CN115920897A - Metal catalyst and preparation method and application thereof - Google Patents
Metal catalyst and preparation method and application thereof Download PDFInfo
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- CN115920897A CN115920897A CN202211687315.9A CN202211687315A CN115920897A CN 115920897 A CN115920897 A CN 115920897A CN 202211687315 A CN202211687315 A CN 202211687315A CN 115920897 A CN115920897 A CN 115920897A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 102
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- 239000007791 liquid phase Substances 0.000 claims abstract description 27
- 230000020477 pH reduction Effects 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012445 acidic reagent Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000003917 TEM image Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- 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
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Abstract
The invention discloses a metal catalyst, a preparation method and application thereof, wherein the carrier of the metal catalyst is Al 2 O 3 The active component is Co and/or Ni; wherein the molar ratio of metal atoms to Al atoms in the metal catalyst is 1:5-40; and/or, the Al 2 O 3 Modifying by acidification treatment. The metal catalyst has excellent furfural liquid phase hydrogenation performance, the conversion rate of furfural is as high as 100% and the yield of 2-methylfuran is as high as 99% in the reaction of preparing 2-methylfuran by furfural liquid phase hydrogenation, and the preparation method of the catalyst only needs low-temperature reduction under a hydrogenation reagent, so that the preparation process is simple, green and environment-friendly.
Description
Technical Field
The invention relates to the field of nano catalysts, in particular to a metal catalyst and a preparation method and application thereof.
Background
The 2-methylfuran is an important chemical raw material, has wide application prospect, can be used for organic solvents and organic synthesis intermediates, and has important application in the fields of chemical industry, medicines, pesticides and energy. In the industry, the chromium and copper catalysts are generally utilized to catalyze the furfural conversion to prepare 2-methylfuran. Because the chromium pollutes the environment seriously in the reaction treatment process, if the chromium is discharged without treatment, the chromium exceeds the standard for soil and underground water, and the chromium is absorbed by human bodies to cause irreversible damage. Meanwhile, the copper-based catalyst has many defects in the catalytic reaction for preparing 2-methylfuran by catalytic hydrogenation of furfural, such as low yield and selectivity of 2-methylfuran, easy loss of Cu particles in the reaction process, more side reactions, and poor recycling effect of the catalyst.
The influence of Cu species in catalyzing furfural to prepare 2-methylfuran is studied in the literature (Applied Catalysis B: environmental,2021,282, 119576), and the effectiveness of Cu on the reaction is verified. Cu/SiO 2 The catalyst is mainly used for furfural hydrogenation reaction, but because of SiO 2 Is a neutral substance and the interaction with the active component is not tight enough, so that the performance of catalyzing furfural is still to be improved. In the literature (Catalysis Today,2021,365 2 The noble metal Pd is added into the catalyst system, so that the yield of the 2-methylfuran is improved. However, the catalyst also suffers from instability of the active component during the reaction, resulting in a decrease in catalyst performance. This makes it important to study the preparation process of the catalyst and to regulate the interaction between the active component and the support to improve the catalyst performance.
Disclosure of Invention
The invention aims to provide a metal catalyst, a preparation method and an application thereof, the metal catalyst has excellent furfural liquid phase hydrogenation performance, the conversion rate of furfural is up to 100% and the yield of 2-methylfuran is up to 99% in the reaction of preparing 2-methylfuran by furfural liquid phase hydrogenation, and the preparation method of the catalyst only needs low-temperature reduction under a hydrogenation reagent, and the preparation process is simple, green and environment-friendly.
In order to achieve the above object, the present invention provides a metal catalystThe carrier of the metal catalyst is Al 2 O 3 The active component is Co and/or Ni;
wherein said Al is 2 O 3 The modification is carried out by organic acid acidification treatment.
The invention also provides a preparation method of the metal catalyst, which comprises the following steps:
1) Mixing Al 2 O 3 Acidifying, filtering, washing and drying to obtain carrier Al 2 O 3 ；
2) Dissolving metal salt in solvent, adding carrier Al 2 O 3 Adding a reducing agent to obtain a mixed solution for reaction, and carrying out second filtration, second washing and second drying to obtain a metal catalyst;
wherein the metal salt is Co salt and/or Ni salt.
The invention further provides an application of the metal catalyst in a reaction for preparing 2-methylfuran by furfural liquid-phase hydrogenation.
The invention further provides a method for preparing 2-methylfuran by hydrogenating furfural, which comprises the following steps: in a hydrogen environment, catalyzing furfural to perform liquid-phase hydrogenation reaction on a miniature slurry bed reaction device by using a metal catalyst to convert furfural into 2-methylfuran;
wherein the metal catalyst is the metal catalyst of claim 1 or 2; and/or the presence of a gas in the atmosphere,
the mass concentration of the furfural is 0.01-0.05g/mL; and/or the presence of a gas in the gas,
the pressure of the hydrogen is 0.6-1MPa; and/or the presence of a gas in the gas,
the liquid phase hydrogenation reaction comprises the following steps: the temperature is 180-260 ℃ and the time is 2-6h; preferably at a temperature of 220-240 ℃ for 4h.
In the technical scheme, the Al is modified by treating with organic acid 2 O 3 Carrier, effectively improves Al 2 O 3 The surface acidic group of the carrier is special, which is beneficial to promoting Al 2 O 3 The action of the carrier and Ni or Co; on the other hand, the catalyst is prepared by adopting a liquid-phase in-situ reduction method,the thermal agglomeration of active components of the catalyst and the reduction of the number of active centers can be effectively avoided, and meanwhile, the method only needs to be carried out at low temperature, so that the preparation period of the catalyst can be shortened and the energy consumption can be effectively reduced; and the prepared catalyst shows excellent furfural liquid phase hydrogenation performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows Co/Al prepared in example 1 2 O 3 -N (1;
FIG. 2 shows Co/Al prepared in example 1 2 O 3 -Transmission Electron Micrograph (TEM) of N (1;
FIG. 3 shows Ni/Al prepared in example 6 2 O 3 -a (1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a metal catalyst, the carrier of which is Al 2 O 3 The active component is Co and/or Ni;
wherein said Al is 2 O 3 The modification is carried out by organic acid acidification treatment.
The metal catalyst of the invention has excellent furfural liquid phase hydrogenation performance, and furfural can realize complete conversion.
The molar ratio of metal atoms to Al atoms according to a preferred embodiment of the present invention may be selected within a wide range, but for better catalytic performance of the catalyst the molar ratio of metal atoms to Al atoms in the metal catalyst is 1:5-40.
The invention also provides a preparation method of the metal catalyst, which comprises the following steps:
1) Mixing Al 2 O 3 Acidifying, filtering, washing and drying to obtain carrier Al 2 O 3 ；
2) Dissolving metal salt in solvent, adding carrier Al 2 O 3 Adding a reducing agent to obtain a mixed solution for reaction, and carrying out second filtration, second washing and second drying to obtain a metal catalyst;
wherein the metal salt is a Co salt and/or a Ni salt.
In the preparation method of the catalyst, the catalyst only needs to be reduced at low temperature under a hydrogenation reagent, and the preparation process is simple, green and environment-friendly.
According to a preferred embodiment of the invention, the conditions of the acidification can be selected within wide limits, but in order to improve the support Al 2 O 3 Surface acidic group characteristics, promoting the action of the carrier and Ni or Co, in step 1), the acidification treatment comprises the following steps: treating in an acidic reagent at 80-150 deg.C for 1-3h.
According to a preferred embodiment of the invention, the type of acidic reagent can be selected within wide limits, but in order to support Al as carrier 2 O 3 The surface acidic group is effectively improved, and the acidic agent is at least one of citric acid, formic acid and acetic acid.
According to a preferred embodiment of the invention, the concentration of the acidic reagent can be wideSelected within the range, but in order to support Al 2 O 3 The modification is complete, and the mass fraction of the acidic reagent is 10-30%.
According to a preferred embodiment of the present invention, the kind of the metal salt may be selected from a wide range, but in order to make the catalyst have more excellent catalytic hydrogenation performance, the metal salt is at least one of Co nitrate, co halide, co acetate, ni nitrate, ni halide and Ni acetate in step 2).
According to a preferred embodiment of the present invention, the kind of the reducing agent may be selected within a wide range, but in order that the catalyst may be rapidly reduced at a low temperature, the reducing agent is sodium borohydride and/or potassium borohydride in step 2).
According to a preferred embodiment of the present invention, the kind of the solvent in step 2) can be selected from a wide range, but in order to allow the reduction reaction to proceed rapidly and completely, the solvent in step 2) is deionized water.
