US006252124B1

(12) United States Patent

Zakoshansky et al.

(10) Patent N0.: (45) Date of Patent:

US 6,252,124 B1
Jun. 26, 2001

(54) WASTELESS ECONOMIC METHOD OF PRODUCTION OF PHENOL AND ACETONE

Primary ExaminerSreeni Padmanabhan

(74) Attorney, Agent, or FirmEdWard Etkin, Esq.

(75) Inventors: Vladimir Mikhailovitch Zakoshansky, Mt. Vernon, IN (US); Irina Ivanovna

(57)

ABSTRACT

Vassilieva, St. Petersburg (RU)

(73) Assignee: ILLA International, LLC, Reno, NV

A neW phenol and acetone production process reduces the

amount of necessary stages for obtaining phenol and acetone, results in higher yield of desired products and

(Us)
(*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35

requires less complex equipment implementation and less

energy than current processes of a similar type. The neW

process comprises a stage of cumene hydroperoxide pro

duction via cumene oxidation, a stage of cumene oxidation

U.S.C. 154(b) by 0 days.

products concentration to produce technical cumene hydro peroxide and recycle of unreacted cumene to oxidation stage
after treatment, a stage of separation of cumene oxidation products in a continuous or cycle adsorption-desorption With the purpose of producing CHP that is free from DMBA and AP utilizing predetermined adsorbents and desorbents, a stage of heterogeneous or homogeneous cumene hydroper oxide cleavage With the use of acidic catalysts to produce at least phenol and acetone, a stage of AP fractionation from
AP-cumene fraction and return of cumene to the separation

(21) Appl. No.: 09/301,605 (22) Filed: Apr. 29, 1999 (30) Foreign Application Priority Data
Sep. 24, 1998 (RU) .............................................. .. 96120810

(51)
(52)

Int. Cl.7 ................................................... .. C07C 37/08

US. Cl. ................ .. . 568/798; 568/385; 568/735

(58)

Field of Search ................................... .. 568/385, 798,

568/735; 585/435
(56) References Cited
U.S. PATENT DOCUMENTS
4,358,618 * 11/1982 Sifniades et a1. .................. .. 568/385 5,017,729 * 5/1991 Fukuhara et al. ....... .. 568/798

stage, a stage of catalytic DMBA hydrogenation into cumene, and a stage of separating phenol, acetone, and desorbent to produce required product phenol and acetone. This results in (1) elimination of formation of by-products at the CHP cleavage stage and the fractionation stage; (2)

simpli?cation and reduced complexity of CHP cleavage products fractionation; and (3) a signi?cant decrease in
energy expenses compared to the conventional phenol and acetone production processes.

5,254,751 * 10/1993 Zakoshansky et al.

5,530,166 * 6/1996

568/385

Zakoshansky et al. ............ .. 568/798

* cited by examiner

11 Claims, 5 Drawing Sheets

U.S. Patent

Jun. 26, 2001

Sheet 1 0f 5

US 6,252,124 B1

1. cumene oxidation to CHP

a) main reaction

Cumene + 02 > CHP

b) side-reactions. Cumene + 02 Cumene + 02

> AP -> DMBA

Cumene + 02

> DCP (dicumy/peroxide)

2. acidic-catalytic cleavage of oxidation products:

a) main reaction
4.

H
CHP > b) side reactions Phenol + Acetone

DMBA CHP+DMBA

<' 1:2

AMS + H20 DCP + H2O

AMS dimers

DMBA i,
\
where DCP - d/cumyloeroxio'e

Complex
Deep condensation products

phenol tar

3. catalyst neutralization

H2504 + NaOH -> Na2504

4. partial cracking ofphenol tar

phenol tar >

5. AMS hydrogenation to cumene

phenol + AMS + heavy tar

catalyst
AMS + H2 > cumene 6. removal of microimpurities from phenol

H+
HA + phenol> ZMBF _> tar
+

H
AMS *> tar

carbonyl compounds > tar

where HA - hydroxyacetone, Z-MBF - Z-methy/benzotbran

7. remova/ of micro/'mpuritles mom acetone

lVaOH

aldehydes C1-C3 -> a/dol

FIGURE 1 (Prior Art)

U.S. Patent

Jun. 26, 2001

Sheet 2 0f 5

US 6,252,124 B1

CUMENE
Curnene oxidation stage
to CHP
V

Cumene
treatment

l
CHP concentration stage
H2SO4>
W

CHP cleavage stage

NaOH '> H20

Cleavage products neutralization

W

Waste waters

AMS hydrogenation
stage, 3 columns

Fractionation stage, 7-10 columns

Column of cleavage products

separation to acetone

and phenol ?ow

l
Column of aldehyde
removal from acetone stream
v

Column of phenol tar removal

Column of phenol
removal from phenol tar
u

from phenol ?ow

v

Product acetone

Column of hydrocarbon and ZMBF

Phenol tar

column
M

removal from crude phenol

W

cracking

Phenol puri?cation
on ion-exchange resin
u

Product phenol column

Steam :

v Phenol tar bottom

burning

FIGURE. 2 (Prior Art)

U.S. Patent

Jun. 26, 2001

Sheet 5 0f 5

US 6,252,124 B1

mun

QIU

BmEBFE
MEDUE m

a5:

US 6,252,124 B1
1
WASTELESS ECONOMIC METHOD OF PRODUCTION OF PHENOL AND ACETONE
BACKGROUND OF THE INVENTION

2
TWo different technologies (UOP disclosed in US. Pat.
No. 4,358,618, and FAN disclosed in US. Pat. Nos.

5,254,751 and 5,530,166) succeeded in achieving an AMS

yield at commercial unit at a level of 80% theoretical. The

The present invention is directed to a method for produc ing phenol and acetone in Which: (1) no side-products are formed due to production of cumene hydroperoxide (CHP); (2) the products are free from dimethyl benZene alcohol

yield of phenol tar Was minimiZed doWn to approximately 35 kg/t phenol When cumene usage per 1 ton of phenol Was 13071310 kg (taking into account the stage of phenol tar cracking) and minimiZed to 5558 kg/t and cumene usage of

(DMBA); (3) the selectivity at cleavage stage approaches

the theoretical level of 100%; (4) the stage of product fractionation is greatly simpli?ed due to the production of technical CHP free from acetophenone (AP), DMBA, alpha
10

approximately 1330 kg per ton of phenol Without phenol tar

cracking.
Thus, even the best above-indicated technologies result in losses of initial feed cumene from 33 kg/t to 53 kg/t While

methylstyrene (AMS) and products of their conversion; (5)

the energy expenses are reduced at least 1.52 times; (6) the process construction and technology are substantially sim
15

the yield of non-utiliZed Wastes remains high. Finally, large

number of chemical stages increases the complexity of

required implementation technology and further requires

increased energy expenditures. Referring noW to FIG. 2, a

pli?ed; and (7) capital costs for fractionation stage are

signi?cantly decreased.
There are numerous patents that refer to various methods

diagram of a typical implementation of conventional tech nology as described above is shoWn. This typical implemen
20

for improving the parameters of important commercial pro

cess of phenol and acetone production. These patents
include, but are not limited to: Us. Pat. No. 2,663,740; US. Pat. No. 4,358,618; U.S. Pat. No. 5,254,751; U.S. Pat. No. 5,530,166; US. Pat. No. 5,510,543; and US. Pat. No.

tation is described in Whole or in part in the following US. patents: U.S. Pat. No. 2,663,740; U.S. Pat. No. 4,358,618; US. Pat. No. 5,254,751; US. Pat. No. 5,502,259; US. Pat. No. 5,510,543; US. Pat. No. 5,530,166. It should be noted that it is nearly impossible to obtain

5,502,259.
Without exception, the phenol and acetone production processes and methodology taught and disclosed by these
patents are generally based on one or more of the folloWing
25

principles:
1. Oxidation of cumene to cumene hydroperoxide to

produce the oxidation products containing from 20 to 40% CHP; 2. Concentration of oxidation products by distilling unre
acted cumene under vacuum in one, tWo or sometimes

30

100% AMS yield utiliZing conventional technology due to existing equilibrium of reaction DMBA<=> AMS+H2O and due to formation of AMS dimers and complex phenols form DMBA. With current technology it is also impossible to avoid complexity and high energy requirements of CHP cleavage products fractionation as such products contain AMS, acetophenone and other impurities such as mesityl

oxide, hydroxyacetone and others.

Each of the patents mentioned above in connection With
FIG. 1 provides some innovation to one or several of the
35

three steps and then directing the recycle to oxidation

stage While being pretreated from impurities; 3. Homogeneous cleavage in phenol-acetone-cumene

medium using sulfuric acid as a catalyst to produce

stages of the process of FIG. to improve the parameters and overall results of the process. HoWever, the basic chemistry of the process and its implementation in terms of required

equipment remain unchanged.

40

phenol, acetone, alpha-methylstyrene and by-products

(for example, the phenol tar Which is hard to utiliZe

commercially);
4. NeutraliZation of sulfuric acid in CHP cleavage prod ucts by alkaline agents and removal of salts from the

It Would thus be desirable to provide an improved chemi cal process that reduces the amount of necessary stages for obtaining phenol and acetone via the cumene method. It Would also be desirable to provide a neW process that results

in higher yield of desired products and by-products. It Would

further be desirable to provide a chemical process that

above named products (eg Na2SO4, NaHSO4);

5. Fractionation of cleavage products to produce phenol, acetone, AMS and phenol tar;
6. Hydrogenation of AMS obtained at CHP cleavage stage
to convert it into cumene and further recycling cumene
45

requires less complex equipment implementation than cur

rent processes of similar type. It Would ?nally be desirable to provide a chemical process that had signi?cantly loWer

energy requirements.
SUMMARY OF THE INVENTION
50

to the oxidation stage; 7. Phenol puri?cation from micro impurities With the use

of acidic ion-exchange resins;

8. Acetone treatment from impurities With the use of

The novel chemical process of the present invention reduces the amount of necessary stages for obtaining phenol

and acetone (from 7 to 4), results in higher yield of desired

alkalis; and 9. Implementation of a stage of partial thermal cracking of

production Wastes or their incineration to produce
steam.
55

products and requires less complex equipment implementa

tion and less energy than current processes of a similar type. At the outset it should be noted that the Words reaction and

From the chemical vieW point, the vast majority of

previously knoWn (hereinafter conventional) processes of

phenol and acetone production via the cumene method that exist in the industry and in patent and other literature, can be characteriZed by the chemical reactions shoWn in FIG. 1 It is readily apparent to one skilled in the art that the main

objective of the designers of this commonly-used process

Was in ?nding a Way to increase the yield of desired

stage are used interchangeably. The basis of the improved process is a complete separa tion of technical CHP into components present therein by a method of continuous adsorption-desorption. This approach eliminates from the folloWing reactions from the previously knoWn series of chemical reactions: (1) all DMBA and CHP+DMBA side reactions at a CHP cleavage stage; (2) the entire neutraliZation stage if the cleavage stage is conducted

using heterogeneous or homogenous catalysts; (3) the entire

stage of phenol tar cracking and all related occurring desired and undesired reactions; (4) the hydrogenation stage of AMS to cumene; and (5) stages of removal of micro impurities

by-product AMS at a CHP cleavage stage (after the ultimate

selectivity of 9495 % theoretical Was obtained at cumene

oxidation stage).

US 6,252,124 B1
3
from phenol and acetone. Furthermore, the process of the present invention eliminates the need for complex prepara tion of feed to A.M. hydrogenation. In summary, the novelty of the chemical reactions and

4
present therein by a method of continuous adsorption desorption. The process of the present invention reduced the number of reactions necessary in previously knoWn pro
cesses as shoWn in FIG. 1. The improved process of the

technological implementation of the improved process of the present invention may be characteriZed by the following:
1. Cleavage of CHP that does not contain DMBA, AP and DCP, elimination of all chemical reactions that form

present invention eliminates all DMBA side reactions 2(b) at a CHP cleavage stage (FIG. 1), eliminates a neutraliZation

stage (reaction 3, FIG. 1) if the cleavage stage is conducted on heterogeneous catalysts, eliminates the stage of phenol
tar cracking and all occurring desired and undesired reac
10

side products;
2. Hydrogenation of DMBA separated from cumene oxi dation products to cumene; 3. Production of CHP that is free from DMBA, AP and other impurities conducted by a method of continuous

tions (reaction 4, FIG. 1), eliminates reactions 5, 6 and 7 (FIG. 1), and eliminates complex preparation of feed to AMS hydrogenation.

adsorption-desorption;
4. DMBA hydrogenation to cumene; and 5. The use of initial process feed (i.e. cumene) as a

Referring noW to FIG. 3, the neW process of the present invention includes a cumene oxidation stageTraditional Stage 1Which is carried out as usual (i.e. in the same 15 manner as reaction/stage 1 of FIG. 1), and a stage of acidic

desorbent and its further recycle to CHP production

(heterogeneous or homogeneous) CHP cleavage to phenol

and acetoneStage 3that is performed in a manner simi lar to the traditional Reaction/Stage 2 of FIG. 1. HoWever, the neW process comprises only tWo neW additional stages of (1) separation of DMBA and AP from CHP by a method of

stage.
Advantages of the improved process of the present inven
tion include, but are not limited to the folloWing: 1. Elimination of formation of by-products at the CHP

cleavage stage and the fractionation stage; 2. Signi?cant simpli?cation and reduced complexity of equipment necessary for the CHP decomposition stage; 3. Simpli?cation and reduced complexity of CHP cleav age products fractionation (i.e. the number of recti?
cation columns at the fractionation stage can be reduced by a factor of 2 in accordance With the present invention as compared to the conventional scheme); and 4. A signi?cant decrease in energy expenses compared to the conventional scheme (by a factor of approximately

continuous adsorption-desorption (NeW Stage 2), and (2)

hydrogenation of DMBA separated from oxidation products at NeW Stage 2 to cumene (NeW Stage 4). Thus, the
improved process utiliZes only four stages instead of seven
25

required in a conventional process. Furthermore, due to DMBA separation from cumene

oxidation products, at the stage of CHP cleavage (NeW Stage

2, FIG. 3): (1) there are no side-reactions to form AMS,

1.52).
The various features of novelty Which characteriZe the invention are pointed out With particularity in the claims appended to and forming a part of this speci?cation. For a
35

AMS dimers, o- and p-cumene phenols (i.e. complex phenols) and other numerous by-products (i.e. no phenol tar is formed); (2) CHP cleavage reaction occurs at 100% selectivity; and (3) the CHP cleavage process (due to lack of presence of tar) on heterogeneous or homogenous catalysts
can operate in a much safer manner because the absence of

better understanding of the invention, its operating advan tages and speci?c objects obtained by its use, reference should be had to the accompanying draWings and descriptive
matter in Which there is illustrated and described a preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS

DMBA enables the CHP cleavage process to be conducted in a softer regime and at loWer temperatures. The improved process of the present invention is shoWn

in FIG. 4. The improved process for producing phenol and acetone in accordance With the present invention comprises
a stage 10 of cumene hydroperoxide production via cumene oxidation, a stage 20 of cumene oxidation products concen

In the draWings, Wherein like reference characters denote corresponding or similar elements throughout the various

tration to produce technical cumene hydroperoxide and recycle of unreacted cumene to oxidation stage after treat ment 30, a stage 40 of separation of cumene oxidation

products in a continuous or cycle adsorption-desorption

45

?gures:
FIG. 1 shoWs a series of prior art chemical reactions

utiliZing predetermined adsorbents and desorbents, a stage 50 of heterogeneous cumene hydroperoxide cleavage With
the use of acidic catalysts to produce at least phenol and acetone, a stage 60 of AP fractionation from AP-cumene fraction and return of cumene to the stage 40 (or, optionally, to stage 10), a stage 70 of catalytic DMBA direct

representative of a conventional process for producing acetone and phenol via the cumene method; FIG. 2 schematically shoWs a diagram of a prior art conventional process for producing acetone and phenol via
the traditional cumene method; FIG. 3 shoWs a series of chemical stages representative of

hydrogenation, and a stage 80 of separating phenol, acetone, and desorbent to produce required product phenol and
acetone.
55

the improved process for producing acetone and phenol via

the cumene method in accordance With the present inven

tion;
FIG. 4 schematically shoWs a diagram of the improved
process for producing phenol and acetone via the cumene method in accordance With the present invention; and

Studies conducted during the development of the improved process shoW that heterogeneous and homogenous one-stage cleavage technologies cannot be used at high selectivity When using technical CHP With conventional composition and containing DMBA, due to principle differ
ences (approximately 200 times) in the CHP cleavage rate and DCP cleavage rate (DCP being formed from DMBA and CHP). HoWever, such heterogeneous or homogenous one stage technologies may be utiliZed in the process of the
present invention With the use of acidic catalysts With a Wide

FIG. 5 is a liquid separation chromatogram for experi

mental Example 2-A in accordance With the process of
FIGS. 3 and 4 using cumene as an adsorbent.

DESCRIPTION OF THE PREFERRED EMBODIMENT

65

The basis of the improved process of the present invention is a complete separation of technical CHP into components

spectrum of effectiveness. Preferably, the main catalysts at the stage 50 of heterogeneous/homogenous CHP cleavage are selected from at least the folloWing:

US 6,252,124 B1
5
protonic and aprotonic acids on supports, for instance
H3PO4 on aluminum oxide or kiselgur, BF3 on alumi num oxide, FP(O)OH)2 and/or F2P(O)OH or HF on oxides of Al, Si or Ti;

6
The aim is to produce, after desorption, the mixtures of acetophenone-light impurities of cumene oxidation

products-desorbent, DMBA-desorbent, CHP-desorbent, and

DCP-desorbent. The applied desorbents are separated from DMBA, AP and CHP and directed to recycle to adsorption
desorption stage 40 or, if cumene is used as a desorbent, it

natural or synthetic alumosilicate catalyst of the general

formula (Al2O3)m(SiO2)n(H2O)p, mainly amorphous

alumosilicates at a ratio of SiO2: Al2O3=0.1 to 10 and

is recycled either to adsorption-desorption stage 40 or to

cumene oxidation stage 10.
10

crystalline alumosilicates (Zeolites) at a ratio SiO2: Al2O3=3 to 100. Preferably the catalysts are used With Weak Luis and Brensted acidic sites and total value of Hammet acidity

Preferably, CHP as free as possible from DMBA, AP and DCP is used as a feed to cleavage stage 50. At the CHP

function HO=0.31.05 (0.30.8) and having the effective

pore diameter of 2040A. Homogenous acidic catalysts such as H2SO4, HCl, and others may also be utiliZed successfully and With high selectivity in the inventive process assuming that DMBA is absent from products arriving at the cleavage
15

cleavage stage 50, HZSO4 may be used as a catalyst. The most preferable heterogeneous acidic catalyst is the acidic catalyst With Hammet acidity function Ho =0.31.05 (0.30.8) and effective pore diameter 2040A.
If other catalysts are used, it is more preferable to use

heterogeneous catalysts at CHP cleavage stage 50 that may

be selected from, but are not limited to, the folloWing: 1. protonic and aprotonic acids on support, for instance H3PO4 on aluminum oxide or kiselgur, BF3 on alumi num oxide, FP(O)OH)2 and/or F2P(O)OH or HF on oxides of Al, Si or Ti; 2. natural or synthetic alumosilicate catalyst of the general

stage. HoWever, changing CHP cleavage technology from

homogeneous to heterogeneous, enables elimination of the neutraliZation stage and further eliminates related problems of salts removal from cleavage products.
As discussed above, the lack of DMBA in technical CHP
enables elimination of numerous condensation reactions.
20

Hence, the fractionation of cleavage products at stage 50 is substantially simpli?ed as the only cleavage products are
phenol and acetone. When no AP is present in technical CHP delivered to stage 40, the fractionation stage 60 is also simpli?ed as AP reacts With phenol to form aZeotrope that
25

formula (Al2O3)m(SiO2)n(H2O)p, mainly amorphous

alumosilicates at a ratio of SiO2/Al2O3/ H20=

(1:0.1:0.1)(1:10:10) and crystalline alumosilicates

(Zeolites) at a ratio SiO2/Al2O3/H2O=(1:3:1)

causes difficulties in their separation and, hence, large energy expenditures.

The above-described approach requires that CHP that is
free from AP and DMBA is used. Conventional methods of
30

(1:100:10).
It is preferable to direct DMBA separated from cumene

oxidation products to the stage 70 of catalytic direct hydro

genation to convert it into cumene With further cumene

oxidation product distillation do not provide technical CHP that is completely free from DMBA and AP. Furthermore,
use of 100% CHP Without any cumene is dangerous because

recycle to the cumene oxidation stage 10 after treatment 30. It is further preferable to carry out the process of DMBA direct hydrogenation to cumene at stage 70 in presence of
35

the thermal stability of highly concentrated (>92% Wt) CHP is reduced signi?cantly.
The improved process of the present invention utiliZes technical CHP Which alWays contains a quantity of cumene,

catalysts selected from the folloWing: Pd, Fe, Pt, Cu and/or

Ag on aluminum oxide and at temperature 7030 C. and hydrogen pressure of 540 atm. In summary the inventive and distinctive features of the process of the present invention include, but are not limited

thus resolving the safety problems. The inventive method of

separating technical CHP is completed via continuous or
40

to, the folloWing:

1. Separation of DMBA and AP from CHP; 2. Elimination of formation of by-products at the CHP

cyclic adsorption-desorption.
Adsorbents may be selected from, but are not limited to

the folloWing:
1. Entirely ion-exchanged Zeolites having an inlet WindoW of less than 6A in dimension;
45

cleavage stage and the fractionation stage;

3. Direct hydrogenation of DMBA into cumene; 4. Simpli?cation and reduced complexity of CHP cleav

2. Magnesium silicate;
3. Synthetic polymeric materials in macropore or gel state

age products fractionation (ie the number of recti?

cation columns at the fractionation stage can be

produced via polymeriZation of amines, amides, acry

lamides or via polymeriZation of styrene and divinyl

benZene;
4. Anionites in macropore or gel state comprising a

50

polystyrene matrix prepared via polymeriZation of sty

rene or styrene and divinylbenZene, and/or polycon densate matrix prepared via condensation of amines or amides or acrylamides and Wherein anion is the amine group of general formula-N(RR) Where RR is a hydrogen atom or alkyl radical, or amide-group of general formula RCON(RR") Where RR and R are hydrogen atom or alkyl radical.
Desorbents may be selected from, but are not limited to
55

reduced by a factor of 2 in accordance With the present invention as compared to the conventional scheme); and 5. A signi?cant decrease in energy expenses compared to the conventional scheme (by a factor of approximately

1.52).
The above-described advantages and distinctions of the present invention are illustrated by Examples 24. Example 1 illustrates a prior art approach to production of acetone and phenol using the cumene method and is presented for comparative purposes only. It should be noted that the beloW described examples are presented for illustrative purposes
only and are not intended to limit the scope of the present invention.

60

the folloWing: 1. Aromatic hydrocarbon C6C22;

2. Ketones C3C6;

EXAMPLE 1 (comparative)
65

3. Glycols C2C6;
4. Mixture of Water and acetone; 5. Water.

Cumene is oxidiZed in a cascade of bubbling reactors. By this oxidation 100 kg of the reaction oxidation mass (ROM)

have been produced With the folloWing composition: Wt. %

US 6,252,124 B1
7

8
6. Phenol Which is practically free of hydrocarbons and

Cumene AP DMBA CHP

73.117 0.186 1.206 25.409

2-MBF but containing hydroxyacetone and mesityl oxide as impurities is passed to ion-exchange resin (IER) puri ?cation Which results in hydroxyacetone and mesityl
oxide removal.

