CN113797966B - Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethyl hydroxylamine by using same - Google Patents
Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethyl hydroxylamine by using same Download PDFInfo
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- CN113797966B CN113797966B CN202111193114.9A CN202111193114A CN113797966B CN 113797966 B CN113797966 B CN 113797966B CN 202111193114 A CN202111193114 A CN 202111193114A CN 113797966 B CN113797966 B CN 113797966B
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- 239000002245 particle Substances 0.000 title claims abstract description 102
- 229910000925 Cd alloy Inorganic materials 0.000 title claims abstract description 100
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- 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 68
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011258 core-shell material Substances 0.000 title claims abstract description 66
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001174 Diethylhydroxylamine Polymers 0.000 title abstract description 25
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 22
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 150000001661 cadmium Chemical class 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 7
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000010718 Oxidation Activity Effects 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 1
- 229910001297 Zn alloy Inorganic materials 0.000 abstract 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 abstract 1
- LGDOCZGADCEJIG-UHFFFAOYSA-N ethane;trimethoxysilicon Chemical compound CC.CO[Si](OC)OC LGDOCZGADCEJIG-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 2
- -1 end terminator Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- VWUQHKHOYGKMQK-UHFFFAOYSA-N [O].[Si].[Ti] Chemical compound [O].[Si].[Ti] VWUQHKHOYGKMQK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical class ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000007353 oxidative pyrolysis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/10—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of unsubstituted hydrocarbon radicals or of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
-
- 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
- B01J2229/60—Synthesis on support
- B01J2229/66—Synthesis on support on metal supports
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and a method for preparing N, N-diethyl hydroxylamine by the same, wherein the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst is prepared by using SiO 2 And the zinc-cadmium alloy particles coated by the titanium-zinc alloy particles are used as cores, tetrabutyl titanate is used as a titanium source to be assembled as a shell, and the core-shell titanium-silicon molecular sieve is coated with zinc-cadmium alloy particle catalyst to carry out green oxidation reaction of diethylamine to prepare N, N-diethyl hydroxylamine. The core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst disclosed by the invention has both titanium oxygen sites and transition metal particles, is a dual-function catalyst, has the advantages of large pore diameter, large specific surface area, stable framework, high catalytic oxidation activity, particularly high selectivity to N, N-diethyl hydroxylamine, easiness in separation and recovery after reaction, reusability and good application prospect.
Description
[ field of technology ]
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and a preparation method of N, N-diethyl hydroxylamine.
[ background Art ]
N, N-diethyl hydroxylamine is an important olefin monomer polymerization inhibitor, end terminator, antioxidant and organic synthesis intermediate, and with the expansion of N, N-diethyl hydroxylamine application, the demands of China are increasing year by year. At present, the industrial production technology of N, N-diethyl hydroxylamine mainly adopts a triethylamine oxidative pyrolysis method, namely, the N, N-diethyl hydroxylamine is prepared by taking triethylamine as a raw material through an oxidation and pyrolysis process, the process is complex, the pollution is heavy, the production period is long, and particularly, flammable and explosive gas ethylene is generated in the reaction, so that certain potential safety hazard exists in the production process. In recent years with diethylamine and H 2 O 2 The method is a clean route for raw materials to replace the technology for producing the N, N-diethyl hydroxylamine with high added value by the traditional pyrolysis method, and meets the green environment-friendly requirement, and the research and development of the route can not only realize the clean and efficient utilization of the diethylamine, but also realize the clean updating of the N, N-diethyl hydroxylamine production technology in China.
