CN105498788B - The catalyst and preparation method of a kind of preparing furancarbinol from liquid-phase furol hydrogenation - Google Patents
The catalyst and preparation method of a kind of preparing furancarbinol from liquid-phase furol hydrogenation Download PDFInfo
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Abstract
The invention discloses a kind of catalyst of preparing furancarbinol from liquid-phase furol hydrogenation and preparation method.Catalyst includes:CuO, Cr2O3、La2O3And SiO2；CuO/Cr2O3Mol ratio be 1.8~2.4；CuO/La2O3Mol ratio be 60~160；CuO/SiO2Mol ratio be 2~6.Method includes：The component is prepared the catalyst of described preparing furancarbinol from liquid-phase furol hydrogenation by the dosage using coprecipitation.The shortcomings that catalyst of the present invention overcomes prior art, there is furfuryl alcohol activity and selectivity height, it is cheap, the characteristics of can continuously applying mechanically.
Description
Technical field
The present invention relates to furfuryl alcohol production field, further say, be to be related to a kind of catalysis of preparing furancarbinol from liquid-phase furol hydrogenation
Agent.
Background technology
Furfuryl alcohol is a kind of important industrial chemicals, and second phthalein propionic acid can be made through hydrolysis in furfuryl alcohol, be nutrient drug calcium levulinate
Intermediate；Furan type resin, furfuryl alcohol-Lauxite and phenolic resin of better performances etc. can be produced using furfuryl alcohol as raw material；Chaff
Alcohol is the good solvent and rocket fuel of furane resins, varnish, pigment again；In addition, furfuryl alcohol synthetic fibers, rubber, agricultural chemicals and
Also it is widely used in foundary industry.
The production technology of furfuryl alcohol can be divided into two kinds of liquid-phase hydrogenatin technique and gas phase hydrogenation technique at present.Furfural liquid-phase hydrogenatin is given birth to
The catalyst of production furfuryl alcohol is broadly divided into copper chromium system and the class of copper silicon systems two, and the two is compared, and the former activity and selectivity is preferable, separation
It is easier to, but price is higher, causes the total usage amount of two kinds of catalyst in production to remain basically stable.Above two catalyst lacks
Point is to use once to discard afterwards, causes the serious waste of catalyst.
The CuO/Cr that German patent DE 3425758 is reported2O3And Cu/SiO2Two parts catalyst mixed catalytic furfural liquid phase
Hydrogenation, 150-300 DEG C of reaction temperature, reaction pressure 2-10MPa, catalyst are divided into two parts, add the difficulty of preparation process.
Chinese patent ZL01141837.0 reports addition metallic nickel Cu-Cr catalyst, is prepared using coprecipitation, furfural liquid phase adds
Hydrogen condition is 180-200 DEG C and 3.5-5.0MPa hydrogen pressures, and catalyst can not recycle.Chinese patent ZL02140489.5 and
ZL200410012190.5 discloses the VIIIth race's precious metals pt of addition and Pd Cu-Cr catalyst respectively, and both catalyst are lived
Property is preferable but expensive, nor can recycle.
Chinese patent ZL201210053574.6 discloses a kind of one or more member containing in molybdenum, tungsten, iron, cobalt and nickel
The skeletal copper catalyst of element.Although the catalyst can be applied mechanically continuously, the catalyst is in preparation process, it is necessary to substantial amounts of copper gold
Category, add the expense of catalyst；Other catalyst addition in furfural liquid-phase hydrogenatin produces furfuryl alcohol is high, and its dosage accounts for chaff
2~8 (wt) % of aldehyde amount.
The content of the invention
To solve produced problem in the prior art, the invention provides a kind of catalysis of preparing furancarbinol from liquid-phase furol hydrogenation
Agent.The shortcomings that overcoming prior art, there is furfuryl alcohol activity and selectivity height, it is cheap, the characteristics of can continuously applying mechanically.
