CN115106124B - Titanium silicon molecular sieve solid gold catalyst and its preparation method and application - Google Patents
Titanium silicon molecular sieve solid gold catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN115106124B CN115106124B CN202210848018.1A CN202210848018A CN115106124B CN 115106124 B CN115106124 B CN 115106124B CN 202210848018 A CN202210848018 A CN 202210848018A CN 115106124 B CN115106124 B CN 115106124B
- Authority
- CN
- China
- Prior art keywords
- gold
- catalyst
- preparation
- molecular sieve
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010931 gold Substances 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 79
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002808 molecular sieve Substances 0.000 title claims description 42
- 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 description 42
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims description 30
- 239000007787 solid Substances 0.000 title description 64
- 239000010936 titanium Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 63
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 38
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 239000001257 hydrogen Substances 0.000 abstract description 32
- 238000011068 loading method Methods 0.000 abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052719 titanium Inorganic materials 0.000 abstract description 18
- 239000012716 precipitator Substances 0.000 abstract description 15
- -1 propane oxyhydroxide Chemical compound 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- XHDNAIAXAZKUAI-UHFFFAOYSA-N OOO.C=CC Chemical compound OOO.C=CC XHDNAIAXAZKUAI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 description 48
- 239000000243 solution Substances 0.000 description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- 239000011521 glass Substances 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000001294 propane Substances 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 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
- 239000011734 sodium Substances 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 230000002950 deficient Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 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
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000002156 mixing Methods 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
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 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
- 239000007789 gas Substances 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
- 239000002149 hierarchical pore Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000003993 interaction Effects 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 238000005406 washing Methods 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- 230000003213 activating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 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
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a titanium silicalite immobilized gold catalyst and a preparation method and application thereof, wherein an improved deposition-precipitation method is adopted, volatile amine solution or ammonia water is used as a precipitator, the precipitator and slurry containing a gold precursor solution and the titanium silicalite are separately placed, the amine solution or the ammonia water slowly volatilizes into the slurry containing the gold precursor solution and the titanium silicalite to realize the deposition of gold on the titanium silicalite to obtain a catalyst precursor, the catalyst precursor is dried and activated to obtain a supported Au-Ti bifunctional catalyst, the preparation method improves the dispersity of gold particles, promotes the formation of defect sites Ti (OSi) 3 OH active sites in the titanium silicalite, remarkably improves the gold loading efficiency, improves the propylene oxide generation rate in propylene oxyhydroxide reaction and the acetone generation rate in propane oxyhydroxide reaction, and simultaneously improves the selectivity of target products and the hydrogen utilization efficiency.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a titanium-silicon molecular sieve immobilized gold catalyst, and a preparation method and application thereof.
Background
Propylene oxide (Propylene Oxide, PO for short) 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. In many PO production processes, the direct epoxidation of propylene, H 2 and O 2 to synthesize PO has the advantages of low cost and easy availability of raw materials, green and environment-friendly process and the like, and has long been regarded as an ideal process for PO production.
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 improved, and the domestic acetone market demand is continuously increased. Compared with the current mainstream cumene method, the novel process for preparing the acetone by directly oxidizing the propane in the hydrogen/oxygen atmosphere has the unique advantages of i) low-cost and easily-obtained production raw materials of propane, hydrogen and oxygen, ii) high acetone selectivity and good atom economy, iii) simple process, and no need of organic solvent, and the reaction is carried out in a gas phase.
At present, the catalyst used for catalyzing the reaction of propylene to generate PO and propane to prepare acetone by hydrogen oxidation is a nano gold catalyst immobilized on a titanium-silicon molecular sieve. The research shows that the gold catalyst supported by the titanium silicalite molecular sieve is an Au-Ti bifunctional catalyst, wherein Au sites catalyze H 2 and O 2 to generate hydroperoxide species, and then the hydrogen species diffuse to Ti sites to generate Ti-OOH active intermediates, and the active intermediates catalyze propylene or propane to generate oxidation reactions to generate PO and acetone respectively.
Numerous studies have found that the type of Ti 4+ site is an important factor affecting the catalytic performance of Au-Ti bifunctional catalysts. Studies have shown that Ti 4+ (e.g., ti (OSi) 3 OH) at the defective site in TS-1 is more active in propylene epoxidation than Ti 4+ (e.g., ti (OSi) 4) at the non-defective site. This suggests that transferring the non-defective sites Ti 4+ to the defective sites Ti 4+ may facilitate uniform deposition of gold while increasing Ti active sites, thereby improving catalytic performance. In addition, the size of the gold nanoparticles has an important influence on the catalytic performance of the Au-Ti bifunctional catalyst. In general, small sized gold nanoparticles exhibit higher activity in catalyzing the oxyhydrogen reaction of propylene.
Research shows that the catalyst preparation method has a significant effect on the size of gold nanoparticles. Among the reported catalyst preparation methods, the deposition-precipitation method (DP method) is the most widely used method of uniformly dispersing and fixing gold nanoparticles on Ti-containing materials, because it can effectively remove chlorine by gradually hydrolyzing AuCl 4- species to [ AuCl x(OH)4-x]-, thereby preventing gold particles from agglomerating caused by chloride ions. However, the performance of the au—ti bifunctional catalyst prepared by the conventional DP method is very sensitive to preparation parameters, and these preparation parameters include the concentration of the gold precursor, pH, the type of precipitant, the preparation temperature, the preparation time, and the like, which involve numerous and complicated factors, and thus bring great challenges to the controllable preparation and engineering amplification of the au—ti bifunctional catalyst. In addition, the traditional DP method has low gold loading efficiency, and the performance of the catalyst prepared by adopting the traditional DP method has a certain gap from industrial application. Although the present research discovers that the DP Urea method (namely the DPU method) adopting Urea as a precipitator can achieve very high gold loading efficiency (about 90%) when the unfired titanium-silicon molecular sieves TS-1 and TS-2 are used for preparing the gold-loaded catalyst, the performance of the catalyst prepared by the DPU method is very sensitive to preparation parameters such as preparation time, urea/gold mole ratio, preparation temperature and the like, especially the preparation temperature, and the engineering amplification of the catalyst is also challenged. In addition, the performance of the catalyst prepared by adopting the DPU method is different from the industrial application to a certain extent. Therefore, further development and research on a preparation method of the high-efficiency titanium-silicon molecular sieve immobilized gold catalyst are needed.
Disclosure of Invention
Aiming at the defects of the existing catalyst preparation method and performance in the reaction of preparing PO by propylene hydrogen oxidation and the reaction of preparing acetone by propane hydrogen oxidation, the invention provides an improved catalyst preparation method for preparing PO by propylene hydrogen oxidation and the reaction of preparing acetone by propane hydrogen oxidation by using a DP method. By improving the DP method, the dispersibility of gold particles can be improved and the formation of active sites of defect sites Ti (OSi) 3 OH in the titanium silicalite molecular sieve can be promoted. Compared with the Au-Ti bifunctional catalyst prepared by the traditional DP method and the DPU method using urea as a precipitator, the improved DP method has gold loading efficiency close to 100%, and the prepared catalyst has remarkable promotion effects on improving the reaction rate of preparing PO by propylene hydrogen oxidation and the reaction rate of preparing acetone by propane hydrogen oxidation, and can also obviously improve the selectivity and hydrogen efficiency of target products (PO and acetone). The invention not only clarifies a new 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 on other reactions.
According to the preparation method, a volatile amine solution or ammonia water is used as a precipitant, the precipitant is not directly added into slurry formed by mixing a gold precursor solution and a titanium silicalite molecular sieve according to a traditional deposition-precipitation method, the precipitant and the slurry containing the gold precursor solution and the titanium silicalite molecular sieve are separately placed in a closed container, the amine solution or the ammonia water slowly volatilizes into 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, and the catalyst precursor is dried and activated to obtain the supported Au-Ti dual-function catalyst.
The invention further provides that the amine solution or the ammonia water and the slurry containing the gold precursor solution and the titanium-silicon 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-silicon molecular sieve can be placed in two different closed containers, and the two closed containers are communicated through a pipeline. Specifically, the preparation method of the improved DP method comprises the following steps:
(1) Adding a gold precursor solution and a titanium silicalite molecular sieve into a first open container, stirring uniformly 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 to a second open container, placing the second open container in the first sealable container, and sealing the first sealable 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, and communicating the first sealable container seal with the second sealable container through a pipeline, and sealing the first sealable container seal with 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 the first sealable container is sealed with the second sealable container;
(3) And (3) placing the mixed slurry for a period of time under the sealing condition of the step (2), slowly volatilizing the amine solution or ammonia water into the mixed slurry to realize the deposition of gold on the titanium-silicon molecular sieve, and obtaining a catalyst precursor, and drying and activating the catalyst precursor to obtain the supported Au-Ti dual-function catalyst.
The invention further provides that water is added in the step (1) as a diluted solvent, and preferably, the water, the gold precursor solution and the titanium-silicon molecular sieve are added in sequence.
The invention further provides that the titanium-silicon molecular sieve in the step (1) is one or more titanium-silicon molecular sieves in the field of preparing propylene oxide by propylene oxyhydroxide or preparing acetone by propane oxyhydroxide, wherein the titanium-silicon molecular sieves comprise one or more titanium-silicon molecular sieves selected from 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, and the titanium-silicon molecular sieves can be titanium-silicon molecular sieves subjected to roasting treatment at 150-1000 ℃ or titanium-silicon molecular sieves without roasting treatment and pore canal blockage by a template agent.
The invention further provides 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 one gold precursor as shown in the general formula, and the solvent used in the gold precursor solution is one or a mixture of two or more of water, ethanol and acetone.
The invention further provides that the amine solution in the step (2) is a volatile amine solution taking organic amine with the carbon number less than 7 as a solute component, the ammonia water and the amine solution take water as a solvent, or partial alcohol with the carbon number less than 5 is added into the water as a solvent or all alcohols with the carbon number less than 5 are taken as a solvent, and the concentration of the ammonia water and the amine solution is not higher than 5wt%.
The invention further provides that the mixed slurry in the step (3) can be stirred or not, the pH of the mixed slurry is 10-12, gold in the mixed slurry is deposited on the titanium-silicon molecular sieve, the temperature for preparing the catalyst precursor is 5-50 ℃, the room temperature is preferred, the preparation time is 0.15-6h, the preparation time is preferred to be 3-6 h, and the catalyst precursor obtained after the preparation time is reached can be washed and filtered, or can be washed and filtered.
The invention further provides that the drying in step (3) is carried out by a drying method conventionally used in the field of catalyst preparation, preferably vacuum drying.
The invention further provides that the activation mode in the step (3) is that the catalyst precursor is treated in a certain temperature and a certain atmosphere, wherein the certain temperature is 50-800 ℃, preferably 200-350 ℃, more preferably 300-320 ℃, the atmosphere is a reducing atmosphere or 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 invention, a titanium silicalite molecular sieve supported gold catalyst is provided, which is a supported Au-Ti dual function catalyst, using the improved DP process as described above.
The invention further provides that the particle size of the nano gold particles on the titanium silicon molecular sieve immobilized gold catalyst obtained by the method is less than 10nm, preferably less than 5nm, and more preferably less than 2.5nm.
In a third aspect, the invention provides an application of the titanium-silicon molecular sieve immobilized gold catalyst for a reaction for preparing PO by propylene oxyhydroxide and a reaction for preparing acetone by propane oxyhydroxide.
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 can remarkably enhance the dispersibility of gold through the strong interaction between N and Au in the nitrogen-containing groups grafted on the surface of the molecular sieve, so that smaller and narrower Au particle size distribution is obtained, which is beneficial to improving the generation rate of hydrogen peroxide species on nano gold particles, thereby improving the activity of the catalyst.
(2) Compared with the traditional DP method and DPU method, the improved DP method for preparing the supported Au-Ti bifunctional catalyst, which is developed by the invention, has the advantages that the adopted strong alkaline environment is favorable for hydrolyzing Ti-O-Si bonds to form a defect site Ti (OSi) 3 OH active site with higher activity, thereby improving the performance of the catalyst.
(3) The improved DP method developed by the invention for preparing the supported Au-Ti bifunctional catalyst introduces ammonia water or a volatile amine solution as a precipitator, and a positively charged gold-ammonia complex is formed in the deposition process, while the surface of the titanium silicalite molecular sieve is negatively charged when the supported Au-Ti bifunctional catalyst is prepared, so that the catalyst prepared by the improved DP method shows gold loading efficiency approaching 100 percent due to the strong interaction between the positively charged gold-ammonia complex and the negatively charged titanium silicalite molecular sieve surface.
