CN114433128A - Furfural hydrogenation catalyst, preparation method and application thereof, and method for preparing furfuryl alcohol by furfural gas-phase hydrogenation - Google Patents
Furfural hydrogenation catalyst, preparation method and application thereof, and method for preparing furfuryl alcohol by furfural gas-phase hydrogenation Download PDFInfo
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- CN114433128A CN114433128A CN202011126665.9A CN202011126665A CN114433128A CN 114433128 A CN114433128 A CN 114433128A CN 202011126665 A CN202011126665 A CN 202011126665A CN 114433128 A CN114433128 A CN 114433128A
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- palladium
- furfural
- cobalt
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 162
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 54
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011701 zinc Substances 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012696 Pd precursors Substances 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021118 PdCo Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- YOCPASLAHODCDG-UHFFFAOYSA-N [Cr].[Cu].[La] Chemical compound [Cr].[Cu].[La] YOCPASLAHODCDG-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940078480 calcium levulinate Drugs 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- HCAJEUSONLESMK-UHFFFAOYSA-N cyclohexylsulfamic acid Chemical compound OS(=O)(=O)NC1CCCCC1 HCAJEUSONLESMK-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- AVOLMBLBETYQHX-UHFFFAOYSA-N etacrynic acid Chemical compound CCC(=C)C(=O)C1=CC=C(OCC(O)=O)C(Cl)=C1Cl AVOLMBLBETYQHX-UHFFFAOYSA-N 0.000 description 1
- 229960003199 etacrynic acid Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of furfuryl alcohol production, and discloses a furfural hydrogenation catalyst, a preparation method and application thereof, and a method for preparing furfuryl alcohol by furfural gas-phase hydrogenation. The catalyst comprises a carrier, and an active component and a co-active component which are loaded on the carrier, wherein the active component comprises palladium and cobalt, and the co-active component comprises zinc and/or magnesium; wherein, based on the total weight of the catalyst, the content of palladium is 0.1-10 wt%, and the content of the auxiliary active component calculated by metal elements is 1-15 wt%; the molar ratio of palladium to cobalt is 1: (0.5-10). The catalyst of the invention shows excellent activity, selectivity and stability when used for preparing furfuryl alcohol by furfural gas phase hydrogenation.
Description
Technical Field
The invention relates to the field of furfuryl alcohol production, in particular to a furfural hydrogenation catalyst, a preparation method and application thereof, and a method for preparing furfuryl alcohol by furfural gas-phase hydrogenation.
Background
Furfuryl alcohol is an important chemical raw material, which can be hydrolyzed to prepare ethacrynic acid, which is an intermediate of calcium levulinate as a nutritional medicament; furan-type resin, furfuryl alcohol-urea resin and phenolic resin with better performance can be prepared by taking furfuryl alcohol as a raw material; furfuryl alcohol is again a good solvent for furan resins, varnishes, pigments and rocket fuels; in addition, furfuryl alcohol has wide applications in the synthetic fiber, rubber, pesticide and foundry industries.
At present, the production process of furfuryl alcohol can be divided into a liquid phase hydrogenation process and a gas phase hydrogenation process, the latter has high safety, high furfural purity and long service life of a catalyst, and is a development trend of the process for producing furfuryl alcohol by furfural hydrogenation. At present, the catalyst for producing furfuryl alcohol by furfural gas phase hydrogenation mainly comprises a copper-silicon system and a copper-chromium system, and compared with the copper-silicon system and the copper-chromium system, the catalyst has the problems of low activity, poor structural stability and short service life, and the copper-chromium catalyst is mostly adopted in the current industrial practice.
CN1107079A discloses a catalyst, which comprises the following components by weight: 30-52% of CuO and 28-53% of Cr2O3, 5-15% CaO, and group VIII and zinc oxide. When the catalyst is used for catalysis, under the conditions of reaction temperature of 90-170 ℃, reaction pressure of 0.5MPa and load of 0.1-0.65g furfural/catalyst, the catalyst has higher activity and selectivity at the initial operation stage, but the activity of the catalyst at the later operation stage is not good enough. The space velocity of the furfural liquid is 0.4-0.5h-1The conversion rate of furfural is 95-100%, and the selectivity of 2-methylfuran is 95-97%. However, this catalyst has a major disadvantage in that the catalyst is easily coked and deactivated when the reaction temperature is high.
