CN109833897A - A method of for produce furfuryl alcohol catalyst and its preparation and production furfuryl alcohol - Google Patents
A method of for produce furfuryl alcohol catalyst and its preparation and production furfuryl alcohol Download PDFInfo
- Publication number
- CN109833897A CN109833897A CN201711216725.4A CN201711216725A CN109833897A CN 109833897 A CN109833897 A CN 109833897A CN 201711216725 A CN201711216725 A CN 201711216725A CN 109833897 A CN109833897 A CN 109833897A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- furfuryl alcohol
- carrier
- producing
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The catalyst and its preparation and the method for producing furfuryl alcohol that the present invention relates to a kind of for producing furfuryl alcohol.Wherein, catalyst is made of the carrier of main active component, auxiliary agent and Passivation Treatment.Wherein main active component is Cu, and auxiliary agent is one or more of alkali metal, alkaline-earth metal and rare-earth oxide, and the carrier of Passivation Treatment is silicon oxide-containing class inorganic carrier.The characteristics of catalyst of the present invention is that used carrier passes through Passivation Treatment, specifically one or more of heat treatment, silanization or etherificate.According to the present invention, for the catalyst using ammonia evaporation induction and deposition precipitation method preparation, preparation method is simple and convenient, low to equipment requirement needed for raw material storage and catalyst preparation, is easy to amplify application on a large scale.Furfural hydrogenation is carried out using catalyst of the invention, shows high furfural conversion per pass, high furfuryl alcohol selectivity, long catalyst life has good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of catalyst for producing furfuryl alcohol and its preparations and the method for producing furfuryl alcohol, belong to biomass conversion
And catalysis technical field.
Background technique
The energy supply and demand contradiction and increasingly harsh environmental requirement being on the rise promote renewable biomass resources conversion
The research utilized.Furfural is a kind of industrial chemicals for being mainly derived from the Wooden Biomass such as agriculture and forestry organic waste material.China is in the world
Maximum furfural production state, but it is extremely limited for the higher value application of furfural.The chosen property hydrogenation reaction of furfural can be with
Prepare the furfuryl alcohol of high added value.Core binder needed for furfuryl alcohol can be used for producing foundary industry, thermostable phenolic resin bonding
Agent, the superior plasticizer of cold tolerance, synthetic fibers, polyurethane foam, tetrahydrofurfuryl alcohol etc..In addition, furfuryl alcohol is also varnish, pigment
Deng good solvent, be produce pesticide, fragrance and medicine intermediate.Therefore, carry out furfural selective hydrogenation and prepare furfuryl alcohol
Study the extensive concern by academia and industrial circle.
Furfural hydrogenation to furfural alcohol has two kinds of techniques of liquid phase method and vapor phase method.Using the liquid phase method of Cu-Cr catalyst 1948
Year realizes industrialization.The features such as liquid phase method has temperature higher, and catalyst separation regeneration is difficult, the high requirements on the equipment.Compared to it
Under, vapor phase method has the advantages such as reaction temperature is low, pressure is low, inhibits deep hydrogenation, catalyst recycling simple.Currently, vapor phase method
Mainly there are copper silicon systems and copper chromium system using catalyst, although copper chromium-based catalysts have highly selective and high stability advantage,
But heavy metal Cr because can cause environmental pollution with human body bring harm due to limit the development of Cu-Cr catalyst.Thus, nothing
Pollute research hotspot and development trend that harmless Chrome-free copper-based catalysts are developed into gas phase hydrogenation of furfural catalyst.
Patent CN 101423505A discloses the Cu catalyst of MgO load, catalyst show high furfural conversion ratio and
Furfuryl alcohol selectivity, does not refer to the stability of catalyst.CN 1410161A discloses the Cu-Co bimetallic catalyst of MgO load,
The method for preparing catalyst that the invention is related to is simple, but furfuryl alcohol yield is lower.Patent CN 1149507A and CN 1876233A
Individually disclose the CuO-ZnO-Al of preparation by furfural gas phase hydrogenation furfuryl alcohol2O3Alkaline earth oxide-transition metal oxide and
CuO-Ce2O3-Fe2O3-SiO2-TiO2Five yuan of chromium-free catalysts, although they all show excellent catalytic performance, group
The cumbersome preparation uncontrollability for leading to the catalyst of complicated and preparation process is divided to increase and invest increase.Patent CN
103007941A discloses a kind of copper oxide-monox composite oxides catalyst, although catalyst composition it is simple and have compared with
High furfural conversion ratio and furfuryl alcohol selectivity, but the use of sodium hydroxide is catalyst preparation process band in catalyst preparation process
Alkaline waste water processing problem is carried out.Shanxi coalification institute (Catal.Sci.Technol., 2017,7,1880-1891) reports one
Kind silica solution is the cupric silicate presoma base copper silicon furfuraldehyde hydrogenation catalyst system of silicon source, is found under high-speed, furfural conversion
Rate and furfuryl alcohol selectivity are related with metallic copper content, but do not provide catalyst stability, simultaneously because the shakiness of silica solution
It is qualitative that it is stored and using certain limitation is brought, limits the large scale preparation of catalyst.