The titanium silicalite molecular sieve with titanyl sites is a green and environment-friendly catalyst for secondary amine catalytic oxidation, but has poor directional selectivity on target product hydroxylamine and the characteristic of promoting the deep oxidation of hydroxylamine into nitrone compounds, which limits the application of the titanium silicalite molecular sieve in secondary amine oxidation reaction, and the traditional titanium silicalite molecular sieve has smaller pore diameter (0.56-0.58 nm) and specific surface area (360-420 m) 2 And/g) and steric hindrance, such that diffusion during the reaction is a controlling process. Compared with the traditional titanium-silicon molecular sieve, the hollow titanium-silicon molecular sieve has high titanium content and large pore volume, but the phenomenon of framework collapse caused by the dissolution and falling of the framework in a secondary amine catalytic oxidation system is unavoidable. In the presence of transition metal salt-zinc salt or cadmium salt, H 2 O 2 The solution oxidizes secondary amine to obtain hydroxylamine product, and the existence of transition metal cation reduces the activation energy of reaction, which makes the reaction easy to occur, but has the problems of difficult recovery and recycle of catalyst and lower selectivity of hydroxylamine. Patent CN111909054A discloses diethylamine, H 2 O 2 In a solvent such as acetoneThe titanium silicon oxygen catalyst has low selectivity of N, N-diethyl hydroxylamine, is not suitable for efficient conversion of diethylamine oxidation, and is difficult to reach the industrial application level. The core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst is a bifunctional catalyst with both titanium oxygen sites and transition metal particles, and no public report exists on the preparation of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and the preparation of N, N-diethylhydroxylamine.
[ invention ]
The invention aims to provide a preparation method of a zinc-cadmium alloy particle catalyst coated by a core-shell titanium-silicon molecular sieve and a method for preparing N, N-diethyl hydroxylamine by using the same. The core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst prepared by the invention has the advantages of large pore diameter, large specific surface area, stable framework, easy recovery, recycling and high selectivity to N, N-diethyl hydroxylamine.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention discloses a preparation method of a zinc-cadmium alloy particle catalyst coated with a core-shell titanium-silicon molecular sieve, which comprises the following steps:
1) Preparing a zinc-cadmium alloy particle precursor solution:
zinc salt, cadmium salt, polyvinylpyrrolidone and water are mixed according to the molar ratio of 1:0.1-2.0:0.015:2.0-3.0, and 2-10 mLNaBH with the mol/L of 0.05-0.15 is added at the temperature of 25-35 DEG C 4 Dropwise adding the aqueous solution into an aqueous solution containing zinc salt, cadmium salt and polyvinylpyrrolidone, and fully stirring for 0.5-2 h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution; the zinc salt is ZnCl 2 、Zn(NO 3 ) 2 、Zn(CH 3 COO) 2 One of the following; the cadmium salt is CdCl 2 、Cd(NO 3 ) 2 、Cd(CH 3 COO) 2 One of the following;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water at the temperature of 25-35 ℃ according to the molar ratio of ethyl orthosilicate to ethanol of 15-28% ammonia water=1:0.01-0.90:1500-3000:100-300:5-15, fully stirring for 0.5-2 h after the addition is finished, uniformly mixing, raising the temperature to 40-45 ℃, slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:20-60 and zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.1-1 h after the addition is finished, uniformly mixing, raising the temperature to 60-100 ℃, slowly dropwise adding 1, 2-bis (trimethoxy silicon-based) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 10-20:1-2:1, fully stirring for 1-4 h after the addition is finished, filtering the final mixed solution obtained in the above process, washing a filter cake with deionized water and ethanol to neutral at the temperature of 25 ℃ for 20h, and drying the core-12 ℃ to obtain zinc-cadmium alloy particle coated with a core-shell type titanium catalyst;
3) Roasting
And 2) roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 1-3 ℃/min from room temperature to 400-600 ℃ for 2-6 hours to remove organic matters, thereby obtaining the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst.
