SU1133253A1 - Process for preparing cyclohexadiene-1,3 or methylcyclohexadienes-1,3 - Google Patents

Abstract

1. METHOD FOR OBTAINING CYCLOHEXADIENE-1, 3 OR ISETH1 CYCLOGEXEX-ENOV-1,3 by liquid-phase oxidation of the corresponding cycloolefin with oxygen in the presence of cumene hydroperoxide, followed by dehydration of the resulting oxy-products on an oxide catalyst at elevated temperature, will be treated with a non-conducting flow, and then the flow will be treated with a non-conducting flow, and then, the application will be treated with a non-conducting flow, and then the flow will be treated with a non-conducting flow, and then the flow would be treated with a non-conducting flow, then the flow would be treated with a non-conducting flow, then the flow would be treated with a non-absorbent, one would be treated with a non-conducting flow, and the flow would be treated with a non-absorbing, cyclohexene-ENOV-1, 3 or 3 The yield of the target products and the process technology simplification, nor the dehydration is directed directly to the reaction mixture, oxidation. A mixture of natural clinoptilolite and bentonite is used as an oxide catalyst with the following component content, wt%: Natural clinoptilolite 70-87 Bentonite Up to 100 2 The method according to claim 1, wherein the dehydration is carried out at a temperature of 240-300 ° C. he ate with

Description

The invention relates to the preparation of conjugated six-membered cyclic dienes, in particular cyclohexadiene 1, 3 or methylcyclohexadienes-1,3, which, due to the presence of a conjugate double bond, can be used as a raw material for the production of high-density components of jet fuels, polymers, copolymers, oligomers5 hardeners of epoxy resins and other useful products and intermediates used in various areas of the national economy. A known method for the preparation of cyclo-sadien-1,3 is performed by oxidative dehydrogenation of cyclohexene in the presence of a Cr-Ca-Ni-phosphate catalyst at 500-520 ° C. The molar ratio cyclohexene: water vapor: oxygen is 1: 10: 1. The yield of the target product reaches 21.2% with a cyclohexane conversion of 47.3%. As a side product, benzene is formed in an amount up to 26%. The selectivity of the process for cyclohexadiene-1,3 reaches 44. The disadvantages of this method are the low yield of cyclohexadiene-1,3 (21.2%), the formation of a large amount of benzene by-product (up to 26%), which leads to an irretrievable loss of cyclohexene, as well as stringent process conditions (temperature 500520 ° C). There is also known a method according to which cyclohexadiene-1,3 is obtained by oxidative dehydrogenation of cyclohexene over manganese ferrite (Fe: Kn 2: 1) at 500-520 ° C and the molar ratio of cyclohexene: water vapor: oxygen - 1: 20: 1. The reaction time is 1.5 hours. The cyclode sadiene-1,3 cycle is 19.5-23.8% with a cyclohexene conversion of 36.7-49.6, v ... The amount of benzene forming is 11.4 - --- 19.0%. The selectivity of the process varies between 47-63.8% 2. The disadvantages of this method are also low yield of the target product (19.5-23.8%), the formation of a significant amount of benzene (11.4-19%) and the need for high temperature (500-520 ° C) to carry out the process. A known method of producing methylcyclohexadiene-1, 3 by liquid-phase oxidation of individual isomers of methyl cyclohexene at 90-105 with oxygen in the air, with an air flow rate of 18 l / h per 300 g of load and duration of experiments for 6 h, followed by the reduction of the oxidate and the release of methylcyclohexaol from the oxidate its dehydration over - - aluminum oxide at 200-300 C and a space velocity of 0.5. The yield of methyl cyclohexen of yen-1, 3 under these conditions is 21.8-28.0% on the initial and 70-75% on the converted methylcyclohexene 3J. The disadvantages of this method are the multistage process (oxidation of methyl cyclohexene isomers, reduction of hydroperoxides formed, separation of methyl cyclohexanols from a hardly separated mixture of hydroxy products and dehydration in the presence of alumina of the active form), low yield of the target product (21.8-28.0%), and the formation of a large number of coke deposits on the catalyst surface, leading to its rapid deactivation within 2-2.5 hours. The closest to the invention in its technical essence is the method of cyclohexadiene-1,3 for liquid phase oxidation of cyclohexene with atmospheric oxygen at 90-100 ° C and 6-10 aiM pressure in the presence of cumene hydroperoxide followed by dehydration of oxidate oxidized products (oxyproducts) above y-alumina at about 300 ° C and a space velocity of 0.5 in the presence of crystalline iodine at the boiling point of the oxidate. The yield of cyclohexadiene-1, 3 under the specified conditions is 11-12% for taken and 4550, 2% for incremental cyclohexene 4. The disadvantages of this method are the low yield of cyclohexadi 11/41 ena-1,3 (.11-12% ), low selectivity of the process (45-50.2%), preliminary separation of oxidate from the composition of oxidation products, requiring the use of additional technological units, as well as catalysts for dehydration of oxyproducts (f-oKHCb aluminum and crystalline iodine) used in this method quickly lose its activity as a result of coxot accumulation on their surface, and the regeneration of spent catalysts requires considerable energy in the process.

The purpose of the invention is to increase the yield of target products and simplify. process technology.

This goal is achieved in that according to the method of producing cyclohexadiene-1,3 or methylcyclohexadienes-1, 3 by liquid-phase oxidation of the corresponding cycloolefin with oxygen in the presence of cumene hydroperoxide, followed by dehydration of the oxygenate on the oxide catalyst at elevated temperature, the reaction is directed to the dehydration oxides and as an oxide catalyst use a mixture of natural clinoptilolite and bentonite with the following content of components, May.%:

Natural clinoptilolite 70-87

Bentonite up to 100

. In addition, the dehydration is carried out at a temperature of 240-300 ° C.

The catalyst is prepared by mixing 70-87 wt.% Zeolite composition, wt.%:

SiO 65.9;

12.2; ReaOz. 1.0;

FeOO, l8; MgOO, 57; Sar4.05; Ti020.09; KajO 2.55; Kj.O 1.18; HjO 11.45, COj 1.0 and 13-30 wt.% Bentonite composition, wt.%: SiOj 49.8; Al2, 5; FejOj 2.7; MgO 3.8; TiOj 0.3 CaO 2.3;

kjO 1,2; Na20 0.6; SO 0.4; H, 0 20.4

After threshing and mixing, the catalyst is formed into granules with a size of 3-4 mm. The degree of crystallinity of the obtained catalyst is -56.0-69.6 wt.%, Depending on the content of clinoptilolite in it.

The method is carried out as follows.

Cyclohexene or methylcyclohexene, taken in an amount of 1 mol (82 g of cyclohexene or 96 g of methyl cyclohexene) is subjected to liquid phase oxidation in the presence of 0.5 wt.% Cumene hydroperoxide at 90-105 C, atm pressure, air flow rate 0.3-0 4 l / min and the duration of 7h. The yield of hydroxy products during the oxidation of cyclohexene and methylcyclohexene is 38% and 68.9%, respectively (the composition is given in the examples). Conversion of the original cyclohexene in the oxidation of 37.4%, and methylcyclohexenes 54.8%.

Then, the resulting oxidate is directed to dehydration in a flow system over a fixed bed of the specified catalyst with a degree of crystallinity of 56.0-69.6 wt.%, Specific surface area 24-30, bulk density 0.45-0.50 g / cm without prior reduction. and selection | hydroxy compounds from the oxidation reaction mixture. The catalyst in the amount of 20 ml is placed in the reactor and heated to “240-300 C. After the temperature has stabilized, 20 ml of cyclohexene or methylcyclohexene oxidate are fed into the reactor using a micro-dosing unit with a volume rate of 0.5-1.0 h.

Liquid reaction products are collected in cooled receivers and, after water separation and drying, are analyzed by GLC. The oxidation products contained in the oxidate composition are converted into cyclohexadiene-1, 3 and methylcyclohexadiene, 3, respectively, according to the following scheme:

R

OfHgO + 2H, 0

where R N,

The analysis carried out by gas-liquid chromatographic method shows that the resulting catalyst during dehydration of cyclohexene oxidate consists of cyclohexadiene-1.3 recycle cyclohexene, oxo compounds and benzene, and in dehydration of methyl cyclohexene isomer oxidate from a mixture of methyl cyclohexadiene-1 isomers, recycled methylcyclohexene from isomers of methyl cyclohexadiene-1, 3, and methylcyclohexene isomers from methylcyclohexene isomers from isomers of methyl cyclohexadiene-1, 3, and methylcyclohexene isomers from methylcyclohexene isomers from isomers of methyl cyclohexadiene-1, 3; and toluene Methylcyclohexadiene-1,3. consists of the following isomers, wt.%: 29,130, 5 - 1-methylcyclohexadiene-1,3; 31.7-37.9 - 2-methylcyclohexadiene-1 33.0-38.1 - 5-methylcyclohexadiene1, 3. The yields of cyclohexadiene-1,3 and methylcyclohexadiene-1,3 are 25.9-33.3% and 42.7-48.8% for the starting cycloolefins, and the selectivity of the process is 62.7-73.0% and 70.0-83.4% for converted cyclohexene and methylcyclohexene, respectively. The content of cyclohexadiene-1,3 or methylcyclohexadiene-1,3 in the catalyzate is also determined using maleic anhydride. The target products, cyclohexadi, en-1,3 and methylcyclohexadiene-1,3, are separated from catalysate as a dinar by dimerizing catalysate and atmospheric vacuum distillation of unreacted cyclohexene (or methylcyclohexene) and cyclohexadiene-1 dimer (or methyl cyclohexadiene-1 , 3) with the subsequent de-dimerization of dimers. After cyclohexadiene-1, 3 or methyl cyclohexadiene-1 isomers, 3, cyclohexene luiK isomers, methyl cyclohexene isomers are returned in the process of liquid-phase oxidation, and unreacted hydroxy products are returned to the dehydration process. Example 1. For the oxidation reaction cyclohexene 82 g (1 mol) and cumene hydroperoxide 0.4 g are taken. The experiment was performed at a temperature, a pressure of 6 atm, an air supply rate of 0.3-0.4 l / min, and a duration of 7 hours. An oxidate of 88.5 g is obtained. The composition of the oxidate is according to GLC-analysis, wt% (g): Cyclohexene-1-ol-C 31.5 (27.9) Cyclohexene oxide 5.0 (4.5) i Hydroperoxide cyclohexene 3, 2 (2.8) Cyclohexene-.1-one-C 2.3 (2.0) Return cyclohexene 58.0 (51.3) The content of hydroxy products in catalyzate is 42.0 wt.%;.%. The yield of hydroxy products - 38 mol.% On the original cyclohexene. Conversion of cyclohexene 37, 4 wt.%. For the dehydration reaction of cyclohexene oxidate (the content of hydroxy products is 42.0 wt.%) 20 ml (17.4 g) and the catalyst composition are taken, wt.%: Natural clinoptilolite 87, bentonite 13; degree of crystallinity 69.6% (A) - 20 ml. Conduct the experiment at a temperature of 300 ° C, flow rate, feedstock 1, duration 60 minutes. Get catalyzate 16 g (91.9 wt.% From the original). The composition of the catalyzate according to GLCHANALYSIS, wt.% (G): Methylcyclopentene 1,5 (0,2) Cyclohexene 55,0 (8,8) Cyclohexadiene-1,3 33,5,5 (5,4) Benzene 4,4 (0, 7) Hydroxy products 5.6 (0.9) The con-version of cyclohexene is 45.7%. The selectivity of the process for cyclohexadiene-1, 3 is 73.0% for the converted cyclohexene. The output of cyclohexadiene-1, 3 - 33.3 wt.% On the original cyclohexene. PRI me R. 2. For the dehydration reaction, cyclohexene oxidate obtained according to example 1 is taken (the content of hydroxy products is 42.0 wt.%, 20 ml (17.4 g) and the catalyst composition, May 7,: natural clinoptilolite 80, bentonite 20; degree of crystallinity 64, 0% (B) - 20 ml. Conducting the experiment at a temperature, the bulk feed rate of 0.5 h, the duration of 120 minutes. Receive catalyzate 16.2 g (93.1 wt.% From the original)., The composition of the catalyzate according to GZHKhANaliz, wt.% (G): Methylcyclopentenes 3.0 (0.5) Cyclohexene 54.7 (8.9) Cyclohexadiene-1,3 29.8 (4.8) Benzene 6.4 (1.0) Hydroxy products 6 , 1 (1.0) Cyclohexene conversions leaves 45.0%. The selectivity of the process for iclohexene is 1.3-62.7% for the converted cyclohexene. The yield of cyclohexadine-1, 3 is 29.6% by weight for the initial cytohexene. Example 3. Take for the ehydration reaction cyclohexene oxide, prepared according to example 1 (content of 71 hydroxy products 42 wt.%), 20 ml (17.4 g) and catalyst composition, wt.%: natural clinoptilolite 70, bentonite 30; degree of crystallinity 56% (B) - 20 ml. The experiment was conducted at a temperature of 270 ° C, a volumetric feed rate of 0.5 m, and a duration of 120 minutes. Get catalyzate 16.2 g (93.1 wt.% From the original). The composition of the catalyzate according to GLCHANALYSIS, wt.%. (G): Methylcyclopentenes 0.5 (0.1) Cyclohexene 60.2 (9.7) Cyclohexadiene-1.3 25.7 (4.2) Benzene3.1 (0 , 5) Hydroxy products 10.5 (1.7) Cyclohexene conversion was 39.8%. The selectivity of the process on cyclohexadiene-1,3 is 64.2% for the converted cyclohexene. The output of cyclohexadi-ene-1,3 25.9 wt.% On the initial cycle of hexene. Example 4 A cyclohexene oxidate obtained in example 1 is taken for the dehydration reaction (hydroxy products content is 42 wt.% 20 ml (17.4 g and the catalyst in example 1 (A) 20 ml. The experiment is conducted at temperatures, flow rate cheese 0 , 75, duration 80 min. Receive catalysate 16.1 g (9.5 wt.% From the initial). Catalysate composition according to GLCANalysis, wt.% (G): 63.5 (10, Cyclohexene 26 1 (4 2 Cyclohexadiene 1.3 2.7 (0.4 Benzene 7.7 (1.3 Hydroxy Products Conversion of cyclohexene is 37%. Selectivity of the process for cyclohexadiene - 1.3-70.0% for the converted cyclohexene. Output c Clohexadiene-1, 3-25.9 wt.% to the starting Cyclohexene Example 5. Take for the dehydration reaction cyclohexene oxidate prepared according to Example 1 (content of hydroxy products 42%), 20 ml (17.4 g) and the composition catalyst according to Example 1 (A) - 20 MP. The experiment was carried out at a temperature of 280 ° C, a bulk feed rate of 0.75 h, the duration of VO min. Catalysate 15.8 g (90.8 wt.% from the initial) is obtained. The composition of the catalyzate is according to GZHKHANALIZ, wt.% (g): Methylcyclopentene 0.6 (0.1) Cyclohexene 59.7 (9.4) 3 Cyclohexadiene-1.3 30.1 (4.8) Benzene 3.6 (0.6 ) Hydroxy products 6.0 (0.9) Cyclohexene conversions - 41.8%. The selectivity of the process on cyclohexene - 1.3-69.9 wt.% On the converted cyclohexene. The output of cyclohexadiene-1, 3 - 29.6 wt.% On the original cyclohexene. EXAMPLE 6 A mixture of methylcyclohexenes (composition, wt.%: 70.0 - 3-methylcyclohexene + 30.0 1-methylcyclohexene) 96 g (1 mol) and hydroperoxide are taken for the reaction of oxidation; cumene 0.5 g. Conducted the test at a temperature of 105 ° C, a pressure of 6 atm, an air supply rate of 0.3-0.4 l / min, a duration of 7 hours. An oxidate is obtained - 104.9 g. The composition of the oxidate is according to GLCANanalysis, wt.% (G): Methylcyclohexenols 47.7 (50.0) Methylcyclohexenes oxides7, 8 (8.2) Methylcyclohexenes hydroperoxide 1,2 (1,3) Methylcyclohexenones 1.9 (2.0) Methylcycloacene 41 4 (43 4) hexenes The content of hydroxy products in catalyzate is 58.6 wt.%. The yield of hydroxy products - 68.9 mol.% On the original methylcyclohexene. Conversion of methylcycloxene - 54.8 wt.%. For the dehydration reaction, methyl cyclohexene (hydroxyproducts content is 58.6%) are taken for the dehydration reaction, 20 ml (19.9 g) and the catalyst of example 1 (A) - 20 cl. The experiment was conducted at a temperature of 300 ° C, a bulk feed rate of 1, for a duration of 60 minutes. Get catalyzate 17.8 g (89.4 wt.% From the original). The composition of the catalyzate according to GLCHANALYSIS, wt.% (G): 22.1 (3.9) 3-Methylcyclohexene 19.5 (3.5) 1-Methylcyclohexene 1-Methylcyclohex12, 3 (2.2) diene-1,3 2-Methylcyclohexa 16, 0 (2.8) diene-1,3 5-Methylcyclohex a13, 9 (2.5) diene-1.3 8.4 (1.5) Toluene 7.8 (1.4) Oxime products Conversion the initial methylcyclohexane is 58.5%. The selectivity of the process of methylcyclohexadiene-1,3 is 73.5% for the methylcyclohexene converted. The yield of methylcyclohexadiene-1,3 is 43.0 wt.% To the starting methylcyclohex. Example 7: Take for the dehydration reaction of methylcyclohexene oxidate prepared according to example 6 (content of hydroxy products 58.6 wt.%), 20 ml (19.9 g) and catalyst in example 1 (A) - 20 ml. Conduct the experiment at a temperature of 270C, the volume of feed rate of the raw material is 1 hour, the duration is 60 minutes. Get catalyzate 18.1 g (90.95 wt.% From the original) The composition of the catalyzate according to GC, analysis, wt.% (G): 24.1. (4,4) 2-Methscyclohexene. 14.3 (2.6) 1-Methylcyclohexene 1-Methylcyclohexa12, 8 (2.3) diene-1,3 2-MethylCyclohex13 .3 (2.4) diene-1.3 5-Methylcyclohexa 15, 8 (2 , 9) diene-153 5.3 (1.0) Toluene 14.4 (2.5) Hydroxy products Conversion of methylcyclohexene is 61.4%. The selectivity of the procedure for methylcyclohexadiene-3 is 70.0. The yield of methylcyclohexadiene is 1.3 42, 7 wt.%. Example 8. Take for the reaction of dehydration of methyl cyclohexene oxidate prepared according to example 6 (content of oxyproducts 58, bpm.% 20 ml 19.9 g) and a catalyst according to Example 1 (A) - 20 ml. The experiment was carried out at a temperature of 240 ° C, a bulk feed rate of 0.5 hours and a duration of 120 minutes. Catalysis was obtained 17.9 g (89, 9 wt.% Of the initial). Catalizate composition according to GLCHANALYSIS, wt.% (G): 3-Methylcyclohexene 24.6 (4.4) 1-Methylcyclohexene 16.7 (3.0) 1-Methylcyclohexadien-1, 314 , 2 (2.5 ) 2-Methylcyclohexadiene-1, 315.9 (2.9) 5-Metsch1cyclohexadiene-1, 318.5 (3.3) Toluene 3.7 (0.7) Oxyproducts 6.5 (1.1) Conversion of methylcyclohexene was em 59, 0%. The selectivity of the process for methylcyclohexene-1,3 83, 4 wt.% on the converted methylcyclohexane. The yield of methylcyclohexadiene1, 3 is 48.8 wt.% on the original methylcyclohexene. For the oxidation reaction, cyclohexene 82 g (101.2 ml, 1 mol) and cumene hydroperoxide 0.4 g are taken. The experiment was carried out at a temperature, a pressure of 6 atm, an air supply rate of 0.3-0.4 l / min, and a duration of 7 .4. About 88.5 g of ssidat are obtained. The composition of the oxidate according to GLCH analysis, wt.% (G): 31.5 (27.9) Cyclohexen-1-ol-C 5.0 (4.5) Cyclohexene oxide Cyclohexene hydroperoxide3 .2 (2.8). hexene 2.3 (2,0) Cyclohexen-1-oi-3 Return cyclo58, 0 (51.3) hexene The content of hydroxy products in catalyzate is 42.0 wt.%. The output of hydroxy products 38 mol.% On the original cyclohexene. Conversion of cyclohexene - 37.4 wt.% Reaction. Dehydration cyclohexene oxidate (content of hydroxy products 42.0 wt.%) 100 ml (87.0 g) and catalyst composition, wt.%: Natural clinoptilolite 80, bentonite 20; degree of crystallinity 84.0 wt.% (B) 100 ml. The experiment was conducted at a temperature of 300 ° C, a bulk feed rate of 0.5 h, and a duration of 120 min. Get catalyzate 80 g (92 wt.% From the original). The composition of the catalyzate according to GLCHANALYSIS, wt.% (G): 3.5 (2.8) Methylcyclopentene 56.25 (45.0) Cyclohexene 31.1 (24.9) Cyclohexadiene-1.3 2.9 (2, 3) Benzene 6.25 (5.0) Hydroxy products Conversion of cyclohexene is 44.4%. The selectivity of the process for cyclohexadiene-1,3 - 69,1% on transformed cyclohexene. The output of cyclohexadiene-1, 3 - 39.7 wt.% On the original cyclohexene. For the dimerization reaction, a catalyzate of 80 g is taken. The experiment is carried out at a temperature of 4 hours, a pressure of 4-5 atm. Get dimerizat 78 g (97.5 wt.% From the original). Atmospheric distillation of dimerizate is carried out. Get 1 FR (67-82 C) 49, 6 g (a mixture of cyclohexene, benzene and methyl cyclopentene isomers); the residue is 28.0 g. The residue from the atmospheric distillation of dimerizate is taken to be vacuum distilled to 28.0 g. 1 fr is obtained. (5057 C and 16 mm Hg) 4.8 g (mixture of hydroxy products); 2 fr. (7 -78 ° С and 4 mm of mercury.) - 17.1 g (cyclohexadiene dimer-1, 3); Zfr. (107-113 ° С and 4 mm of mercury.) - 2.7 g (cyclohexadiene trimer-1, 3); the residue is 3.0 g. Thus, the target product cyclohexadiene-1, 3 is isolated from the catalyzate as a dimer with a purity of 98.7% (according to GLC analysis). Cyclohexadiene-1,3 as a monomer is obtained by depolymerizing dimer over broken glass at 260-300 ° C. The obtained target products have the following physicochemical properties: cyclohexadiene dimer1, 3 - - 74-78s (15 mm Hg) n | ° - 1.5245; df - 0.9865; N «« «449, 66 (calculated 49,782). Cyclohex -81 ° C; diene-1,3 - T ,, „- 80; MK -.-. 26.5 0.8441; d4 - 1, D on (calculated 26,624). Example 10. For the oxidation reaction, a mixture of methylcyclohexes (composition, wt.%: 70.0 - 3-methylcyclohexene + 30.0 1-methylcyclohexene) 96 g (1 mol) and cumene hydroperoxide 0.5 g are taken. temperature 105 ° С, pressure 6 atm, air supply rate 0.3-0.4 l / min, duration 7 hours. Date windows are obtained 104.9 g. The composition of the oxidate according to GLC analysis, wt.% ( d) 1 Methylcyclohexenols 47.7 (50, Methylcyclohexenone oxides7.8 (8.2 Methylcyclohexanes hydroperoxides1, 2 (1.3 Methylcyclohexenones 1.9 (2.0 Returned methylcyclohexenes41.4 (43, Content of hydroxyl products in catal then 58.6 wt.%. Vypsod hydroxy product to 68.9 mol.% On the original methyl cyclogenous C. Methylcyclohexene conversion 54, 8 wt.%. Taken for the dehydration reaction of methyl cyclohexene (content of hydroxy products - 58.6 wt.%) 100 ml ( 99.5 g) and the catalyst of example 1, (A) - 100 ml. The experiment was carried out at a temperature of 270 ° C, a space feed rate of 1 h, duration 60 minutes, 90 g of catalyst was obtained (904% of the initial value). The composition of the catalyzate according to GLCHANALYSIS, wt.% (G): 3-Methylcyclohexene 23.9 (21.5) 1-Methylcyclohexene 15.0 (13.5) 1-Mstilcyclohexadiene-1, 313.3 (12.0) 2 -Metylcyclohexadiene-1, 313.3 (12.0) 5-Methylcyclohexadiene-1, 315.0 (13.5). Toluene 5.6 (5.0) Hydroxy products 13.9 (12.5) Methylcyclohexene conversion is 61.6%. The selectivity of the process for methylcyclohexadiene is 74.0%. The output of methylcyclohexadium-1345, 6 wt.%. The resulting catalyzate (90 g) is subjected to dimerization. The experiment was carried out at a temperature of 200 ° C, a duration of 4 hours, a pressure of 4-5 atm. Get dimerizat 88.9 g (98.9 wt.% From the original). Atmospheric distillation of dimerizate is carried out. Get: 1 FR. (99-110 ° C) 39, 1 g (a mixture of isomers of methylcyclohexene and toluene); the residue is 49.0 g. Take on vacuum distillation, the residue from the atmospheric distillation of dimerizate is 49.0 g. Receive: 1 fr. (6575 ° C and 15 mmHg) - 10.6 g (mixture 2 fr. (89-93C and hydroxy products); 64 mmHg - 24.7 g (methyl-, cyclohexadiene dimer); residue (trimer and tetramer methylcyclohexadiene) 13, 3 g. The purity of methyl cyclohexadiene dimer is 97.6% (according to GLC analysis). Methylcyclohexadiene-1,3 in the form of a monomer is obtained by depolymerization of the dimer as in Example 9. The obtained target products have the following physicochemical data. Dimer methylcyclohexadiene-1,3 89-93C (4 mm Hg. Art.); P 1, 5276; df - 0.9836; MRj ,, - 58.8. (calculated 59.018). Isomers of methylcyclohexadiene-1, 3 - 105-112 ° С; 1.4740 df - 0.8417; MR 31.38 (calculated 31.242). Example 11. For the dehydration reaction, cyclohexene oxide is taken (hydroxy products content is 42.0%) 20 ml (17.4 g) and the catalyst composition, wt.%: 90.0 - natural clinoptilolite; 10.0 - bentonite - 20 ml. The degree of crystallinity is 72 wt.%. Conduct the experiment at a temperature of volumetric feed rate of 1.0 h, the duration of 60 min. Get catalyzate 46.7 g (96.0 wt.% From the original). The composition of the catalyzate according to GLCHANALYSIS, wt.% (G): Methylcyclopentenes 2.9 Cyclohexene 58.1 Cyclohexadiene-1,3 24,7 Benzene1,6 Oxyproducts 12.7 Conversion of cyclohexene is 40.8%. The selectivity of the process for cyclohexadiene is 1.3-62.7% for the converted cyclohexene. The output of cyclohexane diene-1,3 - 25.6 wt.% On the source Cyclohexene. Example 12; An oxidate is taken for the dehydration reaction; cyclohex on (content of hydroxy products 42.0%) 20 ml (17.4 g) and catalyst composition in wt.%: 65.0 - natural clinoptilolite 35.0 - bentonite. The degree of crystallinity - 52.0 wt.%. The experiment was carried out at a temperature of 300 ° C, a volumetric feed rate, after 1.0 h, duration of the experiment 60 min. Get catalyzate 16.3 g (93.7 wt.% Of the initial). The composition of the catalyzate according to GLCHANALYSIS, wt.% (G): Methylcyclopentenes 4.8 (0.8) Cyclohexene 56.1 (9.2) Cyclohexadiene-1.3 26.5 (4.3) Benzene 6.7 (1, 1) Hydroxyproducts 5.9 (0.9) Cyclohexene conversion was 43.9%. The selectivity of the cyclohexadiene process is 1.3-61.4% for the converted cyclohexene. The yield of cyclohexad, yen-1,3 - 26.9 wt.% On the original Cyclohexene. Example 13. Methylcyclohexane oxidate is taken for the dehydration reaction (content of hydroxy products is 58.6 wt.% 20 ml (19.9 g) and catalyst composition, wt.%: 65.0 - natural clinoptilolite, 35.0 - bentonite - 50

20 ml. The degree of crystallinity 52, 0 wt.%. The experiment was conducted at a temperature, the volumetric feed rate of the raw material was 1 h, the duration of the experiment was 60 min. Get catalyzate 55 18.3 g of C92.0 wt.% From the original).

The composition of the catalyzate according to GLCHANALYSIS, wt.% (G):

as used in the proposed method, the catalyst of the above composition loses activity between 8 and 10 hours. Under identical conditions, the duration of coke burning out from spent aluminum oxide is 120 minutes, and only 80 minutes from natural zeolite. 3-Methylcyclohexene 28.0 (51,) 1-Methylcyclohexene 22.7 (4.2) 1-Methylcyclohexadiene-1, 37.8 (1.4) 2-Methylcyclohexane diene-1.38.2 (1.5) 5-Methylcyclohexadiene-1, 310.6 (2.0) Toluene 10.2 (1.9) Hydroxy products 12.5 (2.2) The methyl cyclohexene conversion is 48.8%. The selectivity of the process for methylcyclohexene-ST, 3%. As shown in the above examples 11-13, with an increase in the composition of the catalyst, the content of clinoptilolite above 8 decreases the degree of oxidation dehydration, which leads to a decrease in the selectivity of the process, and vice versa, with an increase in The catalyst composition of the bentonite content is higher than 30 wt.%, along with the oxidate dehydration reaction, an increase in the proportion of isomerization and aromatization reactions of the initial hydrocarbon is also observed, which also leads to a decrease in the selectivity of the process. From the above examples it can be seen that the proposed method yields cyclohexadiene-1,3 of 25.933, 3 wt.% On the starting Cyclohexene versus 11-12 wt.% According to a known method; the selectivity of the process for cyclohexadiene-1,3 reaches 73.0% against 50.2% by a known method; the yield of methyl cyclohexadiene isomers 1, 3 is 42.7-48.8 wt.% on the initial methylcyclohexene versus 21.828, 0% according to the known method of the CP. Moreover, the hydroxy products obtained by the liquid phase oxidation of cyclohexene and methyl cyclohexene are not reduced or removed from the oxidate composition, which allows to simplify the process technology, and the catalyst used in the known method, y-alumina, after working for 2-2.5 hours cokes and loses its catalytic activity, while

I, 5113325316

The proposed Catalyst possesses a reaction according to the target intermediate dehydrating and isomerizate.

The first-rate ability than y-alumina-known dehydratamine catalysts, which contributes to a greater selection of cyclohexanols, in particular to the dehydrate-5 v-AlgOj dehydration, has a large isomerization of hydroxy products, mines of the stage in m-capacity, therefore, when dehydrating and restoring yus. Using oxidate in their presence, forming it as a raw material during dehydra- tion without isolating and reducing oxidation of the oxidate obtained directly to the products, a significant part (30 sec) by liquid phase oxidation 10 | 40 i4ac.% Of the original cyclohexene) cyclohexene or methylcyclohexene is isomerized into methylcyclopentene prevents fast coking and the possibility of recycling its catalyst and increases the selec- tion in the process.

Claims (2)

1. METHOD FOR PRODUCING CYCLOHEXADIENE-1,3 OR METHYLCYCLOHEXADIENE-1,3 by liquid-phase oxidation of the corresponding cycloolefin with atmospheric oxygen in the presence of cumene hydroperoxide, followed by dehydration of the obtained hydroxy products on an oxide catalyst at elevated temperature, which is aimed at increasing the yield so that products and simplification of the process technology, dehydration direct the oxidation reaction mixture directly and a mixture of natural clinoptiloli is used as an oxide catalyst and bentonite in the following components, wt. X: Natural clinoptilolite 70-87 Bentonite Up to 100 2. The method according to p. 1, with the fact that dehydration is carried out at a temperature of 240-300 ° C. ^ .SU w, 1133253> t