CN103373975A - Oxidation method of cycloparaffin - Google Patents
Oxidation method of cycloparaffin Download PDFInfo
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- CN103373975A CN103373975A CN2012101284001A CN201210128400A CN103373975A CN 103373975 A CN103373975 A CN 103373975A CN 2012101284001 A CN2012101284001 A CN 2012101284001A CN 201210128400 A CN201210128400 A CN 201210128400A CN 103373975 A CN103373975 A CN 103373975A
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Abstract
The invention relates to an oxidation method of cycloparaffin. The oxidation method is characterized by comprising the following steps of: enabling reaction materials which include the cycloparaffin, hydrogen peroxide, an entrainer and water to contact to obtain a product under the condition of oxidation reaction in the presence of a catalyst; and continuously adding and extracting the reaction materials and the product in a reaction device, wherein the entrainer generates azeotropism with the water, an azeotrope formed under a reaction condition is continuously removed and separated, the reaction materials and the entrainer are recycled, and the catalyst is a titanium-silicon molecular sieve.
Description
Technical field
The present invention relates to a kind of cycloalkanes oxidation method, more specifically to a kind of reaction method of cycloalkanes oxidation reaction preparation corresponding lactone, alcohol acid and di-carboxylic acid.
Background technology
6-caprolactone, colourless oil liquid has aromatic odour, density 1.0693 ,～5 ℃ approximately of 98～99 ℃ of boiling points, fusing point, specific refractory power 1.4611, soluble in water, ethanol, benzene are insoluble to sherwood oil, and heating becomes dimer or macromolecule polyester.6-caprolactone has the advantages such as low, the easy processing of viscosity, VOC content is low, be used as oligopolymer and denaturing agent in producing the technological processs such as poly-epsilon-caprolactone, ε-caprolactam, modifier, aqueous polyurethane coating, cast elastomers, hot melt adhesive, elastomerics, it is functional to improve toughness, cold property and reactivity etc.
6-caprolactone is just under lab successfully synthetic as far back as the thirties in 20th century.The synthetic method of the 6-caprolactone that occurs successively thereafter mainly contains the Baeyer-Villiger oxidation style; 1,6-hexylene glycol catalytic dehydrogenation method; 6 hydroxycaproic acid intramolecular condensation method etc.In the aforesaid method, consider from aspects such as raw material, device and reaction conditionss, the Baeyer-Villiger oxidation style is the most effective method.The suitability for industrialized production of 6-caprolactone mainly adopts the Baeyer-Villiger oxidizing process of pimelinketone and peroxycarboxylic acid at present, but peroxide acids oxygenant also has larger shortcoming: can produce a large amount of organic carboxyl acid (salt) refuses after has reacted (1), have greater environmental impacts, recovery or intractability are larger; (2) reactor product separates, purification ratio is difficult, selectivity is low, and Atom economy is relatively poor, does not meet the Green Chemistry fundamental principle; (3) organic peroxide acid needs to use the hydrogen peroxide of high density in process of production, and character is unstable, production cost is higher, and danger is larger in transportation, storage and operating process, thereby has limited its application in industrial production.
Bhaumik etc. have studied the Baeyer-Villiger oxidation three-phase reaction system (ketone+H of the pimelinketone take TS-1 as catalyzer
2O
2/ H
2And investigated and have or not second cyanogen as Solvent effect the O+ catalyzer).If discovery adds a small amount of H in three-phase reaction system
2SO
4, can obtain higher transformation efficiency.But catalyst system therefor character activity is low, unstable, poor repeatability, and do not have follow-up the further investigation and process exploitation.
The Sn-beta-molecular sieve is considered to one of the most effective Baeyer-Villiger oxide catalyst at present, and this molecular sieve is the most synthetic and come into operation by people such as Spain Corma early than the phase beginning of this century.They find to use this molecular sieve respectively catalysis of pimelinketone and 35%H under 56 ℃ of conditions
2O
2Reactant aqueous solution obtains corresponding lactone.The selectivity of lactone is very high, and reusable, and through the circulation of four secondary responses, catalytic activity does not obviously reduce.But the catalyzer syntheti c route is long, be difficult to synthesize, expensive etc. limited its large-scale development.
