CN112892586A - Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethylhydroxylamine by using core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst - Google Patents
Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethylhydroxylamine by using core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst Download PDFInfo
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- 229910000925 Cd alloy Inorganic materials 0.000 title claims abstract description 111
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002245 particle Substances 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 82
- 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 82
- 239000011258 core-shell material Substances 0.000 title claims abstract description 77
- 229920001174 Diethylhydroxylamine Polymers 0.000 title claims abstract description 33
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 58
- 239000010936 titanium Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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 13
- 239000000243 solution Substances 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 45
- 239000002243 precursor Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 238000010438 heat treatment 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
- 238000001035 drying Methods 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
- 238000005406 washing Methods 0.000 claims description 11
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical group Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 10
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical compound [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 9
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001661 cadmium Chemical class 0.000 claims description 7
- 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
- 239000011592 zinc chloride Substances 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 230000001588 bifunctional effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 230000010718 Oxidation Activity Effects 0.000 abstract 1
- 230000009467 reduction Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 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
- 150000003335 secondary amines Chemical class 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- -1 transition metal salt Chemical class 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 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
- HEHINIICWNIGNO-UHFFFAOYSA-N oxosilicon;titanium Chemical compound [Ti].[Si]=O HEHINIICWNIGNO-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B01J35/398—
-
- B01J35/617—
-
- B01J35/647—
-
- 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
-
- 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
Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst and a method for preparing N, N-diethylhydroxylamine by using the same2And the zinc-cadmium alloy particles coated by the zinc-cadmium alloy catalyst are taken as cores, tetrabutyl titanate is taken as a titanium source and assembled into shells, and the zinc-cadmium alloy particle catalyst coated by the core-shell type titanium-silicon molecular sieve is used for performing a diethylamine green oxidation reaction to prepare N, N-diethylhydroxylamine. The core-shell type of the inventionThe titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst has titanium oxide sites and transition metal particles, is a bifunctional catalyst, has large aperture, large specific surface area, stable skeleton and high catalytic oxidation activity, particularly has high selectivity on N, N-diethylhydroxylamine, is easy to separate and recover after reaction, can be repeatedly used, and has good application prospect.
Description
Technical Field
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 method for preparing N, N-diethylhydroxylamine by using the same.
Background
N, N-diethylhydroxylamine is an important olefin monomer polymerization inhibitor, an end terminator, an antioxidant and an organic synthesis intermediate, and as the application of N, N-diethylhydroxylamine is expanded, the demand of China is increased year by year. At present, the industrial production technology of N, N-diethylhydroxylamine mainly adopts a triethylamine oxidation pyrolysis method, namely, N, N-diethylhydroxylamine is prepared by taking triethylamine as a raw material through oxidation and pyrolysis processes, the process is complicated, the pollution is serious, the production period is long, and particularly, flammable and explosive gas ethylene is generated in the reaction, so that certain potential safety hazards exist in the production process. In recent years diethylamine and H2O2The method replaces the traditional pyrolysis method to produce the N, N-diethylhydroxylamine with high added value by a clean route of raw materials, meets the requirement of environmental protection better, and the research and development of the route can realize the clean and efficient utilization of the diethylamine and the clean updating of the N, N-diethylhydroxylamine production technology in China.