CN1978051A discloses a catalyst, whose molar composition comprises: 25-55% of CuO and 25-60% of Cr2O35-9% of SiO21-6% of other auxiliary agents. When used for catalysis, the reaction temperature is 120--1The catalyst reflects higher activity and selectivity, but the liquid hourly space velocity is lower and does not give an evaluation of the long run of the catalyst.
CN102631930A discloses a catalyst, which comprises the following components by weight: 26-50% of CuO and 22-40% of Cr2O30.1-11% of Al2O30.1-11% of SiO21-15% of auxiliary agent. When the catalyst is used for catalysis, the reaction temperature is 120-210 ℃, the reaction pressure is 0.001-0.0.5MPa, and the liquid hourly space velocity is 0.4-0.6h-1Under the condition of (2), the selectivity of furfuryl alcohol is low and is only 93.5 percent.
Therefore, a new catalyst preparation method is needed to prepare a hydrogenation catalyst with high catalytic activity and selectivity, difficult coking in the catalytic process and long catalytic life.
Disclosure of Invention
The invention aims to overcome the defects of poor activity and selectivity of a catalyst in furfuryl alcohol preparation by furfural hydrogenation and easy coking and inactivation of the catalyst in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a furfural hydrogenation catalyst, which comprises a carrier, and an active component and a co-active component supported on the carrier, wherein the active component comprises palladium and cobalt, and the co-active component comprises zinc and/or magnesium;
wherein, based on the total weight of the catalyst, the content of palladium is 0.1-10 wt%, and the content of the auxiliary active component calculated by metal elements is 1-15 wt%; the molar ratio of palladium to cobalt is 1: (0.5-10).
In a second aspect, the present invention provides a process for preparing a furfural hydrogenation catalyst, which comprises:
(1) contacting an alumina carrier with a precipitant to obtain a first mixture;
(2) mixing the first mixture with a zinc precursor and/or a magnesium precursor to obtain a second mixture, and performing first drying and first roasting on the second mixture to obtain modified alumina;
(3) under the ultrasonic condition, dipping the modified alumina by dipping liquid of a precursor containing an active component, and then sequentially carrying out second drying and second roasting;
wherein the precursor of the active component comprises a precursor of palladium and a precursor of cobalt;
wherein the palladium precursor, the cobalt precursor and the zinc precursor and/or the magnesium precursor are used in an amount such that the obtained catalyst contains 0.1-10 wt% of palladium and 1-15 wt% of the co-active component calculated by metal elements, based on the total weight of the catalyst; the molar ratio of palladium to cobalt is 1: (0.5-10);
preferably, the content of palladium is 0.5-2 wt% based on the total weight of the catalyst, and the content of the auxiliary active component calculated by metal elements is 1-5 wt%; the molar ratio of palladium to cobalt is 1: (1-5).
In a third aspect, the present invention provides a catalyst prepared by the method of the second aspect.
In a fourth aspect, the invention provides a use of the catalyst of the first or third aspect in the gas phase hydrogenation of furfural to produce furfuryl alcohol.
The fifth aspect of the invention provides a method for preparing furfuryl alcohol by furfural through gas-phase hydrogenation, which comprises the following steps: carrying out contact reaction on the catalyst of the first aspect or the third aspect and furfural in the presence of hydrogen;
wherein the conditions of the contact reaction comprise: the temperature is 90-200 ℃, the pressure is 0.1-5MPa, and the liquid hourly space velocity of the furfural is 0.2-5h-1The molar ratio of the hydrogen to the furfural is (2-15): 1.
the novel PdCo catalyst is prepared and used for the reaction of preparing furfuryl alcohol by furfural gas phase hydrogenation. Compared with the prior art, the catalyst provided by the invention has a regular layered structure, acid-base centers on the surface of a modified carrier (modified alumina) are arranged in order, active components are dispersed on the surface of the carrier in a regular manner, and the active components and the carrier have strong interaction, so that the catalyst has good catalytic performance, and particularly, the catalyst shows excellent activity, selectivity and stability when being used for preparing furfuryl alcohol by furfural gas-phase hydrogenation.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
Detailed Description
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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a furfural hydrogenation catalyst, which comprises a carrier, and an active component and an auxiliary active component which are loaded on the carrier, wherein the active component comprises palladium and cobalt, and the auxiliary active component comprises zinc and/or magnesium;
wherein, based on the total weight of the catalyst, the content of palladium is 0.1-10 wt%, and the content of the auxiliary active component calculated by metal elements is 1-15 wt%; the molar ratio of palladium to cobalt is 1: (0.5-10).
