CN117566751A - Photo-thermal synergistic catalyst for liquid phase selective oxidation reaction and one-step synthesis method thereof - Google Patents

Photo-thermal synergistic catalyst for liquid phase selective oxidation reaction and one-step synthesis method thereof Download PDF

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CN117566751A
CN117566751A CN202311530334.5A CN202311530334A CN117566751A CN 117566751 A CN117566751 A CN 117566751A CN 202311530334 A CN202311530334 A CN 202311530334A CN 117566751 A CN117566751 A CN 117566751A
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metal silicate
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李石擎
彭如斯
陈士夫
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Huaibei Normal University
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Abstract

The invention discloses a photo-thermal synergic catalyst for liquid phase selective oxidation reaction and one-step synthesis method, which is characterized in that a three-dimensional crystal skeleton with silicon and oxygen as main elements is prepared by using a commercial organic template agent, and metal oxide sites with photo-catalytic and thermal-catalytic activities are generated and compounded in situ at the same time, and the chemical composition of the catalyst is M m n+ N p q+ SiO x The method comprises the steps of carrying out a first treatment on the surface of the The composite metal silicate catalyst is used for catalyzing liquid phase selective oxidation reaction of hydrocarbons to prepare corresponding high-added-value oxygen-containing chemicals. Compared with the prior art, the preparation method has the advantages of fewer preparation steps and low preparation cost, the quantity and the state of the photocatalytic and thermocatalytic active sites can be effectively regulated, the hydrocarbon liquid phase selective oxidation performance of the catalytic photo-thermal synergistic system is obviously improved, and the higher target product yield at a lower temperature is shown.

Description

Photo-thermal synergistic catalyst for liquid phase selective oxidation reaction and one-step synthesis method thereof
Technical Field
The invention relates to the technical field of inorganic chemical synthesis and chemical application, in particular to a composite metal silicate catalyst for photo-thermal synergistic catalysis liquid phase selective oxidation reaction and a one-step synthesis method thereof.
Background
At present, the production process for preparing the functionalized hydrocarbon based on hydrocarbon base chemicals mainly depends on heat energy support, and the pressure on the environment in the process of converting non-renewable energy sources into heat energy greatly promotes the innovation of an energy system. The light energy is inexhaustible, the photocatalysis technology becomes a research hot spot in the field of organic synthesis due to environmental friendliness and low energy consumption, but the current attractive technology is far away from the actual industrial application, and the national light energy utilization rate is not as high as 1%. From the practical application point of view, a high-efficiency photo-thermal composite catalytic system is constructed, and the effective utilization of the optical energy in the production process is expected to be truly realized by compensating part of the thermal energy with clean optical energy, so that a cleaner chemical energy system is promoted to be constructed.
Over 60% of the chemical production process involves hydrocarbon selective oxidation reactions. The framework metal site on the heteroatom silicate represented by TS-1 (MFI topology, titanium Silicalite-1) can activate an oxidant (such as oxygen, hydrogen peroxide, cumene hydroperoxide, etc.) and realize the active oxygen transfer process (US Patent 1983,4410501), and the three-dimensional pore channel structure can realize the regulation and control of the product selectivity through the shape-selective limiting effect on the guest molecule. The heteroatom silicate has excellent catalytic activity in a liquid phase selective oxidation system driven by heat energy, and has the potential of constructing a high-efficiency photo-thermal synergistic catalyst. It has been reported in the literature that by doping a photocatalytically active site with photo-responsiveness in a heteroatom silicate, a composite catalyst suitable for photo-thermal synergistic catalytic liquid phase selective oxidation reactions can be constructed (appl. However, the current preparation method of the photo-thermal synergistic catalyst usually adopts a post-doping method, namely, the corresponding photo-catalyst and the thermal catalyst are synthesized respectively and doped and compounded (mol.catalyst, 2019,8,473,110389), so that the cost of synthesis steps and equipment is increased, and the industrialized application of the photo-thermal synergistic catalyst is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the photo-thermal synergic catalyst for the liquid phase selective oxidation reaction and the one-step synthesis method thereof, wherein the three-dimensional crystal skeleton with silicon and oxygen as main elements is prepared by using a commercial organic template agent, and meanwhile, metal active sites with photocatalysis and thermocatalytic activity are generated and compounded in situ, so that the photo-thermal synergic catalyst is used for catalyzing the liquid phase selective oxidation reaction of hydrocarbons, has higher oxidation product yield, is mild in reaction condition and environment-friendly, and has good catalytic stability; the preparation process has few steps and low preparation cost, the quantity and the state of the photocatalytic and thermocatalytic active sites can be effectively regulated, the hydrocarbon liquid phase selective oxidation performance of the catalytic photo-thermal synergistic system is obviously improved, and the higher target product yield at lower temperature is shown.
