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The conventional production of epichlorohydrin takes place via allyl chloride and dichlorohydrin.
A major disadvantage of this chemica1 process is the formation of a large amount of chiorinated
organic by-products, which are found panially in the voiuminous effluent. In order to reduce
thic emicsion to surface water, measures have to be taken. Technica( measures varying from
end-of-pipe techniques to alternative processes have been evaluated. Application of end-of-
pipe techniques is not the optimal solution for emission reduction, either technically or
economically. Results from in-proces measures focused on reduction of the amount of waste
water and contaminants are more promising. However, the development of an alternative
route is necessary in order to obtain a process with minimal emiscions and minimal costs.
Keywords: clean technology; epìchlorohydrin; chemica1 industry
techniques is not thc optima1 solution for EOCI the effect of a measure on the final EOCI emission, as
cmissioi? rcduction. This is caused by the large amount a measure can result in different effects. The effect of
of waste water which has to be treated (-40 m3 per the desired minimization of the amount of water is
ton ECH produced). It is advisable to reduce the discussed as an example.
amount of waste water first by in-process measures Excess water is prìmarily applied for preventing the
iind subsequently treat the smaller waste water flow. formation of by-products. With excess water, formation
of the organic phase is prevented. So, TCP formation
In-process measures onginating from AC in the organic phase does not
occur. Excess water also limits the formation of ether
In-proccss mcasures are airned at reducing the arnount and TCP. Minimizing the amount of water wil1 result
of wiistc water and the rtmount of EOCI in the effluent. in an organic phase and in higher DCH and chloronium
As the largect amount of waste water and contaminants ion concentration. These effects result in higher EOCI
is formcd duriiig the DCH synthesis, in-process meas- concentration, as explained earlier. Therefore, reduction
urcs iirc íocused on this renction step. The DCH of the amount of water wed is not that easy.
synthcsis wil1 he discusscd in more detail in order to In-process measures for EOCI reduction are focused
understand the possible measures. on minimizing the C12 and C1- concentration, since
The mcchanisms for the formation of chlorinated these species are also responsible for the formation of
compounds Juriny DCH syntliesis are given in Scheme EOCI compounds. As Clz and C1- ions originate from
24*s.T h e chloronium ion is the reactive intermediate the HOC1 solution, it is advisable to decrease their
species in DCH synthesis. During this reaction step, concentration in that solution. This is difficult, since the
this ion reiicts with water to form 1,3- and 1,2-DCH. HOC1 synthesis is an equilibrium reaction. Recently, an
I-lowever, the chl«ronium ion also reacts with other alternative pathway for the production of HOC1 has
nucleophilic species in the aqueous phase, like chloride been commercialized, in which a more concentrated
ions, t o h r m TCP (equation (4) in Scheme 2). TCP HOC1 solution is prepared6s7.i t is interesting to study
can also he fornied in an orgenic phase by reaction of whether this Olin process can be integrated in the
CI2 ancl AC, which is sliown in equation ( 5 ) of Scherne ECH production process. The expected reduction in
2. Tetracliloropropylether is forined by reaction of the waste water is about 30 m3 per ton ECH. The effect
cliioronium ion with BCH (equiition (6) in Scheme on the EOCl level is not known and is difficult to
2). prcdict. TCP formation wil1 probably not occur, but
It is shown that EOCI compounds are formed via the formation of chlorinated ethers can increase. This
several mechanisms. This makes it difficult to predict must be studied in practice.
Scheme 2 Three mechanistic pathways for the formation of chlorinated organic by-products: (4) trichloropropane in the
aqueous phase, ( 5 ) trichloropropane in the organic phase, and (6) tetrachloropropylether
As the effects of in-process measures are not Mainly as a result of the lower production of by-
completely clear, it is interesting to study the possibilit- products and waste water and the lower costs for
ies of alternative, cleaner process routes. feedstock, the estimated cost price for ECH is about
20% lower than that of conventionally produced ECH.
Alternative process routes
Patent literature shows that research o n several alterna- Concluding remarks
tive routes for ECH has been performed. In most This study has shown that application of end-of-pipe
cases, propene is used as a feed-stock. Propene techniques is not the optimal solution for EOCI
is converted into allyl chloride, allyl alcohol, or emission reduction. Due to the large amount of waste
dichloropropylacetate. Almost al1 routes include the water that has to be treated, these techniques become
conversion of DCH t o ECH as a final step. A survey very expensive. It is advisable to minimize the amount
of these routes can be found eisewhere'. A selection of waste water first, before these techniques are
of these routes is made, based on selectivity and waste installed. Therefore, in-process measures have to be
water production. This has resulted in three promising taken. A problem with in-proces measures is that by
routes. minimizing the amount of water, the EOCI load can
One of these promising routes is commercialized - increase.
the Showa-Denko process. It is developed due to a The most elegant solution is to develop a new
lack of Clz. T h e chemistry wil1 be discussed brieñy; process in which environmental aspects are also
technica1 details can be found elsewhere. Four reactions taken into account. One alternative process has been
play a role, which are shown in Scheme 3: commercialized in Japan - thc Showa-Denko process.
synthesis of allyl acetate This process is worth studying in more detail, especially
synthesis of allyl alcohol the environmental aspects. The non-commerciaiized
synthesis of i ,2-dichlorohydrin routes are also interesting to study in more detail as,
synthesis of epichlorohydrin compared to the conventional process, their selectivity
is higher and waste water formation is less. This study
i n the Showa-Denko process, only 0.035 kg organic has sliown that research must nut be focused on end-
by-products per kg ECH produced is reported to be of-pipe techniques, but that the total industrial process
forrned, which is separated and incinerated'. This is must be involved.
ten times lower than in the conventional production
process. The amount of waste water is 8 m3 per ton
ECH, which is a decrease of about 80% compared to References
the conventional process. Details about the EOCI Das. A. 'Markt en produktieprocessen voor cpichl<iortiydrinc'.
level in the effluent are not known. report no. 61382-(10-373111-02,May 1994 RIZA (in Dutcli)
Kanaev. G.I.and Muchutdinov. R.C.'Vcrldhren zur Herstel-
It is estimated that the total amount of organic lung van Glyzerin-Dichlorohydrin'.Gcrinan Patent 3.437.520.
mateial in the effluent is about 60 kg per ton ECH, i986
which is 50% lower than in the conventional process. Carra, s., Santacesaria, E. and Morbidelli. M. Ind. Eng.
Chem. Process. Res. Dev. 1079. 18, 424
Although the selectivity of the reactions in this process de Ia Mare, P.B.D. and Gíilandauer, S. 1. Chcrn. Soc. 195X,
is higher than in the conventional process, TCP 36
formation still occurs. If the rnechanism is comparable Israel, G.C..Martin. J.K. and Sopcr. F.G.1. Clrem. Soc.
1950, 1282
to that of the conventional route (via the chioroniurn Hilliard, G.E.. Melton, J.K. and Helmstettcr, D.A. 'Sak
ion), the formation of chlorinated ethers can also be Handling AppdfatUS lor a Hypochlorous Acid Reacior', WO
expected. Unfortunately , no information about the Patent 90.14.155 Olin, 1991
Melton, J.K.,Hilliard, G.E., Shaffer. J.F. and Woitowicz.
emission of these compounds is known at the moment. J.A. 'Improved Hypochlorous Acid Process', EP Patent
This is an important topic for further research. O440736 O h , 1988