According to some embodiments of the present invention, preferably, the palladium is present in an amount of 0.5 to 2 wt%, and the co-active component is present in an amount of 1 to 5 wt%, calculated as the metal element, based on the total weight of the catalyst; the molar ratio of palladium to cobalt is 1: (1-5).
According to some embodiments of the invention, preferably, the co-active component is zinc.
In the present invention, preferably, the support may be an alumina support.
In a second aspect, the present invention provides a process for preparing a furfural hydrogenation catalyst, which comprises:
(1) contacting an alumina carrier with a precipitant to obtain a first mixture;
(2) mixing the first mixture with a zinc precursor and/or a magnesium precursor to obtain a second mixture, and performing first drying and first roasting on the second mixture to obtain modified alumina;
(3) under the ultrasonic condition, dipping the modified alumina by dipping liquid of a precursor containing an active component, and then sequentially carrying out second drying and second roasting;
wherein the precursor of the active component comprises a precursor of palladium and a precursor of cobalt;
wherein the palladium precursor, the cobalt precursor and the zinc precursor and/or the magnesium precursor are used in an amount such that the obtained catalyst contains 0.1-10 wt% of palladium and 1-15 wt% of the co-active component calculated by metal elements, based on the total weight of the catalyst; the molar ratio of palladium to cobalt is 1: (0.5-10).
According to a preferred embodiment of the present invention, the palladium content is 0.5 to 2% by weight, based on the total weight of the catalyst, and the content of the co-active component is 1 to 5% by weight, calculated as the metal element; the molar ratio of palladium to cobalt is 1: (1-5).
According to some embodiments of the present invention, the precursor of active palladium may be selected from soluble palladium salts, more preferably from palladium nitrate or palladium chloride, and even more preferably from palladium chloride.
According to some embodiments of the present invention, preferably, the precursor of the active cobalt may be selected from soluble cobalt salts, more preferably at least one selected from cobalt chloride, cobalt nitrate and cobalt sulfate, and further preferably cobalt chloride.
In the present invention, preferably, an aqueous solution of a precursor of the active component may be prepared to form an impregnation solution of the precursor containing the active component, and the modified alumina may be impregnated with the impregnation solution.
According to some embodiments of the present invention, preferably, in step (1), the precipitating agent may be selected from alkaline precipitating agents, more preferably from Na2CO3And/or urea, more preferably urea.
According to some embodiments of the present invention, preferably, in step (1), the contacting conditions may include: the temperature is 60-200 ℃, and the time is 5-30 h; more preferably, the temperature is 70-100 ℃ and the time is 8-20 h.
According to some embodiments of the present invention, the precipitant may be used in an amount of 0.3 to 3mol, and more preferably 0.5 to 1mol, per 10 g of the alumina support.
In the present invention, preferably, the precipitant can be dissolved in water to form an aqueous solution, and then contacted with alumina; more preferably, said water is used in an amount of 50-80mL per mole of said precipitant.
According to some embodiments of the present invention, preferably, in step (2), the zinc precursor may be selected from soluble zinc salts, more preferably at least one selected from zinc nitrate, zinc sulfate and zinc chloride, and further preferably zinc nitrate.
According to some embodiments of the present invention, the precursor of magnesium may be selected from soluble magnesium salts, more preferably at least one selected from magnesium nitrate, magnesium sulfate and magnesium chloride, and even more preferably magnesium nitrate.
In the present invention, preferably, the zinc precursor and/or the magnesium precursor may be dissolved in water to form an aqueous solution, and then mixed with the first mixture.
According to some embodiments of the present invention, preferably, in step (2), the mixing conditions include: the temperature can be 50-200 ℃, and the time can be 5-40 h; more preferably, the temperature is 100-150 ℃ and the time is 15-30 h.
According to some embodiments of the present invention, preferably, in the step (2), the temperature of the first drying may be 50 to 120 ℃, more preferably 70 to 100 ℃; the time may be from 5 to 30 hours, more preferably from 8 to 15 hours.
According to some embodiments of the present invention, preferably, in the step (2), the temperature of the first calcination may be 300-600 ℃, more preferably 350-500 ℃, and the time may be 5-30h, more preferably 5-8 h.
