Currently, 1,3-butadiene is almost entirely produced as a by-product from the ethylene steam cracking of naphtha or gas oil feedstocks. A switch to lighter feedstocks has reduced the amount of butadiene available from ethylene cracking. Foreseeable market demand for on-purpose butadiene will increase as ethane for cracking is exported from the United States. The small amount of butadiene produced during steam cracking of light feedstocks is not economically recoverable.
The demand for 1,3 butadiene continues to grow, driven primarily by the development of demand in the emerging markets, especially for motor vehicle tires. As a result of the decline in supply and the growth trend in demand, the price of butadiene more than doubled in 2008, and again in 2011, but has been volatile since, dropping to a range about one-third to one-fourth the 2012 peak price. These supply and price conditions have renewed interest in on-purpose butadiene production.
PEP Report 35E (2012) presented the process economics for two commercially successful processes: n-butane dehydrogenation based on the Lummus Catadiene® process, and mixed butenes oxidative dehydrogenation based on the TPC Oxo-D™ process. We also presented process economics for our version of the American Process, developed by Carbide and Carbon Chemicals Corporation in the 1940s, which converts ethanol to butadiene. Purification of the crude butadiene product by NMP extraction was covered as a separate process.
In PEP Report 35F, we concentrate on new processes. We first review proven or potential technologies for producing 1,3-butadiene. Since 2011, emphasis has been on developments for dehydrogenation of n-butane or mixed butenes feedstocks. Based on our concept of the processes from patent information, process economics are then developed for producing 100,000 mt/year of 1,3-butadiene by two new oxidative dehydrogenation processes, processes that react linear butenes to crude butadiene products. The first process is a low energy intense process disclosed by TPC. The second process uses a dual catalyst system disclosed by SK Energy, but with a conventional oxidative dehydrogenation flowsheet used in PEP Report 35E.

1. Introduction 1

2. Conclusions 3

3. Summary 5

Commercial aspects 5

Technology 7

Process economics 9

4. Industry status 13

Uses 14

Butadiene demand 16

Butadiene supply 19

      Crude C4 20

      Extraction capacity utilization 22

      On-purpose butadiene 22

Prices 23

      Mixed C4s 23

      1,3 Butadiene 24

Specifications 27

      C4 Stream 27

      1,3 Butadiene 28

Plant capacity 30

New capacity 37

5. Chemistry 39

Direct dehydrogenation reactions 39

Oxidative dehydrogenation reactions 41

Dehydrogenation reaction equilibrium and kinetics 42

      Mars Van Krevelen mechanism 46

      Kinetics over VOx catalyst 47

      Kinetics of H-MFI zeolite 47

CO2 oxidant 48

Dehydrogenation Catalysts 50

Catalysts 51

Direct Dehydrogenation Catalysts 51

Oxidative dehydrogenation Catalysts 59

Crude butadiene composition 75

6. Process review 77

Direct Dehydrogenation Processes 78

      Catadiene (Houdry) Process 78

      Isobutene tolerant process 80

Oxidative Dehydrogenation Processes 80

      Feedstock 82

      TPC Oxo-D 82

      SK Energy 84

      Mitsubishi 86

      LG 90

      BASF 91

      Asahi Kasei 92

      China Petroleum & Chemical 93

      Wison Engineering 94

      JSR Corporation 95

Other R&D Stage Processes 95

      Combined oxidation and non-oxidation 95

      Membrane processes 95

      Monolith catalyst process 97

      Carbon monoxide based butadiene 97

      Rapid pressure swing reaction process 97

      Radiation assisted 97

Selective Hydrogen Combustion 97

      Reactors 99

Butadiene Reactivity and instability 100

      Inhibitors 101

      Polymerization 101

      Material of construction 102

7. Low energy oxidative dehydrogenation process 104

Process description 104

Process discussion 117

      Feedstock 118

      Reactor 118

      Product 120

      Emissions 120

Cost estimates 120

      Capital cost 121

      Production Costs 126

      Profitability 132

8. Dual bed process 133

Process description 133

Process discussion 145

      Feedstock 145

      Reactor 146

      Catalyst 146

      Downstream 147

      Product 147

      Emissions 148

Cost estimates 148

      Capital Cost 148

      Production Costs 153

      Profitability 159

Appendix A: Patent summary tables 160

Appendix B: Design and cost bases 193

Design conditions 193

Cost bases 193

Appendix C: Cited references 198

Appendix D: Patent references by company 230

Appendix E: Process flow diagrams 239

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