CN110270375A - A kind of unsaturation carbon-carbon triple bond selective hydrocatalyst and preparation method thereof - Google Patents
A kind of unsaturation carbon-carbon triple bond selective hydrocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN110270375A CN110270375A CN201910586139.1A CN201910586139A CN110270375A CN 110270375 A CN110270375 A CN 110270375A CN 201910586139 A CN201910586139 A CN 201910586139A CN 110270375 A CN110270375 A CN 110270375A
- Authority
- CN
- China
- Prior art keywords
- carbon
- cnf
- catalyst
- carrier
- noble metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000010970 precious metal Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 150000001345 alkine derivatives Chemical group 0.000 claims description 31
- 238000010792 warming Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 229910006069 SO3H Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- 229910004042 HAuCl4 Inorganic materials 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
- 238000000034 method Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005253 cladding Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 23
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 239000010931 gold Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910018830 PO3H Inorganic materials 0.000 description 3
- 229910021132 PdIr Inorganic materials 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- 101100135888 Mus musculus Pdia5 gene Proteins 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 229910021069 Pd—Co Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- 229910020708 Co—Pd Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910021118 PdCo Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 olefin hydrocarbon Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2286—Alkynes, e.g. acetylides
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/18—Gold
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of unsaturated carbon-carbon triple bond selective hydrocatalysts and preparation method thereof.The catalyst is using the carbon nano-fiber of functionalization as carrier-supported precious metal active component, its main feature is that active metal surface cladding thickness controllably has infiltrative carbon-coating, with a thickness of 0.5~3nm, and active component is stably dispersed on carrier, size uniformity, partial size are 1~3nm.Preparation method of the present invention is that one or two kinds of precious metal salts are dissolved in deionized water to be made into mixing salt solution, is impregnated in carrier surface, is heat-treated after reduction through reaction atmosphere, forms carbon layers having thicknesses controllably in active metal surface and has infiltrative CHx@M/CNF-A noble metal catalyst.The catalyst can be applied to during a variety of unsaturated carbon-carbon triple bond selective hydrogenations in the fields such as petrochemical industry, fine chemistry industry, and catalytic performance is prominent, have high activity and C=C double bond selectivity.The catalyst also has good recycling, is easily recycled and reuses.
Description
Technical field
The invention belongs to petrochemical industries and field of fine chemical, and in particular to one kind is for unsaturated carbon-carbon triple bond selection
Property hydrogenation reaction the modified noble metal/carbon nano-fiber catalyst and preparation method thereof of hydrocarbon intermediate species.
Background technique
Unsaturated carbon-carbon triple bond selective hydrogenation is the important support of fine chemistry industry and petrochemical industry, extensively
For in the industrial productions such as chemicals synthesis, pharmaceutical synthesis and agricultural chemicals synthesis.In early days, support type monometallic Pd catalyst
It is commonly used for being catalyzed unsaturated carbon-carbon triple bond selective hydrogenation.Highly selective in order to obtain, industrial common strategy is
The substances such as lead acetate and quinoline are added during catalyst treatment poisons Pd catalyst (Lindlar catalyst) to modify.So
And it is increasingly strict with requiring environment sustainable development, there are more highly toxic lead species seriously to limit Lindlar and urge
The use of agent.
In view of the above problems, researcher selects suitable carrier and exploration by regulation activity component the Nomenclature Composition and Structure of Complexes
New synthetic method improves its catalytic activity, selectivity and stability.Document Identification of non-
precious metal alloy catalysts for selective hydrogenation of acetylene,
Science with Au, Pt, Zn, Ni, Cu etc. is active component in 2008,320,1320-1322, and discovery is urged compared to monometallic Pd
Agent, non-noble metal Ni-Zn alloy are more advantageous to alkynes and convert to the orientation of alkene.For loaded catalyst, carrier
And its concern of researcher is also resulted in interaction at metal interface.Wherein carbon nanomaterial, especially carbon nano-fiber
(carbon nanofiber, CNF) is being urged due to having many advantages, such as high-ratio surface, electronics transfer and rock-steady structure as carrier
Change field of hydrogenation and shows excellent performance.Deng in Bimetallic Co-Pd catalysts:Study of
preparation methods and their influence on the selective hydrogenation of
Acetylene, J.Catal.2013,300 are prepared for loading type Pd-Co catalysis using carbon nanomaterial as carrier in 125-135
Agent is simultaneously applied in selective hydrogenation of acetylene reaction.Catalytic evaluation the result shows that, compared to Al2O3The PdCo catalyst of load,
Pd-Co/C is due to showing excellent ethylene selectivity with strong carrier and metal interaction.Importantly, metal-
Carrier interface site has the characteristics that coordination is unsaturated, to show special electronic state, therefore constructs Metal-Support interface
Structure realizes that selective hydrogenation performance boost becomes the hot spot of the area research.Zaera etc. is in Sub-Monolayer
Control of Mixed-Oxide Support Composition in Catalysts via Atomic Layer
Deposition:Selective Hydrogenation of Cinnamaldehyde Promoted by(SiO2-ALD)-
Pt/Al2O3, by SiO in ACS Catal., 2018,8,8513-85242It is deposited on the surface Pt, has constructed Pt-SiO2Interface position
Point improves the electronic structure of Pt particle, promotes C=O bond activation, improves selectivity.However, in the process for constructing interface
In, the species thickness for being deposited on surface of metal particles is difficult to be precisely controlled and does not have permeability, easily causes the excessive of active site
Cladding, so as to cause catalytic activity sharp fall.In the recent period, Christopher etc. is in Adsorbate-mediated strong
metal-support interactions in oxide-supported Rh catalysts,Nat.Chem.,2017,9,
In 120-127, using reaction gas CO2And H2Revulsion constructs interfacial structure.The study found that compared to conventional Ti OxThe Rh of modification
Catalyst forms Rh-TiO abundant in the catalyst that atmosphere revulsion is constructedx-HCOxInterface site promotes Rh metallic particles electric
While sub- state changes, surface coating layer has permeability, is conducive to the diffusion and absorption of reactant molecule, realizes
CH4Selectivity and CO2Active common promotion.However, improving catalyst in insatiable hunger by the property and structure at regulation interface
Research with performance in carbon-carbon triple bond selective hydrogenation has no relevant report.
