CN112892537A - Preparation method and application of easily-recycled high-selectivity furfural hydrogenation catalyst - Google Patents
Preparation method and application of easily-recycled high-selectivity furfural hydrogenation catalyst Download PDFInfo
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 25
- 230000009467 reduction Effects 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- -1 transition metal copper salt Chemical class 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000005294 ferromagnetic effect Effects 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003349 gelling agent Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 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 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000852 hydrogen donor Substances 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 3
- 230000006911 nucleation Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 19
- 239000000523 sample Substances 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 229910015189 FeOx Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 229910017827 Cu—Fe Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006462 rearrangement reaction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 240000001548 Camellia japonica Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 235000018597 common camellia Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 239000000386 donor Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- C07D307/36—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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- 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 preparation method and application of an easily-recycled high-selectivity furfural hydrogenation catalyst, and belongs to the technical field of biomass catalytic conversion. A kettle type stirring reactor is adopted, a solvent is used as a hydrogen transfer reagent to provide a hydrogen source in the reaction, the molar ratio of furfural to the solvent is 0.1-20 mol%, the reaction lasts for 1-8h, the ratio of the catalyst amount to the furfural mass is 0.01-1, furfural is directly hydrogenated to generate a downstream product with high added value through hydrogen transfer, and the downstream product is converted into 2-methylfuran or furfuryl alcohol in a high-selectivity and controllable manner. Under the optimized condition, furfural is completely converted, the yield of furfuryl alcohol as a product is up to 91.5%, and the highest yield of 2-methylfuran can be up to 82.2%. The method has the advantages of simple process, low production cost, strong magnetism of the catalyst, easy separation and recovery, environmental protection and the like, simple preparation process, good dispersibility, good economic benefit and good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of biomass conversion, and particularly relates to a preparation method and application of an easily-recycled high-selectivity furfural hydrogenation catalyst, wherein a kettle type stirring reactor is adopted, a transition metal (non-noble metal) Cu-Fe-based catalyst is used for catalyzing hydrogen transfer to reduce furfural to prepare a downstream high value-added product, under an optimized condition, the yield of furfuryl alcohol of the product is up to 91.5%, and the highest yield of 2-methylfuran can be up to 82.2%. Meanwhile, because the catalyst has strong magnetism, a catalyst sample can be effectively separated from the reaction liquid through magnet attraction after reaction.
Background
The biomass resource is used as the only renewable carbon-containing resource and has important strategic position in industrial production, national economy and daily life. Furfural is an important biomass platform molecule, can be directly obtained from agricultural wastes including corncobs, cottonseed hulls, oil-tea camellia hulls, bagasse and the like, and can be used for obtaining downstream products with high added values, such as 2-methylfuran, furfuryl alcohol, cyclopentanol, cyclopentanone and the like, by means of selective hydrogenation under different conditions. Wherein, the furfuryl alcohol is a good solvent for resin, varnish, pigment and anticorrosive paint, and has wide application in the industries of synthetic fiber, rubber, pesticide and casting. 2-methylfuran is an important chemical raw material, has great application value in downstream dye and rubber industries, has excellent energy density and boiling point, has octane number of 103 (higher than 96.8 of gasoline), has great development space in the aspect of fuel substitution, and has strong strategic significance for relieving the current energy crisis situation, improving the energy structure and reducing the dependence on fossil energy. In a water phase system, through furfural hydrogenation rearrangement reaction, furan rings can be subjected to rearrangement reaction to generate cyclopentanone, cyclopentanol and other products. However, due to the presence of water species in the reaction system, polymerization and resinification are likely to occur between the reactants and the product, and the catalyst is likely to deposit carbon, resulting in low utilization of the reactants, poor stability of the catalyst and inactivation during the reaction.
Currently, the preparation of various downstream products by furfural hydrogenation processes mainly uses Cu-Cr catalysts with Cu species as the active center. Chinese patent, publication No.: CN101961652B introduces a method for preparing 2-methylfuran by gas phase furfural hydrogenation by using a copper-chromium-aluminum-silicon catalyst, wherein the use temperature of the catalyst is 170-200 ℃, and the reaction space velocity is 0.4-0.6h-1The reaction pressure is 0.001-0.5 MPa. The optimal conversion rate of the furfural can reach 100%, the optimal selectivity of the 2-methylfuran is as high as 96.6%, and the stability is good. However, the inevitable loss of chromium in the operation process causes serious environmental pollution and does not meet the requirement of sustainable development.