The invention discloses a method for preparing N, N-diethyl hydroxylamine by coating zinc-cadmium alloy particle catalysts with a core-shell titanium-silicon molecular sieve, which comprises the following steps:
1) Adding catalyst, diethylamine and methanol solvent into a closed reactor, stirring, and when the reaction temperature reaches 45-60 ℃, slowly dripping H with the concentration of 30-50wt% 2 O 2 The dropping speed is 1d/2s, after the dropping is finished, the temperature is raised to 65-80 ℃, the reaction is continued for 1-2 h, after the reaction is finished, the catalyst is separated out through filtration, and the diethylamine conversion rate and the N, N-diethylhydroxylamine selectivity are determined through titration by perchloric acid standard titration solution;
2) Diethylamine and H 2 O 2 The molar ratio of the catalyst to the diethylamine is 0.5-2:1, the weight ratio of the catalyst to the diethylamine is 0.005-0.3:1, and the weight ratio of the methanol to the diethylamine is 3-8:1.
Compared with the prior art, the invention has the beneficial effects that:
1) The core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst is a bifunctional catalyst with titanium oxide sites and transition metal particles, and has the advantages of large pore diameter, large specific surface area and stable framework.
2) When the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst is used for the green oxidation reaction of diethylamine, the catalyst has good catalytic activity and recycling property, particularly has high selectivity to N, N-diethyl hydroxylamine, and the catalyst is easy to separate from a reaction system, so that the production cost and the operation difficulty are reduced.
[ detailed description ] of the invention
The following specific embodiments are used to specifically describe the technical solutions of the present invention, but the scope of protection of the present invention is not limited thereto:
example 1
1) Preparing a zinc-cadmium alloy particle precursor solution:
in a molar ratio of ZnCl 2 :CdCl 2 Polyvinylpyrrolidone: water=1:0.1:0.015:2.0, 10ml of LNaBH at a temperature of 25℃of 0.05mol/L 4 Drop-wise adding aqueous solution to ZnCl 2 、CdCl 2 And polyvinylpyrrolidone, fully stirring for 0.5h after the addition is finished, so as to obtain zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water at the temperature of 25 ℃ according to the molar ratio of ethyl orthosilicate to water to ethanol of 15% ammonia water=1:0.01:1500:100:5, fully stirring for 0.5h after the addition, uniformly mixing, then slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:20 and zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.1h after the addition, uniformly mixing, then slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 10:1:1 to 60 ℃, fully stirring for 1h after the addition, filtering the final mixed solution obtained in the process, washing a filter cake to neutrality by deionized water and ethanol, and drying for 12h at 25 ℃ to obtain a core-shell titanium-silicon molecular sieve zinc-cadmium alloy particle catalyst intermediate;
3) Roasting
Roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 1 ℃/min from room temperature to 400 ℃ for 6 hours to remove organic matters, and obtaining the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
Example 2
1) Preparing a zinc-cadmium alloy particle precursor solution:
in a molar ratio of ZnCl 2 :Cd(NO 3 ) 2 Polyvinylpyrrolidone: water=1:2.0:0.015:3.0, at a temperature of 35℃0.15mol/L of 2mLNaBH 4 Drop-wise adding aqueous solution to ZnCl 2 、Cd(NO 3 ) 2 And polyvinylpyrrolidone, fully stirring for 2 hours after the addition is finished, so as to obtain zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water according to the molar ratio of ethyl orthosilicate to water to ethanol of 28 percent of ammonia water=1:0.90:3000:300:15 at the temperature of 35 ℃, fully stirring for 2 hours after the addition, slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:60 and zinc-cadmium alloy particle precursor solution obtained in the step 1) after the uniform mixing, fully stirring for 1 hour after the addition, uniformly mixing, slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 20:2:1 at the temperature of 100 ℃, fully stirring for 4 hours after the addition, filtering a final mixed solution obtained in the process, washing a filter cake to neutrality by deionized water and ethanol, and drying for 20 hours at 25 ℃ to obtain a core-shell titanium-silicon molecular coated zinc-cadmium alloy particle catalyst intermediate;
3) Roasting
And 2) roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 3 ℃/min from room temperature to 600 ℃ for 2 hours to remove organic matters, so as to obtain the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
Example 3
1) Preparing a zinc-cadmium alloy particle precursor solution:
