Method of decomposing cumene hydroperoxide with acid catalyst to phenol and acetone

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

 

The invention relates to the field of organic and petrochemical synthesis, in particular the production of phenol and acetone "Kukolnik" way, namely to improve the decomposition of technical gidroperekisi hydroperoxide (CHP). Technical CCP contains reactive admixture - dimethylphenylcarbinol (DMPC) and inert at the stage of acid decomposition of CPC impurities - residual cumene and acetophenone (ACP).

Decomposition GPK - exothermic reaction with the release of 486 kcal of heat per kilogram unfolded gidroperekisi cumene, so on an industrial scale, this process is carried out in water systems reverse mixing, in which thermal decomposition reaction of the CCP is perceived by circulating decomposition products GPK - reaction mass decomposition (PMP). These systems represent a closed recirculation circuit comprising the reactor (which may be hollow or reactor-heat exchanger, heat exchangers cooling the circulating reaction mass decomposition (usually water shell and tube), a circulation pump PMP and connecting piping (Kruglov B.B., Golovenko BN. Joint production of phenol and acetone. M: Goskomizdat, 1963) [1].

The decomposition process of the CCP and reactions involving by-products occur according to the scheme specified in the table of reactions (Fig 1.

Technical code of civil procedure to the flowsheet decomposition is introduced into the circulation system before the reactor in line PMP, or directly into the reactor.

In the circulation system introduces an acid catalyst (usually in the suction pipe of the circulation pump PMP), as well as various additives moderators of the decomposition process, if required by the rules of the process. Upon contact with the acidic reaction mass decomposition of the CCP is decomposed to phenol and acetone, and PMP, heated perceived warmth exothermic decomposition of the CCP, gives it to heat circulating water circulating heat exchangers and enters the suction of the circulation pump, and then again enters the reactor.

PMP continuously withdrawn from the system for further processing (usually after exchangers PMP) in an amount corresponding to the amount introduced into the reaction mass decomposition components (GCA, acid catalyst, additives). Performance (applied to the decomposition of the CCP in t/h) such circulation system does not depend on the reactor design, and depends only on the surface of heat exchangers circulating PMP, type of refrigerant for these heat exchangers and performance of the circulation pumps.

Depending on the applied reactor (hollow or reactor-heat exchanger) is the process of decomposition occurs or approaching isothermal (in the case of reactor-heat exchanger) type of process or mixed o adiabatically-isothermal (in the case of the use of the hollow reactor).

The required temperature of the process is supported by the ratio of GCA and circulating PMP, as well as the feed rate of the refrigerant in the heat exchangers. The number entered in the circulation system of an acid catalyst should ensure the completeness of the decomposition of the CCP.

One of the major characteristics of systems decomposition reverse confusion is its volume, which determines the residence time of the decomposition products of the CCP (including reactive DMFC) in the acidic environment of the RAP.

For example, if the volume of the system back-mixing (volume of the reactor, the amount of heat exchangers, the volume of the connecting pipelines) is equal to 20 m3and load the CCP equal to 10 t/h, the residence time of PMP in the acidic environment (prior to neutralization) will constitute 20:10=2 hours.

From technical sources (Zakashansky V.M. "the Mechanism of formation of dimers of alfamethylstyrene and ortho-pair cumylphenol", W-l "Catalysis in industry", No. 1/2005 [2]; U.S. patent 2757209 Obtaining phenol and alfamethylstyrene of semolinas mixture of the oxidation reaction" [3]) it is known that to reduce unwanted reactions leading to the formation of components of phenolic resin (reactions 4 and 5, figure 1), the residence time of the RAP in the acidic environment should not exceed 2-4 minutes, which may not be postign then existing process units. The minimum achievable time to stay PMP in the acidic environment in industrial conditions is 1 hour, which is far from recommended.

Stay PMP in the system decomposition has a significant impact on the selectivity of the decomposition of technical CCP. In acidic PMP in addition to the target of phenol and acetone, side alfamethylstyrene (AMS), which is also a commodity product, the formation of side reaction products: peroxide Dicumyl (MPC), cumylphenol (KF), the dimer of alfamethylstyrene (DAS) (figure 1).

While DAS and KF - components of phenolic resin, reduce commodity phenol and acetone, thereby increasing their costs [2].

Research to improve the selectivity of the decomposition process of the CCP in the reverse mixing gave the following results.

When the process of decomposition of the CCP under mild conditions (low temperature, low concentration of acid catalyst in the PMP, the presence of moderators and diluents in PMP) in the main flow reactions 1 and 3 and to a lesser extent, up to and including termination, reactions 2, 4, and 5 (figure 1). Thus, the amount of phenolic resin is not reduced, so as to reduce the output of KF and DAS abundantly compensated by the increase in the education of MPC, which in cubes rectification columns for the separation of PMP trademark products are thermally decomposed with the formation of resins, ACF, polyphenol is. The yield valuable AMC is 30-40% of capacity.