According to a preferred embodiment of the invention, the reaction conditions in step 2) can be selected within wide limits, but in order to allow better reactive bonding of the support and the metal atoms, the reaction conditions in step 2) include: the mixed solution is sealed by a cover and stirred for 3-24h at the temperature of 40-80 ℃.
According to a preferred embodiment of the present invention, in step 2), the conditions of the second washing include conditions that can be selected within a wide range, but in order to make the catalyst possess better catalytic hydrogenation performance, in step 2), the conditions of the second washing include: the filtered product was washed to neutrality with deionized water.
The invention further provides an application of the metal catalyst in a reaction for preparing 2-methylfuran by furfural liquid-phase hydrogenation.
The invention further provides a method for preparing 2-methylfuran by hydrogenating furfural, which comprises the following steps: in a hydrogen environment, catalyzing furfural to perform liquid-phase hydrogenation reaction on a miniature slurry bed reaction device by using a metal catalyst to convert furfural into 2-methylfuran;
wherein, the metal catalyst is the metal catalyst prepared by the preparation method;
according to a preferred embodiment of the present invention, the mass concentration of furfural may be selected within a wide range, but for higher conversion efficiency of the reaction, the mass concentration of furfural is 0.01 to 0.05g/mL.
According to a preferred embodiment of the invention, the pressure of the hydrogen can be chosen within wide limits, but in order to enable complete conversion of furfural into 2-methylfuran, the pressure of the hydrogen is between 0.6 and 1MPa.
According to a preferred embodiment of the present invention, the conditions of the liquid phase hydrogenation reaction may be selected within a wide range, but in order to allow complete conversion of furfural into 2-methylfuran, the conditions of the liquid phase hydrogenation reaction include: the temperature is 180-260 ℃ and the time is 2-6h.
According to a preferred embodiment of the present invention, the conditions of the liquid phase hydrogenation reaction can be selected within a wide range, but in order to allow the complete conversion of furfural into 2-methylfuran, the conditions of the liquid phase hydrogenation reaction include: the temperature is 220-240 ℃ and the time is 4h.
The application of the metal catalyst in the reaction of preparing 2-methylfuran by furfural liquid phase hydrogenation has the advantages that the conversion rate of furfural is up to 100 percent, and the yield of 2-methylfuran is up to 99 percent.
The present invention will be described in detail below by way of examples. In the following examples, the drugs and medicaments are all conventional commercial products.
Example 1
(1) Weighing 10g of Al 2 O 3 Placing the powdery small particles in 10% citric acid solution, acidifying at 100 ℃ for 3h, then washing with deionized water, and drying at 110 ℃ for later use.
(2) 2.31g of cobalt nitrate hexahydrate is weighed, fully dissolved in 15mL of deionized water and mixed with the Al treated in the step (1) 2 O 3 Fully stirring and mixing the carrier for 0.5h, adding sodium borohydride, covering and sealing, stirring for 12h at 40 ℃, cleaning with deionized water to be neutral, placing in a vacuum drier, and drying for 10h at 40 ℃ to obtain Co/Al 2 O 3 -N (1.
As shown in FIG. 2, it can be seen that the particle size distribution was at most 3.5 to 4.0nm and the average particle size was 3.98nm.
Example 2
The procedure and conditions were the same as in example 1 except that 10% citric acid solution was changed to 10% acetic acid solution to obtain Co/Al 2 O 3 Catalyst — a (1.
The TEM image thereof substantially corresponds to example 1.
Example 3
The procedure and conditions were the same as in example 1 except that the mass of cobalt nitrate hexahydrate was changed from 2.31g to 3.46g to obtain Co/Al 2 O 3 Catalyst — a (1.
The TEM image thereof substantially corresponds to example 1.
Example 4
The procedure and conditions were the same as in example 1 except that the mass of cobalt nitrate hexahydrate was changed from 2.31g to 6.92g to obtain Co/Al 2 O 3 Catalyst — a (1.
The TEM image thereof substantially corresponds to example 1.
Example 5
The procedure and conditions were the same as in example 1 except that the mass of cobalt nitrate hexahydrate was changed from 2.31g to 0.87g to obtain Co/Al 2 O 3 Catalyst — a (1.
The TEM image thereof substantially corresponds to example 1.
Example 6
The procedure and conditions were the same as in example 1 except that cobalt nitrate hexahydrate was changed to nickel nitrate in an amount of 1.91g to obtain Ni/Al 2 O 3 -a (1.
As shown in FIG. 3, the particle size distribution was mainly 2.0 to 3.5nm, and the average particle size was 2.97nm.
Example 7
The procedure and conditions were the same as in example 6 except that the mass of nickel nitrate was changed from 1.91g to 2.85g to obtain Ni/Al 2 O 3 Catalyst — a (1.
The TEM image thereof substantially corresponds to example 6.
Example 8
The procedure and conditions were the same as in example 6 except that nickel nitrate was changed to nickel chloride in an amount of 1.56g to obtain Ni/Al 2 O 3 -a (1.
The TEM image thereof substantially corresponds to example 6.
Example 9
The procedure and conditions were the same as in example 7 except that the mass of furfural was changed from 0.5g to 0.25g to obtain Ni/Al 2 O 3 Catalyst — a (1.
The TEM image thereof substantially corresponds to example 6.
Example 10
The procedure and conditions were the same as in example 1 except that the mass of furfural was changed from 0.5g to 0.1g to obtain Ni/Al 2 O 3 -N (1.
The TEM image thereof substantially corresponds to example 6.
Example 11
(1) Weighing 10g of Al 2 O 3 Placing the powdery small particles in 30% citric acid solution, acidifying at 80 deg.C for 1h, washing with deionized water, and drying at 100 deg.C.
(2) 2.31g of cobalt nitrate hexahydrate is weighed, fully dissolved in 15mL of deionized water and mixed with the Al treated in the step (1) 2 O 3 Fully stirring and mixing the carrier for 0.5h, adding potassium borohydride, covering and sealing, stirring for 3h at 80 ℃, cleaning with deionized water to be neutral, placing in a vacuum drier, and drying for 10h at 40 ℃ to obtain Co/Al 2 O 3 -N (1.
The TEM image thereof substantially corresponds to example 1.
Example 12
(1) Weighing 10g of Al 2 O 3 Putting the powdery small particles in 10% citric acid solution, acidifying at 150 ℃ for 3h, then washing with deionized water, and drying at 120 ℃ for later use.
(2) 2.31g of cobalt nitrate hexahydrate is weighed, fully dissolved in 15mL of deionized water and mixed with the Al treated in the step (1) 2 O 3 Fully stirring and mixing the carrier for 0.5h, adding sodium borohydride, covering and sealing, stirring for 24h at 40 ℃, cleaning with deionized water to be neutral, placing in a vacuum drier, and drying for 10h at 40 ℃ to obtain Co/Al 2 O 3 -N (1.
The TEM image thereof substantially corresponds to example 1.
Comparative example 1
The procedure and conditions were the same as in example 1 except that the 10% citric acid solution was changed to 10% sodium hydroxide solution to obtain Co/Al 2 O 3 -S (1.
Comparative example 2
The procedure and conditions were as in example 1, al 2 O 3 Obtaining Co/Al without pre-treatment with 10% citric acid solution 2 O 3 -NE (1.
Application example 1
Respectively weighing 0.2g of catalysts Cat1-Cat5, cat 10-12, cat A and Cat B,0.5g of furfural and 10mL of isopropanol, placing the catalysts into a slurry bed reactor, replacing air in the reactor by using hydrogen, maintaining the pressure at 1.0MPa, controlling the reaction temperature at 220 ℃, heating and stirring for 4 hours for reaction, cooling to room temperature, collecting filtrate, and analyzing products by using gas chromatography, wherein the liquid-phase hydrogenation reaction performance of the furfural is shown in Table 1.
The gas chromatogram of the product of furfural reaction using Cat1, a catalyst prepared in example 1, is shown in fig. 1.
Application example 2
Respectively weighing 0.2g of catalyst Cat 6-9,0.5g of furfural and 10ml of isopropanol, putting the catalyst Cat and the isopropanol into a slurry bed reactor, replacing air in the reactor by using hydrogen, maintaining the pressure at 0.6MPa, controlling the reaction temperature to be 240 ℃, heating and stirring for 4h for reaction, cooling to room temperature, collecting filtrate, and analyzing products by using gas chromatography, wherein the liquid-phase hydrogenation reaction performance of the furfural is shown in Table 1.
TABLE 1 liquid phase hydrogenation of furfural over various catalysts
As can be seen from table 1 above, when the ratio of Co atoms or Ni atoms to Al atoms in the catalyst is in the range of 1.
Further, as shown in the gas chromatogram of the product of the furfural liquid-phase hydrogenation reaction performed by catalyst Cat1 prepared in example 1 of fig. 1, there is no furfural peak, which indicates that furfural is completely converted, and the gas chromatograms of the products of furfural liquid-phase hydrogenation reactions performed by catalysts Cat1 to Cat12 are substantially the same, which are not described herein again.
Meanwhile, the carrier Al in comparative example 1 2 O 3 Cat A obtained by alkaline treatment and carrier Al in comparative example 2 2 O 3 In the liquid-phase hydrogenation reaction of furfural, the conversion rate of furfural in the untreated catalyst Cat B is respectively 97 percent and 88 percent, and the yield of 2-methylfuran is respectively 53 percent and 27 percent, which are both less than that of the carrier Al in the invention 2 O 3 The conversion rate of furfural and the yield of 2-methylfuran of the catalyst obtained by the acid treatment were found to be good for the carrier Al in the present invention 2 O 3 The acid treatment is carried out, so that Al is effectively improved 2 O 3 The surface acidic group characteristics of the carrier are beneficial to promoting the action of the carrier and Ni or Co, so that the prepared catalyst shows excellent furfural liquid phase hydrogenation performance.
Furthermore, as can be seen from the TEM images of the Co catalyst and the Ni catalyst in fig. 2 to 3, the catalyst prepared by the present invention has a small particle size, the average particle size of the Co catalyst is 3.98nm, and the average particle size of the Ni catalyst is 2.97nm, indicating that the catalyst of the present invention has good dispersibility.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The metal catalyst is characterized in that the carrier of the metal catalyst is Al 2 O 3 The active component is Co and/or Ni;
wherein said Al is 2 O 3 The modification is carried out by organic acid acidification treatment.
2. The metal catalyst according to claim 1, wherein the molar ratio of Co and/or Ni to Al in the metal catalyst is 1:5-40.
3. A method for preparing the metal catalyst of claim 1 or 2, comprising:
1) Mixing Al 2 O 3 Acidifying, filtering, washing and drying to obtain carrier Al 2 O 3 ；
2) Dissolving metal salt in solvent, adding carrier Al 2 O 3 Adding a reducing agent to obtain a mixed solution for reaction, and performing second filtration, second washing and second drying to obtain a metal catalyst;
wherein the metal salt is Co salt and/or Ni salt.
4. The preparation method according to claim 3, wherein in step 1), the acidification treatment comprises: treating in an acidic reagent at 80-150 deg.C for 1-3h.
5. The production method according to claim 4, wherein the acidic agent is at least one of citric acid, formic acid, and acetic acid; and/or the presence of a gas in the gas,
the mass fraction of the acidic reagent is 10-30%.
6. The production method according to claim 3 to 5, wherein in step 2), the metal salt is at least one of Co nitrate, co halide, co acetate, ni nitrate, ni halide, and Ni acetate.
7. The production method according to claims 3 to 6, wherein, in step 2), the reducing agent is sodium borohydride and/or potassium borohydride; and/or the presence of a gas in the gas,
the solvent is deionized water.
8. The production method according to claims 2 to 7, wherein, in step 2), the reaction conditions include: covering the mixed solution, sealing, and stirring at 40-80 deg.C for 3-24 hr; and/or the presence of a gas in the gas,
the conditions of the second washing include: the filtered product was washed to neutrality with deionized water.
9. Use of the metal catalyst of claim 1 or 2 in the liquid phase hydrogenation of furfural to 2-methylfuran.
10. A method for preparing 2-methylfuran by hydrogenating furfural is characterized by comprising the following steps: in a hydrogen environment, catalyzing furfural to perform liquid-phase hydrogenation reaction on a miniature slurry bed reaction device by using a metal catalyst to convert furfural into 2-methylfuran;
wherein the metal catalyst is the metal catalyst of claim 1 or 2; and/or the presence of a gas in the gas,
the mass concentration of the furfural is 0.01-0.05g/mL; and/or the presence of a gas in the atmosphere,
the pressure of the hydrogen is 0.6-1MPa; and/or the presence of a gas in the gas,
the conditions of the liquid phase hydrogenation reaction include: the temperature is 180-260 ℃ and the time is 2-6h; preferably at a temperature of 220-240 ℃ for 4h.
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