CN103657658A - Carboxylic ester hydrogenation catalyst and method for preparing cyclohexanol and ethanol - Google Patents
Carboxylic ester hydrogenation catalyst and method for preparing cyclohexanol and ethanol Download PDFInfo
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- CN103657658A CN103657658A CN201210347463.6A CN201210347463A CN103657658A CN 103657658 A CN103657658 A CN 103657658A CN 201210347463 A CN201210347463 A CN 201210347463A CN 103657658 A CN103657658 A CN 103657658A
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Abstract
The invention relates to a carboxylic ester hydrogenation catalyst and a method for preparing cyclohexanol and ethanol. The catalyst comprises the following components in parts by mass: 5-60 parts of copper oxide (a), 10-50 parts of zinc oxide (b) and 5-60 parts of oxide (c) of metal selected from one or more of aluminum, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide metals and actinide metals, and (d) one or more of 0.2-2 parts of alkali metal hydroxides and alkaline-earth metal hydroxide. According to the catalyst and the method, the cyclohexanol and the ethanol can be coproduced through carboxylic ester hydrogenation.
Description
Technical field
The present invention relates to carboxylate hydrogenation catalyst and prepare cyclohexanol and the method for ethanol.
Background technology
Cyclohexanol and ethanol are all important chemical raw material and solvents.Cyclohexanol is mainly for the production of nylon 6, nylon 66 etc., and ethanol is the raw material of the multiple chemical products such as synthesizing ester, is also widely used as the fuel additive of gasoline.
Industrial, the production method of cyclohexanol mainly comprises air oxidation of cyclohexane method, phenol hydrogenation method and cyclohexene hydration method.Air oxidation of cyclohexane method, because poor selectivity produces a large amount of accessory substances, product yield is low, and produces a large amount of spent lyes, and enjoys industry to denounce.Phenol hydrogenation method is to produce the comparatively clean technology path of cyclohexanol, and has the advantages such as technological process is short, product purity is high, quality is good, but due to phenol shortage, expensive, so commercial Application is restricted.Cyclohexene hydration method is a newer cyclohexanol production route, and this method reaction selectivity is high, and process does not almost have three waste discharge, but exist hydration reaction conversion ratio very low, to the more high deficiency of cyclohexene purity requirement.
The conventional production methods of ethanol is fermentation method and ethylene hydration method.Because China is populous, cultivated area is not enough, and grain fermentation legal system ethanol " is striven grain with mouth ", do not meet China's national situation, and zymotechnique pollutes comparatively serious.Ethylene hydration method need to carry out under HTHP, and China's oil relative inadequacy of resources, and ethene price is subject to the influence of fluctuations of international oil price very large.Therefore, developing new ethanol synthetic route is the inexorable trend of technical development.
CN86105765A proposes a kind of carboxylate Hydrogenation that passes through for the method for alcohol, the method is under the existence of solid Cu-contained catalyst that has reduction activation, under high temperature, normal pressure or high pressure by carboxylate hydrogenation, outside this catalyst copper removal, also contain magnesium, at least one in lanthanide series metal or actinide metals.Catalyst represented with following general formula before reduction activation: Cu
am
1m
2 ba
co
x, M
1magnesium, at least one in lanthanide series metal or actinide metals, M
2be selected from Ca, Mo, Rh, Pt, Cr, Zn, Al, T i, V, Ru, Re, Pd, Ag and Au; A is a kind of alkali metal; A is 0.1～4; B is 0～1.0; C is 0～0.5; X is for can meet the numeral of other element to the total valence mumber requirement of oxygen.Alkali metal in this catalyst is a kind of selection component, and its form by alkali metal salt is introduced catalyst.The acyclic monobasic that the applicable carboxylate of the method and catalyst is C1-C24 or binary, saturated or unsaturated, straight or branched carboxylate, do not relate to the production of the cyclic alkanol as cyclohexanol.
CN1075048C proposes a kind of method and catalyst of direct hydrogenation of carboxylic esters, comprise and make one or more esters contact and react under following catalyst exists with hydrogen, this catalyst contains a kind of copper compound, a kind of zinc compound and at least one and is selected from the compound of aluminium, zirconium, magnesium, a kind of rare earth element or its mixture as its component, by these catalytic components are made to this catalyst 200 to being less than roasting in the temperature range of 400 ℃, the method is under liquid phase, at 170～250 ℃ and 20.7～138 bar tables, depresses and carries out.The applicable carboxylate of the method and catalyst is the ester exchange by the natural oil C6～C22 dimethyl ester, C6～C66 natural glycerin three esters that make or the C6～C44 compound making do ester exchange for natural glycerin three esters.
US4939307 proposes the technique of a kind of ester through hydrogenation alcohol processed.By general formula, be R
1-CO-OR
2or R
4o-CO-R
3-CO-OR
2(R wherein
1for H or C
1～C
20alkyl, R
2and R
4for C
1～C
20alkyl, R
3for-(CH
2) n-group, n=1～10) ester and H
2with CO gaseous mixture, at 30～150 ℃, under 5～100 bar pressures, carry out hydrogenation reaction and generate alcohol, its catalyst is composed of the following components: (a) VIII family metal ion compound in a kind of periodic table; (b) alkoxide of a kind of alkali metal or alkaline-earth metal; (c) a kind of alcohol.
US4113662 and USP4149021 disclose a kind of ester through hydrogenation catalyst, and this catalyst is comprised of element, oxide, hydroxide or the carbonate of cobalt, zinc, copper.
US4611085 discloses a kind of C
1～C
20the method of carboxylate gas phase hydrogenation alcohol processed, it is characterized in that catalyst is comprised of a kind of VIII family element, a kind of auxiliary agent and charcoal carrier, wherein said VIII family element comprises Ru, Ni, Rh, auxiliary agent comprises IA (except Li), I IA family (except Be and Mg), group of the lanthanides and actinides, and the BET specific area of charcoal carrier is greater than 100m
2/ g.Hydrogenation reaction is at 100～400 ℃, gas space velocity 100～120000h
-1under condition, carry out.Alkali metal in this catalyst is to introduce with the form of alkali metal salt, as alkali-metal nitrate, carbonate or acetate.
GB2250287A(Eduard Karek Poles, Dirk Ryk Evert Polman, Johanned Joesphus Vreeswijk.Unichema Chemie BV) disclose a kind of method of fatty acid ester Hydrogenation alcohol, the feature of the method is that hydrogenation adopts Cu-contained catalyst and in ester raw material, adds a certain amount of water to maintain the activity of catalyst.
US5334779 discloses a kind of carbon monoxide-olefin polymeric and the application in carboxylate hydrogenation thereof, its catalyst as the 3rd component, is characterized in that the content of the 3rd component is no more than 4% under hydrogenation temperature and pressure by cupric oxide, zinc oxide and the oxide that is selected from aluminium, magnesium, zirconium or their mixture.
CN102149661A discloses a kind of platinum/tin catalyst that uses and has directly selectively prepared the method for ethanol by acetic acid, comprise: the incoming flow containing acetic acid and hydrogen contacts with applicable hydrogenation catalyst in rising temperature, described hydrogenation catalyst be included in platinum in applicable catalyst carrier and tin group and and optional load on the 3rd metal on described carrier, wherein said the 3rd metal choosing is the following group forming freely: palladium, rhodium, ruthenium, rhenium.Iridium, chromium, copper, molybdenum, tungsten, vanadium and zinc.
CN1022228831A discloses a kind of catalyst of acetic acid gas phase hydrogenation ethanol production, this catalyst is comprised of main active component, auxiliary agent and carrier three parts, carrier is any one in active carbon, graphite or multiple-wall carbon nanotube, main active component is 0.1～30.0% of catalyst weight, the weight of auxiliary agent is 0.1～10.0% of catalyst weight, and surplus is carrier.Main active component is any one or two kinds of metal W or Mo.Auxiliary agent is one or more of Pd, Re, Pt, Rh or Ru.
From open source literature, in prior art, there is not any information disclosure about ethyl cyclohexyl ester through hydrogenation energy coproduction cyclohexanol and ethanol.
Summary of the invention
First the present invention provides a kind of carboxylate hydrogenation catalyst, and next provides under the existence of this catalyst, by the method for ethyl cyclohexyl ester through hydrogenation coproduction cyclohexanol and ethanol.Adopt catalyst of the present invention and method of hydrotreating, cyclohexyl acetate can almost be converted into quantitatively cyclohexanol and ethanol under higher space velocity, and does not almost have side reaction to occur.
The invention provides a kind of carboxylate hydrogenation catalyst, comprise: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxide; In described catalyst, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～60 parts, and component (d) is 0.2～2 part.
The present invention also provides a kind of method of preparing cyclohexanol and ethanol, comprising: under the existence of hydrogenation catalyst, by cyclohexyl acetate and hydrogen haptoreaction;
Described hydrogenation catalyst comprises: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxide; In described catalyst, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～30 parts, and component (d) is 0.2～2 part;
Reaction condition is: 150～400 ℃ of temperature, reaction pressure 1～20MPa, hydrogen/oil mol ratio 1～1000:1; While adopting continuous reaction, cyclohexyl acetate liquid charging air speed is 0.1～20h
-1; While adopting intermittent reaction, the reaction time is 0.2～20h.
The specific embodiment
Below elaborate the present invention.
In the hydrogenation process of cyclohexyl acetate, at least there is following chemical reaction.
Main reaction:
Because the ethanol and the cyclohexanol that generate all have reactivity, under reaction condition, also may further there is following side reaction:
(1) ester exchange reaction
(2) dehydration of cyclohexanol, hydrogenation reaction
(3) cyclohexanol, ethanol dehydration etherification reaction
Therefore the key that, realizes ethyl cyclohexyl ester through hydrogenation coproduction cyclohexanol and ethanol is the preparation of hydrogenation catalyst.First hydrogenation catalyst must have good activity, realizes the conversion completely of cyclohexyl acetate, and secondly, catalyst will have higher selective, prevents the generation of the side reactions such as dehydration of cyclohexanol, etherificate.
For realizing object of the present invention, first the present invention provides a kind of carboxylate hydrogenation catalyst, comprise: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxide; In described catalyst, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～60 parts, and component (d) is 0.2～2 part.
In preferred situation, in described catalyst, in mass fraction, component (a) is 10～50 parts, and component (b) is 15～45 parts, and component (c) is 15～55 parts, and component (d) is 0.2～2 part.
In preferred situation, in described catalyst, in mass fraction, component (a) is 30～45 parts, and component (b) is 20～35 parts, and component (c) is 20～50 parts, and component (d) is 0.5～1.5 part.
In preferred situation, component (c) is selected from the oxide of one or more metals in following group: aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanum and cerium.
From being easy to get property, cost and the result of use of raw material, consider, component (d) is preferably one or more in potassium hydroxide, NaOH and barium hydroxide.
Be to be understood that, catalyst is generally concluded the business and stores with the form of precursor (or being called precursor), although catalyst precarsor can not direct catalytic reaction, yet traditionally catalyst precarsor is just being called to " catalyst ".Catalyst precarsor just has catalytic activity after reduction, and this is completed by the operating personnel of commercial plant conventionally, and those skilled in the art know this reduction process, and the present invention does not repeat them here.Catalyst precarsor can be made the shape of various needs according to user's demand, as the bead through overmolding, can be also the state before moulding, as powder.
The present invention also provides a kind of preparation method of carboxylate hydrogenation catalyst, comprising:
(1) by coprecipitation, prepare composite metal oxide; Described composite metal oxide comprises (a) cupric oxide, and (b) zinc oxide (c) is selected from the oxide of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals; In described composite metal oxide, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～60 parts;
(2) alkali metal hydroxide that composite metal oxide step (1) being obtained is 0.5～5% with mass fraction and/or alkaline earth metal hydroxide aqueous solution dipping, more after filtration, dry, roasting, obtain product.
In preferred situation, component (c) is selected from the oxide of one or more metals in following group: aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanum and cerium.
In preferred situation, in step (2), dipping temperature is 30 ℃～80 ℃, and dip time is 1～48h; Baking temperature is 100 ℃～200 ℃, and be 3～48h drying time; Sintering temperature is 250 ℃～400 ℃, and roasting time is 3～48h.
In step (2), described alkali metal hydroxide and/or alkaline earth metal hydroxide are preferably one or more in potassium hydroxide, NaOH and barium hydroxide.
The product that step (2) obtains is Powdered, and it can be according to user's the shape that requires processing and forming to become user to need.No matter be powdery product, or the product after processing and forming, in hydrogen atmosphere, after reduction, just there is the activity of catalysis carboxylate hydrogenation reaction.Reduction process can be both an extra step before catalyst is used, and also can in the process of carrying out carboxylate hydrogenation reaction, complete; Preferably as catalyst, by front one extra step, undertaken.
Coprecipitation refers to homogeneous phase two or more metal cations that exist in solution reacts with precipitating reagent, metal cation in solution is precipitated, obtain the precipitation of various uniform component, the precipitation mixture or the solid solution presoma that generate, after filtration, washing, roasting (making precipitation mixture or the thermal decomposition of solid solution presoma), obtain the method for composite metal oxide.Described coprecipitation can take different modes to realize, both the solution that contains metal cation can be joined in precipitant solution, also precipitant solution can be joined in the solution that contains metal cation, the solution that contains metal cation and precipitant solution can also be joined in solvent simultaneously.The solvent that coprecipitation is used both can make water, also can use the mixed solvent of second alcohol and water.
In more detail, the coprecipitation in step (1) comprises:
(I) preparation mixes soluble metal saline solution, and described metal comprises (a) copper, (b) zinc and (c) be selected from one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals;
(II), at 15 ℃～80 ℃, adds the precipitating reagent aqueous solution to the aqueous solution of step (I), to pH be 6～9, generate the mixed precipitation of metallic element described in step (I), described precipitating reagent meets that to make the precipitation energy pyrolysis generating be metal oxide;
The precipitation system that (III) obtains step (II), between 30 ℃～80 ℃, keep after 1～48h, filter and wash, until the metal cation in filtrate is less than 100ug/g, at 100 ℃～200 ℃, dry 3～48h, 250 ℃～400 ℃ roasting 3～48h, obtain composite metal oxide powder.
In step (I), the implication of described " solubility " refers to that the solubility of every kind of slaine in water can meet the composition requirement of the composite metal oxide of preparation.
In step (I), suitable soluble metallic salt can be selected from: the nitrate of described metal, sulfate, hydrochloride, acetate or their hydrate.
In step (II), preferably under agitation, to the aqueous solution of step (I), add the precipitating reagent aqueous solution, this will be conducive to improve the homogeneity of catalyst.
In step (II), described precipitating reagent is preferably one or more in NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate, ammonia, urea, sodium oxalate, potassium oxalate and ammonium oxalate.
The present invention also provides a kind of method of preparing cyclohexanol and ethanol, comprising: under the existence of hydrogenation catalyst, by cyclohexyl acetate and hydrogen haptoreaction;
Described hydrogenation catalyst comprises: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxide; In described catalyst, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～30 parts, and component (d) is 0.2～2 part;
Reaction condition is: 150～400 ℃ of temperature, reaction pressure 1～20MPa, hydrogen ester mol ratio 1～1000:1; While adopting continuous reaction, cyclohexyl acetate liquid charging air speed is 0.1～20h
-1; While adopting intermittent reaction, the reaction time is 0.2～20h.
In preferred situation, in described hydrogenation catalyst, component (c) is selected from the oxide of one or more metals in following group: aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanum and cerium.
The reactor that enforcement said method adopts is one or more, and type of reactor is selected from one or more in tank reactor, tubular fixed-bed reactor, fluidized bed reactor and fluidized-bed reactor.
Said method both can adopt mode intermittently to implement, and also can adopt continuous mode to implement.Batch (-type) hydrogenation reaction generally adopts reactor to make reactor, cyclohexyl acetate and hydrogenation catalyst are dropped in reactor, pass into hydrogen reacts under certain temperature and pressure, after reaction finishes, product is adopted and drawn off from still, isolate product, then drop into next group material and react.Continous way hydrogenation reaction can adopt shell-and-tube shell and tube reactor, and hydrogenation catalyst is fixed in tubulation, at shell side by cooling water to remove the liberated heat of reaction.
Cyclohexyl acetate hydrogenation reaction temperature, is generally 150～400 ℃, and optimizing reaction temperature is 200～300 ℃.Reaction pressure is normal pressure～20MPa, and optimization reaction pressure is 4～10MPa.
The control of the hydrogen ester mol ratio of ethyl cyclohexyl hydrogenation reaction is also very important.High hydrogen ester is than the hydrogenation that is conducive to ester, but too high hydrogen ester is than the energy consumption that will increase hydrogen compression cycle.General hydrogen ester mol ratio is 1～1000:1, and optimal conditions is 5～100:1.
The size of charging air speed of hydrogenation reaction ester is relevant with the activity of catalyst.High activated catalyst can adopt higher air speed.For selected catalyst, reaction conversion ratio reduces with the increase of reaction velocity.In order to meet certain conversion ratio, air speed must be limited within the specific limits.In the present invention, the liquid charging air speed of cyclohexyl acetate is 0.1～20h
-1, be preferably 0.2～2h
-1.
If employing intermittent reaction, the preferred reaction time is 0.2～20h.
Further illustrate by the following examples the present invention, but not thereby limiting the invention.
The preparation of embodiment 1～6(catalyst)
The catalyst of embodiment 1～6 is prepared by follow procedure: by table 1 formula, take a certain amount of soluble metallic salt, be placed in 2000mL there-necked flask, be dissolved in water preparation into about 1000mL solution, on flask, load onto agitator, pH meter and thermometer, and flask is placed in to the adjustable water bath with thermostatic control of temperature, open and stir, regulating thermostatic bath temperature, certain density precipitant solution is splashed in flask gradually, control the rate of addition of the precipitating reagent aqueous solution, the temperature rising of solution is controlled in 1 ℃.With pH value of solution, raising, there is precipitation in solution, and raises and increase gradually with pH, stops dripping the precipitating reagent aqueous solution when pH value of solution arrives setting.Then continuing to keep the aging certain hour of uniform temperature under the condition stirring.Stop stirring, naturally cool to room temperature, will be deposited in centrifugal filtration on supercentrifuge, and with deionized water washing 5 times, gained is deposited in baking oven and is dried, transfer in muffle furnace and carry out roasting, obtain mixed-metal oxides.This metal oxide is at room temperature flooded with certain density aqueous slkali, through vacuum filtration, remove maceration extract, mixture is dried in baking oven, transfer to roasting in muffle furnace, finally obtain mixed-metal oxides.Adopt ICP method to analyze the composition of gained sample.Concrete preparation condition and the results are shown in Table 1.
Embodiment 7～15(autoclave evaluate catalysts)
Embodiment 7～15 for carrying out the cyclohexyl acetate hydropyrolysis experiment of example 1～6 obtained catalyst in autoclave, test procedure is as follows: get a certain amount of that catalyst fines is placed in 500mL autoclave, add 250g cyclohexyl acetate, reactor is sealed, with nitrogen replacement three times, pass into hydrogen to certain pressure, heat up gradually, in the time of about 80 ℃, still internal pressure starts to decline, show that still inner catalyst starts reduction, and start to carry out ester through hydrogenation reaction, hydrogen make-up makes reactor maintain certain pressure in time, finally be warmed up to fixed temperature, and at this temperature, maintain after stress reaction certain hour, stop reaction, cool to after room temperature, draw off product and catalyst.Use gas chromatographic analysis product composition, and by following formula, calculate the selective of ethyl cyclohexyl ester conversion rate and cyclohexanol according to analysis result.
Ethyl cyclohexyl ester conversion rate=[1-unreacted cyclohexyl acetate molal quantity/(unreacted cyclohexyl acetate molal quantity+cyclohexane molal quantity+cyclohexanol molal quantity+ethyl hexamethylene ether molal quantity] * 100%
Cyclohexanol is selective=[cyclohexanol molal quantity/(cyclohexanol molal quantity+cyclohexane molal quantity+ethyl cyclohexyl ether molal quantity)] * 100%
In embodiment 16(fixed bed, carry out ester through hydrogenation)
By the resulting catalyst fines compression molding of embodiment 3, and break screening 40～60 order particles into pieces, get this catalyst granules of 40g and pack φ 20 * 2.5 * 800mm into the middle part in the stainless steel tube reactor of chuck, a certain amount of quartz sand is filled at two ends.Pass into hydrogen (500mL/min) and after reductase 12 4h, be down to the temperature of reaction under 280 ℃, 6MPa condition.Cyclohexyl acetate is squeezed in reactor by measuring pump, and hydrogen enters reaction system through mass flow controller and carries out hydrogenation reaction, by passing into conduction oil in reaction tube external jacket, controls reaction temperature, by reactor outlet counterbalance valve, controls reactor pressure.Product is carried out on-line chromatograph analysis by the online sample valve sampling at reactor rear portion.Reaction condition and the results are shown in Table 3.Result demonstration, cyclohexyl acetate hydrogenation reaction conversion ratio can reach more than 99.5%, and ester products is selectively greater than 99.0%, moves 1000 hours, and conversion ratio and selective decline are not obvious.
Comparative example 1～2
Press example 1 formula Kaolinite Preparation of Catalyst, but without NaOH solution-treated, and do not dry for the second time and calcination process.Preparation condition and obtained catalyst form in Table the comparative example 1 in 1.
Adopt autoclave to carry out the evaluation of ethyl cyclohexyl ester through hydrogenation the prepared catalyst of said method.Appreciation condition and the results are shown in Table the comparative example 2 in 2.
Result shows, catalyst, without alkali treatment, generates more cyclohexane and ethyl hexamethylene ether accessory substance, and hydrogenation reaction is selectively very poor.
Table 1 catalyst is prepared result and is gathered
Table 2 autoclave evaluating catalyst result gathers
Table 3 example 16 fixed bed ethyl cyclohexyl ester through hydrogenation data
Claims (17)
1. a carboxylate hydrogenation catalyst, comprise: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxide; In described catalyst, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～60 parts, and component (d) is 0.2～2 part.
2. according to catalyst claimed in claim 1, it is characterized in that, in described catalyst, in mass fraction, component (a) is 10～50 parts, and component (b) is 15～45 parts, and component (c) is 15～55 parts, and component (d) is 0.2～2 part.
3. according to catalyst claimed in claim 2, it is characterized in that, in described catalyst, in mass fraction, component (a) is 30～45 parts, and component (b) is 20～35 parts, and component (c) is 20～50 parts, and component (d) is 0.5～1.5 part.
4. according to catalyst claimed in claim 1, it is characterized in that, component (c) is selected from the oxide of one or more metals in following group: aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanum and cerium.
5. according to catalyst claimed in claim 1, it is characterized in that, component (d) is one or more in potassium hydroxide, NaOH and barium hydroxide.
6. a preparation method for carboxylate hydrogenation catalyst, comprising:
(1) by coprecipitation, prepare composite metal oxide; Described composite metal oxide comprises (a) cupric oxide, and (b) zinc oxide (c) is selected from the oxide of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals; In described composite metal oxide, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～60 parts;
(2) alkali metal hydroxide that composite metal oxide step (1) being obtained is 0.5～5% with mass fraction and/or alkaline earth metal hydroxide aqueous solution dipping, more after filtration, dry, roasting, obtain product.
7. in accordance with the method for claim 6, it is characterized in that, component (c) is selected from the oxide of one or more metals in following group: aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanum and cerium.
8. in accordance with the method for claim 6, it is characterized in that, in step (2), dipping temperature is 30 ℃～80 ℃, and dip time is 1～48h; Baking temperature is 100 ℃～200 ℃, and be 3～48h drying time; Sintering temperature is 250 ℃～400 ℃, and roasting time is 3～48h.
9. in accordance with the method for claim 6, it is characterized in that, the coprecipitation in step (1) comprises:
(I) preparation mixes soluble metal saline solution, and described metal comprises (a) copper, (b) zinc and (c) be selected from one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals;
(II), at 15 ℃～80 ℃, adds the precipitating reagent aqueous solution to the aqueous solution of step (I), to pH be 6～9, generate the mixed precipitation of metallic element described in step (I), described precipitating reagent meets that to make the precipitation energy pyrolysis generating be metal oxide;
The precipitation system that (III) obtains step (II), between 30 ℃～80 ℃, keep after 1～48h, filter and wash, until the metal cation in filtrate is less than 100ug/g, at 100 ℃～200 ℃, dry 3～48h, 250 ℃～400 ℃ roasting 3～48h, obtain composite metal oxide powder.
10. in accordance with the method for claim 9, it is characterized in that, in step (I), soluble metallic salt is selected from: nitrate, sulfate, hydrochloride, acetate or their hydrate.
11. in accordance with the method for claim 9, it is characterized in that, in step (II), under agitation, to the aqueous solution of step (1), adds the precipitating reagent aqueous solution.
12. in accordance with the method for claim 9, it is characterized in that, in step (II), described precipitating reagent is one or more in NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate, ammonia, urea, sodium oxalate, potassium oxalate and ammonium oxalate.
13. catalyst of preparing according to the arbitrary described method of claim 6～12.
14. 1 kinds of methods of preparing cyclohexanol and ethanol, comprising: under the existence of hydrogenation catalyst, by cyclohexyl acetate and hydrogen haptoreaction;
Described hydrogenation catalyst comprises: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxide; In described catalyst, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～30 parts, and component (d) is 0.2～2 part;
Reaction condition is: 150～400 ℃ of temperature, reaction pressure 1～20MPa, hydrogen ester mol ratio 1～1000:1; While adopting continuous reaction, cyclohexyl acetate liquid charging air speed is 0.1～20h
-1; While adopting intermittent reaction, the reaction time is 0.2～20h.
15. in accordance with the method for claim 14, it is characterized in that, in described hydrogenation catalyst, component (c) is selected from the oxide of one or more metals in following group: aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanum and cerium.
16. in accordance with the method for claim 14, it is characterized in that, the reactor adopting is one or more, and type of reactor is selected from one or more in tank reactor, tubular fixed-bed reactor, fluidized bed reactor and fluidized-bed reactor.
17. in accordance with the method for claim 14, it is characterized in that, reaction temperature is 200～300 ℃, and reaction pressure is 4～10Mpa, and hydrogen ester mol ratio is 5～100:1, and the liquid charging air speed of cyclohexyl acetate is 0.2～2h
-1.
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| CN201210347463.6A CN103657658B (en) | 2012-09-18 | 2012-09-18 | Carboxylic ester hydrogenation catalyst and prepare the method for cyclohexanol and ethanol |
| US14/429,189 US9561991B2 (en) | 2012-09-18 | 2013-09-17 | Process and apparatus for co-producing cyclohexanol and alkanol |
| PCT/CN2013/001100 WO2014044020A1 (en) | 2012-09-18 | 2013-09-17 | Method and device for coproducing cyclohexanol and alkanol |
| TW102133691A TWI612031B (en) | 2012-09-18 | 2013-09-17 | Method and device for co-production of cyclohexanol and alkanol |
| KR1020157010078A KR102008352B1 (en) | 2012-09-18 | 2013-09-17 | Method and device for coproducing cyclohexanol and alkanol |
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