The method of producing cyclododecanone or cyclohexanone
(57) Abstract:The inventive product - cyclododecane or cyclohexanone. Reagent 1: the corresponding alcohol. Reaction conditions: dehydration is carried out in the presence of a copper alloy, aluminum, zinc, catalyst, videokniga to 8-50% aluminum. 2 C.p. f-crystals. The invention relates to an improved process for the preparation of cyclododecanone and cyclohexanone by catalytic dehydrogenation of cyclododecanol and cyclohexanol and can be used in the production of cyclododecanone, cyclohexanone, dodecalactam and caprolactam.Known methods for producing cyclododecanone and cyclohexanone were mixed copper-containing catalysts. So when getting cyclododecanone dehydration cyclododecanol copper-chromanol the catalyst at temperatures of 200-210oC conversion cyclododecanol is to 97.1-98.2 per cent in selectivity 95,7-98,1% /patent England N 1312086, class C 07 C, 49/27, 1973/ a upon receipt of cyclohexanone by dehydrogenation of cyclohexanol on copper-magnesium catalyst at temperatures 240-280oC conversion is 55,0-66,6% with a selectivity of 99.5% /auth.St. The USSR, N 232231, class C 07 C 49 /30,1977/ /1/.The disadvantage of the methods is nischay essence is a way of obtaining cycloaliphatic alcohols fused aluminum catalyst is Raney copper. So, at a temperature of 290oC and time of contact less than 15 min on copper Raney received cyclododecanone with a conversion of 97% and a content of cyclododecene 0,02% /Japan patent N 75031145, class C 07 C 49/27, 1975/ /2/.The disadvantage of this method is that the process is conducted in a reactor with stirrer on powdered catalyst, the reaction product requires stage filter, it is difficult to separate completely the ketone from the catalyst. Shown in patent low cyclododecene is achieved due to the short time of contact, in stationary conditions, this mode is set at high space velocities and leads to mechanical destruction of the catalyst.Object of the invention is improved method of producing cyclododecanone and cyclohexanone by increasing the mechanical strength of the catalyst and the selectivity of the process.This task is achieved by the fact that cyclododecane and cyclohexanone is produced by dehydrogenation cyclodecanone and cyclohexanol on aluminum alloy catalyst with partially leached aluminum. The criterion of videochannel alloy is the degree of leaching of aluminum, which is determined by the number of match is Yes) and particle size of 1-3 mm To achieve low levels of leaching (5-15% ) using 3% aqueous solution of caustic soda, adding it to the alloy cooled by flowing water (17oC). To achieve a deeper degree of leaching (30-50%) gradually raising the temperature to 30 to 60oC and for complete leaching (100%) use 25% aqueous solution of alkali, the temperature was raised to 60oC.Example 1. The degree of leaching of aluminium 5%
Leached and have plenty of alcohol alloy without washing alkali load in the dehydrogenation reactor cyclododecanol, which is a stainless steel tube heated coolant, which continuously from the bottom up fed a liquid cyclododecanol. The catalyst is heated in a current of hydrogen, and then let the reaction product and begin the dehydration.Digitalout cyclododecanol at a temperature of 260oC and a flow rate of 1 h-1. Get cyclododecanone with a conversion of 92% selectivity of 99.9% of the content of cyclododecene 0,03% After 300 h of operation, the conversion decreased to 90% of the Catalyst was unloaded without reducing the selectivity and mechanical destruction.Leached alloy is loaded into the dehydrogenation reactor, cyclohex is served cyclohexanol, passed through the evaporator. The catalyst is heated in a current of hydrogen, and then let the reaction product and begin the dehydration.Digitalout cyclohexanol at a temperature of 250oC and a flow rate of 1 h-1. Get cyclohexanone with a conversion of 42% selectivity 100% cyclohexen and phenol not detected. After 20 hours, the conversion dropped to 13% other parameters unchanged.Examples 2-6 carried out analogously to example 1, varying the degree of leaching of aluminum. Example 6 (prototype) for dehydrogenation selected intact particles of alloy.Thus, the proposed method of obtaining cyclododecanone and cyclohexanone partially leached copper alloy, aluminum, zinc allows you to:
to increase the mechanical strength of the catalyst, which is especially seen in the dehydrogenation cyclododecanol, where the process carried out in a gas-liquid environment, predstavljaet increasing demands on the mechanical strength of the catalyst: 500 h operation not lead to the destruction of the catalyst, while fully leached alloy destroyed by 45% after 150 hours of work;
to improve the selectivity of the dehydrogenation cyclododecanol compared to proto,5%
This dehydrogenation cyclododecanol optimal degree of leaching of aluminum is 8-15% and for dehydrogenation of cyclohexanol 30-50% reduction in leaching below these limits leads to a drop in conversion, the increase above the fall selectivity and mechanical strength while maintaining the achieved conversion. 1. The method of producing cyclododecanone or cyclohexanone by catalytic dehydrogenation of the corresponding alcohol in the presence of a copper-containing catalyst, wherein the catalyst used is an alloy of copper, aluminum, zinc, in which the aluminum leached 8 50%
2. The method according to p. 1, characterized in that the dehydrogenation cyclododecanol use alloy in which aluminum is leached 8 15%
3. Way but p. 1, characterized in that the dehydrogenation of cyclohexanol used alloy in which aluminum is leached by 30 to 50%
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
SUBSTANCE: method involves preparation of a reaction mixture at room temperature consisting of the alcohol to be oxidised, sodium bicarbonate, an organic solvent and a nitroxyl radical. Electrolysis is carried out on platinum electrodes with current of 1 A and temperature of 20-25°C. Potassium iodide is added to the reaction mixture. The organic solvent used is dichloromethane and the nitroxyl radical used is 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl of formula: with ratio of alcohol to nitroxyl radical equal to 10:1.
EFFECT: invention ensures high output of end products a within short period of time and less expenses on electricity using a high-technology method.
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
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: process engineering.
SUBSTANCE: invention relates to catalyst for dehydration of cyclohexanol to cyclohexane and to method of its production. Proposed catalyst comprises the following components in wt %: calcium carbonate - 16.4-37.0, graphite - 1.0-3.0, and zinc oxide making the rest. Proposed method comprises preparing reaction mix of previously mentioned composition containing sources of zinc oxide and calcium carbonate, moulding, drying, and calcinating. Note here that said mix comprises the following components in wt %: calcium carbonate - 12.4-29.8, carboxymethylcellulose or methylcellulose - 0.1-1.0, and base zinc carbonate making the rest, while graphite is added into amounts sufficient for production of said catalyst.
EFFECT: higher strength, lower costs, simplified production, reduced harmful effects.
3 cl, 2 tbl, 2 ex
FIELD: oxidation catalysts.
SUBSTANCE: invention relates to catalytic oxidation of saturated hydrocarbons with oxygen-containing gas. Process according to invention comprises contacting alkane with oxygen source in presence of catalyst including compound of general formula: , where R1 and R2 independently represent hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxy, alkoxy, carboxyl, alkoxycarbonyl, or acyl, or R1 and R2 can together form double bond or aromatic or non-aromatic ring; Y represents oxygen atom; X oxygen atom to hydroxyl group; m is integer 1 or 2; and n = 1. Process is conducted at 20 to 100°C. Advantageously, catalyst includes cocatalyst.
EFFECT: increased efficiency of catalytic system.
14 cl, 5 tbl, 6 ex