A. Kovácsem. Assoc.prof

BME/MOL/University of Pannonia

Hydrocarbon Technology Development Engineer Postgraduate Course

DS Development Academy

„Chemical engineering around products of Borsochem”

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Plastic value chain

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Products range–

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Vinylidene-chloride (Vynil-chloride): 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 basisBy the use of chloride obtained in electrolysisTo lead to Vinylidene-chloride

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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

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Catalyst action mechanism

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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 hydrogenSome 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 isocyanates for 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:

2Na 2Cl H2O 2Na 2OH H2 Cl2

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Major reactions:

2Claq 2e Cl2(g )

4OHaq 4e 2H2O( l ) O2(g )

2Haq 2e H2(g )

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Allows the passage of only positive ions, but not chlorine!

Cooled, treated with sulfuric acid, snift gas converted to hypochlorite

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Bulk, suspension, Emulsion, solution,

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

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TDI

MDI

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METHYL DI-P-PHENYLENE ISOCYANATE-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]; Diphenylmethane diisocyanate; Diphenylmethyl diisocyanate; Hylene M50; Isocyanic acid, ester with diphenylmethane; Isocyanic acid, methylenedi-p-phenylene ester; Isonate; Isonate 125 MF; Isonate 125M; MDI; MDR; Methylbisphenyl isocyanate; Methylene di-p-phenylene isocyanate; Methylenebis(4-isocyanatobenzene); Methylenebis(4-phenyl isocyanate); Methylenebis(4-phenylene isocyanate); Methylenebis(p-phenyl isocyanate); Methylenebis(p-phenylene isocyanate); Methylenebis(para-phenyl isocyanate); Methylenebis(para-phenylene isocyanate); Methylenedi-p-phenylene diisocyanate; Methylenedi-para-phenylene diisocyanate; Nacconate 300; Rubinate 44; p,p'-Diphenylmethane diisocyanate; p,p'-Methylenebis(phenyl isocyanate); para,para'-Diphenylmethane diisocyanate; para,para'-Methylenebis(phenyl isocyanate); [ChemIDplus is

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Methylene diphenylene diisocyanate isomers (MDI) and the mixtures of the diisocyanates with higher molecular weight homologues known as poly-(methylene diphenylene di-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-(diamino diphenyl methane) (hereinafter DADPM) formed from condensation of aniline and formaldehydeRead more: http://www.faqs.org/patents/app/20080312405#b#ixzz2hrhPvYjW

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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 NEWCrude MDIprices in US: $3,130–3,394/tonne, bulk.

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MDI chemical fprmula PMDI

Diiso-cyanates are dermal and inhalation sensitizer, documentedly casue asthma, lung demage, in severe cases are fatal. Concerns are focused on preventing exposuzre to unreacted (uncured) MDI and the related isocyanates

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Property value

Molecular weight 250,3

Appearance Solid

Color White-yellowish

density, g/cm3, @43 C 1.180

Boiling point, atm Decomposes at 230 C

Boiling pointt @ 5 Hgmm, C

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Flash point, closed cup, C 177+

Melting point, C 33

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Production:Formation of nitronium ion:

Attack of the benzene ring:

Exothermic hydrogenation:(H=544 KJ/mol)

Aniline is reacted with form-Aldehyde in F:An= 1:1…1:4

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urethanes:, urethane polymers?

-NHCOO- carbamate groups are also called urethanes and polyuretthanes areThos 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

O O

ROCII

NHR'NHCII

O

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O O O O

ROCII

NHR'NHCII

OCH2CH2OCII

NHR'NHCII

O

n

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MDI is manufactured by phosphogenation of di-phenyl-methane

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TDI

MDI

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Flexible polyurtehane foam

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