Way of production of phenol, acetone, α-methylsterene and device for its implementation

FIELD: chemistry.

SUBSTANCE: invention refers to the way of production of phenol, acetone and α-methylsterene, and to the installation for its implementation. The way consists in decompounding of cumene hydroperoxide and dimethylphenyl carbinol that are included into the technical cumene hydroperoxide, in the solvent with the presence of heterogeneous catalyst by means of catalytical distillation in the continuous isothermal mode at the boiling point of the solvent and with the latter's recirculation; as a solid heterogeneous catalyst, heteropoly acid H3PW12O40 or caesium-displaced salt of heteropoly acid Cs2.5H0.5PW12O40 is applied on the silicon dioxide, and as a solvent, acetone is employed. As a bearer, mesoporous silicon dioxide of MCM-41 grade is used, and decompounding of the cumene hydroperoxide and dimethylphenyl carbinol is carried out in two stages; the first stage stipulates decompounding of cumene hydroperoxide thus releasing phenol and acetone, and the second one - of dimethylphenyl carbinol thus releasing a-methylsterene; the mesoporous silicon dioxide and heteropoly acid or caesium-displaced salt of the heteropoly acid are used with the following component ratio, weight %: heteropoly acid - 10-50; silicon dioxide - the rest; or caesium-displaced salt of the heteropoly acid - 10-20; silicon dioxide - the rest.

EFFECT: decompounding of the cumene hydroperoxide and dimethylphenyl carbinol with 100 % conversion and 100 % selectance.

8 cl, 1 dwg, 8 ex

 

The invention relates to the field of industrial organic synthesis, more specifically to the joint receipt of phenol, acetone, α-methylstyrene Kukolnik method.

Widely known komorny method Kruglova production of phenol and acetone is one of the first places among the original industrial processes of the twentieth century and still remains the dominant model among chemical technology (Kruglov D., Golovenko B. I. - M.: Goskomizdat, 1963), and more than 90% of the phenol in the world produced by this method.

Komorny the process of production of phenol and acetone consists of three main stages: the alkylation of benzene to cumene oxidation of cumene to cumene hydroperoxide (CHP) and the decomposition of the CCP to phenol and acetone. At the stage of oxidation receive technical cumene hydroperoxide or technical gitaris containing CCP 88-91%, cumene 1-3%, dimethylphenylcarbinol (DMPC) not more than 7% and acetophenone not more than 1% of the mass. At the stage of decomposition of technical hyperize use a homogeneous catalyst is sulfuric acid. In the presence of sulfuric acid in addition to phenol and acetone are formed more than 300 species of organic impurities, which reduce both the quality of target products of phenol and acetone, and lead to the formation of non-recyclable organic waste that significantly increase spending ratio GIC per ton of phenol. In the presence of sulphuric islamicist DMFC split into a valuable product α-methylsterols and water, a other part DMFC reacts with the CCP, the phenol with the formation of heavy by-products (dicumylperoxide, cumylphenol and others), and α-methylstyrene are formed of the high-boiling dimers and other, i.e. the components of the so-called phenolic resin. In the classic version of the single-stage process sulfuric acid decomposition technical hyperize output phenolic resin remains significant and is up to 200 kg/t of phenol.

Known methods for producing phenol and acetone in the framework Kumanovo method Kruglova (Patent RU№№2265586, 2068404, 2121477, 2108318, 2114816), where for improving the selectivity of the decomposition of technical hyperize sulfuric acid to phenol and acetone and increase the degree of conversion DMFC in α-methylsterol or decrease in the output of phenolic resin decomposition of technical hyperize carried out in two stages.

There is also known a method (patent application JP 2000-344698), according to which exercise effective decomposition of the CCP and DMFC included in technical hyperize, in two stages, the first of which decomposition of the CCP mainly phenol and acetone, and the second from dicumylperoxide and residual CPC is formed α-methylsterols, phenol and acetone. The first stage is carried out at 55-90°C, while the second 55-120°C in an environment of acetone in the presence of dissolved in acetone of heteroalicyclic H3PW12O40the content of the m 20-300 ppm (JP 200-344698, publ. 12.12.2000). For the two-stage decomposition of technical hyperize using homogeneous catalyst (sulfuric acid, heteroalicyclic and others) declareroles output of the waste - phenolic resin is 25-100 kg/t of phenol.

However, in industrial conditions, the two-stage decomposition of technical hyperize output phenolic resin is much higher. In addition, the lower output of the phenolic resin is achieved by the complexity of the technology decomposition technical hyperize due to the introduction of additional equipment for safe operation. Significant disadvantages of both classic and modern two-stage variant of the decomposition of technical hyperize are using a homogeneous catalyst is sulfuric acid or heterophilically with low selectivity, as a consequence, the formation of organic waste - phenolic resin and corrosion of the equipment, the necessity of neutralizing the sulfuric acid reaction mass of decomposition with the formation of significant quantities of environmentally hazardous wastewater.

Alternative homogeneous catalyst sulfuric acid with a Lewis acidity of the decomposition of the CCP on the phenol and acetone from the standpoint of activity and selectivity, environmental, safety, ease of separation of the reaction products and ease of regeneration are solid catalysis is ora with Pentecostal acidity. Among the solid catalysts are the most effective of heteroalicyclic or azizanesin heterophilically with polyanion of Keggin, which have a purely Pentecostal acidity and high thermal stability and are a new generation of so-called "green" catalysts. High efficiency heteropolyacids as catalysts due to their strong Pentecostal acidity, excess acidity and mineral acids, and traditional solid catalysts. This allows for a catalytic process at lower concentrations of catalyst and/or a lower temperature, thereby increasing the selectivity of the process. In addition, due to the inertia of polyanion heteroalicyclic not enter into side reactions with organic reagents, which is typical for conventional mineral acids, in particular sulfuric acid. In particular, dodecamolybdophosphoric acid (H3PW12O40has the highest bresadola acidity, higher than 100%sulfuric acid. Among the salts casinomasino heteroalicyclic (Cs)mH3-mPW12O40(the number of cesium atoms 0≤m≤3) extremely high catalytic activity and selectivity with the crystal structure of polyanion of Keggin has Csthe 2.5H0,5PW12O40or reducing the NGOs Cs2,5 with the number of cesium atoms m=2,5. Catalytic activity Cs2.5 more than 10 times the activity of zeolites and 3 times higher than the activity of the source heteroalicyclic. High activity Cs2,5 due to the high surface bresadola acidity due to the large surface area of 150÷200 m2/year Surface Cs2,5 is hydrophobic, insoluble in liquids of any type. Heteroalicyclic and their compounds with metals are used as homogeneous and heterogeneous (solid and supported) catalysts. Heterogeneous catalysts have high catalytic activity in the low-temperature reactions. For practical purposes, the use of solid heterogeneous catalysts on inert media with intact structure polyanion of Keggin obtained by impregnation (20÷50)% of the mass. heteroalicyclic or applying Cs2,5 by a special technique. As a porous inert media used clay K-10, mesoporous silica MCM-41, etc. and receive, for example, catalysts with formula 20% (mass.) H3PW12O40/MCM-41 or 20% (mass.) Csthe 2.5H0,5PW12O40/MCM - 41.

The known method and device for production of phenol and acetone, where as a solid heterogeneous catalyst is used or heteroalicyclic H3PW12O40(R.Selvin et al. / Applied Catalysis A: General 219, 2001, 125-129) or azizam the seal salt heteroalicyclic Cs the 2.5H0,5PW12O40(Makoto Misono / Chem. Commun., 2001, 1141-1152; G.D.Yadav, N.S.Asthana / Applied Catalysis A: General 244, 2003, 341-357)supported on mesoporous media MSM-41. The decomposition of the CCP carried out in a batch reactor, the environment cumene as solvent at a temperature of 30-50°C. increase in temperature increases the rate of decomposition of the CCP, for example, at a temperature of 30°With the CCP decomposes within 5 minutes with 100% conversion and 100% selectivity solely on phenol and acetone in the presence of H3PW12O40deposited on an inert carrier. The batch reactor, the is a cylindrical glass vessel with a flat bottom volume of 50-100 ml equipped with a reflux condenser and a magnetic or turbine agitator. The reactor is placed in a thermostat to maintain constant temperature. For experiments using GPC with a basic substance content of 100%. In the reactor load cumene, code of civil procedure, the catalyst and the system is stirred with a speed of 800 rpm Typical reaction mixture consists of 13 mmol or 1,976 g of the CCP in the cumene to the total volume of liquid in the reactor 25 ml In a batch reactor, the obtained maximum content of phenol 5% in the reaction mass decomposition.

