CN105344361A - Ester hydrogenation catalyst, preparation method thereof, and ester hydrogenation reaction method - Google Patents
Ester hydrogenation catalyst, preparation method thereof, and ester hydrogenation reaction method Download PDFInfo
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Abstract
The invention discloses an ester hydrogenation catalyst, a preparation method thereof, and an ester hydrogenation reaction method. The preparation method of the ester hydrogenation catalyst comprises the following steps: 1, adjusting the pH value of a water-soluble aluminum salt solution to 4-10 to obtain a slurry A; 2, preparing a mixed solution B and a mixed solution C respectively containing a water-soluble copper salt solution and a water-soluble zinc salt solution, wherein the copper/zinc molar ratio of the mixed solution B is smaller than the copper/zinc molar ratio of the mixed solution C; 3, mixing the mixed solution B with the slurry A, adjusting the pH value to 4-10, adding the mixed solution C, adjusting the pH value to 4-10, carrying out solid-liquid separation, drying, and roasting to obtain a copper-zinc-aluminum composite oxide; and 4, loading at least one metal component selected from platinum, palladium and tin on the copper-zinc-aluminum composite oxide as an assistant. The ester hydrogenation catalyst obtained through the preparation method still has high cyclohexanol selectivity and use stability in the presence of a trace amount of acetic acid.
Description
Technical field
The preparation method that the present invention relates to a kind of ester through hydrogenation catalyst, the ester through hydrogenation catalyst prepared by the method and the method adopting this ester through hydrogenation catalyst ester through hydrogenation to react.
Background technology
Cyclohexanol is a kind of important solvent and organic synthesis intermediate, dehydrogenation high selectivity can generate cyclohexanone.And cyclohexanone is the raw material manufacturing nylon, caprolactam and adipic acid, be also widely used in the production processes such as paint, agricultural chemicals, dyestuff, aeroengine oil, fat, wax, demoulding, decontamination, bate pits as solvent.
Cyclohexanol production technology category is more.Different according to raw material, phynol method and benzene method can be divided into.The former is that raw material hydrogenation directly prepares cyclohexanol with phenol, and its shortcoming is expensive starting materials, and Technical Economy is poor.The latter is first is that cyclohexene prepared by raw material with benzene, then prepares cyclohexanol through hydration; Or first is that cyclohexane prepared by raw material with benzene, then prepares cyclohexanone and cyclohexanol through oxidation.But, adopt the accessory substance of phynol method and benzene method all more, and conversion per pass is lower.In order to improve cyclohexene to the conversion ratio of cyclohexanol process and selective, researcher has carried out positive trial, and relatively typical exploration has: (JChemEngData, 2005,50 (4): 1277-1282 such as Steyer; IndEngChemRes, 2007,46 (4): 1099-1104; IndEngChemRes, 2008,47 (23): 9581-9587) propose the method utilizing cyclohexene and formic acid esterification to generate cyclohexyl formate, the method overcome the thermodynamics restriction of cyclohexene direct hydration reaction.Based on this, this seminar proposes cyclohexanol production new technology: namely benzene selective Hydrogenation is for cyclohexene, and then cyclohexene and acetic acid esterified generate cyclohexyl acetate, and cyclohexyl acetate repeated hydrogenation generates cyclohexanol.This technology path advantage is: esterification and hydrogenation reaction all have very high selective, and Atom economy is high; Ester through hydrogenation reaction can co-producing ethanol, has higher economic feasibility and technological competitiveness.
Less for cyclohexyl acetate catalyst for hydrogenation Patents, but for other ester classes, as more in hydrogenation Cu-series catalyst researchs such as dimethyl oxalate, dimethyl adipate, maleates.Such as, CN103657658A discloses the preparation method of a kind of carboxylic ester hydrogenation catalyst and cyclohexanol, ethanol, and specifically disclose described carboxylic ester hydrogenation catalyst with copper, zinc oxide for main composition, oxide simultaneously also containing at least one metal in aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, and at least one in alkali metal hydroxide and alkaline earth metal hydroxide.Research shows, when this carboxylic ester hydrogenation catalyst is used for the hydrogenation reaction of cyclohexyl acetate, and the conversion ratio of cyclohexyl acetate and cyclohexanol is selective all can reach more than 99%.But this carboxylic ester hydrogenation catalyst is only applicable to for the hydrogenation reaction of cyclohexyl acetate not containing carboxylic acid, and is not suitable for and adopts acetic acid and prepared by cyclohexene esterification, the hydrogenation reaction of cyclohexyl acetate containing a small amount of acetic acid.CN101474561A discloses a kind of catalyst of producing ethylene glycol from hydrogenation of oxalic ester, its active component comprises oxide of copper and copper and composition thereof, auxiliary agent is the one in zinc, manganese, barium, nickel, chromium and iron, carrier is aluminium oxide, and specifically disclose this catalyst and adopt a step coprecipitation to prepare, precipitated product adds powdered graphite compression molding and is applied in oxalate hydrogenation after washing, dry and roasting.Result shows, this catalyst has higher conversion, but the selective of ethanol is only about 85%.CN101138726A discloses a kind of copper-based catalysts for industrial production hexylene glycol, and disclose adopt coprecipitation prepare this catalyst.Particularly, copper nitrate and zinc nitrate are mixed with the aqueous solution, aluminium-hydroxide powder is dispersed in water formation slurries, then be neutralized to pH value 7-8 by after the mixing of the slurries of copper zinc mixed aqueous solution and aluminium hydroxide with the aqueous slkali containing NaOH and sodium carbonate, then carry out successively filtering, wash, drying, granulation, roasting, add that intermixture mixes, compression molding.Research shows, this copper-based catalysts has greater activity.But existing zinc-copper class catalyst all only considered the ratio problems of copper and Zn-ef ficiency, and does not consider the distribution problem of copper and Zn-ef ficiency.CN86105765A discloses the method for a kind of ethyl acetate Hydrogenation for alcohol, under the method is included in the existence of solid Cu-contained catalyst of reduction activation, by carboxylate hydrogenation under high temperature, normal pressure or high pressure, apart from copper, described Cu-contained catalyst is also containing at least one in magnesium, lanthanide series metal and actinide metals.Research shows, this Cu-contained catalyst can tolerate a small amount of moisture, and ethanol is selective higher than 99%, but the conversion ratio of ethyl acetate is usually less than 35%.