The titanium silicalite molecular sieve with the titanium oxygen sites is a green and environment-friendly catalyst for secondary amine catalytic oxidation, but the application of the titanium silicalite molecular sieve in secondary amine oxidation reaction is limited due to the characteristics of poor directional selectivity of a target product hydroxylamine and promotion of deep oxidation of hydroxylamine into nitrone compounds, and the traditional titanium silicalite molecular sieve has small aperture (0.56-0.58 nm) and small specific surface area (360-420 m)2The/g) and steric hindrance, so that diffusion becomes a control process in the reaction process. Compared with the traditional titanium silicalite molecular sieve, the hollow titanium silicalite molecular sieve has high titanium content and large pore volume, but the phenomenon of skeleton collapse caused by the dissolution and the falling of the skeleton in a secondary amine catalytic oxidation system is inevitable. In the presence of a transition metal salt, zinc or cadmium, with H2O2The solution oxidizes secondary amine to obtain hydroxylamine products, and the existence of transition metal cations reduces the reaction activation energy to facilitate the reaction, but has the problems that the catalyst is difficult to recycle and the selectivity of hydroxylamine is low. Patent CN111909054A discloses diethylamine, H2O2The mixed contact reaction of solvents such as acetone and the like in a titanium silicon oxide catalyst has low selectivity of N, N-diethylhydroxylamine and is not suitable forThe high-efficiency conversion of the diethylamine oxidation is difficult to reach the industrial application level. The catalyst with the zinc-cadmium alloy particles coated by the core-shell titanium-silicon molecular sieve is a bifunctional catalyst with titanium oxide sites and transition metal particles, and at present, the preparation of the catalyst with the zinc-cadmium alloy particles coated by the core-shell titanium-silicon molecular sieve and the public report of preparing N, N-diethylhydroxylamine do not exist.
Disclosure of Invention
The invention aims to provide a preparation method of a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and a method for preparing N, N-diethylhydroxylamine by using the same, aiming at the defects in the prior art. The core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst prepared by the invention has the advantages of large aperture, large specific surface area, stable framework, easy recovery and recycling, and high selectivity to N, N-diethylhydroxylamine.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst comprises the following steps:
1) preparing a zinc-cadmium alloy particle precursor solution:
adding 2-10 mL of NaBH in an amount of 0.05-0.15 mol/L at a temperature of 25-35 ℃ according to a mol ratio of 1: 0.1-2.0: 0.015: 2.0-3.0 of zinc salt, cadmium salt, polyvinylpyrrolidone and water4Dropwise 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;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly and dropwise adding ethyl orthosilicate, hexadecyl trimethyl ammonium bromide, water, ethanol and 15-28% ammonia water into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at a temperature of 25-35 ℃ for 0.01-0.90: 1500-3000: 100-300: 5-15, fully stirring for 0.5-2 hours after the addition is finished, raising the temperature to 40-45 ℃ after the uniform mixing, slowly and dropwise adding ethyl orthosilicate with the volume ratio of 1: 20-60 and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.1-1 hour after the addition is finished, raising the temperature to 60-100 ℃ after the uniform mixing, slowly and dropwise adding 1, 2-bis (trimethoxy silicon-based) ethane with the volume ratio of 10-20: 1-2: 1, tetrabutyl titanate and isopropanol, fully stirring for 1-4 hours after the addition is finished, filtering the final mixed liquid obtained in the above process, washing the filter cake to be neutral by deionized water and ethanol, and drying at 25 ℃ for 12-20 h to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate obtained in the step 2) for 2-6 h at the heating rate of 1-3 ℃/min in the air atmosphere from the room temperature to 400-600 ℃ to remove organic matters, and then roasting in N2Roasting at 300-500 deg.c for 0.5-4 hr and then in H2Reducing for 0.5-4 h at 500-600 ℃ in the atmosphere to obtain the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst.
The zinc salt is ZnCl2、Zn(NO3)2、Zn(CH3COO)2One of (1); the cadmium salt is CdCl2、Cd(NO3)2、Cd(CH3COO)2One of (1);
the method for preparing N, N-diethylhydroxylamine by coating zinc-cadmium alloy particle catalyst with the core-shell titanium-silicon molecular sieve comprises the following steps:
adding a catalyst, diethylamine and a methanol solvent into a closed reactor, stirring, and slowly dropwise adding H with the concentration of 30-50 wt% when the reaction temperature reaches 45-60 DEG C2O2The dropping speed is 1d/2s, after the dropping is finished, the temperature is raised to 65-80 ℃, the reaction is continued for 1-2H, after the reaction is finished, the catalyst is separated out by filtration to obtain the N, N-diethylhydroxylamine, and in the steps, the diethylamine and the H are mixed2O2The molar ratio of (A) 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; determination of the conversion of diethylamine by titration with perchloric acid standard titration solution andselectivity to N, N-diethylhydroxylamine.
