View metadata, citation and similar papers at [Link].
uk brought to you by CORE
provided by University of Groningen
University of Groningen
Some aspects of the chlorination of benzene
Berg, Hendrikus van den
IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from
it. Please check the document version below.
Document Version
Publisher's PDF, also known as Version of record
Publication date:
1973
Link to publication in University of Groningen/UMCG research database
Citation for published version (APA):
Berg, H. V. D. (1973). Some aspects of the chlorination of benzene. s.n.
Copyright
Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the
author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).
Take-down policy
If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately
and investigate your claim.
Downloaded from the University of Groningen/UMCG research database (Pure): [Link] For technical reasons the
number of authors shown on this cover page is limited to 10 maximum.
Download date: 12-11-2019
SUM{ARY
This thesis describes some aspects of the chlorination of
benzene into monochlorobenzene.
The greater part of al-l industrially produced- monochloroben-
zene is mad.e by means of the chlorination of liqLlid. benzene.
In this process iron trichlorid-e is used- as a catalyst. This
is formed- in the reactor by reaction of chlorine with iron
rings.
The lower the chlorination rate is, the smaller the percent-
age of higher chlorinated" benzenes will be.
It is a commonly accepted fact that the materials used- in
the industrial process have to be very carefully [Link]. in
ord-er to ensure a satisfactory conversion rate. It has ap-
peared. from laboratory research, on the other hand-, that
small traces of water speed- up this kind. of reaction. We ex-
pected-, therefore, that the best reaction rate might be ob-
tained. somewhere in the range of very low concentrations of
water.
It was our main intention to try and. determine guantitative-
1y this influence of traces of water on the reaction rate.
lle also wanted. to gain a better insight into the several
process steps appearing in the absorption of chlorine from
the gas into the liqrid- phase and. in the [Link] of
[Link] acid- the other way rouJrd.
In ord-er to [Link]- this complex reaction system it bras
absolutely essential to analyse the kinetics of the chlori-
nation reaction camied out in a homogeneous liguid phase
consisting of reacti-on components. We used. iron trichloride
and, iodine as catalysts. Although not applied- industrially,
[Link] has been analysed. because we were looking for a cat-
alyst the activity of which is not affected by traces of
water.
The kinetic analysis mad.e by other scientists have either
produced. contrad-ictory results or are of little use to us
because the mixture of benzene a^[Link] was not
employed as a solvent.
The kinetic relations d-escribed. in chapter three have been
[Link]. either by measuring the [Link] of the chlorine
concentration with timer or by measuring the rise in temper-
ature in a small, stimed. reactor, well isolated and. contin-
uously fed-. It is possible to keep the quality of the
IJU
catalyst constant using this reactor for the analysis of the
catalytic activity of iron trichlorid.e; more so, in fact,
than in a (semi-) U*tchwise operate,J. reactor.
We determined for both catalysts to what extent the chlori-
nation rates depend. on the concentration of the components
taking part in the reaction.
The reaction rates measured. when using iron trichlorid.e can
be explained by assuming that a monocomplex of iron trichlo-
rid"e and- water j-s the catalytically active cornpound.. The part
of iron trichlorid.e present as the monocomplex is largest
when the molecular raiio of water and. i-ron trichlorid"e is
one. When this ratio increases the catalytic activity will
go down rapi-d-Iy because the monocomplex will be converted.
into higher hyd-rates.
This assertion is closely bound up with,and is supported by,
the evid-ence found- by [Link]-ng part of the phase d-iagram
FFeC13-H2O-HC1. It appeared, that only the monocomplex is
properly soluble in benzene. The higher hyd-rates, on the
other hand., are almost completely insoluble, although their
solubility is increased- when Lrydrochloric acid- is present.
We see, therefore, that a small trace of water i-s essential
for the preparation of a catalytically actj-ve solution of
j,ron trichlorid-e. Only too easily, however, so rmrch water
may be d-rawn from the air or otherwj-se that higher hydrates
of iron trichlorid.e will precipitate (tfre so-cal1ed "poison-
ing" of, the catalyst ).
We are now in a positj-on as a result of the researches done,
to prepare catalyst solutions of reproducible acti-vity and.
lo nrprli nt - fa'i r'l v á . í r í l 1 r aw .v ïv .r e
J l
-. *uhr rae n h l n - i nr fai t i O n
vrrrvr fate When
t
using iron trichlorid.e as a catalyst.
