Europaisches Patentamt | | | | | 1 1| | | | | || | | | | || || | | | | | | |

(19) J European Patent Office

Office europeen des brevets (11) EP 0 670 296 B1

(12) E U R O P E A N PATENT S P E C I F I C A T I O N

(45) Date of publication and mention (51) int. CI 6: C07C 37/08, C07C 3 9 / 0 4 ,
of the grant of the patent: C07C 45/53, C07C 4 9 / 0 8 ,
28.10.1998 Bulletin 1998/44
C07C 1/24, C07C 1 5 / 4 4
(21) Application number: 95301267.1

(22) Date of filing: 28.02.1995

(54) Acid cleavage of cumene hydroperoxide to phenol, acetone and alpha-methylstyrene

Saurespaltung von Cumolhydroperoxid in Phenol, Aceton und Alphamethylstyrol
Clivage acide de I'hydroperoxide de cumene dans phenol, acetone et alpha-methylstyrene

(84) Designated Contracting States: (72) Inventors:

BE DE ES FR GB IT NL PT • Zakoshansky, Vladimir Mikhailovich
Mount Vernon, Indiana 47620 (US)
(30) Priority: 01.03.1994 RU 94007336 • Griaznov, Andrei Konstantinovich
13.01.1995 US 369104 St Petersburg 193435 (RU)

(43) Date of publication of application: (74) Representative:

06.09.1995 Bulletin 1995/36 Szary, Anne Catherine, Dr. et al
London Patent Operation,
(73) Proprietors: GE International, Inc.,
• GENERAL ELECTRIC COMPANY Essex House,
Schenectady, NY 12345 (US) 12-13 Essex Street
• ILLA INTERNATIONAL LTD London WC2R 3AA (GB)
St. Petersburg, 193148 (RU)
(56) References cited:
US- A- 2 668 180 US-A-4 358 618
US-A- 5 254 751

CO
CO
CM

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
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a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
Q_ 99(1) European Patent Convention).
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 EP 0 670 296 B1

Description

This invention relates to the synthesis of phenol, acetone and alphamethylstyrene (AMS) by the cumene method.
The cumene method comprises two stages: the first one is cumene oxidation by air oxygen to cumene hydroper-
5 oxide (CHP), the second one is CHP acidic-catalytic cleavage (decomposition) to phenol and acetone. During CHP
cleavage some unutilized products known as "phenol tar" form along with the phenol, acetone and AMS. The phenol tar
amount is mostly determined by the method of implementing the CHP cleavage process and makes 50-60 kg/t in the
best current technologies and over 120-180 kg/t of phenol in traditional technology.
Up to now the efforts of skilled artisans were directed to increasing the process selectivity or yield. However, along
10 with selectivity, the process throughput or rated capacity is also an important factor in measuring the overall productivity
of a phenol-acetone production unit. Up until now it was impossible to meet both of these requirements simultaneously.
The most recent technical advance is based on the CHP cleavage method disclosed in US Patent No. 5,254,751 .
Technical CHP cleavage is carried out in accordance with this process as set forth in Figure 1. This process is carried
out in two stages:
15 The first stage is the CHP cleavage stage catalyzed by sulfuric acid which is carried out in three shell and tube type
reactors A, B and C, installed in series, with reaction heat removal by cooling water fed to the reactors' tube space and
cleavage products circulating through the reaction unit with a ratio of 10-25/1 for recirculation weight to weight of CHP
fed. The sulfuric acid catalyst is most conveniently supplied to the reactors by adding it to the recirculated cleavage
products through line 14. Pump 2 moves the recirculated cleavage products and sulfuric acid catalyst to mixer 16 into
20 which fresh technical CHP is added through line 17 from which the mixture moves to reactor A. In order to increase
process selectivity an additional amount of water and acetone is fed to the circulating cleavage stream. Acetone is fed
by the following algorithm (I) depending upon the loading of CHP.

Gac = GCHPx0.17[CHP] + Q - ^ H p ]

where: Gac - acetone amount, t/hr

GChp - technical CHP amount in t/hr
30 [CHP] - CHP concentration in technical CHP by weight

In establishing each of the algorithms set forth in this specification the amounts were measured in terms of metric
tons (ton or t). However, any weight quantity measurement may be employed so long as the same selected quantity
units are used consistently for each component.
35 Technical CHP is known to the skilled artisan as impure cumylhydroperoxide containing varying amounts of impu-
rities such as DMBA, cumene, AP and other similar materials which is the product stream from cumene oxidation which
is the initial step in the phenol from cumene manufacturing process.
The technique of recycling acetone is very important to provide process selectivity which is determined by closely
controlled temperature ranges in each of the three reactors (A, B and C of process section 1 of the first stage of the
40 process) as 50-62°C, 62-57°C and 57-50°C respectively at atmospheric pressure and CHP conversions in each of the
reactors 30-60%. 25-50% and 30-10% respectively. Reactors A, B and C are vented to the atmosphere through appro-
priately designed vents 13.
As the reaction of CHP cleavage is highly exothermic, reactors with a total specific heat exchange area of not less
than 30-35 m2 per metric ton of 100% CHP are used. Because of the potential danger of the CHP cleavage reaction it
45 is safer practice to design reactors with a specific area not less than 45-60 m2 per metric ton of fed 100% CHP.
On-line monitoring of the progress of CHP decomposition in the first stage is carried out by a specially designed
calorimeter (mini-reactor) 3 installed on the outlet line of the last reactor. The temperature difference between the cal-
orimeter inlet and outlet streams (delta T-|) is a quantitative measure of the amount of undecomposed CHP remaining
in the cleavage product stream. A typical delta T-| is 4-1 6°C which corresponds to 0.6 to 2.3 wt% of free CHP exiting the
so last reactor of stage 1 of the process. Also during cleavage of CHP, the dimethylbenzyl alcohol (DMBA) impurity present
in the technical CHP feed stream simultaneously reacts in part with CHP to form the intermediate dicumylperoxide
(DCP).
The CHP cleavage time is varied from 30 seconds to 3 minutes, preferably 45 sec. - 2 min., within the above men-
tioned ranges for circulation ratio and CHP conversion.
55 The second stage, DCP cleavage, is carried out subsequently in two apparatuses 4 and 7 which are plug flow reac-
tors. Aqueous ammonium hydroxide solution is fed through line 15 to the first of the reactors 4 to convert part of the
sulfuric acid to NH4HS04. Thus DCP cleavage is carried out with a binary catalyst (H2S04 + NH4HS04) with a control-
led ratio of the components and at a temperature of 90-1 10°C in apparatus 7. Product heating is implemented by heat

2
 EP 0 670 296 B1

exchanger 6.
CHP cleavage in reactors A, B, and C of process section 1 is carried out under atmospheric pressure and are
vented to the atmosphere through appropriately designed vents 13.. DCP cleavage in reactor 4 is carried out under 1.0
bar (atmospheric) pressure and in reactor 7 under pressure of not less than 2.0 bar (2 atm). Between reactor 7 and
5 evaporator 8 is a pressure reduction valve 22.
A portion of the acetone in the cleavage products is evaporated in evaporator 8 at 1.0 bar (atmospheric) pressure
or below and preferably at between 0.67-0.80 bar (500-600 mm Hg absolute). The remainder of the cleavage products
leave evaporator as a bottoms stream and move through line 20 for further processing into product phenol and product
acetone. The evaporated acetone is cooled and condensed to the liquid state in cooler 9. The liquid acetone is fed to
w vessel 10 before being pumped through pump 11 to reactors A, B and C in process section 1.
The above described method gives the highest levels of process selectivity up to the present invention. But it has
a few areas which can be substantially improved:

1) Big volume reactors are required to provide the substantial amount of heat exchange (more than 50 m2/t. of
15 100% CHP) which leads to high equipment cost and high capital investment for construction and surge capacities
of unit;
2) The intermediate vessel (reactor 4) operates under atmospheric pressure and pump 5 is required to deliver the
cleavage mass to the downstream DCP conversion reactor 7 in the second stage of the process.
3) The reduced temperature in CHP cleavage process section I allows a high level of nondecomposed CHP (from
20 0.5 to 2%) in reactor 4 which, if there is a wrong ratio between H2S04 : NH4HS04, could result in a hazardous con-
dition.
4) Precise dosing of small amounts of aqueous ammonia solutions and H2S04 to maintain the correct ratio is diffi-
cult and lack of precision leads to AMS dimers and formation of phenol complexes, in case of low H2S04 neutrali-
zation, or to incomplete DCP conversion in case of over neutralization of H2S04. Desired products yield is reduced
25 in both cases and "phenol tar" yield increases accordingly.
5) H2S04 and NH4HS04 presence in cleavage products causes the acidic-catalytic properties of these catalysts to
increase by 4-7 times and their concentration to increase simultaneously in vessel 8 during acetone evaporation.
Side reactions continue in this vessel and by-product formation reduces process selectivity. The above mentioned
low dosing of NH4OH aggravates this situation leading to a loss of 10-20 kg. of starting cumene feed on the basis
30 of 1 ton of phenol and AMS yield can be reduced to as low as 60% theoretical.
6) Operating the DCP cleavage reactor 7 with a very weak acidic catalyst (H2S04 + NH4HS04) requires a high
reactor volume, 0.8 m3/t of feed to the reactor which unfavorably compares with 0.4-0.5 m3/t of feed in the process
of the present invention.
7) Acetone feed to the CHP cleavage unit by the above algorithm (I) leads to high energy requirements for its con-
35 densation and requires apparatus with increased heat exchange capacity which also leads to high costs for equip-
ment sized to accommodate surge.