Drawings
FIG. 1 is a scanning transmission electron microscope (HAADF-STEM) of the catalyst prepared in example 1;
FIG. 2 is a scanning transmission electron microscope (HAADF-STEM) of the catalyst prepared in comparative example 1;
FIG. 3 is a 29 Si nuclear magnetic resonance spectrum (29 Si NMR) of the catalyst precursor prepared in example 1 and comparative example 1;
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 PO production rates of the catalyst for propylene hydrogenation in example 1 and comparative example 1;
FIG. 7 is a graph showing the comparison of the acetone production rate by the catalytic oxidation of propane with the catalyst prepared in example 1 and comparative example 1.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with specific embodiments. It is to be understood that the described embodiments are only some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. Unless otherwise indicated, all percentages, ratios, proportions, or parts by weight, room temperature refers to temperatures of 20-30 ℃.
Example 1
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, taking unburnt TS-1 (namely TS-1-B) as a carrier and taking 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 (100 mL) to be mixed and stirred for 5min to obtain a suspension, the suspension is transferred into a sealed glass dryer with the diameter of 18cm, a small beaker (10 mL) containing 8mL of ammonia water (2 wt%) is fixed on the side wall of the sealed glass dryer, the suspension is vigorously stirred at room temperature for 6h, the pH of the suspension is measured to be 10.6, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.11wt percent according to the measurement.
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 (100 mL) to be mixed and stirred for 5min to obtain a suspension, the suspension is transferred into a sealed glass dryer with the diameter of 18cm, a small beaker (10 mL) containing 8mL of ammonia water (2 wt%) is fixed on the side wall of the sealed glass dryer, the suspension is vigorously stirred at room temperature for 6h, the pH of the suspension is measured to be 10.6, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 320 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.11wt percent according to the measurement.
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) Sequentially adding 1g of TS-1-B, 40mL of water and 0.83mL of chloroauric acid solution (1.10 mg Au/mL) into a quartz beaker (100 mL), mixing and stirring for 5min to obtain a suspension, transferring the suspension into a sealed glass dryer with the diameter of 18cm, fixing a small beaker (10 mL) containing 6mL of ammonia water/ethanol solution (3 wt%) on the side wall of the sealed glass dryer, namely, taking NH 3 as a solute and adding part of ethanol into water as a solvent, vigorously stirring the suspension at room temperature for 6h to obtain the pH of the suspension of 10.7, separating and washing the solid and the liquid by adopting a centrifugal method, and vacuum drying the obtained solid at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.09wt percent according to the measurement.
Example 4
The Au-Ti bifunctional catalyst is prepared by taking chloroauric acid as a precursor, TS-1-B as a carrier and ethylamine aqueous solution 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 (100 mL) to be mixed and stirred for 5min to obtain a suspension, the suspension is transferred into a sealed glass dryer with the diameter of 18cm, a small beaker (10 mL) containing 8mL of ethylamine aqueous solution (3 wt%) is fixed on the side wall of the sealed glass dryer, the suspension is vigorously stirred at room temperature for 6h, the pH of the suspension is measured to be 10.9, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.11wt percent according to the measurement.
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 and 1.00mL of chloroauric acid solution (1.10 mg Au/mL) are sequentially added into a quartz beaker (100 mL) to be mixed and stirred for 5min to obtain a suspension, the suspension is transferred into a sealed glass dryer with the diameter of 18cm, a small beaker (10 mL) containing 8mL of ethylenediamine water solution (3 wt%) is fixed on the side wall of the sealed glass dryer, the suspension is vigorously stirred at room temperature for 6h, the pH of the suspension is measured to be 10.4, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.11wt percent according to the measurement.
Example 6
The Au-Ti bifunctional catalyst is prepared by taking sodium chloroaurate as a precursor, taking unburnt TS-2 (namely TS-2-B) as a carrier and taking ammonia water as a precipitator, and comprises the following steps:
(1) 1g of TS-2-B, 40mL of water and 1.00mL of sodium chloroaurate solution (1.10 mg Au/mL) are sequentially added into a quartz beaker (100 mL) to be mixed and stirred for 5min to obtain a suspension, the suspension is transferred into a sealed glass dryer with the diameter of 18cm, a small beaker (10 mL) containing 8mL of ammonia water (2 wt%) is fixed on the side wall of the sealed glass dryer, the suspension is vigorously stirred at room temperature for 6h, the pH of the suspension is measured to be 11.3, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.11wt percent according to the measurement.
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 of TS-1, 20mL of water, 1.55mL of chloroauric acid solution (1.10 mg Au/mL) and 1mL of potassium nitrate solution (0.4M) are sequentially added into a quartz beaker (100 mL) to be mixed and stirred for 5min to obtain a suspension, the suspension is transferred into a sealed glass dryer with the diameter of 18cm, a small beaker (10 mL) containing 8mL of ammonia water (5 wt%) is fixed on the side wall of the sealed glass dryer, the suspension is vigorously stirred for 3h at room temperature, the pH of the suspension is measured to be 11.2, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid to 200 ℃ from room temperature at a rate of 0.5 ℃ per minute at a flow rate of 35mL/min in a reaction atmosphere comprising oxygen, hydrogen and propylene and nitrogen=1:1:7 (volume ratio), so as to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.17wt% according to the measurement.
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) were sequentially added to a quartz beaker (100 mL) and mixed and stirred for 5min to obtain a suspension, the suspension was transferred to a sealed glass dryer having a diameter of 18cm, a small beaker (10 mL) containing 8mL of aqueous ammonia (4 wt%) was fixed to the side wall of the sealed glass dryer, the suspension was vigorously stirred at room temperature for 4h to obtain a pH of 11.0, the solid and the liquid were separated and washed by centrifugation, and the obtained solid was dried under vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.18wt percent according to the measurement.
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 and 0.65mL of chloroauric acid solution (1.10 mg Au/mL) are sequentially added into a quartz beaker (100 mL) to be mixed and stirred for 5min to obtain a suspension, the suspension is transferred into a sealed glass dryer with the diameter of 18cm, a small beaker (10 mL) containing 8mL of ammonia water (2 wt%) is fixed on the side wall of the sealed glass dryer, the suspension is vigorously stirred at room temperature for 6h, the pH of the suspension is measured to be 10.8, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 320 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.07wt percent according to the measurement.
Comparative example 1
The Au-Ti bifunctional catalyst is prepared by using chloroauric acid as a precursor and TS-1-B as a carrier through a DPU method, and comprises the following steps:
(1) 1g of TS-1-B, 40mL of water and 1.14mL of chloroauric acid solution (1.10 mgAu/mL) are sequentially added into a beaker, mixed and stirred to obtain a suspension, 0.09g of urea is added into the suspension, the suspension is heated to 90 ℃ in a water bath kettle and kept for 6 hours, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.11wt percent according to the measurement.
Comparative example 2
The Au-Ti bifunctional catalyst is prepared by using sodium chloroaurate as a precursor and TS-2-B as a carrier through a DPU method, and comprises the following steps:
(1) 1g of TS-2-B, 40mL of water and 1.2mL of sodium chloroaurate solution (1.10 mgAu/mL) are sequentially added into a beaker, mixed and stirred to obtain a suspension, 0.09g of urea is added into the suspension, the suspension is heated to 90 ℃ in a water bath kettle and kept for 6 hours, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.11wt percent according to the measurement.
Comparative example 3
The method takes sodium chloroaurate as a precursor, TS-1 as a carrier, potassium hydroxide as a precipitator, and prepares the Au-Ti bifunctional catalyst by a DP method, and the method comprises the following steps:
(1) Sequentially adding 1g of TS-1, 20mL of water and 10mL of sodium chloroaurate solution (9.000 mgAu/mL) into a beaker, mixing and stirring to obtain a suspension, stirring at room temperature for 8h, dropwise adding 0.1M KOH solution into the suspension to keep the pH of the suspension between 7 and 7.5, separating and washing the solid and the liquid by adopting a centrifugal method, and vacuum drying the obtained solid at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid to 200 ℃ from room temperature at a rate of 0.5 ℃ per minute at a flow rate of 35mL/min in a reaction atmosphere comprising oxygen, hydrogen and propylene and nitrogen=1:1:7 (volume ratio), so as to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.15wt% according to the measurement.
Comparative example 4
The preparation method of the Au-Ti bifunctional catalyst by using sodium chloroaurate as a precursor, ti-SBA-15 as a carrier and sodium hydroxide as a precipitant through a DP method comprises the following steps:
(1) 1g of Ti-SBA-15, 20mL of water and 10mL of sodium chloroaurate solution (9.000 mgAu/mL) are sequentially added into a beaker to be mixed and stirred to obtain a suspension, the suspension is stirred at room temperature for 8 hours, 0.1M NaOH solution is added dropwise into the suspension to keep the pH of the suspension between 7 and 7.5, the solid and the liquid are separated and washed by adopting a centrifugal method, and the obtained solid is dried in vacuum at room temperature.
(2) And (3) placing the dried solid in a fixed bed reactor, heating the solid from room temperature to 300 ℃ at a speed of 1.5 ℃ per minute at a flow rate of 50mL/min in a reaction atmosphere with the composition of hydrogen and nitrogen=0.36 and 0.64 (volume ratio), and reducing the solid for 2 hours to obtain the supported Au-Ti bifunctional catalyst, wherein the gold loading is 0.16wt percent according to the measurement.
Example 10
The catalysts prepared in examples 1-9 and comparative examples 1-4 were used for the evaluation of catalytic performance in the epoxidation of propylene to propylene oxide in a gas phase epoxidation of propylene in an atmospheric fixed bed reactor, the reaction atmosphere consisting of propylene to hydrogen to oxygen to nitrogen=1:1:1:7 (volume ratio), the space velocity being 14000ml·h -1·gcat -1, and the outlet product being analyzed by gas chromatography. The catalytic results are shown in Table 1.
TABLE 1
In combination with fig. 1-6, the relevant physicochemical properties and catalytic performance of the catalyst of example 1 and comparative example 1 are compared, and as shown in fig. 1-2, HAADF-STEM diagrams of the catalysts prepared in example 1 and comparative example 1 are shown, and the average particle size of the nano gold particles 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 and the like. The invention can obviously improve the dispersibility of gold particles through an improved DP method. As can be obtained from the nuclear magnetic resonance and uv spectra of fig. 3-5, the present invention promotes the formation of the defective Ti (OSi) 3 OH site in the titanium-containing support by a modified DP method. Compared with the catalyst prepared by the traditional DPU method, the catalyst obtained by the improved DP method remarkably improves the generation rate of PO in the propylene oxidation reaction, and can also 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 on the carrier and easiness in industrial amplification. The invention not only clarifies a novel method for synthesizing the high-efficiency Au-Ti bifunctional catalyst in the propylene hydrogen oxidation reaction, but also provides a novel thought for improving the catalytic activity of the zeolite supported gold nano catalyst on other reactions.
Example 11
The catalysts prepared in examples 1 and 9 and comparative example 1 were used for evaluating catalytic performance in the reaction of preparing acetone by oxidizing propane, the propane-oxidizing reaction was performed in an atmospheric fixed bed reactor, the reaction atmosphere was composed of propane-hydrogen-oxygen-nitrogen=1:1:1:7 (volume ratio), the space velocity was 14000ml·h -1·gcat -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 comparison of the physicochemical properties and catalytic properties associated with example 1 and comparative example 1, as shown in FIGS. 1-5 and 7, the present invention can significantly improve the dispersibility of gold particles and promote the formation of defective Ti (OSi) 3 OH sites in a titanium-containing carrier by improving the DP method. 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 simultaneously has higher acetone selectivity and hydrogen efficiency. The invention not only clarifies a novel method for synthesizing the high-efficiency Au-Ti bifunctional catalyst in the reaction of preparing the acetone by the propane hydrogen oxidation, but also provides reference for improving the catalytic activity of the zeolite supported gold nano catalyst on other reactions.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210848018.1A CN115106124B (en) | 2022-07-19 | 2022-07-19 | Titanium silicon molecular sieve solid gold catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210848018.1A CN115106124B (en) | 2022-07-19 | 2022-07-19 | Titanium silicon molecular sieve solid gold catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115106124A CN115106124A (en) | 2022-09-27 |
| CN115106124B true CN115106124B (en) | 2024-12-31 |
Family
ID=83331365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210848018.1A Active CN115106124B (en) | 2022-07-19 | 2022-07-19 | Titanium silicon molecular sieve solid gold catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115106124B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115745919B (en) * | 2022-10-20 | 2024-03-19 | 中国科学院大连化学物理研究所 | A kind of synthesis method of propylene oxide |
| CN116139920A (en) * | 2023-01-31 | 2023-05-23 | 浙江师范大学 | Catalyst for preparing ethylene glycol and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530814A (en) * | 2008-03-10 | 2009-09-16 | 中国科学院成都有机化学有限公司 | Nanosized gold catalyst used for preparing propylene oxide by direct propylene oxidation and preparation method thereof |
| CN102513151A (en) * | 2010-03-08 | 2012-06-27 | 中国科学院成都有机化学有限公司 | Method for preparing high-performance nano gold catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665256B (en) * | 2008-09-04 | 2012-07-25 | 中国石油化工股份有限公司 | Method for treating titanium silicate molecular sieve by using noble metal source |
| CN101850266B (en) * | 2009-03-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for preparing precious metal-containing titanium silicalite |
| CN109928942B (en) * | 2017-12-15 | 2023-03-24 | 中国科学院大连化学物理研究所 | Catalyst for preparing epoxypropane by epoxidation of modified propylene with bimetallic additive and application thereof |
-
2022
- 2022-07-19 CN CN202210848018.1A patent/CN115106124B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530814A (en) * | 2008-03-10 | 2009-09-16 | 中国科学院成都有机化学有限公司 | Nanosized gold catalyst used for preparing propylene oxide by direct propylene oxidation and preparation method thereof |
| CN102513151A (en) * | 2010-03-08 | 2012-06-27 | 中国科学院成都有机化学有限公司 | Method for preparing high-performance nano gold catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115106124A (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115106124B (en) | Titanium silicon molecular sieve solid gold catalyst and its preparation method and application | |
| CN109433205B (en) | Copper-based catalyst for dimethyl oxalate hydrogenation and preparation method and application thereof | |
| JP5434162B2 (en) | Propylene oxide production method | |
| JP4000392B2 (en) | Catalyst for partial oxidation of hydrocarbons and process for producing oxygenated organic compounds | |
| CN102463105B (en) | Preparation method of silicon dioxide coated titanium dioxide hollow core-shell structure material | |
| CN112371146A (en) | Preparation method and application of Z-type carbon nitride-iron oxide catalyst containing nitrogen defect structure | |
| CN109589973B (en) | A kind of method for preparing stable monodisperse nanocatalyst | |
| CN111822044A (en) | Modification method of Au/TS-1 catalyst | |
| CN113275011A (en) | Preparation method of cuprous oxide photocatalyst with flower-ball-shaped multi-stage structure | |
| CN102179268B (en) | Preparation of Ti-MCM-41 mesoporous material with functionalized ionic liquid and application thereof | |
| CN112275283A (en) | Metal supported catalyst system for preparing ethylene by photocatalytic oxidation ethane dehydrogenation and ethane direct dehydrogenation | |
| CN107879898A (en) | A kind of method that vicinal diamines class compound is synthesized using difunctional characteristic catalyst | |
| JP4016121B2 (en) | Hydrocarbon partial oxidation catalyst and method for producing oxygen-containing organic compound | |
| CN107376988B (en) | High-activity propylene gas-phase epoxidation catalyst, and preparation method and application thereof | |
| CN105689002A (en) | Supported tungsten-gallium polyoxometallate catalyst and preparation method and application thereof | |
| Jia et al. | Polydopamine‐Mediated Contact‐Electro‐Catalysis for Efficient Partial Oxidation of Methane | |
| CN112973744A (en) | Novel photoelectric catalyst and preparation method thereof | |
| CN109482184B (en) | Preparation method of catalyst for synthesizing ethylene glycol by dimethyl oxalate hydrogenation | |
| CN115283011B (en) | A method for improving the dispersion of nano-gold particles of titanium silicon molecular sieve immobilized gold catalyst and its application | |
| CN110813283B (en) | A kind of titanium dioxide/gold/titanium dioxide photocatalyst and preparation method thereof | |
| CN115155653B (en) | A sulfur-promoter-modified titanium-silicon molecular sieve immobilized gold catalyst and its preparation method and application | |
| CN112264042B (en) | High-activity modified titanium dioxide catalyst for formaldehyde degradation and preparation method and application thereof | |
| CN109433206B (en) | Preparation method of mesoporous silica supported copper catalyst with central radial pore passage | |
| CN112441591A (en) | Green one-step hydrothermal synthesis method and application of manganese silicate microspheres | |
| CN110813364B (en) | Preparation method of bimetallic nanocatalyst and use thereof for catalyzing oxidation of 1,2-propanediol to prepare pyruvic acid and hydroxyacetone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |