USOO5998677A

United States Patent (19) 11 Patent Number: 5,998,677

Yasaka et al. (45) Date of Patent: Dec. 7, 1999
54 PROCESS FOR THE PRODUCTION OF 5.530,166 6/1996 Zakoshansky et al. ................. 568/798
PHENOL
FOREIGN PATENT DOCUMENTS
75 Inventors: Naoto Yasaka; Tatsuo Shirahata, both 251408 11/1990 Japan.
of Chiba, Japan
73 Assignee: Mitsui Chemicals, Inc., Tokyo, Japan Primary Examiner Jeffrey C. Mullis
Attorney, Agent, or Firm-Birch, Stewart, Kolasch & Birch,
LLP
21 Appl. No.: 08/674,567
57 ABSTRACT
22 Filed: Jul. 5, 1996
30 Foreign Application Priority Data The improved proceSS for producing phenol, acetone and
C.-methylstyrene in the cumene-phenol process comprising
Jul. 7, 1995 JP Japan .................................... 7-171923 cumene hydroperoxide, cumene and dimethylphenyl
51) Int. Cl. ............................ C07C37/08; CO7C 45/53 carbinol in the presence of Sulfuric acid has the Steps of
decomposing the cumene hydroperoxide in a back mixing
52 U.S. Cl. ............................................. 568/798; 568/768 reactor with the yield of C.-methylstyrene as produced from
58 Field of Search ...................................... 568/798, 768 dimethylphenylcarbinol being controlled and the Step of
56) References Cited forming O-methylstyrene in Such a way that the reaction
mixture produced in the first Step is Supplied into a plug-flow
U.S. PATENT DOCUMENTS reactor after acetone is added to Said reaction mixture. The
process is capable of consistent production of phenol and
4,358,618 11/1982 Sifniades et al.. C.-methylstyrene in high yields under mild reaction condi
4,449,828 5/1984 Mansour ................................. 366/147 tions.
5.245,090 9/1993 DeCaria et al. . ... 568/798
5,254,751 10/1993 Zakoshansky ....... ... 568/798
5,463,136 10/1995 Blackbourn et al. ................... 568/385 10 Claims, No Drawings
 5,998,677
1 2
PROCESS FOR THE PRODUCTION OF cumene oxidation which is chiefly composed of CHP is
PHENOL Subjected to acid cleavage reaction and the reaction mixtures
are distilled to Separate a crude phenol from acetone, low
FIELD OF THE INVENTION boiling point components (e.g. hydrocarbons) and high
This invention relates to a process for the production of boiling point components (e.g. unreacted DMPC, cumylphe
phenol which is useful as an intermediate for the manufac
nol and methylstyrene dimer); the crude phenol is treated
ture of Synthetic resins, agrichemicals, dyes, with an cation-exchange resin Such that the HA in the crude
pharmaceuticals, etc. phenol is converted to an easily Separable high-boiling
impurities, which is thereafter Separated from the crude
DESCRIPTION OF THE RELATED ARTS phenol by distillation. According to U.S. Pat. No. 5,064,507,
the crude phenol is treated with an organic polyamine,
There have been proposed various processes for produc whereupon the HA in the crude phenol reacts with the added
ing phenol and one of the most commonly used processes is organic polyamine to form a high-boiling point compound,
the cumene-phenol process which starts with cumene to which is then Separated from the crude phenol with a
Synthesize phenol. In this proceSS, cumene is oxidized with 15 distillation column.
oxygen or air to produce cumene hydroperoxide (hereunder However, these methods simply complicate the process of
abbreviated as “CHP) which is cleaved to phenol and phenol manufacture and require an expensive facility for HA
acetone in the presence of an acid catalyst. The main removal. Thus, controlling the production of cumylphenol,
products of the cumene-phenol proceSS are phenol and methylstyrene dimer and other high-boiling point compo
acetone. In addition, dimethylphenylcarbinol (hereunder nents that will lower the yields of the end products, as well
“DMPC) is formed as a by-product in the cumene oxidation as the production of HA which will deteriorate the quality of
reaction, and then DMPC is dehydrated in the acid cleavage the pure phenol is critical to the commercial implementation
of CHP to give O-methylstyrene (hereunder “C-MS) as a of the cumene-phenol process.
