CN106749120A - The method that furfural hydrogenation prepares furfuryl alcohol - Google Patents
The method that furfural hydrogenation prepares furfuryl alcohol Download PDFInfo
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- CN106749120A CN106749120A CN201710026196.5A CN201710026196A CN106749120A CN 106749120 A CN106749120 A CN 106749120A CN 201710026196 A CN201710026196 A CN 201710026196A CN 106749120 A CN106749120 A CN 106749120A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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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
- B01J23/72—Copper
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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Abstract
The invention discloses a kind of method that furfural hydrogenation prepares furfuryl alcohol.Furfural and hydrogen are reacted in the presence of furfuraldehyde hydrogenation catalyst；Reaction temperature is 205~209 DEG C, and reaction pressure is 6.3~6.6MPa, and the reaction time is 1~5 hour；The furfuraldehyde hydrogenation catalyst is included as the calcium carbonate and silica of carrier, as the cupric oxide of active component；The weight of the cupric oxide is the 30wt%~75wt% of the gross weight of the furfuraldehyde hydrogenation catalyst.The method of the present invention uses cheap catalyst, the suitable catalytic reaction condition of selection so that catalyst activity is high, thus production cost to be reduced, and furfural conversion ratio and hydrogenation selectivity are high.
Description
Technical field
The present invention relates to a kind of method that furfural hydrogenation prepares furfuryl alcohol.
Background technology
Furfuryl alcohol is widely used in the industries such as synthetic fibers, rubber.In China, 80%~90% furfuryl alcohol is consumed in furans tree
Fat.Furane resins are widely used in foundary industry as binding agent.Furfuryl alcohol is the good solvent of varnish, pigment etc..Furfuryl alcohol is additionally operable to
Production friction pulley thermostable phenolic resin binding agent.Furfuryl alcohol is also production spices, flavouring agent, medicine, the intermediate of agricultural chemicals.
Furfuryl alcohol is mainly derived from furfural deep processing, is the partial hydrogenation product that hydrogenation reaction is occurred over just on carbonyl.Furfural
Containing there is carbon-to-carbon double strong on active aldehyde and furan nucleus in molecule, determine that the carbon oxygen in its hydrogenation reaction mainly aldehyde radical is double
The double strong hydrogenation saturations of carbon-to-carbon, generate furfuryl alcohol or tetrahydrofurfuryl alcohol on strong and furan nucleus；Further, since by the shadow of adjacent furan nucleus
Ring, the carbon-oxygen bond on furfuryl alcohol side chain easily disconnects, and is hydrogenated to 2- methylfurans.
Furfuraldehyde hydrogenation catalyst includes SiO2The catalyst of load, TiO2-SiO2The catalyst of load, Al2O3What is loaded urges
Agent, catalyst of houghite load etc..Technical furfural catalyst is with Cu/SiO2Based on, the advantage of the series catalysts is to urge
Agent is free of Cr, but its selectivity also certain gap compared with catalyst containing Cr.
On the one hand, furfuraldehyde hydrogenation catalyst is carried using the oxide-based carriers such as silica or porous mass class mostly
Body, for example, modenite, CNT, carbon fiber, Graphene, SBA-15, gama-alumina, titanium dioxide, float stone, pyrolysis silicon
Stone, clay, mesoporous silicon oxide etc. (referring to US5591873A, US5977010A, US4185022A, CN102247883A,
CN103007941A, CN105148923A and TOHKEMY 2015-229657A etc.).Additionally, the carrier of furfuraldehyde hydrogenation catalyst is also
There are γ-A12O3, activated carbon, TM grades of white carbon, general purpose grade SiO2、SiO2(40-120 mesh) or SiO2(110-120 mesh) etc. (referring to
" Li Guoan, Speciality Petrochemicals, the 1st phase, the 40-44 pages, nineteen ninety-five ").Above-mentioned furfural hydrogenation prepares the catalyst of furfuryl alcohol
Production cost is higher.In order to the market competitiveness, in addition it is also necessary to further reduce its production cost.But, it is existing with carbon
Sour calcium is mainly used in the reduction of unsaturated carbon carbon bond for the catalyst of carrier, and mostly using the calcium carbonate that granularity is larger.Example
Such as, CN101811042A discloses a kind of catalyst with calcium carbonate or barium sulfate as carrier, and it is used for Isosorbide-5-Nitrae-butynediols also
Originally it was 1,4- butylene glycols.And for example, CN104394988A discloses a kind of calcium carbonate of support material for particle diameter more than 10 μm
The pull-up catalyst of Lin De.These catalyst are the reduction reaction to carbon-carbon double bond for triple carbon-carbon bonds.As can be seen here, it is existing
Catalyst with calcium carbonate as carrier is not used to the reduction of carbon oxygen unsaturated bond (such as carbonyl).Additionally, it is existing such
The granularity of catalyst requirement calcium carbonate have to be larger than 10 μm.
On the other hand, reaction condition has important influence for the activity and hydrogenation selectivity of catalyst.Chinese patent
Document CN104841436A discloses integral type high capacity amount copper-based catalysts, under 180 DEG C, condition of normal pressure, carries out furfural and adds
Hydrogen prepares furfuryl alcohol, and, up to 90~99%, its selectivity to furfuryl alcohol is up to 90-99% for conversion ratio.
