CN106622327B - A kind of catalyst and its preparation method and application of N doping porous carbon carried metal - Google Patents
A kind of catalyst and its preparation method and application of N doping porous carbon carried metal Download PDFInfo
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- CN106622327B CN106622327B CN201611187583.9A CN201611187583A CN106622327B CN 106622327 B CN106622327 B CN 106622327B CN 201611187583 A CN201611187583 A CN 201611187583A CN 106622327 B CN106622327 B CN 106622327B
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- porous carbon
- nitrogen
- acid
- loaded catalyst
- furfural
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 32
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 114
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 93
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000012620 biological material Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 8
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 244000082204 Phyllostachys viridis Species 0.000 claims description 8
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 8
- 239000011425 bamboo Substances 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 claims description 6
- 240000003259 Brassica oleracea var. botrytis Species 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 235000009337 Spinacia oleracea Nutrition 0.000 claims description 6
- 244000300264 Spinacia oleracea Species 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002028 Biomass Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000005406 washing 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
- 240000005528 Arctium lappa Species 0.000 claims description 3
- 235000003130 Arctium lappa Nutrition 0.000 claims description 3
- 235000008078 Arctium minus Nutrition 0.000 claims description 3
- 244000003416 Asparagus officinalis Species 0.000 claims description 3
- 235000005340 Asparagus officinalis Nutrition 0.000 claims description 3
- 235000017647 Brassica oleracea var italica Nutrition 0.000 claims description 3
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 3
- 244000189548 Chrysanthemum x morifolium Species 0.000 claims description 3
- 240000000491 Corchorus aestuans Species 0.000 claims description 3
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 3
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 3
- 241001313708 Dictyophora phalloidea Species 0.000 claims description 3
- 241000196324 Embryophyta Species 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 3
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 241000245665 Taraxacum Species 0.000 claims 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 2
- 238000004321 preservation Methods 0.000 claims 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- 239000012071 phase Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000008346 aqueous phase Substances 0.000 abstract description 4
- LBPYPRXFFYUUSI-UHFFFAOYSA-N furan-2-carbaldehyde;hydrate Chemical compound O.O=CC1=CC=CO1 LBPYPRXFFYUUSI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract 1
- 238000005255 carburizing Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 230000009467 reduction Effects 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 4
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- 239000003208 petroleum 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
- -1 alkyl cyclopentanone Chemical compound 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DHNDDRBMUVFQIZ-UHFFFAOYSA-N 4-hydroxycyclopent-2-en-1-one Chemical compound 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
- 238000003763 carbonization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 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 compound 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
- 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
- 239000012190 activator Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003205 fragrance 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 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
- 239000005060 rubber Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 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
- 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 catalyst that the present invention relates to a kind of using N doping porous carbon as carrier to load metal, the catalyst is made of the biology base nitrogen-doped porous carbon material carrier of the metallic of 0.1wt%~30wt% and 70wt%~99.9wt%, can be used for catalysis biological base furfural water phase and hydrogen is added to prepare furfuryl alcohol or cyclopentanone with high selectivity.All raw materials of the catalyst are renewable resource, widely distributed, environmentally protective, simple and easy to get, resourceful, cheap, and 50 times or more non-inactivations can be recycled, all very stable to empty gas and water and heat.For being catalyzed furfural hydrogenation and prepare furfuryl alcohol reaction, metal-supported catalyst according to the present invention, in aqueous phase system, conversion ratio can reach 100%, and the selectivity of furfuryl alcohol is greater than 99%.
Description
Technical field
The invention belongs to field of fine chemical, are related to a kind of catalysis using N doping porous carbon as carrier to load metal
Agent, the catalyst can be used for catalysis biological base furfural water phase and hydrogen added to prepare furfuryl alcohol or cyclopentanone and the catalysis with high selectivity
The preparation method and purposes of agent.
