CN106622327A - N-doped porous carbon supported metal catalyst, and preparation method and application thereof - Google Patents
N-doped porous carbon supported metal catalyst, and preparation method and application thereof Download PDFInfo
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- CN106622327A CN106622327A CN201611187583.9A CN201611187583A CN106622327A CN 106622327 A CN106622327 A CN 106622327A CN 201611187583 A CN201611187583 A CN 201611187583A CN 106622327 A CN106622327 A CN 106622327A
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- porous carbon
- bio
- nitrogen
- furfural
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 22
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 87
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 84
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 55
- 239000003575 carbonaceous material Substances 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000012620 biological material Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 244000082204 Phyllostachys viridis Species 0.000 claims description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 4
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 claims description 4
- 240000003259 Brassica oleracea var. botrytis Species 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 235000009337 Spinacia oleracea Nutrition 0.000 claims description 4
- 244000300264 Spinacia oleracea Species 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 240000005528 Arctium lappa Species 0.000 claims description 2
- 235000003130 Arctium lappa Nutrition 0.000 claims description 2
- 235000008078 Arctium minus Nutrition 0.000 claims description 2
- 244000003416 Asparagus officinalis Species 0.000 claims description 2
- 235000005340 Asparagus officinalis Nutrition 0.000 claims description 2
- 235000017647 Brassica oleracea var italica Nutrition 0.000 claims description 2
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 2
- 244000189548 Chrysanthemum x morifolium Species 0.000 claims description 2
- 240000000491 Corchorus aestuans Species 0.000 claims description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 2
- 241001313708 Dictyophora phalloidea Species 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- LBPYPRXFFYUUSI-UHFFFAOYSA-N furan-2-carbaldehyde;hydrate Chemical compound O.O=CC1=CC=CO1 LBPYPRXFFYUUSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 241000245665 Taraxacum Species 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000008346 aqueous phase Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 238000005255 carburizing Methods 0.000 description 15
- 239000012071 phase Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical class CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- DHNDDRBMUVFQIZ-UHFFFAOYSA-N 4-hydroxycyclopent-2-en-1-one Chemical class OC1CC(=O)C=C1 DHNDDRBMUVFQIZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl cyclopentanone Chemical compound 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000565675 Oncomelania Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000001949 Taraxacum officinale Species 0.000 description 1
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 description 1
- ZDPALFHDPFYJDY-UHFFFAOYSA-N [Na].OC=O Chemical compound [Na].OC=O ZDPALFHDPFYJDY-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003560 cancer drug Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000009466 transformation Effects 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/618—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
-
- 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
Abstract
The invention relates to a catalyst which using N-doped porous carbon as a carrier to support metal. The catalyst is composed of 0.1wt%-30wt% of metal particles and 70wt%-99.9wt% of bio-N-doped porous carbon carrier, and can be used for catalyzing aqueous phase hydrogenation of bio-furfural to highly selectively prepare furfural alcohol or cyclopentanone. The catalyst uses the raw materials which are renewable resources, wide in distribution, green and environmental, simple and easy to obtain, rich in resource, low in cost, free from inactivation when recycled for more than 50 times, and stable to air, water and heat. For example, in reaction of catalyzing the hydrogenation of the furfural to prepare the furfural alcohol, conversion rate of the supported metal catalyst can reach 100% and selectivity of the furfural alcohol is larger than 99% in an aqueous phase system.
Description
Technical field
The invention belongs to field of fine chemical, is related to a kind of catalysis using N doping porous carbon as carrier to load metal
Agent, the catalyst can be used to catalysis biological Ji Kangquanshui phases and be hydrogenated with prepare with high selectivity furfuryl alcohol or cyclopentanone, and the catalysis
The preparation method and purposes of agent.
Background technology
Cyclopentanone is a kind of important fine chemical material, can be used to produce the spices such as alkyl cyclopentanone, oncomelania cyclic ketones, resists
Cancer drug, herbicide and rubber etc..At present, it is industrial main with the downstream product of petroleum cracking as raw material, it is de- using adipic acid
Carboxylic is cyclized method and cyclopentene oxidizing production cyclopentanone.Both route raw materials are all highly dependent in oil, and there is reaction
The problems such as complex steps complexity, theoretical yield not high (being less than 60%).With the growing tension of global petroleum resources, utilizing can
Regeneration agriculture and forestry organic waste material resource prepares cyclopentanone not only can reduce dependence of the important chemical to petroleum resources, and can be effective
The added value of agriculture and forestry organic waste material is improved, is expected to become the substituting variation route of conventional petroleum route.
