Report 94A Specialty Polyamides 11 and 12

IHS Chemical

Process Economics Program

By Richard H. Nielsen with a contribution by R. J. Chang

IHS Chemical Process Economics Program | Report 94A

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PEP Report 94A

Specialty Polyamides 11 and 12

By Richard H. Nielsen with a contribution by R. J. Chang

December 2013

Abstract

A severe shortage of polyamide 12 developed in 2012 when a fatal explosion occurred at Evonik’s Marl, Germany cyclododecatriene (CDT) plant. CDT is a feedstock for laurolactam, the monomer to produce polyamide 12. This event triggered a search for alternative polyamides to supply the automotive industry for several applications including fuel tanks and brake lines. Polyamide 12 also finds applications in solar panels and in cable coverings for offshore oil and gas production.

Polyamide producers proposed the use of other specialty polyamides as alternatives to polyamide 12 including polyamides 6/10, 6/12, 10/10, 10/12, and 11. Higher polyamides like polyamides 11 and 12 offer better resistance to humidity, enhanced mechanical and thermal properties and more resistance to most common acids and solvents than do PA 6 or PA 6/6. PA 11 and PA 12 can be extruded, molded, made into film, or used in fibers.

PA 11 is a renewable polymer made from 11-aminoundecanoic acid obtained from castor oil. Sebacic acid, a monomer that is polymerized with diamines to produce a couple higher polyamides, is also made from castor oil.

In this PEP report, we first review proven or potential technologies for producing polyamides 11 and 12, the major commercial specialty polyamides. We then review processes for making the major acidic monomers for specialty polyamides: 11-aminoundodecanoic acid (PA 11), laurolactam (PA-12), dodecanedioic acid (PA 6/12, PA 10/12, and PA12/12), and sebacic acid (PA 6/10 and PA 10/10). Working back the supply chain to 1,3-butadiene raw material we also review technology for cyclododecatriene (CDT) and cyclododecane (CDAN), intermediates for laurolactam (CDAN), dodecanedioic acid and sebacic acids.

We then develop the process economics for producing PA 11 and PA 12 and the monomers: laurolactam from CDAN, two dodecanedioic acid processes reacting CDT and sebacic acid made from castor oil. Process economics are also developed for the CDT and CDAN intermediates.

Contents

1. Introduction ...... 1-1 2. Conclusions ...... 2-1 3. Summary ...... 3-1 Commercial aspects ...... 3-1 Technical aspects ...... 3-2 Economic aspects ...... 3-4 4. Industry status ...... 4-1 PA 6 and PA 66 supply and demand ...... 4-1 PA 6 capacity ...... 4-1 PA 66 capacity ...... 4-2 Major producers ...... 4-2 Demand ...... 4-4 Specialty polyamides supply and demand ...... 4-6 Specialty polyamide capacity ...... 4-7 Demand for specialty polyamides ...... 4-9 Bio-polyamides ...... 4-10 End-use applications ...... 4-10 Monomer and intermediates supply ...... 4-12 CDT (cyclododecatriene) capacity ...... 4-12 Dodecanedioic acid capacity ...... 4-13 Sebacic acid capacity ...... 4-13 Specifications ...... 4-14 1,3-Butadiene ...... 4-15 Castor oil ...... 4-17 Sebacic acid ...... 4-19 Prices ...... 4-20 Butadiene ...... 4-20 Castor oil ...... 4-21 Polyamide 12 ...... 4-22 Polyamide 11 ...... 4-22 Dodecanedioic acid ...... 4-22 5. Polyamides 11 and 12 ...... 5-1 Polyamide properties ...... 5-1 Polyamide 12 ...... 5-2 Polyamide 11 ...... 5-6 Nomenclature ...... 5-9 Chemistry ...... 5-10 Polyamide reaction mechanisms ...... 5-11 Polyamide 12 hydrolytic polymerization ...... 5-13 Ring opening mechanism ...... 5-14

Contents (continued)

Polyamide 12—ionic polymerization ...... 5-16 Polyamide 11...... 5-17 Renewable raw materials ...... 5-17 Castor oil ...... 5-18 11-aminoundecanoic acid...... 5-18 Research ...... 5-19 Ageing ...... 5-20 Process review ...... 5-21 Fiber production requirements ...... 5-21 Plastics production requirements ...... 5-22 Solid-phase polymerization ...... 5-23 Polyamide-12 ...... 5-23 Polyamide 11 ...... 5-24 Process economics ...... 5-25 Polyamide 12 ...... 5-25 Process description ...... 5-25 Process discussion ...... 5-29 Cost estimates ...... 5-30 Capital costs ...... 5-30 Production costs ...... 5-32 Profitability ...... 5-35 Polyamide 11 ...... 5-35 Process description ...... 5-35 Process discussion ...... 5-41 Cost estimates ...... 5-42 Capital costs ...... 5-42 Production costs ...... 5-43 Profitability ...... 5-47 6. Laurolactam ...... 6-1 Chemistry ...... 6-1 Four step process ...... 6-1 Direct photo oximation process ...... 6-2 Beckmann rearrangement ...... 6-3 SNIA Viscosa process ...... 6-4 New processes ...... 6-4 Process review ...... 6-5 Degussa process ...... 6-5 Ube Industries ...... 6-5 Ube Industries-EMS process ...... 6-5 Ube Industries-BP process ...... 6-6

