Energy-saving and highly selective method for production of phenol and acetone (process interfax-96)

 

(57) Abstract:

Phenol and acetone receive the acid decomposition of technical cumene hydroperoxide (CHP), obtained by the oxidation of cumene. The decomposition of the CCP lead after concentration of oxidation products to a residual content of cumene in the CCP 21 to 30 wt.% in the reactor the mixture at a molar ratio of phenol:acetone:cumene 1: 1: (0,38-0,61). Decomposition of dicumylperoxide (DCT) is carried out in a reactor displacement when the molar ratio of the same components of the mixture 1:(1-0,77): (0,35-0,87), at a temperature of 150 -168oWith feed in it somolinos fraction and water. The degree of transformation of DCT over 97%. On the stage of neutralization of an acid catalyst (sulfuric acid) additionally serves fraction of cumene and water, followed by separation additionally introduced somolinos fraction and recycling part somolinos fraction in the reactor for the decomposition of dicumylperoxide and on the stage of neutralization. Due to increased amount of hydroperoxide to decomposition products, content of salts after the stage of neutralization is 10-20 ppm. As a result, total steam consumption is reduced by 0.4-0.6 t/t of phenol. The process has a high selectivity is characterized by the level of consumption of cumene 1302-1305 kg/t of phenol and aprove methods for production of phenol and acetone Kukolnik method include major stages:

1) the oxidation of cumene to cumene hydroperoxide (CHP);

2) distillation oxidation products obtaining technical CCP;

3) acid dissolution of the CCP and present it dimethylphenylcarbinol (DMPC) to target products of phenol, acetone and alpha-methylstyrene (AMS);

4) the stage of neutralization of the acid catalyst and the separation of salts from the reaction products;

5) the stage of separation and purification of the products obtained.

Usually research all developers phenol process, with the goal of improving belong to any one of the stages of the process, without mutual coupling to simultaneously improve the selectivity of the process, its energy performance, the main of which is the consumption of steam, and process safety.

If to consider the selectivity of the process, since the main byproducts are formed at the stage of acid decomposition of the CCP, that is what determines the particular attention of researchers to this stage.

Decomposition of technical CCP because of the presence of such reactive product, as DMPK, chemical reactions, leading to loss of target products and the formation of hard the SSA is a valuable by-product, alpha-methylstyrene, which, as a rule, hereroense in the cumene or sometimes visible in the form of targeted commercial product.

Approaches in addressing the issue of increasing the output of AMC's different. The key points of the path are:

1) chemical - choice of reaction medium composition;

2) technology - the choice of the type of reactors and methods of removal of the heat;

3) combination of chemical and technological approaches.

As shown by our studies, in the environment of the phenol-acetone because of the formation of strong hydrogen bonds between molecules of phenol and between molecules of phenol and acetone to change the ratio between phenol and acetone, as well as with the introduction of such an inert solvent as cumene, catalytic properties of sulfuric acid used as the catalyst, can change dozens of times.

No less influence on the value of the activity of the catalyst has water.

The combination of the changing values of the ratio of phenol:acetone:water:cumene:sulfuric acid leads to a qualitative change in the catalytic properties of this multi-component solvent that shows how we obtained the data shown in Fig. 1 - 3.

Such romaleidae, confirm extremely strong change of the rate constants of decomposition of CPC (Fig. 1 to 3), there is nothing but the transition from one type of catalyst to another, as the transition from super-strong "magic acid to weak acid catalyst having a fundamentally different nature and structure.

From here it became clear why in various patents in various technologies phenolic processes with the composition of the reaction medium get fundamentally different selectivity. So, when using equimole mixture of phenol-acetone outlet AMS is 40-45% of theory.

In the process [U.S. patent 2663735, 1953], where a large excess of acetone (molar ratio of acetone:phenol to 5:1), the output of the AMS does not exceed 55% of theory. In the process [patent Romania, 63168, 1971], where the reaction medium is used Aquamarina a mixture of phenol-acetone containing up to 20 wt.% cumene, exit AMS is about 60% of theoretical. In reaction medium containing 20 wt.% excess acetone and practically do not contain cumene (only 1-2 wt. % output AMC achieved in practice, is about 70% of theoretical. In the processes [U.S. patent, 5254751, 1993] and [U.S. patent, 5530166, 1996] made out AMC for 80% of theoretical., where the approach of changing the composition of the medium (and mixing and displacement. Moreover, the above high yield AMC reached for one of the largest industrial plants.

Close to patents [U.S. patent, 5254751, 1993; U.S. patent, 5530166, 1996] the success of the content up to 15 wt.% cumene at equimolar the ratio of acetone: phenol reached in the patent [U.S. patent, 4358618, 1982], which uses a combination of reactor mixing and two reactors displacement, and the composition of the reaction medium (the molar ratio of phenol:acetone:cumene = 1:1:0,23) in all reactors remains constant, but applies different temperature range in the reactor mixing 50-90oC, and in reactors displacement from 120 to 150oC.