To sum up, existing copper-based chromium-free catalyst produces furfuryl alcohol activity, selectivity, stability and catalyst system in furfural hydrogenation
There is still a need for improvement for the one or more aspects such as standby.
Summary of the invention
For the deficiencies in the prior art, the purpose of the present invention is to provide a kind of for producing the catalyst of furfuryl alcohol
And its method of preparation and production furfuryl alcohol, the method for the catalyst and furfuryl alcohol production may be implemented one in following or more
: (1) catalyst activity is improved, (2) improve the furfural treating capacity of catalyst, and (3) reduce furfural loss, and (4) simplify catalyst
Regeneration condition, the production of (5) furfuryl alcohol realize that (6) catalyst composition is simple, and raw material storage request is low under more low reaction temperatures, fit
In large-scale production.
The inventors found that: carrier selection with reactivity worth have it is close contact, it is white after Passivation Treatment
Carbon black, SiO2, the carrier surface hydroxyl quantity decrease to some degree rich in oxidation silicon components such as SBA-15 and MCM-41, drop
The low surface acidity of catalyst, reduces raw material furfural and product furfuryl alcohol in the polymerization of catalyst surface, reduces furfural
Catalyst inactivation is inhibited while loss.After carrier loaded main active component and auxiliary agent after Passivation Treatment, in furfural gas
While showing high activity in addition hydrogen production furfuryl alcohol reaction, the high furfuryl alcohol selectivity of catalyst is maintained, is reduced anti-
The loss of furfural during answering, extends the service life of catalyst.Meanwhile it being prepared using the deposition-precipitation method of ammonia evaporation induction
Catalyst ensure that interaction strong between metal and carrier, promote metallic copper and auxiliary agent high dispersive in carrier surface,
A possibility that providing high reactivity and cyclic regeneration.Using the use of silica type solid carrier, especially white carbon black,
The storage of silica solution unstability bring is avoided and using limitation, catalyst has been made to produce large-scale application preferably.As a result, may be used
To realize one or more of above-mentioned purpose.
Therefore, on the one hand, the present invention provides a kind of for producing the catalyst of furfuryl alcohol, it is characterised in that: the catalyst
It is made of the carrier of main active component, auxiliary agent and Passivation Treatment, wherein main active component is Cu, auxiliary agent is alkali metal, alkaline earth gold
One or more of category and rare-earth oxide, the carrier of Passivation Treatment are silicon oxide-containing class inorganic carrier.
In a preferred embodiment, the alkali metal is one or more of Li, Na and K.
In a preferred embodiment, the alkaline-earth metal is one or more of Mg, Ca, Sr and Ba.
In a preferred embodiment, the rare earth metal includes but are not limited in La, Ce, Pr, Nd, Sm and Eu
It is one or more of.
In a preferred embodiment, the main active component Cu account for 1.0 in the total catalyst weight~
50.0%, the auxiliary agent accounts for 0.1~30.0% in the total catalyst weight.
In a preferred embodiment, the carrier of the Passivation Treatment includes but are not limited to: white carbon black, MCM-41,
SiO2Microballoon, SiO2One or more of nano particle and SBA-15.
In a preferred embodiment, the method for the inorganic carrier Passivation Treatment is high-temperature heat treatment, specific next
It says, carrier is no less than 10min in the roasting temperature not less than 600 DEG C.
In a preferred embodiment, the method for the inorganic carrier Passivation Treatment is silanization treatment, specific next
It says, carrier is contacted 0.5 to 48 hour with silylating reagent at 80~200 DEG C.
In a preferred embodiment, the method for the inorganic carrier Passivation Treatment is etherification process, specifically,
Carrier is contacted 0.5 to 48 hour with etherifying reagent.
In a preferred embodiment, the silylating reagent includes but are not limited to: trim,ethylchlorosilane, dichloro two
One of methyl-monosilane, trichloromethyl silane, hexamethyldisilazane, aminopropyl triethoxysilane and bromotrimethylsilane
Or it is several.
In a preferred embodiment, the etherifying reagent includes but are not limited to: methanol, ethyl alcohol, propyl alcohol, isopropyl
One or more of alcohol, ethylene glycol, butanol, amylalcohol, propylene glycol, glycerine, butanediol, hexanol and phenol.
The present invention also provides a kind of methods for preparing above-mentioned catalyst, which is characterized in that the method is ammonia induction
Deposition-precipitation method, specifically includes the following steps:
A) by silica type inorganic carrier (carbon black, MCM-41, SiO2Microballoon, SiO2Nano particle and SBA-15) carry out it is blunt
Change processing；
B) in deionized water by the dissolving metal salts of required metal component, ammonia is passed through to saturation；
C) carrier that Passivation Treatment in a) obtains is added in b) metal salt solution, is uniformly mixed；
D) heat mixture system c), the ammonia in removing system；
E) mixture pH is filtered close to after neutrality, and washing obtains filter cake.
F) filter cake obtains catalyst through thermal activation treatment.
In a preferred embodiment, metal salt described in step b) is nitrate, carbonate or oxalates.
In a preferred embodiment, heat treatment temperature described in step d) is 50~100 DEG C.
In a preferred embodiment, heat treatment method described in step f) is: 60~150 DEG C of drying 2~48h, 350
~750 DEG C of 2~48h of roasting.
