Technology Profile

Polychloroprene Production
By Intratec Solutions
The need to find a substitute the isomerization step and fed to a is controlled by means of a chain-
for natural rubber during series of continuously stirred ves­ transfer agent (tertiary dodecyl mer­
World War II boosted the sels. The gaseous effluent is cooled,captan). The reaction is terminated
development of polychloro­ condensed and then settled for with the addition of shortstop agents
prene (chloroprene rubber), the first separating the organic and aqueous (for example, sodium polysulfide).
synthetic rubber produced industrial­phases. The aqueous phase is dis­ Recovery and finishing. The latex
ly. Today, it is one of the most impor­carded, while the organic phase is produced is steam-stripped for the
tant special rubbers, alongside butyl stripped against steam. This column removal of residual chloroprene,
rubber, nitrile rubber (NBR) and ethyl­ is designed to recover a gaseous which is recycled. The hot latex is
ene propylene diene rubber (EPDM).chloroprene-rich stream from the mixed with antioxidants and fed to
top, while the unconverted 3,4-di- a freeze roll to be coagulated into a
The process chloro-1-butene is recovered in the polymer sheet, which is fed to a wash
The following describes a process column's bottom. belt for removing polymerization-
for polychloroprene production from The bottom product is then al­ reaction medium. The washed poly­
butadiene and chlorine. Figure 1 lowed to settle, in order to separate chloroprene film is dried in squeeze
presents a simplified flow diagram. the organic and aqueous phases. rolls and continuous-belt dryers.
Chlorination. In the first step, buta­ Then the aqueous phase is discard­ After drying, the film is formed into
diene, chlorine, recycled butadiene ed, while the organic phase is dried a rope and cut into polychloroprene
and hydrochloric acid are mixed andand directed to a falling-film evapo­ chips, which are packed in bags.
fed to the chlorination reactor, whererator. The evaporator is used to re­
butadiene is chlorinated in the vapormove heavy-end byproducts. Economic performance
phase. A large excess of butadiene The gaseous stream from the The total operating cost (including
is used to prevent the formation of evaporator is mixed with the top raw materials, utilities, fixed costs
super-chlorinated species during stream from the stripping column, and depreciation costs) estimated
this reaction. The two main productsand this mixture is distilled for the to produce polychloroprene was
of the chlorination are 1,4-dichloro- recovery of 3,4-dichloro-1-butene about $2,400 per ton of polychloro­
2-butene and 3,4-dichloro-1 -butene.(bottom) and chloroprene (top). Bothprene in the fourth quarter of 2014.
Isomerization. An isomerization column products are allowed to set­ The analysis is based on a plant
step is used to convert 1,4-dichloro- tle, and the resulting aqueous phas­ constructed in the U.S. with the
2-butene into 3,4-dichloro-1-butene es are discarded, while the organic capacity to produce 50,000 metric
(the precursor to chloroprene). The phase is dried in molecular sieves. tons per year of polychloroprene.
isomerization is conducted in the re­The dried column-bottom stream is This column is based on the report
boiler of a distillation column. In this recycled, while the dried crude-chlo- “Polychloroprene Production - Cost
way, 3,4-dichloro-1-butene is con­ roprene stream is purified in a final Analysis,” published by Intratec. It
tinuously removed from the liquid re­distillation step and routed to the po­can be found at the following URL:
action medium by evaporation. The lymerization stage. www. intratec. us/analysis/polychlo-
3.4- dichloro-1-butene is recovered Polymerization. The polymerization roprene-production-cost. ■
from the top stream of the column, is carried out in continuously stirred, Edited by Scott Jenkins
while the column’s bottom product isjacketed tank reactors connected in
Edfor's note: The content for this column is supplied
recycled to the process. series, and cooled by a brine solu­ by Intratec Solutions LLC (Houston; www.intratec.us) and
Dehydrochlorination and puri­ tion. Chloroprene is first mixed with edted by Chemca/ Engineering. The analyses and models
fication. Caustic soda is diluted emulsifier, demineralized water and presented are prepared on the basis of publicly avaiable
and non-confidentral ntormation. The content represents
in process water, mixed with the initiators (hydroperoxides/ferrous sul­the opinions of Intratec only. More information about the
3.4- dichloro-Tbutene stream from fates). The polymer molecular weightmethodology lor preparing analysis can be found, along with
terms of use. at www.intratec.us/che

1. Chlorination
2. Isomerization
-* Catalysts and chemicals
3. Dechlorination
• Demineralized water 4. Polymerization reactors

Caustic
□ 5. Chloroprene stripping
6. Finishing
Chlorine soda Brine Brine
Poly­ 7. Cooling tower
Brine-. ©■.® chloroprene 8. Steam boiler
Butadiene * (T) 9. Refrigeration system

Shortstop agent
i CW--Q ® CW Cooling water
' Waste
ST Steam
ST water ST
-Ti®
Brine •
FIGURE 1. The diagram shows a process for the production of polychloroprene
e®
32 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM DECEMBER 2018