Conducted research in conjunction with the analysis of patent data showed that the number of additional input acetone or hydroperoxide in the reaction medium from the viewpoint of the selectivity of the process is important, but insufficient. Much more important, as shown by our research, is the combination of all together these factors - optimal molar ratio between phenol, acetone, cumene and water, and in which of the reactor (mixing reactor for the decomposition of the CCP or displacement reactor decomposition of the DCT and DMFC) the specified value for aracteristic molar ratio phenol:acetone:cumene, in the reactor mixing and displacement remains constant. In our research we found that the composition of the reaction medium in said reactor should be significantly different in order to achieve both high selectivity and minimal trace (examples 2 to 9).

In the industrial process for production of phenol and acetone is extremely important not only the selectivity but also the number of generated trace contaminants such as oxide mesityl (ACM), hydroxyacetone (HA), which complicate the process of separation of the products and lead to a significant increase in energy costs.

Unfortunately, this aspect is not covered in the patents. As shown by our studies (table. 1), the optimal conditions from the point of view of output AMS do not meet the condition of minimizing the above-mentioned impurities. So, on the basis of conducted research for equimole mixture of phenol and acetone containing 15 wt.% cumene, with respect to the temperature regime of patent [U.S. patent, 4358618, 1982], we have experimentally found that the increase in temperature leads to an undesirable increase of the ACM (750 ppm). I.e., on the one hand, with increasing temperature dostigaev all processes requirements phenol content OKM extremely hard (<10-15 ppm), the optimization process not only from the point of view of output AMS, but also from the point of view of minimization of the output trace is extremely important.

In the process with a high content of acetone in the reaction medium [U.S. patent 2663735, 1953; U.S. patent, 5371305, 1994] the concentration of the ACM in the decomposition achieves an even larger value of 1200 ppm. The presence of a large number of trace leads to significant energy costs in the process.

Since the depth of oxidation of cumene in industrial processes ranging from 15 to 35 wt.%, the resulting oxidation products are subjected to concentration. Concentration is carried out in several stages so that the residual concentration of cumene in receiving technical CCP ranged from 1 to 2 wt.% up to 10-15 wt.%. T. O., forced to a low conversion of cumene arises the need for additional energy cost of separating unreacted cumene from CCP with subsequent recycling of the cumene to the stage of oxidation. Settlements and industrial experience shows that at 100% conversion of 1 ton of cumene (with conversion of 20 mol.% for passage) in the oxidation products through a stage of concentration are a 3.87 tons of cumene, which leads to cost a pair of 12 ton/tons fooproject, as shown by our study, selective loss of the CCP in DMPC and acetophenone (ACP). The number of the latter increases by 20% relates. when the residual content of cumene 1-2 wt.% in technical CCP. The increase in the content of cumene in technical CCP to 10-15 wt. % reduces losses of up to 8-10% of the carries. A study of the effect of cumene on the stability of the CCP showed that completely eliminate thermal decomposition of the CCP is possible if the concentration of cumene in technical CCP more than 20 wt.%.

As shown by our studies and calculations, in case of increase in technical CCP concentration of cumene to 25 wt.% almost simultaneously with the elimination of chemical losses GPK energy costs at the stage of consolidation reduced by approximately 20% abs. and amount of 0.95 tonnes of steam per 1 t of phenol (table.2).

The increase in the share Polignano cumene in technical CCP reduces chemical loss and energy costs at this stage, but causes complications at the stage of homogeneous acid digestion of the CCP.

It stopped researchers, developers and practitioners of this process on the level of concentration of cumene in technical GPC, of not more than 10-12 wt.%, although the number of patents and ukazyvala on stage acid digestion GPK - this is the problem of safe conduct this stage. Without solving this problem, the process in an environment containing high concentration of cumene, will lead to predictable consequences to the accumulation of the CCP in the reactor and subsequent explosion, because the magnitude of thermal effect decomposition of the CCP is 380 kcal/kg, which is equivalent to increasing the temperature to 700oC.

The second problem for which no solution had been found, this is a significant increase in energy costs at the stage of rectification of decomposition products in case of increase in the amount of cumene.

As shown by our analysis and calculations, in the case of a standard approach and solutions within the traditional scheme of rectification decomposition products when all the incoming cumene passed all the stages of separation and subsequent thorough cleaning from phenol to a few ppm (to return it to the stage of oxidation), energy and operating costs increase so that substantially overlap to reduce energy costs, obtained by reducing the fraction distillation of cumene at the stage of concentration of the CCP.

As we developed an integrated approach of all these shortcomings UD is at the stage of decomposition with simultaneous increase in selectivity, by reducing the number of trace contaminants and a significant improvement in the degree of removal of salts at the stage of neutralization. This is demonstrated by the results of laboratory tests, is shown in Fig. 4 to 6 and examples 2 to 9.

As shown by our studies, reaction conversion of DCT and DMFC should be carried out in a reaction medium, which must be different from the composition of the reaction medium, which is the decomposition of the CCP. This allows you to achieve a higher selectivity and a higher conversion of DCT.

So, in the environment equimole mixture of phenol-acetone containing up to 15 wt.% cumene [U.S. patent, 4358618, 1982], the optimal selectivity is achieved when the residual content of DCT 0.5 wt.%, that is equivalent to the loss of 0.5% abs. target products of phenol, acetone and AMS combined.