Contents (continued)

Ube Industries new process ...... 6-7 Arkema ...... 6-8 Process economics ...... 6-8 Process description ...... 6-9 Oxidation of CDAN to CDOL (Section 100) ...... 6-22 Dehydrogenation of CDOL to CDON (Section 200) ...... 6-23 Conversion of CDON to CDON oxime (Section 300) ...... 6-23 Rearrangement of CDON oxime to laurolactam (Section 400) ...... 6-23 Purification of laurolactam (Section 500) ...... 6-24 Ammonium sulfate recovery (Section 600) ...... 6-24 Process discussion ...... 6-24 Recovery of boric acid ...... 6-25 Recovery of unreacted CDAN ...... 6-25 Oximation...... 6-25 Hydroxylamine sulfate ...... 6-25 Ammonium sulfate by-product handling ...... 6-26 Laurolactam handling ...... 6-26 Tempered water system ...... 6-27 Cost estimates ...... 6-27 Capital costs ...... 6-27 Production costs ...... 6-31 Profitability ...... 6-34 7. 1,5,9-Cyclododecatriene and cyclododecane ...... 7-1 Chemistry ...... 7-1 Mechanism ...... 7-3 Process review ...... 7-4 Cyclododecatriene ...... 7-4 Cyclododecane ...... 7-5 Process economics of 1,5,9-cyclododecatriene ...... 7-5 Process description ...... 7-5 Materials preparation (Section 100) ...... 7-11 Reaction section (Section 200)...... 7-11 Separation section (Section 300) ...... 7-11 Process discussion ...... 7-12 Cost estimates ...... 7-13 Capital costs ...... 7-13 Production costs ...... 7-17 Profitability ...... 7-20 Process economics of cyclododecane ...... 7-20 Process description ...... 7-20

Contents (continued)

Materials preparation (Section 100) ...... 7-26 Reaction section (Section 200)...... 7-26 Separation section (Section 300) ...... 7-27 Hydrogenation (Section 400) ...... 7-27 Process discussion ...... 7-27 Cost estimates ...... 7-28 Capital costs ...... 7-29 Production costs ...... 7-32 Profitability ...... 7-36 8. Dodecanedioic acid ...... 8-1 Chemistry ...... 8-1 Process review ...... 8-3 From cyclododecatriene via cyclododecane ...... 8-4 From cyclododecatriene via cyclododecene ...... 8-4 From castor oil or ricinoleic acid ...... 8-5 From other feedstocks...... 8-5 Process economics ...... 8-6 Via cyclododecane ...... 8-6 Process description ...... 8-6 CDAN hydrogenation (Section100) ...... 8-16 Oxidation of CDAN (Section 200) ...... 8-16 Cyclododecanol separation (Section 300) ...... 8-17 Acid oxidation (Section 400) ...... 8-17 Acid separation (Section 500) ...... 8-17 Dodecanedioic acid purification (Section 600) ...... 8-17 Process discussion ...... 8-18 Cost estimates ...... 8-19 Capital costs ...... 8-19 Production costs ...... 8-22 Profitability ...... 8-25 Via cyclododecene ...... 8-25 Process description ...... 8-25 Cyclododecatriene hydrogenation section (Section 200) ...... 8-29 1,12-Dodecanedioic acid production (Section 300) ...... 8-29 Process discussion ...... 8-30 Cost estimates ...... 8-30 Capital costs ...... 8-30 Production costs ...... 8-33 Profitability ...... 8-39 9. Sebacic acid ...... 9-1

Contents (concluded)

Chemistry ...... 9-1 Process review ...... 9-2 Process economics ...... 9-3 Process description ...... 9-3 Reaction (Section 100) ...... 9-9 Octanol recovery (Section 200) ...... 9-9 Sebacic acid recovery (Section 300) ...... 9-9 By-produced acids (Section 400) ...... 9-10 Process discussion ...... 9-10 Cost estimates ...... 9-11 Capital costs ...... 9-11 Production costs ...... 9-15 Profitability ...... 9-18 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 diagrams ...... E-1

