„CHEMICAL ENGINEERING AROUND
PRODUCTS OF BORSOCHEM”
A. Kovács
em. Assoc.prof
BME/MOL/University of Pannonia
Hydrocarbon Technology Development Engineer
Postgraduate Course
DS Development Academy
POSITION OF
PRODUCTS IN
QUESTION
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Plastic value chain
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PRODUCTS RANGE– “SIMPLE BYPRODUCTS”
BYPRODUCTS RANGE
.
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BYPRODUCTS RANGE
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BYPRODUCTS RANGE
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VINYLIDENE-CHLORIDE (Vynil-chloride, Vynilchloride-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
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To 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 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 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:
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Major reactions:
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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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BEYOND PVC
URETHANES
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TDI
Toluene-di-isocyanate
MDI
Methyl di-p-phenylene isocyanate
PU
Poly-urethane
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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(1,4isocyanatophenyl)methane; Bis(4-isocyanatophenyl)methane; Bis(pisocyanatophenyl)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-para37
phenylene diisocyanate; Nacconate 300; Rubinate 44; p,p'-Diphenylmethane
diisocyanate; p,p'-Methylenebis(phenyl isocyanate); para,para'-
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 NEW
Crude MDIprices in US: $3,130–3,394/tonne,
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bulk.
MDI CHEMICAL FORMULA AND POLYMERIZED TO 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
200
Flash point, closed cup, C
177+
Melting point, C
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PRODUCTION:
Formation of nitronium ion:
Attack of the benzene ring:
Exothermic hydrogenation:
(DH=544 KJ/mol)
Aniline is reacted with formAldehyde mol:mol= 1:1…1:4
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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
O
O
O
O
II
II
é
ù
-ê-ROC NHR' NH C O -ú ë
ûn
O
O
II
II
II
II
é
ù
-ê-ROC NHR' NH C OCH 2CH 2OC NHR' NH C O -ú ë
ûn
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Thermoset PU: already cured products
TPU: granulated products for molding and
pressing
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MDI is manufactured by phosphogenation of di-phenyl-methane
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TDI
MDI
PU
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Flexible polyurtehane foam
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WPU: water born polyurethane, ie. Emulsion polymerized
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