CN107519881A - The preparation method and the method for hydrotreating of prepared hydrogenation catalyst and cyclohexyl acetate of a kind of cyclohexyl acetate hydrogenation catalyst - Google Patents
The preparation method and the method for hydrotreating of prepared hydrogenation catalyst and cyclohexyl acetate of a kind of cyclohexyl acetate hydrogenation catalyst Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a kind of preparation method of cyclohexyl acetate hydrogenation catalyst and the method for hydrotreating of prepared hydrogenation catalyst and cyclohexyl acetate, the preparation method includes：A, first aqueous solution containing water-soluble aluminum salt and water-soluble zinc salt and the first alkaline solution cocurrent are added in the cushioning liquid that pH value is 6 10, form precipitation between making aluminium salt and zinc salt be 6 10 in pH value, obtain sediment slurry；Wherein, the mol ratio of aluminium element and Zn-ef ficiency is 1 in first aqueous solution：(0.2‑5)；B, second aqueous solution containing water-soluble mantoquita and water-soluble zinc salt and the second alkaline solution cocurrent are added in the sediment slurry, form precipitation between making mantoquita and zinc salt be 6 10 in pH value, obtain cyclohexyl acetate hydrogenation catalyst；Wherein, the mol ratio of copper and Zn-ef ficiency is (1.5 15) in second aqueous solution：1.The hydrogenation catalyst prepared using the inventive method can reduce the content of accessory substance in cyclohexyl acetate hydrogenation products.
Description
Technical field
The present invention relates to a kind of preparation method of cyclohexyl acetate hydrogenation catalyst and prepared hydrogenation catalyst and vinegar
The method of hydrotreating of sour cyclohexyl.
Background technology
Cyclohexanol is a kind of important solvent and organic synthesis intermediate, and paint, agricultural chemicals, dye are widely used in as solvent
The production processes such as material, aeroengine oil, fat, wax, demoulding, decontamination, bate pits.Cyclohexanol can generate ring with high selectivity through dehydrogenation
Hexanone, for producing the chemicals such as caprolactam monomer and adipic acid.
Cyclohexanol production technique is more, mainly there is phenol hydrogenation method, cyclohexane oxidation process and cyclohexene hydration method etc., phenol
Phenol hydrogenation is directly prepared cyclohexanol by hydrogenation method, and selectivity and conversion ratio can but have the disadvantage that phenol more than 99%
Price is high, and economic benefit is not high.For cyclohexane oxidation process using benzene as raw material, first hydrogenation obtains hexamethylene, then reoxidizes to obtain ring
Hexanol and cyclohexanone, the process is ripe, but conversion rate of oxidation and selectivity are low, and side reaction is more, and is related to oxidizing process,
With potential safety hazard.Cyclohexene hydration method is succeeded in developing first by Japanese Asahi Kasei Corporation, and benzene elder generation selectivity adds in this method
Hydrogen generates cyclohexene and a small amount of hexamethylene, the cyclohexene being then demultiplex out carry out hydration reaction under molecular sieve catalyst, directly
Generate cyclohexanone.The good product quality that this method obtains, three waste discharge is few, and process units is safer compared with oxidation technology.Shortcoming
It is：Cyclohexene hydration reaction conversion per pass only has 10% or so, and cyclohexene needs a large amount of circulations, and investment and energy consumption are larger.
Sinopec Research Institute of Petro-Chemical Engineering proposes a kind of brand-new cyclohexanol production method, and this method is by pure hexamethylene
The cyclohexene mixture that alkene or benzene selective are hydrogenated with to obtain carries out esterification with acetic acid and obtains cyclohexyl acetate, then by acetic acid
Cyclohexyl is hydrogenated to cyclohexanol and ethanol.In this method, esterification is good to adaptability to raw material, and esterification and hydrogenation step have
There are high conversion and selectivity, while a co-producing ethanol, Technical Economy is good.
Because this method has novelty, therefore the hydrogenation catalyst of intermediate products cyclohexyl acetate hydrogenation process has no text
Report is offered, specific reaction equation is as follows：
Existing literature common are other esters hydrogenation catalysts such as dimethyl oxalate, dimethyl adipate and maleate
Agent.
Chinese patent CN 101474561A disclose a kind of catalyst of producing ethylene glycol from hydrogenation of oxalic ester, the catalyst
Active component include copper, the oxide and its mixture of copper, auxiliary agent is one kind of zinc, manganese, barium, nickel, chromium and iron, and carrier is oxygen
Change aluminium, prepared using a step coprecipitation, add powdered graphite compression molding after precipitating scrubbed drying and roasting and be applied to
Oxalate hydrogenation process, has higher conversion but selectivity is 85% or so.
Chinese patent CN 101138726A disclose a kind of Cu-series catalyst for industrial production hexylene glycol, the catalysis
Agent is prepared using coprecipitation, and the preparation method of the catalyst includes copper nitrate, zinc nitrate being configured to the aqueous solution, by hydroxide
Aluminium powder is dispersed in water to form slurries, with containing hydrogen after then the slurry of copper zinc mixed aqueous solution and aluminium hydroxide is mixed
It is 7-8 that sodium oxide molybdena, the aqueous slkali of sodium carbonate, which are neutralized to pH, obtained catalyst to dimethyl adipate Hydrogenation for 1,6- oneself two
Alcohol has greater activity.
Chinese patent CN102125843A discloses a kind of preparation method for the catalyst that silicon is carrier, and alkali is used as using urea
Property precipitating reagent, urea and copper nitrate are configured to the aqueous solution, slurry is mixed into Ludox, then in autoclave stirring plus
Heat, lean against line generation ammoniacal liquor and obtain more uniform cupric oxide precipitation.But the catalyst prepared by the preparation method is in oxalic acid
Application effect in ester through hydrogenation conversion is poor, and the patent does not account for improving copper in catalyst surface and body phase rationally yet
The problem of distribution.
For cyclohexyl acetate hydrogenation catalyst when being catalyzed cyclohexyl acetate hydrogenation reaction, aluminum oxide is as carrier, copper component
As active component and auxiliary agent, the preparation method of existing hydrogenation catalyst often uses a step precipitation method, some copper group
Divide together with aluminum oxide and be located at the inside of catalyst, participation reaction can not be contacted with reactant.
The content of the invention
It is an object of the invention to provide a kind of preparation method of cyclohexyl acetate hydrogenation catalyst and prepared hydrogenation to urge
The method of hydrotreating of agent and cyclohexyl acetate, the hydrogenation catalyst prepared using the inventive method can reduce cyclohexyl acetate and add
The content of accessory substance in hydrogen product.
To achieve these goals, the present invention provides a kind of preparation method of cyclohexyl acetate hydrogenation catalyst, the preparation
Method includes：A, first aqueous solution containing water-soluble aluminum salt and water-soluble zinc salt and the first alkaline solution cocurrent are added to pH
It is worth in the cushioning liquid for 6-10, aluminium salt and zinc salt is formed precipitation between 6-10 in pH value, obtain sediment slurry；Wherein,
The mol ratio of aluminium element and Zn-ef ficiency is 1 in first aqueous solution：(0.2-5)；B, water-soluble mantoquita and water solubility will be contained
Second aqueous solution of zinc salt and the second alkaline solution cocurrent are added in the sediment slurry, make mantoquita and zinc salt in pH value be 6-
Precipitation is formed between 10, obtains cyclohexyl acetate hydrogenation catalyst；Wherein, copper and Zn-ef ficiency in second aqueous solution
Mol ratio is (1.5-15)：1；Wherein, by the gauge of the material of element and on the basis of the amount of the total material of aluminium, copper and zinc, institute
State in cyclohexyl acetate hydrogenation catalyst, the content of copper is 10-70 moles of %, and the content of zinc is 10-60 moles of %, the content of aluminium
For 10-50 moles of %.
Preferably, the cushioning liquid is selected from alkali metal hydrogen phosphate disalt-highly basic cushioning liquid, alkali metal biphosphate
Salt-highly basic cushioning liquid, acetic acid-ammoniacal liquor cushioning liquid, formic acid-ammoniacal liquor cushioning liquid and alkali carbonate-ammoniacal liquor buffering are molten
At least one of liquid.
Preferably, first alkaline solution and the second alkaline solution are each independently selected from sodium carbonate, sodium acid carbonate, hydrogen
At least one of sodium oxide molybdena and ammoniacal liquor.
Preferably, the substance withdrawl syndrome of solute is each independently in first alkaline solution and the second alkaline solution
0.1-2 mol/Ls.
Preferably, in first aqueous solution, the mass concentration of aluminium salt is 10-30 mass %, and the mass concentration of zinc salt is
5-25 mass %；In second aqueous solution, the mass concentration of mantoquita is 5-25 mass %, and the mass concentration of zinc salt is 5-25 matter
Measure %.
Preferably, the water-soluble aluminum salt is aluminum sulfate and/or aluminum nitrate, the water-soluble mantoquita be copper sulphate and/or
Copper nitrate, the water-soluble zinc salt are zinc sulfate and/or zinc nitrate.
Preferably, in step a, aluminium salt and zinc salt is made to form precipitation between 6-8 in pH value；In stepb, mantoquita is made
And zinc salt forms precipitation in pH value between 6-8.
Preferably, the preparation method also includes：Gained mixed serum will be precipitated in step b to carry out aging successively, filter, wash
Wash, dry and be calcined, obtain the cyclohexyl acetate hydrogenation catalyst.
Preferably, the temperature of the aging is 40-60 DEG C, and the time of aging is 3-10 hours；The temperature of the drying is
60-150 DEG C, the dry time is 12-48 hours；The temperature of the roasting is 300-700 DEG C, and the time of roasting is small for 2-10
When.
The present invention also provides the hydrogenation catalyst prepared by preparation method provided by the present invention.
The present invention also provides a kind of method of hydrotreating of cyclohexyl acetate, and the method for hydrotreating includes：Using provided by the present invention
Hydrogenation catalyst carry out cyclohexyl acetate hydrogenation reaction.
The present invention is first precipitated aluminium salt using step-by-step precipitation method, then will be precipitated after mantoquita, makes gained hydrogenation catalyst
Copper component can be located at the outer layer of catalyst in agent, improve the conversion ratio and selectivity of reaction, and reduce the production of accessory substance.
Because copper ion precipitates just relatively more complete in pH value for 5 or so, and zinc ion typically just starts in pH value more than 5
Precipitation, therefore, if alkali lye is not added dropwise control ph, Kocide SD often first precipitates, and the zinc hydroxide then precipitated can coat
On the surface of Kocide SD, and in shaping of catalyst roasting process, zinc component also can be to the surface migration of catalyst.Therefore,
The inventive method uses cushioning liquid to control copper ion and zinc ion to produce precipitation between 5-9 in pH value, makes copper in catalyst
Component and zinc component mix more uniform, improve the conversion ratio and selectivity of hydrogenation reaction, in addition, the present invention is also by part zinc
Ion first precipitates with aluminium ion, zinc component in part in gained sediment is located at the inside of copper component, prevents roasting gained to be hydrogenated with
Zinc component coats the copper component of catalyst surface in catalyst, improves the conversion ratio and selectivity of reaction, and reduce accessory substance
Production.
Precipitation is produced using a step coprecipitation of routine or double drop methods, the pH scopes of gained sediment slurry can be in larger model
Enclose it is interior fluctuated, and the present invention method using cushioning liquid be used as bottom liquid, by the metal salt solution and alkali lye that need to precipitate drop
It is fixed into cushioning liquid the pH value of sediment slurry in titration process to be controlled to be fluctuated between ± 0.5, so that each in catalyst
Component is distributed more uniform.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of cyclohexyl acetate hydrogenation catalyst, and the preparation method includes：A, will contain
It is molten that first aqueous solution of water-soluble aluminum salt and water-soluble zinc salt and the first alkaline solution cocurrent are added to the buffering that pH value is 6-10
In liquid, aluminium salt and zinc salt is formed precipitation between 6-10 in pH value, obtain sediment slurry；Wherein, in first aqueous solution
The mol ratio of aluminium element and Zn-ef ficiency is 1：(0.2-5), preferably 1:(0.5-3.5)；B, water-soluble mantoquita and water-soluble will be contained
Second aqueous solution of property zinc salt and the second alkaline solution cocurrent are added in the sediment slurry, make mantoquita and the zinc salt be in pH value
Precipitation is formed between 6-10, obtains cyclohexyl acetate hydrogenation catalyst；Wherein, copper and Zn-ef ficiency in second aqueous solution
Mol ratio be (1.5-15)：1, be preferably (2-8)：1；Wherein, with the gauge of the material of element and with total thing of aluminium, copper and zinc
On the basis of the amount of matter, in the cyclohexyl acetate hydrogenation catalyst, the content of copper is 10-70 moles of %, and the content of zinc is 10-60
Mole %, the content of aluminium is 10-50 moles of %.
According to the present invention, cushioning liquid is well-known to those skilled in the art, such as can be selected from alkali metal phosphoric acid
Hydrogen disalt-highly basic cushioning liquid, alkali metal dihydric phosphate-highly basic cushioning liquid, acetic acid-ammoniacal liquor cushioning liquid, formic acid-ammoniacal liquor
At least one of cushioning liquid and alkali carbonate-ammoniacal liquor cushioning liquid.
For the present invention using the scope of slurry pH value in cushioning liquid control precipitation process, a kind of embodiment can be with
The pH value of slurries is controlled between X ± 0.5, is preferably controlled between X ± 0.3, wherein X is some value in 6-10, and X ±
0.5 also in the range of 6-10.
According to the present invention, alkaline solution is well-known to those skilled in the art, for example, first alkaline solution and
Two alkaline solutions can be each independently selected from least one of sodium carbonate, sodium acid carbonate, sodium hydroxide and ammoniacal liquor, and described
The substance withdrawl syndrome of solute can be each independently 0.1-2 mol/Ls in one alkaline solution and the second alkaline solution.Separately
Outside, in general, the usage amount of the first alkaline solution and the second alkaline solution be enough to make in first aqueous solution aluminium salt and zinc salt with
And the second mantoquita and zinc salt in the aqueous solution generates precipitation completely, by taking mantoquita as an example, 1 mole of mantoquita, which carries out precipitation, needs 1 mole
Carbonate or 2 moles of bicarbonate radical or 2 moles of hydroxyl.During specific experiment, in step a and b, if the first water
The addition speed and addition of solution and second aqueous solution can control the pH value of slurries, then containing the water-soluble of water soluble salt
When liquid is added dropwise, stop adding first aqueous solution and second aqueous solution (if not stopping, sediment slurry pH value can raise), now
Water soluble salt can generate precipitation completely, from the point of view of the yield of catalyst prod, be carried out according to 100 grams of catalyst preparation amounts
Experiment, the yield of catalyst is typically 95~98% when precipitating complete.
According to the present invention, water-soluble aluminum salt, mantoquita and zinc salt are well-known to those skilled in the art, for example, the water
Dissolubility aluminium salt can be aluminum sulfate and/or aluminum nitrate, and the water-soluble mantoquita can be copper sulphate and/or copper nitrate, the water
Soluble zinc salt can be zinc sulfate and/or zinc nitrate, and in first aqueous solution, the mass concentration of aluminium salt can be 10-30 matter
% is measured, the mass concentration of zinc salt can be 5-25 mass %；In second aqueous solution, the mass concentration of mantoquita can be 5-25
Quality %, the mass concentration of zinc salt can be 5-25 mass %.
According to the present invention, in order that aluminium salt and the distribution of the precipitation of zinc salt and mantoquita and zinc salt are more uniform, in step a
In, aluminium salt and zinc salt can be made to form precipitation between 6-8 in pH value；In stepb, mantoquita and the zinc salt can be made to be in pH value
Precipitation is formed between 6-8.
According to the present invention, precipitation gained mixed serum, which generally requires progress subsequent treatment, could turn into what can really be used
Catalyst, preparation method of the present invention can also include：Step b is precipitated into gained mixed serum to carry out aging successively, filter, wash
Wash, dry and be calcined, obtain the cyclohexyl acetate hydrogenation catalyst.In order that reaction is thoroughly, it is necessary to by sediment slurry one
Determine to carry out stable a period of time, i.e. described aging under the inactive state at temperature, the temperature of the aging can be 40-60
DEG C, the time of aging can be 3-10 hours.Filtering, washing, dry and roasting are well-known to those skilled in the art, this hairs
The temperature of the bright drying can be 60-150 DEG C, and preferably 90-120 DEG C, the dry time can be 12-48 hours；It is described
The temperature of roasting can be 300-700 DEG C, and preferably 350-450 DEG C, the time of roasting can be 2-10 hours.
