J. Ckaner Prod., Vol. 2, No. 3-4, pp.

181-184, 1994
Elsevier Science Ltd
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Clean technology in the production of

epichlorohydrin
Jowi W. Bijsterbosch, A. Das* and F.P.J.M. Kerkhof*
RIZA, Institute for Inland Water Management and Waste Water Treatment, Ministry
of Transport, Public Works and Water Management, PO Box 17, 8200 AA Lelystad,
The Netherlands
*Comprimo Consulting Services, PO Box 58026, 7040 HA Amsterdam,
The Netherlands

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.

Keywords: clean technology; epichlorohydrin; chemical industry

Introduction water treatment facilities. However, the EOCl

reduction obtained is considered to be insufficient
In the early 195Os, the first industrial production of
from an environmental point of view.
epichlorohydrin (ECH) took place. Nowadays, there
Within the framework of the Dutch government
are about 20 production locations worldwide at which
programme SPA (focused on pollution prevention,
ECH is produced by the conventional route starting
clean technology and advanced waste water treatment),
with propene and chlorine via ally1 chloride (AC) and
a project has been set up by RIZA (Institute for Inland
dichlorohydrin (DCH) to ECH. The world production
Water Management and Waste Water Treatment)
capacity of ECH amounts to about 800 kton per year.
and Comprimo Consulting Services (engineering and
ECH is mainly used for the production of epoxy resins
consulting company), in which the possibilities of end-
(about 50% of the ECH produced) and glycerin (about
of-pipe techniques, in-process measures and clean
20%). The primarily chlorine-free epoxy resins are
production processes for reduction of the EOCl
applied in paints, electric circuits, construction, gum,
emission to surface water are comparedl.
and so on. Important properties of epoxy resins
are chemical inertness, insensitivity to corrosion and
aggressive chemicals, and good electrical isolation
and adhesion properties. ECH is considered as an Conventional production of ECH
irreplaceable chemical compound for the production
of epoxy resins at the moment. The chemistry of ECH production is briefly discussed.
A major problem with the conventional production Details about technical aspects of this production
process for ECH is the formation of a large amount process can be found elsewherel. The synthesis of
of chlorinated by-products, which are found partially ECH can be divided into four steps:
in the voluminous effluent. The amount of by-products
is about 0.3 kg per kg ECH produced. The by-products l synthesis of allylchloride (AC)
are generally considered as waste and incinerated. l synthesis of dichlorohydrin (DCH)
Without waste water treatment facilities, about 1 to l synthesis of epichlorohydrin (ECH)
3 g EOCl (extractable organochlorine compounds) per l synthesis of hypochlorite (HOCl)
kg ECH produced is present in the effluent. In western
countries, ECH production plants usually have waste The main reaction equations are given in Scheme 1.

J. Cleaner Prod. Volume 2 Number 3-4 181

Clean technology in ECH production: J.W. Bijsterbosch et al.

H2C = CH-CH3 + Clz + H&Z = CH-CH2Cl + HCl (1)

propene chlorine ally1 chloride hydrochloric acid

H&Z = CH-CH&l + HOC1 -+ CH2Cl-CHOH-CH&l + CH20H-CHCl-CH2Cl (21

ally1 chloride hypochlorite 1,3-dichlorohydrin 1,2-dichlorohydrin

CH&l-CHOH-CH2Cl + BCa(OH)2 + CH2Cl-Hy--5H2 + !KZaC& + Hz0 (3)

0
1,3-dichlorohydrin calcium hydroxide epichlorohydrin calcium chloride

Scheme 1 Reaction equations for the synthesis of (1) ally1 chloride, (2) dichlorohydrin, and (3) eipichlorohydrin

Synthesis of AC 40 m3 per ton ECH) originates from the DCH synthesis.

The effluent contains not only CaCl, in high concen-
The synthesis of AC takes place by reaction of propene
tration, but also EOCl compounds. Typical concen-
with chlorine at a temperature of 500-520°C (equation
trations are 25-75 mg l-l, which corresponds to an
(1) in Scheme 1). The selectivity of this reaction is
EOCl emission of l-3 kg per ton ECH produced. In
rather low; by-products such as mono- and dichloropro-
some cases, the effluent of the ECH plant is biologically
pene and mono- and dichloropropane are formed.
treated before it is emitted to surface water. Generally
the EOCl compounds are only partially removed by
Synthesis of DCH
biological treatment. Therefore, additional measures
The reaction of AC and HOC1 to form DCH is are necessary.
performed in water at a temperature of 30°C (equation In this paper, three points of view for emission
(2) in Scheme I). Excess water has to be used in order reduction are considered: (i) end-of-pipe techniques
to prevent formation of an organic phase, as the and combinations of end-of-pipe techniques; (ii) in-
undesirable side-reaction of AC to form 1,2,3-trichloro- process measures; and (iii) alternative, cleaner pro-
propane (TCP) takes place in the organic phase. The cesses. It will be shown that for the production of
low solubility of AC in water makes the large amount ECH, application of most end-of-pipe techniques is
of water necessary2. Besides TCP, chlorinated ethers insufficient for reaching an EOCl level of 0.1 mg 1-l.
are formed as by-products. They originate from From both an environmental and an economic point
the reaction of the reactive intermediate species of view, in-process measures and especially alternative
(chloronium ions) with DCH. Their formation is process routes are much more promising.
suppressed by the large amount of water.
Application of end-of-pipe techniques
Synthesis of ECH
Several end-of-pipe techniques and combinations of
ECH is formed by dehydrochlorination of DCH with
these techniques are theoretically considered for treat-
Ca(OH), in water at a temperature of 90°C (equation
ment of the ECH effluent. These include (i) biological
(3) in Scheme I). ECH is immediately removed
treatment, (ii) biological treatment, reverse osmosis
from the solution in order to prevent formation of
and evaporation of the concentrate flow, (iii) biological
monochlorohydrin (MCH) and consequently glyceroP.
treatment and active-carbon adsorption, (iv) biological
treatment, active-carbon adsorption and wet-air oxi-
Synthesis of HOC1
dation for regeneration of the carbon, and (v) evapor-
The HOC1 solution is used in the DCH synthesis is ation.
prepared by the reaction of chlorine and calcium Table 1 shows the assumed removal levels and a
hydroxide (Ca(OH),). HOC1 is partially converted rough estimate of the costs of the techniques for a
into other chlorine-containing inorganic compounds, typical production plant with a capacity of 24 kton
which play a role in the formation of chlorinated per year. By biological treatment, about 50% of the
organic by-products. EOCl is removed. Additional application of reverse
osmosis or active-carbon adsorption results in EOCl
Environmental aspects of the conventional removal of 90%. Evaporation yields 100% EOCl
removal. Only by application of evaporation can the
process
desired EOCl level of 0.1 mg 1-l be reached. The
As mentioned earlier, the conventional production costs of this technique are estimated to be about 800
process for ECH is characterized by a large amount guilders (fl) per ton ECH produced, which is high
of by-products and a voluminous waste water flow. In compared to the cost price of ECH (about 3000
nearly all processes, the by-products (-0.3 kg per kg guilders per ton). Application of the other techniques
ECH produced) have to be considered as waste and is cheaper, but their performance is insufficient.
are incinerated. About 80% of the effluent (about It is concluded that application of end-of-pipe

182 J. Cleaner Prod. Volume 2 Number 3-4

 Clean technology in ECH production: J. W. Bijsterbosch et al.

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’

EOCI costs costs costs

Techniques removal (%) (fl/m3) (fliton ECH) @/kg EOCl)

Biological treatment 50 6 240 400

Biological treatment active-carbon adsorption 90 9 360 330
Biological treatment t- active-carbon adsorption + wet-air oxidation 90 8 320 300
Biological treatment + reverse osmosis + evaporation 90 16 640 590
Evaporation 100 20 800 670
-

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.

CH2-CH-CH&l + Cl- + CH2Cl-CHCl-CH&l (4)

‘cl+’

chloronium ion trichloropropane

H2C = CH-CH2C1 + Cl1 -+ CH2C1-CHCl-CH&l (5)

ally1 chloride chlorine trichloropropane

CH2Cl-CHCl-CH*OH + CH2-CH-CH&l --+ CH&l-CHCl-CH2-0-CH*-CHCl-CH$Zl + H+ (6)

‘cl+’
dichlorohydrin chloronium ion tetrachloropropylether

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

J. Cleaner Prod. Volume 2 Number 3-4 183

Clean technology in ECH production: J. W. Bijsterbosch et al.

HzC = CH-CH3 + HAc + ;O, -+ H2C = CH-CH,Ac + Hz0 (7)

propene acetic acid ally1 acetate

H2C = CH-CH,Ac + Hz0 + H2C = CH-CH20H + HAc (8)

ally1 acetate ally1 alcohol acetic acid

H2C = CH-CH20H + Cl2 + CH&l-CHCl-CH20H (9

ally1 alcohol chlorine 1,2-dichlorohydrin

CH2Cl-CHCl-CH20H + &Ca(OH)2 -+ CH2Cl-HF-FH2 + $CaC12 + Hz0 (10)

0
1,2-dichlorohydrin calcium hydroxide epichlorohydrin

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

184 J. Cleaner Prod. Volume 2 Number 3-4