CN113649004A - Hollow carbon sphere loaded metal particle catalyst and preparation method and application thereof - Google Patents
Hollow carbon sphere loaded metal particle catalyst and preparation method and application thereof Download PDFInfo
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- CN113649004A CN113649004A CN202110766499.7A CN202110766499A CN113649004A CN 113649004 A CN113649004 A CN 113649004A CN 202110766499 A CN202110766499 A CN 202110766499A CN 113649004 A CN113649004 A CN 113649004A
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- hollow carbon
- metal
- carbon sphere
- catalyst
- metal particle
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002923 metal particle Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008346 aqueous phase Substances 0.000 claims abstract description 10
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 239000005011 phenolic resin Substances 0.000 claims abstract description 8
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000012141 vanillin Nutrition 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 238000006462 rearrangement reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of catalysis, and particularly relates to a hollow carbon sphere loaded metal particle catalyst, and a preparation method and application thereof. The catalyst consists of a hollow carbon sphere shell layer and metal particles distributed on the inner surface of the hollow carbon sphere shell. The preparation method comprises the following steps: preparing silicon dioxide nanospheres coated with phenolic resin, preparing a carbon-coated silicon dioxide material, preparing hollow carbon spheres and preparing a hollow carbon sphere-loaded metal particle catalyst; the size of the hollow carbon spheres can be controlled by controlling the size of the silicon spheres, and the thickness of the spherical shell can be controlled by controlling the amounts of resorcinol and formaldehyde; the catalyst prepared by the invention has a large internal cavity, the active metal is coated to a lower degree, the space confinement effect of the shell layer protects the active metal, the activity loss is small, the stability is good, and the problem of inactivation caused by loss, agglomeration and the like of metal components in the catalytic process is solved. Can be applied to catalyzing furfural aqueous phase hydrogenation to prepare cyclopentanone and vanillin aqueous phase hydrogenation deoxidation reaction.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a hollow carbon sphere loaded metal particle catalyst, and a preparation method and application thereof.
Background
The catalyst is an essential part in the industrial production of chemicals. Most of the existing chemical production reactions need to be carried out in a liquid phase system, and the separation of the catalyst becomes a problem to be solved. The heterogeneous catalyst is one of catalysts, and is widely favored because it is easily separated from the reaction system after the reaction is completed, thereby greatly reducing the cost of the production process. The heterogeneous catalysts used today are mostly supported metal catalysts made of oxides (e.g. SiO)2，Al2O3Etc.) or carbon materials (e.g., activated carbon, graphene, carbon black, etc.) as the catalyst support, while metals serve as the catalytic active centers. The oxide often faces the problems of structure collapse, phase change and the like under a high-temperature environment, so that the reduction of the specific surface area and the loss of active sites are caused, and the great loss of the activity is caused. Carbon materials are more stable in high temperature environments than oxides, but because carbon materials are generally inert surfaces, it is difficult to create strong interactions with the active metal and not anchor the metal. Therefore, the active metal can easily fall off from the surface of the carbon material, so that the loss of the active metal is caused, and the catalytic performance is greatly influenced, and the phenomenon is more prominent in an aqueous solution system. Therefore, the stability of the catalyst in a high-temperature liquid phase environment is an urgent problem to be solved.
Scientific research finds that the stability of the carbon-based metal catalyst can be greatly improved by changing the morphology of the carbon material and utilizing the space confinement effect generated by the pore channels and the like of the material. The core-shell structure is a common material configuration for improving the stability of the catalyst by utilizing the space confinement effect. By utilizing the protective effect of the shell layer on the active metal, the precipitation and agglomeration of the metal in the catalytic process can be effectively prevented, so that the stability of the catalyst is improved. However, the core-shell structure may affect the sufficient contact between the reactant and the catalyst, so that the activity of the catalyst may be reduced, and most of the existing core-shell catalysts are complicated in preparation process and high in cost.
Disclosure of Invention
The invention aims to solve the technical problems that active metal is easy to lose in a high-temperature liquid phase environment and a catalyst is inactivated in the prior art, and provides a hollow carbon sphere loaded metal particle catalyst with high-temperature liquid phase stability, and a preparation method and application thereof.
In order to solve the technical problem, the technical scheme is that the catalyst comprises a plurality of hollow carbon sphere-metal particle units, wherein the hollow carbon sphere-metal particle units comprise hollow carbon spheres and metal particles distributed on the inner surfaces of the hollow carbon sphere shells, and the mass ratio of the metal particles to the hollow carbon spheres is 1 (1-20); the outer diameter of the hollow carbon ball is 100-1000nm, the thickness of the shell is 10-50nm, and pore channels penetrating through the shell are distributed on the shell; the diameter of the pore channel is 2-12nm, the number of the pore channels on each hollow carbon sphere-metal particle unit is 1000-3000, and the particle size of the metal particles is 3-30 nm.
The catalyst is further improved as a hollow carbon sphere loaded metal particle catalyst:
preferably, the metal particles are a single metal or a composite metal formed of two or more metals.
Preferably, the metal particles are a single metal or a composite metal of two or more metals selected from iron, cobalt, nickel, copper, zinc, platinum, palladium and ruthenium.
In order to solve the technical problem of the invention, another technical scheme is that the preparation method of the hollow carbon sphere loaded metal particle catalyst comprises the following steps:
s1, generating a layer of phenolic resin high polymer on the surface of the silicon dioxide nanospheres to prepare a precursor with a core-shell structure;
s2, carrying out high-temperature treatment on the precursor with the core-shell structure in a nitrogen or argon atmosphere to carbonize the phenolic resin high polymer on the surface to obtain a carbon-coated silicon dioxide material;
s3, soaking the carbon-coated silicon dioxide material in an alkaline solution or a hydrofluoric acid solution, and dissolving the silicon dioxide nanospheres to obtain hollow carbon spheres;
s4, adding the hollow carbon spheres into a solution dissolved with metal salt, uniformly mixing by ultrasonic waves, removing the solvent by using a rotary evaporator to obtain black solid powder, and placing the black solid powder in H2In the/Ar mixed atmosphere, heating and then preserving heat to prepare the hollow carbon sphere loaded metal particle catalyst.
The preparation method of the catalyst as the hollow carbon sphere loaded metal particle is further improved:
preferably, in the solution dissolved with the metal salt in step S4, the solvent is ethanol, methanol, acetone or water.
Preferably, the amount of the hollow carbon spheres added to the solution dissolved with the metal salt in step S4 is 50-500 mg/L.
Preferably, said H in step S42H in mixed Ar atmosphere2The volume ratio of the gas to the Ar gas is (2-10):100 percent.
Preferably, in the step S4, the heating is performed first and then the heat preservation is performed for 1-4h when the temperature is increased to 600 ℃ of 250-10 ℃, wherein the heating speed is 2-10 ℃/min.
Preferably, in step S4, the metal salt is any one or a combination of two or more of ferric nitrate, ferric chloride, ferric sulfate, ferric acetylacetonate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetylacetonate, copper nitrate, copper chloride, copper sulfate, copper acetylacetonate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetylacetonate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetylacetonate, platinum chloride, chloroplatinic acid, palladium chloride, ammonium chloropalladate, and ruthenium chloride.
In order to solve the technical problem of the invention, another technical scheme is that the hollow carbon sphere loaded metal particle catalyst is used in the water-phase hydrodeoxygenation reaction for preparing cyclopentanone or vanillin by furfural water-phase hydrogenation.
Compared with the prior art, the invention has the beneficial effects that:
1) solid silicon dioxide is used as a precursor, a phenolic resin high polymer is generated on the surface of the solid silicon dioxide to prepare a precursor with a core-shell structure, then the precursor with the core-shell structure is carbonized at high temperature, a silicon dioxide core is removed through acid/alkali etching, micropores are formed on a hollow carbon sphere shell in the etching process, and reactants enter the inside of the carbon sphere shell through the micropores to react with the silicon dioxide to prepare a carbon sphere with a hollow structure; and loading active metal on the inner surface of the shell layer by a rotary evaporation method to prepare the hollow carbon sphere loaded metal particle catalyst, wherein the size of the hollow carbon sphere can be controlled by controlling the size of the silicon sphere, and the thickness of the spherical shell can be controlled by controlling the amounts of resorcinol and formaldehyde.
2) Different from the traditional core-shell catalyst, the hollow carbon-supported catalyst prepared by the invention has a large internal cavity, the degree of coating active metal is low, the activity loss of the catalyst is low, and the selectivity of a product can be improved by utilizing a micro-reactor effect brought by the cavity in a plurality of multi-step reactions.
3) The hollow carbon sphere shell layer adopted by the invention has a sufficient protection effect on the active metal, and the space confinement effect of the carbon sphere shell layer is utilized to protect the active metal, so that the problems of loss, agglomeration and the like of the active metal in the catalysis process can be avoided, and the problem of the stability of the heterogeneous catalyst in a high-temperature liquid phase, particularly a high-temperature water phase environment is solved.
4) When the catalyst prepared by the invention is used in a catalytic experiment for preparing cyclopentanone by furfural aqueous phase hydrogenation, reactants enter the cavity from the channel of the cavity, and the cavity becomes a micro-reactor, the stability of the nickel-based catalyst loaded by the hollow carbon spheres prepared by the invention reaches more than 3 times of that of the nickel-based catalyst loaded by activated carbon, and the activity reaches 90% of that of the activated carbon catalyst. The invention provides a new solution path for improving the stability of the catalyst.
Drawings
Fig. 1 is a scanning electron microscope image of hollow carbon spheres.
Fig. 2 is a transmission electron microscope image of hollow carbon spheres.
Fig. 3 is a transmission electron microscope image of the hollow carbon spheres loaded with metallic nickel.
Fig. 4(a) and (b) are stability comparisons of nickel-based catalysts respectively supported on hollow carbon spheres and activated carbon.
Fig. 5 is a transmission electron microscope image of the hollow carbon spheres loaded with metallic copper.
Fig. 6(a) and (b) are stability comparisons of copper-based catalysts respectively supported on hollow carbon spheres and activated carbon.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.
Comparative example 1
100mg of activated carbon with the particle size range of 2-20 mu m is taken and added into 10ml of ethanol solution dissolved with 75mg of nickel nitrate hexahydrate. Mixing with ultrasonic wave, removing ethanol with rotary evaporator, and placing the obtained black solid powder in H2And in the/Ar mixed atmosphere, raising the temperature to 400 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2 hours to obtain the active carbon-supported nickel catalyst.
Example 1
A hollow carbon supported nickel-based catalyst with high stability is prepared by mixing hollow carbon and metallic nickel according to a mass ratio of 1: 0.15. The preparation method of the hollow carbon sphere and the loading method of the metal nickel are as follows:
s1, adding 3ml of ammonia water into the mixed solution of 70ml of ethanol and 10ml of water. 3.56ml of tetraethyl silicate were then added rapidly to the above solution with vigorous stirring. Stirring was continued until a white suspension was formed, and then 0.4g of resorcinol and 0.56ml of aqueous formaldehyde were added thereto, and stirring was continued for 24 hours. Centrifugally separating the obtained yellowish-brown solid, washing the yellowish-brown solid for multiple times by using deionized water and absolute ethyl alcohol, and drying the yellowish-brown solid;
and S2, raising the temperature of the dried product to 700 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, and keeping for 5h to fully carbonize the phenolic resin on the surface.
S3, weighing 1g of carbonized solid, adding 4.5ml of hydrofluoric acid, adding 50ml of deionized water, stirring for 2h, filtering and drying to obtain the hollow carbon sphere with the shell thickness of 10-15nm and the diameter of 300 nm.
S4, 100mg of the hollow carbon spheres are added into 10ml of ethanol solution dissolved with 75mg of nickel nitrate hexahydrate. Mixing with ultrasonic wave, removing ethanol with rotary evaporator, and placing the obtained black solid powder in H2And in the/Ar mixed atmosphere, raising the temperature to 400 ℃ at the heating rate of 5 ℃/min, and keeping for 2h to obtain the nickel catalyst loaded on the hollow carbon spheres.
Fig. 1 is a scanning electron micrograph of the hollow carbon sphere prepared in step S3, which shows that the carbon sphere has a uniform morphology and size. FIG. 2 is a transmission electron microscope image of a hollow carbon sphere, which shows that the carbon sphere is hollow inside and the shell thickness is about 10-15 nm.
Fig. 3 is a transmission electron microscope picture of the nickel catalyst supported on the hollow carbon spheres, and it can be seen that nickel particles are uniformly distributed on the inner surface of the shell layer of the hollow carbon spheres.
The nickel catalyst supported by the activated carbon of comparative example 1 and the nickel catalyst supported by the hollow carbon spheres of example 1 are respectively used in the aqueous phase hydrogenation rearrangement reaction of furfural, the reaction is carried out at 150 ℃, after the reaction is finished, the two catalysts are respectively taken out, washed and dried for multiple times by using deionized water and absolute ethyl alcohol, and repeatedly used in the aqueous phase hydrogenation rearrangement reaction of furfural, the product of each reaction and the yield of each product are tested, and the results are respectively shown in (a) and (b) of fig. 4, wherein fig. 4(a) is a bar chart of the product of the nickel catalyst supported by the hollow carbon spheres which is recycled for 10 times and the yield of each product; fig. 4(b) is a bar graph of the products of 5 cycles of activated carbon supported nickel catalyst and the yield of each product.
As can be seen from fig. 4, the hollow carbon sphere supported nickel catalyst still maintains good activity after being recycled for 10 times, while the activated carbon supported nickel catalyst loses 60% of activity after being used once. This comparison fully demonstrates the improvement of the hollow carbon sphere structure for catalyst stability. The activated carbon-supported nickel catalyst is more active for the first use because the active metal nickel is mostly supported on the surface of the activated carbon, the reactant is more easily contacted with the active site, shows higher activity in a short time, and produces cyclopentanol, which is a further hydrogenation product of cyclopentanone. However, due to the lack of effective stabilization measures for activated carbon, activated carbon-supported nickel catalysts are very susceptible to deactivation in aqueous phase reactions and have poor cycle stability.
Comparative example 2
100mg of activated carbon with the particle size range of 2-20 mu m is taken and added into 10ml of ethanol solution dissolved with 40mg of copper nitrate trihydrate. Mixing with ultrasonic wave, removing ethanol with rotary evaporator, and placing the obtained black solid powder in H2And in the/Ar mixed atmosphere, raising the temperature to 250 ℃ at the temperature rise rate of 5 ℃/min, and keeping the temperature for 2h to obtain the activated carbon-supported copper catalyst.
Example 2
A hollow carbon supported copper-based catalyst with high stability is prepared by mixing hollow carbon and metal copper according to a mass ratio of 1: 0.1. The preparation method of the hollow carbon sphere and the loading method of the metal copper are as follows:
s1, adding 3ml of ammonia water into the mixed solution of 70ml of ethanol and 10ml of water. 3.56ml of tetraethyl silicate were then added rapidly to the above solution with vigorous stirring. Stirring was continued until a white suspension was formed, and then 0.3g of resorcinol and 0.56ml of aqueous formaldehyde were added thereto, and stirring was continued for 24 hours. Centrifugally separating the obtained yellowish-brown solid, washing with deionized water and absolute ethyl alcohol for multiple times, and drying;
and S2, raising the temperature of the dried product to 700 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, and keeping for 5h to fully carbonize the phenolic resin on the surface.
S3, weighing 1g of carbonized solid, adding 4.5ml of hydrofluoric acid, adding 50ml of deionized water, stirring for 2h, filtering and drying to obtain the hollow carbon sphere with the shell thickness of 10nm and the diameter of 100 nm.
S4, 100mg of the hollow carbon spheres are added into 10ml of ethanol solution dissolved with 40mg of copper nitrate trihydrate. Mixing with ultrasonic wave, removing ethanol with rotary evaporator, and placing the obtained black solid powder in H2And in the/Ar mixed atmosphere, raising the temperature to 250 ℃ at the temperature rise rate of 5 ℃/min, and keeping for 2h to obtain the hollow carbon sphere-supported copper catalyst.
Fig. 5 is a transmission electron microscope picture of the copper catalyst supported on the hollow carbon spheres prepared in the present example, which shows that the copper particles have a size of about 10nm and are distributed inside the hollow carbon spheres.
The activated carbon-supported copper catalyst of comparative example 2 and the hollow carbon sphere-supported copper catalyst of example 2 were used in a vanillin aqueous phase hydrodeoxygenation experiment, which was conducted at 120 ℃. After the reaction is finished, the two catalysts are respectively taken out, washed and dried for multiple times by using deionized water and absolute ethyl alcohol, and repeatedly used in a vanillin water phase hydrodeoxygenation experiment, and the product of each reaction and the yield of each product are tested, wherein the results are respectively shown in (a) and (b) of fig. 6, wherein the fig. 6(a) is a bar graph of the product of the hollow carbon sphere loaded copper catalyst which is recycled for 5 times and the yield of each product; fig. 6(b) is a bar graph of the products of 5 cycles of activated carbon supported nickel catalyst and the yield of each product.
As can be seen from fig. 6, the hollow carbon sphere supported copper catalyst still maintained good activity after 5 cycles, while the activated carbon supported copper catalyst lost two thirds of its activity after one experiment. The improvement of the hollow carbon sphere structure on the stability of the catalyst is fully demonstrated. The activated carbon-supported copper catalyst has higher activity when being used for the first time, because the active metal copper is mostly supported on the surface of the activated carbon, reactants are more easily contacted with active sites, and the activated carbon-supported copper catalyst shows higher activity in a short time. However, due to the lack of effective stabilizing measures for the activated carbon support, the activated carbon-supported copper catalyst is very easy to deactivate in aqueous phase reaction, and the cycle stability is poor.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (10)
1. The catalyst is characterized by consisting of a plurality of hollow carbon sphere-metal particle units, wherein the hollow carbon sphere-metal particle units comprise hollow carbon spheres and metal particles distributed on the inner surfaces of the hollow carbon sphere shells, and the mass ratio of the metal particles to the hollow carbon spheres is 1 (1-20); the outer diameter of the hollow carbon ball is 100-1000nm, the thickness of the shell is 10-50nm, and pore channels penetrating through the shell are distributed on the shell; the diameter of the pore channel is 2-12nm, the number of the pore channels on each hollow carbon sphere-metal particle unit is 1000-3000, and the particle size of the metal particles is 3-30 nm.
2. The hollow carbon sphere-supported metal particle catalyst according to claim 1, wherein the metal particle is a single metal or a composite metal formed of two or more metals.
3. The hollow carbon sphere-supported metal particle catalyst according to claim 1 or 2, wherein the metal particle is a single metal or a composite metal of two or more metals selected from iron, cobalt, nickel, copper, zinc, platinum, palladium, and ruthenium.
4. A method for preparing a hollow carbon sphere-supported metal particle catalyst according to any one of claims 1 to 3, comprising the steps of:
s1, generating a layer of phenolic resin high polymer on the surface of the silicon dioxide nanospheres to prepare a precursor with a core-shell structure;
s2, carrying out high-temperature treatment on the precursor with the core-shell structure in a nitrogen or argon atmosphere to carbonize the phenolic resin high polymer on the surface to obtain a carbon-coated silicon dioxide material;
s3, soaking the carbon-coated silicon dioxide material in an alkaline solution or a hydrofluoric acid solution, and dissolving the silicon dioxide nanospheres to obtain hollow carbon spheres;
s4, adding the hollow carbon spheres into a solution dissolved with metal salt, uniformly mixing by ultrasonic waves, removing the solvent by using a rotary evaporator to obtain black solid powder, and placing the black solid powder in H2In the/Ar mixed atmosphere, heating and then preserving heat to prepare the hollow carbon sphere loaded metal particle catalyst.
5. The method of claim 4, wherein the solvent in the solution containing the metal salt dissolved therein in step S4 is ethanol, methanol, acetone or water.
6. The method of claim 4, wherein the hollow carbon sphere is added to the solution containing the metal salt in an amount of 50 to 500mg/L in step S4.
7. The method for producing a hollow carbon sphere-supported metal particle catalyst as claimed in claim 4, wherein the H in step S42H in mixed Ar atmosphere2The volume ratio of the gas to the Ar gas is (2-10): 100.
8. The method as claimed in claim 4, wherein the step S4 comprises heating and then maintaining the temperature at 600 ℃ for 1-4h, wherein the heating rate is 2-10 ℃/min.
9. The method of claim 4, wherein the metal salt in step S4 is any one or a combination of two or more selected from the group consisting of ferric nitrate, ferric chloride, ferric sulfate, ferric acetylacetonate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetylacetonate, copper nitrate, copper chloride, copper sulfate, copper acetylacetonate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetylacetonate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetylacetonate, platinum chloride, chloroplatinic acid, palladium chloride, ammonium chloropalladate, and ruthenium chloride.
10. Use of the hollow carbon sphere-supported metal particle catalyst of any one of claims 1 to 3 in an aqueous phase hydrodeoxygenation reaction for the preparation of cyclopentanone or vanillin by aqueous phase hydrogenation of furfural.
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