Waste-free cost-effective method of producing phenol and acetone

 

(57) Abstract:

Phenol and acetone receive acid decomposition gidroperekisi cumene, which is isolated from the products of oxidation of cumene. The selection is performed by the method of continuous or cyclic adsorption-desorption using adsorbents selected from the group: fully cationization zeolites with the size of the input window is not less than 6A; magnesium silicate; synthetic polymeric materials in macroporous or gelina condition, obtained by polymerization of amines, amides, acrylamides or polymerization of styrene and divinylbenzene; in the macroporous anion exchange resin or gelina condition. As desorbent use aromatic hydrocarbons WITH6- C22the ketones3- C6the glycols WITH2- C6the mixture of water and acetone or water. Desorbent separated and sent to recycling to the stage of adsorption-desorption. In the case of cumene as desorbent the latter is either on stage adsorption-desorption, or phase oxidation of cumene. Preferably at the stage of decomposition of the CCP uses a heterogeneous catalyst selected from the group: proton and aprotic acid media; natural and synthetic aluminosilicate is Ino of dimethylphenylcarbinol, selected products from the oxidation of cumene, direct to the stage catalytic hydro-dehydration from turning into cumene and recycle the last stage of its oxidation to cumene hydroperoxide with a heterogeneous catalyst at 70 - 300oC and a pressure of 5 to 40 ATM. This results in a simpler technology that reduces energy costs, increases the yield of phenol by reducing the formation of by-products. 8 C.p. f-crystals, 1 table. 3 Il.

The present invention relates to a method for production of phenol and acetone, which due to technical cumene hydroperoxide (CHP), not containing dimethylphenylcarbinol (DMPC), no formation of by-products and, accordingly, the selectivity on the stage of decomposition reaches a theoretical level - 100% of theoretical., and by obtaining technical cumene hydroperoxide, not containing acetophenone (ACP), and in the absence DMFC, a-methylstyrene (AMS) and products of their transformation is greatly simplified phase separation of the products, reduce energy costs of the process is at least 1.5-2 times, dramatically simplifies the technology and decrease several times the capital cost of phase separation.

There are large quantities of the 3740, 1953 ; U.S. Patent 4358618, 1982; U.S. Patent 5254751, 1993; U.S. Patent 5530166, 1996: U.S. Patent 5510543, 1996; U.S. Patent 5502259,1996,].

All (without exception) the processes of these patents are based on the principles of:

1) oxidation of cumene to cumene hydroperoxide with obtaining oxidation products containing from 20 to 40% of the CCP (cumene hydroperoxide);

2) the concentration of oxidation products by distillation under vacuum (one, two, and sometimes three stages) of unreacted cumene and return it (with preliminary purification from impurities) on the stage of oxidation;

3) homogeneous decomposition in the environment of the phenol-acetone - cumene using as a catalyst of sulfuric acid with obtaining phenol, acetone, alpha-methylstyrene and by-products - the so-called "phenolic resin", which trudnookislyaemymi product;

4) neutralization with alkaline agents, sulfuric acid decomposition products of the CCP and excretion (Na2SO4, NaHSO4from the above products;

5) separation of the products of decomposition of obtaining phenol, acetone, AMC and phenolic resins;

6) hydrogenation of AMS obtained at the stage of decomposition of the CCP, with the aim of turning it into cumene and return of the latter 8) purification of the acetone from the trace, as a rule, using alkalis;

9) partial thermal cracking of waste or burning for the purpose of generating steam.

From a chemical point of view, all existing in practice and in the patent literature, the processes for production of phenol-acetone Kukolnik method can be described by the following reactions:

1. the oxidation of cumene to SBC:

a) the main reaction

IPA + O2_ _ _ _ THE CCP;

b) adverse reactions

IPA + O2_ _ _ _ ACF

IPA + O2_ _ _ _ DMFC

IPA + O2_ _ _ _ DCT (dicumylperoxide)

2. acid-catalyzed decomposition of the obtained oxidation products:

a) the main reaction

< / BR>
b) adverse reactions

DMFC AMC + H2O

CCP + DMFC DCT + H2O

< / BR>
where DCT - dicumylperoxide

3. neutralization of the catalyst

H2SO4+ NaOH_ _ _ _ Na2SO4.

4. partial cracking phenolic resin

phenolic resin_ _ _ _ phenol + AMC + "hard resin"

5. hydrogenation of AMS to cumene

< / BR>
6. remove traces of phenol

< / BR>
< / BR>
carbonyl compounds _ _ _ resin

where HA - hydroxyacetone, 2-MBF - 2-methylbenzofuran

7. removal of trace contaminants from acetonitrile maximum possible selectivity 94-95% of theory. at the stage of cumene oxidation) on the search for a method to increase the yield valuable by-product - AMS on the stage of decomposition of the CCP.