When the process of decomposition in harsh environments (high temperature, high concentration of acid catalyst, the lack of moderators and diluents) in the main flow reactions 1, 2, 4, 5 (figure 1), which leads to the same high yields of phenolic resin and low yield of AMS.

Improvement of technical and economic indicators of the decomposition process of the CCP is to increase its selectivity in relation to phenol and acetone.

The known method of stepwise decomposition of the CCP, in the system of the reactor back-mixing [3]. CCP decompose under mild conditions, achieving flow in the main reactions 1 and 3, while reactions 2, 4, and 5 (figure 1) are to a small extent. PMP, derived from the system back-mixing, subjected to short-term heat exposure and subsequent cooling to terminate the reaction, for maximum yield AMC. It does not consider the formation of MPC and its decomposition in the system rectification.

During a short heating and soaking in PMP, mainly controlled by reaction 2, reaction 4 and 5 have time to go to a small extent, and the reaction 6 (1) was not controlled, which did not allow to optimize the process.

Modern methods of acid decomposition of the CCP on the phenol is acetone solve the problem of increasing the selectivity of the process (reduce output low phenolic resin and increasing the yield of marketable products), it is by manual turning of the CCP in the products of its decomposition, but with regard to the formation and decomposition of the MPC (RF patent 2108318 "Method for production of phenol, acetone and alfamethylstyrene" [4], RF patent 2142932 "highly Selective method for production of phenol and acetone (Process FAN 98)" [5], U.S. patent 4358618 "Decomposition product of cumene oxidation [6]).

One of the main tasks of improvement of technological process is the reduction or even elimination of education components of the phenolic resin in the reactor system back-mixing, and this is achieved if at any point in the circulation circuit will be at least a small (yet safe) number of HPC.

The disadvantage of this method [5] is the danger of decomposition of the original CCP in the pipeline before entering it into the reactor, namely the insertion point in her cycle of acetone, which is a single product (without rectification) evaporation PMP, containing according to the law of Raul (Plonowski A.M. and other Processes and apparatus of chemical technology. M.: Chemistry, 1968, [7]), all the components of the PMP in the ratio of their partial pressures. This acetone to serve in the CCP dangerous.

Enterprises operating under the scheme recycle acetone, is used for this purpose are acetone, purified by distillation and send it to the mix is not in the CCP, and in-line circulation PMP.

izvestno, what PMP from the moment you enter the CCP in the reactor, passing the path from the rector through the heat exchangers, through the circulation pump to the inlet of the reactor system back-mixing, should contain a small amount of residual CPC. This residual concentration of the CCP should be strictly controlled and regulated as accurately as possible at the point of the thread PMP, close to her entrance into the reactor. This decomposition of the CCP is in the floor of the reactor and heat exchangers of the system back-mixing.

This condition is fully satisfied when using acid digestion methods GPC using "pipe control decomposition and is used as an acid catalyst solution of sulfuric acid in acetone (RF patent 2179167 "Method for production of phenol, acetone and alfamethylstyrene" [8], RF patent 2114816 "Method of decomposition gidroperekisi cumene acid catalyst to phenol and acetone" [9]).

The method described in [8], aims to improve the known methods stepwise acid digestion of the CCP to phenol and acetone, namely to increase the selectivity of the process (increasing the yield of the AMC and the reduction of the yield of phenolic resin).

The disadvantages of the method-analogue of [8] are constructive solutions:

1) In the hollow reactor POS.1 directly in the area of swirling flow is mounted stationary design,which greatly distort and inhibit rotational movement at the critical moment of its formation, reducing the efficiency of the reactor.

2) selection of the PMP from the reactor executed locally on the periphery of the single tube without averaging composition PMP cross-sectional area of the reactor, which contributes to the appearance of zones with different time PMP in the reactor (dead zones) and reduce its efficiency. This is confirmed by the invention [9], where the decomposition is carried out in the reactor with the vortex motion of the products of the reaction, and the organization of vortex motion requires (as in the tube Wound-hilsa) tangential entry of fluid into the chamber-swirl (where the chamber diameter and the diameter of the inlet is connected by the relations [4]) and the output of the swirling flow of fluid through the Central opening of smaller diameter, coaxially with the chamber turbulence. According to the law of conservation of angular momentum, the linear speed of rotation of the RAP by the diameter of the output is almost equal to the speed of input z in the apparatus, and since the diameter of the hole in the diaphragm is small, the frequency of rotation of the fluid when passing through the aperture is very high - this place is a place of education vortex motion.