Furfural is a kind of important biomass transformation platform compound, industrially mainly with cheap corncob, sugarcane
The agriculture and forestry organic waste materials such as slag are that raw material Jing is hydrolyzed, cyclodehydration is produced.Furfural can by selective hydrogenation produce furfuryl alcohol, four
The downstream chemical product such as hydrogen furfuryl alcohol, 2- methylfurans, 2- methyltetrahydrofurans, pentadiene, pentanediol, cyclopentanone, cyclopentanol, improve
The added value of furfural.But because furfural contains C=C, C=O of conjugation and easy open loop five-ring heterocycles, may send out in different positions
Raw hydrogenation reaction, such as C=O is hydrogenated to furfuryl alcohol；C=O hydrogenolysis generates 2- methylfurans；Decarboxylation generates furans；Hydrogenation-rearrangement is given birth to
Into cyclopentanone or cyclopentanol etc., therefore the selectivity of control hydrogenated products is difficult in the reaction.Additionally, bio-based furfural is by life
Raw material of substance hydrolysis is obtained, and resulting bio-based furfural is partially dissolved in water, and the separating-purifying in later stage can also increase product
Cost.Angle considers in terms of economy, environment friendly and security etc., and water is that the reaction of bio-based furfural hydrogenation is optimal
Reaction medium, it is optimal reactant that furfural directional catalyzing is changed into single product such as furfuryl alcohol or cyclopentanone in water phase
System.Therefore, develop a kind of to aqueous systems high activity and the heterogeneous catalyst and efficient aqueous catalysis reactant of high selectivity
It is for the downstream product production of bio-based furfural is significant.
The content of the invention
For above-mentioned the problems of the prior art, purpose of the invention is to provide a kind of be mutually hydrogenated with furfural water to urge
Change the high and selectively high bio-based N doping porous carbon load type metal catalyst of activity.
The loaded catalyst is by the metallic of 0.1wt%～30wt% and the bio-based of 70wt%～99.9wt%
Nitrogen-doped porous carbon material carrier is constituted, wherein the specific surface area 100 of the bio-based nitrogen-doped porous carbon material carrier～
2000m2/ g, nitrogen content is 1～20wt%, and the metallic is one kind in palladium, gold, silver, platinum, ruthenium, rhodium, iridium or many
Plant noble metal.
Preferably, the loaded catalyst is given birth to by the metallic and 95wt%～99.5wt% of 0.5wt%～5wt%
Thing base nitrogen-doped porous carbon material carrier is constituted, wherein the specific surface area 150 of the bio-based nitrogen-doped porous carbon material carrier
～1500m2/ g, nitrogen content is 1～10wt%.
Another purpose of the invention is to provide a kind of bio-based N doping porous carbon load type metal to urge
The preparation method of agent, the preparation method comprises the steps：
1) biological material is dried, grinds to form fine powder；
2) by biological material powder be added to the water or the dilute acid soln of low concentration in be well mixed, biomass and water or dilute
The mass ratio of acid solution is 1:3 to 1:30, preferably 1:5 to 1:20；
3) by step 2) in the mixture that obtains be transferred in reactor, be heated to 100～300 under hydrothermal reaction condition
DEG C, preferably 150～250 DEG C, 1～72 hour is incubated, select 3～48 hours, cooling, washing obtains brown solid；
4) by step 3) in the solid that obtains be dried, grind, then calcined in tube furnace, in inert gas
In 300～1500 DEG C of scope inside holdings 0.5～100 hour in atmosphere；Sample is taken out after tube furnace drops to room temperature, that is, is obtained
The nitrogen-doped porous carbon material of bigger serface；
5) by noble-metal-supported in step 4) in the porous nitrogen-doped carbon material surface that obtains obtain loaded catalyst.
Wherein, in step 1) described in biological material be rich protein-contg plant, comprising sweet potato leaf, fruits of elm, dandelion
At least one in leaf, chrysanthemum seedling leaf, roundpod jute leaf, burdock leaf, asparagus, bamboo shoots, Cauliflower, spinach, broccoli, dictyophora phalloidea, preferably
For at least one in spinach, bamboo shoots, it is simultaneously as carbon source and nitrogen source.
Preferably, in step 2) described in the diluted acid of low concentration can be sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid or phosphoric acid
In at least one, preferably sulfuric acid or acetic acid, the weight percent concentration of acid is 0.1～50%, preferably 0.5～10%.
In step 4) described in calcining heat be 300～1500 DEG C, preferably 500～1000 DEG C, the inert gas be nitrogen
One or more in gas, argon gas and helium, temperature retention time is preferably 1～24 hour.
Preferably, other reactants, such as activator or other nitrogen source materials are not adopted in preparation in accordance with the present invention
Material etc., only with biological material.
In step 5) described in loaded catalyst preferably by 0.1wt%～30wt% metallic and 70wt%～
The porous carbon materials carrier composition of 99.9wt%, its metallic content is preferably 0.5wt%～10wt%, and porous carbon materials are carried
Body content is preferably 90wt%～99.5wt%.The metallic be noble metal, its presoma can for palladium, gold, silver,
One or more slaine in platinum, ruthenium, rhodium, iridium.There is no particular restriction for the preparation method of the metal load type catalyst, can
So that using deposition process and method of reducing conventional in prior art, such as nitrating porous carbon materials prepared by Jing are used as catalyst
Carrier mixes with the salting liquid of noble metal, by ultrasonic method, deposition-precipitation, sol-gal process and Photodeposition in appoint
It is a kind of by Metal Supported in carrier surface, then using hydrogen reducing, sodium borohydride reduction, hydrazine hydrate reduction, formic acid sodium reduction,
It is arbitrary in formaldehyde reduction, reduction of sodium citrate, ascorbic acid reduction, reduction of ethylene glycol, ethanol reduction and Reduction of methanol method
Planting carries out the reduction of metallic atom, and the catalyst of N doping porous carbon supported precious metal is finally obtained.
Another purpose of the invention is to provide the bio-based N doping porous carbon load type metal catalyst
The purposes during high selectivity prepares furfuryl alcohol or cyclopentanone is reacted in water phase furfural hydrogenation.
Another purpose of the invention is to provide a kind of using the bio-based N doping porous carbon load type gold
Metal catalyst reacts the method that high selectivity prepares furfuryl alcohol or cyclopentanone using water phase furfural hydrogenation, and methods described includes following step
Suddenly：Add a certain amount of furfural, the loaded catalyst, deionized water in autoclave high-pressure reactor, it is closed after be filled with 0.1～
10MPa hydrogen, is reacted at 50～250 DEG C, after reacting 0.5～48 hour, is cooled to room temperature, filtering reacting liquid.
Preferably, loaded catalyst consumption described in the method for preparing furfuryl alcohol or cyclopentanone is furfural weight
0.01%～100%, preferably 1%～20%；Water consumption is 20～500 times, preferably 50～200 times of furfural weight；Reaction
Pressure is 0.1MPa～10MPa, preferred 0.1MPa～5MPa；Reaction temperature is 50～250 DEG C, preferably 100～200 DEG C；Instead
It is 0.5～48 hour, preferably 1～12 hour between seasonable.
Preferably, it is of the invention that water phase is utilized using the bio-based N doping porous carbon load type metal catalyst
The method that furfural hydrogenation reaction high selectivity prepares furfuryl alcohol or cyclopentanone, reaction temperature is 80～120 DEG C in methods described, hydrogen
Reaction pressure is 0.1MPa～2MPa, and the reaction time is 0.5～6 hour, the selectivity more than 99% of furfuryl alcohol, the life of employing
The specific surface area of thing base N doping porous carbon load type metal catalyst is about 150～500m2/ g, nitrogen content is about 4-10%,
Calcining heat in the preparation method of the bio-based N doping porous carbon load type metal catalyst is 400 to 700 DEG C.
Preferably, it is of the invention that water phase is utilized using the bio-based N doping porous carbon load type metal catalyst
The method that furfural hydrogenation reaction high selectivity prepares furfuryl alcohol or cyclopentanone, reaction temperature is 140～250 DEG C in methods described, hydrogen
Solid/liquid/gas reactions pressure is 2MPa～8MPa, and the reaction time is 0.5～6 hour, and the selectivity of cyclopentanone is more than 90%, the institute of employing
The specific surface area for stating bio-based N doping porous carbon load type metal catalyst is about 500～1500m2/ g, nitrogen content is about
1.5-3.5%, the calcining heat in the preparation method of the bio-based N doping porous carbon load type metal catalyst be 800 to
1000℃。
Beneficial effect
The present invention has compared with prior art following advantage：
1st, the use of cheap, renewable biomass is that raw material prepares porous nitrogen-doped carbon material.All raw materials are renewable money
Source, widely distributed, environmental protection, simple and easy to get, aboundresources is cheap.Closed using the hydro-thermal method of environmental protection simultaneously
Into the nitrogen-doped carbon material with bigger serface, abundant pore structure.With this bio-based porous nitrogen-doped carbon as catalyst
Carrier is capable of achieving the higher value application of agriculture and forestry organic waste material.
2nd, when metal load type catalyst of the present invention is used to be catalyzed in aqueous phase system furfural hydrogenation reaction, performance
Go out excellent catalysis activity and stability.The ratio of material with carbon element is capable of achieving by adjusting catalyst carrier carburizing temperature and carbonization time
Surface area, pore-size distribution and nitrogen content；Furfural orientation is capable of achieving by adjusting catalyst carrier physicochemical property, catalytic reaction technique
It is converted into furfuryl alcohol and hydrogenation-rearrangement is converted into cyclopentanone.And metal load type catalyst can be recycled more than 50 times and not lose
It is living, and catalyst itself is all very stable to empty gas and water and heat.As a example by being catalyzed furfural hydrogenation and prepare furfuryl alcohol reaction, using this
Bright metal load type catalyst, in aqueous phase system, conversion ratio can reach 100%, and the selectivity of furfuryl alcohol is more than 99%.
Description of the drawings
Fig. 1 is the TEM photos of the Pt loaded catalysts prepared according to the preparation embodiment 1 of the present invention；
Fig. 2 is the TEM photos of the Pt loaded catalysts prepared according to the preparation embodiment 2 of the present invention；
Specific embodiment
It is of the invention to be added using water phase furfural using the bio-based N doping porous carbon load type metal catalyst
The method that hydrogen reaction high selectivity prepares furfuryl alcohol or cyclopentanone, the present inventor has found through numerous studies, in the present invention
Aqueous catalysis reaction system in, when catalytic reaction temperature it is relatively low (<120 DEG C), hydrogenation reaction is tended to generate furfuryl alcohol, carbonization temperature
The low nitrogen-doped carbon material of degree is selective higher for the activity and furfuryl alcohol of the loaded catalyst of carrier, and the conversion ratio of its furfural can
Up to 100%, the selectivity of furfuryl alcohol can reach more than 99%.Under identical catalytic reaction condition, mixed using the low nitrogen of carburizing temperature
Miscellaneous material with carbon element is all high higher than carburizing temperature for the activity and selectivity that the loaded catalyst furfural hydrogenation of carrier generates furfuryl alcohol
Nitrogen-doped carbon material is the loaded catalyst of carrier.
When catalytic reaction temperature it is higher (>140 DEG C), hydrogenation reaction is tended to generate cyclopentanone, and the high nitrogen of carburizing temperature is mixed
Miscellaneous material with carbon element is selective higher for the activity and cyclopentanone of the loaded catalyst of carrier, the conversion ratio of its furfural up to 100%,
The selectivity of cyclopentanone can reach more than 90%.Under identical catalytic reaction condition, using the high N doping carbon materials of carburizing temperature
When expecting the loaded catalyst for carrier, the selectivity that its furfural hydrogenation resets generation cyclopentanone is low apparently higher than carburizing temperature
Nitrogen-doped carbon material is the loaded catalyst of carrier.
Above-mentioned loaded noble metal catalyst, its in aqueous phase system furfural hydrogenation reaction have efficient catalysis activity,
Single-minded selectivity and stability.When catalytic reaction temperature is 80～120 DEG C, hydrogen reaction pressure is 0.1MPa～2MPa, instead
It is 0.5～6 hour between seasonable, during using the loaded catalyst that the low nitrogen-doped carbon material of carburizing temperature is carrier, furfural
Up to 100%, the selectivity of furfuryl alcohol can reach more than 99% to conversion ratio；Under identical catalytic reaction condition, carburizing temperature is high
Nitrogen-doped carbon material generates the active relatively low of furfuryl alcohol for the furfural hydrogenation of the loaded catalyst of carrier.When reaction temperature is 140
～250 DEG C, hydrogen reaction pressure is 2MPa～8MPa, and the reaction time is 0.5～6 hour, the selectivity of cyclopentanone be 90% with
On, under identical catalytic reaction condition, adopt the high nitrogen-doped carbon material of carburizing temperature (to compare table for the loaded catalyst of carrier
Area is about 500～1500m2/ g, nitrogen content is about 1.5-3.5%) when, its furfural hydrogenation resets the selectivity for generating cyclopentanone
Apparently higher than the loaded catalyst that the low nitrogen-doped carbon material of carburizing temperature is carrier, (specific surface area is about 150～500m2/
G, nitrogen content is about 4-10%).
