CN103373915B - A kind of catalytic oxidation prepares the method for di-carboxylic acid - Google Patents
A kind of catalytic oxidation prepares the method for di-carboxylic acid Download PDFInfo
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Abstract
A kind of catalytic oxidation prepares the method for di-carboxylic acid, it is characterized in that catalyzer and comprise solvent, aqueous hydrogen peroxide solution and naphthenic hydrocarbon or derivatives thereof add the conversion zone of catalytic distillation tower at interior liquid reactions material, while the mixture of catalyzer and said liquid reactions material flows in tower, liquid reactions material generation catalytic oxidation, from the material after the catalytic oxidation of vaporization, isolate solvent cycle use, and catalyzer and the liquid material after the catalytic oxidation of not vaporizing use through being separated Posterior circle, be separated from tower top or kettle material and obtain unreacted naphthenic hydrocarbon or derivatives thereof and recycle, product di-carboxylic acid is isolated to from kettle material, wherein, said catalyzer is the HTS of HTS or modification.The method utilization of Heat of Reaction rate is high, improves the selectivity of oxidation products di-carboxylic acid, effectively prevent the thermolysis of hydrogen peroxide.
Description
Technical field
The present invention relates to the suspension catalytic process of the corresponding di-carboxylic acid of a kind of cycloalkanes hydrocarbons and their derivates oxidation preparation.More particularly, the invention relates to the oxidizing reaction that cycloalkanes hydrocarbons and their derivates and hydrogen peroxide occur under the katalysis of fine particle HTS and carry out fractionation by distillation, the method for highly selective production corresponding oxide simultaneously.
Background technology
It is white crystal under hexanodioic acid normal temperature, fusing point 153 DEG C, boiling point 332.7 DEG C (101kPa decomposition), relative density 1.360 (25/4 DEG C), flash-point (opening cup) 209.85 DEG C, burning-point (opening cup) 231.85 DEG C, melt viscosity 4.54mPas (160 DEG C), flash-point 196 DEG C.Be slightly soluble in water (15 DEG C, 1.44g/100ml), hexanodioic acid is industrial significant di-carboxylic acid, and in all di-carboxylic acid, output occupies second.Be mainly used in adiponitrile processed and then produce hexanediamine, and produce nylon66 fiber (polymeric amide) and engineering plastics etc. together with hexanediamine.Next is for the production of various esters product, as softening agent and quality lubricant.In addition, hexanodioic acid is also used as the raw material of polyurethane elastomer, produces the raw material of unsaturated polyester, hexylene glycol and adipic acid ester class, the souring agent of various food and drink, medicine, yeast purificant, sterilant, tackiness agent, synthetic leather, synthetic dyestuff and spices.
Nineteen thirty-seven, du pont company's nitric acid oxidation hexalin, first achieves the suitability for industrialized production of hexanodioic acid.Enter the sixties, industrially progressively use cyclohexane oxidation process instead, namely first by hexanaphthene intermediate product pimelinketone and cyclohexanol mixture (namely keto-alcohol is oily, oily also known as KA), and then carry out nitric acid or the atmospheric oxidation of KA oil.Nitric acid oxidation KA oil process is generally the nitric acid of 50% ~ 60% by excessive concentration, carries out through two-stage reactor series connection.The catalyzer that reaction uses is copper-vanadium system (copper 0.1% ~ 0.5%, vanadium 0.1% ~ 0.2%), temperature 60 ~ 80 DEG C, pressure 0.1 ~ 0.4MPa.Yield is 92% ~ 96% of theoretical value.After KA oil oxidation products distills out nitric acid, then through two-stage crystal refining, just high-purity adipic acid can be obtained.Raw material consumption quota: hexalin (or KA oil) 740kg/t, nitric acid (100%) 908kg/t, copper 0.2kg/t, vanadium are (with V
2o
5meter) 0.1kg/t.But this reaction exists deep-etching problem to equipment, environmental pollution is serious, complex process, and energy consumption is higher, do not meet Green Chemistry principle.(nitric acid oxidation hexalin, direct mix and blend, does not have solvent, cannot realize catalytic distillation).
Air oxidation process is that acetic acid is solvent with neutralized verdigris and manganese acetate mixture for catalyzer, with air direct oxidation KA oil.General employing two-stage reactor series connection: first step temperature of reaction 160 ~ 175 DEG C, pressure 0.7MPa (gauge pressure), the reaction times is about 3h; Second stage temperature of reaction 80 DEG C, pressure 0.7MPa (gauge pressure), the reaction times is about 3h.Oxidation products is through two-stage crystal refining, and recovered solvent can be recycled after treatment.This method reaction times is very long, reaction efficiency is lower, product separation is difficult, therefore adopts still few.
Japanese Scientists Ryoji Noyori etc. develops with heteropolyacid Na
2wO
42H
2o is catalyzer, [CH
3n (n-C
8h
17)
3] HSO
4for phase-transfer catalyst, hexanodioic acid prepared by hydrogen peroxide direct oxidation tetrahydrobenzene.Reactant ratio is tetrahydrobenzene: Na
2wO
42H
2o: [CH
3n (n-C
8h
17)
3] HSO
4=100: 1: 1,30%H
2o
2for oxygenant, under 75-90 DEG C of condition, react 8h, the yield of hexanodioic acid reaches 93%.But heteropolyacid catalyst character is unstable, specific surface is little, easy in inactivation, difficult to reclaim and the shortcoming such as work-ing life is short, thus could not reaches at present and extensively promote.
Other production methods of hexanodioic acid have: chlorocyclohexane method, from Utilize Cyclohexane Oxidation By-Product, reclaim hexanodioic acid, and by acrylate obtaining adipic acid etc., Japanese Asahi Kasei Corporation has also carried out the research of hexanaphthene one step atmospheric oxidation hexanodioic acid.Chinese patent CN101337879 disclose a kind of in hexanaphthene, be dissolved with 1-500ppm catalyzer monometallic porphyrin or the mixed catalyst that forms of μ-oxygen bimetallic porphyrin or they and transition metal salt or oxide compound, the technology and equipment of hexanodioic acid prepared by catalytic air oxidation hexanaphthene.