in a molar ratio of ZnCl 2 :Cd(CH 3 COO) 2 Polyvinylpyrrolidone: water=1:1.5:0.015:2.5, at a temperature of 30℃0.1mol/L of 5mLNaBH 4 Drop-wise adding aqueous solution to ZnCl 2 、Cd(CH 3 COO) 2 And polyvinylpyrrolidone, fully stirring for 1.25h after the addition is finished, so as to obtain zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water according to the molar ratio of ethyl orthosilicate to water to ethanol of 25 percent of ammonia water=1:0.45:2000:200:10 at the temperature of 30 ℃, fully stirring for 1.25 hours after the addition, uniformly mixing, then slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:40 and zinc-cadmium alloy particle precursor solution obtained in the step 1) to the temperature to 42 ℃, fully stirring for 0.5 hour after the addition, uniformly mixing, then slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 15:1.5:1 to the temperature to 80 ℃, fully stirring for 2.5 hours after the addition, filtering the final mixed solution obtained in the process, washing a filter cake to neutrality with deionized water and ethanol, and drying for 16 hours at 25 ℃ to obtain a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) Roasting
And 2) roasting the intermediate of the core-shell type titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 1.5 ℃/min for 4 hours from room temperature to 500 ℃ to remove organic matters, thereby obtaining the final core-shell type titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
Example 4
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (NO) 3 ) 2 :CdCl 2 Polyvinylpyrrolidone: water=1:0.5:0.015:2.2, at a temperature of 28℃0.08mol/L of 7mLNaBH 4 The aqueous solution is added dropwise to a solution containing Zn (NO) 3 ) 2 、CdCl 2 And polyvinylpyrrolidone, fully stirring for 1.5h after the addition is finished, so as to obtain zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water at the temperature of 28 ℃ according to the molar ratio of ethyl orthosilicate to cetyl trimethyl ammonium bromide to ethanol to 20% ammonia water=1:0.35:2500:150:8, fully stirring for 0.8h after the addition, uniformly mixing, raising the temperature to 44 ℃, slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:25 and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.3h after the addition, uniformly mixing, raising the temperature to 65 ℃, slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane with the volume ratio of 12:1.3:1, tetrabutyl titanate and isopropanol, fully stirring for 1.5h after the addition, filtering the final mixed solution obtained in the process, washing a filter cake with deionized water and ethanol to neutrality, and drying for 15h at 25 ℃ to obtain a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) Roasting
And (2) roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step (2) in an air atmosphere at a heating rate of 2 ℃/min from room temperature to 450 ℃ for 5 hours to remove organic matters, so as to obtain the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
Example 5
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (NO) 3 ) 2 :Cd(NO 3 ) 2 Polyvinylpyrrolidone: water=1:1.8:0.015:2.4, at a temperature of 32℃0.12mol/L of 4mLNaBH 4 The aqueous solution is added dropwise to a solution containing Zn (NO) 3 ) 2 、Cd(NO 3 ) 2 And polyvinylpyrrolidone, fully stirring for 0.8h after the addition is finished, so as to obtain zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water at the temperature of 32 ℃ according to the molar ratio of ethyl orthosilicate to cetyl trimethyl ammonium bromide to ethanol to 22% ammonia water=1:0.25:1800:170:12, fully stirring for 0.65h after the addition, uniformly mixing, then slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:30 and zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.2h after the addition, uniformly mixing, then slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 14:1.6:1 at the temperature of 70 ℃, fully stirring for 2h after the addition, filtering the final mixed solution obtained in the process, washing a filter cake with deionized water and ethanol to neutrality, and drying for 18h at 25 ℃ to obtain a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) Roasting
And (2) roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step (2) in an air atmosphere at a heating rate of 2.5 ℃/min for 3 hours from room temperature to 550 ℃ to remove organic matters, so as to obtain the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
Example 6
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (NO) 3 ) 2 :Cd(CH 3 COO) 2 Polyvinylpyrrolidone: water=1:0.3:0.015:2.1, 8ml of 0.065mol/L of LNaBH at a temperature of 26 ℃ 4 Dropwise adding the aqueous solution into an aqueous solution containing zinc salt, cadmium salt and polyvinylpyrrolidone, and fully stirring for 0.65h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water according to the molar ratio of ethyl orthosilicate to water to ethanol of 17 percent of ammonia water=1:0.15:1700:120:6.5 at the temperature of 26 ℃, fully stirring for 1.0h after the addition is finished, raising the temperature to 40 ℃, slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:35 and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.4h after the addition is finished, raising the temperature to 75 ℃ after the addition is finished, slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 11:1.2:1, fully stirring for 3h after the addition is finished, filtering the final mixed solution obtained in the process, washing a filter cake with deionized water and ethanol to neutrality, and drying for 13h at 25 ℃ to obtain a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) Roasting
