CN110860307A - Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method - Google Patents
Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method Download PDFInfo
- Publication number
- CN110860307A CN110860307A CN201911177663.XA CN201911177663A CN110860307A CN 110860307 A CN110860307 A CN 110860307A CN 201911177663 A CN201911177663 A CN 201911177663A CN 110860307 A CN110860307 A CN 110860307A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- beta molecular
- beta
- additive
- sample
- 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.)
- Pending
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 164
- 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 164
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000005917 acylation reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000010933 acylation Effects 0.000 title claims abstract description 9
- 150000008365 aromatic ketones Chemical class 0.000 title abstract description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- PIIRYSWVJSPXMW-UHFFFAOYSA-N 1-octyl-4-(4-octylphenoxy)benzene Chemical compound C1=CC(CCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCC)C=C1 PIIRYSWVJSPXMW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 25
- 229910001868 water Inorganic materials 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 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 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000005342 ion exchange Methods 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 14
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 14
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims 1
- 229960001826 dimethylphthalate Drugs 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 29
- 238000002425 crystallisation Methods 0.000 abstract description 28
- 230000008025 crystallization Effects 0.000 abstract description 28
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 abstract description 7
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- IQZLUWLMQNGTIW-UHFFFAOYSA-N acetoveratrone Chemical compound COC1=CC=C(C(C)=O)C=C1OC IQZLUWLMQNGTIW-UHFFFAOYSA-N 0.000 description 22
- 239000012265 solid product Substances 0.000 description 21
- 239000002253 acid Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 12
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 12
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- 229910001388 sodium aluminate Inorganic materials 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 230000002779 inactivation Effects 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
Abstract
A high-performance Beta molecular sieve catalyst, a preparation method and application thereof in aromatic ketone preparation by an acylation method belong to the technical field of heterogeneous catalysis. The Beta molecular sieve catalyst is synthesized by the method that gel is obtained by fully mixing a silicon source, an aluminum source, an inorganic alkali source, a micropore template agent and an additive and is subjected to hydrothermal crystallization. The additive used is polyethylene glycol or polyethylene glycol mono octyl phenyl ether. The invention introduces the green, environment-friendly and cheap additive into a hydrothermal synthesis system to synthesize the small-grain Beta molecular sieve, shortens the crystallization time, and adjusts the grain size and acidity of the molecular sieve. Aromatic ketone is prepared by Friedel-crafts acylation reaction of anisole or o-phenylether and acetic anhydride, and the performance of the synthesized molecular sieve catalyst is investigated. The experimental result shows that compared with the Beta molecular sieve synthesized by the traditional method, the Beta molecular sieve catalyst synthesized by the additive method has higher catalytic activity and stability.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis, and particularly relates to a high-performance Beta molecular sieve catalyst, a preparation method and application thereof in aromatic ketone preparation by an acylation method.
Background
Aromatic ketone is an important chemical intermediate, and has wide development prospect in the fields of fine chemicals, medicines, pesticides and the like. At present, the most important method for producing aromatic ketone compounds is the friedel-crafts acylation. In the actual industrial production, the catalyst for producing aromatic ketone is mainly AlCl3、BF3、HCl、H2SO4And the like, using acyl halide such as acid anhydride or benzoyl chloride and the like as an acylating agent to directly introduce acyl for reaction by using a traditional homogeneous phase Lewis acid catalyst. The process has the advantages of simple operation, mild reaction conditions, high selectivity of the aromatic ketone compound and the like. However, the used homogeneous catalyst has the problems of large catalyst dosage, difficult separation from products, serious equipment corrosion, large environmental hazard and the like. Therefore, research and development of novel environmentally friendly solid acid catalysts have become important.
At present, various types of solid acid catalysts are used in the Friedel-crafts acylation reaction process, including zeolite molecular sieves, supported heteropolyacids, metal organic framework materials and the like. The results of the literature show that the Beta molecular sieve has higher catalytic activity and selectivity for various types of acylation reactions with acid anhydride and acyl chloride as acylation reagents, and the catalyst can be recycled and regenerated by high-temperature roasting and the like (Freese U.et al.Catal.today.1999, 49: 237; Kim S D, et al.J.mol.Catal.A-chem.2000, 152: 33). In addition, compared with other types of molecular sieves and solid acid catalysts, the Beta molecular sieve has high structural stability and hydrothermal stability, and the silicon-aluminum ratio of the molecular sieve framework can be adjusted in a larger range, so that the acidity and the acylation reaction performance of the molecular sieve can be effectively adjusted. However, the Beta molecular sieve synthesized by the traditional hydrothermal method generally has the problems of poor activation capability on macromolecular aromatic hydrocarbon, rapid inactivation in the acylation reaction process and the like (RohanD.et al.J.Catal, 1998, 177: 296; Xiong Y.et al.Res.Chem.Intermedia, 2016, 43: 1557), thereby limiting the research and development of practical technology to a certain extent.
In order to solve the above problems, researchers have made continuous improvements to the synthesis process of Beta molecular sieves. For example, Al-Turkustani and the like synthesize nano-scale Beta molecular sieve grains by step-by-step treatment and hydrothermal crystallization treatment at high temperature of 175 ℃, and the activity of Friedel-crafts acylation reaction is improved (Al-Turkustani A M A, et Al. journal of Nanococience and Nanotechnology, 2016, 16: 4247.). However, too small a molecular sieve crystallite size can make separation of the catalyst from the product difficult, and is not suitable for practical production applications. Huang et al, which uses a layered silicate precursor (h-kanemite) as a silicon source, synthesize a hierarchical zeolite composed of uniform nanocrystals with high pore volume and high external surface area, and improve the acylation reaction performance (Huang G, et al, Microporous and Mesoporous Materials, 2017, 248: 30.); however, the method has the problems of complex precursor preparation process, long period and the like, and is not beneficial to industrial practical application.
Therefore, aiming at the Friedel-crafts acylation reaction, the exploration of a simple, efficient and cheap method for preparing the high-performance Beta molecular sieve catalyst has important scientific significance and practical application value, and the application prospect is wide.
Disclosure of Invention
The invention aims to provide a high-performance Beta molecular sieve catalyst, a preparation method and application thereof in aromatic ketone preparation by an acylation method, so as to solve the problems of relatively low catalyst activity, quick inactivation and the like in a Friedel-crafts acylation reaction.
The invention mainly solves the technical problems by introducing the additive into a Beta molecular sieve synthesis system. In order to achieve the purpose, one or more cheap additives are added in the preparation process to regulate and control the properties of the Beta molecular sieve catalyst, such as morphology, grain size, surface acidity and the like, so that the activity and stability of the acylation reaction of the catalyst are improved.
The invention adopts the traditional hydrothermal method, regulates the composition and concentration of sol-gel by introducing additives, and synthesizes the Beta molecular sieve acylation catalyst with high performance in a high-pressure reaction kettle through hydrothermal crystallization.
The invention relates to a preparation method of a high-performance Beta molecular sieve catalyst, which comprises the following steps:
(1) dissolving an alkali source and an aluminum source in a microporous template agent, stirring uniformly, adding a silicon source, stirring vigorously, transferring to a constant-temperature water bath at 30-50 ℃, stirring to a milky state, and continuously stirring for 4-6 hours to obtain a Beta molecular sieve initial sol-gel mixture;
(2) weighing the additive, adding the additive into the initial sol-gel mixture, and continuously stirring for 3-4 h, wherein the molar ratio of each component is 1.0SiO2:0.025Al2O3:(0.03～0.06)Na2O (0.20-0.30) micropore template agent (8-18) H2O (0.002-0.30) additive;
(3) transferring the sol-gel mixture obtained in the step (2) to a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 1-5 days at 140-160 ℃, cooling to room temperature after the reaction is finished, fully washing the product to be neutral by using deionized water, and fully drying at 70-90 ℃ to obtain Beta molecular sieve raw powder;
(4) and (4) calcining the Beta molecular sieve raw powder obtained in the step (3) at 500-600 ℃ for 4-8 h to remove the template agent in the raw powder, so as to obtain the sodium Beta molecular sieve.
(5) And (4) carrying out ion exchange on the sodium type Beta molecular sieve obtained in the step (4) to obtain a hydrogen type Beta molecular sieve, namely the high-performance Beta molecular sieve catalyst.
The silicon source is one or more of white carbon black, ethyl orthosilicate, water glass and silica sol;
the aluminum source is one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum powder and pseudo-boehmite;
the alkali source is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
the micropore template agent is one or more of tetraethyl ammonium hydroxide (TEAOH), tetraethyl ammonium bromide, tetraethyl ammonium chloride or tetraethyl ammonium fluoride;
the pure phase Beta molecular sieve can be synthesized in an accelerated way by adjusting the raw material ratio and the crystallization conditions; the sample has the advantages of short crystallization time, high crystallinity and the like. Obtaining a hydrogen type Beta molecular sieve by an ion exchange technology;
the additive is one of polyethylene glycol (PEG, the molecular weight is 600-20000) and polyethylene glycol mono-octyl phenyl ether (Triton-100).
It is a further object of the present invention to provide a high performance Beta molecular sieve catalyst prepared by the above process.
The third purpose of the invention is to provide the application of the prepared high-performance Beta molecular sieve catalyst in the preparation of p-methoxyacetophenone/3, 4-dimethoxyacetophenone through the acylation reaction of anisole/o-dimethylether and acetic anhydride.
The Beta molecular sieve catalyst applied to the Friedel-crafts acylation reaction accounts for 0.1-0.2 g, the acylation reagent acetic anhydride accounts for 10mmol, the anisole substrate accounts for 60mmol, the o-phenylether substrate accounts for 20mmol, the reaction temperature is 70-90 ℃, and the reaction time is 3-5 h. The obtained product is p-methoxyacetophenone or 3, 4-dimethoxyacetophenone.
Compared with the prior art, the invention has the advantages that:
1. compared with the traditional preparation method for synthesizing the Beta molecular sieve with small crystal grains or hierarchical pores, the method takes the cheap green additive as the auxiliary template agent, can effectively shorten the crystallization time, and obtains the Beta molecular sieve with relatively small crystal grain size, uniform step by step and high crystallinity;
2. under the same reaction condition, the prepared Beta molecular sieve catalyst has higher acylation reaction activity, the inactivation rate of the catalyst is reduced, and the stability is improved.
Drawings
FIG. 1 is an XRD pattern of a sample synthesized in comparative example 1 and specific examples 1 to 3 of the present invention; beta-ref-1, b.B1, c.B2 and d.B 3;
FIG. 2 is an XRD pattern of the sample synthesized in embodiments 4-7 of the present invention; e.B4, f.B5, g.B6 and h.B 7;
FIG. 3 is an XRD pattern of the samples synthesized in comparative example 2 and embodiments 8 to 10 of the present invention; beta-ref-2, q.B8, r.B9, s.B10;
FIG. 4 is an SEM photograph of the samples synthesized in comparative example 1 and embodiments 1 to 3 of the present invention; beta-ref-1, b.B1, c.B2 and d.B 3;
FIG. 5 is an SEM photograph of the samples synthesized in comparative example 2 and embodiments 8 to 10 of the present invention; beta-ref-2, q.B8, r.B9, s.B10;
FIG. 6 shows NH of samples synthesized in comparative example 1 and specific examples 1 to 3 of the present invention3-a TPD map; beta-ref-1, b.B1, c.B2 and d.B 3;
FIG. 7 is a graph showing the conversion rate of a sample synthesized in comparative example 1 and specific examples 1 to 3 of the present invention to o-dimethylether and acetic anhydride by acylation reaction to produce 3, 4-dimethoxyacetophenone;
FIG. 8 is a graph showing the conversion rate of p-anisole and acetic anhydride generated by the acylation reaction of anisole and acetic anhydride in the samples synthesized in comparative example 2 and specific examples 8 to 10 of the present invention;
FIG. 9 is a schematic diagram showing the stability of the regeneration cycle of the acylation reaction of o-dimethyl ether and acetic anhydride by the sample synthesized in the embodiment 1-3 of the present invention;
FIG. 10 is a graph showing the deactivation rates of the acylation reactions of anisole and acetic anhydride of the samples synthesized in comparative example 2 and specific examples 8 to 9 in the present invention.
Detailed description of the preferred embodiments
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
The conversions mentioned in the examples are the conversions of acetic anhydride (5h of the catalytic reaction) calculated by chromatographic analysis as follows:
comparative example 1
Fully and uniformly mixing 0.06g of sodium hydroxide, 0.25g of sodium aluminate, 10.60g of 25% tetraethylammonium hydroxide solution and 10.77g of deionized water, adding 3.60g of white carbon black into the solution, mixing at room temperature, and violently stirring for 6 hours to obtain an initial sol-gel mixture of the Beta molecular sieve, wherein the mole ratio of each component in the mixture is SiO2:0.025Al2O3:0.038Na2O:0.30TEAOH:17H2O; transferring the solid product to a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven at 140 ℃, standing and crystallizing for 5d under the condition of water heat under the autogenous pressure at constant temperature (140 ℃), centrifugally separating the solid product after crystallization is finished, repeatedly washing the solid product with deionized water until the supernatant is neutral, drying the solid product at 80 ℃ to obtain Beta molecular sieve raw powder, calcining the Beta molecular sieve raw powder at 550 ℃ for 6 hours to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging for 5 hours in a water bath at constant temperature of 80 ℃), centrifuging, washing and drying the Beta molecular sieve raw powder to obtain Beta molecular sieve solid, and roasting the Beta molecular sieve solid for 5 hours at 550 ℃ after twice exchange to obtain the hydrogen type Beta molecular sieve (the serial number is Beta-ref-1). The XRD spectrogram of the sample is shown in figure 1a, and the sample can be proved to be a Beta molecular sieve, and a scanning electron micrograph is shown in figure 4a, so that the grain diameter of the Beta-ref-1 molecular sieve is 700-800 nanometers. NH of the sample3TPD As shown in FIG. 6a, it can be seen that there are higher weak acid peaks and strong acid peaks, indicating that the surface acid amount of the sample is higher.
The Beta molecular sieve catalyst Beta-ref-1 prepared above is used for catalyzing the acylation reaction of the o-dimethyl ether and the acetic anhydride for 5 hours, as shown in figure 7, and the result of gas chromatography analysis shows that the acetic anhydride conversion rate is 58.7% when the selectivity of the reaction product 3, 4-dimethoxyacetophenone is 100%.
Example 1
0.06g of sodium hydroxide, 0.25g of sodium aluminate, 10.60g of 25% tetraethylammonium hydroxide solution and 8.77g of deionized water are fully and uniformly mixed, and 3.60g of white waterAdding carbon black into the solution, mixing at room temperature, stirring vigorously for 6h, weighing 0.19g of PEG (molecular weight 600) and dissolving in 2g of deionized water, mixing uniformly to obtain a polyethylene glycol solution, adding the polyethylene glycol solution into the mixture, transferring to a constant-temperature water bath at 50 ℃, stirring vigorously for 4h to obtain a Beta molecular sieve initial sol-gel mixture, wherein the molar ratio of each component in the mixture is SiO2:0.025Al2O3:0.038Na2O:0.30TEAOH:17H20.05PEG, transferring the obtained sol-gel mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven at 140 ℃, carrying out hydrothermal condition under autogenous pressure, standing and crystallizing for 1d at constant temperature (140 ℃), carrying out centrifugal separation on a solid product after crystallization is finished, repeatedly washing the solid product with deionized water until the supernatant is neutral, drying at 80 ℃ to obtain Beta molecular sieve raw powder, calcining at 550 ℃ for 6h to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging in a constant temperature water bath at 80 ℃ for 5h, centrifuging, washing and drying to obtain Beta molecular sieve solid, and roasting at 550 ℃ for 5h after twice exchange to obtain the hydrogen type Beta molecular sieve (the number is B1). The XRD spectrogram of the sample is shown in figure 1b, and the sample can be proved to be Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree. The scanning electron micrograph is shown in fig. 4B, and it can be seen that the size and the morphology of the B1 molecular sieve are uniform, the dispersity is good, and the particle size is 250-350 nanometers. NH of the sample3TPD As shown in FIG. 6b, it can be seen that the sample has lower weak acid and strong acid peak areas than the Beta-ref-1 sample in comparative example 1, indicating that the sample surface acid amount is reduced.
The acylation reaction of the o-dimethyl ether and the acetic anhydride is catalyzed by the prepared hydrogen type Beta molecular sieve B1 for 5 hours, as shown in figure 7, the result of gas chromatography analysis shows that when the selectivity of the reaction product 3, 4-dimethoxyacetophenone is 100%, the conversion rate of the acetic anhydride is 64.5%, and as shown in figure 9, the sample has stable regeneration cycle performance.
Example 2
0.06g of sodium hydroxide, 0.25g of sodium aluminate, 10.60g of 25% tetraethylammonium hydroxide solution and 8.77g of deionized water are fully and uniformly mixed, and 3.60g of white carbon black is added into the solutionMixing at room temperature, stirring vigorously for 6h, dissolving 0.19g PEG (molecular weight 1000) in 2g deionized water, mixing well to obtain polyethylene glycol solution, adding into the mixture, transferring to 50 deg.C constant temperature water bath, stirring vigorously for 4h to obtain initial sol-gel mixture of Beta molecular sieve, wherein the molar ratio of each component in the mixture is SiO2:0.025Al2O3:0.038Na2O:0.30TEAOH:17H20.05PEG, transferring the obtained sol-gel mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven at 140 ℃, carrying out hydrothermal condition under autogenous pressure, standing and crystallizing at constant temperature (140 ℃) for 2d, carrying out centrifugal separation on a solid product after crystallization is finished, repeatedly washing with deionized water until the supernatant is neutral, drying at 80 ℃ to obtain Beta molecular sieve raw powder, calcining at 550 ℃ for 6h to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging in a constant temperature water bath at 80 ℃ for 5h, centrifuging, washing and drying to obtain Beta molecular sieve solid, and roasting at 550 ℃ for 5h after twice exchange to obtain the hydrogen type Beta molecular sieve (the number is B2). The XRD spectrogram of the sample is shown in figure 1c, which can prove that the sample is a Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree. The scanning electron micrograph is shown in fig. 4c, and it can be seen that the size and the morphology of the B2 molecular sieve are uniform, the dispersity is good, and the particle size is 300-400 nanometers. NH of the sample3TPD As shown in FIG. 6c, it can be seen that the sample has lower weak acid and strong acid peak areas than the Beta-ref-1 sample in comparative example 1, indicating a decrease in the surface acid amount of the sample, wherein the strong acid peak area of the sample slightly increases compared to the B1 sample, indicating an increase in the surface acid amount with the increase in crystallization time.
The acylation reaction of o-dimethyl ether and acetic anhydride is catalyzed by the prepared hydrogen type Beta molecular sieve B2 for 5h, as shown in figure 7, the result of gas chromatography analysis shows that when the selectivity of the reaction product 3, 4-dimethoxyacetophenone is 100%, the acetic anhydride conversion rate is 70.8%, and as shown in figure 9, the sample has stable performance after 2 times of regeneration cycles.
Example 3
0.06g of sodium hydroxide, 0.25g of sodium aluminate, 10.60g of 25% tetraethylFully and uniformly mixing an ammonium hydroxide solution and 8.77g of deionized water, adding 3.60g of white carbon black into the solution, mixing at room temperature and violently stirring for 6 hours, weighing 0.19g of PEG (molecular weight 2000) and dissolving in 2g of deionized water, uniformly mixing to obtain a polyethylene glycol solution, adding the polyethylene glycol solution into the mixture, transferring the mixture to a constant-temperature water bath at 50 ℃, and violently stirring for 4 hours to obtain a Beta molecular sieve initial sol-gel mixture, wherein the molar ratio of components in the mixture is SiO2:0.025Al2O3:0.038Na2O:0.30TEAOH:17H20.05PEG, transferring the obtained sol-gel mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven at 140 ℃, carrying out hydrothermal condition under autogenous pressure, standing and crystallizing for 3d at constant temperature (140 ℃), carrying out centrifugal separation on a solid product after crystallization is finished, repeatedly washing the solid product with deionized water until the supernatant is neutral, drying at 80 ℃ to obtain Beta molecular sieve raw powder, calcining at 550 ℃ for 6h to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging in a constant temperature water bath at 80 ℃ for 5h, centrifuging, washing and drying to obtain Beta molecular sieve solid, and roasting at 550 ℃ for 5h after twice exchange to obtain the hydrogen type Beta molecular sieve (the number is B3). The XRD spectrogram of the sample is shown in figure 1d, and the sample can be proved to be Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree. The scanning electron micrograph is shown in fig. 4d, and it can be seen that the size and the morphology of the B3 molecular sieve are uniform, the dispersity is good, and the particle size is 300-450 nanometers. NH of the sample3TPD As shown in FIG. 6d, it can be seen that the sample has lower weak acid peak and strong acid peak areas than the Beta-ref-1 sample in comparative example 1, indicating a decrease in the surface acid amount of the sample, wherein the sample has a significant decrease in both weak acid peak area and strong acid peak area compared to B2, indicating a decrease in the surface acid amount with increasing crystallization time.
The acylation reaction of the o-dimethyl ether and acetic anhydride is catalyzed by the hydrogen type Beta molecular sieve catalyst B3 prepared above for 5h, as shown in figure 7, and the result of gas chromatography analysis shows that when the selectivity of the reaction product 3, 4-dimethoxyacetophenone is 100%, the acetic anhydride conversion rate is 65.0%, and as shown in figure 9, the sample has stable performance after 2 times of regeneration cycles.
Example 4
Fully and uniformly mixing 0.06g of sodium hydroxide, 0.25g of sodium aluminate, 10.60g of 25% tetraethyl ammonium hydroxide solution and 8.77g of deionized water, adding 3.60g of white carbon black into the solution, mixing at room temperature and vigorously stirring for 6 hours, weighing 0.37g of PEG (molecular weight 2000), dissolving in 2g of deionized water, uniformly mixing to obtain a polyethylene glycol solution, adding the polyethylene glycol solution into the mixture, transferring the mixture to a constant-temperature water bath at 50 ℃, and vigorously stirring for 4 hours to obtain a Beta molecular sieve initial sol-gel mixture, wherein the molar ratio of the components in the mixture is SiO2:0.025Al2O3:0.038Na2O:0.30TEAOH:17H20.10PEG, transferring the obtained sol-gel mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven at 140 ℃, performing hydrothermal condition under autogenous pressure, standing and crystallizing at constant temperature (140 ℃) for 2d, performing centrifugal separation on a solid product after crystallization is completed, repeatedly washing with deionized water until the supernatant is neutral, drying at 80 ℃ to obtain Beta molecular sieve raw powder, calcining at 550 ℃ for 6h to remove a template agent to obtain a sodium type molecular sieve, performing ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging in a constant temperature water bath at 80 ℃ for 5h, performing centrifugation, washing and drying to obtain Beta molecular sieve solid, and calcining at 550 ℃ for 5h after twice exchange to obtain the hydrogen type Beta molecular sieve (the number is B4). The XRD spectrum of the sample is shown in figure 2e, which can prove that the sample is Beta molecular sieve, the baseline of the spectrum is relatively flat, and the sample has relatively high crystallization degree.
The acylation reaction of the o-dimethyl ether and the acetic anhydride is catalyzed by the hydrogen type Beta molecular sieve catalyst B4 prepared in the above way for 5 hours, and the result of gas chromatographic analysis shows that the acetic anhydride conversion rate is 61.9% when the selectivity of the reaction product 3, 4-dimethoxyacetophenone is 100%.
Example 5
Fully and uniformly mixing 0.06g of sodium hydroxide, 0.25g of sodium aluminate, 10.60g of 25% tetraethylammonium hydroxide solution and 8.77g of deionized water, adding 3.60g of white carbon black into the solution, mixing at room temperature, violently stirring for 6 hours, weighing 0.37g of PEG (molecular weight 2000), dissolving in 2g of deionized water, uniformly mixing to obtain a polyethylene glycol solution, adding the polyethylene glycol solution into the mixture, transferring the mixture to constant-temperature water at 50 DEG CVigorously stirring the bath for 4h to obtain an initial sol-gel mixture of the Beta molecular sieve, wherein the molar ratio of each component in the mixture is SiO2:0.025Al2O3:0.038Na2O:0.30TEAOH:17H20.10PEG, transferring the obtained sol-gel mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven at 140 ℃, carrying out hydrothermal condition under autogenous pressure, standing and crystallizing for 3d at constant temperature (140 ℃), carrying out centrifugal separation on a solid product after crystallization is finished, repeatedly washing the solid product with deionized water until the supernatant is neutral, drying at 80 ℃ to obtain Beta molecular sieve raw powder, calcining at 550 ℃ for 6h to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging in a constant temperature water bath at 80 ℃ for 5h, centrifuging, washing and drying to obtain Beta molecular sieve solid, and roasting at 550 ℃ for 5h after twice exchange) to obtain the hydrogen type Beta molecular sieve (the number is B5). The XRD spectrogram of the sample is shown in figure 2f, which can prove that the sample is a Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree.
The acylation reaction of the o-dimethyl ether and the acetic anhydride is catalyzed by the prepared hydrogen type Beta molecular sieve B5 for 5 hours, and the result of gas chromatography analysis shows that the acetic anhydride conversion rate is 65.7% when the selectivity of the reaction product 3, 4-dimethoxyacetophenone is 100%.
Example 6
Fully and uniformly mixing 0.06g of sodium hydroxide, 0.25g of sodium aluminate and 10.60g of 25% tetraethylammonium hydroxide solution, adding 9.00g of silica sol with the mass fraction of 40% into the solution, mixing at room temperature and vigorously stirring for 6 hours, weighing 0.93g of PEG (with the molecular weight of 6000), dissolving in 0.96g of deionized water, uniformly mixing to obtain a polyethylene glycol solution, adding the polyethylene glycol solution into the mixture, and vigorously stirring for 4 hours to obtain a Beta molecular sieve initial sol-gel mixture, wherein the molar ratio of the components in the mixture is SiO2:0.025Al2O3:0.038Na2O:0.30TEAOH:17H20.25PEG, transferring the obtained sol-gel mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a drying oven with the temperature of 140 ℃, standing and crystallizing for 4 days under the hydrothermal condition under autogenous pressure and at constant temperature (140 ℃), and standing until the crystallization is finishedAnd (3) centrifugally separating a product, repeatedly washing the product with deionized water until the supernatant is neutral, drying the product at 80 ℃ to obtain Beta molecular sieve raw powder, calcining the product at 550 ℃ for 6 hours to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging the solution in a 80 ℃ constant-temperature water bath for 5 hours, centrifuging, washing and drying the solution to obtain Beta molecular sieve solid, and calcining the solid at 550 ℃ for 5 hours after twice exchange) to obtain the hydrogen type Beta molecular sieve (the number is B6). The XRD spectrogram of the sample is shown in figure 2g, which can prove that the sample is a Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree.
The prepared molecular sieve catalyst B6 is used for catalyzing the acylation reaction of the o-dimethyl ether and the acetic anhydride for 5 hours, and the result of gas chromatography analysis shows that the acetic anhydride conversion rate is 66.1% when the selectivity of the reaction product 3, 4-dimethoxyacetophenone is 100%.
Example 7
Fully and uniformly mixing 0.06g of sodium hydroxide, 0.25g of sodium aluminate and 10.60g of 25% tetraethylammonium hydroxide solution, adding 9.00g of silica sol with the mass fraction of 40% into the solution, mixing at room temperature and vigorously stirring for 6 hours, weighing 0.93g of PEG (molecular weight 20000) and dissolving into 0.96g of deionized water, uniformly mixing to obtain a polyethylene glycol solution, adding the polyethylene glycol solution into the mixture, and vigorously stirring for 4 hours to obtain a Beta molecular sieve initial sol-gel mixture, wherein the molar ratio of the components in the mixture is SiO2:0.025Al2O3:0.038Na2O:0.30TEAOH:17H20.25PEG, transferring the obtained sol-gel mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle in an oven at 140 ℃, carrying out hydrothermal condition under autogenous pressure, standing and crystallizing for 5d at constant temperature (140 ℃), carrying out centrifugal separation on a solid product after crystallization is finished, repeatedly washing the solid product with deionized water until the supernatant is neutral, drying at 80 ℃ to obtain Beta molecular sieve raw powder, calcining at 550 ℃ for 6h to remove a template agent to obtain a sodium type molecular sieve, then carrying out stirring exchange for 5h in a constant-temperature water bath at 80 ℃ by using an ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, centrifuging, washing and drying to obtain Beta molecular sieve solid, and roasting at 550 ℃ for 5h after twice exchange) to obtain a hydrogen type Beta molecular sieve (the serial number is that the Beta molecular sieve solid isB7) In that respect The XRD spectrogram of the sample is shown in figure 2h, which can prove that the sample is a Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree.
The prepared molecular sieve catalyst B7 is used for catalyzing the acylation reaction of the o-dimethyl ether and the acetic anhydride for 5 hours, and the result of gas chromatography analysis shows that the acetic anhydride conversion rate is 68.4% when the selectivity of the reaction product 3, 4-dimethoxyacetophenone is 100%.
Comparative example 2
Fully and uniformly mixing 0.23g of sodium hydroxide, 0.33g of sodium aluminate, 6.73g of 35% tetraethylammonium hydroxide solution and 16.86g of deionized water, adding 4.80g of white carbon black into the solution, mixing at room temperature, and violently stirring for 4 hours to obtain an initial sol-gel mixture of the Beta molecular sieve, wherein the molar ratio of each component in the mixture is 1.0SiO2:0.025Al2O3:0.06Na2O:0.20TEAOH:15H2And O, transferring the obtained sol-gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven with the temperature of 150 ℃, carrying out hydrothermal condition under autogenous pressure, standing and crystallizing for 4d at constant temperature (150 ℃), carrying out centrifugal separation on a solid product after crystallization is finished, repeatedly washing the solid product with deionized water until the supernatant is neutral, drying the solid product at the temperature of 80 ℃ to obtain Beta molecular sieve raw powder, calcining the powder at the temperature of 560 ℃ for 5h to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging for 5h in a water bath with the constant temperature of 80 ℃, carrying out centrifugation, washing and drying to obtain Beta molecular sieve solid, and roasting for 5h at the temperature of 550 ℃ after twice exchange to obtain the hydrogen type Beta molecular sieve (the number is Beta-ref-2). The XRD spectrogram of the sample is shown in figure 3p, which proves that the sample is a Beta molecular sieve, and the scanning electron micrograph is shown in figure 5p, which shows that the size and the grain diameter of the Beta-ref-2 molecular sieve are about 2.5 microns.
The prepared molecular sieve catalyst Beta-ref-2 is used for catalyzing the acylation reaction of anisole and acetic anhydride for 5 hours, as shown in figure 8. The result of gas chromatographic analysis shows that when the selectivity of the reaction product p-methoxyacetophenone is more than 99%, the acetic anhydride conversion rate is 64.5%. The deactivation rate of this sample is shown in FIG. 10, where it can be seen that Beta-ref-2 molecular sieve deactivates faster.
Example 8
Fully and uniformly mixing 0.23g of sodium hydroxide, 0.33g of sodium aluminate, 6.73g of 35% tetraethylammonium hydroxide solution and 16.86g of deionized water, adding 4.80g of white carbon black into the solution, mixing at room temperature, violently stirring for 4 hours, adding 0.10g of Triton-100, and violently stirring for 3 hours to obtain a Beta molecular sieve sol-gel mixture, wherein the molar ratio of each component in the mixture is 1.0SiO2:0.025Al2O3:0.06Na2O:0.20TEAOH:15H2O is 0.002Triton-100, the obtained sol-gel mixture is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is placed in a drying oven with the temperature of 150 ℃, the mixture is kept still and crystallized for 4d under the hydrothermal condition under the autogenous pressure at the constant temperature (150 ℃), the solid product after crystallization is washed by deionized water repeatedly until the supernatant is neutral, the mixture is dried at the temperature of 80 ℃ to obtain Beta molecular sieve raw powder, the Beta molecular sieve raw powder is calcined at the temperature of 560 ℃ for 5h to remove a template agent to obtain a sodium type molecular sieve, then the sodium type molecular sieve is subjected to ion exchange technology (the Beta molecular sieve raw powder is dissolved in 1mol/L ammonium nitrate solution, the mixture is stirred and exchanged for 5h in a constant-temperature water bath with the temperature of 80 ℃, the Beta molecular sieve solid is obtained through centrifugation, washing and drying, and the hydrogen type Beta molecular sieve (the number is B8) is obtained through twice calcination at. The XRD spectrogram of the sample is shown in figure 3q, which can prove that the sample is a Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree. The scanning electron micrograph is shown in FIG. 5q, and it can be seen that the size and the morphology of the B8 molecular sieve are uniform, the dispersity is good, and the particle size is 400-500 nanometers.
The acylation reaction of anisole and acetic anhydride was catalyzed by the hydrogen form Beta molecular sieve B8 prepared above for 5h, as shown in FIG. 8. The result of gas chromatographic analysis shows that when the selectivity of the reaction product p-methoxyacetophenone is more than 99%, the acetic anhydride conversion rate is 90.5%, the inactivation rate of the sample is shown in a graph of fig. 10, and the inactivation rate of the B8 molecular sieve is slower.
Example 9
Fully and uniformly mixing 0.23g of sodium hydroxide, 0.33g of sodium aluminate, 6.73g of 35% tetraethylammonium hydroxide solution and 16.86g of deionized water, adding 4.80g of white carbon black into the solution, mixing at room temperature, stirring vigorously for 4 hours, adding 0.26g of Triton-10Stirring vigorously for 3h to obtain initial sol-gel mixture of Beta molecular sieve with the molar ratio of each component of 1.0SiO2:0.025Al2O3:0.06Na2O:0.20TEAOH:15H2O:0.005Triton-100, transferring the obtained sol-gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven at 150 ℃, carrying out hydrothermal condition under autogenous pressure, standing and crystallizing for 1d at constant temperature (150 ℃), repeatedly washing the solid product after crystallization is finished until the supernatant is neutral by deionized water, drying at 80 ℃ to obtain Beta molecular sieve raw powder, calcining at 560 ℃ for 5h to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging for 5h in a constant temperature water bath at 80 ℃, carrying out centrifugation, washing and drying to obtain Beta molecular sieve solid, and roasting at 550 ℃ for 5h after twice exchange to obtain the hydrogen type Beta molecular sieve (the number is B9). The XRD spectrogram of the sample is shown in figure 3r, which can prove that the sample is a Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree. The scanning electron micrograph is shown in FIG. 5r, and it can be seen that the size and the morphology of the B9 molecular sieve are uniform, the dispersity is good, and the particle size is 500-600 nanometers.
The acylation reaction of anisole and acetic anhydride was catalyzed by the hydrogen form Beta molecular sieve B9 prepared above for 5h, as shown in FIG. 8. The result of gas chromatographic analysis shows that when the selectivity of the reaction product p-methoxyacetophenone is more than 99%, the acetic anhydride conversion rate is 91.8%, the inactivation rate of the sample is shown in a graph of fig. 10, and the inactivation rate of the B9 molecular sieve is slower.
Example 10
Fully and uniformly mixing 0.23g of sodium hydroxide, 0.33g of sodium aluminate, 6.73g of 35% tetraethylammonium hydroxide solution and 16.86g of deionized water, adding 4.80g of white carbon black into the solution, mixing at room temperature, violently stirring for 4 hours, adding 0.52g of Triton-100, and violently stirring for 3 hours to obtain an initial sol-gel mixture of the Beta molecular sieve, wherein the molar ratio of each component in the mixture is 1.0SiO2:0.025Al2O3:0.06Na2O:0.20TEAOH:15H20.01Triton-100, transferring the resulting sol-gel mixture to a Teflon linerPlacing the reaction kettle in a 150 ℃ oven, standing and crystallizing for 3d under the condition of hydrothermal at a constant temperature (150 ℃) under the autogenous pressure, centrifugally separating a solid product after crystallization is finished, repeatedly washing the solid product with deionized water until the supernatant is neutral, drying at 80 ℃ to obtain Beta molecular sieve raw powder, calcining at 560 ℃ for 5h to remove a template agent to obtain a sodium type molecular sieve, then carrying out ion exchange technology (dissolving the Beta molecular sieve raw powder in 1mol/L ammonium nitrate solution, stirring and exchanging for 5h in 80 ℃ constant temperature water bath, centrifuging, washing and drying to obtain Beta molecular sieve solid, and roasting at 550 ℃ for 5h after twice exchange to obtain the hydrogen type Beta molecular sieve (the number is B10). The XRD spectrogram of the sample is shown in figure 3s, which can prove that the sample is a Beta molecular sieve, the baseline of the spectrogram is relatively flat, and the sample has relatively high crystallization degree. The scanning electron micrograph is shown in FIG. 5s, and it can be seen that the size and the morphology of the B10 molecular sieve are uniform, the dispersity is good, and the particle size is 800-900 nanometers.
The acylation reaction of anisole and acetic anhydride was catalyzed by the hydrogen form Beta molecular sieve B10 prepared above for 5h, as shown in FIG. 8. The result of gas chromatographic analysis shows that when the selectivity of the reaction product p-methoxyacetophenone is more than 99%, the acetic anhydride conversion rate is 88.7%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (6)
1. A preparation method of a high-performance Beta molecular sieve catalyst comprises the following steps:
(1) dissolving an alkali source and an aluminum source in a microporous template agent, stirring uniformly, adding a silicon source, stirring vigorously, transferring to a constant-temperature water bath at 30-50 ℃, stirring to a milky state, and continuously stirring for 4-6 hours to obtain a Beta molecular sieve initial sol-gel mixture;
(2) weighing the additive, adding the additive into the initial sol-gel mixture, and continuously stirring for 3-4 h, wherein the molar ratio of each component is 1.0SiO2:0.025Al2O3:(0.03～0.06)Na2O (0.20-0.30) micropore template agent (8-18) H2O (0.002-0.30) additive;
(3) transferring the sol-gel mixture obtained in the step (2) to a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 1-5 days at 140-160 ℃, cooling to room temperature after the reaction is finished, fully washing the product to be neutral by using deionized water, and fully drying at 70-90 ℃ to obtain Beta molecular sieve raw powder;
(4) and (4) calcining the Beta molecular sieve raw powder obtained in the step (3) at 500-600 ℃ for 4-8 h to remove the template agent in the raw powder, so as to obtain the sodium Beta molecular sieve.
(5) And (4) carrying out ion exchange on the sodium type Beta molecular sieve obtained in the step (4) to obtain a hydrogen type Beta molecular sieve, namely the high-performance Beta molecular sieve catalyst.
2. The method of claim 1, wherein said Beta zeolite catalyst is prepared by the steps of: the silicon source in the step (1) is one or more of white carbon black, ethyl orthosilicate, water glass and silica sol; the aluminum source is one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum powder and pseudo-boehmite; the alkali source is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
3. The method of claim 1, wherein said Beta zeolite catalyst is prepared by the steps of: the microporous template agent in the step (1) is one or more of tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride or tetraethylammonium fluoride.
4. The method of claim 1, wherein said Beta zeolite catalyst is prepared by the steps of: the additive in the step (2) is one of polyethylene glycol and polyethylene glycol mono-octyl phenyl ether.
5. A high-performance Beta molecular sieve catalyst is characterized in that: is prepared by the method of any one of claims 1 to 4.
6. The use of the high performance Beta molecular sieve catalyst of claim 5 in the acylation of anisole/dimethyl phthalate and acetic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911177663.XA CN110860307A (en) | 2019-11-27 | 2019-11-27 | Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911177663.XA CN110860307A (en) | 2019-11-27 | 2019-11-27 | Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110860307A true CN110860307A (en) | 2020-03-06 |
Family
ID=69656969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911177663.XA Pending CN110860307A (en) | 2019-11-27 | 2019-11-27 | Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110860307A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441175A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | Molecular sieve supported metal catalyst and preparation method thereof |
| CN113694961A (en) * | 2021-09-26 | 2021-11-26 | 吉林化工学院 | Nano hierarchical pore BEA structure molecular sieve catalyst and preparation method and application thereof |
| CN114426488A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methylamine by amination of methanol |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086792A (en) * | 1993-09-20 | 1994-05-18 | 中国石油化工总公司 | Synthetizing BETA zeolite by guide agent method |
| JP2004149460A (en) * | 2002-10-30 | 2004-05-27 | Mitsubishi Chemicals Corp | Solid-supported organophosphorus compound, transition metal complex and method for catalytic reaction |
| CN102211779A (en) * | 2010-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | Method for preparing beta zeolite |
| WO2013102027A1 (en) * | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| CN104944437A (en) * | 2015-06-24 | 2015-09-30 | 辽宁工业大学 | Preparation method of mesoporous molecular sieve with mesoporous walls of Beta zeolite structures |
| CN105396608A (en) * | 2015-12-11 | 2016-03-16 | 复旦大学 | A preformed catalyst used for a fixed-bed Fenton reaction and a preparing method thereof |
| CN105985227A (en) * | 2015-02-06 | 2016-10-05 | 上海特化医药科技有限公司 | Preparation method and application of 4,4'-dihalide acetodiphenyl |
| CN106397295A (en) * | 2016-09-06 | 2017-02-15 | 凯莱英医药集团（天津）股份有限公司 | 2-branch acylation method of solid acid continuous loaded catalyzed aromatic heterocyclic compound |
| CN110127715A (en) * | 2019-04-17 | 2019-08-16 | 中国科学院大连化学物理研究所 | A method of accelerating Beta Zeolite synthesis |
-
2019
- 2019-11-27 CN CN201911177663.XA patent/CN110860307A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086792A (en) * | 1993-09-20 | 1994-05-18 | 中国石油化工总公司 | Synthetizing BETA zeolite by guide agent method |
| JP2004149460A (en) * | 2002-10-30 | 2004-05-27 | Mitsubishi Chemicals Corp | Solid-supported organophosphorus compound, transition metal complex and method for catalytic reaction |
| CN102211779A (en) * | 2010-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | Method for preparing beta zeolite |
| WO2013102027A1 (en) * | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| CN105985227A (en) * | 2015-02-06 | 2016-10-05 | 上海特化医药科技有限公司 | Preparation method and application of 4,4'-dihalide acetodiphenyl |
| CN104944437A (en) * | 2015-06-24 | 2015-09-30 | 辽宁工业大学 | Preparation method of mesoporous molecular sieve with mesoporous walls of Beta zeolite structures |
| CN105396608A (en) * | 2015-12-11 | 2016-03-16 | 复旦大学 | A preformed catalyst used for a fixed-bed Fenton reaction and a preparing method thereof |
| CN106397295A (en) * | 2016-09-06 | 2017-02-15 | 凯莱英医药集团（天津）股份有限公司 | 2-branch acylation method of solid acid continuous loaded catalyzed aromatic heterocyclic compound |
| CN110127715A (en) * | 2019-04-17 | 2019-08-16 | 中国科学院大连化学物理研究所 | A method of accelerating Beta Zeolite synthesis |
Non-Patent Citations (2)
| Title |
|---|
| ATSUSHI ISHIHARA等: ""Preparation of amorphous silica-alumina using polyethylene glycol and its role for matrix in catalytic cracking of n-dodecane"", 《APPLIED CATALYSIS A: GENERAL》 * |
| 张庆华等: "分子筛催化剂的酸性表征及研究进展", 《石油化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441175A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | Molecular sieve supported metal catalyst and preparation method thereof |
| CN114426488A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methylamine by amination of methanol |
| CN113694961A (en) * | 2021-09-26 | 2021-11-26 | 吉林化工学院 | Nano hierarchical pore BEA structure molecular sieve catalyst and preparation method and application thereof |
| CN113694961B (en) * | 2021-09-26 | 2023-11-10 | 吉林化工学院 | Nano hierarchical pore BETA structure molecular sieve catalyst, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2490985B1 (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
| CN110860307A (en) | Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method | |
| CN106348312B (en) | A kind of synthesis methods for inorganic compounds of regulation and control ZSM-5 molecular sieve pattern | |
| WO2016029591A1 (en) | Method for preparing y-type molecular sieve having high silica-alumina ratio | |
| Cheong et al. | Rapid synthesis of nanocrystalline zeolite W with hierarchical mesoporosity as an efficient solid basic catalyst for nitroaldol Henry reaction of vanillin with nitroethane | |
| CN105645427B (en) | The preparation method of the molecular sieves of ZSM 22 with mesoporous micropore graded structure | |
| WO2003074423A1 (en) | Preparation of mfi-type crystalline zeolitic aluminosilicate | |
| JP2001247309A (en) | Hydrothermally stable metal-containing mcm-41 type intermediate fine pore molecular sieve | |
| CN107954437B (en) | Preparation method of ITQ-24 zeolite molecular sieve | |
| CN104098109A (en) | Spherical ZSM-5 zeolite molecular sieve and its preparation method and use | |
| CN108358216A (en) | A kind of preparation of ultrathin nanometer piece accumulation multi-stage porous TS-2 microsphere of zeolite | |
| CN108946764B (en) | Hierarchical pore nano ferrierite aggregate and preparation method thereof | |
| CN107020145B (en) | Mesoporous IM-5 molecular sieve and preparation method thereof | |
| CN110127719B (en) | Preparation method of ZSM-48 molecular sieve with low Si/Al ratio | |
| CN109694086B (en) | Preparation method of nano ZSM-5 zeolite molecular sieve aggregate | |
| CN105347358A (en) | Preparation method of zeolite molecular sieve material having three-dimensional penetrating mesoporous multistage tunnel structure | |
| CN113135578A (en) | Preparation method of silicon-germanium ISV zeolite molecular sieve | |
| CN106976889A (en) | Si-Al zeolite molecular sieve with BOG structures and preparation method thereof | |
| SG194087A1 (en) | Process for producing molecular sieve materials | |
| CN115010146A (en) | Hierarchical pore ZSM-5 nano aggregate molecular sieve and preparation method thereof | |
| CN112591764A (en) | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof | |
| CN114804136A (en) | Preparation method and application of nano SSZ-13 molecular sieve | |
| KR20160020317A (en) | Nano-porous sponge or sheet type zeolite catalyst for synthesis of p-xylene from 2.5-dimethylfuran and ethylene | |
| CN115043414B (en) | Hierarchical pore molecular sieve and preparation method and application thereof | |
| CN114804141B (en) | Nanocluster mesoporous ZSM-5 molecular sieve and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200306 |