Chinese patent, publication No.: CN101422731A introduces a catalyst for preparing 2-methylfuran by furfural gas phase hydrogenation, which is characterized in that the catalyst comprises an active component CuO, a metal oxide auxiliary agent ZnO and a carrier Al2O3The composite material consists of active component CuO in 18-22 wt%, metal oxide assistant in 3-7 wt% and carrier Al2O3The mass percent of the catalyst is 73-77%, and the reaction temperature is 230 ℃. Under normal pressure, the liquid space velocity is 0.4h-1Under the condition (2), the conversion rate of furfural is 100%, the selectivity of 2-methylfuran is 91% -94%, and although the selectivity of 2-methylfuran of the catalyst is high, the reaction temperature is high, and the stability of the catalyst is poor. Chinese patent, publication No.: CN110054602A introduces a method for preparing 2-methylfuran by using cobalt phosphide catalyst in furfural gas phase hydrogenation, wherein the reaction temperature range is 180-230 ℃, and the reaction pressure is 0.5-2.5 MPa. The conversion rate of furfural can reach 100%, and the selectivity of 2-methylfuran can reach 89.1%. And molecular hydrogen is used as a hydrogen source in the reaction process, so that the energy consumption and the economic cost are high. Chinese patent, CN106732706A, discloses a catalyst containing rare earth elements, which uses calcium carbonate as a carrier, copper oxide as an active component, and a rare earth compound as an active assistant; the mass fraction of the copper oxide is 2 of the catalyst8-75 wt%, the weight percentage of the rare earth compound is 0.1-5 wt% of the catalyst, and the conversion rate and the selectivity of furfuryl alcohol can respectively reach 99.2% and 99.6%. However, the use of high levels of copper species and rare earth metals results in higher catalyst cost, difficult separation, and unsuitability for large-scale use. Chinese patent, CN109731596A, discloses a method for catalyzing hydrogen transfer, which adopts organic copper salt and alkali metal to prepare modified copper-based catalyst, uses formic acid as hydrogen source under certain conditions, and uses hydrogen transfer method to prepare furfuryl alcohol by furfural hydrogenation, the conversion rate of furfural can reach 100%, and the selectivity of furfuryl alcohol can reach 99%. However, the catalyst takes an organic copper salt and alkali metal modifier salt compound as a precursor, the product takes furfuryl alcohol as a main component, the preparation cost of the catalyst is high, and the operation is complex.
Therefore, the method finds a Cu-based catalyst, a proper reaction path and a hydrogen source donor which can be replaced by the noble metal catalyst, and simultaneously, furfural is reduced through hydrogen transfer to controllably produce downstream high-added-value products such as furfuryl alcohol or 2-methylfuran products with high selectivity, thereby having important significance for the chemical production process.
Disclosure of Invention
The invention provides a preparation method and application of an easily-recovered high-selectivity furfural hydrogenation catalyst, which are used for developing a cheap magnetic transition metal Cu-Fe-based catalyst, adopting a kettle type stirring reactor, taking a solvent as a hydrogen transfer reagent to provide a hydrogen source in the reaction, directly reducing furfural through hydrogen transfer at normal pressure and a lower temperature (150-. Under the optimal condition, the yield of furfuryl alcohol corresponding to a product can reach 91.5 percent at most, and the yield of 2-methylfuran can reach 82.2 percent at most.
The technical scheme of the invention is as follows:
a preparation method of an easily-recycled high-selectivity furfural hydrogenation catalyst comprises the following steps:
dissolving transition metal copper salt and iron salt in ethanol solution, mixing, adding gel promoter at 20-80 deg.C, stirring for 5-120min to form transparent colloid, aging at 25-80 deg.C for 5-48 hr to convert colloid colorChanging to dark red to brownish black; the volume of the colloid is shrunk after overnight drying, and roasting heat treatment is carried out in 1/4(v/v) oxygen-argon mixed gas at the temperature of 300-800 ℃ for 2-6 hours to promote decomposition and nucleation of precursor salt; followed by a volume fraction of 10% H2And carrying out reduction pretreatment for 2-8 hours at 200-500 ℃ in an/Ar atmosphere to obtain black ferromagnetic catalyst powder with exposed metal active centers, separating the black ferromagnetic catalyst powder from reaction liquid through a magnet after reaction, and directly recovering the black ferromagnetic catalyst powder through washing and drying.
The gel promoter is one or a mixture of more than two of propylene oxide, polyethylene glycol, citric acid and oxalic acid, the content range of Cu in the catalyst is 20-40 mol%, the content range of Fe in the catalyst is 60-80 mol%, and the metal salt comprises one or a mixture of more than two of nitrate, chloride, carbonate and acetate; the mass ratio of the gel accelerator to the metal salt is 0.5-2.5.
The application of the easily-recovered high-selectivity furfural hydrogenation catalyst comprises the following steps:
adding a furfural solution dissolved in a solvent and a catalyst into a reactor, sealing, filling 1-3MPa hydrogen, discharging redundant air in the reactor after three times of inflation and deflation, keeping the pressure in the reactor between 0.1MPa and 5.0MPa, fully stirring and mixing, reacting at the temperature of 150 ℃ and 240 ℃ for 1-8 hours, and separating and purifying to obtain products of 2-methylfuran and furfuryl alcohol; the catalyst is separated from the reaction solution by a magnet and directly recovered by washing and drying.
The reactor is a kettle type stirring reactor; the solvent comprises one or more than two of isopropanol, ethanol, tetrahydronaphthalene and formic acid, and simultaneously serves as a hydrogen donor; the mass ratio of the catalyst to the furfural is 0.01-1.00; the molar concentration of the furfural in the reaction system is 0.1-20 mol%.
The invention has the beneficial effects that: the invention provides a technology for directly catalytically converting furfural into 2-methylfuran or furfuryl alcohol downstream products with high added value, which is easy to recover after reaction, has high selectivity by a liquid-phase hydrogen transfer method and is controllable. Using transition metal Cu-Fe base catalyst, using Cu and Cu2O、Fe、Fe3O4Is the main chemical composition substance. By rotatingThe hydrogen reagent is used as hydrogen donor to perform catalytic reaction in inert gas. After the reaction, the catalyst sample can be effectively separated from the reaction solution by magnet attraction, and the problems of metal loss and pollution are avoided. By adopting the technology provided by the invention, the effective conversion of furfural can be realized at a lower reaction temperature and under normal pressure, a hydrogen gas source is not needed in the reaction, the preparation process of the catalyst is simple, the separation and recovery process is convenient and quick, and the technology provided by the invention has a green and efficient practical application value and is very suitable for being used in industrial production. According to the method of the invention, in some embodiments, according to the set reaction parameters, the furfural can be completely converted, the yield of 2-methylfuran can reach 82.2%, and the yield of furfuryl alcohol can reach 91.5% at most.
Drawings
Fig. 1 is a transmission electron microscope image of a catalyst sample.
FIG. 2 is an X-ray diffraction image of a catalyst sample.
FIG. 3 shows Cu/FeO uniformly dispersed in the reaction solution after hydrogen transfer reduction of furfuralxAn electron photograph of the catalyst. FIG. 4 shows Cu/FeO directly recoverable by using magnetite after hydrogen transfer reduction of furfuralxAn electron photograph of the catalyst.
FIG. 5 is an X-ray photoelectron spectrum of the Cu2p region of the catalyst sample.
FIG. 6 is N as catalyst2Adsorption/desorption isotherms.
FIG. 7 is a transmission electron microscope image of a 400 ℃ baked sample after reduction pretreatment.
FIG. 8 is a transmission electron microscope image of a 600 ℃ baked sample after reduction pretreatment.
FIG. 9 is a transmission electron microscope image of the catalyst in reference example 1.