In two differ from other technologies {UOP (USA) [U.S. Patent 4358618, 1982] and FAN ("illa" Russia") [U.S. Patent 5254751, 1993. and U.S. Patent 5530166, 1996 ] } these attempts were unsuccessful in practice, which has made the release of AMC for 80% of theoretical. and therefore minimized the release of phenolic resin to 35 kg/t of phenol and achieved the consumption of cumene per 1 t of phenol 1307-1310 kg (taking into account the stage of processing of phenolic resins) and 55-58 kg/t and 1330 kg/t, respectively, in the absence of the stage of processing of phenolic resins.

Thus, even in the above best technologies to loss of raw materials - cumene range from 33 kg/t kg to 53 kg/t and the output unusable waste remains high, and a large number of chemical stages (seven) determines the complexity and intensity of the existing technology.

Simplified traditional technology can be represented as shown in Fig. 1.

It should be noted that in the framework of the traditional technologies provides 100% output AMS impossible in principle, because of the existing equilibrium in the reaction DMFC AMC + H2O. Excluded under this possibly due to the presence of AMC, of acetophenone and various impurities, such as oxide mesityl, hydroxyacetone and others.

In each of the above stages of the process in various patents [U.S. Patent 2663740, 1953 ; U.S. Patent 4358618, 1982; U.S. Patent 5254751, 1993; U.S. Patent 5530166, 1996; U.S. Patent 5510543, 1996; U.S. Patent 5502259, 1996] has its own peculiarities and differences, aimed at the achievement of the authors of the cited patents in the improvement process. However, the chemistry of the process and its technological design remain generally unchanged.

As we developed the process found a fundamentally different chemical approach, allowing to reduce the number of chemical stages from 7 to 3, and in accordance with this fundamentally different technological design process in comparison with traditional.

The basis of this new technology is a complete separation of technical CCP components present in it, using the continuous adsorption-desorption, which excludes the occurrence of all adverse reactions 2B on the stage of decomposition of the CCP, eliminates the stage of neutralization (reaction 3) in the event of this stage on heterogeneous acid catalysts, excludes stage and all the current numerous want the need for reactions 6 and 7.

From a chemical point of view, the improved process after phase oxidation of cumene, which is the traditional way consists of two stages:

a) acid (heterogeneous or homogeneous) decomposition of the CCP for phenol and acetone

< / BR>
b) hydrogenation of DMPC separated from the oxidation products at the stage of continuous adsorption - desorption, to cumene

DMFC + H2_ _ _ IPA

Thus, instead of seven chemical stages, describing the traditional process, new and improved process has only three stages.

At the stage of decomposition of the CCP due to the release DMFC of products of oxidation of cumene

1) eliminates the reactions of education AMS, AMS dimers, complex phenols and numerous other by-products, i.e., eliminated the formation of phenolic resins;

2) the reaction of the decomposition of the CCP runs with 100% selectivity;

3) the decomposition of the CCP (due to the absence of tar) on heterogeneous catalysts can operate almost without regeneration.

As shown by our studies, translation technology for heterogeneous one-step decomposition, is not feasible with high selectivity within the Trad is ogene CCP and the speed of decomposition of the DCT (formed from DMPC and CCP), it is possible to successfully implement the proposed technology using acidic catalysts wide range (except acidic cation exchangers).

The main catalysts for phase heterogeneous catalytic decomposition of CPC are

- proton and aprotic acid media, such as H3PO4on alumina or diatomaceous earth, BF3on aluminium oxide, FP(O)(OH)2and/or F2P(O)OH, or HF oxide of Al, Si or Ti,

natural and synthetic aluminosilicate catalysts of the General formula (Al2O3)m(SiO2)n(H2O)h, which primarily include amorphous silicates with a ratio of SiO2/Al2O3= 0,1-10 and crystalline aluminosilicates (zeolites) with a ratio of Al2O3=3-100.

Preferably used catalysts, which is characterized by weak Lisovskii and Pentecoste acid centers and a total value functions acidity Gamete Ho= from 0.3 to 1.05 (0.3 to 0.8) and having an effective pore diameter of 20 to 40

The translation stage of decomposition of the CCP from homogeneous to heterogeneous eliminates the stage of neutralization and the associated complex problem of the separation of salts from the p the e the numerous reactions of condensation. As a consequence, significantly simplifies the separation stage of decomposition products, since the only decomposition products are phenol and acetone. No ACF technical GPK coming to decomposition, also contributes to the simplification phase separation, because ACF with phenol forms an azeotrope, which leads to the complexity of their separation and, accordingly, significant energy costs.

