WO2022042636A1 - 一种锡钛硅分子筛及其制备方法和应用 - Google Patents

一种锡钛硅分子筛及其制备方法和应用 Download PDF

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WO2022042636A1
WO2022042636A1 PCT/CN2021/114731 CN2021114731W WO2022042636A1 WO 2022042636 A1 WO2022042636 A1 WO 2022042636A1 CN 2021114731 W CN2021114731 W CN 2021114731W WO 2022042636 A1 WO2022042636 A1 WO 2022042636A1
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tin
titanium
molecular sieve
source
silicon
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PCT/CN2021/114731
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English (en)
French (fr)
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夏长久
刘聿嘉
彭欣欣
林民
朱斌
舒兴田
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Priority to US18/042,365 priority Critical patent/US20230356202A1/en
Priority to EP21860470.0A priority patent/EP4206134A1/en
Priority to KR1020237010728A priority patent/KR20230058145A/ko
Priority to JP2023513998A priority patent/JP2023539882A/ja
Publication of WO2022042636A1 publication Critical patent/WO2022042636A1/zh

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Definitions

  • the invention relates to a tin-titanium-silicon molecular sieve and a preparation method and application thereof.
  • heteroatom molecular sieves show the incomparable advantages of conventional methods.
  • TS-1 molecular sieve for the first time.
  • People successively inserted other heteroatoms such as Fe, Sn, V, Zr and Ga, etc.
  • heteroatoms such as Fe, Sn, V, Zr and Ga, etc.
  • the Sn-containing molecular sieve uniformly inserts the four-coordinated tin atoms into the molecular sieve framework space structure through isomorphous substitution, which endows it with unique acid catalytic performance and becomes a heteroatom molecular sieve catalytic material with important potential industrial application value.
  • the empty orbital of the four-coordinated tin atom in the framework can accept lone pair electrons and has strong activation performance for oxygen-containing functional groups. Therefore, tin-silicon molecular sieves show good catalytic performance in solid Lewis acid catalysis reactions. It is often used in saccharide isomerization, preparation of milk powder and its derivatives, Baeyer-Villiger reaction and Meerwein-Ponndorf-Verley Oxidation reaction.
  • tin-silicon molecular sieves include Sn-MFI, Sn-BEA, Sn-MEL, Sn-MWW, Sn-USY, etc.
  • Sn-MFI molecular sieve not only has the acid catalytic function of tin, but also has the shape-selective effect of ZSM-5 molecular sieve.
  • Tin-silicon molecular sieves contain limited four-coordinate framework tin active centers.
  • tin atoms may It is deposited on the surface of molecular sieve particles, which leads to the inability to uniformly insert into the tin-silicon molecular sieve framework and produce SnO2 aggregates.
  • the purpose of the present invention is to provide a tin-titanium-silicon molecular sieve and a preparation method and application thereof.
  • the tin-titanium-silicon molecular sieve of the present invention has more catalytic active centers and better catalytic performance.
  • the first aspect of the present invention provides a tin-titanium-silicon molecular sieve, wherein the electron binding energy of the active center of the framework tin in the tin-titanium-silicon molecular sieve is below 488.5 eV.
  • the molar ratio of titanium to silicon in the tin-titanium-silicon molecular sieve is 0.005-0.03, and/or the molar ratio of tin to silicon is 0.005-0.025.
  • the electron binding energy of the framework tin active center is 488.0-488.4 eV.
  • the electron binding energy of the active center of the framework titanium in the tin-titanium-silicon molecular sieve is 460.0-461.2 eV.
  • the phosphorus chemical shift data corresponding to the adsorption of the double quantum nuclear magnetic framework tin species by the trimethylphosphine probe molecules in the tin-titanium-silicon molecular sieve is ⁇ -23ppm.
  • the phosphorus chemical shift data corresponding to the adsorption of trimethylphosphine probe molecules in the tin-titanium-silicon molecular sieve to the titanium species of the double quantum nuclear magnetic framework is ⁇ -34ppm.
  • the external specific surface area of the tin-titanium-silicon molecular sieve is 100-150 m 2 /g, and the total pore volume is 0.25-0.35 cm 3 /g.
  • the tin-titanium-silicon molecular sieve is Sn-Ti-MFI molecular sieve or Sn-Ti-MEL molecular sieve.
  • the Sn-Ti-MEL molecular sieve has a structure in which elongated crystal grains are cross-stacked, and preferably, the crystal grains are 10-50 nm long and 10-30 nm wide.
  • the second aspect of the present invention provides a method for preparing the tin-titanium-silicon molecular sieve provided by the first aspect of the present invention, the method comprising:
  • organic silicon source, organic base, solvent, tin source, titanium source and basic template agent are mixed, obtain the first mixture;
  • described organic base is tetrapropylammonium hydroxide and/or tetrabutylammonium hydroxide;
  • the molar ratio of the amount of the organosilicon source, the organic base, the solvent, the tin source and the titanium source is 1:(0.05-0.6):(10-30):(0.005-0.04):( 0.005-0.04), wherein the organosilicon source is calculated as SiO 2 , the tin source is calculated as SnO 2 , and the titanium source is calculated as TiO 2 ;
  • the molar ratio of the tin source to the amount of the alkaline template agent is 1:(1-10), the tin source is calculated as anion;
  • the second mixture is subjected to a hydrothermal reaction at 120-200° C. for 2-7 days to obtain a third mixture;
  • the molar ratio of the tin source to the amount of the basic template agent is 1:(4-8).
  • the molar ratio of the amount of the organosilicon source, the organic base, the solvent, the tin source and the titanium source is 1:(0.1-0.4):(15-30):(0.01- 0.03): (0.01-0.03).
  • step S1 includes: mixing the organosilicon source, the organic base, the solvent and the titanium source to obtain a fourth mixture, and mixing and stirring the obtained fourth mixture with the tin source for 0.5-2 After 1 hour, the basic templating agent is further added to obtain the first mixture.
  • the organosilicon source has the structure shown in the following formula (I),
  • R 1 , R 2 , R 3 and R 4 are each independently selected from C1-C4 alkyl groups, such as C1-C4 straight-chain alkyl groups and C3-C4 branched-chain alkyl groups; preferably normal One or more of tetramethyl silicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate and tetra-n-butyl orthosilicate; more preferably tetraethyl orthosilicate and/or orthosilicate tetramethyl ester;
  • the solvent is selected from deionized water and/or distilled water;
  • the basic template agent is selected from one or more of ammonia, aliphatic amines, aliphatic alcohol amines and quaternary ammonium bases; preferably ammonia water, ethylamine, tetrapropylammonium hydroxide and triethanolamine one or more of them;
  • the tin source is selected from tin chloride, tin chloride pentahydrate, stannous chloride, stannous chloride dihydrate, calcium stannate, potassium stannate, sodium stannate, lithium stannate, sulfite
  • tin chloride pentahydrate stannous chloride, stannous chloride dihydrate
  • calcium stannate potassium stannate
  • sodium stannate lithium stannate
  • sulfite One or more of tin and stannous pyrophosphate; preferably tin chloride pentahydrate;
  • the titanium source has the structure shown in the following formula (II),
  • R 1 ', R 2 ', R 3 ' and R 4 ' are each independently selected from C1-C6 alkyl groups, such as C1-C6 straight chain alkyl groups and C3-C6 branched chain alkyl groups
  • the titanium source is preferably one or more of tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.
  • the conditions for the hydrothermal reaction in S3 include: a temperature of 120-170° C. and a time of 2-5 days.