As a result of the proposed technology due to the variable composition of the reaction medium are solved several technical problems:

1) effective, not achievable with other technologies, the excretion of sodium salts (Na2SO4NaHSO4the reaction of sodium) products from entering the separation;

2) reduce energy costs by reducing the concentration of water in the PMP, heat the decomposition of the CCP at the site of its decomposition;

4) provides a high selectivity in the reactor DCT transformation and DMFC not achieved in other technologies;

5) decreases the output of trace - oxide mesityl, hydroxyacetone (PL. 3.)

Schematic diagram of the process shown in Fig. 7. The oxidation products are received in the apparatus 1A, which is the evaporation of part of cumene by the heat coming from the oxidation products. Further concentration is carried out in one or two serial devices so that the concentration of cumene in technical CCP exceeded 21 wt.%, but would be less than 30 wt. %. For distillation oxidation products can be applied to machines of standard construction with built-in or external boilers, with or without irrigation irrigation, film evaporators. Regardless of the type of evaporator, the concentration of cumene as the product is supported preferably 28-26 wt.%.

Get technical CCP has a composition, wt.%:

GPC - 75 - 64, preferably 67-65

The cumene - 21 - 30, preferably 28-26

DMPC - 8 - 3

ACF - 1,2 - 0,4

DCT - 0,5 - 0,2

Concentration DMFC, ACF and DCT depending on the extent of oxidation, temperature, pH in the oxidation reactors may vary in a wide range the Mall and the CCP.

Node decomposition of the CCP are decorated in a traditional way (Fig.7) and consists of one to three heat exchangers, preferably three, 2A,B,C, cooled water is directed into the tube space, whereas the CCP and the circulating decomposition products are received in the annular space. Decomposition of CPC by using H2SO4the concentration of 200-300 ppm is maintained automatically by sensors conductivity meter. Decomposition of GIC flows in the environment of the phenol-acetone containing preferably 28-26 wt.% cumene, and a molar ratio of phenol:acetone = 1:1. The concentration of cumene may vary in the range of 21 to 30 wt.%.

Decomposition of technical GIC containing variable concentration of cumene in the above range, hold, depending on the concentration of cumene in accordance with a ratio of

< / BR>
where Gcircus- the number of circulating products of decomposition, t/h;

GTGPC- quantity supplied to the decomposition of technical GPK, t/h;

% cumene mass % cumene in technical CCP.

Through the process of decomposition of the CCP specified ensures its stability and safety in AC content of cumene in technium phenol: acetone: cumene, equal 1:1: (0,38-0,61).

When changing the concentration of cumene in technical CCP, the conversion value of the CCP in accordance with the above ratio remains constant and is adjusted by the value of the temperature difference T1calorimeter consisting of minireactor wipe, installed as shown in the diagram (Fig.7). The amount of conversion of CCP for the passage is from 76 to 88%. When the deviation from the ratio defined by the formula (1), the adjustment signal T1served on the valves regulating the flow of cooling water into the reactors 2A,B,C.

The relationship between the ratio represented by the formula (1), and a corrective influence on the regulators that control the flow of cooling water in the reactor for the decomposition of CPC depending on T1provides dual protection degree of decomposition of the CCP, and also minimizes the formation of dimers of alpha-methylstyrene and complex phenols at this stage.

Decomposition products containing neprevyshenie CCP, proceed to the evaporator 3, where the use of heat decomposition of the CCP evaporates a portion of the acetone in order to reduce its concentration and thus reduce the number formed from the hydroxy acetone is respectfully under vacuum 400 - 500 mm RT.article or at atmospheric pressure.

Depleted acetone product from the bottom of the evaporator 3 to reactor 4 decomposition of the DCT and DMFC, working on the principle of reactors displacement. The concentration of CPC in the stream is set to 0%. Thanks to the distillation in the evaporator 3 parts of acetone decomposition of the DCT and dehydration DMFC are carried out in a reaction medium that is different from the reaction medium, which is the decomposition of the CCP in the reactor mixture.

To optimize the composition of the reaction medium in order to obtain an increased output of the AMC, in the reactor eviction is served semolina fraction (stream IV) up to 160 kg/t technical CCP and recycle water (stream III) in an amount of from 1 kg to 30.4 kg per 1 t technical code of civil procedure, fed to the process. The composition of the reaction medium as a result of changes in the reactor is characterized by a molar ratio of phenol:acetone:cumene, equal 1:(1 - 0,77): (0,35 - 0,87).

The decomposition products after reactor 4 is cooled to a temperature of 30-50oC. To it is added fraction of cumene in an amount up to 255 kg/t from the upper part of the column 7, and water in an amount up to 24 kg/t of gazorazdelitel shoulder straps column 8 per 1 t technical CCP.

Naturalistichnosti changing the composition of the medium due to the additive somolinos faction to decomposition products effectively and in a short time (2-3 times smaller in comparison with standard technology) and with a high degree of separation (>95%) to separate from the organic phase formed by neutralization of the salt. The residual salt content of these products (flow VI) does not exceed 10-20 ppm. For comparison it should be noted that all the existing technologies, the process of separation of salts is slow (1.5 to 24 h), which requires the installation of bulky tanks. Notwithstanding the above, the degree of separation of salts does not exceed 90% and as a result to achieve stable operation of the heat exchange apparatus of the columns split internally set to clear the decomposition products from salts special design expensive coalescent filters, through which the salt content is brought to the same level of 10-20 ppm, which is achieved in our technology in the absence of filters.

The selection of cumene decomposition products is carried out in two sequential columns 7 and 8. In column 7 on the top stands out kamaladasa fraction, which is not more than 1 wt.% AMC and 0.3 wt. % phenol. On top of this column stands out almost all the water that is separated from somolinos fraction in the phase separator and fed to the column 8. Top of the column 8 is the fraction of the cumene-AMS (thread IX) coming to the stage of its processing according to the traditional technology, the bottom is in phase separator is separated from the cumene and AMS and fed into the reactor DCT transformation and DMFC. This technique allows to minimize the consumption of fresh water in the process 2-3 times and therefore proportionately reduce the amount of waste water.

The total reduction of energy costs in the scheme of division into two-column system due to the fact that the solubility of water when we apply the composition of decomposition products coming to the division, reduced to 10-12 wt.% to 3-3 .5 wt.%.

The total reduction of the power consumption in the process of heat due to its economy at the stage of concentration and oxidation products at the stage of separation of the products of decomposition is 0.4-0.6 t/t of phenol.

Distinctive features of our process are:

1. The concentration step of the CCP is carried out to a residual content of cumene from 21 to 30 wt.%, preferably 26-28 wt.%.

2. The decomposition of the CCP and CSD, respectively, in the reactor mixing and reactor displacement is carried out at differing in said reactor comprising a reaction medium, while all other technologies the composition of the reaction medium is maintained.

3. Decomposition of the DCT and DMPC in the reactor displacement is:

a) under reduced content of acetone TBA somolinos fraction and water;

b) at a temperature capable of displacing the equilibrium of the reaction conversion DMPC in the direction of the AMC and to achieve the DCT conversion close to 100%.

In the comparable technologies, the reaction medium is responsible for the composition of phenol: acetone 1:1 to 1:1,5, i.e., using the technique of introducing an additional amount of acetone. We applied the technique of lowering the concentration of acetone in the reaction medium has not been used, as well as the supplementation simultaneously somolinos fraction and water in the reactor DCT transformation and DMFC.

The combination of these techniques allows to achieve high selectivity is almost close to 100% conversion DCT and DMFC, not attainable in other technologies (90%).

4. The management process of decomposition of the CCP and CSD via the relation (T2/T1), where (T2) the temperature difference between the inlet and outlet of the reactor for the decomposition of the DCT-DMFC, a (T1) the temperature difference between the calorimeter node decomposition of the code of civil procedure, which allows to achieve the required safety of the process and its high selectivity.

In the comparable technologies used the method of using only calorimeter (T1to ensure the safety of the process.

whom I formed salts (no analogues).

6. Flooding of the decomposition products after the stage of neutralization is not more than 3.5 wt.% (in the comparable technologies 6-12 wt.%), that helps reduce energy costs in the process.

7. Additionally entered semolina fraction in the reactor for the decomposition of the DCT-DMFC and the stage of removal of salts excreted by using specially installed column and returned to the recycling at these stages of the process.

8. In the process it reduces the consumption of consumption of fresh water and, accordingly, the cost of processing chemically contaminated wastewater.

The advantages and differences of the developed technology are demonstrated by examples 1-9 (summary table examples table. 34).

Example 1 (example of comparison).

Products from the stage of oxidation of cumene, having the composition specified in the table. 3, which corresponds to the achieved selectivity 93,17 mol.%, come to the stage of concentration with the purpose of obtaining technical CCP. In the concentration technical CCP has the composition specified in the table. 4, which corresponds reached a total of two stages (oxidation and concentration) selectivity of 92.7 mol. %. The loss of selectivity due to partial collapse of the CCP on DMFC, ACF is camping on the stage of decomposition, which is carried out in the presence of 200-300 ppm H2SO4in the reaction medium, the composition of which is determined by the resulting decomposition products of the CCP and additionally put into them with acetone.

The decomposition is carried out in accordance with the patent [U.S. patent, 5530166, 1996; example 2] in the reactor unit consisting of three reactors installed in series, operating on the principle of reactor mixing generated due to the circulation of products of decomposition.

The decomposition products, leaving the latter in the course of the decomposition reactor CCP, proceed to the reactor decomposition of the DCT, working on the principle of reactors eviction.

In the reaction environment, which is the decomposition of the code of civil procedure, shall be filed in accordance with the stated ratio of acetone in the number 6025 kg/h

As a result of introducing into the reactor an additional amount of acetone, the reaction medium has a composition characterized by a molar ratio of phenol:acetone:cumene, equal in this particular example 1:1,36:0,2.

In the reactor, in which the decomposition of the DCT, supported the same composition as the reaction medium in the reactor for the decomposition of the CCP.

The temperature in the reactor decay DCT support is entered on the preliminary stage of decomposition of the CCP in the reaction medium acetone is excreted in the evaporator, established after the reactor decomposition of the DCT. Whisked into the evaporator and condensed in the refrigerator acetone is sent to recycling to the stage of decomposition of the CCP.

To reduce non-selective loss of target products (phenol and AMC) in the evaporator is fed an aqueous solution of ammonia for partial neutralization of sulfuric acid.

Control and management of the stage of decomposition of the CCP from the point of view of safety by maintaining a certain temperature difference between the two calorimeters installed on the circulation line of products and supply products in the reactor DCT decomposition.

The composition of the main impurities and by-products downstream of the evaporator acetone are presented in table. 5.

The release of AMC after the stage of decomposition is 76% of theoretical., the output of the phenolic resin with the stage of decomposition - 44 kg/t of phenol.

The resulting decomposition products are neutralized with NaOH, water out to the water content of 10-12 wt.%, going to alienate them from salts. After separation of the greater part of the salt content in the last reaction mass decomposition (PMP) is 2000 ppm.

PMP, containing 12 wt.% water is directed to the standard partitioning scheme, wclra allocation of acetone and a mixture of cumene and AMS is 2.9 t/t of phenol.

Expense ratio the cumene/phenol at a stage of decomposition is 1318 kg/so

In the process the received data is listed in table. 6.

Example 2.

Products from the stage of oxidation of cumene, which achieved selectivity 93,17 mol. % composition of example 1, proceed to the stage of concentration of the CCP. In the concentration technical CCP has the composition specified in the table. 7, which corresponds to the achieved selectivity 93,17 mol.% a total of two stages and proves the absence of selective disintegration of the CCP at the stage of kontsentrirovaniya.

The cost of a couple on the stage of concentration of CPC amount per 1 ton of 100% CCP - 0,576 tons per 1 ton of produced phenol - 0,933 so

Received technical GIC in the amount of 63 t/h is fed to the stage of decomposition performed, as given in the description of the process diagram above.

The decomposition of the CCP is carried out in a reaction medium, in which is supported the molar ratio of phenol:acetone:cumene, which is 1:1:0,61.

The circulating flow of products is carried out in accordance with the ratio of Gcircus=(48063)/30=1008 m3/h, which allows to maintain the conversion of CCP for passage, defined as the difference between the concentration of CPC in entrale CCP at the entrance to the reactor(4,3-0,73)/4,3100 = 83,0%. The ratio of T2/T1= 2,3. The temperature of decomposition of the CCP when the ratio T2/T1= 2,3, Gcircus= 1008 m3/h is equal to 50oC due to the change of the cooling water in the heat exchangers 2A,B,C.

Reaction mass decomposition enters the evaporator, where under vacuum (340 mm RT.CT.) Argonauts mixture containing acetone, cumene, water and phenol in the amount of 4400 kg/h

In coming out of the bottom of the evaporator 3 products introduces the cumene in the amount of 10000 kg/h, and water in quantities of 1000 kg/h as a result of the changes, the reaction medium is characterized by a molar ratio of phenol:acetone:cumene = 1:0,78:0,87, the concentration of water in the products coming into the decomposition reactor DMPC and DCT is 2.5 wt.%. The decomposition process DMPC and DCT is carried out at a temperature of 168oC.

The composition of the main impurities and by-products after decomposition reactor DCT and DMFC presented in table. 8.

The release of AMC after the stage of decomposition of the DCT-DMFC is 90.6% of theoretical., the output of phenolic resin 24,4 CT/t of phenol.

The resulting decomposition products are neutralized with NaOH, water out to the water content of 3.5 wt.% and sent to PTA is 40 wt.%) Department of salts proceeds efficiently and at the outlet of the apparatus 5 at a concentration in the organic phase is 3 ppm.

Purified from salts products (stream VI) are fed to the column 6, where the horse stands acetone fraction (stream VII). VAT product of this column is fed to column 7, where the selection somolinos fraction and water separate in the separator. Semolina fraction in the amount of 10000 kg/h into the reactor 4, and the aqueous phase (stream III) from the separator column 7 in the amount of 1000 kg/h is fed to the column 8, where the top is highlighted directed to the hydrogenation of a fraction of the cumene-AMS (thread IX) with the difference that allocated in the separator water phase (1000 kg/h) is sent to the recycling in the node decomposition of the DCT-DMFC. Steam consumption allocation of acetone and a mixture of cumene-AMS is 2.46 t/t of phenol. Expense ratio the cumene/phenol at a stage of decomposition is 1300 kg/so

The separation of the decomposition products receive the data listed in table. 9.

Example 3.

The process of example 2, when the technical CCP has the composition specified in the table. 10, which corresponds to the achieved selectivity br93.1 mol.% a total of two stages and indicates the minimum disintegration of the CCP (0.07% abs.) at the stage of kontsentrirovaniya. The cost of a couple on the stage of concentration of CPC amount per 1 ton of 100% CCP 0,58 t, 1 t obtained Fe is implemented, as given in the description of the process diagram above.

The decomposition of the CCP is carried out in a reaction medium, in which is supported the molar ratio of phenol:acetone:cumene, which is 1:1:0,55.

The circulating flow of products is carried out in accordance with the ratio of Gcircus= (48061,31)/28= 1051 m3/h, which allows to maintain the conversion of CCP for the passage 76,0% when the ratio T2/T1= 1,5.

Reaction mass decomposition enters the evaporator, where under vacuum (345 mm RT.CT.) Argonauts mixture of acetone, cumene, phenol and water in the amount of 4400 kg/h

In coming out of the bottom of the evaporator 3 products introduces the cumene in the number of 6200 kg/h, and water in the amount of 900 kg/h as a result of the changes, the reaction medium is characterized by a molar ratio of phenol: acetone: cumene = 1: 0,78:0,70, the concentration of water in the products coming into the decomposition reactor DMPC and DCT is to 2.75 wt.%. The decomposition process DMPC and DCT is carried out at a temperature of 160oC.

The composition of the main impurities and by-products after decomposition reactor DCT and DMFC presented in table. 11.

The release of AMC after the stage of decomposition of the DCT-DMFC is 90.3% of theory., the output of the phenolic resin of 25.4 kg/s total concentration of cumene and AMS was equal to 40 wt.%. Semolina fraction allocated to the top of the column 7 in the number 8790 kg/h, is distributed as: 6200 kg/h is fed to the stage of decomposition of the DCT and DMPK and 2590 kg/h on the stage of neutralization.

Neutralization of the acid, separating salts from the reaction products is carried out according to example 2. The salt content of the PMP is 17 ppm.

Steam consumption allocation of acetone and a mixture of cumene-AMS is 2.46 t/t of phenol. Expense ratio the cumene/phenol at a stage of decomposition is 1301 kg/so

The separation of the decomposition products receive the data listed in table. 12.

Example 4.

The process of example 2, when the technical CCP has the composition specified in the table. 13, which corresponds to the achieved selectivity of 93 mol.% a total of two stages and shows selective disintegration of the CCP in 0.17% of abs. at the stage of kontsentrirovaniya.

The cost of a couple on the stage of concentration of CPC amount per 1 ton of 100% CCP 0,63 t, 1 t of the obtained phenol - of 1.027 so

Received technical GIC in the amount of 55,94 t/h is fed to the stage of decomposition performed, as given in the description of the process diagram above.

The decomposition of the CCP is carried out in a reaction medium, which is supported mo is according to the algorithm Gcircus= (48055,94)/21 = 1278 m3/h, which allows to maintain the conversion of CCP for the passage 88,0% when the ratio T2/T1= 3,76.

Reaction mass decomposition enters the evaporator, where under vacuum (340 mm RT.CT.) Argonauts mixture of acetone, cumene, phenol and water in the amount of 4400 kg/h

In coming out of the bottom of the evaporator 3 products introduces the cumene in the amount of 8500 kg/h, and water in quantities of 1000 kg/h as a result of the changes, the reaction medium is characterized by a molar ratio of phenol: acetone: cumene = 1: 0,77:0,61, the concentration of water in the products coming into the decomposition reactor DMPC and DCT is 2.8 wt.%. The decomposition process DMPC and DCT is carried out at a temperature of 151oC.

The composition of the main impurities and by-products after decomposition reactor DCT and DMFC presented in table. 14.

The release of AMC after the stage of decomposition of the DCT - DMFC is 88.6% of theoretical., the output of the phenolic resin to 28.1 kg/t of phenol.

To the resulting decomposition products are added semolina fraction so that the total content of cumene and AMS in the decomposition products was 40 wt.%. Semolina fraction allocated to the top of the column 7 in the number 14200 kg/h, is distributed that the Oia acid, the separation of salts from the reaction products is carried out according to example 2. The salt content of the PMP is 15 ppm.

Steam consumption allocation of acetone and a mixture of cumene-AMS is 2.55 t/t of phenol.

Expense ratio the cumene/phenol at a stage of decomposition is 1303 kg/so

The separation of the decomposition products receive the data listed in table. 15.

Example 5.

The process of example 4, when the technical CCP has the composition specified in the table. 16.

Received technical GIC in the amount of 61,314 t/h is fed to the stage of decomposition carried out in a reaction medium, in which is supported the molar ratio of phenol:acetone:cumene, which is 1:1:0,55.

The circulating flow of products is carried out in accordance with the algorithm of Gcircus= (48061,31)/28 = 1051 m3/h, which allows to maintain the conversion of CCP for the passage 76,0% when the ratio T2/T1= 2,3.

In the reactor, decomposition of the DCT and DMPK the composition of the reaction medium is characterized by a molar ratio of phenol: acetone:cumene=1:1:0,53, the concentration of water in the products coming into the decomposition reactor DMPC and DCT is 2.8 wt.%. The decomposition process DMPC and DCT is carried out at a temperature of 156o

The release of AMC after the stage of decomposition of the DCT-DMFC is 88,31% of theoretical., the output of the phenolic resin to 27.7 kg/t of phenol.

To the resulting decomposition products are added semolina fraction so that the content of cumene and AMS was 40 wt.%. Semolina fraction allocated to the top of the column 7 in the amount of 10,915 kg/h, comes only at the stage of neutralization.

Neutralization of the acid, separating salts from the reaction products is carried out according to example 2. The salt content of the PMP is 18 ppm.

Steam consumption allocation of acetone and a mixture of cumene-AMS is 246 t/t of phenol.

Expense ratio the cumene/phenol at a stage of decomposition is 1302 kg/so

The separation of the decomposition products receive the data listed in table. 18.

Example 6.

Products from the stage of oxidation of cumene, having the composition specified in the table. 19, which corresponds to the achieved selectivity 86,47 mol.%, come to the stage of concentration with the purpose of obtaining technical CCP. In the result of kontsentrirovanija technical CCP has the composition specified in the table. 20, which corresponds reached a total of two stages (oxidation and concentration) selectivity 86,3 mol.%. P is.

Received technical GIC in the amount of 58,09 t/h is fed to the stage of decomposition.

If the decomposition of the given technical GIC containing 8,35 wt.% DMFC, conduct as described in example 1 (comparison), then the process will get fixed impurities and by-products downstream of the evaporator acetone, are presented in table. 21.

The release of AMC after the stage of decomposition is 77.8% of theoretical., the output of the phenolic resin with the stage of decomposition and 77.6 kg/t of phenol.

Steam consumption allocation of acetone and a mixture of cumene and AMC is 3.2 t/t of phenol.

Expense ratio the cumene/phenol at a stage of decomposition is 1350 kg/so

In the process the received data is listed in table. 22.

When carrying out the decomposition obtained technical GPK content DMFC 8,35 wt.% under the scheme of the process of if-96, we get the following.

The composition of the reaction medium decomposition of the CCP is characterized by a molar ratio of phenol:acetone:cumene, which is 1:1:0,42.

The circulating flow of products is carried out in accordance with the algorithm of Gcircus= (48058,09)/21 = 1328 m3/h, which allows to maintain the conversion of CCP for the passage of 77.0% when the ratio T23/h is equal 52oC due to changes in coolant oxen in the heat exchangers 2A,B,C.

In coming out of the bottom of the evaporator 3 products enter the water in the number 1156 kg/h In the decomposition reactor DCT and DMPK the composition of the reaction medium is characterized by a molar ratio of phenol:acetone:cumene = 1:1:0,39, the concentration of water in the products coming into the decomposition reactor DMPC and DCT, is 3.0 wt. %. The decomposition process DMPC and DCT is carried out at a temperature of 168oC.

The composition of the main impurities and by-products after decomposition reactor DCT and DMFC presented in table. 23.

The release of AMC after the stage of decomposition of the DCT - DMFC is 85,4% of theoretical., the output of phenolic resin 60,4 kg/t of phenol.

To the resulting decomposition products are added semolina fraction to of cumene 40 wt.%. Semolina fraction allocated to the top of the column 7 in the number 13710 kg/h is fed to the stage of neutralization.

Neutralization of the acid, separating salts from the reaction products is carried out according to example 2. The salt content of the PMP is 8 ppm.

Steam consumption allocation of acetone and a mixture of cumene-AMS is 2.8 t/t of phenol.

Expense ratio the cumene/phenol data, listed in the table. 24.

Example 7.

The process of example 3, when the technical CCP has the composition specified in the table. 25.

Received technical GIC in the amount of 55,94 t/h is fed to the stage of decomposition carried out in a reaction medium, in which is supported the molar ratio of phenol:acetone:cumene, which is 1:1:0,38.

The circulating flow of products is carried out in accordance with the algorithm of Gcircus= (48055,94)/21 = 1279 m3/h, which allows to maintain the conversion of CCP for the passage 88,0% when the ratio T2/T1= 5,7.

Reaction mass decomposition enters the evaporator, where under vacuum (330 mm RT.CT.) Argonauts mixture of acetone, cumene, phenol and water in the amount of 4400 kg/h

In coming out of the bottom of the evaporator 3 products introduces the cumene in the amount of 8500 kg/h, and water in the amount of 580 kg/h as a result of the changes, the reaction medium is characterized by a molar ratio of phenol: acetone: cumene = 1: 0,77:0,61, the concentration of water in the products coming into the decomposition reactor DMPC and DCT, is 21 wt.%. The decomposition process DMPC and DCT is carried out at a temperature of 151oC.

The composition of the main impurities and by-products after reactored 87,6% of theoretical., the output of the phenolic resin of 28.8 kg/t of phenol.

To the resulting decomposition products are added semolina fraction to of cumene 40 wt.%. Semolina fraction allocated to the top of the column 7 in the number 14100 kg/h, is distributed as: 8500 kg/h is fed to the stage of decomposition of the DCT and DMPK and 5600 kg/h on the stage of neutralization.

Neutralization of the acid, separating salts from the reaction products is carried out according to example 2. The salt content of the PMP is 16 ppm.

Steam consumption allocation of acetone and a mixture of cumene-AMS is 2.55 t/t of phenol.

Expense ratio the cumene/phenol at a stage of decomposition is 1305 kg/t the separation of the products of decomposition receive the data listed in table. 27.

Example 8.

The process of example 3, when the technical CCP has the composition specified in the table. 28.

Received technical GIC in the amount of 55,94 t/h is fed to the stage of decomposition carried out in a reaction medium, in which is supported the molar ratio of phenol:acetone:cumene, which is 1:1:0,38.

The circulating flow of products is carried out in the amount of 335 m3/h, which allows to maintain the relation of T2/T1= 21,4.

Reaction mass of RA is in the amount of 4400 kg/h

In coming out of the bottom of the evaporator 3 products introduces water in the amount of 1,700 kg/h as a result of the changes, the reaction medium is characterized by a molar ratio of phenol:acetone:cumene = 1:0,77:0,35, the concentration of water in the products coming into the decomposition reactor DMPC and DCT is 45 wt.%. The decomposition process DMPC and DCT is carried out at a temperature of 168oC.

The composition of the main impurities and by-products after decomposition reactor DCT and DMFC presented in table. 29.

The release of AMC after the stage of decomposition of the DCT - DMFC is 83% of theoretical., the output of the phenolic resin of 35.6 kg/t of phenol.

To the resulting decomposition products are added semolina fraction to of cumene 40 wt.%. Semolina fraction allocated to the top of the column 7 in the number 14200 kg/h is fed to the stage of neutralization. Neutralization of the acid, separating salts from the reaction products is carried out according to example 2. The salt content of the PMP is 18 ppm.

Steam consumption allocation of acetone and a mixture of cumene-AMS is 2.55 t/t of phenol.

Expense ratio the cumene/phenol at a stage of decomposition is 1309 kg/so

The separation of the decomposition products receive the data listed in table. 31.

Received technical GIC in the amount of 61,314 t/h is fed to the stage of decomposition carried out in a reaction medium, in which is supported the molar ratio of phenol:acetone:cumene, which is 1:1:0,55.

The circulating flow of products is carried out in accordance with the algorithm of Gcircus= (48061,31)/28 = 1051 m3/h, which allows to maintain the conversion of CCP for the passage 76,0% when the ratio T2/T1= 3,16.

In the reactor, decomposition of the DCT and DMPK the composition of the reaction medium is characterized by a molar ratio of phenol:acetone:cumene = 1:1,80:0,51, the concentration of water in the products coming into the decomposition reactor DMPC and DCT, is 1.3 wt.%. The decomposition process DMPC and DCT is carried out at a temperature of 150oC.

The composition of the main impurities and by-products after decomposition reactor DCT and DMFC presented in table. 32.

The release of AMC after the stage of decomposition of the DCT-DMFC is 85.7% of theory.

To the resulting decomposition products are added semolina fraction so that the content of cumene and AMS was 40 wt.%. Semolina fraction allocated to the top of the column 7 in the number 9434 kg/h, comes only at the stage of neutralization.

Neutralization Ki is m.

Steam consumption allocation of acetone and a mixture of cumene-AMS is 2.46 t/t of phenol.

Expense ratio the cumene/phenol at a stage of decomposition is 1306 kg/so

The separation of the decomposition products receive the data listed in table. 33.

Method for production of phenol and acetone by acid decomposition of technical cumene hydroperoxide (CHP) in the reactor mixing and dicumylperoxide (DCT) in the reactor displacement while maintaining a certain conversion of the CCP in each of the three reactors installed in series decomposition of the CCP, evaporating part of the acetone after reactor DCT transformation with subsequent neutralization of the acid catalyst alkaline agents, salts of the products of decomposition and separation of reaction products, wherein the concentration of oxidation products obtaining technical GPC is carried out to a residual content of cumene in technical CPC 21 - 30 wt.%, the decomposition obtained technical CCP carried out depending on the concentration of cumene in technical GPC ratio

< / BR>
where Gcircus- the number of circulating products of decomposition, t/h;

Gtgpc- quantity supplied to the decomposition-the x, which the reaction medium stage of decomposition of the CCP, the molar ratio phenol : acetone : cumene= 1 : 1 : (0,38 - 0,61) and with the subsequent decomposition of the DCT and dimethylphenylcarbinol (DMPC) in the reactor displacement at a temperature of 151 - 168oIn the reaction medium, in which due to the excretion part of the acetone in the evaporator and feed additionally somolinos fractions up to 160 kg/t technical CCP and supply additional water in an amount of from 1 to 30.4 kg/t technical CCP supported the molar ratio of phenol : acetone : cumene, equal 1 : (1 - 0,77) : (0,35 - 0,87), the degree of transformation of DCT over 97%, and control of the process in the reactor mixing and displacement to achieve high selectivity and safety through the value of the ratio of the temperature difference in the range of from 1.5 to 21.4, preferably 3 to 8, with subsequent supply somolinos fraction in an amount up to 255 kg/t technical CCP, so that the total concentration of cumene and alpha-methylstyrene (AMS) in the reaction mass decomposition (PMP) at the stage of neutralization was 40 wt.%, and water in an amount up to 24 kg/t technical CCP, so that its concentration in the PMP at the stage of neutralization was not more than 3.5 wt.%, with achievement of the salt content in the organic phase is not more than 10 - 2 the AI on the stage of decomposition of the DCT DMPC and phase separation of products from salts.

 

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