Background technique
Cyclopentanone is a kind of important fine chemical material, can be used for producing the fragrance such as alkyl cyclopentanone, oncomelania cyclic ketones, resists
Cancer drug, herbicide and rubber etc..Currently, it is industrial mainly using the downstream product of petroleum cracking as raw material, it is de- using adipic acid
Carboxylic is cyclized method and cyclopentene oxidizing produces cyclopentanone.Both route raw materials are all highly dependent in petroleum, and there is reactions
The problems such as complex steps are complicated, theoretical yield not high (less than 60%).With the growing tension of global petroleum resources, using can
Regeneration agriculture and forestry organic waste material resource, which prepares cyclopentanone not only, can reduce dependence of the important chemical to petroleum resources, but also can be effective
The added value for improving agriculture and forestry organic waste material is expected to the alternative variation route as 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 is produced through hydrolysis, cyclodehydration.Furfural can produce furfuryl alcohol, four by selective hydrogenation
The downstream chemicals product such as hydrogen furfuryl alcohol, 2- methylfuran, 2- methyltetrahydrofuran, pentadiene, pentanediol, cyclopentanone, cyclopentanol improve
The added value of furfural.But it since furfural contains C=C, C=O and easy open loop five-ring heterocycles of conjugation, may be sent out in different positions
Raw hydrogenation reaction, as C=O is hydrogenated to furfuryl alcohol；C=O hydrogenolysis generates 2- methylfuran；Decarboxylation generates furans；Hydrogenation-rearrangement is raw
At cyclopentanone or cyclopentanol etc., therefore it is difficult to control the selectivity of hydrogenated products in the reaction.In addition, biology base furfural passes through life
Raw material of substance hydrolysis obtains, and obtained biology base furfural is partially dissolved in water, and the separating-purifying in later period also will increase product
Cost.Consider from economy, environment friendly and safety etc. angle, water is that the reaction of biology base furfural hydrogenation is optimal
Reaction medium, it is optimal reactant that furfural directional catalyzing, which is converted to single product such as furfuryl alcohol or cyclopentanone, in water phase
System.Therefore, a kind of pair of aqueous systems high activity and highly selective heterogeneous catalyst and efficient aqueous catalysis reactant are developed
It is to be of great significance for the downstream product production of biology base furfural.
Summary of the invention
It is according to the present invention to be designed to provide a kind of pair of furfural water phase hydrogen is added to urge for above-mentioned the problems of the prior art
Change the biology base N doping porous carbon load type metal catalyst that activity is high and selectivity is high.
The loaded catalyst is by the metallic of 0.1wt%~30wt% and the biology base of 70wt%~99.9wt%
Nitrogen-doped porous carbon material carrier is constituted, wherein the specific surface area 100 of the biology base nitrogen-doped porous carbon material carrier~
2000m2/ g, nitrogen content are 1~20wt%, and the metallic is selected from one of palladium, gold, silver, platinum, ruthenium, rhodium, iridium or more
Kind noble metal.
Preferably, the loaded catalyst is raw by the metallic and 95wt%~99.5wt% of 0.5wt%~5wt%
Object base nitrogen-doped porous carbon material carrier is constituted, wherein the specific surface area 150 of the biology base nitrogen-doped porous carbon material carrier
~1500m2/ g, nitrogen content are 1~10wt%.
According to the present invention another is designed to provide a kind of biology base N doping porous carbon load type metal and urges
The preparation method of agent, the preparation method include the following steps:
1) biological material is dry, it is ground into fine powder；
2) by biological material powder be added to the water or the dilute acid soln of low concentration in be uniformly 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) mixture obtained in step 2) is transferred in reaction kettle, is heated to 100~300 under hydrothermal reaction condition
DEG C, preferably 150~250 DEG C, 1~72 hour is kept the temperature, is selected 3~48 hours, cooling, washing obtains brown solid；
4) solid obtained in step 3) is dried, ground, then calcined in tube furnace, in inert gas
In atmosphere in 300~1500 DEG C range inside holding 0.5~100 hour；Sample is taken out to get arriving after tube furnace drops to room temperature
The nitrogen-doped porous carbon material of bigger serface；
5) noble-metal-supported porous nitrogen-doped carbon material surface obtained in step 4) is obtained into loaded catalyst.
Wherein, the biological material described in step 1) is rich protein-contg plant, includes sweet potato leaf, fruits of elm, dandelion
At least one of leaf, chrysanthemum miaoye, roundpod jute leaf, burdock leaf, asparagus, bamboo shoots, Cauliflower, spinach, broccoli, dictyophora phalloidea, preferably
For at least one of spinach, bamboo shoots, it is used as carbon source and nitrogen source simultaneously.