  • the third aspect of the present invention provides an application of the tin-titanium-silicon molecular sieve provided in the first aspect of the present invention in the preparation of lactate from dihydroxyacetone, aldehyde and ketone ammoximation reaction, olefin epoxidation reaction or aromatic/alkane oxidation reaction.
  • the fourth aspect of the present invention provides a catalyst containing the tin-titanium-silicon molecular sieve provided in the first aspect of the present invention.
  • the tin-titanium-silicon molecular sieve of the present invention has many catalytic active centers, the electron binding energy of the framework tin is shifted to a low value, and the electron cloud density is increased, which is beneficial to improve the catalytic performance of the molecular sieve.
  • Fig. 1 is the XPS figure of the tin-titanium-silicon molecular sieve prepared in Example 1 of the present invention
  • a first aspect of the present invention provides a tin-titanium-silicon molecular sieve, wherein the electron binding energy of the framework tin active center in the tin-titanium-silicon molecular sieve is below 488.5 eV.
  • the molar ratio of titanium to silicon in the tin-titanium-silicon molecular sieve may be 0.005-0.03, preferably 0.005-0.02, and/or the molar ratio of tin to silicon may be 0.005-0.025, preferably 0.005-0.02.
  • framework tin refers to tin atoms capable of inserting into the framework of the molecular sieve.
  • the tin-titanium-silicon molecular sieve of the present invention also contains framework titanium on the basis of containing framework tin, which can further increase the type and quantity of Lewis acid of the molecular sieve, increase the catalytic active center, and the electron binding energy of framework tin in the molecular sieve of the present invention is relatively high.
  • the electron binding energy of the framework tin active center is 488.0-488.4 eV.
  • the electron binding energy of the framework titanium active center is 460.8-461.2 eV.
  • the external specific surface area of the tin-titanium-silicon molecular sieve can be 100-150 m 2 /g
  • the total pore volume can be 0.25-0.35 cm 3 /g
  • the external specific surface area is 100-140 m 2 /g
  • the total pore volume can be 100-140 m 2 /g
  • the volume is 0.27-0.32 cm 3 /g.
  • External specific surface area refers to the total area (except the micropore surface area) possessed by the molecular sieve per unit mass of material.
  • the tin-titanium-silicon molecular sieve can be Sn-Ti-MFI molecular sieve or Sn-Ti-MEL molecular sieve.
  • the Sn-Ti-MEL molecular sieve has a structure in which elongated crystal grains are cross-stacked, and the length of the crystal grains may be 10-50 nm and the width may be 10-30 nm.
  • the elongated shape means that the aspect ratio of the molecular sieve grains is greater than 1, preferably greater than 1.5, more preferably greater than 2.
  • the grain cross-stacking structure refers to the random stacking and overlapping morphological structure of the Sn-MEL molecular sieves observed by high-resolution transmission electron microscopy.
  • the second aspect of the present invention provides a method for preparing the tin-titanium-silicon molecular sieve provided by the first aspect of the present invention, the method comprising:
  • organic silicon source organic base, solvent, tin source, titanium source and basic template agent are mixed, obtain the first mixture;
  • organic base is tetrapropylammonium hydroxide and/or tetrabutylammonium hydroxide;
  • the molar ratio of the organic silicon source, the organic base, the solvent, the tin source and the titanium source is 1:(0.05-0.6):(10-30):(0.005-0.04):(0.005- 0.04), wherein the organosilicon source is calculated as SiO 2 , the tin source is calculated as SnO 2 , and the titanium source is calculated as TiO 2 ;
  • the molar ratio of the tin source to the amount of the alkaline template agent is 1: (1-10), the tin source is calculated as an anion;
  • the second mixture is subjected to a hydrothermal reaction at 120-200° C. for 2-7 days to obtain a third mixture;
  • the method of the invention can increase the molar ratio of tin to silicon and the molar ratio of titanium to silicon in the tin-titanium-silicon molecular sieve, and makes the electron binding energy of the skeleton tin shift to a low value, increases the density of the electron cloud, and the prepared tin-titanium-silicon Molecular sieves have excellent catalytic properties for the preparation of lactate esters from dihydroxyacetone, aldehyde and ketone ammoximation reactions, olefin epoxidation reactions or aromatic/alkane oxidation reactions.
  • the molar ratio of the amount of organic silicon source, organic base, solvent, tin source and titanium source can be 1:(0.1-0.4):(15-30):(0.01-0.03):(0.01 -0.03), wherein the organosilicon source is calculated as SiO2 , the tin source is calculated as SnO2 , and the titanium source is calculated as TiO2 .
  • the molar ratio of the tin source and the amount of the basic template agent is preferably 1: (4-8), more preferably, the molar ratio of the tin source and the amount of the basic template agent is 1: (4-6), the tin source In terms of anions.
  • step S1 may include: mixing an organosilicon source, an organic base, a solvent and a titanium source to obtain a fourth mixture, and after mixing and stirring the obtained fourth mixture with a tin source for 0.5-2 hours, Additional basic templating agent is added to obtain a first mixture.
  • step S2 may include: heating the first mixture at 50-80° C. for 5-8 hours under stirring to obtain the second mixture.
  • Stirring can be in a manner conventionally used by those skilled in the art, such as mechanical stirring, electromagnetic stirring and the like.
  • the method for taking out the solid in the third mixture is not particularly limited, for example, filtration, centrifugal separation and other methods may be used.
  • the removed solid is washed and then dried and calcined.
  • the solution used for washing is not limited, and can be any liquid that does not react with solids, such as deionized water. Drying and roasting are operations well known to those skilled in the art.
  • the drying can be in a constant temperature drying oven, and the drying conditions can include: the temperature is 50-150°C, and the time is 2-10 hours, Preferably 3-10 hours; the roasting can be in a muffle furnace or a tube furnace, and the roasting conditions can include: the temperature is 550-750 ° C, the time is 3-10 hours, and the atmosphere is an air atmosphere or an inert atmosphere, wherein the inert atmosphere It contains nitrogen and/or inert gas, and the inert gas can be argon, helium, etc.
  • the organosilicon source may have the structure shown in formula (I),
  • R 1 , R 2 , R 3 and R 4 are each independently selected from C1-C4 alkyl groups, and the C1-C4 alkyl groups may include C1-C4 straight-chain alkyl groups and C3-C4 alkyl groups
  • the branched alkyl group of for example, can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
  • the organosilicon source is one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate and tetra-n-butyl orthosilicate; More preferably, it is tetraethylorthosilicate and/or tetramethylorthosilicate.
  • the titanium source may have the structure shown in the following formula (II),
  • R 1 ', R 2 ', R 3 ' and R 4 ' are each independently selected from C1-C6 alkyl groups, and the C1-C6 alkyl groups may include C1-C6 straight-chain alkyl groups and C3-C6 branched chain alkyl; in a preferred embodiment, the titanium source is tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate one or more of them.
  • the basic template agent can be selected from one or more of ammonia, aliphatic amines, aliphatic alcohol amines and quaternary ammonium bases; preferably ammonia water, ethylamine, tetrapropylammonium hydroxide and triethanolamine one or more of them.
  • the aliphatic amine can be a compound formed after at least one hydrogen in various NH 3 is replaced by an aliphatic hydrocarbon group (preferably an alkyl group)
  • the aliphatic alcohol amine can be a compound formed by replacing at least one hydrogen in various NH 3 with a hydroxyl group The compound formed by the substitution of the aliphatic hydrocarbon group (preferably an alkyl group).