The aim of the invention is realized by the following technical scheme:
the invention firstly provides a one-step synthesis method of a photo-thermal synergistic catalyst for liquid phase selective oxidation reaction, which is characterized in that: mixing a silicon source, a metal source, an alkali source, a commercial organic template agent and deionized water, stirring for 0.5-8 hours at 15-150 ℃, crystallizing for 1-8 days, washing, filtering, drying and roasting at 300-750 ℃ for 3-10 hours to obtain the composite metal silicate catalyst, namely the photo-thermal synergistic catalyst for liquid phase selective oxidation reaction.
Further, the silicon source is SiO 2 Meter, metal source with M m n+ O is measured, and alkali source is N p q+ The mol ratio of O to the commercial organic template agent and deionized water is 0.4-0.9:0.02-0.5:0-0.4:0.01-1.0:2-200, wherein: m is metal in a metal source, M is the molar ratio of metal ions in the metal source to Si in a silicon source, and n is the valence of M; n is metal ion in the alkali source, p is the molar ratio of the metal ion in the alkali source to Si in the silicon source, and q is the valence of N.
Further: the silicon source is at least one of tetraethyl silicate, silica sol, fuming silica gel, white carbon black, water glass, silicon dioxide microspheres and molecular sieves; the metal source is at least one of oxides, sulfates, nitrates, phosphates, carbonates, chloride salts or metal-containing organic matters of aluminum, titanium, tin, cobalt and/or zinc; the alkali source is at least one of sodium hydroxide, sodium metaaluminate, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the organic template agent is at least one of a quaternary ammonium salt or a quaternary ammonium base form of a compound shown in a structural formula (A) or a compound shown in a structural formula (B):
in formula (A): r is R 1 、R 2 、R 3 And R is 4 Each independently selected from linear or cyclic C 1-10 Alkyl, preferably C 1-5 An alkyl group;
in formula (B): r is R 5 、R 6 And R is 7 Each independently selected from linear orRing C 1-10 Alkyl, preferably C 1-6 An alkyl group.
Further, the topology of the molecular sieve that may be the source of silicon includes at least one of MFI, BEA, MWW, MOR, FAU, and FER.
Further, the crystallization implementation method comprises at least one of heating, ultrasound, illumination and microwaves.
Further, the quaternary ammonium salt form of the compound having the structural formula (A) has a quaternary nitrogen (N) + ) The counter-anion of the structure being a halide (e.g. Cl - 、Br - 、I - Etc.); a quaternary ammonium base form of a compound of formula (A), a quaternary nitrogen (N) + ) The counter anion of the structure is hydroxide ion (OH) - )。
The composite metal silicate catalyst prepared by the one-step synthesis method adopts silicon and oxygen as main elements to be connected in a tetrahedral form to form a three-dimensional crystal skeleton of a composite metal oxide site with photocatalytic and thermocatalytic activity, and the chemical composition of the composite metal silicate catalyst is M m n+ N p q+ SiO x The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is metal in a metal source, M is the molar ratio of metal ions in the metal source to Si in a silicon source, and n is the valence of M; n is metal ion in the alkali source, p is the molar ratio of the metal ion in the alkali source to Si in the silicon source, and q is the valence of N; x is the molar ratio of O to Si, and x= (m×n+p×q+4)/2.
The second purpose of the invention is to provide the composite metal silicate prepared by the method as a catalyst, which is used for catalyzing hydrocarbon liquid phase selective oxidation reaction of a photo-thermal synergistic system to synthesize an oxygen-containing compound with high added value, and the specific method comprises the following steps: mixing the composite metal silicate catalyst with hydrocarbon compound and solvent, adding oxidant into the reactor, stirring and reacting for 0.5-5 hours at 20-140 ℃ under the irradiation of ultraviolet lamp, filtering to remove the catalyst after the reaction is finished, and separating and purifying the filtrate to obtain hydrocarbon oxide; the weight ratio of the hydrocarbon compound to the solvent to the composite metal silicate catalyst is 1:0-20:0.02-0.35.
Further: the solvent is methanol, ethanol, propanol, isopropanol, butanol, tertiary butanol, acetonitrile, acetone, n-hexane, cyclohexane or deionized water; the oxidant is oxygen, mixed gas containing oxygen, hydrogen peroxide water solution, tert-butyl hydroperoxide or cumene hydroperoxide; the hydrocarbon compound is at least one of straight-chain alkane with 1-10 carbon atoms, straight-chain alkene and cyclic alkane with 1-10 carbon atoms.
Compared with the prior art, the invention has the beneficial effects that:
the composite metal silicate catalyst has higher photo-thermal composite catalytic selective oxidation performance and oxygen-containing compound yield, milder reaction conditions and good catalytic stability, and the preparation process is simpler and more efficient and has lower cost by adopting a one-step synthesis method, the quantity and the state of photo-catalytic and thermal catalytic active sites can be effectively regulated, the performance is obviously improved during the liquid phase selective oxidation reaction of the hydrocarbon compound in a catalytic photo-thermal composite system, the high yield of the target oxygen-containing compound at a low reaction temperature is displayed, and the research and application fields of the photo-thermal composite catalyst are further widened.
Drawings
FIG. 1 is a scanning electron microscope image of the composite metal silicate prepared in example 1;
FIG. 2 is an ultraviolet-visible light absorption spectrum of the metal silicate prepared in example 1;
FIG. 3 is an X-ray diffraction pattern of the complex metal silicate prepared in example 2;
FIG. 4 is a transmission electron microscope image of the composite metal silicate prepared in example 2, and the inset is an electron diffraction image thereof;
FIG. 5 is a transmission electron microscope image of the composite metal silicate prepared in example 3;
FIG. 6 is a transmission electron microscope image of the composite metal silicate prepared in example 4.
Detailed Description
The invention mixes silicon source, metal source, alkali source, commercial organic template agent and deionized water, stirs for 0.5-8 hours at 15-150 ℃, then crystallizes for 1-8 days, and the product after crystallization is washed, filtered and dried,Roasting at 300-750 deg.c for 3-10 hr to prepare three-dimensional crystal skeleton with Si and O as main elements, and compounding metal oxide sites with photocatalytic and thermocatalytic activity, and the chemical composition is M m n+ N p q+ SiO x Wherein: m is metal (at least one selected from aluminum, titanium, tin, cobalt and zinc) in a metal source, M is the molar ratio of metal ions in the metal source to Si in a silicon source, and n is the valence of M; n is a metal ion (at least one selected from lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, and hydrogen ion) in the alkali source, p is a molar ratio of the metal ion in the alkali source to Si in the silicon source, and q is a valence of N; x is the molar ratio of O to Si, and x= (m×n+p×q+4)/2.
The preparation and use of the invention are further illustrated by the following specific examples:
example 1
Smoke silica gel (SiO) 2 Calculated by K), potassium carbonate (in K 2 O meter), tetrabutyl titanate (in TiO 2 Meter), and organic template agent A (R) with structural formula shown as formula (A) 1 、R 2 、R 3 Selecting methyl, R 4 Selecting adamantyl and counter anion to select OH - Namely N, N, N-trimethyl-1-adamantylammonium hydroxide), and an organic template agent B (R) with a structural formula shown as a formula (B) 1 、R 2 Is cyclohexyl, R 3 Hydrogen, namely dicyclohexylamine) and deionized water are mixed according to the molar ratio of 0.9:0.08:0.5:0.25:0.3:33.5, stirred for 6 hours at 25 ℃, then crystallized for 5 days at 150 ℃, and the crystallized product is washed, filtered, dried and baked for 6 hours at 600 ℃ to prepare the composite metal silicate.
Referring to fig. 1, the composite metal silicate prepared in example 1 is shown as a flake stack morphology by scanning electron microscopy.
Referring to fig. 2, the composite metal silicate prepared in example 1 shows the presence of framework tetra-coordinated titanium species and anatase species in the sample via uv-vis absorption spectroscopy.
Example 2
30wt.% silica sol in water(in SiO) 2 Meter), sodium hydroxide (in Na 2 O meter), tetrabutyl titanate (in TiO 2 Meter), and organic template agent A (R) with structural formula shown as formula (A) 1 、R 2 、R 3 、R 4 Selecting propyl and counter anions selected from OH - I.e., tetrapropylammonium hydroxide) and deionized water at a molar ratio of 1.0:0.05:0.4:0.35:13.1, stirring at 75 ℃ for 6 hours, crystallizing at 170 ℃ for 3 days, washing, filtering, drying, and calcining at 600 ℃ for 6 hours to obtain the composite metal silicate.