In conclusion constructing coordination unsaturated Metal-Support interface site is to improve loaded catalyst adding hydrogen anti-
While answering the effective means of middle selectivity of product, but construct interfacial structure realization selectivity raising in the conventional way, it is deposited on
The species thickness of surface of metal particles is difficult to be precisely controlled and do not have permeability, easily excessively coats to active site, thus
Seriously affect catalytic activity.For the present invention using carbon nano-fiber as catalyst carrier, proposed adoption atmosphere revulsion constructs cladding thickness
Degree is controllable and has infiltrative CHx- Pd-CNF interfacial structure, and it is regulated and controled, obtaining has best coating thickness
And the good single-metal reforming catalyst of permeability, to realize that alkynes molecule is converted to the orientation of olefin hydrocarbon molecules.
Summary of the invention
The object of the present invention is to provide a kind of active metal surface carbon coating layer thickness controllably and with infiltrative CHx@
M/CNF catalyst and preparation method thereof.The catalyst is mainly used for unsaturated carbon-carbon triple bond selective hydrogenation, shows
The characteristics of high activity, selectivity and stability.
Catalyst provided by the invention, is expressed as CHx@M/CNF-A, wherein CHxIt is your gold for bicarbonate x=1 or 2, M
Belong to active component, CNF-A is functionalized carbon nanofiber；The M is one of precious metals pd, Au, Ir, Rh, Ag or two
Kind, preferably Pd, Au or Ir, wherein noble metal quality accounts for the 0.5~5.0% of catalyst gross mass, it is preferred that 0.5~
2.0%；A is functionalization group NO in CNF-A3、SO3H、Cl、PO3One kind of H.
The structure feature of the catalyst is: M is supported on CNF-A carrier, the CH of heat-treating atmosphere induced synthesisxLayer cladding
On noble metal M, coating thickness is controllable and has permeability, with a thickness of 0.5~3nm；Active metal component height and stabilization
It is dispersed in carrier surface, size uniformity, partial size is 1~3nm, and particle size distribution range is narrow.
The preparation method of the catalyst is the carbon nano-fiber using the group containing functionalization as carrier, and noble metal is active group
Point, under alkynes atmosphere and/or alkene atmosphere and hydrogen mixed gas induction, through Overheating Treatment, obtain what hydrocarbon was modified
Loaded noble metal catalyst.
The preparation method of above-mentioned unsaturated carbon-carbon triple bond selective hydrocatalyst provided by the invention, specific steps are such as
Under:
A. by carbon nano-fiber presoma in 2000~3000 DEG C of 2~6h of roasting, and being dispersed in concentration is 30~60%
It is acidified in acid solution, after 60~160 DEG C of 3~48h of reflux, discharging, centrifugation, is washed to neutrality at filtering.The precipitating of acquisition
Object is dried in vacuo 10 in 60~120 DEG C of freeze-day with constant temperature machines~for 24 hours, the carbon nano-fiber that group containing functionalization is A is obtained, is indicated
For CNF-A.
The carbon nano-fiber presoma is that one of PR24-HHT, PR24-XT-HHT and SD2240 model carbon is received
Rice fiber, partial size are 80~300nm, and specific surface is 300~1000m2/g；
The acid solution is one of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and acidification keeps carbon nano-fiber surface band specific
Functionalization group A；The functionalization group A is NO3、SO3H、Cl、PO3One of H.
B. soluble precious-metal salt is dissolved in deionized water, is made into the dipping solution that concentration is 10~50mmol/L, preferably
Concentration be 20~30mmol/L.
The precious metal salt is Na2PdCl4、Pd(NH3)2Cl2、Pd(NO3)2、NaAuCl4、HAuCl4、H2IrCl6、
Na2IrCl6、RhCl3·3H2O、Rh(CH3COO)3、Rh(NO3)3、AgNO3、AgC2H3O2One or both of.Preferably
Na2PdCl4、HAuCl4And Na2IrCl6One of.
C. in the case where room temperature continues stirring condition, the 0.5~5.0% of carrier quality is accounted for according to noble metal, it will be in step A
In the fully dispersed dipping solution to step B of CNF-A carrier, 0.5~2h, filtering are persistently stirred, and do in 60~120 DEG C of constant temperature
Dry 6~for 24 hours；Again in H2The H that volume fraction is 10%2With 2~10 DEG C of min in/Ar gaseous mixture-1Rate be warming up to 200~
400 DEG C of reductase 12~6h, obtain M/CNF-A.
D. the obtained M/CNF-A of step C is placed in reactor, be passed through heat-treating atmosphere keep 5~50h, flow velocity 10~
50mL/min, and with 2~10 DEG C of min-1Rate be warming up to 50~350 DEG C, be down to room temperature taking-up after keeping 15~50h, obtain
To coating thickness controllably and with infiltrative CHx@M/CNF-A catalyst.
The heat-treating atmosphere is containing unsaturated carbon-carbon bond gas and H2Gaseous mixture；Described contains unsaturated carbon-
The gas of carbon key is alkynes and olefin gas, is C2H2、C2H4、C3H6、C3H4、C3H6、C4H6、C4H6、C4H8One of or two
Kind, preferable combination is C2H2/C2H4/H2、C3H4/C3H6/H2And C4H6/H2One of.Wherein, the molar ratio of alkynes and alkene
For 0.01~0.1, H2Molar ratio with alkynes is 2~10.
The characteristics of preparation method is: reaction atmosphere induction forms CH on the surface active metal MxSpecies promote active gold
Metal particles electronic state changes, and by regulation induction atmosphere type, ratio and processing time, forms thickness controllably and has and seep
The CH of permeabilityx@M-CNF is conducive to the diffusion and absorption of reactant molecule, therefore activity with higher and selectivity of product；
In addition, CHx- M-CNF interface interaction keeps catalytically-active metals particle size smaller, and inhibits migration and group during the reaction
Poly- generation is conducive to the stable dispersion of active component, has excellent stability.
Fig. 1 is embodiment 1 in C2H2/C2H4/H2The CH prepared under atmospherex@Pd/CNF-NO3The high-resolution of catalyst transmits
Electron microscope (HRTEM) photo.It can be seen that active metal component is evenly dispersed in carrier surface from HRTEM photo,
Particle size range is 1~3nm, average grain diameter 2.2nm, and active metal surface forms carbon coating layer, with a thickness of 1nm.
It is embodiment 1 in Fig. 2 in C2H2/C2H4/H2The CH prepared under atmospherex@Pd/CNF-NO3Catalyst is in acid solution
Course of dissolution photo, it can be seen that the clad of active metal surface has permeability from photo, and permeability is good.
Fig. 3 is embodiment 2 in C4H6/H2The CH prepared under atmospherex@Pd/CNF-NO3The high-resolution transmitted electron of catalyst is aobvious
Micro mirror (HRTEM) photo.It can be seen that active metal is uniformly distributed from HRTEM photo, range is 1.5~7.0nm, average grain diameter
For 5.0nm.Active metal surface forms carbon coating layer, with a thickness of 2nm.
It is embodiment 2 in Fig. 4 in C4H6/H2The CH prepared under atmospherex@Pd/CNF-NO3Catalyst dissolved in acid solution
Journey photo, it can be seen that the clad of active metal surface has permeability from photo.
Fig. 5 is CH prepared by embodiment 1x@Pd/CNF-NO3Experiment knot of the catalyst in selective hydrogenation of acetylene reaction
Fruit, a are curve of the conversion of alkyne to reaction temperature, and b is curve of the ethylene selectivity to reaction temperature.When reaction temperature is
250 DEG C, for conversion of alkyne close to 100%, corresponding ethylene selectivity is 90%.
Fig. 6 is CH prepared by embodiment 1x@Pd/CNF-NO3Stability column of the catalyst in selective hydrogenation of acetylene reaction
Shape figure.Catalyst successive reaction 25h, every 0.5h take a little primary, conversion of alkyne 100%, and ethylene selectivity is 90% ±
3%, no significant change.
Fig. 7 is CH prepared by embodiment 2x@Pd/CNF-NO3Experiment knot of the catalyst in selective hydrogenation of acetylene reaction
Fruit, a are curve of the conversion of alkyne to reaction temperature, and b is curve of the ethylene selectivity to reaction temperature.When reaction temperature is
250 DEG C, conversion of alkyne 100%, corresponding ethylene selectivity is 80%.
Fig. 8 is CH prepared by embodiment 2x@Pd/CNF-NO3Stability column of the catalyst in selective hydrogenation of acetylene reaction
Shape figure.Catalyst successive reaction 25h, every 0.5h take a little primary, conversion of alkyne 100%, and ethylene selectivity is 80% ±
3%, no significant change.
Beneficial effects of the present invention:
Preparation method feature provided by the present invention is: the carbon nano-fiber handled using acid solution is carrier, using tradition
Infusion process is heat-treated in the mixed atmosphere containing alkynes in load after noble metal active component, makes active noble metals nano particle
Surface forms CHxClad obtains CHx@M/CNF catalyst.Preparation condition is mild, and preparation process is not necessarily to that surfactant is added,
Simple process.
The catalyst activity metal particle size being prepared is smaller, dispersion degree is high, and particle diameter distribution is relatively narrow, and active metal
Surface coated carbon layers having thicknesses are controllable and have permeability, result in CH abundantxThe interface-M-CNF site, solve due to
Conventional method constructs interfacial structure coating thickness and is difficult to be precisely controlled and do not have permeability, easily excessively wraps to active site
The problems such as covering.
The catalyst can be applied to during a variety of unsaturated carbon-carbon triple bond selective hydrogenations, have excellent C ≡
C key hydrogenation activity and C=C key selectivity, catalytic performance is prominent, is easily recycled and reuses, with good stability.
Detailed description of the invention:
Fig. 1 is embodiment 1 in C2H2/C2H4/H2The CH prepared under atmospherex@Pd/CNF-NO3The high-resolution of catalyst transmits
Electron microscope (HRTEM) photo.
Fig. 2 is embodiment 1 in C2H2/C2H4/H2The CH prepared under atmospherex@Pd/CNF-NO3Catalyst is molten in acid solution
Solution preocess photo.
Fig. 3 is embodiment 2 in C4H6/H2The CH prepared under atmospherex@Pd/CNF-NO3The high-resolution transmitted electron of catalyst is aobvious
Micro mirror (HRTEM) photo.
It is embodiment 2 in Fig. 4 in C4H6/H2The CH prepared under atmospherex@Pd/CNF-NO3Catalyst dissolved in acid solution
Journey photo.
Fig. 5 is CH prepared by embodiment 1x@Pd/CNF-NO3Experiment knot of the catalyst in selective hydrogenation of acetylene reaction
Fruit, a are curve of the conversion of alkyne to reaction temperature, and b is curve of the ethylene selectivity to reaction temperature.
Fig. 6 is CH prepared by embodiment 1x@Pd/CNF-NO3Stability of the catalyst in selective hydrogenation of acetylene reaction is bent
Line.
Fig. 7 is CH prepared by embodiment 2x@Pd/CNF-NO3Experiment knot of the catalyst in selective hydrogenation of acetylene reaction
Fruit, a are curve of the conversion of alkyne to reaction temperature, and b is curve of the ethylene selectivity to reaction temperature.
Fig. 8 is CH prepared by embodiment 2x@Pd/CNF-NO3Stability of the catalyst in selective hydrogenation of acetylene reaction is bent
Line.
Specific embodiment:
Embodiment 1
A. by the carbon matrix precursor of 2g model PR24-HHT in 3000 DEG C of roasting 2h, and it is dispersed in the nitric acid that concentration is 50%
In be acidified, after 100 DEG C of reflux 48h, discharging, centrifugation, is washed to neutrality at filtering.The sediment of acquisition is in 60 DEG C of constant temperature
10h is dried in vacuo in drying machine, obtaining group containing functionalization is NO3Carbon nano-fiber, be denoted as CNF-NO3, carrier dimensions are
200nm。
B. 0.6440g PdCl is weighed2100mL is dissolved in deionized water and be settled to 0.4250g NaCl, is configured to
36mmol/L Na2PdCl4Solution.
C. in the case where room temperature continues stirring condition, by the carbon nano-fiber CNF-NO of acid processing in 0.4g step A3, sufficiently divide
The concentration for being scattered to 560 μ L step B preparation is 36mmol/L Na2PdCl4In solution, wherein active metal Pd accounts for carrier quality content
1.0wt.%, persistently stir 2h, be placed in 60 DEG C of thermostatic driers it is dry for 24 hours, then 10% H2In/Ar gaseous mixture
With 10 DEG C of min-1Rate be warming up to 250 DEG C of reduction, and keep 2h, obtain Pd/CNF-N catalyst.
D. the Pd/CNF-N catalyst that step C is obtained is placed in reactor, is passed through heat-treating atmosphere C2H2/C2H4/H2It protects
50h, flow velocity 40mL/min are held, wherein the molar ratio of alkynes and alkene is 0.01, H2Molar ratio with alkynes is 2, and with 10
℃·min-1Rate be warming up to 250 DEG C, be down to room temperature taking-up after keeping 50h, obtain coating thickness and be 1nm and there is infiltration
The CH of propertyx@Pd/CNF-NO3Catalyst.
The catalyst of above-mentioned preparation is used for selective hydrogenation of acetylene reaction experiment:
It weighs after the quartz sand that 0.05g catalyst and 1.7mL partial size are 20~40 mesh is sufficiently mixed, loadings diameter is 7mm
Crystal reaction tube in.Gas componant is 0.6% acetylene/1.2% hydrogen/5.4% ethylene/nitrogen balance in reactor feed gas
Gas, catalytic performance test temperature are 50~250 DEG C, and 25 DEG C of test temperature interval, test pressure is 1bar.Reactant, product
Composition and content are analyzed by gas-chromatography, and data processing method is internal standard method, and internal standard compound is propane.To guarantee test essence
Degree reaches assigned temperature and 5h, every 0.5h is kept to take a little 1 time, as a result sees Fig. 5；Catalyst successive reaction 25h, every 0.5h take a little 1
It is secondary, as a result see Fig. 6.
Embodiment 2
A. by the carbon matrix precursor of 2g model PR24-XT-HHT in 3000 DEG C of processing 2h, and being dispersed in concentration is 30%
In nitric acid, after 100 DEG C of reflux 48h, discharging, centrifugation, is washed to neutrality at filtering.The sediment of acquisition is in 100 DEG C of freeze-day with constant temperature
10h is dried in vacuo in machine, obtaining group containing functionalization is NO3Carbon nano-fiber, be denoted as CNF-NO3, carrier dimensions 200nm.
B. 0.6440g PdCl is weighed2100mL is dissolved in deionized water and be settled to 0.4250g NaCl, is configured to
36mmol/L Na2PdCl4Solution.
C. in the case where room temperature continues stirring condition, by the carbon nano-fiber CNF-NO of acid processing in 0.4g step A3, sufficiently divide
The concentration for being scattered to 560 μ L step B preparation is 36mmol/L Na2PdCl4In solution, wherein active metal Pd accounts for carrier quality content
1.0wt.%, persistently stir 2h, be placed in 60 DEG C of thermostatic driers it is dry for 24 hours, then in H2Volume fraction is 10%
H2With 10 DEG C of min in/Ar gaseous mixture-1Rate be warming up to 250 DEG C of reduction, and keep 2h, obtain Pd/CNF-NO3Catalyst.
D. the Pd/CNF-N catalyst that step C is obtained is placed in reactor, is passed through heat-treating atmosphere C4H6/H2It keeps
The molar ratio of 25h, flow velocity 50mL/min, alkynes and alkene is 0.01, H2Molar ratio with alkynes is 2, and with 10 DEG C of min-1
Rate be warming up to 250 DEG C, be down to room temperature taking-up after keeping 50h, obtain coating thickness and be 2nm and there is infiltrative CHx@
Pd/CNF-N catalyst.
The catalyst of above-mentioned preparation is used for selective hydrogenation of acetylene reaction experiment according to the method for embodiment 1, is as a result seen
Fig. 7, Fig. 8.
Embodiment 3
A. it by the carbon matrix precursor of 2g model SD2240 in 3000 DEG C of processing 6h, and is dispersed in the sulfuric acid that concentration is 30%
It is acidified, after 120 DEG C of reflux for 24 hours, discharging, centrifugation, is washed to neutrality at filtering.The sediment of acquisition is dry in 100 DEG C of constant temperature
It is dried in vacuo 10h in dry machine, obtaining group containing functionalization is SO3The carbon nano-fiber of H, is denoted as CNF-SO3H, carrier dimensions are
100nm。
B. 1g AuCl is weighed3It is dissolved in deionized water and is settled to 100mL, is configured to 50mmol/L HAuCl4Solution.
C. by the HAuCl of 1mL 50mmol/L4Solution is added in 110 μ L deionized waters, continues stirring condition in room temperature
Under, by the carbon nano-fiber CNF-SO of acid processing in 0.2g step A3H is added in above-mentioned solution, and wherein active metal Au accounts for load
The 5.0wt.% of weight content, persistently stirs 4h, dry 10h is placed in 80 DEG C of thermostatic driers, then in H2Volume point
The H that number is 10%2With 2 DEG C of min in/Ar gaseous mixture-1Rate be warming up to 350 DEG C of reduction, and keep 4h, obtain Au/CNF-
SO3H catalyst.
D. Au/CNF-SO step C obtained3H catalyst is placed in reactor, is passed through heat-treating atmosphere C2H2/H2It keeps
The molar ratio of 12h, flow velocity 30mL/min, alkynes and alkene is 0.1, H2Molar ratio with alkynes is 10, and with 2 DEG C of min-1's
Rate is warming up to 350 DEG C, is down to room temperature taking-up after keeping 20h, obtains coating thickness and is 2.5nm and has infiltrative CHx@
Au/CNF-SO3H catalyst.
Embodiment 4
A. by the carbon matrix precursor of 2g model PR24-HHT in 2000 DEG C of processing 6h, and it is dispersed in the sulfuric acid that concentration is 50%
In be acidified, after 60 DEG C of reflux 18h, discharging, centrifugation, is washed to neutrality at filtering.The sediment of acquisition is in 120 DEG C of constant temperature
12h is dried in vacuo in drying machine, obtaining group containing functionalization is SO3The carbon nano-fiber of H, is denoted as CNF-SO3H, carrier dimensions are
150nm。
B. 1g AuCl is weighed3It is dissolved in deionized water and is settled to 100mL, is configured to 50mmol/L HAuCl4Solution.
C. by the HAuCl of 1mL 50mmol/L4Solution is added in 110 μ L deionized waters, continues stirring condition in room temperature
Under, by the carbon nano-fiber CNF-SO of acid processing in 0.2g step A3H is added in above-mentioned solution, and wherein active metal Au accounts for load
The 5.0wt.% of weight content, persistently stirs 1.5h, dry 20h is placed in 80 DEG C of thermostatic driers, then in H2Volume
The H that score is 10%2With 2 DEG C of min in/Ar gaseous mixture-1Rate be warming up to 300 DEG C of reduction, and keep 4h, obtain Au/
CNF-SO3H catalyst.
D. Au/CNF-SO step C obtained3H catalyst is placed in reactor, pulse heat-treating atmosphere C3H4/C3H6/H2
25h, flow velocity 10mL/min are kept, the molar ratio of alkynes and alkene is 0.1, H2Molar ratio with alkynes is 10, and with 5 DEG C
min-1Rate be warming up to 50 DEG C, be down to room temperature taking-up after keeping 15h, obtain coating thickness and be 1nm and have infiltrative
CHx@Au/CNF-SO3H catalyst.
Embodiment 5
A. by the carbon matrix precursor of 2g model PR24-XT-HHT in 2500 DEG C of processing 4h, and being dispersed in concentration is 30%
It is acidified in phosphoric acid, after 120 DEG C of reflux for 24 hours, discharging, centrifugation, is washed to neutrality at filtering.The sediment of acquisition is in 80 DEG C
It is dried in vacuo 10h in freeze-day with constant temperature machine, obtaining group containing functionalization is PO3The carbon nano-fiber of H, is denoted as CNF-PO3H, carrier ruler
Very little is 200nm.
B. 0.26g RhCl is weighed3·3H2O is dissolved in deionized water and is settled to 100mL, is configured to 25mmol/L Rh's
Precursor solution.
C. by 1.0ml 25mmol/L RhCl3Solution is added in 150 μ L deionized waters, continues stirring condition in room temperature
Under, by the carbon nano-fiber CNF-PO of acid processing in 0.0858g step A3H is added in above-mentioned solution, wherein active metal Rh
The 3.0wt.% for accounting for carrier quality content, persistently stirs 1h, is placed in 100 DEG C of thermostatic driers and dries for 24 hours, then in H2Body
The H that fraction is 10%2With 5 DEG C of min in/Ar gaseous mixture-1Rate be warming up to 35 DEG C of C reduction, and keep 6h, obtain Rh/
CNF-PO3H catalyst.
D. Rh/CNF-PO step C obtained3H catalyst is placed in reactor, is passed through heat-treating atmosphere C2H2/C2H4/H2
5h, flow velocity 50mL/min are kept, the molar ratio of alkynes and alkene is 0.01, H2Molar ratio with alkynes is 5, and with 5 DEG C of min-1Rate be warming up to 100 DEG C, be down to room temperature taking-up after keeping 50h, obtain coating thickness and be 0.5nm and have infiltrative
CHx@Rh/CNF-PO3H catalyst.
Embodiment 6
A. by the carbon matrix precursor of 2g model PR24-HHT in 2000 DEG C of processing 3h, and it is dispersed in the hydrochloric acid that concentration is 50%
In be acidified, after 60 DEG C of reflux 18h, discharging, centrifugation, is washed to neutrality at filtering.The sediment of acquisition is dry in 90 DEG C of constant temperature
It is dried in vacuo 12h in dry machine, the carbon nano-fiber that group containing functionalization is Cl is obtained, is denoted as CNF-Cl, carrier dimensions are
100nm。
B. it weighs 0.3878g Ir and is dissolved in chloroazotic acid and is settled to 100mL, be configured to the Na of 20mmol/L2IrCl6Solution；
Weigh 0.6440g PdCl2100mL is dissolved in deionized water and be settled to 0.4250g NaCl, is configured to 36mmol/
LNa2PdCl4Solution.
C. by the 20mmol/L Na of 5.0ml2IrCl6With 36mmol/L Na2PdCl4Solution is added to 150 μ L deionized waters
In, in the case where room temperature continues stirring condition, the carbon nano-fiber CNF-Cl of acid processing in 1.0g step A is added to above-mentioned solution
In, wherein active metal Pd and Ir accounts for the 2.0wt.% of carrier quality content respectively, persistently stirs 0.5h, is placed in 90 DEG C of constant temperature
Dry 6h in drier, then in H2The H that volume fraction is 10%2With 10 DEG C of min in/Ar gaseous mixture-1Rate be warming up to
400 DEG C of reduction, and 6h is kept, obtain PdIr/CNF-Cl catalyst.
D. the PdIr/CNF-Cl catalyst that step C is obtained is placed in reactor, is passed through heat-treating atmosphere C4H6/C4H8/H2
45h, flow velocity 20mL/min are kept, the molar ratio of alkynes and alkene is 0.1, H2Molar ratio with alkynes is 8, and with 10 DEG C
min-1Rate be warming up to 250 DEG C, be down to room temperature taking-up after keeping 45h, obtain coating thickness and be 3nm and have infiltrative
CHx@PdIr/CNF-Cl catalyst.
Claims (4)
1. a kind of preparation method of unsaturation carbon-carbon triple bond selective hydrocatalyst, the specific steps are as follows:
A. by carbon nano-fiber presoma in 2000~3000 DEG C of 2~6h of roasting, and it is molten to be dispersed in the acid that concentration is 30~60%
Be acidified in liquid, after 60~160 DEG C of 3~48h of reflux, discharging, centrifugation, is washed to neutrality at filtering, by sediment in 60~
120 DEG C of constant-temperature vacuums dry 10~for 24 hours, the carbon nano-fiber that group containing functionalization is A is obtained, CNF-A is expressed as；
The carbon nano-fiber presoma is one of PR24-HHT, PR24-XT-HHT and SD2240 model, partial size 80
~300nm, specific surface are 300~1000m2/g；
The acid solution is one of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and acidification makes carbon nano-fiber surface band specific function
Change group A；The functionalization group A is NO3、SO3H、Cl、PO3One of H；
B. soluble precious-metal salt is dissolved in deionized water, is made into the dipping solution that concentration is 10~50mmol/L；
The precious metal salt is Na2PdCl4、Pd(NH3)2Cl2、Pd(NO3)2、NaAuCl4、HAuCl4、H2IrCl6、Na2IrCl6、
RhCl3·3H2O、Rh(CH3COO)3、Rh(NO3)3、AgNO3、AgC2H3O2One or both of；
C. at room temperature, the 0.5~5.0% of carrier quality is accounted for according to noble metal, the CNF-A carrier in step A is fully dispersed
Into the dipping solution of step B, 0.5~2h is persistently stirred, filtering, and in 60~120 DEG C of freeze-day with constant temperature 6~for 24 hours；Again in H2Body
The H that fraction is 10%2With 2~10 DEG C of min in/Ar gaseous mixture-1Rate be warming up to 200~400 DEG C of reductase 12~6h, obtain
To the functionalized carbon nanofiber for having loaded noble metal, it is expressed as M/CNF-A, M represents noble metal；
D. the obtained M/CNF-A of step C is placed in reactor, is passed through heat-treating atmosphere and keeps 5~50h, 10~50mL/ of flow velocity
Min, and with 2~10 DEG C of min-1Rate be warming up to 50~350 DEG C, be down to room temperature taking-up after keeping 15~50h, coated
Thickness degree is controllable and has infiltrative CHx@M/CNF-A catalyst；
The heat-treating atmosphere is alkynes, alkene and H containing unsaturated carbon-carbon bond2Gaseous mixture；The alkynes, alkene
It is C2H2、C2H4、C3H6、C3H4、C3H6、C4H6、C4H6、C4H8One or both of；Wherein, the molar ratio of alkynes and alkene is
0.01~0.1, H2Molar ratio with alkynes is 2~10.
2. the preparation method of unsaturation carbon-carbon triple bond selective hydrocatalyst according to claim 1, it is characterized in that step
The concentration of dipping solution described in rapid B is 20~30mmol/L；The precious metal salt is Na2PdCl4、HAuCl4And Na2IrCl6
One of；It is C that noble metal described in step C, which accounts for heat-treating atmosphere described in 0.5~2.0% step D of carrier quality,2H2/
C2H4/H2、C3H4/C3H6/H2And C4H6/H2One of.
3. the unsaturated carbon-carbon triple bond selective hydrocatalyst of preparation according to the method for claim 1, is expressed as CHx@
M/CNF-A, wherein CHxFor bicarbonate, x=1 or 2, M are noble metal active component, and CNF-A is functionalized carbon nanofiber；
The M is one or both of precious metals pd, Au, Ir, Rh, Ag, and wherein noble metal quality accounts for the 0.5 of catalyst gross mass
~5%；The A is functionalization group NO3、SO3H、Cl、PO3One kind of H；The structure feature of the catalyst is: M is supported on
On CNF-A carrier, the CH of heat-treating atmosphere induced synthesisxLayer is coated on noble metal M, and coating thickness is controllable and has infiltration
Property, with a thickness of 0.5~3nm；Active metal component height and it is stably dispersed in carrier surface, size uniformity, partial size is 1~3nm.
4. unsaturation carbon-carbon triple bond selective hydrocatalyst according to claim 3, it is characterized in that the M is expensive
Metal Pd, Au or Ir, wherein noble metal quality accounts for the 0.5~2.0% of catalyst gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910586139.1A CN110270375B (en) | 2019-07-01 | 2019-07-01 | Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910586139.1A CN110270375B (en) | 2019-07-01 | 2019-07-01 | Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110270375A true CN110270375A (en) | 2019-09-24 |
| CN110270375B CN110270375B (en) | 2020-09-11 |
Family
ID=67963876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910586139.1A Active CN110270375B (en) | 2019-07-01 | 2019-07-01 | Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110270375B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337509A (en) * | 2020-11-05 | 2021-02-09 | 北京化工大学 | MOF-based transition metal monatomic catalyst for carbon-carbon triple bond selective hydrogenation and preparation method thereof |
| CN114797845A (en) * | 2022-05-18 | 2022-07-29 | 北京化工大学 | Pd catalyst for carbon-carbon triple bond selective hydrogenation reaction and preparation method thereof |
| CN115055181A (en) * | 2022-07-06 | 2022-09-16 | 四川大学 | Method for preparing high-performance CO catalyst by recycling waste noble metal catalyst |
| CN115282955A (en) * | 2022-08-16 | 2022-11-04 | 北京化工大学 | Catalyst for selective hydrogenation of alkyne and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389295A (en) * | 2002-06-10 | 2003-01-08 | 中国科学院大连化学物理研究所 | Ru-based ammonia synthesizing catalyst carried by nano carbon fiber and its prepn. |
| CN1966144A (en) * | 2006-09-06 | 2007-05-23 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
| CN101444728A (en) * | 2007-11-27 | 2009-06-03 | 北京化工大学 | Method for preparing novel carbon nano-fiber platinum catalyst |
| CN107970919A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Modified carbon nano tube material |
-
2019
- 2019-07-01 CN CN201910586139.1A patent/CN110270375B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389295A (en) * | 2002-06-10 | 2003-01-08 | 中国科学院大连化学物理研究所 | Ru-based ammonia synthesizing catalyst carried by nano carbon fiber and its prepn. |
| CN1966144A (en) * | 2006-09-06 | 2007-05-23 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
| CN101444728A (en) * | 2007-11-27 | 2009-06-03 | 北京化工大学 | Method for preparing novel carbon nano-fiber platinum catalyst |
| CN107970919A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Modified carbon nano tube material |
Non-Patent Citations (2)
| Title |
|---|
| JOHN C. MATSUBU等: "Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts", 《NATURE CHEMISTRY》 * |
| ZHIHUANWENG等: "Sub-Monolayer Control of Mixed-Oxide Support Composition in Catalysts via Atomic Layer Deposition:Selective Hydrogenation of Cinnamaldehyde Promoted by(SiO2-ALD)-Pt/Al2O3", 《ACS CATAL.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337509A (en) * | 2020-11-05 | 2021-02-09 | 北京化工大学 | MOF-based transition metal monatomic catalyst for carbon-carbon triple bond selective hydrogenation and preparation method thereof |
| CN112337509B (en) * | 2020-11-05 | 2023-05-26 | 北京化工大学 | MOF-based transition metal single-atom catalyst for selective hydrogenation of carbon-carbon triple bond and preparation method thereof |
| CN114797845A (en) * | 2022-05-18 | 2022-07-29 | 北京化工大学 | Pd catalyst for carbon-carbon triple bond selective hydrogenation reaction and preparation method thereof |
| CN115055181A (en) * | 2022-07-06 | 2022-09-16 | 四川大学 | Method for preparing high-performance CO catalyst by recycling waste noble metal catalyst |
| CN115282955A (en) * | 2022-08-16 | 2022-11-04 | 北京化工大学 | Catalyst for selective hydrogenation of alkyne and preparation method thereof |
| CN115282955B (en) * | 2022-08-16 | 2024-02-06 | 北京化工大学 | Catalyst for alkyne selective hydrogenation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110270375B (en) | 2020-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110270375A (en) | A kind of unsaturation carbon-carbon triple bond selective hydrocatalyst and preparation method thereof | |
| Vilé et al. | Advances in the design of nanostructured catalysts for selective hydrogenation | |
| CN109718806B (en) | Noble metal monoatomic catalyst and preparation method and application thereof | |
| CN106732567B (en) | A kind of metal composite oxide supported active metals catalyst and preparation method thereof | |
| CA2297651C (en) | Process for producing catalysts comprising nanosize metal particles on a porous support, in particular for the gas-phase oxidation of ethylene and acetic acid to give vinyl acetate | |
| CN102513104B (en) | Preparation method of benzaldehydes compound and novel double-metal catalyst loaded by mesoporous carbon for preparation method | |
| CN103447031B (en) | Catalyst comprising palladium and silver, and its application for selective hydrogenation | |
| Feng et al. | Preparation and structure-property relationships of supported trimetallic PdAuAg catalysts for the selective hydrogenation of acetylene | |
| EP3092072B1 (en) | A process for vapor-phase methanol carbonylation to methyl formate | |
| CN102883809B (en) | Preparation has the method for the catalyst of the noble metal nano particles being deposited on carrier | |
| JP6005151B2 (en) | Method for depositing metal on support oxide | |
| CN106540690A (en) | A kind of load type palladium ruthenium bimetallic catalyst and preparation method thereof | |
| CN107626304B (en) | Supported noble metal catalyst and preparation and application thereof | |
| Yu et al. | Enhanced catalytic performance for hydrogenation of substituted nitroaromatics over Ir-based bimetallic nanocatalysts | |
| CN111686721A (en) | Palladium ruthenium alloy catalyst and preparation method and application thereof | |
| Liu et al. | Copper single-atom-covered Pt nanoparticles for selective hydrogenation of phenylacetylene | |
| Tate et al. | Preparation of Pt-containing bimetallic and trimetallic catalysts using continuous electroless deposition methods | |
| CN114849694B (en) | Catalyst for hydrogenation of nitroaromatic hydrocarbon based on metal-loaded tungsten oxide, preparation method and application thereof | |
| CN109718807B (en) | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming | |
| CN112221502A (en) | Hollow spherical shell carrier loaded nickel-based alloy catalyst and preparation method thereof | |
| CN108607576A (en) | A method of simply preparing monodisperse platinoid duplex metal nano granule | |
| Anand et al. | Recent advances in hydrogenation reactions using bimetallic nanocatalysts: a review | |
| CN101616736B (en) | Catalysts containing platinum group metal nanoparticles and process for production of dispersions of nanoparticles of platinum group metal | |
| Reyes et al. | Hydrogenation of crotonaldehyde on Rh-Sn/SiO2 catalysts prepared by reaction of tetrabutyltin on prereduced Rh/SiO2 precursors | |
| CN110508290B (en) | High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |