8-1

UNION CARBIDE HYDROFORMYLATION TECHNOLOGY .................................... 8-2

PROCESS DESCRIPTION ........................................................................................ 8-3

Methanolysis............................................................................................................... 8-6

Hydroformylation ........................................................................................................ 8-7

Hydrogenation ............................................................................................................ 8-7

Polymerization ............................................................................................................ 8-8

PROCESS DISCUSSION........................................................................................... 8-22

Plant Capacity............................................................................................................. 8-22

Methanolysis Design .................................................................................................. 8-22

Hydroformylation Design ............................................................................................ 8-23

On-Steam Factor ........................................................................................................ 8-23

Waste Treatment ........................................................................................................ 8-23

CAPITAL AND PRODUCTION COSTS ..................................................................... 8-24

DISCUSSION OF CAPITAL COST AND PRODUCT VALUE.................................... 8-25

Capital-Related Elements........................................................................................... 8-25

Soybean Oil Cost........................................................................................................ 8-25

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

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CONTENTS (Concluded)

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

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FIGURES

2.1 Soy-Based Polyols by Hydroformylation ............................................................... 2-5

3.1 U.S. Polyether Polyol Prices ................................................................................. 3-2

3.2 Crude Vegetable Oil Prices ................................................................................... 3-7

4.1 Schematic Representation of the Soy-Polyol Structure ........................................ 4-3

4.2 Production of Epoxidized Oils ............................................................................... 4-4

4.3 Cross Counter Continuous Epoxidation Process.................................................. 4-5

4.4 Methanolysis Process ........................................................................................... 4-7

4.5 Hydroformylation Process ..................................................................................... 4-7

4.6 Hydrogenation Process ......................................................................................... 4-7

4.7 Polymerization Process......................................................................................... 4-8

4.8 Gellation Reactivity of Various Polyols.................................................................. 4-9

5.1 Oilseed Processing................................................................................................ 5-2

5.2 Oilseed Screw Press ............................................................................................. 5-5

5.3 Belt Percolation Extrator........................................................................................ 5-6

5.4 Soybean Processing.............................................................................................. E-3

5.5 Total Fixed Capital Vs. Soybean Capacity............................................................ 5-19

5.6 Prices Received For Us Soybeans ....................................................................... 5-20

6.1 Soyol Product Specifications................................................................................. 6-2

6.2 Blown Soybean Oil ................................................................................................ E-7

7.1 Epoxidized Oils...................................................................................................... 7-1

7.2 Bioh Viscosity Vs Temperature ............................................................................. 7-3

7.3 Soy-Based Polyols by Ring Opening Oligomerization .......................................... E-9

7.4 Polyol Product Value Vs Epoxidized Soybean Oil Price ....................................... 7-10

8.1 Four Step Process For Producing Polyols From Seed Oils .................................. 8-2

8.2 Separation and Recovery of Aldehyde From Non-Aqueous Hydroformylation .... 8-3

8.3 Soy-Based Polyols by Hydroformylation ............................................................... E-11

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TABLES

2.1 U.S. Soybean Oil Use For Industrial Purposes ..................................................... 2-3

2.2 Capital Investment Comparison-Soy-Based Polyols ............................................ 2-6

2.3 Soy-Based Polyols Manufacturing Cost Summary............................................................................... 2-8

3.1 2006 NAFTA Polyether Urethane Polyols Consumption ...................................... 3-1

3.2 U.S. Soybean Oil Use For Industrial Purposes ..................................................... 3-3

3.3 Estimated U.S. 2006 Demand For Soy-Beased Polyols....................................... 3-3

3.4 U.S. Soy Based Polyol Companies ....................................................................... 3-5

3.5 2007 U.S. Polyol Prices......................................................................................... 3-6

4.1 Compositions of Selected Natural Oils.................................................................. 4-2

4.2 Typical Expoxidized Oil Properties........................................................................ 4-4

4.3 Bio-Based Polyols Patent Summary.................................................................................................... A-1

4.4 Typical Properties of Oleochemical Polyols Based on Fatty Acid Esters ............. 4-8

4.5 Odor Properties of Hydroperoxides and Epoxides Identified in Stored SoybeanOil ............................................................................................................ 4-10

4.6 Mechanical Properties of Benchmark Foam Vs 40% Soy Foam .......................... 4-11

5.1 Average Compositions for Crude and Refined Soybean Oil................................. 5-8

5.2 Oilseed World Crushings....................................................................................... 5-9

5.3 Canadian Oilseed Crushing Facilities ................................................................... 5-10

5.4 Soybean Processing Design Bases ........................................................................................................ 5-12

5.5 Soybean Processing Major Equipment ................................................................................................... 5-13

5.6 Soybean Processing Utilities Summary................................................................................................... 5-15

5.7 Approximate Soybean Composition ...................................................................... 5-16

5.8 Soybean Processing Waste Streams.................................................................... 5-17

5.9 Soybean Processing Total Capital Investment........................................................................................ 5-21

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TABLES (Continued)

5.10 Soybean Processing Capital Investment by Section............................................................................... 5-22

5.11 Soybean Processing Production Costs ................................................................................................... 5-23

5.12 Soybean Processing Direct Costs by Section ......................................................................................... 5-25

6.1 Soyol Viscosity Vs Temperature ........................................................................... 6-2

6.2 Blown Soybean Oil Design Bases ........................................................................................................ 6-4

6.3 Blown Soybean Oil Stream Flows......................................................................................................... 6-6

6.4 Blown Soybean Oil Major Equipment ................................................................................................... 6-7

6.5 Blown Soybean Oil Utilities Summary................................................................................................... 6-8

6.6 Soyol Properties Versus US 6,759,542................................................................. 6-9

6.7 Blown Soybean Oil Total Capital Investment........................................................................................ 6-11

6.8 Blown Soybean Oil Production Costs ................................................................................................... 6-12

7.1 Properties of Palm-Based Polyols......................................................................... 7-2

7.2 BIOHTM Typical Properties..................................................................................... 7-2

7.3 Soy-Based Polyols by Ring-Opening Oligomerization Design Bases ........................................................................................................ 7-4

7.4 Soy-Based Polyols by Ring-Opening Oligomerization Stream Flows......................................................................................................... 7-5

7.5 Soy-Based Polyols by Ring-Opening Oligomerization Major Equipment ................................................................................................... 7-6

7.6 Soy-Based Polyols by Ring-Opening Oligomerization Utilities Summary................................................................................................... 7-7

7.7 BIOH Properties Versus WO 2006/116456........................................................... 7-8

7.8 Soy-Based Polyols by Ring-Opening Oligomerization Total Capital Investment........................................................................................ 7-11

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TABLES (Concluded)

7.9 Soy-Based Polyols by Ring-Opening Oligomerization Production Costs ................................................................................................... 7-12

8.1 Soy-Based Polyols by Hydroformylation Design Bases ........................................................................................................ 8-5

8.2 Soy-Based Polyols by Hydroformylation Stream Flows......................................................................................................... 8-9

8.3 Soy-Based Polyols by Hydroformylation Major Equipment ................................................................................................... 8-17

8.4 Soy-Based Polyols by Hydroformylation Utilities Summary................................................................................................... 8-21

8.5 Soy-Based Polyols by Hydroformylation Total Capital Investment........................................................................................ 8-26

8.6 Soy-Based Polyols by Hydroformylation Capital Investment by Section............................................................................... 8-27

8.7 Soy-Based Polyols by Hydroformylation Production Costs ................................................................................................... 8-29

8.8 Soy-Based Polyols by Hydroformylation Direct Costs by Section ......................................................................................... 8-31