WO2022156391A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2022156391A1 WO2022156391A1 PCT/CN2021/135733 CN2021135733W WO2022156391A1 WO 2022156391 A1 WO2022156391 A1 WO 2022156391A1 CN 2021135733 W CN2021135733 W CN 2021135733W WO 2022156391 A1 WO2022156391 A1 WO 2022156391A1
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- alloy particle
- cadmium alloy
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- silicon molecular
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- 239000002245 particle Substances 0.000 title claims abstract description 112
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 81
- 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 81
- 239000011258 core-shell material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920001174 Diethylhydroxylamine Polymers 0.000 title claims abstract description 31
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 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
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 22
- 235000013855 polyvinylpyrrolidone Nutrition 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
- 239000011701 zinc Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 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
- 230000009467 reduction Effects 0.000 claims description 11
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 claims description 11
- 150000001661 cadmium Chemical class 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 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
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 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 abstract description 10
- 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000010718 Oxidation Activity Effects 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 terminal terminator Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 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
- 238000004064 recycling Methods 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
- 238000001354 calcination Methods 0.000 description 1
- 230000007812 deficiency 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 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
Definitions
- Patent CN111909054A discloses the mixed contact reaction of diethylamine, H 2 O 2 , acetone and other solvents in a titanium-silicon-oxygen catalyst.
- the N,N-diethylhydroxylamine reach the level of industrial application.
- Core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst is a dual-functional catalyst with both titanium-oxygen sites and transition metal particles. At present, there is no preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. And the public report on the preparation of N,N-diethylhydroxylamine.
- the zinc salt is one of ZnCl 2 , Zn(NO 3 ) 2 , and Zn(CH 3 COO) 2 ;
- the cadmium salt is CdCl 2 , Cd(NO 3 ) 2 , Cd(CH 3 COO) one of 2 ;
- diethylamine and H The molar ratio of 2 O 2 is 0.5 to 2:1, the weight ratio of catalyst to diethylamine is 0.005 to 0.3:1, and the weight ratio of methanol to diethylamine is 3 to 8:1; the perchloric acid standard titration solution
- the diethylamine conversion and N,N-diethylhydroxylamine selectivity were determined by titration.
- the obtained 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 has the advantages of large pore size, large specific surface area and stable framework.
- Ethyl orthosilicate with a volume ratio of 1:20 and the zinc-cadmium alloy particle precursor solution obtained in step 1) after the addition is completed, fully stir for 0.1 h, after mixing evenly, the temperature is raised to 60 ° C, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 10:1:1, after the addition of materials, fully stir for 1 h, and filter the final mixed solution obtained in the above process , washed the filter cake with deionized water and ethanol to neutrality, and dried at 25 °C for 12 h to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
- the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 3 °C/min from room temperature to 600 °C for 2 h in an air atmosphere to remove organic matter, and then heated in N 2 was calcined at 500 °C for 0.5 h in an atmosphere, and then reduced at 600 °C for 0.5 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. Its pore size and specific surface area are listed in Table 1.
- Ethyl orthosilicate with a volume ratio of 1:40 and the zinc-cadmium alloy particle precursor solution obtained in step 1) after the addition is completed, fully stir for 0.5h, and after mixing evenly, the temperature is raised to 80 °C, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 15:1.5:1, after the addition of materials, fully stirred for 2.5h, and the final mixed solution obtained by the above process was Filtration, washing the filter cake with deionized water and ethanol to neutrality, drying at 25 °C for 16 h, to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
- the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 1.5 °C/min from room temperature to 500 °C for 4 h in an air atmosphere to remove organic matter, and then heated in N After calcining at 400 °C for 2.5 h in an atmosphere of 2 , and reducing at 550 °C for 3 h in a H2 atmosphere, the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst was obtained. Its pore size and specific surface area are listed in Table 1.
- Ethyl orthosilicate with a volume ratio of 1:25 and the zinc-cadmium alloy particle precursor solution obtained in step 1) after the addition is completed, fully stir for 0.3h, and after mixing evenly, the temperature is raised to 65 °C, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 12:1.3:1, after the addition of materials, fully stirred for 1.5h, and the final mixed solution obtained by the above process was Filter, wash the filter cake with deionized water and ethanol to neutrality, and dry it at 25°C for 15h to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
- the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 2 °C/min from room temperature to 450 °C for 5 h in an air atmosphere to remove organic matter, and then heated in N 2 was calcined at 350 °C for 3.5 h in an atmosphere, and then reduced at 530 °C for 3.5 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst.
- the pore size and specific surface area are listed in Table 1.
- Ethyl orthosilicate with a volume ratio of 1:45 and the zinc-cadmium alloy particle precursor solution obtained in step 1) after the addition is completed, fully stir for 0.6h, after mixing uniformly, the temperature is raised to 85 °C, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 13:1.4:1, after the addition of materials, fully stirred for 3.5h, and the final mixed solution obtained by the above process was Filtration, washing the filter cake with deionized water and ethanol until neutral, drying at 25 °C for 14 h, to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
- the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 2.2 °C/min from room temperature to 530 °C for 3.5 hours in an air atmosphere to remove organic matter, and then calcined at 420 °C for 2.0 h in a N2 atmosphere, and then reduced at 570 °C for 1.0 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst.
- the pore size and specific surface area are listed in Table 1. .
- Ethyl orthosilicate with a volume ratio of 1:55 and the zinc-cadmium alloy particle precursor solution obtained in step 1) after the addition is completed, fully stir for 0.85h, and after mixing evenly, the temperature is raised to 95 °C, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 18:1.9:1, after the addition of materials, fully stirred for 2.5h, and the final mixed solution obtained by the above process was Filtration, washing the filter cake with deionized water and ethanol until neutral, drying at 25 °C for 19 h, to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
- the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 2.8°C/min from room temperature to 580°C for 2.5h in an air atmosphere to remove organic matter, and then calcined at 2.8°C/min.
- the catalyst was calcined at 480 °C for 1 h in a N 2 atmosphere, and then reduced at 590 ° C for 0.7 h in a H 2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst.
- the pore size and specific surface area are listed in Table 1.
- the method for preparing N,N-diethylhydroxylamine by a core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention comprises the following steps:
- the catalyst prepared by embodiment 1-9 is used to prepare N,N-diethylhydroxylamine successively, wherein catalyzer, diethylamine and solvent methanol are added in the closed reactor, according to the weight ratio of catalyzer and diethylamine, it is 0.15: 1.
- the weight ratio of methanol to diethylamine is 6:1.
- 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
- Example 1 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
- the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention is used for the green oxidation reaction of diethylamine, which not only has high selectivity of N,N-diethylhydroxylamine, but also has a high recycling rate. After being used for 5 times, the activity retention is high, and the selectivity and conversion rate decrease very little, indicating that the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst alloy particles and skeleton of the present invention are stable and can be recycled many times.