  • the quaternary ammonium base can be an organic quaternary ammonium base, and the organic quaternary ammonium base has a structure as shown in formula (III) Formula (III), wherein R 5 , R 6 , R 7 and R 8 are each independently an alkyl group having 1-4 carbon atoms, and the alkyl group may include a straight-chain alkyl group having 1-4 carbon atoms and a branched alkyl group having 3 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
  • formula (III) Formula (III) wherein R 5 , R 6 , R 7 and R 8 are each independently an alkyl group having 1-4 carbon atoms, and the alkyl group may include a straight-chain alkyl group having 1-4 carbon atoms and a branched alkyl group having 3 to 4 carbon
  • the aliphatic amine has the structure shown in formula (IV), R 9 (NH 2 ) n of formula (IV), wherein n is 1 or 2.
  • R 9 can be an alkyl group with 1-6 carbon atoms, and the alkyl group can include a straight-chain alkyl group with 1-6 carbon atoms and a branched-chain alkane with 3-6 carbon atoms
  • the group for example, can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, and isopentyl.
  • R9 can be an alkylene group with 1-6 carbon atoms, and the alkylene group can include a straight-chain alkyl group with 1-6 carbon atoms and a branched chain with 3-6 carbon atoms
  • the alkylene group may be, for example, a methylene group, an n-propylene group, an n-butylene group, and an n-pentylene group.
  • the aliphatic amine compound is one or more of ethylamine, n-butylamine and butanediamine.
  • the aliphatic alcohol amine has the structure shown in formula (V), (HOR 1u ) m (NH) 3m formula (V), wherein m is 1, 2 or 3, and m R 10 Can be the same or different, each independently selected from alkylene groups with 1-4 carbon atoms, the alkylene group can include straight-chain alkylene groups with 1-4 carbon atoms and alkylene groups with 3-4 carbon atoms Branched alkylene groups, for example, may be methylene, ethylene, n-propylene and n-butylene.
  • the aliphatic alcoholamine compound is one or more of monoethanolamine, diethanolamine and triethanolamine.
  • the solvent may be selected from deionized water and/or distilled water.
  • the tin source can be any water-soluble inorganic tin salt, preferably self-tin chloride, tin chloride pentahydrate, stannous chloride, stannous chloride dihydrate, calcium stannate, potassium stannate, tin One or more of sodium, lithium stannate, stannous sulfate and stannous pyrophosphate; more preferably tin chloride pentahydrate.
  • the hydrothermal reaction is well known to those skilled in the art, for example, it can be carried out in an autoclave.
  • the pressure of the hydrothermal reaction is not specifically limited, and it can be the autogenous pressure of the reaction, or it can be an additional pressure applied to pressure of the reaction system.
  • the conditions of the hydrothermal reaction may include: a temperature of 120-170° C. and a time of 2-5 days.
  • the third aspect of the present invention provides an application of the tin-titanium-silicon molecular sieve provided in the first aspect of the present invention in the preparation of lactate from dihydroxyacetone, aldehyde and ketone ammoximation reaction, olefin epoxidation reaction or aromatic/alkane oxidation reaction.
  • dihydroxyacetone is used to prepare lactate
  • solvent used for dihydroxyacetone to prepare lactate is well known to those skilled in the art, such as lower alcohol, More specifically, methanol, ethanol, propanol, butanol and the like can be used.
  • the present invention provides the application of a tin-titanium-silicon molecular sieve in the preparation of methyl lactate from dihydroxyacetone, and the solvent is methanol.
  • the solvent used is well known to those skilled in the art, for example, it can be a lower alcohol, more specifically, methanol, ethanol, isopropanol, tert-butanol and the like.
  • the solvent used is well known to those skilled in the art, for example, it can be a lower alcohol, more specifically, methanol, ethanol, isopropanol, tert-butanol and the like.
  • the solvent used is well known to those skilled in the art, for example, it can be a lower alcohol, more specifically, methanol, ethanol, isopropanol, tert-butanol and the like.
  • the fourth aspect of the present invention provides a catalyst containing the tin-titanium-silicon molecular sieve provided in the first aspect of the present invention.
  • Tetraethyl orthosilicate was purchased from Hunan Jianchang Petrochemical Co., Ltd.
  • tetrabutyl titanate was purchased from Hunan Jianchang Petrochemical Co., Ltd.
  • tetrabutylammonium hydroxide was purchased from Beijing Inoke Technology Co., Ltd.
  • tin chloride pentahydrate was purchased from Beijing Inuokai Technology Co., Ltd.
  • tetrapropyl ammonium hydroxide was purchased from Beijing Inuokai Technology Co., Ltd.
  • dihydroxyacetone was purchased from Beijing Inuokai Technology Co., Ltd.
  • methanol was purchased from Beijing Inuokai Technology Co., Ltd.
  • chlorinated Stannous was purchased from Beijing Enoke Technology Co., Ltd.
  • stannous chloride dihydrate was purchased from Beijing Enoke Technology Co., Ltd.
  • triethanolamine was purchased from Beijing Enoke Technology Co.
  • the electron binding energy of the framework titanium active center in the molecular sieve was obtained by XPS characterization
  • Double quantum NMR analysis uses trimethyl phosphine as the probe molecule. After pretreatment of the sample, trimethyl phosphine is adsorbed on the molecular sieve, and then the 31 P and 1 H NMR spectra are measured. Figure 31 P- 31 P or 31 P- 1 H correlation to obtain the double quantum nuclear magnetic analysis spectrum;
  • the molar ratio of titanium and silicon, the molar ratio of tin and silicon in the molecular sieve are measured by XRF method;
  • the length and width of the grains were characterized by high-resolution (50nm resolution) transmission electron microscopy.
  • the yield of methyl lactate in the test example was analyzed by gas chromatography, and the analysis result was quantified by an internal standard method, and the internal standard was naphthalene.
  • the chromatographic analysis conditions are: Agilent-6890 chromatograph, HP-5 capillary chromatographic column, injection volume 0.5 ⁇ L, and injection port temperature 280°C. The column temperature was held at 100°C for 2 min, then increased to 200°C at a rate of 15°C/min and held for 3 min. FID detector, detector temperature 300 °C.
  • the first mixture is placed on a magnetic stirrer with a reaction temperature of 70 ° C and heated to drive off alcohol for 6 hours to obtain the second mixture;
  • the second mixture is placed in a stainless steel sealed reaction kettle, and the crystallization reaction is carried out at 160° C. and autogenous pressure for 3 days to obtain the third mixture;
  • Sn-Ti-MFI molecular sieve was prepared according to the method of Example 1, and its proportion, synthesis conditions and material proportions were as described in Table 1; Synthesis conditions refer to Example 1.
  • the second mixture is placed in a stainless steel sealed reaction kettle, and the crystallization reaction is carried out at 160° C. and autogenous pressure for 3 days to obtain the third mixture;
  • Sn-Ti-MEL molecular sieve was prepared according to the method of Example 22, and its proportion, synthesis conditions and material proportion were as described in Table 1; Synthesis conditions refer to Example 22.
  • the Sn-Ti-MFI molecular sieve was prepared by a hydrothermal method.
  • the dosage of TEOS was 15.31 g
  • the dosage of TPAOH was 33.67 g
  • the dosage of SnCl 4 .5H 2 O was 0.38 g
  • the dosage of TBOT was 0.38 g
  • the dosage of water was 39.64 g.
  • the XPS diagram of the prepared Sn-Ti-MFI molecular sieve is shown in Figure 2.
  • the Sn-Ti-MEL molecular sieve was prepared by a hydrothermal method.
  • the dosage of TEOS was 15.31 g
  • the dosage of TBAOH was 42.96 g
  • the dosage of SnCl 4 .5H 2 O was 0.38 g
  • the dosage of TBOT was 0.38 g
  • the dosage of water was 39.64 g.
  • Sn-Ti-MFI molecular sieve was prepared according to the method of Comparative Example 1, and its proportion, synthesis conditions and material proportions were as described in Table 1; Synthesis conditions refer to Comparative Example 1.
  • the reaction of preparing methyl lactate catalyzed by dihydroxyacetone was carried out.
  • the specific reaction conditions are as follows: in a slurry bed reactor, the reactant dihydroxyacetone and solvent methanol are in a molar ratio of 1:200, the amount of catalyst is 3.0% by weight of the total reaction solution, and the reaction is carried out at 60 ° C and autogenous pressure. , the composition of the product is determined by sampling every 1 hour of the reaction, and the calculation results are shown in Table 2.
  • R is selected from alkyl and aryl, such as phenyl, and R1 is selected from hydrogen and alkyl, or R and R1 taken together form a ring.
  • the specific reaction conditions are as follows: in the slurry bed reactor, the reactants aldehydes and ketones, hydrogen peroxide and solvent (such as tert-butanol) are 1: 1: 200 according to the molar ratio, and the amount of the catalyst is 5.0% by weight of the total reaction solution, The reaction was carried out at 80° C. and autogenous pressure, and the composition of the product was determined by sampling every 1 hour of the reaction. The results are shown in Table 3.
  • R 1 and R 2 are independently selected from hydrogen and an alkyl group optionally containing a heteroatom (eg, oxygen), or R 1 and R 2 are taken together to form a ring.
  • the specific reaction conditions are as follows: in the slurry bed reactor, the reactant olefin, hydrogen peroxide and solvent (such as tert-butanol) are 1: 1: 200 according to the molar ratio, and the amount of the catalyst is 5.0% by weight of the total reaction solution.
  • the reaction was carried out at 50° C. and autogenous pressure, and the composition of the product was determined by sampling every 1 hour of the reaction. The results are shown in Table 3.
  • R is selected from hydrogen, alkyl and hydroxyl, where R may represent two substituents, R1 and R2 are independently selected from hydrogen and alkyl, or R1 and R2 taken together form an optionally alkyl - substituted ring.
  • the specific reaction conditions are as follows: in the slurry bed reactor, the reactant (aromatic hydrocarbon or alkane), hydrogen peroxide and solvent (such as tert-butanol) are 1: 1: 200 in a molar ratio, and the amount of the catalyst is 5.0% of the total reaction solution. % by weight, the reaction was carried out at 80° C. and autogenous pressure, and the composition of the product was determined by sampling every 1 hour of the reaction. The results are shown in Table 3.
  • organosilicon source titanium source: organic base: solvent refers to the molar ratio of the amount of organosilicon source, titanium source, organic base and solvent
  • organosilicon source: tin source refers to the molar amount of organosilicon source and tin source.
  • the ratio, tin source: basic template refers to the molar ratio of the amount of tin source and basic template.
  • the tin-titanium-silicon molecular sieve of the invention has more active centers, lower electron binding energy of skeleton tin, and higher catalytic activity.

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Abstract

本发明涉及一种锡钛硅分子筛及其制备方法和应用，锡钛硅分子筛中骨架锡活性中心的电子结合能为488.5eV以下。锡钛硅分子筛中钛与硅的摩尔比优选为0.005-0.03，锡与硅的摩尔比优选为0.005-0.025。本发明的锡钛硅分子筛催化活性中心较多，骨架锡活性中心的电子结合能较低，具有较优的催化性能。

Description

一种锡钛硅分子筛及其制备方法和应用 技术领域
本发明涉及一种锡钛硅分子筛及其制备方法和应用。
背景技术
近年来，在工业生产过程中，非均相催化剂具有可重复利用和易分离等优点而引起了人们的高度重视。在含氧烃环境友好转化反应中，杂原子分子筛展示出了常规方法无可比拟的优势。1983年，Taramasso等首次合成TS-1分子筛，人们陆续将其它杂原子(如Fe、Sn、V、Zr和Ga等)***到分子筛拓扑结构中，制备出了多种杂原子分子筛。含Sn分子筛通过同晶取代作用将四配位锡原子均匀***到分子筛骨架空间结构中，赋予了其独特的酸催化性能，成为具有重要潜在工业应用价值的杂原子分子筛催化材料。骨架四配位锡原子的空轨道可以接受孤对电子，对含氧官能团具有较强的活化性能，因此锡硅分子筛在固体Lewis酸催化反应中展现出了良好的催化性能。常应用于糖类异构化反应、制备乳散及其衍生物反应、Baeyer-Villiger反应及Meerwein-Ponndorf-Verley Oxidation反应。
常见的锡硅分子筛包括Sn-MFI、Sn-BEA、Sn-MEL、Sn-MWW、Sn-USY等。1994年，Ramaswamy等通过水热法首次合成了Sn-MFI分子筛。Sn-MFI分子筛不但具有锡的酸催化功能，而且还具有ZSM-5分子筛的择形作用。但是，水热法合成锡硅分子筛时采用的无机锡源都带有一定酸性，其对分子筛合成的碱性环境产生一定影响，导致锡源投料较多时，分子筛无法结晶，因此，水热合成的锡硅分子筛含有的四配位骨架锡活性中心有限。
为了克服这一问题，近年来研究人员开发了后***法合成锡硅分子筛。Li等(The Journal of Physical Chemistry C，2011，115(9)：3663-3670.)将脱铝Beta分子筛与SnCl4蒸气在673-773K充分接触，可合成锡含量高达6.1wt％的Sn-Beta分子筛。Hammond等(Angewandte Chemie International Edition，2012，51(47)：11736-11739.)将乙酸锡和脱铝Beta分子筛混合均匀，再经高温焙烧得到较高锡含量的Sn-Beta分子筛。虽然后***法可以制备高骨架锡含量的锡硅分子筛，但是后***法合成过程中仍存在诸多问题：脱铝过程随机产生骨架缺陷类型和数量，因 此很难通过增补锡原子来消除全部羟基缺陷，导致合成重复性较差；后***的锡原子随机分布于分子筛骨架上，而不是全位于热力学稳定位置，因此骨架锡在反应过程中易流失，导致其活性稳定性较差；锡原子可能会沉积在分子筛颗粒表面，导致其无法均匀***锡硅分子筛骨架而产生SnO 2聚集体。
发明内容
本发明的目的是提供一种锡钛硅分子筛及其制备方法和应用，本发明的锡钛硅分子筛的催化活性中心较多，具有较优的催化性能。
为了实现上述目的，本发明第一方面提供一种锡钛硅分子筛，所述锡钛硅分子筛中骨架锡活性中心的电子结合能为488.5eV以下。
可选地，所述锡钛硅分子筛中钛与硅的摩尔比为0.005-0.03，和/或锡与硅的摩尔比为0.005-0.025。
可选地，所述骨架锡活性中心的电子结合能为488.0-488.4eV。
可选地，该锡钛硅分子筛中骨架钛活性中心的电子结合能为460.0-461.2eV。
可选地，该锡钛硅分子筛中三甲基膦探针分子吸附双量子核磁骨架锡物种对应的磷化学位移数据为≤-23ppm。
可选地，该锡钛硅分子筛中三甲基膦探针分子吸附双量子核磁骨架钛物种对应的磷化学位移数据为≥-34ppm。
可选地，所述锡钛硅分子筛的外比表面积为100-150m 2/g，总孔体积为0.25-0.35cm 3/g。
可选地，所述锡钛硅分子筛为Sn-Ti-MFI分子筛或Sn-Ti-MEL分子筛。
可选地，所述Sn-Ti-MEL分子筛具有长条状晶粒交叉堆叠的结构，优选地所述晶粒的长为10-50nm，宽为10-30nm。
本发明第二方面提供一种制备本发明第一方面提供的锡钛硅分子筛的方法，该方法包括：
S1、将有机硅源、有机碱、溶剂、锡源、钛源和碱性模板剂混合，得到第一混合物；其中，所述有机碱为四丙基氢氧化铵和/或四丁基氢氧化铵；所述有机硅源、所述有机碱、所述溶剂、所述锡源和所述钛源用量的摩尔比为1∶(0.05-0.6)∶(10-30)∶(0.005-0.04)∶(0.005-0.04)，其中所述有机硅源以SiO 2计，所述锡源以SnO 2计，所述钛源以TiO 2 计；所述锡源与所述碱性模板剂用量的摩尔比为1∶(1-10)，所述锡源以阴离子计；
S2、将所述第一混合物在30-80℃下加热2-10小时，得到第二混合物；
S3、使所述第二混合物在120-200℃下进行水热反应2-7天，得到第三混合物；
S4、将所述第三混合物中的固体取出，并进行干燥和焙烧。
可选地，所述锡源与所述碱性模板剂用量的摩尔比为1∶(4-8)。
可选地，所述有机硅源、所述有机碱、所述溶剂、所述锡源和所述钛源用量的摩尔比为1∶(0.1-0.4)∶(15-30)∶(0.01-0.03)∶(0.01-0.03)。
可选地，步骤S1包括：将所述有机硅源、所述有机碱、所述溶剂和所述钛源混合得到第四混合物，将得到的第四混合物与所述锡源混合搅拌0.5-2小时后，再加入所述碱性模板剂，得到所述第一混合物。
可选地，所述有机硅源具有如下式(I)所示的结构，
Figure PCTCN2021114731-appb-000001
式(I)中，R 1、R 2、R 3和R 4各自独立地选自C1-C4烷基，例如C1-C4的直链烷基和C3-C4的支链烷基；优选为正硅酸四甲酯、正硅酸四乙酯、正硅酸四正丙酯和正硅酸四正丁酯中的一种或几种；更优选为正硅酸四乙酯和/或正硅酸四甲酯；
可选地，所述溶剂选自去离子水和/或蒸馏水；
可选地，所述碱性模板剂选自氨、脂肪族胺、脂肪族醇胺和季铵碱中的一种或几种；优选为氨水、乙胺、四丙基氢氧化铵和三乙醇胺中的一种或几种；
可选地，所述锡源选自氯化锡、五水氯化锡、氯化亚锡、二水氯化亚锡、锡酸钙、锡酸钾、锡酸钠、锡酸锂、硫酸亚锡和焦磷酸亚锡中的一种或多种；优选为五水氯化锡；
可选地，所述钛源具有如下式(II)所示的结构，
Figure PCTCN2021114731-appb-000002
式(II)中，R 1′、R 2′、R 3′和R 4′各自独立地选自C1-C6烷基，例如C1-C6的直链烷基和C3-C6的支链烷基；所述钛源优选为钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯和钛酸四丁酯中的一种或几种。
可选地，S3中所述水热反应的条件包括：温度为120-170℃，时间为2-5天。
本发明第三方面提供一种本发明第一方面提供的锡钛硅分子筛在二羟基丙酮制备乳酸酯，醛酮氨肟化反应，烯烃环氧化反应或芳烃/烷烃氧化反应中的应用。
本发明第四方面提供一种含有本发明第一方面提供的锡钛硅分子筛的催化剂。
通过上述技术方案，本发明的锡钛硅分子筛的催化活性中心多，骨架锡的电子结合能向低偏移，电子云密度增大，有利于提高分子筛的催化性能。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：
图1是本发明实施例1制备的锡钛硅分子筛的XPS图；
图2是本发明对比例1制备的锡钛硅分子筛的XPS图。
具体实施方式
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