by-product. The C-MS is readily hydrogenated back to Examined Japanese Patent Publication No. 51408/1990
cumene which is reusable as a raw materials. The C-MS is 25 teaches a two-stage process. In the first stage, a back mixing
also industrially useful as a resin modifier. reactor is used to perform the reaction at a Sulfuric acid
In this process, various Side-reactions take place that will concentration of 30-100 ppm and at a temperature of 50-90
lower the yields of phenol (which is one of the end products C. Such that the concentration of CHP in the reaction mixture
of CHP cleavage reaction), C-MS, etc. as exemplified by the is reduced to 0.5-5 wt %. In the first-stage reaction, the
reaction between C-MS and phenol to produce cumylphenol conversion of DMPC to dicumyl peroxide (hereunder
and the dimerization of C-MS to produce a methylstyrene “DCP) is at least 40%. The product of the first-stage
dimer. Another by-product of the CHP cleavage reaction is reaction is then Sent to a plug-flow reactor, where the
a very small amount of hydroxyacetone (hereunder “HA"). Second-stage reaction is carried out at 120-150° C. to cleave
The HA is difficult to separate from phenol by distillation the DCP produced in the first-stage reaction.
and can deteriorate the quality of the phenol if it is present 35 U.S. Pat. No. 5,254,751 teaches another two-stage pro
in this otherwise pure final product. If bisphenol A is ceSS. In the first Stage, the reaction is carried out in a
manufactured from a phenol containing HA, a colored non-isothermal reactor at an acid catalyst concentration of
product will result that is very low in commercial value. 150-500 wt. ppm and at a temperature of 50-62. C. in the
What is more, the HA is water-soluble and has such a high presence of added acetone Such that the concentration of
COD load that it dissolves in the effluent from the cumene
phenol process, making the biological or other treatment of
40 CHP is lowered to 0.3-1.5%. After being mixed with aque
ous ammonia, the product of the first-stage reaction is sent
the effluent necessary. to a plug-flow reactor and the Second-stage reaction is
Among these problems, the Side reactions that lower the carried out at a temperature of 80-110° C. to cleave the DCP
yields of phenol and C-MS have been addressed by the produced in the first-stage reaction.
proposal of a method for performing acid cleavage of CHP 45 A critical problem with the reaction for the acid catalized
after it is diluted with a Solvent Such as acetone (See, for cleavage of CHP is that the reaction rate is very fast, with the
example, Examined Japanese Patent Publication Nos. 3875/ half life being only a few seconds, and that the heat of the
1952 and 4619/1953) or a method of carrying out the resulting cleavage reaction is Several times as great as what
reaction in more than one stage (see, for example, U.S. Pat. develops in common exothermic reactions of organic chem
No. 2,757,209 and Examined Japanese Patent Publication 50 istry. Therefore, if a few percent of CHP is cleaved momen
No. 13464/1962). According to the references that teach the tarily due to changes in the reaction conditions, the tem
first proposal, the Side reactions are controlled by the dilut perature of the reaction mixture will rise sharply and acetone
ing effect of the solvent and the improved efficiency of which is a low-boiling point component of the reaction
contact between the acid catalyst and CHP. The second mixture will evaporate to increase the pressure in the reactor,
proposal described in U.S. Pat. No. 2,757,209 is to perform 55 potentially causing the reactor to burst. Hence, for the
the CHP cleavage reaction in multi Stages, in the first Stage, Success of the multi-stage process in which unreacted CHP
the acid cleavage reaction is carried out under mild condi remains in the first-stage reactor, it is desired that the proceSS
tions at a lower acid catalyst concentration and a lower be operated under Stable conditions and that yet the end
temperature than in the conventional method of completing products be obtained in high yields.
the reaction for the production of phenol and C-MS in one 60
stage, such that a few percent of CHP is left in the product; SUMMARY OF THE INVENTION
in the Second Stage, the product of the first-Stage reaction is An object, therefore, of the present invention is to provide
introduced into a plug-flow reactor for cleaving the organic a process by which both phenol and C-MS can be produced
peroxides in the product and for dehydration of DMPC. consistently in high yield under mild reaction conditions
Methods to prevent contamination of an otherwise pure 65 with controlled HA formation.
phenol with HA are described in BP 1,231,991, U.S. Pat. No. With a view to attaining this object, the present inventors
5,064,507, etc. According to BP 1,231,991, the product of conducted intensive Studies on the aforementioned problems
 5,998,677
3 4
with the adoption of the multi-stage method in the cumene consists of a first-stage reaction intended primarily for
phenol process. As a result, they found that the cumylphenol performing acid catalized cleavage of CHP in a back mixing
and methylstyrene dimer which would reduce the yields of reactor and a Second-stage reaction intended primarily for
phenol and C-MS were more likely to be formed with the producing C-MS in a plug-flow reactor.