Figures

4.1 World 2012 PA 6 capacity by region ...... 4-1 4.2 World 2012 PA 66 capacity by region ...... 4-2 4.3 World 2012 PA 6 demand by end-use applications...... 4-5 4.4 World 2012 PA 6 demand by region ...... 4-5 4.5 World 2012 PA 66 demand by end-use applications ...... 4-6 4.6 World 2012 PA 66 demand by region ...... 4-6 4.7 Relationship between chain length of repeating unit and physical properties ...... 4-11 4.8 Butadiene spot price history by region ...... 4-21 4.9 Castor oil price history ...... 4-22 4.10 Dodecanedioic acid price history ...... 4-23 5.1 Polyamide 12 chip manufacture ...... E-3 5.2 Polyamide 11 chip manufacture ...... E-5 6.1 Structure of laurolactam ...... 6-1 6.2 Ube Industries new laurolactam process ...... 6-7 6.3 Laurolactam from cyclododecane via cyclododecanone ...... E-7 7.1 1,5,9-Cyclododecatriene stereoisomers ...... 7-1 7.2 Ziegler catalyst π-bonding ...... 7-3

7.3 Conversion of three butadiene molecules to C12 ring in cyclododecatriene formation ...... 7-3 7.4 Formation of cyclododecatriene by-products ...... 7-4 7.5 Cyclododecatriene from butadiene ...... E-13 7.6 Cyclododecane from butadiene via cyclododecatriene ...... E-15 8.1 Routes to dodecanedioic acid ...... 8-2 8.2 Products of selective hydrogenation of epoxycyclododecadiene ...... 8-3 8.3 Dodecanedioic acid from cyclododecatriene via cyclododecane ...... E-17 8.4 Cyclododecatriene via cyclodedecene ...... E-21 9.1 Sebacic acid from castor oil 20 million lb/yr at 0.9 stream factor ...... E-25

Tables

1.1 Polyamides and starting monomers ...... 1-1 1.2 Physical properties of polyamides ...... 1-2 3.1 Summary of cost estimates for polyamides 11 and 12 and specialty polyamide monomers ...... 3-7 4.1 PA 6 major producers—2012 average annual capacities ...... 4-3 4.2 PA 66 major producers—2012 average annual capacities ...... 4-4 4.3 World 2012 specialty polyamides capacity ...... 4-7 4.4 Suppliers of polyamides 11 or 12 ...... 4-9 4.5 End-use applications for long chain polyamides ...... 4-12 4.6 Major dodecanedioic acid producers ...... 4-13 4.7 World sebacic acid capacity ...... 4-14 4.8 Examples of reactant and by-product specifications ...... 4-15 4.9 Example of a 1,3-butadiene product specification ...... 4-16 4.10 Typical specifications for butadiene ...... 4-17 4.11 Castor oil grades and specifications ...... 4-18 4.12 Commercial castor oil specifications ...... 4-18 4.13 Commercial and refined castor oil specifications ...... 4-19 4.14 Sebacic acid specifications ...... 4-20 5.1 Physical properties of polyamide 12 compared to polyamide 6 and polyethylene (in conditioned state unless otherwise stated) ...... 5-4 5.2 Effect of plasticizer on polyamide 12 ...... 5-6 5.3 Properties of polyamides 6, 11, and 12 ...... 5-8 5.4 Selected properties of plasticized and unplasticized polyamide 11 ...... 5-9 5.5 Selected properties of castor oil...... 5-18 5.6 Injection molding temperatures for polyamides 6, 11, and 12 ...... 5-22 5.7 Typical extrusion temperatures for polyamides 6 and 12 ...... 5-22 5.8 Polyamide 12 chip manufacture Design bases ...... 5-26 5.9 Polyamide 12 chip manufacture Stream flows ...... 5-26 5.10 Polyamide 12 chip manufacture Major equipment ...... 5-27 5.11 Polyamide 12 chip manufacture Utilities summary ...... 5-28 5.12 Polyamide 12 chip manufacture Total capital investment ...... 5-31 5.13 Polyamide 12 chip manufacture Production costs...... 5-32 5.14 Polyamide 12 product value sensitivity to feedstock cost ...... 5-35 5.15 Polyamide 11 chip manufacture Design bases ...... 5-37 5.16 Polyamide 11 chip manufacture Stream flows ...... 5-38

Tables (continued)