3) Application for mixing RAP with the catalyst charge (CABG) (sulfuric acid solution in acetone) jet mixer worsened the sensitivity of the measurement of temperature differences AT the device, namely, the increased distance between p the pout thermocouple (in the direction z) and the feed point of a catalyst mixture in PMP, because these faucets have a large linear dimensions (GOST 8.586.4-2005 "Venturi Tubes" [10]).

The closest set of features and the achieved technical result is a method of decomposition of gidroperekisi in accordance with the patent of the Russian Federation 2114816 "Method of decomposition gidroperekisi cumene acid catalyst to phenol and acetone" [9], in which the average output AMS is 87,39% of capacity, which makes it economically attractive this process.

Strictly controlled and regulated the amount of residual CPC in the PMP prior to entering it into the reactor with minimal or even no components phenolic resin (DAS, KF) in PMP on the stage of decomposition of the CCP and synthesis of MPC, which is provided "pipe control decomposition".

Identification of the technological potential of the decomposition process of the CCP on commodity products has led to the creation of the proposed advanced technology.

The purpose of the claimed invention is to increase the selectivity of formation of phenol and acetone, and improving process control at all stages of its holding and improving the safety of this dangerous process (classification of industrial enterprises) (figure 2).

The problem is that reactive DMFC coming to acid decomposition in the composition of the technical code of civil procedure, retecal in the reactor system back-mixing (1st step), only one transformation is the conversion in the reaction of synthesis with the CCP (reaction 3, figure 1) in the peroxide Dicumyl (MPC). The 1st step will be missing components of phenolic resin - cumylphenol (KF) and the dimer of alfamethylstyrene (DAS), because for these reactions is neither AMC nor DMPC and CCP on this level is almost completely decomposed to phenol and acetone (in addition to went to the synthesis of MPC). In this case, the 2nd stage of the system will be PMP comprising phenol, acetone, MAC, ACF and cumene. The passage of the heated apparatus 6 (2) PMP on unit 7 (figure 2) MPC smoothly makes phenol, acetone and AMS (reaction 6, figure 1) As well as reaction formation cumylphenol (KF) and dimer of alfamethylstyrene (DAS) via AMC (reactions 4 and 5, Fig.1) less intensive [1], [2], than the reaction of the decomposition of MPC (reaction 6, figure 1), the process will be directed to obtain the desired phenol and acetone, as well as side AMS.

The declared objective is achieved by the fact that:

1. Decomposition of technical CCP acid catalyst in the reactor system reverse mixing using a hollow reactor is carried out at hardware design with performance conditions:

Vp≥VMTR.,

where: Vp- the volume of the hollow reactor, m3;

VMTR.- the volume of the annulus of heat exchangers, m3.

I.e. the first half of the reaction time razlozheny is carried out under adiabatic conditions, and the second half in isothermal.

As shown, the process of acid decomposition of technical CCP under adiabatic conditions contributes to a more complete reaction of the synthesis of MPC (reaction 3, figure 1) and leads to an increase in the output of the MPC at this stage. This consequently reduces the amount of unreacted DMFC in arriving at the 2nd level of decomposition of the PMP. Because the reactions of formation of KF (reactions 5 and 7, figure 1) and DAS (reactions 4 and 8, figure 1), it is preferable involved DMPC and not AMS [3], i.e. undergo reactions 7 and 8 (figure 1), and AMS obtained by acid digestion MPC (reaction 6, figure 1), low activity in reactions 4 and 5 (figure 1) [1], the decomposition of the MPC to the 2nd-speed flows with greater selectivity.

The maximum amount of adiabatic reactor is limited by the mandatory presence of residual CPC (0,1-0,3%) in PMP discharge line of the circulation pump (i.e. at any point of the cycle in the PMP must be HPC concentration not less than 0.1%). This is very important - the ratio of the volume of the reactor and the volume of the annulus is not taken into account other sources mentioned above.

2. To increase the sensitivity of the "pipe control decomposition" (TKR), controllability decomposition process of the CCP and synthesis of MPC, as well as increase the security of your process system is Birmingham reactor back-mixing, the regulation of residues of the CCP, PMP discharge of the circulating pump is performed according to the indications ΔT on TKR which is supplied with a constant amount of CABG and PMP.

The temperature difference on the pipe control decay is controlled by varying the feed part of the catalyst mixture directly into the suction of the circulation pump, bypassing the "pipe control decomposition". In TKR is constantly supplied to 0.5 tons/hour PMP with the discharge of the circulating pump and a constant amount of CABG, providing it acidity, 6 times greater than in a PMP system decomposition with back mixing. In our case this condition is ensured a constant supply of SH in TKR in the amount of 80 kg/hour. The catalyst mixture according to the testimony ΔT passing Tcrit, is also fed directly to the suction of the circulation pump, in an amount necessary to maintain the desired speed of decomposition of the CCP. When such binding TCR excluded disadvantages of monitoring ΔT inherent in the use of variable feed CABG in the tube control the decomposition described in patents [8] and [9], this increases security and selectivity of the process of decomposition and synthesis of MPC on the 1-St stage.

3. To increase the accuracy of measurement of ΔT on the pipe control decomposition" on the entrance components (PMP and CABG) is mounted vortex mixer with min the maximum linear dimension (the distance from the point of contact of the components to the first thermocouple).

Vortex mixer consists of a chamber of the swirl flow PMP entering tangentially into it by pipeline ⌀12 mm supply pipe CABG ⌀20 mm included in the camera with the pipe end and the mixing of the diaphragm with a Central hole ⌀30 mm separating chamber turbulence from the actual pipe control decomposition.

The main tube ⌀70 mm and a length of 3000 mm - provides the residence time of the mixture in the pipe about 70 seconds.

The size of the swirler is made in accordance with the recommendations of [11] and allows you to place the measuring end of thermocouple at a distance of 20 mm from the mixing of the diaphragm (i.e. 55 mm from the contact point PMP and CABG). The speed of the input z to the camera (500 l/h through the tube ⌀12 mm) 1.2 m/sec, the rotation of the PMP on ⌀70 mm with a speed of 5.6 Rev/sec (336 rpm), the same in the aperture - 13 Rev/sec (785 rpm), the linear speed of the output rotating mixture through ⌀30 mm (180 mm/sec). Thus, the time from the beginning of contact CS and PMP to approach to the first thermocouple will be:

55:180=0,31 sec.

This is 0.01% (0,31×100/3000) from the residence time of the mixture in the pipe control decomposition and no significant impact on the measurement accuracy ΔT.

4. To eliminate disadvantages in terms of organization of the rotational movement of the mixing of components (CPC and PMP) and selection of the RAP from the top of the reactor the reactor 1 oborudovanie mixer (the ratio of the diameters of the mixing chamber is known from [7]) and the known device the average selection PMP in the upper part of the reactor, consisting of a diaphragm with a cylindrical glass in its Central hole, forming a receiving pocket from which PMP is directed by gravity to the heat exchangers. The dimensions of the reactor are the following:

The diameter of the reactor 1200 mm

Pipe diameter tangential entry PMP - 200 mm

The diameter of the hole in the mixing aperture - 400 mm

The diameter of the center hole with a select device 600 mm

In the system decomposition GPK-back confusion has 3 heat exchanger (standard) apparatus with an area of 500 m2and the volume of the annulus (MTR.) at 3.3 m3each.

Thus in the system decomposition reactor (hollow) volume Vp=9.9 m3and three sequentially bound heat exchanger total area of Fabout=1500 m2and volume MTR. space VMTR=3×3,3=9.9 m3.

The literature has not been previously described manual method of decomposition gidroperekisi cumene acid catalyst in the circulating system back-mixing of the hollow reactor, in which to improve the selectivity of the process on both steps of the reaction volume of the hollow reactor and the annulus of the heat exchangers were connected would be a ratio that allows the reaction of the decomposition of the CCP in terms of adiabatic process (in the hollow reactor) for at least 50% of the total reaction time (BP is like one cycle), with conditioning for the presence of PMP residual (0,1÷0,3%) of the CCP at the end of the cycle (injection pump) control and regulation of the application process for the catalytic cycle using the "pipe control decomposition" (TKR), and temperature regulation process (measured in TKR ΔT) is performed by applying part of the catalyst directly into the RAP on the suction of the circulation pump, bypassing the TKR.

In TRC serves a constant number of CABG and PMP, providing the acidity of the mixture in TKR 6÷7 times higher than in the PMP circulation system.

To improve the accuracy of the TCR at the entrance to her PMP and CABG mounted a vortex mixer (with camera turbulence and mixing aperture) with a small linear size (the distance from the point of contact CS with PMP to the measuring head during the first thermocouple)that increases precision TKR.

The mentioned circumstances allow us to state that the proposed facility meets the first criterion characteristic of the invention is a novelty.

On the other hand a map of known characteristics taken into account the ways and characteristics of the proposed technical solution does not allow to predict the observed positive effect of increasing the selectivity of the process in the stages of decomposition of the CCP, as well as improving the accuracy and reliability of residual control is th content of the CCP, PMP (process safety), which is indicative of inventive step of the invention.

This solution can be implemented at the enterprises of organic synthesis.

The proposed method presents the flowsheet (figure 2), where:

1 - hollow reactor with tangential entry y;

2 - heat exchanger-refrigerator circulating PMP;

3 - circulation pump;

4 - capacity for preparation of a solution of sulfuric acid in acetone;

5 - pump PMP at the final stage;

6 - heat exchanger-heater;

7 is a structural unit of the stream;

8 - heat exchanger-refrigerator;

9 - the compilation of the final product of the decomposition of the CCP;

10 - pipe control decomposition;

11 - a collection of PMP for transmission to the second stage.

According to this scheme, the process of acid decomposition of technical GPC is carried out as follows. Technical CCP. containing in its composition DMFC, ACF, the residual cumene, some organic acids, is fed continuously to the bottom pricebuy part of the hollow vortex reactor 1, in the lower part of which is tangentially injected stream is cooled to 35÷45°C circulating PMPs containing 0.005÷of 0.015 wt.% (50÷150 ppm) acid catalyst (in this case, sulfuric acid).

The reactor 1 is a hollow vertical unit with camera turbulence, mixing the diaphragm and to lavim pocket for the average selection PMP from the upper part of the reactor volume, equal to the volume of the annulus of the heat exchanger-refrigerator.

It does not matter from the point of view of chemical reactions under what pressure the device works in this way he operates under atmospheric pressure.

Mix sour PMP entered the CCP, good mixing at the point of introduction into the reactor (diameter input GPK ~ 150 mm mixture will rotate with a frequency of about 600 rpm) and with the passage of the Central hole of the mixing of the diaphragm, is rotating the reactor from the bottom up and through the annular pocket of selected devices and viewing lantern enters the heat exchanger-refrigerator.

2. When passing from the bottom up of the reactor mixture PMP with GCA 3 times changes the vector of changes (inhibitory linear velocity) linear velocity: for the first time in the chamber turbulence (linear velocity decreases from the periphery to the center hole in the diaphragm), the second time from the center to the periphery when the mixing passage aperture and the third time again from the periphery to the center place center hole of the selected device.

Heat exothermic decomposition reaction of the CCP is perceived by the mass circulation PMP, and the temperature increases to 50-75°C in the upper part of the reactor. Heated PMP with some residual contents of the CCP from the top of the reactor through a sight flashlight gravity continuously supplied to the heat exchange of the IR (in this case three shell-and-tube heat exchanger 500 m 2the surface of each, tied for PMP consistently). With the passage of the heat exchanger, the residual content of the CCP is reduced (down to 0.1÷0.3%) and PMP is cooled to 35÷44°C. part of the PMP after the heat exchanger 2 in the quantity introduced into the circulation system of the source code of civil procedure, CABG and various diluents and moderators (according to regulations) drained by gravity into the collection 11 for transmission to the second stage of decomposition, and the main part - the circulation PMP - fed to the suction of the circulation pump 3 and then tangentially into the lower part of the reactor 1.

Acid catalyst (catalyst charge - CS) - acid solution in acetone 0,3÷0,5% concentration in an amount necessary to maintain the desired speed of decomposition of the CCP (usually when 0,005÷of 0.015 wt.% acid PMP) is introduced into the circulation system (into the suction pipe of the pump 3). In this part CSH - constant number - enters the suction line of the pump 3 through a special pipe 10 (trumpet controlling decomposition - TCR), which is mixed in a vortex mixer from 0.5 t/h PMP from the discharge pump 3, resulting in the concentration of PMP in this pipe is six times higher than in the circuit of system decomposition. The volume of this pipe should ensure that the residence time of the mixture of 0.5 tons/hour PMP and 80 kg/h CS for at least 1 min (n is Shem the case of this tube ⌀70, 3000 mm length). The rest of CABG (over 80 kg/h filed TKR), without passing Tcrit, is fed into the suction line of the pump 3 in a variable quantity sufficient to adjust the acidity in the circulation system, providing the residual content of the CCP, PMP on the pump 3 in the range of 0.1÷0.3 wt.%. Residual CPC present in the circulation system PMP submitted to the suction of the pump 3, with a sixfold excess of an acid catalyst in a TRC be dissolved, and the selected heat will heat the mixture in a TRC that is recorded by thermocouple as the temperature difference between the mixture at the beginning and end of pipe control decomposition". Thus it is necessary to perform the installation during the first mixture thermocouple at a minimum from the point of contact CS and y distance (in our case 20 mm from the orifice of the mixing vortex diaphragm mixing device (TKR). The sulfuric acid solution in acetone (0.3 to 0.5 wt.%) prepared in a special tank 4 where it enters the suction line of the pump 3 (80 kg/h through a pipe control decomposition, and the remainder passing Tcrit).

The number you enter in the system acid catalyst is adjusted on-line, bypassing the TKR - 10 for a given temperature difference (ΔT1) TKR.

Sufficient selectivity and process security is guaranteed if ∆ T1within 0,3÷2,1°C (which corresponds containing the s residual CPC in circulating PMP 0,04÷0.3 wt.%). It is preferable to withstand ΔT1=0,7÷1,6°C. Upon reaching ΔT1given extreme values are included alarm and lock.

Selected from the circulating system PMP, containing a residual amount of the CCP (the same that is logged on TKR) from the tank 11 by the pump 5 under pressure 2÷4 MPa is supplied to the steam heater 6 (in our case shell-and-tube four-way), where it is heated to a temperature of 100÷140°C and at this temperature in the apparatus structural thread 7 (in this case the tube ⌀350 mm and a length of 15,000 m) PMP runs for 3÷15 min (depends on temperature and concentration of acid catalyst in PMP), during which undergo decomposition reactions, EQS (reaction 6, figure 1) and dehydration residual DMFC (reaction 2, figure 1), and reactions 4 and 5 (figure 1) able to pass in a minor (especially with regard to measures taken to reduce DMFC in PMP 2nd degree) degree.

When reaching the maximum output of the AMG, which is directly dependent on the output of phenol and acetone, the reaction of 6 (figure 1) is terminated by cooling down, PMP in the refrigerator for 8, then cooled PMP comes in a collection of 9 onwards for further processing by known methods. The content of the target products in PMP is: phenol - 50-58%, acetone - 31-37%.

If necessary increase the selectivity of the process (in p the risk period) provides water supply to the unit 7 (in the amount of 0.5 to 6.0 wt.%) at a distance of 1/4the length of the tank 7 through the pipe with the holes on the pipe profile ⌀350 mm and the axes of the holes (⌀2 mm) across the axis of this tube. For additional control over the completeness of the decomposition of the MPC at the end of the apparatus are mounted two thermocouples with a spacing of 1 m for a particular (δ t2) residual MPC. Stay PMP between these thermocouples is about 1 minutes

Below are examples of the decomposition of technical CCP in the system, the corresponding shown in the drawing.

Example 1. Technical code of civil procedure, comprising: a cumene - 1.9 wt.%, dimethylphenylcarbinol of 6.1 wt.%, the acetophenone - 1.0 wt.% and Gidropress cumene - 91,0 wt.% the number 9,14 t/h is fed continuously into the reactor 1, where in the amount of 320 t/h enters sour circulation PMP with the concentration of sulfuric acid of 0.01 wt.% and a temperature of 37°C. is Heated to the decomposition of the CCP to 57°C PMP by gravity through the inspection lamp and through the heat exchanger-refrigerator 2, where it is cooled to 37°C, is fed to the suction of the circulation pump 3 and then again in the reactor 1.

Acid catalyst (in the form of 0.38 wt.% solution of sulfuric acid in acetone) in the amount of 189 kg/h is fed continuously into the suction pipe of the pump 3, and 80 kg/h of acid catalyst is pre-mixed with 0.5 t PMP from the discharge of the circulating pump in pipes the control decomposition (TKR), it is for ≈70 seconds and is also fed to the suction of the circulation pump.

The temperature difference ΔT1at the ends of the TCR (arising due to the heating of the mixture of heat decomposition of the residual amount of the CCP, PMP discharge pump 3) is 1.4°C (which corresponds to the concentration of GPC, equal to 0.18%). Part of the PMP in the number 9,38 t/h after cooler 2 through the overflow device is discharged into the container 11 where the pump 5 is supplied to the next stage of decomposition. Entering the pump 5 PMP was analyzed for content of MPC, cumene, ACF, DMPK, AMC, DAS and KF. The results are shown in table 1.

The resulting decomposition of the CCP, the reaction mixture from the tank 11 by the pump 5 pressure of 3 MPa is pumped sequentially through the steam heater 6 where it is heated to 120°C, the structural unit of stream 7, water cooler 8 where it is cooled to 40°C and flows into the collector 9 for further processing by known methods. Stay PMP apparatus 7-9,4 minutes At a distance of1/4the total length of the device 7, through pipe branched network of holes in the device 7 is fed 40 l/h of water.

Example 2. Technical code of civil procedure, comprising: a cumene - 0.7 wt.%, the acetophenone - 0.9 wt.%, dimethylphenylcarbinol - 6,45 wt.% and Gidropress cumene - to 91.2 wt.%, by the same procedure as in example 1, in the amount of 8,97 t/h type is implemented in the system of the reactor back-mixing. The temperature of the refrigerated PMP is 37°C, the temperature of the top of the reactor 1-57°C, the amount fed to the reactor recycle PMP - 320 t/h, the number you enter in the system 0,41% solution of sulfuric acid in acetone - 157 kg/h 80 kg/h of which is fed through a TKR). The content of acid in the circulating PMP 0.007 wt.%. From the system is taken 9,169 t/h PMP to the next level (collected in a tank 11).

The temperature difference on TKR (ΔT) is 2.1°C, equivalent to 0.27 wt.% CCP, PMP.

The result of the analysis of PMP with pump 5 shown in table 1.

The resulting decomposition of the CCP, the reaction mixture by the pump 5 is pumped under pressure 3 MPa sequentially through the steam heater 6 where it is heated to 120°C, the structural unit of stream 7, water cooler 8 where it is cooled to 40°C and flows into the collector 9. The residence time in the apparatus 7 and the water supply to this unit is the same as in example 1. The result of analysis of the sample from the apparatus 9 shown in table 2.

Example 3. Technical code of civil procedure, comprising: a cumene - 1.4 wt.%, the acetophenone - 1.1 wt.%, dimethylphenylcarbinol to 6.8 wt.% and Gidropress cumene - 90,7 wt.% by the same procedure as in example 1, the number of 8.95 t/h is introduced into the system decomposition. The temperature of the refrigerated PMP is 37°C, the temperature of the top of the reactor 1 58.4; the number entered into the reactor circulating PMP 30 t/h, the number you enter in the system of 0.4%solution of sulfuric acid in acetone 196 kg/h 80 kg/h through the TCR with 500 kg/hour PMP from pump 3), the content of acid in the circulating PMP 0,009 wt.%, from the system by gravity into the container 11 is selected 9,113 t/h PMP to the next stage.

The temperature difference on TKR (∆T1) is 2°, which corresponds to the residual of the CCP, PMP equal to 0.25 wt.%.

The results of the analysis of PMP from the pump 5 shown in table 1.

The resulting decomposition of the CCP, the reaction mixture by the pump 5 pressure of 3 MPa is pumped sequentially through the steam heater 6 where it is heated to 120°C, the structural unit of stream 7, water cooler 8 where it is cooled to 40°C and flows into the collector 9. The residence time in the apparatus 7 and the water supply to the unit 7 are the same as in example 1.

The result of analysis of the sample from the apparatus 9 shown in table 2.

Example 4. Technical code of civil procedure, comprising: a cumene - 1.7 wt.%, the acetophenone - 1.0 wt.%, dimethylphenylcarbinol - 6.3 wt.% and Gidropress cumene - 91,0 wt.% by the same procedure as in example 1, in the amount of 8,96 t/h is introduced into the system decomposition.

The temperature of the refrigerated PMP is 36°C, the temperature of the top of the reactor 1 is equal to 57°C, the amount introduced into the reactor 1 PMP 310 t/h, the number you enter in the system of 0.38 wt.% solution of sulfuric acid in acetone 240 kg/h (80 kg/hour of the cat is ryh filed in TKR, and the rest it directly on the suction of the pump 3), the content of acid in the circulating PMP - 0,008 wt.%, from the system are selected (overflow into the tank 11) 9,168 t/h PMP to the next stage.

The temperature difference on TKR (∆T1) is 2°, which corresponds to the residual concentration of the CCP, PMP 0.25 wt.%. The results of the analysis of samples with pump 5 shown in table 1.

The resulting decomposition of the CCP, the reaction mixture by the pump 5 pressure of 3 MPa is pumped sequentially through the steam heater 6 where it is heated to 120°C, the structural unit of stream 7, water cooler 8 where it is cooled to 40°C and flows into the collector 9. The residence time in the apparatus 7 and the feed water are the same as in example 1.

The result of analysis of the sample from the apparatus 9 shown in table 2.

When analyzing the results of the decomposition of the technical code of civil procedure to the claimed method and compared with the results of the decomposition for the prototype method [9] and [8] shows that:

1. The claimed method provides a safer and more selective process at the 1st stage, as evidenced by the high output of MPC from 86,2% to 87.6% of capacity (table 1), which is higher than that of the prototype [9] 68,7÷76,7% and also higher than that of the method [8] 66,4÷78.9%, while logically decrease the content of free DMPC in PMP.

2. The claimed method provides for the selective behaviour is th process to the 2nd stage (table 2), as can be seen from the results of the release of AMC from the potential. According to the claimed method - the average output 93,03 wt.% (92,8÷93,3). According to the method of [8] is the average output 87,39% (85,1 to 88,64). In the prototype method [9] is the average of the actual data - 80,1%, and declare 92,62%.

Thus, the stated goal is reached.

The method of decomposition gidroperekisi cumene acid catalyst to phenol and acetone in the system of the hollow reactor with back-mixing and vortex motion of the products of the reaction, the cooled reaction mass decay in the heat exchanger-refrigerator, using a catalytic system in the form of 0.3-0.5 wt.% solution of sulfuric acid in acetone, when applying catalyst in-line suction of the circulation pump in the environment of the reaction mass, regulation residual content of gidroperekisi at the end of the cycle reverse mixing using the "pipe control decomposition", in which a small portion of the reaction mass is mixed with the entire quantity of acid catalyst introduced into the system decomposition, decomposition of the reaction products selected from the system back-mixing, by heating them, soaking in the apparatus structural flow and speed reducing acidity in the apparatus through the water at the end of the first quarter of the length of the apparatus and rapid cooling of the reaction is ionic mixture at the outlet of apparatus structural flow, characterized in that the volume of the hollow reactor in the system back-mixing of equal to or greater than the volume of the annulus of the heat exchanger-refrigerator reaction mass, in the tube control the decomposition serves a constant number of parts of an acid catalyst at a constant amount of the reaction mixture, the remaining portion of the catalyst through the flow regulator from the temperature difference at the ends of the "pipe control decomposition" is fed directly into the suction line of the circulation pump, the mixing of the reaction mass decomposition with an acid catalyst at the entrance to the pipe control decay occurs in the vortex mixer with short construction length to reduce the distance from the contact point of the reaction mass decomposition with the catalyst to the first thermocouple "pipe control decomposition".



 

Same patents:

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 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.

9 cl, 2 tbl, 1 dwg, 13 ex

FIELD: chemistry.

SUBSTANCE: crude acetone is successively distilled in two distillation columns, whereby in the first distillation column low-molecular impurities are separated 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-molecular impurities and extraction of commercial-grade acetone. An alkaline reagent is fed into the second distillation column higher than the feeding point, which enables production of acetone with permanganate oxidation time of not less than 8 hours. The alkaline reagent is fed into the first distillation column in form of 0.1-30 wt % of an aqueous solution in amount of 0.05-0.8 wt % of the substance fed into the column. An oxidative reagent is also fed into the first distillation column in amount of 0.02-0.5 wt % of the substance fed into the column with weight ratio of the alkaline reagent fed into the first column to the oxidative reagent between 1:0.1 and 1:100, preferably between 1:0.5 and 1:10. An alkaline reagent is also fed into the second column higher than the feeding point in amount of 0.03-0.5 wt % of the substance fed. The weight ratio of the alkaline reagent fed into the second column to the alkaline reagent fed into the second column lies between 1:0.1 and 1:0.5. The second distillation column is used at atmospheric pressure.

EFFECT: method enables production high-quality acetone with maximum use of existing equipment and reagents, with minimum capital expenses on modernisation.

7 cl, 2 tbl, 1 dwg, 13 ex

FIELD: chemistry.

SUBSTANCE: method of processing carbon-carbonate mineral involves burning limestone in a reactor, obtaining calcium oxide, production of calcium carbide by reacting part of calcium oxide obtained from burning limestone with carbon, bringing part of the obtained calcium carbide into contact with water, obtaining acetylene and caustic lime, bringing gaseous wastes from burning limestone into contact with water to obtain carbonic acid. Limestone is burnt using heat obtained from burning part of the volume of acetylene, obtained from part of the volume of calcium carbide. At least part of the obtained acetylene is used in synthesis of ethanol and/or dichloroethane and/or ethyleneglycol and/or acetone. During synthesis of ethanol and/or dichloroethane, acetylene is reacted with hydrogen in the presence of palladium as catalyst, after which at least part of synthesised C2H4 material is reacted with water vapour, obtaining ethanol, and/or reacted with chlorine, obtaining dichloroethane. Also at least part of the obtained acetylene is subjected to hydrolysis, obtaining ethyleneglycol. Also during synthesis of acetone, part of the obtained acetylene is reacted with water vapour, where the hydrogen obtained is used in said synthesis of ethanol and/or dichloroethane and/or burnt in the burning process. Carbon dioxide obtained from synthesis of acetone is used in the process of producing carbonic acid.

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

4 cl, 1 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: method of producing cumene includes interaction of benzene with acetone and hydrogen with catalytic compound added as containing one or more zeolite in acid form or preferentially acid form, copper and, optionally, one or more element chosen from elements of groups IIIA, VIB, VIIB. Additionally the given invention concerns method of producing phenol with using cumene prepared by the method as described, catalytic compound for production cumene, and also methods of producing catalytic compound for cumene.

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.

14 cl, 1 dwg, 6 ex

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.

10 cl, 3 dwg, 4 ex

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.

10 cl, 3 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: 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: invention relates to the method of obtaining phenol and acetone by acid-catalysable decomposition of hydro-peroxide of cumene in the environment of the reaction products at elevated temperatures in one stage. In this case the process is carried out in the presence of a catalyst, prepared immediately before its introduction into the reactor for the decomposition of hydro-peroxide of cumene by mixing sulfuric acid with phenol at the ratio of from 2:1 till 1:1000 and the waiting time from mixing till putting into the reactor for the decomposition of hydro-peroxide of cumene from 1 to 600 minutes at a temperature from 20 to 80°C. As a rule, sulfuric acid has a concentration of higher than 75% or oleum is used.

EFFECT: it makes it possible to decrease the output of the by-product hydroxyacetone, improves the quality of market-grade phenol and decreases the consumption of sulfuric acid.

2 cl, 4 tbl, 4 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

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