Detailed Description
The following section describes the embodiments of the present invention in detail with reference to the technical solutions and the accompanying drawings.
Example 1: preparing a certain volume of Cu (NO) with the concentration of 0.012mol/L3)2·3H2O and 0.024mol/L Fe (NO)3)3·9H2And (3) uniformly mixing the alcoholic solution of O, adding a gel promoter into the mixed solution at the temperature of 40 ℃, continuously stirring for 5 minutes to form a brownish red transparent colloid, stopping stirring, and aging for 24 hours at the temperature of 40 ℃ to ensure that the colloid is changed into dark red. After drying overnight, the colloid volume had shrunk, after grinding, a calcination heat treatment was carried out in 1/4(v/v) in a mixed gas of oxygen and argon to promote nucleation of precursor salts, and H was used2The reduction pretreatment results in a catalyst powder with exposed metal active centers. The main active phase of the Cu is obtained by controlling the species and the mixing ratio of the gel accelerator, the molar ratio of the gelling agent to the Cu metal, the molar ratio of the Cu salt to the Fe salt precursor, the adding speed of the gel accelerator, and the temperature and the duration of the roasting treatment and the hydrogen reduction pretreatment2O、Cu、CuO、Fe、Fe3O4Co-existing Cu/FeOxA series of catalyst powders. It should be emphasized that all the catalysts in the examples of this patent can be directly recovered from the reaction solution by magnet attraction after the reaction, the catalyst separation method is simple, and the loss of active metal and subsequent pollution do not exist in the production process. Transmission electron microscopy images of a typical catalyst as shown in fig. 1, Cu nanoparticles having a minute particle size and uniformly distributed on the surface are present in the catalyst; fig. 2 is an X-ray diffraction image of the catalyst sample.
Example 2: the catalyst with the Cu/Fe molar ratio of 0.5 is prepared by the method, propylene oxide is used as a gel accelerator, and the catalyst is roasted for 3 hours in air at 500 ℃, and H2Reduction pretreatment for 3h at 280 ℃ in atmosphere to prepare Cu/FeOxAdding the catalyst into a reaction kettle filled with 0.3 mol% furfural isopropanol solution, sealing the reaction kettle, and filling inert gas N2After charging and discharging gas for three times, charging N with the pressure of 0.1MPa into the reaction kettle2The stirring speed is controlled to be 800rpm, and the furfural hydrogen transfer reduction reaction is carried out for 4 hours at the temperature range of 170 ℃ and 200 ℃. Separating and purifying to obtain 2-methylfuran and furfuryl alcohol; the catalyst is separated from the reaction solution by a magnet and directly recovered by washing and drying. Using an inert gas N at normal pressure2Under the condition of Cu/FeOxCatalysis of furfural by catalystThe hydrogen transfer hydrogenation process can effectively reduce the reaction cost and energy consumption. The following table 1 shows the results of the liquid phase hydrogen transfer reduction of furfural to the downstream products, furfuryl alcohol and 2-methylfuran, at different reaction temperatures at atmospheric pressure. FIG. 3 shows Cu/FeO uniformly dispersed in the reaction solution after hydrogen transfer reduction of furfuralxAn electron photograph of the catalyst. FIG. 4 shows Cu/FeO directly recoverable by using magnetite after hydrogen transfer reduction of furfuralxAn electron photograph of the catalyst. Fig. 5 shows the X-ray photoelectron spectrum of the catalyst sample in the Cu2p interval. FIG. 6 shows the catalyst at H2Pretreated N2Adsorption/desorption isotherms. An obvious mesoporous pore channel structure is formed in the sample.
aOther liquid phase products whose composition cannot be determined.
Example 3: the catalyst with the Cu/Fe molar ratio of 0.5 is prepared by the method, propylene oxide is used as a gel accelerator, and the catalyst is roasted for 3 hours in air at 500 ℃, and H2Reducing and pretreating Cu/FeO for 3h at 280 ℃ in atmospherexAdding the powder as catalyst into a reaction kettle containing 0.3 mol% furfural isopropanol solution, sealing the reaction kettle, and introducing inert gas N2After charging and discharging gas for three times, charging N with the pressure of 3.0MPa into the reaction kettle2The stirring speed is controlled to be 800rpm, and the furfural hydrogen transfer reduction reaction is carried out for 4 hours at the temperature range of 170 ℃ and 200 ℃. Separating and purifying to obtain 2-methylfuran and furfuryl alcohol; the catalyst is separated from the reaction solution by a magnet and directly recovered by washing and drying. The following table 2 shows the results of liquid-phase hydrogen transfer catalyzed furfural hydrogenation to 2-methylfuran and furfuryl alcohol at 3.0 MPa.
aOther liquid phase products whose composition cannot be determined.
Example 4: the catalyst with the Cu/Fe molar ratio of 0.5 is prepared by the method, propylene oxide is used as a gel accelerator, and the catalyst is roasted for 3 hours and H in the air at different temperatures2Reducing and pretreating Cu/FeO for 3h at 280 ℃ in atmospherexAdding the powder as catalyst into a reaction kettle containing 0.3 mol% furfural isopropanol solution, sealing the reaction kettle, and introducing inert gas N2After charging and discharging gas for three times, charging N with the pressure of 3.0MPa into the reaction kettle2The stirring speed is controlled to be 800rpm, and the furfural is reduced by hydrogen transfer at 180 ℃ for 4 hours. Separating and purifying to obtain 2-methylfuran and furfuryl alcohol; the catalyst is separated from the reaction solution by a magnet and directly recovered by washing and drying. Change of firing temperature for Cu/FeOxCu active species and FeO in catalystxThe formation of the crystal phase structure of the carrier and the size of the active species have obvious influence, and have direct effect on the catalytic activity and stability of the hydrogen transfer reduction furfural reaction. The following table 3 shows the results of reducing furfural by liquid-phase hydrogen transfer at different roasting temperatures in the temperature range of 300-600 ℃ under normal pressure to prepare the downstream products of furfuryl alcohol and 2-methylfuran. FIGS. 7 and 8 show TEM images of the baked samples at 400 ℃ and 600 ℃ after reduction pretreatment.
aOther liquid phase products whose composition cannot be determined.
Example 5: the catalyst with the Cu/Fe molar ratio of 0.5 is prepared by the method, propylene oxide is used as a gel accelerator, and the catalyst is roasted for 3 hours in air at 500 ℃, and H2Reducing and pretreating Cu/FeO for 3h at 280 ℃ in atmospherexAdding the powder as catalyst into a reaction kettle containing 0.3 mol% furfural isopropanol solution, sealing the reaction kettle, and introducing inert gas N2After charging and discharging gas for three times, charging N with certain pressure into the reaction kettle2Control N2The pressure is 0.1MPa, 1.0MPa, 2.0MPa, 3.0MPa, etc., the stirring speed is 800rpm and is 190The furfural is reduced by hydrogen transfer for 4 hours at the temperature. Separating and purifying to obtain 2-methylfuran and furfuryl alcohol; the catalyst is separated from the reaction solution by a magnet and directly recovered by washing and drying. Table 4 below shows the results of different reaction pressures on liquid phase hydrogen transfer reduction of furfural to produce downstream products-furfuryl alcohol and 2-methylfuran.
aOther liquid phase products whose composition cannot be determined.
The reference ratio is 1: mixing Fe (NO)3)3·9H2And roasting the O crystals for three hours at the temperature of 250 ℃ to obtain the iron oxide carrier powder. Adding a certain amount of the powder into 50mL deionized water, ultrasonic processing to obtain solution A with iron element concentration of 0.024mol/L, adding a certain amount of Cu (NO)3)2·3H2Dissolving the O crystal in 50mL of water to prepare a B solution with the concentration of 0.012mol/L, mixing the mother solution A and the B solution, and dropwise adding a NaOH precipitant solution with the concentration of 0.025mol/L until the pH value is 9.0. Aging was continued for 8 hours, washed with deionized water, filtered, dried overnight, and the resulting powder sample was calcined in air at 550 ℃ for 3 hours, followed by H2Performing thermal atmosphere reduction treatment at the temperature of 280 ℃ for 3 hours to obtain a reference sample Cu/FeOxA powder catalyst. The morphology of the sample after the reduction pretreatment is shown in FIG. 9.
And 2, reference ratio: preparation of Cu/FeO by the method of reference ratio 1xAdding a certain amount of catalyst into a reaction kettle filled with 0.3 mol% furfural isopropanol solution, sealing the reaction kettle, and filling inert gas N2After charging and discharging gas for three times, charging N with certain pressure into the reaction kettle2Gas, control of N2The pressure is 0.1MPa, 1.0MPa, 2.0MPa and 3.0MPa respectively, the furfural is reduced by hydrogen transfer at 190 ℃ for 4 hours, and the products of 2-methylfuran and furfuryl alcohol are obtained after separation and purification. Table 5 below shows the normal pressure N2Preparation of downstream products-furfuryl alcohol and 2-methylfuran by liquid-phase hydrogen transfer reduction of furfural at different reaction temperaturesThe result of (1). It can be seen that, with the embodiments 1 to 5 of the present patent, there is no need for an alkaline precipitant and other pretreatment processes of filtration and washing, and no need for an additional calcination process to prepare the treated iron oxide carrier, and the activity of the catalyst and the highest selectivity for 2-methylfuran and furfuryl alcohol are superior to those of the reference ratio 1 to 2.
aOther liquid phase products whose composition cannot be determined.
The present invention and its several embodiments have been described above in an illustrative and non-restrictive manner. Those of ordinary skill in the art, upon reading this specification, will recognize other alternative embodiments that are also within the scope of the present invention.
Claims (6)
1. A preparation method of an easily-recovered high-selectivity furfural hydrogenation catalyst is characterized by comprising the following steps:
dissolving transition metal copper salt and iron salt in ethanol solution, mixing, adding gel promoter into the mixed solution at 20-80 deg.C, stirring for 5-120min to form transparent colloid, aging at 25-80 deg.C for 5-48 hr to convert the colloid color into dark red to brown black; the volume of the colloid is shrunk after overnight drying, and roasting heat treatment is carried out in an oxygen-argon mixed gas with the volume ratio of 1/4 at the temperature of 800 ℃ for 2-6 hours to promote decomposition and nucleation of precursor salts; followed by a volume fraction of 10% H2And carrying out reduction pretreatment for 2-8 hours at 200-500 ℃ in an/Ar atmosphere to obtain black ferromagnetic catalyst powder with exposed metal active centers, separating the black ferromagnetic catalyst powder from reaction liquid through a magnet after reaction, and directly recovering the black ferromagnetic catalyst powder through washing and drying.
2. The preparation method according to claim 1, wherein the mass ratio of the gel accelerator to the metal salt is 0.5-2.5, wherein the gel accelerator is one or more of propylene oxide, polyethylene glycol, citric acid and oxalic acid.
3. The preparation method of claim 1 or 2, wherein the Cu content of the catalyst is 20-40 mol%, the Fe content is 60-80 mol%, and the metal salt comprises one or more of nitrate, chloride, carbonate and acetate.
4. The application of the easily-recovered high-selectivity furfural hydrogenation catalyst is characterized by comprising the following steps of:
adding a furfural solution dissolved in a solvent and a catalyst into a reactor, sealing, filling 1-3MPa hydrogen, discharging redundant air in the reactor after three times of inflation and deflation, keeping the pressure in the reactor between 0.1MPa and 5.0MPa, fully stirring and mixing, reacting at the temperature of 150 ℃ and 240 ℃ for 1-8 hours, and separating and purifying to obtain products of 2-methylfuran and furfuryl alcohol; the catalyst is separated from the reaction solution by a magnet and directly recovered by washing and drying.
5. The use according to claim 4, wherein the reactor is a stirred tank reactor; the solvent comprises one or more than two of isopropanol, ethanol, tetrahydronaphthalene and formic acid, and simultaneously serves as a hydrogen donor.
6. Use according to claim 4 or 5, characterized in that the ratio of the mass of the catalyst to the mass of furfural is 0.01 to 1.00; the molar concentration of the furfural in the reaction system is 0.1-20 mol%.
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