Due to the easy inactivation of existing Cu-Cr catalyst, short life, catalyst is caused to recycle.Ordinary circumstance
Under, in the normal operation of industrial catalyst, the inactivation of catalyst is an inevitable phenomenon.The inactivation of catalyst is not
The activity for referring exclusively to inactivation phase catalyst completely completely loses, more for the active of stationary phase catalyst or selectivity make
Gradually reducing during.The inactivation of catalyst is a complicated physics and chemical process.Generally, can be with the reason for inactivation
It is divided into following three aspects：Activated centre covering and duct blocking, the poisoning of catalyst, catalyst caused by catalyst carbon deposition etc.
Inactivation is one of common cause of catalyst inactivation caused by heat inactivation and sintering, wherein carbon distribution.For metallic catalyst, although
The reaction of catalysis is different, and it is different to form the mechanism, quantity and speed of carbon distribution, but with the increase of carbon distribution, the ratio of catalyst
Surface area, aperture and Active sites etc. can all decline, the catalyst inactivation when carbon distribution adds up to a certain degree, now catalyst
Regenerate or be replaced with for necessity.The present invention sets about in terms of the composition of raw materials of catalyst and preparation method two, develops
A kind of new furfural liquid phase hydrogenating catalyst for lowering catalyst carbon deposition speed, extending catalyst life.
An object of the present invention is to provide a kind of catalyst of preparing furancarbinol from liquid-phase furol hydrogenation.
The catalyst includes:CuO, Cr2O3、La2O3And SiO2；
CuO/Cr2O3Mol ratio be 1.8~2.4；It is preferred that 2.0~2.3；
CuO/La2O3Mol ratio be 60~160；It is preferred that 80~120
CuO/SiO2Mol ratio be 2~6, preferably 3~4.
The one kind of the precursor of the cupric oxide in soluble copper salt, preferably copper nitrate, copper sulphate, copper chloride or acetic acid
Copper, more preferably copper nitrate；
The one kind of the precursor of the chromium oxide in soluble chromic salts, preferably chromic nitrate, chromium sulfate, chromium chloride, acetic acid
Chromium or chromic anhydride, more preferably chromic anhydride；
The precursor of the lanthana is selected from lanthanum chloride or lanthanum nitrate, preferably lanthanum nitrate；
The precursor of the silica is selected from Ludox or waterglass, preferably Ludox, more preferably acidic silicasol.
The second object of the present invention is to provide a kind of preparation method of the catalyst of preparing furancarbinol from liquid-phase furol hydrogenation.
Comprise the following steps：
(1) cupric oxide, chromium oxide, lanthana and silica precursors are mixed and soluble in water obtains mixed solution；
(2) surfactant is dissolved in aqueous slkali, the content of surfactant is 3~5wt%；
(3) deionized water is added in reactor, under conditions of 25-40 DEG C, aqueous slkali and step (1) obtain mixed solution
The aqueous slkali cocurrent obtained with step (2), which is added in reactor, reacts, and is stirred continuously, and the pH value for controlling reaction is 5-8, stirring
To there is sediment generation；
(4) by the sediment of step (3) after filtering, dry, catalyst fines is made after roasting；
The surfactant is APES, polyvinylpyrrolidone, one kind or group in polyethylene glycol
Close；It is preferred that APES, more preferably NPE.
The aqueous slkali is ammoniacal liquor and/or sal volatile.
In step (4), dry and roasting can use common process conditions in the prior art, in of the invention, preferably：
Drying temperature is 100-120 DEG C, 10~20 hours drying times；Sintering temperature is 350~400 DEG C, roasting time
For 2~6 hours.
Silica is added in the form of colloidal sol in the present invention, plays skeletal support effect, increases the ratio surface of catalyst
Product and pore passage structure, and cupric oxide, chromium oxide, lanthana and silica are added by way of co-precipitation, form tiny
Grain, the decentralization of active component is improved, and then improve the specific surface area active of per volume of catalyst, be finally reached extension catalysis
The purpose in agent life-span.In addition, adding lanthana in the catalyst, because lanthana is alkalescence, the big (chaff of ability of water vapour is adsorbed
Contain a small amount of water in aldehyde) so that therefore the steam/hydrocarbons ratio of catalyst surface, improves much larger than the steam/hydrocarbons ratio in reaction body phase
The resistive connection charcoal ability of catalyst.