6 hydroxycaproic acid, fusing point are 38～40 ℃, and boiling point is 113～116 ℃, and density is 0.98lg/ml, and specific refractory power is 1044, flash-point＞110 ℃.It is a kind of important Organic Chemicals, and it has widely application in organic synthesis and polymeric material field.For example, preparation 6-aldehyde radical caproic acid, 6-caprolactone, hexanodioic acid etc.Its derivative 6 hydroxycaproic acid ethyl ester etc. is organic chemical industry's intermediate of commonly using.US Patent No. P2008306153 has introduced a kind of in the CH2Cl2 solvent, and under 37 ℃ of conditions, 6 hydroxycaproic acid is oxidized to 6-aldehyde radical caproic acid take PCC (pyridinium chlorochromate Pyridinium Chlorochromate) as oxygenant.
Nineteen thirty-seven, du pont company nitric acid oxidation hexalin has at first been realized the suitability for industrialized production of hexanodioic acid.Enter the sixties, the industrial cyclohexane oxidation process of progressively using instead namely first by hexanaphthene intermediate product pimelinketone processed and hexalin mixture (be keto-alcohol oil, claim again KA oil), and then carries out nitric acid or the atmospheric oxidation of KA oil.Nitric acid oxidation KA oil process generally is 50%～60% nitric acid with excessive concentration, carries out through the two-stage reactor series connection.The catalyzer that uses of reaction is copper-vanadium system (same 0.1%～0.5%, vanadium 0.1%～0.2%), 60～80 ℃ of temperature, pressure 0.1～0.4MPa.Yield is 92%～96% of theoretical value.After KA oil oxidation products distills out nitric acid, pass through again the two-stage crystal refining, just can obtain high-purity adipic acid.Raw material consumption quota: hexalin (or KA oil) 740kg/t, nitric acid (100%) 908kg/t, copper 0.2kg/t, vanadium (in V2O5) 0.1kg/t.But there is the deep-etching problem in this reaction to equipment, and environmental pollution is serious, complex process, and energy consumption is higher, do not meet the Green Chemistry principle.
Traditional catalyzed oxidation is inevitable to be existed shortcomings such as equipment corrosion are strong, energy consumption is higher, complex process, processing cost are higher.Take hydrogen peroxide because of its reduzate only as water, environmental friendliness, and be called as " Green Oxidant ", be the developing direction in following catalyzed oxidation field.But this class exothermic heat of reaction is large, if heat-obtaining is untimely, and easy temperature runaway, the decomposition of increase hydrogen peroxide.
Summary of the invention
The purpose of this invention is to provide a kind of effective control temperature of reaction, improve the cycloalkanes oxidation method of hydrogen peroxide utilising efficiency.
Cycloalkanes oxidation method provided by the invention, it is characterized in that being included in oxidation reaction condition and catalyzer exists lower, the reaction mass that comprises naphthenic hydrocarbon, hydrogen peroxide, entrainer and water is contacted, reaction mass and product add and extraction in reaction unit continuously, said entrainer and steeping in water for reconstitution are given birth to azeotropism, the azeotrope that forms under the reaction conditions is constantly shifted out and is separated, and wherein reaction mass and entrainer recycle, and said catalyzer is HTS.
Method provided by the invention, make catalyzer and with the reaction system of naphthenic hydrocarbon, hydrogen peroxide, water, entrainer with HTS, to react and fractionation by distillation dewaters to be coupling in the individual system and carries out, have following advantage: a large amount of reaction heat that oxidising process is emitted are used directly to evaporation and separate remaining reactant and entrainer, make the utilization ratio of reaction heat high, need not special heat-obtaining facility and energy consumption and greatly reduce; Adopt entrainer evaporation absorbing heat, the control of real reaction temperature has steadily prevented the hydrogen peroxide thermolysis effectively, and the hydrogen peroxide utilization ratio is high; Because water and the water in the raw material that reaction generates can in time remove reaction zone, increase hydrogen peroxide concentration, promoted the carrying out of oxidizing reaction, improved the selectivity of purpose product.
Description of drawings
Accompanying drawing is the principle process synoptic diagram that the invention provides method.
Embodiment
Cycloalkanes oxidation method provided by the invention, it is characterized in that being included in oxidation reaction condition and catalyzer exists lower, the reaction mass that comprises naphthenic hydrocarbon, hydrogen peroxide, entrainer and water is contacted, reaction mass and product add and extraction in reaction unit continuously, said entrainer and steeping in water for reconstitution are given birth to azeotropism, the azeotrope that forms under the reaction conditions is constantly shifted out and is separated, and wherein reaction mass and entrainer recycle, and said catalyzer is HTS.