According to some embodiments of the present invention, preferably, in the step (3), the temperature of the ultrasound may be 40 to 100 ℃, more preferably 50 to 70 ℃; the time may be 0.5 to 5 hours, more preferably 1 to 3 hours.
According to some embodiments of the present invention, in step (3), the impregnation method may be an equal volume impregnation method.
According to some embodiments of the present invention, preferably, in the step (3), the temperature of the second drying may be 70 to 150 ℃, more preferably 80 to 120 ℃; the time may be from 5 to 40 hours, more preferably from 8 to 12 hours.
According to some embodiments of the present invention, preferably, in the step (3), the temperature of the second calcination may be 300-700 ℃, more preferably 300-500 ℃, and the time may be 2-30h, more preferably 4-8 h.
In a particularly preferred embodiment of the invention, the method comprises:
(1) weighing an alumina carrier, uniformly mixing the alumina carrier with deionized water of a precipitator, and aging for 8-20 hours at 90-100 ℃ to obtain a first mixture. Wherein, the dosage of the precipitator is 0.6-0.9mol per 10 g of the alumina carrier; the precipitating agent is preferably urea (CO (NH)2)2)；
(2) Adding an aqueous solution of a zinc precursor into the first mixture to obtain a second mixture, and heating the second mixture to 100-120 ℃ for 10-24 hours. Filtering to obtain solid, drying at 70-90 deg.C for 8-12 hr, and calcining at 400-450 deg.C for 5-8 hr to obtain modified alumina, wherein the zinc precursor is preferably Zn (NO)3)2·6H2O；
(3) Preparation of PdCl2And CoCl2The deionized mixed aqueous solution (the molar ratio of Pd to Co is 1 (2-4)) is treated by ultrasonic treatment at 50-70 ℃ for 1-3h, the modified alumina prepared by the equal-volume impregnation method is impregnated with the mixed aqueous solution prepared above, and the catalyst is prepared by drying at 90-120 ℃ for 8-10 h and calcining at 350-450 ℃ for 4-8 h.
Based on the total weight of the catalyst, the content of palladium is 1-2 wt%, and the content of zinc is 2-5 wt%; the molar ratio of palladium to cobalt is 1: 1.5-5.
In a third aspect, the present invention provides a catalyst prepared by the method of the second aspect.
In a fourth aspect, the invention provides a use of the catalyst of the first or third aspect in the gas phase hydrogenation of furfural to produce furfuryl alcohol.
The fifth aspect of the invention provides a method for preparing furfuryl alcohol by furfural gas-phase hydrogenation, which comprises the following steps: carrying out contact reaction on the catalyst of the first aspect or the third aspect and furfural in the presence of hydrogen;
wherein the conditions of the contact reaction comprise: the temperature is 90-200 ℃, the pressure is 0.1-5MPa, and the liquid hourly space velocity of the furfural is 0.2-5h-1The molar ratio of the hydrogen to the furfural is (2-15): 1.
according to a preferred embodiment of the present invention, the conditions of the contacting include: the temperature is 110--1The molar ratio of the hydrogen to the furfural is (3-10): 1.
in the present invention, the catalyst may be further reduced before the catalyst is subjected to the contact reaction with furfural, and the reduction manner is not particularly limited, and for example, the catalyst may be reduced with hydrogen at 220-230 ℃ for 4-8 hours, and preferably, the catalyst may be reduced with a nitrogen-hydrogen mixture, wherein the volume ratio of nitrogen to hydrogen may be (1-5): 1.
in the present invention, the pressure used is a gauge pressure unless otherwise specified.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials are commercially available unless otherwise specified;
the evaluation method of the catalyst provided by the following embodiments in the reaction for preparing furfuryl alcohol by furfural gas-phase hydrogenation comprises the following steps: the catalyst prepared in each example is reduced by a nitrogen-hydrogen mixture (the volume ratio of nitrogen to hydrogen is 1:1) for 6 hours at 220 ℃ in a stainless steel reactor, and then the catalyst and furfural are subjected to contact reaction in the presence of hydrogen; wherein the conditions of the contact reaction comprise: the temperature is 120 ℃, the pressure is 0.1MPa, and the liquid hourly space velocity of the furfural is 1h-1The molar ratio of the hydrogen to the furfural is 10: 1. the furfural furfuryl alcohol content was determined by chromatography. The elemental composition of the resulting catalyst was determined by elemental analysis.
The furfural conversion rate (furfural content before reaction-furfural content after reaction)/furfural content before reaction x 100%;
the selectivity of furfuryl alcohol is the furfural content after reaction/furfural content before reaction x 100%.
Example 1
(1) 10 g of alumina carrier was weighed out and mixed with 50mL of a solution containing 0.8mol of urea (CO (NH)2)2) Was mixed well and then transferred to a 500mL autoclave and aged at 90 ℃ for 12 hours.
(2) Then Zn (NO) is added3)2·6H2And (4) heating the O aqueous solution to 120 ℃, and aging for 24 hours. Filtering, taking out the solid, washing with deionized water for 5 times, drying in a drying oven (80 ℃) for 12 hours, and roasting at 400 ℃ for 6 hours to obtain modified alumina for later use.
(3) Preparation of PdCl2And CoCl2The deionized mixed aqueous solution (mole ratio of Pd to Co: 1) was subjected to ultrasonic treatment at 60 ℃ for 1 hour, the modified alumina obtained by the equivalent-volume impregnation method was impregnated with the mixed aqueous solution prepared above, dried at 100 ℃ for 10 hours, and calcined at 350 ℃ for 4 hours to obtain catalyst S1.
In the obtained catalyst, based on the total weight of the catalyst, the content of palladium was 0.5% by weight, the content of zinc was 3% by weight, and the molar ratio of palladium to cobalt was 1: 1.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.6%, and the selectivity of furfuryl alcohol is 97.3%.
Examples 2 to 10
The catalyst was prepared in the same manner as in example 1, except that,
catalysts S2, S3, S4, S5, S6, S7, S8, S9 and S10 were prepared in the same manner as in example 1 except that the kinds and amounts of the raw materials used in the respective examples were different and the conditions of the parameters for preparing the catalysts were different,
catalyst S2: the amount of the raw materials used was different from that used in example 1, and the aging temperature was 100 ℃, the aging time was 8 hours, the first baking temperature was 500 ℃, and the first baking time was 5 hours.
In the obtained catalyst, based on the total weight of the catalyst, the content of palladium is 1 wt%, the content of zinc is 3 wt%, and the molar ratio of palladium to cobalt is 1: 3.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.8%, and the selectivity of furfuryl alcohol is 98%.
Catalyst S3: the amount of the raw materials used was different from that used in example 1, and the second calcination temperature was 450 ℃ and the second calcination time was 8 hours.
In the catalyst obtained, based on the total weight of the catalyst, the palladium content was 1.5% by weight, the zinc content was 4% by weight, and the molar ratio of palladium to cobalt was 1: 2.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.9%, and the selectivity of furfuryl alcohol is 99.1%.
Catalyst S4: the raw materials used in the method are different from those used in example 1, and the aging temperature is 70 ℃, the aging time is 20 hours, the first roasting temperature is 350 ℃, the first roasting time is 8 hours, the second roasting temperature is 500 ℃, and the second roasting time is 4 hours.
In the obtained catalyst, based on the total weight of the catalyst, the content of palladium was 2% by weight, the content of zinc was 5% by weight, and the molar ratio of palladium to cobalt was 1: 5.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.9%, and the selectivity of furfuryl alcohol is 97.9%.
Catalyst S5: the amount of the raw materials used was different from that used in example 1.
In the obtained catalyst, based on the total weight of the catalyst, the content of palladium is 1 wt%, the content of zinc is 2 wt%, and the molar ratio of palladium to cobalt is 1: 4.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.8%, and the selectivity of furfuryl alcohol is 98.1%.
Catalyst S6: the amount of the raw materials used was different from that used in example 1.
In the obtained catalyst, the content of palladium was 1% by weight, the content of zinc was 1% by weight, and the molar ratio of palladium to cobalt was 1: 5.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.9%, and the selectivity of furfuryl alcohol is 97.6%.
Catalyst S7: the amount of the raw material used was different from that used in example 1, and the support was modified with magnesium.
In the obtained catalyst, based on the total weight of the catalyst, the content of palladium is 1 wt%, the content of magnesium is 4 wt%, and the molar ratio of palladium to cobalt is 1: 1.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.4%, and the selectivity of furfuryl alcohol is 97.2%.
Catalyst S8: the amount of the raw materials used was different from that used in example 1.
In the obtained catalyst, based on the total weight of the catalyst, the content of palladium was 0.1 wt%, the content of zinc was 0.5 wt%, and the molar ratio of palladium to cobalt was 1: 10.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 98.9%, and the selectivity of furfuryl alcohol is 96.9%.
Catalyst S9: the amount of the raw materials used was different from that used in example 1.
In the obtained catalyst, based on the total weight of the catalyst, the content of palladium was 0.5% by weight, the content of zinc was 5% by weight, and the molar ratio of palladium to cobalt was 1: 1.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.1%, and the selectivity of furfuryl alcohol is 98.1%.
Catalyst S10: a catalyst was prepared as in example 1, except that PdCl was used2And CoCl2Deionized mixed water solutionLiquid, Zn (NO)3)2·6H2The alumina carrier is impregnated in one pot with the water solution of O.
In the obtained catalyst, based on the total weight of the catalyst, the content of palladium was 0.3% by weight, the content of zinc was 4% by weight, and the molar ratio of palladium to cobalt was 1: 3.
the evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 98% and the selectivity of furfuryl alcohol is 97.9%.
Comparative example
151g of copper nitrate (Cu (NO) were weighed3)2·3H2O), 50g of chromic anhydride (CrO)3) And 4.6g of lanthanum nitrate (La (NO)3)3·6H2O) was mixed and dissolved in 700mL of deionized water, and 12.1g of barium nitrate (Ba (NO)3)2) Dissolved in 300mL of deionized water. Firstly, adding 100mL of deionized water into a reaction kettle, adding the copper-chromium-lanthanum mixed solution, the barium nitrate solution and 18 wt% of ammonia water in a concurrent flow manner under stirring, controlling the pH value of the reaction to be 6, simultaneously raising the temperature of the reaction solution to 40 ℃, continuing to preserve heat and stir for 2 hours after the addition is finished, filtering, drying at 120 ℃ for 12 hours, and then roasting in a muffle furnace at 350 ℃ for 4 hours to obtain a catalyst powder sample, wherein the catalyst powder sample comprises the following components: CuO/Cr2O3Is 2.5, CuO/La2O3The molar ratio of (1) is 118, the molar ratio of CuO/BaO is 13.5, and then 1 wt% of graphite is added for tabletting and forming to obtain the catalyst DS 1.
The evaluation of the method for preparing furfuryl alcohol by furfural gas phase hydrogenation shows that after the catalyst is stabilized for 24 hours, the conversion rate of furfural is 99.5%, and the selectivity of furfuryl alcohol is 96%.
The results of the above examples and comparative examples show that when the catalyst prepared by the invention is used in the reaction process of preparing furfuryl alcohol by furfural gas phase hydrogenation, the active components of the catalyst are uniformly distributed, and the catalyst has high catalytic activity and selectivity. The catalyst of the invention has furfural conversion rate of 99.9% and furfuryl alcohol selectivity of 99.1%, and shows excellent furfuryl alcohol preparing performance by aldehyde hydrogenation. In the comparative example, the furfuryl alcohol selectivity was only 96%. Therefore, compared with the prior art, the catalyst provided by the invention has excellent activity and selectivity when used for preparing furfuryl alcohol by furfural gas-phase hydrogenation.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A furfural hydrogenation catalyst is characterized by comprising a carrier, and an active component and a co-active component which are loaded on the carrier, wherein the active component comprises palladium and cobalt, and the co-active component comprises zinc and/or magnesium;
wherein, based on the total weight of the catalyst, the content of palladium is 0.1-10 wt%, and the content of the auxiliary active component calculated by metal elements is 1-15 wt%; the molar ratio of palladium to cobalt is 1: (0.5-10).
2. The catalyst of claim 1, wherein the palladium is present in an amount of 0.5 to 2 wt%, and the co-active component is present in an amount of 1 to 5 wt%, calculated as the metal element, based on the total weight of the catalyst; the molar ratio of palladium to cobalt is 1: (1-5);
and/or the co-active component is zinc.
3. A method for preparing a furfural gas-phase hydrogenation catalyst, characterized by comprising:
(1) contacting an alumina carrier with a precipitant to obtain a first mixture;
(2) mixing the first mixture with a zinc precursor and/or a magnesium precursor to obtain a second mixture, and performing first drying and first roasting on the second mixture to obtain modified alumina;
(3) under the ultrasonic condition, dipping the modified alumina by dipping liquid of a precursor containing an active component, and then sequentially carrying out second drying and second roasting;
wherein the precursor of the active component comprises a precursor of palladium and a precursor of cobalt;
wherein the palladium precursor, the cobalt precursor and the zinc precursor and/or the magnesium precursor are used in an amount such that the obtained catalyst contains 0.1-10 wt% of palladium and 1-15 wt% of the co-active component calculated by metal elements, based on the total weight of the catalyst; the molar ratio of palladium to cobalt is 1: (0.5-10);
preferably, the content of palladium is 0.5-2 wt% based on the total weight of the catalyst, and the content of the auxiliary active component calculated by metal elements is 1-5 wt%; the molar ratio of palladium to cobalt is 1: (1-5).
4. A process according to claim 3, wherein the palladium precursor is selected from soluble palladium salts, preferably from palladium nitrate or palladium chloride, more preferably palladium chloride;
and/or the precursor of the cobalt is selected from soluble cobalt salt, preferably at least one selected from cobalt chloride, cobalt nitrate and cobalt sulfate, and more preferably cobalt chloride.
5. The process according to claim 3 or 4, wherein in step (1), the precipitating agent is selected from alkaline precipitating agents, preferably from Na2CO3And/or urea, more preferably urea.
6. The method according to any one of claims 3 to 5, wherein in step (1), the contacting conditions comprise: the temperature is 60-200 ℃, and the time is 5-30 h; preferably, the temperature is 70-100 ℃, and the time is 8-20 h;
and/or, the amount of said precipitant is 0.3 to 3mol, preferably 0.5 to 1mol, per 10 g of said alumina support.
7. The method according to any one of claims 3 to 6, wherein in step (2), the zinc precursor is selected from soluble zinc salts, preferably from at least one of zinc nitrate, zinc sulfate and zinc chloride, more preferably zinc nitrate;
and/or the precursor of the magnesium is selected from soluble magnesium salt, preferably at least one selected from magnesium nitrate, magnesium sulfate and magnesium chloride, and more preferably magnesium nitrate.
8. The method according to any one of claims 3 to 7, wherein in step (2), the mixing conditions comprise: the temperature is 50-200 ℃, and the time is 5-40 h; preferably, the temperature is 100-150 ℃, and the time is 15-30 h;
and/or, in the step (2), the temperature of the primary drying is 50-120 ℃, preferably 70-100 ℃; the time is 5 to 30 hours, preferably 8 to 15 hours;
and/or, in the step (2), the temperature of the first roasting is 300-.
9. The method according to any one of claims 3 to 8, wherein in step (3), the temperature of the ultrasound is 40 to 100 ℃, preferably 50 to 70 ℃;
and/or, in the step (3), the impregnation mode is an equal-volume impregnation method;
and/or, in the step (3), the temperature of the second drying is 70-150 ℃, preferably 80-120 ℃; the time is 5 to 40 hours, preferably 8 to 12 hours;
and/or, in the step (3), the temperature of the second roasting is 300-700 ℃, preferably 300-500 ℃, and the time is 2-30h, preferably 4-8 h.
10. A catalyst prepared by the process of any one of claims 3 to 9.
11. Use of a catalyst according to any one of claims 1-2 and 10 in the gas phase hydrogenation of furfural to furfuryl alcohol.
12. A method for preparing furfuryl alcohol by furfural gas-phase hydrogenation is characterized by comprising the following steps: in the presence of hydrogen, carrying out contact reaction on the catalyst of any one of 1-2 and 10 and furfural;
wherein the conditions of the contact reaction comprise: the temperature is 90-200 ℃, the pressure is 0.1-5MPa, and the liquid hourly space velocity of the furfural is 0.2-5h-1The molar ratio of the hydrogen to the furfural is (2-15): 1.
13. the method of claim 12, wherein the conditions of the contacting comprise: the temperature is 110--1The molar ratio of the hydrogen to the furfural is (3-10): 1.
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| CN115779949A (en) * | 2022-11-28 | 2023-03-14 | 东南大学 | N-doped Pd-Co bimetallic magnetic catalyst, preparation method and application thereof in furfuryl alcohol preparation process by furfural hydrogenation |
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