petrochemistry BUTADIENE

1. petrochemistry BUTADIENE Kovács András, +36302114101, andras@kukk.hu, BME, FII, 2. em 6.

3. Properties. A colorless gas, with typical hydrocarbon smell, dangerous because of toxicity, reactivity, evaporative, flammability tendencies. MW: 54,09, BP: -4,4 oC, MP: -108,9 oC, Tcr:: 152 oC, Pcr: 42,8 bar 2 vol%<EL>11,5 vol% Solubility: H2O ppm Autoignition: 428,8 oC Toxicity: The Department of Health and Human Services (DHHS), the Internaltion Agency for Research on Cancer (IARC), and the EPA have determined that 1,3-butadiene is a human carcinogen. Studies have shown that workers exposed to 1,3-butadiene may have an increased risk of cancers of the blood and lymphatic system. Animal studies found increases in a variety of tumor types from exposure to 1,3-butadiene. Best source: Butadiene, Product Stewardship Gudiance Manual, 2010

6. Recent/2013 activities and construction decisions • OMV: “the synergies” Burghausen+new/2015- €230M- and Schwechat-upgrade/2014, • Versalis – Genomatica: JV for bio-based BD technology, • Invista Technologies: Arzeda's enzyme design and synthetic biology technology platform, • Global Bioenergies and Synthos, direct, gaseous fermentation process, • TCP Group – 2 US sites: shale gas based butadiene byproduct separation/2016 - flexible feedstock structure and meet demands • BASF new butadiene extraction at Verbund, Antwerp, Belgium, to address the short supplies of butadiene on global markets. Capacity: 155,000mtpa, Capex:” €double digit million” • 2011: PT Chandra Asri Petrochemical, $110 m, 100 kt/y (associated investment: $150 m LPG terminal) • Braskem builds 100 kt /y BD plant by 2013, (increase prodn cap. by 30%. Capex: $179m. Braskem's largest steam cracker in Camacari, Bahia produces 700 kt ethylene, 363 kt propylene 92 kt BD/y.

8. Popcorn (cauliflower) polymer formation: High concentration of conjugated dienes in vapor phase that contain some oxygen, but it was found in heat exchangers and distillation columns, where concentrations were lower and was free of oxygen. Rust and water can substitute air or peroxide in the vapor phase., Threaded joints are not recommended, but welded flanges. Popcorn polymers behave is just like pyrophoric compounds

9. Supply chain – • styrene-butadiene rubber (SBR: 28% of global use) • for automobile tyre and adhesives, sealants, coatings and rubber articles

10. Supply chain – • Polybutadiene(PB): 26%, tires and other polymers, plastics

11. Supply chain – • acrylonitrile-butadiene-styrene (ABS), 12%, an ouptut for PB, telephones, computer casings and other appliances. 

12. Supply chain – • styrene-butadiene latex (SBL), 12%, carpet, adhesives;

13. Supply chain – • styrene-butadiene block copolymers, 10%: asphalt modifiers (road and roofing), adhesives, footwear and toys.

14. Supply chain – • Adiponitrile, 6%, nylon6, nylon 6,6,

15. Supply chain – • nitrile rubber 4%, hoses, fuel lines, gasket seals, gloves and footwear

16. Supply chain – • Chemical intermediates: 1,4-hexadiene, sulfolane, nylon and other synthetic fibers

17. Supply chain – • Methyl methacrylate–butadiene–styrene (MMBS): autoparts, bottles, food packaging

18. Supply chain – • Chloroprene, 2%: gloves, coatings, adhesives, binders, sealants, tires, belts, hoses, faucet washers, footwear

19. 95% of global 9-10 Mt/y BD is obtained by this route Natural gas based steam cracking

20. Nafta based steam cracking

24. WO2013098760  (A1)  -  PROCESS FOR THE PRODUCTION OF 1,3-BUTADIENE, VERSALIS SPA: The present invention relates to a process for the production of 1, 3 -butadiene which comprises the following phases : a) extracting, by means of extractive distillation, in an extraction section, an end-product containing 1, 3 -butadiene and a raffinate product, starting from mixtures of saturated and unsaturated compounds having from 2 to 10 carbon atoms in the chain; b) sending the raffinate product to a dehydrogenation section; c) dehydrogenating the raffinate product in the dehydrogenation section in the presence of a dehydrogenation catalyst and an inert product so as to form a reaction effluent containing 1,3- butadiene; d) recirculating the reaction effluent containing 1, 3 -butadiene directly to the extraction section after separating the incondensable compounds.

