CN115106124A - Titanium-silicon molecular sieve solid-supported gold catalyst and preparation method and application thereof - Google Patents
Titanium-silicon molecular sieve solid-supported gold catalyst and preparation method and application thereof Download PDFInfo
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- CN115106124A CN115106124A CN202210848018.1A CN202210848018A CN115106124A CN 115106124 A CN115106124 A CN 115106124A CN 202210848018 A CN202210848018 A CN 202210848018A CN 115106124 A CN115106124 A CN 115106124A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000010931 gold Substances 0.000 title claims abstract description 86
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 82
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 94
- 238000000034 method Methods 0.000 claims abstract description 47
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 239000012716 precipitator Substances 0.000 claims abstract description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 20
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 16
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- 238000006243 chemical reaction Methods 0.000 claims description 34
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- 239000001294 propane Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000006735 epoxidation reaction Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
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- 238000011068 loading method Methods 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
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- 239000011734 sodium Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- DFCVQVFZSSOGOG-UHFFFAOYSA-N N.[Au] Chemical compound N.[Au] DFCVQVFZSSOGOG-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
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- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B01J35/40—
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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 a titanium-silicon molecular sieve solid-supported gold catalyst and a preparation method and application thereof, wherein an improved deposition-precipitation method is adopted, a volatile amine solution or ammonia water is used as a precipitator, the precipitator and slurry containing a gold precursor solution and a titanium-silicon molecular sieve are separately placed, the amine solution or the ammonia water is slowly volatilized into the slurry containing the gold precursor solution and the titanium-silicon molecular sieve to realize deposition of gold on the titanium-silicon molecular sieve, and the catalyst is obtainedA body; drying and activating the catalyst precursor to obtain a supported Au-Ti bifunctional catalyst; the preparation method improves the dispersity of gold particles and promotes defect sites Ti (OSi) in the titanium silicalite molecular sieve 3 The formation of OH active sites obviously improves the loading efficiency of gold, the generation rate of propylene oxide in propylene hydro-oxidation reaction and the generation rate of acetone in the propylene hydro-oxidation reaction, and simultaneously improves the selectivity of target products and the utilization efficiency of hydrogen.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a titanium silicalite molecular sieve supported gold catalyst, and a preparation method and application thereof.
Background
Propylene Oxide (PO) is the second largest Propylene derivative next to polypropylene, and is mainly used for producing chemical products such as polyether polyol, Propylene glycol, Propylene carbonate and the like. Propylene and H in a number of PO production processes 2 And O 2 The direct epoxidation synthesis of PO has the advantages of cheap and easily obtained raw materials, green and environment-friendly process and the like, and is always regarded as an ideal process for PO production for a long time.
Acetone is one of important chemical raw materials, and is mainly used as a solvent and used for producing various chemical products such as Methyl Methacrylate (MMA), isopropanol, polycarbonate intermediate bisphenol A and the like. In recent years, with the rapid development of the polycarbonate industry and the epoxy resin industry, the consumption of products such as bisphenol A, MMA and the like is greatly increased, and the continuous increase of the domestic acetone market demand is driven. Compared with the current mainstream cumene method, the new process for preparing acetone by directly oxidizing propane in the hydrogen/oxygen atmosphere has unique advantages: i) the production raw materials are propane, hydrogen and oxygen, and are cheap and easy to obtain; ii) acetone selectivity is high, atom economy is good; iii) the process is simple, the reaction is carried out in gas phase, and no organic solvent is needed.
Currently used for the catalytic oxidation of propylene to PO and the catalytic oxidation of propane to acetoneThe catalyst is a nano-gold catalyst immobilized on a titanium-silicon molecular sieve. Researches find that the titanium silicalite molecular sieve loaded gold catalyst is an Au-Ti bifunctional catalyst: au site catalysis H 2 And O 2 A hydroperoxide species is generated which then diffuses to the Ti sites to form a Ti-OOH reactive intermediate which catalyzes the oxidation of propylene or propane to PO and acetone, respectively.
A great deal of research shows that Ti 4+ The type of the site is an important factor influencing the catalytic performance of the Au-Ti dual-functional catalyst. Studies have shown that Ti with defective bits in TS-1 4+ (e.g. Ti (OSi)) 3 OH) is less defective than Ti of non-defective sites in epoxidation of propene 4+ (e.g. Ti (OSi)) 4 ) Has better activity. This indicates that non-defective sites Ti 4+ Transfer to defect site Ti 4+ It is possible to facilitate uniform deposition of gold while increasing Ti active sites, thereby improving catalytic performance. In addition, the size of the gold nanoparticles also has an important influence on the catalytic performance of the Au-Ti bifunctional catalyst. In general, gold nanoparticles of small size exhibit higher activity in catalyzing the oxyhydrogen reaction of propylene.
Research shows that the preparation method of the catalyst has obvious influence on the size of the gold nanoparticles. Among the reported catalyst preparation methods, the deposition-precipitation method (DP method) is the most widely used method for uniformly dispersing and immobilizing gold nanoparticles on Ti-containing materials, because it can be prepared by dispersing AuCl 4- The species is gradually hydrolyzed to [ AuCl ] x (OH) 4-x ] - To effectively eliminate chlorine and thus prevent the gold particles from agglomerating due to chloride ions. However, the performance of the Au-Ti bifunctional catalyst prepared by the conventional DP method is very sensitive to preparation parameters, and the preparation parameters include gold precursor concentration, pH, precipitant type, preparation temperature, preparation time and the like, which involve a lot of factors, and thus, great challenges are brought to the controllable preparation and engineering amplification of the Au-Ti bifunctional catalyst. In addition, the gold loading efficiency of the conventional DP method is low, and the performance of the catalyst prepared by the conventional DP method is far from industrial application. Although the present research finds that the DP Urea method (i.e. DPU method) using Urea as a precipitant is used for preparing the uncalcined titanium silicalite TS-1 and the uncalcined titanium silicalite TS-1The TS-2 supported gold catalyst can achieve high gold loading efficiency (about 90%), but the performance of the catalyst prepared by adopting the DPU method is very sensitive to preparation parameters such as preparation time, urea/gold molar ratio, preparation temperature and the like, particularly the preparation temperature, and the method also brings challenges to engineering amplification of the catalyst. In addition, the performance of the catalyst prepared by the DPU method is different from the industrial application. Therefore, further development and research of a preparation method of the titanium silicalite supported gold catalyst with high efficiency are needed.
Disclosure of Invention
The invention provides an improved DP method for preparing a catalyst for the reaction of preparing PO by hydrogen-oxygen epoxidation of propylene and the reaction of preparing acetone by hydrogen oxidation of propane, aiming at the defects of the existing catalyst preparation method and performance in the reaction of preparing PO by hydrogen oxidation of propylene and the reaction of preparing acetone by hydrogen oxidation of propane. By the improved DP method, the dispersity of gold particles can be improved, and the defect sites Ti (OSi) in the titanium silicalite molecular sieve can be promoted 3 Formation of OH active sites. Compared with the Au-Ti dual-function catalyst prepared by the traditional DP method and the DPU method taking urea as a precipitator, the improved DP method has the gold load efficiency close to 100 percent, and the prepared catalyst has obvious promotion effect on improving the reaction rate of preparing PO by propylene oxyhydrogen and the reaction rate of preparing acetone by propane oxyhydrogen, and can also obviously improve the selectivity and the hydrogen efficiency of target products (PO and acetone). The invention not only clarifies a novel preparation method of the high-efficiency Au-Ti bifunctional catalyst for propylene/propane hydrogen oxidation reaction, but also provides an effective scheme for improving the catalytic activity of the zeolite-supported gold nano catalyst to other reactions.
The invention provides a preparation method of a titanium silicalite molecular sieve supported gold catalyst, which improves the existing DP method, adopts volatile amine solution or ammonia water as a precipitator, and the preparation process does not directly add the precipitator into slurry formed by mixing gold precursor solution and titanium silicalite molecular sieve according to the traditional deposition-precipitation method, but separately places the precipitator and the slurry containing the gold precursor solution and the titanium silicalite molecular sieve in a closed container, and slowly volatilizes the amine solution or the ammonia water and enters the slurry containing the gold precursor solution and the titanium silicalite molecular sieve to realize the deposition of gold on the titanium silicalite molecular sieve, so as to obtain a catalyst precursor; the catalyst precursor is dried and activated to obtain the supported Au-Ti bifunctional catalyst.
The invention is further configured that the amine solution or the ammonia water and the slurry containing the gold precursor solution and the titanium silicalite molecular sieve can be placed in the same closed container, or the amine solution or the ammonia water and the slurry containing the gold precursor solution and the titanium silicalite molecular sieve can be placed in two different closed containers, and the two closed containers are communicated through a pipeline. Specifically, the improved DP method comprises the following steps:
(1) adding a gold precursor solution and a titanium-silicon molecular sieve into a first open container, uniformly stirring to obtain mixed slurry, and transferring the first open container into a first sealable container;
or directly adding the gold precursor solution and the titanium silicalite molecular sieve into a first sealable container, and uniformly stirring to obtain mixed slurry;
(2) adding the amine solution or ammonia water into a second open container, placing the second open container into the first closable container, and sealing the first closable container;
or adding the amine solution or ammonia water into a second open container, placing the second open container in a second sealable container seal, communicating the first sealable container seal and the second sealable container through a pipeline, and sealing the first sealable container and the second sealable container;
or adding the amine solution or ammonia water into a second sealable container, wherein the first sealable container is communicated with the second sealable container through a pipeline, and sealing the first sealable container and the second sealable container;
(3) placing the mixed slurry under the sealing condition of the step (2) for a period of time, slowly volatilizing the amine solution or ammonia water into the mixed slurry to deposit gold on the titanium silicalite molecular sieve to obtain a catalyst precursor; the catalyst precursor is dried and activated to obtain the supported Au-Ti bifunctional catalyst.
The invention is further configured that water is added as a diluting solvent in step (1); preferably, the feeding sequence is that water, the gold precursor solution and the titanium silicalite molecular sieve are sequentially added.
The invention is further configured that the titanium silicalite molecular sieve in the step (1) is one or more of Ti-SBA-15, Ti-MCM-41, Ti-MCM-48, Ti-MCM-36, Ti-MWW, Ti-MOR, Ti-Beta, Ti-TUD-1, TS-1, hierarchical pore TS-1, TS-2 and hierarchical pore TS-2, which are conventionally used in the field of preparing propylene oxide by propylene oxyhydrogen epoxidation or preparing acetone by propane oxyhydrogen; the titanium-silicon molecular sieve can be a titanium-silicon molecular sieve which is subjected to roasting treatment at the temperature of 150-1000 ℃, or a titanium-silicon molecular sieve which is not subjected to roasting treatment and has pore channels blocked by a template agent.
The invention is further arranged that the general formula of the gold precursor used in the gold precursor solution in the step (1) is MAuCl 4 Wherein M is H, Na, K, Cs, Li or NH 4 The gold precursor solution at least comprises a gold precursor as shown in the general formula; the solvent used by the gold precursor solution is one or a mixture of two or more of water, ethanol and acetone.
The invention is further provided that the amine solution in the step (2) is a volatile amine solution with organic amine with the carbon atom number less than 7 as a solute component; the ammonia water and the amine solution use water as a solvent, or partial alcohol with the carbon number less than 5 is added into the water as a solvent, or the alcohol with the carbon number less than 5 is used as a solvent; the concentration of the ammonia water and the amine solution is not higher than 5 wt%.
The invention is further provided that the mixed slurry in the step (3) can be stirred or not; the pH value of the mixed slurry is 10-12; the gold in the mixed slurry is deposited on the titanium-silicon molecular sieve, and the temperature of the prepared catalyst precursor is 5-50 ℃, preferably room temperature; the preparation time is 0.15-6h, preferably 3-6 h; the catalyst precursor obtained after the preparation time is reached may or may not be washed and filtered.
