The method of producing cyclohexanone
(57) Abstract:Cyclohexanone is obtained from the bottoms of the process of obtaining cyclohexanone. Are hydrolytic decomposition of cyclohexanone dimer in the vapor phase at a temperature of 360 - 460oWith a heterogeneous catalyst: 1 - 10% NaOH based on the weight of the porous media. The process is preferably carried out in the presence of 1 to 3% aqueous NaOH solution in the stoichiometric ratio of NaOH to the dimers of cyclohexanone. 1 C.p. f-crystals, 7 PL. The invention relates to an improved process for the preparation of cyclohexanone (Chona), which is an intermediate for the synthesis of caprolactam.A known method of producing cyclohexanone hydrolytic decomposition products seal Chona, in particular of cyclohexylcyclohexanes (cyclohexanone dimer - DCG) at 105 - 130oC and atmospheric pressure in the presence of two mass excess catalyst cation exchanger in relation to DCG. Output Chona is 70-72 mol. % reacted DCG.the disadvantages of this method is the high consumption of catalyst, the complexity of its regeneration and low yield of the target product .A method of obtaining Chona hydrolytic razrisovanny DCG .The disadvantages of this method is the complexity of the design process and the presence of high pressure.The closest in technical essence is a way of decomposition DCG in the presence of solid potassium hydroxide (KOH) with the simultaneous processing of the product superheated steam in the liquid phase at a temperature of 180oC .Disadvantages of the method are: the use of large amounts of superheated steam at a temperature of 400oC (consumption of the process), low output Chona (78% of theory) due to prolonged contact of the reaction products with solid alkali and deficit KOH.Technical solution to the problem is to obtain the target products Chona and cyclohexanol (Chola) hydrolytic decomposition in the gas phase products of the condensation of cyclohexanone contained in the VAT balance of caprolactam production. Currently, the VAT residue to be burning.This task is solved by the method of hydrolytic decomposition products seal DCG, wherein the process is conducted in the vapor phase in the presence of a heterogeneous catalyst NaOH on a porous carrier with a NaOH content of 1-10 wt.% when 360-460oC and the contact time between 2-10 C. To maintain actively processing in this way is used CBM product of the column selection cyclohexanol (Chola) caprolactam production by oxidation of cyclohexane following composition, wt.%: DCG 64,9; the amount of impurities 28,2; Chona 1,1; Zgola 5,8.Processing of the cubic product is carried out according to the following scheme: CBM product of the column selection Chola from the intermediate tank is mixed in the stoichiometric ratio (in terms of DCG) with 3% aqueous NaOH solution and then flows through the heater in an isothermal tubular reactor. The temperature in the reactor 360-460oC supported flue gases. After the reactor can produce arrives on cooling, and then into the production scheme Chona and Chola. The following examples illustrate the method of hydrolytic decomposition DCG.Example 1. Fraction DCG without additional purification composition, wt.%: DCG 64,9; Zgola 5,8; Chona 1,1); the amount of unidentified impurities 28,2 in the amount of 49.5 ml/h in 3% aqueous NaOH solution and through the heater comes with 400oC in an isothermal tubular reactor. The reactor is made of stainless steel AISI IXI8H9T (inner diameter 22 mm, length 400 mm). In the Central part of the reactor were placed ball catalyst with a diameter of 4 mm Al2O3with 5% NaOH in 20 %. The upper and lower part of the reaction tube was filled with an inert nozzle - rings process.The reactor was placed in thermosta vapors in the reaction zone is 2-3 temperatures 400oC.After the reactor was obtained organic layer in amounts to 48.6 ml/h composition, wt. %: DCG 40,0; Zgola 5,9; Chona 29,3; impurities 24,8. Conversion DCG 39,5; output Chona on decomposed DCG to 98.4% (see tab. 1).Example 2. The process is carried out analogously to example 1, using as catalyst in 20 ml of 1 wt.% NaOH/Al2O3. Decomposition temperature DCG 400oC, the contact time of the vapors in the reaction zone 2 C.After the reactor was received for 48.7 ml/h organic layer composition, wt.%: DCG 44,7; Zgola 5,9; Chona 21,2; impurities 28,2. Conversion DCG 32,2%, output Chona 86.2 per cent (see table. 2).Example 3. The process is carried out analogously to example 1, using as catalyst 20 ml of 10 wt.% NaOH/Al2O3. This limits the amount of NaOH, because further increase leads to fusion of the catalyst. After the reactor was received for 48.7 ml/h organic layer composition, wt.%: DCG 40,1; Zgola 6,1; Chona 28,6; impurities 25,2. Conversion DCG 39,1%, output Chona to 96.9% (see tab. 3).Example 4. The process is carried out analogously to example 1, using as catalyst 5 wt.% NaOH/Al2O3. The decomposition process DCG led with 360oC, contact time of the vapors in the reaction zone 2 C. After the reactor had been the heat (selectivity) to 98.1% (see table. 4).Example 5. The process is carried out analogously to example 1, using as catalyst 5 wt.% NaOH/Al2O3. The decomposition process was conducted at 460oC, contact time 2 C. After the reactor has been 48,7 ml/h organic layer composition, wt.%: DCG 35,8; Zgola 5,0; Chona 29,7); the amount of impurities to 29.5. Conversion DCG of 45.7%, output Chona on decomposed DCG 86,3% (table. 5).Example 6. The process is carried out analogously to example 1, using as catalyst a 5 wt. % NaOH on hard-shelled media (refractory brick, the fraction with a diameter of 5 mm). After the reactor received 48.6 ml/h of the organic layer, wt.%: DCG 39,1; Zgola 5,7; Chona 29,8); the amount of impurities 25,4. Conversion DCG 40,8, output Chona on decomposed DCG to 96.9% (see tab. 6).The obtained data are given in the summary table 7. 1. The method of producing cyclohexanone hydrolytic decomposition products of the condensation of cyclohexanone in the presence of a catalyst at atmospheric pressure, wherein the process is conducted in the vapor phase at 360 - 460oIn the presence of a heterogeneous catalyst, which is used as NaOH on a porous carrier in a quantity of 1 to 10% by weight of the carrier.2. The method according to p. 1, characterized in that the decomposition of waikaremoana in the original seal products.
FIELD: oxidation catalysts.
SUBSTANCE: SO2-into-SO3 conversion catalyst contains following active components: vanadium oxide, alkali metal (K, Na, Rb, Contains) oxides, sulfur oxides, and silica framework formed from natural and/or synthetic silica and having pores with radii up to 65000 , among which fraction of pores with radii larger 10000 does not exceed 50%, while content of sulfuric acid-insoluble vanadium compounds (on conversion to V2O5) does not exceed 4.0% by weight. Fraction of pores with radii 1000-10000 does not exceed 35% and that less than 75 at most 9%.
EFFECT: improved performance characteristics of catalyst operated in reactor zones at medium and maximum temperature due to under conditions activity at 420-530оС.
3 cl, 1 tbl, 8 ex
FIELD: chlororganic chemistry.
SUBSTANCE: invention relates to hydrochlorination catalyst containing aluminum η-oxide, doped with cesium chloride. Also method for methanol hydrochlorination in vapor phase using claimed catalyst is disclosed.
EFFECT: decreased selectivity to dimethyl ether and inhibited coke deposition on working catalyst.
16 cl, 6 tbl, 1 dwg, 20 ex
FIELD: chemical and petrochemical industries; isomerization of olefins.
SUBSTANCE: the invention is dealt with of the field of deposition on carbon materials of catalysts of the basic nature being of interest for processes of isomerization of olefins. There is a description of a catalyst of isomerization of olefins containing metal sodium deposited on a composite porous carbon material, which represents a three-dimensional porous carbon die with the following structural characteristics: d002 =0.343-0.350 nm, the average size of the crystallite in a direction of "a"-La=l-14 nm, the average size of the crystallite in a direction of "c"-Lc=2-12 nm, real density of 1.8-2.1 g/cm3, with distribution of pores by sizes having a maximum in the range of 20-200 nm and an additional maximum in the range of 1-20 nm. Also there is a description of a method of preparation of the catalyst providing for deposition of metal sodium on the composite porous carbon material and a method of isomerization of olefins with use of this catalyst. The technical result is a possibility to conduct the process of isomerization at low temperatures, increased catalytic activity and selectivity, decreased output of by-products.
EFFECT: the invention ensures a possibility to conduct the process of isomerization at low temperatures, increased catalytic activity and selectivity, decreased output of by-products.
6 cl, 10 ex, 2 tbl
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention relates to production of olefin or diolefin hydrocarbons via dehydrogenation of corresponding paraffinic C3-C5-hydrocarbons carried out in presence of catalyst comprising chromium oxide and alkali metal deposited on composite material including alumina and aluminum wherein percentage of pores larger than 0.1 μm is 10.0-88.5% based on the total volume of open pores equal to 0.10-0.88 cm3/g. Preparation of catalyst involves treatment of carrier with chromium compound solution and solution of modifying metal, preferably sodium or sodium and cerium. Carrier is prepared by from product resulting from thermochemical activation of amorphous hydrargillite depicted by formula Al2O3·nH2O, where 0.25<n<2.0, added to homogenous mass in amount 1.0 to 99.0% using, as additional material, powdered aluminum metal, which is partly oxidized in hydrothermal treatment and calcination stages. Hydrocarbon dehydrogenation process in presence of the above-defined catalyst is also described.
EFFECT: increased activity and selectivity of catalyst.
3 cl, 2 dwg, 4 tbl, 7 ex
FIELD: industrial organic synthesis.
SUBSTANCE: method comprises contacting vapor-phase mixture at 150-205°C with alkali and/or alkali-earth metal carboxylate dispersed on activated carbon resulting in conversion of alkyl iodides into corresponding carboxylic acid esters, while iodine becomes bound in the form of inorganic iodide.
EFFECT: facilitated freeing of carboxylic acid product from organic iodine compounds.
4 cl, 2 tbl, 32 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention concerns catalysts for dehydrogenation of C2-C5-alkanes into corresponding olefin hydrocarbons. Alumina-supported catalyst of invention contains 10-20% chromium oxide, 1-2% alkali metal compound, 0.5-2% zirconium oxide, and 0.03-2% promoter oxide selected from zinc, copper, and iron. Precursor of alumina support is aluminum oxide hydrate of formula Al2O3·nH2O, where n varies from 0.3 to 1.5.
EFFECT: increased mechanical strength and stability in paraffin dehydrogenation process.
9 cl, 1 dwg, 3 tbl, 7 ex
FIELD: catalyst preparation methods.
SUBSTANCE: invention relates to alumina-supported catalyst preparation method and employment thereof in reactions of nucleophilic substitution of aromatic halides containing electron-accepting group. In particular, alumina support impregnated with alkali selected from alkali metal hydroxides is prepared by treating alkali metal hydroxide aqueous solution with aluminum oxide in organic solvent followed by drying thus obtained catalyst mixture at temperature not lower than 150°C. Catalyst is, in particular, used to introduce electron-accepting protective groups into organic compounds comprising at least one of -OH, -SH, and -NH, as well as in reaction of substituting amino, thio, or ether group for halogen in a haloarene and in preparation of 2-puperidinobenzonitrile.
EFFECT: simplified preparation of catalyst and regeneration of spent catalyst, and avoided involvement of dangerous reactants.
11 cl, 20 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention provides catalyst for oxidation of ethylene into ethylene oxide, which catalyst contains no rhenium and no transition metals and comprises up to 30% silver on solid support and promoter combination mainly consisted of (i) component containing alkali metal on amount from 700 to 3000 ppm of the mass of catalyst and (ii) component containing sulfur in amount from 40 to 100% by weight of amount required to form alkali metal sulfate and, optionally, a fluorine-containing component in amount from 10 to 300 ppm of the mass of catalyst. Ethylene oxide is produced via reaction of ethylene with molecular oxygen in presence of above-defined catalyst.
EFFECT: increased selectivity of catalyst.
9 cl, 3 tbl
FIELD: gas treatment catalyst.
SUBSTANCE: invention relates to treatment of sulfur-containing emission gases according to Claus method and can find use in enterprises of gas, petroleum, and chemical industries as well as of ferrous and nonferrous metallurgy. Task of invention was to provide a catalyst with elevated strength and elevated activity simultaneously in three Claus process reactions: oxidation of hydrogen sulfide with sulfur dioxide; oxidation of hydrogen sulfide with sulfur dioxide in presence of oxygen; and carbonyl sulfide hydrolysis. The task is solved with the aid of sulfur-removing catalyst including titanium oxide, vanadium oxide, calcium sulfate and modifying metal compound. The latter is at least one of metal compounds selected from alkali metal (Me = K, Na, Cs or mixture thereof) oxides take at following proportions, wt %: V2O5 5.5-10.0, CaSO4 10.0-20.0, Me2O 0.1-2.0, provided that weight ratio Me2O/V2O5 = 0.01-0.36. Catalyst contains pores 10-40 nm in size in amount 50-70%. Preparation of catalyst comprises preparation of catalyst mass, extrusion, drying, and calcinations at temperature not higher than 400°C.
EFFECT: simplified catalyst preparation procedure, which is wasteless, energy efficient, and environmentally friendly.
6 cl, 2 tbl, 2 ex
FIELD: petrochemical processes catalysts.
SUBSTANCE: invention relates to production of catalysts used in hydrocarbon feed processing and can be, in particular, used in the hydrodealkylation of toluene and benzene-toluene-xylene fraction isolated from pyrocondensate resulting from hydrocarbon pyrolysis. Alumina-supported catalyst contains 16-20% chromium oxide, 0.3-1.5% sodium oxide, 0.5-3.0 boron oxide. Preparation of alumina comprises adding fine aluminum hydroxide powder to aluminum hydroxide in the form of "wet cake" in amount 15-50% of the weight of "wet cake" in presence of organic acid. As a result, process of hydrodealkylation of real feed material (industrial benzene-toluene-xylene fraction) is stabilized under conditions of temperature gradient throughout the catalyst bed, while high catalytic activity and selectivity are preserved. Simultaneously, coking resistance of the catalyst is enhanced, porous structure thereof shows improvement (increased percentage of wide pores), mechanical strength is increased, and specific surface optimized.
EFFECT: enlarged assortment of high-efficiency hydrodealkylation catalysts.
2 dwg, 4 tbl, 6 ex
FIELD: organic chemistry, in particular production of carbonyl compounds such as aldehydes and ketones.
SUBSTANCE: claimed method includes reaction of nitrous oxide with alkenes in presence of inert gas as diluent. Reaction is carried out in gas phase at 401-700°C and under pressure of 2-300 atm. Target compounds represent value intermediates for precise and base organic synthesis.
EFFECT: method of high selectivity in relation to target products and improved explosion proofing.
5 cl, 1 tbl, 14 ex
FIELD: organic chemistry, chemical technology, catalysts.
SUBSTANCE: invention relates to catalytic decomposition of organic hydroperoxides representing important compounds on organic synthesis. Decomposition of cycloalkyl hydroperoxides comprising from 6 to 12 carbon atoms results to formation a mixture of corresponding alcohols and ketones. Process is carried out in the presence of a solvent (alkane, halogen-containing hydrocarbon) at temperature from 20°C to 200°C. Catalyst comprises ruthenium as a catalytically active metal added to a solid carrier chosen from the following group: carbon prepared by pyrolysis of acetylene and metal oxides chosen from the group comprising zirconium, aluminum, lanthanum and manganese. The amount of catalyst expressed as the mole percents of ruthenium to the amount of moles of hydroperoxide to be decomposed is from 0.0001% to 20%. Preferably, the catalyst comprises one additional rare-earth element as a component of alloy. The carrier represents, as a rule, metal oxide with high specific surface above 10 m2/g but preferably, above 100 m2/g that is resistant against oxidation. The hydroperoxide concentration is in the range from 1 to 80 wt.-% with respect to the solution mass. Preferably, hydroperoxide represents cyclohexyl, cyclododecyl, tetraline, ethyl benzene or pinane hydroperoxide and hydrocarbon used in preparing the parent hydroperoxide is used as a solvent. Invention provides the development of the modified catalyst enhancing conversion and selectivity in decomposition of hydroperoxides.
EFFECT: improved method for decomposition.
8 cl, 24 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to an improved method for synthesis of 2,6-di-(3,3',5,5'-di-tert.-butyl-4,4'-oxybenzyl)-cyclohexane-1-one used as a stabilizing agent of polyolefins and low-unsaturated carbon=chain rubbers. Method involves interaction of cyclohexanone with N,N-dimethyl-(3,5-di-tert.-butyl-4-oxybenzyl)amine in the ratio = (1-1.2):2, respectively, and process is carried out at temperature 125-145°C up to ceasing isolation of dimethylamine. Method provides simplifying technology and preparing the end product with the yield 61-85.4%.
EFFECT: improved method of synthesis.
12 tbl, 23 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 3-bromoadamantyl-1-alkyl(aryl)-ketones of the general formula: , wherein that can be used as intermediate substances for synthesis of some biologically active compounds. Method involves interaction of 1,3-dehydroadamantane with α-bromoketones of the following order: α-bromoacetone, α-bromoacetophenone, α-bromocyclohexanone in the mole ratio of reagents = 1:(2-3), respectively, in absolute diethyl ether medium, at temperature 34-40°C for 3-4 h. Method provides preparing the claimed compounds with high yield.
EFFECT: improved method of synthesis.
SUBSTANCE: present invention relates to a method of continuous oxidation of saturated cyclic hydrocarbons using oxygen, into a mixture of hydroperoxide, alcohol and ketones. The method involves feeding into the lower part of a column and in parallel flow, a stream of oxidisable liquid hydrocarbon and a gas stream containing oxygen, and degassing the liquid phase in the upper part of the column by forming a gas dome and extraction of the degassed liquid phase. The gas containing oxygen is let into different compartments of the column, and into the dome and/or liquid phase at the level of the degassing zone, or directly above. A stream of non-oxidising gas with output sufficient for maintaining concentration of oxygen in the gas layer at the level of volume concentration, less than or equal to the upper limiting concentration of oxygen is supplied.
EFFECT: possibility of implementing a method with high selectivity on an explosion safe level.
9 cl, 1 dwg, 1 ex
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