The application of the above approach is possible only in case of receipt of code of civil procedure, does not contain ACF and DMFC. The traditional method of distillation oxidation products, it is impossible to get technical cumene hydroperoxide, not containing DMPC and ACF. In addition, obtaining 100% of the CCP, not containing cumene, is dangerous, because thermal stability of highly concentrated (> mos.%) CCP is sharply reduced.

In the developed method, technical CCP always contains a certain amount of cumene, which removes the threat of danger.

As adsorbents can be used

-fully cation-exchanged zeolites with the size of the input window is not less than 6A;

- magnesium silicate;

-synthetic polymeric materials in macroporous or gelina status - the anion exchange resin, which represents a polystyrene matrix (prepared by polymerization of styrene or of styrene and divinylbenzene ) and/or polycondensate matrix (prepared by condensation of amines or amides, or acrylamido, where anion exchange represents an amino group (General formula N(R R), where R', R" is a hydrogen atom or an alkyl radical) or aminogroup (General formula R CON(R"R"', where R', R" and R"' is hydrogen atom or alkyl radical).

As desorbent can be used

aromatic hydrocarbon, C6-C22;

- ketones C3-C6,

- glycols C2-C6,

- a mixture of water and acetone,

is water.

Thus, the proposed process is different from traditional Kumanovo process for production of phenol and acetone as chemical and technological points of view.

Novelty from a chemical point of view is

1. in the decomposition of the CCP, not containing DMPC, ACF and DCT, and the exclusion of all chemical reactions of side products formation equivalents in patent literature are absent;

2. in the hydrogenation of selected products from the oxidation DMFC to cumene equivalents in patent literature are missing.

Nowis the adsorption;

2. in the hydrogenation DMFC to cumene;

3. in the application as desorbent feedstock process of cumene and in implementing its recycling to the stage of obtaining the CCP.

The advantage of the proposed technology is

1) the exclusion of by-products formation at the stage of decomposition of the CCP and the stage of separation of the products;

2) the simplicity of the stage of separation of the products of decomposition of the CCP (the number of distillation columns at the stage of separation may be reduced in 2 times in comparison with the conventional circuit);

3) significant reduction in energy costs compared to the traditional process (1.5-2 times).

Schematic diagram of the proposed process is shown in Fig. 2.

Thus, the process of production of phenol and acetone by the proposed method consists of the process of cumene hydroperoxide by oxidation of cumene stage of concentration of the products of the oxidation of cumene with obtaining technical cumene hydroperoxide and returning unreacted cumene on stage oxidation stage of decomposition of cumene hydroperoxide using acidic catalysts, phase separation of the products of decomposition to obtain phenol and acetone, and distinguishing persons who eskay adsorption-desorption using adsorbents, selected from the group:

-fully cation-exchanged zeolites with the size of the input window is not less than

- magnesium silicate;

- synthetic polymeric materials in macroporous or gelina condition, obtained by polymerization of amines, amides, acrylamides or polymerization of styrene and divinylbenzene;

the anion exchange resin, which represents a polystyrene matrix (prepared by polymerization of styrene or of styrene and divinylbenzene ) and/or polycondensate matrix (prepared by condensation of amines or amides, or acrylamido, where anion exchange represents an amino group (General formula N(R R), where R', R" is a hydrogen atom or an alkyl radical) or aminogroup (General formula R CON(R"R"', where R', R" and R"' is hydrogen atom or alkyl radical).

Preferably as desorbent use aromatic hydrocarbons WITH6-C22the glycols WITH2-C6the mixture of water and acetone or water with the receiving after desorption of the compounds include acetophenone-light particles produce cumene oxidation-desorbent, DMPC-desorbent, CPC-desorbent, DCT-desorbent.

Applied desorbent separated from DMPC, ACP and CCP and sent to recycling on stage adsorption-desorption or in the case ol the Dios cumene oxidation.

Preferably as raw material for the stage of decomposition of the use of the CCP, not containing DMPC, ACF and DCT.

Preferably as a catalyst on the stage of decomposition of the CCP using H2SO4.

More preferably at the stage of decomposition of the CCP using heterogeneous catalysts selected from the group:

- proton and aprotic acid media, such as H3PO4on alumina or diatomaceous earth, BF3on aluminium oxide, FP(O)OH)2and/or F2P(O)HE or HF oxide of Al, Si or Ti,

natural and synthetic aluminosilicate catalysts of the General formula (Al2O3)m(SiO2)n(H2O)p, which primarily include amorphous silicates with a ratio of SiO2/Al2O3/H2O= (1:0,1:0,1) - (1:10:10) and crystalline aluminosilicates (zeolites) with a ratio of SiO2/Al2O3/H2O=(1:3:1)-(1: 100:10).

Even more preferred is the use as catalysts heterogeneous acid catalysts, characterized by the value function of the acidity of Gamete Ho= from 0.3 to 1.05 (0.3 to 0.8) and having an effective pore diameter of 20 to 40

Preferably DMFC isolated from selling clam the last stage of oxidation in the CCP.