The invention further provides that the drying mode in the step (3) is a drying method which is conventionally used in the field of catalyst preparation, and vacuum drying is preferred.
The invention is further provided that the activation mode in the step (3) is that the catalyst precursor is treated in a certain temperature and a certain atmosphere, and the certain temperature is in the range of 50-800 ℃, preferably 200-350 ℃, and more preferably 300-320 ℃; the atmosphere is a reducing atmosphere, an oxidizing atmosphere or an inert atmosphere, more than one atmosphere can be used for treatment, and the composition and the sequence of the atmosphere are not limited.
In a second aspect of the present invention, a supported Au-Ti dual-function catalyst, which is a supported Au-Ti catalyst, is provided.
The invention further provides that the particle size of the gold nanoparticles on the titanium silicalite supported gold catalyst obtained by the method is less than 10nm, preferably less than 5nm, and more preferably less than 2.5 nm.
The third aspect of the invention provides an application of the titanium silicalite molecular sieve supported gold catalyst, which is used for the reaction of preparing PO by propylene oxyhydrogen epoxidation and the reaction of preparing acetone by propane oxyhydrogen.
The invention has the following beneficial effects:
(1) compared with the traditional DPU method, the improved DP method for preparing the supported Au-Ti bifunctional catalyst disclosed by the invention has the advantages that the dispersity of gold can be obviously enhanced through the strong interaction between the Au and the N grafted on the surface of the molecular sieve and a nitrogen-containing group, so that smaller and narrower Au particle size distribution is obtained, the generation rate of hydroperoxides on nano gold particles is favorably improved, and the activity of the catalyst is improved.
(2) Compared with the traditional DP method and the DPU method, the improved DP method for preparing the supported Au-Ti bifunctional catalyst adopts the strong alkaline environment which is favorable for hydrolyzing Ti-O-Si bonds to form defect sites Ti (OSi) with higher activity 3 OH active sites, thereby improving the performance of the catalyst.
(3) According to the improved DP method for preparing the supported Au-Ti dual-functional catalyst, ammonia water or volatile amine solution is introduced as a precipitator, a gold-ammonia complex with positive electricity can be formed in the deposition process, the surface of a titanium-silicon molecular sieve is negatively charged when the supported Au-Ti dual-functional catalyst is prepared, and the strong interaction between the gold-ammonia complex with positive electricity and the surface of the titanium-silicon molecular sieve with negative electricity enables the catalyst prepared by the improved DP method to show gold supporting efficiency close to 100%.
Drawings
FIG. 1 is a scanning transmission electron micrograph (HAADF-STEM) of a catalyst prepared in example 1;
FIG. 2 is a scanning transmission electron micrograph (HAADF-STEM) of the catalyst prepared in comparative example 1;
FIG. 3 shows the catalyst precursors prepared in example 1 and comparative example 1 29 Si NMR spectrum ( 29 Si NMR)；
FIG. 4 is an ultraviolet spectrum (UV-Vis) of the catalyst precursor prepared in example 1;
fig. 5 is an ultraviolet spectrum (UV-Vis) of the catalyst precursor prepared in comparative example 1;
FIG. 6 is a comparison of the rate of PO formation by the oxidation of propylene with hydrogen catalyzed by the catalysts prepared in example 1 and comparative example 1;
FIG. 7 is a comparison of the rate of acetone production from the oxidation of propane with hydrogen catalyzed by the catalyst prepared in example 1 and comparative example 1.
Detailed Description
The technical solution of the present invention is clearly and completely described below with reference to specific embodiments. It is to be understood that the described embodiments are only a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without making creative efforts, fall within the scope of the invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. All percentages, ratios, proportions, or parts are by weight and room temperature means a temperature of 20-30 deg.C, unless otherwise specified.
Example 1
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, taking unbaked TS-1 (namely TS-1-B) as a carrier and ammonia water as a precipitator, and comprises the following steps:
(1) 1g of TS-1-B, 40mL of water, 1.00mL of chloroauric acid solution (1.10 mg) Au Ml) are sequentially added into a quartz beaker (100ml) to be mixed and stirred for 5min to obtain suspension; transferring the suspension into a sealed glass dryer with a diameter of 18 cm; a small beaker (10mL) containing 8mL of ammonia (2 wt%) was fixed to the side wall of the sealed glass desiccator; vigorously stirring the suspension at room temperature for 6h, and measuring the pH of the suspension to be 10.6; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.11 wt%.
Example 2
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, TS-1-B as a carrier and ammonia water as a precipitator, and comprises the following steps:
(1) 1g of TS-1-B, 40mL of water, and 1.00mL of chloroauric acid solution (1.10 mg) Au Ml) are sequentially added into a quartz beaker (100ml) to be mixed and stirred for 5min to obtain suspension; transferring the suspension to a sealed glass dryer of 18cm diameter, to the side wall of which a small beaker (10mL) containing 8mL of aqueous ammonia (2 wt%) was fitted; violently stirring the suspension at room temperature for 6 hours, and measuring the pH of the suspension to be 10.6; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 320 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.11 wt%.
Example 3
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, TS-1-B as a carrier and ammonia water/ethanol solution as a precipitator, and comprises the following steps:
(1) 1g of TS-1-B, 40mL of water, 0.83mL of chloroauric acid solution (1.10 mg) Au /ml) were sequentially added to a quartz beaker (100ml) and mixed and stirred for 5min to obtain a suspension; the suspension was transferred to a sealed glass desiccator 18cm in diameter, to the side of which was fixed a small beaker (10mL) containing 6mL of an aqueous ammonia/ethanol solution (3 wt%), i.e. the precipitant was NH 3 Adding part of ethanol into water as a solvent as a solute; vigorously stirring the suspension at room temperature for 6h, and measuring the pH of the suspension to be 10.7; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.09 wt%.
Example 4
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, TS-1-B as a carrier and an ethylamine aqueous solution as a precipitator, and comprises the following steps:
(1) 1g of TS-1-B, 40mL of water, 1.00mL of chloroauric acid solution (1.10 mg) Au Ml) are sequentially added into a quartz beaker (100ml) to be mixed and stirred for 5min to obtain suspension; transferring the suspension to a sealed glass dryer of 18cm diameter, holding a small beaker (10mL) containing 8mL of an aqueous solution of ethylamine (3 wt%) on the side wall of the sealed glass dryer; violently stirring the suspension at room temperature for 6 hours, and measuring the pH of the suspension to be 10.9; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.11 wt%.
Example 5
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, TS-1-B as a carrier and ethylenediamine aqueous solution as a precipitator, and comprises the following steps:
(1) 1g of TS-1-B, 40mL of water, 1.00mL of chloroauric acid solution (1.10 mg) Au Ml) are sequentially added into a quartz beaker (100ml) to be mixed and stirred for 5min to obtain suspension; transferring the suspension to a sealed glass dryer of 18cm diameter, holding a small beaker (10mL) containing 8mL of an aqueous solution of ethylenediamine (3 wt%) on the side wall of the sealed glass dryer; vigorously stirring the suspension at room temperature for 6h, and measuring the pH of the suspension to be 10.4; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.11 wt%.
Example 6
The Au-Ti bifunctional catalyst is prepared by taking sodium chloroaurate as a precursor, taking unbaked TS-2 (namely TS-2-B) as a carrier and ammonia water as a precipitator, and comprises the following steps:
(1) 1g of TS-2-B, 40mL of water, 1.00mL of a sodium chloroaurate solution (1.10 mg) Au Ml) are sequentially added into a quartz beaker (100ml) to be mixed and stirred for 5min to obtain suspension; transferring the suspension to a sealed glass dryer of 18cm diameter, fixing a small beaker (10mL) containing 8mL of ammonia (2 wt%) on the side wall of the sealed glass dryer; violently stirring the suspension at room temperature for 6 hours, and measuring the pH of the suspension to be 11.3; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.11 wt%.
Example 7
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, TS-1 as a carrier and ammonia water as a precipitator, and comprises the following steps:
(1) 1g TS-1, 20mL water, 1.55mL chloroauric acid solution (1.10 mg) Au Ml) and 1ml of potassium nitrate solution (0.4M) were sequentially added to a quartz beaker (100ml) and mixed and stirred for 5min to obtain a suspension; transferring the suspension to a sealed glass dryer having a diameter of 18cm, and fixing a small beaker (10mL) containing 8mL of ammonia water (5 wt%) to the side wall of the sealed glass dryer; vigorously stirring the suspension at room temperature for 3h, and measuring the pH value of the suspension to be 11.2; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises oxygen: hydrogen gas: propylene: nitrogen gas 1: 1: 1: 7 (volume ratio) at a flow rate of 35mL/min, heating from room temperature to 200 ℃ at a speed of 0.5 ℃/min to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is 0.17 wt% by determination.
Example 8
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, Ti-SBA-15 as a carrier and ammonia water as a precipitator, and comprises the following steps:
(1) 1g of Ti-SAB-15, 38mL of water, 1.65mL of chloroauric acid solution (1.10 mg) Au /ml) and 1ml of sodium nitrate solution (0.4M) are sequentially added into a quartz beaker (100ml) to be mixed and stirred for 5min to obtain suspension; transferring the suspension to a sealed glass dryer having a diameter of 18cm, and fixing a small beaker (10mL) containing 8mL of ammonia water (4 wt%) to the side wall of the sealed glass dryer; vigorously stirring the suspension at room temperature for 4 h, and measuring the pH value of the suspension to be 11.0; centrifuging to separate solid and liquid, and washing to obtainThe solid of (2) was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.18 wt%.
Example 9
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, TS-1-B as a carrier and ammonia water as a precipitator, and comprises the following steps:
(1) 1g of TS-1-B, 40mL of water, 0.65mL of chloroauric acid solution (1.10 mg) Au Ml) are sequentially added into a quartz beaker (100ml) to be mixed and stirred for 5min to obtain suspension; transferring the suspension to a sealed glass dryer of 18cm diameter, fixing a small beaker (10mL) containing 8mL of ammonia (2 wt%) on the side wall of the sealed glass dryer; vigorously stirring the suspension at room temperature for 6h, and measuring the pH value of the suspension to be 10.8; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 320 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.07 wt%.
Comparative example 1
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor and TS-1-B as a carrier through a DPU method, and comprises the following steps:
(1) sequentially adding 1g of TS-1-B, 40mL of water and 1.14mL of chloroauric acid solution (1.10mgAu/mL) into a beaker, mixing and stirring to obtain a suspension, and adding 0.09g of urea into the suspension; heating the suspension to 90 ℃ in a water bath kettle and keeping the temperature for 6 hours; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.11 wt%.
Comparative example 2
The Au-Ti bifunctional catalyst is prepared by taking sodium chloroaurate as a precursor and TS-2-B as a carrier through a DPU method, and comprises the following steps:
(1) adding 1g of TS-2-B, 40mL of water and 1.2mL of sodium chloroaurate solution (1.10mgAu/mL) into a beaker in sequence, mixing and stirring to obtain a suspension, and adding 0.09g of urea into the suspension; heating the suspension to 90 ℃ in a water bath kettle and keeping the temperature for 6 hours; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.11 wt%.
Comparative example 3
The Au-Ti bifunctional catalyst is prepared by a DP method by taking sodium chloroaurate as a precursor, TS-1 as a carrier and potassium hydroxide as a precipitator, and comprises the following steps:
(1) sequentially adding 1g of TS-1, 20mL of water and 10mL of sodium chloroaurate solution (9.000mgAu/mL) into a beaker, mixing and stirring to obtain a suspension, stirring at room temperature for 8 hours, and dropwise adding 0.1M KOH solution into the suspension to keep the pH of the suspension between 7 and 7.5; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises oxygen: hydrogen gas: propylene: nitrogen gas 1: 1: 1: 7 (volume ratio) at a flow rate of 35mL/min, heating from room temperature to 200 ℃ at a speed of 0.5 ℃/min to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is 0.15 wt% by determination.
Comparative example 4
The Au-Ti bifunctional catalyst is prepared by a DP method by taking sodium chloroaurate as a precursor, Ti-SBA-15 as a carrier and sodium hydroxide as a precipitator, and comprises the following steps:
(1) sequentially adding 1g of Ti-SBA-15, 20mL of water and 10mL of sodium chloroaurate solution (9.000mgAu/mL) into a beaker, mixing and stirring to obtain a suspension, stirring at room temperature for 8 hours, and dropwise adding 0.1M NaOH solution into the suspension to keep the pH of the suspension between 7 and 7.5; the solid and liquid were separated and washed by centrifugation and the resulting solid was dried under vacuum at room temperature.
(2) Placing the dried solid in a fixed bed reactor, wherein the reaction atmosphere comprises hydrogen: nitrogen gas 0.36: heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min in the flow rate of 50mL/min in 0.64 (volume ratio) and reducing for 2h to obtain the supported Au-Ti bifunctional catalyst, wherein the loading amount of gold is determined to be 0.16 wt%.
Example 10
The catalysts prepared in the above examples 1 to 9 and comparative examples 1 to 4 were used for evaluating the catalytic performance in the reaction for preparing propylene oxide by the oxyhydrogen epoxidation of propylene, the gas-phase epoxidation of propylene was carried out in a fixed-bed reactor at normal pressure, and the reaction atmosphere consisted of propylene: hydrogen gas: oxygen: nitrogen gas 1: 1: 1: 7 (volume ratio) and the space velocity of 14000 mL.h -1 ·g cat -1 The outlet product was analyzed by gas chromatography. The catalytic results are shown in table 1.
TABLE 1
Referring to fig. 1-6, the physicochemical properties and catalytic performance of example 1 are compared with those of comparative example 1, and as shown in fig. 1-2, HAADF-STEM graphs of the catalysts prepared in example 1 and comparative example 1 are shown, and the average particle size of the gold nanoparticles in the catalyst of example 1 is 1.6 ± 0.3nm, which has the advantages of narrow particle size distribution, small particle size, uniform distribution, etc. of the gold nanoparticles. The invention can obviously improve the gold particles by the improved DP methodAnd (4) dispersibility. The present invention promotes defects in titanium-containing supports, Ti (OSi), by an improved DP process, as can be obtained by NMR and UV spectra of FIGS. 3-5 3 Formation of OH sites. Compared with the catalyst prepared by the traditional DPU method, the catalyst prepared by the improved DP method obviously improves the generation rate of PO in the propylene hydrogen oxidation reaction, and simultaneously can keep higher PO selectivity and hydrogen efficiency. The preparation method of the catalyst provided by the invention has the advantages of simple process, high gold loading efficiency, wide application range of the carrier and easy industrial amplification. The invention not only clarifies a new method for synthesizing the high-efficiency Au-Ti bifunctional catalyst in the propylene hydrogen oxidation reaction, but also provides a new idea for improving the catalytic activity of the zeolite-supported gold nano catalyst on other reactions.
Example 11
The catalysts prepared in the above examples 1 and 9 and comparative example 1 were used to evaluate the catalytic performance in the reaction of preparing acetone by propane-hydrogen oxidation, the propane-hydrogen oxidation reaction was carried out in a fixed-bed reactor at normal pressure, and the reaction atmosphere composition was propane: hydrogen gas: oxygen: nitrogen gas 1: 1: 1: 7 (volume ratio) and the space velocity of 14000 mL.h -1 ·g cat -1 The reaction temperature was 200 ℃ and the outlet product was analyzed by gas chromatography. The catalytic results are shown in table 2.
TABLE 2
In combination with the comparison between the physicochemical properties and the catalytic performances of example 1 and comparative example 1, as shown in FIGS. 1 to 5 and FIG. 7, the present invention can significantly improve the dispersibility of gold particles and promote defects in a titanium-containing support, Ti (OSi), by an improved DP method 3 Formation of OH sites. Compared with the Au-Ti bifunctional catalyst prepared by the traditional DPU method, the Au-Ti catalyst obtained by the improved DP method remarkably improves the generation rate of acetone in the propane hydrogen oxidation reaction, and has higher acetone selectivity and hydrogen efficiency. The invention not only clarifies a novel method for synthesizing a high-efficiency Au-Ti dual-function catalyst in the reaction of preparing acetone by propane hydrogen oxidation, but also aims toThe catalytic activity of the zeolite supported gold nano-catalyst on other reactions is improved.
Claims (10)
1. The preparation method of the titanium silicalite molecular sieve supported gold catalyst is characterized in that a volatile amine solution or ammonia water is used as a precipitator, the precipitator and slurry containing a gold precursor solution and a titanium silicalite molecular sieve are separately placed, and the amine solution or ammonia water is volatilized and enters the slurry containing the gold precursor solution and the titanium silicalite molecular sieve to deposit gold on the titanium silicalite molecular sieve, so that a catalyst precursor is obtained; the catalyst precursor is dried and activated to obtain the supported Au-Ti bifunctional catalyst.
2. The preparation method according to claim 1, wherein the amine solution or the ammonia water and the slurry containing the gold precursor solution and the titanium silicalite molecular sieve are placed in the same closed container, or placed in two different closed containers, and the two closed containers are communicated through a pipeline.
3. The preparation method of claim 1, wherein the titanium silicalite molecular sieve comprises one or more of Ti-SBA-15, Ti-MCM-41, Ti-MCM-48, Ti-MCM-36, Ti-MWW, Ti-MOR, Ti-Beta, Ti-TUD-1, TS-1, hierarchical pore TS-1, TS-2, and hierarchical pore TS-2; the titanium-silicon molecular sieve is a titanium-silicon molecular sieve which is subjected to roasting treatment at 150-1000 ℃, or a titanium-silicon molecular sieve of which the pore channels are blocked by a template agent without being subjected to roasting treatment.
4. The method according to claim 1, wherein the gold precursor solution uses a gold precursor having a general formula of MAuCl 4 Where M ═ H, Na, K, Cs, Li or NH 4 The gold precursor solution at least comprises one gold precursor shown in the general formula.
5. The preparation method according to claim 1, wherein the amine solution is a volatile amine solution with organic amine with less than 7 carbon atoms as a solute; the concentration of the precipitant is not higher than 5 wt%.
6. The preparation method according to claim 1, wherein the precipitant uses water as a solvent, or adds a part of alcohol with the carbon number less than 5 as a solvent or all of alcohol with the carbon number less than 5 as a solvent into water.
7. The method according to claim 1, wherein the slurry comprising the gold precursor solution and the titanium silicalite molecular sieves has a pH of 10 to 12; the temperature for preparing the catalyst precursor is 5-50 ℃, and room temperature is preferred; the time for preparing the catalyst precursor is 0.15 to 6 hours, preferably 3 to 6 hours; the drying mode is preferably vacuum drying.
8. The preparation method according to claim 1, wherein the activation is performed by treating the catalyst precursor at a temperature in a certain atmosphere, wherein the certain temperature is in a range of 50-800 ℃, preferably 200-350 ℃, and more preferably 300-320 ℃; the atmosphere is one or more of reducing atmosphere, oxidizing atmosphere and inert atmosphere.
9. The titanium silicalite supported gold catalyst prepared by the preparation method of any one of claims 1 to 8, wherein the particle size of the gold nanoparticles on the titanium silicalite is less than 10nm, preferably less than 5nm, and more preferably less than 2.5 nm.
10. The use of the titanium silicalite molecular sieve-supported gold catalyst of claim 9, wherein the catalyst is used in the reaction of propylene oxyhydrogen epoxidation to PO and the reaction of propane oxyhydrogen to acetone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115745919A (en) * | 2022-10-20 | 2023-03-07 | 中国科学院大连化学物理研究所 | Synthesis method of propylene oxide |
| CN115745919B (en) * | 2022-10-20 | 2024-03-19 | 中国科学院大连化学物理研究所 | Synthetic method of epoxypropane |
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