Summary of the invention
The object of this invention is to provide a kind of catalytic reaction method being different from the production di-carboxylic acid of prior art.
A kind of catalytic oxidation provided by the invention prepares the method for di-carboxylic acid, it is characterized in that catalyzer and comprise solvent, aqueous hydrogen peroxide solution and naphthenic hydrocarbon or derivatives thereof add the conversion zone of catalytic distillation tower at interior liquid reactions material, while the mixture of catalyzer and said liquid reactions material flows in tower, liquid reactions material generation catalytic oxidation, from the material after the catalytic oxidation of vaporization, isolate solvent cycle use, and catalyzer and the liquid material after the catalytic oxidation of not vaporizing use through being separated Posterior circle, be separated from tower top or kettle material and obtain unreacted naphthenic hydrocarbon or derivatives thereof and recycle, product di-carboxylic acid is isolated to from kettle material, wherein, said catalyzer is the HTS of HTS or modification, size range is 0.2 ~ 800 μm, in said conversion zone, temperature of reaction is the temperature lower than product di-carboxylic acid boiling point, , reaction pressure is 0.1 ~ 2.0MPa, the mass ratio of catalyzer and said cycloalkanes hydrocarbons and their derivates is 1: 5 ~ 100, the mass space velocity of said liquid reactions material is 0.01 ~ 10h
-1, overhead mixture material reflux ratio is 1 ~ 30: 1, and in said liquid reactions material, the mol ratio of cycloalkanes hydrocarbons and their derivates and solvent is 1: 1.5 ~ 30, be 0.1 ~ 10: 1 with the mol ratio of hydrogen peroxide.
Method provided by the invention, is placed on inside a tower by reaction and separation processes, a large amount of reaction heat is used directly to evaporation and is separated remaining reactant and solvent, and utilization of Heat of Reaction rate is high, and energy consumption reduces greatly; Effectively inhibit the generation of product side reaction, effectively prevent the thermolysis of aqueous hydrogen peroxide solution, improve the selectivity of catalyzed oxidation product lactone; Catalyzer add with convenient to remove, without the need to stop work.
Accompanying drawing explanation
Accompanying drawing is the principle process schematic diagram that catalyzed oxidation provided by the invention prepares di-carboxylic acid.
Embodiment
Catalytic oxidation provided by the invention prepares the method for di-carboxylic acid, it is characterized in that catalyzer and comprise solvent, aqueous hydrogen peroxide solution and naphthenic hydrocarbon or derivatives thereof add the conversion zone of catalytic distillation tower at interior liquid reactions material, while the mixture of catalyzer and said liquid reactions material flows in tower, liquid reactions material generation catalytic oxidation, from the material after the catalytic oxidation of vaporization, isolate solvent cycle use, and catalyzer and the liquid material after the catalytic oxidation of not vaporizing use through being separated Posterior circle, be separated from tower top or kettle material and obtain unreacted naphthenic hydrocarbon or derivatives thereof and recycle, product di-carboxylic acid is isolated to from kettle material, wherein, said catalyzer is the HTS of HTS or modification, size range is 0.2 ~ 800 μm, in said conversion zone, temperature of reaction is the temperature lower than product di-carboxylic acid boiling point, reaction pressure is 0.1 ~ 2.0MPa, the mass ratio of catalyzer and said cycloalkanes hydrocarbons and their derivates is 1: 5 ~ 100, the mass space velocity of said liquid reactions material is 0.01 ~ 10h
-1, overhead mixture material reflux ratio is 1 ~ 30: 1, and in said liquid reactions material, the mol ratio of cycloalkanes hydrocarbons and their derivates and solvent is 1: 1.5 ~ 30, be 0.1 ~ 10: 1 with the mol ratio of hydrogen peroxide.
In method provided by the invention, in said cycloalkanes hydrocarbons and their derivates, naphthenic hydrocarbon be containing 3 ~ 18 carbon atoms in molecular structure containing one or more ring filling hydrocarbon compound.Said cycloalkane derivatives can be cycloolefin, polycyclic olefin, cyclic ketones or cyclic alcohol.In specific embodiment provided by the invention, said naphthenic hydrocarbon or derivatives thereof can be pentamethylene, hexanaphthene, tetrahydrobenzene or pimelinketone.Cycloalkanes hydrocarbons and their derivates can be sterling, also containing some, oxidizing reaction and product separation can not produced to the material of negative effect.
In method provided by the invention, said HTS can be selected from one or more the mixture in TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 and Ti-MCM-48, wherein preferred TS-1, in US Patent No. P4410501, disclose the synthetic method of titanium-silicon molecular sieve TS-1 first.As preferred embodiment, adopt the TS-1 HTS with hollow structure in 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 chamber portion of this hollow crystal grain is 5 ~ 300 nanometers; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm.The said TS-1 HTS with hollow structure, has larger mesopore volume, is generally more than 0.16mL/g, and the TS-1 HTS of routine, mesopore volume is generally at about 0.084mL/g.The TS-1 HTS of said hollow structure, can buy commercially available product, also can with reference to the method preparation disclosed in the Chinese patent of ZL99126289.1.
Contriver is surprised to find that, above-mentioned hollow HTS is introduced modifying element through secondary hydro-thermal in MFI structure, after tin element, use it in the oxidizing reaction of cycloalkanes hydrocarbons and their derivates, under the same reaction conditions, the transformation efficiency of cycloalkanes hydrocarbons and their derivates and the selectivity of optimized product can effectively be improved.Therefore, the HTS of said modification in the present invention is preferably stanniferous HTS, said stanniferous HTS be on HTS basis by with the compound in stanniferous source, template, alkali and water at 100 ~ 160 DEG C through intermediate water thermal synthesis, obtain through operations such as filtering separation, drying and roastings again, in molecular sieve, Theil indices is 1 ~ 5wt.%, form stronger Lewis acid site at frame position, thus in organic reaction, strengthen its activation to substrate.
In method provided by the invention, said catalyzer, directly can use the former powder of HTS, also can be the product of the former powder of HTS through spray shaping of HTS and modification.Be no matter the product of former powder or spray shaping, its granular size is wanted to ensure that it can be evenly dispersed in liquid material under suitable stirring, continuous flow in tower and can not block up tower; But the granularity of catalyzer can not be meticulous, meticulous catalyzer can increase the separating difficulty of catalyzer and material, therefore, catalyst grain size scope is 0.2-800 μm, preferably 0.5-600 μm, more preferably 1-500 μm.The binding agent that the product of said spray shaping generally uses is non-acid colloidal sol, these colloidal sols can be selected from the one in titanium dioxide, silicon-dioxide, aluminum oxide and silica-alumina, silica-titania etc., also some non-acid clays can be selected, as polynite, kaolin, wilkinite and sepiolite, the content of the catalyzer Middle molecule sieve of spray shaping is 5-80%, preferably 15-60%.
In method provided by the invention, taking hydrogen peroxide as oxygenant, because its reduzate is only water, environmental friendliness, is Green Oxidant.Character is unstable in higher concentrations for the aqueous solution (hydrogen peroxide) of hydrogen peroxide, potential safety hazard is there is in production, accumulating, use procedure, and cost is higher, therefore, be normally that the form of the aqueous hydrogen peroxide solution of 10 ~ 60% adds in reaction system with mass percentage concentration, the aqueous hydrogen peroxide solution of such as technical grade has 27.5%, 30% and 35% etc., usually select mass percentage concentration be 30% hydrogen peroxide.In proportioning raw materials, said hydrogen peroxide is in hydrogen peroxide.
In method provided by the invention, described solvent can be selected from alcohol, ketone, ester, acid, preferably containing the organic acid of the alcohol of 1 ~ 4 carbon atom, the ketone of 3 ~ 5 carbon atoms and 2 ~ 4 carbon atoms, be more preferably methyl alcohol, ethanol, propyl alcohol, butanols, acetone, methylethylketone, acetic acid or propionic acid etc.These solvents, except the dissolving function had pointed by prior art, also have evaporation heat-obtaining function, thus reach the object controlling temperature of reaction.Contriver is surprised to find that, particularly naphthenic hydrocarbon: the mol ratio of hydrogen peroxide (in hydrogen peroxide) is 1: (0.2 ~ 10) and the mass ratio of catalyzer and naphthenic hydrocarbon is 1: 5 ~ 100, be (0.2 ~ 10) with the mol ratio proportioning of naphthenic hydrocarbon: 1, temperature is the temperature lower than product di-carboxylic acid boiling point, when pressure is under the condition of 0.1 ~ 3.0MPa, said HTS is stanniferous HTS (is by the compound with stanniferous source on HTS basis, template, alkali and water at 100 ~ 160 DEG C through intermediate water thermal synthesis, again through filtering separation, dry and baking operation and obtaining, be 1 ~ 5 % by weight with oxide basis Theil indices in molecular sieve) when, when adopting acetic acid or propionic acid as solvent, comparatively with other organic solvents, the selectivity of corresponding di-carboxylic acid is improved largely.
Said conversion zone in method provided by the invention, its reaction pressure is absolute pressure, the change of reaction pressure is not obvious on the impact of reaction product, can be between 0.1MPa ~ 2.0MPa, consider from the economy of operation, preferred 0.1MPa ~ the 1.0MPa of reaction pressure, is more preferably 0.1 ~ 0.5MPa.Said temperature of reaction is the temperature lower than product di-carboxylic acid boiling point.
The concentration of said catalyzer based on solvent, for weight of solvent 0.5 ~ 30 % by weight, preferably 1.0 ~ 15 % by weight, the mass space velocity of reaction mass is 0.01 ~ 10h
-1, preferred 0.1 ~ 8h
-1, in reaction mass, the mol ratio of cycloalkanes hydrocarbons and their derivates and hydrogen peroxide is preferably 1.5 ~ 10: 1, and more preferably 2 ~ 6: 1.In order to ensure cycloalkanes hydrocarbons and their derivates, peroxidation Hydrogen Energy dissolves in the presence of solvent mutually, and in conversion zone, the mol ratio of cycloalkanes hydrocarbons and their derivates and solvent is 1: 5 ~ 30, preferably 1: 8 ~ 20; Trim the top of column ratio is 1 ~ 30: 1, preferably 5 ~ 20: 1, said trim the top of column material, and when boiling point of reactant is higher than temperature of reaction, said backflow material is mainly solvent; When reactant be liquid and boiling point lower than temperature of reaction time, said backflow material is the mixture comprising solvent and cycloalkanes hydrocarbons and their derivates.
Method provided by the invention is a kind of Suspend catalytic distillation processing method, and this technique is a kind of new catalytic distil process between common homogeneous reaction distillation and heterogeneous catalysis distillation.Described catalytic distillation tower is identical with common catalyzed distillation tower, does not need particular design, manufacture.They can be the packing tower, sieve-tray tower, valve tray column etc. of various types.Conversion zone, distilling period and stripping section can adopt dissimilar tower to combine.For preventing blocking, preferred sieve-tray tower or packing tower.If employing packing tower, filler should be greater than 1000 with catalyst particle size ratio, and the voidage of filler should between 40-80%.The stage number of distilling period, conversion zone and stripping section or packed height are with the system of reaction, catalyst activity height, fixed to transformation efficiency and the requirement be separated.
In method provided by the invention, said liquid material is separated with catalyzer, can take various Technology in Solid/Liquid Separation, as centrifugal, membrane filtration, sedimentation, spinning liquid, evaporation etc.
Below for a kind of be followed successively by from top to bottom distilling period, conversion zone, stripping section catalytic distillation tower three kinds of concrete embodiments are described, but the present invention is not limited to this three kinds of embodiments.
The first embodiment is the cycloalkanes hydrocarbons and their derivates raw material of gas under, normal temperature low for boiling point.Powdery solid titanium-silicon molecular sieve catalyst and solvent add catalyzer storage tank, enter in tower from the top of the conversion zone of tower together with hydrogen peroxide after mixing, react with the cycloalkanes hydrocarbons and their derivates counter current contact of dividing one or more to enter tower from conversion zone in decline process.The corresponding oxide compound di-carboxylic acid that reaction generates, react after remaining cycloalkanes hydrocarbons and their derivates and partial solvent reacted liberated heat vaporization, enter gas-liquid separator through distilling period and condenser, unreacted Ring alkane hydrocarbons and their derivates uses through removing oxygen Posterior circle.From gas-liquid separator liquid solvent out, a part flows in tower through tundish, and another part removes catalyzer tundish as thinner.Partial solvent, water, di-carboxylic acid crude product, a small amount of byproduct and catalyzer enter stripping section, solvent is partly or entirely proposed to enter conversion zone, unclassified stores enters catalyst separator through tower reactor, isolated catalyzer enters catalyzer tundish, after dilution, be transported to catalyzer storage tank recycle, the liquid dihydric carboxylic acid crude product that catalyst separator separates enters follow-up refining manufacturing procedure.Tower reactor and the heat needed for stripping section are provided by reboiler.
The second embodiment be for be liquid under normal temperature but its boiling point lower than the cycloalkanes hydrocarbons and their derivates of temperature of reaction.Powdery solid titanium-silicon molecular sieve catalyst and solvent add catalyzer storage tank, enter in tower from the top of the conversion zone of tower together with hydrogen peroxide after mixing, react with the cycloalkanes hydrocarbons and their derivates counter current contact of dividing one or more to enter tower from conversion zone in decline process.React remaining cycloalkanes hydrocarbons and their derivates and solvent and reacted liberated heat vaporization, through distilling period and condenser, enter gas-liquid separator, the noncondensable gas separated is emptying, liquid enters distillation tower, and tower top goes out unreacted cycloalkanes hydrocarbons and their derivates, recycles, the solvent part gone out at the bottom of tower removes catalyzer tundish as thinner, and another part flows in tower through tundish.The material of not vaporizing of conversion zone is descending enters stripping section, proposition cycloalkanes hydrocarbons and their derivates and solvent enter conversion zone, do not carry and heat up in a steamer thing and enter catalyst separator through tower reactor, the catalyzer separated enters catalyzer tundish, is transported to catalyzer storage tank and recycles after dilution; From the thick product introduction subsequent processing operations of liquid dihydric carboxylic acid that catalyst separator separates.Tower reactor and the heat needed for stripping section are provided by reboiler.
The third embodiment is for the cycloalkanes hydrocarbons and their derivates of boiling point higher than temperature of reaction.Embodiment provided by the invention is: powdery solid titanium-silicon molecular sieve catalyst and solvent enter catalyzer storage tank, enters in tower after sufficiently mixing together with hydrogen peroxide from the top of the conversion zone of tower; Meanwhile, cycloalkanes hydrocarbons and their derivates divides one or more to enter in tower from the top of conversion zone, and reacts with catalyst exposure.Distilling period is up to by the material that reaction heat is vaporized, wherein cycloalkanes hydrocarbons and their derivates gets back to conversion zone through fractionation, solvent vapo(u)r enters gas-liquid separator after condenser condenses, the non-condensable gas separated is emptying, a liquid solvent part is back in tower through tundish, and another part removes catalyzer tundish as thinner.The material that conversion zone is not vaporized comes downwards to stripping section, proposes whole solvents and gets back to conversion zone, does not carry heating up in a steamer thing and entering catalyst separator through tower reactor, and the catalyzer separated enters catalyzer tundish, is transported to catalyzer storage tank and recycles after dilution; The liquid material that catalyst separator separates enters the distillation tower separately established, and tower top goes out cycloalkanes hydrocarbons and their derivates and recycles; Go out liquid di-carboxylic acid crude product at the bottom of tower and enter follow-up refining manufacturing procedure.Tower reactor and the heat needed for stripping section are provided by reboiler.
Figure below combination principle schematic flow sheet is further detailed embodiment provided by the present invention, but does not limit the present invention.
Powdery solid titanium-silicon molecular sieve catalyst 1 and solvent 2 add catalyzer storage tank 3 respectively through pipeline, the top of the conversion zone 5 from tower together with hydrogen peroxide 4 after mixing enters in tower, is divided into one or more cycloalkanes hydrocarbons and their derivates 6 counter current contact entering tower and reacts in decline process with conversion zone 5 bottom.The di-carboxylic acid product that reaction generates, react after remaining cycloalkanes hydrocarbons and their derivates and partial solvent reacted liberated heat vaporization, enter gas-liquid separator 9 through distilling period 7, condenser 8 successively, unreacted Ring alkane hydrocarbons and their derivates uses through removing oxygen Posterior circle.Distillation tower 10 is entered from gas-liquid separator 9 liquid out, the thick product of di-carboxylic acid at distillation tower 10 top is recovered, and the solvent bottom distillation tower 10 is divided into two portions, wherein a part is back in tower through tundish 11, another part then removes catalyzer tundish 12 as thinner, partial solvent, water, a small amount of by product and catalyzer autoreaction section 5 enter stripping section 13, solvent is suggested and enters conversion zone, other material then enters catalyst separator 14 through tower reactor 9, isolated catalyzer enters catalyzer tundish 12, after the solvent cut from distillation tower 10, send catalyzer storage tank 3 back to recycle, the liquid material that catalyst separator 14 separates enters subsequent processing operations.Extension mixture between tower reactor 15 and catalyst separator 14, enters reboiler 16, and gets back to stripping section 13 through boiling again, and therefore provides tower reactor 9 and the heat needed for stripping section 13.
Method provided by the invention, for being liquid under normal temperature but its boiling point to be distinguished in the accompanying drawings lower than the cycloalkanes hydrocarbons and their derivates of temperature of reaction and is, in gas-liquid separator 9, noncondensable gas (primarily of peroxide decomposition) is out emptying, unreacted naphthenic hydrocarbon and derivative from overhead extraction, and recycle.
Method provided by the invention, for boiling point higher than temperature of reaction cycloalkanes hydrocarbons and their derivates in the accompanying drawings, difference is in the accompanying drawings, in gas-liquid separator 9, noncondensable gas (primarily of peroxide decomposition) is out emptying; Unreacted naphthenic hydrocarbon and derivative and di-carboxylic acid product flow out from tower reactor, the distillation tower entering after solid catalyst and separately establish is separated through catalyst separator 14, the cycloalkanes hydrocarbons and their derivates that distillation tower separates recycles, and liquid dihydric carboxylic acid crude product then enters follow-up refining manufacturing procedure.
Below by embodiment, the invention will be further described.
The HTS molecular sieve used in embodiment is built feldspathization company by Hunan and is produced, and is 2.5 % by weight in the titanium content of titanium oxide, has hollow crystal grain, and the radical length of the chamber portion of hollow crystal grain is 15 ~ 180 nanometers, at 25 DEG C, P/P
0=0.10 and the adsorption time condition of 1 hour under the benzene adsorptive capacity that records be at least 78 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of nitrogen absorption under low temperature and desorption isotherm.
TS-1 molecular sieve is in the lab according to synthesized by patent US4410501 method.Ti-beta molecular sieve is according to document (Takashi Tatsumi, et al., Synthesis of Ti-beta Zeolite with HighOxidation Activity by Dry-gel Conversion Technique, Chemistry Letters 1997 pp.677-678.; Pp.677-678.) described method synthesis; 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, andCatalytic Properties of a Titanium Silicate; TS-2; with Mel Structure ", Aug.1,1991.) described method synthesis; Ti-MWW molecular sieve, according to method synthesis described in patent US 8124555, is 2.5 % by weight in the titanium content of titanium oxide in various molecular sieve containing titanium.
In embodiment, the transformation efficiency of ring hydrocarbons and their derivates etc., corresponding di-carboxylic acid selectivity calculate respectively according to the following equation:
Embodiment 1
The present embodiment illustrates the situation of pimelinketone direct oxidation hexanodioic acid.
Reaction tower is sieve-tray tower, and use catalyzer is HTS, and catalyst particle diameter is distributed as 1 ~ 200 μm; Reaction raw materials is the pimelinketone of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.In catalyzer storage tank, prepare the acetone slurry that catalyst concn is 5%, and fully dispersed with stirring, with for subsequent use, carries out trial trip to device under conditions set with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, pimelinketone are added conversion zone in tower.Absolute pressure is 0.23MPa, and conversion zone temperature is 110 DEG C, the mol ratio 1: 5 of conversion zone pimelinketone and acetone, and pimelinketone mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 6: 1.The raw materials components mole ratio of pimelinketone and hydrogen peroxide is 1: 3, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pimelinketone recycles.Reaction result: pimelinketone transformation efficiency is 90.23%, the selectivity of hexanodioic acid is 94.84%.
Embodiment 2
The present embodiment illustrates the situation of pimelinketone direct oxidation hexanodioic acid.
Reaction tower is sieve-tray tower, and use catalyzer to be take silicon sol as the HTS of binding agent spray shaping, the content of HTS is 50%, and catalyst particle diameter is distributed as 40 ~ 600 μm; Reaction raw materials is the pimelinketone of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.The acetone slurry that catalyst concn is 15% is prepared in catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under conditions set trial trip is carried out to device with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, pimelinketone are added conversion zone in tower.Absolute pressure is 0.20MPa, and conversion zone temperature is 108 DEG C, the mol ratio 1: 7 of conversion zone pimelinketone and acetone, and pimelinketone mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 8: 1.The raw materials components mole ratio of pimelinketone and hydrogen peroxide is 1: 4, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pimelinketone recycles.Reaction result: pimelinketone transformation efficiency is 99.23%, the selectivity of hexanodioic acid is 97.84%.
Embodiment 3
The present embodiment illustrates the situation of pentamethylene direct oxidation pentanedioic acid.
Reaction tower is sieve-tray tower, and use catalyzer is HTS, and catalyst particle diameter is distributed as 1 ~ 200 μm; Reaction raw materials is the cyclopentanone of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.In catalyzer storage tank, prepare the acetone slurry that catalyst concn is 5%, and fully dispersed with stirring, with for subsequent use, carries out trial trip to device under conditions set with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, cyclopentanone are added conversion zone in tower.Absolute pressure is 0.19MPa, and conversion zone temperature is 108 DEG C, the mol ratio 1: 5 of conversion zone pentamethylene and acetone, and pentamethylene mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 6: 1.The raw materials components mole ratio of pentamethylene and hydrogen peroxide is 1: 5, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pentamethylene recycles.Reaction result: pentamethylene transformation efficiency is 94.73%, the selectivity of pentanedioic acid is 98.34%.
Embodiment 4
The present embodiment illustrates the situation of pentamethylene direct oxidation pentanedioic acid.
Reaction tower is sieve-tray tower, and use catalyzer to be take silicon sol as the HTS of binding agent spray shaping, the content of HTS is 50%, and catalyst particle diameter is distributed as 40 ~ 600 μm; Reaction raw materials is the pentamethylene of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.The acetone slurry that catalyst concn is 15% is prepared in catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under conditions set trial trip is carried out to device with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, pentamethylene are added conversion zone in tower.Absolute pressure is 0.26MPa, and conversion zone temperature is 120 DEG C, the mol ratio 1: 7 of conversion zone pentamethylene and acetone, and pentamethylene mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 8: 1.The raw materials components mole ratio of pentamethylene and hydrogen peroxide is 1: 6, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pentamethylene recycles.Reaction result: pentamethylene transformation efficiency is 99.63%, the selectivity of pentanedioic acid is 93.36%.
Embodiment 5
The present embodiment illustrates with the method for the pimelinketone direct oxidation hexanodioic acid provided by the invention of stanniferous titanium molecular sieve catalysis.
The preparation of stanniferous HTS: 22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOH, and add 59.8 grams of distilled water, at normal pressure and 60 DEG C, 1.0 hours are hydrolyzed after mixing, obtain the hydrating solution of tetraethyl orthosilicate, add the solution be made up of 1.1 grams of tetrabutyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring lentamente, gained mixture is stirred 3 hours at 75 DEG C, by the time clear colloid.This colloid is put into stainless steel sealed reactor, and at the temperature of 170 DEG C and autogenous pressure, constant temperature places 6 days, obtains the mixture of crystallization product; Being filtered, be washed with water to PH by this mixture is 6 ~ 8, and in 110 DEG C of dryings 60 minutes, obtains the former powder of TS-1 of non-roasting.By the roasting 4 hours in air atmosphere at 550 DEG C of former for this TS-1 powder, obtain TS-1 molecular sieve.According to molecular sieve (gram): sulfuric acid (mole): the ratio uniform mixing of water (mole)=100: 0.15: 15, react 5.0 hours at 90 DEG C, then conventionally filter, wash and drying, obtain acid-treated TS-1 molecular sieve.By above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): trolamine (mole): TPAOH (mole): the ratio of water (mole)=100: 0.20: 0.15: 180 mixes, put into stainless steel sealed reactor, under 190 DEG C and autogenous pressure, constant temperature places 0.5 day time, after cooling release, conventionally filter, wash, dry, and air atmosphere roasting 3 hours at 550 DEG C, hollow structure molecular sieve.Be the HTS of MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15 ~ 180 nanometers; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram.Again by hollow structure molecular sieve 140 DEG C, TPAOH is template, anhydrous stannic chloride is in the system of Xi Yuan, according to molecular sieve (gram): anhydrous stannic chloride (mole): TPAOH (mole): the ratio of water (mole)=100: 0.06x: 0.15: 180 mixes, through enclosed high pressure still, Hydrothermal Synthesis 72 hours at 140 DEG C, introduce with oxide basis, the tin element being respectively 2.4wt% in its MFI skeleton, catalyzer is designated as Sn-HTS.
Reaction tower is sieve-tray tower, and use catalyzer is Sn-HTS, and catalyst particle diameter is distributed as 1 ~ 200 μm; Reaction raw materials is the pimelinketone of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.In catalyzer storage tank, prepare the acetone slurry that catalyst concn is 5%, and fully dispersed with stirring, with for subsequent use, carries out trial trip to device under conditions set with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, pimelinketone are added conversion zone in tower.Absolute pressure is 0.25MPa, and conversion zone temperature is 113 DEG C, the mol ratio 1: 5 of conversion zone pimelinketone and acetone, and pimelinketone mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 6: 1.The raw materials components mole ratio of pimelinketone and hydrogen peroxide is 1: 3, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pimelinketone recycles.Reaction result: pimelinketone transformation efficiency is 92.58%, the selectivity of hexanodioic acid is 99.31%.
Embodiment 6
The present embodiment illustrates the situation of hexanaphthene direct oxidation hexanodioic acid.
Reaction tower is sieve-tray tower, and use catalyzer to be take silicon sol as the Sn-HTS of binding agent spray shaping, the content of Sn-HTS is 45%, and catalyst particle diameter is distributed as 40 ~ 600 μm; Reaction raw materials is the hexanaphthene of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.The acetone slurry that catalyst concn is 15% is prepared in catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under conditions set trial trip is carried out to device with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, hexanaphthene are added conversion zone in tower.Absolute pressure is 0.19MPa, and conversion zone temperature is 109 DEG C, the mol ratio 1: 7 of conversion zone pimelinketone and acetone, and pimelinketone mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 8: 1.The raw materials components mole ratio of pimelinketone and hydrogen peroxide is 1: 8, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pimelinketone recycles.Reaction result: cyclohexane conversion is 100%, the selectivity of hexanodioic acid is 98.94%.
Embodiment 7
The present embodiment illustrates the situation of pentamethylene direct oxidation pentanedioic acid.
Reaction tower is sieve-tray tower, and use catalyzer is Sn-HTS, and catalyst particle diameter is distributed as 1 ~ 200 μm; Reaction raw materials is the pentamethylene of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.In catalyzer storage tank, prepare the acetone slurry that catalyst concn is 5%, and fully dispersed with stirring, with for subsequent use, carries out trial trip to device under conditions set with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, cyclopentanone are added conversion zone in tower.Absolute pressure is 0.27MPa, and conversion zone temperature is 118 DEG C, the mol ratio 1: 5 of conversion zone pentamethylene and acetone, and pentamethylene mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 6: 1.The raw materials components mole ratio of pentamethylene and hydrogen peroxide is 1: 5, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pentamethylene recycles.Reaction result: pentamethylene transformation efficiency is 99.47%, the selectivity of pentanedioic acid is 100%.
Embodiment 8
The present embodiment illustrates the situation of cyclopentanone direct oxidation pentanedioic acid.
Reaction tower is sieve-tray tower, and use catalyzer to be take silicon sol as the Sn-HTS of binding agent spray shaping, the content of Sn-HTS is 55%, and catalyst particle diameter is distributed as 40 ~ 600 μm; Reaction raw materials is the cyclopentanone of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.The acetone slurry that catalyst concn is 15% is prepared in catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under conditions set trial trip is carried out to device with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, cyclopentanone are added conversion zone in tower.Absolute pressure is 0.26MPa, and conversion zone temperature is 120 DEG C, the mol ratio 1: 7 of conversion zone cyclopentanone and acetone, and cyclopentanone mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 8: 1.The raw materials components mole ratio of cyclopentanone and hydrogen peroxide is 1: 6, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted cyclopentanone recycles.Reaction result: cyclopentanone transformation efficiency is 99.87%, the selectivity of pentanedioic acid is 100%.
Embodiment 9
The present embodiment illustrates the situation of hexanaphthene direct oxidation hexanodioic acid.
Reaction tower is sieve-tray tower, and use catalyzer to be take silicon sol as the Ti-Beta of binding agent spray shaping, the content of Ti-Beta is 45%, and catalyst particle diameter is distributed as 40 ~ 600 μm; Reaction raw materials is the hexanaphthene of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.The acetone slurry that catalyst concn is 15% is prepared in catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under conditions set trial trip is carried out to device with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, hexanaphthene are added conversion zone in tower.Absolute pressure is 0.22MPa, and conversion zone temperature is 116 DEG C, the mol ratio 1: 7 of conversion zone pimelinketone and acetone, and pimelinketone mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 8: 1.The raw materials components mole ratio of pimelinketone and hydrogen peroxide is 1: 8, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pimelinketone recycles.Reaction result: cyclohexane conversion is 10.05%, the selectivity of hexanodioic acid is 23.74%.
Embodiment 10
The present embodiment illustrates the situation of pimelinketone direct oxidation hexanodioic acid.
Reaction tower is sieve-tray tower, and use catalyzer is TS-2, and catalyst particle diameter is distributed as 1 ~ 200 μm; Reaction raw materials is the pimelinketone of 30% hydrogen peroxide and more than 99.9%; Solvent is acetone.In catalyzer storage tank, prepare the acetone slurry that catalyst concn is 5%, and fully dispersed with stirring, with for subsequent use, carries out trial trip to device under conditions set with acetone, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, pimelinketone are added conversion zone in tower.Absolute pressure is 0.18MPa, and conversion zone temperature is 106 DEG C, the mol ratio 1: 5 of conversion zone pimelinketone and acetone, and pimelinketone mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 6: 1.The raw materials components mole ratio of pimelinketone and hydrogen peroxide is 1: 3, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pimelinketone recycles.Reaction result: pimelinketone transformation efficiency is 63.23%, the selectivity of hexanodioic acid is 71.52%.
Embodiment 11
The present embodiment illustrates the situation of pimelinketone direct oxidation hexanodioic acid.
Reaction tower is sieve-tray tower, and use catalyzer to be take silicon sol as the HTS of binding agent spray shaping, the content of HTS is 50%, and catalyst particle diameter is distributed as 40 ~ 600 μm; Reaction raw materials is the pimelinketone of 30% hydrogen peroxide and more than 99.9%; Solvent is acetic acid.The acetic acid slurries that catalyst concn is 15% are prepared in catalyzer storage tank, and abundant dispersed with stirring is with for subsequent use, under conditions set trial trip is carried out to device with acetic acid, after horizontalization to be installed is steady, catalyst slurry, hydrogen peroxide, pimelinketone are added conversion zone in tower.Absolute pressure is 0.24MPa, and conversion zone temperature is 115 DEG C, the mol ratio 1: 8 of conversion zone pimelinketone and acetic acid, and pimelinketone mass space velocity is 1.5h
-1, the reflux ratio of tower top material is 8: 1.The raw materials components mole ratio of pimelinketone and hydrogen peroxide is 1: 4, and the disposable adding apparatus of catalysts and solvents, recycles in a device, and unreacted pimelinketone recycles.Reaction result: pimelinketone transformation efficiency is 99.57%, the selectivity of hexanodioic acid is 100%.
Claims (14)
1. a catalytic oxidation prepares the method for di-carboxylic acid, it is characterized in that catalyzer and comprise solvent, aqueous hydrogen peroxide solution and naphthenic hydrocarbon or derivatives thereof add the conversion zone of catalytic distillation tower at interior liquid reactions material, while the mixture of catalyzer and said liquid reactions material flows in tower, liquid reactions material generation catalytic oxidation, from the material after the catalytic oxidation of vaporization, isolate solvent cycle use, and catalyzer and the liquid material after the catalytic oxidation of not vaporizing use through being separated Posterior circle, be separated from tower top or kettle material and obtain unreacted naphthenic hydrocarbon or derivatives thereof and recycle, product di-carboxylic acid is isolated to from kettle material, wherein, said catalyzer is the titanium-silicon molecular sieve TS-1 of the stanniferous hollow structure being 1 ~ 5 % by weight with oxide basis Theil indices, said catalyzer is by the compound with stanniferous source on hollow titanium-silicon molecular sieve TS-1 basis, template, alkali and water at 100 ~ 160 DEG C through intermediate water thermal synthesis, again through filtering separation, dry and baking operation and the catalyzer that obtains, the titanium-silicon molecular sieve TS-1 of said hollow structure, its crystal grain is hollow structure, and the radical length of the chamber portion of this hollow structure crystal grain is 5 ~ 300 nanometers, and the titanium-silicon molecular sieve TS-1 of this hollow structure is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of the titanium-silicon molecular sieve TS-1 of this hollow structure and desorption isotherm, said catalyst grain size scope is 0.2 ~ 800 μm, in said conversion zone, temperature of reaction is the temperature lower than product di-carboxylic acid boiling point, reaction pressure is 0.1 ~ 2.0MPa, the mass ratio of catalyzer and said cycloalkanes hydrocarbons and their derivates is 1:5 ~ 100, and the mass space velocity of said liquid reactions material is 0.01 ~ 10h
-1, overhead mixture material reflux ratio is 1 ~ 30:1, and in said liquid reactions material, the mol ratio of cycloalkanes hydrocarbons and their derivates and solvent is 1:1.5 ~ 30, be 0.1 ~ 10:1 with the mol ratio of hydrogen peroxide.
2. according to the process of claim 1 wherein, said naphthenic hydrocarbon be containing 3 ~ 18 carbon atoms in molecular structure containing one or more ring filling hydrocarbon compound.
3., according to the process of claim 1 wherein, said cycloalkane derivatives is cycloolefin, polycyclic olefin, cyclic ketones or cyclic alcohol.
4., according to the process of claim 1 wherein, said naphthenic hydrocarbon or derivatives thereof is pentamethylene, hexanaphthene, tetrahydrobenzene or pimelinketone.
5., according to the process of claim 1 wherein, said solvent is containing the alcohol of 1 ~ 4 carbon atom or the ketone for containing 3 ~ 5 carbon atoms.
6. according to the method for claim 1, wherein, in said conversion zone, reaction pressure is 0.1 ~ 1.0MPa, the mol ratio of cycloalkanes hydrocarbons and their derivates and solvent is 1:8 ~ 20, and the mol ratio of cycloalkanes hydrocarbons and their derivates and hydrogen peroxide is (0.5 ~ 10): 1.
7., according to the process of claim 1 wherein, the mol ratio of cycloalkanes hydrocarbons and their derivates and hydrogen peroxide is 2 ~ 6:1.
8., according to the process of claim 1 wherein, the size range of catalyzer is 0.5 ~ 600 μm.
9., according to the process of claim 1 wherein, the concentration of reacting section catalyst is 0.5 ~ 30 % by weight of solvent.
10., according to the method for claim 1, said solvent is acetic acid or propionic acid.
11. according to the process of claim 1 wherein, said catalytic distillation tower is made up of conversion zone, distilling period and stripping section, and wherein distilling period is positioned at the top of conversion zone, and stripping section is positioned at the below of conversion zone.
12. according to the method for claim 1 or 11, titanium-silicon molecular sieve catalyst and solvent is it is characterized in that to add catalyzer storage tank, enter in tower from the top of the conversion zone of tower together with the aqueous solution of hydrogen peroxide after mixing, react with the cycloalkanes hydrocarbons and their derivates counter current contact of dividing one or more to enter tower from conversion zone in decline process; The corresponding oxide compound lactone that reaction generates, react after remaining cycloalkanes hydrocarbons and their derivates and partial solvent reacted liberated heat vaporization, enter gas-liquid separator through distilling period and condenser, unreacted Ring alkane hydrocarbons and their derivates uses through removing oxygen Posterior circle; The thick product of di-carboxylic acid, partial solvent, water, a small amount of byproduct and catalyzer enter stripping section, solvent is suggested and enters conversion zone, unclassified stores enters catalyst separator through tower reactor, isolated catalyzer enters catalyzer tundish, after dilution, be transported to catalyzer storage tank recycle, the liquid dihydric carboxylic acid product that catalyst separator separates enters follow-up refining manufacturing procedure; Tower reactor and the heat needed for stripping section are provided by reboiler, are gas under said cycloalkanes hydrocarbons and their derivates normal temperature.
13. according to the method for claim 1 or 11, titanium-silicon molecular sieve catalyst and solvent is it is characterized in that to add catalyzer storage tank, enter in tower from the top of the conversion zone of tower together with the aqueous solution of hydrogen peroxide after mixing, react with the cycloalkanes hydrocarbons and their derivates counter current contact of dividing one or more to enter tower from conversion zone in decline process; React remaining cycloalkanes hydrocarbons and their derivates and solvent and reacted liberated heat vaporization, through distilling period and condenser, enter gas-liquid separator, the noncondensable gas separated is emptying, liquid enters distillation tower, and tower top goes out unreacted cycloalkanes hydrocarbons and their derivates, recycles, the solvent part gone out at the bottom of tower removes catalyzer tundish as thinner, and another part flows in tower through tundish; The material of not vaporizing of conversion zone is descending enters stripping section, proposition cycloalkanes hydrocarbons and their derivates and solvent enter conversion zone, do not carry and heat up in a steamer thing and enter catalyst separator through tower reactor, the catalyzer separated enters catalyzer tundish, is transported to catalyzer storage tank and recycles after dilution; From the follow-up refining manufacturing procedure of the thick product introduction of liquid dihydric carboxylic acid that catalyst separator separates; Tower reactor and the heat needed for stripping section are provided by reboiler, said cycloalkanes hydrocarbons and their derivates be liquid at normal temperatures and its boiling point lower than temperature of reaction.
14., according to the method for claim 1, it is characterized in that titanium-silicon molecular sieve catalyst and solvent to enter catalyzer storage tank, enter in tower after sufficiently mixing together with aqueous hydrogen peroxide solution from the top of the conversion zone of tower; Meanwhile, cycloalkanes hydrocarbons and their derivates divides one or more to enter in tower from the top of conversion zone, and reacts with catalyst exposure; Distilling period is up to by the material that reaction heat is vaporized, wherein cycloalkanes hydrocarbons and their derivates gets back to conversion zone through fractionation, solvent vapo(u)r enters gas-liquid separator after condenser condenses, the non-condensable gas separated is emptying, a liquid solvent part is back in tower through tundish, and another part removes catalyzer tundish as thinner; The material that conversion zone is not vaporized comes downwards to stripping section, proposes whole solvents and gets back to conversion zone, does not carry heating up in a steamer thing and entering catalyst separator through tower reactor, and the catalyzer separated enters catalyzer tundish, is transported to catalyzer storage tank and recycles after dilution; The liquid material that catalyst separator separates enters the distillation tower separately established, and tower top goes out cycloalkanes hydrocarbons and their derivates and recycles; Go out di-carboxylic acid crude product at the bottom of tower and enter follow-up refining manufacturing procedure; Tower reactor and the heat needed for stripping section are provided by reboiler, and said cycloalkanes hydrocarbons and their derivates boiling point is higher than temperature of reaction.
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| CN102206149A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for preparing corresponding diacid by catalytic oxidization of naphthene |
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