Preferably the process of hydro-dehydration DMPC in the hydroperoxide is carried out in the presence of catalysts selected from the group of Pd, Fe, Pt, Cu and/or Ag aluminum oxide, and the process is carried out at a temperature of 70 - 300oC and a hydrogen pressure of 5 to 40 ATM.

Specified is illustrated by the following examples (table).

EXAMPLE 1 (comparison).

The oxidized cumene in the cascade bubble reactors. As a result of oxidation obtained 100 kg reaction mass oxidation (RMO) of the following composition, wt.% :

The cumene - 73,117

ACF - 0,186

DMPC - 1,206

HPC - 25,409

DCT (dicumylperoxide) - 0,082

Organic acids - 3000 ppm.

Selectivity at the stage of oxidation is 94% of theory.

Received the RMI sent to stage 3-stage concentration of the CCP to the concentration of the latter 92-93%. The result is technical CCP composition: cumene - 1,53 wt.%, Act to 0.69 wt.%, DMFC is 4.45 wt.%, HPC - br93.1 wt. %, DCT - 0.3 wt.%. Impurities, including organic acids. - 3000 ppm. The decrease in selectivity at the stage of CPC concentration is 0.3% abs.

The result is a decomposition of the CCP - phenol and acetone, as well as by - products dicumylperoxide (DCT), cumylphenol (KF), the AMS dimers and m is assy decomposition (PMP) below, wt.% :

Phenol - 56,47

Acetone - 35,00

AMS - 3,19

DCT - 0,9

DMPC - 0,26

ACF - 0,59

KF - 0,55

The dimer - 0,36

Organic acids - 3000 ppm

The oxide mesityl - 500 ppm

Hydroxyacetone - 1500 ppm

The yield valuable by-product AMC is 80% of theoretical. Consumption of cumene per 1 t of phenol after stage of decomposition is 1300 kg of Sulfuric acid in PMP is neutralized with sodium hydroxide.

For better removal of the formed salts PMP watered with concentrations up to water 7-12 wt.%, and the products arrive at the stage of their separation, consisting of 8 rectification columns:

- reaction mass decomposition entered in column 1, where the separation of acetone and phenol streams

- acetone stream containing acetone, water, cumene, AMS, aldehydes, a small amount of phenol, arrives in column 2, where the bulk of aldehydes Argonauts,

- acetone stream, barely containing aldehydes, arrives in column 3, where the commodity is allocated acetone (cube columns allocated hydrocarbon fraction containing cumene and AMS),

- phenol stream containing phenol, a small amount of hydrocarbons (cumene and AMS), ACF, KF, AMS dimers and tacitly products Act, KF, dimers AMC,

- phenol raw goes in column 6, where the water is fed to the column is cleaned phenol raw from hydrocarbons and 2-MBF,

- phenol, containing no hydrocarbons and 2-MBF, but having as additives hydroxyacetone and the oxide mesityl goes for trail clearing, which resulted in hydroxyacetone and the oxide mesityl removed,

- phenol after trail cleanup enters the column 7 - column extraction of commercial phenol,

- phenolic resin, selected cube column 4, entered in column 8, where additional distillation of phenol from phenol resin,

- selected cube column 8 phenolic resin or processed for fetching phenol and AMC, or disposed of.

In the course of adverse reactions in cubes columns separating out the AMC is reduced to 78%, the expense ratio of the cumene/phenol increases to 1333 and waste outlet - phenolic resin increases to 56 kg/T. Thus, at the stage of separation by chemical reactions of loss of raw materials accounted for 20-30 kg/so

Phenolic resin from the cube column 4 into the reactor thermal processing. The degree of conversion of resin in the data nontransportable products. Formed during thermal cracking of phenolic resins useful products - phenol, AMS go on stage rectification. As a result of partial processing of phenolic resin yield of the latter is reduced to 32 - 40 kg/t of phenol and consumption of cumene reaches 1310 kg/t of phenol.

Nepravishta phenolic resin is directed to combustion to produce steam. As a result, the process is characterized by the following parameters:

1. consumption of cumene/phenol after the stage of decomposition of the CCP, kg/t, 1305 kg/t of phenol;

2. the release of AMC after the stage of decomposition of the CCP, % theoretical., 80%;

3. the output of phenolic resin, after the stage of decomposition of the CCP 35 kg/t of phenol;

4. consumption of cumene/phenol after stage rectification 1333 kg/t of phenol;

5. loss of output AMS stage after rectification;

6. consumption of cumene/phenol after cracking phenolic resin 1310 kg/t of phenol;

7. the output of phenolic resin - 35 kg/t of phenol;

8. steam consumption per 1 t of phenol is 4 so

EXAMPLE 2.