7. After the IER puri?cation phenol is passed into column

DCP (dicumyl peroxide)

Organic acids

0.082
3000 ppm

7the product phenol column.

8. Phenol tar produced at the bottom of column 4 is passed into column 8 Where additional phenol distillation from
10

Selectivity at the oxidation stage is 94% theoretical. The produced ROM is passed to the 3-step stage of CHP con
centration to obtain CHP ?nal concentration of 9293%. As

phenol tar occurs.

9. Phenol tar produced at the bottom of column 8 is passed to cracking to produce phenol and AMS or is utilized.
As a result of side reactions in the bottoms of fractionation
15

a result, technical CHP is produced With the following composition: cumene-1.53 Wt. %, AP-0.69 Wt. %, DMBA 4.45 Wt. %, CHP-93.1 Wt. %, DCP-0.3 Wt. %. Impurities including organic acids are 3000 ppm. The selectivity reduc tion at the CHP concentration stage is 0.3% abs. The technical CHP With said composition is supplied to the CHP cleavage stage according to the method speci?ed in US. Pat. No. 5,254,751.

columns, the AMS yield is reduced to 78%, the consumption coef?cient of cumene/phenol is increased to 1333 kg/t, and the Waste yield of phenol tar is increased to 56 kg/t. Thus the
raW material losses at the fractionation stage due to chemical reactions are about 2030 kg/t.

20

As a result, CHP cleavage products (phenol and acetone) as Well as by-products (dicumyl peroxide (DCP), cumylphe nol (CP), AMS dimers) and micro-impurities

As described above, phenol tar from column 4 bottom is passed into the reactor of its thermal cracking. The rate of tar conversion into useful products is beloW 40% since an increase of the conversion depth Will result in coke-like

untransportable products formation. The useful products

25

(hydroxyacetone, mesityl oxide, organic acids (C1C2)) are

produced.
The composition of the reaction cleavage mass (RCM) is
as folloWs: Wt. %

formed in the thermal crackingphenol and AMSare recycled to the fractionation stage. As a result of the phenol tar partial cracking the phenol tar yield is reduced to 3240 kg/t and the cumene consumption value reaches about 1310

kg/t of phenol.
30

Unconverted phenol tar is passed to incineration to pro duce steam. Therefore the process is characterized by the

Phenol Acetone AMS

56.47 35.00 3.19

folloWing parameters:
1. Cumene/phenol consumption after the CHP cleavage

DCP (dicumyl peroxide)

DMBA AP CP Dimers

0.9
0.26 0.59 0.55 0.36

stage1305 kg/t of phenol;

2. AMS yield after the CHP cleavage stage80% theo
35

retical;
3. phenol tar yield after the CHP cleavage stage35 kg/t of phenol; 4. cumene/phenol consumption after the fractionation

Organic acids Mesityl oxide Hydroxyacetone

3000 ppm 500 ppm 1500 ppm

40

stage1333 kg/t of phenol;

5. AMS yield losses after the fractionation stage; 6. cumene/phenol consumption after the phenol tar

The yield of AMS, a valuable by-product, is 80% theo retical. The cumene consumption per 1 t phenol after the

cleavage stage is 1300 kg. Sulfuric acid in the ROM is

cracking1310 kg/t of phenol;

45

neutralized by sodium hydroxide.

To improve the removal of salts formed, the RCM is
Watered to a Water concentration of about 712 Wt. % and

7. phenol tar yield35 kg/t of phenol;

8. steam consumption per 1 t of phenol4 t.
EXAMPLES 2-A to 2-T

the products are passed to the stage of their fractionation comprising 8 fractionation columns (in a typical Well-knoWn

con?guration):
1. The RCM is passed into column 1 Wherein it undergoes a separation into acetone and phenol streams. 2. The acetone stream containing acetone, Water, cumene, AMS, aldehydes and a little phenol is passed into column 1 Wherein the basic amount of aldehydes is distilled aWay. 3. The acetone stream Which is already practically free of aldehydes is passed into column 3 Where product acetone

50

Examples 2-A to 2-P Were preformed using a variety of combinations of adsorbents and desorbents. Examples 2-Q to 2-T Were performed similarly to Examples 2-A to 2-P, except that a variety of different acidic catalysts Were used.
Cumene Was oxidized as in Example 1 and the reaction oxidation mass (ROM) Was produced With the same com

55

position as described in Example 1. The produced ROM Was passed to the ?rst step of the CHP concentration stage. CHP
Was concentrated to its concentration in technical CHP no

is produced (a hydrocarbon fraction containing cumene

and AMS goes from the column bottom). 4. The phenol stream containing phenol, a feW percent of

less than 40 Wt. %.

As a result, 100 kg of technical CHP Was produced With

hydrocarbons (cumene and AMS), AP, CP, AMS dimers,

and such impurities as mesityl oxide, hydroxyacetone, 2-MBF, is passed into column 4 Wherein phenol is sepa rated from heavy productsAP, CP, AMS dimers. 5. Crude phenol is passed into column 6 to Which Water is also supplied. In this column crude phenol is treated from hydrocarbons and 2-MBF.

the folloWing composition: Wt. %

65

Cumene AP DMBA

57.68 0.29 1.90

US 6,252,124 B1
9
-continued
CHP DCP 40.00 0.13

10
Example 2-N: Similar to Examples 2-A to 2-K, but Water
is used as a desorbent.

Example 20: Similar to Examples 2-A to 2-K, but ketones

C3C6 are used as a desorbent.

Example 2-P: Similar to Examples 2-A to 2-K, but glycols

There Were no selectivity losses at the CHP concentration
C2C6 are used as a desorbent.

stage. The technical CHP having the said composition Was passed to the continuous adsorption-desorption stage 40
Wherein in Example 2-A polyamide Was used as an adsor
bent and cumene Was used as a desorbent.
10

The component separation degree is close to 100% in each case. Liquid separation chromatogram for Example
2-A using cumene as a desorbent is shoWn in FIG. 5. The

In the end of the continuous adsorption-desorption pro

cumenelights (aldehydes, organic acids, methanol and

others) and AP fraction are passed to separation 60 by the
standard fractionation method. The lights are taken off as
15

cess the folloWing fractions are produced (in kg)

Cumene-light (CH3OH, organic

60.0 (cumene content-99.96 Wt. %)

23.4 (cumene content-87.32 Wt. %) 41.5 (cumene content-10.63 Wt. %) 0.1 (cumene content-9.75 Wt. %)
20

an overhead product and the produced fraction containing lights and 0.1 kg cumene is burnt up. Cumene is produced
in an amount of 59.88 g as a side-draW and recycled to the

acids)-AP
Cumene-DMBA Cumene-CHP Cumene-DCP

oxidation stage 10. In the column bottom pure phenol, Which

is a commercial product, is produced in an amount of 0.29

In Examples 2-B to 2-P, the folloWing parameters Were used: Example 2-B: Magnesium silicate is used as an adsorbent. At the end of the continuous adsorption-desorption process the fractions similar to Example 2-A are produced.

kg. The produced acetophenone can be hydrogenated to produce ethylbenZene Which is also a commercial product.
The binary cumene-DMBA fraction produced at the con

tinuous adsorption-desorption stage is passed to the catalytic

25

dehydration-hydrogenation stage 70 to convert DMBA into

cumene.

Example 2-C: Synthetic polymeric materials produced by

amines polymeriZation are used as an adsorbent. At the end

of the continuous adsorption process the fractions similar to Example 2-A are produced.

In Example 2-A, Pd/Al2O3 Was used as a catalyst. The

process Was carried out at a temperature of 130 C., a
30

Example 2-D: Synthetic polymeric materials produced by

amides polymeriZation are used as an adsorbent. At the end

hydrogen pressure of 6 atm. DMBA conversion Was 100%, selectivity Was 99.9%.

of the continuous adsorption process the fractions similar to Example 2-A are produced.

In Example 2-B, Fe/Al2O3, Pt/Al2O3, Cu/Al2O3 and

Ag/Al2O3 Were used as a catalyst. When using these cata
35

Example 2-E: Synthetic polymeric materials produced by

acrylamides polymeriZation are used as an adsorbent. At the

end of the continuous adsorption process the fractions similar to Example 2-A are produced.

lysts the temperature Was varied in the range of 70300 C., and the pressure540 atm. As a result of the process being
carried out on these catalysts, the DMBA conversion Was

Example 2-F: Synthetic polymeric materials produced by

styrene and divinylbenZene polymeriZation are used as an

100%, selectivity Was 99.9%.

The cumene produced in an amount of 14.98 kg after standard treatment, is passed to the stage 10 of cumene oxidation into cumene hydroperoxide. The binary cumene-CHP fraction produced at the con tinuous adsorption-desorption stage 40 in an amount of

adsorbent. At the end of the continuous adsorption process the fractions similar to Example 2-A are produced.

40

Example 2-G: Anionites (being a polystyrene matrix) are

used as an adsorbent. At the end of the continuous adsorp tion process the fractions similar to Example 2-A are pro duced.

44.89 kg is passed to the acidic cleavage stage 50. Sulfuric

acid, a conventional catalyst, can be used as an acidic
45

Example 2-H: Anionites (being a polycondensate matrix)

made by amines condensation are used as an adsorbent. In

the amines condensation the exchanged anion is an amino group With a common formulaN(RR) Wherein R and R are a hydrogen atom or an alkyl radical. At the end of the

continuous adsorption process the fractions similar to Example 2-A are produced.

50

catalyst, so that the process is carried out according to conventional scheme as described in US. Pat. No. 5,254, 751. As a result of CHP cleavage at a temperature of 55 C., phenol in an amount of 24.73 kg and acetone15.27 kg Were produced. There Were no DCP, AMS dimers, cumyl

Example 21: Anionites (being a polycondensate matrix)

made by acrylamides condensation are used as an adsorbent.

phenol, AMS, DMBA or AP in the cleavage products.

Furthermore, there Were no deep condensation products in

In the acrylamides condensation the exchanged anion is an amino group RCON(RR") Wherein R, R and R" are a hydrogen or alkyl atom. At the end of the continuous adsorption process the fractions similar to Example 2-A are

the cleavage products. The CHP cleavage products Were

55

passed to the stage of their fractionation. The fractionation is performed according to a Well-knoWn 3-column scheme.

produced.
Example 2-J: Totally ion-exchanged Zeolites With an inlet
WindoW of dimension 640 A are used as a desorbent.
60

Heterogeneous acidic catalysts such as (Example 2-A)

synthetic Zeolites in H+-form With the ratio SiO2/Al2O3=8.5
can be used at the CHP cleavage stage 50 as acidic catalysts. As a result of the cleavage, phenol in an amount of 24.7 kg and acetone in the amount of 15.2 kg Were produced. Examples 2-Q to 2-T Were conducted similarly to Examples 2-A to 2-P, except that a different set of hetero geneous catalysts Was used in each example. Table 1 beloW

Example 2-K: Anionites in a gel or macroscopic state

(being a polycondensate matrix) made by amines conden

sation are used as an adsorbent.

Example 2-L: Similar to Examples 2-A to 2-K, but

aromatic hydrocarbons C6C22 are used as a desorbent.
65

Example 2-M: Similar to Examples 2-A to 2-K, but a

mixture of Water and acetone is used as a desorbent.

summariZes the Wide variety of heterogeneous catalysts that

Were used.

US 6,252,124 B1
11
TABLE I
Heterogeneous catalysts of DMBA and AP free CHP cleavage
Example 2-Q
1. 2.
3. 4. 5.

12
Cumene-light hydrocarbons (CH3OH, organic acids)-AP
Cumene-DMBA Cumene-CHP Cumene-DCP

46.28 (cumene content-99.05 Wt. %)

Protonic acids on supports

H3PO4 on H3PO4 on
HF on HF on HF on

A1203 Kieselguhr
A1203 SiO2 TiO2

10.75 (cumene content-73.5 Wt. %) 66.76 (cumene content-10.12 Wt. %) 0.21 (cumene content-9.73 Wt. %)

10

Example 2-R
1. 2.

Aprotonic acids on supports

BF3 on FP (O)(OH)2 on A1203 A1203

3.
Example 2-S
1. 2.

F2P

A1203

The separation of cumene-lights-AP fraction Was per formed as in Example 2-A. As a result of the separation, AP in an amount of 0.44 kg and cumene45 .74 kg Were produced. 0.1 kg cumene and lights taken off as an overhead product and Were passed to incineration. The produced cumene Was recycled to the oxidation stage 10.

15

The dehydration-hydrogenation of the binary cumene

DMBA fraction Was performed as in Example 2-A. DMBA

Amorphous aluminosilicates With

the ratio Si/Al in the range 01-10
Ratio Si/Al = 0.1 Ratio Si/Al = 10

conversion Was 100%, selectivity is 99.9%.

20

The cumene produced in an amount of 10.75 kg after standard treatment Was passed to the stage 10 of cumene oxidation into cumene hydroperoxide.

Example 2-T

Crystalline alumosilicates
(zeolites) With the ratio Si/Al in
the range 310

The separated binary cumene-CHP fraction in an amount of 66.76 kg Was passed to the stage 50 of acidic heteroge
25

1. 2.

ratio Si/Al = 3 ratio Si/Al = 10

neous cleavage as in Examples 2-Q to 2-T. As a result of CHP cleavage, phenol in an amount of 37.1

kg and acetone22.9 kg Were produced.

With no DMBA, the cleavage stage selectivity Was 100%. There Were no DCP, AMS dimers, cumyl-phenol, AMS, DMBA or AP in the cleavage products. There Were no deep condensation products in the cleavage products as Well. The CHP cleavage products Were passed to the stage of their fractionation. The fractionation Was performed according to
a 3-column scheme.

The produced cumene/DCP fraction in an amount of 0.1 kg Was passed to fractionation and the production of com mercial DCP being used as a polymerization initiator. Cumene separated from the cumene/DCP fraction Was

passed to the stage 10 of its oxidation. In the end of the process according to Examples 2-A to 2-T the following Were produced:
35

Phenol Acetone Acetophenone

DCP
Phenol tar

24.73 kg (selectivity 100%) 15.27 kg (selectivity 100%) 0.29 kg

0.13 kg
None

The produced cumene/DCP fraction in an amount of 0.21 kg Was passed to fractionation and the production of com mercial DCP being used as a polymerization initiator etc. Cumene produced from the cumene/DCP fraction Was passed to the stage 10 of its oxidation. In the end of the process according to Example 3 the

40

folloWing Were produced:

Cumene consumption Was 1278 kg/t of phenol.

Steam consumption Was 2 t per 1 t of phenol.
EXAMPLE 3 45 Cumene Was oxidized as in Example 1 and the reaction oxidation mass (ROM) Was produced With the same com
Phenol Acetone Acetophenone
DCP
Phenol tar

37.1 kg (selectivity 100%) 22.9 kg (selectivity 100%) 0.44 kg

0.19 kg
No

position as described in Example 1. The produced ROM Was

passed to the tWo-stage CHP concentration (stage 20). CHP

less than 60 Wt. %. As a result, 100 kg of technical CHP Was produced With

Cumene consumption Was 1279 kg/t of phenol.

EXAMPLE 4
Cumene Was oxidized as in Example 1 and the reaction oxidation mass (ROM) Was produced With the same com

Was concentrated to its concentration in technical CHP no 50 Steam consumption Was 2.05 t per 1 t of phenol.

the following composition: Wt. %

55
Cumene AP DMBA CHP DCP 36.52 0.44 2.85 60.00 0.19

position as described in Example 1. The produced ROM Was

passed to the three-step stage of CHP concentration (stage

20). CHP Was concentrated to its concentration in technical CHP no less than 8,0 Wt. %. As a result, 100 kg of technical CHP Was produced With

60

the folloWing composition: Wt. %

Selectivity losses at the CHP concentration stage Were 0.1% abs. The fractionation of the technical CHP having the above composition Was performed as in Example 2-A. In the end of the continuous adsorption-desorption pro

65

Cumene AP DMBA

1.53 0.68 4.39

cess the folloWing fractions Were produced: (in kg)

US 6,252,124 B1
13
-continued
CHP DCP 93.10 0.30

14
preferred embodiments thereof, it Will be understood that various omissions and substitutions and changes in the form and details of the devices and methods illustrated, and in their operation, may be made by those skilled in the art Without departing from the spirit of the invention. For example, it is expressly intended that all combinations of those elements and/or method steps Which perform substan
tially the same function in substantially the same Way to achieve the same results are Within the scope of the inven tion. It is the intention, therefore, to be limited only as

Selectivity losses at the CHP concentration stage Were 0.3% abs. The fractionation of the technical CHP having the above composition Was performed as in Example 2-A. In the end of the continuous adsorption-desorption process, the folloW ing fractions Were produced: Wt. %

10

indicated by the scope of the claims appended hereto.

We claim:

Cumene-light hydrocarbons (CH3OH, organic acids)-AP

Cumene-DMBA Cumene-CHP Cumene-DCP

10.87 (cumene content-93.8 Wt. %) 11.63 (cumene content-62.3 Wt. %) 102.88 (cumene content-9.51 Wt. %) 0.33 (cumene content-9.00 Wt. %)

15

1. Amethod for producing phenol and acetone comprising the steps of: (a) producing cumene hydroperoxide via cumene oxida

tion;
(b) concentration of cumene oxidation products to pro duce technical cumene hydroperoxide;
20

The separated binary cumene-lights-AP fraction Was passed to separation by the standard fractionation method.
As a result of the separation, AP in an amount of 0.68 kg and

(c) recycling unreacted cumene produced at said step (b) to said step (a); (d) performing cumene oxidation products separation via
a continuous cyclic adsorption-desorption With the use
of at least one adsorbent and at least one desorbent;

cumene9.19 kg Were produced. The produced cumene Was recycled to the oxidation stage. 0.1 kg cumene, and lights taken off as overhead products Were passed to incineration.

25

(e) performing cumene hydroperoxide cleavage using at

least one acidic catalyst to produce cleavage products;
and

The separated binary cumene-DMBA fraction, avoiding

fractionation, Was passed to the catalytic DMBA hydroge
nation stage 70 to convert DMBA into cumene. The process Was performed as in Example 2-A. DMBA conversion Was
30

(f) performing cleavage products fractionation to produce

phenol and acetone.
2. The method of claim 1, Wherein said at least one adsorbent is selected from a group of:

100%, selectivity Was 99.99%.

The cumene produced in an amount of 11.63 kg after standard treatment Was passed to the stage 10 of cumene

entirely ion-exchanged Zeolites having an inlet WindoW of dimension less than about 6A,
35

oxidation into cumene hydroperoxide. The separated binary

cumene-CHP fraction in an amount of 102.88 kg Was passed

magnesium silicate,
synthetic polymeric materials that are in a macropore or

to the stage of acidic cleavage. Synthetic Zeolites HY Were used as acidic catalysts as in Examples 2-Q to 2-T. As a result of CHP cleavage, at a temperature of 55 C. phenol in an amount of 57.57 kg and acetone in the amount

gel state produced via polymeriZation of amines, amides, acrylamides or via polymeriZation of styrene and divinylbenZene,
40

of 35.52 kg Were produced. With no DMBA, the cleavage

stage selectivity Was 100%. There Were no DCP, AMS

anionites in macropore or gel state being a polystyrene matrix prepared via polymeriZation of one of styrene,

dimers, cumyl-phenol, AMS, DMBA or AP in the cleavage products. There Were no deep condensation products in the

and styrene and divinylbenZene, and polycondensate matrix prepared via condensation of
amines or amides or acrylamides, and Wherein anion is
45

cleavage products.
The CHP cleavage products Were passed to the stage of
their fractionation. The fractionation Was performed accord ing to a 3-column scheme. The produced cumene/DCP fraction in an amount of 0.33 kg Was passed to fractionation and the production of commercial DCP being used as a

an amine-group of general formula N(RR) Where

RR is one of a hydrogen atom, alkyl radical, and

amide-group, of general formula RCON(RR") Where

RR and R" are one of a hydrogen atom and an alkyl
50

polymeriZation initiator etc. Cumene produced from the cumene/DCP fraction is passed to the stage 10 of its oxidation. In the end of the process according to Example 4, the folloWing Were pro duced:

radical. 3. The method of claim 1 Wherein said at least one desorbent is selected from a group of: aromatic hydrocar

bons C6C22, ketones C3C6, glycols C2C6, the mixture of

Water and acetone, and Water, further comprising the step of: (g) using said at least one desorbent to produce mixtures of acetophenone-light impurities of cumene oxidation

products-desorbent, DMBA-desorbent, CHP

Phenol Acetone Acetophenone
DCP
Phenol tar

57.57 kg (selectivity 100%) 32.52 kg (selectivity 100%) 0.68 kg

0.30 kg
No

60

desorbent, and DCP-desorbent. 4. The method of claim 3, further comprising the steps of: (h) separating said at least one desorbent from dimethyl benZene alcohol, acetophenone and cumene hydroper

oxide;
(i) recycling said at least one desorbent to said step (d); and
65

Cumene consumption Was 1280 kg/t of phenol.

Steam consumption Was 2.1 t per 1 t of phenol.

When cumene is used as said at least one desorbent,

Thus, While there have shoWn and described and pointed

out fundamental novel features of the invention as applied to

recycling cumene to one of said step (a) and said step

(d)

US 6,252,124 B1
15
5. The method of claim 1, further comprising the step of:

16
the Hammet acidity function HO=0.30.8 and pore diameter
of about 2040A.

(k) feeding cumene hydroperoXide substantially free from dimethyl benZene alcohol, acetophenone and dicumylperoXide to said step (e).
6. The method of claim 1, Wherein said at least one acidic

catalyst comprises sulfuric acid.

7. The method of claim 5, Wherein said at least one acidic

9. The method of claim 1, further comprising the steps of: (l) separating dimethyl benZene alcohol from cumene oxidation products at said step (d);

(m) performing catalytic hydrogenation on said dimethyl

benZene alcohol to convert said dimethyl benZene alcohol into cumene; and

catalyst is selected from: protonic and aprotonic acids on supports including:

H3PO4 on one of aluminum oXide, and

kiselgur; BF3 on aluminium oXide;

one of FP(O)OH and HF on one of aluminium, silicium

(n) recycling said cumene to said step (a). 10. The method of claim 9, Wherein said step

is

and titanium oxides; from: Pd, Fe, Pt, Cu and Ag on aluminium oXide, and natural and synthetic alumosilicate catalysts of general 5 Wherein said step is conducted at a temperature of about

conducted in the presence of at least one catalyst selected

formula (Al2O3)m(SiO2)n(H2))h including:

(1:0.1:0.1)(1:10:10), and

alumosilicates at a ratio of SiO2 to A1203 to H2O of

70300 C. and hydrogen pressure of about 540 atm.

crystalic alumosilicates (Zeolites) at a ratio of SiO2 to

11. The method of claim 1, Wherein said step (c) further comprises the step of treating said recycled cumene prior to
20 delivering said cumene to said step (a).
* * * * *

A1203 to H2O of (1:3:1)(1:100:10).

8. The method of claim 7, Wherein said at least one acidic

catalyst is selected from heterogeneous acidic catalysts With