Compared with the prior art, the invention has the beneficial effects that:
1) the obtained core-shell titanium silicalite 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 aperture, large specific surface area and stable framework.
2) When the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst is used in a green diethylamine oxidation reaction, the catalyst shows good catalytic activity and cycle usability, particularly has high selectivity on N, N-diethylhydroxylamine, is easy to separate from a reaction system, and reduces production cost and operation difficulty.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
ZnCl with molar ratio2:CdCl2Polyvinylpyrrolidone and water (1: 0.1:0.015: 2.0) by mixing 0.05mol/L of 10mL of NaBH at 25 ℃4Dropwise addition of an aqueous solution to a solution containing ZnCl2、CdCl2And polyvinylpyrrolidone in the aqueous solution, fully stirring for 0.5h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly dripping ethyl orthosilicate into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 25 ℃, fully stirring for 0.5h after the addition is finished, raising the temperature to 40 ℃ after the uniform mixing is finished, slowly dripping ethyl orthosilicate with the volume ratio of 1:20 and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.1h after the addition is finished, raising the temperature to 60 ℃ after the uniform mixing is finished, slowly dripping 1, 2-bis (trimethoxy silicon-based) ethane with the volume ratio of 10:1:1, tetrabutyl titanate and isopropanol with the volume ratio of 10:1:1, fully stirring for 1h after the addition is finished, filtering the final mixed solution obtained in the process, washing a filter cake to be neutral by deionized water and ethanol, drying at 25 ℃ for 12h to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate obtained in the step 2) for 6 hours at the heating rate of 1 ℃/min from room temperature to 400 ℃ in the air atmosphere to remove organic matters, and then roasting the obtained product in the presence of N2Roasting at 300 deg.C for 4H in atmosphere, and then in H2Reducing for 4h at 500 ℃ in the atmosphere 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 are listed in Table 1.
Example 2
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
ZnCl with molar ratio2:Cd(NO3)2Polyvinylpyrrolidone and water 2mL of NaBH 0.15mol/L at 35 deg.C4Dropwise addition of an aqueous solution to a solution containing ZnCl2、Cd(NO3)2And polyvinylpyrrolidone in the aqueous solution, fully stirring for 2h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly dripping ethyl orthosilicate into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 35 ℃ according to the mol ratio of 1:0.90:3000:300:15, fully stirring for 2 hours after the feeding is finished, raising the temperature to 45 ℃ after the uniform mixing, slowly dripping ethyl orthosilicate with the volume ratio of 1:60 and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 1 hour after the feeding is finished, raising the temperature to 100 ℃ after the uniform mixing is finished, slowly dripping 1, 2-bis (trimethoxysilyl) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 20:2:1, fully stirring for 4 hours after the feeding is finished, filtering the final mixed solution obtained in the process, washing a filter cake by deionized water and ethanol, drying at 25 ℃ for 20h to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) for 2 hours at a heating rate of 3 ℃/min in the air atmosphere from room temperature to 600 ℃ to remove organic matters, and then roasting the obtained product in an N atmosphere2Roasting at 500 deg.C for 0.5H in atmosphere, and then in H2Reducing for 0.5h at 600 ℃ in the atmosphere 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 are listed in Table 1.