On the other hand, the present invention also provides a kind of methods for producing furfuryl alcohol, which is characterized in that described above to urge
In the presence of agent, furfural carries out hydrogenation reaction, highly selective generation furfuryl alcohol in fixed bed reactors.
In a preferred embodiment, the method is implemented under the following conditions: temperature is 90~300 DEG C, and pressure is
0.01~2.0MPa, furfural air speed are 0.01~10g/g- catalyst/h, and the molar ratio of hydrogen and furfural is 1~50.
In a preferred embodiment, the catalyst used is lived under the atmosphere of hydrogen before the use
Change, temperature is 150~500 DEG C, and the time is 0.5~48h.
Compared with prior art, the present invention the beneficial effect is that: white carbon black, SiO in catalyst of the present invention2、
The carrier rich in oxidation silicon components such as SBA-15 and MCM-41 is by the side such as high-temperature heat treatment, silanization treatment or etherification process
Formula is passivated.There are a large amount of hydroxyl, especially white carbon black carrier surfaces to have greatly on carrier surface rich in oxidation silicon components
The hydroxyl of amount exists, and makes catalyst surface that certain acidic environment be presented, and is conducive to furfural and furfuryl alcohol polymerization generates carbon distribution, increase
The loss of furfural accelerates catalyst inactivation simultaneously.And the carrier surface hydroxyl quantity after Passivation Treatment have it is a degree of
It reduces, reduces the surface acidity of catalyst, reduce raw material furfural and product furfuryl alcohol in the polymerization of catalyst surface, reduce
Catalyst inactivation is inhibited while the loss of furfural.After carrier loaded main active component and auxiliary agent after Passivation Treatment,
While showing high activity in furfural hydrogasification producing furancarbinol reaction, the high furfuryl alcohol selectivity of catalyst, drop are maintained
The loss of furfural, extends the service life of catalyst in low reaction process.The solid oxidations silicon class carrier such as white carbon black makes
With overcoming silica solution class siliconoxide precursor using bring deactivation of support and handle infeasible barrier, while avoiding silicon
Trouble in the storage of colloidal sol unstability bring and use process.Meanwhile it being prepared using the deposition-precipitation method of ammonia evaporation induction
Catalyst ensure that interaction strong between metal and carrier, promote metallic copper and auxiliary agent high dispersive in carrier surface,
A possibility that providing high reactivity and cyclic regeneration.
Specific embodiment
Below by specific embodiment, the present invention will be further described, and the content and percentage in the application press quality
Meter.
Embodiment 1
40%Cu-6%CaO-2%CeO2The preparation and application of/SBA-15 catalyst
10g SBA-15 powder is placed in 200ml dry toluene, 2g trim,ethylchlorosilane, reflow treatment 12h, mistake is added
Filter obtains solid, is washed to filtrate using ethanol water without chlorine.By the solid of acquisition in 120 DEG C of drying 12h.By 14.62g
Cu(NO3)2·3H2O、1.79g Ca(NO3)2·4H2O and 0.49gCe (NO3)2·6H2O is dissolved in 50ml deionized water, will
High-purity ammon gas pulse is passed through in above-mentioned solution, and after system pH no longer increases, stopping is passed through ammonia, and the solution system of acquisition is stirred
Mix processing 20min.It weighs the SBA-15 powder that the above-mentioned silanization treatment of 5g obtains to be added in solution, stirs 4h at room temperature.It will
The mixture system stirred evenly is transferred in 80 DEG C of water-baths, is continued the ammonia in stirring removing mixture, is reduced to system pH
To close to after neutrality, mixture is removed into water-bath cooling.It is cooled to room temperature to system, filtering obtains filter cake.Deionized water washing
After filter cake 5 times, by filter cake in 120 DEG C of drying 12h, then in 450 DEG C of roasting 4h, tabletting screening obtains catalyst, is denoted as A.
Catalyst in 300 DEG C of hydrogen before use, restore 5 hours.After reactor batch temperature is down to 130 DEG C, by furfural
It is squeezed into reactor with the rate of 1.4g/h, adjusts H2/ furfural molar ratio is 10, after reaction 48 hours, sampling analysis.Reaction knot
Fruit is listed in table 1.
Embodiment 2
10%Cu-1%MgO-2%CeO2The preparation and application of/MCM-41 catalyst
10g MCM-41 powder is placed in 200ml dry toluene, 3g aminopropyl triethoxysilane is added, 110 DEG C are returned
Stream process 12h, filtering are obtained solid, are washed to filtrate using ethanol water without chlorine.The solid of acquisition is dried at 120 DEG C
12h.By 2.18g Cu (NO3)2·3H2O、0.37g Mg(NO3)2·6H2O and 0.29g Ce (NO3)2·6H2O is dissolved in 50ml
In deionized water, high-purity ammon gas pulse is passed through in above-mentioned solution, after system pH no longer increases, stopping is passed through ammonia, will obtain
The solution system stir process 20min obtained.The MCM-41 powder for weighing 5g Passivation Treatment is added in solution, is stirred at room temperature
4h.The mixture system stirred evenly is transferred in 80 DEG C of water-baths, continues the ammonia in stirring removing mixture, to system pH
It is reduced to close to after neutrality, mixture is removed into water-bath cooling.It is cooled to room temperature to system, filtering obtains filter cake.Deionized water
After washing filter cake 5 times, by filter cake in 120 DEG C of drying 12h, then in 400 DEG C of roasting 8h, tabletting screening obtains catalyst, is denoted as
B.Evaluating catalyst scheme is referring to embodiment 1.Reaction result is listed in table 1.
