A. Kovács em . Assoc.prof BME/MOL/University of Pannonia

1. A. Kovács em. Assoc.prof BME/MOL/University of Pannonia Hydrocarbon Technology Development Engineer Postgraduate Course „Chemical engineering around products of Borsochem” DS Development Academy

2. Position of Products in question

4. Plastic value chain

5. Products range– “simple byproducts” Byproducts range .

6. Byproducts range

7. Byproducts range

8. Vinylidene-chloride (Vynil-chloride, Vynil-chloride-monomer:VNC): IARC: carcinogenic, colorless, sweet odor mobile liquid (bp: 31.6C), soluble in most polar and nonpolar organic solvents Obsolete technology: acetylene + HCl over mercury catalyst, just in China and in small units, based on inexpensive resources from coal chemistry, today Dominant: on Ethylene basis By the use of chloride obtained in electrolysis To lead to Vinylidene-chloride

12. Direct oxychlorination: highly exothermic (ΔH=-239 KJ/mol EDC. Other sources: -290 KJ/mol) over CuCl2/Al2O3 catalyst. In fixed bed system t=230-300 °C, 2-16 bar, in fluidized bed: t=220-245 °C, 2-6 bar air

14. Catalyst action mechanism

16. the European chlor-alkali producers using mercury (cathode) technology committed to phase-out mercury by 2020. One ton of salt (and water) yields around 600 kg of chlorine, 680 kg of sodium hydroxide (caustic soda) and 17 kg of hydrogen Some 9 million tons of chlorine are produced in Western Europe and used in more than half of all chemical activities. The electrolysis of salt therefore is a basic process to get important raw materials used in the chemical industry. Some 34% of chlorine is used to produce PVC, 23% to produce isocyanatesfor the production of polyurethanes, chlorine is also used in the production of polycarbonates or silicones and low amounts to keep 98% of Western Europe’s drinking water safe and produce other chemicals. Sodium hydroxide is important for the manufacture of paper, soap and textiles and other applications. Hydrogen is either used chemically or to generate energy. The overall electrolysis equation, including “spectator” ions:

20. Major reactions:

21. Allows the passage of only positive ions, but not chlorine! Cooled, treated with sulfuric acid, snift gas converted to hypochlorite

24. Bulk, suspension, Emulsion, solution,

25. Bulk: gas phase, (Micro)Suspension, Emulsion, (homogeneous, heterogeneous) Solution,

34. Beyond PVC urethanes

36. TDI Toluene-di-isocyanate MDI Methyl di-p-phenyleneisocyanate PU Poly-urethane

37. Methyl di-p-phenyleneisocyanate-MDI: 1,1'-Methylenebis(4-isocyanatobenzene); 4,4'-Diisocyanatodiphenylmethane; 4,4'-Diphenylmethane diisocyanate; 4,4'-Diphenylmethanediisocyante; 4,4'-Methylenebis(phenyl isocyanate); 4,4'-Methylenedi-p-phenylene diisocyanate; 4,4'-Methylenediphenyl diisocyanate; 4,4'-Methylenediphenyl isocyanate; 4,4'-Methylenediphenylene isocyanate; 4-4'-Diisocyanate de diphenylmethane [French]; Benzene, 1,1'-methylenebis(4-isocyanato-; Bis(1,4-isocyanatophenyl)methane; Bis(4-isocyanatophenyl)methane; Bis(p-isocyanatophenyl)methane; Bis(para-isocyanatophenyl)methane; Caradate 30; Desmodur 44; Di-(4-isocyanatophenyl)methane; Difenil-metan-diisocianato [Italian]; Difenylmethaan-dissocyanaat [Dutch]; Diphenyl methane diisocyanate; Diphenylmethan-4,4'-diisocyanat [German]; Diphenylmethanediisocyanate; Diphenylmethyldiisocyanate; Hylene M50; Isocyanic acid, ester with diphenylmethane; Isocyanic acid, methylenedi-p-phenylene ester; Isonate; Isonate 125 MF; Isonate 125M; MDI; MDR; Methylbisphenylisocyanate; Methylenedi-p-phenyleneisocyanate; Methylenebis(4-isocyanatobenzene); Methylenebis(4-phenyl isocyanate); Methylenebis(4-phenylene isocyanate); Methylenebis(p-phenyl isocyanate); Methylenebis(p-phenyleneisocyanate); Methylenebis(para-phenyl isocyanate); Methylenebis(para-phenyleneisocyanate); Methylenedi-p-phenylenediisocyanate; Methylenedi-para-phenylenediisocyanate; Nacconate 300; Rubinate 44; p,p'-Diphenylmethanediisocyanate; p,p'-Methylenebis(phenylisocyanate); para,para'-Diphenylmethanediisocyanate; para,para'-Methylenebis(phenylisocyanate); [ChemIDplusis

38. Methylenediphenylenediisocyanate isomers (MDI) and the mixtures of the diisocyanates with higher molecular weight homologues known as poly-(methylenediphenylenedi-isocyanate) (hereinafter PMDI) are widely used as speciality binders for various composite materials, with polyamines for polyureas and, together with polyether and polyester polyols, to form the diverse range of polyurethane materials including cross-linked rigid foams for insulation, flexible foams for automotive seating and furniture and as elastomers & coatings. PMDI is conventionally produced by phosgenation of the corresponding mixture of polyamines known as poly-(diaminodiphenyl methane) (hereinafter DADPM) formed from condensation of aniline and formaldehydeRead more: http://www.faqs.org/patents/app/20080312405#b#ixzz2hrhPvYjW

39. MDI is mainly consumed in polyurethane foams (accounts for cca 80% of global consumption) to be used in construction, refrigeration, packaging and insulation. Other uses: binders, elastomers, adhesives, sealants, coatings and fibres. Pure MDI can be combined with polyesters, polyols, polyethers. MDI is a basic component in prepolymers. MDI contract prices: EUROPE May-August 2011, crude MDI €2,000-2,050/tonne FD (free delivered) NWE (northwest Europe) and pure MDI at €2,100-2,250/tonne FD NEW Crude MDIprices in US: $3,130–3,394/tonne, bulk.

40. MDI chemical formula and polymerized to PMDI Diiso-cyanates are dermal and inhalation sensitizer, documentedlycasue asthma, lung demage, in severe cases are fatal. Concerns are focused on preventing exposuzre to unreacted (uncured) MDI and the related isocyanates

42. Production: Formation of nitronium ion: Attack of the benzene ring: Exothermic hydrogenation: (DH=544 KJ/mol) Aniline is reacted with form- Aldehydemol:mol= 1:1…1:4

44. urethanes:, urethane polymers? -NHCOO- carbamate groups are also called urethanes and polyurethanes (PU) arethose polymers that contain these carbamate groups in backbone structure. Carbamate is formed in reaction of a di-isocyianate with a macroglycol. This later can be composed by a di-glycol and a short chain glycol extender. Macroglycols are produced by combination of polyethers, polyesters and combination of these. Linear polyurethane structure: segmented polymers

45. Thermoset PU: already cured products TPU: granulated products for molding and pressing

46. MDI is manufactured by phosphogenation of di-phenyl-methane

49. TDI MDI PU 49

50. Flexible polyurtehane foam