Example 3
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
ZnCl with molar ratio2:Cd(CH3COO)2Polyvinylpyrrolidone and water (1: 1.5:0.015: 2.5) by mixing 0.1mol/L of 5mL of NaBH at 30 ℃4Dropwise addition of an aqueous solution to a solution containing ZnCl2、Cd(CH3COO)2And polyvinylpyrrolidone, fully stirring for 1.25h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly dripping ethyl orthosilicate into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 30 ℃ according to the mol ratio of 1:0.45:2000:200:10, fully stirring for 1.25 hours after the feeding is finished, raising the temperature to 42 ℃ after the uniform mixing is finished, then slowly dripping 1:40 of ethyl orthosilicate and the zinc-cadmium alloy particle precursor solution obtained in the step 1) in the volume ratio, fully stirring for 0.5 hour after the feeding is finished, raising the temperature to 80 ℃ after the uniform mixing is finished, slowly dripping 1, 2-bis (trimethoxy silicon-based) ethane, tetrabutyl titanate and isopropanol in the volume ratio of 15:1.5:1, fully stirring for 2.5 hours after the feeding is finished, filtering the final mixed solution obtained in the process, washing a filter cake by deionized water and ethanol to be neutral, drying for 16h at 25 ℃ to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) for 4 hours at the heating rate of 1.5 ℃/min in the air atmosphere from room temperature to 500 ℃, removing organic matters, and then roasting in N2Roasting at 400 deg.C for 2.5H in atmosphere, and then in H2Reducing for 3h at 550 ℃ in the atmosphere 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 are listed in Table 1.
Example 4
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (NO)3)2:CdCl2Polyvinylpyrrolidone and water (1: 0.5:0.015: 2.2) by mixing 0.08mol/L of 7mL of NaBH at 28 ℃4Dropwise adding an aqueous solution to a solution containing Zn (NO)3)2、CdCl2And polyvinylpyrrolidone, fully stirring for 1.5h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly dripping ethyl orthosilicate into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 28 ℃, fully stirring for 0.8h after the feeding is finished, raising the temperature to 44 ℃ after the uniform mixing is finished, slowly dripping 1:25 volume ratio of ethyl orthosilicate and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.3h after the feeding is finished, raising the temperature to 65 ℃ after the uniform mixing is finished, slowly dripping 1, 2-bis (trimethoxy silicon-based) ethane, tetrabutyl titanate and isopropanol at the volume ratio of 12:1.3:1, fully stirring for 1.5h after the feeding is finished, filtering the final mixed solution obtained in the process, washing a filter cake to be neutral by deionized water and ethanol, drying for 15h at 25 ℃ to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate obtained in the step 2) for 5 hours at a heating rate of 2 ℃/min from room temperature to 450 ℃ in an air atmosphere to remove organic matters, and then roasting the obtained product in an N atmosphere2Roasting at 350 deg.C for 3.5H in atmosphere, and then in H2Reducing for 3.5h at 530 ℃ in the atmosphere 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 are listed in Table 1.
Example 5
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (NO)3)2:Cd(NO3)2Polyvinylpyrrolidone and water (1: 1.8:0.015: 2.4) at 32 ℃ in the presence of 0.12mol/L of 4mL of NaBH4Dropwise adding an aqueous solution to a solution containing Zn (NO)3)2、Cd(NO3)2And polyvinylpyrrolidone in the aqueous solution, fully stirring for 0.8h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly dripping ethyl orthosilicate into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 32 ℃, fully stirring for 0.65h after the addition is finished, raising the temperature to 43 ℃ after the uniform mixing is finished, slowly dripping 1:30 volume ratio of ethyl orthosilicate and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.2h after the addition is finished, raising the temperature to 70 ℃ after the uniform mixing is finished, slowly dripping 1, 2-bis (trimethoxy silicon-based) ethane, tetrabutyl titanate and isopropanol at the volume ratio of 14:1.6:1, fully stirring for 2h after the addition is finished, filtering the final mixed solution obtained in the process, washing the filter cake to be neutral by deionized water and ethanol, drying at 25 ℃ for 18h to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) for 3 hours at the heating rate of 2.5 ℃/min in the air atmosphere from room temperature to 550 ℃, removing organic matters, and then roasting in N2Roasting at 450 deg.C for 1.5H in atmosphere, and then in H2Reducing for 2.5h at 560 ℃ in the atmosphere 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 are listed in Table 1.