29. Butane: 6.2% Butene-1: 79.2% t-2-butene: 10.4% c-2-butene: 4.2% BD<0.1% NT70 t-2-butene<0.1% c-2-butene: 2.2% BD:97.85

31. METHOD AND DEVICE FOR DISTILLATIVE EXTRACTION OF PURE 1,3-BUTADIENE FROM RAW 1,3-BUTADIENE, BASF SE two stage, fixed bed Tin: 30-60 CP: 0.6-2.0 MPa, SV: 10-60 1/h H2:acetylene: 0.2-10, catalyst: 0.01-1wt% of Pd, , 0.01-5wt% of Pb, La, Pr and Nd 0.01-10wt%/Al2O3

33. CN101591216  (A)  -  High-efficiency multi-functional polymerization inhibitor for butadiene extraction device and using method thereofThe invention relates to a high-efficiency multi-functional polymerization inhibitor for a butadiene extraction device and a using method thereof. The high-efficiency multi-functional polymerization inhibitor consists of phenolic compounds, aminated compounds and phosphorous acid ester compounds. The high-efficiency multi-functional polymerization inhibitor overcomes the disadvantages that the prior polymerization inhibitor has high cost and single performance and is unsteady in the butadiene extraction device, can passivate metal ions to inhibit metal from being catalyzed when the generation of coked scale is habited, can cleanse and disperse the generated coked scale, and has high efficiency and polyfunctionality.; The high-efficiency multi-functional polymerization inhibitor is safe and environment-friendly, has simple and convenient use, has no influence on downstream processes, and effectively improves the operating efficiency of the butadiene extraction device.

34. Polymerization

36. Transition metal or Ziegler catalysts are used for stereoregular polymer. High cis-isomer provides better green strength and increased cut growth (resistamce to crack) of uncured rubber High trans-isomer polymers are manzfactured by transition metal catalysts and are crytalline, with a metling point above 80C Intermediary: “anionic” catalysts provide a gel free product with close to even distribution of cis and trans

39. €3100-3500/t in Europe, $4550/t in august, up by $550 since May

41. Emulsion polymerization (E-SBR): carried out under mild conditions in a water tolerant, but oxygen-free mode. High solid content can be builét in, by the virtue of low viscosity delivered by colloidal structure. “Feedstocks”: monomers, water, emulsifier, initiator (chelated iron, and sodium formaldehyde sulfoxide), modifier, shortstop (mercaptane), chain transfer agent (thiols) and stabilizer.

43. Solvent – dispersion polymerization generally employs alkanes and mixtures of hydrocarbons – mailybeing the continuous phase - to have high solvency for the monomers – beside styrene and butadiene methacrylates, acylates – but low for the polymer, but should be suitable for efficient stripping

45. Ingredients used in rubber processing and use: Antidegradants (antioxidants, stopping agents, UV protectors) Accelerators, to boost vulcanization, sulfur and sulfur compounds Activators to promote efficiency of accelerators, ZnO, PbO, MgO, organic acids Retarders, phenyl-amines, to control premature vulcanization in processing steps and in use Blowing agents used in producing rubber foams, Plasticizers, to reduce viscosity by the use of esters and resins Processing aids, oils of different kind- paraffinic, naphtenic, aromatic Reinforcing agents, fillers, diluents, carbon black and silica are the most known ones Bonding agents, mainly proprietary compositions Solvents, emulsifiers, flame retarding agents,