CN108043411A - A kind of hydrogenation of n-butyraldehyde prepares catalyst of n-butanol and preparation method thereof - Google Patents
A kind of hydrogenation of n-butyraldehyde prepares catalyst of n-butanol and preparation method thereof Download PDFInfo
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- CN108043411A CN108043411A CN201711284678.7A CN201711284678A CN108043411A CN 108043411 A CN108043411 A CN 108043411A CN 201711284678 A CN201711284678 A CN 201711284678A CN 108043411 A CN108043411 A CN 108043411A
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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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- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
Catalyst of n-butanol and preparation method thereof is prepared the present invention relates to a kind of hydrogenation of n-butyraldehyde.The catalyst includes copper oxide, zinc oxide and silica.The preparation method of the catalyst uses synchronous precipitation method, and copper, zinc is made to precipitate at two different temperatures respectively, obtains two kinds of different pore passage structures, forms diplopore system.The features such as active component dispersion degree of catalyst is high, mass transfer/good heat-transfer, catalyst has excellent activity and selectivity, reduces the generation of by-product n-butyl n-butyrate and octanol, improves the selectivity of n-butanol.
Description
Technical field
Present invention relates particularly to a kind of aldehyde Hydrogenation for the catalyst of alcohol, it is specifically related to a kind of hydrogenation of n-butyraldehyde and prepares just
The catalyst of butanol, belongs to catalysis technical field.
Background technology
N-butanol is a kind of important Organic Chemicals, is the solvent of multiple coating and plasticizer phthalic acid two processed
The raw material of butyl ester is also used for manufacture butyl acrylate, butyl acetate, butyl glycol ether and is used as organic synthesis intermediate and life
The extractant of object chemical drugs is additionally operable to manufacture surfactant.
The industrial making method of n-butanol mainly has three kinds of fermentation method, propenecarbonyl synthetic method and aldol condensation of acetaldehyde method.In addition,
By also by-product n-butanol during ethylene higher aliphatic.Propenecarbonyl synthetic method is since raw material is easy to get, carbonylating process pressure phase
To the features such as relatively low, reaction condition is relatively mild, it has also become produce the most important method of n-butanol.
Propenecarbonyl synthetic method is mainly generated by propylene, carbon monoxide and hydrogen through cobalt or rhodium catalyst carbongl group synthesis reaction
N-butanal and isobutylaldehyde, n-butanal is hydrogenated to obtain n-butanol.Hydrogenation of n-butyraldehyde reaction process is to produce the critical process of n-butanol,
And catalyst is the core of hydrogenation reaction.
Hydrogenation of n-butyraldehyde can make catalyst in gas phase copper, can also be made to carry out under catalyst with nickel in liquid phase.Vapor phase method because
Reaction pressure is low, and process equipment is simple and is widely used, and most domestic butanol device uses gas phase hydrogenation method, and catalyst is adopted
The copper-zinc system catalyst prepared with the precipitation method.
The catalyst that n-butanal gas phase hydrogenation prepares n-butanol all has been reported that in numerous patents.Such as：CN1381311A is public
It has opened a kind of use coprecipitation method and has prepared CuZnAl catalyst, and be with the addition of the alkali metal such as K, Ca, Na, Mg and Ba/alkaline earth gold
Belong to element as auxiliary agent.Such catalyst 130 DEG C, 0.4MPa, n-butanal liquid phase air speed 0.36h-1Under reaction condition, n-butanal
Conversion ratio is about 98%, n-butanol selectively about 99%.
DE4244273 discloses a kind of Na2O is modified CuZnAl catalyst and is used for butyraldehyde gas phase hydrogenation process.
CN1050994A is disclosed adds in the auxiliary agents such as a small amount of alkali metal and nickel, cobalt to improve catalyst choice in copper zinc catalyst
Method for preparing catalyst.
Patent disclosed in CN1695802A uses multiple step coprecipitation method, is co-precipitated using aluminium and auxiliary agent co-precipitation, copper zinc, and
Two kinds are precipitated the method mixed and be prepared for butyraldehyde hydrogenation catalyst.
The butyraldehyde hydrogenation catalyst of report disclosed above is copper-zinc system catalyst prepared by coprecipitation, and maximum asks
Topic is exactly that there are active component dispersion degree is poor, catalyst pores are small, mass transfer/heat transfer property is poor, by-product butyl butyrate growing amount
A series of problems, such as height, n-butanol poor selectivity.
Butyraldehyde gas phase hydrogenation butanol process Main By product is butyl butyrate, the generation of butyl butyrate and catalyst group
Closely related into, acid-base property and mass transfer/heat transfer property, acidity of catalyst is strong, heat transfer property is poor will greatly promote by-product fourth
The generation of acid butyl ester.Therefore method for preparing catalyst, optimization catalyst pore passage structure and acid-base property are improved, improves catalyst heat transfer
Mass-transfer performance is most important for preparing high activity, highly selective butyraldehyde hydrogenation catalyst.
The content of the invention
Catalyst of n-butanol and preparation method thereof is prepared the object of the present invention is to provide a kind of hydrogenation of n-butyraldehyde, using same
The features such as active uniform component distribution of catalyst of step precipitation method preparation, hole are flourishing, mass transfer/good heat-transfer, simultaneously
Catalyst has excellent activity and selectivity.
For achieving the above object, the technical solution adopted by the present invention is：
A kind of hydrogenation of n-butyraldehyde prepares the catalyst of n-butanol, includes following components：Copper oxide 24-50wt%, zinc oxide
49-75wt%, silica 0.5-2wt%, is counted on the basis of catalyst weight.
Preferably, the catalyst composition that prepared by the method for the invention includes：Copper oxide 28-45wt%, zinc oxide 54-
70wt%, silica 0.5-2wt%, is counted on the basis of catalyst weight.
It is highly preferred that catalyst composition prepared by the method for the invention includes：Copper oxide 30-45wt%, zinc oxide 54-
69wt%, silica 0.5-2wt%, is counted on the basis of catalyst weight.
A kind of hydrogenation of n-butyraldehyde prepares the preparation method of the catalyst of n-butanol, comprises the following steps：Proportionally,
(1) pore creating material aqueous dispersions are added in reactor A, by the mixed liquor containing mantoquita, zinc salt and auxiliary agent Si and alkalescence
Precipitating reagent cocurrent is added in A, controls 60-80 DEG C of the precipitation temperature of A, preferably 65-75 DEG C, pH=6.5-8.0, preferably pH=
6.8-7.5；
(2) pore creating material aqueous dispersions are added in reactor B, by the mixed liquor containing mantoquita, zinc salt and auxiliary agent Si and alkalescence
Precipitating reagent cocurrent is added in B, controls 45-60 DEG C of the precipitation temperature of B, preferably 48-58 DEG C, pH=6.5-8.0, preferably pH=
6.8-7.5；
(3) aging 2-4h is carried out after the slurries in obtained A and B are mixed, controls 65-80 DEG C of aging temperature, preferably 68-
78℃；
(4) slurry that step (3) obtains is filtered, and is washed with organic solvent, obtain filter cake；By filter cake into
Row is dry, roasting, and then compression molding obtains catalyst.
Step (1) of the present invention and the pore creating material in step (2), mantoquita, the raw material sources point of zinc salt and auxiliary agent Si
Not identical, dosage difference is equal.For example, step (1) and step (2) use the copper nitrate of equal weight as mantoquita.This hair
It is bright it is described it is equal can be according to being allocated within the acceptable error range of those skilled in the art, it is preferred that for
For homogeneous raw material, the ropy absolute value and quality of step (1) and step (2) and ratio be more than or equal to 0 and less than 2%；
It is further preferred that for homogeneous raw material, the ropy absolute value and quality of step (1) and step (2) and ratio be equal to 0.
Pore creating material aqueous dispersions of the present invention are to be dispersed in water pore creating material.The pore creating material be selected from field mountain valley with clumps of trees and bamboo powder,
One or more in methylcellulose and microcrystalline cellulose etc..The dosage of pore creating material is final system in step (1) or step (2)
Obtain the 0.25-7.5wt%, preferably 0.5-5wt%, more preferable 1-4wt% of catalyst weight.