Example 6
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (NO)3)2:Cd(CH3COO)2Polyvinylpyrrolidone and water (1: 0.3:0.015: 2.1) at 26 deg.C, 0.065mol/L of 8mL NaBH4Dropwise 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 catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly and dropwise adding ethyl orthosilicate, hexadecyl trimethyl ammonium bromide, water, ethanol and 17% ammonia water into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 26 ℃, fully stirring for 1.0 hour after the addition is finished, raising the temperature to 40 ℃ after the uniform mixing is finished, slowly and 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 0.4 hour after the addition is finished, raising the temperature to 75 ℃ after the uniform mixing is finished, slowly and dropwise adding 1, 2-bis (trimethoxysilyl) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 11:1.2:1, fully stirring for 3 hours after the addition is finished, filtering the final mixed solution obtained in the process, washing a filter cake by deionized water and ethanol to be neutral, drying at 25 ℃ for 13h to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Heating the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate obtained in the step 2) from room temperature to 420 ℃ at a heating rate of 1.2 ℃/min in the air atmosphere for 5.5h to remove organic matters, and then roasting the intermediate in the N atmosphere2Roasting at 320 deg.C for 3.8H in atmosphere, and then in H2Reducing for 3.8h at 520 ℃ in the atmosphere 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 are listed in Table 1.
Example 7
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (CH)3COO)2:CdCl2Polyvinylpyrrolidone and water (1: 0.7:0.015: 2.6) by mixing 0.09mol/L of 6mL of NaBH at 29 deg.C4Dropwise adding an aqueous solution to the Zn (CH) -containing solution3COO)2、CdCl2And polyvinylpyrrolidone, fully stirring for 1.0h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly dripping ethyl orthosilicate into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 29 ℃, fully stirring for 1.4 hours after the feeding is finished, raising the temperature to 41 ℃ after the uniform mixing is finished, slowly dripping 1, 2-bis (trimethoxy silicon-based) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 13:1.4:1, after the feeding is finished, fully stirring for 0.6 hour, raising the temperature to 85 ℃ after the uniform mixing is finished, slowly dripping 1, 2-bis (trimethoxy silicon-based) ethane, tetrabutyl titanate and isopropanol with the volume ratio of 13:1.4:1, fully stirring for 3.5 hours after the feeding is finished, filtering the final mixed solution obtained in the process, washing a filter cake by deionized water and ethanol to be neutral, drying for 14h at 25 ℃ to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) for 4.5h at the heating rate of 1.8 ℃/min from room temperature to 480 ℃ in the air atmosphere to remove organic matters, and then roasting the intermediate in the N atmosphere2Roasting at 380 deg.C for 3.0H in atmosphere, and then in H2Reducing for 3.2h at 540 ℃ in the atmosphere 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 are listed in Table 1.
Example 8
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (CH)3COO)2:Cd(NO3)2Polyvinylpyrrolidone and water (1: 0.9:0.015: 2.8) by mixing 0.13mol/L of 3.5mL of NaBH at 31 ℃4Dropwise adding an aqueous solution to the Zn (CH) -containing solution3COO)2、Cd(NO3)2And polyvinylpyrrolidone, fully stirring for 1.35h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly dripping ethyl orthosilicate into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 31 ℃ according to the mol ratio of 1:0.65:2600:260:11, fully stirring for 1.6 hours after the feeding is finished, raising the temperature to 42 ℃ after the uniform mixing is finished, then slowly dripping 1:50 of ethyl orthosilicate and the zinc-cadmium alloy particle precursor solution obtained in the step 1) in the volume ratio, fully stirring for 0.7 hour after the feeding is finished, raising the temperature to 90 ℃ after the uniform mixing is finished, slowly dripping 1, 2-bis (trimethoxy silicon-based) ethane, tetrabutyl titanate and isopropanol in the volume ratio of 16:1.7:1, fully stirring for 2 hours after the feeding is finished, filtering the final mixed solution obtained in the process, washing the filter cake to be neutral by deionized water and ethanol, drying for 17h at 25 ℃ to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) for 3.5h at the heating rate of 2.2 ℃/min from room temperature to 530 ℃ in the air atmosphere to remove organic matters, and then roasting the intermediate in the N atmosphere2Roasting at 420 deg.C for 2.0H in atmosphere, and then in H2Reducing for 1.0h at 570 ℃ in the atmosphere 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 are listed in Table 1.
Example 9
The invention relates to a preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst
1) Preparing a zinc-cadmium alloy particle precursor solution:
in molar ratio Zn (CH)3COO)2:Cd(CH3COO)2Polyvinylpyrrolidone and water (1: 1.2:0.015: 2.3) at 34 deg.C, 3mL of NaBH in an amount of 0.14mol/L4Dropwise adding an aqueous solution to the Zn (CH) -containing solution3COO)2、Cd(CH3COO)2And polyvinylpyrrolidone, fully stirring for 1.7h after the addition is finished to obtain a zinc-cadmium alloy particle precursor solution;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly and dropwise adding ethyl orthosilicate, hexadecyl trimethyl ammonium bromide, water, ethanol and 26% ammonia water into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at the temperature of 34 ℃, fully stirring for 1.8 hours after the addition is finished, raising the temperature to 45 ℃ after the uniform mixing is finished, slowly and 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 hour after the addition is finished, raising the temperature to 95 ℃ after the uniform mixing is finished, slowly and dropwise adding 1, 2-bis (trimethoxysilyl) 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 be neutral by deionized water and ethanol, drying at 25 ℃ for 19h to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reduction
Roasting the intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst obtained in the step 2) for 2.5h at the heating rate of 2.8 ℃/min in the air atmosphere from room temperature to 580 ℃, removing organic matters, and then roasting in N2Roasting at 480 deg.C for 1H in atmosphere, and then in H2Reducing for 0.7h at 590 ℃ in the atmosphere 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 are listed in Table 1.
TABLE 1
Example 10
The invention relates to a method for preparing N, N-diethylhydroxylamine by coating a zinc-cadmium alloy particle catalyst on a core-shell titanium-silicon molecular sieve, which comprises the following steps:
the catalysts prepared in examples 1 to 9 were used in the preparation of N, N-diethylhydroxylamine in sequence, wherein the catalyst, diethylamine and the solvent methanol were added to a closed reactor in a weight ratio of 0.15:1 catalyst to diethylamine, the weight of methanol to diethylamineThe quantity ratio is 6:1, when the temperature in the closed reactor reaches 50 ℃, H with the concentration of 35wt percent is slowly dripped2O2Diethylamine with H2O2The molar ratio of the N, N-diethylhydroxylamine to the N, N-diethylhydroxylamine 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, and after the reaction is finished, the catalyst is separated out by filtration to obtain the N, N-diethylhydroxylamine; the conversion of diethylamine and the selectivity of N, N-diethylhydroxylamine were determined by titration with perchloric acid standard titration solution, and the results are shown in Table 2.
TABLE 2
The results in table 1 show that the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst of the invention is used for the diethylamine green oxidation reaction, and the selectivity of N, N-diethylhydroxylamine is high.
Example 11
The catalysts prepared in examples 1 to 9 were reacted according to example 10, then separated by filtration, dried, and subjected to green diethylamine oxidation according to the reaction conditions of example 10, and the reaction-separation-reaction cycle was repeated 5 times, and the results are shown in table 3.
TABLE 3
| Sample source | Conversion of diethylamine,% | Selectivity of N, N-diethylhydroxylamine% |
| 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 |
The results in table 3 show that the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst is used for the diethylamine green oxidation reaction, not only has high selectivity of N, N-diethylhydroxylamine, but also has high activity retention after 5 times of cyclic utilization, and has small reduction range of selectivity and conversion rate, which indicates that the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst particles and the framework are stable and can be repeatedly recycled for multiple times. Compared with the prior art, in the oxidation reaction, the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst has large aperture and large specific surface area, is beneficial to the diffusion of reactants and products, and reduces the diffusion resistance; the simultaneous existence of the titanium oxide sites and the transition metal particles improves the selectivity of the N, N-diethylhydroxylamine; 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, 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.