To sum up, urging for furfuryl alcohol is not prepared as carrier, the furfural hydrogenation with copper as active component using calcium carbonate at present
Agent；Particular without the catalyst for preparing furfuryl alcohol as carrier, the furfural hydrogenation with copper as active component using calcium carbonate superfine powder.
Additionally, not reporting the process conditions on above-mentioned catalyst to be used to produce furfuryl alcohol at present yet.Furfuryl alcohol is prepared in furfural hydrogenation
Industrialized production in, catalyst occupies its very big cost.If can using cheap calcium carbonate as carrier and with compared with
For cheap copper activity composition replaces palladium isoreactivity composition, and suitable process conditions are selected to play catalyst to greatest extent
Activity, and then reduce the consumption of catalyst, the production cost for reducing furfuryl alcohol is extremely important, for improving furfuryl alcohol product
The market competitiveness also it is critical that.
The content of the invention
It is an object of the present invention to provide a kind of method that furfural hydrogenation prepares furfuryl alcohol, it uses cheap catalysis
Agent, production cost is reduced, and furfural conversion ratio and hydrogenation selectivity are also higher.
The application reaches above-mentioned purpose by following technical solution.
The present invention provides a kind of method that furfural hydrogenation prepares furfuryl alcohol, and in furfural hydrogenation be catalyzed for furfural and hydrogen by the method
Reacted in the presence of agent；Wherein, reaction temperature is 205~209 DEG C, and reaction pressure is 6.3~6.6MPa, and the reaction time is 1~5
Hour；The furfuraldehyde hydrogenation catalyst is included as the calcium carbonate and silica of carrier, as the cupric oxide of active component；Institute
The weight for stating cupric oxide is the 30wt%~75wt% of the gross weight of the furfuraldehyde hydrogenation catalyst.
Method in accordance with the invention it is preferred that the reaction temperature be 206~208 DEG C, the reaction pressure be 6.38~
6.53MPa, the reaction time is 1.5~2 hours.
Method in accordance with the invention it is preferred that comprising the following specific steps that：
The furfuraldehyde hydrogenation catalyst is mixed to form pre-composition with the furfural, the pre-composition is heated to 36~50
DEG C, then enter in reactor after mixing with the hydrogen, maintain the reaction temperature by reaction self-heat generation；In the reaction
When temperature is less than 205 DEG C, the furfuraldehyde hydrogenation catalyst is added, when the reaction temperature is more than 209 DEG C, stop supply described
The consumption of hydrogen or the reduction furfuraldehyde hydrogenation catalyst.
Method in accordance with the invention it is preferred that the consumption of the furfuraldehyde hydrogenation catalyst is the weight of the furfural
0.1wt%~0.33wt%.
Method in accordance with the invention it is preferred that the hydrogen is 5~15 with the mol ratio of the furfural:1.
Method in accordance with the invention it is preferred that the particle diameter D50 of described calcium carbonate is 150~300nm, particle diameter D90 is
200~600nm.
Method in accordance with the invention it is preferred that calcium carbonate is 0.1~8 with the mass ratio of silica:1.
Method in accordance with the invention it is preferred that described furfuraldehyde hydrogenation catalyst is also included as the alkali gold of coagent
Category compound, alkaline earth metal compound or rare earth compound, the weight of the coagent is the furfuraldehyde hydrogenation catalyst
Gross weight 0.1wt%~6wt%.
Method in accordance with the invention it is preferred that the alkali metal compound is selected from lithia, sodium oxide molybdena, potassium oxide, nitric acid
Lithium, sodium nitrate or potassium nitrate；The alkaline earth metal compound is selected from magnesia or calcium oxide；The rare earth compound is selected from oxidation
Lanthanum, cerium oxide, cerous nitrate, lanthanum nitrate, lanthanum sulfate, cerous sulfate, lanthanum acetate, cerous acetate, lanthanum chloride or cerium chloride.
Method in accordance with the invention it is preferred that the described method also preparation process including the furfuraldehyde hydrogenation catalyst：
(1) under low whipping speed is the lasting stirring action of 100~200rpm, will be flowed after silicon source and the bifilar cocurrent of ammoniacal liquor
Add in copper-bath, continue to stir 15~60min after stream plus end；Wherein, the copper-bath in terms of cupric sulfate pentahydrate
Quality and the silicon source mass ratio counted with silica are 1~15:1, copper-bath quality and ammonia in terms of cupric sulfate pentahydrate
The ratio between water quality is 6~18:1, water and the mass ratio of cupric sulfate pentahydrate in copper-bath are 3.3~3.8:1；Silicon source
Flow acceleration is 6~15ml/min, and the flow acceleration of ammoniacal liquor is 0.2~1.0ml/min；It is dispersed with described copper-bath
Calcium carbonate, described silicon source is waterglass or Ludox；
(2) under low whipping speed is the lasting stirring action of 100~200rpm, by sodium hydroxide solution, gradually stream adds to institute
State in mixed liquor, compressed gas are passed through 1~3 hour after stream plus end, ammonia is escaped, so that slurries are formed, in the slurries
Cu2+No more than 30ppm；Wherein, the copper-bath quality and NaOH mass ratio counted with cupric sulfate pentahydrate are 5~6:1,
Water and the mass ratio of NaOH in sodium hydroxide solution are 1.6~2.0:1；The flow acceleration of sodium hydroxide solution is 3
~8ml/min；
(3) filter cake is obtained after the slurries filtering for obtaining step (2), filter cake is dried up using compressed gas；
(4) it is 7~8 that the filter cake after step (3) is dried up is used and is washed to filtrate pH value, then with compressed gas by after washing
Filter cake drying；
(5) filter cake that step (4) is obtained is heated to catalyst butt not less than 98wt% at 105~115 DEG C.