In addition, obtain cyclohexyl acetate for employing acetic acid and cyclohexene esterification, then hydrogenation generates the technology path of cyclohexanol, for ensureing that cyclohexene transforms completely, acetic acid consumption exceedes variable usually, after rectifying is separated, acetic acid can be produced in cyclohexyl acetate remain, thus there is certain acid number.And the existence of acetate in minute, catalyst performance can be caused to decline by oxides such as the zinc in catalyst-solvent, aluminium.But above-mentioned ester through hydrogenation catalyst is only applicable to the hydrogenation reaction of pure ester class, and for containing a small amount of hydrogenation reaction remaining the ester type compound of acetic acid, the hydrogenation activity of above-mentioned ester through hydrogenation catalyst is lower and the life-span is shorter.Therefore, for expanding the accommodation of ester through hydrogenation catalyst, need a kind of ester through hydrogenation catalyst with Antacid effectiveness of exploitation at present badly.
Summary of the invention
The object of the invention is the defect not being suitable for the hydrogenation reaction of the ester type compound containing a small amount of residual acetic acid in order to overcome existing ester through hydrogenation catalyst, and a kind of method preparation method of new ester through hydrogenation catalyst, the ester through hydrogenation catalyst prepared by the method being provided and adopting this ester through hydrogenation catalyst ester through hydrogenation to react.
Present invention also offers a kind of preparation method of ester through hydrogenation catalyst, the method comprises the following steps:
(1) pH value of aqueous aluminum salt solution the first alkaline matter is adjusted to 4-10, obtains slurries A;
(2) the mixed solution B of preparation all containing water-soluble copper salting liquid and water-soluble zinc salt solution and mixed solution C, the copper in mixed solution C described in the copper in described mixed solution B/zinc mol ratio </zinc mol ratio;
(3) described mixed solution B is mixed with slurries A, obtain mixture D, and the pH value of described mixture D the second alkaline matter is adjusted to 4-10, add described mixed solution C again, obtain mixture E, and then the pH value of described mixture E the 3rd alkaline matter is adjusted to 4-10, then carry out Separation of Solid and Liquid, and the solid product obtained is carried out drying and roasting, obtain copper Zn Al composite oxide;
(4) by auxiliary agent load on described copper Zn Al composite oxide, described auxiliary agent is selected from least one metal component in platinum, palladium and tin.
Present invention also offers the ester through hydrogenation catalyst prepared by said method.
In addition, present invention also offers the method for a kind of ester through hydrogenation reaction, ester type compound is carried out hydrogenation reaction under being included in the existence of above-mentioned ester through hydrogenation catalyst by the method.
The preparation method of ester through hydrogenation catalyst provided by the invention first prepares copper Zn Al composite oxide deposit seed by three sections of precipitation method, and then using at least one metal component in platinum, palladium and tin as auxiliary agent load on copper Zn Al composite oxide deposit seed, the described ester through hydrogenation catalyst adopting this specific preparation method to obtain still has the selective and stability in use of higher hydrogenation activity, cyclohexanol under the existence of trace acetic acid, has prospects for commercial application.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The preparation method of ester through hydrogenation catalyst provided by the invention comprises the following steps:
(1) pH value of aqueous aluminum salt solution the first alkaline matter is adjusted to 4-10, obtains slurries A;
(2) the mixed solution B of preparation all containing water-soluble copper salting liquid and water-soluble zinc salt solution and mixed solution C, the copper in mixed solution C described in the copper in described mixed solution B/zinc mol ratio </zinc mol ratio;
(3) described mixed solution B is mixed with slurries A, obtain mixture D, and the pH value of described mixture D the second alkaline matter is adjusted to 4-10, add described mixed solution C again, obtain mixture E, and then the pH value of described mixture E the 3rd alkaline matter is adjusted to 4-10, then carry out Separation of Solid and Liquid, and the solid product obtained is carried out drying and roasting, obtain copper Zn Al composite oxide;
(4) by auxiliary agent load on described copper Zn Al composite oxide, described auxiliary agent is selected from least one metal component in platinum, palladium and tin.
In the present invention, described auxiliary agent exists usually in the form of the oxide.
The consumption of the present invention to described aqueous aluminum salt solution, water-soluble copper salting liquid and water-soluble zinc salt solution is not particularly limited, and those skilled in the art can determine the suitable amounts of above-mentioned three kinds of components with reference to existing method.Usually, the consumption of described aqueous aluminum salt solution, water-soluble copper salting liquid and water-soluble zinc salt solution makes in the copper Zn Al composite oxide obtained, with the integral molar quantity of metallic element in described copper Zn Al composite oxide for benchmark, in described copper Zn Al composite oxide, the content of aluminium element can be 10-50%, is preferably 20-50mol%; The content of copper can be 10-70mol%, is preferably 20-40mol%; The content of Zn-ef ficiency can be 10-70mol%, is preferably 20-40mol%.
The consumption of the present invention to copper Zn Al composite oxide and auxiliary agent is not particularly limited, preferably, the consumption of described copper Zn Al composite oxide and auxiliary agent makes in the ester through hydrogenation catalyst obtained, with the gross weight of described ester through hydrogenation catalyst for benchmark, with the content of the described auxiliary agent of oxide basis for 0.1-5 % by weight, be more preferably 0.5-2 % by weight, the ester through hydrogenation catalyst obtained can be made like this to have good Antacid effectiveness, be highly suitable for the hydrogenation reaction to the ester type compound containing micro-carboxylic acid.
According to the preparation method of ester through hydrogenation catalyst provided by the invention, as long as although at least one metal component be selected from platinum, palladium and tin just can be improved on described copper Zn Al composite oxide the Antacid effectiveness of ester through hydrogenation catalyst as auxiliary agent load, but in order to improve the Antacid effectiveness of described ester through hydrogenation catalyst more significantly, particularly preferably, described auxiliary agent is the mixture of palladium and tin, and with the weight ratio of the palladium of oxide basis and tin two kinds of metal components for 0.1-2:1.
According to the preparation method of ester through hydrogenation catalyst provided by the invention, demand fulfillment " copper in mixed solution C described in the copper in described mixed solution B/zinc mol ratio </zinc mol ratio ".Be to be understood that, the copper/zinc mol ratio difference of described mixed solution B and described mixed solution C should be enough to make a significant impact (may be embodied in and be at least improved on a certain item technique effect) the performance of ester through hydrogenation catalyst.Preferably, in described mixed solution B, copper zinc mol ratio is 1:2-10; More preferably, in described mixed solution C, copper zinc mol ratio is 1.5-15:1.In addition, in described mixed solution B, in the content of copper and described mixed solution C, the mol ratio of the content of copper is particularly preferably 1:1.5-10.Be to be understood that equally, in described mixed solution B, in the content of copper and described mixed solution C, the mol ratio of the content of copper also should meet and makes a significant impact (may be embodied in and be at least improved on a certain item technique effect) the performance of ester through hydrogenation catalyst.
The kind of the present invention to described water-soluble aluminum salt, water-soluble mantoquita and water-soluble zinc salt is not particularly limited.Such as, described water-soluble aluminum salt can be at least one in aluminum nitrate, aluminum sulfate, aluminium chloride etc.From the angle that raw material is ready availability, described water-soluble aluminum salt is particularly preferably aluminum nitrate and/or aluminum sulfate.Described water-soluble mantoquita can be at least one in copper nitrate, copper sulphate, copper chloride etc.From the angle that raw material is ready availability, described water-soluble mantoquita is particularly preferably copper nitrate and/or copper sulphate.Described water-soluble zinc salt can be at least one in zinc nitrate, zinc sulfate, zinc chloride etc.From the angle that raw material is ready availability, described water-soluble zinc salt is particularly preferably zinc nitrate and/or zinc sulfate.In addition, described water-soluble aluminum salt, water-soluble mantoquita and water-soluble zinc salt can not be with the crystallization water, also can with the crystallization water.Such as, described aluminum nitrate can use with the form of nine water aluminum nitrates, described copper nitrate can use with the form of nitrate trihydrate copper, and described copper sulphate can use with the form of cupric sulfate pentahydrate, and described zinc nitrate can use with the form of zinc nitrate hexahydrate and/or white vitriol.
The present invention is not particularly limited the kind of solvent in described aqueous aluminum salt solution, water-soluble copper salting liquid and water-soluble zinc salt solution, as long as described water-soluble aluminum salt, water-soluble mantoquita and water-soluble zinc salt can be dissolved respectively and be suitable for precipitating, such as, can be any one or a few mixed solvent formed in water or water and alcohol, ether, aldehyde and ketone, be preferably water.In addition, the mass concentration of described aqueous aluminum salt solution can be 10-60%, and the mass concentration of described water-soluble copper salting liquid can be 5-50%, and the mass concentration of described water-soluble zinc salt solution can be 5-50%.
According to the preparation method of ester through hydrogenation catalyst provided by the invention, described first alkaline matter, the second alkaline matter can be identical with the kind of the 3rd alkaline matter, also can be different, and can be at least one in sodium carbonate, potash, sodium acid carbonate, saleratus, NaOH and potassium hydroxide independently of one another.In addition, described first alkaline matter, the second alkaline matter and the 3rd alkaline matter can use with solid-state form, also can use with the form of its aqueous solution.When using with the form of its aqueous solution, concentration can be 1-5mol/L usually.
According to the preparation method of ester through hydrogenation catalyst provided by the invention, as mentioned above, in step (1), the pH value of aqueous aluminum salt solution the first alkaline matter is adjusted to 4-10 to produce precipitation, thus obtains slurries A.Preferably, in step (1), the pH value of described aqueous aluminum salt solution the first alkaline matter is adjusted to 4-9, is more preferably adjusted to 5-7.
According to the preparation method of ester through hydrogenation catalyst provided by the invention, in step (3), the pH value of described mixture D the second alkaline matter is adjusted to 4-10 to generate precipitation, and the pH value of described mixture E the 3rd alkaline matter is adjusted to 4-10 to generate precipitation.Preferably, in step (3), the pH value of described mixture D the second alkaline matter is adjusted to 6-8.More preferably, in step (3), the pH value of described mixture E the 3rd alkaline matter is adjusted to 6-8.
Described Separation of Solid and Liquid can adopt and well known to a person skilled in the art that the various mode that can realize solid and fluid separation applications is carried out, and such as, any one mode in suction filtration, press filtration, centrifugation etc. can be adopted to carry out, and therefore not to repeat here.
In addition, preferably, after the preparation method of ester through hydrogenation catalyst provided by the invention is also included in Separation of Solid and Liquid, before drying, the solid product obtained is washed, the non-precipitating material being attached to solid product surface can be removed like this, and then obtain the more excellent ester through hydrogenation catalyst of catalytic performance.
The condition of the present invention to described drying is not particularly limited, as long as the solvent be attached in described solid product can be removed substantially.Such as, the condition of described drying generally includes: baking temperature can be 60-150 DEG C, is preferably 90-120 DEG C; Drying time can be 12-48 hour, is preferably 20-30 hour.
The condition of the present invention to described roasting is also not particularly limited, as long as water-soluble aluminum salt, water-soluble mantoquita and water-soluble zinc salt can be made to be separately converted to corresponding oxide.Such as, the condition of described roasting generally includes: sintering temperature can be 300-700 DEG C, is preferably 350-450 DEG C; Roasting time can be 1-10 hour, is preferably 2-8 hour.
The present invention is not particularly limited by the method for described auxiliary agent load on described copper Zn Al composite oxide, preferably, equi-volume impregnating can be adopted to carry out load.Particularly, the method of described auxiliary agent load on copper Zn Al composite oxide is comprised: copper Zn Al composite oxide is immersed in the solution of water-soluble additive compound, then carry out drying and roasting, described water-soluble additive compound is selected from least one in water-soluble platinum compound, water-soluble palladium compounds and water-soluble tin compound.
The kind of the present invention to described water-soluble platinum compound, water-soluble palladium compounds and water-soluble tin compound is not particularly limited.Such as, described water-soluble platinum compound can be chloroplatinic acid, and described water-soluble palladium compounds can be palladium nitrate and/or tetrachloro-palladium acid sodium hydrate, and described water-soluble tin compound can be at least one in stannic chloride, tin acetate, tin oxalate and stannous sulfate.
The present invention is not particularly limited the kind of solvent in the solution of described solubility auxiliary compound, as long as described water-soluble platinum compound, water-soluble palladium compounds and water-soluble tin compound can be dissolved respectively, such as, can be any one or a few mixed solvent formed in water or water and alcohol, ether, aldehyde and ketone, be preferably water.In addition, the concentration of the solution of described water-soluble additive compound for 0.01-0.15mol/L, can be preferably 0.05-0.12mol/L with elemental metal.
By in the process of described auxiliary agent load on copper Zn Al composite oxide, as long as the condition of described dipping can make at least part of water-soluble additive compound loaded on copper Zn Al composite oxide, such as, it can be 10-60 DEG C that the condition of described dipping generally includes dipping temperature, is preferably 20-40 DEG C; Dip time can be 2-12 hour, is preferably 2-8 hour.
By in the process of described auxiliary agent load on copper Zn Al composite oxide, as long as the solvent be attached on described copper Zn Al composite oxide can be removed by the condition of described drying substantially.Such as, it can be 100-150 DEG C that the condition of described drying generally includes baking temperature, is preferably 120-140 DEG C; Drying time can be 3-12 hour, is preferably 5-10 hour.
By in the process of described auxiliary agent load on copper Zn Al composite oxide, as long as water-soluble additive converting compounds can be corresponding oxide by the condition of described roasting, such as, it can be 300-700 DEG C that the condition of described roasting generally includes sintering temperature, is preferably 350-450 DEG C; Roasting time can be 1-10 hour, is preferably 2-8 hour.
Present invention also offers the ester through hydrogenation catalyst prepared by said method.
Be to be understood that, ester through hydrogenation catalyst generally carries out concluding the business and storing with the form of precursor (or being called precursor), although ester through hydrogenation catalyst precarsor can not direct catalytic reaction, but is just being called " catalyst " by catalyst precarsor traditionally.Ester through hydrogenation catalyst precarsor just has catalytic activity after reduction, and this has been come by the operating personnel of commercial plant usually, and those skilled in the art know this reduction process, and therefore not to repeat here.Ester through hydrogenation catalyst precarsor can make the shape of various needs according to the demand of user, such as, can be through shaping bead, also can be shaping front state, as powder.
Under the method that ester through hydrogenation provided by the invention reacts is included in the existence of above-mentioned ester through hydrogenation catalyst, ester type compound is carried out hydrogenation reaction.
Main improvements of the present invention are to have employed a kind of new ester through hydrogenation catalyst, and the routine that the kind of described ester type compound and the condition etc. of hydrogenation reaction can be all this area is selected.Such as, described ester type compound can be monobasic acid ester class, also can be dibasic acid ester class, its instantiation includes but not limited to: at least one in sec-butyl acetate, cyclohexyl acetate, ethyl acetate, LCFA methyl esters, dimethyl oxalate, dimethyl adipate, terephthalate etc.Wherein, in described LCFA methyl esters, the chain length of LCFA is preferably C
4-C
10, its instantiation includes but not limited to: at least one in methyl caproate, methyl heptanoate, methyl caprylate, methyl pelargonate etc.Particularly preferably, described ester type compound is the cyclohexyl acetate adopting acetic acid and cyclohexene esterification to prepare, and described cyclohexyl acetate contains the following acetic acid of 3000 μ g/g, the acetic acid more preferably containing 500-2000 μ g/g.
When described ester type compound is the cyclohexyl acetate adopting acetic acid and cyclohexene esterification to prepare, and described cyclohexyl acetate is when containing the 3000 following acetic acid of μ g/g, it can be 200-600 DEG C that the condition of described ester through hydrogenation reaction generally includes reaction temperature, reaction pressure can be 1-7MPa, and the mass space velocity of reaction raw materials can be 0.1-0.6h
-1, hydrogen ester mol ratio can be 5-60:1.In the present invention, described reaction pressure all refers to gauge pressure.
In addition, as mentioned above, usually, ester through hydrogenation catalyst precarsor just has catalytic activity after reduction.Therefore, before carrying out hydrogenation reaction, usually need described ester through hydrogenation catalyst to reduce in the hydrogen gas stream at 150-250 DEG C 12-24 hour.
Below will be described the present invention by embodiment.
In following preparation example, contrast preparation example, embodiment and comparative example, in copper Zn Al composite oxide, the content of each metallic element and the content of auxiliary agent all adopt Rigaku electric machine industry Co., Ltd. 3271E type Xray fluorescence spectrometer to carry out analysis mensuration.
Preparation example 1
This preparation example adopts three sections of precipitation method to prepare copper Zn Al composite oxide.
150.01g (0.40mol) nine water aluminum nitrate is dissolved in 300mL deionized water, obtains aluminum nitrate aqueous solution.Under agitation with the sodium hydrate aqueous solution of 1mol/L, the pH value of this aluminum nitrate aqueous solution is titrated to 7.0, obtains white casse slurries A.72.48g nitrate trihydrate copper is dissolved in 128g deionized water, and the solution obtained is divided into 20.48g and 180g two parts.89.25g zinc nitrate hexahydrate is dissolved in 150g deionized water, and the solution obtained is divided into 23.25g and 216g two parts.The copper nitrate aqueous solution (content of copper nitrate is 0.03mol) of 20.48g and the zinc nitrate aqueous solution (content of zinc nitrate is 0.27mol) of 216g are mixed to get mixed solution B.The copper nitrate aqueous solution (content of copper nitrate is 0.27mol) of 180g and the zinc nitrate aqueous solution (content of zinc nitrate is 0.03mol) of 23.25g are mixed to get mixed solution C.Then add in slurries A by mixed solution B, the sodium hydrate aqueous solution stirring lower 1mol/L is titrated to pH value 7.5.Then add mixed solution C, then be titrated to pH value 7.5 with the sodium hydrate aqueous solution of 1mol/L, obtain white mixed serum.After suction filtration, washing, dried overnight at 120 DEG C, then roasting 4h at 400 DEG C, obtain copper Zn Al composite oxide C1#, wherein, in the mol ratio of copper zinc-aluminium three kinds of metal components of element for 3:3:4.
Contrast preparation example 1
This contrast preparation example adopts coprecipitation to prepare copper Zn Al composite oxide.
150.01g (0.40mol) nine water aluminum nitrate is dissolved in 300mL deionized water, obtains aluminum nitrate aqueous solution.72.48g (0.30mol) nitrate trihydrate copper is dissolved in 128g deionized water, obtains copper nitrate aqueous solution.89.25g (0.30mol) zinc nitrate hexahydrate is dissolved in 150g deionized water, obtains zinc nitrate aqueous solution.Then above-mentioned aluminum nitrate aqueous solution, copper nitrate aqueous solution and zinc nitrate aqueous solution are mixed, be then under agitation titrated to pH value 7.5 with the sodium hydroxide solution of 1mol/L, obtain mixed serum.After suction filtration, washing, dried overnight at 120 DEG C, then roasting 4h at 400 DEG C, obtain reference copper Zn Al composite oxide D1#, wherein, in the mol ratio of copper zinc-aluminium three kinds of metal components of element for 3:3:4.
Preparation example 2
This preparation example adopts three sections of precipitation method to prepare copper Zn Al composite oxide.
150.01g (0.40mol) nine water aluminum nitrate is dissolved in 300mL deionized water, obtains aluminum nitrate aqueous solution.Under agitation with the sodium hydrate aqueous solution of 1mol/L, the pH value of this aluminum nitrate aqueous solution is titrated to 6.0, obtains white casse slurries A.99.87g cupric sulfate pentahydrate is dissolved in 150g deionized water, and the solution obtained is divided into 24.87g and 225g two parts.59.50g zinc nitrate hexahydrate is dissolved in 90g deionized water, and the solution obtained is divided into 119.50g and 30g two parts.The copper sulfate solution (content of copper sulphate is 0.04mol) of 24.87g and the zinc nitrate aqueous solution (content of zinc nitrate is 0.15mol) of 119.50g are mixed to get mixed solution B.The copper sulfate solution (content of copper sulphate is 0.36mol) of 225g and the zinc nitrate aqueous solution (content of zinc nitrate is 0.05mol) of 30g are mixed to get mixed solution C.Then add in slurries A by mixed solution B, the sodium hydrate aqueous solution stirring lower 1mol/L is titrated to pH value 7.5.Then add mixed solution C, then be titrated to pH value 7.5 with the sodium hydrate aqueous solution of 1mol/L, obtain white mixed serum.After suction filtration, washing, dried overnight at 120 DEG C, then roasting 4h at 450 DEG C, obtain copper Zn Al composite oxide C2#, wherein, in the mol ratio of copper zinc-aluminium three kinds of metal components of element for 4:2:4.
Contrast preparation example 2
This contrast preparation example adopts coprecipitation to prepare copper Zn Al composite oxide.
150.01g (0.40mol) nine water aluminum nitrate is dissolved in 300mL deionized water, obtains aluminum nitrate aqueous solution.99.87g (0.40mol) cupric sulfate pentahydrate is dissolved in 150g deionized water, obtains copper sulfate solution.59.50g (0.20mol) zinc nitrate hexahydrate is dissolved in 90g deionized water, obtains zinc nitrate aqueous solution.Then above-mentioned aluminum nitrate aqueous solution, copper sulfate solution and zinc nitrate aqueous solution are mixed, be then under agitation titrated to pH value 7.5 with the sodium hydroxide solution of 1mol/L, obtain mixed serum.After suction filtration, washing, dried overnight at 120 DEG C, then roasting 4h at 400 DEG C, obtain reference copper Zn Al composite oxide D2#, wherein, in the mol ratio of copper zinc-aluminium three kinds of metal components of element for 4:2:4.
Embodiment 1
This embodiment is for illustration of the preparation method of ester through hydrogenation catalyst provided by the invention.
0.0944g palladium nitrate is dissolved in 8mL deionized water, obtain palladium nitrate aqueous solution, then this palladium nitrate aqueous solution is added drop-wise in isopyknic copper Zn Al composite oxide C1#, at room temperature 30 DEG C, 6 hours are left standstill after abundant stirring, then at 120 DEG C dry 12 hours, roasting 3 hours at 350 DEG C again, obtains ester through hydrogenation catalyst C3#.With the gross weight of described ester through hydrogenation catalyst C3# for benchmark, be 0.5 % by weight with the content of the palladium component of oxide basis.
Comparative example 1
This comparative example is for illustration of the preparation method of the ester through hydrogenation catalyst of reference.
Ester through hydrogenation catalyst is prepared according to the method for embodiment 1, unlike, the reference copper Zn Al composite oxide D1# of copper Zn Al composite oxide C1# same volume is substituted, obtains reference ester hydrogenation catalyst D3#.With the gross weight of described reference ester hydrogenation catalyst D3# for benchmark, be 0.5 % by weight with the content of the palladium component of oxide basis.
Embodiment 2
This embodiment is for illustration of the preparation method of ester through hydrogenation catalyst provided by the invention.
0.1326g chloroplatinic acid and 0.159g stannous sulfate are dissolved in 9mL deionized water, obtain the aqueous solution of chloroplatinic acid and stannous sulfate, then the aqueous solution of this chloroplatinic acid and stannous sulfate is added drop-wise in isopyknic copper Zn Al composite oxide C1#, at room temperature 30 DEG C, 6 hours are left standstill after abundant stirring, then at 120 DEG C dry 12 hours, roasting 3 hours at 350 DEG C again, obtains ester through hydrogenation catalyst C4#.With the gross weight of described ester through hydrogenation catalyst C4# for benchmark, being 0.5 % by weight with the content of the platinum component of oxide basis, is 1 % by weight with the content of the tin component of oxide basis.
Embodiment 3
This embodiment is for illustration of the preparation method of ester through hydrogenation catalyst provided by the invention.
0.0377g palladium nitrate and 0.159g stannous sulfate are dissolved in 8mL deionized water, obtain the aqueous solution of palladium nitrate and stannous sulfate, then the aqueous solution of this palladium nitrate and stannous sulfate is added drop-wise in isopyknic copper Zn Al composite oxide C2#, at room temperature 30 DEG C, 6 hours are left standstill after abundant stirring, then at 120 DEG C dry 12 hours, roasting 3 hours at 350 DEG C again, obtains ester through hydrogenation catalyst C5#.With the gross weight of described ester through hydrogenation catalyst C5# for benchmark, being 0.5 % by weight with the content of the palladium component of oxide basis, is 0.5 % by weight with the content of the tin component of oxide basis.
Embodiment 4
This embodiment is for illustration of the preparation method of ester through hydrogenation catalyst provided by the invention.
Ester through hydrogenation catalyst is prepared according to the method for embodiment 3, unlike, the palladium nitrate of stannous sulfate identical weight part is substituted, obtains ester through hydrogenation catalyst C6#.With the gross weight of described ester through hydrogenation catalyst C6# for benchmark, be 1.0 % by weight with the content of the palladium component of oxide basis.
Comparative example 2
This comparative example is for illustration of the preparation method of the ester through hydrogenation catalyst of reference.
Ester through hydrogenation catalyst is prepared according to the method for embodiment 3, unlike, the reference copper Zn Al composite oxide D2# of copper Zn Al composite oxide C2# same volume is substituted, obtains reference ester hydrogenation catalyst D4#.With the gross weight of described reference ester hydrogenation catalyst D4# for benchmark, being 0.5 % by weight with the content of the palladium component of oxide basis, is 0.5 % by weight with the content of the tin component of oxide basis.
Embodiment 5
This embodiment is for illustration of the preparation method of ester through hydrogenation catalyst provided by the invention.
0.0566g chloroplatinic acid and 0.080g stannous sulfate are dissolved in 8mL deionized water, obtain the aqueous solution of chloroplatinic acid and stannous sulfate, then the aqueous solution of this chloroplatinic acid and stannous sulfate is added drop-wise in isopyknic copper Zn Al composite oxide C2#, at room temperature 30 DEG C, 6 hours are left standstill after abundant stirring, then at 120 DEG C dry 12 hours, roasting 3 hours at 350 DEG C again, obtains ester through hydrogenation catalyst C7#.With the gross weight of described ester through hydrogenation catalyst C7# for benchmark, being 0.3 % by weight with the content of the platinum component of oxide basis, is 0.5 % by weight with the content of the tin component of oxide basis.
Test case
Test case is for illustration of the investigation of ester through hydrogenation catalyst catalytic performance and contrast.
Catalyst performance evaluation is carried out on fixed bed reactors, concrete operations are as follows: respectively by copper Zn Al composite oxide C1#-C2#, reference copper Zn Al composite oxide D1#-D2#, ester through hydrogenation catalyst C3#-C7# and reference ester hydrogenation catalyst D3#-D4# compressing tablet, then be broken into 20 order to 40 object particles and load in fixed bed reactors, loadings is 10.0g.All need before using to carry out the online reduction treatment of catalyst, reducing condition comprises: temperature is 260 DEG C, and pure hydrogen flow velocity is 50mL/min, and the recovery time is 15 hours.The condition of evaluation test comprises: reaction temperature is respectively 200 DEG C, 230 DEG C and 250 DEG C, reaction pressure is respectively 4.0MPa and 4.5MPa, reaction raw materials is the cyclohexyl acetate (adopting the titration acetic acid content recorded wherein to be 600 μ g/g) adopting acetic acid and cyclohexene esterification to prepare, use measuring pump charging, the mass space velocity of reaction raw materials is 0.4h
-1, hydrogen flow rate is 210mL/min (hydrogen ester mol ratio is about 20:1), and concrete outcome is as shown in table 1.
Table 1
In table 1, as can be seen from the contrast of copper Zn Al composite oxide C1#-C2# and reference copper Zn Al composite oxide D1#-D2# and ester through hydrogenation catalyst C3#-C5# and reference ester hydrogenation catalyst D3#-D4#, the copper Zn Al composite oxide that the copper Zn Al composite oxide adopting the multistage precipitation method to obtain and corresponding ester through hydrogenation catalyst are better than adopting direct co-precipitation to obtain on effect and corresponding ester through hydrogenation catalyst.The contrast of the ester through hydrogenation catalyst C5#-C6# obtained after the ester through hydrogenation catalyst C3#-C4# obtained after loaded modified with it as can be seen from copper Zn Al composite oxide C1# and copper Zn Al composite oxide C2# is loaded modified with it, in reaction 24h initial activity, conversion ratio difference is less, but selective upper modifier (ester through hydrogenation catalyst) all wants high 2 to 3 percentage points than former powder (copper Zn Al composite oxide) substantially, 1000h life test shows, conversion ratio between former powder and modifier and selective aspect differ greatly, the conversion ratio of modifier is high about 5 percentage points, and it is selective high about 7 percentage points.In sum, three sections of coprecipitations are adopted to obtain and the modified ester through hydrogenation catalyst of at least one metal component in palladium, platinum and tin all has better performance in initial activity and life experiment.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (23)
1. a preparation method for ester through hydrogenation catalyst, the method comprises the following steps:
(1) pH value of aqueous aluminum salt solution the first alkaline matter is adjusted to 4-10, obtains slurries A;
(2) the mixed solution B of preparation all containing water-soluble copper salting liquid and water-soluble zinc salt solution and mixed solution C, the copper in mixed solution C described in the copper in described mixed solution B/zinc mol ratio </zinc mol ratio;
(3) described mixed solution B is mixed with slurries A, obtain mixture D, and the pH value of described mixture D the second alkaline matter is adjusted to 4-10, add described mixed solution C again, obtain mixture E, and then the pH value of described mixture E the 3rd alkaline matter is adjusted to 4-10, then carry out Separation of Solid and Liquid, and the solid product obtained is carried out drying and roasting, obtain copper Zn Al composite oxide;
(4) by auxiliary agent load on described copper Zn Al composite oxide, described auxiliary agent is selected from least one metal component in platinum, palladium and tin.
2. method according to claim 1, wherein, the consumption of described aqueous aluminum salt solution, water-soluble copper salting liquid and water-soluble zinc salt solution makes in the copper Zn Al composite oxide obtained, with the integral molar quantity of metallic element in described copper Zn Al composite oxide for benchmark, the content of aluminium element is 10-50%, the content of copper is 10-70mol%, and the content of Zn-ef ficiency is 10-70mol%.
3. method according to claim 1, wherein, the consumption of described copper Zn Al composite oxide and auxiliary agent makes in the ester through hydrogenation catalyst obtained, with the gross weight of described ester through hydrogenation catalyst for benchmark, with the content of the described auxiliary agent of oxide basis for 0.1-5 % by weight.
4. method according to claim 3, wherein, described auxiliary agent is the mixture of palladium and tin, and with the weight ratio of the palladium of oxide basis and tin two kinds of metal components for 0.1-2:1.
5. according to the method in claim 1-4 described in any one, wherein, in described mixed solution B, copper zinc mol ratio is 1:2-10; In described mixed solution C, the mol ratio of copper zinc is 1.5-15:1.
6. method according to claim 5, wherein, in described mixed solution B, in the content of copper and described mixed solution C, the mol ratio of the content of copper is 1:1.5-10.
7. according to the method in claim 1-4 described in any one, water-soluble aluminum salt in described aqueous aluminum salt solution is aluminum nitrate and/or aluminum sulfate, water-soluble mantoquita in described water-soluble copper salting liquid is copper nitrate and/or copper sulphate, and the water-soluble zinc salt in described water-soluble zinc salt solution is zinc nitrate and/or zinc sulfate.
8. method according to claim 7, wherein, the mass concentration of described aqueous aluminum salt solution is 10-60%, and the mass concentration of described water-soluble copper salting liquid is 5-50%, and the mass concentration of described water-soluble zinc salt solution is 5-50%.
9. according to the method in claim 1-4 described in any one, wherein, the kind of described first alkaline matter, the second alkaline matter and the 3rd alkaline matter is identical or different, and is at least one in sodium carbonate, potash, sodium acid carbonate, saleratus, NaOH and potassium hydroxide independently of one another.
10. according to the method in claim 1-4 described in any one, wherein, in step (1), the pH value of described aqueous aluminum salt solution the first alkaline matter is adjusted to 4-9, is preferably adjusted to 5-7.
11. according to the method in claim 1-4 described in any one, wherein, in step (3), the pH value of described mixture D the second alkaline matter is adjusted to 6-8.
12. according to the method in claim 1-4 described in any one, wherein, in step (3), the pH value of described mixture E the 3rd alkaline matter is adjusted to 6-8.
13. according to the method in claim 1-4 described in any one, and wherein, in step (3), it is 60-150 DEG C that the condition of described drying comprises baking temperature, and drying time is 12-48 hour.
14. according to the method in claim 1-4 described in any one, and wherein, in step (3), it is 300-700 DEG C that the condition of described roasting comprises sintering temperature, and roasting time is 1-10 hour.
15. according to the method in claim 1-4 described in any one, wherein, the method of described auxiliary agent load on copper Zn Al composite oxide is comprised: copper Zn Al composite oxide is immersed in the solution of water-soluble additive compound, then carry out drying and roasting, described water-soluble additive compound is selected from least one in water-soluble platinum compound, water-soluble palladium compounds and water-soluble tin compound.
16. methods according to claim 15, wherein, by the process of described auxiliary agent load on described copper Zn Al composite oxide, it is 10-60 DEG C that the condition of described dipping comprises dipping temperature, and dip time is 2-12 hour.
17. methods according to claim 15, wherein, by the process of described auxiliary agent load on described copper Zn Al composite oxide, it is 100-150 DEG C that the condition of described drying comprises baking temperature, and drying time is 3-12 hour.
18. methods according to claim 15, wherein, by the process of described auxiliary agent load on described copper Zn Al composite oxide, it is 300-700 DEG C that the condition of described roasting comprises sintering temperature, and roasting time is 1-10 hour.
19. methods according to claim 15, wherein, described water-soluble platinum compound is chloroplatinic acid, and described water-soluble palladium compounds is palladium nitrate and/or tetrachloro-palladium acid sodium hydrate, and described water-soluble tin compound is at least one in stannic chloride, tin acetate, tin oxalate and stannous sulfate.
20. methods according to claim 15, wherein, the concentration of the solution of described water-soluble additive compound counts 0.01-0.15mol/L with metallic element.
The 21. ester through hydrogenation catalyst prepared by the method in claim 1-20 described in any one.
The method of 22. 1 kinds of ester through hydrogenation reactions, ester type compound is carried out hydrogenation reaction under being included in the existence of ester through hydrogenation catalyst according to claim 21 by the method.
23. methods according to claim 22, wherein, described ester type compound is the cyclohexyl acetate adopting acetic acid and cyclohexene esterification to prepare, and described cyclohexyl acetate contains the following acetic acid of 3000 μ g/g.
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| CN114433098B (en) * | 2020-10-20 | 2024-03-29 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for reducing aldehyde content in polyether polyol |
| CN113828319A (en) * | 2021-10-13 | 2021-12-24 | 江苏扬农化工集团有限公司 | Cu-Zn-M composite oxide catalyst and preparation method and application thereof |
| CN113828319B (en) * | 2021-10-13 | 2024-03-26 | 江苏扬农化工集团有限公司 | Cu-Zn-M composite oxide catalyst and preparation method and application thereof |
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