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United States

atenr

T
C6

2,827,502
Patented Mar. 18, 1958
v2

comprises "contacting the :reactants :with a r?nely: divided


halogenation catalystiintthe form :of a relatively dense
?uidized mass under halogenatiomconditions.

2,827,502
IMANUFACTURE 0F .HALOGENATED AROMATIC
.HYDRQCARBONS

In-accordance withoureinvention the'reactants, which


-may .comprise an oxygen-stable aromatic hydrocarbon,
hydrogen halide. andanoxygen-containing gas, must be

Wilfred 1R. Loesen'New' Brunswick, and John H. Schmidt,

in a vaporous' condition .and . should be at. attemperature

'Upper ~vMontciair, N. $3., assignors _to Union Carbide

of from about 200 ,C.~:to;about"300 .C; before 'beingin


.troduced into the reaction :vessel. Any-suitable means

Corporation, a corporation of New York

Application. February 17, 1954, Serial No. 410,961


'2 Claims. 1(Cl. 260-650)

10

:mayjbe employed itO vaporize and :heat .t'hereactants.


For example, the reactants .can :be introduced into .a

vaporizer operatedrat a temperaturezofirom about'l40"


C. to about 225 C.;andj preferably within the range of
from about 200 C. 'tofabout 220C. and thee?iuent
from the vaporizer :passed tto'a superheater operatedat. a
temperature .of from iab,out225 ;C. :to about 260 C.

vThis invention relates to an improved method for carry

;ing out the halogenation of aromatic hydrocarbons and


jmore'particularly relates'to the chlorination of benzene.

and preferably withinihe'range ofi-fromabout 225 C.


to about 240 C.
Halogenated hydrocarbons are of great industrial im
The vaporous, superheated reactants are then introduced
portance as base materials in the production of many
chemicals. Monochlorobenzene, for example, is used 20 .into a reaction zone ;which contains a mass ofcatalyst
particles maintained in a state ofiiuidization resembling
commercially as a reactive intermediate for the produc
a boiling liquid. Althoughthecatalyst-particles can be
tion of, phenol.
maintained in a '?uidized state-by usingan inert gas as
.It is known in the art that chlorobenzene can be pro
?uidizing medium, thexcombined .reactant stream from
duced by reacting benzene, hydrogenchloride and air in

the presence ,of a ?xed bed of a suitable catalyst. One 25 the .superheater is preferably passed up through the

such process involves continuously passing .a vaporous

catalyst bed at-su?icient velocity to maintain the particles

mixture of benzene, hydrochloric acid and 'air through

in a relatively dense ?uidized state. Velocities .of from


about 0.1 to'a'oout l.5'ft./sec.have beenfound to be

a ?xed bed of catalyst and recycling unreacted com

,ponents back through the catalyst bed. The catalyst em

lployed .in this operation usually comprises a chloride of

to O

satisfactory when the catalyst .particle size is between


about 40 and about 200 mesh. Obvicusly,'any combina

;a metalhaving a variable valence or an oxide of a'metal

tion of reactant vapors and inertgasican be used to main

having a variable valence which will convert to the corre

tain the desired conditions-of ?uidization.


The catalyst may be any halogenat'ion catalyst, such as

sponding chloride in the presence of hydrogen chloride.


A suitable catalyst of this type is cupric chloride, which
readily contributes chlorine atoms for the chlorination of
benzene and reduces to a lower valence state, i. e. cuprous

chloride.

The higher valence state is again obtained

a halide of a metal having- a variable valence or an oxide

of such a metal which .will converttothe corresponding


halide in the presence of hydrogen halide. Supported
copper chloride is a satisfactory catalyst for thechlorina

tion of benzene and coprecipitated copper hydroxide


the hydrogen chloride and is converted to cupric chloride. 40 alumina has been found to bean excellent catalyst for
the ?uidized operation of our invention. Particles of any
-~Although this process for producing chlorobenzene is
?uidizable size may be utilized but a preferred rangeof
.apparently continuous in nature, it actually involves
particles is between 40 and 200 mesh.
..periods of inoperation, occurring every three to six
The reaction vessel may comprise any suitable closed
months, during which the reaction must be completely
stopped and the chloride catalyst in the reactor complete 45 vessel having provisions for introduction of reactants and
separate withdrawal of catalyst- particles and reaction
1y replaced or regenerated. Regeneration of the catalyst
e?luent, but preferably comprises an outer shell'having
whichnormally comprises burning off the tars and other
a conical bottom and an inner open-top vessel having a.
residual matter formed on the catalyst during the chlori
conical bottom. .Theireaction zone should-be maintained
nation reaction, is generally considered uneconomical in
.view. oftheheat requirements and explosion hazards in 50 at a temperature from about 150 Cato about 300 C.
when the cuprous chloride accepts chlorine atoms from

and preferably within the range. of from about'l90" C. to


volved. .Such a regeneration requires'an initial purge of
about 210 C. A portion of the catalyst-particles is
,the catalyst .with steam in order to remove entrapped
withdrawn from the reactor. When'the preferred'fcrm
.benzene and monochlorobenzene, which would other
of reactor is used, the fluidized catalyst bed is maintained
wise tviolently react with the regeneratingair in an ex
:plosivemanner. The steam purge results in both heat 55 in the inner vessel and a portion of the catalyst is caused
to spill over the top of theinner vessel to the bottom
.losses and product losses. For these reasons when the
of the reactor from which the catalyst can be withdrawn.
processis shut down due to lowered catalyst activity,
Withdrawn catalyst is then passed to arseparate re
.spent catalyst is usually removed and replaced with fresh
generator, which may be of ?xed bed, moving bed or
catalyst. One of the big problems that arises due to
such shutdowns relates to corrosion, since the reduced 60 ?uidized bed design. Preferably, the regeneratorris con
structed similarly to thereactor. The catalyst particles
temperatures during shutdowns result in water conden
may be passed from the 'reactor to the regeneratorrby
- sation and concomitant corrosion of the reaction vessels.
means of gravity ?ow, mechanical conveyor or gas lift.
We propose to overcome the above disadvantages by
In the regenerator, tars and other impurities on the cata
.providing a continuous process for halogenating an

aromatic hydrocarbon which requires no shutdowns for 65 lyst are removed by treating the catalyst with a-regen
crating gas, such as steam or an oxygen-containing gas,
catalyst regeneration or replacement and which is simpler,
at a temperature within the range offrom about 350. C.
more economical and more ef?cient than prior processes.
to about 500 C. Advantageously, the catalyst inthe
A speci?c object of our invention is to provide an im~

regeneration zone is maintained in a fluidized state, the

proved process for the continuous production of chloro


70 preferred ?uidizing medium comprising the regenerating
benzene from benzene, hydrogen chloride and air.
gases. A portion of the catalyst particles is removed from
Broadly stated, our invention comprises an improved
the regenerator and passedto the reactor. This is, pref
' process'for halogenating an aromatic hydrocarbon which

;.erably accomplished.by;suspending the regenerated;cata

2,827,502 '

drops to the bottom. of regenerator 15. The hot e?uent

lyst particles in a stream of hot e?luent gases from the re


generator and passing the suspension to a separation zone,
such as a cyclone separator from which catalyst par
'ticles are removed and passed to the reactor. The hot
gases removed from the separation zone maybe passed

gases from regeneration chamber 14 leave the bottom


of regenerator 15 and carry the regenerated catalyst par
ticles from the bottom of regenerator 15 through line 16
to cyclone separator 18. The catalyst particles are
separated from the hot gases in cyclone separator 18,
and pass/through screw conveyor 20 and line 11 to, re

to suitable means, such as a heat exchanger, for recovery

of their useful heat.