Know the use as catalyst for the decomposition of the CCP and DMFC included in technical hyperize, obtaining phenol, acetone and α m is telestial casinomasino salt heteroalicyclic (Cs)mH 3-mPW12O40(the number of cesium atoms 0≤m≤3)supported on mesoporous silica brand MCM-41 (patent application US 2008/0188694). When this silicon dioxide brand MCM-41 and (Cs)mH3-mPW12O40(the number of cesium atoms 0≤m≤3) use, including, at a ratio (wt.%): salt 10-20, silicon dioxide - the rest. The decomposition of the CCP and DMFC included in technical hyperize, carried out in test mode to verify the activity and selectivity of the catalyst casinomasino salt heteroalicyclic (Cs)mH3-mPW12O40(the number of cesium atoms 0≤m≤3)supported on mesoporous silica brand MCM-41. For example, the decomposition of technical hyperize carried out in a glass vessel with a volume of 50 cm3with stirring, a mixture of 4 grams of catalyst and 4 grams of technical hyperize and 36 cm3equimolar mixture of phenol and acetone 1:1 with stirring for 25 minutes and a temperature of 50-70°C.

Undoubted advantage and the advantage of the described known technical solution is the decomposition of cumene hydroperoxide with 100% conversion and 100% selectivity solely on phenol and acetone in the presence of heteroalicyclic H3PW12O40or casinomasino salt Csthe 2.5H0,5PW12O40on the media MCM-41, while the other reaction products and impurities do not form the Xia.

The disadvantages of the known technical solutions include: inadequate equipment design; use of periodic action; constant contact of the catalyst with phenol, which gradually leads to the deactivation of the active centers of the catalyst; the absence of conditions o phenol from the reaction zone; used as a solvent cumene with a high boiling point or phenol and acetone in equimolecular a mixture of 1:1, and as raw material 100% CCP and receiving the reaction mass decomposition with low phenol content.

The closest in technical essence and the achieved effect to the claimed method is a method for production of phenol, acetone, α-methylstyrene by decomposition of the CCP and DMFC included in technical hyperize, in the presence of a solid heterogeneous catalyst, which can be used heteroalicyclic H3PW12O40deposited on silicon dioxide or silica gel, in the environment of the solvent is acetone under the action of temperature (patent application US 2002/0058845). When this decomposition is conducted by catalytic distillation in a continuous isothermal mode at the boiling temperature of acetone 56,3°C With recirculation of the solvent. The solvent is used in a quantity sufficient to reduce the formation of wysokosc Pasig by-products and maintain isothermal mode process. There is a method allows the process to the conversion of the initial reagents 100% with minimum formation of high-boiling by-products, high yield of target products and low capital cost.

Closest to the claimed device is to install the decomposition of technical piperita (patent application US 2002/0058845) for the production of phenol, acetone and α-methylstyrene, containing a single reactive distillation unit containing solid heterogeneous catalyst, distillation column, having a cubic part, and has two outputs and an input for recirculation of acetone and supply technical hyperize with the solvent, with a distillation column equipped with a heater and connected with a reflux condenser. When this catalyst is located in a bottom part of the distillation column for wetting the catalyst layer bottom liquid, with the input of technical hyperize with the solvent is above the catalyst, and the output of the high-boiling products for further processing is located in the lower bottom part of the column.

The advantages of the known method and installation decomposition technical hyperize are: the use of solid heterogeneous catalyst; catalytic distillation of phenol, acetone and α-methylstyrene in the isothermal mode, kipriyanets; no corrosion of equipment; obtaining additional useful product α-methylstyrene; used as a solvent of acetone; removing thermal effect of the reaction of decomposition of CPC technical hyperize and maintaining low temperatures in the reaction zone by evaporation of the solvent. Known installation process is done with the conversion of the initial reagents closer to 100% with minimal formation of high-boiling by-products, high yield of target products and low capital cost.

Significant disadvantages of the known method and installation include: use as an inert carrier for heteroalicyclic H3PW12O40silicon dioxide or silica gel with a very small pore size, where the reaction of the decomposition of the CCP and DMFC occurs mainly on the active centers of the surface of the heterogeneous catalyst; weak link of the catalyst on the surface of the medium and, as a consequence, the possibility of ablation or erosion heterophilically with the surface of the carrier with a hit of acid in cubic liquid, which may lead to the need for neutralization of heteroalicyclic bottom liquid alkali and the formation of harmful wastewater containing heavy metals, particularly tungsten; the use of only one reactive distillation b is an eye for catalytic distillation phenol, acetone and α-methylstyrene decomposition of the CCP and DMFC included in technical hyperize, which can lead to incomplete decomposition of the CCP and DMFC due to selectivity and consistency decomposition reaction components technical hyperize - first decomposition of the active SBC with great content, and after less active DMFC with less content or due to the decomposition of the CCP and DMFC technical hyperize sequentially in two stages; the possibility of formation of residual DMFC taglocity by-products in the presence of heteroalicyclic gone with the carrier surface during further processing of the bottom liquid of the distillation column; the location of the catalyst layer below the middle - very close to a bottom part of the reaction-distillation column (see figure 1-3, US 2002/0058845), as a consequence, the possibility of wetting catalyst layer bottom liquid that contains phenol, which eventually leads to deactivation of heterogeneous catalyst, reducing the total mileage or the lifetime of the catalyst.

The task of the group of inventions is the development of waste processing technologies technical hyperize by catalytic distillation of phenol, acetone, α-methylstyrene in a continuous isothermal mode.

The technical result is achieved due to the decomposition of SE and DMFC, included in the technical goberis, with 100% conversion and 100% selectivity for solid heterogeneous catalyst in the environment of the solvent to form easily separated reaction mixture decomposition, containing phenol, acetone, α-methylsterols, cumene and acetophenone without the formation of by-products and impurities.

The problem is solved in that in the method for production of phenol, acetone, α-methylstyrene, including the decomposition of cumene hydroperoxide and dimethylphenylcarbinol included in technical hyperize, in the environment of a solvent in the presence of a solid heterogeneous catalyst by catalytic distillation in a continuous isothermal mode at the boiling temperature of the solvent and recycling the solvent, the solid heterogeneous catalyst used heteroalicyclic H3PW12O40or casinomasino salt heteroalicyclic Csthe 2.5H0,5PW12O40deposited on the silicon dioxide and the solvent used is acetone, according to the invention, as a carrier using mesoporous silica, brand MCM-41, and the decomposition of cumene hydroperoxide and dimethylphenylcarbinol carried out in two stages, the first of which is exercised by the decomposition of cumene hydroperoxide with the separation of phenol and acetone, the second - dimethylaniline the Ola emitting α-methylstyrene, this mesoporous silica and heteroalicyclic or casinomasino salt heteroalicyclic used in the following ratio of components, wt.%:

heteroalicyclic- 10÷50
silicon dioxiderest

or

asiamedia salt heteroalicyclic- 10÷20
silicon dioxide- the rest.

The solvent and technical gitaris can be used at a volume ratio (1÷11):1.

The task is also solved by the fact that the installation of the production of phenol, acetone, α-methylstyrene, comprising at least one reactive distillation unit containing a layer of a solid heterogeneous catalyst in the form deposited on the silicon dioxide of heteroalicyclic H3PW12O40or casinomasino salt heteroalicyclic Csthe 2.5H0,5PW12O40, distillation column, having a cubic part, has two outputs and input technical hyperize solvent heater and reflux condenser, with solid heteroge the hydrated catalyst is located in a distillation column above the bottom part, and the entrance to the filing of the technical hyperize with the solvent is above the catalyst according to the invention, contains a second reactive distillation unit, a pump located between the first and second reactive distillation units.

In addition, the installation further comprises a feeder technical hyperize with solvent, United with the first and second reactive distillation units, while the output of the first pump unit is connected to the input of the rectifying column of the second block, the outputs of reflux condensers of the first and second reactive distillation units are connected to the input feeder technical hyperize with the solvent, the output of which is connected to the input of the rectifying column of the first block, which is equipped with a cooling jacket layer of a solid heterogeneous catalyst.

Distillation column can be provided with a device for measuring the level of the bottom liquid, which represents a thick-walled glass tube with a control marks the minimum and maximum level of the bottom liquid, mounted on the outer side of a bottom part of the distillation column and made communicating with the cavity of the bottom part of the distillation column. In addition, the distillation column can be equipped with a thermocouple, located on the solid heterogeneous catalyst.