5.17 Polyamide 11 chip manufacture Major equipment ...... 5-39 5.18 Polyamide 11 chip manufacture Utilities summary ...... 5-40 5.19 Polyamide 11 chip manufacture Total capital investment ...... 5-43 5.20 Polyamide 11 chip manufacture Production costs...... 5-44 5.21 Polyamide 11 product value sensitivity to feedstock cost ...... 5-46 6.1 Laurolactam from cyclododecane via cyclododecanone Design bases ...... 6-10 6.2 Laurolactam from cyclododecane via cyclododecanone Stream flows ...... 6-12 6.3 Laurolactam from cyclododecane via cyclododecanone Major equipment ...... 6-19 6.4 Laurolactam from cyclododecane via cyclododecanone Utilities summary ...... 6-21 6.5 Laurolactam from cyclododecane via cyclododecanone Total capital investment ...... 6-29 6.6 Laurolactam from cyclododecane via cyclododecanone Capital investment by section ...... 6-30 6.7 Laurolactam from cyclododecane via cyclododecanone Production costs...... 6-31 6.8 Laurolactam product value sensitivity to feedstock cost ...... 6-34 6.9 Laurolactam from cyclododecane via cyclododecanone—no ammonium sulfate production case Production costs...... 6-35 7.1 Cyclododecatriene from butadiene Design bases ...... 7-6 7.2 Cyclododecatriene from butadiene Stream flows ...... 7-7 7.3 Cyclododecatriene from butadiene Major equipment ...... 7-9 7.4 Cyclododecatriene from butadiene Utilities summary ...... 7-10 7.5 Cyclododecatriene from butadiene Total capital investment ...... 7-15 7.6 Cyclododecatriene from butadiene Capital investment by section ...... 7-16 7.7 Cyclododecatriene from butadiene Production costs...... 7-17 7.8 Cyclododecatriene product value sensitivity to feedstock cost ...... 7-19 7.9 Cyclododecane from butadiene via cyclododecatriene Design bases ...... 7-21

Tables (continued)

7.10 Cyclododecane from butadiene via cyclododecatriene Stream flows ...... 7-22 7.11 Cyclododecane from butadiene via cyclododecatriene Major equipment ...... 7-24 7.12 Cyclododecane from butadiene via cyclododecatriene Utilities summary ...... 7-25 7.13 Cyclododecane from butadiene via cyclododecatriene Total capital investment ...... 7-30 7.14 Cyclododecane from butadiene via cyclododecatriene Capital investment by section ...... 7-31 7.15 Cyclododecane from butadiene via cyclododecatriene Production costs...... 7-33 7.16 Cyclododecane product value sensitivity to feedstock cost ...... 7-35 8.1 Dodecanedioic acid from CDT via cyclododecane Design bases ...... 8-7 8.2 Dodecanedioic acid from CDT via cyclododecane Stream flows ...... 8-8 8.3 Dodecanedioic acid from CDT via cyclododecane Major equipment ...... 8-14 8.4 Dodecanedioic acid from CDT via cyclododecane Utilities summary ...... 8-16 8.5 Dodecanedioic acid from CDT via cyclododecane Total capital investment ...... 8-20 8.6 Dodecanedioic acid from CDT via cyclododecane Capital investment by section ...... 8-21 8.7 Dodecanedioic acid from CDT via cyclododecane Production costs...... 8-22 8.8 Dodecanedioic acid product value sensitivity to feedstock cost ...... 8-24 8.9 Dodecanedioic acid from cyclododecatriene via cyclododecene Design bases ...... 8-26 8.10 Dodecanedioic acid from cyclododecatriene via cyclododecene Major equipment ...... 8-27 8.11 Dodecanedioic acid from cyclododecatriene via cyclododecene Utilities summary ...... 8-28 8.12 Dodecanedioic acid from cyclododecatriene via cyclododecene Total capital investment ...... 8-32 8.13 Dodecanedioic acid from cyclododecatriene via cyclododecene Capital investment by section ...... 8-33 8.14 Dodecanedioic acid from cyclododecatriene via cyclododecene Production costs...... 8-34 8.15 Dodecanedioic acid product value sensitivity to feedstock cost ...... 8-36 8.16 Dodecanedioic acid from CDT via cyclododecene—scaled to 20 mm lb/yr Production costs...... 8-38 8.17 Dodecanedioic acid product value—process comparison at 20 million lb/year ...... 8-39

Tables (concluded)

9.1 Sebacic acid from castor oil Design bases ...... 9-4 9.2 Sebacic acid from castor oil Stream flows ...... 9-5 9.3 Sebacic acid from castor oil Major equipment ...... 9-7 9.4 Sebacic acid from castor oil Utilities summary ...... 9-8 9.5 Sebacic acid from castor oil Total capital investment ...... 9-12 9.6 Sebacic acid from castor oil Capital investment by section ...... 9-13 9.7 Sebacic acid from castor oil Production costs...... 9-15 9.8 Sebacic acid product value sensitivity to feedstock cost ...... 9-17