The cumene was oxidized as described in example 1 and was obtained reaction mass oxidation (RMO) of the composition described in example 1.

Received the RMI is directed to the first stage of stage of concentration of the CCP. The concentration of the latter was carried out before BR>
The cumene - 57,68

ACF - 0,29

DMPC - 1,90

HPC - 40,00

DCT - 0,13

Loss of selectivity at the stage of concentration of the CCP no.

Technical GPK above composition is fed into a continuous adsorption-desorption, where the adsorbent in example 2.1 is used polyamide, and as desorbent in example 2.1.A cumene is used.

In the process of continuous adsorption-desorption get a fraction, kg:

The cumene-light (CH3HE, organic acids)

ACF - 60,0 (the content of cumene of 99.96 wt.%)

the cumene-DMPK - 23,4 (the content of cumene 87,32 wt.%)

the cumene-CCP - 41,5 (the content of cumene 10,63 wt.% )

the cumene-DCT - 0.1 (content of cumene of 9.75 wt.%)

In examples 2.2-2.11 and 2.1.B-2.1.E. use

2.2. as the adsorbent is magnesium silicate, in the process of continuous adsorption-desorption get faction similar to 2.1,

2.3. as the adsorbent used synthetic polymeric materials obtained by polymerization of an amine, in the process of continuous adsorption get faction similar to 2.1,

2.4. as the adsorbent used synthetic polymeric materials, received the e 2.1,

2.5. as the adsorbent used synthetic polymeric materials obtained by polymerization of acrylamide, in the process of continuous adsorption get faction similar to 2.1,

2.6. as the adsorbent used synthetic polymeric materials obtained by polymerization of styrene and divinylbenzene, in the process of continuous adsorption get faction similar to 2.1,

2.7. as the adsorbent used anion exchange resin, which represents a polystyrene matrix, the result of the process of continuous adsorption get faction similar to 2.1,

2.8. as the adsorbent used anion exchange resin constituting polycondensate matrix prepared by the condensation of amines, where the exchange anion represents the amino group of the General formula - N(R R), where R', R" is a hydrogen atom or alkyl radical is a hydrogen atom, or an alkyl radical, in the process of continuous adsorption get faction similar to 2.1,

2.9. as the adsorbent used anion exchange resin constituting polycondensate matrix prepared by the condensation of acrylamido, where anion exchange represents epreryvno adsorption get faction, similar to 2.1,

2.10. as the adsorbent using a fully cation-exchanged zeolites with the size of the input window 6-40

2.11. as the adsorbent using the anion exchange resin in gelina or macroscopic state, representing polycondensate matrix prepared by the condensation of amines,

2.1. B is similar to examples 2.1-2.11, but as desorbent used aromatic hydrocarbons, C6-C22,

2.1. C. analogously to examples 2.1-2.11, but as desorbent uses a mixture of water and acetone,

2.1. Similarly, examples 2.1-2.11, but as desorbent water is used,

2.1.D. analogously to examples 2.1 -2.11, but as desorbent use ketones3-C6,

2.1.E. analogously to examples 2.1-2.11, but as desorbent used glycols C2-C6.

Separation of components in all cases close to 100%. Chromatogram of liquid-phase separation for example 2.1 using cumene as desorbent shown in Fig. 3.

A fraction of the cumene-light (aldehydes, organic acids, methanol and others)-ACF sent to the division by the standard method of rectification. "Light" is divided into upper shoulder strap, and a dedicated fractorama on stage oxidation. In Cuba columns pure phenol in the amount of 0.29 kg, which is a commercial product. The resulting acetophenone can gidrirovaniya obtaining ethylbenzene, which in turn also is a commodity product.

Selected at the stage of continuous adsorption-desorption binary fraction of the cumene-DMFC goes on stage catalytic dehydration-hydrogenation to convert DMFC in cumene.

As the catalyst in example 2.1 was used Pd/Al2O3. The process was carried out at a temperature of 130oC, hydrogen pressure of 6 ATM. Conversion DMFC is 100%, the selectivity of 99.9 %.

In example 2.2 as a catalyst was used Fe/Al2O3Pt/Al2O3, Cu/Al2O3and Ag/Al2O3. When using these catalysts, the temperature was changed in the range 70 - 300oC and a pressure of 5 to 40 ATM. In the process these catalysts conversion DMFC was 100%, the selectivity of 99.9%.

The resulting cumene - 14,98 kg after standard processing goes to the step oxidation of the latter in the cumene hydroperoxide.

Selected at the stage of continuous adsorption-desorption binary fraction of the cumene-CCP to romanatica traditional catalyst sulfuric acid, i.e., the process is carried out according to the traditional scheme (USA 5254751, 1993).

As a result of decomposition of the CCP at a temperature of 55oC the obtained phenol 24,73 kg, acetone 15,27 kg

In decomposition products no DCT, dimers of alpha-methylstyrene, cumylphenol and AMC, DMPK and ACF. In decomposition products no products deep condensation.

The decomposition products of the CCP are going to stage their separation. The separation is carried out on a 3-column scheme.

As acid catalysts on the stage of decomposition of the CCP can be used heterogeneous acid catalysts, in particular (example 2-I) synthetic zeolites in the H+form at a ratio of SiO2/Al2O3= 8,5.

As a result of decomposition obtained

phenol - 24,7 kg

acetone - 15,2 kg

Examples 2-II - 2-V

Table

Heterogeneous catalysts for the decomposition of the CCP, not containing DMPC and ACF

II Proton acid media

1. H3PO4on - Al2O3< / BR>
2. H3PO4on - kieselguhr

3. HF - Al2O3< / BR>
4. HF - SiO2< / BR>
5. HF - TiO2< / BR>
III Aprotic acid media

1. BF3on - Al
a) the ratio Si/Al of 0.1

b) the ratio of Si/Al 10

V Crystalline aluminosilicates (zeolites) with a ratio Si/Al from 3 to 10

a) the ratio Si/Al = 3

b) the ratio Si/Al = 10

Received a fraction of the cumene-DCT in an amount of 0.1 kg is directed to the separation and to obtain commercial DCT used as the polymerization initiator. The cumene isolated from fractions of a cumene-DCT, is sent to the stage of oxidation.

In the result of the process in this example is taken

phenol - 24,73 kg (selectivity 100%)

acetone - 15,27 kg (selectivity 100%)

the acetophenone - 0,29 kg

DCT - 0,13 kg

phenolic resin - no

Consumption of cumene/phenol is 1278 kg/tonne phenol.

Steam consumption per 1 ton of phenol is 2 so

EXAMPLE 3.

The cumene was oxidized as described in example 1 and was obtained reaction mass oxidation (RMO) of the composition described in example 1. Received the RMI was sent on a two-stage concentration of CPC. Concentration was carried out before the concentration of CPC in the technical GPK not less than 60 wt.%).

The result was 100 kg technical CCP composition, wt.%:

the cumene - 36,52

ACF - 0,44

DMPC - 2,85

HPC - 60,00

DCT - 0,a mini-GIC of the above composition was carried out in the same way, as in example 2.

In the process of continuous adsorption-desorption was obtained fractions: kg

the cumene - light hydrocarbons (CH3HE, organic acids)

ACF - 46,28 (the content of cumene 99,05 wt.%)

the cumene-DMPK - 10,75 (the content of the cumene is 73.5 wt.%)

the cumene-CCP - 66,76 (the content of cumene 10,12 wt.%)

the cumene-DCT - 0,21 (the content of cumene 9,73 wt.%)

The division of fractions the cumene-light-ACP was carried out as described in example 2. The separation of receive ACF 0,44 kg of cumene 45,74 kg 0.1 kg of cumene + "light", the selected upper shoulder strap, sent for incineration. The resulting cumene recycled on the stage of oxidation.

Dehydration-hydrogenation binary fraction of the cumene-DMFC is the same as in example 2. Conversion DMFC is 100%, the selectivity of 99.9 %.

The resulting cumene - 10,75 kg after standard processing goes to the step oxidation of the latter in the cumene hydroperoxide.

The selected binary fraction of the cumene-GIC in the amount of 66,76 kg goes on stage acidic heterogeneous decomposition of synthetic zeolites as in examples 2-I - 2-V

As a result of decomposition of the CCP obtained phenol 37,1 kg, acetone 22,9 kg In the absence of the f-methylstyrene, cumylphenol and AMC, DMPK and ACF. In decomposition products there are no products are deeply condensation.

The decomposition products of the CCP are going to stage their separation.

The separation is carried out on a 3-column scheme.

Received a fraction of the cumene-DCT in the amount of 0.21 kg is directed to the separation and to obtain commercial DCT used as the polymerization initiator, etc.

The cumene isolated from fractions of a cumene-DCT, is sent to the stage of oxidation.

In the result of the process in this example is taken

phenol was 37.1 kg (selectivity 100 %)

acetone - 22,9 kg (selectivity 100%)

the acetophenone - 0,44 kg

DCT - 0,19 kg

phenolic resin - no

Consumption of cumene/1 ton of phenol is 1279 kg

Steam consumption/1 tonne phenol is 2,05 so

EXAMPLE 4.

The cumene was oxidized as described in example 1 and was obtained reaction mass oxidation (RMO) of the composition described in example 1. Received the RMI were sent to the three-phase concentration of CPC. The concentration of the latter was carried out not less than 80 wt.%.

The result is 100 kg technical CCP composition, wt.% :

the cumene - 1,53

ACF - ablaut 0.3 abs. %.

The technical division of the CCP of the above composition is the same as described in example 2.

In the process of continuous adsorption-desorption get a fraction, wt.%:

the cumene - light hydrocarbons (CH3HE, organic acids)

ACF - 10,87 (the content of cumene 93,8 wt.%)

the cumene-DMPK - 11,63 (the content of cumene of 62.3 wt.%)

the cumene-CCP - 102,88 (the content of cumene 9,51 wt.%)

the cumene-DCT - 0,33 (the content of the cumene to 9.00 wt.%)

The selected binary fraction of the cumene-light-ACF sent to the division by the standard method of rectification. The separation of receive ACP 0.68 kg, cumene 9,19 kg of the resulting cumene recycled on stage oxidation, 0.1 kg of cumene + light, selected upper shoulder strap, burned.

The selected binary fraction of the cumene-DMFC without separation goes on stage catalytic dehydration-hydrogenation to convert DMFC in cumene. The process was carried out as described in example 2. The conversion is 100%, the selectivity is 99,99%.

The resulting cumene - 11,63 kg after standard processing goes to the step oxidation of the latter in the cumene hydroperoxide.

The selected binary fraction of the cumene-GIC in the amount the synthetic zeolites HY examples 2-I - 2-V.

As a result of decomposition of the CCP at a temperature of 55oC the obtained phenol 57,57 kg, acetone 35,52 kg

In the absence of DMPC selectivity stage of decomposition is 100%. In decomposition products no DCT, dimers of alfamethylstyrene, cumylphenol and AMC, DMPK and ACF. In decomposition products no products deep condensation.

The decomposition products of the CCP are going to stage their separation. The separation is carried out on a 3-column scheme.

The obtained fraction IPA-DCT in the amount of 0.33 kg is directed to the separation and to obtain commercial DCT used as the polymerization initiator, etc.

The cumene isolated from fractions of a cumene-DCT, is sent to the stage of oxidation.

In the process according to the examples received

phenol - 57,57 kg (selectivity 100%)

acetone - 32,52 kg (selectivity 100%)

the acetophenone - 0.68 kg

DCT - 0.30 kg

phenolic resin - no

Consumption of cumene/1 ton of phenol is 1280 kg

Steam consumption/1 ton of phenol is 2.1 so

1. Method for production of phenol and acetone, which includes a step for cumene hydroperoxide by oxidation of cumene, the stage of the end of aerowaves cumene to the stage of oxidation, the stage of decomposition of cumene hydroperoxide using acidic catalysts, phase separation of the products of decomposition to obtain phenol and acetone, characterized in that the separation of the products of cumene oxidation carried out by the method of continuous or cyclic adsorption-desorption using adsorbents selected from the group: a fully cation-exchanged zeolites with the size of the input window is not less than 6A; magnesium silicate; synthetic polymeric materials in macroporous or gelina condition, obtained by polymerization of amines, amides, acrylamides or polymerization of styrene and divinylbenzene; in the macroporous anion exchange resin or gelina condition, representing a polystyrene matrix, prepared by polymerization of styrene or of styrene and divinylbenzene, and/or polycondensate matrix prepared by the condensation of amines or amides, or acrylamide, and where the exchange anion represents the amino group of the General formula - N(R R), where R', R" is a hydrogen atom or alkyl radical or aminogroup General formula R CON(R"R"', where R', R" and R"' is hydrogen atom or alkyl radical.

2. The method according to p. 1, characterized in that as desorbent used aromatic hydrocarbons, C6

3. The method according to p. 2, characterized in that desorbent separated from dimethylphenylcarbinol, acetophenone and cumene hydroperoxide and sent to recycling on stage adsorption-desorption or in the case of cumene as desorbent latest sent either on stage adsorption-desorption, or phase oxidation of cumene.

4. The method according to p. 2, characterized in that the raw material at the stage of decomposition using cumene hydroperoxide, not containing dimethylphenylcarbinol, acetophenone and dicumylperoxide.

5. The method according to p. 4, characterized in that the catalyst used sulphuric acid.

6. The method according to p. 4, characterized in that the catalyst used proton and aprotic acid media, including H3PO4on the alumina or diatomaceous earth; BF3aluminum oxide, FP(O)(OH)2and/or F2P(O)OH or HF on the oxides of aluminum, silicon or titanium; natural and synthetic aluminosilicate catalysts of the General formula (Al2O3)m(SiO2)n(H2O)h, : 10 : 10), and crystalline aluminosilicates (zeolites) with a ratio of SiO2: Al2O3: H2O= (1 : 3 : 1) - (1 : 100 : 10).

7. The method according to p. 6, characterized in that the catalysts used acid catalyst, preferably a heterogeneous acid catalysts, characterized by the value function of the acidity of Gamete H0= 0,3oC of 1.05 (0.3 to 0.8) and pore diameter of 20 to 40

8. The method according to p. 1, characterized in that dimethylphenylcarbinol separated from the oxidation products of cumene, direct to the stage catalytic hydro-dehydration from turning into cumene recycle the last stage of oxidation to cumene hydroperoxide.

9. The method according to p. 8, characterized in that the process of hydro-dehydration dimethylphenylcarbinol in the hydroperoxide is carried out in the presence of catalysts selected from the group of Pd, Fe, Pt, Cu and/or Ag aluminum oxide, and the process is carried out at a temperature of 70 - 300oC, hydrogen pressure of 5 to 40 ATM.

 

Same patents:

The invention relates to the production of phenol and acetone "Kukolnik method, in particular to the improvement of the process of decomposition gidroperekisi hydroperoxide (CHP) acid catalyst to phenol and acetone

The invention relates to a method of obtaining a mixture containing cyclic saturated alkane and the corresponding alkanol

The invention relates to the production of phenol and acetone "Kukolnik method, in particular to the improvement of the process of decomposition gidroperekisi hydroperoxide (CHP) acid catalyst to phenol and acetone

The invention relates to a method of purification of phenol obtained in the process of co-production of acetone and phenol Kukolnik method

The invention relates to methods of cleaning product of phenol, the resulting acid-catalytic decomposition of cumene gidroperekisi

The invention relates to 4-methoxyethyl-2-tert.-butylphenol (1) (alkyl = ethyl-, propyl-), which is obtained by processing 4-chloroalkyl-2,6-di-tert.-butylphenols the sodium methylate or sodium hydroxide solution in methanol) under heating, followed by thermolysis of the resulting 4-methoxyethyl-2,6-di-tert
The invention relates to petrochemistry and can be used in the production of phenol and acetone Kukolnik method

The invention relates to the field of organic chemistry and petrochemicals, and in particular to catalysts for the production of phenol and acetone

The invention relates to the production of phenol and acetone "Kukolnik method, in particular to the improvement of the process of decomposition gidroperekisi hydroperoxide (CHP) acid catalyst to phenol and acetone

methylstyrene" target="_blank">

The invention relates to the field of petrochemical synthesis, in particular to a method for production of phenol, acetone and alpha-methylstyrene Kukolnik method
The invention relates to petrochemistry and can be used in the production of phenol and acetone Kukolnik method

FIELD: petroleum chemical technology.

SUBSTANCE: invention relates to utilization of phenolic resin and preparing additional amounts of cumene, phenol and α-methylstyrene. For this aim phenolic resin containing less 0.2 wt.-% of salts is subjected for thermocatalytic decomposition in the range of temperatures 420-550oC in the presence of steam on catalyst comprising the following components, wt.-%: aluminum, oxide, 5.0-30.0; iron oxide, 0.4-1.0; magnesium oxide, 0.4-1.0; calcium oxide, 5.2-7.0; sodium oxide, 1.0-3.0; potassium oxide, 1.0-3.0; titanium (IV) oxide, 0.4-1.0; silicon (IV) oxide, 0.4-1.0, the balance, up to 100%. The proposed method provides preparing 61.5 wt.-% of useful products - cumene, phenol and α-methylstyrene for a single run. Invention can be used in the process for combined preparing phenol and acetone by cumene method.

EFFECT: improved preparing method.

2 cl, 3 tbl, 6 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of phenol via acid catalytic decomposition of cumene hydroperoxide followed by isolation of phenol from decomposition products and purification of phenol to remove trace impurities including acetol. Purification of phenol is accomplished through hetero-azeotropic rectification with water. Acetol is isolated as a part of liquid-phase side stream from semiblind plate located within exhausting section of hetero-azeotropic rectification column. Side stream is supplemented by cumene and used to supply stripping column, from which fraction of acetol/cumene azeotropic mixture is taken as distillate and residue is returned under semiblind plate of hetero-azeotropic rectification column to be further exhausted. From the bottom of the latter, crude phenol is withdrawn and passed to final purification from the rest of reactive trace impurities. Acetol/cumene azeotropic mixture is subjected to heat treatment at 310-350°C, which may be performed in mixtures with high-boiling production waste or in mixtures with bottom product of rectification column for thermal degradation of high-boiling synthesis by-products, which bottom product is recycled via tubular furnace. Above-mentioned semiblind plate, from which side stream is tapped, is disposed in column zone, wherein content of water is minimal and below which contact devices are positioned with efficiency at least 7.5 theoretical plates. Side stream with cumene added to it is passed to the vat of stripping column with efficiency at least 15 theoretical plates.

EFFECT: minimized content of acetol in purified phenol and reduced power consumption.

5 cl, 3 dwg, 6 tbl, 4 ex

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