A possible embodiment of a distillation column, whereby the column is a metal tube with two metal grids, arranged perpendicular to the longitudinal axis of the pipe, one of which is designed to accommodate solid heterogeneous catalyst and has a cell size that is smaller than the minimum particle size of the solid heterogeneous catalyst, and the second is designed to distribute the flow of liquid flowing in the distillation column. Feeder technical hyperize and solvent made in the form of a container of solvent and United with her pump, in line between tank and pump mounted nozzle for the supply of technical hyperize.

The solid heterogeneous catalyst is a deposited on mesoporous silica heteroalicyclic H3PW12O40or casinomasino salt heteroalicyclic Csthe 2.5H0,5PW12O40. Distillation column provided with a device for measuring the level of the bottom liquid, which represents a thick-walled glass tube with a control marks the minimum and maximum level of the bottom liquid, mounted on the outer side of a bottom part of the distillation column and made communicating with the cavity bottom is Asti distillation column. Distillation column can be provided with a thermocouple above the solid heterogeneous catalyst. Distillation column is a metal tube with two metal grids, arranged perpendicular to the longitudinal axis of the pipe, one of which is designed to accommodate solid heterogeneous catalyst and has a cell size that is smaller than the minimum particle size of the solid heterogeneous catalyst, and the second is designed to distribute the flow of liquid flowing in the distillation column. The installation may contain a second reactive distillation unit, is identical to the first reactive distillation unit, and connected with it, and feeder technical hyperize with solvent, United with the first and second reactive distillation units, while the output of the first pump unit is connected to the input of the rectifying column of the second block, the outputs of reflux condensers of the first and second reactive distillation units are connected to the input feeder technical hyperize with the solvent, the output of which is connected to the input of the rectification column of the first block, which is equipped with a cooling jacket layer of a solid heterogeneous catalyst. Feeder technical hyperize and restoresession in the form of a container of solvent and United with her pump, in line between tank and pump mounted nozzle for the supply of technical hyperize.

The claimed group of inventions is illustrated by a drawing, which shows a schematic diagram of the proposed installation. Positions on the drawing: a and B, the first and second reactive distillation units, respectively, 1 and 2 distillation column with a layer of a solid heterogeneous catalyst function which is reactive distillation columns, 3 and 4 were installed, 5 - collector, 6 - tube feeding technical hyperize, 7-9 - pumps 10 and 11 of thermocouple.

The drawing shows an embodiment of an installation with two connected pipes reactive distillation units a and B (see drawing). The unit has a reactive distillation column 1 and 2 loaded catalysts located on the bottom part of the column, with entrances located above the catalyst layer, and the upper and lower outputs. The upper outlet of the column 1 is connected via the reflux condenser 3 to the input of the collector 5, the output of which through the pump 7 is connected with the inlet of the column 1. In the piping between the collector 5 and the pump 7 is mounted the feed pipe 6 technical hyperize. The collector 5, the pump 7 and the pipe 6 to form the feeder technical hyperize with the solvent at the inlet of the first reaction-rectifica the ion block. To supply raw materials - technical hyperize in the pipe 6 is used calibrated measuring burette. Bottom outlet bottom part of column 1 through the pump 8 is connected to the inlet of the column 2, the upper end of which is through the reflux condenser 4 is connected to the inlet of the column 2 and the inlet of the collector 5. Bottom outlet bottom part of column 2 is connected to the pump 9. In the upper part of columns 1 and 2 above the catalyst bed mounted thermocouples 10 and 11. The catalyst section of the column 1 is equipped with a cooling jacket (not shown). Columns 1 and 2 is provided with devices for measuring the level of the bottom liquid (positionandin the drawing). Device for measuring the level of the bottom liquid is a thick-walled glass tube with a control marks the minimum and maximum level of the bottom liquid, mounted on the outer side of a bottom part of the distillation column and made communicating with the cavity of the bottom part of the distillation column. In column 1 and 2 the bottom level of the fluid should not reach the catalyst layer and must be within the minimum and maximum level. The columns used solid heterogeneous catalyst comprising a deposited on mesoporous silica heteroalicyclic H3PW12O40or casinomasino salt heteroalicyclic Csthe 2.5H0,5PWsub> 12O40.

Technical solutions are carried out by the non-waste technology in the catalytic distillation (see the drawing) in a continuous isothermal mode at the boiling temperature of acetone. The start and conclusion on the installation mode is performed with the use of acetone during loading of solid heterogeneous catalyst in the reaction part of the distillation columns 1 and 2 in the amount of 100 ml. Main parameters are: the temperature of the saturated vapor of acetone 56,3°C, which is controlled by means of thermocouples 10 and 11 or the boiling point of acetone; the levels of still liquids columns 1 and 2 within the minimum and maximum levels that track control marks; continuous feed rate of the solvent or solvent mixture with the technical Hypericum 300 ml/hour. In the first reactive distillation unit (see the drawing) of the first stage in column 1 catalytic distillation obtain phenol and acetone. With capacity 5 pump 7 serves acetone at the inlet of the column 1. With a calibrated burette technical gitaris through pipe 6 by gravity (gravity) is fed into the suction pipe of the pump 7. The total feed rate of solvent and technical hyperize pump 7 is constant and amounts to 300 ml/hour when the variation of the volumetric ratio of solvent to the volume of technical Hyper is for (1÷11):1. The decrease in volume fraction of technical hyperize or, respectively, the increase of the volume fraction of the solvent is not practical point of view, although the proposed technical solutions applicable at low volume contents technical hyperize. Therefore, as the upper limit of the interval values of the volumetric ratio of solvent (acetone) and technical hyperize selected ratio of 11:1. The lower limit of the volume ratio of solvent and technical hyperize 1:1 (characterized by increased content of technical piperita) due to the exothermic effect of the reaction of decomposition of CPC technical hyperize solid heterogeneous catalyst, although much less than in the known technical solutions of sulfuric acid or sulfonated cation exchange resin with a strong acid as a catalyst. At the inlet of the column 1 is fed a mixture of acetone and technical hyperize, through which the metal grid is evenly distributed on the surface layer of the catalyst bed, while the acetone additionally provides irrigation catalyst layer. On the catalyst at the temperature of boiling acetone 56,3°C GPC technical hyperize decomposed with 100% conversion and 100% selectivity to phenol and acetone. From the bottom of column 1 ascending heated couples who Cetona pass through the catalyst bed of the reaction section. The heat released by the decomposition of the CCP, additionally evaporate the acetone. To maintain thermal balance in the column regulate the flow of heat through the heater by reducing the voltage and, if necessary, regulate the flow of water in the jacket of the reaction section of the column 1. The ascending vapors of acetone out of the column 1, is condensed in the reflux condenser 3, the condensate of acetone enters the collector 5, from which the condensate part with technical Hypericum is fed to the input of the column 1. After decomposition of the CCP liquid - phase phenol, DMPK, cumene and acetophenone in acetone flows down from the catalyst layer in the cubic part of the column 1. In the catalyst bed downstream liquid phase containing acetone, in contact with the ascending vapors of acetone and continuously cleans the catalyst from the reaction product of phenol, as well as other impurities technical hyperize. On the catalyst concentration of phenol in the liquid phase is extremely low due to irrigation with acetone, the formation of acetone by decomposition of the CCP, the upward flow of vapors of acetone and runoff from the catalyst liquid phase containing phenol, which eliminates the deactivation of the catalyst phenol and provides long-lasting activity or "mileage" of the catalyst in the column 1. The temperature of the saturated vapor of acetone in column 1 control thermocouple 10. In column 1 controls the level of the bottom liquid, which should not come into contact with the layer of catalyst and must be located within the minimum and maximum level control labels (positionandin the drawing). To maintain an acceptable level bottom liquid in the column 1 is constantly pump 8 part of the bottom liquid is served in the second reactive distillation unit B (see drawing) to obtain α-methylstyrene from DMPC technical hyperize. Cubic liquid from the column 1 is fed to the inlet of the column 2 through the metal grid is evenly distributed on the surface of the catalyst layer of the catalyst. On the catalyst at the temperature of boiling acetone 56,3°C dehydration takes place DMFC with a 100% conversion of α-methylsterol. From the bottom of column 2 heated ascending vapors of acetone are passed through the catalyst bed reaction section, reach the top of the column 2, enter the reflux condenser 4 and is condensed. Part of the condensation of acetone with a reflux condenser 4 is returned to the column 2 for irrigation, and the other part flows into the collector 5. After dehydration DMPC in the catalyst layer of the liquid - phase phenol, α-methylsterols, cumene and acetophenone in acetone flows down from the catalyst layer in the cubic part of the column 2. In the catalyst bed downstream liquid phase containing acetone, in contact with the vos is odashima pairs of acetone and continuously cleans the catalyst from the reaction product - phenol, as well as other impurities technical hyperize. On the catalyst concentration of phenol in the liquid phase is extremely low due to irrigation with acetone, the upward flow of vapors of acetone and runoff from the catalyst liquid phase containing phenol, which eliminates the deactivation of the catalyst phenol and provides long-lasting activity or "mileage" of the catalyst in the column 2. The temperature of the saturated vapor of acetone in column 2 control thermocouple 11. In column 2 controls the level of the bottom liquid, which should not come into contact with the catalyst bed and is within the minimum and maximum level control labels. To maintain the required level of the bottom liquid of the column 2 of the second reactive distillation unit B part of the bottom liquid or reaction mass decomposition containing phenol, acetone, α-methylsterols, cumene and acetophenone, the pump 9 is continuously withdrawn on stage rectification. The composition of the reaction mass decomposition determine chromatographic method for capillary column, and quantitative water content after dehydration DMPC determined by the method of Fisher.

The amount of heat which must be submitted to column 1 of the heater is reduced due to heat decomposition of CPC technical piperitae the excess heat of the reaction section with catalyst layer is cooled, adjusting the flow of water in the cooling jacket. The boiling point of acetone provides isothermal mode catalytic distillation of phenol and acetone in column 1 of the first reactive distillation unit and catalytic distillation α-methylstyrene in column 2 of the second reactive distillation unit B. This method of regulating the temperature of decomposition of the CCP or dehydration DMFC at the boiling temperature of the solvent is more accurate than in the known technical solutions. When designing reactive distillation columns 1 and 2 of the industrial scale of basic variables are the height of the catalyst layer, the temperature of the saturated vapor or boiling point of acetone and thermal effect of the reaction of decomposition of CPC technical hyperize in column 1, is required for the recycling of excess acetone in columns 1 and 2 of reactive distillation units a and B.

Obtained after decomposition of the CCP and DMFC technical hyperize its bottom liquid of the column 2 or the reaction mass decomposition containing phenol, acetone, α-methylsterols, cumene and acetophenone, easily separated at the stage of rectification. Organic waste - phenolic resin and wastewater is not formed. Selected at the stage of distillation of the acetophenone is additionally useful product in demand in the market of perfumery industry the items, and the cumene is used to produce technical hyperize in the second stage Kumanovo method Kruglova.

Technical solutions have been implemented at the facility (see drawing). Reactive distillation column 1 and 2 have the same size and contain a layer of a solid heterogeneous catalyst, located in the upper part of the column above the bottom part. Reactive distillation column 1 is intended for production of phenol and acetone by decomposition of CPC technical hyperize with 100% conversion and 100% selectivity solely on phenol and acetone in the layer of solid heterogeneous catalyst at the temperature of boiling acetone 56,3°C catalytic distillation of phenol and acetone in a continuous isothermal mode. Reactive distillation column 2 is intended for receipt by dehydration DMFC with 100% conversion in the solid heterogeneous catalyst at the temperature of boiling acetone 56,3°C catalytic distillation α-methylstyrene in a continuous isothermal mode. Column 1 or 2 is a vertical metal pipe with a height of 480 mm and an inner diameter of 27 mm, with end sides of which are mounted flanges with holes for the mounting bolts. The useful volume of the column 275 cm3. Inside the pipe at a height of 200 mm is mounted the supporting metal ring perpendicular to prodelin the y axis of the pipe with a metal grid, holding the catalyst bed, which has a cell size of 1 mm On a metal grid supporting metal rings placed a layer of solid heterogeneous catalyst in the amount of 100 ml, the Height of the catalyst layer was 180 mm Above the catalyst bed also installed a metal grid with a cell size of 1 mm, which prevents the entrainment of the catalyst and provides uniform distribution of fluid flow. The entrance of the distillation column is located at a height of 40 mm, thermocouple mounted at a height of 70 mm from the top of the metal mesh layer of the catalyst. The lower and upper column cover made in the form of "deaf" flanges with the corresponding outputs in the form of fittings with thread. The flanges of the caps and tubes are ledges and gaps type of "father-mother"ensuring the integrity of connected elements. The cover and the pipe is additionally sealed with a gasket and through the flange tightened bolts with nut. A section of the catalyst layer of the column 1 has a water cooling jacket. The bottom of column 1 or 2 is provided with an electric heater in the form of a spiral of tungsten, which regulates the temperature of the bottom part of column a change in voltage. Therefore, through the voltage regulator is set to the desired heat, which is necessary to ensure the temperature of saturated vapors of acetone 56,3°C at the top of Castillon 1 and 2 thermocouples 10 and 11. To maintain thermal balance in column 1 due to thermal effect of the exothermic decomposition reaction of the CCP regulate the flow of heat to the heater in the direction of decreasing voltage and, if necessary, regulate the flow of water in the jacket of the reaction section of the column 1. The signals from thermocouples 10 and 11 through two channels are converted in the form of temperature recorded by the potentiometer in real-time. The reflux condensers 3 and 4 are the same size and are designed for cooling of saturated vapors of acetone and represent the product "pipe in pipe size inner tube: length 500 mm, diameter 50 mm, Material columns, reflux condensers and their elements, pipelines are steel 12X18H10T. Collection of 5 acetone is a glass container with a volume of 10 liters with a plastic lid with holes for input of acetone with columns 1 and 2 and the vapor outlet, and with the bottom drain valve of excess acetone or for feeding into the suction pipe of the pump 7. To supply hyperize is calibrated measuring burette. Pumps 7-9 represent dosing pumps brand NDM 1,6/100KV with explosion-proof execution. The maximum feed rate of 1.6 l/h, pressure of 16 kgf/cm2, material flow part 12X18H10T. To prevent heat loss column and all the pipes are insulated with asbestos and asbestos is m cord on the sodium silicate.

Below are examples of implementation of technical solutions that demonstrate the benefits of waste processing technologies technical hyperize obtaining phenol, acetone, α-methylstyrene. Download the same solid heterogeneous catalyst in the reaction part of the distillation columns 1 and 2 in the following examples the same and is 100 ml.

Example 1.

For the production of phenol, acetone, α-methylstyrene from technical hyperize as a solid heterogeneous catalyst used heteroalicyclic with formula (10÷50)% (mass.) H3PW12O40/MCM-41. Solid heterogeneous catalysts were prepared by impregnation of silica MCM-41 heteroalicyclic in butanol by weight according to the methodical recommendations (R.Selvin et al. / Applied Catalysis A: General 219, 2001, 125-129). Physico-chemical characteristics of heteroalicyclic meet the standards and requirements of THE 6-09-01-744-88. Pre-hydrated H3PW12O40·nH2O determine the number of molecules of water of crystallization gravimetric method, by heating for 1 hour at 220°C. depending on the party acid number of molecules n=5-13. The number of water of crystallization considered in the impregnation of a silica MCM-41 heteroalicyclic H3PW12O40·nH2O from the solution in butanol. After impregnation and the adoption of excess fluids wet precipitate was dried at 110°C during the day and then caliciviral at 300°C for 3 hours. The resulting catalyst was washed with acetone, reagent grade brand. and dried at 100°C for 1 hour. The resulting catalyst was determined by the content of heteroalicyclic. Made catalysts with the formula 10% (mass.) H3PW12O40/MCM-41, 20% (mass.) H3PW12O40/MCM-41 and 50% (mass.) H3PW12O40/MCM-41 was tested for activity and selectivity of the decomposition of the CCP and dehydration DMFC in acetone at minilaparotomy installation. To test specifically obtain cumene hydroperoxide content of the basic substance 100% of the reaction mass decomposition production of phenol and acetone by the method (Kruglov D., Golovenko B. I. - M.: Goskomizdat, 1963). For testing used DMFC from the company Lankaster with a basic substance content of more than 98%.

Tested catalyst 10% (mass.) H3PW12O40/MCM-41 in the amount of 100 ml was loaded into the reaction part of the columns 1 and 2. For start-up and output mode setup used acetone, reagent grade brand. Mode of operation: the temperature of the saturated vapor of acetone 56,3°C for thermocouples 10 and 11 columns 1 and 2, the feed rate of acetone, 300 ml/HR pump 7 from the collection 5 in the inlet of the column 1, the bottom levels of the liquid in the columns 1 and 2 between the control labels. Technical gitaris composition (mass.) 89% of the CCP, 7% DMPC, 3% cumene and 1% of acetophenone in the amount of 50 ml/hour and the and 51.5 g/h from the volumetric burette by gravity (gravity) was applied through the pipe 6 into the stream of acetone suction pipe of the pump 7. When a volume ratio of acetone and technical hyperize 5:1 feed rate of acetone solution technical hyperize pump 7 into the inlet of the column 1 was constant at 300 ml/hour. The acetone solution technical hyperize in column 1 was received through a metal mesh distributor of fluid flow in the catalyst bed. After decomposition of the CCP in column 1 and dehydration DMFC in column 2 received after the pump 9, the reaction mass decay in the amount of 300 ml/hour. The composition of the reaction mixture decomposition (PMP) was determined by the chromatographic method. As part of the RAP, in addition to acetone, phenol, α-methylstyrene, cumene and acetophenone, other organic products and impurities not detected. In continuous mode operation received 212 g/h of acetone, 28 g/h of phenol, 3 g/h of α-methylstyrene, 1.5 g/hour hydroperoxide and 0.5 g/hour of acetophenone and 0.5 g/hour of water. The content of phenol in the reaction mass decomposition of 11.4% of the mass.

Example 2.

Getting phenol, acetone, α-methylstyrene was carried out analogously to example 1, except that the feed rate of hyperize 100 ml/hour or 103 g/hour. For the heat balance in column 1 due to thermal effect of the decomposition reaction of the CCP adjust the heat in the cubic part of the column 1 in the direction of decreasing the voltage regulator heater and regulate water in the jacket of the reaction section with a catalyst layer of columns is 1. When the volumetric ratio of acetone and hyperize 2:1 feed rate of acetone solution technical hyperize pump 7 into the inlet of the column 1 was constant at 300 ml/hour. After decomposition of the CCP in column 1 and dehydration DMFC in column 2 were obtained after the pump 9, the reaction mass decay in the amount of 300 ml/hour. The composition of the reaction mixture decomposition was determined by the chromatographic method. As part of the RAP, in addition to acetone, phenol, α-methylstyrene, cumene and acetophenone, other organic products and impurities not detected. In continuous mode operation received 191 g/h of acetone, 56 g/h of phenol, 6 g/h, α-methylstyrene, 3 g/hour of cumene and 1 g/hour of acetophenone, 1 g/hour of water. The content of phenol in the reaction mass decomposition of 21.7% of the mass.

Example 3.

Getting phenol, acetone, α-methylstyrene was carried out analogously to example 1, except that used catalyst with the formula of 20% (mass.) H3PW12O40/MCM-41 and the feed rate of technical hyperize 25 ml/hour or 25.8 g/hour. When the volumetric ratio of acetone and technical hyperize 11:1 feed rate of acetone solution technical hyperize pump 7 into the inlet of the column 1 was constant at 300 ml/hour. After decomposition of the CCP in column 1 and dehydration DMFC in column 2 were obtained after the pump 9, the reaction mass decay in the amount of 300 ml/hour. The composition of the reaction mixture decomposition (WP who) was determined by the chromatographic method. As part of the RAP, in addition to acetone, phenol, α-methylstyrene, cumene and acetophenone, other organic products and impurities not detected. In continuous mode operation received 223 g/h of acetone, 14 g/h of phenol, 1.5 g/h, α-methylstyrene, 0.7 g/hour hydroperoxide and 0.2 g/hour of acetophenone and 0.2 g/hour of water. The content of phenol in the reaction mass decomposition of 5.8% of the mass.

Example 4.

Getting phenol, acetone, α-methylstyrene was carried out analogously to example 1, except that used catalyst with the formula of 50% (wt.) H3PW12O40/MCM-41 and the feed rate of technical hyperize 60 ml/h or 62 g/hour. When the volumetric ratio of acetone and technical hyperize 4:1 feed rate of acetone solution technical hyperize pump 7 into the inlet of the column 1 was constant at 300 ml/hour. After decomposition of the CCP in column 1 and dehydration DMFC in column 2 were obtained after the pump 9, the reaction mass decay in the amount of 300 ml/hour. The composition of the reaction mixture decomposition (PMP) was determined by the chromatographic method. As part of the RAP, in addition to acetone, phenol, α-methylstyrene, cumene and acetophenone, other organic products and impurities not detected. In continuous mode operation received 198 g/h of acetone, 34 g/h of phenol, 4 g/h of α-methylstyrene, 1.8 g/hour of cumene and 0.6 g/hour of acetophenone and 0.6 g/hour of water. The content of phenol in the reaction mass razloga the Oia 14.2% of the mass.

Example 5.

For the production of phenol, acetone, α-methylstyrene from technical hyperize as a solid heterogeneous catalyst used casinomasino salt heterophilically with formula (10÷20)% (mass.) Cs2.5H0.5PW12O40/MCM-41 deposited on mesoporous silica MCM-41. For the preparation of the catalyst used heteroalicyclic H3PW12O40·nH2O and cesium carbonate. Physico-chemical characteristics of heteroalicyclic and cesium carbonate meet the standards and requirements of THE 6-09-01-744-88 and THE 6-09-01-638-80 respectively. Pre-hydrated H3PW12O40·nH2O determine the number of molecules of water of crystallization gravimetric method, by heating for 1 hour at 220°C. depending on the party acid number of molecules n=5-13. The number of water of crystallization considered in the impregnation of a silica MCM-41 heteroalicyclic H3PW12O40·nH2O from the solution in butanol. Preparation of solid heterogeneous catalysts with formula (10°20)% (mass.) Csthe 2.5H0,5PW12O40/MCM-41 was carried out according to the methodical recommendations (Makoto Misono / Chem. Commun., 2001, 1141-1152; G.D.Yadav, N.S.Asthana /Applied Catalysis A: General 244, 2003, 341-357; inorganic synthesis Manual/ edited Gbauer: Mir, Moscow, V.6, 1986, s). Education casinomasino with the is and Cs the 2.5H0,5PW12O40in mesopores of silica MCM-41 as a result of reaction between heteroalicyclic and cesium carbonate controlled quantitatively according to the scheme:

2H3PW12O40·nH2O + 2,5Cs2CO3= 2Csthe 2.5H0,5PW12O40+ 2,5CO2↑ + (2,5+2n)H2O.

The resulting catalyst was dried at 110°C during the day and then caliciviral at 300°C for 3 hours. After the catalyst was washed with acetone, reagent grade brand. and dried at 100°C for 1 hour. The resulting catalyst was determined by the content of heteroalicyclic, as well as the content of cesium and the number of its atoms. The number of cesium atoms m (0≤m≤3) in casinomasino salt heteroalicyclic (Cs)mH3-mPW12O40was calculated by the formula m=0,267·(Cs-1), where Cs is the concentration of cesium (% mass.) controlled by atomic-absorption method. Made catalysts with the formula 10% (mass.) Csthe 2.5H0,5PW12O40/MCM-41 and 20% (mass.) Csthe 2.5H0,5PW12O40/MCM-41 was tested for activity and selectivity of the decomposition of the CCP and dehydration DMFC in acetone on the mini laboratory setting. To test specifically obtain cumene hydroperoxide content of the basic substance 100% of the reaction mass decomposition production of phenol and acetone by the method (Kruglov D., Golovenko B. I. - M.: State imizat, 1963). For testing used DMFC from the company Lankaster with a basic substance content of more than 98%.

Tested catalyst 20% (mass.) Csthe 2.5H0,5PW12O40/MCM-41 in the amount of 100 ml was loaded into the reaction part of the columns 1 and 2. For start-up and output mode setup used acetone, reagent grade brand. Mode of operation: the temperature of the saturated vapor of acetone 56,3°C for thermocouples 10 and 11 columns 1 and 2, the feed rate of acetone, 300 ml/HR pump 7 from the collection 5 in column 1, the bottom levels of the liquid in the columns 1 and 2 between the control labels. Technical gitaris composition (mass.) 89% of the CCP, 7% DMPC, 3% cumene and 1% of acetophenone in the amount of 25 ml/hour or 25.8 g/h from the volumetric burette by gravity (gravity) was applied through the pipe 6 into the stream of acetone suction pipe of the pump 7. Next, the acetone solution hyperize with a constant feed rate of 300 ml/HR pump 7 received through the mesh dispenser flow in the catalyst bed of the column 1. The volumetric ratio of acetone and technical hyperize 11:1. After decomposition of the CCP in column 1 and dehydration DMFC in column 2 were obtained after the pump 9, the reaction mass decay in the amount of 300 ml/hour. The composition of the reaction mixture decomposition (PMP) was determined by the chromatographic method. As part of the RAP, in addition to acetone, phenol, α-methylstyrene, cumene and acetophenone, other about the organic products and impurities not detected. In continuous mode operation received 223 g/h of acetone, 14 g/h of phenol, 1.5 g/h, α-methylstyrene, 0.8 g/hour hydroperoxide and 0.2 g/hour of acetophenone, 0.2 g/hour of water. The content of phenol in the reaction mass decomposition of 5.8% of the mass.

Example 6.

Getting phenol, acetone, α-methylstyrene was carried out analogously to example 5, only as a solid heterogeneous catalyst used catalyst with the formula 10% (mass.) Csthe 2.5H0,5PW12O40/MCM-41 and the feed rate of technical hyperize 50 ml/hour or 51.5 g/hour. The acetone solution hyperize with a constant feed rate of 300 ml/HR pump 7 received through the mesh dispenser flow in the catalyst bed of the column 1. The volumetric ratio of acetone and technical hyperize 5:1. After decomposition of the CCP in column 1 and dehydration DMFC in column 2 received after the pump 9, the reaction mass decay in the amount of 300 ml/hour. The composition of the reaction mixture decomposition (PMP) was determined by the chromatographic method. As part of the RAP, in addition to acetone, phenol, α-methylstyrene, cumene and acetophenone, other organic products and impurities not detected. In continuous mode operation received 212 g/h of acetone, 28 g/h of phenol, 3 g/h of α-methylstyrene, 1.5 g/hour hydroperoxide and 0.5 g/hour of acetophenone and 0.5 g/hour of water. The content of phenol in the reaction mass decomposition of 11.4% of the mass.

Note the p 7.

Getting phenol, acetone, α-methylstyrene was carried out analogously to example 6, only the feed rate of technical hyperize 110 ml/hour or 113 g/hour. For the heat balance in column 1 due to the small thermal effect of the decomposition reaction of the CCP adjust the heat in the cubic part of the column 1 in the direction of decreasing the voltage regulator heater and regulate water in the jacket of the reaction section with a catalyst layer of the column 1. The acetone solution hyperize with a constant feed rate of 300 ml/HR pump 7 received through the mesh dispenser flow in the catalyst bed of the column 1. The volumetric ratio of acetone and technical hyperize of 1.7:1. After decomposition of the CCP in column 1 and dehydration DMFC in column 2 were obtained after the pump 9, the reaction mass decay in the amount of 300 ml/hour. The composition of the reaction mixture decomposition (PMP) was determined by the chromatographic method. As part of the RAP, in addition to acetone, phenol, α-methylstyrene, cumene and acetophenone, other organic products and impurities not detected. In continuous mode operation received 186 g/h of acetone, 62 g/h of phenol, 6 g/h, α-methylstyrene, 3 g/hour of cumene and 1 g/hour of acetophenone, 0.9 g/hour of water. The content of phenol in the reaction mass decomposition of 23.9% of the mass.

Example 8.

Getting phenol, acetone, α-methylstyrene was carried out nelogicno example 6, only the feed rate of technical hyperize 150 ml/hour or 154,5 g/hour. For the heat balance in column 1 because of the significant thermal effect of the decomposition reaction of the CCP adjust the heat in the cubic part of the column 1 in the direction of decreasing the voltage regulator heater and regulate water in the jacket of the reaction section with a catalyst layer of the column 1. The acetone solution hyperize with a constant feed rate of 300 ml/HR pump 7 received through the mesh dispenser flow in the catalyst bed of the column 1. The volumetric ratio of acetone and technical hyperize 1:1. After decomposition of the CCP in column 1 and dehydration DMFC in column 2 were obtained after the pump 9, the reaction mass decay in the amount of 300 ml/hour. The composition of the reaction mixture decomposition (PMP) was determined by the chromatographic method. As part of the RAP, in addition to acetone, phenol, α-methylstyrene, cumene and acetophenone, other organic products and impurities not detected. In continuous mode operation received 169 g/h of acetone, 85 g/h of phenol, 9 g/h of α-methylstyrene, 4 g/h of cumene and 1.5 g/hour of acetophenone, 1 g/hour of water. The content of phenol in the reaction mass decomposition 31,5% of the mass.

In examples 1-8 have not been observed deactivation of the catalysts. The activity and selectivity of catalysts in columns 1 and 2 are preserved, which indicates about olitely service life of catalysts for catalytic distillation.

Examples 1-8 demonstrate the effectiveness of the proposed technical solutions for the production of phenol, acetone, α-methylstyrene non-waste technologies in the solvent (acetone) decomposition of the CCP and dehydration DMFC technical hyperize in continuous isothermal mode catalytic distillation on heteroalicyclic or casinomasino salt heteroalicyclic. In addition can be easily removed from the reaction mass decomposition of useful products cumene and acetophenone. Organic waste such as phenolic resin and dangerous toxic wastewater is not formed. The proposed method for the production of phenol, acetone, α-methylstyrene and installation for its implementation by the decomposition of the CCP and DMFC technical hyperize for wasteless technology has economic and ecological effect.

1. Method for production of phenol, acetone, α-methylstyrene, including the decomposition of cumene hydroperoxide and dimethylphenylcarbinol included in the technical hyperize, in the environment of a solvent in the presence of a solid heterogeneous catalyst by catalytic distillation in a continuous isothermal mode at the boiling temperature of the solvent and recycling the solvent, the solid heterogeneous catalyst used heteroalicyclic H3PW12O40or casinomasino salt hetaeras the polyacid Cs the 2.5H0,5PW12O40deposited on the silicon dioxide and the solvent used is acetone, characterized in that as the carrier using mesoporous silica, brand MCM-41, and the decomposition of cumene hydroperoxide and dimethylphenylcarbinol carried out in two stages, the first of which is exercised by the decomposition of cumene hydroperoxide with the separation of phenol and acetone, the second - dimethylphenylcarbinol emitting α-methylstyrene, while mesoporous silica and heteroalicyclic or casinomasino salt heteroalicyclic used in the following ratio, wt.%:

heteroalicyclic10÷50
silicon dioxidethe rest,

or
asiamedia salt heteroalicyclic10÷20
silicon dioxiderest

2. The method according to claim 1, characterized in that the solvent and technical gitaris used in the following volume ratio (1÷11):1.

3. Installation for production of phenol, acetone, α-methylstyrene according to claim 1, comprising at least one reactio is but distillation unit, containing a layer of a solid heterogeneous catalyst in the form deposited on the silicon dioxide of heteroalicyclic H3PW12O40or casinomasino salt heteroalicyclic Csthe 2.5H0,5PW12O40, distillation column, having a cubic part, has two outputs and input technical hyperize solvent heater and reflux condenser, with a solid heterogeneous catalyst is in a distillation column above the bottom part, and the entrance to the filing of the technical hyperize with the solvent is above the catalyst, characterized in that it contains a second reactive distillation unit, a pump located between the first and second reactive distillation units.

4. Installation according to claim 3, characterized in that it further comprises a feeder technical hyperize with solvent, United with the first and second reactive distillation units, while the output of the first pump unit is connected to the input of the rectifying column of the second block, the outputs of reflux condensers of the first and second reactive distillation units are connected to the input feeder technical hyperize with the solvent, the output of which is connected to the input of the rectifying column of the first block, which is equipped with a cooling jacket layer TV is Gogo heterogeneous catalyst.

5. Installation according to claim 3, characterized in that the distillation column provided with a device for measuring the level of the bottom liquid, which represents a thick-walled glass tube with a control marks the minimum and maximum level of the bottom liquid, mounted on the outer side of a bottom part of the distillation column and made communicating with the cavity of the bottom part of the distillation column.

6. Installation according to claim 3, characterized in that the distillation column is equipped with a thermocouple above the solid heterogeneous catalyst.

7. Installation according to claim 3, characterized in that the distillation column is a metal tube with two metal grids, arranged perpendicular to the longitudinal axis of the pipe, one of which is designed to accommodate solid heterogeneous catalyst and has a mesh size smaller than the minimum particle size of the solid heterogeneous catalyst, and the second is designed to distribute the flow of liquid flowing in the distillation column.

8. Installation according to claim 4, characterized in that the feeder technical hyperize and solvent made in the form of a container of solvent and United with her pump, in line between tank and pump mounted nozzle for supplying a technologically advanced, the economic hyperize.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method of decomposing cumene hydroperoxide with an acid catalyst to phenol and acetone in the system of a hollow reactor with back-mixing and swirling motion of reaction products, cooling the decomposition reaction mass in a cooling heat exchanger, using a catalyst system in form of 0.3-0.5 wt % solution of sulphuric acid in acetone, while feeding the catalyst into suction line of a circulating pump in the medium of the reaction mass, regulation of residual content of hydroperoxide at the end of the back-mixing cycle using a "control decomposition tube", in which a small portion of the reaction mass is mixed with the whole amount of the acid catalyst fed into the decomposition system, decomposition of the reaction products output from the back-mixing system by heating, holding in a structured flow apparatus and stepwise reduction of acidity in said apparatus by feeding water at the end of the first quarter of the length of the apparatus and fast cooling of the reaction mixture at the output of the structured flow apparatus. The volume of the hollow reactor in the back-mixing system is equal to or greater than the volume of the inter-tube space of the cooling heat exchanger of the reaction mass, wherein a constant amount of a portion of the acid catalyst per constant amount of the reaction mass is fed into the "control decomposition tube", the remaining portion of the catalyst through the flow regulator from the temperature difference at the ends of the "control decomposition tube" is directly fed into the suction line of the circulating pump, and mixing the decomposition reaction mass with the acid catalyst at the input of the tube with structural length in order to reduce the distance from the point of contact of the decomposition reaction mass with the catalyst to the first thermocouple of the "control decomposition tube".

EFFECT: invention enables to conduct a high-selectivity process for decomposition of cumene hydroproxide.

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FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing phenol and acetone through acid-catalysed decomposition of cumene hydroperoxide in series-connected reactors in two steps at high temperature with simultaneous formation of dicumyl peroxide at the first step followed by its decomposition in a reaction medium at the second step. The process is carried out using a catalyst in form of 2-hydroxy- benzene sulphonic acid of general formula , where X and Y denote hydrogen, alkyl, arakyl, halogen, oxyalkyl, sulpho group, alkyl(2-hydroxy benzene sulphonic acid group) in amount of 0.1-1 mmol/l.

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FIELD: chemistry.

SUBSTANCE: invention relates to a method of purifying acetone obtained together with phenol during decomposition of cumene hydroperoxide. The method involves distillation of crude acetone successively in three distillation columns. Low-boiling impurities are separated in the first distillation column with addition of an alkaline reagent into the column and then extracting the remaining mixture of components in form of a bottom product and feeding it into the second distillation column for separation of high-boiling impurities and extraction of the larger portion of acetone in form of commercial-grade acetone. Content of acetone in the still of the second distillation column is kept at a level not lower than 0.5 wt % of the supply by extracting the remaining components of the mixture in form of a bottom product of the second distillation column and then feeding into the third distillation column in order to separate the remaining acetone together with the remaining low-boiling impurities, including the remaining aldehydes and feeding this mixture into the first distillation column. An additional alkaline reagent is fed into the second distillation column which enables production of acetone having permanganate oxidation time of not less than nine hours. The alkaline reagent is fed into the first distillation column in form of a 0.1-30 % aqueous solution in amount of 0.05-0.8 wt % of the supply, and an oxidative reagent is also added in form of a 0.1-30% aqueous solution in amount of 0.02-0.5 wt % of the supply in weight ratio of the alkaline reagent to the oxidative reagent between 1:0.1 and 1:100, preferably between 1:0.5 and 1:10; the alkaline reagent is also fed into the second distillation column in amount of 0.03-0.5 wt % of the supply and the ratio of the alkaline reagent fed into the first column to the alkaline reagent fed into the second column is 1:0.2, wherein the second and third columns are used at atmospheric pressure.

EFFECT: disclosed method enables production of high-quality acetone with minimal operational costs and achieving maximum possible output.

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EFFECT: wide range of obtained finished products and prevention of formation of industrial wastes.

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FIELD: chemistry.

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EFFECT: application of the methods and catalytic compounds specified above allows simplifying considerably producing phenol from cumene, allowing for simultaneous one-stage reaction for all chemical transformations required to produce high-yield cumene from acetone, benzene and hydrogen with minimum amount of secondary reactions of various reagents, intermediate compounds and products.

69 cl, 16 ex, 2 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: one of method versions is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification and possibly partial recycling into reaction zone(s) of one or several components of reaction mixture. Decomposition is carried out in presence of inert easily-boiling solvent, which contains mainly hydrocarbons, whose boiling temperature is lower than 70°C, preferably lower than 40°C, but not lower than minus 1°C, which is partially evaporated directly from reaction zone(s) and partially distilled from obtained reaction mixture, is in liquid state returned to reaction zone(s) with supporting in it (them) temperature from 1 to 70°C, preferably from 10 to 45°C. Second method version is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification. Applied is easily-boiling solvent, which after separation from reaction mixture, possibly with part of ketone, is recycled into reaction zone(s), and sulfocationite catalyst in H+ form, resistant in liquid media, containing alkylaromatic hydroperoxides, ketones, phenol and hydrocarbons in large amount, at temperatures up to 70°C, in fine-grain or coarse-grain form, possibly, in form of mass-exchange filling with size from 1.5 to 25 mm.

EFFECT: obtaining phenol and ketones without formation of large amount of by-products and resins and practically without equipment corrosion.

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FIELD: chemistry.

SUBSTANCE: cumane hydroperoxide is decomposed in presence of catalyst from processed with acid clay in order to transform cumane hydroperoxide into mass, which after decomposition contains mainly phenol and acetone, and mass reaction after decomposition is carried out in presence of cation catalyst, composed of cation-exchange resin and mercaptane promoter or promoter in form of mercaptoalkane acid in order to transform phenol and acetone in mass after decomposition mainly into diphenol A.

EFFECT: high product output with low admixture formation without necessity of stages of intermediate purification.

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FIELD: chemistry.

SUBSTANCE: cumane hydroperoxide is decomposed in presence of acid catalyst from sulfated metal in order to transform cumane hydroperoxide into mass, which after decomposition contains mainly phenol and acetone, and mass reaction after decomposition is carried out, preferably without intermediate purification, in presence of cation catalyst, composed of cation-exchange resin and mercaptane promoter or promoter in form of mercaptoalkane acid in order to transform phenol and acetone in mass after decomposition mainly into diphenol A.

EFFECT: high product output with low admixture formation without necessity of stages of intermediate purification.

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EFFECT: increased process selectivity in relatively mild conditions.

7 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of decomposing cumene hydroperoxide with an acid catalyst to phenol and acetone in the system of a hollow reactor with back-mixing and swirling motion of reaction products, cooling the decomposition reaction mass in a cooling heat exchanger, using a catalyst system in form of 0.3-0.5 wt % solution of sulphuric acid in acetone, while feeding the catalyst into suction line of a circulating pump in the medium of the reaction mass, regulation of residual content of hydroperoxide at the end of the back-mixing cycle using a "control decomposition tube", in which a small portion of the reaction mass is mixed with the whole amount of the acid catalyst fed into the decomposition system, decomposition of the reaction products output from the back-mixing system by heating, holding in a structured flow apparatus and stepwise reduction of acidity in said apparatus by feeding water at the end of the first quarter of the length of the apparatus and fast cooling of the reaction mixture at the output of the structured flow apparatus. The volume of the hollow reactor in the back-mixing system is equal to or greater than the volume of the inter-tube space of the cooling heat exchanger of the reaction mass, wherein a constant amount of a portion of the acid catalyst per constant amount of the reaction mass is fed into the "control decomposition tube", the remaining portion of the catalyst through the flow regulator from the temperature difference at the ends of the "control decomposition tube" is directly fed into the suction line of the circulating pump, and mixing the decomposition reaction mass with the acid catalyst at the input of the tube with structural length in order to reduce the distance from the point of contact of the decomposition reaction mass with the catalyst to the first thermocouple of the "control decomposition tube".

EFFECT: invention enables to conduct a high-selectivity process for decomposition of cumene hydroproxide.

2 tbl, 2 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of lowering the flash point temperature of a fixed catalyst bed during synthesis of acrylic acid through heterogeneously catalysed gas-phase partial oxidation of propylene, in which a) at the first reaction step, propane undergoes heterogeneously catalysed dehydrogenation to obtain a product gas mixture 1, b) a partial amount of components in the formed product mixture 1 which are different from propane and propylene are converted to other compounds if needed and if needed a partial amount of components of the product gas mixture 1 formed at the first reaction step which are different from propane and propylene are separated, wherein a product gas mixture 1', which contains propane and propylene, as well as compounds different from oxygen, propane and propylene, is obtained from the product gas mixture 1, and c) as a component of the initial reaction gas mixture 2 at the second reaction step, the product gas mixture 1 or 1' undergoes heterogeneously catalysed partial oxidation in the gas phase of propylene contained in the product gas mixture 1 or 1' to acrolein, where the product gas mixture 2 is obtained, and d) temperature of the product gas mixture leaving the second reaction step, if needed, is lowered through direct and/or indirect cooling and molecular oxygen and/or inert gas is added to the said mixture 2 if needed, and e) further, as an initial reaction gas mixture 3 at the third reaction step, acrolein contained in the initial reaction gas mixture 3 undergoes heterogeneously catalysed gas-phase partial oxidation to acrylic acid, where the product gas mixture 3 is obtained, and f) acrylic acid and at least unreacted propane and propylene contained in the product gas mixture 3 are separated from the product gas mixture 3 in a separation zone A an then returned to at least the first of three reaction steps, where i) the second reaction step is carried out until achieving propylene degree of conversion Up ≤99 mol % for one-time passage through the zone, and ii) the third reaction step is carried out until achieving acrolein degree of conversion UA ≥96 mol % for one-time passage through the zone. The method involves at least one separate selection for components different from propane and propylene, which contains propane and propylene in amount ≤5 vol %.

EFFECT: low temperature.

39 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: method involves a step for oxidising cyclohexane to obtain cyclohexyl hydroperoxide, a step for catalytic decomposition of cyclohexyl hydroperoxide on a heterogeneous catalyst to obtain a mixture of cyclohexanol and cyclohexanone and a step for distilling cyclohexane, carried out at high temperature and pressure. Said steps form a single circulation loop in which the reaction mixture is circulated through transfer of cyclohexane vapour from the boiler of the distillation apparatus into an oxidation reactor, as well as due to subsequent spontaneous overflow under gravitational forces of the liquid reaction mixture from the oxidation reactor to a decomposition reactor and then into the boiler of the distillation apparatus. The cyclohexane oxidation reactor lies over the cyclohexyl hydroperoxide decomposition reactor which is on the same level as or below the level of the boiler of the distillation apparatus. Conversion of cyclohexane in the oxidation zone is not more than 1.0 mol % and conversion of cyclohexyl hydroperoxide in the decomposition zone is not less than 90.0 mol %.

EFFECT: high selectivity of the cyclohexane oxidation process.

8 cl, 1 tbl, 1 dwg, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing phenol and acetone through acid-catalysed decomposition of cumene hydroperoxide in series-connected reactors in two steps at high temperature with simultaneous formation of dicumyl peroxide at the first step followed by its decomposition in a reaction medium at the second step. The process is carried out using a catalyst in form of 2-hydroxy- benzene sulphonic acid of general formula , where X and Y denote hydrogen, alkyl, arakyl, halogen, oxyalkyl, sulpho group, alkyl(2-hydroxy benzene sulphonic acid group) in amount of 0.1-1 mmol/l.

EFFECT: method enables to obtain desired products with high output while maintaining low content of hydroxy acetone in the reaction mass.

2 cl, 9 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a mixture of cyclohexanol and cyclohexanone which are intermediate products in production of polyamides nylon-6 and nylon-6.6. The method is realised at high temperature and high pressure and involves the following successive cycles: oxidation of cyclohexane - decomposition of cyclohexylhydroperoxide, wherein oxidation of cyclohexane and decomposition of cyclohexylhydroperoxide are carried out in separate series-connected reactors without intermediate separation of the aqueous phase, whereby in each separate cycle, cyclohexane is oxidised with air or an oxygen-containing gas in liquid phase in the absence of a catalyst until conversion of cyclohexane of not more than 1.5 mol %, and the cyclohexylhydroperoxide formed during oxidation of cyclohexane is decomposed on a heterogeneous catalyst in a separate reactor until conversion of not less than 90 mol %.

EFFECT: method increases overall selectivity of converting cyclohexane to cyclohexanone and cyclohexanol and also considerably reduces formation of by-products.

9 cl, 19 ex, 2 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing cyclohexanone from cyclohexane, involving the following stages: oxidation of cyclohexane to hydroperoxide of cycohexyl with oxygen in the absence of a catalyst, purification of the reaction medium by washing with water, decomposition of hydroperoxide of cycohexyl to cyclohexanol and cyclohexanone in the presence of a catalyst, extraction of the cyclohexanol/cyclohexanone mixture for separating unreacted cyclohexane and separation of products with boiling point higher than that of the cyclohexanol/cyclohexanone mixture, dehydrogenating cyclohexanol contained in the cyclohexanol/cyclohexanone mixture, in the presence of a dehydrogenation catalyst, distillation of the obtained mixture so as to obtain first run (F1) at the first stage, containing compounds with boiling point lower than that of cyclohexanone, and a last run (Q1) and distillation of the last run (Q1) to obtain a first run (F2) at the second stage, formed from cyclohexanone, and a last run (Q2).

EFFECT: obtaining highly pure cyclohexanone, suitable for use as raw material for synthesis of ε-caprolactam.

6 cl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to production of phenol, method of extracting phenol from products of splitting cumene hydroperoxide and to a device for extracting phenol from products of splitting cumene. The method of producing phenol involves the following stages: i) oxidation of cumene, obtaining a reaction mixture containing cumene hydroperoxide and unreacted cumene; ii) splitting products obtained from stage i), obtaining a mixture of splitting products containing at least phenol, acetone, hydroxyacetone, unreacted cumene and water; iii) treatment of the mixture of splitting products obtained on stage ii) through distillation, which involves separation of the mixture of splitting products into at least three fractions using a single fractional distillation stage through: putting the mixture of splitting products into a distillation column, removal of the first fraction, containing acetone, from the upper part of the distillation column, removal of the second fraction, containing phenol, from the lower part of the distillation column, and removal of the third fraction, containing at least unreacted cumene, hydroxyacetone and water, in form of an off-stream. The outlet opening of the off-stream is higher the area for putting in the mixture of splitting products into the distillation column, characterised by removal of heat from the distillation column. The section for removing heat is higher than the outlet opening of the off-stream of the third fraction.

EFFECT: increased energy efficiency of methods using old technology, while maintaining quality standards and total output of end products.

25 cl, 6 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: one of method versions is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification and possibly partial recycling into reaction zone(s) of one or several components of reaction mixture. Decomposition is carried out in presence of inert easily-boiling solvent, which contains mainly hydrocarbons, whose boiling temperature is lower than 70°C, preferably lower than 40°C, but not lower than minus 1°C, which is partially evaporated directly from reaction zone(s) and partially distilled from obtained reaction mixture, is in liquid state returned to reaction zone(s) with supporting in it (them) temperature from 1 to 70°C, preferably from 10 to 45°C. Second method version is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification. Applied is easily-boiling solvent, which after separation from reaction mixture, possibly with part of ketone, is recycled into reaction zone(s), and sulfocationite catalyst in H+ form, resistant in liquid media, containing alkylaromatic hydroperoxides, ketones, phenol and hydrocarbons in large amount, at temperatures up to 70°C, in fine-grain or coarse-grain form, possibly, in form of mass-exchange filling with size from 1.5 to 25 mm.

EFFECT: obtaining phenol and ketones without formation of large amount of by-products and resins and practically without equipment corrosion.

14 cl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: H-form of ultrastable dealuminated Y-zeolites HUSY with SiO2/Al2O3 ratio within 5 to 120 is used as catalyst. As a rule, zeolites are combined with a binding agent represented by aluminum oxide, silicon oxide or their mix. Usually the catalyst is preliminarily activated by calcination in air at 300-600°C, while the method is implemented at 20-100°C. As a rule, cumol hydroperoxide concentration in the raw mix varies within 3 to 80%, and acetone, cumol, phenol or their mix with various component ratio are used as solvent.

EFFECT: increased process selectivity in relatively mild conditions.

7 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method includes two-stage acid-catalysed decompounding of cumene hydroperoxide in series reactors under heat resulted in simultaneous generation dicumene peroxide in the first stage followed with its decompounding in reaction medium environment in the second stage. Thus any catalytic agent is not used; it is prepared in separate reactor immediately prior to introduce to the first reactor of cumene hydroperoxide decompounding by mixing sulphuric acid with phenol in ratio 2:1 to 1:1000 and keeping produced mixture at temperature 20-80°C within 1-600 minutes.

EFFECT: method allows for considerable yield reduction of hydroxyacetone.

4 cl, 7 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: method of producing phenol involves: a) oxidising cumene to obtain an oxidation product containing cumene hydroperoxide; b) splitting said oxidation product using an acid catalyst to obtain a splitting product containing phenol, acetone, hydroxyacetone and impurities; c) neutralising and washing said splitting product with an alkaline aqueous medium to form a neutralised splitting product; d) separating said neutralised splitting product via at least one distillation step to obtain at least a fraction containing phenol, and an aqueous fraction containing hydroxyacetone; e) treating said aqueous fraction with an oxidative reagent in the presence of a base to obtain an alkaline aqueous medium with low content of hydroxyacetone; f) recirculating at least a portion of said aqueous alkaline medium to the neutralisation and washing step (c) and g) extracting phenol from said phenol-containing fraction obtained at step d).

EFFECT: obtaining the desired product with efficient removal of the by-product - hydroxyacetone.

25 cl, 1 dwg, 2 ex

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