Embodiment 3
20%Cu-4%CaO-2%CeO2The preparation and application of/white carbon black catalyst
By 10g white carbon black in air atmosphere, 750 DEG C of calcination process 1h obtain the white carbon black of passivation.By 5.14g Cu
(NO3)2·3H2O、0.84g Ca(NO3)2·4H2O and 0.34g Ce (NO3)2·6H2O is dissolved in 50ml deionized water, will be high
Pure ammonia pulse is passed through in above-mentioned solution, and after system pH no longer increases, stopping is passed through ammonia, and the solution system of acquisition is stirred
Handle 20min.The white carbon black for weighing 5g Passivation Treatment is added in solution, stirs 4h at room temperature.The mixture that will be stirred evenly
System is transferred in 80 DEG C of water-baths, is continued the ammonia in stirring removing mixture, is reduced to after system pH close to after neutrality, will mix
It closes object and removes water-bath cooling.It is cooled to room temperature to system, filtering obtains filter cake.After deionized water is washed filter cake 5 times, filter cake is existed
120 DEG C of drying 12h, then in 600 DEG C of roasting 3h, tabletting screening obtains catalyst, is denoted as C.Evaluating catalyst scheme is referring to reality
Apply example 1.Reaction result is listed in table 1.
Embodiment 4
The preparation and application of 20%Cu-4%CaO/ white carbon black catalyst
By 10g white carbon black in air atmosphere, 750 DEG C of calcination process 1h obtain the white carbon black of passivation.By 5.00g Cu
(NO3)2·3H2O and 0.82g Ca (NO3)2·4H2O is dissolved in 50ml deionized water, high-purity ammon gas pulse is passed through above-mentioned molten
In liquid, after system pH no longer increases, stopping is passed through ammonia, by the solution system stir process 20min of acquisition.Weigh 5g passivation
The white carbon black of processing is added in solution, stirs 4h at room temperature.The mixture system stirred evenly is transferred in 80 DEG C of water-baths,
Continue the ammonia in stirring removing mixture, be reduced to after system pH close to after neutrality, mixture is removed into water-bath cooling.To body
System is cooled to room temperature, and filtering obtains filter cake.After deionized water is washed filter cake 5 times, by filter cake in 120 DEG C of drying 12h, then exist
500 DEG C of roasting 3h, tabletting screening obtain catalyst precarsor, are denoted as F.Evaluating catalyst scheme is referring to embodiment 1.Reaction result column
In table 1.
Embodiment 5
20%Cu-4%CaO-4La2O3The preparation and application of/white carbon black catalyst
By 0.46g La (NO3)2·6H2O is dissolved in 10ml deionized water and is formulated as solution, impregnates sample using the solution
Product F, stands overnight at room temperature, 120 DEG C of drying 12h, and then in 450 DEG C of roasting 4h, tabletting screening obtains catalyst, is denoted as G.It urges
Agent evaluation of programme is referring to embodiment 1.Reaction result is listed in table 1.
Embodiment 6
20%Cu-4%CaO-1Li2The preparation and application of O/ white carbon black catalyst
By 0.15g Li (NO3) be dissolved in 10ml deionized water and be formulated as solution, use solution impregnated sample F, room
It is stood overnight under temperature, 160 DEG C of drying 12h, then in 450 DEG C of roasting 4h, tabletting screening obtains catalyst, is denoted as H.Catalyst is commented
Valence scheme is referring to embodiment 1.Reaction result is listed in table 1.
Embodiment 7
20%Cu-4%CaO-2CeO2The preparation and application of/white carbon black catalyst
10g white carbon black is placed in 200ml dry toluene, 2g trim,ethylchlorosilane, reflow treatment 12h is added, filtering obtains
Solid is obtained, is washed to filtrate using ethanol water without chlorine.By the solid of acquisition in 120 DEG C of drying 12h.By 5.14g Cu
(NO3)2·3H2O、0.84g Ca(NO3)2·4H2O and 0.34gCe (NO3)2·6H2O is dissolved in 50ml deionized water, will be high
Pure ammonia pulse is passed through in above-mentioned solution, and after system pH no longer increases, stopping is passed through ammonia, and the solution system of acquisition is stirred
Handle 20min.The white carbon black for weighing 5g Passivation Treatment is added in solution, stirs 4h at room temperature.The mixture that will be stirred evenly
System is transferred in 80 DEG C of water-baths, is continued the ammonia in stirring removing mixture, is reduced to after system pH close to after neutrality, will mix
It closes object and removes water-bath cooling.It is cooled to room temperature to system, filtering obtains filter cake.After deionized water is washed filter cake 5 times, filter cake is existed
100 DEG C of drying 12h, then in 450 DEG C of roasting 4h, tabletting screening obtains catalyst, is denoted as I.Evaluating catalyst scheme is referring to reality
Apply example 1.Reaction result is listed in table 1.
Embodiment 8
The stability test of catalyst, the catalyst by the method for preparing catalyst preparation in embodiment 3 are anti-in fixed bed
Answer in device, reaction condition: temperature is 383~443K, and pressure 0.1MPa, the liquid air speed of furfural is 0.4g/g- catalyst/h,
H2/ furfural molar ratio was 10, every 12 hours sampling analyses.1000 hours reaction results show that Catalyst Conversion maintains
90% or more, furfuryl alcohol is selectively greater than 98%.
Comparative example 1
The 20%Cu/SiO of silica bead load2Catalyst preparation and application
By 4.75g Cu (NO3)2·3H2O is dissolved in 10ml deionized water and is configured to solution, by the commercialized oxidation of 5g
Silicon bead is added in above-mentioned solution, is stored at room temperature overnight, 120 DEG C of drying 12h are catalyzed then in 450 DEG C of roasting 4h
Agent is denoted as J.Evaluating catalyst scheme is referring to embodiment 1.Reaction result is listed in table 1.
Comparative example 2
20%Cu-4%CaO/SiO is prepared by carrier of silica solution2Catalyst preparation and application
By 4.75g Cu (NO3)2·3H2O and 0.80g Ca (NO3)2·4H2O is dissolved in 50ml deionized water, will be high-purity
Ammonia pulse is passed through in above-mentioned solution, and after system pH no longer increases, stopping is passed through ammonia, at the solution system stirring of acquisition
Manage 20min.It weighs the silica solution that 16.5g silica content is 30% to be added in solution, stirs 4h at room temperature.It will stir evenly
Mixture system be transferred in 80 DEG C of water-baths, continue stirring removing mixture in ammonia, to system pH be reduced to close in
Property after, by mixture remove water-bath cooling.It is cooled to room temperature to system, filtering obtains filter cake.Deionized water is washed filter cake 5 times
Afterwards, by filter cake in 120 DEG C of drying 12h, then in 450 DEG C of roasting 4h, tabletting screening obtains catalyst, is denoted as I.Evaluating catalyst
Scheme is referring to embodiment 1.Reaction result is listed in table 1.
Comparative example 3
The 20%Cu-4%CaO/ white carbon black catalyst preparation and application of the unpassivated processing of carrier
By 4.75g Cu (NO3)2·3H2O and 0.80g Ca (NO3)2·4H2O is dissolved in 50ml deionized water, will be high-purity
Ammonia pulse is passed through in above-mentioned solution, and after system pH no longer increases, stopping is passed through ammonia, at the solution system stirring of acquisition
Manage 20min.The white carbon black for weighing the unpassivated processing of 5g is added in solution, stirs 4h at room temperature.The mixing that will be stirred evenly
Objects system is transferred in 80 DEG C of water-baths, is continued the ammonia in stirring removing mixture, is reduced to after system pH close to after neutrality, will
Mixture removes water-bath cooling.It is cooled to room temperature to system, filtering obtains filter cake.After deionized water is washed filter cake 5 times, by filter cake
In 120 DEG C of drying 12h, then in 450 DEG C of roasting 4h, tabletting screening obtains catalyst, is denoted as K.Evaluating catalyst scheme referring to
Embodiment 1.Reaction result is listed in table 1.
By above-mentioned result it is found that catalyst of the invention can selectively be added under high furfural air speed with efficient catalytic furfural
Hydrogen prepares furfuryl alcohol.Furfural conversion per pass is greater than 90%, and furfuryl alcohol is selectively higher than 98%, and by-product only has 2- methylfuran.It adopts
When being fed with mild furfural, catalyst maintains good stability, furfural conversion ratio in 1000 hours reaction process
90% or more is maintained, furfuryl alcohol is selectively higher than 98.5%.
Comprehensive comparative analysis result above can be assumed that, select the white carbon black class solid oxidation silicon of Passivation Treatment as silicon
Source prepares copper silica-base catalyst using the quiet precipitation method that ammonia induces, and the catalyst is applied in furfural hydrogenation production furfuryl alcohol
It may be implemented one or more in following: (1) improving catalyst activity, (2) improve the furfural treating capacity of catalyst, (3) drop
Low furfural loss, (4) simplify catalyst regeneration conditions, and the production of (5) furfuryl alcohol is realized under more low reaction temperatures, (6) catalyst group
At simple, raw material storage request is low, is suitable for large-scale production.
Above to the present invention have been described in detail, but the invention is not limited to specific embodiment parties described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and deformation can be made.This hair
Bright range is defined by the following claims.
Table 1
Claims (17)
1. a kind of for producing the catalyst of furfuryl alcohol, which is characterized in that the catalyst is by main active component, auxiliary agent and passivation
The carrier of reason forms, wherein main active component is Cu, auxiliary agent is one of alkali metal, alkaline-earth metal and rare-earth oxide
Or it is several, the carrier of Passivation Treatment is silicon oxide-containing class inorganic carrier.
2. according to claim 1 for producing the catalyst of furfuryl alcohol, which is characterized in that the alkali metal is in Li, Na and K
One or more.
