Advances in Adiponitrile (ADN) and Hexamethylenediamine (HMDA) Processes

Report 31C

Table of Contents

Section Page Number

Introduction 1-1
What are adiponitrile and hexamethylenediamine? 1-1
Molecular structure 1-2
Hydrogenation of adiponitrile to form HMDA1-2
Reaction to form nylon 66 1-2
Commercial uses for ADN and HMDA1-3
Commercial uses for nylon 66 1-3
Nylon 66 integrated product chain diagram1-4
Physical properties of ADN and HMDA 1-5
Process safety 1-8
Adiponitrile 1-9
Hexamethylenediamine 1-9
Hydrogen 1-9
Butadiene 1-10
Acrylonitrile 1-10
Nylon market overview 1-10
ADN and HMDA production overview1-11
ADN and HMDA product grades and specifications 1-12
Adiponitrile 1-12
Hexamethylenediamine 1-13
Prior PEP reports on HMDA and ADN 1-13
Summary 2-1
Process safety 2-4
Supply and demand 2-5
Nylon demand 2-5
HMDA demand 2-5
ADN demand 2-6
Ascend/Monsanto Electro-dimerization of Acrylonitrile to HMDA2-10
Rennovia HMDA process 2-11
ADN and HMDA industry status 3-1
Uses of ADN and HMDA 3-1
Uses of nylon 66 3-2
Inter-material substitution between nylon 66 and nylon 63-2
Polymer inter-material substitution3-3
Other forms of polyamide 3-5
Market desire for bio-based nylon 3-5
Adiponitrile demand 3-6
Hexamethylenediamine demand 3-7
ADN and HMDA producers 3-8
Regional distribution of capacity 3-10
ADN and HMDA announced changes in capacity3-11
Demand growth for ADN and HMDA3-12
Nylon 66 product pricing 3-13
Fundamental energy and feedstock costs 3-13
Butadiene pricing outlook 3-14
Acrylonitrile pricing outlook 3-15
Invista legal proceedings 3-17
Chemistry and process technology 4-1
Chemical structure of adiponitrile and hexamethylenediamine 4-1
Chemical reaction for producing nylon 66 4-1
Nylon 66 process summary 4-1
Nylon 66 historical background 4-2
Technology basis for nylon 66 competing with nylon 6 4-3
Chemical reactions for hydrogenating ADN to HMDA4-4
Hydrogen cyanide production 4-4
Hydrogen cyanide properties 4-4
HCN safety considerations 4-5
Commercial HCN uses 4-6
Commercial HCN production technologies4-6
Process description 4-7
Adiponitrile from butadiene via DuPont/Invista hydrocyanation 4-8
Background 4-8
Chemistry 4-8
Block flow diagram 4-10
Adiponitrile from acrylonitrile by electrodimerization 4-12
Chemistry 4-12
Process technology 4-12
HMDA from acrylonitrile via electrohydrodimerization in solution 4-12
HMDA from acrylonitrile via electrohydrodimerization in emulsion 4-14
HMDA from acrylonitrile via electrohydrodimerization in an undivided cell 4-16
Adiponitrile from adipic acid 4-18
Chemistry 4-18
Process technology 4-18
HMDA from biomass via Rennovia processing4-19
Chemistry 4-20
Process technology 4-21
Other HMDA production processes 4-21
HMDA from butadiene via direct chlorination4-21
HMDA from adipic acid and hydroxycaproic acid4-23
Hexamethylenediamine and caprolactam from adiponitrile by partial hydrogenation and cyclization of aminocapronitrile 4-23
Process Design Basis 5-1
Process safety 5-1
Hexamethylenediamine (HMDA) 5-1
Adiponitrile (ADN) 5-2
Acrylonitrile 5-2
Hydrogen 5-3
Butadiene 5-3
Hydrogen cyanide 5-3
Ammonia (NH3) 5-4
Business objectives 5-4
Scope of project 5-5
Design philosophy 5-6
Design priorities 5-6
Process safety 5-7
Operating reliability 5-7
Environmental emission conformance5-7
Hazardous waste incineration 5-9
Flexibility for economic optimization 5-9
Ease of operations and maintenance5-9
Scheduled plant turnarounds 5-10
Reciprocating machinery drivers 5-10
Maximum return on investment 5-10
Buildings 5-11
Security and vulnerability analysis5-11
Production design criteria 5-12
Plant location factor 5-12
PEP capital cost factor 5-13
Regulatory environment and EH&S standards 5-14
Construction methodology 5-14
Off-site facilities 5-15
Black start capability 5-15
Process control philosophy 5-16
Project to provide machine condition monitoring instrumentation 5-16
Materials of construction 5-16
Engineering and design standards 5-17
Site specific design conditions 5-17
Capital and operating cost bases 5-18
Capital investment 5-18
Project construction timing 5-19
Available utilities 5-19
Production cost factors 5-20
Feedstock, product, and energy pricing5-20
Effect of operating level on production costs 5-21
Project design capacity 5-22
Feedstock and product specifications5-22