Obviously, other means may be used

action chamber 9. Su?icient catalyst is maintained in


the bottom of cyclone separator 18 to serve as a gas seal.
generator to the reactor. For. example, inert gases can be
used rather than regenerating gases or a mechanical con 10 The hot gases separated in cyclone separator 18 pass
through line 19, from which they may be passed to suit- ,
veyor can be used instead of a gas lift. A vaporous
e?iuent containing the product is withdrawn from the re- . able heat exchange means for recovery of their useful
to pass the'regenerated catalyst particles from the re- _

heat. A vaporous ef?uent comprising halogenated aro

actor and passed to a separation system for recovery of the


halogenated aromatic compound.

-'

matic hydrocarbon, unconverted aromatic hydrocarbon

'

A suitable separation system comprises passing the

15 and water, is'withdrawn from thevtop of reactor 10

through line 21, and passed to cyclone separator 22.


ef?uent through a cyclone separator, to remove catalyst
?nes, to a packed column in order to condensethe chlori- V Catalyst ?nes are withdrawn from cyclone separator 22
through line 23, and may be discarded or recycled to
'nated hydrocarbon and some of the unreactedreactants.
reactor 10 by means of a suitable recycle, line. A vapor
- The condensed stream is then passed to a'decanter where
7 two immiscible, layers are formed comprising a lower
aqueous layer and an upper hydrocarbon layer. . The

20 ous eftluent is passed from cyclone separator 22 through


line 24 to packed column 25; from which an aromatic

hydrocarbon stream is withdrawn overhead and recycled


through line 26. via line 33 to aromatic hydrocarbon feed

hydrocarbon layer is passed to a fractionatiug column


from which a substantially, pure halogenated aromatic

line 2. A condensed liquid mixturcrof aromatic hydro


carbon, halogenated aromatic hydrocarbon and water

product is recovered. Otherrrecovery systems may be


25

employed instead of the above described system, For ex

" is withdrawnfrom the bottom of column 25, andpassed

ample, the halogenated aromatic hydrocarbon can be ex


tracted from the reaction e?iuent by countercurrently

through line 27'to decanter 23, where two immiscible


layers are formed. f The lower aqueous layer 1s withdrawn

contacting the e?iuent with a solvent for the halogenated '

from the bottom of decanter 28 through: line 29 and the

aromatic compound, such as a higher boiling halogenated


aromatic compound.

'

upper layer, comprising aromatic hydrocarbon and halo

30

i >

Our processis particularly suitable as the ?rst stagere


action of the Rashig Process for the production of phenol

' genated . aromatic hydrocarbon,

is withdrawn from the

side of the decanter and passed through line. 30to frac


tionating column 31-; Aromatic hydrocarbon is with

which comprises reacting benzene, hydrogen chloride and

drawnoverheadrifrom column 31 and. recycled through

- air in a ?rst stage process to form monochlorobenzene and

reacting the monochlorobenzene with steam in asecond 35 Substantially


line 32 via liney33
pure halogenated
tov aromatic aromatic
hydrocarbonfeed
hydrocarbon
line' is
stage process to form phenol. The aqueous hydrogen

chloride recovered from the second stage process-is a _ I ' withdrawn from 'the bottom of column 31 through line

suitable source of the hydrogen chloride feed when the

34 as the product of the process.

'

process.

40

A more speci?c embodiment of our invention is de


scribed in detail below, in connection with the drawing. ,
The drawing is a schematic represenation of one method
of operating in accordance with the teachings of our in
vention.

_ .

The following example'is given to lllustrate thermven

process of. our invention is utilized as the first fstage

tion in more detail.