3. according to claim 1 for producing the catalyst of furfuryl alcohol, which is characterized in that the alkaline-earth metal is Mg, Ca, Sr
One or more of with Ba.
4. according to claim 1 for producing the catalyst of furfuryl alcohol, which is characterized in that the rare earth metal be La, Ce,
One or more of Pr, Nd, Sm and Eu.
5. according to claim 1 for producing the catalyst of furfuryl alcohol, which is characterized in that the main active component Cu is described
1.0~50.0% are accounted in total catalyst weight, the auxiliary agent accounts for 0.1~30.0% in the total catalyst weight.
6. according to claim 1 for producing the catalyst of furfuryl alcohol, which is characterized in that the carrier of the Passivation Treatment are as follows:
White carbon black, MCM-41, SiO2Microballoon, SiO2One or more of nano particle and SBA-15.
7. according to claim 1 for producing the catalyst of furfuryl alcohol, which is characterized in that the method for the Passivation Treatment is height
Warm processing, specifically, carrier is no less than 10min in the roasting temperature not less than 600 DEG C.
8. according to claim 1 for producing the catalyst of furfuryl alcohol, which is characterized in that the method for the Passivation Treatment is silicon
Alkanisation processing, specifically, carrier is contacted 0.5 to 48 hour at 80-200 DEG C with silylating reagent.
9. according to claim 1 for producing the catalyst of furfuryl alcohol, which is characterized in that the method for the Passivation Treatment is ether
Change processing, specifically, carrier is contacted 0.5 to 48 hour with etherifying reagent.
10. silanization treatment according to claim 8, which is characterized in that the silylating reagent are as follows: trimethylchloro-silicane
Alkane, dichlorodimethylsilane, trichloromethyl silane, hexamethyldisilazane, aminopropyl triethoxysilane and front three bromide silicon
One or more of alkane.
11. etherification process according to claim 9, which is characterized in that the etherifying reagent are as follows: methanol, ethyl alcohol, propyl alcohol,
One or more of isopropanol, ethylene glycol, butanol, amylalcohol, propylene glycol, glycerine, butanediol, hexanol and phenol.
12. a kind of preparation method of catalyst described in claim 1, which is characterized in that catalyst preparation is heavy using ammonia induction
The product precipitation method, the described method comprises the following steps:
A) silica type inorganic carrier is passivated processing；
B) in deionized water by the dissolving metal salts of required metal component, ammonia is passed through to saturation；
C) carrier that Passivation Treatment in a) obtains is added in above-mentioned metal salt solution, is uniformly mixed；
D) heat mixture system in c), the ammonia in removing system；
E) mixture pH is filtered close to after neutrality, and washing obtains filter cake.
F) filter cake obtains catalyst through thermal activation treatment.
13. the preparation method of catalyst according to claim 12, which is characterized in that heat treatment temperature described in step d)
It is 50~100 DEG C.
14. the preparation method of catalyst according to claim 12, which is characterized in that thermal activation treatment side described in step f)
Method is: 60~150 DEG C of drying 2~48h, 350~750 DEG C of 2~48h of roasting.
15. a kind of method for producing furfuryl alcohol, which is characterized in that in the fixed bed reaction for being filled with catalyst described in claim 1
In device, so that furfural and hydrogen is reacted and generate furfuryl alcohol.
16. a kind of method for producing furfuryl alcohol according to claim 15, which is characterized in that the method temperature be 90~
300 DEG C, pressure is 0.01~2.0MPa, and furfuraldehyde liquid air speed is 0.01~10g/g- catalyst/h, mole of hydrogen and furfural
Than carrying out under conditions of being 1~50.
17. producing the method for furfuryl alcohol according to claim 15, which is characterized in that the catalyst is before the use hydrogeneous
It is activated under the atmosphere of gas, temperature is 150~500 DEG C, and the time is 0.5~48 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711216725.4A CN109833897B (en) | 2017-11-28 | 2017-11-28 | Catalyst for producing furfuryl alcohol, preparation method thereof and method for producing furfuryl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711216725.4A CN109833897B (en) | 2017-11-28 | 2017-11-28 | Catalyst for producing furfuryl alcohol, preparation method thereof and method for producing furfuryl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109833897A true CN109833897A (en) | 2019-06-04 |
| CN109833897B CN109833897B (en) | 2022-05-31 |
Family
ID=66881134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711216725.4A Active CN109833897B (en) | 2017-11-28 | 2017-11-28 | Catalyst for producing furfuryl alcohol, preparation method thereof and method for producing furfuryl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109833897B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111632597A (en) * | 2020-04-16 | 2020-09-08 | 天津大学 | Copper-silicon catalyst modified by silanization of silane coupling agent containing tertiary amine, and preparation method and application thereof |
| CN112221536A (en) * | 2020-10-15 | 2021-01-15 | 昆山普瑞凯纳米技术有限公司 | Titanium-silicon molecular sieve packaged nano-copper catalyst and preparation method and application thereof |
| CN113713817A (en) * | 2020-05-26 | 2021-11-30 | 中国科学院大连化学物理研究所 | Method for preparing n-propanol by hydrogenation of propionaldehyde under catalysis of nickel-based catalyst |
| CN113908841A (en) * | 2021-10-11 | 2022-01-11 | 华东师范大学 | Application of Cu-based catalyst in preparation of pentanediol through furfuryl alcohol hydrogenolysis |
| CN115007159A (en) * | 2022-06-07 | 2022-09-06 | 中国科学院大连化学物理研究所 | Magnetic supported nickel catalyst and preparation method and application thereof |
| CN115318331A (en) * | 2021-05-10 | 2022-11-11 | 中国科学院大连化学物理研究所 | Catalyst for directly preparing difurfuryl ether by furfural hydrogenation and preparation and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5591873A (en) * | 1994-02-02 | 1997-01-07 | Degussa Aktiengesellschaft | Formed copper catalyst for the selective hydrogenation of furfural to furfuryl alcohol |
| CN102350358A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
| CN103071495A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Palladium metal catalyst comprising silica auxiliary agent, and application thereof |
| CN103071491A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst with large specific surface and low acid amount, and application thereof |
| CN103084201A (en) * | 2012-12-31 | 2013-05-08 | 天津大学 | Copper-based catalyst prepared by ammonia distillation method and application of copper-based catalyst in oxidation carbonylation synthesis of alkyl carbonate |
| CN103418429A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Methane oxygen-free dehydrogenation aromatization catalyst and preparation method thereof |
| CN104672185A (en) * | 2013-11-26 | 2015-06-03 | 中国科学院大连化学物理研究所 | Method for preparing tetrahydrofurfuryl alcohol from furfural by aqueous phase hydrogenation |
| CN105102124A (en) * | 2013-03-27 | 2015-11-25 | 巴斯夫欧洲公司 | Passivation of a zeolite catalyst in a fluidized bed |
| CN105130746A (en) * | 2015-08-05 | 2015-12-09 | 中国科学院兰州化学物理研究所 | Method for producing pentanediol through selective hydrogenolysis of furan derivative |
| CN106582652A (en) * | 2015-10-16 | 2017-04-26 | 上海华谊能源化工有限公司 | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof |
| CN106669754A (en) * | 2017-01-13 | 2017-05-17 | 中国石油化工股份有限公司 | Copper-containing catalyst and preparation method thereof |
| CN106732742A (en) * | 2016-12-23 | 2017-05-31 | 中国石油天然气股份有限公司 | A kind of application of load type palladium catalyst in selective hydrogenation |
| CN107118076A (en) * | 2017-04-12 | 2017-09-01 | 天津大学 | A kind of method that dimethyl adipate gas phase hydrogenation prepares 1,6 hexylene glycols |
-
2017
- 2017-11-28 CN CN201711216725.4A patent/CN109833897B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5591873A (en) * | 1994-02-02 | 1997-01-07 | Degussa Aktiengesellschaft | Formed copper catalyst for the selective hydrogenation of furfural to furfuryl alcohol |
| CN102350358A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
| CN103071495A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Palladium metal catalyst comprising silica auxiliary agent, and application thereof |
| CN103071491A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst with large specific surface and low acid amount, and application thereof |
| CN103418429A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Methane oxygen-free dehydrogenation aromatization catalyst and preparation method thereof |
| CN103084201A (en) * | 2012-12-31 | 2013-05-08 | 天津大学 | Copper-based catalyst prepared by ammonia distillation method and application of copper-based catalyst in oxidation carbonylation synthesis of alkyl carbonate |
| CN105102124A (en) * | 2013-03-27 | 2015-11-25 | 巴斯夫欧洲公司 | Passivation of a zeolite catalyst in a fluidized bed |
| CN104672185A (en) * | 2013-11-26 | 2015-06-03 | 中国科学院大连化学物理研究所 | Method for preparing tetrahydrofurfuryl alcohol from furfural by aqueous phase hydrogenation |
| CN105130746A (en) * | 2015-08-05 | 2015-12-09 | 中国科学院兰州化学物理研究所 | Method for producing pentanediol through selective hydrogenolysis of furan derivative |
| CN106582652A (en) * | 2015-10-16 | 2017-04-26 | 上海华谊能源化工有限公司 | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof |
| CN106732742A (en) * | 2016-12-23 | 2017-05-31 | 中国石油天然气股份有限公司 | A kind of application of load type palladium catalyst in selective hydrogenation |
| CN106669754A (en) * | 2017-01-13 | 2017-05-17 | 中国石油化工股份有限公司 | Copper-containing catalyst and preparation method thereof |
| CN107118076A (en) * | 2017-04-12 | 2017-09-01 | 天津大学 | A kind of method that dimethyl adipate gas phase hydrogenation prepares 1,6 hexylene glycols |
Non-Patent Citations (5)
| Title |
|---|
| FANG DONG ET AL.: "Highly dispersed Cu nanoparticles as an efficient catalyst for the synthesis of the biofuel 2-methylfuran", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
| JINGWU ET AL.: "Vapor phase hydrogenation of furfural to furfuryl alcohol over environmentally friendly Cu–Ca/SiO2 catalyst", 《CATALYSIS COMMUNICATIONS》 * |
| XINBIN MA ET AL.: "Synthesis of Ethanol via Syngas on Cu/SiO2 Catalysts with Balanced Cu0–Cu+ Sites", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| XINLEI ZHENG ET AL.: "Lanthanum Oxide-Modified Cu/SiO2 as a High-Performance Catalyst for Chemoselective Hydrogenation of Dimethyl Oxalate to Ethylene Glycol", 《ACS CATALYSIS》 * |
| 肖钢，常乐: "《低碳经济与氢能开发》", 30 June 2011, 武汉理工大学出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111632597A (en) * | 2020-04-16 | 2020-09-08 | 天津大学 | Copper-silicon catalyst modified by silanization of silane coupling agent containing tertiary amine, and preparation method and application thereof |
| CN111632597B (en) * | 2020-04-16 | 2021-06-01 | 天津大学 | Copper-silicon catalyst modified by silanization of silane coupling agent containing tertiary amine, and preparation method and application thereof |
| CN113713817A (en) * | 2020-05-26 | 2021-11-30 | 中国科学院大连化学物理研究所 | Method for preparing n-propanol by hydrogenation of propionaldehyde under catalysis of nickel-based catalyst |
| CN113713817B (en) * | 2020-05-26 | 2023-06-27 | 中国科学院大连化学物理研究所 | Method for preparing n-propanol by catalyzing propanal hydrogenation by nickel-based catalyst |
| CN112221536A (en) * | 2020-10-15 | 2021-01-15 | 昆山普瑞凯纳米技术有限公司 | Titanium-silicon molecular sieve packaged nano-copper catalyst and preparation method and application thereof |
| CN112221536B (en) * | 2020-10-15 | 2023-07-04 | 昆山普瑞凯纳米技术有限公司 | Titanium-silicon molecular sieve encapsulated nano copper catalyst and preparation method and application thereof |
| CN115318331A (en) * | 2021-05-10 | 2022-11-11 | 中国科学院大连化学物理研究所 | Catalyst for directly preparing difurfuryl ether by furfural hydrogenation and preparation and application thereof |
| CN115318331B (en) * | 2021-05-10 | 2023-09-26 | 中国科学院大连化学物理研究所 | Catalyst for directly preparing difurfuryl ether by furfural hydrogenation and preparation and application thereof |
| CN113908841A (en) * | 2021-10-11 | 2022-01-11 | 华东师范大学 | Application of Cu-based catalyst in preparation of pentanediol through furfuryl alcohol hydrogenolysis |
| CN115007159A (en) * | 2022-06-07 | 2022-09-06 | 中国科学院大连化学物理研究所 | Magnetic supported nickel catalyst and preparation method and application thereof |
| CN115007159B (en) * | 2022-06-07 | 2023-10-13 | 中国科学院大连化学物理研究所 | Magnetic supported nickel catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109833897B (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109833897A (en) | A method of for produce furfuryl alcohol catalyst and its preparation and production furfuryl alcohol | |
| CN102068986B (en) | Catalyst used in ring-opening hydrogenation reaction of furan derivative | |
| EP2636448B1 (en) | Catalyst for ethanol production via hydrogenation of oxalate esters and preparation method and use thereof | |
| CN110152663A (en) | It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application | |
| CN103007941B (en) | Preparation method for catalyst used in process of preparing furfuryl alcohol by furfural through selective hydrogenation | |
| CN105727930A (en) | Catalyst for propylene production using propane dehydrogenation and preparation method and application of catalyst | |
| CN104226354A (en) | Catalyst for preparing isopropanol by hydrogenating acetone as well as preparation method and application thereof | |
| CN103846082B (en) | A kind of O composite metallic oxide catalyst being supported in mesoporous carbon and application thereof | |
| CN103638963A (en) | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof | |
| CN102600860A (en) | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof | |
| CN101462044A (en) | Catalyst for producing crotonaldehyde | |
| CN104785261A (en) | Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof | |
| CN108816227B (en) | Metal frame derived supported copper-based catalyst and preparation method thereof | |
| CN104230643B (en) | Prepare the method for isopropyl benzene | |
| CN104230641B (en) | Produce the method for isopropyl benzene | |
| CN112191253A (en) | Supported nano metal catalyst, preparation method and application thereof | |
| CN105727954B (en) | A kind of preparation method of synthesis gas preparing natural gas catalyst | |
| CN102872897B (en) | Catalytic agent capable of utilizing furfuryl alcohol liquid-phase catalytic hydrogenation to prepare 1,5- pentanedio as well asl preparation method and application of same | |
| CN105642289A (en) | Preparation method of catalyst for complete methanation of syngas | |
| CN105727972A (en) | Preparation method of catalyst for methane reforming with carbon dioxide to synthetic gas | |
| CN105903471A (en) | Catalyst for preparing MEK (Methyl Ethyl Ketone) by carrying out dehydrogenation on 2-butanol and preparation method and application thereof | |
| CN103357427A (en) | Nano-metal/solid alkali composite catalyst, preparation method and applications | |
| CN106944079B (en) | A kind of preparation method of iso-butane preparing isobutene catalyst | |
| CN103240102B (en) | A kind of copper-metal oxide preparation method and hydrogenolysis of glycerin prepare the method for 1,2-PD | |
| CN105396584B (en) | CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |