CN106732706B - Furfuraldehyde hydrogenation catalyst and preparation method thereof containing rare earth element - Google Patents
Furfuraldehyde hydrogenation catalyst and preparation method thereof containing rare earth element Download PDFInfo
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- CN106732706B CN106732706B CN201710026056.8A CN201710026056A CN106732706B CN 106732706 B CN106732706 B CN 106732706B CN 201710026056 A CN201710026056 A CN 201710026056A CN 106732706 B CN106732706 B CN 106732706B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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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Abstract
The invention discloses a kind of furfuraldehyde hydrogenation catalyst and preparation method thereof containing rare earth element.The catalyst is using calcium carbonate as carrier, using copper oxide as active component, using rare earth compound as coagent；The weight of copper oxide is 28wt%~75wt% of total catalyst weight, and the weight of rare earth compound is 0.1wt%~5wt% of total catalyst weight.Being produced into for furfuraldehyde hydrogenation catalyst of the invention is effectively controlled, and furfural conversion ratio and hydrogenation selectivity are very high.
Description
Technical field
The present invention relates to a kind of, and the furfuraldehyde hydrogenation catalyst and preparation method thereof containing rare earth element, especially one kind contain rare earth
The furfural hydrogenation of element prepares catalyst of furfuryl alcohol and preparation method thereof.
Background technique
Furfuryl alcohol is widely used in the industries such as synthetic fibers, rubber and pesticide.Furfuryl alcohol can be used for manufacturing various kinds of resin, wherein chaff
The excellent plasticizer of cold tolerance can be made in alcohol resin.Furfuryl alcohol is mainly derived from the deep processing of furfural, is that hydrogenation reaction only occurs
Partial hydrogenation product on carbonyl.Furfuraldehyde hydrogenation catalyst includes SiO2The catalyst of load, TiO2-SiO2The catalysis of load
Agent, Al2O3The catalyst etc. of load.Technical furfural catalyst is with Cu/SiO2Based on, the advantages of series catalysts be catalyst not
Containing Cr, but its selectivity has a certain gap compared with catalyst containing Cr.In addition, the production cost of furfuraldehyde hydrogenation catalyst is still
It is relatively high.
Currently, furfuraldehyde hydrogenation catalyst mostly uses greatly the oxide-based carrier such as silica or porous mass class carrier,
For example, modenite, carbon nanotube, carbon fiber, graphene, SBA-15, gama-alumina, titanium dioxide, float stone, fumed silica,
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 ").
The existing reduction for being mainly used for unsaturated carbon carbon bond using calcium carbonate as the catalyst of carrier, and grain is mostly used greatly
Spend biggish calcium carbonate.For example, CN101811042A discloses one kind using palladium as active component, calcium carbonate or barium sulfate are carrier
Selective hydrocatalyst.The catalyst is used to 1,4- butynediols being reduced to 1,4- butylene glycol.That is, this is urged
Reduction reaction of the agent for triple carbon-carbon bonds to carbon-carbon double bond.For another example, CN104394988A discloses a kind of part hydrogenated carbon carbon
The pull-up catalyst of woods moral of three keys, support material are the calcium carbonate that partial size is greater than 10 μm, and active component is Pd and Pb.The catalyst
It is also the reduction reaction for triple carbon-carbon bonds to carbon-carbon double bond.The document it is specifically that: when the support material for calcium carbonate
When partial size is greater than 10 μm, the selectivity of hydrogenation process is significantly improved.It can be seen that existing using calcium carbonate as the catalyst of carrier
It is not used to the reduction of carbon oxygen unsaturated bond (such as carbonyl).
To sum up, in existing furfuraldehyde hydrogenation catalyst, there is no using calcium carbonate as carrier, using copper as active component,
Using rare earth compound as the catalyst of coagent；Particular without using calcium carbonate superfine powder as carrier, using copper as active component,
Using rare earth compound as the catalyst of coagent.In the industrialized production that furfural hydrogenation prepares furfuryl alcohol, catalyst is occupied
Its very big cost.If palladium etc. can be replaced using cheap calcium carbonate as carrier and with relatively inexpensive copper activity component
Active component is then conducive to the production cost for controlling furfuryl alcohol, improves the market competitiveness.In addition it is also necessary to improve adding for catalyst
Hydrogen selectivity and furfural conversion ratio, further control production cost.
Summary of the invention
It is an object of the present invention to provide a kind of furfuraldehyde hydrogenation catalyst containing rare earth element, production cost is obtained
Effectively control, and furfural conversion ratio and hydrogenation selectivity are very high.
It is another object of the present invention to provide a kind of preparation method of furfuraldehyde hydrogenation catalyst containing rare earth element,
Production cost is rationally controlled, and product stability is good.
The present invention provides a kind of furfuraldehyde hydrogenation catalyst containing rare earth element, and the catalysis of furfuryl alcohol is prepared for furfural hydrogenation
Agent, using calcium carbonate as carrier, using copper oxide as active component, using rare earth compound as coagent；The weight of the copper oxide
For 28wt%~75wt% of total catalyst weight, and the weight of the rare earth compound is the 0.1wt% of total catalyst weight
~5wt%.
Furfuraldehyde hydrogenation catalyst according to the present invention, it is preferable that the weight of the copper oxide is total catalyst weight
40wt%~70wt%, and the weight of the rare earth compound is 0.3wt%~3wt% of total catalyst weight.
Furfuraldehyde hydrogenation catalyst according to the present invention, it is preferable that the catalyst without containing silica, silicate and
Palladium.
Furfuraldehyde hydrogenation catalyst according to the present invention, it is preferable that rare earth element in the rare earth compound be selected from lanthanum,
Cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium or scandium.
Furfuraldehyde hydrogenation catalyst according to the present invention, it is preferable that the rare earth compound be selected from lanthana, cerium oxide,
Cerous nitrate, lanthanum nitrate, lanthanum sulfate, cerous sulfate, lanthanum acetate, cerous acetate, lanthanum chloride or cerium chloride.
Furfuraldehyde hydrogenation catalyst according to the present invention, it is preferable that the partial size D50 of the calcium carbonate is 150~300nm,
Partial size D90 is 150~700nm.
The present invention also provides the preparation methods of above-mentioned furfuraldehyde hydrogenation catalyst comprising following steps:
(1) under lasting stirring action, ammonia aqua stream is added in copper-bath to form mixed liquor；Wherein, described
Calcium carbonate is dispersed in copper-bath；
(2) under lasting stirring action, by sodium hydroxide solution, gradually stream is added in the mixed liquor, and stream leads to after adding
Enter compressed gas to escape ammonia, so that slurries are formed, the Cu in the slurries2+No more than 30ppm；
(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 7~7.6, then with compressed gas by washing
Filter cake drying afterwards；
(5) filter cake that step (4) obtains is heated to catalyst butt not less than 98wt% at 106~115 DEG C, obtains object
Material；
(6) material that step (5) obtains is uniformly mixed with the rare earth compound, by crushing, is obtained described
Furfuraldehyde hydrogenation catalyst.
Preparation method according to the present invention, it is preferable that water and cupric sulfate pentahydrate in step (1), in copper-bath
Mass ratio be 3.3~3.8:1；Copper-bath quality and ammonium hydroxide mass ratio in terms of cupric sulfate pentahydrate are 5~18:1,
Mixing speed is 110~300rpm；And the flow acceleration of ammonium hydroxide is 0.1~1.5ml/min, and stream continues stirring 15 after adding
~60min；In step (2), the mass ratio of water and sodium hydroxide in sodium hydroxide solution is 1.6~2.0:1；With five water
The copper-bath quality and sodium hydroxide mass ratio of copper sulfate are 5~6:1, and mixing speed is 110~300rpm；And
The flow acceleration of sodium hydroxide solution is 2~8ml/min, and stream is passed through compressed gas time after adding is 1~3 hour.
Preparation method according to the present invention, it is preferable that in step (3), the slurries that step (2) is obtained are filtered, by institute
It obtains filtrate cycle filtering to dry up gained filter cake using compressed gas until filtrate is limpid, compressed gas therein is compression sky
Gas.
Preparation method according to the present invention, it is preferable that in step (4), by the filter cake after step (3) drying using washing
It is 7~7.5 to filtrate pH value, then is dried up the filter cake after washing with compressed gas, compressed gas therein is compressed air；?