Referring to fig. 3, the X-ray diffraction pattern of the composite metal silicate prepared in example 2 shows good crystallinity.
Referring to fig. 4, the composite metal silicate prepared in example 2 is shown as a nanomaterial around 40nm by transmission electron microscopy.
Example 3
All-silicon MFI molecular sieves (in SiO 2 Calculated by Na), sodium bicarbonate (in terms of Na 2 O meter), titanium sulfate (in TiO form 2 Meter), and organic template agent A (R) with structural formula shown as formula (A) 1 、R 2 、R 3 、R 4 Selecting ethyl, selecting counter anions from OH - Namely tetraethylammonium hydroxide) and deionized water are mixed according to the molar ratio of 1.0:0.12:0.45:0.25:35.0, stirred for 1 hour at the temperature of 25 ℃, then the microwave assisted crystallization is carried out for 12 hours, and the crystallized product is washed, filtered, dried and baked for 6 hours at the temperature of 550 ℃ to prepare the composite metal silicate.
Referring to fig. 5, the composite metal silicate prepared in example 3 is shown as a nanomaterial of about 65nm by transmission electron microscopy.
Example 4
Tetraethyl orthosilicate (in SiO) 2 Meter), sodium hydroxide (in Na 2 O meter), tin chloride (in SnO 2 Meter), and organic template agent A (R) with structural formula shown as formula (A) 1 、R 2 、R 3 、R 4 Selecting ethyl, selecting counter anions from OH - I.e., tetraethylammonium hydroxide) and deionized water were mixed in a molar ratio of 1.0:0.1:0.35:0.5:7.5, and stirred at 100 ℃ for 1 hour, howeverAnd crystallizing at 140 ℃ for 1 day, washing, filtering, drying and roasting the crystallized product at 600 ℃ for 6 hours to obtain the composite metal silicate.
Referring to fig. 6, the composite metal silicate prepared in example 4 is shown as a flower-like cluster morphology by transmission electron microscopy.
Example 5
High si BEA molecular sieves (as SiO 2 Calculated by Na), sodium metaaluminate (calculated by Na 2 O meter), zinc nitrate (ZnO), and organic template agent A (R) with structural formula shown as formula (A) 1 、R 2 Selecting propyl, R 3 、R 4 Selecting methyl, selecting counter anions to be OH - I.e., dimethyl dipropylammonium hydroxide) and deionized water in a molar ratio of 1.0:0.08:0.32:0.53:12.0, stirring for 1 hour at 25 ℃, then ultrasonically crystallizing for 8 hours at 80 ℃, washing, filtering, drying and roasting the crystallized product at 650 ℃ for 6 hours to obtain the composite metal silicate.
Example 6
White carbon black (SiO) 2 Meter), potassium hydroxide (in K 2 O meter), tin tetrachloride (in SnO 2 Meter), and organic template agent A (R) with structural formula shown as formula (A) 1 、R 2 、R 3 Selecting butyl, R 4 Selecting methyl, counter anions selecting I - Namely tributyl methyl ammonium iodide), and an organic template agent B (R) with a structural formula shown as a formula (B) 1 、R 2 Is cyclohexyl, R 3 Hydrogen, namely dicyclohexylamine) and deionized water are mixed according to a molar ratio of 1.0:0.03:0.4:0.22:0.34:41.1, stirred for 6 hours at 25 ℃, then crystallized for 4 days at 160 ℃, and the crystallized product is washed, filtered, dried and baked for 5 hours at 600 ℃ to prepare the composite metal silicate.
Example 7
Tetraethyl orthosilicate (in SiO) 2 Calculated by Na), sodium carbonate (in terms of Na 2 O meter), titanium trichloride (in TiO form 2 Meter), and organic template agent A (R) with structural formula shown as formula (A) 1 、R 2 、R 3 、R 4 Selecting propyl and counter anions to select Br - I.e., tetrapropylammonium bromide) and deionized water in a molar ratio of 1.0:0.05:0.42:0.41:15.0, stirring at 60 ℃ for 5 hours, crystallizing at 140 ℃ for 2 days, washing, filtering, drying, and roasting at 600 ℃ for 6 hours to obtain the composite metal silicate.
Example 8
The composite metal silicate catalyst prepared in the embodiment 1 is applied to cyclohexane oxidation reaction to characterize the catalytic activity of the composite metal silicate catalyst under a photo-thermal composite system, and the specific application is as follows: adding 0.5 g of composite metal silicate catalyst and 8.4 g of cyclohexane into a photocatalytic reactor in sequence, mixing, introducing oxygen into the reaction liquid, replacing air in the reactor, regulating the pressure of the reactor to 0.5MPa, keeping constant, transferring the reactor into a constant-temperature water bath, stirring and reacting for 1 hour at 120 ℃ under illumination, filtering the reaction liquid to separate out a solid catalyst, and separating and purifying filtrate to obtain oxidation products of cyclohexanone and cyclohexanol.
The above products were analyzed by gas chromatography (Shimadzu 2014, fid) and the yield of the oxidized products was 21.1% with the proportions of cyclohexanone and cyclohexanol in the products being 40.5% and 59.5%, respectively.
The catalytic activity of the composite metallosilicate prepared in example 1 compared with that of TS-1 titanosilicate is shown in Table 1 below:
TABLE 1 comparison of catalytic Activity of composite metallosilicates with TS-1 titanosilicates
Catalyst Oxide yield (%) Cyclohexanone Selectivity (%) Cyclohexanol selectivity (%)
Composite metal silicate 21.1％ 40.5％ 59.5％
TS-1 titanosilicate 4.2％ 47.9％ 52.1％
The TS-1 titanosilicate catalyst is synthesized by the method of the patent (CN 112978747A), the Si/Ti molar ratio is 40, the reaction conditions of the catalyst applied to cyclohexane oxidation reaction are the same as those of the example 8, and the gas chromatographic analysis of the two catalysts shows that the catalytic activity of the prepared composite metallosilicate in the light-heat synergistic cyclohexane oxidation reaction is obviously improved.
Example 9
The composite metal silicate catalyst prepared in the embodiment 1 is applied to cyclohexane oxidation reaction to characterize the catalytic activity of the composite metal silicate catalyst under a photo-thermal composite system, and the specific application is as follows: adding 0.5 g of composite metal silicate catalyst and 11.4 g of cyclohexane into a photocatalytic reactor in sequence, mixing, introducing oxygen into the reaction liquid, replacing air in the reactor, regulating the pressure of the reactor to 0.5MPa, keeping constant, transferring the reactor into a constant-temperature water bath, stirring and reacting for 1.5 hours at 95 ℃ under illumination, filtering the reaction liquid to separate out a solid catalyst, and separating and purifying filtrate to obtain oxidation products of cyclohexanone and cyclohexanol.
The above products were analyzed by gas chromatography (Shimadzu 2014, fid) and the yield of the oxidized products was 17.9% with the ratios of cyclohexanone and cyclohexanol in the products being 41.3% and 58.7%, respectively.
The catalytic activity of the composite metallosilicate prepared in example 1 compared with that of TS-1 titanosilicate is detailed in Table 2 below:
TABLE 2 comparison of catalytic Activity of composite metallosilicates with TS-1 titanosilicates
Catalyst Oxide yield (%) Cyclohexanone Selectivity (%) Cyclohexanol selectivity (%)
Composite metal silicate 17.9％ 41.3％ 58.7％
TS-1 titanosilicate 2.7％ 48.6％ 51.4％
The TS-1 titanosilicate catalyst is synthesized by the method of patent (CN 112978747A), the Si/Ti molar ratio is 40, the reaction conditions of the catalyst applied to cyclohexane oxidation reaction are the same as those of example 9, and the gas chromatographic analysis of the two catalysts shows that the catalytic activity of the prepared composite metallosilicate in the light-heat synergistic cyclohexane oxidation reaction is obviously improved.
Example 10
The composite metal silicate catalyst prepared in the embodiment 3 is applied to cyclohexane oxidation reaction to characterize the catalytic activity of the composite metal silicate catalyst under a photo-thermal composite system, and the specific application is as follows: adding 1.0 g of composite metal silicate catalyst and 8.4 g of cyclohexane into a photocatalytic reactor in sequence, mixing, introducing air into the reaction liquid, regulating the pressure of the reactor to 1.0MPa and keeping constant, transferring the reactor into a constant-temperature water bath, stirring and reacting for 1 hour at 100 ℃ under illumination, filtering the reaction liquid to separate out a solid catalyst, and separating and purifying filtrate to obtain oxidation products of cyclohexanone and cyclohexanol.
The above product was analyzed by gas chromatography (Shimadzu 2014, fid) and the yield of the oxidized product was 29.4% with the ratios of cyclohexanone and cyclohexanol in the product being 43.3% and 56.7%, respectively.
The catalytic activity of the composite metal silicate prepared in example 3 compared with that of the composite semiconductor material is shown in Table 3 below:
TABLE 3 composite metallosilicate and Mn 3 O 4 Comparison of the catalytic Activity of CdZnS
Catalyst Oxide yield (%) Cyclohexanone Selectivity (%) Cyclohexanol selectivity (%)
Composite metal silicate 29.4％ 43.3％ 56.7％
Mn 3 O 4 /CdZnS 12.2％ 48.5％ 51.5％
Mn as described above 3 O 4 The reaction conditions of the CdZnS catalyst, which is synthesized by referring to the method of appl. Surf. Sci. 2022,3,579,151978, applied to cyclohexane oxidation reaction as a catalyst are the same as those of the example 10, and the gas chromatographic analysis of the two catalysts shows that the catalytic activity of the composite metallosilicate prepared by the invention in the photo-thermal synergistic cyclohexane oxidation reaction is obviously improved.
Example 11
The composite metal silicate catalyst prepared in the embodiment 1 is applied to cyclohexane oxidation reaction to characterize the catalytic activity of the composite metal silicate catalyst under a photo-thermal composite system, and the specific application is as follows: adding 1.5 g of composite metal silicate catalyst and 12.8 g of cyclohexane into a photocatalytic reactor in sequence, mixing, introducing oxygen into the reaction liquid, replacing air in the reactor, regulating the pressure of the reactor to 0.5MPa, keeping constant, transferring the reactor into a constant-temperature water bath, stirring and reacting for 1 hour under the illumination at the temperature of 100 ℃, filtering the reaction liquid to separate out a solid catalyst, and separating and purifying filtrate to obtain oxidation products of cyclohexanone and cyclohexanol.
The above products were analyzed by gas chromatography (Shimadzu 2014, fid) and the yield of the oxidized products was 32.5% with the ratios of cyclohexanone and cyclohexanol in the products being 39.5% and 60.5%, respectively.
The catalytic activity of the composite metal silicate prepared in example 1 compared with that of the composite semiconductor material is shown in Table 4 below:
TABLE 4 composite metallosilicate and Cr 2 O 3 -Al 2 O 3 Is to be used in the catalytic activity comparison of (a)
Catalyst Oxide yield (%) Cyclohexanone Selectivity (%) Cyclohexanol selectivity (%)
Composite metal silicate 21.1％ 40.5％ 59.5％
Cr 2 O 3 -Al 2 O 3 8.7％ 38.9％ 61.1％
Cr as described above 2 O 3 -Al 2 O 3 The catalyst is synthesized by referring to ACS appl. Mater. Interfaces,2020,12,22531 method, the reaction conditions of the catalyst applied to cyclohexane oxidation reaction are the same as those of example 11, and the gas chromatographic analysis of the two catalysts shows that the catalytic activity of the prepared composite metal silicate in the light-heat synergistic cyclohexane oxidation reaction is obviously improved.
Example 12
The composite metal silicate catalyst prepared in the example 2 is applied to the 1-hexene epoxidation reaction to characterize the catalytic activity of the composite metal silicate catalyst under a photo-thermal composite system, and the specific application is as follows: adding 0.5 g of composite metal silicate catalyst, 79 g of methanol and 8.4 g of 1-hexene into a photocatalytic reactor in sequence, mixing, introducing oxygen into the reaction liquid, replacing air in the reactor, regulating the pressure of the reactor to 0.4MPa and keeping constant, transferring the reactor into a constant temperature water bath kettle, stirring and reacting for 2 hours at 60 ℃ under the illumination, filtering the reaction liquid to separate out a solid catalyst, and separating and purifying filtrate to obtain an oxidation product of 1, 2-epoxyhexane.
The above product was analyzed by gas chromatography (Shimadzu 2014, fid) to give a yield of 5.1% and a selectivity of 90.7% for 1, 2-epoxyhexane.
The catalytic activity of the composite metallosilicate prepared in example 2 compared with that of TS-1 titanosilicate is detailed in Table 5 below:
TABLE 5 comparison of catalytic Activity of composite metallosilicates with TS-1 titanosilicates
Catalyst Yield of 1, 2-epoxyhexane (%) 1, 2-epoxyhexane Selectivity (%)
Composite metal silicate 5.1％ 90.7％
TS-1 titanosilicate 0.5％ 75.8％
The TS-1 titanosilicate catalyst is synthesized by the method of patent (CN 112978747A), the Si/Ti molar ratio is 40, the reaction conditions of the catalyst applied to the epoxidation of 1-hexene are the same as those of example 12, and the gas chromatographic analysis of the two catalysts shows that the catalytic activity of the prepared composite metallosilicate in the oxidation of cyclohexane by photo-thermal synergy is obviously improved.
Example 13
The composite metal silicate catalyst prepared in the example 1 is applied to the 1-hexene epoxidation reaction to characterize the catalytic activity of the composite metal silicate catalyst under a photo-thermal composite system, and the specific application is as follows: adding 0.5 g of composite metal silicate catalyst, 79 g of methanol and 8.4 g of 1-hexene into a photocatalytic reactor in sequence, mixing, introducing oxygen into the reaction liquid, replacing air in the reactor, regulating the pressure of the reactor to 0.5MPa and keeping constant, transferring the reactor into a constant temperature water bath kettle, stirring and reacting for 2 hours at 45 ℃ under the illumination, filtering the reaction liquid to separate out a solid catalyst, and separating and purifying filtrate to obtain an oxidation product of 1, 2-epoxyhexane.
The above product was analyzed by gas chromatography (Shimadzu 2014, fid) to yield 3.4% of 1, 2-epoxyhexane with a selectivity of 87.9%.
The catalytic activity of the composite metallosilicate prepared in example 1 compared with that of TS-1 titanosilicate is detailed in Table 6 below:
TABLE 6 comparison of catalytic Activity of composite metallosilicates with TS-1 titanosilicates
Catalyst Yield of 1, 2-epoxyhexane (%) 1, 2-epoxyhexane Selectivity (%)
Composite metal silicate 3.4％ 87.9％
TS-1 titanosilicate 0.2％ 79.4％
The TS-1 titanosilicate catalyst is synthesized by the method of patent (CN 112978747A), the Si/Ti molar ratio is 40, the reaction conditions of the catalyst applied to the epoxidation of 1-hexene are the same as those of example 13, and the gas chromatographic analysis of the two catalysts shows that the catalytic activity of the prepared composite metallosilicate in the oxidation of cyclohexane by photo-thermal synergy is obviously improved.
Example 14
The composite metal silicate catalyst prepared in the above example 7 is applied to the 1-hexene epoxidation reaction to characterize the catalytic activity under a photo-thermal composite system, and the specific application is as follows: 1.0 g of composite metal silicate catalyst, 79 g of methanol and 11.4 g of 1-hexene are sequentially added into a photocatalytic reactor and mixed, 10.9 g of hydrogen peroxide aqueous solution (27.5 wt.%) is added, the reactor is transferred into a constant temperature water bath kettle, the mixture is stirred and reacted for 2 hours under the condition of illumination at 60 ℃, the solid catalyst is separated out from the reaction liquid through filtration, and the filtrate is separated and purified to obtain the oxidized product 1, 2-epoxyhexane.
The above product was analyzed by gas chromatography (Shimadzu 2014, fid) and the yield of 1, 2-epoxyhexane was 33.7% and the selectivity was 94.2%.
The catalytic activity of the composite metallosilicate prepared in example 7 compared with that of TS-1 titanosilicate is shown in Table 7 below:
TABLE 7 comparison of catalytic Activity of composite metallosilicates with TS-1 titanosilicates
Catalyst Yield of 1, 2-epoxyhexane (%) 1, 2-epoxyhexane Selectivity (%)
Composite metal silicate 33.7％ 94.2％
TS-1 titanosilicate 18.6％ 93.1％
The TS-1 titanosilicate catalyst is synthesized by the method of patent (CN 112978747A), the Si/Ti molar ratio is 40, the reaction conditions of the catalyst applied to the epoxidation of 1-hexene are the same as those of the example 14, and the gas chromatographic analysis of the two catalysts shows that the catalytic activity of the prepared composite metallosilicate in the photo-thermal synergistic cyclohexane oxidation reaction is obviously improved.
The present invention is not limited to the above embodiments, and variations and advantages which can be conceived by those skilled in the art are included in the present invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is defined.

Claims (10)

1. A one-step synthesis method of photo-thermal synergistic catalyst for liquid phase selective oxidation reaction, which is characterized in that: mixing a silicon source, a metal source, an alkali source, a commercial organic template agent and deionized water, stirring for 0.5-8 hours at 15-150 ℃, crystallizing for 1-8 days, washing, filtering, drying and roasting at 300-750 ℃ for 3-10 hours to obtain the composite metal silicate catalyst, namely the photo-thermal synergistic catalyst for liquid phase selective oxidation reaction.
2. The one-step synthesis method according to claim 1, wherein: the silicon source is SiO 2 Meter, metal source with M m n+ O is measured, and alkali source is N p q+ Mole ratio of O meter to commercial organic template and deionized water0.4-0.9:0.02-0.5:0-0.4:0.01-1.0:2-200, wherein: m is metal in a metal source, M is the molar ratio of metal ions in the metal source to Si in a silicon source, and n is the valence of M; n is metal ion in the alkali source, p is the molar ratio of the metal ion in the alkali source to Si in the silicon source, and q is the valence of N.
3. The one-step synthesis method according to claim 1, wherein: the silicon source is at least one of tetraethyl silicate, silica sol, fuming silica gel, white carbon black, water glass, silicon dioxide microspheres and molecular sieves; the metal source is at least one of oxides, sulfates, nitrates, phosphates, carbonates, chloride salts or metal-containing organic matters of aluminum, titanium, tin, cobalt and/or zinc; the alkali source is at least one of sodium hydroxide, sodium metaaluminate, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the organic template agent is at least one of a quaternary ammonium salt or a quaternary ammonium base form of a compound shown in a structural formula (A) or a compound shown in a structural formula (B):
in formula (A): r is R 1 、R 2 、R 3 And R is 4 Each independently selected from linear or cyclic C 1-10 An alkyl group;
in formula (B): r is R 5 、R 6 And R is 7 Each independently selected from linear or cyclic C 1-10 An alkyl group.
4. A one-step synthesis method according to claim 3, wherein: the topology of the molecular sieve that can be used as the silicon source includes at least one of MFI, BEA, MWW, MOR, FAU, and FER.
5. The one-step synthesis method according to claim 1, wherein: the crystallization implementation method comprises at least one of heating, ultrasonic, illumination and microwaves.
6. A one-step synthesis method according to claim 3, wherein: the quaternary ammonium salt form of the compound of formula (A), its quaternary nitrogen (N) + ) The balance anion of the structure is halogen ion; a quaternary ammonium base form of a compound of formula (A), a quaternary nitrogen (N) + ) The counter anion of the structure is hydroxide ion.
7. A composite metal silicate catalyst obtainable by the one-step synthesis process of any one of claims 1 to 6, characterized in that: adopts silicon and oxygen as main elements and connects them in tetrahedral form to form a three-dimensional crystal skeleton with metal oxide sites with photocatalytic and thermocatalytic activities, its chemical composition is M m n+ N p q+ SiO x The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is metal in a metal source, M is the molar ratio of metal ions in the metal source to Si in a silicon source, and n is the valence of M; n is metal ion in the alkali source, p is the molar ratio of the metal ion in the alkali source to Si in the silicon source, and q is the valence of N; x is the molar ratio of O to Si, and x= (m×n+p×q+4)/2.
8. Use of the composite metal silicate catalyst according to claim 7, characterized in that: the composite metal silicate catalyst is used for hydrocarbon liquid phase selective oxidation reaction of a photo-thermal synergistic system.
9. The use according to claim 8, wherein the composite metal silicate catalyst is specifically applied by the following method: mixing the composite metal silicate catalyst with hydrocarbon compound and solvent, adding oxidant into the reactor, stirring and reacting for 0.5-5 hours at 20-140 ℃ under the irradiation of ultraviolet lamp, filtering to remove the catalyst after the reaction is finished, and separating and purifying the filtrate to obtain hydrocarbon oxide; the weight ratio of the hydrocarbon compound to the solvent to the composite metal silicate catalyst is 1:0-20:0.02-0.35.
10. The use according to claim 9, characterized in that: the solvent is methanol, ethanol, propanol, isopropanol, butanol, tertiary butanol, acetonitrile, acetone, n-hexane, cyclohexane or deionized water; the oxidant is oxygen, mixed gas containing oxygen, hydrogen peroxide water solution, tert-butyl hydroperoxide or cumene hydroperoxide; the hydrocarbon compound is at least one of straight-chain alkane with 1-10 carbon atoms, straight-chain alkene and cyclic alkane with 1-10 carbon atoms.
CN202311530334.5A 2023-11-16 2023-11-16 Photo-thermal synergistic catalyst for liquid phase selective oxidation reaction and one-step synthesis method thereof Pending CN117566751A (en)

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