[Link] not been able to demonstrate the mutual depend-ence
of chlorination rates and the quantities of water in the
r e a c t i o n m e d . i u mw h e n i o d , i n e w a s u s e d _ . A c o m p o u n d _o f i o d i n e
and- chlorine, most probably ICI formed. in a equílibrium
rar n* i nn i a *v1r [Link] e n * i rvrvo na rf Of tvhr e ea.f a.l vSt
wvvr
}rer
v vf rv vqvqlJ .
In mixtures of benzene and. monochlorobenzene the chlorina-
tion rate of benzene is higher than in pure benzene.
Both kind-s of catalyst have been employed. when we carrj-ed.
out the chlorination reaction i-n a bubble column, cf . Chap-
ter {. Gaseous chlorine is add-ed to this type of reactor and
it has to 'lissolve into the liquid phase to get the reaction
started. [Link] acidformed. during the reaction desorbs
from the reaction [Link],
131
When we ad"d-iron trichl-orid-e catalyst as a solution to the
bubbl-e column, the reactor can be manipul-ated in such a way
(Uy aling the ad-d-edbenzene with the gaseous hyd-rochloric
acid.) that only the water combined- with the iron trichlorid-e
remains in the reaction med-ium. Great catalytic activity is
achieved, in this way. The conversion rates measured seam to
be higher than those pred-icted" inthe kinetic relations. The
confidence Ínterval-s of the two measurements overlap however.
When, in the bubble column, the catalyst is formed- from iron
rings in the reactor itself, as is the case in the industrial
production, the phenomena then observed- can almost complete-
ly be erplained by means of the kinetic relations and. the
lcrowled-ge obtained. by [Link] part of the phase diagram
B-FeCI3-H2O-HCt.
As the reaction system in the bubble column is practically
[Link] as the one used" in industry, it j-s now possible to
explain the catalyst formation and- the d-epend-enceof the
chlorination rate on traces of water in the latter.
When iod-ine is used. as a catalyst in the bubble column the
actual reaction rates appear to be about five times as high
as the ones pred-icted- from the kineti-c measurements. No
simple erplanation can be offered" for this [Link].
The solubility of chlorine in benzene saturated with hyd-ro-
chloric acid. appears to be at least twice the solubÍlity,
known from the literature on the subject, in benzene con-
taining no hyd,rochloric acid..
When chlorine is absorbed- the hyd-rochloric acid- which d-esorbs
andtheevaporating benzene may very probably cause gas phase
resistance.
The cooperation of the mixing in the liquid. phase and the
chemical reaction is an unknown factor. It is impossible,
because of these three factors, to determine from the mea-
sured- quantities the mass transfer coefficients of absorption
of chlorine into benzene.
More work has to be [Link]. to each of these three points.
Generally the reaction components are separated. in one or
more distillation columns i-n order to obtain pure monochlo-
robenzene. In the rectifying chlorination, as [Link]. in
Chapter 5, reaction and [Link] are concentrated- in one
apparatus. We checked- the useful-ness of this procedure in
the chlorinations [Link]. out in distillation columns.
Over the chlorine supply, about halfway the column, the
chlorination reaction takes pIace. Benzene and- monochloro-
benzene are separated- in the bottom half of the column, the
stripper.
tJ.
Due to the fact that there is a minirru.m heteroazeotrope for
benzene and. water, the ever present traces of water gather
at the top of the column. It is ind-ispensable for satisfac-
tory, reproducible catalyst formation that there are iron
rings just beneath the top cooler.
Both when iron trichlorid.e is ad.d-ed-as a sol-ution i-n benzene
and. when it is formed" in the column from iron rings,decompo-
siti-on reactions will take place in the stripper and- a larger
quantity of [Link] will consequently be formed..
When iodine is added- as a càtalyst it reacts with the chlo-
rine prebent giving iod-ochlorine. This component has a vola-
tility somewhere between those of benzene aÍrd. monochloroben-
zene and accumulates therefore at a given height in the
column. This i-s a suspend-ed. catalyst. Unfortunately,however,
the application of iod-ine entails the formation of consid-er-
able quantitj-es of by-products. The bottom product contained"
so nmch iodine that it d-oesfnt seem feasible to maintain the
chlorination reaction with iod-ine for a longer period. with
only one d-ose of catalyst.
To apply the rectifying chlorination with ar5r success it is
therefore necessary to find a catal-yst having its boiling
point near the one of benzene, glving no equilibrium reaction
with chlorine and" which is preferable not susceptible to
traces of water.
In the final chapter considerations on the choice of a reac-
tor for industrial- use are elaborated. into a [Link] for a
reactor; a limited number of bound"ary cond-itj-ons were taken
into account. This d-esign, a bubble column, appears to agree
reasonably well with the reactor [Link] empirically in
industry.
133