In the present invention, the addition of pore creating material begins as nucleus in reaction, induces the forerunner of copper zinc class peacock stone structure
The formation of body improves the dispersion degree of catalyst activity component copper；In roasting process, pore creating material oxygenolysis is overflow into gas
Go out, form many tiny ducts in catalytic inner so that catalyst pores are more flourishing, improve catalyst mass transfer/biography
Hot property is conducive to the raising of catalyst activity and selectivity.
In the present invention, one or more of the mantoquita in copper nitrate, copper chloride and copper acetate etc.；The zinc salt choosing
One or more from zinc nitrate, zinc chloride and zinc acetate etc..
One or more of the auxiliary agent Si of the present invention in Ludox, sodium metasilicate and sodium silicoaluminate etc..
The dosage of auxiliary agent Si of the present invention is converted into SiO2It is calculated, SiO2Account for the 0.5-2wt% of catalyst weight.
The addition of auxiliary agent Si in the present invention can promote byproduct of reaction n-butyl n-butyrate hydrogenolysis as n-butanol, effectively
Improve catalyst choice.
The total concentration of metal ion is mole of 0.5-2mol/L, copper ion and zinc ion in mixed liquor of the present invention
Than for 1:3-1:1, preferably 1:2.5-1:1.2.
In the present invention, the alkaline precipitating agent includes but not limited to sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, hydrogen
One or more in sodium oxide molybdena, potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate and ammonium hydroxide etc..Alkaline precipitating agent is preferably with aqueous solution
Form use, the concentration of alkaline precipitating agent aqueous solution is 10wt%-20wt%.By adjusting the dosage of alkaline precipitating agent, come
Realize the regulation and control to the pH value of precipitation process.
Washing organic solvent includes but not limited to one in methanol, ethyl alcohol, ethylene glycol etc. in step (4) of the present invention
Kind is a variety of；Washing to cleaning solution electrical conductivity is less than 100 μ s/cm.
Detergent selects volatile organic solvent in the present invention, since the molecule of organic solvent is greater than hydrone, because
This in the drying process, the volatilization of organic solvent enables to catalyst duct to become much larger, is more loose, enables to be catalyzed
Agent duct is more loose, and mass transfer enhancement/heat-transfer capability can effectively improve catalyst activity and selectivity.
The drying temperature of step (4) of the present invention is 95-125 DEG C, preferably 105-115 DEG C, drying time 4-16h, excellent
Select 6-14h.
In step (4) of the present invention the calcination temperature of filter cake be 260-330 DEG C, preferably 280-320 DEG C, roasting time 3-
12h, preferably 4-8h.
Catalyst prepared by the method for the invention using synchronous precipitation method, makes copper, zinc difference at two different temperatures
Precipitation obtains two kinds of different pore passage structures, forms diplopore system, in 2-5nm, pore volume accounts for always the wherein pore diameter range of aperture
The 20%-50% of pore volume, preferably 30%-45%；The pore diameter range of macropore is in 10-20nm, and pore volume accounts for the 40- of total pore volume
60%, preferably 45%-55%, macropore are conducive to mass-and heat-transfer, reduce the hot(test)-spot temperature of reaction, so as to reduce Main By product just
The generation of butyric acid N-butyl；Aperture is conducive to inhibit the generation of the by-product octanol of macromolecular.Two kinds of apertures are combined, and are reduced
The amount of by-product in reaction process improves the selectivity of n-butanol.
Catalyst prepared by the present invention just possesses corresponding catalytic activity after need to carrying out reduction activation, for n-butanal gas phase
Hydrogenation is for n-butanol.
The method of the reduction activation of catalyst prepared by the present invention includes：Keep the volume space velocity 800-1200h of nitrogen-1,
Temperature of reactor is risen to 130-160 DEG C, the mechanical water of constant temperature 1-2h Removal of catalyst absorption then passes to hydrogen, hydrogen and
The volume ratio of nitrogen is 1:10, prereduction 2h is carried out, steps up the ratio of hydrogen afterwards to 1:5、1:4、1:2、1:1, control
The process catalyst bed hot(test)-spot temperature is no more than 220 DEG C, and reactor finally is warming up to 220 DEG C, nitrogen is closed, in pure hydrogen
3-6h is reduced under atmosphere, obtains the catalyst of reduction-state.
Catalyst after reduction activation of the present invention prepares n-butanol, reaction pressure 0.4- for n-butanal gas phase hydrogenation
0.5MPa, reaction temperature are 120-160 DEG C, H2/ aldehyde molar ratio 10-30:1, Feed space velocities 0.5-1.0mlIBA·ml-1 Cat·h-1。
Pressure of the present invention is relative pressure.
Catalyst of the present invention with just preparing n-butanol in aldehyde gas phase hydrogenation, catalyst activity component is evenly distributed,
Hole is flourishing, has good heat transfer/mass-transfer performance, and catalyst has excellent activity and selectivity.
Specific embodiment
The method of the present invention is described in detail in reference to embodiment, but is not limited to embodiment.
Raw material n-butanal and hydrogenation liquid use Agilent 7890A chromatographics.Detector is hydrogen flame detector,
Chromatographic column is DB-5MS (30m × 0.25mm × 0.25 μm).Operation condition of chromatogram：Carrier is nitrogen, and column flow 1ml/min divides
Flow ratio 50:1,250 DEG C of injector temperature, 250 DEG C of detector temperature, 0.2 μ L of sample size.
The characterizing method of catalyst pore passage structure be BET, instrument model：ASAP2020M.Parameter is as follows：
Analysis Absorptive：N2 Analysis Bath Temp：77.299K
Cold Free Space：81.7371 Equilibration Interval：10s.
Embodiment 1
The reactor A and B of two equivalent specifications are taken, dispersion liquid is made in each addition 1.3g field mountain valley with clumps of trees and bamboo powder and 300g water；Take 68.5g
Copper chloride, 150.3g zinc chloride are soluble in water is made into salting liquid, and it is 1mol/L to make copper ion and zinc ion total concentration；To what is prepared
4.3g 30wt% Ludox is added in salting liquid, mixed liquor is made.The mixed liquor configured is divided into two parts, respectively with
10wt% sodium carbonate liquors carry out cocurrent in two reactors, control A temperature 70 Cs, pH value 7.0；Control B temperature 50 Cs, pH value
7.0。
After the completion for the treatment of cocurrent, the slurries of A and B are mixed into C reactors and carry out aging, control 75 DEG C of aging temperature, always
Change 2h.
After the completion of aging, slurries are filtered, and is washed with methanol to cleaning solution electrical conductivity and is less than 100 μ s/cm.It will wash
Filter cake after washing dries 10h at 110 DEG C, carries out compression molding after roasting 8h at 280 DEG C, obtains 4*4mm cylinder (diameters
4mm, height 4mm) catalyst is up to catalyst A.
Activation of catalyst：Catalyst A is loaded in fixed bed hydrogenation reactor, loaded catalyst 50ml.It keeps first
The volume space velocity 1000h of nitrogen-1, temperature of reactor is risen to the mechanical water of 150 DEG C of constant temperature 2h Removal of catalyst absorption, Ran Houtong
It is 1 to enter hydrogen and nitrogen ratio:10 gaseous mixture carries out prereduction 2h, steps up the ratio of hydrogen and nitrogen afterwards to 1:5、1:
4、1:2、1:1, the process catalyst bed hot(test)-spot temperature is controlled to be no more than 220 DEG C, 220 DEG C are finally warming up to, in pure hydrogen atmosphere
Lower reduction 4h.
Embodiment 2
The reactor A and B of two equivalent specifications are taken, dispersion liquid is made in each addition 2.25g microcrystalline celluloses and 300g water；It takes
110g copper nitrates, 190.6g zinc nitrates are soluble in water is made into salting liquid, and it is 1.5mol/L to make copper ion and zinc ion total concentration；To
4.3g 30wt% Ludox is added in the salting liquid prepared, mixed liquor is made.The mixed liquor configured is divided into two parts, respectively
With 10wt% sodium bicarbonate solutions cocurrent, 65 DEG C of control A temperature, pH value 7.2 are carried out in two reactors；54 DEG C of B temperature is controlled,
PH value 7.2.
After the completion for the treatment of cocurrent, the slurries of A and B are mixed into C reactors and carry out aging, control 70 DEG C of aging temperature, always
Change 3h.
After the completion of aging, slurries are filtered, and is washed with ethyl alcohol to cleaning solution electrical conductivity and is less than 100 μ s/cm.It will wash
Filter cake after washing dries 6h at 115 DEG C, carries out compression molding after roasting 6h at 300 DEG C, obtains 4*4mm cylinder (diameters
4mm, height 4mm) catalyst is up to catalyst B.
Remaining condition is with reference to embodiment 1.
Embodiment 3
The reactor A and B of two equivalent specifications are taken, dispersion liquid is made in each addition 5.2g microcrystalline celluloses and 300g water；It takes
131g copper acetates, 176g zinc acetates and 2.64g sodium metasilicate is soluble in water is made into salting liquid, make copper ion and the zinc ion total concentration be
2mol/L；The solution configured is divided into two parts, carries out cocurrent, control in two reactors with 15wt% sal volatiles respectively
75 DEG C of A temperature processed, pH value 7.1；Control 55 DEG C of B temperature, pH value 7.1.
After the completion for the treatment of cocurrent, the slurries of A and B are mixed into C reactors and carry out aging, control 80 DEG C of aging temperature, always
Change 4h.
After the completion of aging, slurries are filtered, and spent glycol washs to cleaning solution electrical conductivity and is less than 100 μ s/cm.It will
Filter cake after washing dries 12h at 105 DEG C, carries out compression molding after roasting 4h at 320 DEG C, obtains 4*4mm cylinder (diameters
4mm, height 4mm) catalyst is up to catalyst C.
Remaining condition is with reference to embodiment 1.
Embodiment 4
The reactor A and B of two equivalent specifications are taken, dispersion liquid is made in each addition 1.3g microcrystalline celluloses and 300g water；It takes
110g copper nitrates, 187.6g zinc nitrates and 5.28g sodium metasilicate is soluble in water is made into salting liquid, make copper ion and zinc ion total concentration
For 1mol/L；The solution configured is divided into two parts, carries out cocurrent in two reactors with 20wt% sodium carbonate liquors respectively,
Control 65 DEG C of A temperature, pH value 6.8；Control 54 DEG C of B temperature, pH value 7.1.
After the completion for the treatment of cocurrent, the slurries of A and B are mixed into C reactors and carry out aging, control 70 DEG C of aging temperature, always
Change 3h.
After the completion of aging, slurries are filtered, and is washed with a certain amount of ethyl alcohol to cleaning solution electrical conductivity and is less than 100 μ s/
cm.Filter cake after washing at 110 DEG C is dried into 10h, compression molding is carried out after roasting 6h at 290 DEG C, obtains 4*4mm cylinders
(diameter 4mm, height 4mm) catalyst is up to catalyst D.
Remaining condition is with reference to embodiment 1.
Embodiment 5
The reactor A and B of two equivalent specifications are taken, dispersion liquid is made in each addition 1.3g microcrystalline celluloses and 300g water；It takes
116g copper nitrates, 183g zinc nitrates and 3.97g sodium metasilicate is soluble in water is made into salting liquid, make copper ion and the zinc ion total concentration be
2mol/L；The solution configured is divided into two parts, carries out cocurrent, control in two reactors with 15wt% sodium carbonate liquors respectively
68 DEG C of A temperature processed, pH value 7.0；Control 52 DEG C of B temperature, pH value 7.5.
After the completion for the treatment of cocurrent, the slurries of A and B are mixed into C reactors and carry out aging, control 72 DEG C of aging temperature, always
Change 3h.
After the completion of aging, slurries are filtered, and is washed with a certain amount of methanol to cleaning solution electrical conductivity and is less than 100 μ s/
cm.Filter cake after washing at 115 DEG C is dried into 6h, compression molding is carried out after roasting 8h at 300 DEG C, obtains 4*4mm cylinders
(diameter 4mm, height 4mm) catalyst is up to catalyst E.
Remaining condition is with reference to embodiment 1.
Comparative example 1
The dispersion liquid of 4.5g microcrystalline celluloses and 600g water is added in reactor, by 110g copper nitrates, 190.6g nitric acid
Zinc is soluble in water to be made into salting liquid so that copper ion and zinc ion total concentration are 1.5mol/L；It is added in into the salting liquid prepared
Mixed liquor is made in 4.3g 30wt% Ludox.The salting liquid prepared and 10wt% sodium carbonate are dissolved in and carry out cocurrent mode instillation
In reactor, it is 7.2 to control 55 DEG C of precipitation process temperature in the kettle, precipitation pH, after precipitation at 70 DEG C aging 3h, it is then right
Slurries are filtered, and are washed with ethyl alcohol to cleaning solution electrical conductivity and be less than 100 μ s/cm, obtain filter cake.By the filter after washing
Cake dries 6h at 115 DEG C, carries out compression molding after roasting 6h at 300 DEG C, obtains 4*4mm cylinders (diameter 4mm, height
4mm) catalyst is to get catalyst F.
Remaining condition is with reference to embodiment 1.
Comparative example 2
For preparation process with comparative example 1, it is 65 DEG C to change precipitation temperature, obtains catalyst G.
Comparative example 3
The usage ratio of homogeneous raw material in reactor A and reactor B is 1：3, remaining condition is urged with embodiment 1
Agent H.
Comparative example 4
The usage ratio of homogeneous raw material in reactor A and reactor B is 3：1, remaining condition is urged with embodiment 1
Agent I.
Comparative example 5
Silicon additive is not added with, remaining condition obtains catalyst J with embodiment 2.
BET characterizations, duct parameter such as table 1 are carried out to the catalyst of embodiment 1-5 and comparative example 1-5.
1 catalyst BET of table is characterized
As shown in table 1, the pore passage structure of catalyst A-E is similar obtained by embodiment, mainly by 2-5nm and 10-20nm two
Kind duct is formed, and the ratio between pore volume and total pore volume are respectively between 30%-45% and 45%-55%.Catalyst is made in comparative example
F, G only has a kind of duct, and the G apertures of the aperture ratio pyroreaction of the F of low-temp reaction are big.H and I is also double-pore structure, but
Since reaction solution allocation proportion difference causes macropore and small hole number (being embodied in pore volume ratio) different.The preparation condition phase of J and B
Together, do not have adding assistant silicon simply, so its pore passage structure is basically identical.
Embodiment 6
Evaluating catalyst：Embodiment 1-5, comparative example 1-5 the catalyst A-J being prepared are respectively used to n-butanal to add
Hydrogen.
Hydroconversion condition is as follows：50ml catalyst, 120 DEG C of reaction temperature, reaction pressure are packed into the reaction tube of internal diameter 32mm
(gauge pressure, similarly hereinafter) 0.5MPa, hydrogen aldehyde molar ratio 15:1, in liquid hourly space velocity (LHSV) 1.0mlIBA·mlcat -1·h-1Under the conditions of carry out butyraldehyde
Hydrogenation reaction obtains reaction solution, and reaction result refers to table 2.
2 hydrogenation of n-butyraldehyde reaction result of table
* content %：It refers in gas chromatographic analysis, the peak area of each substance in the peak area and reaction solution of corresponding product
The sum of percentage.
As shown in Table 2, the catalyst F activity that prepared by (55 DEG C) precipitations of low temperature is poor, and prepared by (65 DEG C) precipitations of high temperature urges
Agent G poor selectivities, n-butyl n-butyrate growing amount are more.Catalyst H causes the growing amount of by-product octanol since macropore is more
Become larger, and more macropore reduces specific surface area so that conversion ratio declines.Catalyst I, since aperture is more, heat-transfer capability becomes
Difference causes the generation quantitative change of by-product n-butyl n-butyrate more, while hot spot becomes higher.Catalyst J does not add in silicon additive, decomposes
The ability of n-butyl n-butyrate dies down, and the quantitative change for causing by-product n-butyl n-butyrate is more.
Above example can be seen that the catalyst prepared using the method for the present invention and prepare positive fourth for hydrogenation of n-butyraldehyde
Alcohol has catalyst activity height, hot(test)-spot temperature is low, feed stock conversion is high, the amount of by-product n-butyl n-butyrate is few, product selectivity
The advantages that good.
Claims (10)
1. a kind of hydrogenation of n-butyraldehyde prepares the catalyst of n-butanol, following components is included：It is counted on the basis of catalyst weight,
Copper oxide 24-50wt%, preferably 28-45wt%, more preferable 30-45wt%；Zinc oxide 49-75wt%, preferably 54-
70wt%, more preferable 54-69wt%；Silica 0.5-2wt%.
2. catalyst according to claim 1, which is characterized in that aperture is that the pore volume of 2-5nm accounts for always in the catalyst
The 20%-50% of pore volume, preferably 30%-45%,；Aperture is that the pore volume of 10-20nm accounts for the 40%-60% of total pore volume, preferably
45%-55%.
3. catalyst according to claim 1 or 2, which is characterized in that the preparation method of the catalyst, including following step
Suddenly：Proportionally,
(1) pore creating material aqueous dispersions are added in reactor A, by mixed liquor and alkaline sedimentation containing mantoquita, zinc salt and auxiliary agent Si
Agent cocurrent is added in A, controls 60-80 DEG C of the precipitation temperature of A, preferably 65-75 DEG C, pH=6.5-8.0, preferably pH=6.8-
7.5；
(2) pore creating material aqueous dispersions are added in reactor B, by mixed liquor and alkaline sedimentation containing mantoquita, zinc salt and auxiliary agent Si
Agent cocurrent is added in B, controls 45-60 DEG C of the precipitation temperature of B, preferably 48-58 DEG C, pH=6.5-8.0, preferably pH=6.8-
7.5；
(3) aging 2-4h is carried out after the slurries in obtained A and B are mixed, controls 65-80 DEG C of aging temperature, preferably 68-78
℃；
(4) slurry that step (3) obtains is filtered, and is washed with organic solvent, obtain filter cake；Filter cake is done
Dry, roasting, obtains catalyst.
4. catalyst according to claim 3, which is characterized in that the mantoquita is selected from copper nitrate, copper chloride and copper acetate
One or more in；One or more of the zinc salt in zinc nitrate, zinc chloride and zinc acetate etc.；The auxiliary agent Si
One or more in Ludox, sodium metasilicate and sodium silicoaluminate etc..
5. the catalyst according to claim 3 or 4, which is characterized in that the pore creating material is selected from field mountain valley with clumps of trees and bamboo powder, methylcellulose
With the one or more in microcrystalline cellulose.
6. according to claim 3-5 any one of them catalyst, which is characterized in that pore-creating in the step (1) or step (2)
The dosage of agent is the 0.25-7.5wt%, preferably 0.5-5wt%, more preferable 1-4wt% of catalyst weight.
7. according to claim 3-6 any one of them catalyst, which is characterized in that the alkaline precipitating agent include sodium carbonate,
One kind or more in potassium carbonate, sodium acid carbonate, saleratus, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate and ammonium hydroxide
Kind.
8. according to claim 3-7 any one of them catalyst, which is characterized in that the roasting temperature of filter cake in the step (4)
It spends for 260-330 DEG C, preferably 280-320 DEG C, roasting time 3-12h, preferably 4-8h.
9. according to claim 3-8 any one of them catalyst, which is characterized in that organic solvent includes in the step (4)
One or more in methanol, ethyl alcohol, ethylene glycol；Washing to cleaning solution electrical conductivity is less than 100 μ s/cm.
10. according to claim 3-9 any one of them catalyst, which is characterized in that in the step (1) and step (2)
Pore creating material, mantoquita, the raw material sources difference of zinc salt and auxiliary agent Si it is identical, dosage difference is equal.
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