Hexamethylenediamine 5-22
Adiponitrile 5-23
Butadiene 5-23
Acrylonitrile 5-23
HMDA and ADN via Invista butadiene processing6-1
Butadiene hydrocyanation technology background 6-1
Invista the company 6-1
Invista next-generation adiponitrile technology 6-2
Intended commercialization of Invista ADN technology6-2
Hydrogen cyanide production 6-3
Andrussow HCN process chemistry6-4
Andrussow process design 6-5
Andrussow HCN reactor design 6-5
Reaction gas purification 6-8
Development status of Invista ADN process technology6-9
Invista's HMDA and ADN patent position6-10
Major characteristics of Invista butadiene-based patents and applications6-11
Hydrocyanation catalyst composed of Group VIII metal and phosphonite ligand 6-13
Butadiene feed pretreatment 6-15
Process configuration of Invista hydrocyanation of butadiene 6-16
Hydrocyanation of butadiene to form mononitriles (first hydrocyanation reaction) 6-18
Distillation of reactor products from butadiene hydrocyanation reaction 6-20
Isomer properties 6-22
Isomerization of 2M3BN to 3PN 6-23
Distillation of reactor products from isomerization reactor6-24
Hydrocyanation of 3PN to produce crude ADN6-25
Liquid:liquid extraction of hydrocyanation reactor product6-27
Crude adiponitrile product purification by distillation 6-27
Adiponitrile hydrogenation to HMDA6-28
Historical development 6-28
IHS Markit Design basis for ADN hydrogenation to HMDA6-29
Hydrocyanation catalyst purification and recycle system6-30
Contaminant removal from homogeneous catalyst by liquid-liquid extraction6-30
Contaminated ADN polar solvent recovery scheme6-31
Crude HMDA purification by distillation versus crystallization 6-32
Process description 6-33
Plant sections 6-33
Section 100—hydrogen cyanide (HCN) production6-33
Section 200—butadiene hydrocyanation to 3PN6-35
Section 300—3PN hydrocyanation to ADN6-36
Section 400—ADN hydrogenation to HMDA6-37
Section 500—catalyst purification and recycle6-38
Stream-by-stream material balance 6-39
Equipment list with duty specifications 6-52
Itemized capital cost 6-59
Total fixed capital cost estimate 6-68
Production cost estimate 6-69
Economic analysis 6-74
Monsanto/Ascend process for making HMDA from acrylonitrile7-1
Ascend Performance Materials 7-1
Ascend's capital plans 7-2
Monsanto/Ascend chemistry 7-2
Electrochemical cell arrangement 7-4
Process design 7-5
Adiponitrile from acrylonitrile via electrohydrodimerization in an undivided cell7-5
Feedstock composition 7-6
Process configuration 7-6
Process description/PFDs 7-7
Section 100—electrodimerization and aqueous phase treatment 7-8
Section 200—adiponitrile purification 7-9
Section 400—ADN hydrogenation to HMDA 7-10
Stream-by-stream material balance 7-11
Equipment list with duty specifications 7-18
Itemized capital cost estimate 7-23
Total fixed capital cost estimate 7-29
Production cost estimate 7-30
Economic analysis 7-34
Bio-based HMDA via Rennovia process technology8-1
Introduction 8-1
Other bio nylon developers 8-1
Rennovia feedstock 8-2
Rennovia intellectual property 8-4
Conversion of HFCS-90 to HMF 8-5
US Patent 6743928 (International Furan Technology) 8-8
US Patent 6518440 (Lightner) 8-10
World Patent 2011 / 149339 (Netherlands Organization for Scientific Research) 8-12
Commercially available 5-HMF 8-12
IHS Markit HMF production design approach 8-13
Hydrogenation of HMF to 1,2,6-Hexanetriol and 1,6-Hexanediol 8-18
Ammoniation of 1,6-hexanediol to HMDA 8-24
Rennovia input/output and block flow diagrams8-26
Process description 8-27
Section 100 – Hydroxymethylfurfural from HFCS by dehydration 8-28
Section 200 – Hydrogenation of HMF to 1,2,6-Hexanetriol 8-30
Section 300 – Hydrogenation of 1,2,6-Hexanetriol to 1,6-Hexanediol 8-31
Section 400 – Ammoniation of 1,6-Hexanediol to HMDA8-32
Section 500 – HMDA Purification 8-35
Stream by stream material balance 8-36
Equipment List 8-52
Itemized capital cost estimate 8-58
Total fixed capital cost estimate 8-66
HMDA production cost 8-68
Variable raw material production cost8-68
Variable utility production cost 8-69
Economic analysis 8-72
Appendix A: Patent summary table A-1
Appendix B: References B-1
Appendix C: Invista block flow diagram C-1
Appendix D: Process flow diagramsD-1
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