The present invention also provides the hydrogenation catalyst prepared by the preparation method of the present invention.The hydrogenation catalyst can be used for
The hydrogenation reaction of other monobasic acid esters or dibasic acid ester.
The present invention also provides a kind of method of hydrotreating of cyclohexyl acetate, and the method for hydrotreating includes：Using provided by the present invention
Hydrogenation catalyst carry out cyclohexyl acetate hydrogenation reaction.The condition of the cyclohexyl acetate hydrogenation reaction includes：Temperature is
150-400 DEG C, pressure is 1-20 MPas, and cyclohexyl acetate mass space velocity is 0.1-20 hours-1, hydrogen ester mol ratio is 1-1000.
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction.
If without specified otherwise, the reagent used in the embodiment of the present invention and comparative example is that analysis is pure.
In testing example and test comparison example of the present invention：
Cyclohexyl acetate conversion ratio=[1- unreacted cyclohexyl acetates molal quantity/(unreacted cyclohexyl acetate molal quantity+
Hexamethylene molal quantity+cyclohexanol molal quantity+cyclohexyl ether molal quantity+methylcyclopentanol molal quantity] × 100%；
Cyclohexanol selectivity=[cyclohexanol molal quantity/(hexamethylene molal quantity+cyclohexanol molal quantity+cyclohexyl ether mole
Number+methylcyclopentanol molal quantity] × 100%；
Hexamethylene yield=[hexamethylene molal quantity/(unreacted cyclohexyl acetate molal quantity+hexamethylene molal quantity+cyclohexanol
Molal quantity+cyclohexyl ether molal quantity+methylcyclopentanol molal quantity] × 100%；
Methylcyclopentanol yield=[methylcyclopentanol molal quantity/(unreacted cyclohexyl acetate molal quantity+hexamethylene mole
Number+cyclohexanol molal quantity+cyclohexyl ether molal quantity+methylcyclopentanol molal quantity] × 100%.
Embodiment 1
The present embodiment prepares copper zinc-aluminium molar ratio as 4:4:2 hydrogenation catalyst.
50 milliliters of the biphosphate sodium water solution of 0.2 mol/L is prepared, is dripped with the sodium hydrate aqueous solution of 0.1 mol/L
It is 7.0 to determine to pH value, adds water to 120 milliliters and obtains cushioning liquid A.Prepare the sodium hydrate aqueous solution E of 0.5 mol/L.Weigh
64.80 grams of nitrate trihydrate copper are dissolved in 105.20 grams of deionized waters, obtain 170.00 grams of copper nitrate aqueous solution.Weigh 79.79 grams
Zinc nitrate hexahydrate is added in 100.21 grams of deionized waters, obtains 180.00 grams of zinc nitrate aqueous solution.Weigh ANN aluminium nitrate nonahydrate
50.31 grams are dissolved in 109.69 grams of deionized waters, obtain 160.00 grams of aluminum nitrate aqueous solution.Zinc nitrate aqueous solution is divided into 90 grams
With 90 grams two parts, be separately added into aluminum nitrate aqueous solution and copper nitrate aqueous solution, obtain containing water-soluble aluminum salt and water-soluble zinc salt
The first aqueous solution B and the second aqueous solution C containing water-soluble mantoquita and water-soluble zinc salt.1 is put into by bottom liquid of cushioning liquid A
In the beaker risen, under quick stirring, the first aqueous solution B and aqueous solution E cocurrents are added dropwise, by controlling the first aqueous solution B and water
The rate of addition of solution E come control slurries pH be 7.0 ± 0.5, after the first aqueous solution B is added dropwise, at the same stop be added dropwise hydrogen-oxygen
Change sodium water solution E, obtain sediment slurry D.Using sediment slurry D as bottom liquid, by the second aqueous solution C and aqueous solution E under quick stirring
Cocurrent is added dropwise, and slurry pH value is controlled as 7.5 ± 0.5, second by controlling the second aqueous solution C and aqueous solution E rate of addition
After aqueous solution C is added dropwise, while stop that aqueous solution E is added dropwise, and continue after stirring 1 hour, aging 3 hours at 45 DEG C.It is right
After sediment slurry after aging is filtered and washed, obtained solid is dried overnight (12 hours) at 120 DEG C, then 420
DEG C roasting 4 hours, obtain hydrogenation catalyst 1#.
Embodiment 2
The present embodiment prepares copper zinc-aluminium molar ratio as 4:2:4 hydrogenation catalyst.
25 grams of formic acid are dissolved in 80 milliliters of water, is 6.5 with 15 mass % ammonia water titration to pH value, adds water to 150 millis
Rise and obtain cushioning liquid A.Prepare the aqueous sodium carbonate E of 0.5 mol/L.Weigh 70.55 grams of nitrate trihydrate copper and be dissolved in 119.45
In gram deionized water, 190.00 grams of copper nitrate aqueous solution is obtained.Weigh 43.44 grams of zinc nitrate hexahydrates and add 96.56 grams of deionizations
In water, 140.00 grams of zinc nitrate aqueous solution is obtained.109.54 grams of ANN aluminium nitrate nonahydrate is weighed to be dissolved in 100.46 grams of deionized waters,
Obtain 210.00 grams of aluminum nitrate aqueous solution.Zinc nitrate aqueous solution is divided into 90 grams and 50 grams two parts, it is water-soluble to be separately added into aluminum nitrate
Liquid and copper nitrate aqueous solution, obtain the first aqueous solution B containing water-soluble aluminum salt and water-soluble zinc salt and containing water-soluble mantoquita
With the second aqueous solution C of water-soluble zinc salt.It is put into using cushioning liquid A as bottom liquid in 1 liter of beaker, under quick stirring, by first
Aqueous solution B and aqueous solution E cocurrents are added dropwise, and control the slurries pH to be by controlling the first aqueous solution B and the aqueous solution E rate of addition
6.5 ± 0.5, after the first aqueous solution B is added dropwise, while stop that aqueous solution E is added dropwise, obtain sediment slurry D.With sediment slurry D
For bottom liquid, the second aqueous solution C and aqueous solution E cocurrents are added dropwise under quick stirring, by controlling the second aqueous solution C and aqueous solution E
Rate of addition come control slurry pH value be 7.5 ± 0.5, after the second aqueous solution C is added dropwise, at the same stop be added dropwise aqueous solution E,
And after continuing stirring 1 hour, aging 3 hours at 45 DEG C.After sediment slurry after aging is filtered and washed, obtain
Solid is dried overnight (12 hours) at 120 DEG C, is then calcined 4 hours at 420 DEG C, obtains hydrogenation catalyst 2#.
Embodiment 3
The present embodiment prepares copper zinc-aluminium molar ratio as 4:4:2 hydrogenation catalyst.
30 grams of glacial acetic acid are dissolved in 100 ml deionized waters, being titrated to pH value with 15 mass % ammonia spirit is
7.0, add water to 150 milliliters and obtain cushioning liquid A.Prepare 0.5 mol/L sodium hydrate aqueous solution E.Weigh 66.81 gram of five water
Copper sulphate is dissolved in 113.19 grams of deionized waters, obtains 180.00 grams of copper nitrate aqueous solution.79.79 grams of zinc nitrate hexahydrates are weighed to add
Enter in 100.21 grams of deionized waters, obtain 180.00 grams of zinc nitrate aqueous solution.50.31 grams of ANN aluminium nitrate nonahydrate is weighed to be dissolved in
In 109.69 grams of deionized waters, 160.00 grams of aluminum nitrate aqueous solution is obtained.Zinc nitrate aqueous solution is divided into 120 grams and 60 gram two
Part, aluminum nitrate aqueous solution and copper nitrate aqueous solution are separately added into, obtains the first water containing water-soluble aluminum salt and water-soluble zinc salt
Solution B and the second aqueous solution C containing water-soluble mantoquita and water-soluble zinc salt.1 liter of beaker is put into using cushioning liquid A as bottom liquid
In, under quick stirring, the first aqueous solution B and aqueous solution E cocurrents are added dropwise, by the drop for controlling the first aqueous solution B and aqueous solution E
Acceleration come control slurries pH be 7.0 ± 0.5, after the first aqueous solution B is added dropwise, at the same stop be added dropwise sodium hydrate aqueous solution
E, obtain sediment slurry D.Using sediment slurry D as bottom liquid, the second aqueous solution C and aqueous solution E cocurrents are added dropwise under quick stirring, led to
Cross and control the second aqueous solution C and aqueous solution E rate of addition to control slurry pH value be 7.5 ± 0.5, the second aqueous solution C is added dropwise
After, while stop that aqueous solution E is added dropwise, and continue after stirring 1 hour, aging 3 hours at 45 DEG C.To the precipitation after aging
After slurries are filtered and washed, obtained solid is dried overnight (12 hours) at 120 DEG C, is then calcined 4 hours at 420 DEG C,
Obtain hydrogenation catalyst 3#.
Embodiment 4
The present embodiment prepares copper zinc-aluminium molar ratio as 4:2:4 hydrogenation catalyst.
15 grams of natrium carbonicum calcinatums are dissolved in 150 milliliters of water, it is 7.5 to be titrated to pH value with 15 mass % ammonia spirit,
Obtain cushioning liquid A.Prepare the sodium hydrate aqueous solution E of 0.5 mol/L.Weigh 70.55 grams of nitrate trihydrate copper and be dissolved in 119.45
In gram deionized water, 190.00 grams of copper nitrate aqueous solution is obtained.Weigh 43.44 grams of zinc nitrate hexahydrates and add 96.56 grams of deionizations
In water, 140.00 grams of zinc nitrate aqueous solution is obtained.Weigh 58.28 grams of aluminum sulfate to be dissolved in 141.72 grams of deionized waters, obtain nitre
Sour 200.00 grams of aluminum water solution.Zinc nitrate aqueous solution is divided into 70 grams and 70 grams two parts, is separately added into aluminum nitrate aqueous solution and nitre
Sour copper liquor, obtain the first aqueous solution B containing water-soluble aluminum salt and water-soluble zinc salt and contain water-soluble mantoquita and water-soluble
Second aqueous solution C of property zinc salt.It is put into using cushioning liquid A as bottom liquid in 1 liter of beaker, under quick stirring, by the first aqueous solution B
It is added dropwise with sodium hydrate aqueous solution E cocurrents, slurries pH is controlled by controlling the first aqueous solution B and aqueous solution E rate of addition
For 7.5 ± 0.5, after the first aqueous solution B is added dropwise, while stop that aqueous solution E is added dropwise, obtain sediment slurry D.With sediment slurry
D is bottom liquid, the second aqueous solution C and aqueous solution E cocurrents is added dropwise under quick stirring, by controlling the second aqueous solution C and aqueous solution E
Rate of addition come control slurry pH value be 8.0 ± 0.5, after the second aqueous solution C is added dropwise, at the same stop be added dropwise solution E, and
After continuing stirring 1 hour, aging 3 hours at 45 DEG C.After sediment slurry after aging is filtered and washed, what is obtained consolidates
Body is dried overnight (12 hours) at 120 DEG C, is then calcined 4 hours at 420 DEG C, obtains hydrogenation catalyst 4#.
Embodiment 5
The present embodiment prepares copper zinc-aluminium molar ratio as 4:4:2 hydrogenation catalyst.
50 milliliters of the aqueous dibasic potassium phosphate solution of 0.2 mol/L is prepared, is dripped with the sodium hydrate aqueous solution of 0.1 mol/L
It is 8.0 to determine to pH value, adds water to 120 milliliters and obtains cushioning liquid A.Prepare the aqueous sodium carbonate E of 0.2 mol/L.Weigh
64.80 grams of nitrate trihydrate copper are dissolved in 105.20 grams of deionized waters, obtain 170.00 grams of copper nitrate aqueous solution.Weigh 79.79 grams
Zinc nitrate hexahydrate is added in 100.21 grams of deionized waters, obtains 180.00 grams of zinc nitrate aqueous solution.Weigh ANN aluminium nitrate nonahydrate
50.31 grams are dissolved in 109.69 grams of deionized waters, obtain 160.00 grams of aluminum nitrate aqueous solution.Zinc nitrate aqueous solution is divided into 100
Gram and 80 grams two parts, be separately added into aluminum nitrate aqueous solution and copper nitrate aqueous solution, obtain containing water-soluble aluminum salt and water-soluble zinc
First aqueous solution B of salt and the second aqueous solution C containing water-soluble mantoquita and water-soluble zinc salt.Put by bottom liquid of cushioning liquid A
Enter in 1 liter of beaker, under quick stirring, the first aqueous solution B and aqueous solution E cocurrents be added dropwise, by control the first aqueous solution B and
Aqueous solution E rate of addition come control slurries pH be 8.0 ± 0.5, after the first aqueous solution B is added dropwise, at the same stop be added dropwise water
Solution E, obtain sediment slurry D.Using sediment slurry D as bottom liquid, by the second aqueous solution C and aqueous solution E and drip under quick stirring
Add, by controlling the second aqueous solution C and the aqueous solution E rate of addition to control slurry pH value be 8.0 ± 0.5, the second aqueous solution C
After being added dropwise, while stop that aqueous solution E is added dropwise, and continue after stirring 1 hour, aging 3 hours at 45 DEG C.After aging
After sediment slurry is filtered and washed, obtained solid is dried overnight (12 hours) at 120 DEG C, then small in 420 DEG C of roastings 4
When, obtain hydrogenation catalyst 5#.
Embodiment 6
The present embodiment prepares copper zinc-aluminium molar ratio as 4:2:4 hydrogenation catalyst.
50 milliliters of the biphosphate sodium water solution of 0.3 mol/L is prepared, is dripped with the sodium hydrate aqueous solution of 0.1 mol/L
It is 7.5 to determine to pH value, adds water to 120 milliliters and obtains cushioning liquid A.Prepare the aqueous sodium carbonate E of 0.5 mol/L.Weigh
70.55 grams of nitrate trihydrate copper are dissolved in 119.45 grams of deionized waters, obtain 190.00 grams of copper nitrate aqueous solution.Weigh 43.44 grams
Zinc nitrate hexahydrate is added in 96.56 grams of deionized waters, obtains 140.00 grams of zinc nitrate aqueous solution.Weigh ANN aluminium nitrate nonahydrate
109.54 grams are dissolved in 100.46 grams of deionized waters, obtain 210.00 grams of aluminum nitrate aqueous solution.Zinc nitrate aqueous solution is divided into 100
Gram and 40 grams two parts, be separately added into aluminum nitrate aqueous solution and copper nitrate aqueous solution, obtain containing water-soluble aluminum salt and water-soluble zinc
First aqueous solution B of salt and the second aqueous solution C containing water-soluble mantoquita and water-soluble zinc salt.Put by bottom liquid of cushioning liquid A
Enter in 1 liter of beaker, under quick stirring, the first aqueous solution B and aqueous solution E cocurrents be added dropwise, by control the first aqueous solution B and
Aqueous solution E rate of addition come control slurries pH be 7.5 ± 0.5, after the first aqueous solution B is added dropwise, at the same stop be added dropwise water
Solution E, obtain sediment slurry D.Using sediment slurry D as bottom liquid, by the second aqueous solution C and aqueous solution E and drip under quick stirring
Add, by controlling the second aqueous solution C and the aqueous solution E rate of addition to control slurry pH value be 8.0 ± 0.5, the second aqueous solution C
After being added dropwise, while stop that aqueous solution E is added dropwise, and continue after stirring 1 hour, aging 3 hours at 45 DEG C.After aging
After sediment slurry is filtered and washed, obtained solid is dried overnight (12 hours) at 120 DEG C, then small in 420 DEG C of roastings 4
When, obtain hydrogenation catalyst 6#.
Embodiment 7
The present embodiment prepares copper zinc-aluminium molar ratio as 4:2:4 hydrogenation catalyst.
25 grams of glacial acetic acid are dissolved in 100 ml deionized waters, being titrated to pH value with 20 mass % ammonia spirit is
7.0, add water to 150 milliliters and obtain cushioning liquid A.Prepare the sodium hydrate aqueous solution E of 0.5 mol/L.Weigh 70.55 gram three
Water copper nitrate is dissolved in 119.45 grams of deionized waters, obtains 190.00 grams of copper nitrate aqueous solution.Weigh 43.44 grams of zinc nitrate hexahydrates
Add in 96.56 grams of deionized waters, obtain 140.00 grams of zinc nitrate aqueous solution.109.54 grams of ANN aluminium nitrate nonahydrate is weighed to be dissolved in
In 100.46 grams of deionized waters, 210.00 grams of aluminum nitrate aqueous solution is obtained.Zinc nitrate aqueous solution is divided into 70 grams and 70 grams two parts,
Aluminum nitrate aqueous solution and copper nitrate aqueous solution are separately added into, obtains first aqueous solution containing water-soluble aluminum salt and water-soluble zinc salt
B and the second aqueous solution C containing water-soluble mantoquita and water-soluble zinc salt.It is put into using cushioning liquid A as bottom liquid in 1 liter of beaker,
Under quick stirring, the first aqueous solution B and aqueous solution E cocurrents are added dropwise, by the dropwise addition for controlling the first aqueous solution B and aqueous solution E
Speed come control slurries pH be 7.0 ± 0.5, after the first aqueous solution B is added dropwise, at the same stop be added dropwise aqueous solution E, precipitated
Slurries D.Using sediment slurry D as bottom liquid, the second aqueous solution C and aqueous solution E cocurrents are added dropwise under quick stirring, pass through control second
Aqueous solution C and the aqueous solution E rate of addition are come to control slurry pH value be 7.5 ± 0.5, after the second aqueous solution C is added dropwise, simultaneously
Stop that aqueous solution E is added dropwise, and continue after stirring 1 hour, aging 3 hours at 45 DEG C.Sediment slurry after aging is taken out
After filter and washing, obtained solid is dried overnight (12 hours) at 120 DEG C, is then calcined 4 hours at 420 DEG C, obtains hydrogenation and urge
Agent 7#.
Comparative example 1
The present embodiment prepares copper zinc-aluminium molar ratio as 4:4:2 hydrogenation catalyst.
Prepare the sodium hydrate aqueous solution of 0.5 mol/L.Weigh 64.80 grams of nitrate trihydrate copper be dissolved in 105.20 grams go from
In sub- water, 170.00 grams of copper nitrate aqueous solution is obtained.79.79 grams of zinc nitrate hexahydrates are weighed to add in 100.21 grams of deionized waters,
Obtain 180.00 grams of zinc nitrate aqueous solution.Weigh 50.31 grams of ANN aluminium nitrate nonahydrate to be dissolved in 109.69 grams of deionized waters, obtain nitre
Sour 160.00 grams of aluminum water solution.As bottom liquid after copper nitrate aqueous solution, zinc nitrate aqueous solution and aluminum nitrate aqueous solution are mixed, soon
Sodium hydrate aqueous solution is added dropwise under speed stirring, forms sediment slurry, adds sodium hydrate aqueous solution until sediment slurry pH
It is worth for 7.5.Cocurrent terminates after continuing stirring 1 hour, aging 3 hours at 45 DEG C.Sediment slurry after aging is filtered
After washing, obtained solid is dried overnight (12 hours) at 120 DEG C, is then calcined 4 hours at 420 DEG C, obtains hydrogenation catalyst
Agent D1#.
Comparative example 2
The present embodiment prepares copper zinc-aluminium molar ratio as 4:2:4 hydrogenation catalyst.
Prepare the aqueous sodium carbonate of 0.5 mol/L.Weigh 70.55 grams of nitrate trihydrate copper and be dissolved in 119.45 grams of deionizations
In water, 190.00 grams of copper nitrate aqueous solution is obtained.Weigh 43.44 grams of zinc nitrate hexahydrates to add in 96.56 grams of deionized waters, obtain
140.00 grams of zinc nitrate aqueous solution.Weigh 109.54 grams of ANN aluminium nitrate nonahydrate to be dissolved in 100.46 grams of deionized waters, obtain nitric acid
210.00 grams of aluminum water solution.As bottom liquid after copper nitrate aqueous solution, zinc nitrate aqueous solution and aluminum nitrate aqueous solution are mixed, quickly
Sodium hydrate aqueous solution is added under stirring, forms sediment slurry, adds sodium hydrate aqueous solution until sediment slurry pH value is
7.5.Cocurrent terminates after continuing stirring 1 hour, aging 3 hours at 45 DEG C.Sediment slurry after aging is filtered and washed
After washing, obtained solid is dried overnight (12 hours) at 120 DEG C, is then calcined 4 hours at 420 DEG C, obtains hydrogenation catalyst
D2#。
Testing example 1-7
Hydrogenation catalyst prepared by embodiment 1-7 is subjected to performance evaluation using fixed bed reactors.Specific evaluation side
Method is as follows：Catalyst is broken into 20 mesh to 40 mesh particles after tabletting, and reactor loadings are 10.0 grams.Using preceding in reactor
Middle reducing catalyst, reducing condition are 260 DEG C, and hydrogen flow rate is 50 ml/mins, and the time is 15 hours.By cyclohexyl acetate
Fed to contact with the hydrogenation catalyst after reduction in reactor with measuring pump and carry out cyclohexyl acetate hydrogenation reaction, each test is real
Apply example to be reacted under two different reaction conditions from a hydrogenation catalyst, specific evaluation result is shown in Table 1.
Reaction condition 1：Reaction temperature is 220 DEG C, and reaction pressure is 4.0 MPas, and cyclohexyl acetate mass space velocity is 0.4 small
When-1, hydrogen flow rate is 210 ml/mins (control of hydrogen ester mol ratio is 20)；Reaction condition 2：Reaction temperature is 240 DEG C, reaction
Pressure is 5.5 MPas, and cyclohexyl acetate mass space velocity is 0.4 hour-1, hydrogen flow rate is 210 ml/mins (hydrogen ester mol ratio
Control as 20).
Test comparison example 1-2
Hydrogenation catalyst prepared by comparative example 1-2 is evaluated according to testing example 1-7 evaluation method, specifically
Evaluation result is shown in Table 1.
It can be seen from the data in Table 1 that when reaction temperature and reaction pressure raise, on cyclohexyl acetate conversion ratio is obvious
Rise, but selectivity decreases.According to the method provided by the present invention prepare hydrogenation catalyst conversion ratio and selectivity and
It is superior to that hydrogenation catalyst prepared by cushioning liquid is not used in terms of by-product yields.Because the hexamethylene in accessory substance can be with production
Ethanol in product forms azeotropic mixture, it is difficult to the alcohol product of high-purity is obtained, in addition, being used to gather with cyclohexanol production high-purity
Exemplified by the cyclohexanone for closing level caprolactam production, methylcyclopentanol has pollution to cyclohexanone in cyclohexanol, and methylcyclopentanol with
The boiling point of principal product cyclohexanol, polarity approach, and separating difficulty is high, the cost of the continuous separation of product after raising.
The testing example 1-7 of the table 1 and test comparison example 1-2 specific evaluation result of hydrogenation catalyst
Claims (11)
1. a kind of preparation method of cyclohexyl acetate hydrogenation catalyst, the preparation method include：
A, first aqueous solution containing water-soluble aluminum salt and water-soluble zinc salt is added into pH value with the first alkaline solution cocurrent is
In 6-10 cushioning liquid, aluminium salt and zinc salt is formed precipitation between 6-10 in pH value, obtain sediment slurry；Wherein, it is described
The mol ratio of aluminium element and Zn-ef ficiency is 1 in first aqueous solution：(0.2-5)；
B, it is described heavy to be added to second aqueous solution containing water-soluble mantoquita and water-soluble zinc salt and the second alkaline solution cocurrent
In the slurries of shallow lake, mantoquita and zinc salt is formed precipitation between 6-10 in pH value, obtain cyclohexyl acetate hydrogenation catalyst；Wherein,
The mol ratio of copper and Zn-ef ficiency is (1.5-15) in second aqueous solution：1；
Wherein, by the gauge of the material of element and on the basis of the amount of the total material of aluminium, copper and zinc, the cyclohexyl acetate hydrogenation
In catalyst, the content of copper is 10-70 moles of %, and the content of zinc is 10-60 moles of %, and the content of aluminium is 10-50 moles of %.
2. preparation method according to claim 1, wherein, the cushioning liquid is selected from alkali metal hydrogen phosphate disalt-strong
Alkali cushioning liquid, alkali metal dihydric phosphate-highly basic cushioning liquid, acetic acid-ammoniacal liquor cushioning liquid, formic acid-ammoniacal liquor cushioning liquid
At least one of with alkali carbonate-ammoniacal liquor cushioning liquid.
3. preparation method according to claim 1, wherein, first alkaline solution and the second alkaline solution are each independent
Ground is selected from least one of sodium carbonate, sodium acid carbonate, sodium hydroxide and ammoniacal liquor.
4. preparation method according to claim 1, wherein, solute in first alkaline solution and the second alkaline solution
Substance withdrawl syndrome is each independently 0.1-2 mol/Ls.
5. preparation method according to claim 1, wherein, in first aqueous solution, the mass concentration of aluminium salt is 10-30
Quality %, the mass concentration of zinc salt is 5-25 mass %；In second aqueous solution, the mass concentration of mantoquita is 5-25 matter
% is measured, the mass concentration of zinc salt is 5-25 mass %.
6. preparation method according to claim 1, wherein, the water-soluble aluminum salt is aluminum sulfate and/or aluminum nitrate, described
Water-soluble mantoquita is copper sulphate and/or copper nitrate, and the water-soluble zinc salt is zinc sulfate and/or zinc nitrate.
7. preparation method according to claim 1, in step a, aluminium salt and zinc salt is set to be formed in pH value between 6-8 heavy
Form sediment；In stepb, mantoquita and zinc salt is made to form precipitation between 6-8 in pH value.
8. preparation method according to claim 1, the preparation method also includes：By precipitation gained mixed serum in step b
Aging, filtering, washing, drying and roasting are carried out successively, obtain the cyclohexyl acetate hydrogenation catalyst.
9. preparation method according to claim 8, wherein, the temperature of the aging is 40-60 DEG C, and the time of aging is 3-
10 hours；The temperature of the drying is 60-150 DEG C, and the dry time is 12-48 hours；The temperature of the roasting is 300-700
DEG C, the time of roasting is 2-10 hours.
10. the hydrogenation catalyst prepared by preparation method in claim 1-9 described in any one.
11. a kind of method of hydrotreating of cyclohexyl acetate, the method for hydrotreating include：Using the hydrogenation catalyst described in claim 10
Carry out cyclohexyl acetate hydrogenation reaction.
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