increasing concentration of C-MS in the reaction mixture. In the first stage of the invention process, CHP which is
Stated more Specifically, the reaction mixture in a back the main component of the starting material (i.e., the product
mixing reactor has a uniform composition, So that the of cumene oxidation) is cleaved to phenol and acetone in a
composition of the reaction mixture within the reactor is back mixing reactor in the presence of Sulfuric acid. The
identical to that at the exit of the reactor. Hence, perfor product of cumene oxidation which is Supplied as the
mance of the reaction for producing C-MS from DMPC Starting material is prepared by first oxidizing cumene with
within the back mixing reactor gives a high concentration of air or oxygen at a temperature of about 100° C. in the
C-MS in the reactor. The present inventors found that this presence of Sodium carbonate and then Separating the unre
caused an increased production of cumylphenol and meth acted cumene from the oxidation product to give a Specified
ylstyrene dimer both of which were heavier forms of C-MS. CHP concentration in a distillation column. The product of
The inventors found that in order to control the formation of 15 cumene oxidation has typically the following composition:
cumylphenol and methylstyrene dimer, it was preferable to
carry out the C-MS forming reaction in a plug-flow reactor
which would allow the reaction mixture to change compo CHP 65-85 wt %
DMPC 2-10 wt %
Sition with the progreSS of the reaction, namely, a reactor of Cumene 15-35 wt %
the type that would create a non-uniform composition. Acetophenone 0.2-2 wt %
Better results were attained by diluting the reaction mixture
with a solvent. A preferred solvent is acetone which has the
lowest boiling point of the main components of the reaction The first-stage reaction to be carried out in the invention
mixture and it was found to be economical to circulate the process is for producing phenol and acetone from CHP while
Solvent between the reactor in the Subsequent Stage and the 25 controlling the formation of C-MS and HA. In this first-stage
distillation column. reaction, the conversion of CHP is desirably in the range of
AS already mentioned in connection with the prior art, HA 97-99.5%, preferably 98-99.0%, and the yield of C-MS as
is difficult to separate from phenol by distillation and will produced from the dimethylphenylcarbinol in the product of
deteriorate the quality of the phenol if it contaminates the cumene oxidation is desirably not more than 35%, prefer
otherwise pure final product. This HA is produced from ably no more than 30%. The reaction conditions are desir
acetone in the presence of CHP. Acetone is formed in a ably mild as exemplified by a Sulfuric acid concentration of
molar amount equal to that of CHP which is being cleaved 150-300 wt. ppm and a reaction temperature of 55-80 C.
with an acid catalyst and, hence, it is difficult to ensure that According to the teaching of Examined Japanese Patent
HA will not be formed at all. However, the present inventors Publication No. 9971/1958, the temperature for carrying out
found that the formation of HA could be reduced by carrying 35 the reactions for the acid catalized cleavage of CHP and the
out the acid cleavage of CHP at a low acetone concentration, formation of C-MS is preferably in the range of 50-80 C.
namely, without addition of the acetone separated in the If the temperature for carrying out the reaction for the acid
distillation Zone. catalized cleavage of CHP in the present invention is higher
Based on these findings, the present inventors concluded than specified in Examined Japanese Patent Publication No.
that in order to produce phenol, acetone and C-MS from the 40 9971/1958, thermal decomposition of CHP will occur, lead
product of cumene oxidation efficiently while controlling the ing to lower yields of phenol and acetone. If the reaction
temperature is unduly low, an expensive facility is required
formation of HA which would deteriorate the quality of to remove the heat of reaction and, in addition, temperature
otherwise pure phenol, it was preferable to divide the instability occurs during continuous reaction. The invention
reaction into two or more Stages and perform the respective 45 process adopts a lower concentration of Sulfuric acid than
reactions under appropriate conditions. the method described in Examined Japanese Patent Publi
Accordingly, in order to attain the above-Stated object, the cation No. 9971/1958, the optimal temperature range for the
present invention provides a process for producing phenol, invention process is narrower than the temperature range
acetone and C.-methylstyrene from the product of cumene described in Said patent publication.
oxidation comprising cumene hydroperoxide, cumene and 50 In the invention process, the water concentration for
dimethylphenylcarbinol in the presence of Sulfuric acid, carrying out the reactions for the acid catalized cleavage of
characterized by comprising the Step of decomposing the CHP and the formation of C-MS is preferably in the range
cumene hydroperoxide in a back mixing reactor with the from 0.5 to 3 wt %. As already described in Examined
yield of C.-methylstyrene as produced from dimethylphenyl Japanese Patent Publication No. 9971/1958, the water con
carbinol being controlled to no more than 35%, and the step 55 centration for carrying out the reaction need to be So
of forming C.-methylstyrene in Such a way that the reaction adjusted as to provide a uniform reaction mixture. Even if
mixture produced in the first Step is Supplied into a plug-flow the reaction mixture is uniform, an unduly high water
reactor after acetone is added to Said reaction mixture. concentration will lower the acid Strength of the Sulfuric acid
DETAILED DESCRIPTION OF THE used as a catalyst, thus increasing the concentration of CHP
INVENTION 60 in the reactor. Hence, it is not preferable to employ a water
concentration higher than the upper limit specified for the
The process of the invention for producing phenol (which practice of the invention process.
