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Clean Technology in The Production of Epichlorohydrin: Jowi W. Bijsterbosch, A. Das and F.P.J.M. Kerkhof
Clean Technology in The Production of Epichlorohydrin: Jowi W. Bijsterbosch, A. Das and F.P.J.M. Kerkhof
181-184, 1994
Elsevier Science Ltd
Printed in Great Britain
0959-6526(95)00024-O 09.59-6526194 $10.00 + 0.00
The conventional production of epichlorohydrin takes place via ally1 chloride and dichlorohydrin.
A major disadvantage of this chemical process is the formation of a large amount of chlorinated
organic by-products, which are found partially in the voluminous effluent. In order to reduce
this emission to surface water, measures have to be taken. Technical 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-process 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 emissions and minimal costs.
Scheme 1 Reaction equations for the synthesis of (1) ally1 chloride, (2) dichlorohydrin, and (3) eipichlorohydrin
Table 1 EOCl removal and estimate of the costs for end-of-pipe techniques applied at an ECH plant with a production capacity of 24
kton per year’
techniques is not the optimal solution for EOCl the effect of a measure on the final EOCl emission, as
emission reduction. 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 primarily applied for preventing the
and subsequently treat the smaller waste water flow. formation of by-products. With excess water, formation
of the organic phase is prevented. So, TCP formation
originating from AC in the organic phase does not
In-process measures
occur. Excess water also limits the formation of ether
In-process measures are aimed at reducing the amount and TCP. Minimizing the amount of water will result
of waste water and the amount of EOCl in the effluent. in an organic phase and in higher DCH and chloronium
As the largest amount of waste water and contaminants ion concentration. These effects result in higher EOCl
is formed during the DCH synthesis, in-process meas- concentration, as explained earlier. Therefore, reduction
ures are focused on this reaction step. The DCH of the amount of water used is not that easy.
synthesis will be discussed in more detail in order to In-process measures for EOCl reduction are focused
understand the possible measures. on minimizing the Cl, and Cl- concentration, since
The mechanisms for the formation of chlorinated these species are also responsible for the formation of
compounds during DCH synthesis are given in Scheme EOCl compounds. As Cl2 and Cl- ions originate from
24,5. The 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 reacts with water to form 1,3- and 1,2-DCH. HOC1 synthesis is an equilibrium reaction. Recently, an
However, the chloronium 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, to form TCP (equation (4) in Scheme 2). TCP HOC1 solution is prepared6,‘. It is interesting to study
can also be formed in an organic phase by reaction of whether this Olin process can be integrated in the
Cl2 and AC, which is shown in equation (5) of Scheme ECH production process. The expected reduction in
2. Tetrachloropropylether is formed by reaction of the waste water is about 30 m3 per ton ECH. The effect
chloronium ion with DCH (equation (6) in Scheme on the EOCl level is not known and is difficult to
4. predict. TCP formation will probably not occur, but
It is shown that EOCl 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
Scheme 3 Reaction equations for the synthesis of epichlorohydrin in the Showa-Denko process
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 on 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 EOCl
is converted into ally1 chloride, ally1 alcohol, or emission reduction. Due to the large amount of waste
dichloropropylacetate. Almost all routes include the water that has to be treated, these techniques become
conversion of DCH to ECH as a final step. A survey very expensive. It is advisable to minimize the amount
of these routes can be found elsewherel. 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-process measures is that by
routes. minimizing the amount of water, the EOCl 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 CIZ. The chemistry will be discussed briefly; process in which environmental aspects are also
technical 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 - the Showa-Denko process.
@ synthesis of ally1 acetate This process is worth studying in more detail, especially
l synthesis of ally1 alcohol the environmental aspects. The non-commercialized
l synthesis of 1,2-dichlorohydrin routes are also interesting to study in more detail as,
compared to the conventional process, their selectivity
0 synthesis of epichlorohydrin
is higher and waste water formation is less. This study
In the Showa-Denko process, only 0.035 kg organic has shown that research must not be focused on end-
by-products per kg ECH produced is reported to be of-pipe techniques, but that the total industrial process
formed, which is separated and incineratedl. 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 EOCl Das, A. ‘Markt en produktieprocessen voor epichloorhydrine’,
level in the effluent are not known. report no. 61382-00-37301-02, May 1994 RIZA (in Dutch)
Kanaev, G.I. and Muchutdinov, R.C. ‘Verfahren zur Herstel-
It is estimated that the total amount of organic lung van Glyzerin-Dichlorohydrin’, German Patent 3.437520,
material in the effluent is about 60 kg per ton ECH, 1986
which is 50% lower than in the conventional process. Carra, S., Santacesaria, E. and Morbidelli, M. Ind. Eng.
Chem. Process. Res. Dev. 1979, 18, 424
Although the selectivity of the reactions in this process de la Mare, P.B.D. and Galandauer, S. J. Chem. Sot. 1958,
is higher than in the conventional process, TCP 36
formation still occurs. If the mechanism is comparable Israel, G.C., Martin, J.K. and Soper, F.G. J. Chem. Sot.
1950, 1282
to that of the conventional route (via the chloronium Hilliard, G.E., Melton, J.K. and Helmstetter, D.A. ‘Salt
ion), the formation of chlorinated ethers can also be Handling Apparatus for a Hypochlorous Acid Reactor’, 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. 0440736 Olin, 1988