Document JvE88NXQvG95Xw01M0zGDn1EO
Jamury'tS, 'MV'
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&*topM Chemical news
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- - - :Since the chlorination
Vinyl cUwlde ls pT>tfiy fl most^nportant example ofd
between acetylene and ethylene chemistry.,,. Dunlop bas bas joined % EH$. field,having prodaced &n ethylene prop3ft_,, ,, . Monsanto's ugnomt process Bsesjsatural gas as feedstock Wm1:
- 3#y .; VT^dffmctioB titjosr of high temperature. that It - Ounne yvoanriant of ttiejitocett solves these
[jmer^ilflt-5tB0e^ntv^.fclWtfti|[raml the '*
miMu -eriAicne fotoa tetwfrecirBiiatingstream
is Stored at prassare In spheres of 2000 ton cap^. :JneaTOTytraim ^j^pUcc and in chthe^acrion of the l.CJL feijowsfeips has been increased from 900 to 1 WO per year. ^-g^ickly dissipated." v^>-' t"
- -->i(--r ''"
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-^"Sfcsa* fcv Knesset.-
that a.jppre dhyiefie-stresto nysw^
Vinyl Chloride's
strictly necessary--nor indeed even pir^ tkitlariy -advantageous. An unsplit etbane-etfiytene - stream can be used ;
Feedstocks r
which reduces the cost of the ethylene -
feed, " ,.
.............
r;'fbe'decotnposition of dkbleroetene
to give vinyl chloride arid HCilsdsdsJly
carried out in the tubes of a tfired W1NYL chloride is probably the most tion Final purification to remove furnace at sbotet '300*C.
important example of direct com petition between acetylene anJ ethylene chemistry. The acetylene route bas die advantage of simplicity and. therefore, of low operating cost. 7 he ethylene
aldehydes and ethyltdene dichloride is bv low temperature tracuonation. Pure
vinyl chloride is then stored under nitro gen in stainless steel unks. . The route via ethylene is more
' route has -the advantage, of a cheaper complex tred involves .two .stages---the
feedstock. - All that is involved: ia the .chlorination rof-ethylene to give di-
acetylene route is the simple addition of ' chloroethane and the thermal decom
hydrogen chloride acrossjthe - triple position of tire dichlororthane to give,
bond.
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vinyl chloride.and HCl.,
' CHeCH+HC1-wCH,=CHCI
The mechanism of the chlorination of ethylene to give dichloroethane has bad
Dry hydrogen chloride is passed lo a
a good deal of study." But in 'practice' ,
vapour blender to^be .mixed m equi the important thing h tq prevent the
Recovered Front Steam
The vapour from the furnace con* taming vinyl chloride, - HCl and unconverted dichloroethane is quenched immediately downstream of the. furaace m ordehto freeze- the.equilibrium, Hat
vinyl- chloride .and. dtdttotptohawytj* theits recovered from the-., quenched stream . either .by_ absorption..-or . by distillation at a presuresuffident.to jjiye
liquid HCl reflux. The vinyl chloride is recovered.from the dichloroethane-by udimstimllautioi/niii. *Ptaotrt VoIf ttfhifec UdiiWchmloUrfo^eftUthIaIInHwe k. recycled as. quench-and the rest-
molar .proportions *with dry acetylene. substitutive chlorntorioa of tfichibro- w^dchjt*tbe uoamv^rreq dicbloroethilie
Since at this stage the presence of chlorine will cause an explosion, there is a_device, which on detecting any sudden rise in . temperature, automalically diverts the hydrogen chloride stream to the atmosphere.
From the vapour blender the gas mix ture is lel into a mulutubular reactor, each tube bang packed with a mercuric chloride catalyst on an activated carbon support. The reaction has to be initi ated by heal, but once started, cooling
ethane to give tri- and tetra-chloroethane.
--n sent 'to ciean' up columns before
-being returned to. the furnace. . j~r
- -In the ethylene-based procepvia
cbchloroethanc, half the chlorine U con
verted to by-product HCl--a doubtful
commodity since the acid inevitably
contains traces of chiminated hydrocar
bons which makes its sale as food grade
acid difficult without dean-up opera
tions.
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Comparison Of Coats
bat to be applied to control the 'highly
In comparing the cost of the acetylene
exothermic addition at around
and ethylene routes, i: is reasonable to
90-100'C
assume that the user of acetylene will
To avoid the presence of moisture w the hydrogen cMondc rigorous drying
have to manufacture HCl from chlorine. On the other hand, the user of the ethy
procedures are earned oul during ail
lene route may or may not be able to
stage* m m, preparation. High purity hydrogen--which can be prepared on
sire by the partial oxidation of a light hydrocarbon--is dried firstly by cording
to freeze out most of the moisture and then by passing through an alumina packed tower The tin hydrogen is burned with chlorine under such con ditions that all the chlorine i-. convened
to bydrogen chloride In addition to the main reactions, side
reactions producing acetaldehyde and
ethyltdene dtehionde also proceed
Caret A tomgKtt cKr
prien f wiWylitit
aiNno tfhyitMo<Nhtollrtof% fMwCtboM.fc tor HCt
CD
B cootMfM Hre brafcr**' prif ? th* two
iMlKMtto vwtaato hiw6 tof i,\s WDtl to
V
HCt,
The reaction is usually carried out in
dispose of the by-product HCl.
llte graph gives for any ethylene price the. acetylene price at which the two
routes break even hr terms of~vin<ji chloride production 'costs (mchidmg depreciation}. The companion has been carried out tor the ease of zero HCl net back to the ethylene uv*r and for a netback of 15/ton
The graph shows that if an HC! netback is taken it is very difficult for carbide-based acetylene to compete. Roughly 4 tons of carbide are needed
CHClfJ-H,0--s-CH,CHO CH.-CHCl +HO--CH.CBCJ,
The gases leaving the reactor are cooled before being caustic washed to remove unreaded hydrogen chloride, followed by a methanol wash to remove water picked out from the caustic solu
the liquid phase and in ute presence of an iron chlonde catalyst. The reaction
temperature ts very important and is uvuailv earned out at about 30-50*0. Increasing the temperature much above this level sharply favours the substitu tive chlorination. A temperature'much below this level ieduces the velocity of
to produce 1 ton of acetylene which in
countries such as the UJC. gives raw
material cost for the acetylene of at least 1Oft ton. - In these areas ethylene will certainly win. Only in areas where either cheap natural gas or very cheap power is available, is acetylene able to compete on a cost basis.
CBY 1019798
' 7-r.-ewir?
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RSV0031813