And 2) roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 1.2 ℃/min from room temperature to 420 ℃ for 5.5 hours to remove organic matters, thereby obtaining the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
Example 7
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (CH) 3 COO) 2 :CdCl 2 Polyvinylpyrrolidone: water=1:0.7:0.015:2.6, 0.09mol at a temperature of 29 ℃6mLNaBH of/L 4 The aqueous solution is added dropwise to a solution containing Zn (CH) 3 COO) 2 、CdCl 2 And polyvinylpyrrolidone, fully stirring for 1.0h after the addition is finished, so as to obtain zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water according to the molar ratio of ethyl orthosilicate to water to ethanol of 19 percent of ammonia water=1:0.55:2300:230:9 at the temperature of 29 ℃, fully stirring for 1.4 hours after the addition, uniformly mixing, then slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:45 and zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.6 hour after the addition, uniformly mixing, then slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 13:1.4:1 at the temperature of 85 ℃, fully stirring for 3.5 hours after the addition, filtering the final mixed solution obtained in the process, washing a filter cake with deionized water and ethanol to neutrality, and drying for 14 hours at 25 ℃ to obtain a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) Roasting
And 2) roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 1.8 ℃/min from room temperature to 480 ℃ for 4.5 hours to remove organic matters, thereby obtaining the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
Example 8
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (CH) 3 COO) 2 :Cd(NO 3 ) 2 Polyvinylpyrrolidone: water=1:0.9:0.015:2.8, 0.13mol/L of 3.5mLNaBH is added at a temperature of 31 ℃ 4 The aqueous solution is added dropwise to a solution containing Zn (CH) 3 COO) 2 、Cd(NO 3 ) 2 And polyvinylpyrrolidone,after the charging is finished, fully stirring for 1.35h to obtain zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water at the temperature of 31 ℃ according to the molar ratio of ethyl orthosilicate to water to ethanol of 24 percent ammonia water=1:0.65:2600:260:11, fully stirring for 1.6 hours after the addition, uniformly mixing, then slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:50 and zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.7 hour after the addition, uniformly mixing, then slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 16:1.7:1 at the temperature of 90 ℃, fully stirring for 2 hours after the addition, filtering the final mixed solution obtained in the process, washing a filter cake with deionized water and ethanol to neutrality, and drying for 17 hours at 25 ℃ to obtain a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) Roasting
And 2) roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 2.2 ℃/min from room temperature to 530 ℃ for 3.5 hours to remove organic matters, thereby obtaining the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
Example 9
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (CH) 3 COO) 2 :Cd(CH 3 COO) 2 Polyvinylpyrrolidone: water=1:1.2:0.015:2.3, at 34℃3mLNaBH at 0.14mol/L 4 The aqueous solution is added dropwise to a solution containing Zn (CH) 3 COO) 2 、Cd(CH 3 COO) 2 And polyvinylpyrrolidone, fully stirring for 1.7h after the addition is finished, so as to obtain zinc-cadmium alloy particle precursor solution;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water according to the molar ratio of ethyl orthosilicate to water to ethanol of 26 percent of ammonia water=1:0.75:2800:280:13.5 at the temperature of 34 ℃, fully stirring for 1.8 hours after the addition is finished, uniformly mixing the solution, then raising the temperature to 45 ℃, slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:55 and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.85 hours after the addition is finished, uniformly mixing, raising the temperature to 95 ℃, slowly dropwise adding 1, 2-bis (trimethoxy silicon) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 18:1.9:1, fully stirring for 2.5 hours after the addition is finished, filtering the final mixed solution obtained in the process, washing a filter cake to neutrality by deionized water and ethanol, and drying for 19 hours at 25 ℃ to obtain a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle intermediate;
3) Roasting
And 2) roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 2.8 ℃/min from room temperature to 580 ℃ for 2.5 hours to remove organic matters, thereby obtaining the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, wherein the pore diameter and the specific surface area of the catalyst are shown in Table 1.
