Method of extracting isobutylene

FIELD: chemistry.

SUBSTANCE: invention relates to a method of extracting isobutylene from an isobutylene containing fraction through hydration of the isobutylene containing fraction, obtaining a tert-butanol containing fraction and its subsequent dehydration. The method is characterised by that, dehydration is done in two stages. At the first stage, temperature is kept at 90-120°C and pressure at 1-3 kgf/cm2 and concentrated isobutylene and an aqueous solution of tert-butyl and sec-butyl alcohol are extracted, from which concentrated sec-butyl alcohol and an isobutylene containing fraction, which is taken for hydration, are extracted at the second stage. Process at the second stage is carried out at temperature 100-130°C and pressure 2-6 kgf/cm2.

EFFECT: use of the given method allows for extracting isobutylene without butene or butadiene impurities, and reduction of tert-butyl alcohol loss.

1 cl, 1 tbl, 8 ex, 1 dwg

 

The invention relates to the field of petrochemicals, namely, to obtain high purity isobutylene used as a monomer for various polymeric materials.

A known method of producing isobutylene processing tert-butanol or mixtures thereof, with tert-butyl esters of fatty carboxylic acids at a temperature of 60-120°C and a pressure of less than 4.5 kgf/cm2acidic ion-exchange agents and subsequent distillation (Japan's bid No. 56-15220, IPC SS 1/20, publ. 14.02.1981). The main disadvantage of this method is the low yield of isobutylene.

A known method of separation of isobutylene dehydration of tert-butanol in the stream containing tert-butanol, water and oxidized organic compounds C1-C4. This method involves extraction of tert-butanol and oxidized organic compounds hydrocarbon solvent, separating the extract from the aqueous phase, the allocation of tert-butanol hydrocarbon solvent and dehydration selected tert-butyl alcohol with obtaining isobutylene. (U.S. patent No. 5436382, IPC SS 1/24, publ. 25.07.1995).

A known method of separation of isobutylene from isobutylester hydrocarbon mixtures by hydration at elevated pressures in the presence of an aqueous solution of an acid catalyst to obtain tert-butyl alcohol and its subsequent dehydration is the presence of inert is not miscible with water solvent. The method is characterized by the fact that the stage of dehydration is carried out at a temperature of 80-150°C. and a pressure of 1-50 MPa in the presence of inert is not miscible with water solvent, with a volumetric ratio of aqueous solution:solvent-support from 1: 0.2 to 1: 20. The solvent may be used n-hexane, benzene and other (A.S. USSR №695168, IPC SS 11/05, publ. 20.08.1996). The common disadvantage of these two methods is the need for additional separation of the solvent.

Closest to the proposed to the technical essence and the achieved result is a method of producing isobutylene by hydration isobutylester faction in tert-butanol and subsequent decomposition of the alcohol to isobutylene and water (Kirpichnikov P.A., Beresnev V.V., Popova L. / Album technological schemes the main production of the synthetic rubber industry. - L.: Chemistry, 1976, p.44). Hydration of isobutylene in tert-butanol occurs at a temperature of 90°C and a pressure of 20 kgf/cm2. A solution of tert-butanol is separated from the unreacted hydrocarbons, is subjected to concentration, degassing and sent to the second stage of dehydration. The decomposition of tert-butanol occurs in dehydrator when the temperature of the cube 110°C and a pressure of 1.5 to 2 kgf/cm2. A pair of upper dehydrator enter the condenser. Skondensirovany the th tert-butanol is returned in dehydrator, and isobutylene passes through the drop entrainment, wash the column sump, the rectification column from the heavy products and azeotropic dehydration. The result is isobutylene with 99.95%.

A significant disadvantage of this method and other methods is that tert-butanol or aqueous solutions of tert-butanol obtained by the hydration of isobutylene contained in C4hydrocarbon fractions, always contain as an impurity of the second-butyl alcohol (WBS), especially when used at the stage of hydration fractions with a high content of butenes, for example butylene-isobutilene fraction (beef). In this case, the content VBS in tert-butanol reaches more than 1 wt.% (HE Pavlov isolation and purification of monomers for synthetic rubber. - L.: Chemistry, 1987, p.131). In addition, beef contains impurities butadiene (0.5-0.7 wt.%), in the process of hydration forms butylene alcohols. At the stage of dehydration along with tert-butanol decomposition undergoes VBS and butylene alcohols, resulting in the contamination of isobutylene-butenes, predominantly butene-2 and butadiene content in the isobutylene polymerization of purity should be minimal.

When conducting dehydration under more mild conditions (temperatures below 90°C, a pressure of less than 1.0 kgf/cm2in Cuba dehydrator along with the water accumulated is moved a significant amount of tert-butanol, which ultimately leads to the loss of the tertiary alcohol due to its fly ash derived from a cube of dehydrator liquid.

The task of the invention is the production of isobutylene, not contaminated by the impurities of butenes and butadiene, and reducing the loss of tert-butanol with an aqueous phase output from a cube of dehydrator.

The problem is solved in that the separation of isobutylene from isobutylester fraction is carried out by hydration isobutylester fraction to obtain tert-butanolate fraction and subsequent dehydration in two stages, the first stage to maintain the temperature of 90-120°C and a pressure of 1-3 kgf/cm2and produce a concentrated isobutylene and an aqueous solution of tert-butyl and sec-butyl alcohol, from which the second stage secrete concentrated sec-butyl alcohol and isobutylester fraction used for hydration, and in the second stage, the process is carried out at a temperature of 100-130°C and a pressure of 2 to 6 kgf/cm2.

Synthesis of tert-butanol is carried out in the reaction-extraction apparatus by countercurrent contact isobutylester fraction of water in the presence of sulfocationites catalyst, with subsequent concentration of tert-butanol stream withdrawn from the lower part of the reactor. The process of dehydration provocat two stages. A concentrated solution of tert-butanol containing impurities VBS, is sent to the reactor-dehydrator, the middle part of which is filled with a molded selfactivity catalyst, and above and below the reaction zone are distillation zone. The original aqueous solution of tert-butanol served in the upper part of the lower distillation zone. The stream containing tert-butanol, passing the reaction zone is decomposed to isobutylene and water. Top of dehydrator output high purity isobutylene, cube - water stream that contains4the alcohols. CBM flow of dehydrator direct the power of the reactor-rectifier, in the upper part of which is placed a layer sulfocationites catalyst, where the preferential decomposition of the residual amount of tert-butanol to isobutene, which again return to the stage of hydration, and the concentration of sec-butanol. Isobutylene and kontsentrirovannyi second-butanol isolated in the form of the top ring of the reactor-rectifier.

As isobutylester fractions can be used isobutylester fraction of pyrolysis and/or dehydrogenation of isobutane and/or catalytic cracking and/or isomerization of normal butenes.

As catalysts may be used sulfonated ion-exchange resin such as KSM-2, KU-23 or mortie analogues of Amberlist 15, Amberlyst 35, Amberlyst 36, Purolite ARTICLE 175, Purolite ARTICLE 275, as well as molded catalysts, representing a composition sulfonated copolymer of styrene and divinylbenzene with a thermoplastic polymeric material is polyethylene and/or polypropylene.

Way along with high purity isobutylene allows to obtain a concentrated solution of sec-butanol, optionally extract from the aqueous layer carried away in the form of a tertiary alcohol, isobutylene and return it to the hydration. The selection of high purity isobutylene reach keeping in dehydrator temperature of 90-120°C and a pressure of 1-3 kgf/cm2that excludes receipt of sec-butanol, having a higher boiling point than that of tert-butanol in the reaction zone and provides favorable conditions for the selective decomposition of tert-butanol. Moreover, under specified conditions from a cube reactor-dehydrator deduce aqueous liquid stream with a total content of C4alcohols of 3.5-7.5 wt.% when the mass ratio of tert-butanol:second-butanol (0,85-2,5):1. The stream output from the cube of dehydrator, served in the reactor-rectifier, in which at a temperature of 100-130°C and a pressure of 2 to 6 kgf/cm2carry out the decomposition of the residual tert-butanol to isobutylene, the return on the hydration, and the concentration of sec-butanol. The process in the reactor is rectificatory at a temperature of 100-130°C, the pressure of 2-6 kg/cm2and keeping the mass ratio of tert-butanol: sec-butanol, equal of 0.85 to 2.5):1, when the total content of C4alcohols in the source stream of the reactor-rectifier in the range of 3.5-7.5 wt.%, provides preferential decomposition of tert-butanol and contributes to the accumulation of sec-butanol in the upper pursuit of the reactor-rectifier. When this cube reactor-rectifier output stream that does not contain alcohol, and return to the stage of hydration. This eliminates the accumulation of sec-butanol and butylene alcohol in the system at the expense of recycle streams.

The difference of the proposed method from the analog is carrying out dehydration of the mixture in two stages, the first stage produce a concentrated isobutylene and an aqueous solution of tert-butyl and sec-butyl alcohol, and the second stage is concentrated sec-butyl alcohol and isobutylester fraction used for hydration, which provides selective decomposition of tert-butanol with the separation of high purity isobutylene, eliminates loss of the tertiary alcohol and allows to obtain a concentrated solution of sec-butanol.

The proposed method can be carried out according to the scheme shown in the drawing as follows.

The original aqueous solution of butyl alcohols, obtained by hydration isobutylester f the shares, after stages of hydration and concentration from line 1 enters the tank E-1, where served in the upper part of the lower distillation zone of the reactor-dehydrator D-1. The upper part of the reactor-dehydrator D-1 fill selfactivity catalyst. A stream containing tert-butanol, passing through the layer of sulfonato-netic catalyst is decomposed into isobutylene and water. In the reactor-dehydrator D-1 to maintain the temperature of 90-120°C and a pressure of 1-3 kgf/cm2. A pair of isobutylene, tert-butanol and water from the upper part of the reactor-dehydrator d-1, line 2 and enter the condenser T-1, where it is cooled to a temperature of 40-50°C. the Condensed tert-butanol and water lines 3 drain into a collection of E-2, from line 4 through the heat exchanger T-2 are sent as phlegmy in the reactor-dehydrator D-1 for irrigation catalyst layer. The amount of flow supplied for irrigation in the reactor-dehydrator D-1, 0.5 to 1.0 mass parts, the amount of power. The isobutylene from the condenser T-1 gone with drops of water and tert-butanol into the separator s-1, from the bottom of which the liquid flow is directed into the collection of E-2. The isobutylene from the top of separator s-1 is directed to a condenser T-3, where it is cooled to a temperature of 30-35°C and sent to the separator S-2. The liquid phase from the separator S-2, line 5 return in tank E-1, concentrated image is tilen output line 6. The liquid flow from the cube reactor-dehydrator D-1, containing water and butyl alcohols, available on line 7 on the power of the reactor-rectifier R-1. In the upper part of the reactor-rectifier R-1 place selfactivity catalyst. The decomposition of the residual tert-butanol is carried out at a temperature of 100-130°C and a pressure of 2 to 6 kgf/cm2. When these conditions is a primary decomposition of tert-butanol. Formed pairs, mainly containing isobutylene, water and sec-butanol, with the upper part of the reactor-rectifier R-1 come through the line 8 to the condenser T-4. The condensed mixture of water and sec-butanol flows into tank E-3, from line 9 partially serves as phlegmy in the reactor-rectifier R-1, and carrying excess on line 10 output as a commodity product, containing up to 70 wt.% second-butanol. Water cube reactor-rectifier R-1 line 11 and isobutylester faction on line 12 recycle on stage hydration of isobutylene.

The invention is illustrated by the following examples.

Example 1 (the prototype).

The original aqueous solution butyl alcohol composition (wt.%): tert-butanol - 70,0, sec-butanol - 3,5, water - 26,5, in the amount of 10000 kg/h is served by line 1 in tank E-1, then in the upper part of the lower distillation zone of the reactor-dehydrator D-1. The temperature in the cube support is t equal to 110°C, pressure of 1.5 kgf/cm2. The flow from the top of reactor-dehydrator d-1, line 2 and is sent to the condenser T-1, where it is cooled to a temperature of 50°C. the Condensed liquid in line 3 flows into a collection of E-2, from where it is along the line 4 through the heat exchanger T-2 are referred to as phlegmy in the reactor-dehydrator D-1 for irrigation catalyst layer. The amount of flow supplied to irrigation, is 5000 kg/hour (0.5 mass parts, the amount of power). The isobutylene from the condenser T-1 is carried out drops of tert-butanol and water enters the separator s-1, from the bottom of which the liquid stream is output in the collection of E-2. The isobutylene from the top of separator s-1 is directed to a condenser T-3, where it is cooled to a temperature of 35°C and sent to the separator S-2. The liquid from separator S-2, line 5 return in tank E-1, concentrated pure isobutylene output line 6. The liquid flow from the cube reactor-dehydrator D-1, containing mostly water and a small amount of butyl alcohol, output line 7.

As the catalyst in the reactor-dehydrator D-1 use molded sulfonation obtained by extrusion of a mixture consisting of 30 wt. parts of polypropylene and 70 wt. parts powdered macroporous ion-exchange resin KU-23. Get the isobutylene content of the basic substance of 99.97 wt.%. The amount and composition of flows to depict what aulani in the table.

Example 2.

The original aqueous solution butyl alcohol composition (wt.%): tert-butanol - 70,0, sec-butanol - 3,5, water - 26,5, in the amount of 10000 kg/h is served by line 1 in tank E-1, thence into the upper part of the lower distillation zone of the reactor-dehydrator D-1. The temperature in the reaction zone support equal to 110°C pressure

3.0 kgf/cm2. The flow from the top of reactor-dehydrator d-1, line 2 and is sent to the condenser T-1, where it is cooled to a temperature of 50°C. the Condensed liquid in line 3 flows into a collection of E-2, from where it is along the line 4 through the heat exchanger T-2 are referred to as phlegmy in the reactor-dehydrator D-1 for irrigation catalyst layer. The amount of flow supplied to the irrigation is 5000 kg/hour (0.5 mass parts, the amount of power). The isobutylene from the condenser T-1 is carried out drops of tert-butanol and water enters the separator s-1, from the bottom of which the liquid stream is output in the collection of E-2. The isobutylene from the top of separator s-1 is directed to a condenser T-3, where it is cooled to a temperature of 35°C and sent to the separator S-2. The liquid from separator S-2, line 5 return in tank E-1, concentrated pure isobutylene output line 6.

The liquid flow from the cube reactor-dehydrator D-1, containing mainly water and 2.91 wt.% tert-butanol, to 7.25 wt.% second-butanol serves on line 7 on the power reactor is-rectifier R-1, which can withstand temperatures up to 130°C and a pressure of 6.0 kgf/cm2. The flow from the upper part of the reactor-rectifier R-1 is directed along the line 8 to the condenser T-4. The condensed mixture is collected in the tank E-3, thence by line 9 partially serves as phlegmy in the reactor-rectifier R-1, and carrying excess on line 10 output as a commodity product. Water cube reactor-rectifier R-1 line 11 and isobutylester faction on line 12 recycle on stage hydration of isobutylene. As the catalyst in the reactor-dehydrator D-1 use molded sulfonation obtained by extrusion of a mixture consisting of 30 wt. parts of polypropylene and 70 moschata powder macroporous ion-exchange resin KU-23. In the reactor-rectifier R-1 use macroporous sulfonation Amberlyst 36. Get the isobutylene content of the basic substance of 99.98 wt.%. The number and composition of the flows presented in the table.

Example 3.

Spend on technological scheme of example 2. The original thread from the tank E-1 served in the quantity of 10000 kg/h) composition (wt.%): tert-butanol - 87,2, sec-butanol and 0.3, the water is 12.5. The mode of operation of the reactor-dehydrator D-1: temperature 92°C, pressure of 1.8 kg/cm2. The number of phlegmy in the reactor-dehydrator D-1 7550 kg/hour (0,76 mass parts, the amount of power). The mode of operation of the reactor rectificado is a R-1: temperature 115°C, the pressure of 4.2 kg/cm2. The temperature in the condenser T-1 47°C in the condenser T-3 35°C. as the catalyst in dehydrator D-1 use molded sulfonation obtained by extrusion of a mixture consisting of 30 wt. parts of polypropylene and 70 wt. parts of powdered ion-exchange resin KU-2-8. In the reactor-rectifier R-1 download molded sulfonation obtained by extrusion of a mixture consisting of 30 wt. parts of polypropylene and 70 wt. parts powdered macroporous ion-exchange resin Am barlist 36. Get the isobutylene content of the basic substance of 99.98 wt.%. The number and composition of the flows presented in the table.

Example 4.

Spend on technological scheme of example 2. The original thread from the tank E-1 served in a number of 8500 kg/h) composition (wt.%): tert-butanol -78,0, sec-butanol and 1.5, water - 20,5. The mode of operation of the reactor-dehydrator D-1: temperature 90°C, pressure of 1.0 kgf/cm2. The number of phlegmy in the reactor-dehydrator D-1 8500 kg/h (1,0 mass parts, the amount of power). The mode of operation of the reactor-rectifier R-1: temperature 115°C, a pressure of 4.2 kg/cm2. The temperature in the condenser T-1 - 40°C, condenser T-3 - 35°C. In the reactor-dehydrator D-1 and the reactor-rectifier R-1 download molded cation exchange resin KU-2 FRR obtained from 30 wt. parts of polypropylene and 70 wt. parts powdered gel resin Q2-8. Get the isobutylene of 99.99% purity. The number and composition of the flows presented in the table.

Example 5.

Spend on technological scheme of example 2. The amount of flow supplied from the tank E-1, - 10500 kg/h composition (wt.%): tert-butanol - 82,0, sec-butanol - 1,2, water - 16,8. The mode of operation of the reactor-dehydrator D-1: temperature 95°C, pressure of 1.9 kg/cm2. The number of phlegmy in the reactor-dehydrator D-1 8000 kg/h (0,76 mass parts, the amount of power). The mode of operation of the reactor-rectifier R-1: temperature 125°C, pressure of 5.3 kg/cm2. The temperature in the condenser T-1 at 48°C, condenser T-3 - 34°C. In the reactor-dehydrator D-1 and the reactor-rectifier R-1 download molded sulfonation obtained by extrusion of a mixture consisting of 30 wt. parts of polypropylene and 70 wt. parts powdered gel ion-exchange resin KU-23. Get the isobutylene of 99.99% purity. The number and composition of the flows presented in the table.

Example 6.

Spend on technological scheme of example 2. The original thread from the tank E-1 served in a number 11800 kg/h) composition (wt.%): tert-butanol - 78,0, sec-butanol and 1.5, the water is 16.5. The mode of operation of the reactor-dehydrator D-1: temperature 105°C, pressure : 2.4 kgf/see the Number of phlegmy in the reactor-dehydrator D-1 7500 kg/h (mass of 0.64 parts on the amount of power). The mode of operation of the reactor-rectifier R-1: temperature 120°C,a pressure of 4.5 kgf/cm 2. The temperature in the condenser T-1 - 41°C in the condenser T-3 - 31°C. as the catalyst in the reactor-dehydrator D-1 use molded sulfonation obtained by extrusion of a mixture consisting of 30 wt. parts of polypropylene and 70 wt. parts powdered gel ion-exchange resin KU-2-8. In the reactor-rectifier R-1 download macroporous sulfonation Amberlyst 36. Get the isobutylene of 99.99% purity. The number and composition of the flows presented in the table.

Example 7.

Spend on technological scheme of example 2. The original thread from the tank E-1 served in a number of 8500 kg/h) composition (wt.%): tert-butanol - 78,0, sec-butanol and 1.5, butenylamine alcohols - 0,05, water - 20,45. The mode of operation of the reactor-dehydrator D-1: temperature 90°C, pressure of 1.7 kg/cm2.

The number of phlegmy in the reactor-dehydrator D-1 8500 kg/h (1,0 mass parts, the amount of power). The mode of operation of the reactor-rectifier R-1: temperature 115°C, a pressure of 4.2 kg/cm2. The temperature in the condenser T-1 - 41°C in the condenser T-3 - 35°C. In the reactor-dehydrator D-1 and the reactor-rectifier R-1 download molded cation exchange resin KU-2 FRR obtained from 30 wt. parts of polypropylene and 70 wt. parts powdered gel resin KU-2-8. Get the isobutylene of 99.99% purity. The number and composition of the flows presented in the table.

Example 8.

Spend on technology with the Birmingham example 2. The original thread from the tank E-1 served in a number 11800 kg/h) composition (wt.%): tert-butanol - 80,50, sec-butanol - 1,50, butenylamine alcohols - 0,12, water - 17,88. The mode of operation of the reactor-dehydrator D-1: temperature 105°C, pressure : 2.4 kgf/cm2. The number of phlegmy in the reactor-dehydrator D-1 7500 kg/h (mass of 0.64 parts on the amount of power). The mode of operation of the reactor-rectifier R-1: temperature 120°C, a pressure of 4.5 kgf/cm2. The temperature in the condenser T-1 - 41°C in the condenser T-3 - 31°C. as the catalyst in the reactor-dehydrator D-1 use molded sulfonation obtained by extrusion of a mixture consisting of 30 wt. parts of polypropylene and 70 wt. parts powdered macroporous ion-exchange resin KU-2-8. In the reactor-rectifier R-1 download macroporous sulfonation Amberlyst 36. Get the isobutylene of 99.99% purity. The number and composition of the flows presented in the table.

The proposed method allows to obtain isobutylene polymerization purity content of the basic substance is not less of 99.98 wt.%. Furthermore, the method allows to obtain a solution of sec-butanol with a concentration of not less than 58 wt.% and optionally extract from the aqueous layer carried away in the form of tert-butanol isobutylene and return it to the stage of hydration.

The table is a
Method of extraction of isobutylene
The composition of the stream, wt.%The number of threads
Example 1 (the prototype)
167121011
Isobutylene-99,971----
The butenes-0,029----
Tert-butanol70,0-of 5.75---
Second-butanol3,5-7,08--
Water26,587,17---
Flow, kg/h1000050854915---
Example 2
167121011
Isobutylene-99,982-93,46--
The butenes-0,018-6,54--
Tert-butanol70-2,91-0,42 -
Second-butanol3,5-7,25-69,99-
Water26,5-89,84-29,56100
Flow, kg/h1000051924808,3111,6484,34212
Example 3
Isobutylene-99,983-99,9--
The butenes-0,017-0,1--
Tert-butanol87,2-of 7.36- --
Second-butanol0,3-0,79-67,47-
Water12,5-91,85-32,53100
Flow, kg/h100006399,73600,3200,741,53358,1
Example 4
Isobutylene-99,999-83,7--
The butenes-0,001-16,3--
Tert-butanol78,03,1 -1,0-
Second-butanol1,5-3,6-66,50,4
Water20,5-93,3-32,599,6
Flow, kg/h85004934,53565,598,1148, 8 persons3318,6

0,05
Continuation of the table
The composition of the stream, wt.%The number of threads
Example 5
Isobutylene-99,985-83,46--
The butenes-0,01 -16,54--
Tert-butanol82,0-2,85--
Second-butanol1,2-3,06-65,0-
Water16,8-94,09-35,0100
Flow, kg/h105006429,24070,8105,2156,03809,6
Example 6
167121011
Isobutylene -99,991-82,8--
The butenes-0,009-17,2--
Tert-butanol82,0-1,85-1,3-
Second-butanol1,5-3,88-58,70,09
Water16,5-94,27-40,099.91 per
Flow, kg/h118007259,54540,573.5265,74197,8
Example 7
167121011
Isobutylene-99,998-82,57--
The butenes-0,001-16,50--
Butadiene-1,30,0008-0,93--
Tert-butanol78,0-3,15-0,91-
Second-butanol1,5-3,62-66,70,09
Butenylamine alcohols-0,12-2,05-
Water20,45-93,11-30,3499.91 per
Flow, kg/h85004940,03560,096,7146,53316,8

Continuation of the table
The composition of the stream, wt.%The number of threads
Example 8
167121011
Isobutylene-99,988-72,5--
The butenes-0,01-of 17.5--
Butadiene-1,3-0,0015-10,0--
Tert-butanol80,50-1,75-1,20
Second-butanol1,50-3,90-60,100,1
Butenylamine alcohols0,12-0,31-0,180,07
Water11,88-94,04-38,5299,83
Sweat is to, kg/h118007270,04520,078,5281,04160,5

The method of separation of isobutylene from isobutylester fraction by hydration isobutylester fraction to obtain tert-butanolate faction and its subsequent dehydration, characterized in that the dehydration is carried out in two stages at the first stage to maintain the temperature of 90-120°C and a pressure of 1-3 kgf/cm2and produce a concentrated isobutylene and an aqueous solution of tert-butyl and sec-butyl alcohol, from which the second stage secrete concentrated sec-butyl alcohol and isobutylester fraction used for hydration, and in the second stage, the process is carried out at a temperature of 100-130°C and a pressure of 2 to 6 kgf/cm2.



 

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8 cl, 2 tbl, 1 dwg, 1 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to treatment of C5-hydrocarbons in order to remove cyclopentadiene impurities, which process may be, in particular, used in rubber production industry when producing hydrocarbon monomers applicable in stereospecific polymerization processes. Treatment of hydrocarbons is accomplished with cyclohexane in presence of organic solvent and alkali catalyst, after which C5-hydrocarbons are separated from reaction products via rectification. Organic solvent is selected from alkylene glycol monoalkyl ethers including their mixtures taken in amounts 0.5 to 5.0 wt % based on C5-hydrocarbons.

EFFECT: increased degree of cyclopentadiene extraction at lower reagent consumption.

8 cl, 1 tbl, 23 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: crude alpha-olefin is heated, raw vinylidene olefins are isomerized in the presence of catalyst and alpha-olefin is separated from isomerized vinylidene olefin by rectification. Separation of alpha-olefin is carried out for at least two successive steps at similar temperatures on top of vat and reducing pressure of rectifying column at each following step. Condensed phase removing from top of the rectifying column at previous step is fed to feeding zone of the following step and the rectifying column at top and vat section is sprayed. For spraying the top section of column the condensed phase removing from the top of rectifying column at the same step is used and for spraying the vat section of column the vat liquid of rectifying column at the same step is used. Separated alpha-olefin is purified additionally from oxygen-containing impurities by adsorption up to polymerization degree of purity. Raw heating, isomerization, separation and adsorption are carried out in atmosphere in inert gas. The unit used for treatment of alpha-olefin includes reactor for isomerization of vinylidene olefins in raw, rectifying column wherein feeding zone is joined with reactor outlet and wherein alpha-olefin of high purity degree is removed from the column top. The unit includes also at least one rectifying column for additional treatment of alpha-olefin of high purity from isomerized vinylidene olefins and adsorption column for separation of oxygen-containing impurities in alpha-olefin of high purity wherein the column inlet is joined with the top outlet of the last rectifying column used for additional treatment of alpha-olefin of high purity and outlet is used for removing alpha-olefin of the polymerization purity degree. Invention provides enhancing quality of the end product.

EFFECT: improved method for treatment.

8 cl, 1 dwg, 1 ex

The invention relates to petrochemistry, namely the production of oligomers of propylene by oligomerization of propylene in phosphoroclastic catalysts and the method of purification of oligomers of propylene

The invention relates to the petrochemical industry, for production of high-purity benzene, used in the petrochemical syntheses

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of selective isolation of recycling flow, which contains dimethyl ester (DME), from flow, which leaves zone of methanol conversion into olefins (MTO), where said leaving flow contains water, methanol, DME, ethylene, propylene, C4-C6-olefins. Claimed method includes stages: (a) cooling and separation of at least part of leaving flow into liquid flow, which contains methanol and DME, liquid hydrocarbon flow, which contains methanol, DME and C2-C6-olefins, and vaporous hydrocarbon flow, which contains DME, methanol, ethylene and propylene; (b) distillation of DME from at least part of liquid hydrocarbon flow, separated at stage (a) in zone of DME distillation, functioning in conditions of distillation, efficient for formation of vaporous main flow, which contains DME, methanol, ethylene and propylene, and liquid hydrocarbon bottom flow, which contains C4-C6-olefins; (c) mixing of at least part of vaporous hydrocarbon flow, separated at stage (a), with at least part of main vaporous flow, produced at stage (b), with formation of enriched DME vaporous flow of light hydrocarbons; (d) supply of formed enriched with DME vaporous flow of light hydrocarbons into zone of primary absorption of DME, where said vaporous flow is brought in contact with methanol-containing selective with respect to DME solvent in conditions of wet purification, which allows to form (1) liquid bottom solvent flow, containing methanol, DME, water and substantial and undesirable amount of ethylene and propylene, and (2) main vaporous flow of product, enriched with light olefins and depleted of DME; (e) directing of at least part of liquid bottom flow, separated at stage (d), into zone of light olefins distillation, functioning in conditions of distillation, efficient for distillation of at least considerable part of ethylene and propylene, contained in liquid bottom flow, without distilling from there any considerable part of methanol, which results in formation of main flow of distillation section, containing DME, ethylene and propylene, and liquid bottom flow, containing DME, methanol, water and light olefins in amount reduced in comparison with amount of light olefins in liquid bottom solvent flow, supplied to this stage, and (f) recycling of at least part of liquid bottom flow, separated at stage (e) into zone of conversion MTO, thus selectively introducing to it additional oxygenated reactants.

EFFECT: reduction of undesirable increase of C2 and C3-olefins in recycling DME flow.

10 cl, 4 tbl, 2 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of obtaining 2-methyl-2-butene from isopentane, including gas phase dehydrogenation of isopentane in the dehydrogenation zone, extraction of the C5-fraction from contact gas, mainly consisting of isopentane, tert pentanes, isoprene impurities and other hydrocarbons and obtaining a stream from it, mainly consisting of 2-methyl-2-butene, with use of a liquid phase isomerisation catalyst in a C5-fraction 2-methyl-1-butene in 2-methyl-2-butene and distillation. The method is characterised by that, the above mentioned C5-fraction, possibly containing extra piperylene and 2-pentene, directly or after distillation from the larger part of 2-methyl-2-butene, undergoes liquid phase hydroisomerisation in the presence of a solid catalyst, containing group VIII metal(s), capable of simultaneous catalysing hydrogenation of pentadienes, isoprene and possibly, piperylenes, and positional isomerisation of tert pentenes, preferably with subsequent additional isomerisation of 2-methyl-1-butene in 2-methyl-2-butene on a sulfocationite catalyst, and distillation with output of a distillate stream of mainly isopentane, containing not more than 1.0% mass, preferably not more than 0.2% mass of pentadiene(s), which are mainly recirculated in the hydrogenation zone, and output from the lower part of the recirculation stream of mainly 2-methyl-2-butene with impurities of n.pentane and possibly 2-pentenes. The invention also pertains to the method of obtaining isoprene from isopentane, which involves reaction of 2-methyl-2-butene, obtained from gas phase dehydrogenation of isopentane, with hydroperoxide with further conversion of the oxide or products of hydroxylation in isoprene.

EFFECT: obtaining 2-methyl-2-butene and isoprene from isopentane.

13 cl, 8 ex, 2 tbl, 3 dwg

FIELD: industrial organic synthesis.

SUBSTANCE: production of styrene is effected via gas-phase dehydration of 1-phenylethanol at elevated temperature in presence of dehydration catalyst including molded particles of alumina-based catalyst having BET surface area 80 to 140 m2/g and pore volume (Hg) above 0.65 ml/g.

EFFECT: reduced amount of by-products and prolonged service cycle of catalyst.

3 cl, 1 tbl, 5 ex

FIELD: one-stage production of isoprene.

SUBSTANCE: proposed one-stage production method includes continuous or cyclic delivery of isobutylene and/or tert-butanol, formaldehyde and water to aqueous acid solution and interaction of reaction mixture at distillation of mixture containing isoprene to be produced, water, unreacted starting materials and other low-boiling components from reaction mixture beyond reaction system where said reaction is conducted at regulation of concentration of high-boiling byproducts which are accumulated in said reaction mixture at interval of from 0.5 to 40 mass-%.

EFFECT: enhanced efficiency.

10 cl, 2 dwg, 1 tbl, 13 ex

FIELD: chemical industry; methods of production of the pure isobutene out of the isobutene-containing mixture.

SUBSTANCE: the invention is pertaining to the method of production of the pure isobutene out of the isobutene-containing mixture predominantly - out of hydrocarbon С4 with usage of the catalysis by the strong-acid cationite(s) including the liquid-phase interaction of the isobutene with the water at the temperature of from 60 up to 130°С in one or several sections at the stage of hydration, delamination of the being withdrawn from it stream(s), distillation of the unreacted hydrocarbons С4 from the hydrocarbon layer, decomposing of the tret-butanol in the section(s) at the stage of dehydration, separation of the formed isobutene from the water and its) purification and characterized by that isobutene and the total amount of the returned from the stage of dehydration fresh water is fed in the section of hydration in the total molar ratio from 1:0.4 up to 1:20, and it is preferential from 1:1 up to 1:5, in the straight-flow or bubbling mode in the absence of the emulsifier hydrate from 30 up to 97 % of isobutene. From the stage of the hydration in the stage of the dehydration at least one-third of the produced tret-butanol is fed in the stream, separated by the rectification from the layer of the unreacted hydrocarbons and containing from 5 up to 30 mass % of the water, and, possibly, the rest amount - in the stream of the water layer, at the total content of the different, than the isobutene, the hydrocarbons not exceeding their admissible quantity in the target isobutene, and from the stage of the dehydration the water at least partially is returned into the stage of the hydration. The presented method requires the low power input and the low metal input.

EFFECT: the invention ensures the low power input and the low metal input.

14 cl, 2 dwg, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of styrene. At the first step the method involves interaction of ethylbenzene hydroperoxide with propene in the presence of catalyst to yield propylene oxide and 1-phenylethanol followed by separate treatment of reaction flow and removing propylene oxide. At the second step the method involves interaction of 1-phenylethanol-containing distillate with a heterogenous dehydration catalyst at temperature 150-320°C to obtain styrene. Distillate contains 0.30 wt.-%, not above, compounds of molecular mass at least 195 Da. Invention provides decreasing the content of by-side compounds in styrene and to enhance it's the conversion degree.

EFFECT: improved method of synthesis.

3 cl, 3 tbl

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides a method for processing methanol into dimethyl ether and liquid hydrocarbons, the latter being used as high-octane components of gasolines Ai-92, 95. Processing comprises contacting of raw material, in at least one step, in at least one reactor containing catalyst: Pentasil-type zeolite and binder, followed by cooling resulting products, condensation and separation thereof to isolate methanol conversion hydrocarbon gases, water, and desired products, after which cooled hydrocarbon gases are recycled to methanol conversion stage in at least one reactor. Catalyst is characterized by SiO2/Al2O3 molar ratio 20-100, content of sodium oxide not higher than 0.2%, and additionally contained silicon dioxide and zirconium dioxide at following proportions of components: 1.0-15.0% silicon dioxide, 1.0-5.0% zirconium dioxide, 20-70% zeolite, and binder - the balance.

EFFECT: increased yield of desired products and improved performance characteristics of catalyst.

4 cl, 5 tbl, 18 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of alkylaryl hydroperoxides useful as starting material in production of propylene oxide and alkenylaryl. Process of invention comprises following stages: oxidation of alkylaryl compound to form reaction product containing alkylaryl hydroperoxide; contacting at least part of reaction product with basic aqueous solution; separation of hydrocarbon phase containing alkylaryl hydroperoxide from aqueous phase; containing at least part of above hydrocarbon phase with aqueous solution containing waste water, said aqueous solution containing less than 0.2% alkali metal and/or salt (determined as ratio of metal component to total amount of solution); and separation of hydrocarbon phase from aqueous phase. By bringing at least part of above hydrocarbon phase containing alkylaryl hydroperoxide into interaction with propylene and catalyst, alkylaryl hydroxide and propylene oxide are obtained. At least part of propylene oxide is then separated from alkylaryl hydroxide. Dehydration of at least part of alkylaryl hydroxide results in formation of alkenylaryl.

EFFECT: reduced amount of contaminating by-products in alkylaryl hydroperoxide preparation stage.

8 cl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: embodiments of invention are accomplished via liquid-phase dehydration of methyl phenyl carbinol-containing feedstock in presence of acid-type catalyst in column-type reactor-rectifier comprising still portion, built-in heat-exchanger, and rectification portion, volume of still portion constituting 80% of built-in heat-exchanger volume. Temperature of till portion of reactor-rectifier is 140-205°C and temperature in rectification portion 130-180°C. Advantageously, methyl phenyl carbinol-containing feedstock is supplied to and/or under built-in heat-exchanger and catalyst or mixture of catalyst with feedstock and/or still product is supplied to still portion at mixing. Linear velocity of reaction mass vapors within free cross-section of reactor is 0.05 to 0.9 m/s, residence time of styrene in reaction zone 0.05 to 50 sec, and residence time of still product in reactor 5 to 500 h.

EFFECT: increased conversion of feedstock and final product formation selectivity.

5 cl, 14 ex

The invention relates to a method for producing olefin vapor-phase dehydration of alcohols in the presence of a catalyst at elevated temperature

FIELD: chemistry.

SUBSTANCE: invention refers to method of isobutylene production by decomposition methyl-tertiary-butyl ether with heterogeneous catalyst at raised temperature and pressure, characterised that catalyst is multi-purpose synthetic zeolite NaX, while process is enables at atmospheric pressure with water vapour with observing the conditions as follows: temperature 200-250°C, volumetric MTBE feed rate 1.0-2.0 h-1. These conditions ensure minimal generation of MTBE decomposition by-products.

EFFECT: MTBE conversion per run is 96-99% with isobutylene selectivity at least 99%.

1 cl, 3 tbl, 9 ex

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