CN1847206A - Synthesis process of cyclohexanone and cyclohexanol - Google Patents
Synthesis process of cyclohexanone and cyclohexanol Download PDFInfo
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- CN1847206A CN1847206A CNA2006100506822A CN200610050682A CN1847206A CN 1847206 A CN1847206 A CN 1847206A CN A2006100506822 A CNA2006100506822 A CN A2006100506822A CN 200610050682 A CN200610050682 A CN 200610050682A CN 1847206 A CN1847206 A CN 1847206A
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Abstract
The present invention relates to synthesis process of cyclohexanone and cycloexanol, especially through hydrogenating phenol. Phenol material, C1-C2 fatty alcohol and water in the weight proportion of 1 to 2.5-40 to 10-160 are reacted in one step at 100-300 deg.c temperature and 1-10 MPa pressure and in the action of Renny Ni catalyst or active carbon supported palladium catalyst to synthesize cyclohexanone and cycloexanol. The present invention features no need of outer hydrogen supply for hydrogenating phenol and the use of relatively cheap Renny Ni catalyst, and has the advantages of high safety, simplified technological process, low production cost, high phenol converting rate, high total cyclohexanone and cycloexanol selectivity near 100 %, no side product and easy product separation.
Description
(1) technical field
The present invention relates to the synthetic method of a kind of pimelinketone and hexalin, particularly the method for phenol hydrogenation synthesizing cyclohexanone and hexalin.
(2) background technology
Pimelinketone and hexalin (KA oil) are important Organic Chemicals, be the monomer hexanolactam of synthon nylon 6 and nylon 66 and the main raw material of hexanodioic acid, it also is the important intermediate of fine chemicals such as medicine, coating, dyestuff, but also be the raw material of producing spices, rubber antiager, fruit mould inhibitor phenylphenol etc., the auxiliary agent that also can be used as fine chemicals is also having very big purposes aspect the recovery of printing and plastics.Existing KA oil industrial making method has: benzene hydrogenation-air oxidation of cyclohexane method, phenol hydrogenation method, benzene partial hydrogenation-cyclohexene hydration method.
Benzene hydrogenation-cyclohexane oxidation process is to be starting raw material with benzene, and benzene at first hydrogenation is produced hexanaphthene, and cyclohexane oxidation obtains pimelinketone and hexalin (KA oil) then, and this method is industrial most popular method.Cyclohexane oxidation prepares pimelinketone and hexalin (KA oil) comprises catalytic oxidation and non-catalytic oxidation method.Catalytic oxidation uses cobalt salt to be catalyzer usually, carries out liquid phase reaction under 125～165 ℃, 0.8～1.5MPa condition, and cyclohexane oxidation is become pimelinketone and hexalin (KA oil).In the catalytic oxidation process of hexanaphthene, generate multiple oxidized byproduct easily, thereby adopt the method for low-conversion (general＜10%), highly selective (about 80%).Another major issue of air oxidation of cyclohexane method is its security, and hexanaphthene contacts with air and may set off an explosion.Need to handle a large amount of by product organic acid waste liquids in addition, and owing to adopting the low turnover ratio technology of hexanaphthene to need to reclaim a large amount of unreacted hexanaphthene of circulation etc., and the carboxylic acid that produces in the reaction process is easy and catalyst reaction generation carboxylic acid cobalt salt remains on equipment and the pipeline, slagging scorification blocking pipe and valve shorten the device driving cycle.With boric acid or metaboric acid is the selectivity (about 90%) that the air oxidation of cyclohexane method of catalyzer can improve cyclohexane conversion and pimelinketone and hexalin, but the reaction product of boric acid oxidation is very complicated, organic phase after the hydrolysis also must be removed impurity, complex process through further handling.The non-catalytic oxidation method is at first developed by French Rhone-Ponlene company, be characterized in that reaction was divided into for two steps, the first step is under 160～170 ℃ condition, the direct oxidation by air of hexanaphthene is a cyclohexyl hydroperoxide, second step, cyclohexyl hydroperoxide was decomposed into pimelinketone and hexalin under alkaline condition and catalyst action.The advantage of this technology is the reaction proceed step by step, and oxidation stage does not adopt catalyzer, has avoided the problem of oxidation reactor slagging scorification, make device operation continuously under the condition that equipment allows, and the yield of cyclohexyl hydroperoxide can reach more than 95% in the oxidising process.Its shortcoming be the selectivity of pimelinketone and hexalin in the cyclohexyl hydroperoxide decomposition course less than 90%, and need a large amount of alkali because this technology hexanaphthene per pass conversion is lower, make technical process long, energy consumption is higher.Guo Cancheng etc. are under iron porphyrin or the katalysis of cobalt porphyrin, and under suitable temperature and pressure, conversion of cyclohexane can reach more than 7%, and the selectivity of hexalin and pimelinketone can reach more than 87%.
