CN106749120B - The method that furfural hydrogenation prepares furfuryl alcohol - Google Patents
The method that furfural hydrogenation prepares furfuryl alcohol Download PDFInfo
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- CN106749120B CN106749120B CN201710026196.5A CN201710026196A CN106749120B CN 106749120 B CN106749120 B CN 106749120B CN 201710026196 A CN201710026196 A CN 201710026196A CN 106749120 B CN106749120 B CN 106749120B
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- furfural
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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
Abstract
The invention discloses a kind of methods 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 includes the calcium carbonate and silica as carrier, the copper oxide as active constituent；The weight of the copper oxide is 30wt%~75wt% of the total weight of the furfuraldehyde hydrogenation catalyst.Method of the invention uses cheap catalyst, selects suitable catalytic reaction condition, so that catalyst activity is high, thus production cost is reduced, and furfural conversion ratio and hydrogenation selectivity are high.
Description
Technical field
The present invention relates to a kind of methods that furfural hydrogenation prepares furfuryl alcohol.
Background technique
Furfuryl alcohol is widely used in the industries such as synthetic fibers, rubber.In China, 80%~90% furfuryl alcohol is consumed in furans tree
Rouge.Furane resins are widely used in foundary industry as binder.Furfuryl alcohol is the good solvent of varnish, pigment etc..Furfuryl alcohol is also used to
Produce friction pulley thermostable phenolic resin binder.Furfuryl alcohol is also the intermediate for producing fragrance, flavouring agent, medicine, pesticide.
Furfuryl alcohol is mainly derived from furfural deep processing, is that hydrogenation reaction occurs over just partial hydrogenation product on carbonyl.Furfural
Containing there is carbon-to-carbon double strong on active aldehyde and furan nucleus in molecule, determine that its hydrogenation reaction is mainly the carbon oxygen pair in aldehyde radical
Double the be good for plus hydrogen 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
It rings, the carbon-oxygen bond on furfuryl alcohol side chain is easy to disconnect, and is hydrogenated to 2- methylfuran.
Furfuraldehyde hydrogenation catalyst includes SiO2The catalyst of load, TiO2-SiO2The catalyst of load, Al2O3Load is urged
Agent, the catalyst etc. of houghite load.Technical furfural catalyst is with Cu/SiO2Based on, the advantages of series catalysts is to urge
Agent is free of Cr, but its selectivity has a certain gap compared with catalyst containing Cr.
On the one hand, furfuraldehyde hydrogenation catalyst mostly uses greatly the oxide-based carrier such as silica or porous mass class to carry
Body, for example, modenite, carbon nanotube, 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 JP Tetsukai 2015-229657A etc.).In addition, the carrier of furfuraldehyde hydrogenation catalyst is also
There is γ-A12O3, active carbon, TM grades of white carbon blacks, 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 relatively high.In order to the market competitiveness, it is also necessary to further decrease its production cost.But it is existing with carbon
Sour calcium is that the catalyst of carrier is mainly used for the reduction of unsaturated carbon carbon bond, and mostly uses the biggish calcium carbonate of granularity greatly.Example
Such as, CN101811042A is disclosed a kind of using calcium carbonate or barium sulfate as the catalyst of carrier, is used for Isosorbide-5-Nitrae-butynediols also
It originally was 1,4- butylene glycol.For another example, it is calcium carbonate of the partial size greater than 10 μm that CN104394988A, which discloses a kind of support material,
The pull-up catalyst of Lin De.These catalyst are the reduction reactions for triple carbon-carbon bonds to carbon-carbon double bond.It can be seen that existing
The reduction of carbon oxygen unsaturated bond (such as carbonyl) is not used to using calcium carbonate as the catalyst of carrier.In addition, it is existing such
The granularity of catalyst requirement calcium carbonate has 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 load amount copper-based catalysts, under 180 DEG C, condition of normal pressure, carries out furfural and adds
Hydrogen prepares furfuryl alcohol, and conversion ratio is up to 90~99%, to the selectivity of furfuryl alcohol up to 90-99%.
To sum up, there is no prepare urging for furfuryl alcohol using calcium carbonate as carrier, by the furfural hydrogenation of active constituent of copper at present
Agent；Particular without the catalyst for preparing furfuryl alcohol using calcium carbonate superfine powder as carrier, using copper as the furfural hydrogenation of active constituent.
In addition, at present also without reporting about the process conditions that above-mentioned catalyst is used to produce furfuryl alcohol.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
Palladium isoreactivity ingredient is replaced by cheap copper activity ingredient, and selects suitable process conditions to play catalyst to the maximum extent
Activity, and then reduce the dosage of catalyst, it is extremely important for the production cost for reducing furfuryl alcohol, for improving furfuryl alcohol product
The market competitiveness is also vital.
Summary of the invention
It is an object of the present invention to provide a kind of methods that furfural hydrogenation prepares furfuryl alcohol, use cheap catalysis
Agent, production cost are reduced, and furfural conversion ratio and hydrogenation selectivity are also relatively high.
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 furfural and hydrogen are catalyzed by this method in furfural hydrogenation
It is 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 includes the calcium carbonate and silica as carrier, the copper oxide as active constituent；Institute
The weight of copper oxide is stated as 30wt%~75wt% of the total 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 are 1.5~2 hours.
Method in accordance with the invention it is preferred that comprising the following specific steps that:
The furfuraldehyde hydrogenation catalyst and the furfural are mixed to form pre-composition, the pre-composition is heated to 36~50
DEG C, then enter in reactor after being mixed with the hydrogen, the reaction temperature is maintained 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, is stopped described in supply
Hydrogen or the dosage for reducing the furfuraldehyde hydrogenation catalyst.
Method in accordance with the invention it is preferred that the dosage 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 molar ratio of the hydrogen and the furfural is 5~15:1.
Method in accordance with the invention it is preferred that the partial size D50 of the calcium carbonate is 150~300nm, partial size D90 is
200~600nm.
Method in accordance with the invention it is preferred that the mass ratio of calcium carbonate and silica is 0.1~8:1.
Method in accordance with the invention it is preferred that the furfuraldehyde hydrogenation catalyst further includes the alkali gold as coagent
Belong to compound, alkaline earth metal compound or rare earth compound, the weight of the coagent is the furfuraldehyde hydrogenation catalyst
Total 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 method further includes the preparation step of the furfuraldehyde hydrogenation catalyst:
(1) it under the lasting stirring action that low whipping speed is 100~200rpm, will be flowed after silicon source and the bifilar cocurrent of ammonium hydroxide
It adds in copper-bath, stream continues 15~60min of stirring after adding；Wherein, the copper-bath in terms of cupric sulfate pentahydrate
Quality is 1~15:1, copper-bath quality and ammonia in terms of cupric sulfate pentahydrate with the silicon source mass ratio in terms of silica
The ratio between water quality is 6~18:1, and the mass ratio of water and cupric sulfate pentahydrate in copper-bath is 3.3~3.8:1；Silicon source
Flow acceleration is 6~15ml/min, and the flow acceleration of ammonium hydroxide is 0.2~1.0ml/min；It is dispersed in the copper-bath
Calcium carbonate, the silicon source are waterglass or silica solution；
(2) under the lasting stirring action that low whipping speed is 100~200rpm, by sodium hydroxide solution, gradually stream adds to institute
It states in mixed liquor, stream is passed through compressed gas 1~3 hour after adding, and ammonia is escaped, so that slurries are formed, in the slurries
Cu2+No more than 30ppm；Wherein, the copper-bath quality in terms of cupric sulfate pentahydrate and sodium hydroxide mass ratio are 5~6:1,
The mass ratio of water and sodium hydroxide in sodium hydroxide solution is 1.6~2.0:1；The flow acceleration of sodium hydroxide solution is 3
~8ml/min；
(3) filter cake is obtained after filtering the slurries that step (2) obtains, is dried up filter cake using compressed gas；
(4) by step (3) drying after filter cake use be washed to filtrate pH value be 7~8, then with compressed gas will washing after
Filter cake drying；
(5) filter cake that step (4) obtains is heated to catalyst butt not less than 98wt% at 105~115 DEG C.
Method of the invention uses cheap furfuraldehyde hydrogenation catalyst, and it is living to improve catalyst by control reaction condition
Property, and improve furfural conversion ratio and hydrogenation selectivity.The carrier of catalyst of the invention is calcium carbonate and silica, activity
Ingredient is copper oxide, optionally includes coagent, thus its lower production costs.Preferred technical solution according to the present invention,
Catalyst amount can be reduced, production cost is further decreased.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, 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
Preparing furfuryl alcohol is to restore the C=O bond outside ring, and carbon-carbon double bond is not reduced then, is detailed in following formula.
<preparation method of furfuryl alcohol>
The method that furfural hydrogenation of the invention prepares furfuryl alcohol are as follows: 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
It is selected as 1.5~1.6 hours.
According to embodiment of the present invention, furfuraldehyde hydrogenation catalyst and furfural are mixed to form pre-composition, it 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, certainly by reaction
Body heat release maintains the reaction temperature.It can be anti-to control by adjusting dosage or the hydrogen usage of the furfuraldehyde hydrogenation catalyst
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 dosage of furfuraldehyde hydrogenation catalyst.Preferably, when reaction temperature is more than
At 209 DEG C, the dosage of furfuraldehyde hydrogenation catalyst is reduced, production cost can be further decreased in this way.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 dosage of hydrogenation catalyst.Preferably, when reaction temperature is more than 208 DEG C, the dosage of furfuraldehyde hydrogenation catalyst is reduced, in this way may be used
To further decrease production cost.
In the present invention, the dosage of furfuraldehyde hydrogenation catalyst is 0.1wt%~0.33wt% of the weight of furfural, preferably
0.2wt%~0.3wt%.It can guarantee production cost reduction as far as possible under the premise of not reducing furfural conversion ratio in this way.Hydrogen
Molar ratio with furfural is 5~15:1, preferably 7~9:1.
In the present invention, furfuraldehyde hydrogenation catalyst includes the calcium carbonate and silica as carrier, as active constituent
Copper oxide, optionally include coagent.The weight of copper oxide is the 30wt% of the total weight of the furfuraldehyde hydrogenation catalyst
~75wt%.The present invention replaces part of silica as carrier using cheap calcium carbonate, and the life of catalyst can be significantly reduced
Produce cost.Preferably, the weight of copper oxide is 45wt%~70wt% of furfuraldehyde hydrogenation catalyst total weight, more preferably
48wt%~60wt%.Copper content control will be aoxidized in above range, to the greatest extent can may be used in the case where not reducing catalyst activity
It can ground reduction production cost.
In the present invention, the mass ratio of calcium carbonate and 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
Belong to compound or rare earth compound.The weight of coagent be furfuraldehyde hydrogenation catalyst total weight 0.1wt%~
6wt%, preferably 0.2wt%~5wt%, more preferably 0.3wt%~3wt%.Alkali metal compound of the invention can select
Autoxidation lithium, sodium oxide molybdena, potassium oxide, lithium nitrate, sodium nitrate or potassium nitrate；Preferably potassium oxide.Alkaline-earth metal of the invention
Magnesia or calcium oxide can be selected from by closing object；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 partial size D50 of the calcium carbonate is 150~300nm, and partial size D90 is 200~600nm.As
It is preferred that the partial size D50 of the calcium carbonate is 200~250nm, partial size D90 is 230~500nm.More preferably, described
The partial size D50 of calcium carbonate is 210~230nm, and partial size D90 is 250~380nm.Above-mentioned partial size of the invention is all made of laser grain
Degree instrument is measured.In the present invention, institute is right when the cumulative particle sizes percentile of one sample of partial size D50 expression reaches 50%
The partial size answered.Partial size D90 indicates that the cumulative particle sizes percentile of a sample reaches partial size corresponding when 90%.The present invention
By the size controlling of calcium carbonate in above range, it can be further improved the reduction reaction of C=O bond, inhibit carbon-carbon double bond
Reduction reaction, and be conducive to the raising of catalytic activity.
In the present invention, the furfuraldehyde hydrogenation catalyst be graininess, granularity be 8~200 μm, preferably 15~
100 μm, more preferably 20~50 μm.Above-mentioned granularity is measured by the way of sieving.The granularity of furfuraldehyde hydrogenation catalyst is controlled
The furfural conversion ratio of catalyst can be improved in above range, and improve furfuryl alcohol hydrogenation selectivity.