Preferably, the diluted acid of the low concentration described in step 2) can be sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid or phosphoric acid
At least one of, preferably sulfuric acid or acetic acid, sour weight percent concentration are 0.1~50%, preferably 0.5~10%.
The calcination temperature described in step 4) is 300~1500 DEG C, and preferably 500~1000 DEG C, the inert gas is nitrogen
One of gas, argon gas and helium are a variety of, and soaking time is preferably 1~24 hour.
Preferably, other reactants are not used in preparation method according to the present invention, such as activator or other nitrogen source materials
Material etc., only with biological material.
The loaded catalyst described in step 5) preferably by the metallic of 0.1wt%~30wt% and 70wt%~
The porous carbon materials carrier of 99.9wt% forms, and metallic content is preferably 0.5wt%~10wt%, and porous carbon materials carry
Body content is preferably 90wt%~99.5wt%.The metallic be noble metal, presoma can for palladium, gold, silver,
One of platinum, ruthenium, rhodium, iridium or various metals salt.There is no particular restriction for the preparation method of the metal-supported catalyst, can
To use conventional in the prior art deposition method and restoring method, such as the nitrating porous carbon materials through preparing are as catalyst
Carrier is mixed with the salting liquid of noble metal, passes through appointing in ultrasonic method, deposition-precipitation, sol-gal process and Photodeposition
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,
Any in formaldehyde reduction, reduction of sodium citrate, ascorbic acid reduction, reduction of ethylene glycol, ethanol reduction and Reduction of methanol method
Kind carries out the reduction of metallic atom, and the catalyst of the porous carbon supported precious metal of N doping finally can be obtained.
According to the present invention another is designed to provide the biology base N doping porous carbon load type metal catalyst
The highly selective purposes prepared in furfuryl alcohol or cyclopentanone is reacted in water phase furfural hydrogenation.
According to the present invention another is designed to provide a kind of using the biology base N doping porous carbon load type gold
Metal catalyst reacts the highly selective method for preparing furfuryl alcohol or cyclopentanone using water phase furfural hydrogenation, and the method includes walking as follows
It is rapid: a certain amount of furfural, the loaded catalyst, deionized water is added in autoclave high-pressure reactor, it is filled with 0.1 after closed~
10MPa hydrogen is reacted at 50~250 DEG C, after reaction 0.5~48 hour, is cooled to room temperature, filtering reacting liquid.
Preferably, loaded catalyst dosage 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, preferably 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, according to the present invention that water phase is utilized using the biology base N doping porous carbon load type metal catalyst
Furfural hydrogenation reacts the highly selective method for preparing furfuryl alcohol or cyclopentanone, and reaction temperature is 80~120 DEG C in the method, hydrogen
Reaction pressure is 0.1MPa~2MPa, and the reaction time is 0.5~6 hour, 99% or more the selectivity of furfuryl alcohol, the life of use
The specific surface area of object base N doping porous carbon load type metal catalyst is about 150~500m2/ g, nitrogen content are about 4-10%,
Calcination temperature in the preparation method of the biology base N doping porous carbon load type metal catalyst is 400 to 700 DEG C.
Preferably, according to the present invention that water phase is utilized using the biology base N doping porous carbon load type metal catalyst
Furfural hydrogenation reacts the highly selective method for preparing furfuryl alcohol or cyclopentanone, and reaction temperature is 140~250 DEG C in the method, hydrogen
Solid/liquid/gas reactions pressure is 2MPa~8MPa, and the reaction time is 0.5~6 hour, and the selectivity of cyclopentanone is 90% or more, the institute of use
The specific surface area for stating biology base N doping porous carbon load type metal catalyst is about 500~1500m2/ g, nitrogen content are about
1.5-3.5%, the calcination temperature in the preparation method of the biology base N doping porous carbon load type metal catalyst be 800 to
1000℃。
Beneficial effect
The present invention has the advantage that compared with prior art
It 1, the use of cheap, renewable biomass is that raw material prepares porous nitrogen-doped carbon material.All raw materials are renewable money
Source, it is widely distributed, it is environmentally protective, it is simple and easy to get, it is resourceful, it is cheap.It is closed simultaneously using environmentally protective hydro-thermal method
At the nitrogen-doped carbon material with bigger serface, abundant pore structure.Using the porous nitrogen-doped carbon of this biology base as catalyst
Carrier can realize the higher value application of agriculture and forestry organic waste material.
2, when metal-supported catalyst of the present invention is used to be catalyzed furfural hydrogenation reaction in aqueous phase system, performance
Excellent catalytic activity and stability out.The ratio of carbon material can be realized by adjusting catalyst carrier carburizing temperature and carbonization time
Surface area, pore-size distribution and nitrogen content；By adjusting catalyst carrier physicochemical property, catalysis reaction process can realize that furfural orients
It is converted into furfuryl alcohol and hydrogenation-rearrangement is converted into cyclopentanone.And metal-supported catalyst can be recycled 50 times or more and not lose
It is living, and catalyst itself is all very stable to empty gas and water and heat.For being catalyzed furfural hydrogenation and prepare furfuryl alcohol reaction, this hair is used
Bright metal-supported catalyst, in aqueous phase system, conversion ratio can reach 100%, and the selectivity of furfuryl alcohol is greater than 99%.
Detailed description of the invention
Fig. 1 is the TEM photo of Pt loaded catalyst prepared by preparation embodiment 1 according to the present invention；
Fig. 2 is the TEM photo of Pt loaded catalyst prepared by preparation embodiment 2 according to the present invention；
Specific embodiment
It is according to the present invention to be added using the biology base N doping porous carbon load type metal catalyst using water phase furfural
Hydrogen reacts the highly selective method for preparing furfuryl alcohol or cyclopentanone, and the present inventor has found by numerous studies, in the present invention
Aqueous catalysis reaction system in, when catalytic reaction temperature is lower (< 120 DEG C), hydrogenation reaction is tended to generate furfuryl alcohol, carbonization temperature
Activity and the furfuryl alcohol selectivity for spending the loaded catalyst that low nitrogen-doped carbon material is carrier are higher, and the conversion ratio of furfural can
Up to 100%, the selectivity of furfuryl alcohol can reach 99% or more.Under identical catalytic reaction condition, mixed using the low nitrogen of carburizing temperature
Miscellaneous carbon material is that the loaded catalyst furfural hydrogenation of carrier generates the activity and selectivity of furfuryl alcohol to be all higher than carburizing temperature high
Nitrogen-doped carbon material is the loaded catalyst of carrier.
When catalytic reaction temperature is higher (> 140 DEG C), hydrogenation reaction is tended to generate cyclopentanone, and the high nitrogen of carburizing temperature is mixed
Miscellaneous carbon material be the loaded catalyst of carrier activity and cyclopentanone selectivity it is higher, the conversion ratio of furfural up to 100%,
The selectivity of cyclopentanone can reach 90% or more.Under identical catalytic reaction condition, the high N doping carbon materials of carburizing temperature are used
When material is the loaded catalyst of carrier, it is low that the selectivity that furfural hydrogenation resets generation cyclopentanone is apparently higher than carburizing temperature
Nitrogen-doped carbon material is the loaded catalyst of carrier.
Above-mentioned loaded noble metal catalyst, in aqueous phase system furfural hydrogenation reaction have efficient catalytic 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, when using the loaded catalyst that the low nitrogen-doped carbon material of carburizing temperature is carrier, furfural
For conversion ratio up to 100%, the selectivity of furfuryl alcohol can reach 99% or more；Under identical catalytic reaction condition, carburizing temperature is high
Nitrogen-doped carbon material is that the furfural hydrogenation of the loaded catalyst of carrier generates the active lower of furfuryl alcohol.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, the nitrogen-doped carbon material for using carburizing temperature high (compares table for the loaded catalyst of carrier
Area is about 500~1500m2/ g, nitrogen content are about 1.5-3.5%) when, furfural hydrogenation resets the selectivity for generating cyclopentanone
Being 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 are about 4-10%).
The preparation method of biology base N doping porous carbon load type metal catalyst according to the present invention obtains most
100~2000m of specific surface area of whole nitrogen-doped porous carbon material2/ g, nitrogen content are 1~20wt%.When carburizing temperature is lower
When, carbon material specific surface area is smaller, and nitrogen content is higher；With the raising of carburizing temperature, carbon material specific surface area is gradually increased, nitrogen
Content gradually decreases.Such as using bamboo shoots as raw material, when carburizing temperature is 550 DEG C, specific surface area is about 180m2/ g, nitrogen content is about
It is 7%；When carburizing temperature is 950 DEG C, specific surface area is about 1000m2/ g, nitrogen content are 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 being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.Unless stated otherwise, reagent and instrument used in the following embodiment are commercially available product.
Material characterization instrument:
(1) transmission electron microscope: model H-7650, manufacturer are Hitachi Hitachi, Ltd
(2) elemental analyser: model Vario-EL-cube, manufacturer are Elementary company of Germany
(3) physical adsorption appearance: model ASAP2020, manufacturer are U.S. micrometritics company
Prepare embodiment 1: the preparation of nitrogen-doped porous carbon material supported Pt catalysts
The bamboo shoots that 1kg is cleaned up cut into pieces, and are heated to drying for 70 DEG C in an oven, obtain solid and be ground into a powder.
It takes 2g powder to be added in the 20mL dilute sulfuric acid that weight percent is 1.5%, is uniformly mixed and moves back in hydrothermal reaction kettle, in
180 DEG C are reacted 8 hours, are filtered, washed, are dried to obtain brown solid.Obtained drying solid is put in tube furnace later
Calcined in nitrogen gas atmosphere, 550 DEG C range inside holding 5 hours.Sample is taken out to get arriving after tube furnace drops to room temperature
Nitrogen-doped porous carbon material, nitrogen content are about 7.0at%, specific surface area 180m2/g.The N doping for taking 1.0g to prepare is porous
Carbon material, with 50mL deionized water, 5mL H2PtCl6Solution (Pt concentration 0.01g/mL) mixing, using 2mL 0.1M sodium borohydride
It is restored, carries out filtering and washing, the dry Pt catalyst loaded to get N doping porous carbon later.Fig. 1 is according to this implementation
The TEM figure of the Pt catalyst of the N doping porous carbon load of example preparation, as shown in Figure 1, Pt nano particle uniformly divides in the material
It dissipates in carbon material surface, granular size is about 4.3nm.
Prepare embodiment 2:
Other than carburizing temperature is changed to 850 DEG C, other prepare nitrating carbon materials according to the preparation identical method of embodiment 1
Material and Pt supported catalyst.The result shows that the material nitrogen content is 2.8at%, BET test result shows specific surface for elemental analysis
Product is about 650m2/ g, Fig. 2 are that the TEM of the Pt catalyst loaded according to N doping porous carbon manufactured in the present embodiment schemes, such as Fig. 2
Shown, Pt nano particle is dispersed in carbon material surface in the material, and 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 preparation identical method of embodiment 1.
Embodiment 1
It is put into 0.25g furfural in autoclave high-pressure reactor, it is porous that the N doping prepared in 0.025g preparation embodiment 1 is added
Carbon material supported Pt catalyst, 20mL deionized water are filled with 1MPa hydrogen, are reacted at 100 DEG C after closed, reaction 4 is small
Shi Hou is cooled to room temperature, filtering reacting liquid, carries out gas chromatographic analysis to reaction solution.The result shows that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 100%, and the selectivity of furfural is greater than 99%.
Embodiment 2
It is put into 0.25g furfural in autoclave high-pressure reactor, it is porous that the N doping prepared in 0.025g preparation embodiment 2 is added
Carbon material supported Pt catalyst, 20mL deionized water are filled with 1MPa hydrogen, are reacted at 100 DEG C after closed, reaction 4 is small
Shi Hou is cooled to room temperature, filtering reacting liquid, carries out gas chromatographic analysis to reaction solution.The result shows that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 45%, and the selectivity of furfural about 88%, there are also a small amount of cyclopentenone (about 3%) and 4- hydroxyl -2- cyclopentene
Ketone (4%) generates.
Embodiment 3
It is put into 0.25g furfural in autoclave high-pressure reactor, it is porous that the N doping prepared in 0.025g preparation embodiment 1 is added
Carbon material supported Pt catalyst, 20mL deionized water are filled with 3MPa hydrogen, are reacted at 160 DEG C after closed, reaction 4 is small
Shi Hou is cooled to room temperature, filtering reacting liquid, carries out gas chromatographic analysis to reaction solution.The result shows that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 100%, and the selectivity of cyclopentanone is about 49%, and cyclopentanol selectively about 7%, cyclopentenone selectivity is about
It is 20%, furfuryl alcohol is selectively about 14%, 4- hydroxyl -2- cyclopentenone about 10%.
Embodiment 4
It is put into 0.25g furfural in autoclave high-pressure reactor, it is porous that the N doping prepared in 0.025g preparation embodiment 2 is added
Carbon material supported Pt catalyst, 20mL deionized water are filled with 3MPa hydrogen, are reacted at 160 DEG C after closed, reaction 4 is small
Shi Hou is cooled to room temperature, filtering reacting liquid, carries out gas chromatographic analysis to reaction solution.The result shows that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 100%, and the selectivity of cyclopentanone is 90% or more, cyclopentanol selectively about 5%, cyclopentenone selectivity
About 2%, 4- hydroxyl -2- cyclopentenone about 3%.
Embodiment 5
It is put into 0.25g furfural in autoclave high-pressure reactor, it is porous that the N doping prepared in 0.025g preparation embodiment 3 is added
Carbon material supported Au catalyst, 20mL deionized water are filled with 1MPa hydrogen, are reacted at 100 DEG C after closed, reaction 4 is small
Shi Hou is cooled to room temperature, filtering reacting liquid, carries out gas chromatographic analysis to reaction solution.The result shows that furfural hydrogenation is anti-in water phase
The conversion ratio answered is 35%, the selectivity of furfural about 58%.
Claims (10)
1. a kind of react highly selective using water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst
The method for preparing furfuryl alcohol, which is characterized in that described method includes following steps: furfural, biology is added in autoclave high-pressure reactor
Base N doping porous carbon load type metal catalyst, deionized water, are filled with 0.1~10MPa hydrogen, at 50~250 DEG C after closed
Under reacted, reaction 0.5~48 hour after, be cooled to room temperature, filtering reacting liquid, the loaded catalyst dosage be furfural
The 1%~20% of weight；Water consumption is 50 ~ 200 times of furfural weight, and reaction temperature is 80~120 DEG C, and hydrogen reaction pressure is
The MPa of 0.1 MPa~2, reaction time are 0.5 ~ 6 hour, 99% or more the selectivity of furfuryl alcohol,
Wherein, the loaded catalyst by the wt% of 0.5wt%~5 metallic and the wt% biology base nitrogen of 95 wt%~99.5
Doped porous carbon material carrier is constituted, wherein the specific surface area 150~500 of the biology base nitrogen-doped porous carbon material carrier
m2/ g, nitrogen content are 4~10 wt%, and the metallic is selected from one of palladium, gold, silver, platinum, ruthenium, rhodium, iridium or a variety of expensive
Metallic；
The loaded catalyst is prepared as follows:
1) biological material is dry, it is ground into fine powder；
2) by biological material powder be added to the water or the dilute acid soln of low concentration in be uniformly mixed, biomass and water or diluted acid are molten
The mass ratio of liquid is 1:5 to 1:20；
3) mixture obtained in step 2 is transferred in reaction kettle, 150~250 DEG C is heated under hydrothermal reaction condition,
Heat preservation 3~48 hours, cooling, washing obtains brown solid；
4) solid obtained in step 3) is dried, ground, then calcined in tube furnace, in inert gas or nitrogen
Atmosphere enclose in 400~700 DEG C range inside holding 0.5~100 hour；After tube furnace drops to room temperature by sample take out to get
To the nitrogen-doped porous carbon material of bigger serface；
5) noble-metal-supported nitrogen-doped porous carbon material surface obtained in step 4) is obtained into the loaded catalyst；
Wherein, the biological material described in the step 1) of the loaded catalyst preparation method is rich protein-contg plant,
Comprising sweet potato leaf, fruits of elm, Folium Taraxacum, chrysanthemum miaoye, roundpod jute leaf, burdock leaf, asparagus, bamboo shoots, Cauliflower, spinach, broccoli,
At least one of dictyophora phalloidea is used as carbon source and nitrogen source simultaneously.
2. utilizing water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst according to claim 1
React the highly selective method for preparing furfuryl alcohol, which is characterized in that the institute in the step 1) of the loaded catalyst preparation method
Stating biological material is at least one of spinach, bamboo shoots.
3. utilizing water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst according to claim 1
React the highly selective method for preparing furfuryl alcohol, which is characterized in that the institute in the step 2) of the loaded catalyst preparation method
The diluted acid for stating low concentration is at least one of sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid or phosphoric acid, sour weight percent concentration
It is 0.1~50%.
4. utilizing water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst according to claim 1
React the highly selective method for preparing furfuryl alcohol, which is characterized in that the institute in the step 2) of the loaded catalyst preparation method
The diluted acid for stating low concentration is sulfuric acid or acetic acid.
5. utilizing water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst according to claim 1
React the highly selective method for preparing furfuryl alcohol, which is characterized in that the institute in the step 4) of the loaded catalyst preparation method
Stating inert gas is one of argon gas and helium or a variety of.
6. a kind of react highly selective using water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst
The method for preparing cyclopentanone, which is characterized in that described method includes following steps: furfural, life is added in autoclave high-pressure reactor
Object base N doping porous carbon load type metal catalyst, deionized water, are filled with 0.1~10MPa hydrogen, 50~250 after closed
It is reacted at DEG C, after reaction 0.5~48 hour, is cooled to room temperature, filtering reacting liquid, the loaded catalyst dosage is chaff
The 1%~20% of aldehyde weight；Water consumption is 50 ~ 200 times of furfural weight, and reaction temperature is 140~250 DEG C, hydrogen reaction pressure
For the MPa of 2 MPa~8, the reaction time is 0.5 ~ 6 hour, and the selectivity of cyclopentanone is 90% or more,
Wherein, the loaded catalyst by the wt% of 0.5wt%~5 metallic and the wt% biology base nitrogen of 95 wt%~99.5
Doped porous carbon material carrier is constituted, wherein the specific surface area 500~1500 of the biology base nitrogen-doped porous carbon material carrier
m2/ g, nitrogen content are 1.5~3.5wt%, and the metallic is selected from one of palladium, gold, silver, platinum, ruthenium, rhodium, iridium or a variety of
Noble metal；
The loaded catalyst is prepared as follows:
1) biological material is dry, it is ground into fine powder；
2) by biological material powder be added to the water or the dilute acid soln of low concentration in be uniformly mixed, biomass and water or diluted acid are molten
The mass ratio of liquid is 1:5 to 1:20；
3) mixture obtained in step 2 is transferred in reaction kettle, 150~250 DEG C is heated under hydrothermal reaction condition,
Heat preservation 3~48 hours, cooling, washing obtains brown solid；
4) solid obtained in step 3) is dried, ground, then calcined in tube furnace, in inert gas or nitrogen
Atmosphere enclose in 800~1000 DEG C range inside holding 0.5~100 hour；After tube furnace drops to room temperature by sample take out to get
To the nitrogen-doped porous carbon material of bigger serface；
5) noble-metal-supported nitrogen-doped porous carbon material surface obtained in step 4) is obtained into the loaded catalyst；
Wherein, the biological material described in the step 1) of the loaded catalyst preparation method is rich protein-contg plant,
Comprising sweet potato leaf, fruits of elm, Folium Taraxacum, chrysanthemum miaoye, roundpod jute leaf, burdock leaf, asparagus, bamboo shoots, Cauliflower, spinach, broccoli,
At least one of dictyophora phalloidea is used as carbon source and nitrogen source simultaneously.
7. utilizing water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst according to claim 6
React the highly selective method for preparing cyclopentanone, which is characterized in that in the step 1) of the loaded catalyst preparation method
The biological material is at least one of spinach, bamboo shoots.
8. utilizing water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst according to claim 6
React the highly selective method for preparing cyclopentanone, which is characterized in that in the step 2) of the loaded catalyst preparation method
The diluted acid of the low concentration is at least one of sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid or phosphoric acid, and sour weight percent is dense
Degree is 0.1~50%.
9. utilizing water phase furfural hydrogenation using biology base N doping porous carbon load type metal catalyst according to claim 6
React the highly selective method for preparing cyclopentanone, which is characterized in that in the step 2) of the loaded catalyst preparation method
The diluted acid of the low concentration is sulfuric acid or acetic acid.
10. being added according to claim 6 using biology base N doping porous carbon load type metal catalyst using water phase furfural
Hydrogen reacts the highly selective method for preparing cyclopentanone, which is characterized in that in the step 4) of the loaded catalyst preparation method
Described in inert gas be one of argon gas and helium or a variety of.
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