Claims (3)
1. A preparation method of a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst is characterized by comprising the following steps:
1) preparing a zinc-cadmium alloy particle precursor solution:
adding 2-10 mL of NaBH in an amount of 0.05-0.15 mol/L at a temperature of 25-35 ℃ according to a mol ratio of 1: 0.1-2.0: 0.015: 2.0-3.0 of zinc salt, cadmium salt, polyvinylpyrrolidone and water4Dropwise 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;
2) preparing a catalyst intermediate of the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particles:
slowly and dropwise adding ethyl orthosilicate, hexadecyl trimethyl ammonium bromide, water, ethanol and 15-28% ammonia water into a water-ethanol mixed solution containing hexadecyl trimethyl ammonium bromide and ammonia water at a temperature of 25-35 ℃ for 0.01-0.90: 1500-3000: 100-300: 5-15, fully stirring for 0.5-2 hours after the addition is finished, raising the temperature to 40-45 ℃ after the uniform mixing, slowly and dropwise adding ethyl orthosilicate with the volume ratio of 1: 20-60 and the zinc-cadmium alloy particle precursor solution obtained in the step 1), fully stirring for 0.1-1 hour after the addition is finished, raising the temperature to 60-100 ℃ after the uniform mixing, slowly and dropwise adding 1, 2-bis (trimethoxy silicon-based) ethane with the volume ratio of 10-20: 1-2: 1, tetrabutyl titanate and isopropanol, fully stirring for 1-4 hours after the addition is finished, filtering the final mixed liquid obtained in the above process, washing the filter cake to be neutral by deionized water and ethanol, and drying at 25 ℃ for 12-20 h to obtain a core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;
3) roasting and reducing:
roasting the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst intermediate obtained in the step 2) for 2-6 h at the heating rate of 1-3 ℃/min in the air atmosphere from the room temperature to 400-600 ℃ to remove organic matters, and then roasting in N2Roasting at 300-500 deg.c for 0.5-4 hr and then in H2Reducing for 0.5-4 h at 500-600 ℃ in the atmosphere to obtain the final core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst.
2. The preparation method of the catalyst with the zinc-cadmium alloy particles coated by the core-shell titanium-silicon molecular sieve according to claim 1, wherein the zinc salt is ZnCl2、Zn(NO3)2、Zn(CH3COO)2One of (1); the cadmium salt is CdCl2、Cd(NO3)2、Cd(CH3COO)2One kind of (1).
3. The method for preparing N, N-diethylhydroxylamine by using the core-shell titanium silicalite molecular sieve coated zinc-cadmium alloy particle catalyst as claimed in claim 1 or 2, which is characterized by comprising the following steps:
adding catalyst, diethylamine and methanol solvent into the closed containerStirring in a reactor, and slowly dripping H with the concentration of 30-50 wt% when the reaction temperature reaches 45-60 DEG C2O2The dropping speed is 1d/2s, after the dropping is finished, the temperature is raised to 65-80 ℃, the reaction is continued for 1-2H, after the reaction is finished, the catalyst is separated out by filtration to obtain the N, N-diethylhydroxylamine, and in the steps, the diethylamine and the H are mixed2O2The molar ratio of (A) 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; the conversion rate of diethylamine and the selectivity of N, N-diethylhydroxylamine are determined by titration of perchloric acid standard titration solution.
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| WO2022156391A1 (en) * | 2021-01-20 | 2022-07-28 | 济宁学院 | Preparation method for core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst, and method for preparing n,n-diethylhydroxylamine by using core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst |
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| Publication number | Publication date |
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| WO2022156391A1 (en) | 2022-07-28 |
| CN113797966A (en) | 2021-12-17 |
| CN113797966B (en) | 2024-02-27 |
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