In contrast, the present invention increases productivity of the process units, reduces capital investment through
equipment volume reduction in new units being constructed and simplifies the technology but maintains high process
40 selectivity.
The process of the prior art is represented in Figure 1.
The process of the present invention is represented in Figure 2.
In the process of this invention, CHP and DCP cleavage stages are carried out in reactors connected in series
under the same pressure. The CHP feed stream is fed into a circulating loop of the products of the cleavage reaction
45 containing sulfuric acid catalyst. As in the prior art process, the sulfuric acid catalyst is conveniently added to the circu-
lating loop through line 14 and technical CHP is added through line 17 and mixed with the recirculating CHP cleavage
mass in mixer 16. Although in the prior art process reactors A, B and C are vented to the atmosphere, in the process of
the present invention line 21 connects the overheads of reactors A, B, C and 7 together to keep all reactors at the same
elevated pressure. Since all four reactors, A, B, C and 7, are at the same pressure, and reactor 4 has been eliminated
so in the process of the present invention, the aqueous ammonia solution, fed to the prior art process shown in Figure 1
through line 15, is fed to the line feeding evaporator 8 after the pressure seducing valve 22 in the process of the present
invention. Although it is most convenient to add the aqueous ammonia immediately before evaporator 8 as shown in
Figure 2 and be certain no ammonia is present in reactor 7, the point of addition after reactor 7 whether before or after
valve 22 is not critical so long as no ammonia is present in reactor 7.
55 In the present invention this investment in pumps and reactor 4 is not required since both the first and second
stages of the process are designed to operate at identical elevated pressures. The first stage reactors in the present
invention operate at a higher temperature than in the prior art method and this higher temperature requires the use of
a higher pressure to suppress the boiling point of the cleavage mass. This higher pressure in the first stage of the proc-

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 EP 0 670 296 B1

ess of the present invention is the same as the pressure in the second stage thus eliminating the need for pumps.
The pressure in the cumylhydroperoxide cleavage and dicumylperoxide cleavage vessels is preferably from 2.0 to
10.1 bar (2 to 10 atmospheres), more preferably from 3.0 to 5.1 bar (3 to 5 atmospheres).
As cleavage of CHP occurs, the heat liberated is removed by cooling water in reactors A, B and C of process sec-
5 tion 1 of the first stage of the process. The weight ratio of reactor circulation rate to CHP feed rate is not less than 26:1
but not more than 40:1 , preferably 26:1 to 35:1 .
According to the process of the present invention, acetone is fed to reactor A of process section 1 of the first stage
of the process and its ratio is determined depending on technical CHP amount fed for cleavage by the following algo-
rithm (II):
10
Gac = GCHPx0.125[CHP] + Q - 3 ^ H p ]

15 where: Gac - acetone amount fed for cleavage in t/hr

GChp - technical CHP amount fed for cleavage, t/hr
[CHP] - CHP concentration in technical CHP by weight.

This algorithm is suitable for most currently available technical CHP streams, e.g. having a CHP concentration of
20 from 74 percent by weight to 92 percent by weight.
A broader algorithm which has a broader range of applicability has been discovered and provides a basis for con-
trolling the process employing a wider range of technical CHP feedstocks.
This algorithm (III) is as follows:

25
G c- x( 1315[CHp] 3CHP] [DMBA] [cumene] [APh
" "
chp V50+0.25[CHP] 152 136 120 "120V1

where: Gac - acetone amount fed for cleavage in t/hr

30 GChp - technical CHP amount fed for cleavage in t/hr
[CHP] - CHP concentration in technical CHP by weight.
[DMBA] - DMBA concentration in technical CHP by weight
[Cumene] - Cumene concentration in technical CHP by weight
[AP] - Acetophenone (AP) concentration in technical CHP by weight
35
This algorithm expands the application of the present invention to streams having a CHP concentration as low as
40 percent by weight CHP and as high as about 98% by weight CHP, preferably 50 percent to 90 percent and more pref-
erably 60 percent to 85 percent. However, this algorithm can be used in a process employing any level of CHP concen-
trations.
40 In the present invention, higher temperatures and higher conversion rates of CHP are employed in the first stage
of the CHP decomposition process. The conversion profile of reactors A, B and C is controlled respectively at: 55-78%;
60-94%; and 90-98%, respectively. Overall conversion of CHP may be nearly complete in the present invention. A cal-
orimeter (mini-reactor) 3 is installed on the outlet of the reactor C to indicate overall degree of CHP conversion via the
delta Ti signal described earlier. A typical value for delta T-, is from about 0.4 to about 2.1 °C. Atypical temperature pro-
45 file for reactors A, B and C is: 57-82°C, 65-82°C and 57-70 °C at a pressure of from about 3 to about 4 atmospheres.
The CHP concentration at reactor C outlet is held at a 0. 1-0.45 wt% and preferably 0.2-0.4 wt% and CHP cleavage
time from 17 to 28 sec. Reactors with heat exchange total specific area of 17-25 m2/t. of 100% CHP are used in the
process of the present invention.
The cleavage mass from reactor C is fed to reactor 7 through heater 6 where conversion of DCP and DMBA to
so desired products is carried out.
Water in an amount sufficient to provide 98% DCP and DMBA conversion in reactor 7 is fed through line 20 to static
mixer 19 in the product line exiting reactor C. The water content in the cleavage products is controlled so as not to
exceed 3 wt% and preferably 1.3-20 wt%.
Control of the extent of DCP and DMBA decomposition after the point of water mixing with the cleavage products
55 is accomplished by on-line monitoring the temperature difference (delta T2) of a second mini-reactor (calorimeter) 12
installed in parallel to the line connecting reactors A, B and C of process section 1 of the first stage of the process to
reactor 7. The temperature in mini-reactor 12 is controlled at both its inlet and outlet.
The design of calorimeter 12 is not critical so long as the residence time of the cleavage products in the calorimeter

4
 EP 0 670 296 B1

12 is sufficient for total conversion of DCP and DMBA into phenol, acetone and AMS. Typically, this is achieved by a low
flow of the cleavage products slipstream.
Temperature control of the process is carried out through the temperature difference (delta T) which is the differ-
ence between the delta T-| of the first calorimeter and the delta T2 of the second calorimeter. This delta T absolute value
5 is held in a range of 0.2-3°C.
To exclude chemical losses during acetone evaporation at the product inlet to evaporator 8, a neutralizing alkaline
agent is fed through line 18 in an amount necessary to totally neutralize H2S04 into neutral salts (sulfates). Na2C03,
NH4OH, NaOH may be used as the neutralizing agent, but an aqueous ammonia solution of from 1 to 10 wt% concen-
tration is preferable.
10 The process of the present invention provides the following benefits:

1) More forgiving process which can utilize a broader range of CHP concentration in technical CHP (40-98% by
weight) at a high level of process efficiency.
2) Equipment productivity increases 2-2.5 times without substantial capital investment. In spite of high process
15 throughput, selectivity stays maximal (AMS yield is 78-80% theoretical);
3) Investment in a new cleavage unit to be constructed is reduced by 50 to 60 percent because:

a) The CHP cleavage reaction takes place in reactors with a low specific heat exchange area (17-25 m2/t. of
CHP) compared to traditional reactors with a specific heat exchange area of 40-60 m2/t. of CHP;
20 b) The DCP cleavage reaction takes place in one reactor instead of two. The two reactors may be integrated
to one unit because both reactors operate under the same pressure;

4) Energy consumption for process operation is lowered by the reduction of the recycled acetone amount and elim-
ination of pump 5 from the process scheme.
25 5) Elimination of the ammonia feed stream to the DCP cleavage step and addition of only water simplifies the con-
trol of the acidic-catalytic properties of H2S04.
6) CHP cleavage process is simplified by process control through delta T = delta T2 - delta T1 which helps to
maintain process selectivity automatically at the CHP cleavage stage and at the DCP cleavage stage as well.
7) Complete H2S04 neutralization before the acetone evaporator helps to exclude undesired side reactions.
30
In addition, emission sources of low boiling acetone in the prior art process are eliminated by connecting reactors
A, B and C of process section 1 and the DCP cleavage reactor in the process embodying this new technology.
The present invention is illustrated but not limited by the following Examples 2-14 as compared to comparative
Example 1 which represents the prior art
35
COMPARATIVE EXAMPLE 1

Using the prior art process described in Figure 1, technical CHP of the following composition in % wt is fed contin-
uously to a reactor block consisting of three shell and tube reactors which have a total reaction volume 10.08 m3:
40

cumene hydroperoxide 82.500 % by weight

45 cumene 12.721 % by weight

dimethylbenzyl alcohol 4.325 % by weight
acetophenone 0.453 % by weight

50 26 tons per hour of technical CHP are fed to CHP reactors A, B and C. Based upon calculations using algorithm (I),
5492 kg/h of acetone is added. 16 kg/h of sulfuric acid are fed to this reactor where the cleavage products are recircu-
lating. For the cleavage reaction, the reactors have a total heat transfer surface 1254 m2 that corresponds to the value
of the specific heat transfer, which makes 58 m2/t of CHP for each ton of 100% CHP.
The residence time in the reactor of CHP cleavage is 74 sec. The temperatures at the output line from each reactor
55 is, respectively, 58°C, 55 °C and 50°C. The CHP conversion at the output from each reactor is, respectively, 38%, 73%,
85%. The value of the temperature drop (delta T-,) in the mini-reactor 3 is 5.6°C. The CHP mixes with the reactive cleav-
age mass at the cleavage reactor inlet in a ratio of 1: 16 (the circulation ratio is 16). 10 kg of sulfuric acid is added to
the circulating loop.

5
 EP 0 670 296 B1

DCP cleavage is carried out in two plug flow reactors working in succession with a low temperature in the first reac-
tor, which is 58°C, and 93°C in the second reactor. 33.8 kg/h of an aqueous ammonia solution at a concentration of 5%
wt is fed to the first reactor, so that the degree of sulfuric acid neutralization for the conversion of the latter into ammonia
bisulfate would be 50%.
5 The CHP cleavage in the three shell and tube reactors and the DCP cleavage in the two plug flow reactors are car-
ried out at different pressures; 1.0 bar (atmospheric) pressure in the CHP cleavage reactors and in the first reactor of
the DCP cleavage and 3.0-5.1 bar (3-5 atm) in the second reactor of the DCP cleavage.
The residence time in the DCP cleavage reactors is 420 sec in reactor 4 and 2030 sec in reactor 7.
Acetone is fed to the cleavage unit from vessel 10 by pump 11. This acetone is evaporated from the reactive cleav-
10 age mass of DCP under reduced pressure in evaporator 8 and condensed to liquid in cooler 9.
As a result of all the reactions, which occur in the reactors, one gets:

phenol - 13174.5 kg/h (yield 99.2%)

acetone - 8084.5 kg/h (yield 98.9%)
15 alphamethylstyrene - 54.5 kg/t. of phenol (the yield of AMS is 73.4 theoretical % taking into consideration the fed
DMBA)
yield of phenol tar - 59.2 kg/t of phenol
cumene consumption - 1333 kg per ton of phenol

20 The cumene consumption values in this example and the subsequent examples are presented only for purposes
of comparison of the effectiveness of the process of the present invention which relates only to a portion of the total phe-
nol process. When other cumene recovery operations, not a part of the present invention, are included in the measure-
ment of cumene consumption in the total process, the net cumene consumption is much lower, typically 1307-1310 kg
per ton.
25
EXAMPLE 2

This example of the present invention shows an increase in productivity of 2.3 times over example 1. The process
of the present invention as described in this example and in the following examples is carried out as described in Figure
30 2. All the reactors of the present example operate under the same pressure and the pressure under which the entire
system operates is 4 kg/cm2.
60 tons per hour of technical CHP are fed to the CHP cleavage reactors. The composition is the same as in Exam-
ple 1. The cleavage of technical CHP is carried out at a recirculating ratio of 26/1 at temperatures at the inlet of each
reactor of 68°C, 67°C and 60°C respectively with a cumulative CHP conversion in each reactor of 62%, 94%, 98%
35 respectively.
Condensed acetone from vessel 10 is fed to the cleavage unit (process section 1) at a rate of 6890 kg/h calculated
by the formula (II):

Gac=GCHPx0.125[CHP] + Q - 3 ^ H p ]

where Gac, is the amount of acetone and GChp is the amount of technical CHP, both of which are expressed in tons per
hour. As used herein a ton (t) is equal to 1000 kilograms (kg).
45 [CHP] is the CHP concentration in technical hydroperoxide expressed as % wt. In the mini-reactor 3 of the cleavage unit
the value of the temperature drop is a delta T-| = 0.4°C.
Through the line feeding into the DCP cleavage reactor 7, water is fed at the rate of 482 kg/h so that the concen-
tration of the water in the cleavage products at the reactor outlet will be 1.63 wt% and the cleavage time is 485 seconds.
At the point after mixing cleavage products with water a second mini-reactor (calorimeter) 12 is installed where the
so value of the drop of temperatures (delta T2jat the outlet and at the inlet is measured. The process control essentially is
carried out by means of the value of the absolute temperature drop

delta T = delta T2 - delta T1 = 0.65°C.

55 To the product inlet line into the acetone evaporator 8 an aqueous ammonia solution at a concentration of 10% wt
and at the rate of 145 kg/h is fed through line 18 to exclude chemical losses of desired products in the acetone evapo-
rator 8.
As a result one gets:

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 EP 0 670 296 B1

phenol - 30431 .2 kg/h (yield 99.5%)

acetone - 18769.7 kg/h (yield 98.5%)
alphamethylstyrene - 58.5 kg/t. of phenol (the yield of AMS is 79.9 theoretical % taking into consideration the fed
DMBA)
5 yield of phenol tar - 54.2 kg/t of phenol
cumene consumption - 1328 kg per ton of phenol

EXAMPLE 3

10 This example shows conducting the process of the invention in reactors A, B and C of reduced volume with reduced
heat transfer surface and consequently with low specific surface of heat transfer. This process is carried out according
to the scheme described in Example 2. However, for the apparatus used in Example 3:

the volume of the reactor system of CHP cleavage is 2.8 times less than Example 1,
15 the surface of heat transfer of this system is 3.5 times less than in Example 1 and
the specific surface of heat exchanger of DCP cleavage is 3 times less than analogous values described in Exam-
ple 1.

26 tons per hour of technical CHP, which has the same composition as defined in Example 1, is fed to the CHP
20 cleavage reactors. To the recirculating loop which consists of the CHP cleavage reactors (A, B and C of process section
1) 9.3 kg/h of sulfuric acid is fed. The cleavage of technical CHP is carried out at the temperatures at the reactors' A, B
and C outlet which are 79°C, 75°C and 69°C respectively and with CHP conversion which is 77%, 96%, 98% respec-
tively.
Recycle acetone at the rate of 4312 kg/h calculated by formula II which was presented in Example 2, is fed to the
25 CHP cleavage unit from the vessel 10.
The residence time of reaction products in the DCP cleavage reactor 7 is 638 seconds.
As a result one gets:

phenol - 13185.3 kg/h (yield 99.4%)

30 acetone - 8075.4 kg/h (yield 98.8%)
alphamethylstyrene - 58.02 kg/ton of phenol (the yield of AMS 79.9 theoretical % taking into consideration the fed
DMBA)
yield of phenol tar - 55.03 kg/t of phenol
cumene consumption - 1329 kg per ton of phenol
35
In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta T-| = 0.34°C.
The value of the absolute temperature difference delta T = delta T2 - delta T1 = 0.66°C
To the product inlet line of the acetone evaporator 8 the aqueous ammonia solution at a concentration of 10% wt
and at the rate of 63 kg/h is fed to exclude chemical losses of desired products in the acetone evaporator so that the
40 degree of the conversion of acid into ammonium sulfate in the acetone evaporator 8 is 100%.