本发明第一方面提供一种锡钛硅分子筛，锡钛硅分子筛中骨架锡活性中心的电子结合能为488.5eV以下。锡钛硅分子筛中钛与硅的摩 尔比可以为0.005-0.03，优选0.005-0.02，和/或锡与硅的摩尔比可以为0.005-0.025，优选0.005-0.02。
根据本发明，骨架锡是指能够***分子筛骨架的锡原子。本发明的锡钛硅分子筛在含有骨架锡的基础上还含有骨架钛，可以进一步增加分子筛的Lewis酸的种类和数量，使催化活性中心增加，且本发明的分子筛中骨架锡的电子结合能较低，电子云的密度增大，有利于提高催化性能，特别是提高分子筛对二羟基丙酮制备乳酸酯，醛酮氨肟化反应，烯烃环氧化反应或芳烃/烷烃氧化反应的催化性能。
在本发明的一种具体实施方式中，骨架锡活性中心的电子结合能为488.0-488.4eV。
在本发明的一种具体实施方式中，骨架钛活性中心的电子结合能为460.8-461.2eV。
根据本发明，锡钛硅分子筛的外比表面积可以为100-150m 2/g，总孔体积可以为0.25-0.35cm 3/g，优选地，外比表面积为100-140m 2/g，总孔体积为0.27-0.32cm 3/g。外比表面积是指分子筛单位质量物料所具有的总面积(除微孔表面积外)。
根据本发明，锡钛硅分子筛可以为Sn-Ti-MFI分子筛或Sn-Ti-MEL分子筛。
在一种具体实施方式中，Sn-Ti-MEL分子筛具有长条状晶粒交叉堆叠的结构，晶粒的长可以为10-50nm，宽可以为10-30nm。长条状是指分子筛晶粒的长径比大于1，优选大于1.5，更优选大于2。晶粒交叉堆叠的结构是指通过高分辨率的透射电镜观察到的Sn-MEL分子筛的晶粒无规则堆积、重叠的形貌结构。
本发明第二方面提供一种制备本发明第一方面提供的锡钛硅分子筛的方法，该方法包括：
S1、将有机硅源、有机碱、溶剂、锡源、钛源和碱性模板剂混合，得到第一混合物；其中，有机碱为四丙基氢氧化铵和/或四丁基氢氧化铵；所述有机硅源、所述有机碱、所述溶剂、所述锡源和所述钛源用量的摩尔比为1∶(0.05-0.6)∶(10-30)∶(0.005-0.04)∶(0.005-0.04)，其中所述有机硅源以SiO 2计，所述锡源以SnO 2计，所述钛源以TiO 2计；所述锡源与所述碱性模板剂用量的摩尔比为1∶(1-10)，所述锡源以阴离子计；
S2、将所述第一混合物在30-80℃下加热2-10小时，得到第二混合物；
S3、使所述第二混合物在120-200℃下进行水热反应2-7天，得到第三混合物；
S4、将所述第三混合物中的固体取出，并进行干燥和焙烧。
本发明的方法能够增加锡钛硅分子筛中锡与硅的摩尔比和钛与硅的摩尔比，且使得骨架锡的电子结合能向低偏移，增加电子云的密度，制备得到的锡钛硅分子筛对二羟基丙酮制备乳酸酯，醛酮氨肟化反应，烯烃环氧化反应或芳烃/烷烃氧化反应具有较优的催化性能。
根据本发明，步骤S1中，有机硅源、有机碱、溶剂、锡源和钛源用量的摩尔比可以为1∶(0.1-0.4)∶(15-30)∶(0.01-0.03)∶(0.01-0.03)，其中有机硅源以SiO 2计，锡源以SnO 2计，钛源以TiO 2计。
根据本发明，锡源与碱性模板剂用量的摩尔比优选为1∶(4-8)，更优选地，锡源与碱性模板剂用量的摩尔比1∶(4-6)，锡源以阴离子计。
在一种优选的具体实施方式中，步骤S1可以包括：将有机硅源、有机碱、溶剂和钛源混合得到第四混合物，将得到的第四混合物与锡源混合搅拌0.5-2小时后，再加入碱性模板剂，得到第一混合物。
根据本发明，步骤S2可以包括：在搅拌的条件下，将第一混合物在50-80℃下加热5-8小时，得到第二混合物。搅拌可以为本领域的技术人员所常规采用的方式，例如机械搅拌、电磁搅拌等。
根据本发明，步骤S4中，对将第三混合物中的固体取出的方法不做具体限制，例如可以采用过滤、离心分离等方式。优选地，将取出的固体洗涤后再进行干燥和焙烧。对洗涤采用的溶液不做限制，可以为任意不与固体反应的液体，例如可以为去离子水。干燥和焙烧为本领域的技术人员所熟知的操作，在一种具体实施方式中，干燥可以在恒温干燥箱中，干燥的条件可以包括：温度为50-150℃，时间为2-10小时，优选3-10小时；焙烧可以在马弗炉或者管式炉中，焙烧的条件可以包括：温度为550-750℃，时间为3-10小时，气氛为空气气氛或惰性气氛，其中该惰性气氛中含有氮气和/或惰性气体，惰性气体可以为氩气、氦气等。
根据本发明，有机硅源可以具有式(I)所示的结构，
Figure PCTCN2021114731-appb-000003
式(I)中，R 1、R 2、R 3和R 4各自独立地选自C1-C4的烷基，该C1-C4的烷基可以包括C1-C4的直链烷基和C3-C4的支链烷基，例如可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基。在一种优选的具体实施方式中，有机硅源为正硅酸四甲酯、正硅酸四乙酯、正硅酸四正丙酯和正硅酸四正丁酯中的一种或几种；更优选为正硅酸四乙酯和/或正硅酸四甲酯。
根据本发明，钛源可具有如下式(II)所示的结构，
Figure PCTCN2021114731-appb-000004
式(II)中，R 1′、R 2′、R 3′和R 4′各自独立地选自C1-C6的烷基，该C1-C6的烷基可以包括C1-C6的直链烷基和C3-C6的支链烷基；在一种优选的具体实施方式中，所述钛源为钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯和钛酸四丁酯中的一种或几种。
根据本发明，碱性模板剂可以选自氨、脂肪族胺、脂肪族醇胺和季铵碱中的一种或几种；优选为氨水、乙胺、四丙基氢氧化铵和三乙醇胺中的一种或几种。其中，脂肪族胺可以为各种NH 3中的至少一个氢被脂肪族烃基(优选为烷基)取代后形成的化合物，脂肪族醇胺可以为各种NH 3中的至少一个氢被含羟基的脂肪族烃基(优选为烷基)取代后形成的化合物。
在一种具体实施方式中，季铵碱可以为有机季铵碱，有机季铵碱具有如式(III)所示的结构
Figure PCTCN2021114731-appb-000005
式(III)，其中，R 5、 R 6、R 7和R 8各自独立地为碳原子数为1-4的烷基，该烷基可以包括碳原子数为1-4的直链烷基和碳原子数为3-4的支链烷基，例如可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基。
在一种具体实施方式中，脂肪族胺具有如式(IV)所示的结构，R 9(NH 2) n式(IV)，其中，n为1或2。当n为1时，R 9可以为碳原子数为1-6的烷基，该烷基可以包括碳原子数为1-6的直链烷基和碳原子数为3-6的支链烷基，例如可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、新戊基、异戊基。当n为2时，R9可以为碳原子数为1-6的亚烷基，该亚烷基可以包括碳原子数为1-6的直链烷基和碳原子数为3-6的支链亚烷基，例如可以为亚甲基、亚正丙基、亚正丁基、亚正戊基。在一种优选的具体实施方式中，脂肪族胺化合物为乙胺、正丁胺和丁二胺中的一种或几种。
在一种具体实施方式中，脂肪族醇胺具有式(V)所示的结构，(HOR 1u) m(NH) 3m式(V)，其中，m为1、2或3，m个R 10可以相同或不同，各自独立地选自碳原子数为1-4的亚烷基，该亚烷基可以包括碳原子数为1-4的直链亚烷基和碳原子数为3-4的支链亚烷基，例如可以为亚甲基、亚乙基、亚正丙基和亚正丁基。在一种优选的具体实施方式中，脂肪族醇胺化合物为单乙醇胺、二乙醇胺和三乙醇胺中的一种或几种。
根据本发明，溶剂可以选自去离子水和/或蒸馏水。
根据本发明，锡源可以为任意的水溶性无机锡盐，优选为自氯化锡、五水氯化锡、氯化亚锡、二水氯化亚锡、锡酸钙、锡酸钾、锡酸钠、锡酸锂、硫酸亚锡和焦磷酸亚锡中的一种或多种；更优选为五水氯化锡。