Benzene partial hydrogenation-cyclohexene hydration legal system hexalin technology is that the eighties in 20th century Japan Asahi Chemical Industry at first succeeds in developing.This technology is starting raw material with benzene, and under 100～180 ℃, the condition of 3～10MPa, ruthenium catalyst, benzene carries out incomplete hydrogenation reaction and prepares tetrahydrobenzene, the transformation efficiency 50～60% of benzene, and the tetrahydrobenzene selectivity is that 80%, 20% by product is a hexanaphthene.Under catalyst action, the further hydration of tetrahydrobenzene generates hexalin, the per pass conversion 10～15% of tetrahydrobenzene, and the selectivity of hexalin can reach 99.3%.This processes expend is low, and the yield of carbon almost reaches 100%, and hydrogen gas consumption is about 2/3 of traditional method, and has effectively avoided the waste lye that produces in the cyclohexane oxidation technological process, has reduced environmental protection pressure, has tangible prospect.This technology is insufficient to be, benzene partial hydrogenation when reaction adopted noble metal catalyst Ru, and reaction is to carry out in batch reactor, and this has reduced throughput widely.In addition, owing to contain tetrahydrobenzene, hexanaphthene, unreacted benzene and less water in the resultant organic phase of reaction, these component boiling-point differences adopt common distillating method to be difficult to separate apart from very little (80.1 ℃ of benzene, 81 ℃ of hexanaphthenes, 83.19 ℃ of tetrahydrobenzene).Though with the polar solvent extract distillation, separating effect is better, must consider the problems such as corrosion of extraction agent to device.Hydration reaction comprises homogeneous catalytic reaction and heterogeneous catalytic reaction, and homogeneous catalytic reaction carries out under the effect of strong inorganic acid and salt thereof, and etching problem is serious, and product separates and the recovery difficulty of catalyzer.Heterogeneous catalytic reaction adopts high silica zeolite catalyst, and under the condition of 100 ℃ of temperature of reaction, reaction times 120min, the tetrahydrobenzene transformation efficiency is 18%, and the hexalin selectivity is 99%.
Dutch States Mines (DSM) has at first realized the industrialization that one step of phenol hydrogenation is produced pimelinketone and hexalin, and one step of the phenol hydrogenation method of producing pimelinketone and hexalin has two kinds of gas phase and liquid phases.The Allied Chem. of the U.S. (associating chemistry) company's exploitation and the phenol liquid phase catalytic hydrogenation technology primary product that comes into operation are pimelinketone.Phenol conversion 95%, pimelinketone yield 97% can save the cyclohexanol dehydrogenation operation.Liquid-phase hydrogenatin be with hydrogen by being suspended with the molten phenol of platinum metal catalysts, its technological process comprises remove by filter catalyzer from reaction product, not only troublesome poeration, device is complicated but also the loss of the platinum metals that is difficult to avoid expensive.The gas phase hydrogenation method can overcome above-mentioned shortcoming, and this method adopts 3～5 reactors in series usually, is solvent with methyl alcohol, in temperature is 140～170 ℃, and pressure is 0.1MPa, and the yield of pimelinketone and hexalin can reach 90～95%, equipment can be used carbon steel, and does not have waste water and waste gas generation.Pimelinketone that phenol hydrogenation makes and hexalin quality be (the keto-alcohol overall selectivity is about 90%, and main by product comprises: benzene, hexanaphthene, tetrahydrobenzene, methyl-phenoxide, ortho-cresol etc.) better, and this technology is wanted safety than cyclohexane oxidation process.(the main catalyzer of phenol hydrogenation reaction has Pd, Y, Ru etc. but existing method is all used noble metal catalyst; Carrier mainly contains Al
2O
3, SiO
2, gac, MgO etc.; A spot of CeO of using is arranged
2, ZrO
2, TiO
2As carrier), make that the production cost of pimelinketone and hexalin is higher, the also easy carbon deposit of catalyst surface causes catalyst activity reduction, the lost of life, therefore application is restricted.Japan industrial technology synthetic study institute supercutical fluid research centre is succeeded in developing and is utilized the supercritical carbon dioxide extraction solvent, is pimelinketone and hexalin (KA oil) at phenol 100% hydrocracking under the load rhodium catalyst and under 55 ℃ of temperature.And with the variation of carbonic acid gas and hydrogen pressure, can free gate ring hexanone and the proportion of composing of hexalin.This synthetic method not with an organic solvent, the reaction conditions gentleness, so catalyzer be difficult for aging, carbonic acid gas is easy to recycle etc. significantly reduces the characteristics of environmental cost.But this method has been used expensive more load rhodium catalyst.
(3) summary of the invention
The purpose of this invention is to provide a kind of Raney's nickel or active carbon-supported palladium of adopting is the method for catalyzer by phenol single stage method highly selective synthesizing cyclohexanone and hexalin, and the catalyzer cost is low, is a green synthetic route.
The technical solution used in the present invention is as follows:
The synthetic method of a kind of pimelinketone and hexalin, with phenol is raw material, in the aqueous solution of C1～C2 Fatty Alcohol(C12-C14 and C12-C18), under the effect of Raney's nickel or activated carbon supported palladium catalyst, under 100～300 ℃ temperature, 1.0～10.0MPa pressure, single step reaction synthesizing cyclohexanone and hexalin, described phenol: Fatty Alcohol(C12-C14 and C12-C18): the amount of substance ratio of water is 1: 2.5～40: 10～160.
Described single step reaction is included in hydrogen production reaction and the phenol add in-place hydrogen reduction reaction that Fatty Alcohol(C12-C14 and C12-C18) takes place in the reactor synchronously.Described Fatty Alcohol(C12-C14 and C12-C18) hydrogen production reaction is the reaction of Fatty Alcohol(C12-C14 and C12-C18) decomposing hydrogen-production or Fatty Alcohol(C12-C14 and C12-C18) and water generation aqueous phase reforming hydrogen production reaction.
In this reaction, the reaction of catalysis aqueous phase reforming takes place between the fatty alcohol and water, the hydrogen of generation is reduced into phenol pimelinketone and hexalin in situ, no longer needs outside hydrogen supply; Catalyzer is fatty alcohol and water generation aqueous phase reforming catalyst for reaction, also is phenol hydrogenation synthesizing cyclohexanone and hexalin catalyst for reaction, and the aqueous solution of Fatty Alcohol(C12-C14 and C12-C18) is also as the solvent that reacts.
Further, the synthetic method of described pimelinketone and hexalin is reflected in the fixed-bed reactor and carries out, described catalyst levels 1～3g, and the space-time speed of described Fatty Alcohol(C12-C14 and C12-C18), water and phenol mixing liquid is 0.5～6.0 hour
-1, the space-time speed of described liquid is the volume feeding rate of all reactive material mixed solutions that feed intake and the ratio of the stacking volume of described catalyzer in reactor.
Further again, described temperature of reaction is 160～240 ℃, and described being reflected under the pressure 1.0-4.2MPa carried out, and described Fatty Alcohol(C12-C14 and C12-C18) is a methyl alcohol.
In the method, described catalyzer recommends to use Raney's nickel catalyst, is commercially available or self-control, the Raney's nickel catalyst that the embodiment of the invention is used prepares as follows: slowly add strong base solution in Nickel Aluminium Alloy Powder, as NaOH solution, also available certainly other strong base solution is as KOH etc.The temperature of strong base solution is preferably in 20～50 ℃, concentration is 15～25%, be warming up to 75～85 ℃ behind reinforced the finishing, and keep extracting in 2～3 hours to go out discharging behind the aluminium in the alumel, and leave standstill then, remove solution, be washed to pH value 8～9, promptly get Raney's nickel catalyst, preferred usually earlier with 70～80 ℃ of washings, wash with normal temperature again.Obtained catalyzer will be preserved with dehydrated alcohol.Prepared catalyzer is little to influence of the present invention in the scope of above-mentioned parameter condition variation.
Activated carbon supported palladium catalyst of the present invention is for the palladium loading is 2wt%, can be commercially available or by method self-control well known to those of ordinary skill in the art.Activated carbon supported palladium catalyst in the embodiment of the invention adopts laxative remedy to make: taking by weighing the cocoanut active charcoal that is used to prepare catalyzer, above-mentioned gac is mixed with the slurries of 60～90 ℃ of temperature, is that 2wt% slowly drips H by the palladium loading
2PdCl
4Solution stirs, again with 10%NaOH solution regulator solution pH value to 7.1～9, and cool the temperature to room temperature, filter, filter cake to neutral, is configured to slurries with filter cake with deionized water wash again under 30 ℃, drip 85% hydrazine hydrate solution, stir, filter, filter cake is extremely neutral with deionized water wash, at last in room temperature in air through preliminarily dried, get wet sample and promptly get described activated carbon supported palladium catalyst.
Preferred Raney's nickel catalyst in the described catalyzer.
Concrete, the synthetic method of described pimelinketone and hexalin is: add 1.5 Cray Buddhist nun nickel catalyzators in fixed-bed reactor, according to phenol: methyl alcohol: the amount ratio of water substance is 1: 2.5～20: 20～80 to feed intake, temperature at 200～240 ℃, 2.4 the pressure of～4.2MPa is reaction down, the space-time speed of mixing liquid is 1.76～5.3 hours
-1, more preferably space-time speed is 3～3.6 hours
-1, the product liquid of reactor outlet is separated, promptly get pimelinketone and hexalin after removing excessive methanol.
The present invention, the transformation efficiency of phenol reaches 50～90%, and the selectivity of pimelinketone and hexalin is near 100%.
Compared with prior art, beneficial effect of the present invention is embodied in:
Do not need the outside that hydrogen is provided in the phenol hydrogenation reduction process, but utilize the hydrogen of the catalysis aqueous phase reforming reaction generation that takes place between the first alcohol and water in situ phenol to be reduced into pimelinketone and hexalin, eliminated and needed links such as special Preparation of Hydrogen, storage and conveying in the existing method, avoid the safety issue in the hydrogen use, simplified technology simultaneously, reduced production cost.Further the present invention preferably uses Raney's nickel to be catalyzer, does not use noble metal catalyst, has reduced the cost and the consumption of catalyzer significantly; Phenol conversion height of the present invention, the overall selectivity of pimelinketone and hexalin are near 100%, and basic no coupling product generates, and is the synthetic route of a green; First alcohol and water generation aqueous phase reforming reaction hydrogen manufacturing has effectively utilized the hydrogen in the water, the utilization ratio height of hydrogen; The boiling-point difference of methyl alcohol, water, phenol and pimelinketone, hexalin is big (64.65 ℃ of methyl alcohol, 182 ℃ of phenol, 155.7 ℃ of pimelinketone, 161 ℃ of hexalin), and convenient product separation directly can obtain highly purified pimelinketone and hexalin by common distillation.
To sum up, the present invention is that technological process is simple, production process safety, and production cost is low, the product selectivity height, the green synthetic route of environmental nonpollution can be carried out continuously or batch production.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
The Raney's nickel catalyst of below implementing in one to 36 makes as follows: slowly add mass concentration and be 15～25% highly basic NaOH solution in nickel aluminium mass ratio is 55: 45 Nickel Aluminium Alloy Powder, simultaneously be warming up to 75～85 ℃ from room temperature gradually, and the aluminium that keeps extracting in 2～3 hours to go out in the alumel is less than 6% back discharging until the mass content of aluminium, leave standstill then, remove solution, again earlier with 70～80 ℃ washing, again with normal temperature be washed to pH value 8～9, promptly get Raney's nickel catalyst.
Embodiment one
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 2.5: 20 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 83.32%, and the selectivity of pimelinketone is 16.41%, the selectivity of hexalin is 81.62%, and the selectivity of by product benzene and Ortho Cresol is respectively 1.97% and 0%.
Embodiment two
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 10: 80 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 63.72%, and the selectivity of pimelinketone is 16.36%, the selectivity of hexalin is 83.33%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.23% and 0.07%.
Embodiment three
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 10: 160 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 57.84%, and the selectivity of pimelinketone is 19.67%, the selectivity of hexalin is 79.95%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.38% and 0%.
Embodiment four
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 66.19%, and the selectivity of pimelinketone is 22.48%, the selectivity of hexalin is 76.9%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.23% and 0.4%.