Example I

>

In an arrangement similar to that shown in the draw

ing 600 parts "(by weight) of 40 to 200 mesh catalyst,


comprising coprecipitated copper hydroxide and alumina,

- are charged to the reactonwhich ismaintained at a tem-

Referring now to the'drawing, an aromatic hydrocarbon


is passed through line 1 via line 2 to vaporizer 3. I-Iy- .

perature of about 2009 C. . Benzene at a rate of 600 parts

per hour, hydrochloric acid (17%, conc.) at a rate of


100 parts per hourran'd air ata rate of 50-60 parts per

drogen halide, is passed through lineA to vaporizer 3, and


a an oxygen-containing gas, such as air, is passed. through
line 5 to vaporizer 3. V The vaporous effluent from vapor

. hour are fedintothe vaporizer, which is maintained at

a temperature 10f about 140 C. The e?iuent from the

izer 3 is passed via line 6 to superheater. 7. The ef?uent


. from superheater 7 is passed via line 8 into the bottom of .

vaporizer is passedto the'superheater, which is operated

reaction chamber 9, which is locat'ed'within reactor 10.

at a temperature of 'about,240 C. 7 From the superheater,

the vapors pass throughthe catalyst bed in the'reactor,


where they effect a teetering action in the powdered cata
lyst resembling boiling liquid. Asa result of this action,

Reaction chamber 9 may be in the form of an'. inverted


cone or other open-top vessel. .A stream of ?nely divided

catalyst particles is introduced into reactor'iti through dip


leg 11, and forms a mass of catalyst particles in reaction
chamber 9. The vaporous reactants. introduced into
. chamber 9 via line 8 cause the mass of catalyst particles in

reaction chamber 9 to assume a state resembling boiling

liquid. A portion of the catalyst particles spills over the

so, spent

. top of reaction chamber 9 and passes down to the bottom ,

a portion of the catalyst spills over and out of the bed


area, and drops to the bottom of the reactor, from which
it is passed to the regenerator. In the regeneratonra
stream of air feeding into the catalyst bed agitates the
catalyst in the same manner as the vapor stream

agitates the catalyst bed in the reactor. As the air stream

passes through the spent/catalyst, tars and other materials


of reactor 10, from which it is conveyed through screw
are burned o? thusetfecting regeneration of the catalyst.
conveyor 12 via dip leg 13*;to regenerator' 15, where it
forms a mass of catalyst particles in regeneration cham 65 At the same time, a portion of the regenerated catalyst
spills over the top, of the catalyst bed and drops to the
ber 14. Su?icient catalyst is maintained in the bottom
bottom of the regenerator, where it is picked up by the
of reactor 10 to serve as a gas seal.>_ Regeneration cham- .
exiting gases and conveyed to a cyclone separator at the
ber 14 may be of a' similar shape to reaction chamber'9.
top of the reactor. The'entrained catalystis removed
An oxygen-containing gas, such as air, is: introduced
from the gas stream in the cyclone separator and is con
through line 17 intovthe bottom ofregenerationchamber
veyed via a screw conveyor. into the catalyst bed in the
14 at a su?'iicently high rate to maintain the catalyst in re,

' generation chamber 14in a state. resembling a boiling.


liquid. Tars and other foreign matter are burned oh" by

~ the air in regeneration chamber 14.

A portion of the par

ticles spills over the lip of regeneration chamber 14 and

' reactor. The hot gases from the cyclone separator are
passed to a heat exchanger to recover their useful heat. .
~ About 10% of the benzene is converted to monochloro

benzene in the. reactor. . Thee?iuent vapors from the re

2,827,502

5
actor, comprising monochlorobenzene, unconverted ben

ticles, and simplicity of transfer of the catalyst particles

zene and water, are passed through a cyclone separator


to remove any entrained catalyst. The vapors are then

from one zone to another.

passed up through the recovery column, which comprises

1. A continuous process for chlorinating benzene,


which comprises introducing a ?nely divided copper
hydroxide-alumina catalyst having a particle size in the

a packed column.

Benzene vapors are withdrawn from

What is claimed is:

the top of the recovery column and a condensed liquid


range of 40 to 200 mesh into a reaction zone while main
mixture of benzene, chlorobenzene and water is drawn
o? the bottom. The benzene stream is recycled to the
taining a temperature in said reaction zone of about 190
reactor and the condensed liquid mixture is passed to
C. to about 210 C., suspending said catalyst particles in
the decanter. A bottom layer of water is removed from 10 a stream of benzene vapor, hydrogen chloride and air
the decanter and a top-organic layer, comprising benzene
to form a relatively dense ?uidized mass in said reaction
and chlorobenzene, is passed to the frictionating column.
zone, continuously removing a portion of said catalyst
Benzene vapor is removed from the top of the fraction
particles from said reaction zone, and removing the tarry
ating column and recycled to the reactor, while mono
surface contaminates formed thereon in the reaction zone
chlorobenzene is removed from the bottom of the frac 15 by suspending said catalyst particles in a stream of a gas
tionating column as the product of the process.
selected from the group consisting of steam, oxygen, and
From a reading of the preceding description of our
air at a temperature from about 350 C. to 500 C., and
invention, it can be seen that we have provided a sim

ple, ei'r'icient and economical process for halogenating

aromatic hydrocarbons. By conducting the halogenation

passing said clean surfaced regenerated catalyst particles


to the reaction zone, continuously removing reaction
20 effluent from said reaction zone and recovering chloro

reaction in a ?uidized catalyst bed, we obtain numerous


advantages over the prior art. We obtain better contact
between catalyst and reactants and our process, therefore,

benzene from said reaction e?iuent.


2. A continuous process for chlorinating benzene,
which comprises introducing a ?nely divided copper

requires less catalyst than prior ?xed bed processes. In

hydroxide-alumina catalyst having a particle size in the

addition, our catalyst bed is constantly maintained at a 25 range of 40 to 200 mesh into a reaction zone while main
high level of activity due to the continuous regeneration
taining a temperature in said reaction zone of about 190

of the catalyst particles. Several important advantages

C. to about 210 C., suspending said catalyst particles in

of our process are obtained due to the fact that it does

a stream of benzene vapor, hydrogen chloride and air to


not require periodic shutdowns for replacement or re
form a relatively dense ?uidized mass in said reaction zone,
generation of catalyst. This means that we can operate 30 continuously removing a portion of said catalyst particles
our process more economically than prior art processes,
from said reaction zone, and removing the tarry surface
since we eliminate the expense of frequent replacement
contaminates formed thereon in the reaction zone by
of catalyst particles and the heat and product losses which
suspending said catalyst particles in a stream of air at a

accompany periodic regeneration of catalyst particles. In


addition, by eliminating periodic shutdowns for replace

temperature from about 350 C. to 500 C., and passing


said clean surfaced regenerated catalyst particles to the

ment or regeneration of catalyst, we completely eliminate


reaction zone, continuously removing reaction e?luent
the corrosion problems which would otherwise be pres
from said reaction zone and recovering chlorobenzene
ent due to the condensation of water resulting from the
from said reaction e?iuent.
reduced temperatures during shutdowns. Continuous op
References Cited in the ?le of this patent
eration also has the obvious advantage that no produc 40
tion time is lost due to periodic shutdowns for regenera
UNITED STATES PATENTS
tion or replacement of the catalyst. Other advantages of
1,963,761
Prahl ______________ .._ June 19, 1934
our ?uidized catalyst operation of our invention are uni
2,602,021
Belchetz ____________ __ July 1, 1952
formity of temperature throughout the reaction zone, re
sulting in greatly reduced tendency to form side products 45
FOREIGN PATENTS
as a result of localized overheating, easier control of
487,596
Germany ____________ __ Dec. 12, 1929
temperature in the reaction zone because of the excellent
720,079
Germany ____________ .._ Apr. 23, 1942
heat transfer characteristics of the ?uidized catalyst par