is hereunder referred to simply as the “invention process”) Thus, compared to the one-stage Scheme for carrying out
will now be described in detail. the reactions for the acid catalized cleavage of CHP and the
The invention process is for producing phenol, acetone 65 formation of C-MS, the first-stage reaction to be carried out
and C-MS from the product of cumene oxidation containing in the invention process adopts a mild condition character
CHP as the main component by a multi-stage Scheme that ized by low Sulfuric acid concentration; as a result, the
 5,998,677
S 6
DMPC which is existing as a by-product in the starting The amount of acetone to be added in the Second-stage
cumene oxidation is either converted to DCP which is the reaction should be 1.15-1.8 times as much as the acetone
product of reaction with CHP or present unreacted in the concentration in the first-Stage reaction.
reaction mixture, thereby controlling the conversion of The purpose of adding acetone in the Second-stage reac
DMPC to C-MS. tion is to lower the concentration of C-MS in the second
During prolonged operations of a large System in a Stage reactor, thereby controlling the reaction that yields
commercial plant, the reaction conditions will normally vary heavier forms of C-MS and which will lower the yields of
more or less. Even if Such variations occur, the composi phenol and C-MS. AS just mentioned above, the amount of
tional change in the reaction mixture must be held to a acetone added for this purpose should be 1.15-1.8 times as
minimum. The operational Stability of the process to pro
duce phenol and acetone from CHP is affected by the much as the acetone concentration in the first-stage reaction.
variations in the acid Strength of the catalyst and the reaction Adding a greater amount of acetone is effective in further
temperature. The acid strength of the catalyst is Susceptible controlling the reaction which produces heavier forms of
not only to the increase in the concentration of water in the C-MS but, on the other hand, more acetone need be circu
reaction Solution but also to the concomitant Sodium Salt in lated between the reactor and the acetone distillation
the Starting cumene oxidation product and a lower acid
15 column, causing a corresponding increase in the energy
strength will retard the cleavage of CHP, thereby causing it consumption for distilling acetone and a disadvantage rather
to accumulate in the reactor. Therefore, in order to reduce than an advantage will result in View of overall process
the effects of variations in the process conditions and thereby economy. If the addition of acetone is unduly Small, it is
ensuring that the concentration of CHP in the reaction hardly effective in controlling the reaction that produces
heavier forms of C-MS.
product is kept constant, the reaction has to be carried out
with the acid catalyst concentration being held to no leSS In the invention process, the production of heavier forms
than 100 wt. ppm, preferably no less than 150 wt. ppm. An of C-MS is not likely to occur in the first-stage reaction. This
acid catalyst concentration in the range from 30 to 100 can be explained as follows: in the first-stage reaction, the
wt. ppm is so low that it would be difficult to ensure stable 25
concentration of Sulfuric acid used as a catalyst is So low that
plant operation for a prolonged time. DMPC will undergo dehydrative condensation reaction with
The residence time of the reaction mixture in the back CHP to form DCP and dehydration to C-MS is less likely to
mixing reactor is from 5 to 40 minutes and typically adjusted occur. As a result, the concentration of C-MS in the back
to be in the range from about 15 to about 30 minutes. mixing reaction is low enough to ensure that the reaction for
The heat of reaction that develops when CHP is cleaved producing heavier forms of C-MS is practically unlikely to
with an acid to produce phenol and acetone in the first-stage occur. Therefore, if acetone is added in the first-stage
reaction is Several times as great as the heat of normal reaction, its effectiveness in controlling the reaction that
reactions in organic chemistry. Therefore, in the first-stage produces heavier forms of C-MS is no different from the
reaction, the temperature in the back mixing reactor must be effectiveness of adding acetone in the Second-stage reaction.
controlled Such that the heat of reaction produced is com 35
In other words, the yields of phenol and C-MS that are
pletely removed to maintain a Specified reaction produced when acetone is added in the first-stage reaction
temperature, whereby the rate of CHP cleavage is held are Substantially comparable to the yields obtained by add
constant to insure that the reaction mixture of a stable ing acetone in the Second-stage reaction. AS already men
composition emerges from the exit of the back mixing tioned in connection with the prior art, an unduly high
reactor to enter the Second-stage reactor. To this end, the 40
acetone concentration in the reaction for the acid cleavage of
back mixing reactor need be an apparatus Suitable for CHP increases the production of HA which will deteriorate
controlling the temperature in the reactor to be constant. For the otherwise pure phenol. The first-stage reaction to be
controlling the reaction temperature to be constant, it is performed in the invention process is intended primarily for
preferable to adopt the acetone reflux method in which the effecting the acid cleavage of CHP, the addition of acetone
preSSure in the reactor is lowered to the vapor pressure of the 45
in the first-stage reaction will increase the HA production,
reaction mixture and the latent heat of evaporation of the thereby deteriorating the otherwise pure phenol.
Volatilized acetone is removed So as to maintain the tem On the other hand, the Second-stage reaction is intended
perature in the reactor at a constant level; alternatively, part primarily for producing C-MS and the acid cleavage of CHP
of the reaction mixture in the reactor is withdrawn and in effect will not occur; therefore, there will be no increase
passed through a cooling heat eXchanger So that the devel 50 in HA production even if acetone is added in the Second
oping heat of reaction is removed before it is returned to the Stage reaction. Consequently, the yields of phenol and C-MS
reactOr. that are produced when acetone is added in the Second-stage
In the invention process, the reaction mixture emerging reaction are comparable to those attained by the adding
from the back mixing first-stage reactor to be Subjected to acetone in the first-stage reaction and yet a Smaller amount
the Second-stage reaction contains phenol, acetone, DMPC, 55 of HA is produced.
DCP and cumene as a mainingredient. This reaction mixture The reaction mixture to which acetone is added is passed
is Supplied to a plug-flow reactor for carrying out the through a heat exchanger such that it is heated to 80-100° C.
Second-Stage reaction, primarily for producing C-MS from before it is Supplied into an adiabatic plug-flow reactor.
the DMPC or DCP in the reaction mixture. If the temperature for the Second-stage reaction is
In the invention process, the Second-stage reaction is 60 elevated, the reaction rate is increased, making it necessary
performed with acetone being added in order to control the to shorten the reaction time. In the case where the tempera
reaction that will produce cumylphenol or methylstyrene ture for the Second-stage reaction exceeds 120° C., the rate
dimer from C-MS. The acetone to be added is preferably of of by-producing of cumyl phenol and methylstyrene dimer
a type that is recovered by a separator Such as a distillation which are heavier forms of C-MS will increase abruptly if
column from the reaction product leaving the plug-flow 65 the conversion of DCP and DMPC to C-MS is 70% or more.
reactor after the end of the Second-stage reaction and which Therefore, if the reaction for C-MS formation is carried out
is returned to the same plug-flow reactor. at temperatures higher than the upper limit for the Second
 5,998,677
7 8
Stage reaction in the invention process, the range that 500 to 2,500 wt. ppm. The concentration of water in the
permits appropriate control of the reaction becomes So crude acetone ranges from 0.3 to 3 wt %, preferably from 1
narrow that there may he considerable difficulty in control to 2 wt %. If the concentration of aldehydes or water in the
ling prolonged operations at commercial plants. crude acetone drops, there occurs a marked increase in the
The second-stage reaction for producing C-MS from DP energy consumption required by the distilling operation. If,
is exothermic, So if it is performed in an adiabatic plug-flow on the other hand, the concentration of aldehydes or water
reactor, a non-isothermal State will be dominant in the in the crude acetone increases, the reaction mixture diluted
reactor, causing the temperature at the exit of the reactor to in the Second-stage reaction will contain an increased
be higher than the entrance temperature. Stated more amount of water and then the reaction efficiency will be
Specifically, the temperature difference between the entrance decreased.
and exit of the reactor, which varies with the amount of DCP
that undergoes the Second-stage reaction, is typically from
about 8 to about 20° C. The temperature at the exit of the SPECIFIC EXAMPLES OF THE INVENTION
Second-stage reactor is desirably no more than 120° C.,
preferably no more than 115 C. and it is necessary that the 15 The following examples and comparative examples are
elevation of the temperature of the reaction mixture in the provided for the purpose of further illustrating the present
first-stage reaction be So adjusted that the temperature of the invention but are in no way to be taken as limiting.
reaction mixture at the exit of the Second-stage reactor will
not exceed the above-specified upper limit. Example 1
It is also necessary to ensure against back mixing of the
reaction mixture in the plug-flow Second-stage reactor by Cumene was oxidized with air at 70-115 C. in the
increasing its length compared to the inside diameter or by presence of Sodium carbonate, followed by oil-water Sepa
providing baffle plates within the reactor. The residence time ration and concentrating to prepare the product of cumene
of the reaction mixture in the Second-stage plug-flow reactor 25
oxidation, which had the following composition:
is typically from about 5 to about 30 minutes, preferably
from about 8 to about 20 minutes.
CHP 81.0 wt %
If the second-stage reaction for the production of C-MS DMPC 5.2 wt %
from DCP and DMPC ends in the plug-flow reactor in the Acetophenone 0.8 wt %
invention process, the reaction is quenched by immediately Cumene 13.0 wt %
cooling the reaction mixture and neutralizing the Sulfuric
acid used as the acid catalyst. If the acid catalyst remains in
the reaction mixture, the reaction that produces heavier The product of cumene oxidation was Supplied into a
forms of C-MS (i.e., cumylphenol and methylstyrene dimer) multi-stage reaction System composed of a continuous type
will continue even after the end of the reaction for the
35
back mixing reactor having a heat removing capability and
cleavage of organic peroxides and this will lower the yields an adiabatic plug-flow reactor. In the multi-stage reaction
of C-MS and phenol. To avoid this problem, the acid catalyst System, two reactions were performed Sequentially, the
must be neutralized as Soon as the reaction for the cleavage cleavage of CHP in the first stage and the formation of C-MS
of organic peroxides ends. in the Second Stage.
The Sulfuric acid which is the acid catalyst in the reaction 40
The first-stage reaction was carried out at a temperature of
mixture can be neutralized in accordance with a method that
uses either Sodium hydroxide or Sodium carbonate or 60° C. and at a sulfuric acid concentration of 200 wt. ppm for
Sodium phenolate which is a salt of sodium hydroxide with a residence time of 20 minutes. The temperature in the
phenol. first-stage reactor was kept constant by removing the heat of
The neutralized reaction product is then Subjected to 45
the reaction mixture while agitating it. An acqueous Solution
distillation So that it is separated into acetone, phenol, C-MS, of 5% sulfuric acid was added continuously to ensure that
cumene, etc. A part of the Separated acetone is recycled for the concentration of Sulfuric acid in the reactor would be
use as a diluent in the Second-stage reaction. The distillation held at 200 ppm. As a result, the conversion of CHP to
of the neutralized reaction product is performed with a another component was 98.9% and the yield of C-MS as
distillation column under atmospheric or Subatmospheric 50 produced from DMPC was 18.0%.
preSSure conditions. Subsequently, acetone was added in an amount 1.4 times
The crude acetone produced in the cumene-phenol pro the concentration of acetone in the first-stage reaction mix
ceSS for phenol manufacture contains aldehydes, alcohols, ture. The added acetone had been Separated from the neu
water, etc. Among these components, aldehydes and water tralized product of the Second-Stage reaction by distillation
are difficult to Separate by distillation and much energy is 55
and it contained 1,000 wt. ppm of an aldehyde having a lower
consumed by the purifying operation. Therefore, the use of
purified acetone as a diluent for the reaction mixture is not boiling point than acetone and 1.8 wt % of water. The
economical and adds to the cost of phenol manufacture. If, first-stage reaction mixture was then heated in a heat
on the other hand, crude acetone is used as a diluent for the eXchanger and Supplied into a plug-flow reactor for carrying
reaction mixture in the Second-Stage reaction, the aldehydes 60 out the Second-stage reaction. The residence time of the
in the crude acetone will be converted to heavier forms as reaction mixture in the Second-stage reactor was 10 minutes,
catalyzed by the Sulfuric acid in the reaction mixture, So that the temperature at the exit of the Second-stage reactor was
it is recycled at a given concentration without building up in 110 C.; and the Second-stage reaction mixture had a water
the distillation path. concentration of 1.0 wt %. The final reaction product was
The concentration of aldehydes in the crude acetone for 65 analyzed to determine the yields of phenol and C-MS, as
use as a diluent of the reaction mixture in the Second-stage well as the concentration of HA. The results are shown in
reaction ranges from 100 to 5,000 wt. ppm, preferably from Table 1 below.
 5,998,677
10
ture. The added acetone had been Separated from the neu
TABLE 1. tralized product of the Second-Stage reaction by distillation
Phenol yield 98.3%
and it contained 1,000 wt. ppm of an aldehyde having a lower
C-MS yield 82.8% boiling point than acetone and 1.8 wt % of water. The
HA concentration 680 wt. ppm first-stage reaction mixture was then heated in a heat
eXchanger and Supplied into a plug-flow reactor for carrying
Phenol yield = out the Second-stage reaction. The residence time of the
Phenol in the reaction product (mol/h) x 100 reaction mixture in the Second-stage reactor was 17 minutes,
CHP in the starting cumene oxidation product (mol/h) the temperature at the exit of the Second-stage reactor was
C-MS yield =
108 C.; and the Second-stage reaction mixture had a water
concentration of 1.4 wt %. The Second-stage reaction prod
a-MS in the reaction product (mol/h) uct was analyzed to determine the yields of phenol and
x 100
DCPM in the starting cumene oxidation product (mol/h) C-MS, as well as the concentration of HA. The results are
shown in Table 3 below.
HA concentration: Amount of HA produced per unit feed of the starting 15
cumene oxidation product
TABLE 3
Example 2 Phenol yield 98.2%
C-MS yield 84.1%
The product of cumene oxidation as prepared in Example HA concentration 640 wt. ppm
1 was Subjected to reactions in a reaction System of the same
type as used in Example 1. The first-stage reaction was
carried out at a temperature of 60° C. and at a Sulfuric acid Comparative Example 1
concentration of 250 wt. ppm for a residence time of 15
minutes. An aqueous Solution of 5%. Sulfuric acid was The product of cumene oxidation as prepared in Example
Supplied continuously to ensure that the concentration of 25 1 was Subjected to reactions in a reaction System of the same
sulfuric acid in the reactor would be held at 250 wt. ppm. The type as used in Example 1. Acetone was added to the
conversion of CHP to another component in the first-stage first-stage reaction mixture but no acetone was added in the
reaction was 98.7% and the yield of C-MS as produced from Second-Stage reaction. The first-stage reaction was carried
DMPC was 16.2%. out at a temperature of 75 C. for a residence time of 15
Subsequently, acetone was added in an amount 1.54 times minutes. A Solution containing 2,000 wt. ppm of acetone
the concentration of acetone in the first-stage reaction mix Sulfite was Supplied continuously to ensure that the concen
ture. The added acetone had been Separated from the neu tration of Sulfuric acid in the reactor would be held at 260
tralized product of the second-stage reaction by distillation Wt. ppm. The added acetone had been Separated from the
and it contained 1,000 wt. ppm of an aldehyde having a lower neutralized product of the Second-stage reaction by distilla
boiling point than acetone and 1.8 wt % of water. The 35 tion and it contained 1,000 wt. ppm of aldehyde having a
first-stage reaction mixture was then heated in a heat lower boiling point than acetone and 1.8 wt % of water. The
eXchanger and Supplied into a plug-flow reactor for carrying acetone concentration of the reaction mixture was 1.3 times
out the Second-stage reaction. The residence time of the as high as the value for the case where no acetone was
reaction mixture in the Second-stage reactor was 21 minutes, added. The conversion of CHP to another component in the
the temperature at the exit of the Second-stage reactor was 40 first-stage reaction was 98.5% and the yield of C-MS as
113 C.; and the Second-stage reaction mixture had a water produced from DMPC was 29.0%.
concentration of 1.4 wt %. The Second-stage reaction prod Subsequently, the first-stage reaction mixture was heated
uct was analyzed to determine the yields of phenol and in a heat eXchanger and Supplied into a plug-flow reactor for
C-MS, as well as the concentration of HA. The results are carrying out the Second-Stage reaction. The residence time of
shown in Table 2 below. 45 the reaction mixture in the Second-stage reactor was 17
minutes; the temperature at the exit of the Second-stage
TABLE 2 reactor was 108 C.; and the Second-stage reaction mixture
Phenol yield 98.4%
had a water concentration of 1.4 wt %. The Second-stage
C-MS yield 83.6% reaction product was analyzed to determine the yields of
50 phenol and C-MS, as well as the concentration of HA. The
HA concentration 700 wt. ppm
results are shown in Table 4 below.

Example 3 TABLE 4
The product of cumene oxidation as prepared in Example 55 Phenol yield 98.1%
1 was Subjected to reactions in a reaction System of the same C-MS yield 80.6%
HA concentration 1,100 wt. ppm
type as used in Example 1. The first-stage reaction was
carried out at a temperature of 75 C. and at a sulfuric acid
concentration of 120 wt. ppm for a residence time of 15 Comparative Example 2
minutes. An aqueous Solution of 2.5% Sulfuric acid was 60
Supplied continuously to ensure that the concentration of The product of cumene oxidation as prepared in Example
sulfuric acid in the reactor would be held at 150 wt. ppm. The 1 was Subjected to reactions in a reaction System of the same
conversion of CHP to another component in the first-stage type as used in Example 1. The first-stage reaction was
reaction was 99.1% and the yield of C-MS as produced from carried out at a temperature of 70° C. and at a sulfuric acid
DMPC was 21.0%. 65 concentration of 500 wt. ppm for a residence time of 20
Subsequently, acetone was added in an amount 1.54 times minutes. An acqueous Solution of 5%. Sulfuric acid was
the concentration of acetone in the first-stage reaction mix Supplied continuously to ensure that the concentration of
 5,998,677
11 12
sulfuric acid in the reactor would be held at 500 wt. ppm. The (4) without diverting the first stage reaction mixture with
conversion of CHP to another component in the first-stage added acetone Supplying the resultant reaction mixture
reaction was 99.7% and the yield of C-MS as produced from from Step (3) into the plug-flow Second stage reactor
DMPC was 39.4%. without hydrogenation in Said plug-flow reactor, and
Subsequently, acetone was added in an amount 1.54 times (5) Separating and recovering O-methylstyrene from Said
the concentration of acetone in the first-stage reaction mix plug-flow Second Stage reactor.
ture. The added acetone had been Separated from the neu
tralized product of the Second-stage reaction by distillation 2. The process according to claim 1, wherein the cleavage
and it contained 1,000 wt. ppm of an aldehyde having a lower of the cumene hydroperoxide is performed to give
boiling point than acetone and 1.8 wt % of water. The 97-99.5% conversion of the cumene hydroperoxide.
first-stage reaction mixture was then heated in a heat 3. An improved process for producing phenol using a
eXchanger and Supplied into a plug-flow reactor for carrying Single back mixing reactor and a single plug flow reactor
out the Second-stage reaction. The residence time of the which comprises:
reaction mixture in the Second-stage reactor was 17 minutes, (1) cleaving cumene hydroperoxide in a first stage back
the temperature at the exit of the Second-stage reactor was
105 C.; and the Second-stage reaction mixture had a water 15 mixing reactor in the presence of Sulfuric acid and
concentration of 1.7 wt %. The Second-stage reaction prod controlling the yield of C.-methylstyrene as produced
uct was analyzed to determine the yields of phenol and from dimethylphenylcarbinol to no more than 35%, by
C-MS, as well as the concentration of HA. The results are weight of the reaction mixture output from the first
shown in Table 5 below. Stage,
TABLE 5
(2) adding acetone to the resultant output of the reaction
mixture from the first Stage reactor, and then without
Phenol yield 97.7% diverting the first stage reaction mixture with added
C-MS yield 78.1% acetone Supplying the So-obtained reaction mixture into
HA concentration 870 wt. ppm the plug-flow Second Stage reactor and dehydrating the
25
dimethylphenylcarbinol and cleaving the cumene
Thus, according to the invention process, phenol and hydroperoxide, in the Second Stage reactor without
C-MS can be manufactured in high yields with reduced hydrogenation, and
formation of HA and besides the manufacturing operation is (3) Separating and recovering phenol from the output of
very Stable. Therefore, the invention proceSS is of great value the Second Stage reactor.
in practical applications. 4. The process according to claim 3, wherein after the
We claim:
1. An improved process for producing phenol, acetone addition of the acetone to the resultant output of reaction
and C.-methylstyrene from the product of cumene oxidation mixture from the first stage reactor, said reaction mixture is
using a single back mixing reactor and a single plug flow 35
heated to 80-100° C. in a heat exchanger.
reactor, Said process comprising in a first Stage back mixing 5. The process according to claim 4, wherein the thus
reactor reacting cumene hydroperoxide, cumene and dim heated reaction mixture is Supplied into the Second Stage
ethylphenylcarbinol in the presence of Sulfuric acid, Said plug-flow reactor in a non-isothermal State for producing
improved process comprising the Steps of: C.-methylstyrene from the dimethylphenylcarbinol and
(1) cleaving the cumene hydroperoxide in a first stage 40
dicumyl peroxide.
back-mixing reactor, in the presence of 150-350 6. The process according to claim 3, wherein the tem
wt. ppm of Sulfuric acid based on the product of cumene perature of the reaction mixture at the exit of the Second
oxidation, to form a reaction mixture of phenol and Stage plug-flow reactor is no more than 120° C.
acetone having 0.5-3.0 wt % HO while controlling the 7. The process according to claim 3, wherein the tem
temperature in Said first Stage back mixing reactor at 45 perature of the reaction mixture at the exit of the Second
55-80° C. by: Stage plug-flow reactor is no more than 115 C.
(a) withdrawing a part of the reaction mixture and 8. The process according to claim 3, wherein the reaction
passing the part to a heat eXchanger and thus remov mixture emerging from the Second Stage plug-flow reactor is
ing the heat of reaction for the cleavage of the immediately cooled and neutralized to Stop the reaction.
cumene hydroperoxide in the heat eXchanger and 50 9. The process according to claim 8, wherein acetone is
recycling the part of the reaction mixture to the first Separated from the reaction mixture output from the Second
Stage back mixing reactor, or Stage plug-flow reactor with a distillation column after the
(b) by lowering the pressure in said back mixing reactor reaction is stopped and wherein at least part of the Separated
to the vapor pressure of the reaction mixture, thereby acetone is recycled to the reaction mixture output from the
removing the latent heat of evaporation of the Vola 55 first Stage complete back-mixing reactor in Such an amount
tilized acetone and then returning the resultant liq that the acetone concentration of Said reaction mixture
uefied acetone into the back mixing reactor; output is 35-50 wt % before said reaction mixture output is
(2) controlling the yield of C.-methylstyrene in Said first Supplied into the Second Stage plug-flow reactor.
Stage reactor to no more than 35%; 10. The process according to claim 9, wherein the acetone
(3) adding acetone to the output of the reaction mixture 60 to be added to the reaction mixture from the first stage
produced in the first Stage reactor in Such an amount back-mixing reactor contains 100-5,000 wt. ppm of an alde
that the acetone concentration is 1.15-1.8 times as hyde and 0.3–3 wt % of water.
much as in the reaction mixture produced from the first
Stage reactor, k k k k k