根据本发明，水热反应为本领域的技术人员所熟知的，例如可以在高压反应釜中进行，对水热反应的压力不做具体限制，可以为反应的自生压力，也可以为额外施加于反应体系的压力。在一种具体实施方式中，水热反应的条件可以包括：温度为120-170℃，时间为2-5天。
本发明第三方面提供一种本发明第一方面提供的锡钛硅分子筛在二羟基丙酮制备乳酸酯，醛酮氨肟化反应，烯烃环氧化反应或芳烃/烷烃氧化反应中的应用。
根据本发明，在溶剂和锡钛硅分子筛的存在下采用二羟基丙酮制备乳酸酯，二羟基丙酮制备乳酸酯所采用的溶剂为本领域的技术人员所熟知的，例如可以为低级醇，更具体地可以为甲醇、乙醇、丙醇、丁醇等。
在一种具体实施方式，本发明提供一种锡钛硅分子筛在二羟基丙酮制备乳酸甲酯中的应用，溶剂为甲醇。
对于醛酮氨肟化反应，所采用的溶剂为本领域的技术人员所熟知的，例如可以为低级醇，更具体地可以为甲醇、乙醇、异丙醇、叔丁醇等。
对于烯烃环氧化反应，所采用的溶剂为本领域的技术人员所熟知的，例如可以为低级醇，更具体地可以为甲醇、乙醇、异丙醇、叔丁醇等。
对于芳烃/烷烃氧化反应，所采用的溶剂为本领域的技术人员所熟知的，例如可以为低级醇，更具体地可以为甲醇、乙醇、异丙醇、叔丁醇等。
本发明第四方面提供一种含有本发明第一方面提供的锡钛硅分子筛的催化剂。
下面通过实施例来进一步说明本发明，但是本发明并不因此而受到任何限制。
实施例和对比例中所用原料除特别说明以外，均为化学纯试剂。正硅酸四乙酯购自湖南建长石化有限公司，钛酸四丁酯购自湖南建长石化有限公司，四丁基氢氧化铵购自北京伊诺凯科技有限公司，五水氯化锡购自北京伊诺凯科技有限公司，四丙基氢氧化铵购自北京伊诺凯科技有限公司，二羟基丙酮购自北京伊诺凯科技有限公司，甲醇购自北京伊诺凯科技有限公司，氯化亚锡购自北京伊诺凯科技有限公司，二水氯化亚锡购自北京伊诺凯科技有限公司，三乙醇胺购自北京伊诺凯科技有限公司，乙胺购自北京伊诺凯科技有限公司。
分子筛中骨架锡活性中心的电子结合能通过XPS表征得到；
分子筛中骨架钛活性中心的电子结合能通过XPS表征得到；
双量子核磁分析采用三甲基膦作为探针分子，通过对样品进行前处理后，将三甲基膦吸附到分子筛上，再进行 31P和 1H核磁共振谱图的测量，将得到的谱图进行 31P- 31P或 31P- 1H关联，得到所述的双量子核磁分析谱图；
分子筛中的钛与硅的摩尔比、锡与硅的摩尔比采用XRF方法测量 得到；
采用BET表征测量分子筛的外比表面积和总孔体积；
采用高分辨率(分辨率为50nm尺度)的透射电镜表征晶粒的长和宽。
测试例中的乳酸甲酯产率采用气相色谱进行分析，分析结果采用内标法进行定量，内标物为萘。其中色谱的分析条件为：Agilent-6890型色谱仪，HP-5毛细管色谱柱，进样量0.5μL，进样口温度280℃。柱温在100℃保持2min，而后以15℃/min的速率升至200℃，并保持3min。FID检测器，检测器温度300℃。
采用以下公式计算乳酸甲酯产率：
乳酸甲酯收率％＝产物中乳酸甲酯的摩尔数/原料中二羟基丙酮的摩尔数×100％，即乳酸甲酯收率％＝乳酸甲酯选择性％×二羟基丙酮转化率％。
关于转化率和选择性，采用以下公式计算：
转化率(％)＝转化的有机物质摩尔数/投入的有机物质摩尔数×100％，
选择性(％)＝目的产物的摩尔数/生成的产物的总摩尔数×100％。
实施例1
S1、将正硅酸四乙酯∶钛酸四丁酯∶四丙基氢氧化铵∶去离子水按照1∶0.02∶0.2∶20的摩尔比混合，室温进行搅拌；在上述混合物搅拌过程中，加入五水氯化锡搅拌1h，得到无色透明溶液(正硅酸四乙酯与五水氯化锡的摩尔比为1∶0.02)，其中，正硅酸四乙酯以SiO 2计，五水氯化锡以SnO 2计，钛酸四丁酯以TiO 2计；再加入与五水氯化锡中氯离子等摩尔量的四丙基氢氧化铵，得到第一混合物；
S2、将第一混合物置于反应温度为70℃的磁力搅拌器上加热赶醇6小时，得到第二混合物；
S3、将第二混合物置于不锈钢密封反应釜中，在160℃和自生压力下晶化反应3天，得到第三混合物；
S4、将第三混合物进行过滤取出固体，将得到的固体物质用水洗涤后，于110℃干燥2小时，接着在550℃空气气氛中焙烧6h，得到本发明的锡钛硅分子筛，即Sn-Ti-MFI分子筛，其XPS图见图1。
合成锡钛硅分子筛的具体反应条件于表1中列出。锡钛硅分子筛的 物化表征和活性评价结果见表2。
实施例2-21
按照实施例1的方法制备Sn-Ti-MFI分子筛，其配比和合成条件和物料配比如表1所述；锡钛硅分子筛的物化表征和活性评价结果见表2，表1中未涉及的合成条件参考实施例1。
实施例22
S1、将正硅酸四乙酯∶钛酸四丁酯∶四丁基氢氧化铵∶去离子水按照1∶0.02∶0.2∶20的摩尔比混合，室温进行搅拌。在上述混合物搅拌过程中，加入五水氯化锡搅拌1h，得到无色透明溶液(正硅酸四乙酯与五水氯化锡的摩尔比为1∶0.01，其中，正硅酸四乙酯以SiO 2计，五水氯化锡以SnO 2计，钛酸四丁酯以TiO 2计。再加入与五水氯化锡中氯离子等摩尔量的四丙基氢氧化铵，得到第一混合物；
S2、将第一混合物置于反应温度为70℃的磁力搅拌器上加热赶醇6h，得到第二混合物；
S3、将第二混合物置于不锈钢密封反应釜中，在160℃和自生压力下晶化反应3天，得到第三混合物；
S4、将第三混合物进行过滤取出固体，将得到的固体物质用水洗涤后，于110℃干燥2小时，接着在550℃空气气氛中焙烧6h，得到本发明的锡钛硅分子筛，即Sn-Ti-MEL分子筛。
合成分子筛的具体反应条件于表1中列出。锡钛硅分子筛的物化表征和活性评价结果见表2。
实施例23-24
按照实施例22的方法制备Sn-Ti-MEL分子筛，其配比和合成条件和物料配比如表1所述；锡钛硅分子筛的物化表征和活性评价结果见表2，表1中未涉及的合成条件参考实施例22。
对比例1
本对比例采用水热法制备Sn-Ti-MFI分子筛。
将五水合四氯化锡(SnCl 4.5H 2O)溶于水中，把此水溶液加入正硅酸乙酯(TEOS)搅拌，再加入钛酸四丁酯(TBOT)，在搅拌下加入四丙基氢氧化铵(TPAOH，20％水溶液)和水，持续搅拌30分钟得到化学组成为0.015TiO 2∶0.03SnO 2∶SiO 2∶0.45TPA∶35H 2O的澄清液体，置于70℃老化6小时，然后在433K温度下进行晶化2天，之后将得 到的固体过滤，用蒸馏水洗涤后，在393K温度下烘干5小时，然后在823K条件下焙烧10h得到分子筛样品。其中，TEOS用量为15.31g，TPAOH的用量为33.67g，SnCl 4.5H 2O的用量为0.38g，TBOT用量为0.38g，水的用量为39.64g。制备得到的Sn-Ti-MFI分子筛的XPS图见图2。
对比例2
本对比例采用水热法制备Sn-Ti-MEL分子筛。
将五水合四氯化锡(SnCl 4.5H 2O)溶于水中，把此水溶液加入正硅酸乙酯(TEOS)搅拌，再加入钛酸四丁酯(TBOT)，在搅拌下加入四丁基氢氧化铵(TBAOH，20％水溶液)和水，持续搅拌30分钟得到化学组成为0.015TiO 2∶0.03SnO 2∶SiO 2∶0.45TBA∶35H 2O的澄清液体，置于70℃老化6小时，然后在433K温度下进行晶化2天，之后将得到的固体过滤，用蒸馏水洗涤后，在393K温度下烘干5小时，然后在733K条件下焙烧10h得到分子筛样品。其中，TEOS用量为15.31g，TBAOH的用量为42.96g，SnCl 4.5H 2O的用量为0.38g，TBOT用量为0.38g，水的用量为39.64g。
对比例3-10
按照对比例1的方法制备Sn-Ti-MFI分子筛，其配比和合成条件和物料配比如表1所述；锡钛硅分子筛的物化表征和活性评价结果见表2，表1中未涉及的合成条件参考对比例1。
测试例
(1)二羟基丙酮催化制备乳酸甲酯