The method of the present invention uses cheap furfuraldehyde hydrogenation catalyst, is lived by controlling reaction condition to improve catalyst
Property, and improve furfural conversion ratio and hydrogenation selectivity.The carrier of catalyst of the invention is calcium carbonate and silica, activity
Composition is cupric oxide, and optionally including coagent, thus its production cost is relatively low.According to currently preferred technical scheme,
Catalyst amount can be reduced, production cost is further reduced.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
In the present invention, furfural has the C=O bond (that is, carbonyl) outside the carbon-carbon double bond and ring in ring.Furfural hydrogenation
It is to reduce the C=O bond outside ring to prepare furfuryl alcohol, and carbon-carbon double bond is not reduced then, refers to following formula.
<The preparation method of furfuryl alcohol>
The method that furfural hydrogenation of the invention prepares furfuryl alcohol is：By furfural and hydrogen in the presence of furfuraldehyde hydrogenation catalyst
Reaction.In the present invention, reaction temperature is 205~209 DEG C, preferably 206~208 DEG C.Reaction pressure is 6.3~6.6MPa,
Preferably 6.38~6.53MPa, more preferably 6.53MPa.Reaction time is 1~5 hour, preferably 1.5~2 hours, more excellent
Elect as 1.5~1.6 hours.
An implementation method of the invention, pre-composition is mixed to form by furfuraldehyde hydrogenation catalyst and furfural, will be described
Pre-composition is heated to 36~50 DEG C, preferably 38~40 DEG C, then enters in reactor after mixing with the hydrogen, by reaction from
Body heat release maintains the reaction temperature.Can be controlled by adjusting the consumption or hydrogen usage of the furfuraldehyde hydrogenation catalyst anti-
Temperature is answered to maintain 205~209 DEG C.Specifically, when reaction temperature is less than 205 DEG C, furfuraldehyde hydrogenation catalyst is added；Work as reaction
When temperature is more than 209 DEG C, stops supply hydrogen or reduce the consumption of furfuraldehyde hydrogenation catalyst.Preferably, when reaction temperature exceedes
At 209 DEG C, the consumption of furfuraldehyde hydrogenation catalyst is reduced, so can further reduce production cost.Preferably, when reaction temperature
When degree is less than 206 DEG C, furfuraldehyde hydrogenation catalyst is added；When reaction temperature is more than 208 DEG C, stops supply hydrogen or reduce furfural
The consumption of hydrogenation catalyst.Preferably, when reaction temperature is more than 208 DEG C, the consumption of furfuraldehyde hydrogenation catalyst is reduced, so may be used
Further to reduce production cost.
In the present invention, the consumption of furfuraldehyde hydrogenation catalyst is the 0.1wt%~0.33wt% of the weight of furfural, preferably
0.2wt%~0.3wt%.So can as far as possible ensure production cost reduction on the premise of furfural conversion ratio is not reduced.Hydrogen
It is 5~15 with the mol ratio of furfural:1, preferably 7~9:1.
In the present invention, furfuraldehyde hydrogenation catalyst is included as the calcium carbonate and silica of carrier, as active component
Cupric oxide, optionally including coagent.The weight of cupric oxide is the 30wt% of the gross weight of the furfuraldehyde hydrogenation catalyst
~75wt%.The present invention replaces part of silica as carrier using cheap calcium carbonate, can significantly reduce the life of catalyst
Produce cost.Preferably, 45wt%~70wt% of the weight of cupric oxide for furfuraldehyde hydrogenation catalyst gross weight, more preferably
48wt%~60wt%.Copper content control will be aoxidized in above range, can to the greatest extent may be used in the case where catalyst activity is not reduced
Can ground reduction production cost.
In the present invention, calcium carbonate and the mass ratio of silica can be 0.1~8:1, preferably 0.2~7:1；More
Preferably 0.3~6:1.The mass ratio of calcium carbonate and silica is controlled in above range, production cost is advantageously reduced,
And improve furfural conversion ratio.
In the present invention, furfuraldehyde hydrogenation catalyst can also include alkali metal compound, the alkaline earth gold as coagent
Category compound or rare earth compound.The weight of coagent for furfuraldehyde hydrogenation catalyst gross weight 0.1wt%~
6wt%, preferably 0.2wt%~5wt%, more preferably 0.3wt%~3wt%.Alkali metal compound of the invention can be selected
Autoxidation lithium, sodium oxide molybdena, potassium oxide, lithium nitrate, sodium nitrate or potassium nitrate；Preferably potassium oxide.Alkaline-earth metal of the invention
Compound can be selected from magnesia or calcium oxide；Preferably calcium oxide.Rare earth compound of the invention can be selected from lanthana, oxidation
Cerium, cerous nitrate, lanthanum nitrate, lanthanum sulfate, cerous sulfate, lanthanum acetate, cerous acetate, lanthanum chloride or cerium chloride；Preferably lanthana or oxygen
Change cerium.
In the present invention, the particle diameter D50 of described calcium carbonate is 150~300nm, and particle diameter D90 is 200~600nm.As
It is preferred that, the particle diameter D50 of described calcium carbonate is 200~250nm, and particle diameter D90 is 230~500nm.As it is further preferred that described
The particle diameter D50 of calcium carbonate is 210~230nm, and particle diameter D90 is 250~380nm.Above-mentioned particle diameter of the invention is using laser grain
Degree instrument is measured.In the present invention, institute is right when particle diameter D50 represents that the cumulative particle sizes percentile of a sample reaches 50%
The particle diameter answered.Particle diameter D90 represents that the cumulative particle sizes percentile of a sample reaches particle diameter corresponding when 90%.The present invention
By the size controlling of calcium carbonate in above range, the reduction reaction of C=O bond can be further improved, suppress carbon-carbon double bond
Reduction reaction, and be conducive to the raising of catalysis activity.
In the present invention, described furfuraldehyde hydrogenation catalyst be graininess, its granularity be 8~200 μm, preferably 15~
100 μm, more preferably 20~50 μm.Above-mentioned granularity is determined by the way of sieving.By the Task-size Controlling of furfuraldehyde hydrogenation catalyst
Can improve the furfural conversion ratio of catalyst in above range, and improve furfuryl alcohol hydrogenation selectivity.
<The preparation method of catalyst>
In the method that furfural hydrogenation of the invention prepares furfuryl alcohol, can also include that the preparation of furfuraldehyde hydrogenation catalyst is walked
Suddenly, Details as Follows：
(1) under low whipping speed is the lasting stirring action of 100~200rpm, will be flowed after silicon source and the bifilar cocurrent of ammoniacal liquor
Add in copper-bath, continue to stir 15~60min after stream plus end；Wherein, the copper-bath in terms of cupric sulfate pentahydrate
Quality and the silicon source mass ratio counted with silica are 1~15:1, copper-bath quality and ammonia in terms of cupric sulfate pentahydrate
The ratio between water quality is 6~18:1, water and the mass ratio of cupric sulfate pentahydrate in copper-bath are 3.3~3.8:1；Silicon source
Flow acceleration is 6~15ml/min, and the flow acceleration of ammoniacal liquor is 0.2~1.0ml/min；It is dispersed with described copper-bath
Calcium carbonate, described silicon source is waterglass or Ludox；
(2) under low whipping speed is the lasting stirring action of 100~200rpm, by sodium hydroxide solution, gradually stream adds to institute
State in mixed liquor, compressed gas are passed through 1~3 hour after stream plus end, ammonia is escaped, so that slurries are formed, in the slurries
Cu2+No more than 30ppm；Wherein, the copper-bath quality and NaOH mass ratio counted with cupric sulfate pentahydrate are 5~6:1,
Water and the mass ratio of NaOH in sodium hydroxide solution are 1.6~2.0:1；The flow acceleration of sodium hydroxide solution is 3
~8ml/min；
(3) filter cake is obtained after the slurries filtering for obtaining step (2), filter cake is dried up using compressed gas；
(4) it is 7~8 that the filter cake after step (3) is dried up is used and is washed to filtrate pH value, then with compressed gas by after washing
Filter cake drying；
(5) filter cake that step (4) is obtained is heated to catalyst butt not less than 98wt% at 105~115 DEG C, is obtained
Product.
Optionally, preparation process of the invention also includes step (6)：Step (5) products therefrom is mixed with coagent.
In step of the invention (1), mixing speed can be 100~200rpm, preferably 120~150rpm.This hair
Calcium carbonate is dispersed with bright copper-bath.By in calcium carbonate addition copper-bath, ultrasonic wave disperses or mechanical agitation, obtains
To the copper-bath for being dispersed with calcium carbonate.In above-mentioned mixed liquor, the particle diameter D50 of calcium carbonate is 150~300nm, particle diameter D90
It is 200~600nm.Preferably, the particle diameter D50 of described calcium carbonate is 200~250nm, particle diameter D90 is 230~500nm.
Used as it is further preferred that the particle diameter D50 of described calcium carbonate is 210~230nm, particle diameter D90 is 250~380nm.It is of the invention above-mentioned
Particle diameter is measured using laser particle analyzer.By the size controlling of calcium carbonate in above range, furfural can be further improved
It is reduced to the selectivity and conversion ratio of furfuryl alcohol.In copper-bath of the invention, the copper-bath in terms of cupric sulfate pentahydrate
Quality can be 0.05~25 with the mass ratio of calcium carbonate:1；Preferably 0.5~15:1；More preferably 2~10:1.
In step of the invention (1), during stream after silicon source and the bifilar cocurrent of ammoniacal liquor added into copper-bath.Using this
Planting feed postition can improve the size distribution and dispersiveness of the cupric oxide in catalyst prod, and then improve its hydrogenation selectivity
And conversion ratio.The flow acceleration of silicon source can be 6~15ml/min, more preferably preferably 7~11ml/min, 8~10ml/
min.The flow acceleration of ammoniacal liquor can for 0.2~1.0ml/min, preferably 0.3~0.8ml/min, more preferably 0.4~
0.6ml/min.After silicon source and ammonia aqua stream add end, continue to stir 15~60min, preferably 30~50min.By silicon source, ammonia
The flow acceleration of water is controlled in above range, copper oxide particle can be better dispersed in into calcium carbonate and silica supports
On.
In step of the invention (1), described silicon source can be waterglass or Ludox.Waterglass is represented and contains silicon
The aqueous solution or slurries of sour sodium, can use commercially available waterglass product.For example with densityFor 1.368~
1.394g/cm3Waterglass product.Na in waterglass product2Content >=the 8.2wt% of O；SiO2Content >=26.0wt%.According to
The specific embodiment of the present invention, Na2The content of O is 8.684wt%；SiO2Content is 28.46wt%.Silicon of the invention
Colloidal sol can be the Ludox of gas form or the Ludox of liquid form.In the present invention, the sulfuric acid in terms of cupric sulfate pentahydrate
Copper solution quality is 1~15 with the mass ratio of the silicon source counted with silica:1, preferably 2~13:1；More preferably 3~
10:1.Ammoniacal liquor of the invention is the aqueous solution that ammonia is formed, and its concentration is 13~18wt%.One of the invention specific real
Mode is applied, ammonia concn of the invention is 15.92wt%.In the present invention, the copper-bath quality in terms of cupric sulfate pentahydrate
It is 6~18 with ammoniacal liquor mass ratio:1；Preferably 8~17:1；More preferably 9~16:1.In step (1), copper-bath
In the mass ratio of water and cupric sulfate pentahydrate be 3.3~3.8:1, preferably 3.5~3.7:1.
In step of the invention (2), mixing speed can be 100~200rpm, preferably 120~150rpm.By hydrogen
Sodium hydroxide solution is during gradually stream adds to the mixed liquor, stream plus is passed through compressed gas after terminating and escapes ammonia, preferably by ammonia
Gas is all escaped, so as to form slurries.Cu in the slurries2+No more than 30ppm, preferably no greater than 15ppm.Can so ensure
What the copper ammonia complexation ion of reaction system was tried one's best lacks, and improves the dispersiveness of cupric oxide in catalyst.The stream of sodium hydroxide solution
Acceleration can be 3~8ml/min, preferably 5~7ml/min.The flow acceleration of sodium hydroxide solution is controlled in above-mentioned model
Enclose, can obtain and copper oxide particle is better dispersed on calcium carbonate and silica supports.After stream plus end, compression is passed through
The time of gas is 1~3 hour, preferably 2~2.5 hours.
In step of the invention (2), copper-bath quality and NaOH mass ratio in terms of cupric sulfate pentahydrate
It is 5~6:1, preferably 5.1~5.6:1, more preferably 5.2~5.5:1.NaOH of the invention is made in the way of the aqueous solution
With above-mentioned mass ratio is cupric sulfate pentahydrate and NaOH mass ratio.Water and NaOH in sodium hydroxide solution
Mass ratio is 1.6~2.0:1, preferably 1.8~1.9:1.
In step of the invention (3), the slurries of step (2) are filtered, by the filtering of gained filtrate cycle, until filtrate is clear
It is clear, gained filter cake is dried up using compressed gas.Compressed gas of the invention include compressed air, compressed nitrogen etc., preferably
Compressed air.Circulating filtration is until the limpid purpose of filtrate is to save material, it is to avoid waste.
In step of the invention (4), it is 7~7.5 that the filter cake after step (3) is dried up is used and is washed to filtrate pH value,
Preferably 7~7.2, then dried up the filter cake after washing with compressed gas.Compressed gas of the invention include compressed air, compression
Nitrogen etc., preferably compressed air.
In step of the invention (5), the filter cake that step (4) is obtained is heated to catalyst butt at 105~115 DEG C
Not less than 98wt%, product is obtained.Heating-up temperature is preferably 108~112 DEG C.Heat time can be 30~60 hours, preferably
It is 35~50 hours.
An implementation method of the invention, will obtain catalyst after the crushing of step (5) products therefrom, sieving.Crush
Mode be not particularly limited, such as polishing etc..It is 5~70 DEG C, preferably 15~60 DEG C to crush temperature.After crushing
Catalyst sieves, and obtains granular catalyst prod.
According to another implementation of the invention, preparation process of the invention includes step (6)：By step (5) gained
Product is well mixed with coagent, and catalyst is obtained after crushing, sieving.The present invention can using powdered coagent with
The product mixing of step (5)；The suspension or solution that can also be formed using the product of step (5) dipping coagent, then
Drying.Mixing temperature is 5~70 DEG C, preferably 15~60 DEG C.The mode of crushing is not particularly limited, such as polishing etc..
It is 5~70 DEG C, preferably 15~60 DEG C to crush temperature.By the catalyst sieving after crushing, granular catalyst prod is obtained.
The raw material used in following examples is described as follows：
Copper-bath：Water is 3.57 with the mass ratio of cupric sulfate pentahydrate.
Waterglass：The aqueous solution containing sodium metasilicate, wherein, Na2The content of O is 8.684wt%；SiO2Content is
28.46wt%.
Calcium carbonate：Calcium carbonate superfine powder, the D50 for using laser particle analyzer to determine is 150nm, and D90 is 350nm.
Ammoniacal liquor：Concentration is the aqueous solution of 15.92wt%.
Sodium hydroxide solution：Water is 1.89 with the mass ratio of NaOH.
Method of testing in following examples is described as follows：
The granularity of nano-calcium carbonate is determined using Britain Malvern company MS-2000 laser particle analyzers, nano-calcium carbonate comes
From Beijing Deco Dao Jin Science and Technology Ltd.s.The grain of catalyst is determined using Britain Malvern company MS-2000 laser particle analyzers
Degree.
Preparation example 1
According to the formula of table 1,0.15kg calcium carbonate is dispersed in shape in the copper-bath containing 1.4kg cupric sulfate pentahydrates
Into mixed liquor, then the mixed liquor is placed in container.1.78kg waterglass and 0.1kg ammoniacal liquor are separately added into separatory funnel
In, then according to waterglass 10ml/min and the flow of ammoniacal liquor 0.44ml/min, by waterglass and ammoniacal liquor with the side of bifilar cocurrent
Formula is added in the container for filling mixed liquor, and the mixing speed during stream adds is 120rpm.After stream plus end, stirring is continued to
30min.According to the flow of 5ml/min, by 0.765kg sodium hydroxide solutions during gradually stream adds to above-mentioned reaction system, stream added
Mixing speed in journey is 120rpm.After stream plus end, continue to stir, while being passed through compressed air to container bottom, maintain 2h
Left and right, to ensure that ammonia is all escaped, Cu in slurries2+≯30ppm.The slurries are added into filter tunnel, filtrate cycle is to clear
After clear, then with the dry filter cake of compressed air wind.Gained filter cake is repeated into washed several times with water, until filtrate pH value 7, then use compressed air
Filter cake is dried up.Filter cake is poured out, 48 hours are heated at 110 DEG C to catalyst butt ≮ 98wt%, be crushed to 38~48 μm, i.e.,
It is catalyst A1.
Preparation example 2
According to the formula of table 1,0.15kg calcium carbonate is dispersed in shape in the copper-bath containing 1.4kg cupric sulfate pentahydrates
Into mixed liquor, then the mixed liquor is placed in container.1.78kg waterglass and 0.1kg ammoniacal liquor are separately added into separatory funnel
In, then according to waterglass 10ml/min and the flow of ammoniacal liquor 0.44ml/min, by waterglass and ammoniacal liquor with the side of bifilar cocurrent
Formula is added in the container for filling mixed liquor, and the mixing speed during stream adds is 120rpm.After stream plus end, stirring is continued to
30min.According to the flow of 5ml/min, by 0.765kg sodium hydroxide solutions during gradually stream adds to above-mentioned reaction system, stream added
Mixing speed in journey is 120rpm.After stream plus end, continue to stir, while being passed through compressed air to container bottom, maintain 2h
Left and right, to ensure that ammonia is all escaped, Cu in slurries2+≯30ppm.The slurries are added into filter tunnel, filtrate cycle is to clear
After clear, then with the dry filter cake of compressed air wind.Gained filter cake is repeated into washed several times with water, until filtrate pH value 7, then use compressed air
Filter cake is dried up.Filter cake is poured out, 48 hours are heated at 110 DEG C to catalyst butt ≮ 98wt%, obtain product.Will be based on urging
The potassium oxide powder of agent gross weight (product and coagent weight sum) 1.5wt% is well mixed with above-mentioned product, powder
It is broken to 38~48 μm, as catalyst A2.
Preparation example 3
According to the formula of table 1,0.15kg calcium carbonate is dispersed in shape in the copper-bath containing 1.4kg cupric sulfate pentahydrates
Into mixed liquor, then the mixed liquor is placed in container.1.78kg waterglass and 0.1kg ammoniacal liquor are separately added into separatory funnel
In, then according to waterglass 10ml/min and the flow of ammoniacal liquor 0.44ml/min, by waterglass and ammoniacal liquor with the side of bifilar cocurrent
Formula is added in the container for filling mixed liquor, and the mixing speed during stream adds is 120rpm.After stream plus end, stirring is continued to
30min.According to the flow of 5ml/min, by 0.765kg sodium hydroxide solutions during gradually stream adds to above-mentioned reaction system, stream added
Mixing speed in journey is 120rpm.After stream plus end, continue to stir, while being passed through compressed air to container bottom, maintain 2h
Left and right, to ensure that ammonia is all escaped, Cu in slurries2+≯30ppm.The slurries are added into filter tunnel, filtrate cycle is to clear
After clear, then with the dry filter cake of compressed air wind.Gained filter cake is repeated into washed several times with water, until filtrate pH value 7, then use compressed air
Filter cake is dried up.Filter cake is poured out, 48 hours are heated at 110 DEG C to catalyst butt ≮ 98wt%, obtain product.Will be based on urging
The ceria oxide powder of agent gross weight (product and coagent weight sum) 0.5wt% mixes with above-mentioned product at 25 DEG C
Uniformly, 38~48 μm, as catalyst A3 are crushed at 25 DEG C.
Embodiment 1~3
1 ton of furfural is sufficiently stirred for mixing with furfuraldehyde hydrogenation catalyst (catalyst A1, A2 or A3 of embodiment 1~3) respectively
After conjunction, be preheated to 40 DEG C or so mix with hydrogen after enter reactor, by reaction self-heat generation maintenance reaction temperature, work as reaction
When temperature is less than 205 DEG C, furfuraldehyde hydrogenation catalyst is supplemented；When reaction temperature is more than 209 DEG C, furfuraldehyde hydrogenation catalyst is reduced
Consumption.Reaction pressure 6.53MPa, 205~209 DEG C of reaction temperature.The time about 1.5h that one ton of furfural passes through reactor.Hydrogen with
The mol ratio of furfural is 8:1, furfuraldehyde hydrogenation catalyst is the 3wt% of furfural weight.Experimental result is referring to table 2.
Comparative example 1
In addition to the material quality of addition is replaced with shown in table 1, remaining step and condition are identical with preparation example 1,
Obtain catalyst B.After 1 ton of furfural is thoroughly mixed with catalyst B respectively, it is preheated to 40 DEG C or so and mixes laggard with hydrogen
Enter reactor, by reaction self-heat generation maintenance reaction temperature, when reaction temperature is less than 205 DEG C, supplement furfural hydrogenation catalysis
Agent；When reaction temperature is more than 209 DEG C, the consumption of furfuraldehyde hydrogenation catalyst is reduced.Reaction pressure 6.53MPa, reaction temperature 205
~209 DEG C.The time about 1.5h that one ton of furfural passes through reactor.Hydrogen is 8 with the mol ratio of furfural:1, furfuraldehyde hydrogenation catalyst
It is the 3wt% of furfural weight.Experimental result is referring to table 2.
Table 1
Table 2
The present invention is not limited to above-mentioned implementation method, in the case of without departing substantially from substance of the invention, this area skill
Any deformation that art personnel are contemplated that, improvement, replacement each fall within the scope of the present invention.
Claims (10)
1. a kind of method that furfural hydrogenation prepares furfuryl alcohol, it is characterised in that the depositing in furfuraldehyde hydrogenation catalyst by furfural and hydrogen
In lower reaction；Wherein, reaction temperature is 205~209 DEG C, and reaction pressure is 6.3~6.6MPa, and the reaction time is 1~5 hour；
The furfuraldehyde hydrogenation catalyst is included as the calcium carbonate and silica of carrier, as the cupric oxide of active component；The oxygen
The weight for changing copper is the 30wt%~75wt% of the gross weight of the furfuraldehyde hydrogenation catalyst.
2. method according to claim 1, it is characterised in that the reaction temperature is 206~208 DEG C, the reaction pressure
Power is 6.38~6.53MPa, and the reaction time is 1.5~2 hours.
3. method according to claim 1, it is characterised in that comprise the following specific steps that：
The furfuraldehyde hydrogenation catalyst is mixed to form pre-composition with the furfural, the pre-composition is heated to 36~50 DEG C,
Enter in reactor after mixing with the hydrogen again, the reaction temperature is maintained by reaction self-heat generation；In the reaction temperature
When degree is less than 205 DEG C, the furfuraldehyde hydrogenation catalyst is added, when the reaction temperature is more than 209 DEG C, stop the supply hydrogen
The consumption of gas or the reduction furfuraldehyde hydrogenation catalyst.
4. method according to claim 1, it is characterised in that the consumption of the furfuraldehyde hydrogenation catalyst is the furfural
0.1wt%~the 0.33wt% of weight.
5. method according to claim 1, it is characterised in that the hydrogen is 5~15 with the mol ratio of the furfural:1.
6. method according to claim 1, it is characterised in that the particle diameter D50 of the calcium carbonate is 150~300nm, particle diameter
D90 is 200~600nm.
7. method according to claim 1, it is characterised in that calcium carbonate is 0.1~8 with the mass ratio of silica:
1。
8. method according to claim 1, it is characterised in that the furfuraldehyde hydrogenation catalyst also includes as coagent
Alkali metal compound, alkaline earth metal compound or rare earth compound, the weight of the coagent is the furfural hydrogenation
0.1wt%~the 6wt% of the gross weight of catalyst.
9. method according to claim 8, it is characterised in that the alkali metal compound is selected from lithia, sodium oxide molybdena, oxygen
Change potassium, lithium nitrate, sodium nitrate or potassium nitrate；The alkaline earth metal compound is selected from magnesia or calcium oxide；The rare earth chemical combination
Thing is selected from lanthana, cerium oxide, cerous nitrate, lanthanum nitrate, lanthanum sulfate, cerous sulfate, lanthanum acetate, cerous acetate, lanthanum chloride or cerium chloride.
10. the method according to any one of claim 1~9, it is characterised in that described method also adds including the furfural
The preparation process of hydrogen catalyst：
(1) under low whipping speed is the lasting stirring action of 100~200rpm, stream after silicon source and the bifilar cocurrent of ammoniacal liquor is added to
In copper-bath, continue to stir 15~60min after stream plus end；Wherein, the copper-bath quality in terms of cupric sulfate pentahydrate
It is 1~15 with the silicon source mass ratio counted with silica:1, copper-bath quality and ammoniacal liquor matter in terms of cupric sulfate pentahydrate
The ratio between amount is 6~18:1, water and the mass ratio of cupric sulfate pentahydrate in copper-bath are 3.3~3.8:1；The stream of silicon source adds
Speed is 6~15ml/min, and the flow acceleration of ammoniacal liquor is 0.2~1.0ml/min；Carbonic acid is dispersed with described copper-bath
Calcium, described silicon source is waterglass or Ludox；
(2) under low whipping speed is the lasting stirring action of 100~200rpm, by sodium hydroxide solution, gradually stream adds to described mixing
Close in liquid, compressed gas are passed through 1~3 hour after stream plus end, ammonia is escaped, so that slurries are formed, the Cu in the slurries2+No
More than 30ppm；Wherein, the copper-bath quality and NaOH mass ratio counted with cupric sulfate pentahydrate are 5~6:1, hydrogen-oxygen
The water and the mass ratio of NaOH changed in sodium solution are 1.6~2.0:1；The flow acceleration of sodium hydroxide solution be 3~
8ml/min；
(3) filter cake is obtained after the slurries filtering for obtaining step (2), filter cake is dried up using compressed gas；
(4) filter cake after step (3) is dried up uses that to be washed to filtrate pH value be 7~8, then with compressed gas by the filter after washing
Cake is dried up；
(5) filter cake that step (4) is obtained is heated to catalyst butt not less than 98wt% at 105~115 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018668A (en) * | 2019-12-25 | 2020-04-17 | 淄博诺奥化工股份有限公司 | Green method for preparing mixed butanol by catalytic distillation |
| CN111468121A (en) * | 2020-06-11 | 2020-07-31 | 北京林业大学 | Preparation and application of MXene modified biomass carbon nano metal catalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120975A (en) * | 1995-06-28 | 1996-04-24 | 中国科学院大连化学物理研究所 | Aldose hydrogenating process and catalyst for producing sugar alcohol |
| GB2482887A (en) * | 2010-08-18 | 2012-02-22 | Johnson Matthey Plc | Catalyst and process for hydrogenation of aldehydes |
| CN102408304A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing alcohols by selectively hydrogenating aldehydes |
| CN102631930A (en) * | 2012-03-30 | 2012-08-15 | 南京熙辉新材料有限公司 | Catalyst for preparing furfuryl alcohol from furfural by vapor phase hydrogenation and preparation method thereof |
| CN103007941A (en) * | 2012-12-27 | 2013-04-03 | 珠海凯美科技有限公司 | Catalyst used in process of preparing furfuryl alcohol by furfural through selective hydrogenation and preparation method of catalyst |
| CN105498787A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst for producing 2-methylfuran through gas phase hydrogenation of furfural and preparation method of the catalyst |
-
2017
- 2017-01-13 CN CN201710026196.5A patent/CN106749120B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120975A (en) * | 1995-06-28 | 1996-04-24 | 中国科学院大连化学物理研究所 | Aldose hydrogenating process and catalyst for producing sugar alcohol |
| GB2482887A (en) * | 2010-08-18 | 2012-02-22 | Johnson Matthey Plc | Catalyst and process for hydrogenation of aldehydes |
| CN102408304A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing alcohols by selectively hydrogenating aldehydes |
| CN102631930A (en) * | 2012-03-30 | 2012-08-15 | 南京熙辉新材料有限公司 | Catalyst for preparing furfuryl alcohol from furfural by vapor phase hydrogenation and preparation method thereof |
| CN103007941A (en) * | 2012-12-27 | 2013-04-03 | 珠海凯美科技有限公司 | Catalyst used in process of preparing furfuryl alcohol by furfural through selective hydrogenation and preparation method of catalyst |
| CN105498787A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst for producing 2-methylfuran through gas phase hydrogenation of furfural and preparation method of the catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018668A (en) * | 2019-12-25 | 2020-04-17 | 淄博诺奥化工股份有限公司 | Green method for preparing mixed butanol by catalytic distillation |
| CN111468121A (en) * | 2020-06-11 | 2020-07-31 | 北京林业大学 | Preparation and application of MXene modified biomass carbon nano metal catalyst |
| CN111468121B (en) * | 2020-06-11 | 2022-06-24 | 北京林业大学 | Preparation and application of MXene modified biomass carbon nano metal catalyst |
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