Embodiment five
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 80 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 54.6%, and the selectivity of pimelinketone is 14.44%, the selectivity of hexalin is 85.32%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.24% and 0%.
Embodiment six
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 10: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 49.5%, and the selectivity of pimelinketone is 26.5%, the selectivity of hexalin is 72.55%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.22% and 0.73%.
Embodiment seven
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 40: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 58.73%, and the selectivity of pimelinketone is 18.23%, the selectivity of hexalin is 80.68%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.36% and 0.73%.
Embodiment eight
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 5: 20 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 31.66%, and the selectivity of pimelinketone is 29.52%, the selectivity of hexalin is 69.83%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.65% and 0%.
Embodiment nine
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.52 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Feeding rate join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 80.6%, and the selectivity of pimelinketone is 17.18%, the selectivity of hexalin is 81.8%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.87% and 0.15%.
Embodiment ten
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.52 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 70.6%, and the selectivity of pimelinketone is 21.53%, the selectivity of hexalin is 76.9%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.73% and 0.84%.
Embodiment 11
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.52 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Feeding rate join in the reactor, adjusting temperature of reaction is 240 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 80.8%, and the selectivity of pimelinketone is 18.26%, the selectivity of hexalin is 79.4%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.64% and 1.7%.
Embodiment 12
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 80 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 53.5%, and the selectivity of pimelinketone is 20.84%, the selectivity of hexalin is 78.77%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.28% and 0.1%.
Embodiment 13
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 160 ℃, reaction pressure is 1.0MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 4.41%, and the selectivity of pimelinketone is 36.26%, the selectivity of hexalin is 59.54%, and the selectivity of by product benzene and Ortho Cresol is respectively 4.2% and 0%.
Embodiment 14
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 180 ℃, reaction pressure is 1.6MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 4.28%, and the selectivity of pimelinketone is 25.06%, the selectivity of hexalin is 72.6%, and the selectivity of by product benzene and Ortho Cresol is respectively 2.34% and 0%.
Embodiment 15
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 2.93%, and the selectivity of pimelinketone is 33%, the selectivity of hexalin is 67%, and the selectivity of by product benzene and Ortho Cresol is 0%.
Embodiment 16
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 20.94%, and the selectivity of pimelinketone is 40.93%, the selectivity of hexalin is 58.04%, and the selectivity of by product benzene and Ortho Cresol is respectively 1.03% and 0%.
Embodiment 17
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 240 ℃, reaction pressure is 4.2MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 75.38%, and the selectivity of pimelinketone is 22.31%, the selectivity of hexalin is 76.28%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.88% and 0.53%.
Embodiment 18
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 240 ℃, reaction pressure is 3.0MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 84.57%, and the selectivity of pimelinketone is 26.24%, the selectivity of hexalin is 72.34%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.75% and 0.67%.
Embodiment 19
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 240 ℃, reaction pressure is 2.0MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 84.11%, and the selectivity of pimelinketone is 35.2%, the selectivity of hexalin is 60.61%, and the selectivity of by product benzene and Ortho Cresol is respectively 2.09% and 2.10%.
Embodiment 20
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 240 ℃, reaction pressure is 5.0MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 78.55%, and the selectivity of pimelinketone is 20.69%, the selectivity of hexalin is 78.69%, and the selectivity of by product benzene and Ortho Cresol is respectively 0% and 0.61%.
Embodiment 21
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 0.71 hour with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 80.4%, and the selectivity of pimelinketone is 14.52%, the selectivity of hexalin is 85.49%, and the selectivity of by product benzene and Ortho Cresol is 0%.
Embodiment 22
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 5.29 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 8.29%, and the selectivity of pimelinketone is 56.92%, the selectivity of hexalin is 38.83%, and the selectivity of by product benzene and Ortho Cresol is respectively 4.28% and 0%.
Embodiment 23
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 10: 40 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 20.89%, and the selectivity of pimelinketone is 27.59%, the selectivity of hexalin is 71.68%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.3% and 0.26%.
Embodiment 24
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 10: 80 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 23.81%, and the selectivity of pimelinketone is 40.72%, the selectivity of hexalin is 58.64%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.52% and 0.12%.
Embodiment 25
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 2.5: 20 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 23.01%, and the selectivity of pimelinketone is 18.91%, the selectivity of hexalin is 79.36%, and the selectivity of by product benzene and Ortho Cresol is respectively 1.71% and 0%.
Embodiment 26
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 10: 160 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 53.4%, and the selectivity of pimelinketone is 25.12%, the selectivity of hexalin is 74.39%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.49% and 0%.
Embodiment 27
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 80 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 11.88%, and the selectivity of pimelinketone is 25.74%, the selectivity of hexalin is 73.23%, and the selectivity of by product benzene and Ortho Cresol is respectively 1.02% and 0%.
Embodiment 28
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 5: 10 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 28.25%, and the selectivity of pimelinketone is 31.4%, the selectivity of hexalin is 61.42%, and the selectivity of by product benzene and Ortho Cresol is respectively 4.61% and 2.56%.
Embodiment 29
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 5: 10 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 8.13%, and the selectivity of pimelinketone is 44.68%, the selectivity of hexalin is 53.39%, and the selectivity of by product benzene and Ortho Cresol is respectively 1.57% and 0.39%.
Embodiment 30
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 40: 40 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 9.01%, and the selectivity of pimelinketone is 31.42%, the selectivity of hexalin is 62.35%, and the selectivity of by product benzene and Ortho Cresol is respectively 4.55% and 1.73%.
The embodiment hentriaconta-
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 5: 20 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 31.66%, and the selectivity of pimelinketone is 29.52%, the selectivity of hexalin is 69.84%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.65% and 0%.
Embodiment 32
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 5: 20 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 13.43%, and the selectivity of pimelinketone is 46.49%, the selectivity of hexalin is 51.93%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.91% and 0.7%.
Embodiment 33
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 160 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer AGilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 47.3%, and the selectivity of pimelinketone is 21.96%, the selectivity of hexalin is 77.84%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.2% and 0%.
Embodiment 34
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 70.3%, and the selectivity of pimelinketone is 22.89%, the selectivity of hexalin is 76.31%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.2% and 0.6%.
Embodiment 35
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 2.4MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 80.6%, and the selectivity of pimelinketone is 30.66%, the selectivity of hexalin is 68.14%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.3% and 0.9%.
Embodiment 36
Adding Raney's nickel catalyst 1.5 grams in fixed-bed reactor, is that 1: 20: 40 mixing liquid is 3.53 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 200 ℃, reaction pressure is 1.7MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 58.3%, and the selectivity of pimelinketone is 28.14%, the selectivity of hexalin is 70.36%, and the selectivity of by product benzene and Ortho Cresol is respectively 0.9% and 0.6%.
Embodiment 37
Adding the palladium loading in fixed-bed reactor is 2wt% palladium carbon catalyst 1.0 grams, is that 1: 10: 40 mixing liquid is 1.76 hours with the liquid hourly space velocity rate with the amount ratio of phenol, methyl alcohol, water substance
-1Join in the reactor, adjusting temperature of reaction is 220 ℃, reaction pressure is 3.5MPa, the product of reactor outlet is separated product liquid through gas-liquid separator, product liquid is analyzed with gas chromatograph-mass spectrometer Agilent-GC-MS after removing excessive methyl alcohol, and the transformation efficiency of phenol is 43.39%, and the selectivity of pimelinketone is 43.37%, the selectivity of hexalin is 54.05%, and the selectivity of by product benzene and Ortho Cresol is respectively 0% and 2.57%.
Claims (10)
1. the synthetic method of pimelinketone and hexalin, it is characterized in that with phenol being raw material, in the aqueous solution of C1～C2 Fatty Alcohol(C12-C14 and C12-C18), under the effect of Raney's nickel or activated carbon supported palladium catalyst, under 100～300 ℃ temperature, 1.0～10.0MPa pressure, single step reaction synthesizing cyclohexanone and hexalin, described phenol: Fatty Alcohol(C12-C14 and C12-C18): the amount of substance ratio of water is 1: 2.5～40: 10～160.
2. the synthetic method of pimelinketone as claimed in claim 1 and hexalin, it is characterized in that described being reflected in the fixed-bed reactor carry out, described catalyst levels 1～3g, the space-time speed of described Fatty Alcohol(C12-C14 and C12-C18), water and phenol mixing liquid is 0.5～6.0 hour
-1, the space-time speed of described liquid is the volume feeding rate of all reactive material mixed solutions that feed intake and the ratio of the stacking volume of described catalyzer in reactor.
3. the synthetic method of pimelinketone as claimed in claim 2 and hexalin is characterized in that described temperature of reaction is 160～240 ℃.
4. the synthetic method of pimelinketone as claimed in claim 2 and hexalin is characterized in that described being reflected under pressure 1.0～4.2MPa carry out.
5. the synthetic method of pimelinketone as claimed in claim 1 and hexalin, it is characterized in that described catalyzer is a Raney's nickel, described catalyzer prepares as follows: slowly add strong base solution in Nickel Aluminium Alloy Powder, described strong base solution temperature is controlled at 20～50 ℃, concentration is 15～25%, be warming up to 75～85 ℃ behind reinforced the finishing, and keep extracting in 2～3 hours to go out discharging behind the aluminium in the alumel, leave standstill then, remove the solution after washing to pH value 8～9, promptly get Raney's nickel catalyst.
6. the synthetic method of pimelinketone as claimed in claim 1 and hexalin, the loading that it is characterized in that palladium in the described activated carbon supported palladium catalyst is 2wt%, described activated carbon supported palladium catalyst adopts laxative remedy to make: take by weighing the cocoanut active charcoal that is used to prepare catalyzer, above-mentioned gac is mixed with the slurries of 60～90 ℃ of temperature, is that 2wt% slowly drips H by the palladium loading
2PdCl
4Solution stirs, again with 10% NaOH solution regulator solution pH value to 7.1～9, and cool the temperature to room temperature, filter, filter cake to neutral, is configured to slurries with filter cake with deionized water wash again under 30 ℃, drip 85% hydrazine hydrate solution, stir, filter, filter cake is extremely neutral with deionized water wash, at last in room temperature in air through preliminarily dried, get wet sample and promptly get described activated carbon supported palladium catalyst.
7. the synthetic method of pimelinketone as claimed in claim 2 and hexalin is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) is a methyl alcohol.
8. the synthetic method of pimelinketone as claimed in claim 2 and hexalin, it is characterized in that described synthetic method is: in fixed-bed reactor, add 1.5 Cray Buddhist nun nickel catalyzators, according to phenol: methyl alcohol: the amount ratio of water substance is 1: 2.5～20: 20～80 to feed intake, temperature at 200～240 ℃, 2.4 the pressure of～4.2MPa is reaction down, the space-time speed of mixing liquid is 1.76～5.3 hours-1, the product liquid of reactor outlet is separated, promptly get pimelinketone and hexalin after removing excessive methanol.
9. the synthetic method of pimelinketone as claimed in claim 1 and hexalin is characterized in that described single step reaction is included in hydrogen production reaction and the phenol add in-place hydrogen reduction reaction that Fatty Alcohol(C12-C14 and C12-C18) takes place in the reactor synchronously.
10. the synthetic method of pimelinketone as claimed in claim 9 and hexalin is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) hydrogen production reaction is the reaction of Fatty Alcohol(C12-C14 and C12-C18) decomposing hydrogen-production or Fatty Alcohol(C12-C14 and C12-C18) and water generation aqueous phase reforming hydrogen production reaction.
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| CN100486950C (en) * | 2007-01-22 | 2009-05-13 | 河北大学 | Process of synthesizing 1,4-cyclohexyl dione |
| CN101948375A (en) * | 2010-09-05 | 2011-01-19 | 中南大学 | Method for preparing cyclohexanone or cyclohexanol by recovering phenol |
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| CN101948375A (en) * | 2010-09-05 | 2011-01-19 | 中南大学 | Method for preparing cyclohexanone or cyclohexanol by recovering phenol |
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| CN109704918A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Continuous catalysis prepares 2,6- di-t-butyl -4 methyl cyclohexanol method |
| CN109704918B (en) * | 2017-10-25 | 2022-07-26 | 中国石油化工股份有限公司 | Method for continuously catalytically preparing 2, 6-di-tert-butyl-4-methylcyclohexanol |
| CN108148625B (en) * | 2018-01-23 | 2020-06-16 | 山东亚科环保科技有限公司 | Mixing hydrogenation device and method for waste X oil and waste alcohol in cyclohexanone production |
| CN108148625A (en) * | 2018-01-23 | 2018-06-12 | 山东亚科环保科技有限公司 | A kind of Cyclohexanone Production waste X oil alcohol that gives up is kneaded hydrogenation plant and method |
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