In the method provided by the invention, said HTS can be selected from one or more the mixture among TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 and the Ti-MCM-48, preferred TS-1 wherein, in US Patent No. P4410501, announced first the synthetic method of titanium-silicon molecular sieve TS-1.As preferred embodiment, adopt the TS-1 HTS with hollow structure among the present invention, this molecular sieve has the HTS of MFI crystalline structure, and crystal grain is hollow structure, and the radical length of the cavity part of this hollow crystal grain is 5～300 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, there is hysteresis loop at least 70 milligrams/gram in the benzene adsorptive capacity that records under 1 hour the condition of adsorption time between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and the desorption isotherm.Said TS-1 HTS with hollow structure has larger mesoporous volume, is generally more than the 0.16mL/g, and conventional TS-1 HTS, mesoporous volume is generally about 0.084mL/g.The TS-1 HTS of said hollow structure can be bought commercially available product, the method preparation that has disclosed in also can the Chinese patent with reference to ZL99126289.1.
In the method provided by the invention, said catalyzer can be the former powder of above-mentioned HTS, also the product of the former powder spray shaping of these molecular sieves.The sizing agent of spray shaping normal operation is non-acid colloidal sol, these colloidal sols can be selected from a kind of in titanium dioxide, silicon-dioxide, aluminum oxide and silica-alumina, the silica-titania etc., also can select some non-acid clays, if you would take off soil, kaolin, wilkinite and sepiolite, the content of molecular sieve is the preferred 15-60% of 5-80% in the catalyzer of spray shaping.The granular size of catalyzer can guarantee that it can be evenly dispersed in the liquid material under suitable stirring, continuous flow in reactor and pipeline and can not block up tower; But the granularity of catalyzer can not be meticulous, and meticulous catalyzer can increase the separating difficulty of catalyzer and material.The catalyst grain size scope is 0.02-800 μ m, preferred 0.05-600 μ m, and in specific embodiments more of the present invention, the catalyst grain size scope more preferably can be at 0.5-500 μ m, 1-200 μ m etc.
In the method provided by the invention, said naphthenic hydrocarbon is one or more ring filling hydrocarbon compound that contains that contains 3～18 carbon atoms in the molecular structure, can be but is not limited to hexanaphthene, pentamethylene or methylcyclohexane etc.
In the method provided by the invention, oxygenant is hydrogen peroxide.The reduzate of hydrogen peroxide is water only, is environment amenable Green Oxidant.In the method provided by the invention, there is no particular limitation to hydrogen peroxide, and any concentration all can.The hydrogen peroxide normally aqueous solution of hydrogen peroxide (hydrogen peroxide) form uses.High density hydrogen peroxide character is unstable, has potential safety hazard in production, accumulating, use procedure, and cost is higher.Therefore consider from safety and economy that usually selecting mass percentage concentration is 10～60% hydrogen peroxide, for example the hydrogen peroxide of technical grade has 27.5%, 30% and 35% specification.In proportioning raw materials, said hydrogen peroxide is in hydrogen peroxide.
In the method provided by the invention, entrainer comprises all and can give birth to one or more combination in the organism of azeotropic with steeping in water for reconstitution, said entrainer for example is halohydrocarbon, the alcohol that contains 1～6 carbon, the ester that contains 3～5 carbon, the ketone that contains 2～4 carbon, the carboxylic acid that contains 1～4 carbon, contain in the aromatic hydrocarbon of 6～9 carbon one or more, concrete entrainer kind can include but are not limited to such as benzene, ethyl acetate, pyridine, propyl carbinol, Virahol, acetonitrile, methylene dichloride, ether, formic acid, ethanol, formic acid, tetracol phenixin and toluene etc., preferred ethyl acetate wherein, Virahol, formic acid, ethanol, formic acid, tetracol phenixin, more preferably benzene, ethyl acetate, Virahol, formic acid, in the ethanol one or more.Entrainer also has the evaporation heat-obtaining and shifts out the moisture content function except having the pointed dissolving function of prior art, thereby reaches the purpose of control real reaction temperature.The mass ratio of said entrainer and water is 0.1～20: 1.
In the method provided by the invention, the azeotrope that forms under the said reaction conditions is constantly shifted out and is separated, and the entrainer partial reflux is in reaction system, separation method wherein comprise leave standstill, distill, the combination of one or several modes of the mode such as extraction, absorption, absorption or membrane sepn.
In the method provided by the invention, described reaction also can be done to carry out in the situation of solvent with the inertia organism.The existence of solvent so that the reaction more uniform and stable carry out.Select the inertia organism to make solvent, require in principle it not participate in reaction.The inertia organism is divided into two classes according to its feature, and a class is the compound close with boiling point of reactant, and another kind of is the compound that polarity is large, specific inductivity is high.The former comprises the compounds such as lower aliphatic alcohols, ketone, acid, ester, particular methanol, ethanol, the trimethyl carbinol, acetone, acetic acid, ethyl acetate etc.The latter comprises acetonitrile, chloroform, the organic compound that the tetramethylene sulfone isopolarity is large, specific inductivity is high.The mass ratio of solvent and aromatic hydrocarbon can change in a big way, can be 1: 100～100: 1, considers the economy of operation, generally remains on 1: 10～10: 1, preferred 1: 3～3: 1.
In the method provided by the present invention, the effect of said solvent and entrainer is distinguishing, but the two can be identical or different.The purpose of introducing solvent is the mutual dissolution degree that improves between the various reactants, thereby improves the mass transfer diffusional effect in the reaction process; And the effect of entrainer is to form azeotropism with introducing in the reaction system and/or the water that generates, thereby improves the concentration of hydrogen peroxide, increases the utilising efficiency of hydrogen peroxide.Said entrainer also can be reactant itself, and some entrainer also can play the effect of solvent.For example, methylene dichloride not only can be used as solvent but also can be used as entrainer, its effective degree of dissolving each other of intensified response thing cyclic ketones compound and hydrogen peroxide on the one hand, it can give birth to the azeotropic effect with steeping in water for reconstitution being lower than under self boiling temperature on the other hand, through refluxing and separating, can continually water be shifted out reaction system, thereby increase lower concentration hydrogen peroxide utilization ratio.
Method provided by the invention, said oxidation reaction condition comprise that the reaction set temperature is at least the temperature of water and entrainer generation azeotropism; Preferred set temperature is water and the temperature to 150 of entrainer generation azeotropic ℃; Preferred set temperature is the temperature to 95 ℃ that water and entrainer produce azeotropic; Reaction pressure is normal pressure～1.0MPa, is preferably normal pressure～0.8MPa, more preferably normal pressure～0.5MPa.According to the difference of purpose product, the reaction times can be 0.1～48 hour, can be 0.3～24 hour the selective reaction time further.
In the method provided by the invention, the mass ratio of catalyzer and naphthenic hydrocarbon can be 1: 1～100; The mol ratio of hydrogen peroxide and naphthenic hydrocarbon is 1: 100～100: 1; Considering the balance of speed of reaction and production cost, the mass ratio of catalyzer and naphthenic hydrocarbon is preferably 1: 2～and 20, more preferably 1: 7～20; Preferred 1: 10～10: 1 of the mol ratio of hydrogen peroxide and naphthenic hydrocarbon, more preferably 3: 1～1: 3.
The invention provides in the specific embodiment of method, reaction system mainly is made of reactor, phase splitter and condenser at one, wherein phase splitter is positioned at the top of reactor, and condenser is positioned at the top of phase splitter, and azeotropic steam is entered by the phase splitter stage casing.Method provided by the invention comprises: catalyzer, entrainer, drop in the reactor according to certain proportioning, stir, after rising to certain temperature, add a certain amount of aqueous hydrogen peroxide solution and naphthenic hydrocarbon, holder ties up under certain temperature and pressure, the mixture of catalyzer and liquid material reacts in reactor, water and entrainer form azeotropism, the steam that azeotropic forms enters into condensing works through phase splitter, (liquid phase is separated after the condensation with the organic phase two-phase to be divided into water after the condensation, by organism density less than water, organic phase is positioned at the upper strata), regulate the liquid level of water in the phase splitter, entrainer is constantly got back in the reactor, and water is constantly told system, simultaneously, usually the density of entrainer and raw material can make reaction mass and entrainer be back to reaction unit by the position of controlling liquid level in the phase splitter, thereby shift out the water of reaction system less than water, improve hydrogen peroxide concentration, add fast response and carry out.The reaction mass and the entrainer that reflux out from the component distillation component can be recycled, and reaction mass and product can add and extraction in reaction unit continuously.