TABLE 1
| Sample source | Pore diameter, nm | Specific surface area, m 2 /g | Sample source | Pore diameter, nm | Specific surface area, m 2 /g |
| Example 1 | 3.5 | 924 | Example 6 | 3.4 | 917 |
| Example 2 | 3.4 | 919 | Example 7 | 3.6 | 923 |
| Example 3 | 3.4 | 915 | Example 8 | 3.5 | 910 |
| Example 4 | 3.5 | 925 | Example 9 | 3.4 | 915 |
| Example 5 | 3.3 | 916 |
Test example 1
The catalyst prepared in the example, diethylamine and solvent methanol are added into a closed reactor, the weight ratio of the catalyst to diethylamine is 0.15:1, the weight ratio of the methanol to diethylamine is 6:1, and when the temperature in the closed reactor reaches 50 ℃, the slow dropwise addition of the H with the concentration of 35wt% is started 2 O 2 Diethylamine and H 2 O 2 The molar ratio of (2) is 1:1, the dropping speed is 1d/2s, after the dropping is finished, the temperature is raised to 80 ℃, the reaction is continued for 1h, after the reaction is finished, the catalyst is separated by filtration, and the diethylamine conversion rate and the N, N-diethylhydroxylamine selectivity are determined by titration with a perchloric acid standard titration solution, and the results are shown in Table 2.
TABLE 2
| Sample source | Diethylamine conversion% | N, N-diethylhydroxylamine selectivity,% |
| Example 1 | 51.6 | 88.9 |
| Example 2 | 53.8 | 90.5 |
| Example 3 | 55.2 | 91.6 |
| Example 4 | 54.9 | 93.4 |
| Example 5 | 51.3 | 89.9 |
| Example 6 | 52.9 | 92.5 |
| Example 7 | 54.1 | 93.2 |
| Example 8 | 53.7 | 92.7 |
| Example 9 | 55.0 | 91.9 |
From the results in Table 1, it can be seen that the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst of the invention is used for green oxidation reaction of diethylamine, and the selectivity of N, N-diethylhydroxylamine is high.
Test example 2
The catalyst prepared in the example was reacted according to test example 1, and after filtration, separation and drying, diethylamine green oxidation was carried out according to the reaction conditions of test example 1, and the reaction-separation-reaction cycle was repeated, and the results after 5 cycles are shown in table 3.