- the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention has a large pore size and a large specific surface area, which is conducive to the diffusion of reactants and products, and reduces the diffusion resistance;
- the coexistence of the site and the transition metal particles improves the selectivity of N,N-diethylhydroxylamine; it is easy to separate from the reaction system, reduces the production cost and operation difficulty, can be recycled, and is easy for industrial application.
Abstract
The present invention relates to the technical field of chemical engineering, and specifically relates to a preparation method for a core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and a method for preparing N,N-diethylhydroxylamine by using the 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 uses SiO2 and a zinc-cadmium alloy particle coated with same as a core, and uses tetrabutyl titanate as a titanium source to assemble a shell; and a diethylamine green oxidation reaction is performed by means of the core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst so as to prepare N,N-diethylhydroxylamine. The core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst of the present invention has titanium oxygen sites and transition metal particles, is a bifunctional catalyst, is large in pore size, large in specific surface area, stable in skeleton, and high in catalytic oxidation activity, especially has high selectivity for N,N-diethylhydroxylamine, is easy to separate and recycle after a reaction, can be reused, and has a good application prospect.
Description
本发明属于化工技术领域，具体为涉及一种核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备及其制备N,N-二乙基羟胺的方法。The invention belongs to the technical field of chemical industry, and particularly relates to the preparation of a core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst and a method for preparing N,N-diethylhydroxylamine.
N,N-二乙基羟胺是一种重要的烯烃单体阻聚剂、端基终止剂、抗氧化剂和有机合成中间体，随着N,N-二乙基羟胺用途的扩大，我国需求逐年增加。目前，N,N-二乙基羟胺工业生产技术主要采用三乙胺氧化热解法，即以三乙胺为原料经氧化与热解过程制得N,N-二乙基羟胺，工艺繁琐、污染重且生产周期长，特别是反应中产生易燃易爆气体乙烯，使得该生产过程存在一定的安全隐患。近年来以二乙胺和H
2O
2为原料的清洁路线替代传统热解法生产高附加值的N,N-二乙基羟胺技术，更加符合绿色环保要求，该路线的研发将不仅实现二乙胺的清洁化高效利用，而且可以实现我国N,N-二乙基羟胺生产技术的清洁化更新换代。
N,N-diethylhydroxylamine is an important olefin monomer polymerization inhibitor, terminal terminator, antioxidant and organic synthesis intermediate. With the expansion of the use of N,N-diethylhydroxylamine, my country's demand is increasing year by year Increase. At present, the industrial production technology of N,N-diethylhydroxylamine mainly adopts triethylamine oxidation pyrolysis method, that is, N,N-diethylhydroxylamine is prepared by oxidation and pyrolysis process using triethylamine as raw material. The pollution is heavy and the production cycle is long, especially the flammable and explosive gas ethylene is produced in the reaction, which makes the production process have certain safety hazards. In recent years, the clean route using diethylamine and H 2 O 2 as raw materials has replaced the traditional pyrolysis method to produce high value-added N,N-diethylhydroxylamine technology, which is more in line with the requirements of green environmental protection. The research and development of this route will not only achieve two The clean and efficient utilization of ethylamine can realize the clean replacement of N,N-diethylhydroxylamine production technology in China.
具有钛氧位点的钛硅分子筛是一类绿色环保的仲胺催化氧化用催化剂，但对目标产物羟胺定向选择性差及促进羟胺深度氧化为硝酮类化合物的特点限制了其在仲胺氧化反应中的应用，且传统钛硅分子筛较小的孔径(0.56～0.58nm)和比表面积(360～420m
2/g)及空间位阻作用，使得反应过程中扩散成为控制过程。与传统钛硅分子筛相比，空心钛硅分子筛钛含量高、孔容大，但在仲胺催化氧化体系中骨架的溶解、脱落导致的骨架坍塌现象不可避免。在过渡金属盐-锌盐或镉盐存在下，以H
2O
2溶液氧化仲胺，也可得到羟胺类产品，且过渡金属阳离子的存在，降低了反应活化能，使反应易于发生，但存在催化剂难以回收循环再利用及羟胺的选择性较低的问题。专利CN111909054A披露的是二乙胺、H
2O
2、丙酮等溶剂在钛硅氧催化剂混合接触反应，N,N-二乙基羟胺选择性较低，不适合二乙胺氧化的高效转化，难以达到工业应用水平。核壳型钛硅分子筛包覆锌镉合金粒子催化剂是一种兼具钛氧位点与过渡金属粒子的双功能催化剂，目前，未有核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备及其制备N,N-二乙基羟胺的公开报道。
Titanium-silicon molecular sieves with titanium oxide sites are a kind of green and environmentally friendly catalysts for the catalytic oxidation of secondary amines, but their poor directional selectivity to the target product hydroxylamine and the characteristics of promoting the deep oxidation of hydroxylamine to nitrones limit its use in secondary amine oxidation reactions. In addition, the small pore size (0.56-0.58nm), specific surface area (360-420m 2 /g) and steric hindrance of traditional titanium-silicon molecular sieves make diffusion a controlled process during the reaction. Compared with traditional titanium-silicon molecular sieves, hollow titanium-silicon molecular sieves have higher titanium content and larger pore volume, but in the secondary amine catalytic oxidation system, the skeleton collapse caused by the dissolution and shedding of the skeleton is inevitable. In the presence of transition metal salt-zinc salt or cadmium salt, oxidizing secondary amine with H 2 O 2 solution can also obtain hydroxylamine products, and the existence of transition metal cations reduces the activation energy of the reaction and makes the reaction easy to occur, but there are The catalyst is difficult to recover and recycle and the selectivity of hydroxylamine is low. Patent CN111909054A discloses the mixed contact reaction of diethylamine, H 2 O 2 , acetone and other solvents in a titanium-silicon-oxygen catalyst. The N,N-diethylhydroxylamine reach the level of industrial application. Core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst is a dual-functional catalyst with both titanium-oxygen sites and transition metal particles. At present, there is no preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. And the public report on the preparation of N,N-diethylhydroxylamine.
发明内容SUMMARY OF THE INVENTION
本发明目的在于针对现有技术所存在的不足而提供一种核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法及其制备N,N-二乙基羟胺的方法。本发明所制备的核壳型钛硅分子筛包覆锌镉合金粒子催化剂孔径大、比表面积大、骨架稳定、易于回收循环再利用，同时具有对N,N-二乙基羟胺的选择性高的优点。The purpose of the present invention is to provide a method for preparing a core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst and a method for preparing N,N-diethylhydroxylamine in view of the deficiencies in the prior art. The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst prepared by the invention has large pore size, large specific surface area, stable framework, easy recovery and recycling, and has high selectivity to N,N-diethylhydroxylamine. advantage.
为了解决上述技术问题，本发明采用如下技术方案：In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions:
本发明所述核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法，包括如下步骤：The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention comprises the following steps:
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比锌盐:镉盐:聚乙烯吡咯烷酮:水＝1:0.1～2.0:0.015:2.0～3.0，在25～35℃的温度下，将0.05～0.15mol/L的2～10mL NaBH
4水溶液滴加到含锌盐、镉盐和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌0.5～2h，得到锌镉合金粒子前驱体溶液；
Zinc salt: cadmium salt: polyvinylpyrrolidone: water = 1: 0.1-2.0: 0.015: 2.0-3.0 in molar ratio, at a temperature of 25-35 ℃, 2-10 mL NaBH 4 aqueous solution of 0.05-0.15 mol/L Add dropwise to an aqueous solution containing zinc salt, cadmium salt and polyvinylpyrrolidone, and after the addition is completed, fully stir for 0.5 to 2 hours to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:15～28％氨水＝1:0.01～0.90:1500～3000:100～300:5～15，在25～35℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌0.5～2h，混合均匀后，将温度升至40～45℃，再缓慢滴加体积比为1:20～60的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.1～1h，混合均匀后，将温度升至60～100℃，缓慢滴加体积比为10～20:1～2:1的1,2-双(三甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌1～4h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥12～20h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 15～28% ammonia water = 1:0.01～0.90:1500～3000:100～300:5～15, at 25 At a temperature of ~35°C, slowly add tetraethyl orthosilicate dropwise to the water-ethanol mixed solution containing cetyltrimethylammonium bromide and ammonia water. After the addition is completed, stir well for 0.5-2h, and mix well. Then, the temperature was raised to 40-45° C., and then slowly dropwise added ethyl orthosilicate with a volume ratio of 1:20-60 and the zinc-cadmium alloy particle precursor solution obtained in step 1). After the addition, fully stirred for 0.1 ～1h, after mixing uniformly, the temperature was raised to 60～100℃, and 1,2-bis(trimethoxysilyl)ethane, tetrakis titanate with a volume ratio of 10～20:1～2:1 were slowly added dropwise. After the addition of butyl ester and isopropanol, fully stir for 1 to 4 hours, filter the final mixed solution obtained in the above process, wash the filter cake with deionized water and ethanol until neutral, and dry at 25 ° C for 12 to 20 hours to obtain Core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以1～3℃/min的加热速率从室温升至400～600℃下焙烧2～6h脱除有机物，然后在N
2氛围中于300～500℃焙烧0.5～4h，再于H
2氛围中于500～600℃还原0.5～4h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) is calcined at a heating rate of 1-3° C./min from room temperature to 400-600° C. for 2-6 hours in an air atmosphere. Remove organic matter, then calcinate at 300-500 °C for 0.5-4 h in N 2 atmosphere, and then reduce at 500-600 °C for 0.5-4 h in H 2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particles catalyst.
所述的锌盐为ZnCl
2、Zn(NO
3)
2、Zn(CH
3COO)
2中的一种；所述的镉盐为CdCl
2、Cd(NO
3)
2、Cd(CH
3COO)
2中的一种；
The zinc salt is one of ZnCl 2 , Zn(NO 3 ) 2 , and Zn(CH 3 COO) 2 ; the cadmium salt is CdCl 2 , Cd(NO 3 ) 2 , Cd(CH 3 COO) one of 2 ;
本发明所述的核壳型钛硅分子筛包覆锌镉合金粒子催化剂制备N,N-二乙基羟胺的方法，包括如下步骤：The method for preparing N,N-diethylhydroxylamine by the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention comprises the following steps:
将催化剂、二乙胺和甲醇溶剂加入到密闭反应器中搅拌，当反应温度达到45～60℃时，开始缓慢滴加浓度为30～50wt％的H
2O
2，滴加速率为1d/2s，滴加完毕后，将温度升至65～80℃，继续反应1～2h，反应完毕后，经过滤分离出催化剂，得到N,N-二乙基羟胺，上述步骤中，二乙胺与H
2O
2的摩尔比为0.5～2:1，催化剂与二乙胺的重量比为0.005～0.3:1，甲醇与二乙胺的重量比为3～8:1；经高氯酸标准滴定溶液滴定确定二乙胺转化率及N,N-二乙基羟胺选择性。
Add the catalyst, diethylamine and methanol solvent into the closed reactor and stir, when the reaction temperature reaches 45～60℃, start to slowly drip H 2 O 2 with a concentration of 30～50wt%, and the dripping rate is 1d/2s , after the dropwise addition is completed, the temperature is raised to 65-80 ° C, and the reaction is continued for 1-2 h. After the reaction is completed, the catalyst is separated by filtration to obtain N,N-diethylhydroxylamine. In the above steps, diethylamine and H The molar ratio of 2 O 2 is 0.5 to 2:1, the weight ratio of catalyst to diethylamine is 0.005 to 0.3:1, and the weight ratio of methanol to diethylamine is 3 to 8:1; the perchloric acid standard titration solution The diethylamine conversion and N,N-diethylhydroxylamine selectivity were determined by titration.
与现有技术相比，本发明的有益效果体现在：Compared with the prior art, the beneficial effects of the present invention are embodied in:
1)所得的核壳型钛硅分子筛包覆锌镉合金粒子催化剂是一种兼具钛氧位点与过渡金属粒子的双功能催化剂，同时具有孔径大、比表面积大、骨架稳定的优点。1) The obtained 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 has the advantages of large pore size, large specific surface area and stable framework.
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂用于二乙胺绿色氧化反应时，表现出良好的催化活性和循环使用性，特别是对N,N-二乙基羟胺的选择性高，且催化剂易于从反应体系中分离，降低了生产成本和操作难度。2) When the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst is used for the green oxidation reaction of diethylamine, it shows good catalytic activity and recyclability, especially the selectivity to N,N-diethylhydroxylamine high, and the catalyst is easy to separate from the reaction system, which reduces the production cost and operation difficulty.
下面结合实施例对本发明做进一步说明。The present invention will be further described below in conjunction with the embodiments.
实施例1Example 1
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比ZnCl
2:CdCl
2:聚乙烯吡咯烷酮:水＝1:0.1:0.015:2.0，在25℃的温度下，将0.05mol/L的10mL NaBH
4水溶液滴加到含ZnCl
2、CdCl
2和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌0.5h，得到锌镉合金粒子前驱体溶液；
In a molar ratio of ZnCl 2 : CdCl 2 : polyvinylpyrrolidone: water=1:0.1:0.015:2.0, at a temperature of 25°C, 10 mL of 0.05 mol/L NaBH 4 aqueous solution was added dropwise to the mixture containing ZnCl 2 , CdCl 2 and In the aqueous solution of polyvinylpyrrolidone, after the feeding is completed, fully stir for 0.5h to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:15％氨水＝1:0.01:1500:100:5，在25℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌0.5h，混合均匀后，将温度升至40℃，再缓慢滴加体积比为1:20的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.1h，混合均匀后，将温度升至60℃，缓慢滴加体积比为10:1:1的1,2-双(三甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌1h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥12h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 15% ammonia water = 1: 0.01: 1500: 100: 5 in a molar ratio, at a temperature of 25 °C, the ethyl orthosilicate The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 0.5 h. After mixing evenly, the temperature was raised to 40 °C, and then slowly added dropwise. Ethyl orthosilicate with a volume ratio of 1:20 and the zinc-cadmium alloy particle precursor solution obtained in step 1), after the addition is completed, fully stir for 0.1 h, after mixing evenly, the temperature is raised to 60 ° C, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 10:1:1, after the addition of materials, fully stir for 1 h, and filter the final mixed solution obtained in the above process , washed the filter cake with deionized water and ethanol to neutrality, and dried at 25 °C for 12 h to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以1℃/min的加热速率从室温升至400℃下焙烧6h脱除有机物，然后在N
2氛围中于300℃焙烧4h，再于H
2氛围中于500℃还原4h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined in an air atmosphere at a heating rate of 1 °C/min from room temperature to 400 °C for 6 h to remove organic substances, and then heated in N 2 was calcined at 300 °C for 4 h in an atmosphere, and then reduced at 500 °C for 4 h in an H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. Its pore size and specific surface area are listed in Table 1.
实施例2Example 2
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比ZnCl
2:Cd(NO
3)
2:聚乙烯吡咯烷酮:水＝1:2.0:0.015:3.0，在35℃的温度下，将0.15mol/L的2mL NaBH
4水溶液滴加到含ZnCl
2、Cd(NO
3)
2和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌2h，得到锌镉合金粒子前驱体溶液；
According to the molar ratio of ZnCl 2 : Cd(NO 3 ) 2 : polyvinylpyrrolidone: water=1:2.0:0.015:3.0, at 35°C, 0.15mol/L of 2mL NaBH 4 aqueous solution was added dropwise to the ZnCl 2 , Cd(NO 3 ) 2 and an aqueous solution of polyvinylpyrrolidone, after the addition of materials, fully stirring for 2h to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:28％氨水＝1:0.90:3000:300:15，在35℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌2h，混合均匀后，将温度升至45℃，再缓慢滴加体积比为1:60的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌1h，混合均匀后，将温度升至100℃，缓慢滴加体积比为20:2:1的1,2-双(三甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌4h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥20h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: hexadecyl trimethyl ammonium bromide: water: ethanol: 28% ammonia water = 1: 0.90: 3000: 300: 15 in a molar ratio, at a temperature of 35 ° C, the ethyl orthosilicate The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyltrimethylammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 2 hours. After mixing evenly, the temperature was raised to 45°C, and the volume was slowly added dropwise. The ratio of ethyl orthosilicate to the zinc-cadmium alloy particle precursor solution obtained in step 1) is 1:60. After the addition is completed, fully stir for 1 hour. After mixing is uniform, the temperature is raised to 100 ° C, and the volume ratio is slowly added. 20:2:1 of 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol, after the addition is completed, fully stir for 4h, filter the final mixed solution obtained in the above process, and use The filter cake was washed with deionized water and ethanol until neutral, and dried at 25 °C for 20 h to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以3℃/min的加热速率从室温升至600℃下焙烧2h脱除有机物，然后在N
2氛围中于500℃焙烧0.5h，再于H
2氛围中于600℃还原0.5h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 3 °C/min from room temperature to 600 °C for 2 h in an air atmosphere to remove organic matter, and then heated in N 2 was calcined at 500 °C for 0.5 h in an atmosphere, and then reduced at 600 °C for 0.5 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. Its pore size and specific surface area are listed in Table 1.
实施例3Example 3
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比ZnCl
2:Cd(CH
3COO)
2:聚乙烯吡咯烷酮:水＝1:1.5:0.015:2.5，在30℃的温度下，将0.1mol/L的5mL NaBH
4水溶液滴加到含ZnCl
2、Cd(CH
3COO)
2和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌1.25h，得到锌镉合金粒子前驱体溶液；
According to the molar ratio of ZnCl 2 : Cd(CH 3 COO) 2 : polyvinylpyrrolidone: water = 1: 1.5: 0.015: 2.5, at a temperature of 30 ° C, 0.1 mol/L of 5 mL of NaBH 4 aqueous solution was added dropwise to the ZnCl 2. In an aqueous solution of Cd(CH 3 COO) 2 and polyvinylpyrrolidone, after the feeding is completed, fully stir for 1.25 h to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:25％氨水＝1:0.45:2000:200:10，在30℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌1.25h，混合均匀后，将温度升至42℃，再缓慢滴加体积比为1:40的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.5h，混合均匀后，将温度升至80℃，缓慢滴加体积比为15:1.5:1的1,2-双(三甲氧 基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌2.5h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥16h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 25% ammonia water = 1: 0.45: 2000: 200: 10, at a temperature of 30 ° C, the ethyl orthosilicate The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyltrimethylammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 1.25h. After mixing evenly, the temperature was raised to 42°C, and then slowly added dropwise. Ethyl orthosilicate with a volume ratio of 1:40 and the zinc-cadmium alloy particle precursor solution obtained in step 1), after the addition is completed, fully stir for 0.5h, and after mixing evenly, the temperature is raised to 80 ℃, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 15:1.5:1, after the addition of materials, fully stirred for 2.5h, and the final mixed solution obtained by the above process was Filtration, washing the filter cake with deionized water and ethanol to neutrality, drying at 25 °C for 16 h, to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以1.5℃/min的加热速率从室温升至500℃下焙烧4h脱除有机物，然后在N
2氛围中于400℃焙烧2.5h，再于H
2氛围中于550℃还原3h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 1.5 °C/min from room temperature to 500 °C for 4 h in an air atmosphere to remove organic matter, and then heated in N After calcining at 400 °C for 2.5 h in an atmosphere of 2 , and reducing at 550 °C for 3 h in a H2 atmosphere, the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst was obtained. Its pore size and specific surface area are listed in Table 1.
实施例4Example 4
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比Zn(NO
3)
2:CdCl
2:聚乙烯吡咯烷酮:水＝1:0.5:0.015:2.2，在28℃的温度下，将0.08mol/L的7mL NaBH
4水溶液滴加到含Zn(NO
3)
2、CdCl
2和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌1.5h，得到锌镉合金粒子前驱体溶液；
According to the molar ratio of Zn(NO 3 ) 2 : CdCl 2 : polyvinylpyrrolidone: water = 1: 0.5: 0.015: 2.2, at a temperature of 28 ° C, 0.08 mol/L of 7 mL of NaBH 4 aqueous solution was added dropwise to Zn( In the aqueous solution of NO 3 ) 2 , CdCl 2 and polyvinyl pyrrolidone, after the feeding is completed, fully stir for 1.5 h to obtain the zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:20％氨水＝1:0.35:2500:150:8，在28℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌0.8h，混合均匀后，将温度升至44℃，再缓慢滴加体积比为1:25的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.3h，混合均匀后，将温度升至65℃，缓慢滴加体积比为12:1.3:1的1,2-双(三甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌1.5h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥15h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 20% ammonia water = 1: 0.35: 2500: 150: 8 in a molar ratio, at a temperature of 28 ° C, the ethyl orthosilicate The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyltrimethylammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 0.8h. After mixing evenly, the temperature was raised to 44°C, and then slowly added dropwise. Ethyl orthosilicate with a volume ratio of 1:25 and the zinc-cadmium alloy particle precursor solution obtained in step 1), after the addition is completed, fully stir for 0.3h, and after mixing evenly, the temperature is raised to 65 ℃, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 12:1.3:1, after the addition of materials, fully stirred for 1.5h, and the final mixed solution obtained by the above process was Filter, wash the filter cake with deionized water and ethanol to neutrality, and dry it at 25°C for 15h to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以2℃/min的加热速率从室温升至450℃下焙烧5h脱除有机物，然后在N
2氛围中于350℃焙烧3.5h，再于H
2氛围中于530℃还原3.5h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 2 °C/min from room temperature to 450 °C for 5 h in an air atmosphere to remove organic matter, and then heated in N 2 was calcined at 350 °C for 3.5 h in an atmosphere, and then reduced at 530 °C for 3.5 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. The pore size and specific surface area are listed in Table 1.
实施例5Example 5
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比Zn(NO
3)
2:Cd(NO
3)
2:聚乙烯吡咯烷酮:水＝1:1.8:0.015:2.4，在32℃的温度下，将0.12mol/L的4mL NaBH
4水溶液滴加到含Zn(NO
3)
2、Cd(NO
3)
2和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌0.8h，得到锌镉合金粒子前驱体溶液；
According to the molar ratio of Zn(NO 3 ) 2 : Cd(NO 3 ) 2 : polyvinylpyrrolidone: water=1:1.8:0.015:2.4, at 32°C, 4 mL of 0.12mol/L NaBH 4 aqueous solution was added dropwise into an aqueous solution containing Zn(NO 3 ) 2 , Cd(NO 3 ) 2 and polyvinylpyrrolidone, and after the addition is completed, fully stir for 0.8 h to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:22％氨水＝1:0.25:1800:170:12，在32℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌0.65h，混合均匀后，将温度升至43℃，再缓慢滴加体积比为1:30的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.2h，混合均匀后，将温度升至70℃，缓慢滴加体积比为14:1.6:1的1,2-双(三甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌2h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥18h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 22% ammonia water = 1: 0.25: 1800: 170: 12, at a temperature of 32 ° C, ethyl orthosilicate The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyltrimethylammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 0.65h. After mixing uniformly, the temperature was raised to 43°C, and then slowly added dropwise. Ethyl orthosilicate with a volume ratio of 1:30 and the zinc-cadmium alloy particle precursor solution obtained in step 1), after the addition is completed, fully stir for 0.2h, and after mixing evenly, the temperature is raised to 70 ° C, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 14:1.6:1, after the addition of materials, fully stirred for 2h, and the final mixed solution obtained in the above process was filtered , washed the filter cake with deionized water and ethanol to neutrality, and dried at 25 °C for 18 h to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以2.5℃/min的加热速率从室温升至550℃下焙烧3h脱除有机物，然后在N
2氛围中于450℃焙烧1.5h，再于H
2氛围中于560℃还原2.5h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 2.5°C/min from room temperature to 550°C for 3 hours in an air atmosphere to remove organic matter, and then heated in N 2 was calcined at 450 °C for 1.5 h in an atmosphere, and then reduced at 560 °C for 2.5 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. The pore size and specific surface area are listed in Table 1.
实施例6Example 6
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比Zn(NO
3)
2:Cd(CH
3COO)
2:聚乙烯吡咯烷酮:水＝1:0.3:0.015:2.1，在26℃的温度下，将0.065mol/L的8mL NaBH
4水溶液滴加到含锌盐、镉盐和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌0.65h，得到锌镉合金粒子前驱体溶液；
According to the molar ratio of Zn(NO 3 ) 2 : Cd(CH 3 COO) 2 : polyvinylpyrrolidone: water=1: 0.3: 0.015: 2.1, at a temperature of 26 °C, 8 mL of 0.065 mol/L NaBH 4 aqueous solution was added dropwise Add it to the aqueous solution containing zinc salt, cadmium salt and polyvinylpyrrolidone, and after the addition is completed, fully stir for 0.65h to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:17％氨水＝1:0.15:1700:120:6.5，在26℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌1.0h，混合均匀后，将温度升至40℃，再缓慢滴加体积比为1:35的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.4h，混合均匀后，将温度升至75℃，缓慢滴加体积比为11:1.2:1的1,2-双(三甲氧 基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌3h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥13h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 17% ammonia water = 1: 0.15: 1700: 120: 6.5, at a temperature of 26 ° C, the ethyl orthosilicate The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyltrimethylammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 1.0 h. After mixing evenly, the temperature was raised to 40 °C, and then slowly added dropwise. Ethyl orthosilicate with a volume ratio of 1:35 and the zinc-cadmium alloy particle precursor solution obtained in step 1), after the addition is completed, fully stir for 0.4h, and after mixing evenly, the temperature is raised to 75 ° C, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 11:1.2:1, after the addition of materials, fully stirred for 3h, and the final mixed solution obtained in the above process was filtered , washed the filter cake with deionized water and ethanol to neutrality, and dried at 25 °C for 13 h to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以1.2℃/min的加热速率从室温升至420℃下焙烧5.5h脱除有机物，然后在N
2氛围中于320℃焙烧3.8h，再于H
2氛围中于520℃还原3.8h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 1.2 °C/min from room temperature to 420 °C for 5.5 hours in an air atmosphere to remove organic substances, and then calcined at 320 °C for 3.8 h in a N2 atmosphere, and then reduced at 520 °C for 3.8 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. The pore size and specific surface area are listed in Table 1. .
实施例7Example 7
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比Zn(CH
3COO)
2:CdCl
2:聚乙烯吡咯烷酮:水＝1:0.7:0.015:2.6，在29℃的温度下，将0.09mol/L的6mL NaBH
4水溶液滴加到含Zn(CH
3COO)
2、CdCl
2和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌1.0h，得到锌镉合金粒子前驱体溶液；
In a molar ratio of Zn(CH 3 COO) 2 : CdCl 2 : polyvinylpyrrolidone: water=1:0.7:0.015:2.6, at a temperature of 29°C, 0.09mol /L of 6mL NaBH4 aqueous solution was added dropwise to the Zn-containing In an aqueous solution of (CH 3 COO) 2 , CdCl 2 and polyvinylpyrrolidone, after the addition of materials, fully stirring for 1.0 h to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:19％氨水＝1:0.55:2300:230:9，在29℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌1.4h，混合均匀后，将温度升至41℃，再缓慢滴加体积比为1:45的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.6h，混合均匀后，将温度升至85℃，缓慢滴加体积比为13:1.4:1的1,2-双(三甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌3.5h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥14h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 19% ammonia water = 1: 0.55: 2300: 230: 9 in a molar ratio, at a temperature of 29 ° C, the ethyl orthosilicate The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 1.4 hours. After mixing evenly, the temperature was raised to 41 °C, and then slowly added dropwise. Ethyl orthosilicate with a volume ratio of 1:45 and the zinc-cadmium alloy particle precursor solution obtained in step 1), after the addition is completed, fully stir for 0.6h, after mixing uniformly, the temperature is raised to 85 ℃, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 13:1.4:1, after the addition of materials, fully stirred for 3.5h, and the final mixed solution obtained by the above process was Filtration, washing the filter cake with deionized water and ethanol until neutral, drying at 25 °C for 14 h, to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以1.8℃/min的加热速率从室温升至480℃下焙烧4.5h脱除有机物，然后在N
2氛围中于380℃焙烧3.0h，再于H
2氛围中于540℃还原3.2h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 1.8 °C/min from room temperature to 480 °C for 4.5 h in an air atmosphere to remove organic matter, and then The catalyst was calcined at 380 °C for 3.0 h in a N2 atmosphere, and then reduced at 540 °C for 3.2 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. Its pore size and specific surface area are listed in Table 1. .
实施例8Example 8
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比Zn(CH
3COO)
2:Cd(NO
3)
2:聚乙烯吡咯烷酮:水＝1:0.9:0.015:2.8，在31℃的温度下，将0.13mol/L的3.5mL NaBH
4水溶液滴加到含Zn(CH
3COO)
2、Cd(NO
3)
2和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌1.35h，得到锌镉合金粒子前驱体溶液；
At a molar ratio of Zn(CH 3 COO) 2 : Cd(NO 3 ) 2 : polyvinylpyrrolidone: water=1:0.9:0.015:2.8, at a temperature of 31 °C, 3.5 mL of 0.13 mol/L NaBH 4 aqueous solution was Add dropwise to the aqueous solution containing Zn(CH 3 COO) 2 , Cd(NO 3 ) 2 and polyvinylpyrrolidone, and after the addition is completed, fully stir for 1.35h to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:24％氨水＝1:0.65:2600:260:11，在31℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌1.6h，混合均匀后，将温度升至42℃，再缓慢滴加体积比为1:50的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.7h，混合均匀后，将温度升至90℃，缓慢滴加体积比为16:1.7:1的1,2-双(三甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌2h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥17h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 24% ammonia water = 1: 0.65: 2600: 260: 11 at a temperature of 31 °C The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyl trimethyl ammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 1.6 h. After mixing evenly, the temperature was raised to 42 °C, and then slowly added dropwise. The volume ratio of ethyl orthosilicate and the zinc-cadmium alloy particle precursor solution obtained in step 1) is 1:50. After the addition is completed, fully stir for 0.7h, and after mixing evenly, the temperature is raised to 90 ° C, and the volume is slowly added dropwise. 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 16:1.7:1, after the addition is completed, fully stir for 2h, and filter the final mixed solution obtained in the above process , washed the filter cake with deionized water and ethanol to neutrality, and dried at 25 °C for 17 h to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以2.2℃/min的加热速率从室温升至530℃下焙烧3.5h脱除有机物，然后在N
2氛围中于420℃焙烧2.0h，再于H
2氛围中于570℃还原1.0h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 2.2 °C/min from room temperature to 530 °C for 3.5 hours in an air atmosphere to remove organic matter, and then calcined at 420 °C for 2.0 h in a N2 atmosphere, and then reduced at 570 °C for 1.0 h in a H2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. The pore size and specific surface area are listed in Table 1. .
实施例9Example 9
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法The preparation method of the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention
1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:
按摩尔比Zn(CH
3COO)
2:Cd(CH
3COO)
2:聚乙烯吡咯烷酮:水＝1:1.2:0.015:2.3，在34℃的温度下，将0.14mol/L的3mL NaBH
4水溶液滴加到含Zn(CH
3COO)
2、Cd(CH
3COO)
2和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌1.7h，得到锌镉合金粒子前驱体溶液；
According to the molar ratio of Zn(CH 3 COO) 2 : Cd(CH 3 COO) 2 : polyvinylpyrrolidone: water=1: 1.2: 0.015: 2.3, at a temperature of 34 ° C, 3 mL of 0.14 mol/L NaBH 4 aqueous solution was added Add dropwise to the aqueous solution containing Zn(CH 3 COO) 2 , Cd(CH 3 COO) 2 and polyvinylpyrrolidone, and after the addition is completed, fully stir for 1.7 h to obtain a zinc-cadmium alloy particle precursor solution;
2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:
按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:26％氨水＝1:0.75:2800:280:13.5，在34℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌1.8h，混合均匀后，将温度升至45℃，再缓慢滴加体积比为1:55的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.85h，混合均匀后，将温度升至95℃，缓慢滴加体积比为18:1.9:1的1,2-双(三 甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌2.5h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥19h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 26% ammonia water = 1: 0.75: 2800: 280: 13.5 in molar ratio, at a temperature of 34 ° C, ethyl orthosilicate The ester was slowly added dropwise to the water-ethanol mixed solution containing cetyltrimethylammonium bromide and ammonia water. After the addition was completed, it was fully stirred for 1.8 hours. After mixing evenly, the temperature was raised to 45°C, and then slowly added dropwise. Ethyl orthosilicate with a volume ratio of 1:55 and the zinc-cadmium alloy particle precursor solution obtained in step 1), after the addition is completed, fully stir for 0.85h, and after mixing evenly, the temperature is raised to 95 ℃, and the volume is slowly added dropwise 1,2-bis(trimethoxysilyl)ethane, tetrabutyl titanate and isopropanol in a ratio of 18:1.9:1, after the addition of materials, fully stirred for 2.5h, and the final mixed solution obtained by the above process was Filtration, washing the filter cake with deionized water and ethanol until neutral, drying at 25 °C for 19 h, to obtain the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate;
3)焙烧与还原3) Roasting and reduction
将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以2.8℃/min的加热速率从室温升至580℃下焙烧2.5h脱除有机物，然后在N
2氛围中于480℃焙烧1h，再于H
2氛围中于590℃还原0.7h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂，其孔径及比表面积列于表1。
The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) was calcined at a heating rate of 2.8°C/min from room temperature to 580°C for 2.5h in an air atmosphere to remove organic matter, and then calcined at 2.8°C/min. The catalyst was calcined at 480 °C for 1 h in a N 2 atmosphere, and then reduced at 590 ° C for 0.7 h in a H 2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst. The pore size and specific surface area are listed in Table 1.
表1Table 1
实施例10Example 10
本发明核壳型钛硅分子筛包覆锌镉合金粒子催化剂制备N,N-二乙基羟胺的方法，包括如下步骤：The method for preparing N,N-diethylhydroxylamine by a core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention comprises the following steps:
依次将实施例1-9制备的催化剂用于制备N,N-二乙基羟胺，其中催化剂、二乙胺和溶剂甲醇加入到密闭反应器中，按照催化剂与二乙胺的重量比为0.15:1，甲醇与二乙胺的重量比为6:1，当密闭反应器内温度达到50℃时，开始缓慢滴加浓度为35wt％的H
2O
2，二乙胺与H
2O
2的摩尔比为1:1，滴加速率为1d/2s，滴加完毕后，将温度升至80℃，继续反应1h，反应完毕后，经过滤分离出催化剂，得到N,N-二乙基羟胺；经高氯酸标准滴定溶液滴定确定二乙胺转化率及N,N-二乙基羟胺选择性，结果见表2。
The catalyst prepared by embodiment 1-9 is used to prepare N,N-diethylhydroxylamine successively, wherein catalyzer, diethylamine and solvent methanol are added in the closed reactor, according to the weight ratio of catalyzer and diethylamine, it is 0.15: 1. The weight ratio of methanol to diethylamine is 6:1. When the temperature in the closed reactor reaches 50°C, start to slowly dropwise add H 2 O 2 with a concentration of 35 wt%, the moles of diethylamine and H 2 O 2 The ratio is 1:1, and the dropping rate is 1d/2s. After the dropping is completed, the temperature is raised to 80°C, and the reaction is continued for 1 h. After the reaction is completed, the catalyst is separated by filtration to obtain N,N-diethylhydroxylamine; The conversion rate of diethylamine and the selectivity of N,N-diethylhydroxylamine were determined by perchloric acid standard titration solution titration. The results are shown in Table 2.
表2Table 2
| 样品来源Sample source | 二乙胺转化率，％Diethylamine conversion, % | N,N-二乙基羟胺选择性，％N,N-Diethylhydroxylamine selectivity, % |
| 实施例1Example 1 | 51.651.6 | 88.988.9 |
| 实施例2Example 2 | 53.853.8 | 90.590.5 |
| 实施例3Example 3 | 55.255.2 | 91.691.6 |
| 实施例4Example 4 | 54.954.9 | 93.493.4 |
| 实施例5Example 5 | 51.351.3 | 89.989.9 |
| 实施例6Example 6 | 52.952.9 | 92.592.5 |
| 实施例7Example 7 | 54.154.1 | 93.293.2 |
| 实施例8Example 8 | 53.753.7 | 92.792.7 |
| 实施例9Example 9 | 55.055.0 | 91.991.9 |
从表1的结果可以看出，本发明的核壳型钛硅分子筛包覆锌镉合金粒子催化剂用于二乙胺绿色氧化反应，N,N-二乙基羟胺选择性高。It can be seen from the results in Table 1 that the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention is used for the green oxidation reaction of diethylamine, and has high N,N-diethylhydroxylamine selectivity.
实施例11Example 11
将实施例1-9制备的催化剂按照实施例10进行反应后，经过滤分离、干燥后按照实施例10的反应条件进行二乙胺绿色氧化反应，反复进行反应-分离-反应循环，循环5次后的结果见表3。After the catalysts prepared in Examples 1-9 were reacted according to Example 10, the green oxidation reaction of diethylamine was carried out according to the reaction conditions of Example 10 after separation by filtration and drying, and the reaction-separation-reaction cycle was repeated for 5 times. The following results are shown in Table 3.
表3table 3
| 样品来源Sample source | 二乙胺转化率，％Diethylamine conversion, % | N,N-二乙基羟胺选择性，％N,N-Diethylhydroxylamine selectivity, % |
| 实施例1Example 1 | 51.351.3 | 89.389.3 |
| 实施例2Example 2 | 53.653.6 | 90.690.6 |
| 实施例3Example 3 | 55.155.1 | 91.391.3 |
| 实施例4Example 4 | 54.454.4 | 93.693.6 |
| 实施例5Example 5 | 51.151.1 | 89.689.6 |
| 实施例6Example 6 | 52.552.5 | 92.192.1 |
| 实施例7Example 7 | 54.054.0 | 93.493.4 |
| 实施例8Example 8 | 53.353.3 | 92.692.6 |
| 实施例9Example 9 | 54.754.7 | 91.591.5 |
从表3的结果可以看出，本发明的核壳型钛硅分子筛包覆锌镉合金粒子催化剂用于二乙胺绿色氧化反应，不但N,N-二乙基羟胺的选择性高，且循环利用5次后活性保留度较高，选择性和转化率下降幅度很小，说明本发明的核壳型钛硅分子筛包覆锌镉合金粒子催化剂合金粒子及骨架稳定，可以反复循环利用多次。与现有技术相比，在氧化反应中，本发明的核壳型钛硅分子筛包覆锌镉合金粒子催化剂孔径大、比表面积大有利于反应物和产物的扩散，减少了扩散阻力；钛氧位点与过渡金属粒子的同时存在使N,N-二乙基羟胺的选择性提高；并且易于从反应体系中分离，降低了生产成本和操作难度，可循环利用，易于工业化应用。It can be seen from the results in Table 3 that the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention is used for the green oxidation reaction of diethylamine, which not only has high selectivity of N,N-diethylhydroxylamine, but also has a high recycling rate. After being used for 5 times, the activity retention is high, and the selectivity and conversion rate decrease very little, indicating that the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst alloy particles and skeleton of the present invention are stable and can be recycled many times. Compared with the prior art, in the oxidation reaction, the core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst of the present invention has a large pore size and a large specific surface area, which is conducive to the diffusion of reactants and products, and reduces the diffusion resistance; The coexistence of the site and the transition metal particles improves the selectivity of N,N-diethylhydroxylamine; it is easy to separate from the reaction system, reduces the production cost and operation difficulty, can be recycled, and is easy for industrial application.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
Claims (3)
- 一种核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法，其特征在于，包括以下步骤：A method for preparing a core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst, characterized in that it comprises the following steps:1)锌镉合金粒子前驱体溶液的制备：1) Preparation of zinc-cadmium alloy particle precursor solution:按摩尔比锌盐:镉盐:聚乙烯吡咯烷酮:水＝1:0.1～2.0:0.015:2.0～3.0，在25～35℃的温度下，将0.05～0.15mol/L的2～10mL NaBH 4水溶液滴加到含锌盐、镉盐和聚乙烯吡咯烷酮的水溶液中，加料完毕后，充分搅拌0.5～2h，得到锌镉合金粒子前驱体溶液； Zinc salt: cadmium salt: polyvinylpyrrolidone: water = 1: 0.1-2.0: 0.015: 2.0-3.0 in molar ratio, at a temperature of 25-35 ℃, 2-10 mL NaBH 4 aqueous solution of 0.05-0.15 mol/L Add dropwise to an aqueous solution containing zinc salt, cadmium salt and polyvinylpyrrolidone, and after the addition is completed, fully stir for 0.5 to 2 hours to obtain a zinc-cadmium alloy particle precursor solution;2)核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体的制备：2) Preparation of core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate:按摩尔比正硅酸乙酯:十六烷基三甲基溴化铵:水:乙醇:15～28％氨水＝1:0.01～0.90:1500～3000:100～300:5～15，在25～35℃的温度下，将正硅酸乙酯缓慢滴加到含十六烷基三甲基溴化铵和氨水的水-乙醇混合溶液中，加料完毕后，充分搅拌0.5～2h，混合均匀后，将温度升至40～45℃，再缓慢滴加体积比为1:20～60的正硅酸乙酯与步骤1)所得的锌镉合金粒子前驱体溶液，加料完毕后，充分搅拌0.1～1h，混合均匀后，将温度升至60～100℃，缓慢滴加体积比为10～20:1～2:1的1,2-双(三甲氧基硅基)乙烷、钛酸四丁酯与异丙醇，加料完毕后，充分搅拌1～4h，将上述过程得到的最终混合液过滤，用去离子水和乙醇洗涤滤饼至中性，在25℃下干燥12～20h，得到核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体；Ethyl orthosilicate: cetyl trimethyl ammonium bromide: water: ethanol: 15~28% ammonia water = 1:0.01~0.90:1500~3000:100~300:5~15, at 25 At a temperature of ~35°C, slowly add tetraethyl orthosilicate dropwise to the water-ethanol mixed solution containing cetyltrimethylammonium bromide and ammonia water. After the addition is completed, stir well for 0.5-2h and mix well. Then, the temperature was raised to 40-45° C., and then the ethyl orthosilicate with a volume ratio of 1:20-60 and the zinc-cadmium alloy particle precursor solution obtained in step 1) were slowly added dropwise. After the addition, fully stirred for 0.1 ～1h, after mixing uniformly, the temperature was raised to 60～100°C, and 1,2-bis(trimethoxysilyl)ethane, tetrakis titanate with a volume ratio of 10～20:1～2:1 were slowly added dropwise. After the addition of butyl ester and isopropanol, fully stir for 1 to 4 hours, filter the final mixed solution obtained in the above process, wash the filter cake with deionized water and ethanol until neutral, and dry at 25 ° C for 12 to 20 hours to obtain Core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst intermediate;3)焙烧与还原：3) Roasting and reduction:将步骤2)得到的核壳型钛硅分子筛包覆锌镉合金粒子催化剂中间体在空气氛围中以1～3℃/min的加热速率从室温升至400～600℃下焙烧2～6h脱除有机物，然后在N 2氛围中于300～500℃焙烧0.5～4h，再于H 2氛围中于500～600℃还原0.5～4h，得到最终的核壳型钛硅分子筛包覆锌镉合金粒子催化剂。 The core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst intermediate obtained in step 2) is calcined at a heating rate of 1-3° C./min from room temperature to 400-600° C. for 2-6 hours in an air atmosphere. Remove organic matter, then calcinate at 300-500 °C for 0.5-4 h in N 2 atmosphere, and then reduce at 500-600 °C for 0.5-4 h in H 2 atmosphere to obtain the final core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particles catalyst.
- 根据权利要求1所述的核壳型钛硅分子筛包覆锌镉合金粒子催化剂的制备方法，其特征在于，所述锌盐为ZnCl 2、Zn(NO 3) 2、Zn(CH 3COO) 2中的一种；所述镉盐为CdCl 2、Cd(NO 3) 2、Cd(CH 3COO) 2中的一种。 The method for preparing a core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst according to claim 1, wherein the zinc salt is ZnCl 2 , Zn(NO 3 ) 2 , Zn(CH 3 COO) 2 One of the cadmium salts; the cadmium salt is one of CdCl 2 , Cd(NO 3 ) 2 , and Cd(CH 3 COO) 2 .
- 一种如权利要求1或2所述的核壳型钛硅分子筛包覆锌镉合金粒子催化剂制备N,N-二乙基羟胺的方法，其特征在于，包括如下步骤：A method for preparing N,N-diethylhydroxylamine by a core-shell titanium-silicon molecular sieve-coated zinc-cadmium alloy particle catalyst as claimed in claim 1 or 2, wherein the method comprises the following steps:将催化剂、二乙胺和甲醇溶剂加入到密闭反应器中搅拌，当反应温度达到45～60℃时，开始缓慢滴加浓度为30～50wt％的H 2O 2，滴加速率为1d/2s，滴加完毕后，将温度升至65～80℃，继续反应1～2h，反应完毕后，经过滤分离出催化剂，得到N,N-二乙基羟胺，上述步骤中，二乙胺与H 2O 2的摩尔比为0.5～2:1，催化剂与二乙胺的重量比为0.005～0.3:1，甲醇与二乙胺的重量比为3～8:1；经高氯酸标准滴定溶液滴定确定二乙胺转化率及N,N-二乙基羟胺选择性。 Add the catalyst, diethylamine and methanol solvent into the closed reactor and stir, when the reaction temperature reaches 45～60℃, start to slowly drip H 2 O 2 with a concentration of 30～50wt%, and the dripping rate is 1d/2s , after the dropwise addition is completed, the temperature is raised to 65-80 ° C, and the reaction is continued for 1-2 h. After the reaction is completed, the catalyst is separated by filtration to obtain N,N-diethylhydroxylamine. In the above steps, diethylamine and H The molar ratio of 2 O 2 is 0.5 to 2:1, the weight ratio of catalyst to diethylamine is 0.005 to 0.3:1, and the weight ratio of methanol to diethylamine is 3 to 8:1; the perchloric acid standard titration solution The diethylamine conversion and N,N-diethylhydroxylamine selectivity were determined by titration.
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|---|---|---|---|
| CN202110074519.4A CN112892586A (en) | 2021-01-20 | 2021-01-20 | 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 |
| CN202110074519.4 | 2021-01-20 |
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| CN115414923A (en) * | 2022-09-19 | 2022-12-02 | 常州大学 | Heterogeneous TiO for the synthesis of polycarbonate diols 2 /SiO 2 Catalyst and preparation method thereof |
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| CN112892586A (en) * | 2021-01-20 | 2021-06-04 | 济宁学院 | 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 |
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| CN113797966B (en) | 2024-02-27 |
| CN113797966A (en) | 2021-12-17 |
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