In step (5), heating temperature is 108~112 DEG C, and heating time is 30~60 hours；In step (6), mixing temperature be 5~
70 DEG C, crushing temperature is 5~70 DEG C.
The present invention obtains chaff for active component, by coagent of rare earth compound using calcium carbonate as carrier, copper oxide
Aldehyde hydrogenating catalyst, production cost are effectively controlled, furfural high conversion rate, and hydrogenation selectivity is high.According to the present invention
Preferred technical solution selects the calcium carbonate superfine powder of specified particle size range that can further improve furfural conversion ratio and plus hydrogen selection
Property.The dispersibility and size distribution of the adjustable copper oxide of preparation method of the invention, to improve its catalytic activity.In addition,
The production cost of the preparation method is rationally controlled, and product stability is good.
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, partial size D50 indicates that the cumulative particle sizes percentile of a sample reaches corresponding when 50%
Partial size.Partial size D90 indicates that the cumulative particle sizes percentile of a sample reaches partial size corresponding when 90%.
Furfural has the C=O bond (that is, carbonyl) outside carbon-carbon double bond and ring in ring.Furfural hydrogenation prepare furfuryl alcohol be by
C=O bond reduction outside ring, and carbon-carbon double bond is not reduced then, is detailed in following formula.
Catalyst and preparation method of the invention is described more fully below.
<catalyst>
Furfuraldehyde hydrogenation catalyst of the invention is using calcium carbonate as carrier, using copper oxide as active component, with rare earth compound
For coagent；The weight of copper oxide is 28wt%~75wt% of total catalyst weight, and the weight of rare earth compound is catalysis
0.1wt%~5wt% of agent total weight.The present invention replaces silica as carrier, Ke Yixian completely using cheap calcium carbonate
Write the production cost for reducing catalyst.According to the preferred embodiment of the present invention, the catalyst does not contain silica, silicon
Hydrochlorate and palladium.Since the cost of calcium carbonate is lower than palladium lower than the cost of silica material, copper, thus it can reduce and be produced into
This.
In the present invention, the partial size D50 of the calcium carbonate is 150~300nm, and partial size D90 is 150~700nm；It is preferred that
Ground, the partial size D50 of calcium carbonate are 200~250nm, and partial size D90 is 200~550nm；It is highly preferred that the partial size D50 of calcium carbonate is
210~230nm, partial size D90 are 250~380nm.Above-mentioned partial size of the invention is all made of laser particle analyzer and is measured.This hair
The bright size controlling by calcium carbonate can be further improved the reduction reaction of C=O bond in above range, inhibit carbon-carbon double bond
Reduction reaction, and be conducive to the raising of catalytic activity.
In the present invention, the weight of copper oxide be total catalyst weight 28wt%~75wt%, preferably 40wt%~
70wt%, more preferably 48wt%~60wt%.Copper content control will be aoxidized in above range, can be lived not reducing catalyst
Property in the case where, as much as possible reduction production cost.In the present invention, the weight of rare earth compound is total catalyst weight
0.1wt%~5wt%, preferably 0.3wt%~3wt%, more preferably 0.5wt%~2wt%.By the dosage control of coagent
System can improve hydrogenation selectivity in above range.
In the present invention, the rare earth element in rare earth compound be selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium,
Holmium, erbium, thulium, ytterbium, lutetium or scandium；Preferably lanthanum or cerium.Rare earth compound of the invention can be selected from lanthana, cerium oxide, nitric acid
Cerium, lanthanum nitrate, lanthanum sulfate, cerous sulfate, lanthanum acetate, cerous acetate, lanthanum chloride or cerium chloride；Preferably lanthana, cerium oxide, nitric acid
Cerium or lanthanum nitrate；More preferably lanthana or cerium oxide.
In the present invention, the catalyst be graininess, granularity be 10~150 μm, preferably 15~100 μm, more
Preferably 25~50 μm.Above-mentioned granularity is measured by the way of sieving.The granularity of catalyst is controlled can change in above range
The furfural conversion ratio of kind catalyst, and improve furfuryl alcohol hydrogenation selectivity.
<preparation method>
The present invention also provides the preparation methods of above-mentioned furfuraldehyde hydrogenation catalyst comprising following steps:
(1) under lasting stirring action, ammonia aqua stream is added in copper-bath to form mixed liquor；Wherein, described
Calcium carbonate is dispersed in copper-bath；
(2) under lasting stirring action, by sodium hydroxide solution, gradually stream is added in the mixed liquor, and stream leads to after adding
Enter compressed gas to escape ammonia, so that slurries are formed, the Cu in the slurries2+No more than 30ppm；
(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 7~7.6, then with compressed gas by washing
Filter cake drying afterwards；
(5) filter cake that step (4) obtains is heated to catalyst butt not less than 98wt% at 106~115 DEG C；
(6) material is mixed with rare earth compound, to obtain the catalyst.
In step (1) of the invention, mixing speed can be 110~300rpm, preferably 120~150rpm.This hair
Calcium carbonate is dispersed in bright copper-bath.Calcium carbonate is added in copper-bath, mechanical stirring or ultrasonic wave dispersion can
To obtain the copper-bath for being dispersed with calcium carbonate.In above-mentioned mixed liquor, the partial size D50 of calcium carbonate is 150~300nm, grain
Diameter D90 is 150~700nm.Preferably, the partial size D50 of the calcium carbonate be 200~250nm, partial size D90 be 200~
550nm.More preferably, the partial size D50 of the calcium carbonate is 210~230nm, and partial size D90 is 250~380nm.The present invention
Above-mentioned partial size be all made of laser particle analyzer and be measured.By the size controlling of calcium carbonate in above range, can further mention
High furfural is reduced to the selectivity and conversion ratio of furfuryl alcohol.Sulfuric acid in copper-bath of the invention, in terms of cupric sulfate pentahydrate
Copper solution quality with can be for 0.05~25:1 with the mass ratio of calcium carbonate；Preferably 0.5~15:1；More preferably 2~10:
1.In the present invention, ammonia aqua stream is added in copper-bath.Such adding manner can improve the oxygen in catalyst prod
Change the size distribution and dispersibility of copper, and then improves its hydrogenation selectivity and conversion ratio.The flow acceleration of ammonium hydroxide can for 0.1~
1.5ml/min, preferably 0.2~0.8ml/min, more preferably 0.3~0.6ml/min.Ammonia aqua stream plus after, continue to stir
Mix 15~60min, preferably 30~50min.The flow acceleration of ammonium hydroxide is controlled in above range, it can be by copper oxide particle more
It is dispersed on calcium carbonate carrier well.Ammonium hydroxide of the invention is the aqueous solution that ammonia is formed, and concentration is 13~18wt%.According to
The specific embodiment of the present invention, ammonia concn of the invention are 15.92wt%.In the present invention, with cupric sulfate pentahydrate
The copper-bath quality and ammonium hydroxide mass ratio of meter are 5~18:1；Preferably 8~17:1；More preferably 9~16:1.In step
Suddenly in (1), the mass ratio of water and cupric sulfate pentahydrate in copper-bath is 3.3~3.8:1, preferably 3.5~3.7:1.
In step (2) of the invention, mixing speed can be 110~300rpm, 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 10ppm.It can guarantee in this way
The copper ammonia complexation ion of reaction system is few as far as possible, and improves the dispersibility of copper oxide in catalyst.The stream of sodium hydroxide solution adds
Speed can be 2~8ml/min, preferably 5~7ml/min.The flow acceleration of sodium hydroxide solution is controlled in above range,
It can obtain and copper oxide particle is better dispersed on calcium carbonate carrier.After stream adds, the time for being passed through compressed gas is 1
~3 hours, preferably 2~2.5 hours.Copper-bath quality and sodium hydroxide mass ratio in terms of cupric sulfate pentahydrate are 5
~6:1, preferably 5.1~5.6:1, more preferably 5.2~5.5:1.Sodium hydroxide of the invention is used in a manner of aqueous solution,
Above-mentioned mass ratio is cupric sulfate pentahydrate and sodium hydroxide mass ratio.The quality of water and sodium hydroxide in sodium hydroxide solution
The ratio between be 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.