Added in precipitation process in surfactant APES, polyvinylpyrrolidone, polyethylene glycol
One kind or its two or more mixtures, preferably APES.Add surfactant effect be prevent it is tiny
Particle precipitating and post-processing as reunited in roasting process, make particle growth, lose the excellent catalytic of fine particle
Energy.From thermodynamically, the reunion of ultrafine particle be system total surface can minimization required by, by interparticle model moral
Magnificent power provides power.And interparticle repulsive force is the power for preventing particle aggregation, typically there are two methods to provide this power,
A kind of is that Coulomb repulsion provides interaction of this repulsive force of scattered between the electric double layer of particle periphery, and one is not
Deng distribution of charges always exist between particle surface and solution；Second of antihunt means is steric hindrance repulsion, the present invention
What is utilized is exactly this effect.The absorption of surfactant APES is in particle surface, their water-wet side extension
Make mutually into solution and with solution, the interaction between liquid-surfactant chain is a kind of melange effect, and it is added
The free energy of system prevents that particle is close so as to produce an energy barrier.When particle is close to each other, the surface that extends in liquid
The motion of activating agent chain is restricted so as to produce steric hindrance repulsion.Test result indicates that currently preferred surface-active
Agent APES can efficiently control CuO/Cr2O3/La2O3/SiO2The growth of system particle and prevent particle
Reunite, therefore, further increase the decentralization of active component, and then the activity for improving per volume of catalyst compares surface
Product, it is finally reached the purpose for extending catalyst life.
Catalyst prepared by the present invention has higher specific surface area, is 125~130m2/g；Urging prepared by the present invention
Agent has higher metallic copper decentralization, is 0.6~0.7.The decentralization of Ni metal uses N in catalyst sample2O chemistry
Determination of adsorption method.Generally speaking, in hydrogenation reaction, the decentralization of active metal component is bigger, and its catalytic activity is higher, catalysis
Life-span is also longer.
The catalyst of the present invention is applied to furfural liquid-phase hydrogenatin production furfuryl alcohol, and catalyst and furfural are together mounted in into reactor
Interior, reaction condition is 180-200 DEG C of temperature, and pressure is 5~8MPa.
The present invention has the following advantages that compared with prior art：
(1) catalyst has higher activity and selectivity, furfural conversion ratio >=99%, furfuryl alcohol selectivity >=98.5%；
(2) catalyst preparation process is simple, and cheap；
(3) catalyst can be applied mechanically continuously；
(4) catalyst loading is few, only accounts for 0.5 (wt) % of furfural amount.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Raw materials used in embodiment and comparative example is commercially available.
Embodiment 1:
Weigh copper nitrate (Cu (NO3)2·3H2O) 132.9g, chromic anhydride (CrO3) 50.0g, lanthanum nitrate (La (NO3)3·6H2O)
4.7g and 36g25wt% acidic silica gel is miscible in 500mL deionized waters；100mL deionized waters are put into reactor first
In, in the case where being stirred continuously, by copper-chromium-lanthanum-silicon mixed liquor and the ammoniacal liquor (18wt%) containing 3wt% APESs
Cocurrent adds, and control pH value in reaction rises to 40 DEG C 6, while by the temperature of reaction solution, and it is small that charging finishes continuation insulated and stirred 0.5
When, filtering, 120 DEG C of drying 12 hours, then finally milled as less than 120 purposes in 300 DEG C of roastings 4 hours in Muffle furnace
Catalyst sample, the sample specific surface area are 128m2/ g, the decentralization 0.68 of Ni metal, CuO/Cr in catalyst2O3Mole
Than being 2.2, CuO/La2O3Mol ratio be 101.9, CuO/SiO2Mol ratio be 3.8.By the millis of catalyst 1.75g and 300
Rise furfural to add in autoclave simultaneously, add CaO0.4 grams.It is 195 DEG C in reaction temperature, under conditions of pressure is 7.5MPa,
Furfural conversion ratio is 100%, furfuryl alcohol selectivity 99.0%.
Embodiment 2:
Weigh copper nitrate (Cu (NO3)2·3H2O) 145.0g, chromic anhydride (CrO3) 50.0g, lanthanum nitrate (La (NO3)3·6H2O)
3.35g and 25g25wt% acidic silica gel is miscible in 500mL deionized waters；100mL deionized waters are put into reactor first
In, in the case where being stirred continuously, by copper-chromium-lanthanum-silicon mixed liquor liquid and the ammoniacal liquor (18wt%) containing 5wt% polyvinylpyrrolidones
Cocurrent adds, and control pH value in reaction rises to 40 DEG C 6, while by the temperature of reaction solution, and it is small that charging finishes continuation insulated and stirred 0.5
When, filtering, 120 DEG C of drying 12 hours, then finally milled as less than 120 purposes in 300 DEG C of roastings 4 hours in Muffle furnace
Catalyst sample, the sample specific surface area are 130m2/ g, the decentralization 0.65 of Ni metal, CuO/Cr in catalyst2O3Mole
Than being 2.4, CuO/La2O3Mol ratio be 155.1, CuO/SiO2Mol ratio be 5.9.By the millis of catalyst 1.75g and 300
Rise furfural to add in autoclave simultaneously, add CaO0.4 grams.It is 195 DEG C in reaction temperature, under conditions of pressure is 7.5MPa,
Furfural conversion ratio is 99.5%, furfuryl alcohol selectivity 98.6%.
Embodiment 3:
Weigh copper nitrate (Cu (NO3)2·3H2O) 108.7g, chromic anhydride (CrO3) 50.0g and lanthanum nitrate (La (NO3)3·
6H2O) 6.5g and 54g25wt% acidic silica gel is miscible in 500mL deionized waters；100mL deionized waters are put into instead first
Answer in kettle, in the case where being stirred continuously, by copper-chromium-lanthanum-silicon mixed liquor and ammoniacal liquor (18wt%) cocurrent containing 4wt% polyethylene glycol
Adding, control pH value in reaction rises to 40 DEG C 6, while by the temperature of reaction solution, and charging, which finishes, continues insulated and stirred 0.5 hour,
Filtering, 120 DEG C of drying 12 hours, then finally milled as the catalysis less than 120 mesh in 300 DEG C of roastings 4 hours in Muffle furnace
Agent sample, the sample specific surface area are 125m2/ g, the decentralization 0.61 of Ni metal, CuO/Cr in catalyst2O3Mol ratio be
1.8, CuO/La2O3Mol ratio be 66.6, CuO/SiO2Mol ratio be 2.0.By catalyst 1.75g and 300 milliliters of furfurals
Add simultaneously in autoclave, add CaO0.4 grams.It is 195 DEG C in reaction temperature, pressure 7.5MPaUnder conditions of, furfural turns
Rate is 99.8%, furfuryl alcohol selectivity 99.1%.
Embodiment 4：
Reacted catalyst in embodiment 1 is reclaimed by centrifuging, and supplements what is prepared according to the method for embodiment 1
Raw catelyst 0.5g, repeat the furfural hydrogenation process in embodiment 1, furfural conversion ratio 100%, furfuryl alcohol selectivity 98.6%.
Embodiment 5：
Reacted catalyst in embodiment 4 is reclaimed by centrifuging, and supplements what is prepared according to the method for embodiment 1
Raw catelyst 0.5g, repeat the furfural hydrogenation process in embodiment 1, furfural conversion ratio 99.2%, furfuryl alcohol selectivity 98.6%.
Embodiment 6：
Reacted catalyst in embodiment 5 is reclaimed by centrifuging, and supplements what is prepared according to the method for embodiment 1
Raw catelyst 0.5g, repeat the furfural hydrogenation process in embodiment 1, furfural conversion ratio 99.0%, furfuryl alcohol selectivity 98.4%.
Comparative example 1：
Weigh copper nitrate (Cu (NO3)2·3H2O) 132.9g, chromic anhydride (CrO3) 50.0g is miscible in 500mL deionized waters；
100mL deionized waters are put into reactor first, in the case where being stirred continuously, by copper-chromium mixed liquor and 18 (wt) % ammoniacal liquor simultaneously
Stream adds, and control pH value in reaction rises to 40 DEG C 6, while by the temperature of reaction solution, and it is small that charging finishes continuation insulated and stirred 0.5
When, filtering, 120 DEG C of drying 12 hours, then finally milled as less than 120 purposes in 300 DEG C of roastings 4 hours in Muffle furnace
Catalyst sample, the sample specific surface area are 42m2/ g, the decentralization 0.36 of Ni metal, CuO/Cr in catalyst2O3Mol ratio
It is 2.2.Catalyst 1.75g and 300 milliliters of furfurals are added in autoclave simultaneously, add CaO0.4 grams.In reaction temperature
For 195 DEG C, under conditions of pressure is 7.5MPa, furfural conversion ratio is 90.3%, furfuryl alcohol selectivity 98.2%.Urged reacted
Agent is reclaimed by centrifuging, and supplements the raw catelyst 1g prepared according to method of contrast, repeats the furfural of comparative example 1
Hydrogenation process, furfural conversion ratio 88.4%, furfuryl alcohol selectivity 96.8%.
Comparative example 2：
Weigh copper nitrate (Cu (NO3)2·3H2O) 132.9g, chromic anhydride (CrO3) 50.0g and lanthanum nitrate (La (NO3)3·
6H2O) 4.7g is miscible in 500mL deionized waters；100mL deionized waters are put into reactor first, in the case where being stirred continuously,
Copper-chromium-lanthanum mixed liquor and ammoniacal liquor (18wt%) cocurrent are added, control pH value in reaction rises to 6, while by the temperature of reaction solution
40 DEG C, charging, which finishes, continues insulated and stirred 0.5 hour, filtering, 120 DEG C of drying 12 hours, is then roasted in Muffle furnace in 300 DEG C
Burn 4 hours, it is 68m finally to mill as the catalyst sample less than 120 mesh, the sample specific surface area2/ g, the decentralization of Ni metal
0.42, CuO/Cr in catalyst2O3Mol ratio be 2.2, CuO/La2O3Mol ratio be 101.9.By catalyst 1.75g and
300 milliliters of furfurals are added in autoclave simultaneously, add CaO0.4 grams.It it is 195 DEG C in reaction temperature, pressure is 7.5MPa bar
Under part, furfural conversion ratio is 99.4%, furfuryl alcohol selectivity 98.0%, then by reacted catalyst by centrifuging back
Receive, and supplement the raw catelyst 0.5g prepared according to the method for comparative example 2, repeat the furfural hydrogenation process in comparative example 2, furfural turns
Rate 96.6%, furfuryl alcohol selectivity 98.3%.
Comparative example 3：
Weigh copper nitrate (Cu (NO3)2·3H2O) 132.9g, chromic anhydride (CrO3) 50.0g, lanthanum nitrate (La (NO3)3·6H2O)
4.7g and 36g25wt% acidic silica gel is miscible in 500mL deionized waters；100mL deionized waters are put into reactor first
In, in the case where being stirred continuously, copper-chromium-lanthanum-silicon mixed liquor and ammoniacal liquor (18wt%) cocurrent are added, control pH value in reaction is 6, together
When the temperature of reaction solution risen to 40 DEG C, charging, which finishes, continues insulated and stirred 0.5 hour, filtering, 120 DEG C of dryings 12 hours, so
It is calcined 4 hours in 300 DEG C in Muffle furnace afterwards, finally mill is for the catalyst sample less than 120 mesh, the sample specific surface area
95m2/g, the decentralization 0.46 of Ni metal, CuO/Cr in catalyst2O3Mol ratio be 2.2, CuO/La2O3Mol ratio be
101.9, CuO/SiO2Mol ratio be 3.8.Catalyst 1.75g and 300 milliliters of furfurals are added in autoclave simultaneously, then added
Enter CaO0.4 grams.It it is 195 DEG C in reaction temperature, under conditions of pressure is 7.5MPa, furfural conversion ratio is 99.5%%, furfuryl alcohol choosing
Selecting property 98.7%；Then reacted catalyst is reclaimed by centrifuging, and supplemented according to the new of the method for comparative example 3 preparation
Catalyst 0.5g, repeat the furfural hydrogenation process in comparative example 3, furfural conversion ratio 98.4%, furfuryl alcohol selectivity 99.3%；Then
Catalyst after secondary response is reclaimed by centrifuging, and supplements the raw catelyst 0.5g prepared according to the method for comparative example 3,
Repeat the furfural hydrogenation process in comparative example 3, furfural conversion ratio 96.5%, furfuryl alcohol selectivity 97.6%.
Comparative example 4：
Weigh copper nitrate (Cu (NO3)2·3H2O) 132.9g, chromic anhydride (CrO3) 50.0g and lanthanum nitrate (La (NO3)3·
6H2O) 4.7g is miscible in 500mL deionized waters；100mL deionized waters are put into reactor first, in the case where being stirred continuously,
Copper-chromium-lanthanum mixed liquor and ammoniacal liquor (18wt%) cocurrent containing 3wt% APESs are added, control reaction pH
Value rises to 40 DEG C 6, while by the temperature of reaction solution, and charging, which finishes, continues insulated and stirred 0.5 hour, filtering, 120 DEG C of dryings 12
Hour, then it is calcined 4 hours, finally mills as the catalyst sample less than 120 mesh, the sample ratio in 300 DEG C in Muffle furnace
Surface area is 112m2/ g, the decentralization 0.51 of Ni metal, CuO/Cr in catalyst2O3Mol ratio be 2.2, CuO/La2O3Rub
Your ratio is 101.9.Catalyst 1.75g and 300 milliliters of furfurals are added in autoclave simultaneously, add CaO0.4 grams.Anti-
It is 195 DEG C to answer temperature, and under conditions of pressure is 7.5MPa, furfural conversion ratio is 100%, furfuryl alcohol selectivity 98.8%；
Then reacted catalyst is reclaimed by centrifuging, and supplements and newly urged according to prepared by the method for comparative example 4
Agent 0.5g, repeat the furfural hydrogenation process in comparative example 4, furfural conversion ratio 99.4%, furfuryl alcohol selectivity 98.4%；Then will
Catalyst after secondary response is reclaimed by centrifuging, and supplements the raw catelyst 0.5g prepared according to the method for comparative example 4, weight
Furfural hydrogenation process in multiple comparative example 4, furfural conversion ratio 97.7%, furfuryl alcohol selectivity 97.9%.
From above example 1,4,5,6 and comparative example 3, surfactant is added in preparation process contains Cu-Cr-
The preparing furancarbinol from liquid-phase furol hydrogenation catalyst of La-Si elements has greater activity and selectivity, and catalyst stability is good,
Reaction temperature is 195 DEG C, and under conditions of pressure is 7.5MPa, furfural conversion ratio is 99.8%, and furfuryl alcohol selectivity 99.1%, this is urged
Agent is continuously applied mechanically three times, and furfural conversion ratio is still up to 99.2%, and furfuryl alcohol selectivity is 98.6% (see embodiment 1,4,5,6)；
There is no the preparing furancarbinol from liquid-phase furol hydrogenation catalyst for the element containing Cu-Cr-La-Si for adding surfactant in preparation process
Furfural conversion ratio is 99.5%, furfuryl alcohol selectivity 98.7%；The catalyst continuously applies mechanically secondary, furfural conversion ratio 96.5%, chaff
Alcohol 97.6% (see comparative example 3) of selectivity.
It is in catalyst preparation process in comparative example 1, i.e., also no to add surfactant without Si elements are added,
Its catalytic performance is poor, and reaction temperature is 195 DEG C, and under conditions of pressure is 7.5MPa, furfural conversion ratio is 90.3%, furfuryl alcohol choosing
Selecting property 98.2%.
From above example, preparing furancarbinol from liquid-phase furol hydrogenation specific surface area of catalyst of the invention is big, point of Ni metal
Divergence is high, has greater activity and selectivity, catalyst can be applied mechanically continuously 3 times, and it is still reachable to supplement a small amount of fresh catalyst
The Hydrogenation substantially similar to fresh catalyst.
Claims (7)
1. a kind of catalyst of preparing furancarbinol from liquid-phase furol hydrogenation, it is characterised in that the catalyst includes:
CuO, Cr2O3、La2O3And SiO2；
CuO/Cr2O3Mol ratio be 1.8~2.4；
CuO/La2O3Mol ratio be 60~160；
CuO/SiO2Mol ratio be 2~6；
The catalyst is prepared by the method comprised the following steps：
(1) cupric oxide, chromium oxide, lanthana and silica precursors are mixed and soluble in water obtains mixed solution；
(2) surfactant is dissolved in aqueous slkali, the content of surfactant is 3~5wt%；
(3) deionized water is added in reactor, under conditions of 25-40 DEG C, aqueous slkali and step (1) obtain mixed solution and step
Suddenly the aqueous slkali cocurrent that (2) obtain, which is added in reactor, reacts, and is stirred continuously, and the pH value for controlling reaction be 5-8, stirs to having
Sediment generates；
(4) by the sediment of step (3) after filtering, dry, catalyst fines is made after roasting；
The surfactant is APES, polyvinylpyrrolidone, one kind in polyethylene glycol or combination；
The aqueous slkali is ammoniacal liquor and/or sal volatile.
2. the catalyst of preparing furancarbinol from liquid-phase furol hydrogenation as claimed in claim 1, it is characterised in that：
CuO/Cr2O3Mol ratio 2.0~2.3；
CuO/La2O3Mol ratio 80~120
CuO/SiO2Mol ratio 3~4.
3. the catalyst of preparing furancarbinol from liquid-phase furol hydrogenation as claimed in claim 1, it is characterised in that：
The one kind of the precursor of the cupric oxide in soluble copper salt；
The one kind of the precursor of the chromium oxide in soluble chromic salts.
4. the catalyst of preparing furancarbinol from liquid-phase furol hydrogenation as claimed in claim 3, it is characterised in that：
The precursor of the cupric oxide is selected from copper nitrate, copper sulphate, copper chloride or copper acetate；
The precursor of the chromium oxide is selected from chromic nitrate, chromium sulfate, chromium chloride, chromic acetate or chromic anhydride；
The precursor of the lanthana is selected from lanthanum chloride or lanthanum nitrate；
The precursor of the silica is selected from Ludox or waterglass.
5. the catalyst of preparing furancarbinol from liquid-phase furol hydrogenation as claimed in claim 4, it is characterised in that：
The precursor of the cupric oxide is copper nitrate；The precursor of the chromium oxide is chromic anhydride, and the precursor of the lanthana is lanthanum nitrate；
The precursor of the silica is acidic silicasol.
6. a kind of preparation method of the catalyst of preparing furancarbinol from liquid-phase furol hydrogenation using as described in one of Claims 1 to 5, its
It is characterised by that methods described includes:
(1) cupric oxide, chromium oxide, lanthana and silica precursors are mixed and soluble in water obtains mixed solution；
(2) surfactant is dissolved in aqueous slkali, the content of surfactant is 3~5wt%；
(3) deionized water is added in reactor, under conditions of 25-40 DEG C, aqueous slkali and step (1) obtain mixed solution and step
Suddenly the aqueous slkali cocurrent that (2) obtain, which is added in reactor, reacts, and is stirred continuously, and the pH value for controlling reaction be 5-8, stirs to having
Sediment generates；
(4) by the sediment of step (3) after filtering, dry, catalyst fines is made after roasting；
The surfactant is APES, polyvinylpyrrolidone, one kind in polyethylene glycol or combination；
The aqueous slkali is ammoniacal liquor and/or sal volatile.
7. preparation method as claimed in claim 6, it is characterised in that：
In step (4), drying temperature is 100-120 DEG C, 10~20 hours drying times；Sintering temperature is 350~400 DEG C, roasting
It is 2~6 hours to burn the time.
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| CN106928167B (en) * | 2017-03-14 | 2019-06-11 | 中国科学院广州能源研究所 | A method of furfuryl alcohol is prepared using hydrogen transfer reaction catalysis furfural |
| CN110152663A (en) * | 2018-02-11 | 2019-08-23 | 中国科学院大连化学物理研究所 | It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application |
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| CN110354854A (en) * | 2019-08-22 | 2019-10-22 | 华东师范大学 | A kind of liquid phase selective adds hydrogen furfural to prepare the catalyst of furfuryl alcohol |
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