Cycloalkanes oxidation method provided by the invention, titanium-silicon molecular sieve catalyst, entrainer, hydrogen peroxide and in reactor 1, catalytic oxidation occurs with naphthenic hydrocarbon, reactor top is connected with neutral section 2 (water-and-oil separator) middle part, and neutral section 2 upper ends connect condensing works 3.Azeotropism can occur in reaction mass, entrainer and water three when reaction was carried out, the steam that forms enters into condensing works 3 through phase splitter 2, liquid phase is separated after the condensation, usually the density of entrainer and raw material is less than water, position by liquid level in the control phase splitter 2 can make reaction mass and entrainer be back to reaction unit 1, thereby shift out the water of reaction system, improve hydrogen peroxide concentration, add fast response and carry out.The reaction mass and the entrainer that reflux out from the component distillation component can be recycled, reaction mass and product can add and extraction continuously, liquid material separates with catalyzer, can take various Technology in Solid/Liquid Separations, such as centrifugal, membrane filtration, sedimentation, spinning liquid, evaporation etc.
By reference to the accompanying drawings, the implementation process of method provided by the invention is described: powdery solid titanium-silicon molecular sieve catalyst and entrainer add the catalyzer storage tank, mix rear and naphthenic hydrocarbon, hydrogen peroxide enters from the opening for feed of reactor 1 together, heating makes it that violent azeotropic occur in reactor, the a large amount of azeotropic steam that produce enter (this moment, pipeline 5 was in closing condition) in the phase splitter 2 through pipeline 4, steam continues to rise in the condenser 3, be cooled to the profit two-phase, the layering in phase splitter 2 of profit two-phase, by regulating the uninterrupted of pipeline 5 and pipeline 6, liquid level is kept certain height, and guarantee that oil phase can smooth and easyly be got back in the reactor and isolated water can shift out system.Can carry out continuously the input of material or shift out in reactor, be that whole reaction process keeps continuously.The material that shifts out from system, entrainer, product and catalyzer enter into catalyst separator, separate rear catalyst and continue to recycle, and material, entrainer and product enter separation circuit, and material and entrainer drop into the catalyzer storage tank again to be continued to recycle.
Azeotropic steam-in and backflow material can export separate in the phase splitter, also can unite two into one, be that said pipeline 4 and 5 can unite two into one, in this case, then powdery solid titanium-silicon molecular sieve catalyst and entrainer add the catalyzer storage tank, mix rear and naphthenic hydrocarbon, hydrogen peroxide enters from the opening for feed of reactor 1 together, heating makes it that violent azeotropic occur in reactor, the a large amount of azeotropic steam that produce enter in the phase splitter through pipeline 4, steam continues to rise in the condenser 3, be cooled to the profit two-phase, the layering in phase splitter 2 of profit two-phase, upper oil phase is stayed back in the reactor along lower tube wall by pipeline 4, regulates the uninterrupted of pipeline 6, liquid level is kept certain height, guarantee that oil phase can smooth and easyly be got back in the reactor and isolated water can shift out system.In reactor 1, can carry out continuously the input of material or shift out, make whole reaction process keep highly continuous.The material that shifts out from system, entrainer, product and catalyzer enter into catalyst separator, separate rear catalyst and continue to recycle, and material, entrainer and product enter separation circuit, and material and entrainer drop into the catalyzer storage tank again to be continued to recycle.
The invention will be further described below by embodiment, but therefore do not limit content of the present invention.
Use reagent to be analytical pure among the embodiment, the concentration of hydrogen peroxide is 30%.
Employed HTS molecular sieve is built feldspathization company by the Hunan and is produced among the embodiment, take the titanium content of titanium oxide as 2.5 % by weight, has hollow crystal grain, and the radical length of the cavity part of hollow crystal grain is 15～180 nanometers, at 25 ℃, P/P
0=0.10 and 1 hour condition of adsorption time under the benzene adsorptive capacity that records at least 78 milligrams/gram, have hysteresis loop between the adsorption isothermal line of nitrogen absorption under low temperature and the desorption isotherm; The Ti-beta molecular sieve is according to document (Takashi Tatsumi, et al., Synthesis of Ti-beta Zeolite with High Oxidation Activity by Dry-gel Conversion Technique, Chemistry Letters 1997pp.677-678.) described method is synthetic, in oxide compound, the titanium content of this HTS is 2.6 % by weight; The TS-2 molecular sieve is according to document (Reddy, J.S., et al., Journal of Catalysis, vol.130, No.2, pp.440-446, " Synthesis, Characterization; and Catalytic Properties of a Titanium Silicate; TS-2, with Mel Structure ", Aug.1,1991.) described method is synthetic, take the titanium content of titanium oxide as 2.5 % by weight.
Transformation efficiency, the corresponding selectivity of product of cycloalkanes hydrocarbons and their derivates etc. calculate respectively according to the following equation among the embodiment:
The situation of present embodiment explanation hexanaphthene Direct Catalytic Oxidation 6-caprolactone processed, 6 hydroxycaproic acid and hexanodioic acid.
Reactor is slurry bed reactor, uses catalyzer to be HTS, and the granules of catalyst diameter Distribution is 1～200 μ m; Reaction raw materials is 30% hydrogen peroxide and 99.9% above hexanaphthene; Entrainer is ethyl acetate.The preparation catalyst concn is 5% ethyl acetate slurries in the catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under the condition of setting, device is carried out trial trip with ethyl acetate, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, raw material hexanaphthene are added conversion zone in the tower.Absolute pressure is 0.1MPa, and the reaction set temperature is 80 ℃, and azeotropic temperature is 74 ℃ in the reactor, the mol ratio of conversion zone hexanaphthene and ethyl acetate 1: 5, and the raw materials components mole ratio of hexanaphthene and hydrogen peroxide is 1: 3, reacts 8 hours.Reaction result: cyclohexane conversion is 34.23%, and the selectivity of 6-caprolactone is 16.87%, and the 6 hydroxycaproic acid selectivity is 38.98%, hexanodioic acid selectivity 13.64%.
The situation of present embodiment explanation hexanaphthene Direct Catalytic Oxidation 6-caprolactone processed, 6 hydroxycaproic acid and hexanodioic acid.
Reactor is slurry bed reactor, uses catalyzer to be HTS, and the granules of catalyst diameter Distribution is 1～200 μ m; Reaction raw materials is 30% hydrogen peroxide and 99.9% above hexanaphthene; Entrainer is benzene.The preparation catalyst concn is 5% benzene slurries in the catalyzer storage tank, and fully dispersed with stirring is carried out trial trip to device with benzene with for subsequent use under the condition of setting, and after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, hexanaphthene is added conversion zone in the tower.Absolute pressure is 0.12MPa, and the reaction set temperature is 75 ℃, and azeotropic temperature is 73 ℃ in the reactor, the mol ratio of conversion zone hexanaphthene and hydrogen peroxide 1: 5, and the charging mass ratio of hexanaphthene and catalyzer is 1: 0.15, reacts 2 hours.
Reaction result: cyclohexane conversion is 45.23%, and the selectivity of caprolactone is 32.03%, and the 6 hydroxycaproic acid selectivity is 26.98%, hexanodioic acid selectivity 35.62%.
The situation of present embodiment explanation pentamethylene Direct Catalytic Oxidation δ-valerolactone processed, 5-hydroxypentanoic acid and pentanedioic acid.
Reactor is slurry bed reactor, uses catalyzer to be HTS, and the granules of catalyst diameter Distribution is 1～200 μ m; Reaction raw materials is 30% hydrogen peroxide and 99.9% above pentamethylene; Entrainer is benzene and methyl alcohol.The preparation catalyst concn is 5% methanol slurry in the catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under the condition of setting, device is carried out trial trip with methyl alcohol, after horizontalization to be installed is steady, catalyst slurry, benzene, hydrogen peroxide, pentamethylene are added conversion zone in the tower.Absolute pressure is 0.1MPa, and the reaction set temperature is 85 ℃, and azeotropic temperature is 72 ℃ in the reactor, the mol ratio of conversion zone pentamethylene and methyl alcohol 1: 5, the raw materials components mole ratio of pentamethylene and hydrogen peroxide is 1: 6, and the raw materials components mole ratio of methyl alcohol and benzene 4: 1 reacted 24 hours.
Reaction result: the pentamethylene transformation efficiency is 98.23%, and the selectivity of δ-valerolactone is that 2.36%, 5-hydroxypentanoic acid selectivity is 4.01%, pentanedioic acid selectivity 89.57%.
The situation of present embodiment explanation pentamethylene Direct Catalytic Oxidation δ-valerolactone processed, 5-hydroxypentanoic acid and pentanedioic acid.
Reactor is slurry bed reactor, uses catalyzer to be HTS, and the granules of catalyst diameter Distribution is 1～200 μ m; Reaction raw materials is 30% hydrogen peroxide and 99.9% above pentamethylene; Entrainer is ethyl acetate.The preparation catalyst concn is 5% ethyl acetate slurries in the catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under the condition of setting, device is carried out trial trip with ethyl acetate, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, pentamethylene are added conversion zone in the tower.Absolute pressure is that 0.2MPa reaction set temperature is 90 ℃,, azeotropic temperature is 78 ℃ in the reactor, the mol ratio of conversion zone pentamethylene and ethyl acetate 1: 6, the raw materials components mole ratio of pentamethylene and hydrogen peroxide is 1: 4, reacts 10 hours.
Reaction result: the pentamethylene transformation efficiency is 85.23%, and the selectivity of δ-valerolactone is that 12.43%, 5-hydroxypentanoic acid selectivity is 21.12%, pentanedioic acid selectivity 64.58%.
The situation of present embodiment explanation hexanaphthene Direct Catalytic Oxidation 6-caprolactone processed, 6 hydroxycaproic acid and hexanodioic acid.
Reactor is slurry bed reactor, uses catalyzer to be Ti-Beta, and the granules of catalyst diameter Distribution is 1～200 μ m; Reaction raw materials is 30% hydrogen peroxide and 99.9% above hexanaphthene; Entrainer is benzene.The preparation catalyst concn is 5% benzene slurries in the catalyzer storage tank, and fully dispersed with stirring is carried out trial trip to device with benzene with for subsequent use under the condition of setting, and after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, hexanaphthene is added conversion zone in the tower.Absolute pressure is 0.12MPa, and the reaction set temperature is 82 ℃, and azeotropic temperature is 73 ℃ in the reactor, the mol ratio of conversion zone hexanaphthene and hydrogen peroxide 1: 5, and the charging mass ratio of hexanaphthene and catalyzer is 1: 0.15, reacts 12 hours.
Reaction result: cyclohexane conversion is 16.71%, and the selectivity of 6-caprolactone is 3.21%, and the 6 hydroxycaproic acid selectivity is 76.91%, hexanodioic acid selectivity 18.67%.
The situation of present embodiment explanation pentamethylene Direct Catalytic Oxidation δ-valerolactone processed, 5-hydroxypentanoic acid and pentanedioic acid.
Reactor is slurry bed reactor, uses catalyzer to be TS-2, and the granules of catalyst diameter Distribution is 1～200 μ m; Reaction raw materials is 30% hydrogen peroxide and 99.9% above pentamethylene; Entrainer is benzene and methyl alcohol.The preparation catalyst concn is 5% methanol slurry in the catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under the condition of setting, device is carried out trial trip with methyl alcohol, after horizontalization to be installed is steady, catalyst slurry, benzene, hydrogen peroxide, pentamethylene are added conversion zone in the tower.Absolute pressure is 0.1MPa, and the reaction set temperature is 100 ℃, and azeotropic temperature is 72 ℃ in the reactor, the mol ratio of conversion zone pentamethylene and methyl alcohol 1: 5, the raw materials components mole ratio of pentamethylene and hydrogen peroxide is 1: 6, and the raw materials components mole ratio of methyl alcohol and benzene 4: 1 reacted 24 hours.
Reaction result: the pentamethylene transformation efficiency is 98.23%, and the selectivity of δ-valerolactone is that 2.36%, 5-hydroxypentanoic acid selectivity is 54.12%, pentanedioic acid selectivity 39.57%.
Claims (25)
1. cycloalkanes oxidation method, it is characterized in that being included in oxidation reaction condition and catalyzer exists lower, the reaction mass that comprises naphthenic hydrocarbon, hydrogen peroxide, entrainer and water is contacted, reaction mass and product add and extraction in reaction unit continuously, said entrainer and steeping in water for reconstitution are given birth to azeotropism, the azeotrope that forms under the reaction conditions is constantly shifted out and is separated, and wherein reaction mass and entrainer recycle, and said catalyzer is HTS.
2. according to the process of claim 1 wherein, said HTS is selected from one or more the mixture among TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 and the Ti-MCM-48.
3. according to the method for claim 2, wherein, said TS-1 HTS has hollow crystal grain, and the radical length of the cavity part of hollow crystal grain is 2～300 nanometers, at 25 ℃, P/P
0=0.10 and 1 hour condition of adsorption time under the benzene adsorptive capacity that records at least 70 milligrams/gram, have hysteresis loop between the adsorption isothermal line of nitrogen absorption under low temperature and the desorption isotherm.
4. according to the process of claim 1 wherein, said naphthenic hydrocarbon is one or more ring filling hydrocarbon compound that contains that contains 3～18 carbon atoms in the molecular structure.
5. according to the process of claim 1 wherein, said naphthenic hydrocarbon is hexanaphthene, pentamethylene or methylcyclohexane.
6. according to the process of claim 1 wherein, said entrainer is halohydrocarbon, contain the alcohol of 1～6 carbon, contain 3～5 carbon ester, contain 2～4 carbon ketone, contain 1～4 carbon carboxylic acid, contain in the aromatic hydrocarbon of 6～9 carbon one or more.
7. according to the process of claim 1 wherein, said entrainer is selected from one or more in benzene, ethyl acetate, pyridine, propyl carbinol, Virahol, acetonitrile, methylene dichloride, ether, formic acid, ethanol, formic acid, tetracol phenixin and the toluene.
8. according to the process of claim 1 wherein, the mass ratio of said entrainer and water is 0.1～20: 1.
9. according to the process of claim 1 wherein, the mass ratio of said catalyzer and naphthenic hydrocarbon is 1: 1～100, and the mol ratio of hydrogen peroxide and naphthenic hydrocarbon is 1: 100～100: 1.
10. according to the method for claim 9, wherein, the mass ratio of said catalyzer and naphthenic hydrocarbon is 1: 2～20, and the mol ratio of hydrogen peroxide and naphthenic hydrocarbon is 1: 10～10: 1.
11. according to the method for claim 10, wherein, the mass ratio of said catalyzer and naphthenic hydrocarbon is 1: 7～20, the mol ratio of hydrogen peroxide and naphthenic hydrocarbon is 1: 3～3: 1.
12. according to the process of claim 1 wherein, said oxidation reaction condition comprises that the reaction set temperature extremely
Be the temperature that water and entrainer produce azeotropism less.
13. according to the method for claim 12, wherein, said oxidation reaction condition comprises, the reaction set temperature is water and the temperature to 150 of entrainer generation azeotropic ℃.
14. according to the method for claim 13, wherein, said oxidation reaction condition comprises, the reaction set temperature is water and the temperature to 95 of entrainer generation azeotropic ℃.
15. according to the process of claim 1 wherein, reaction pressure is normal pressure～1.0MPa.
16. according to the method for claim 15, wherein, reaction pressure is normal pressure～0.8MPa.
17. according to the method for claim 16, wherein, reaction pressure is normal pressure～0.5MPa.
18. according to the method for claim 1, it is characterized in that the mol ratio of naphthenic hydrocarbon and entrainer is 1: 1.5～30 in the reactor.
19. according to the method for claim 1, it is characterized in that the mol ratio of naphthenic hydrocarbon and entrainer is 1: 8～20 in the reactor.
20. according to the method for claim 1, the size range that it is characterized in that catalyzer is 0.05～800 μ m.
21. according to the method for claim 20, the size range that it is characterized in that catalyzer is 0.06～600 μ m.
22. according to the method for claim 21, the size range that it is characterized in that catalyzer is 0.5～500 μ m.
23. according to the method for claim 1, the reaction times is 0.1～48 hour.
24. according to the method for claim 1, the reaction times is 0.3～24 hour.
25. according to the method for claim 1, it is characterized in that reaction system mainly is made of reactor, phase splitter and condenser, wherein phase splitter is positioned at the top of reactor, condenser is positioned at the top of phase splitter, and azeotropic steam is entered by the phase splitter stage casing; Said catalyzer, entrainer add naphthenic hydrocarbon, aqueous hydrogen peroxide solution after mix and blend, the intensification in reactor, holder ties up under temperature of reaction and the reaction pressure oxidizing reaction occurs, water and entrainer form azeotropism, the steam that azeotropic forms enters into condensing works through phase splitter, be divided into water and organic phase two-phase after the condensation, regulate the liquid level of water in the phase splitter, make entrainer constantly get back in the reactor, and water is constantly told system, thereby shift out the water of reaction system, improve concentration of hydrogen peroxide.
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| CN111039781A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Process for oxidation of cycloalkanes |
| CN112742467A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of titanium-containing molecular sieve, catalyst and catalytic oxidation method |
| CN116120157A (en) * | 2023-02-24 | 2023-05-16 | 山东京博石油化工有限公司 | Method for preparing cyclopentanone by selective oxidation of cyclopentane |
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| CN112742467B (en) * | 2019-10-30 | 2024-02-20 | 中国石油化工股份有限公司 | Preparation method of titanium-containing molecular sieve, catalyst and catalytic oxidation method |
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