The preparation method of bio-based N doping porous carbon load type metal catalyst according to the present invention is obtained most
100～the 2000m of specific surface area of whole nitrogen-doped porous carbon material2/ g, nitrogen content is 1～20wt%.When carburizing temperature it is relatively low
When, material with carbon element specific surface area is less, and nitrogen content is higher；With the rising of carburizing temperature, material with carbon element specific surface area gradually increases, nitrogen
Content is gradually decreased.Such as with bamboo shoots as raw material, when carburizing temperature is 550 DEG C, its specific surface area is about 180m2/ g, nitrogen content is about
For 7%；When carburizing temperature is 950 DEG C, its specific surface area is about 1000m2/ g, nitrogen content is about 1.8%.
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as and be limited to general sense and dictionary meanings, and inventor should allowed
It is appropriate to define term with the basis of the principle for carrying out best interpretations, according to implication corresponding with the technical elements of the present invention and generally
Thought is explained.Therefore, description presented herein is not intended to limit this merely for the sake of the preferred embodiment for illustrating purpose
The scope of invention, it will thus be appreciated that in the case of without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
Following examples are enumerated only as the example of embodiment of the present invention, do not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that the modification in the range of the essence without departing from the present invention and design each falls within the present invention
Protection domain.Unless stated otherwise, the reagent and instrument used in following examples is commercially available product.
Material characterization instrument：
(1) transmission electron microscope：Model H-7650, manufacturer is Hitachi Hitachi, Ltds
(2) elemental analyser：Model Vario-EL-cube, manufacturer is Elementary companies of Germany
(3) physical adsorption appearance：Model ASAP2020, manufacturer is micrometritics companies of the U.S.
Prepare embodiment 1：The preparation of nitrogen-doped porous carbon material supported Pt catalysts
The bamboo shoots that 1kg is cleaned up are cut into pieces, in an oven 70 DEG C are heated to drying, obtain solid and smash.
It is in 1.5% 20mL dilute sulfuric acids, to move on to after being uniformly mixed in hydrothermal reaction kettle to take 2g powder and add percentage by weight, in
180 DEG C are reacted 8 hours, filtered, are washed, and are dried to obtain brown solid.The drying solid for obtaining is put in tube furnace afterwards
Calcine in nitrogen gas atmosphere, in 550 DEG C of scope inside holdings 5 hours.Sample is taken out after tube furnace drops to room temperature, that is, is obtained
Nitrogen-doped porous carbon material, nitrogen content is about 7.0at%, and its specific surface area is 180m2/g.Take the N doping porous of 1.0g preparations
Material with carbon element, with 50mL deionized waters, 5mL H2PtCl6Solution (Pt concentration 0.01g/mL) mixes, using 2mL 0.1M sodium borohydrides
Reduced, filtering and washing is carried out afterwards, be dried, obtained final product the Pt catalyst of N doping porous carbon load.Fig. 1 is according to this enforcement
The TEM figures of the Pt catalyst of N doping porous carbon load prepared by example, as shown in figure 1, Pt nano particles uniformly divide in the material
Dissipate in carbon material surface, its granular size is about 4.3nm.
Prepare embodiment 2：
In addition to carburizing temperature to be changed to 850 DEG C, other prepare nitrating carbon materials according to the identical method of embodiment 1 is prepared
Material and Pt supported catalysts.Elementary analysis result shows that the material nitrogen content is 2.8at%, and BET test results show specific surface
Product is about 650m2/ g, Fig. 2 are to be schemed according to the TEM of the Pt catalyst of N doping porous carbon manufactured in the present embodiment load, such as Fig. 2
Shown, Pt nano particles are dispersed in carbon material surface in the material, and its granular size is about 3.5nm.
Prepare embodiment 3：The preparation of nitrogen-doped porous carbon material supported Au catalysts
Nitrogen-doped porous carbon material supported Au catalysts are prepared according to the identical method of embodiment 1 is prepared.
Embodiment 1
0.25g furfurals are put into autoclave high-pressure reactor, add 0.025g to prepare the N doping porous prepared in embodiment 1
Carbon material supported Pt catalyst, 20mL deionized waters, it is closed after be filled with 1MPa hydrogen, reacted at 100 DEG C, reaction is 4 little
Shi Hou, is cooled to room temperature, and filtering reacting liquid carries out gas chromatographic analysis to reactant liquor.As a result show that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 100%, and the selectivity of furfural is more than 99%.
Embodiment 2
0.25g furfurals are put into autoclave high-pressure reactor, add 0.025g to prepare the N doping porous prepared in embodiment 2
Carbon material supported Pt catalyst, 20mL deionized waters, it is closed after be filled with 1MPa hydrogen, reacted at 100 DEG C, reaction is 4 little
Shi Hou, is cooled to room temperature, and filtering reacting liquid carries out gas chromatographic analysis to reactant liquor.As a result show that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 45%, the selectivity about 88% of furfural, also a small amount of cyclopentenone (about 3%) and 4- hydroxyl -2- cyclopentene
Ketone (4%) is generated.
Embodiment 3
0.25g furfurals are put into autoclave high-pressure reactor, add 0.025g to prepare the N doping porous prepared in embodiment 1
Carbon material supported Pt catalyst, 20mL deionized waters, it is closed after be filled with 3MPa hydrogen, reacted at 160 DEG C, reaction is 4 little
Shi Hou, is cooled to room temperature, and filtering reacting liquid carries out gas chromatographic analysis to reactant liquor.As a result show that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 100%, and the selectivity of cyclopentanone is about 49%, and cyclopentanol is selectively about 7%, and cyclopentenone is selective about
For 20%, furfuryl alcohol is selectively about 14%, 4- hydroxyl -2- cyclopentenones about 10%.
Embodiment 4
0.25g furfurals are put into autoclave high-pressure reactor, add 0.025g to prepare the N doping porous prepared in embodiment 2
Carbon material supported Pt catalyst, 20mL deionized waters, it is closed after be filled with 3MPa hydrogen, reacted at 160 DEG C, reaction is 4 little
Shi Hou, is cooled to room temperature, and filtering reacting liquid carries out gas chromatographic analysis to reactant liquor.As a result show that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 100%, and the selectivity of cyclopentanone is more than 90%, cyclopentanol selectively about 5%, cyclopentenone selectivity
About 2%, 4- hydroxyl -2- cyclopentenones about 3%.
Embodiment 5
0.25g furfurals are put into autoclave high-pressure reactor, add 0.025g to prepare the N doping porous prepared in embodiment 3
Carbon material supported Au catalyst, 20mL deionized waters, it is closed after be filled with 1MPa hydrogen, reacted at 100 DEG C, reaction is 4 little
Shi Hou, is cooled to room temperature, and filtering reacting liquid carries out gas chromatographic analysis to reactant liquor.As a result show that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 35%, the selectivity about 58% of furfural.
Claims (10)
1. a kind of high to furfural water phase high active of hydrogenation catalysis and selective high bio-based N doping porous carbon load type metal is urged
Agent, the loaded catalyst is by the metallic of 0.1wt%～30wt% and the bio-based nitrogen of 70wt%～99.9wt%
Doped porous carbon material carrier is constituted, wherein the specific surface area 100 of the bio-based nitrogen-doped porous carbon material carrier～
2000m2/ g, nitrogen content is 1～20wt%, and the metallic is one kind in palladium, gold, silver, platinum, ruthenium, rhodium, iridium or many
Plant noble metal.
2. loaded catalyst according to claim 1, it is characterised in that the loaded catalyst by 0.5wt%～
The metallic of 5wt% and 95wt%～99.5wt% bio-based nitrogen-doped porous carbon materials carrier are constituted, wherein the biology
150～the 1500m of specific surface area of base nitrogen-doped porous carbon material carrier2/ g, nitrogen content is 1～10wt%.
3. a kind of preparation method of loaded catalyst according to claim 1 and 2, the preparation method includes following step
Suddenly：
1) biological material is dried, grinds to form fine powder；
2) by biological material powder be added to the water or the dilute acid soln of low concentration in be well mixed, biomass are molten with water or diluted acid
The mass ratio of liquid is 1:3 to 1:30, preferably 1:5 to 1:20；
3) by step 2) in the mixture that obtains be transferred in reactor, 100～300 DEG C are heated under hydrothermal reaction condition,
It is preferred that 150～250 DEG C, 1～72 hour is incubated, select 3～48 hours, cooling, washing obtains brown solid；
4) by step 3) in the solid that obtains be dried, grind, then calcined in tube furnace, in atmosphere of inert gases
In in 300～1500 DEG C of scope inside holdings 0.5～100 hour；Sample is taken out after tube furnace drops to room temperature, i.e., is compared greatly
The nitrogen-doped porous carbon material of surface area；
5) by noble-metal-supported in step 4) in the porous nitrogen-doped carbon material surface that obtains obtain loaded catalyst.
4. the preparation method of loaded catalyst according to claim 3, it is characterised in that in step 1) described in it is biological
Material be rich protein-contg plant, comprising sweet potato leaf, fruits of elm, Folium Taraxacum, chrysanthemum seedling leaf, roundpod jute leaf, burdock leaf, asparagus,
At least one at least one in bamboo shoots, Cauliflower, spinach, broccoli, dictyophora phalloidea, preferably spinach, bamboo shoots, it makees simultaneously
For carbon source and nitrogen source.
5. the preparation method of loaded catalyst according to claim 3, it is characterised in that in step 2) described in it is low dense
The diluted acid of degree is at least one in sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid or phosphoric acid, preferably sulfuric acid or acetic acid, the weight of acid
Percent concentration is 0.1～50%, preferably 0.5～10%；In step 4) described in calcining heat be 300～1500 DEG C, preferably
500～1000 DEG C, the inert gas is one or more in nitrogen, argon gas and helium, and it is little that temperature retention time is preferably 1～24
When.
6. the preparation method of the loaded catalyst according to any one in claim 3 to 5, it is characterised in that described
Activator or other nitrogen source materials are not adopted in preparation method, only with biological material.
7. bio-based N doping porous carbon load type metal catalyst according to claim 1 or claim 2 is anti-in water phase furfural hydrogenation
High selectivity is answered to prepare furfuryl alcohol or the purposes in cyclopentanone.
8. it is a kind of that water phase is utilized using bio-based N doping porous carbon load type metal catalyst according to claim 1 or claim 2
The method that furfural hydrogenation reaction high selectivity prepares furfuryl alcohol or cyclopentanone, methods described comprises the steps：It is anti-in autoclave high pressure
Answer device to add a certain amount of furfural, the loaded catalyst, deionized water, it is closed after be filled with 0.1～10MPa hydrogen, 50～
Reacted at 250 DEG C, after reacting 0.5～48 hour, be cooled to room temperature, filtering reacting liquid；Preferably, it is described prepare furfuryl alcohol or
Loaded catalyst consumption described in the method for cyclopentanone is the 0.01%～100% of furfural weight, preferably 1%～20%；
Water consumption is 20～500 times, preferably 50～200 times of furfural weight；Reaction pressure is 0.1MPa～10MPa, preferred 0.1MPa
～5MPa；Reaction temperature is 50～250 DEG C, preferably 100～200 DEG C；Reaction time be 0.5～48 hour, preferably 1～12
Hour.
9. the method for preparing furfuryl alcohol or cyclopentanone according to claim 8, it is characterised in that reaction temperature in methods described
For 80～120 DEG C, hydrogen reaction pressure is 0.1MPa～2MPa, and the reaction time is 0.5～6 hour, the selectivity 99% of furfuryl alcohol
More than, the specific surface area of the bio-based N doping porous carbon load type metal catalyst of employing is about 150～500m2/ g,
Nitrogen content is about 4-10%, the calcining heat in the preparation method of the bio-based N doping porous carbon load type metal catalyst
For 400 to 700 DEG C.
10. the method for preparing furfuryl alcohol or cyclopentanone according to claim 8, it is characterised in that temperature is reacted in methods described
Spend for 140～250 DEG C, hydrogen reaction pressure is 2MPa～8MPa, the reaction time is 0.5～6 hour, and the selectivity of cyclopentanone is
More than 90%, the specific surface area of the bio-based N doping porous carbon load type metal catalyst of employing is about 500～
1500m2/ g, nitrogen content is about 1.5-3.5%, the preparation method of the bio-based N doping porous carbon load type metal catalyst
In calcining heat be 800 to 1000 DEG C.
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