EXAMPLE 4

This example illustrates implementation of the present invention in reactors A, B and C where the heat exchange
45 specific area is determined to be 25 m2 per ton of 100% CHP.
26 tons per hour of technical CHP, which has the composition defined by Example 1, is fed to the CHP cleavage
reactors. Circulation ratio is 26/1 . To the recirculation loop which consists of the reactors A, B and C of CHP cleavage
9.3 kg/h of sulfuric acid is fed. The cleavage of technical CHP is carried out at temperatures at the reactors A, B and C
outlet which are 67°C, 66°C and 61 °C respectively and at the CHP conversion which are 62%, 87%, 94% respectively.
so The recycle acetone at the rate of 4312 kg/h calculated by the formula II which was presented in Example 2, is fed
to the cleavage unit of CHP from vessel 10.
The residence time of reaction products in the DCP cleavage reactor 7 is 640 seconds.
As a result the following amounts are produced:

55 phenol - 131 88.5 kg/h (yield 99.3%)

acetone - 8078.9 kg/h (yield 98.8%)
alphamethylstyrene - 58.5 kg/ton of phenol (the yield of AMS is 79.9% theor. taking into consideration DMBA sup-
ply)

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 EP 0 670 296 B1

yield of phenol tar - 53.9 kg/t of phenol

cumene consumption - 1328 kg per ton of phenol

In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta Ti = 1.26°C. The value of the tem-
perature drop in mini-reactor 12 installed after water supply to reaction products at circulation loop outlet is 1.98°C.
Absolute temperature difference (delta T = delta T2 - delta T1 ) is 0.72°C.
To the product inlet line into the acetone evaporator 8 the aqueous ammonia solution at a concentration of 10% wt
and at the rate of 63 kg/h is fed through line 18 to exclude chemical losses of desired products in the acetone evaporator
8 so that the degree of the conversion of acid into ammonium sulfate in the acetone evaporator is 100%.

EXAMPLE 5

This example illustrates the high selectivity of the process of the present invention at a lower rate of feed of techni-
cal CHP per cleavage unit and a high circulation ratio.
22 tons per hour of technical CHP, which has the composition defined by Example 1, are fed to the CHP cleavage
reactors . Circulation ratio is 35. To the recirculation loop which consists of the CHP cleavage reactors A, B and C, 7.2
kg/h of sulfuric acid is fed. The cleavage of technical CHP is carried out at the reactor A, B and C outlet temperatures
which are 72°C, 78°C and 67°C respectively and at the CHP conversion which is 65%, 92%, 97% respectively.
Recycle acetone at a rate of 4192 kg/h calculated by the formula II which was presented in Example 2, is fed to the
cleavage unit of CHP (process section 1) from the vessel 10.
The residence time of reaction products in the DCP cleavage reactor 7 is 865 seconds.
In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta Ti = 0.82°C. The temperature drop
in the mini-reactor 12 installed after the water supply to reaction products circulation loop outlet is 1.68°C.
Absolute temperatures difference (delta T = delta T2 - delta T 1) is 0.86°C.
To the product inlet line into the acetone evaporator 8, an aqueous ammonia solution at the concentration of 10%
wt and at the rate of 48 kg/h is fed to exclude chemical losses of desired products in the acetone evaporator so that the
degree of the conversion of acid into ammonium sulfate in the acetone evaporator 8 is 100%.
As a result the following amounts are produced:

phenol - 11156.4 kg/h (yield 99.4%)

acetone - 6815.7 kg/h (yield 98.5%)
alphamethylstyrene - 58.1 kg/ton of phenol (the yield of AMS is 79.9% theoretical taking into consideration DMBA
supply)
yield of phenol tar - 55.14 kg/t of phenol
cumene consumption - 1328 kg per ton of phenol

EXAMPLE 6

This example illustrates high selectivity of the process of the present invention at an intermediate rate of feed of
technical CHP per cleavage unit.
35 tons per hour of technical CHP, which has the composition defined by Example 1 are fed to the reactors of CHP
cleavage. Recirculation ratio is 26. To the recirculation loop which consists of the CHP cleavage reactors 11.80 kg/h of
sulfuric acid is fed. The cleavage of technical CHP is carried out at the reactors A, B and C outlet temperature which
are 74°C, 71 °C and 65°C respectively and at the CHP conversion which makes 70%, 93%, 97% respectively.
The recycle acetone at the rate of 4821 kg/h calculated by the formula II which was presented in Example 2, is fed
to the CHP cleavage unit (process section 1) from vessel 10.
The residence time of reaction products in the DCP cleavage reactor 7 is 487 seconds.
In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta Ti = 0.64°C. The value of the tem-
perature drop in the mini-reactor 12 installed after the supply of water to the reaction products at the circulation loop
outlet is 1.92°C.
The absolute temperature difference (delta T = delta T 2 - delta T 1) is 1.27°C.
To the product inlet line into the acetone evaporator 8 the aqueous ammonia solution at a concentration of 10% wt
and at the rate of 80 kg/h is fed through line 18 to prevent chemical losses of desired products in the acetone evaporator
so that the degree of the conversion of acid into ammonium sulfate in the acetone evaporator is 100%.
As a result the following amounts are produced;

phenol - 17751 kg/h (yield 99.4%)

acetone - 10906 kg/h (yield 98.5%)

8
 EP 0 670 296 B1

alphamethylstyrene- 58.6 kg/t. of phenol (the yield of AMS is 79.9% theor. taking into consideration DMBA supply)
yield of phenol tar - 54.14 kg/t of phenol
cumene consumption - 1328 kg per ton of phenol.

5 EXAMPLE 7

This example illustrates the reproducibility of high selectivity of the process at an intermediate feed rate of technical
CHP per cleavage unit. In this example the concentration of CHP in the technical CHP is substantially higher than in
Comparative Example 1 and Examples 2-6.
10 35 tons per hour of technical CHP, which has the following composition are fed to the CHP cleavage reactors:

CHP 91 .5 % by weight
Cumene 2.0 % by weight
DMBA 5.5 % by weight
Acetophenone 1.0 % by weight
20
Recirculation ratio is 26. To the recirculation loop which consists of the CHP cleavage reactors A, B and C 9.3 kg/h
of sulfuric acid is fed. The cleavage of technical CHP is carried out at reactor outlet temperatures which are 71 °C, 67°C
and 61 °C respectively and at CHP conversions which are 75%, 94%, 98% respectively.
The recycle acetone at the rate of 4444 kg/h calculated by the formula II which was presented in Example 2 is fed
25 to the CHP cleavage unit from vessel 10.
The residence time of reaction products in the DCP cleavage reactor 7 is 640 seconds.
In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta T-, = 0.49°C. Value of drop in mini-
reactor 12 temperature installed after water supply to the reaction products line at the circulation loop outlet is 1.38°C.
The absolute temperature difference (delta T = delta T2 - delta T1 ) is 0.89°C.
30 To the product inlet line into the acetone evaporator 8 the aqueous ammonia solution at the concentration of 10%
wt and at the rate of 63 kg/h is fed to prevent chemical losses of desired products in the acetone evaporator 8 so that
the degree of the conversion of acid into ammonium sulfate in the acetone evaporator is 100%.
As a result the following amounts are produced:

35 phenol - 14610.2 kg/h (yield 99.4%)

acetone - 8972.3 kg/h (yield 98.5%)
alphamethylstyrene - 56.6 kg/t. of phenol (the yield of AMS is 79.9 % theoretical taking into consideration DMBA
supply)
the yield of phenol tar - 62.51 kg/t of phenol
40 cumene consumption - 1335 kg per ton of phenol.

The foregoing examples illustrate the high selectivity of the process at various levels of feed rates of technical CHP
under a variety of conditions with excellent reproducibility.

45 EXAMPLE 8

This example and the examples that follow (Examples 9-14) show an increase in productivity of 2.3 times that of
Example 1 by a preferred embodiment of the process of the present invention which uses algorithm (III) for addition of
acetone and makes the embodiment efficient and effective over a broad range of concentration of CHP in technical
so CHP 40-98 wt %. The process is carried out without changing the equipment layout in comparison with Example 2. All
the reactors of the process of the present invention operate under the same pressure that is why all the reactors are
connected with each other by top, and the total pressure of the system is 4 kg/cm2.
Condensed acetone from vessel 10 is fed to the cleavage unit at a rate of 6890 kg/h calculated by the formula (III):

55
G c -_ „ „ G chp ( 1.315[CHP] 2[CHP] [DMBA] [cumene] [APh
" " " ^20J
V50+0.25[CHP] 152 136 120

9
 EP 0 670 296 B1

where: Gac - acetone amount fed for cleavage in t/hr

GChp - technical CHP amount fed for cleavage in t/hr
[CHP] - CHP concentration in technical CHP by weight.
[DMBA] - DMBA concentration in technical CHP by weight
5 [Cumene] - Cumene concentration in technical CHP by weight [AP] - Acetophenone (AP) concentration in
technical CHP by weight

60 tons per hour of technical CHP are fed to the reactors A, B and C for CHP cleavage. The composition is the
same as in Example 1.21.3 kg/h of sulfuric acid are also fed to the reactors. The cleavage of technical CHP is carried
10 out at a circulation ratio of 26/1 at temperatures at the reactors inlets of 68°C, 67°C and 60°C correspondingly and at a
CHP conversion of 59%, 94%, 98% correspondingly.
In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta Ti = 0.4°C.
To the product feed line into reactor 7 of DCP cleavage, water at a rate of 455 kg/h is fed through line 20 and static
mixer 19 so that the concentration of the latter in the cleavage products at the reactor outlet would be 1.58 wt% and
15 cleavage time is 485 seconds.
At a point after mixing cleavage products with water there is installed a second mini-reactor (calorimeter) 12, where
the value of the drop of temperature delta T2 at outlet and at inlet is measured. And the process control essentially is
carried out by means of the value of absolute temperature drop

20 delta T = delta T2 - delta T1 = 0.62°C.