TABLE 3 Table 3
| Sample source | Diethylamine conversion% | N, N-diethylhydroxylamine selectivity,% |
| Example 1 | 51.3 | 89.3 |
| Example 2 | 53.6 | 90.6 |
| Example 3 | 55.1 | 91.3 |
| Example 4 | 54.4 | 93.6 |
| Example 5 | 51.1 | 89.6 |
| Example 6 | 52.5 | 92.1 |
| Example 7 | 54.0 | 93.4 |
| Example 8 | 53.3 | 92.6 |
| Example 9 | 54.7 | 91.5 |
As can be seen from the results in Table 3, the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst is used for the green oxidation reaction of diethylamine, has high selectivity of N, N-diethyl hydroxylamine, has high activity retention after recycling for 5 times, and has small selectivity and conversion rate reduction, so that the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst has stable alloy particles and a framework, and can be recycled for a plurality of times. Compared with the prior art, in the oxidation reaction, the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst has large pore diameter and large specific surface area, is favorable for the diffusion of reactants and products, and reduces the diffusion resistance; the simultaneous existence of the titanyl site and the transition metal particle improves the selectivity of N, N-diethyl hydroxylamine; and the catalyst is easy to separate from a reaction system, reduces the production cost and the operation difficulty, can be recycled, and is easy for industrial application.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Claims (1)
1. Use of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst in preparationN,N-diethylhydroxylamineThe preparation method of the zinc-cadmium alloy particle catalyst coated by the core-shell titanium-silicon molecular sieve is characterized by comprising the following steps:
1) Preparing a zinc-cadmium alloy particle precursor solution:
the zinc salt, the cadmium salt and the polyvinylpyrrolidone are mixed according to the molar ratio of water=1:0.1-2.0:0.015:2.0-3.0, and 2-10 mLNaBH with the concentration of 0.05-0.15 mol/L is carried out at the temperature of 25-35 DEG C 4 Dropwise adding the aqueous solution into an aqueous solution containing zinc salt, cadmium salt and polyvinylpyrrolidone, and fully stirring for 0.5-2 h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution; the zinc salt is ZnCl 2 、Zn(NO 3 ) 2 、Zn(CH 3 COO) 2 One of the following; the cadmium salt is CdCl 2 、Cd(NO 3 ) 2 、Cd(CH 3 COO) 2 One of the following;
2) Preparing a zinc-cadmium alloy particle catalyst intermediate coated with a core-shell titanium-silicon molecular sieve:
slowly dropwise adding ethyl orthosilicate into a water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water at the temperature of 25-35 ℃ according to the molar ratio of ethyl orthosilicate to ethanol of 15-28% ammonia water=1:0.01-0.90:1500-3000:100-300:5-15, fully stirring for 0.5-2 h after the addition is finished, uniformly mixing, raising the temperature to 40-45 ℃, slowly dropwise adding ethyl orthosilicate with the volume ratio of 1:20-60 and zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.1-1 h after the addition is finished, uniformly mixing, raising the temperature to 60-100 ℃, slowly dropwise adding 1, 2-bis (trimethoxy silicon-based) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 10-20:1:2, fully stirring for 1-4 h after the addition is finished, filtering the final mixed solution obtained in the above process, washing a filter cake with deionized water and ethanol to neutral at the temperature of 25 ℃ and drying the core-20 h to obtain zinc-cadmium alloy particle coated with a core-shell type titanium catalyst;
3) Roasting
Roasting the intermediate of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) in an air atmosphere at a heating rate of 1-3 ℃/min from room temperature to 400-600 ℃ for 2-6 hours to remove organic matters, thereby obtaining the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst;
the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst is used for preparingN,N-diethylhydroxylamine, comprising the following steps:
1) Adding a catalyst, diethylamine and a methanol solvent into a closed reactor, stirring, and slowly dropwise adding H with the concentration of 30-50wt% when the reaction temperature reaches 45-60 DEG C 2 O 2 The dropping speed is 1d/2s, after the dropping is finished, the temperature is raised to 65-80 ℃, the reaction is continued for 1-2 h, after the reaction is finished, the catalyst is separated by filtration, and the conversion rate of diethylamine are determined by titration of perchloric acid standard titration solutionN,N-diethylhydroxylamine selectivity;
2) Diethylamine and H 2 O 2 The molar ratio of the catalyst to the diethylamine is 0.5-2:1, the weight ratio of the catalyst to the diethylamine is 0.005-0.3:1, and the weight ratio of the methanol to the diethylamine is 3-8:1.
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