将各实施例和对比例得到的样品作为催化剂，进行二羟基丙酮催化制备乳酸甲酯的反应。反应具体条件如下：在淤浆床反应器中，将反应物二羟基丙酮和溶剂甲醇按照摩尔比为1∶200，催化剂的量为总反应液的3.0重量％，在60℃和自生压力下反应，每反应1小时取样测定产物的组成，计算结果见表2。
(2)醛酮氨肟化反应，
将各实施例和对比例得到的样品作为催化剂，按下式进行反应
Figure PCTCN2021114731-appb-000006
其中，R选自烷基和芳基，例如苯基，R1选自氢和烷基，或者R和R1合在一起形成环。
反应具体条件如下：在淤浆床反应器中，将反应物醛酮、双氧水与溶剂(如叔丁醇)按照摩尔比为1∶1∶200，催化剂的量为总反应液的5.0重量％，在80℃和自生压力下反应，每反应1小时取样测定产物的组成，结果参见表3。
(3)烯烃环氧化反应
将各实施例和对比例得到的样品作为催化剂，按下式进行反应
Figure PCTCN2021114731-appb-000007
其中，R 1和R 2分别选自氢和任选含有杂原子(例如氧)的烷基，或者R 1和R 2合在一起形成环。
反应具体条件如下：在淤浆床反应器中，将反应物烯烃、双氧水与溶剂(如叔丁醇)按照摩尔比为1∶1∶200，催化剂的量为总反应液的5.0重量％，在50℃和自生压力下反应，每反应1小时取样测定产物的组成，结果参见表3。
(4)芳烃/烷烃氧化反应
将各实施例和对比例得到的样品作为催化剂，按下式进行反应
Figure PCTCN2021114731-appb-000008
其中，R选自氢，烷基和羟基，这里R可以代表两个取代基，R 1和R 2分别选自氢和烷基，或者R 1和R 2合在一起形成任选烷基取代的环。
反应具体条件如下：在淤浆床反应器中，将反应物(芳烃或烷烃)、双氧水与溶剂(如叔丁醇)按照摩尔比为1∶1∶200，催化剂的量为总反应液的5.0重量％，在80℃和自生压力下反应，每反应1小时取样测定产物的组成，结果参见表3。
表1
Figure PCTCN2021114731-appb-000009
Figure PCTCN2021114731-appb-000010
表1中，有机硅源：钛源：有机碱：溶剂是指有机硅源、钛源、有机碱和溶剂用量的摩尔比，有机硅源：锡源是指有机硅源和锡源用量的摩尔比，锡源：碱性模板剂是指锡源和碱性模板剂用量的摩尔比。
表2
Figure PCTCN2021114731-appb-000011
Figure PCTCN2021114731-appb-000012
表3
Figure PCTCN2021114731-appb-000013
Figure PCTCN2021114731-appb-000014
本发明的锡钛硅分子筛具有较多的活性中心，骨架锡的电子结合能较低，催化活性较高。
以上结合附图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。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (16)

  1. 一种锡钛硅分子筛，所述锡钛硅分子筛中骨架锡活性中心的电子结合能为488.5eV以下。
  2. 根据权利要求1所述的锡钛硅分子筛，其中，所述锡钛硅分子筛中钛与硅的摩尔比为0.005-0.03，优选0.005-0.02，和/或锡与硅的摩尔比为0.005-0.025，优选0.005-0.02。
  3. 根据权利要求1或2所述的锡钛硅分子筛，其中，所述骨架锡活性中心的电子结合能为488.0-488.4eV。
  4. 根据权利要求1-3任意一项所述的锡钛硅分子筛，其中，骨架钛活性中心的电子结合能为460.0-461.2eV，优选460.8-461.2eV。
  5. 根据权利要求1-4任意一项所述的锡钛硅分子筛，其中，三甲基膦探针分子吸附双量子核磁骨架锡物种对应的磷化学位移数据为≤-23ppm；和/或三甲基膦探针分子吸附双量子核磁骨架钛物种对应的磷化学位移数据为≥-34ppm。
  6. 根据权利要求1-5任意一项所述的锡钛硅分子筛，其中，所述锡钛硅分子筛的外比表面积为100-150m 2/g，总孔体积为0.25-0.35cm 3/g。
  7. 根据权利要求1-6任意一项所述的锡钛硅分子筛，其中，所述锡钛硅分子筛为Sn-Ti-MFI分子筛或Sn-Ti-MEL分子筛。
  8. 根据权利要求7所述的锡钛硅分子筛，其中，所述Sn-Ti-MEL分子筛具有长条状晶粒交叉堆叠的结构，所述晶粒的长为10-50nm，宽为10-30nm。
  9. 制备权利要求1-8中任意一项所述的锡钛硅分子筛的方法，该方法包括：
    S1、将有机硅源、有机碱、溶剂、锡源、钛源和碱性模板剂混合，得到第一混合物；其中，所述有机碱为四丙基氢氧化铵和/或四丁基氢氧化铵；所述有机硅源、所述有机碱、所述溶剂、所述锡源和所述钛源用量的摩尔比为1∶(0.05-0.6)∶(10-30)∶(0.005-0.04)∶(0.005-0.04)，其中所述有机硅源以SiO 2计，所述锡源以SnO 2计，所述钛源以TiO 2计；所述锡源与所述碱性模板剂用量的摩尔比为1∶(1-10)，所述锡源以阴离子计；
    S2、将所述第一混合物在30-80℃下加热2-10小时，得到第二混合 物；
    S3、使所述第二混合物在120-200℃下进行水热反应2-7天，得到第三混合物；
    S4、将所述第三混合物中的固体取出，并进行干燥和焙烧。
  10. 根据权利要求9所述的方法，其中，所述锡源与所述碱性模板剂用量的摩尔比为1∶(4-8)。
  11. 根据权利要求9或10所述的方法，其中，所述有机硅源、所述有机碱、所述溶剂、所述锡源和所述钛源用量的摩尔比为1∶(0.1-0.4)∶(15-30)∶(0.01-0.03)∶(0.01-0.03)。
  12. 根据权利要求9-11任意一项所述的方法，其中，步骤S1包括：将所述有机硅源、所述有机碱、所述溶剂和所述钛源混合得到第四混合物，将得到的第四混合物与所述锡源混合搅拌0.5-2小时后，再加入所述碱性模板剂，得到所述第一混合物。
  13. 根据权利要求9-12任意一项所述的方法，其中，所述有机硅源具有如下式(I)所示的结构，
    Figure PCTCN2021114731-appb-100001
    式(I)中，R 1、R 2、R 3和R 4各自独立地选自C1-C4烷基，例如C1-C4的直链烷基和C3-C4的支链烷基；优选为正硅酸四甲酯、正硅酸四乙酯、正硅酸四正丙酯和正硅酸四正丁酯中的一种或几种；更优选为正硅酸四乙酯和/或正硅酸四甲酯；
    所述溶剂选自去离子水和/或蒸馏水；
    所述碱性模板剂选自氨、脂肪族胺、脂肪族醇胺和季铵碱中的一种或几种；优选为氨水、乙胺、四丙基氢氧化铵和三乙醇胺中的一种或几种；
    所述锡源选自氯化锡、五水氯化锡、氯化亚锡、二水氯化亚锡、锡酸钙、锡酸钾、锡酸钠、锡酸锂、硫酸亚锡和焦磷酸亚锡中的一种或多种；优选为五水氯化锡；和/或
    所述钛源具有如下式(II)所示的结构，
    Figure PCTCN2021114731-appb-100002
    式(II)中，R 1′、R 2′、R 3′和R 4′各自独立地选自C1-C6烷基，例如C1-C6的直链烷基和C3-C6的支链烷基；所述钛源优选为钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯和钛酸四丁酯中的一种或几种。
  14. 根据权利要求9-13任意一项所述的方法，其中，S3中的所述水热反应的条件包括：温度为120-170℃，时间为2-5天。
  15. 权利要求1-8任意一项所述的锡钛硅分子筛在二羟基丙酮制备乳酸酯，醛酮氨肟化反应，烯烃环氧化反应或芳烃/烷烃氧化反应中的应用。
  16. 催化剂，其含有权利要求1-8任意一项所述的锡钛硅分子筛。
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