Abstract Process Economics Program Report 35E ON-PURPOSE BUTADIENE PRODUCTION (December 2012) 1,3-Butadiene is currently almost entirely produced as a by-product of ethylene steam cracking of naphtha or gas oil feedstocks. A switch to lighter feedstocks has reduced the amount of butadiene available from ethylene cracking and presented a foreseeable market demand for on-purpose butadiene. 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 decreasing trend in supply and the growth trend in demand, the price of butadiene has risen significantly and been volatile. Today there is growing interest in producing butadiene from renewable resources. These conditions have renewed interest in on-purpose butadiene production. In this PEP Report, we first extensively review proven or potential technologies for producing 1,3-butadiene, whether commercial or in the research or development stage such as processing renewable feedstocks. Emphasis is on developments since 1990 for n-butane and mixed butenes feedstocks. The process economics are then developed in this PEP Report for producing 100,000 mt/year of 1,3-butadiene by two currently commercially successful processes: n-butane dehydrogenation and mixed butenes oxidative dehydrogenation. We also develop the process economics for our version of the American Process, a two-stage ethanol to butadiene process developed by Carbide and Carbon Chemicals Corporation in the 1940s. These three processes have demonstrated the most commercial success. © 2012 IHS PEP Report 35E A private report by the Process Economics Program Report No. 35E ON-PURPOSE BUTADIENE PRODUCTION by Richard H. 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CONTENTS 1 INTRODUCTION ........................................................................................................ 1-1 2 CONCLUSION ........................................................................................................... 2-1 3 SUMMARY ................................................................................................................. 3-1 COMMERCIAL ASPECTS ......................................................................................... 3-1 TECHNOLOGY .......................................................................................................... 3-2 PROCESS ECONOMICS ........................................................................................... 3-4 4 INDUSTRY STATUS .................................................................................................. 4-1 USES .......................................................................................................................... 4-2 DEMAND .................................................................................................................... 4-3 SUPPLY...................................................................................................................... 4-8 Northeast Asia ............................................................................................................ 4-13 North America ............................................................................................................. 4-13 Europe ........................................................................................................................ 4-14 Commonwealth of Independent States and Baltic States .......................................... 4-14 Southeast Asia ........................................................................................................... 4-15 Middle East ................................................................................................................. 4-15 South America ............................................................................................................ 4-15 Indian Subcontinent .................................................................................................... 4-15 Africa ........................................................................................................................... 4-15 On-Purpose Production .............................................................................................. 4-15 PRICES ...................................................................................................................... 4-16 Feedstock ................................................................................................................... 4-16 Butadiene.................................................................................................................... 4-18 HANDLING ................................................................................................................. 4-21 SPECIFICATIONS ...................................................................................................... 4-21 Mixed C4 Streams ....................................................................................................... 4-21 1,3-Butadiene ............................................................................................................. 4-22 PLANT CAPACITY ..................................................................................................... 4-24 NEW CAPACITY ........................................................................................................ 4-31 © 2012 IHS iii PEP Report 35E CONTENTS (Continued) 5 CHEMISTRY REVIEW ............................................................................................... 5-1 BUTADIENE REACTIVITY AND INSTABILITY ......................................................... 5-1 Inhibitors ..................................................................................................................... 5-1 Polymerization ............................................................................................................ 5-2 Material of Construction .............................................................................................. 5-3 DEHYDROGENATION REACTION ........................................................................... 5-4 n-Butane Dehydrogenation Mechanism with Ga-ZSM-5 ............................................ 5-6 t-2-Butene Dehydrogenation Mechanism on Pd(110) ................................................ 5-10 Oxidative Dehydrogenation ........................................................................................ 5-11 DEHYDROGENATION REACTION EQUILIBRIUM AND KINETICS ........................ 5-12 DEHYDROGENATION CATALYSIS .......................................................................... 5-17 Adsorption on Pt(111) ................................................................................................. 5-17 Catalysts ..................................................................................................................... 5-17 Bismuth Molybdenum Catalysts ............................................................................ 5-23 Ferrite Catalysts .................................................................................................... 5-24 Pyrophosphate Catalysts ....................................................................................... 5-25 Vanadium Catalysts ............................................................................................... 5-25 Precious Metal Catalysts ....................................................................................... 5-27 Carbon ................................................................................................................... 5-28 Other Catalysts ...................................................................................................... 5-28 CRUDE BUTADIENE COMPOSITION ...................................................................... 5-29 BIO-ETHANOL COMPOSITION................................................................................. 5-30 ETHANOL TO BUTADIENE ....................................................................................... 5-31 6 PROCESS REVIEW ..................................................................................................