<preparation method of catalyst>
It can also include the preparation step of furfuraldehyde hydrogenation catalyst in the method that furfural hydrogenation of the invention prepares furfuryl alcohol
Suddenly, Details as Follows:
(1) it under the lasting stirring action that low whipping speed is 100~200rpm, will be flowed after silicon source and the bifilar cocurrent of ammonium hydroxide
It adds in copper-bath, stream continues 15~60min of stirring after adding；Wherein, the copper-bath in terms of cupric sulfate pentahydrate
Quality is 1~15:1, copper-bath quality and ammonia in terms of cupric sulfate pentahydrate with the silicon source mass ratio in terms of silica
The ratio between water quality is 6~18:1, and the mass ratio of water and cupric sulfate pentahydrate in copper-bath is 3.3~3.8:1；Silicon source
Flow acceleration is 6~15ml/min, and the flow acceleration of ammonium hydroxide is 0.2~1.0ml/min；It is dispersed in the copper-bath
Calcium carbonate, the silicon source are waterglass or silica solution；
(2) under the lasting stirring action that low whipping speed is 100~200rpm, by sodium hydroxide solution, gradually stream adds to institute
It states in mixed liquor, stream is passed through compressed gas 1~3 hour after adding, and ammonia is escaped, so that slurries are formed, in the slurries
Cu2+No more than 30ppm；Wherein, the copper-bath quality in terms of cupric sulfate pentahydrate and sodium hydroxide mass ratio are 5~6:1,
The mass ratio of water and sodium hydroxide in sodium hydroxide solution is 1.6~2.0:1；The flow acceleration of sodium hydroxide solution is 3
~8ml/min；
(3) filter cake is obtained after filtering the slurries that step (2) obtains, is dried up filter cake using compressed gas；
(4) by step (3) drying after filter cake use be washed to filtrate pH value be 7~8, then with compressed gas will washing after
Filter cake drying；
(5) filter cake that step (4) obtains is heated at 105~115 DEG C catalyst butt not less than 98wt%, obtained
Product.
Optionally, preparation step of the invention further includes step (6): step (5) products therefrom is mixed with coagent.
In step (1) of the invention, mixing speed can be 100~200rpm, preferably 120~150rpm.This hair
Calcium carbonate is dispersed in bright copper-bath.Calcium carbonate is added in copper-bath, ultrasonic wave dispersion or mechanical stirring obtain
To the copper-bath for being dispersed with calcium carbonate.In above-mentioned mixed liquor, the partial size D50 of calcium carbonate is 150~300nm, partial size D90
For 200~600nm.Preferably, the partial size D50 of the calcium carbonate is 200~250nm, partial size D90 is 230~500nm.
More preferably, the partial size D50 of the calcium carbonate is 210~230nm, and partial size D90 is 250~380nm.Of the invention is above-mentioned
Partial size is all made of laser particle analyzer and is measured.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.Copper-bath in copper-bath of the invention, in terms of cupric sulfate pentahydrate
Quality and the mass ratio of calcium carbonate can be 0.05~25:1；Preferably 0.5~15:1；More preferably 2~10:1.
In step (1) of the invention, stream after silicon source and the bifilar cocurrent of ammonium hydroxide is added in copper-bath.Using this
Kind adding manner can improve the size distribution and dispersibility of the copper oxide in catalyst prod, and then improve its hydrogenation selectivity
And conversion ratio.The flow acceleration of silicon source can be 6~15ml/min, preferably 7~11ml/min, more preferably 8~10ml/
min.The flow acceleration of ammonium hydroxide 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, continue 15~60min of stirring, 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 calcium carbonate and silica supports
On.
In step (1) of the invention, the silicon source can be waterglass or silica solution.Waterglass expression contains silicon
The aqueous solution or slurries of sour sodium can use commercially available waterglass product.For example, by using densityFor 1.368~
1.394g/cm3Waterglass product.Na in waterglass product2Content >=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 silica solution of gas form or the silica solution of liquid form.In the present invention, the sulfuric acid in terms of cupric sulfate pentahydrate
The mass ratio of copper solution quality and the silicon source in terms of silica is 1~15:1, preferably 2~13:1；More preferably 3~
10:1.Ammonium hydroxide of the invention is the aqueous solution that ammonia is formed, and concentration is 13~18wt%.One according to the present 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 6~18:1 with ammonium hydroxide mass ratio；Preferably 8~17:1；More preferably 9~16:1.In step (1), copper-bath
In water and cupric sulfate pentahydrate mass ratio be 3.3~3.8:1, preferably 3.5~3.7:1.
In step (2) of the invention, mixing speed can be 100~200rpm, preferably 120~150rpm.By hydrogen
Gradually stream adds in the mixed liquor sodium hydroxide solution, and stream is passed through compressed gas after adding and escapes ammonia, preferably by ammonia
Gas all escapes, to form slurries.Cu in the slurries2+No more than 30ppm, preferably no greater than 15ppm.It can guarantee in this way
The copper ammonia complexation ion of reaction system lacking as far as possible, and improve the dispersibility of copper 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
It encloses, can obtain and copper oxide particle is better dispersed on calcium carbonate and silica supports.After stream adds, it is passed through compression
The time of gas is 1~3 hour, preferably 2~2.5 hours.
Copper-bath quality and sodium hydroxide mass ratio in step (2) of the invention, in terms of cupric sulfate pentahydrate
For 5~6:1, preferably 5.1~5.6:1, more preferably 5.2~5.5:1.Sodium hydroxide of the invention is made in a manner of aqueous solution
With above-mentioned mass ratio is cupric sulfate pentahydrate and sodium hydroxide mass ratio.Water and sodium hydroxide in sodium hydroxide solution
Mass ratio is 1.6~2.0:1, preferably 1.8~1.9:1.
In step (3) of the invention, the slurries of step (2) are filtered, gained filtrate cycle is filtered, until filtrate is clear
It is clear, gained filter cake is dried up using compressed gas.Compressed gas of the invention includes compressed air, compressed nitrogen etc., preferably
Compressed air.Circulating filtration is to save material, avoids wasting up to the limpid purpose of filtrate.
In step (4) of the invention, the filter cake after step (3) drying is used and is washed to filtrate pH value as 7~7.5,
Preferably 7~7.2, then dried up the filter cake after washing with compressed gas.Compressed gas of the invention includes compressed air, compression
Nitrogen etc., preferably compressed air.
In step (5) of the invention, the filter cake that step (4) obtains is heated to catalyst butt at 105~115 DEG C
Not less than 98wt%, product is obtained.Heating temperature is preferably 108~112 DEG C.Heating time can be 30~60 hours, preferably
It is 35~50 hours.
According to embodiment of the present invention, step (5) products therefrom crushed, obtain catalyst after sieving.It crushes
Mode be not particularly limited, such as polishing etc..Crushing temperature is 5~70 DEG C, preferably 15~60 DEG C.It will be smashed
Catalyst sieving, obtains granular catalyst prod.
According to another implementation of the invention, preparation step of the invention includes step (6): will be obtained by step (5)
Product is uniformly mixed with coagent, is crushed, is obtained catalyst after sieving.The present invention can using powdered coagent with
The product of step (5) mixes；The suspension or solution that can also be formed using the product dipping coagent of step (5), 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..
Crushing temperature is 5~70 DEG C, preferably 15~60 DEG C.Smashed catalyst is sieved, granular catalyst prod is obtained.
Raw material used in the following embodiment is described as follows:
Copper-bath: the mass ratio of water and cupric sulfate pentahydrate is 3.57.
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 measure is 150nm, D90 350nm.
Ammonium hydroxide: concentration is the aqueous solution of 15.92wt%.
Sodium hydroxide solution: the mass ratio of water and sodium hydroxide is 1.89.
Test method in following embodiment is described as follows:
Using the granularity of Malvern company, Britain MS-2000 laser particle analyzer measurement nanometer calcium carbonate, nanometer calcium carbonate is come
From Beijing Deco Dao Jin Science and Technology Ltd..Using the grain of Malvern company, Britain MS-2000 laser particle analyzer measurement catalyst
Degree.
Preparation example 1
By according to the formula in table 1,0.15kg calcium carbonate is dispersed in shape in the copper-bath containing 1.4kg cupric sulfate pentahydrate
At mixed liquor, then the mixed liquor is placed in container.1.78kg waterglass and 0.1kg ammonium hydroxide are separately added into separatory funnel
In, then according to the flow of waterglass 10ml/min and ammonium hydroxide 0.44ml/min, by waterglass and ammonium hydroxide 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 adds, continue to stir
30min.According to the flow of 5ml/min, by 0.765kg sodium hydroxide solution, gradually stream is added in above-mentioned reaction system, and stream added
Mixing speed in journey is 120rpm.After stream adds, continue to stir, while being passed through compressed air to container bottom, maintains 2h
Left and right, to guarantee that ammonia all escapes, Cu in slurries2+≯30ppm.Filter tunnel is added in the slurries, 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%, is crushed to 38~48 μm, i.e.,
For catalyst A1.
Preparation example 2
By according to the formula in table 1,0.15kg calcium carbonate is dispersed in shape in the copper-bath containing 1.4kg cupric sulfate pentahydrate
At mixed liquor, then the mixed liquor is placed in container.1.78kg waterglass and 0.1kg ammonium hydroxide are separately added into separatory funnel
In, then according to the flow of waterglass 10ml/min and ammonium hydroxide 0.44ml/min, by waterglass and ammonium hydroxide 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 adds, continue to stir
30min.According to the flow of 5ml/min, by 0.765kg sodium hydroxide solution, gradually stream is added in above-mentioned reaction system, and stream added
Mixing speed in journey is 120rpm.After stream adds, continue to stir, while being passed through compressed air to container bottom, maintains 2h
Left and right, to guarantee that ammonia all escapes, Cu in slurries2+≯30ppm.Filter tunnel is added in the slurries, 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%, obtains product.It will be based on urging
The potassium oxide powder of agent total weight the sum of (product with coagent weight) 1.5wt% is uniformly mixed with above-mentioned product, powder
It is broken to 38~48 μm, as catalyst A2.
Preparation example 3
By according to the formula in table 1,0.15kg calcium carbonate is dispersed in shape in the copper-bath containing 1.4kg cupric sulfate pentahydrate
At mixed liquor, then the mixed liquor is placed in container.1.78kg waterglass and 0.1kg ammonium hydroxide are separately added into separatory funnel
In, then according to the flow of waterglass 10ml/min and ammonium hydroxide 0.44ml/min, by waterglass and ammonium hydroxide 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 adds, continue to stir
30min.According to the flow of 5ml/min, by 0.765kg sodium hydroxide solution, gradually stream is added in above-mentioned reaction system, and stream added
Mixing speed in journey is 120rpm.After stream adds, continue to stir, while being passed through compressed air to container bottom, maintains 2h
Left and right, to guarantee that ammonia all escapes, Cu in slurries2+≯30ppm.Filter tunnel is added in the slurries, 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%, obtains product.It will be based on urging
The ceria oxide powder of agent total weight the sum of (product with coagent weight) 0.5wt% mixes at 25 DEG C with above-mentioned product
Uniformly, 38~48 μm, as catalyst A3 are crushed at 25 DEG C.
Examples 1 to 3
1 ton of furfural is sufficiently stirred with furfuraldehyde hydrogenation catalyst (catalyst A1, A2 or A3 of Examples 1 to 3) respectively mixed
After conjunction, be preheated to 40 DEG C or so mixed with hydrogen after enter reactor, by reaction self-heat generation maintaining 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
Dosage.Reaction pressure 6.53MPa, 205~209 DEG C of reaction temperature.One ton of furfural passes through the time about 1.5h of reactor.Hydrogen with
The molar ratio of furfural is 8:1, and furfuraldehyde hydrogenation catalyst is the 3wt% of furfural weight.Experimental result is referring to table 2.
Comparative example 1
Other than replacing with the material quality of addition shown in table 1, remaining step and condition are identical as preparation example 1,
Obtain catalyst B.After 1 ton of furfural is thoroughly mixed with catalyst B respectively, be preheated to 40 DEG C or so mixed with hydrogen it is laggard
Enter reactor, by reaction self-heat generation maintaining 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 dosage of furfuraldehyde hydrogenation catalyst is reduced.Reaction pressure 6.53MPa, reaction temperature 205
~209 DEG C.One ton of furfural passes through the time about 1.5h of reactor.The molar ratio of hydrogen and furfural is 8:1, furfuraldehyde hydrogenation catalyst
For the 3wt% of furfural weight.Experimental result is referring to table 2.
Table 1
Table 2
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (9)
1. a kind of method that furfural hydrogenation prepares furfuryl alcohol, which is characterized 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 includes the calcium carbonate and silica as carrier, the copper oxide as active constituent；The oxygen
Change the weight of copper as 30wt%~75wt% of the total weight of the furfuraldehyde hydrogenation catalyst；
The method further includes the preparation step of the furfuraldehyde hydrogenation catalyst:
(1) under the lasting stirring action that low whipping speed is 100~200rpm, stream after silicon source and the bifilar cocurrent of ammonium hydroxide is added to
In copper-bath, stream continues 15~60min of stirring after adding, and obtains mixed liquor；Wherein, the sulfuric acid in terms of cupric sulfate pentahydrate
Copper solution quality is 1~15:1, the copper-bath matter in terms of cupric sulfate pentahydrate with the silicon source mass ratio in terms of silica
Amount is 6~18:1 with ammonium hydroxide mass ratio, and the mass ratio of water and cupric sulfate pentahydrate in copper-bath is 3.3~3.8:1；
The flow acceleration of silicon source is 6~15ml/min, and the flow acceleration of ammonium hydroxide is 0.2~1.0ml/min；In the copper-bath
It is dispersed with calcium carbonate, the silicon source is waterglass or silica solution；
(2) under the lasting stirring action that low whipping speed is 100~200rpm, by sodium hydroxide solution, gradually stream adds to described mix
It closing in liquid, stream is passed through compressed gas 1~3 hour after adding, ammonia escaped, so that slurries are formed, the Cu in the slurries2+No
Greater than 30ppm；Wherein, the copper-bath quality in terms of cupric sulfate pentahydrate and sodium hydroxide mass ratio are 5~6:1, hydrogen-oxygen
The mass ratio for changing water and sodium hydroxide in sodium solution is 1.6~2.0:1；The flow acceleration of sodium hydroxide solution be 3~
8ml/min；
(3) filter cake is obtained after filtering the slurries that step (2) obtains, is dried up filter cake using compressed gas；
(4) filter cake after step (3) drying is used and is washed to filtrate pH value as 7~8, then with compressed gas by the filter after washing
Cake drying；
(5) filter cake that step (4) obtains is heated to catalyst butt not less than 98wt% at 105~115 DEG C.
2. the method according to claim 1, wherein the reaction temperature be 206~208 DEG C, the reaction pressure
Power is 6.38~6.53MPa, and the reaction time is 1.5~2 hours.
3. the method according to claim 1, wherein comprising the following specific steps that:
The furfuraldehyde hydrogenation catalyst and the furfural are mixed to form pre-composition, the pre-composition is heated to 36~50 DEG C,
Enter in reactor after being mixed again with the hydrogen, maintains the reaction temperature 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, stops supplying the hydrogen
Gas or the dosage for reducing the furfuraldehyde hydrogenation catalyst.
4. the method according to claim 1, wherein the dosage of the furfuraldehyde hydrogenation catalyst is the furfural
0.1wt%~0.33wt% of weight.
5. the method according to claim 1, wherein the molar ratio of the hydrogen and the furfural is 5~15:1.
6. the method according to claim 1, wherein the partial size D50 of the calcium carbonate is 150~300nm, partial size
D90 is 200~600nm.
7. the method according to claim 1, wherein the mass ratio of calcium carbonate and silica is 0.1~8:
1。
8. the method according to claim 1, wherein the furfuraldehyde hydrogenation catalyst further 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%~6wt% of the total weight of catalyst.
9. according to the method described in claim 8, it is characterized 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
Object is selected from lanthana, cerium oxide, cerous nitrate, lanthanum nitrate, lanthanum sulfate, cerous sulfate, lanthanum acetate, cerous acetate, lanthanum chloride or cerium chloride.
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