CN111468110B - Preparation method of double noble metal catalyst - Google Patents
Preparation method of double noble metal catalyst Download PDFInfo
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- CN111468110B CN111468110B CN202010318778.2A CN202010318778A CN111468110B CN 111468110 B CN111468110 B CN 111468110B CN 202010318778 A CN202010318778 A CN 202010318778A CN 111468110 B CN111468110 B CN 111468110B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 81
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 56
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000005260 corrosion Methods 0.000 claims description 37
- 230000007797 corrosion Effects 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 34
- 239000011148 porous material Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- 238000011049 filling Methods 0.000 claims description 20
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 20
- 238000002791 soaking Methods 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000002210 silicon-based material Substances 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005234 chemical deposition Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical compound [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract description 48
- 235000019445 benzyl alcohol Nutrition 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 229940096017 silver fluoride Drugs 0.000 abstract description 7
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 abstract description 7
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 3
- 229910021426 porous silicon Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 22
- 230000008569 process Effects 0.000 description 18
- 239000002585 base Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- -1 silver ions Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910002710 Au-Pd Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NSNVGCNCRLAWOJ-UHFFFAOYSA-N [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] NSNVGCNCRLAWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/40—
-
- B01J35/60—
-
- B01J35/613—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/48—Silver or gold
- C07C2523/50—Silver
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides an Ag-Ru/acupuncture-like alpha-alumina noble metal catalyst for gas-solid phase reaction and a preparation method thereof, porous silicon is used as a template, alumina is coated on the surface of the porous silicon, roasting is carried out, fluorine gas is discharged out of the silicon template to obtain silver or silver fluoride/acupuncture-like alpha-alumina, ag active components are attached to the tips of the acupuncture-like alumina, ru is dispersed on the surface of a catalyst carrier, and the catalyst has excellent selectivity and conversion rate for benzaldehyde preparation by dehydrogenation and oxidation of benzyl alcohol.
Description
Technical Field
The invention relates to a gas-solid phase reaction double-noble metal catalyst and a preparation method thereof, belongs to the field of catalyst carrier preparation, and is particularly suitable for the field of gas-solid phase reaction for preparing benzaldehyde by dehydrogenation and oxidation of benzyl alcohol.
Technical Field
At present, the production process of the benzaldehyde is mainly toluene oxidation method, reduction method, benzyl alcohol direct oxidation method and the like. The toluene oxidation method has the defects of low product yield and more byproducts, so that the industrialized application of the toluene oxidation method is limited, and the reduction method has no market competitiveness due to the excessively high production cost of the hydrogenation reduction process. The benzyl alcohol direct oxidation method has the characteristics of high atom economy, simple process and environmental friendliness, and has good application prospect. In recent years, the research on the catalytic oxidation reaction of alcohol compounds with air, pure oxygen, hydrogen peroxide and derivatives thereof as an oxidant and metal or nonmetal as a catalyst is carried out, and the research has the greatest characteristic of being green and efficient. However, how to prepare green, efficient catalysts remains one of the challenges in this field.
At present, the catalyst carrier for preparing benzaldehyde by dehydrogenation and oxidation of benzyl alcohol is mainly alumina or silica carrier, for example, CN 103497093A discloses a method for preparing benzaldehyde by catalytic oxidation of benzyl alcohol by low-temperature gas phase selectivity, which relates to a method for preparing benzaldehyde by catalytic oxidation of benzyl alcohol by gas phase selectivity under low-temperature condition, so as to solve the problems of high reaction temperature, poor catalyst activity, low selectivity and over-narrow temperature tolerance range in the existing reaction of generating benzaldehyde by gas phase oxidation of benzyl alcohol, and the preparation method comprises the following steps: under normal pressure, using a solid catalyst Ag/SBA-15, gasifying substrate benzyl alcohol, then entering a fixed bed reactor, and taking molecular oxygen as an oxygen source and N 2 As carrier gas, the continuous reaction of preparing benzaldehyde by the gas-solid phase catalytic oxidation of benzyl alcohol is carried out at a certain reaction temperature. The catalyst used in the invention can realize the synthesis of benzaldehyde by low-temperature gas-phase high-selectivity oxidation of benzyl alcohol on the premise of providing higher activity, and is beneficial to realizing the industrial production of preparing benzaldehyde by gas-phase oxidation of benzyl alcohol.
Preparation of gamma-AlO as in CN 109985622A 3 A simple method for preparing the supported Au-Pd catalyst. The invention uses inorganic salt AlCl 3 ·6H 2 O and NaAlO 2 As an aluminum source by HAuCl 4 Is gold source and PdCl 2 As a palladium source, gamma-Al is prepared by a one-pot method in the presence of a coupling agent (3-mercaptopropyl) trimethoxysilane (MPTMS) 2 O 3 The supported Au-Pd catalyst and the influence of MPTMS content on the oxidation reaction performance of benzyl alcohol as the catalyst are investigated. The existence of the coupling agent enables Au and Pd active components to be effectively loaded on gamma-Al 2O 3. The prepared catalyst has the benzaldehyde yield as high as 74.9%. The preparation method has simple process, does not need high-temperature crystallization, and reduces the cost; the catalyst has higher dispersion degree of gold palladium and smaller Au-Pd nanometer size.
For example, CN 107442149A discloses a foam structure catalyst for preparing benzyl alcohol by hydrogenation of benzaldehyde and a preparation method thereof, which solve the problems that the traditional particle catalyst is easy to wear, the catalyst and a reaction product are difficult to separate, the recovery process is complex and the like. The catalyst has a three-dimensional communication network foam structure, the main structure is composed of a foam ceramic material serving as a first carrier, a coating (a second carrier), a catalytic active component and the like, the second carrier is uniformly coated on the surface of foam ribs of the first carrier, and the catalytic active component is uniformly loaded in the second carrier with high specific surface area. The foam structure catalyst is used for the reaction of preparing benzyl alcohol by liquid phase hydrogenation of benzaldehyde, simplifies the process technology and does not need complex equipment. The foam structure catalyst can strengthen the mass transfer process of chemical reaction while avoiding catalyst abrasion and simplifying the separation process, and has the advantages of high mass transfer efficiency, good catalytic activity, high benzyl alcohol selectivity and good stability.
However, the above catalysts all suffer from the following problems: (1) The catalyst has a molecular sieve structure on a carrier, the preparation process is complex, the process requirement is high, and a uniform and effective molecular sieve carrier is difficult to obtain; (2) The active component is required to be loaded after the preparation of the catalyst carrier is finished, namely, the catalyst carrier must have extremely high specific surface area so as to ensure that the active component is highly dispersed on the surface of the catalyst carrier; (3) For gas-solid phase reaction, mesoporous is favorable for the dispersion of active components, but the mass transfer of gas is seriously affected, in short, the active components are dispersed on the surface of the mesoporous, reactants are difficult to enter the mesoporous to react with active sites, and finally the catalytic activity is low; (4) In the crystal form, the alpha alumina has stronger catalytic activity than the gamma alumina, but the specific surface area of the alpha alumina is far lower than that of the gamma alumina, so that the utilization rate of the alpha alumina is reduced; (5) The prior art prepares needled alumina and uses the needled alumina in the field of the gas-solid phase reaction for preparing benzaldehyde by dehydrogenating and oxidizing benzyl alcohol; (6) The catalytic activity and selectivity of single noble metals are to be improved.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a preparation method of the catalyst, wherein the gas-solid phase reaction is a reaction for preparing benzaldehyde by dehydrogenating and oxidizing benzyl alcohol, and the preparation method comprises the following steps: (1) pre-treating a silicon-based material; (2) chemically depositing Ag particles on the silicon surface; (3) Ag particles catalyze and corrode the silicon material to obtain corrosion holes; (4) corrosion reaming; (5) filling alumina silica sol into the corrosion holes; (6) high-temperature roasting; (7) repeating steps (5) and (6); (8) fluorine gas removal of the silicon substrate; (9) immersing the ruthenium nitrosonitrate solution in an equal volume; (10) vacuum freeze-drying; (11) Pre-reducing to obtain the Ag-Ru double noble metal/needled alpha-alumina catalyst, wherein the load of Ru relative to the silver-containing alpha-alumina carrier is 1-3 wt%.
Further, the catalyst is silver or silver fluoride/needled alpha-alumina catalyst, and the preparation method of the catalyst is as follows: (1) pre-treating a silicon-based material; (2) chemically depositing Ag particles on the silicon surface; (3) Ag particles catalyze and corrode the silicon material to obtain corrosion holes; (4) corrosion reaming; (5) filling alumina silica sol into the corrosion holes; (6) high-temperature roasting; (7) repeating steps (5) and (6); (8) fluorine gas removal of the silicon substrate.
Further, the process of pre-treating the silicon-based material in the step (1) is as follows: cutting a monocrystalline silicon wafer to a proper size, sequentially carrying out ultrasonic cleaning by ethanol, acetone and deionized water to remove greasy dirt, repeating the cleaning for 1-3 times, then soaking by 10-15wt% hydrofluoric acid for 10min to remove an oxide layer, washing by deionized water, and drying under an inert atmosphere.
Further, the process of chemically depositing Ag particles on the silicon surface in the step (2) is as follows: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1:2-3:4-8, and the temperature is 30-35 o C, the time is 1-2min.
Further, the step (3) is to catalyze and corrode the technological parameters of the silicon material by Ag particles: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.3-0.45M, H 2 O 2 The concentration of the water is 0.3-0.4M, the time is 60-80min, the temperature is normal temperature, the water is washed by the corroded ionized water, and the air is dried and oxidized.
Further, the parameters of the corrosion reaming in the step (4) are as follows: oxidation temperature of 700 o C, forming disordered silicon oxide on the surface of the monocrystalline silicon for 30-40min, then cooling and soaking in 10-15wt% hydrofluoric acid for 10mAnd removing the oxide layer in, wherein the etching reaming step can be repeated for 1-3 times to obtain the large-aperture etching holes.
Further, the process of filling the alumina silica sol into the corrosion holes in the step (5) is as follows: adding 3-5 g pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.5-2M HNO3 to obtain alumina hydrosol, continuously stirring for 2-3 h, soaking the reamed base material obtained in the step (4) in the alumina hydrosol, vacuumizing, and filling the alumina hydrosol on the surface of a pore canal.
Further, the high-temperature roasting parameter in the step (6) is 300 o C, drying for 20-30min under nitrogen protection, and then 1-2 o C /min -1 Raising the temperature to 1100-1300 ℃, drying at constant temperature for 1-2h, and naturally cooling.
Further, the heating temperature for removing the silicon substrate by the fluorine gas in the step (8) is 35 to 40 o C, the time is 1-2h, and the treatment process of the step (11) is as follows: at 10 vol.% H 2 /N 2 300 in the mixed gas o C reduction pretreatment 1-2 h.
A gas-solid phase reaction double noble metal catalyst is characterized in that the morphology of the catalyst carrier alpha-alumina is in a needling shape, and the needling distribution is 20-40 pieces/mu m 2 15-25nm of needling tip, 130-150nm of distance between adjacent needling tips, 5-8 μm of alumina needling height, 10-13-m of specific surface area 2 And/g, wherein the active components of ruthenium and silver are loaded on the surface of the carrier.
The reagents, concentrations, and principles used in the above needle-shaped alumina catalyst and the method for preparing the catalyst are explained in detail as follows:
(1) Cutting a monocrystalline silicon wafer to a proper size, sequentially carrying out ultrasonic cleaning by ethanol, acetone and deionized water to remove greasy dirt, repeating the cleaning for 1-3 times, then soaking for 10min by using 10-15wt% of hydrofluoric acid to remove an oxide layer, washing by using deionized water, and drying under an inert atmosphere.
No matter what surface treatment process is, the surface pretreatment is the first condition, mainly because the oxide film and grease on the surface of monocrystalline silicon can not be effectively removed, the subsequent silver ions can not be contacted with the silicon substrate, and the silver ions can not be reduced and deposited, so that the subsequent catalytic corrosion can not be initiated, the silver ions can be unevenly distributed in the chemical deposition process, and the aggregation phenomenon of the silver ions, namely the existence of the oxide film and grease can seriously influence the pore channel distribution of the porous silicon template, and in addition, the drying is carried out in an inert atmosphere, so that the oxide layer is formed by avoiding the introduction of oxidizing gas.
(2) Chemically depositing Ag particles on the silicon surface: the process of chemically depositing Ag particles on the silicon surface in the step (2) is as follows: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1:2-3:4-8, and the temperature is 30-35 o C, the time is 1-2min.
The process is that Ag is chemically deposited on the surface of crystalline silicon, a large amount of Si-H bonds are formed on the surface of a silicon wafer after HF treatment, si-H has strong reducibility, ag+ in silver nitrate has strong oxidability, oxidation-reduction reaction is carried out on the Si-H bonds, ag+ obtains electrons to be reduced into Ag atoms, the Ag atoms are deposited on the surface of the Si wafer in the form of nano particles to form discontinuous Ag particle films, and the size and the spacing of the Ag particles directly determine the size and the spacing of pore channels.
In the invention, the concentration of AgNO3 is preferably controlled to be 2-3mM, silver plating time is within 1-2min, the size is generally distributed within 100-300 nm, ag particles are uniformly distributed on the surface of the whole substrate, and the concentration of Ag ions in silver nitrate is strictly controlled, for example, the concentration of the Ag ions is too large, so that corrosion points are too many, pore channels are too dense, the subsequent filling is not facilitated, and if the concentration of the Ag ions is too low, the pore channels are too sparse, and the subsequent filling is not facilitated.
In addition, the catalytic metal selected is Ag, not Au or Pt, in general. Ag and Au are common catalytic metals that can be etched vertically downward in a specific direction, but for Pt particles, the motion is more complex, and it is reported that a vertical, spiral, non-directional motion trace is observed.
Mainly based on the selection consideration of active components in the subsequent catalyst preparation process, in addition, the deposition size of Ag is controlled to be more mature, and uniform pore channels are easy to form.
(3) Ag particles catalyze and corrode silicon materials to obtain corrosion holes, wherein the corrosion liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.3-0.45M, and the concentration of H is 0.3-0.45M 2 O 2 The concentration of the water is 0.3-0.4M, the time is 60-80min, the temperature is normal temperature, the water is washed by the corroded ionized water, and the air is dried and oxidized.
The Ag particles act as catalysts, and Si under the Ag particles is oxidized into SiO2 by an oxidizing agent (e.g., H2O 2) in the etching solution and dissolved by HF, resulting in the Ag particles sinking, so that Si is gradually etched down to form "pits" at the positions covered by the Ag particles. Because the Ag particle film is discontinuous, the voids between adjacent Ag particles are not etched, resulting in the formation of silicon nanowires between adjacent "tunnels". The reaction equations involved in etching are as follows:
2Ag+H 2 O 2 +2H + →2Ag + +2H2O;
Si +4Ag + +6F - →4Ag+SiF 6 2- ;
Si 0 + 2H 2 O 2 + 6F - + 4H + →SiF 6 2 - + 4H 2 O;
in addition, HF, H 2 O 2 The etching time is critical to the shape of the pore canal and whether it is vertically etched,
typically α=hf/(hf+h) is used 2 O 2 ) The pore structure is evaluated, if alpha is between 0.7 and 1, the corroded cavity is cylindrical, if alpha is between 0.2 and 0.7, a conical cavity is obtained, when alpha is less than 0.2, almost no obvious pore is formed, and HF and H are preferred in the application 2 O 2 And the ratio is 1:1, so that a conical cavity is formed, and the subsequent formation of the needled alumina material is facilitated.
In addition, after corrosion, air can be used for drying without inert atmosphere, and the method is mainly used for oxidation in the subsequent reaming treatment, and resources are wasted if the inert atmosphere is used for drying.
(4) And (3) corrosion reaming: oxygen gasA melting temperature of 700 o And C, forming disordered silicon oxide on the surface of the monocrystalline silicon for 30-40min, then cooling and soaking in 10-15wt% hydrofluoric acid for 10min to remove an oxide layer, wherein the etching reaming step can be repeated for 1-3 times to obtain a large-aperture etching hole.
Since silver ions are generally distributed at 10-30 nm, the pore diameter at the opening of the pore canal is 70-200nm after corrosion, and for the subsequent filling of alumina sol, pore canal is smaller, and therefore, the pore canal is required to be reamed, an oxide layer is formed on the surface of the pore canal through oxidation treatment of a silicon substrate at high temperature, then the oxide layer is removed through HF, the purpose of pore canal reaming can be easily realized, if the pore canal size cannot be achieved through one-time reaming, the pore canal can be reamed through multiple times of corrosion, and the optimal pore canal size is 1-3 mu m, as shown in the attached figures 3 and 4.
(5) The process of filling alumina silica sol into the corrosion holes is as follows: adding 3-5 g pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.5-2M HNO3 to obtain alumina hydrosol, continuously stirring for 2-3 h, soaking the reamed base material obtained in the step (4) in the alumina hydrosol, vacuumizing, and filling the alumina hydrosol on the surface of a pore canal.
(6) The high-temperature roasting parameter in the step (6) is 300 o C, drying for 20-30min under nitrogen protection, and then 1-2 o C /min -1 Raising the temperature to 1100-1300 ℃, drying at constant temperature for 1-2h, and naturally cooling.
(7) Repeating steps (5) and (6);
regarding the reason of the selection of the high temperature calcination, the formation of gamma-Al is based on the influence of the alumina crystal form on the strength and catalytic performance of the catalyst carrier, if no calcination is performed 2 O 3 Is powder, can not maintain a needle-like structure, and is alpha-Al 2 O 3 The strength of the catalyst is high, the shape of the template can be effectively maintained, the catalyst adopts alpha-alumina as a base material, and the roasting temperature is 1100-1300 DEG C o C, alumina is formed by gamma-Al 2 O 3 Through delta-Al 2 O 3 Transition to alpha-Al 2 O 3 And alpha-Al 2 O 3 The carrier is compared with other alumina crystalsThe alumina has better low-temperature activity, as shown in XRD of figure 5, the alumina baked at high temperature is alpha-Al 2 O 3 The diffraction peak type is sharp, and the crystal structure is perfect.
In addition, steps (5) - (6) need to be performed multiple times because the alumina shrinks due to water loss and crystal form changes during the calcination process, which uses nitrogen as a shielding gas to protect the silicon substrate template.
(8) The heating temperature for removing the silicon substrate by the fluorine gas is 35-40 DEG o C, the time is 1-2h: the fluorine gas is used for removing the silicon oxide, and the base material is prevented from being corroded by alkali or acid, because the aluminum oxide is amphoteric oxide, although the acid and alkali resistance of the alpha aluminum oxide is superior to that of the silicon base material, the corrosion of the tip of the needle-punched aluminum oxide can be caused in the process of corroding the base material, so that the acid and alkali are prevented from being selected for removing the base material, the fluorine gas, fluorine and silicon are heated simply and are easy to react and volatilize, and the alpha aluminum oxide needs to react with fluorine under the condition of melting high temperature, so that the condition is harsh.
(9) The method does not need to use nitric acid to remove Ag ions, the Ag ions are used as auxiliary metals, the catalytic activity is improved, the treatment process is saved, and the obtained needled alumina structure is shown in the accompanying drawings 1 and 2.
(10) Since the aqueous solution dissolves silver fluoride and part migrates from the tip to other parts, the aqueous solution is required to be impregnated with an equal volume, and since the specific surface area of α -alumina is low, the aqueous solution in the ruthenium nitrosonitrate solution is small, and the aqueous solution is basically moisture contained in the ruthenium nitrosonitrate commodity itself.
(11) The vacuum freeze drying technology is adopted, so that the aluminum oxide needled structure can be effectively maintained.
(12) Pre-reducing; mainly used for reducing ruthenium in nitroso ruthenium nitrate, and silver particles are difficult to maintain in a silver metal state because of being subjected to high-temperature calcination, oxidation treatment and fluorination treatment, but the reduction can effectively reduce silver oxide particles into silver metal, namely ruthenium is reduced to be necessary, and the silver is reducedOptionally, the pre-reduction is at 10 vol.% H 2 /N 2 300 in the mixed gas o C, reduction pretreatment is carried out for 1-2 h.
The scheme of the invention has the following beneficial effects:
(1) The distribution condition and the particle size of Ag particles on the surface of the silicon substrate are effectively controlled, and further corrosion holes with uniform size and morphology are obtained through metal catalytic corrosion.
(2) Through reaming treatment, directional corrosion is effectively realized, pore volume is improved, and subsequent alumina sol coating is facilitated.
(3) The silicon pore canal has complete structure, clear interface and uniform pore canal, and the obtained alumina has a needled structure.
(4) The active component of the catalyst can be used as an active site for metal catalytic corrosion in the process of preparing a catalyst pore canal without subsequent extra load, and can also be used as an active site for subsequent gas-solid phase reaction of preparing benzaldehyde by dehydrogenating and oxidizing benzyl alcohol, namely the Ag has double catalytic effects.
(5) The silver active component is positioned and loaded on the tip of alumina, so that the silver active component is easier to contact with reaction gas, and the catalytic activity and selectivity of the double noble metal are obviously improved.
Drawings
FIG. 1 is a SEM cross-sectional view of a needled alumina of the present invention.
Fig. 2 is a top view of a needled alumina SEM of the present invention.
Fig. 3 is a SEM plan view of a reamed silicon substrate of the present invention.
Fig. 4 is an SEM magnified view of a silicon substrate after reaming in accordance with the present invention.
Figure 5 is an XRD pattern of alpha-alumina of the present invention.
Detailed Description
Example 1
A silver or silver fluoride/needled alpha-alumina catalyst comprising the steps of:
(1) Pretreatment of silicon-based materials: cutting a monocrystalline silicon wafer to a proper size, sequentially carrying out ultrasonic cleaning on the monocrystalline silicon wafer by ethanol, acetone and deionized water to remove greasy dirt for 1 time, then soaking the monocrystalline silicon wafer in 10wt% hydrofluoric acid for 10min to remove an oxide layer, washing the monocrystalline silicon wafer by deionized water, and drying the monocrystalline silicon wafer in an inert atmosphere;
(2) Chemically depositing Ag particles on the silicon surface: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1:2:4, and the temperature is 30% o C, the time is 1min, and the AgNO3 concentration is preferably controlled to be 2mM;
(3) Ag particles catalyze and corrode silicon materials to obtain corrosion holes: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.3M, H 2 O 2 The concentration of (2) is 0.3M, the time is 60min, the temperature is normal temperature, the ion water is used for washing after corrosion, and the air is dried and oxidized;
(4) Corroding and reaming; oxidation temperature of 700 o C, forming disordered silicon oxide on the surface of the monocrystalline silicon for 30min, then cooling and soaking in 10wt% hydrofluoric acid for 10min to remove an oxide layer, wherein the step of etching and reaming can be repeated for 1 time to obtain a large-aperture etching hole;
(5) Filling alumina silica sol into the corrosion holes: adding 3 g pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.5M HNO3 to obtain alumina hydrosol, continuously stirring 2h, soaking the reamed base material obtained in the step (4) in the alumina hydrosol, vacuumizing, and filling the alumina hydrosol on the surface of a pore canal;
(6) High-temperature roasting: 300 o C nitrogen protection drying for 20min, then 1 o C /min -1 Heating to 1100 ℃, drying at constant temperature for 1h, and naturally cooling;
(7) Repeating the steps (5) and (6) for 2 times.
(8) Fluorine gas-removed silicon substrate, heating temperature of the fluorine gas-removed silicon substrate is 35 o C, time 1h.
(9) Impregnating an equal volume of a solution of ruthenium nitrosonitrate; (10) vacuum freeze-drying; (11) Pre-reduction, an Ag-Ru double noble metal/needled alpha-alumina catalyst was obtained, the Ru loading was 1wt.% relative to the silver-containing alpha-alumina support.
Example 2
A silver or silver fluoride/needled alpha-alumina catalyst comprising the steps of:
(1) Pretreatment of silicon-based materials: cutting a monocrystalline silicon wafer to a proper size, sequentially carrying out ultrasonic cleaning by ethanol, acetone and deionized water to remove greasy dirt, repeating the cleaning for 2 times, then soaking by 12.5wt% hydrofluoric acid for 10min to remove an oxide layer, washing by deionized water, and drying under an inert atmosphere;
(2) Chemically depositing Ag particles on the silicon surface: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1:2.5:6, and the temperature is 32.5 o C, the time is 1.5min, and the AgNO3 concentration is preferably controlled to be 2.5mM;
(3) Ag particles catalyze and corrode silicon materials to obtain corrosion holes: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.35M, H 2 O 2 The concentration of (2) is 0.35M, the time is 70min, the temperature is normal temperature, the ion water is used for washing after corrosion, and the air is dried and oxidized;
(4) Corroding and reaming; oxidation temperature of 700 o C, forming disordered silicon oxide on the surface of the monocrystalline silicon for 35min, then cooling and soaking in 12.5wt% hydrofluoric acid for 10min to remove an oxide layer, wherein the etching reaming step can be repeated for 2 times to obtain a large-aperture etching hole;
(5) Filling alumina silica sol into the corrosion holes: adding 4g of pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.75M HNO3 to obtain alumina hydrosol, continuously stirring for 2.5. 2.5 h, soaking the reamed base material obtained in the step (4) in the alumina hydrosol, vacuumizing, and filling the alumina hydrosol on the surface of a pore canal;
(6) High-temperature roasting: 300 o C nitrogen blanket drying for 25min, then 1.5 o C /min -1 Rise to 1200 o C, drying at constant temperature for 1-2h, and naturally cooling;
(7) Repeating the steps (5) and (6) for 3 times.
(8) Fluorine gas-removed silicon substrate, heating temperature of the fluorine gas-removed silicon substrate was 37 o C, time 1.5h.
(9) Impregnating an equal volume of a solution of ruthenium nitrosonitrate; (10) vacuum freeze-drying; (11) Pre-reduction, an Ag-Ru double noble metal/needled alpha-alumina catalyst was obtained, the Ru loading was 2wt.%, relative to the silver-containing alpha-alumina support, designated S-2.
Example 3
A silver or silver fluoride/needled alpha-alumina catalyst comprising the steps of:
(1) Pretreatment of silicon-based materials: cutting a monocrystalline silicon wafer to a proper size, sequentially carrying out ultrasonic cleaning by ethanol, acetone and deionized water to remove greasy dirt, repeating the cleaning for 3 times, then soaking by 15wt% of hydrofluoric acid for 10min to remove an oxide layer, washing by deionized water, and drying under an inert atmosphere;
(2) Chemically depositing Ag particles on the silicon surface: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1:3:8, and the temperature is 35 o C, the time is 2min, and the AgNO3 concentration is preferably controlled to be 3mM;
(3) Ag particles catalyze and corrode silicon materials to obtain corrosion holes: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.45M, H 2 O 2 The concentration of (2) is 0.4M, the time is 80min, the temperature is normal temperature, the ion water is used for washing after corrosion, and the air is dried and oxidized;
(4) Corroding and reaming; oxidation temperature of 700 o C, forming disordered silicon oxide on the surface of the monocrystalline silicon for 40min, then cooling and soaking in 15wt% hydrofluoric acid for 10min to remove an oxide layer, wherein the step of etching and reaming can be repeated for 3 times to obtain a large-aperture etching hole;
(5) Filling alumina silica sol into the corrosion holes: adding 5 g pseudo-boehmite into deionized water in batches under the stirring condition, adding 2M HNO3 to obtain alumina hydrosol, continuously stirring for 3 h, soaking the reamed base material obtained in the step (4) in the alumina hydrosol, vacuumizing, and filling the alumina hydrosol on the surface of a pore canal;
(6) High-temperature roasting: 300 o C nitrogen protection drying for 30min, then 2 o C /min -1 Raising the temperature to 1300 ℃, drying at constant temperature for 2h, and naturally cooling;
(7) Repeating the steps (5) and (6) for 4 times.
(8) Fluorine gas-removed silicon substrate, heating temperature of the fluorine gas-removed silicon substrate was 40 o And C, the time is 2h.
(9) Impregnating an equal volume of a solution of ruthenium nitrosonitrate; (10) vacuum freeze-drying; (11) Pre-reduction, an Ag-Ru double noble metal/needled alpha-alumina catalyst was obtained, the Ru loading was 3wt.% relative to the silver-containing alpha-alumina support.
Comparative example 1
A silver or silver fluoride/needled alpha-alumina catalyst comprising the steps of:
(1) Pretreatment of silicon-based materials: cutting a monocrystalline silicon wafer to a proper size, sequentially carrying out ultrasonic cleaning by ethanol, acetone and deionized water to remove greasy dirt, repeating the cleaning for 2 times, then soaking by 12.5wt% hydrofluoric acid for 10min to remove an oxide layer, washing by deionized water, and drying under an inert atmosphere;
(2) Chemically depositing Ag particles on the silicon surface: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, the volume ratio of AgNO3 to HF to H2O is 1:2.5:6, and the temperature is 32.5 o C, the time is 1.5min, and the AgNO3 concentration is preferably controlled to be 2.5mM;
(3) Ag particles catalyze and corrode silicon materials to obtain corrosion holes: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.35M, H 2 O 2 The concentration of (2) is 0.35M, the time is 70min, the temperature is normal temperature, the ion water is used for washing after corrosion, and the air is dried and oxidized;
(4) Corroding and reaming; oxidation temperature of 700 o C, forming disordered silicon oxide on the surface of the monocrystalline silicon for 35min, then cooling and soaking in 12.5wt% hydrofluoric acid for 10min to remove an oxide layer, wherein the etching reaming step can be repeated for 2 times to obtain a large-aperture etching hole;
(5) Filling alumina silica sol into the corrosion holes: adding 4g of pseudo-boehmite into deionized water in batches under the stirring condition, adding 1.75M HNO3 to obtain alumina hydrosol, continuously stirring for 2.5. 2.5 h, soaking the reamed base material obtained in the step (4) in the alumina hydrosol, vacuumizing, and filling the alumina hydrosol on the surface of a pore canal;
(6) High-temperature roasting: 300 o C nitrogen blanket drying for 25min, then 1.5 o C /min -1 Rise to 1200 o C, drying at constant temperature for 1-2h, and naturally cooling;
(7) Repeating the steps (5) and (6) for 3 times.
(8) Fluorine gas-removed silicon substrate, heating temperature of the fluorine gas-removed silicon substrate was 37 o C, the time is 1.5h, and the needled alumina carrier is obtained and is named as D-1.
As is evident from the above table, the catalytic conversion, selectivity and yield of the double noble metal S-2 are significantly higher than those of the single noble metal D-1 catalyst. When the temperature is 110 o In the case of C, the catalyst had the best catalytic performance, and the catalytic effect was the best, the conversion of benzyl alcohol was 75.3%, the selectivity of benzaldehyde was 90.2%, and the yield was 58.2%.
By the sample test and statistics of examples 1-3, it was found that the needled distribution of the needled alumina was 20-40 pieces/μm 2 15-25nm of needling tip, 130-150nm of distance between adjacent needling tips, 5-8 μm of alumina needling height, 10-13-m of specific surface area 2 /g。
Although the present invention has been described by way of example with reference to the preferred embodiments, the present invention is not limited to the specific embodiments, and may be modified appropriately within the scope of the present invention.
Claims (3)
1. The preparation method of the double noble metal catalyst is used for the gas-solid phase reaction of preparing benzaldehyde by dehydrogenating and oxidizing benzyl alcohol, and is characterized by comprising the following steps of:
(1) Pretreating a silicon-based material;
(2) Chemical deposition of Ag particles on silicon surfaces: the chemical deposition solution is aqueous solution of silver nitrate and hydrofluoric acid, agNO 3 ∶HF∶H 2 The volume ratio of O is 1:2-3:4-8, the temperature is 30-35 ℃ and the time is 1-2min;
(3) Ag particles catalyze and corrode silicon materials to obtain corrosion holes: the corrosive liquid is aqueous solution of hydrofluoric acid and hydrogen peroxide, the concentration of HF is 0.3-0.45M, H 2 O 2 The concentration of the water is 0.3-0.4M, the time is 60-80min, the temperature is normal temperature, the water is washed by the corroded ionized water, and the air is dried and oxidized;
(4) And (3) corrosion reaming: the oxidation temperature is 700 ℃, disordered silicon oxide is formed on the surface of monocrystalline silicon for 30-40min, then the monocrystalline silicon is cooled and soaked in 10-15wt% hydrofluoric acid for 10min to remove an oxide layer, and the etching reaming step can be repeated for 1-3 times to obtain large-aperture etching holes;
(5) Filling alumina silica sol into the corrosion holes;
(6) High-temperature roasting: drying at 300 deg.C under nitrogen protection for 20-30min, heating to 1100-1300 deg.C at 1-2 deg.C/min, drying at constant temperature for 1-2 hr, and naturally cooling;
(7) Repeating the step (5) and the step (6);
(8) Fluorine gas removal of silicon substrate: heating at 35-40deg.C for 1-2 hr;
(9) Impregnating an equal volume of a solution of ruthenium nitrosonitrate;
(10) Vacuum freeze drying;
(11) Pre-reduction: at 10 vol.% H 2 /N 2 And (3) carrying out reduction pretreatment at 300 ℃ in the mixed gas for 1-2h to obtain the Ag-Ru double noble metal/needled alpha-alumina catalyst, wherein the load of Ru relative to the silver-containing alpha-alumina carrier is 1-3 wt.%.
2. The method for preparing a double noble metal catalyst according to claim 1, wherein the pretreatment of the silicon-based material in step (1) comprises the following steps: cutting a monocrystalline silicon wafer to a proper size, sequentially carrying out ultrasonic cleaning by ethanol, acetone and deionized water to remove greasy dirt, repeating the cleaning for 1-3 times, then soaking by 10-15wt% hydrofluoric acid for 10min to remove an oxide layer, washing by deionized water, and drying under an inert atmosphere.
3. The method for preparing a double noble metal catalyst according to claim 1, wherein the step (5) of filling alumina silica sol into the etched holes comprises the following steps: adding 3-5-g pseudo-boehmite into deionized water under stirring, adding 1.5-2M HNO 3 Continuously stirring the obtained alumina hydrosol for 2-3 h, soaking the reamed base material obtained in the step (4) in the alumina hydrosol, vacuumizing, and filling the alumina hydrosol on the surface of a pore canal.
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