Title of Invention

A PROCESS AND DISTILLATION DEVICE FOR THE WORK UP BY DISTILLATION OF CLEAVAGE PRODUCT MIXTURE

Abstract The present invention claims a process and an apparatus for the work-up by distillation of cleavage product mixtures produced in the cleavage of alkylaryl hydroperoxides. Usually, in the work-up by distillation of cleavage product mixtures which are produced in the cleavage of alkylaryl hydroperoxides, the cleavage product mixture is divided into three main fractions, for which at least two distillation columns are used. The use of two distillation columns has the disadvantage that the capital costs, and also the energy costs, in these conventional processes are relatively high. By means of the inventive process for the work-up by distillation of cleavage product mixtures, the equipment requirements and the energy consumption can be markedly reduced in comparison with customary plants, since the cleavage product mixture can be resolved into the three main fractions in only one apparatus. The inventive process can be used for the work-up by distillation of cleavage product mixtures produced in the cleavage of alkylaryl hydroperoxides, in particular in the cleavage of cumene hydroperoxide. By using the inventive process it is possible to separate off phenol and acetone from a cleavage product mixture that was obtained in the cleavage of cumene hydroperoxide.
Full Text Process and apparatus for the work-up by distillation of cleavage
product mixtures produced in the cleavage of alkylaryl
hydroperoxides
The invention relates to an improved process for the work-up by distillation
of cleavage product mixtures produced in the cleavage of alkylaryl
hydroperoxides. In particular, the present invention relates to a process for
the work-up by distillation of cleavage product produced in the cleavage of
cumene hydroperoxide.
The process of acid-catalyzed cleavage of cumene hydroperoxide into
phenol and acetone has long been of particular industrial importance. In
this preparation of phenol from cumene by the Hock process, in a first
reaction stage, the oxidation, cumene is oxidized to cumene hydroperoxide
(CHP) and the CHP is then concentrated in a vacuum distillation, the
concentration stage, to 65 to 90% by weight. In a second reaction stage,
cleavage, the CHP is cleaved into phenol and acetone by the action of an
acid, usually sulfuric acid. In addition to phenol and acetone the cleavage
product has other compounds which can be formed in the reaction steps
preceding the cleavage and which are not converted, or are only partially
converted, in the cleavage. The most important compounds which can be
present in the cleavage product in addition to phenol and acetone are, in
particular, a-methylstyrene (AMS), cumene and acetophenone. In addition,
small amounts of dimethyl phenyl carbinol (DMPC) already formed in the
oxidation may be present in the cleavage product Further impurities
comprise compounds such as methylbenzofuran (MBF), hydroxyacetone,
mesltyl oxide (MO) and carbonyl compounds such as (acet)aldehydes and
2-phenylpropionaldehyde, for example. After neutralizing the cleavage
product and any removal of an aqueous phase, the cleavage product is
worked up by distillation.
Various processes for work-up of the cleavage product by distillation are
known (Ullmann's Encyclopedia of Industrial Chemistry, 5th completely
revised edition, Vol. A19,1991, VCH Verlagsgesellschaft mbH, Weinheim).
In principle, in all these processes, the cleavage product is first neutralized,
with aqueous sodium hydroxide solution, amines, aqueous phenolate lye
and/or ion exchanger resin being used. After a phase separation, the
organic part of the neutralized cleavage product is transferred to a first

column in which crude acetone, which can contain water, hydroxyacetone,
cumene and/or AMS, is distilled off overhead from the residual cleavage
product. This crude acetone is usually treated with alkali in a washer and
again purified by distillation. However, in part, the wash also takes place in
the column. The bottoms product produced in the first column is distilled in
a second column, residual AMS and cumene being taken off from this
column overhead and usually being fed to a hydrogenation in which
cumene is again prepared. AMS and cumene can also be separated off in
an azeotropic distillation with water. The bottoms product remaining in the
second column is distilled in a crude phenol column.
The resultant crude phenol can be further purified by an extractive
distillation with water and/or by treatment with an acid ion exchanger and
subsequent distillation. In the latter process compounds which are difficult
to separate from phenol by distillation, for example mesityl oxide and
hydroxyacetone, are condensed to form higher-boiling compounds.
In DE-AS 1 105 878 (phenol chemistry) also, the neutralized cleavage
product which is separated off from the crude acetone in a crude acetone
column is transferred into a hydrocarbon column in which, in the presence
of water, hydrocarbons boiling lower than phenol, such as AMS and
cumene are distilled off overhead. From the bottom of the column the
organic phase is taken off and applied to the top of a downstream column
in which water is separated off from phenol and high-boilers which are
produced in the bottom of the column. The mixture of phenol and high-
boilers is men transferred to a crude phenol column. The residues
produced in the crude phenol column and in the pure phenol distillation
can then be fed to a cracking still in which the residues are worked up and
one part of phenol is recovered. These recovered products of value can
again be transferred to the hydrocarbon column.
EP 0 032 255 (UOP) describes a process for working up cleavage product
in which the organic part of a virtually neutralized (pH ≈ 6) cleavage
product is again washed with water and then the organic part is transferred
to a crude acetone column in which the crude acetone is separated off
from the remaining cleavage product. The residue remaining in the bottom
phase is transferred directly to a cumene column in which the crude phenol
is produced as bottoms product which in turn is fed to a purifying

distillation. The mixture taken off overhead from the cumene column, which
contains principally AMS, cumene and water, is transferred to a phase-
separation vessel in which an aqueous phase is separated off. The
resultant organic phase is transferred to a washing column in which the
organic mixture is treated with sodium hydroxide solution in order to
remove any phenol still present from the mixture of AMS and cumene as
sodium phenoxtde. The mixture of AMS and cumene which has been freed
from phenol is fed via the top of the column to a hydrogenation.
In US 4,262,150 (UOP), also, the same column circuit is used as described
in EP 0 032 255 (UOP). The difference from EP 0 032 255 is that, to
neutralize the cleavage product, an extraction column is used instead of
one or more combinations of mixers and phase-separation apparatuses.
US 3,322 651 (UOP) describes the use of nitrogen compounds, in
particular amines, for purifying phenol obtained in the cleavage of CHP.
US 5,510,543 (GE) describes a process for working up the cleavage
product from CHP cleavage, in which the cleavage product is adjusted to a
pH of 4.0 to 4.9 in a neutralizer by adding a base, in particular sodium
hydroxide solution. In the neutralizer the cleavage product is separated into
an aqueous phase and an organic phase. The organic phase is transferred
to a column termed the splitter in which the cleavage product is separated
by distillation into an acetone-rich fraction and a phenol-rich fraction. The
phenol-rich fraction is taken off at the bottom of the column and fed to a
phenol purification, which can consist, for example, of one or more further
distillations. The acetone-rich fraction is taken off at the top of the column
and fed to an acetone column, in which case base is added to this fraction
before entry into the column in such an amount that the fraction has a pH
of approximately 9, so that the organic acids which are also present in this
fraction are neutralized. The mixture arising in the bottom phase of the
column which, in addition to water, also contains hydrocarbons and the
salts of organic acids, is transferred to a phase-separation apparatus in
which this mixture is separated into an organic phase and an aqueous
phase. The organic phase can be treated again for recovery of cumene.
Furthermore, processes have been developed in which individual fractions
which arise in the work-up by distillation of cleavage product are treated
specifically. Thus, US 5,487,816 (UOP) describes a process for separating

off AMS from a mixture which contains phenol, AMS and water and which
arises as bottom product of a crude acetone column. The crude acetone
column is operated in this case in such a manner that cumene is taken off
from the cleavage product at the top of the crude acetone column together
with the acetone. The mixture containing AMS and phenol is separated in
a column in such a manner that in the bottom of the column predominantly
phenol is produced, which can be fed to further work-up, and at the top of
the column a mixture of AMS, water and smaller amounts of phenol is
taken off, which mixture is condensed and adjusted to a pH above 6 by
adding a basic reagent. This achieves the phenol being principally present
in the aqueous phase, white the AMS is present in an organic phase in
which only small amounts of phenol are present as impurity. The phases
are separated from one another by a phase-separation apparatus. The
organic phase can be fed to a hydrogenation, white the aqueous phase
can be fed back to the column as reflux.
In US 4,370,205 (UOP), the stream taken off from the bottom of the crude
acetone column also still contains cumene, in contrast to the process
described in US 5,487,816 (UOP). Against this background a different
column circuit is proposed. In particular two columns operated under
virtually the same conditions are used in which the bottoms product
produced is predominantly phenol, whereas predominantly AMS and
cumene are taken off overhead. The crude phenol taken off as bottoms
product in the first column is fed to further work-up steps, and the crude
phenol taken off as bottoms product in the second column is fad back to
the first column. The overhead product of the second column is treated
with sodium hydroxide solution in a wash column. The overhead product of
this column, which comprises AMS and cumene, can be fed to the
hydrogenation.
In US 4,251,325 (BP Chemicals), the work-up of a fraction which has been
freed from low-boilers and acetone is optimized such that the cumene
column is operated in such a manner that at the top a mixture is taken off
which comprises cumene, AMS and hydroxyacetone, where the latter is
virtually completely separated off from residual crude phenol, and thus
need not be separated off in a complex manner during the phenol work-up.

US 4,333,801 (UOP) describes the work-up of a fraction which comprises
AMS, cumene, phenol, water and impurities, for example hydroxyacetone.
This process is chiefly concerned with removing an AMS/cumene fraction,
which has a very low phenol concentration, from the total fraction. This is
achieved by operating the cumene column in such a manner that a mixture
of cumene and AMS is taken off overhead from the column, which mixture
is condensed and run into a phase-separation vessel. Any water possibly
present is separated off and discarded. A portion of the organic phase is
fed back to the column top as reflux. Another portion of the organic phase
is fed to a washer in which phenol residues which would interfere with the
hydrogenation are removed from the phase so that this phase can be fed
to the hydrogenation. From a side stream takeoff of the cumene column
there is taken off a fraction comprising AMS and cumene and an
azeotropic mixture of water and phenol, which fraction is also condensed
and transferred to a phase-separation vessel. The aqueous phase which
can comprise phenol is fed to a work-up stage. The organic phase which
comprises cumene, AMS and as much phenol as remains in the organic
phase in accordance with the phase equilibrium between the organic and
aqueous phases is evaporated and fed back in the vaporous state into the
cumene column above the side stream takeoff. A crude phenol fraction is
taken off from the bottom of the column.
A further process is described in US 5,064,507 (Allied). In this process the
cleavage product is first separated from the crude acetone in a crude
acetone column. The bottoms product is transferred to a cumene column
in which cumene and AMS are removed from the cleavage product. The
column is, however, operated in such a manner that a certain portion of
AMS is still present in the bottoms product, since this is required as a
reaction partner or solvent in the further work-up of the phenol to remove
MBF and other impurities. This bottoms product is reacted with an amine,
preferably hexamethylenediamine, in a reactor having plug flow
characteristics to convert carbonyl impurities, for example acetol
(hydroxyacetone, HA) or MO, into higher-boiling compounds. The product
thus treated is further worked up by distillation. By the purified end product
phenol, flow will have passed through a further four columns and two
reaction zones.

US 5,131,984 (Allied) describes the work-up by distillation of crude phenol,
which has been separated from the predominant portion of acetone,
cumene and AMS. This crude phenol is treated in a vacuum distillation
column in such a manner that a vaporous mixture which comprises phenol
and low-boilers is taken off at the top of the column. This mixture is run into
a condenser in which the predominant portion of the vaporous mixture is
condensed. The condensed portion of the mixture is run back into the
column, in which case the purity of the phenol taken off as product was a
function of whether the condensate was fed back into the column at the
top or below the top. The vaporous portion which, inter alia, comprises low-
boilers and acids, is fed to a further treatment for example a further
distillation column. A phenol-comprising fraction, which can be further
worked up, is taken off from the vacuum distillation column, from a side
stream takeoff which is disposed at least one theoretical stage below the
top of the column.
A similar process is described in US 5,122,234 (AHied) with the difference
mat water is additionally run into the column and at the top of the column a
mixture which predominantly comprises water and phenol is taken off,
which mixture is partly condensed and returned to the column.
Alt known processes for work-up by distillation of cleavage product are
relatively complex, since usually two distillation columns alone are required
for separating the main constituents of the cleavage product into three
main fractions, crude acetone, AMS/cumene and crude phenol. Further
work-up of the mam fractions to remove unwanted byproducts, for example
water, requires a lot of equipment. AN the processes currently used have a
relatively high energy consumption, in particular a high steam
consumption. Since the production of phenol comprises several million
metric tons per year, even small savings in costs of energy or capital costs
can be critical for the competitiveness of a process.
The object of the present invention was therefore to provide a process for
work-up by distillation of cleavage product from the cleavage of cumene
hydroperoxide in which, with a small energy consumption and low
requirements of equipment, the mam products acetone, cumene/AMS and
phenol can be separated from one another and from unwanted
byproducts.

Surprisingly, it has been found that by separating the cleavage product by
distillation into three main fractions in a single distillation step the main
products can be effectively separated from one another with a lower
energy consumption and lower equipment requirements than in customary
processes and the removal of unwanted byproducts is also simplified.
The present invention therefore relates to a process according to claim 1
for the work-up by distillation of cleavage product produced in the cleavage
of alkylaryl hydroperoxides, which comprises resolving the cleavage
product into at least three fractions in a single distillation step.
The present invention also relates to a distillation column for the separation
by distillation of cleavage product mixtures from cumene hydroperoxide
cleavage as claimed in claim 15, which is dimensioned such that a crude
acetone fraction comprising at least 75% by weight of acetone can be
token off at the top of the column, a crude phenol fraction comprising at
least 75% by weight of phenol can be taken off at the bottom of the column
and a fraction which comprises at least hydroxyacetone and cumene
and/or α-methylstyrene can be taken off from the side of the column.
The present invention also relates to a process as claimed in claim 21 for
preparing phenol and acetone which comprises the steps
- oxidation of cumene to cumene hydroperoxide
- cleavage of cumene hydroperoxide
- work-up by distillation of the cleavage product mixture produced
in the cleavage of cumene hydroperoxide, which comprises resolving the
cleavage product mixture into at least three fractions in a single distillation
step.
The invention also relates to phenol that is obtained using a process as
claimed in at least one of claims 1 to 14.
The invention also relates to acetone that is obtained using a process as
claimed in at least one of claims 1 to 14.
The advantage of the inventive process is that the separation steps chosen
in the distillation substantially simplify a further work-up of the cleavage

product mixture or of the individual fractions which are obtained from the
cleavage product mixture. In particular, the combined removal of
hydroxyacetone, AMS and cumene from the phenol-containing residue of
the cleavage product mixture considerably simplifies the work-up of the
phenol-containing residue, since the steps that ate carried out in
conventional processes in which the hydroxyacetone remains in the
phenol-rich fraction and is removed from this by the hydroxyacetone being
reacted with phenol to form compounds having a higher boiling point than
phenol and which can be separated from phenol by distillation, are omitted
and the steam consumption is lower in the resolution into said separation
steps.
Compared with customary processes, the inventive process has a
substantially more favorable energy balance and, compared with
processes in which hydroxyacetone is removed from the process by
reaction with phenol, also has a higher overall yield of phenol, based on
the phenol content in the cleavage product mixture. The customary
procedure requires a relatively high energy consumption. In addition, in
customary processes, the yield of phenol is decreased, since the
hydroxyacetone reacts to exhaustion with the phenol, or expensive
chemicals, for example amines, must be added, which must themselves,
or their reaction products, be removed again from the process in a
complex manner.
The inventive process which avoids this problem by separating off the
hydroxyacetone together with the cumene from the cleavage product
mixture also requires a considerably smaller amount of equipment, since
the separation of the cleavage product mixture into three fractions in a
single distillation step decreases not only the number of the required
distillation columns, but also the number of reaction apparatuses which ate
required to decrease the content of the various byproducts in the fractions.
Depending on the way the individual process steps are carried out, that is
to say oxidation, cleavage with possible post-heating and hydrogenation,
the steam consumption over the entire process per kg of phenol can be
markedly decreased by employing the inventive process, compared with
customary processes for which a consumption of 3.2 kg of steam/kg of
phenol is quoted {from: Phenol/Acetone/Cumene, 96/97-2, from Chem

Systems, 303 South Broadway, Tarrytown, New York 10591). By means of
the inventive process the energy consumption for the preparation of phenol
which is suitable in each case for preparing bisphenol A can be markedly
decreased. Also, depending on the way in which the individual
abovementioned process steps are carried out, the yield of phenol in
relation to the cumene used can be markedly increased, compared with
processes in which HA is reacted with phenol to form high-boilers.
For the purposes of the present invention, the total number of plates
present in a column is defined as 100% separation potential,
independently of the number of plates, in order, in this manner, in the case
of columns having a different number of plates, to be able to specify the
range in which a similar separation potential is present The bottom of the
column, that is to say the region below the first plate, therefore has a
separation potential of 0%. At the top of the column, that is to say in the
range above the uppermost plate, in accordance with the definition, there
is a separation potential of 100%. In accordance with this definition, a
column having 50 plates has a separation potential of 30% in the region of
the 15th. plate.
The inventive process can be used for the work-up by distillation of
mixtures of substances produced as cleavage product mixtures in the
cleavage of alkylaryl hydroperoxides, in particular in the cleavage of
cumene hydroperoxide into acetone and phenol. The cleavage product
mixtures can be obtained by homogeneous or heterogeneous catalysis.
Preferably, the inventive process is applied to cleavage product mixtures
which are obtained by a homogeneous, acid-catalyzed cleavage. The acid
homogeneous catalyst customarily used is sulfuric acid. The alkylaryl
hydroperoxides can have been prepared in various ways known to
chemists. Preferably, the inventive process, however, is applied to
cleavage product mixtures which originate from the cleavage of alkylaryl
hydroperoxides, in particular from the cleavage of cumene hydroperoxide
(CHP), which have been obtained according to the principle of the Hock
phenol synthesis [H. Hock, S. Lang, Ber. Dtsch. Chem. Ges. 77B, 257
(1944)}. Obviously, the inventive process can also be applied to cleavage
product mixtures which are obtained by processes which are
developments of the Hock process, in particular developments of the
process steps oxidation and cleavage.

If acid is used as catalyst for the cleavage of alkylaryl hydroperoxides, in
particular of CHP, the cleavage product mixture is usually, before the work-
up by distillation, adjusted to a pH of 3 to 10, preferably of 4 to 7. This is
achieved in the manner known to those skilled in the art by adding a base
to the cleavage product mixture. The base can be, depending on operating
conditions, a byproduct from the overall process, for example a phenoxide
lye, an alkaline wash solution, as produced, for example, during the
acetone washing, an inorganic base, for example sodium hydroxide
solution, NaOH, ammonia or ammonium hydroxide or an organic base, for
example an amine or diamine, for example hexamethylenediamine.
The pH can also be adjusted by using ion exchange resins before the
work-up by distillation. Such resins and the use of such resins are known
to those skilled in the art
On account of the cleavage reaction, but also due to addition of catalyst or
neutralizing agent, cleavage product mixtures usually contain a portion of
water. This water can be removed in the manner known to those skilled in
the art, before the cleavage product mixture is fed to the inventive process,
by adding further water or removing an aqueous phase from the cleavage
product mixture. Preferably, the aqueous phase is removed from the
cleavage product mixture in at least one phase-separation apparatus, for
example a separation vessel or a coalescer. Very particularly preferably, a
cleavage product mixture which is to be worked up by distillation using the
inventive process has a water content of 1 to 14% by weight, preferably
from 6 to 10% by weight.
From the neutralization or owing to the use of salt-containing process
streams, the cleavage product mixture can contain salts, in particular
sodium salts or organic ammonium safe. Usually these are removed when
the aqueous phase containing them is separated off from the organic part
of the cleavage product phase. To carry out the inventive process it is
advantageous (because of the reduction of salt deposits on heat
exchangers; fouling), If the cleavage product mixture, before the inventive
work-up by distillation, is treated in a manner known to those skilled in the
art such that the sodium ion content is less than 200 ppm, preferably less
than 50ppm.

The inventive process is described hereinafter using as example the work-
up by distillation of a cleavage product mixture produced in the
homogeneous acid-catalyzed cleavage of CHP, without the process being
restricted to this mode of carrying it out
This cleavage product mixture can, depending on how the process steps
oxidation, cleavage with possible post-heating, neutralization and/or phase
separation into aqueous and organic phases are carried out, in addition to
water and the main products phenol and acetone and the stating material
curnene which is unreacted in the oxidation, also comprise various
byproducts, for example α-methyistyrene (AMS), acetophenone,
hydroxyacetone (HA), phenylbutenes, 3-methyl-cyctopentane,
dimethylphenyl carbinol (DMPC), methyl-benzofuran (MBF), mesityl oxide
(MO) ami other carbonyl compounds, for example hexanone, heptanone
and 2-phenylpropionaldehyde. Preferably, tits cleavage product mixture
comprises at least 20 to 70% by weight of phenol, 15 to 45% by weight of
acetone, 5 to 30% by weight of curnene, 1 to 5% by weight of AMS and
200 ppm to 5% by weight of HA.
According to the invention the cleavage product mixture is resolved into at
least three fractions in a single distillation step. This is preferably achieved
by transferring the cleavage product mixture into a distillation apparatus,
preferably a distillation column, which is dimensioned such that resolution
of the cleavage product mixture into three fractions is possible.
Very particularly preferably, the cleavage product mixture '» resolved into
three fractions such that at least one fraction comprises at least 75%,
preferably at least 95%, of a ketone present in the cleavage product before
the distillation step. When a cleavage product mixture from the cleavage of
CHP is used, this ketone is acetone. Preferably, at least one second
fraction is obtained which comprises at least 75%, preferably at least 95%,
of a substituted and/or unsubstituted phenol present in the cleavage
product before the distillation step.
A third fraction obtained in the inventive work-up by distillation of a
cleavage product mixture preferably comprises at least 75%, particularly
preferably at least 85%, of the mono-, di- and/or trialkyl- substituted

benzene used present in the cleavage product before the distillation step.
In the case of work-up by distillation of a cleavage product mixture from the
cleavage of CHP, this third fraction preferably comprises at teast 75%,
particularly preferably at teast 95%, of the cumene present in the cleavage
product before the distillation step and at least 75%, particularly preferably
at teast 95%, of the α-methylstyrene present in the cleavage product
before the distillation step.
The first fraction which comprises the ketone, or acetone, is preferably
removed at the top of the distillation column. The second fraction which
comprises the substituted or unsubstituted phenol is preferably taken off at
the bottom of the column. The third fraction, which comprises the
unreacted mono-, di- and/or tnalkyl-substituted benzene used in the
oxidation, and when phenol is prepared comprises the cumene, is taken off
from a side stream takeoff of the distillation column. Preferably, the side
stream takeoff is situated above the feed of cleavage product mixture into
the column, which is also performed at the side.
The inventive process for work-up by distillation is preferably canted out
such that the bottom temperature in the distillation collumn is 140°C to
200*C, particularly preferably 170 to 190°C. The temperature at the top of
the column is preferably 30 to 90°C, particularly preferably 38 to 58°C. The
temperature in the column interior in the region of the side stream takeoff
is preferabfy 80 to 120°C, paricuterty preferably 65 90°C.
it can be advantageous to feed back into the distillation column as reflux a
portion of the three fractions taken off from the column from the top, from
the bottom and/or from the side stream takeoff.
The recycle from the bottom into the column is preferably heated via a heat
exchanger, in which case the heating medium used can be steam or a
process stream having sufficient thermal energy. Hie recycle ratio, defined
as the amount of bottoms product recycled in the vapor state divided by
the amount of bottoms product removed is preferably 0 to 10.
The reflux of the overhead product token off at the top in the vapor state is
preferably condensed by a heat exchanger and returned as liquid to the
distillation column. The reflux ratio, defined as fie amount of overhead

product returned in the liquid state divided by the amount of overhead
product removed is preferably 0.2 to 20, particular preferably 2 to 4.
in the case of the fraction taken off from the side stream takeoff, which can
comprise water and can be divided into two phases in a phase separation
apparatus, it can be advantageous to recycle at reflux to the column the
organic portion of this fraction, the aqueous portion of this fraction or a
mixture of organic and aqueous portions. Very particularly preferably, the
aqueous portion and the organic portion of this fraction are recycled
separately to the distillation column. The reflux ratio based on the amount
of recycled water and the amount of water token off is preferably 0.2 to 3,
very particularly preferably from 0.4 to 2. The water which is recirculated to
the column can be fed Into the column in the liquid or vapor state,
preferably in the liquid state. The reflux ratio based on the amount
recirculated and the amount of organic phase taken off Is preferably 0.1 to
10, very particularly preferably 0.5 to 5. The remainder of the organic
portion of this third fraction obtained from the phase-separation apparatus
is fed to further work-up, as is the fraction taken off at the top and bottom
of the distillation column. The remainder of the aqueous portion of the the
fraction obtained from the phase-separation apparatus is fed to work-up or
disposal.
However, it can also be advantageous to feed back a portion of the water
provided for the work-up or disposal into the column in the vapor state,
using a heat exchanger. The material is preferably fad in below the point at
which the cleavage product is fad into the distillation column.
Further work-up of the three fractions obtained in the first distillation step is
preferably performed as work-up by distillation and can be performed as
already described in the prior art The work-up can be performed in
particular adapted to the composition of the fractions. Depending on the
procedure of the inventive process, interfering impurities, in particular
hydroxy ketones, can be present in the second and/or third fraction. If the
hydroxy ketones, for example hydroxyacetone, are present in the second
fraction, this fraction can be separated off, for example from phenol, by the
various processes described in the prior art.

In a particularly preferred embodiment of the inventive process, this is
operated in such a manner that the inventive third fraction comprises at
least 20%, preferably at least 50%, and very particularly preferably at least
90%, of the hydroxy ketones present in the cleavage product before the
distillation step. In the case of work-up by distillation of a cleavage product
mixture from the cleavage of CHP, this third fraction preferably comprises
at least 90% of the hydroxyacetone present in the cleavage product before
the distillation step.
The advantage of this type of carrying out the inventive process is that the
hydroxyacetone which is present in the third fraction accumulates in the
water of this fraction. The hydroxyacetone predominantly passes over into
the aqueous phase in the phase-separation apparatus and can thus be
ejected from the process in a simple manner together with the aqueous
portion of the third fraction. Preferably, the aqueous phase comprises at
least 75%, particularly preferably 95%, and very particularly preferably
98%, of the hydroxyacetone present in the third cumene- and/or AMS-
containing fraction.
It can be advantageous if the cleavage product mixture is resolved, not as
described above into three main fractions, but into at least four main
fractions. Such a fourth fraction can be taken off from a further side stream
takeoff which is disposed above the side stream takeoff via which the third,
cumene-containing fraction is taken off, and is disposed below the too of
the column, and/or can be taken off from a further side stream takeoff
which is disposed below the feed of the cleavage product mixture and
above the bottom of the column, and comprises at least one organic acid.
As organic acid, this fourth fraction can comprise, for example, acetic acid,
oxalic acid, formic acid or butyric acid or a mixture consisting of at least
one of these acids. Preferably, such fractions comprising at least one acid
can be fed to a neutralization upstream of the work-up by distillation. It can
be advantageous, to provide a plurality of such side stream takeoffs in
order to be able to eject from the column these fractions which comprise
acids having varying boiling points.
In a further particularly preferred type of carrying out the inventive process,
the first fraction which, in the case of CHP cleavage, comprises at least
75% of the acetone present in the cleavage product mixture before the

work-up by distillation, is transferred to an acetone column, preferably in
the vapor state, preferably at the side. In this column the acetone is
separated from impurities to the extent that it meets the requirements of
pure acetone (meeting the permanganate test as specified in ASTM D
1363 - 94). Impurities present in the crude acetone before entry into the
acetone column which come into question are in particular acetaldehyde
as a compound having a lower boiling point than acetone and compounds
which have a higher boiling point than acetone.
To remove the Impurities, the acetone column must be designed in such a
manner that the pure acetone can preferentially be taken off from a side
stream takeoff while a fraction in which acetaldehyde accumulates may be
taken off at me top of the column. This fraction can in part be recirculated
directly to the acetone column, in which case a heat exchanger can be
provided by which the aceteldehyde-enriched fraction can be completely or
partly condensed. The reflux ratio, defined as the amount of reffux in the
top divided by the amount of the side stream, is preferably 0.1 to 1000.
Particularly preferably, the acetaldehyde-enriched fraction is transferred in
whole or in part into a reaction apparatus, in which case a heat exchanger
can likewise be provided, using which heat exchanger the acetaldehyde-
enriched fraction can be condensed in whole or in part, in which reaction
apparatus the fraction is brought into contact with a reaction partner which
has alkaline properties, preferably with sodium hydroxide solution, and
very particularly preferably with a 5 to 20% strength sodium hydroxide
solution. The temperature in this reaction apparatus is preferably 20 to
60°C. The pressure in this reaction apparatus Is preferably 0.1 to 2 bar. In
this reaction apparatus the acetaJdehyde reacts due to basic catalysis in
an aldol condensation reaction, for example with itself, to form 3-
hydroxybutyraldehyde (acetaldoi) or with acetone to form
hydroxypentanone. In particular the acetaldoi and the hydroxypentanone
have a higher boiling point than acetone. The reaction mixture from this
reaction apparatus is recirculated to the acetone column at the side. A
further portion of the overhead product of the acetone column can also be
ejected directly from the process and fed to a work-up or thermal
utilization.
At the bottom of the acetone column a mixture of compounds which have a
higher boiling point than acetone is taken off. This bottoms product can

comprise, inter alia, small amounts of cumene and/or AMS which are
transferred into the acetone column with the first fraction from the first
distillation column and comprise compounds from the reaction apparatus,
in particular sodium hydroxide solution or water and the secondary
products of acetaldehyde formed by aldol condensation reactions, for
example acetaktol. It can be advantageous to recycle a portion of the
bottoms product to the column in the vapor state. Preferably, the recycle
ratio is 0.2 to 400. The residua! portion of the bottoms product can be fed
to work-up or utilization. In particular, it can be advantageous, to recover
residues of cumene and/or AMS present in the bottoms product to feed the
bottoms product or portions thereof into a cumene column in which
cumene and AMS are enriched.
The acetone column is preferably operated such that at the top of the
column a temperature of 30 to 60°C is established. The bottom
temperature is preferably 40 to 110°C, particular preferably 50 to 80°C.
The temperature in the acetone column at the side stream takeoff from
which the pure acetone is taken off is preferably 30 to 60°C. The acetone
column preferably has 10 to 120 theoretical stages. The side stream
takeoff from which the pure acetone is taken off is preferably in a region of
the column in which this has a separation potential of 80 to 90%,
preferably 90 to 95%. The crude acetone, that is to say the first fraction
from the first distillation column, is preferably fed into a region of (he
acetone column where this has a separation potential of 0 to 36%. The
reaction mixture from the reaction apparatus is preferably fed into a region
of the acetone column where this has a separation column of 0 to 30%.
The organic portion of the third fraction from the phase-separation
apparatus is transferred to a cumene column. This is preferably
dimensioned in such a manner that compounds which have a lower boiling
point than cumene and/or AMS, for example water or acetaldol, can be
removed overhead, and compounds which have a boilling point which is
above that of AMS and cumene can be removed at the bottom of the
column and the compounds cumene and/or AMS can be taken off from a
side stream takeoff. Preferably, not only a portion of the product taken off
at the top but also of the product taken off at the bottom of the column are
fed back into the column. Particularly preferably, the cumene column Is
dimensioned in such a manner and the process parameters are set in such

a manner that a mixture taken off from the side stream takeoff or bottom
region can be fed directly to the hydrogenation.
The cumene column is preferably operated in such a manner that a
temperature of 40 to 170°C is established at the top of the column. The
bottom temperature is preferably 110 to 180°C. The temperature in the
cumene column at the side stream takeoff from which the cumene and/or
the AMS is taken off is preferably 110 to 180°C. The cumene column
preferably has 10 to 90 theoretical stages. The side stream takeoff from
which the cumene and/or AMS is taken off is preferably situated in the
region of the column in which this has a separation potential of 0 to 50%.
The organic phase of the third fraction from the first distillation column is
preferably fed into a region of the cumene column where this has a
separation potential of 10 to 80%.
It can also be advantageous to dimension the cumene column such that
via at least one further side stream takeoff which is disposed above the
side stream takeoff from which cumene and/or AMS is removed from the
cumene column and below the top of the column, at least one further
fraction can be taken off which comprises at least mesityl oxide, ketones
and/or water. By providing one or more such additional aide stream
takeoffs, the overhead product in the cumene column obtained can be a
product which essentially comprises acetone which is free from mesityl
oxide and which can be fed to further work-up, for example in the acetone
column.
The second fraction taken off at the bottom of the first distillation column,
the crude phenol fraction, which has a hydroxyacetone content less than
500 ppm, preferably less than 100 ppm, and very particularly preferably
less than 10 ppm, is preferably transferred at the side into a column which,
in the further course, is termed the crude phenol column. This column is
preferably dimensioned in such a manner mat compounds which have a
lower boiling point than phenol, for example residues of cumene, AMS or
acetone, can be removed overhead, and compounds which have a boiling
point above that of phenol can be taken off at the bottom of the column,
and phenol can be taken off from a side stream takeoff. Preferably, not
only a portion of the product taken off at the top but also of the product
taken off at the bottom of the crude phenol column is recycled to the

column. Particularly preferably, the crude phenol column is dimensioned in
such a manner and the process parameters are set in such a manner that
a phenol fraction withdrawn from the side stream takeoff can be fed to
further phenol purification. It can also be advantageous in the case of the
side stream takeoff to feed back a portion of the fraction taken off into the
crude phenol column as reflux
The crude phenol column is preferably operated in such a manner mat at
the top of the columns a temperature of 120 to 200°C, preferably 130 to
180°C, is set. The bottom temperature is preferably 120 to 220°C, The
temperature in the crude phenol column at the side stream takeoff from
which phenol is taken off is preferably 120 to 190°C, particular preferably
140 to 190°C. The crude phenol column preferably has 10 to 70 theoretical
stages. The side stream takeoff from which the phenol is token off is
preferably in a region of the column in which the has a separation potential
of 30 to 90%. The second fraction from the first distillation column, mat is
to say of the crude phenol, is preferably fed into a region of the crude
phenol column where this has a separation potential of 0 to 80%.
It can be advantageous to recycle the overhead product of the crude
phenol column to the first distillation column. This is useful, in particular,
when the overhead product of the crude phenol column comprises
relatively large amounts of cumene, AMS and/or acetone. The bottoms
product of the crude phenol column, which comprises compounds that
have a higher boiling point than phenol, can be fed, for further
concentration of the high-boilers, to further distillation and/or cracking.
Despite the advantage that in the case of cracking, valuable compounds,
for example AMS or phenol, can be recovered, and thus the overall yield of
the process is increased, it can be advantageous to dispense with cracking
of the high-boilers, since the apparatus requirement and the energy
consumption cannot always be compensated for by the higher overall
yield.
Preferably, the bottoms product of the crude phenol column is transferred
to a further distillation column which is termed below high-boiler column.
The bottoms product from the crude phenol column is preferably fed in to
the side of the high-boiler column. This column is preferably dimensioned

such that compounds that have a boiling point in the region of the boiling
point of phenol, for example residues of phenol, cumene, AMS or acetone,
can be removed overhead, and compounds that have a boiling point
markedly above that of phenol can be taken off at the bottom of the
column. Preferably, not only a portion of the product taken off at the top
but also of the product taken off at the bottom of the high-boiler column is
recycled to the column. The reflux ratio for the overhead product is
preferably 0.5 to 20. The bottoms product can be fed to cracking or
preferably thermal utilization. The overhead product of the higb-boiler
column is preferably fed back into the crude phenol column.
The high-boiler column is preferably operated in such a manner that a
temperature of 90 to 180°C is set at the top of the columns. The bottom
temperature is preferably 120 to 220°C. The high-boiler column preferably
has 5 to 70 theoretical stages. The bottoms product from the crude phenol
column is preferably fed into a region of the high-boiler column where this
has a separation potential of 40 to 100%.
The phenol fraction taken off at the side stream takeoff of the crude phenol
column can be fed to further work-up by distillation. Preferably, this phenol
fraction is treated in advance In a reactor. The treatment preferably
consists of a treatment with an acid catalyst in order to convert unwanted
byproducts into compounds boiling higher or lower than phenol. Very
particularly preferably, acid ion exchangers are used as acid catalysts.
For the further work-up by distillation of the phenol fraction from the crude
phenol column, this is transferred treated or untreated into a distillation
column which is termed below pure phenol column. This column is
preferably dimensioned such that compounds that have a lower boiling
point than phenol, for example residues of cumene, AMS, acetone and/or
water, can be removed overhead, and compounds that have a boiling point
above that of phenol can be taken off at the bottom of the column and
phenol can be taken off from a side stream takeoff. Preferably, not only a
portion of the product taken off at the top but also of the product taken off
at the bottom of the crude phenol column is recycled to the column. The
reflux ratio, defined as the amount of reflux at the top divided by the
amount in the side stream is preferably 0.1 to 1000. The recycle ratio for
the bottoms product is preferably 0.1 to 40. Particularly preferably, the pure

phenol column is dimensioned in such a manner and the process
parameters set in such a manner that a pure phenol fraction withdrawn
from a side stream takeoff has an impurity content less than 0.01% by
weight, preferably less than 0.005% by weight This pure phenol can be
fed to a store or directly for further use.
The pure phenol column is preferably operated such that a temperature of
100 to 190°C is set at the top of the columns. The bottom temperature is
preferably 120 to 210°C. The temperature in the pure phenol column at the
side stream takeoff from which the pure phenol is taken off is preferably
100 to 190°C. The pure phenol column preferably has 10 to 70 theoretical
stages. The side stream takeoff from which the pure phenol is taken off is
preferably situated in the region of the column in which this has a
separation potential of 80 to 95%. The phenol fraction from the crude
phenol column is preferably fed into a region of the pure phenol column
where this has a separation potential of 10 to 80%, but not in the region of
the column which has the same separation potential as the region from
which the pure phenol is withdrawn.
it can be advantageous to recycle the overhead product of the pure phenol
column to the crude phenol column. This is useful, in particular, because
the overhead product of the pure phenol column frequently comprises
cumene, AMS and/or acetone. The bottoms product of the pure phenol
column which comprises compounds that have a higher boiling point than
phenol can also be fed back into the crude phenol column or fed for further
concentration of the high-boilers to further distillation and/or cracking.
The inventive process can be carried out at a pressure of 0.05 to 2 bar.
Depending on the established pressure at which the individual process
steps are carried out, the temperatures in these process steps must be
selected accordingly.
The inventive process can [lacuna] in an inventive process for preparing
phenol and acetone which comprises the steps
oxidation of cumene to cumene hydroperoxide
cleavage of cumene hydroperoxide
work-up by distillation of tire cleavage product mixture produced
in the cleavage of cumene hydroperoxide

and which comprises resolving the cleavage product mixture into at least
three fractions in a single distillation step. By means of such an inventive
process phenol can be prepared in a very favorable manner in terms of
energy.
The inventive process for the work-up by distillation of a cleavage product
mixture produced in the cleavage of an alkylaryl hydroperoxide, in
particular in the cleavage of CHP, is preferably carried out in an inventive
distillation column for separating by distillation cleavage product mixtures
from the cleavage of cumene hydroperoxide, in which the column is
dimensioned in such a manner that a crude acetone fraction comprising at
least 75% by weight of acetone can be taken off at the top of the column, a
crude phenol fraction comprising at least 75% by weight of phenol can be
taken off at the bottom of the column and a fraction which comprises at
least hydroxyacetone and cumene and/or α-methylstyrene can be taken off
from the side of the column.
The inventive distillation column preferably has a number of theoretical
stages of 20 to 200, particularly preferably 30 to 70. The total number of
trays present in the distillation column is defined for the purposes of the
present invention, independently of the number of trays, as 100%
separation potential, in order in this manner, in the case of columns having
a differing number of trays, to be able to specify the range at which a
similar separation potential is present The bottom of the column, that is to
say the region below the first tray, therefore has a separation potential of
0%. At the top of the column, that is to say the region of the uppermost
tray, in accordance with the definition, a separation potential of 100% is
present.
The inventive distillation column has at least one possible feed which is
preferably present in a region of the distillation column in which this has a
separation potential of 20 to 50%.
The inventive distillation column also has at least one side stream takeoff
at which a fraction which comprises at least one hydroxyacetone, that is in
the case of cleavage of CHP, hydroxyacetone, and a mono- or
polyalkylated benzene, in the case of cleavage of CHP, that is cumene
and/or α-methylstyrene, can be taken off. Preferably, this side stream

takeoff is installed at a region of the distillation column at which the
separation potential is 15 to 95%, preferably 60 to 90%. Thus the side
stream takeoff, in the case of an inventive column which has a number of
theoretical stages of 50, is preferably installed between the thirtieth and
forty-fifth stage.
It can be advantageous if the inventive distillation column has at least one
further side stream takeoff at which a fraction which comprises at least one
organic acid can be taken off. As organic acid the fraction can comprise,
for example, acetic acid, oxalic acid, formic acid or butyric acid, or a
mixture consisting of at least one of these acids. An acid takeoff can be
provided above and/or below the feed means and/or below and/or above
the side stream takeoff.
The inventive process and the inventive apparatus are described in the
drawings Figs. 1 and 2 by way of example, without the process or the
apparatus being restricted to these types of implementation.
Fig. 1 shows diagrammatically an embodiment of the inventive distillation
column. The inventive distillation column K1 has a side intake into which
cleavage product mixture SP can be fed for work-up by distillation. The
overhead product KP1 and the bottoms product SP1 can be taken off at
the top and bottom of the column, respectively. The inventive distillation
column has in each case reflux systems by which the bottoms product
and/or the overhead product can be returned to the column in whole or in
part. In these reflux systems the heat exchangers WT1 and WT2 are
installed, by means of which it is possible to add or remove heat energy to
the bottoms product or overhead product recycled as reflux to the column.
If, in the inventive distillation column, a cleavage product mixture which
originates from the cleavage of CHP is worked up by distillation, acetone is
enriched in the overhead product In the bottoms product predominantly
phenol is enriched, and compounds having a boiling point higher than
phenol.
The inventive distillation column furthermore has a side stream takeoff via
which a fraction that has a boiling point between that of the overhead
product and that of the bottoms product is taken off from the column. If, in
the inventive column, a cleavage product mixture from the cleavage of

CHP is worked up by distillation, via this side stream takeoff a mixture
which can comprise at least cumene, AMS and/or water is ejected from the
column. This mixture is transferred via line SCA to a phase-separation
apparatus PT1, for example a decanter. A portion of the organic phase
formed in this phase-separation apparatus can be returned via RO to the
distillation column. The residual portion of the organic phase can be fed to
further work-up via CA. A portion of the aqueous phase can also be
returned to the distillation column K1 via RW1, preferably this aqueous
phase is returned to the column in the liquid stale. The residual portion of
the aqueous phase can be fed via W1 to utilization or work-up.
Optionally, a further portion of the aqueous phase can be returned to the
column via RW2 in the vapor starts or liquid state, in which case the
aqueous phase is preferably fed in below the feed of the cleavage product
mixture SP. Optionally, in addition, one or more further side stream
takeoffs SOS1 and SOS2 can be provided. The side stream takeoff SOS1
is preferably disposed between the feed of the cleavage product mixture
SP and the bottom of the column. The side stream takeoff SOS2 is
preferably disposed between the side stream takeoff SCA and the top of
the column. Fractions that have at least one organic acid can be ejected
from the column via the side stream takeoffs SOS1 and SOS2.
Fig. 2 shows a diagrammatic representation of the overall process for the
work-up by distillation of cleavage product mixtures produced in the
cleavage of atlkylaryl hydroperoxides, for example a cleavage product
mixture produced in the cleavage of CHP. The representation, for
improved clarity, does not show the various refluxes to the columns. Also,
the thermal circuit, that is to say the exchange of heat energy between the
individual fractions or process streams, is not shown.
Via SP, a cleavage product mixture passes for work-up distillation into
column K1. The cleavage product mixture can have already been treated,
for example the pH can have been set and/or any aqueous phase present
can already have been removed. In the column K1 the cleavage product
mixture is divided into three fractions. The overhead product KP1 taken off
at the top of the column is a fraction in which acetone is enriched. A side
stream fraction SCA in which cumene, AMS and/or water are enriched is

taken off at the side from column K1. A phenol-rich bottoms product SP1 is
taken off at the bottom of column K1.
This fraction is transferred into the side of the acetone column K2 in which
the overhead product KP1 is resolved in a pure acetone fraction RA, which
is taken off at the side below the top of the column, an aldehyde- and low-
boiler-containing fraction AA, which is taken off at the top of the column,
and a bottoms fraction SP2, which is taken off at the bottom of the column
and which comprises compounds having a boiling point which is higher
than that of acetone. The fraction AA is fed in part into a washer W, into
which a base B is also fed, or is ejected from the process via KP2. The
product taken off from the washer W is fed back into the column K2. The
pure acetone RA is fed to further utilization or storage. The bottoms
product SP2 can be fed, for example, to work-up AB, in particular to
wastewater treatment A portion of the worked-up bottoms product AB2
can be fed into the side of column K3.
In addition, the organic portion CA of the side stream fraction SCA from
column K1 is fed into column K3. This organic portion is obtained in a
phase-separation apparatus PT1, into which the side stream fraction is fed.
A portion RO of the organic portion of the side stream fraction is recycled
to the column K1. The aqueous portion of the side stream fraction
obtained in the phase-separation apparatus PT1 can either be ejected
from the process as process water W1 and/or can be recycled in whole or
in part to the column K1 as reflux RW.
In column K3 the organic portion of the side stream fraction from column
K1, which comprises cumene and/or AMS, is distilled in such a manner
that via a side stream takeoff from column K3, a fraction CAH is obtained
which comprises cumene and AMS and is suitable for being fed directly to
the hydrogenation of AMS to cumene. Compounds boiling higher than
AMS or lower than cumene are ejected from the overall process as
overhead product KP3 or as bottoms product SP3, and can be fed for
utilization. Optionally, one or more side stream takeoffs KM can be
provided above the side stream takeoff CAH and below the top of the
column K3, via which side stream takeoffs fractions can be taken off that
comprise at least mesityl oxide and/or ketones, in particular ketones
different from acetone.

The phenol-rich bottoms product SP1 from column K1 is fed into the side
of crude phenol column K4. From this column a crude phenol is taken off
at the side which is further treated in a reactor HR which can comprise, for
example, an acid fixed-bed catalyst, and is men transferred to the column
K5. The overhead product KP4 is fed back into the column K1. The
bottoms product SP4 from column K4 is fed into column K6. In this
column, high-boilers, for example tar, are ejected from the process as
bottoms product SP6 and fed for utilization. The overhead product KP6 is
fed back into the column K4.
The crude phenol which was treated in reactor HR and transferred to the
pure phenol column K5 is separated in this column into pure phenol RPH
which is withdrawn at the side of column K5 and fed for use or storage, a
higher-boiling fraction which is taken off from K5 as bottoms product SPG
and recycled to column K4, and a lower-boiling fraction which is withdrawn
from column K5 as overhead product KP5 and is also fed to column K4.
Example 1:
A cleavage product mixture which comprised, inter alia, 48% by weight of
phenol, 10% by weight of cumene, 3% by weight of AMS, 27% by weight of
acetone, 0.03% by weight of acetaldehyde, 0.1% by weight of
acetophenone, 0.1% by weight of hydroxyacetone and 9% by weight of
water was fed into a distillation column as described in Figs. 1 and 2, that
had 90 trays, at the height of the 40th tray.
The temperature in the column was set such that the top temperature was
47°C, the bottom temperature was 179*C and the temperature at the side
stream takeoff was 88 to 89°C. The pressure in the distillation column
corresponded at the bottom to atmospheric pressure. A portion of the
overhead product taken off, which comprised, inter alia, 99 parts of
acetone and 0.1 part of acetaldehyde, was transferred to an acetone
column having 40 trays, at the height of the 8th tray.
The temperature in the acetone column was set in such a manner that the
temperature at the top of the column was 42°C and the temperature at the
bottom of the column was 65°C. At the side stream takeoff, which was

mounted at the height of the 35th tray, and from which pure acetone that
had an impurity content less than 0.25% by weight was taken off, the
temperature was 42.5°C. The overhead product which had an
acetaklehyde content of 100 pom was condensed and passed into a
washer, into which were also passed, per kg of overhead product, 10 g of a
5% strength sodium hydroxide solution. The temperature in the washer
was 56°C. The mixture taken off from the washer had an acetaldehyde
content less than 20 ppm.
The bottoms product from the acetone column, which comprised, inter alia,
cumene, AMS and water, was transferred to the cumene column.
The fraction taken off from the side stream takeoff of the first distillation
column was transferred to a separation vessel. In this separation vessel,
an aqueous phase which comprised, inter alia, 98% by weight of water and
1.3% by weight of hydroxyacetone, was separated from the organic phase
which comprised, inter alia, 65% by weight of cumene, 30% by weight of
AMS, 2% by weight of phenol and 0.2% by weight of water. After the phase
separation, over 95% of the hydroxyacetone present in the fraction taken
off was present in the aqueous phase. A portion of the aqueous phase was
discarded. The remainder of the aqueous phase was returned to the first
distillation column.
The organic phase separated off in the separation vessel from the
aqueous phase had a hydroxyacetone content less than 1000 ppm. This
organic phase was in part returned into the first distillation column. The
remainder of the organic phase was passed into the side of the cumene
column which had 60 frays, at the height of the 25th fray. The cumene
column was operated such that the temperature at the top of the column
was 56°C and the temperature at the bottom of the column was 140°C.
From a side stream takeoff at the height of the 14th tray, at 138°C a
mixture of AMS and cumene was distilled off, which comprised less than
2% by weight of impurities. The low-boilers and high-boilers taken off at the
top and from the bottom of the cumene column were discarded.
The bottoms product taken off from the bottom of the first distillation
column, which comprised, inter alia, 94% by weight of phenol and 1.6% of
acetophenone, was fed into the side of a crude phenol oolumn comprising

70 trays at the height of the 26th tray. This column was operated in such a
manner that the temperature at the top of the column was 176°C and the
temperature at the bottom of the column was 203°C. The fraction taken off
at the top of the crude phenol column was returned to the first distillation
column. The fraction produced in the bottom of the crude phenol column
was transferred to a further column, the high-boiler column, in which the
high-boilers were concentrated. The overhead product of this 5-tray
column obtained at 154°C was a fraction which comprised, inter alia, 95%
by weight of phenol and 5% by weight of acetophenone. This fraction was
fed back Into the crude phenol column. The bottoms product of the high-
boiler column, which was obtained at a temperature of 203°C, consisted of
a tar, which had a phenol content of less than 5% by weight A crude
phenol stream was taken off from the crude phenol column at the height of
the 55th fray, at a temperature of 181°C.
This crude phenol stream had a phenol content of 99% by weight. As
impurities, this crude phenol stream comprised, inter alia, 2-
methytbenzofuran, AMS, mesityl oxide, small amounts of hydroxyacetone
and traces of further impurities. This crude phenol stream was passed
through a reactor which comprised 120 m3 of the acid ton exchange resin
Arnberlyst 15 as catalyst. The crude phenol thus treated was passed into
the side of a 454-tray pure phenol column at the height of the 20th tray. This
column, which was operated at a reduced pressure, had a top temperature
of 139°C and a bottom temperature of 142°C. A pure phenol that had an
impurity content less than 100 ppm was token off from the side of the pure
phenol column at the height of the 40th tray at a temperatare of 140°C.
The fraction taken off at the top of the pure phenol column was fed back
into the crude phenol column below the top. The fraction
bottom of the pure phenol column was fed back into the crude phenol
column above the bottom.

WE CLAIM:
1. A process for the work-up by distillation of cleavage product
mixtures produced In the cleavage of alkylaryl
hydroperoxides, which comprises resolving the cleavage
product mixture into at least three fractions In a single
distillation step by:
- feeding the cleavage product mixture to the side of a
distillation device,
- removing a first fraction comprising ketone at the top
of the device,
- removing a second fraction comprising substituted or
unsubstituted phenol at the bottom of the device, and
- removing a third miction comprising one of unreacted
mono-, di- and trialkyl substituted benzene and
hydroxy ketone as side stream, whereby the side
stream take-off is situated above the feed of cleavage
product mixture to the device.

2. The process as claimed in claim 1, wherein the first fraction
comprises at least 75% of a ketone present in the cleavage
product before the distillation step.
3. The process as claimed in claim 2, wherein the ketone is
acetone.
4. The process as claimed in at least one of claims 1 to 3,
wherein the second fraction comprises at least 75% of one
of a substituted and unsubstituted phenol present in the
cleavage product before the distillation step.
5. The process as claimed in at least one of claims 1 to 4,
wherein the third (Taction comprises one of at least 75% of
the cumene present in the cleavage product before the
distillation step and 75% of the α-methylstyrene present in
the cleavage product before the distillation step.
6. The process as claimed in claim 5, wherein the third fraction,
which comprises one of water cumene and AMS constitutes
at least 20% of the distillation step.

7. The process as claimed in at least one of claims 5 or 6,
wherein the fraction comprising at least 75% of the cumene
present In the cleavage product before one of the distillation
step and 75% of the α-methylstyrene present in the
cleavage product before the distillation step Is separated In a
phase-separation apparatus Into an aqueous phase and an
organic phase.
8. The process as claimed in claim 7, wherein at least a portion
of the organic phase is fed back to the distillation step.
9. The process as claimed in claim 7 or 8, wherein at least a
portion of the organic phase is fed to a distillation column
(cumene column) in which the organic phase is separated in
such a manner that compounds are taken off overhead
which have a lower boiling temperature than cumene or a α-
methylstyrene, compounds are taken off via the bottom
which have a higher boiling temperature than cumene or a-
methylstyrene and the compounds cumene and/or a-
methylstyrene are taken off via a side stream takeoff.

lO.The process as claimed in claim 9, wherein the organic phase is
separated in (he cumene column in such a manner (hat via at
least one farther side stream takeoff which is disposed above the
side stream takeoff from which one of cumene and α-
methyistyrene are removed from the cumene column, and below
the top of the column, at least one further fraction can be taken
off which comprises at least mesltyl oxide, ketones and/or water.
11.The process as claimed in claim 7, wherein at least a portion of
the aqueous phase is fed back to the distillation step in one of the
liquid and vapor state.
12.The process as claimed In claim 7 or 11, wherein the aqueous
phase comprises 75% of the hydroxyacetone present In the
cumene and α-methylstyrene-containing fraction.
13.The process as claimed in at least one of the preceding claims,
wherein the cleavage product mixure, before the work-up by
dlstiiation, has a phenol concentration of 20 to 70% by weight

14. The process as claimed in at least one of the preceding claims,
wherein the cleavage product mixture, before the work-up by
distillation, has a hydroxyacetone concentration of 200 ppm to 5%
by weight
15. A distillation device (K1) for the separation by distillation of
cleavage product mixtures (SP) from cumene hydroperoxide
cleavage, in which the device (K1) is configured such that a crude
acetone fraction (KP1) comprising at least 75% by weight of
acetone can be taken off at the top of the column (K1), a crude
phenol fraction (SP1) comprising at least 60% by weight of phenol
can be taken off at the bottom of the column (K1), and at least
one fraction which comprises one of at least water, cumene and α-
methyistyrene can be taken off from the side of the column(K1)
whereby the side stream take-off (SCA) is situated above the feed
of cleavage product mixture (SP) to the delation column (K1).
16. The device as claimed in claim 15, wherein a fraction
comprising phenol and at least 75% of the hydroxyacetone
present In the cleavage product mixture (SP) can be taken off at
the bottom of the device (K1).

17. The device as claimed in claim 15, wherein a fraction
comprising one of cumene and α-methylstyrene and at least 75%
of the hydroxyacetone present in the cleavage product mixture
(SP) can be taken off at at least one side stream takeoff (SOS1,
SOS2) of the device (K1).
18. The device as claimed in claim 17, comprising a side stream
takeoff (SCA) at which a fraction which comprises one of at least
hydroxyacetone and cumene and α-methylstyrene can be taken off
in a region of the device (K1) in which a separation potential of 60
to 95% is available.
19. The device as claimed in one of claims 15 to 18, wherein the
device has 20 to 200 theoretical stages.
20. The device as claimed in one of claims 15 to 19, comprising at
least one side stream takeoff at which a fraction which comprises
at least one organic add (CA) can be taken off.

21. A process for preparing phenol and acetone which comprises
the steps of:
• oxidation of cumene to cumene hydroperoxide
- cleavage of cumene hydroperoxide
• work-up by distillation of the cleavage product mixture
produced in the cleavage of cumene hydroperoxide which
comprises resolving the cleavage product mixture Into at
least three fractions in a single distillatlon step according to a
process In any of claims 1 to 14.

The present invention claims a
process and an apparatus for the
work-up by distillation of cleavage
product mixtures produced in the
cleavage of alkylaryl
hydroperoxides. Usually, in the
work-up by distillation of cleavage
product mixtures which are
produced in the cleavage of
alkylaryl hydroperoxides, the
cleavage product mixture is
divided into three main fractions,
for which at least two distillation
columns are used. The use of two
distillation columns has the
disadvantage that the capital
costs, and also the energy costs,
in these conventional processes
are relatively high. By means of
the inventive process for the
work-up by distillation of cleavage
product mixtures, the equipment
requirements and the energy
consumption can be markedly
reduced in comparison with
customary plants, since the
cleavage product mixture can be
resolved into the three main
fractions in only one apparatus.
The inventive process can be
used for the work-up by distillation
of cleavage product mixtures
produced in the cleavage of
alkylaryl hydroperoxides, in
particular in the cleavage of
cumene hydroperoxide. By using
the inventive process it is possible
to separate off phenol and
acetone from a cleavage product
mixture that was obtained in the
cleavage of cumene
hydroperoxide.

Documents:

514-KOLNP-2003-FORM 27 1.1.pdf

514-KOLNP-2003-FORM 27-1.2.pdf

514-KOLNP-2003-FORM 27.pdf

514-KOLNP-2003-FORM-27.pdf

514-kolnp-2003-granted-abstract.pdf

514-kolnp-2003-granted-claims.pdf

514-kolnp-2003-granted-correspondence.pdf

514-kolnp-2003-granted-description (complete).pdf

514-kolnp-2003-granted-drawings.pdf

514-kolnp-2003-granted-examination report.pdf

514-kolnp-2003-granted-form 1.pdf

514-kolnp-2003-granted-form 13.pdf

514-kolnp-2003-granted-form 18.pdf

514-kolnp-2003-granted-form 2.pdf

514-kolnp-2003-granted-form 26.pdf

514-kolnp-2003-granted-form 3.pdf

514-kolnp-2003-granted-form 5.pdf

514-kolnp-2003-granted-priority document.pdf

514-kolnp-2003-granted-reply to examination report.pdf

514-kolnp-2003-granted-specification.pdf

514-kolnp-2003-granted-translated copy of priority document.pdf


Patent Number 231466
Indian Patent Application Number 514/KOLNP/2003
PG Journal Number 10/2009
Publication Date 06-Mar-2009
Grant Date 04-Mar-2009
Date of Filing 23-Apr-2003
Name of Patentee INEOS PHENOL GMBH & CO.KG
Applicant Address DECHENSTRASSE 3, 45966 GLADBECK
Inventors:
# Inventor's Name Inventor's Address
1 KORTE, HERMANN HERDERSTRASSE 14, 47521 HALTERNI
2 TANGER, UWE TRAKEHNER STRASSE 2, 44879 BOCHUM
3 ULLRICH, JOCHEN GLUCKSTRASSE 27A, 45966 GLADBECK
4 WEBER, MANFRED DER WORTH 5, 45721 HALTERN
5 SCHWARZ, CHRISTOPH SCHLTITERSTRASSE 5, 45763 MARL
PCT International Classification Number C07C 37/74
PCT International Application Number PCT/EP01/14030
PCT International Filing date 2001-01-30
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 100 60 503.6 2000-12-06 Germany