To the product inlet line into the acetone evaporator 8 the aqueous ammonia solution at a concentration 10% wt
and at a line rate of 141 kg/h is fed through line 18 to exclude chemical losses of desired products in the acetone evap-
orator 8 so that the degree of conversion of acid to ammonia sulfate is 100% in evaporator 8.
25 As a result one gets:

phenol - 30434.1 kg/h (yield 99.5%)

acetone - 18774.8 kg/h (yield 98.5%) alphamethylstyrene 58.4 kg/t. of phenol (the yield of AMS is 78.9 theoretical
% taking into consideration the fed DMBA,
30 yield of phenol tar - 54.0 kg/t of phenol
cumene consumption - 1328 kg per ton of phenol

EXAMPLE 9

35 This example shows conducting the process of the present invention in reactors of reduced volume with reduced
surface of heat transfer and, consequently, with low specific surface of heat transfer. This process is carried out accord-
ing to the scheme described in Example 8. However, for the apparatus used in this example:

the volume of the reactor system of CHP cleavage is 2.8 times less than in Example 1,
40 the surface of heat transfer of this system is 3.5 times less than in Example 1 and
the specific surface of heat exchanger of DCP cleavage is 3 times less than analogous values described in Exam-
ple 1

26 tons per hour of technical CHP, having the composition defined by Example 1 is fed to reactors A, B & C for CHP
45 cleavage. To the circulating system (process section 1) which consists of reactors A, B and C for CHP cleavage 9.3 kg/h
of sulfuric acid is fed. The cleavage of technical CHP is carried out at temperatures at the reactors A, B and C outlet
which are 73°C, 70°C and 65°C correspondingly and at CHP conversion rates which are 66%, 90%, 96%, correspond-
ingly.
Acetone at a rate of 4312 kg/h calculated based on algorithm III which was presented in Example 8 is fed to the
so CHP cleavage unit (process section 1) from the vessel 10.
The residence time of reaction products in reactor 7 of DCP cleavage is 630 seconds.
As a result one gets:

phenol - 13183.2 kg/h (yield 99.4%)

55 acetone - 8072.5 kg/h (yield 98.8%) alphamethylstyrene - 58,02 kg/ton of phenol (the yield of AMB is 78.4
theoretical % taking into consideration the fed DMBA) yield of phenol tar - 55.43 kg/t of phenol
Cumene consumption - 1329 kg for ton of phenol

10
 EP 0 670 296 B1

In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta T-, - 0.95°C.
The value of the absolute temperature difference

T = deltaT2 - delta T1 =0.58°C

5
To the product inlet line of the acetone evaporator 8 an aqueous ammonia solution at a concentration of 10% wt
and at a rate of 63 kg/h is fed through line 18 to exclude chemical losses of desired products in the acetone evaporator
8 so that the degree of the conversion of acid into ammonium sulfate in the acetone evaporator 8 is 100%.

10 EXAMPLE 10

This example illustrates implementation of the process of the present invention in reactors with a heat exchange
specific area of 25 m2/t based upon 100% CHP.
26 tons per hour of technical CHP, which has the composition defined by Example 1, is fed to the reactors for CHP
15 cleavage. Circulation ratio is 26. To the circulation loop which consists of reactors A, B and C for CHP cleavage 9.3 kg/h
of sulfuric acid is fed. The cleavage of technical CHP is carried out at temperatures at reactors A, B and C outlets of
67°C, 66°C and 60°C correspondingly and at a CHP conversion of 62%, 82%, 90% correspondingly.
Acetone at a rate of 4313 kg/h calculated based on algorithm III which is presented in Example 8 is fed to the CHP
cleavage unit from vessel 10.
20 The residence time of reaction products in the reactor 7 of DCP cleavage is 640 seconds.
As a result the following amounts are produced:

phenol - 13188.4 kg/h (yield 99.3%)

acetone - 8082.9 kg/h (yield 98.8%)
25 alphamethylstyrene - 50.1 kg/ton of phenol (the yield of AMS is 79.8 % theor, taking into consideration DMBA sup-
ply)
yield of phenol tar - 52.9 kg/t of phenol
cumene consumption - 1327 kg per ton of phenol

30 In mini reactor 3 of the cleavage unit the value of the temperature drop delta Ti - 2. 17°C. Value of temperature drop
in mini- reactor 12 installed after water supply to the reaction products at the circulation loop outlet is 3.1 1°C.
Absolute temperatures difference (delta T = delta T2 - delta T 1) is 0.94°C.
To the product inlet line into the acetone evaporator 8 the aqueous ammonia solution at a concentration 10% wt
and at a rate of 63 kg/h is fed through line 18 to exclude chemical losses of desired products in the acetone evaporator
35 so that the degree of the conversion of acid into ammonium sulfate in the acetone evaporator is 100%.

EXAMPLE 11

This example illustrates the high selectivity of the process of the present invention at a lower feed rate of technical
40 CHP per cleavage unit and with a higher circulation ratio.
22 tons of technical CHP, which has the composition defined by Example 1, are fed to reactors A, B and C for CHP
cleavage. The circulation ratio is 35. To the circulation loop which consists of the reactors A, B and C for CHP cleavage
8.3 kg/h of sulfuric acid is fed. The cleavage of technical CHP is carried out at temperatures at reactors A, B and C out-
lets which are 72°C, 78°C and 67°C correspondingly and at CHP conversion which all 68%, 94%, 98% correspondingly.
45 Acetone at a rate of 4191 .4 kg/h calculated by the formula III which is presented in Example 8, is fed to the CHP
cleavage unit (process-section 1) from vessel 10.
The residence time of reaction products in the reactor 7 of DCP cleavage is 737 seconds.
In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta Ti = 0.39°C. Value of temperature
drop in mini-reactor 12 installed after water supply to reaction products at the circulation loop outlet is 0.99°C.
so Absolute temperatures difference (delta T = delta T 2 - delta T 1) is 0.6°C
To the product inlet line into the acetone evaporator 8 the ammonium aqueous solution at a concentration of 10%
wt and at a rate of 55.1 kg/h is fed through line 18 to exclude chemical losses of desired products in the acetone evap-
orator so that the degree of the conversion of acid into ammonium sulfate in the acetone evaporator 8 is 100%.
As a result the following amounts are produced:
55
phenol - 11159,1 kg/h (yield 79,4%)
acetone - 6821 ,8 kg/h (yield 98,5%)
alphamethylstyrene - 57,8 kg/ton of phenol (the yield of AMS is 78% theoretical, taking into consideration DMBA

11
 EP 0 670 296 B1

supply)
yield of phenol tar - 55.6 kg/t of phenol
cumene consumption - 1328 kg per ton of phenol

5 EXAMPLE 12

This Example illustrates the high selectivity of the process of the present invention at an intermediate rate of feed
of technical CHP per cleavage unit.
35 tons of technical CHP, which has the composition defined by Example 1, are fed to reactors A, B and C for CHP
10 cleavage The circulation ratio is 26. To the circulation loop which consists of the reactors A, B and C for CHP cleavage
13.1 kg/h of sulfuric acid is fed. The cleavage of technical CHP is carried out at temperatures at reactors A, B and C
outlets which are 73°C, 71°Cand 66°C correspondingly and at a CHP conversion which is 55%, 82%, 91% correspond-
ingly.
Recycle acetone at the rate of 6410 kg/h calculated based on algorithm III which was presented in Example 8, is
15 fed to the cleavage unit (process section 1) from vessel 10.
The residence time of reaction products in the reactor 7 of DCP cleavage is 467 seconds.
In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta Ti = 2.09°C Value of temperatures
drop in mini-reactor 12 installed after the water supply to reaction products at the circulation loop outlet is 3.04°C.
Absolute temperatures difference (delta T = delta T2 - delta T 1) is 0.95°C.
20 To the product inlet line into the acetone evaporator 8 an aqueous ammonia solution at a concentration of 10% wt
and at a rte of 88.7 kg/h is fed to exclude chemical losses of desired products in the acetone evaporator 8 so that the
degree of the conversion of acid into ammonium sulfate in the acetone evaporator is 100%.
As a result the following amounts are produced:

25 phenol - 17752.4 kg/h (yield 99.4%)

acetone - -10904.3 kg/h (yield 99.1%)
alphamethylstyrene - 58.9 kg/t. of phenol (the yield of AMS is 79.67 % theor. taking into consideration DMBA sup-
ply)
yield of phenol tar - 53.84 kg/t of phenol
30 cumene consumption - 1328 kg per ton of phenol.

The foregoing Example 12 illustrates the utility of the present invention at a higher level of throughput through CHP
cleavage unit (i.e. 35 tons per hour vs. 26 tons per hour).
The following examples illustrate the utility of the present invention with differing concentrations of CHP in the tech-
35 nical CHP feed stream. Example 13 illustrates a feed stream very rich in CHP. Example 14 illustrates a feed stream very
lean in CHP.

EXAMPLE 13

40 This technical CHP example illustrates the high selectivity of the process of the present invention with a higher con-
centration of CHP.
26 tons of technical CHP, which has the following composition are fed to the reactors A, B and C of CHP cleavage:

45
CHP 91 .5 % by weight
Cumene 2.0 % by weight
DMBA 5.5 % by weight
Acetophenone 1.0 % by weight

The circulation ratio is 26. To the circulation loop which consists of the reactors A, B and C for CHP cleavage 9.3
kg/h of sulfuric acid is fed. The cleavage of technical CHP is carried out at temperatures at reactors A, B and C outlets
55 which are 72.5°C. 68°C and 61 °C correspondingly and at a CHP conversion which is 78%, 96%, 98% correspondingly.
Recycle acetone at a rate of 4444 kg/h calculated based on algorithm III which is presented in Example 8, is fed to
the CHP cleavage unit (process section 1) from the vessel 10.
The residence time of reaction products in the reactor 7 of DCP cleavage is 642 seconds.

12
 EP 0 670 296 B1

In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta T-, - 0.36°C. The value of the tem-
perature drop in mini-reactor 12 installed after water supply to reaction products at circulation loop outlet is 1.46°C.
Absolute temperature difference (delta T = delta T 2 - delta T 1) is 1.1°C.
To the product inlet line into the acetone evaporator 8 an aqueous ammonia solution at a concentration of 10% wt
5 and at a rate of 63 kg/h is fed in exclude chemical losses of desired products in the acetone evaporator 8 so that the
degree of the conversion of acid into ammonium sulfate in the acetone evaporator is 100%.
As a result the following amounts are produced:

phenol - 14607.4 kg/h (yield 99,3%)

10 acetone - 8975 kg/h (yield 99.9)
alphamethylstyrene - 64.8 kg/t of phenol (the yield of AMS is 77.33% theoretical taking into consideration DMBA
supply)
yield of phenol tar - 69.36 kg/h of phenol
cumene consumption - 1342 kg per ton of phenol.
15
EXAMPLE 14

This example illustrates the high selectivity of the process of the present invention with a lower concentration for
CHP.
20 26 tons of technical CHP, which has the following composition are fed to the of CHP cleavage reactors A, B and C:

CHP 67 % by weight
Cumene 28.6 % by weight
DMBA 4 % by weight
Acetophenone 0.4 % by weight

The circulation ratio is 26. To the circulation loop which consists of the reactors A, B and C CHP cleavage 11.8 kg/h
of sulfuric acid is fed. The cleavage of technical CHP is carried out at temperatures at reactors A, B and C outlets which
are 69°C, 63°C and 62°C correspondingly and at a CHP conversion which is 68%, 96%, 98% correspondingly.
Recycle acetone at a rate of 2376 kg/h calculated based on algorithm III which is presented in Example 8, is fed to
35 the CHP cleavage unit (process section 1) from vessel 10.
The residence time of reaction products in the reactor of DCP cleavage 7 is 516 seconds.
In the mini-reactor 3 of the cleavage unit the value of the temperature drop delta Ti - 1.58°C. Value of the temper-
ature drop in mini-reactor 12 installed after water supply to reaction products at circulation loop outlet is 2.04°C.
Absolute temperatures difference (delta T = delta T2 - delta T 1) is 0.46°C.
40 To the product inlet line into the acetone evaporator 8 an aqueous ammonia solution at a concentration of 10% wt
and at a rate of 79 kg/h is fed through line 18 in exclude chemical losses of desired products in the acetone evaporator
8 so that the degree of the conversion of acid into ammonium sulfate in the acetone evaporator 8 is 100%.
As a result the following amounts are produced:

45 phenol -14402 kg/h (yield 99,2%)

acetone - 8833 kg/h (yield 98.9%)
alphamethylstyrene - 67 kg/t of phenol (the yield of AMS is 79,9% theor taking into consideration DMBA supply)
yield of phenol tar 79.9 kg/h of phenol
cumene consumption - 1331 kg per ton of phenol.
50
The following is a comparison of the operation of the present invention with the operation of the process of U.S. Pat-
ent No. 5,254,751 .
As compared with the process of U.S. Patent No. 5,254,751 the cleavage process of the present invention proceeds
at a faster rate and is more "robust". The three reactors A, B and C in the process of the present invention are smaller
55 and operate at higher temperatures (and higher pressure to suppress boiling).

13
 EP 0 670 296 B1

Temp C Pressure
A B C
present invention 68-79 78-65 69-60 3-4 atm
US 5,254,751 50-62 62-57 57-50 1 atm

CHP conversion profile across the three reactors is different from that of 5,254,751 . In the present invention a much
higher percentage of the CHP feed is reacted away in the first reactor A. And essentially no unreacted CHP is allowed
to exit reactor C. The delta T-, calorimeter is controlled at a very low value: (<1 degree).

% CHP Conversion wt% CHP Calorimeter 3

A B C
present invention 75 90 98 0.2
US 5,254,751 45 75 88 1.0

In the present process a higher circulation rate (26:1 - 40:1) in the A, B and C reactors is employed to give addi-
tional dilution of CHP feed so that safety is maintained at the faster cleavage rate. In the CHP concentration feeding
reactor A is 2.5 - 3 wt% as opposed to 4.5 - 5 wt% with the 5,254,751 process. CHP residence time in stage 1 of the
present process is 17-28 sec compared with 50-60 sec in the 5,254,751 process.
For the first stage reaction, sulfuric acid, water and acetone concentrations are essentially the same in both proc-
esses. Sulfuric catalyst cone is 300 ppm in both cases.
In the present process the first and second stage vents are tied together so that both steps operate at identical ele-
vated pressures. This saves investment in pumps and auxiliary equipment.
The foregoing examples and experimental and predictive results are meant to explain and describe the invention,
and are not intended to limit the invention to only those parameters specifically disclosed.
The data from the examples is summarized in the table below.
.2 § O U fl to-2 ** MPJflOlfllOOONOOMincOOONO ,£2/ n

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*

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iZ J u c J£ oo~ooooo<Nor*o — JJJ 4(
0) 60
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15
 EP 0 670 296 B1

Claims

1. An improved method for the production of phenol and acetone from cumene comprising the acid-catalyzed cleav-
age of technical cumylhydroperoxide and the cleavage of dicumylperoxide wherein the improvement comprises
5 cleaving the technical cumylhydroperoxide in a first vessel at a pressure above atmospheric pressure to obtain a
cumylhydroperoxide cleavage mass comprising dicumylperoxide and cleaving the dicumylperoxide in a second
vessel at the same pressure above atmospheric pressure whereby no pumps and surge vessels are required to
move the cumylhydroperoxide cleavage mass from the cumylhydroperoxide cleavage vessel to the dicumyl perox-
ide cleavage vessel.
10
2. The method of Claim 1 wherein the pressure in the cumylhydroperoxide cleavage and dicumylperoxide cleavage
vessels is from 2.0 to 10.1 bar (2 to 10 atmospheres).

3. The method of Claim 2 wherein the pressure is from 3.0 to 5.1 bar (3 to 5 atmospheres).
15
4. The method of Claim 1 wherein the cumylhydroperoxide is cleaved in a multiplicity of vessels which are circulating
reactors of a shell and tube design connected in series and the dicumylperoxide is cleaved in a single vessel which
is a plug flow reactor.

20 5. The method of Claim 4 wherein the cumylhydroperoxide is cleaved in three reactors with a temperature profile as
follows:

first reactor - from 67°C to 82°C

second reactor - from 63°C to 82°C
25 third reactor - from 57°C to 70°C.

6. The method of Claim 5 wherein the temperature profile is

first reactor - from 68°C to 79°C

30 second reactor - from 65°C to 78°C
third reactor - from 60°C to 69°C.

7. The method of Claim 1 wherein after the second vessel the pressure is reduced to atmospheric pressure or below
and acetone which is present in the cleavage mass is partially evaporated, condensed and returned to the first ves-
35 sel and before the acetone is partially evaporated but after the cleavage mass leaves the second vessel aqueous
ammonia is added to the cleavage mass whereby the residual acid catalyst is converted to its neutral salt.

8. The method of Claim 1 wherein the technical cumylhydroperoxide feed is from 74 percent by weight to 92 percent
by weight cumylhydroperoxide and acetone is recycled to the cumylhydroperoxide cleavage vessel according to the
40 following algorithm:

Gac = GCHP)x0.125[CHP] + G - 3 ^ H p ]

45
wherein: Gac is acetone amount fed for cleavage in t/hr,
GChp is technical cumylhydroperoxide amount fed for cleavage, t/hr and
[CHP] is cumylhydroperoxide concentration in technical cumylhydroperoxide by weight.

so 9. The method of Claim 1 wherein the cumylhydroperoxide cleavage mass is from 40 to 98% by weight cumylhy-
droperoxide and acetone is recycled to the cumyl hydroperoxide cleavage vessel according to the following algo-
rithm:

rUac_U
.nwr J 1-315[CHP] 2[CHP] [DMBA] [cumene] [AP])
55 ;,aUcHpXl50+0.25[CHP] " 152 " 136 " 120 "
120 J

where: Gac is acetone amount fed for cleavage in t/hr

16
 EP 0 670 296 B1

GCHP is technical cumylhydroperoxide amount fed for cleavage in t/hr,

[CHP] is cumylhydroperoxide concentration in technical cumyl by weight,
[DMBA] is dimethylbenzyl alcohol concentration in technical cumylhydroperoxide by weight,
[Cumene] is cumene concentration in technical cumylhydroperoxide by weight and
[AP] is acetophenone concentration in technical cumylhydroperoxide by weight

10. The method of Claim 1 wherein a portion of the cumylhydroperoxide cleavage mass is recycled to the cumylhy-
droperoxide vessel through a recycle line and connected to, and in parallel with, the recycle line is a first calorimeter
having an inlet and an outlet through which a portion of the recycled cumylhydroperoxide cleavage mass passes
and the temperature of the portion is measured at the inlet to the first calorimeter and at the outlet of the first calo-
rimeter to give a first temperature differential and a second calorimeter having an inlet and an outlet is connected
to, and in parallel with, a line connecting the cumylhydroperoxide cleavage vessel to the dicumylperoxide catalyst
cleavage vessel after a point in the line at which water has been added to the cumylhydroperoxide cleavage mass
through which inlet and outlet of said second calorimeter a portion of the cumylhydroperoxide cleavage mass mov-
ing to the dicumylperoxide cleavage vessel passes and the temperature of the portion is measured at the inlet to
the second calorimeter and at the outlet of the second calorimeter to give a second temperature differential and the
absolute difference between the first and second differential, i.e., absolute delta T = delta T2 - delta T 1 , is within
the range of 0.2°C to 3°C.

11. The method of Claim 1 wherein a portion of the cumylhydroperoxide cleavage mass is recirculated through the first
vessel at a ratio of from 20 to 40 parts by weight of recirculated cleavage mass to one part by weight of fed cumene
hydroperoxide.

12. The method of Claim 11 wherein the ratio is from 26 to 35 parts by weight of recirculated cleavage mass to one part
by weight of fed cumene hydroperoxide.

Patentanspruche

1. Verbessertes Verfahren zur Herstellung von Phenol und Aceton aus Cumol, das die saurekatalysierte Spaltung von
technischem Cumolhydroperoxid und die Spaltung von Dicumolperoxid umfaBt, worin die Verbesserung darin
besteht technisches Cumolhydroperoxid in einem ersten GefaB bei einem Druck oberhalb des Atmospharendrucks
zu spalten, urn eine Cumolhydroperoxidspaltmasse zu erhalten, die Dicumolperoxid enthalt und Spalten des Dicu-
molperoxids in einem zweiten GefaB bei dem gleichen Druck oberhalb des Atmospharendrucks, wobei keine Pum-
pen und VorratsgefaBe benotigt werden, urn die Cumolhydroperoxidspaltmasse aus dem
CumolhydroperoxidspaltgefaB zu dein DicumolperoxidspaltgefaB zu befordern.

2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daB der Druck in dem CumolhydroperoxidspaltgefaB und in
dem DicumolperoxidspaltgefaB 2,0 bis 10,1 bar (2 bis 10 Atmospharen) betragt.

3. Verfahren gemaB Anspruch 2, dadurch gekennzeichnet, daB der Druck 3,0 bis 5,1 bar (3 bis 5 Atmospharen)
betragt.

4. Verfahren gemaB Anspruch 1, dadurch gekennzeichnet, daB das Cumolhydroperoxid in einer Vielzahl von Gefa-
Ben gespalten wird, welche in Serie geschaltete Umlaufreaktoren in Schalen- oder Rohren-Bauweise sind, und das
Dicumolperoxid in einem einzigen GefaB gespalten wird, welches ein Kolbenstromreaktor ist.

5. Verfahren gemaB Anspruch 4, dadurch gekennzeichnet, daB das Cumolhydroperoxid in drei Reaktoren gespalten
wird, die folgendes Temperaturprofil aufweisen:

erster Reaktor - von 67°C bis 82°C

zweiter Reaktor - von 63°C bis 82°C
dritter Reaktor - von 57°C bis 70°C.

6. Verfahren gemaB Anspruch 5, dadurch gekennzeichnet, daB das Temperaturprofil verwendet wird:

erster Reaktor - von 68°C bis 79°C

zweiter Reaktor - von 65°C bis 78°C
dritter Reaktor - von 60°C bis 69°C.
 EP 0 670 296 B1

7. Verfahren gemaB Anspruch 1, dadurch gekennzeichnet, daB nach dem zweiten GefaB der Druck auf Atmospha-
rendruck oder darunter reduziert wird und Aceton, welches in der Spaltmasse vorhanden ist, teilweise verdampft,
kondensiert und in das erste GefaB riickgefiihrt wird und bevor das Aceton teilweise verdampft, aber nachdem die
Spaltmasse das zweite GefaB verlaBt, wassriges Ammoniak zur Spaltmasse zugegeben wird, wodurch der restli-
che Saurekatalysator zu seinem Neutralsalz umgewandelt wird.

8. Verfahren gemaB Anspruch 1, dadurch gekennzeichnet, daB das zugegebene technische Cumolhydroperoxid 74
bis 92 Gew.-% des Cumolhydroperoxids betragt, und daB das Aceton zum CumolhydroperoxidspaltgefaB gemaB
der folgenden Gleichung zuruckgefiihrt wird:

Gac = GCHP)xO,125[CHP] + G - 3 ^ H p ]

worin: Gac die Acetonmenge in t/h darstellt, die zur Spaltung zugegeben wird,
GChp die Menge an technischem Cumolhydroperoxid darstellt, die zur Spaltung zugegeben wird, t/h, und
[CHP] die Gewichtskonzentration des Cumolhydroperoxids darstellt, die in technischem Cumolhydroperoxid
vorhanden ist.

9. Verfahren gemaB Anspruch 1, dadurch gekennzeichnet, daB die Cumolhydroperoxidspaltmasse 40 bis 98 Gew.-%
des Cumolhydroperoxids darstellt, und daB das Aceton zu dem CumolhydroperoxidspaltgefaB gemaB folgender
Gleichung zuruckgefiihrt wird:

G 58G chp x( 1-315[CHP] 2[CHP] [DMBA] [Cumol] [APh

c -0
- V50+0.25[CHP] 152 136 120 ^20J

worin: Gac die Acetonmenge darstellt, die in t/h zur Spaltung zugegeben wird
GChp die Menge an technischem Cumolhydroperoxid darstellt, die in t/h zur Spaltung zugegeben wird,
[CHP] die Gewichtskonzentration des Cumolhydroperoxids in technischem Cumol darstellt,
[DMBA] die Gewichtskonzentration des Dimethylbenzylalkohols in technischem Cumolhydroperoxid darstellt,
[Cumol] die Gewichtskonzentration des Cumols in technischem Cumolhydroperoxid darstellt und
[AP] die Gewichtskonzentration des Acetophenons in technischem Cumolhydroperoxid darstellt.

10. Verfahren gemaB Anspruch 1, dadurch gekennzeichnet, daB ein Teil der Cumolhydroperoxidspaltmasse in das
CumolhydroperoxidgefaB uber eine Rucklaufleitung zuruckgefiihrt wird und sich parallel zur Rucklaufleitung ein mit
dieser verbundenes erstes Kalorimeter bef indet, welches einen EinlaB und einen AuslaB hat, durch die ein Teil der
zuriickgefiihrten Cumolhydroperoxidspaltmasse hindurch geleitet wird, wobei die Temperatur dieses Teils am Ein-
laB des ersten Kalorimeters und am AuslaB des ersten Kalorimeters gemessen wird, urn eine erste Temperaturdif-
ferenz zu erhalten und sich parallel zu einer Leitung, welche das CumolhydroperoxidspaltgefaB mit dem
DicumolperoxidkatalysatorspaltgefaB verbindet, ein mit dieser verbundenes zweites Kalorimeter nach einem Punkt
in dieser Leitung befindet, an dem Wasser zur Cumolhydroperoxidspaltmasse zugegeben wird, wobei ein Teil der
Cumolperoxidspaltmasse uber den EinlaB und den AuslaB des zweiten Kalorimeters in das Dicumolperoxidspalt-
gefaB iiberf iihrt wird und die Temperatur dieses Teils am EinlaB des zweiten Kalorimeters und am AuslaB des zwei-
ten Kalorimeters gemessen wird, urn eine zweite Temperaturdifferenz zu erhalten, wobei die absoulte Differenz
zwischen der ersten und der zweiten Differenz, d.h. das absoulte delta T = delta T2 - delta T1 , innerhalb des
Bereichs von 0,2°C bis 3°C ist.

11. Verfahren gemaB Anspruch 1, dadurch gekennzeichnet, daB ein Teil der Cumolhydroperoxidspaltmasse uber das
erste GefaB mit einem Verhaltnis von 20 bis 40 Gewichtsteile der zuriickgefiihrten Spaltmasse zu einem Gewichts-
teil des zugefiihrten Cumolhydroperoxid rezirkuliert wird.

12. Verfahren gemaB Anspruch 11, dadurch gekennzeichnet, daB das Verhaltnis von 26 bis 35 Gewichtsteile der
zuriickgefiihrten Spaltmasse zu einem Gewichtsteil des zugefiihrten Cumolhydroperoxids betragt.

Revendications

1. Procede ameliore pour la production de phenol et d'acetone a partir du cumene, comprenant la coupure catalysee

18
 EP 0 670 296 B1

par un acide de I'hydro-peroxyde de cumyle technique et la coupure du peroxyde de dicumyle, procede qui com-
prend comme amelioration la coupure de I'hydroperoxyde de cumyle technique dans un premier recipient, a une
pression superieure a la pression atmospherique, pour I'obtention d'une masse de produits de coupure de I'hydro-
peroxyde de cumyle, renfermant du peroxyde de dicumyle, et la coupure du peroxyde de dicumyle dans un second
5 recipient, a la meme pression, superieure a la pression atmospherique, grace a quoi il n'est pas necessaire d'utili-
ser des pompes et des recipients intermediates pour faire passer la masse de produits de coupure de I'hydrope-
roxyde de cumyle du recipient de coupure de I'hydroperoxyde de cumyle au recipient de coupure du peroxyde de
dicumyle.

10 2. Procede selon la revendication 1, dans lequel la pression dans les recipients de coupure de I'hydroperoxyde de
cumyle et du peroxyde de dicumyle est comprise entre 2,0 et 10,1 bars ( 2 et 10 atmospheres).

3. Procede selon la revendication 2, dans lequel la pression est comprise entre 3,0 et 5,1 bars (3 et 5 atmospheres).

15 4. Procede selon la revendication 1, dans lequel on effectue la coupure de I'hydroperoxyde de cumyle dans plusieurs
recipients qui sont des reacteurs a circulation, du type tube et enveloppe, relies en serie, et on effectue la coupure
du peroxyde de dicumyle dans un recipient unique qui est un reacteur a ecoulement a bouchons.

5. Procede selon la revendication 4, dans lequel on effectue la coupure de I'hydroperoxyde de cumyle dans trois reac-
20 teurs qui presentent le prof il de temperature suivant :

premier reacteur : temperature de 67 °C a 82 °C,

second reacteur : temperature de 63 °C a 82 °C,
troisieme reacteur: temperature de 57 °C a 70 °C.
25
6. Procede selon la revendication 5, dans lequel le profil de temperature est le suivant :

premier reacteur : temperature de 68 °C a 79 °C,

second reacteur : temperature de 65 °C a 78 °C,
30 troisieme reacteur: temperature de 60 °C a 69 °C.

7. Procede selon la revendication 1, dans lequel, apres le second recipient, on abaisse la pression jusqu'a une valeur
inferieure ou egale a la pression atmospherique et on evapore partiellement I'acetone presente dans la masse de
produits de coupure, on la condense et on la renvoie au premier recipient, et dans lequel, avant I'evaporation par-
35 tielle de I'acetone, mais apres que la masse de produits de coupure a quitte le second recipient, on ajoute une solu-
tion aqueuse d'ammoniac a la masse de produits de coupure, grace a quoi le catalyseur acide residuel est
transforme en son sel neutre.

8. Procede selon la revendication 1, dans lequel I'hydroperoxyde de cumyle technique servant a I'alimentation con-
40 tient 74 pour cent en poids a 92 pour cent en poids d'hydroperoxyde de cumyle et on introduit de I'acetone recyclee
dans le recipient de coupure de I'hydroperoxyde de cumyle, en une quantite fixee par la relation suivante :

Gac = GCHP)xO,125[CHP] + G - 3 ^ H p ]
45

dans laquelle Gac designe la quantite d'acetone introduite pour la coupure, en t/h,
GChp represente la quantite d'hydroperoxyde de cumyle technique introduite pour la coupure, en
t/h, et
so [CHP] designe la teneur en hydroperoxyde de cumyle de I'hydroperoxyde de cumyle technique,
en pour cent en poids.

9. Procede selon la revendication 1, dans lequel le courant d'hydroperoxyde de cumyle servant a I'alimentation con-
tient 40 a 98 % en poids d'hydroperoxyde de cumyle et on introduit de I'acetone recyclee dans le recipient de cou-
55 pure de I'hydroperoxyde de cumyle, en une quantite fixee par la relation suivante :

19
 EP 0 670 296 B1

^r a c_n«-Rr ( 1,315[CHP] 2[CHP] [DMBA] [cumene [APJ\

- " . ^ chp x l,50+0 25[CHP] " 152 " 136 " 120 " 120^

dans laquelle Gac designe la quantite d'acetone introduite pour la coupure, en t/h,
GChp designe la quantite d'hydroperoxyde de cumyle technique introduite pour la coupure, en t/h,
[CHP] designe la teneur en hydroperoxyde de cumyle de I'hydroperoxyde de cumyle technique,
en pour cent en poids,
[DMBA] designe la teneur en alcool dimethylbenzylique de I'hydroperoxyde de cumyle technique,
en pour cent en poids,
[Cumene] designe la teneur en cumene de I'hydroperoxyde de cumyle technique, en pour cent en
poids, et
[AP] designe la teneur en acetophenone de I'hydroperoxyde de cumyle technique, en pour cent
en poids.

0. Procede selon la revendication 1, dans lequel une partie de la masse de produits de coupure de I'hydroperoxyde
de cumyle est renvoyee pour recyclage au recipient de coupure de I'hydroperoxyde de cumyle par une canalisation
de recyclage, et il y a, relie a et en parallele avec la canalisation de recyclage, un premier calorimetre presentant
une entree et une sortie, a travers lequel passe une partie de la masse de produits de coupure de I'hydroperoxyde
de cumyle recyclee, et on mesure la temperature de cette partie a I'entree du premier calorimetre et a la sortie du
premier calorimetre pour obtenir une premiere difference de temperature, et un second calorimetre presentant une
entree et une sortie est relie a et en parallele avec une canalisation raccordant le recipient de coupure de I'hydro-
peroxyde de cumyle au recipient de coupure du peroxyde de dicumyle, apres un point de la canalisation ou de I'eau
a ete ajoutee a la masse de produits de coupure de I'hydroperoxyde de cumyle, et une partie de la masse de pro-
duits de coupure de I'hydroperoxyde de dicumyle se deplagant vers le recipient de coupure du peroxyde de cumyle,
traverse ledit second calorimetre et on mesure la temperature de cette partie a I'entree du second calorimetre et a
la sortie du second calorimetre pour obtenir une seconde difference de temperature, et la difference absolue entre
la premiere difference et la seconde difference, c'est-a-dire delta T absolu = delta T 2 - delta T 1 , est comprise
dans I'intervalle allant de 0,2 °C a 3 °C.

1. Procede selon la revendication 1, dans lequel on fait recirculer une partie de la masse des produits de coupure de
I'hydroperoxyde de cumyle dans le premier recipient, a raison de 20 a 40 parties en poids de masse de produits de
coupure que Ton fait recirculer pour une partie en poids d'hydroperoxyde de cumyle introduit.

2. Procede selon la revendication 11, dans lequel le rapport est de 26 a 35 parties en poids de masse de produits de
coupure que Ton fait recirculer pour une partie en poids d'hydroperoxyde de cumyle introduit.

20
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