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.At this
In the step of invention (5), the filter cake that step (4) obtains is heated to catalyst butt at 106~115 DEG C and is not less than 98wt%,
Obtain material.Heating temperature is preferably 108~112 DEG C.Heating time can be 30~60 hours, preferably 35~50 hours.
In step (6) of the invention, the material is uniformly mixed with rare earth compound, the catalyst is obtained after crushing.This hair
It is bright to be mixed using powdered coagent with the material；The material can also be impregnated to what rare earth compound was formed
Suspension or solution, are then dried.Mixing temperature is 5~70 DEG C, preferably 15~60 DEG C.There is no especially limits for the mode of crushing
System, such as polishing etc..Crushing temperature is 5~70 DEG C, preferably 15~60 DEG C.Smashed catalyst is sieved, is obtained
Granular catalyst prod.Catalyst of the invention can not need high-temperature roasting process, thus can save mass energy, from
And further decrease production cost.
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.
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.
Waterglass: Na2The content of O is 8.684wt%；SiO2Content is 28.46wt%.
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.
Embodiment 1
377g calcium carbonate is dispersed in the copper-bath that 3.2kg contains 700g cupric sulfate pentahydrate and forms mixed liquor, so
The mixed liquor is placed in container afterwards.89g ammonium hydroxide is added in the container for filling mixed liquor according to the traffic flow of 0.5ml/min,
Mixing speed during stream adds is 150rpm.After stream adds, stirring 30min is continued to.By 382g sodium hydroxide solution
According to the flow of 5ml/min, gradually stream is added in above-mentioned reaction system, stream plus during mixing speed be 150rpm.Stream plus knot
Shu Hou continues to stir, while being passed through compressed air to container bottom, maintains 2h or so, to guarantee that ammonia all escapes, in slurries
Cu2+≯30ppm.The slurries are added and are filtered, filtrate cycle is to after limpid, then with the dry filter cake of compressed air wind.By gained
Filter cake repeats washed several times with water, until filtrate pH=7, then dried up filter cake with compressed air.Filter cake is poured out, heats 50 at 110 DEG C
Hour to catalyst butt ≮ 98%, obtains material.Will based on total catalyst weight (above-mentioned material and coagent weight it
With) lanthanum oxide powder of 0.35wt% is uniformly mixed at 25 DEG C with above-mentioned material, 38~48 μm are crushed at 25 DEG C, as
Catalyst V1.
The preparation process of embodiment 1 is repeated to catalyst V2, V3 secondary, then that obtain two batches.
Embodiment 2~3
Other than replacing with the material quality of addition shown in table 1, remaining step and condition are same as Example 1,
Successively obtain catalyst W and X.
Comparative example 1
By according to the formula in table 1, the 3.2kg copper-bath for containing 700g cupric sulfate pentahydrate is placed in container.By 1110g
Waterglass and 45g ammonium hydroxide are separately added into separatory funnel, then according to the stream of waterglass 10ml/min and ammonium hydroxide 0.44ml/min
Amount, waterglass and ammonium hydroxide are added in the container for filling mixed liquor in a manner of bifilar cocurrent, flow the mixing speed during adding
For 150rpm.After stream adds, stirring 35min is continued to.According to the flow of 5ml/min, by 382g sodium hydroxide solution by
Gradually stream adds in above-mentioned reaction system, and the mixing speed during stream adds is 120rpm.After stream adds, continue to stir, simultaneously
It is passed through compressed air to container bottom, maintains 2h or so, to guarantee that ammonia all escapes, Cu in slurries2+≯30ppm.It will be described
Slurries are added filter tunnel, and filtrate cycle is to after limpid, then with the dry filter cake of compressed air wind.Gained filter cake is repeated into washing number
It is secondary, until filtrate pH=7, then dried up filter cake with compressed air.Pour out filter cake, heated at 110 DEG C 48 hours it is dry to catalyst
Base ≮ 98% obtains material, by crushing material to 38~48 μm, as catalyst Y.
Table 1
Experimental example
The catalyst of 10g Examples 1 to 3 and comparative example 1 is weighed respectively, and the reaction kettle for filling 1700ml furfural is then added
In, it is reacted 1.5 hours under conditions of temperature is 200 DEG C, Hydrogen Vapor Pressure is 7MPa.Experimental result is referring to table 2.
In embodiment 1, furfural conversion ratio, the furfuryl alcohol for the catalyst that different batches obtain selectively connect very close.This says
The bright preparation method can be stable with production performance furfuraldehyde hydrogenation catalyst.Examples 1 to 3 is compared with comparative example 1, furfuryl alcohol selection
Property increases, and cost is then effectively controlled.
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 furfuraldehyde hydrogenation catalyst containing rare earth element, which is characterized in that the catalyst is that furfural hydrogenation prepares chaff
The catalyst of alcohol, using calcium carbonate as carrier, using copper oxide as active component, using rare earth compound as coagent；The oxygen
The weight for changing copper is 28wt%~75wt% of total catalyst weight, and the weight of the rare earth compound is total catalyst weight
0.1wt%~5wt%；Wherein, the catalyst does not contain silica, silicate and palladium.
2. furfuraldehyde hydrogenation catalyst according to claim 1, which is characterized in that the weight of the copper oxide is that catalyst is total
40wt%~70wt% of weight, and the weight of the rare earth compound is 0.3wt%~3wt% of total catalyst weight.
3. furfuraldehyde hydrogenation catalyst according to claim 1, which is characterized in that the rare earth member in the rare earth compound
Element is selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium or scandium.
4. furfuraldehyde hydrogenation catalyst according to claim 1, which is characterized in that 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.
5. furfuraldehyde hydrogenation catalyst according to claim 1, which is characterized in that the partial size D50 of the calcium carbonate is 150
~300nm, partial size D90 are 150~700nm.
6. the preparation method of described in any item furfuraldehyde hydrogenation catalysts according to claim 1~5, which is characterized in that it includes
Following steps:
(1) under lasting stirring action, ammonia aqua stream is added in copper-bath to form mixed liquor；Wherein, the sulfuric acid
Calcium carbonate is dispersed in copper solution；
(2) under lasting stirring action, by sodium hydroxide solution, gradually stream is added in the mixed liquor, and stream is passed through pressure after adding
Contracting gas escapes ammonia, so that slurries are formed, the Cu in the slurries2+No more than 30ppm；
(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 7~7.6, then will be after washing with compressed gas
Filter cake drying；
(5) filter cake that step (4) obtains is heated to catalyst butt not less than 98wt% at 106~115 DEG C, obtains material；
(6) material that step (5) obtains is uniformly mixed with the rare earth compound, by crushing, obtains the furfural
Hydrogenation catalyst.
7. preparation method according to claim 6, it is characterised in that:
In step (1), the mass ratio of water and cupric sulfate pentahydrate in copper-bath is 3.3~3.8:1；With five water sulfuric acid
The copper-bath quality and ammonium hydroxide mass ratio of copper meter are 5~18:1, and mixing speed is 110~300rpm；And ammonium hydroxide
Flow acceleration is 0.1~1.5ml/min, and stream continues 15~60min of stirring after adding；With
In step (2), the mass ratio of water and sodium hydroxide in sodium hydroxide solution is 1.6~2.0:1；With five water sulfuric acid
The copper-bath quality and sodium hydroxide mass ratio of copper meter are 5~6:1, and mixing speed is 110~300rpm；And hydrogen-oxygen
The flow acceleration for changing sodium solution is 2~8ml/min, and stream is passed through compressed gas time after adding is 1~3 hour.
8. preparation method according to claim 7, it is characterised in that:
In step (3), the slurries that step (2) is obtained are filtered, and gained filtrate cycle is filtered, until filtrate is limpid, are used
Compressed gas dries up gained filter cake, and compressed gas therein is compressed air.
9. preparation method according to claim 8, which is characterized in that in step (4), by the filter after step (3) drying
Cake, which uses, is washed to filtrate pH value as 7~7.5, then is dried up the filter cake after washing with compressed gas, and compressed gas therein is
Compressed air；In step (5), heating temperature is 108~112 DEG C, and heating time is 30~60 hours；In step (6), mix
Closing temperature is 5~70 DEG C, and crushing temperature is 5~70 DEG C.
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