CN112744830A - Titanium-silicon molecular sieve, preparation method thereof and cyclohexanone oximation reaction method - Google Patents

Titanium-silicon molecular sieve, preparation method thereof and cyclohexanone oximation reaction method Download PDF

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CN112744830A
CN112744830A CN201911051853.7A CN201911051853A CN112744830A CN 112744830 A CN112744830 A CN 112744830A CN 201911051853 A CN201911051853 A CN 201911051853A CN 112744830 A CN112744830 A CN 112744830A
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molecular sieve
titanium
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silicon source
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夏长久
朱斌
林民
彭欣欣
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention relates to the field of molecular sieve preparation, in particular to a titanium silicalite molecular sieve, a preparation method thereof and a cyclohexanone oximation reaction method. The molecular sieve particles are formed by stacking crystal grains with the particle size of 20-50nm, the particle size of the molecular sieve particles is 500-1000nm, the average grain boundary size of the molecular sieve particles is 1-5nm, the grain boundary mesoporous volume is 0.1-0.5mL/g, and the Lewis acid content of the molecular sieve is 15-30 mu mol/g. The preparation method can synthesize the small-grain stacked titanium silicalite molecular sieve under the conditions of lower template agent dosage and lower water-silicon ratio, reduce the synthesis cost, improve the solid content of the synthesized molecular sieve crystallization product and improve the yield of the single-kettle molecular sieve. The titanium silicalite molecular sieve provided by the invention is used in cyclohexanone oximation reaction, and has higher reaction activity and selectivity.

Description

Titanium-silicon molecular sieve, preparation method thereof and cyclohexanone oximation reaction method
Technical Field
The invention relates to the field of molecular sieve preparation, in particular to a titanium silicalite molecular sieve, a preparation method thereof and a cyclohexanone oximation reaction method.
Background
The titanium-silicon molecular sieve synthesized at present has MFI structure TS-1, MEL structure TS-2, MWW structure MCM-22, larger pore structure TS-48 and the like.
TS-1 is the one developed and synthesized by EniChem corporation in Italy at the earliest, and is a new titanium-silicon molecular sieve with excellent catalytic selective oxidation performance formed by introducing transition metal element titanium into a molecular sieve framework with a ZSM-5 structure, and TS-1 not only has the catalytic oxidation effect of titanium, but also has the shape selective effect and excellent stability of the ZSM-5 molecular sieve. The titanium silicalite molecular sieve is used as a catalyst to catalyze various organic oxidation reactions, such as olefin epoxidation, alkane partial oxidation, alcohol oxidation, phenol hydroxylation, cyclic ketone ammoxidation and the like. As the TS-1 molecular sieve can adopt pollution-free low-concentration hydrogen peroxide as an oxidant in the oxidation reaction of organic matters, the problems of complex process and environmental pollution in the oxidation process are avoided, and the molecular sieve has the advantages of incomparable energy conservation, economy, environmental friendliness and the like of the traditional oxidation system and has good reaction selectivity.
The titanium silicalite molecular sieve is considered as a milestone in the field of molecular sieve catalysis as an organic selective oxidation catalyst, and can overcome the defects of complex reaction process, harsh conditions, serious environmental pollution and the like of the traditional catalytic oxidation system from the source, so that the titanium silicalite molecular sieve is highly valued by people at present with increasingly strict environmental protection requirements.
In 1983, a method for synthesizing a titanium silicalite molecular sieve by a hydrothermal crystallization method is reported by Taramasso in a patent US4410501 for the first time. The method is a classical method for synthesizing TS-1, and mainly comprises two steps of glue preparation and crystallization, wherein the synthesis process is as follows: putting Tetraethoxysilane (TEOS) into nitrogen to protect CO2The preparation method comprises the steps of slowly adding TPAOH (template agent), slowly adding tetraethyl titanate (TEOT) dropwise, stirring for 1h to prepare a reaction mixture containing a silicon source, a titanium source and organic alkali, heating, removing alcohol, replenishing water, stirring at 175 ℃ under an autogenous pressure kettle, crystallizing for 10 days, separating, washing, drying and roasting to obtain the TS-1 molecular sieve. However, in the process, the influence factors of the process of inserting titanium into the framework are numerous, and the conditions of hydrolysis and nucleation are not easy to control, so that the TS-1 molecular sieve synthesized by the method has the defects of low catalytic activity, poor stability, difficulty in synthesis and reproduction and the like.
CN1260241A discloses a rearrangement technique of titanium-silicon molecular sieve, which synthesizes a novel titanium-silicon molecular sieve with a unique hollow structure, not only greatly enhances the reproducibility of synthesizing TS-1, but also increases the size of the molecular sieve pore, greatly improves the mass transfer diffusion rate of reactant molecules in the molecular sieve pore and increases the catalytic performance. The method disclosed in the patent is that a titanium hydrolysis solution and a synthesized TS-1 molecular sieve are uniformly mixed according to the ratio of the molecular sieve (g) to the Ti (mol) of 200-. At present, the HTS molecular sieve is applied to the processes of phenol hydroxylation, cyclohexanone ammoximation and the like by catalytic oxidation, has already been industrialized, and has the advantages of mild reaction conditions, high atom utilization rate, simple process, clean and efficient water serving as a byproduct and the like.
The titanium-silicon molecular sieve synthesized by the existing method mainly takes micropores as main components, and the mesoporous volume is small, so that the mass transfer and diffusion in the crystal are not facilitated; and the synthesis difficulty of the molecular sieve is higher.
Disclosure of Invention
The invention aims to solve the problems that a titanium silicalite molecular sieve mainly takes micropores as main components, has small mesoporous volume and is difficult to synthesize in the prior art, and provides a titanium silicalite molecular sieve, a preparation method thereof and a cyclohexanone oximation reaction method. The preparation method of the titanium silicalite molecular sieve provided by the invention can save the cost of raw materials and obtain the high-performance small-grain stacked titanium silicalite molecular sieve, and the prepared titanium silicalite molecular sieve has higher oxidation activity and selectivity.
The invention provides a titanium silicalite molecular sieve, which is characterized in that the molecular sieve particles are formed by stacking crystal grains with the particle size of 20-50nm, the particle size of the molecular sieve particles is 500-1000nm, the average grain boundary size of the molecular sieve particles is 1-5nm, the grain boundary mesoporous volume is 0.1-0.5mL/g, and the Lewis acid content of the molecular sieve is 15-30 mu mol/g.
Preferably, the molecular sieve is at 25 ℃, P/P0The benzene adsorption amount measured under the condition of adsorption time of 1 hour is at least 30 mg/g, which is 0.1.
In a second aspect, the present invention provides a method for preparing a titanium silicalite molecular sieve, the method comprising:
(1) mixing a first liquid titanium source, a first liquid silicon source, an auxiliary agent and a solvent to obtain a first mixture;
(2) aging the first mixture to obtain an aged sol;
(3) heating the aged gel and the solid silicon source to obtain solid gel;
(4) roasting the solid gel to obtain titanium silicon oxide;
(5) and mixing the titanium-silicon oxide, the template agent, a second liquid titanium source, a second liquid silicon source, water and an inorganic ammonium source to obtain a second mixture, and then crystallizing.
Preferably, TiO is used in step (1)2The first liquid titanium source and TiO measured in the step (5)2The molar ratio of the second liquid titanium source is 1: 0.5-8, preferably 1: 2.5-6.
Preferably, SiO is used in step (1)2The first liquid silicon source and SiO in step (5)2The molar ratio of the second liquid silicon source is 1: 0.5-8, preferably 1: 2.5-6.
Preferably, the molar ratio of the total titanium source to the total silicon source is 0.005-0.05: 1, wherein the total titanium source is TiO2The total silicon source is SiO2The total titanium source is calculated as TiO2A first liquid titanium source and in TiO2The total sum of the second liquid titanium source and the total silicon source is SiO2First liquid silicon source in terms of SiO2Second liquid silicon source and SiO2The sum of the calculated solid silicon sources.
Preferably in SiO2The total liquid silicon source and SiO in step (3)2The molar ratio of the solid silicon source is 1: 1-9, preferably 1: 2-8.
Preferably, the molar ratio of the template agent to the total silicon source is 0.08-0.6: 1.
Preferably, the molar ratio of the water to the total silicon source in step (5) is 5-100: 1.
Preferably, the molar ratio of the inorganic ammonium source in step (5) to the first liquid titanium source in step (1) is 0.01-5: 1.
In a third aspect, the invention provides a titanium silicalite molecular sieve prepared by the preparation method.
The fourth aspect of the invention provides a cyclohexanone oxime reaction method, which comprises the step of contacting cyclohexanone, ammonia and hydrogen peroxide with a titanium silicalite molecular sieve under an oximation reaction condition, wherein the titanium silicalite molecular sieve is the titanium silicalite molecular sieve provided by the invention.
According to the preparation method of the titanium silicalite molecular sieve, the expensive liquid silicon source is partially replaced by the cheap and easily-obtained solid silicon source, so that the waste discharge in the production process of the molecular sieve can be reduced, the cost of raw materials is saved, and meanwhile, the high-performance small-crystal-grain stacked titanium silicalite molecular sieve material is obtained, and the prepared molecular sieve has higher oxidation activity. The preparation method of the titanium silicalite molecular sieve can synthesize the small-grain stacked titanium silicalite molecular sieve material under the conditions of lower template agent dosage and lower water-silicon ratio, can reduce the synthesis cost of the titanium silicalite molecular sieve material, improves the solid content of the synthesized molecular sieve crystallized product, and improves the yield of the single-kettle molecular sieve. The titanium silicalite molecular sieve prepared by the preparation method provided by the invention is used in cyclohexanone oximation reaction, and has higher reaction activity and selectivity.
Drawings
FIG. 1 is an SEM photograph of the Ti-MFI molecular sieve prepared in example 1;
FIG. 2 is a TEM photograph of the Ti-MFI molecular sieve prepared in example 1;
FIG. 3 is a TEM photograph of the Ti-MFI molecular sieve obtained from the rearrangement treatment of example 3;
FIG. 4 is an SEM photograph of the Ti-MFI molecular sieve prepared in comparative example 1;
FIG. 5 is a TEM photograph of the Ti-MFI molecular sieve prepared in comparative example 1;
FIG. 6 is an SEM photograph of a Ti-MFI molecular sieve obtained by the rearrangement treatment of comparative example 2;
FIG. 7 is a TEM photograph of a Ti-MFI molecular sieve obtained by the rearrangement treatment of comparative example 2;
fig. 8 is an XRD spectrum of the titanium silicalite molecular sieves prepared in example 1, example 2, comparative example 1 and comparative example 2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a titanium-silicon molecular sieve, wherein the molecular sieve particles are formed by stacking crystal grains with the particle size of 20-50nm, the particle size of the molecular sieve particles is 500-1000nm, the average grain boundary size of the molecular sieve particles is 1-5nm, the grain boundary mesoporous volume is 0.1-0.5mL/g, and the Lewis acid content of the molecular sieve is 15-30 mu mol/g.
According to the invention, the molecular sieve particles of the titanium silicalite molecular sieve are obtained by stacking crystal grains with the particle size of 20-50nm through transmission electron microscope detection.
According to the invention, the particle size of the molecular sieve particles and the particle size of the crystal grains of the titanium-silicon molecular sieve are obtained by transmission electron microscope detection (measured by a TEM scale).
The titanium silicalite molecular sieve provided by the invention contains abundant crystal boundaries in the molecular sieve particles, and the crystal boundaries not only strengthen mass transfer diffusion of reactants and product molecules, but also improve the Lewis acid content of framework titanium species. The average grain boundary size of the molecular sieve particles of the titanium-silicon molecular sieve provided by the invention is 1-5nm, and the mesoporous volume of the grain boundary is 0.1-0.5 mL/g.
According to a preferred embodiment of the present invention, the molar ratio of titanium to silicon in the molecular sieve is 0.005-0.04: 1, preferably 0.01-0.035: 1.
According to a preferred embodiment of the present invention, the molecular sieve particles have an average grain boundary size of 1 to 3nm and a grain boundary mesopore volume of 0.1 to 0.2 mL/g.
According to a preferred embodiment of the present invention, the molecular sieve has a micropore volume of from 0.15 to 0.18 mL/g.
In the present invention, the grain boundaries refer to interfaces between grains having the same structure but different orientations, and the contact interfaces between the grains are called grain boundaries. The grain boundary size refers to the distance between crystal grains, and is obtained by transmission electron microscope detection (measured by a TEM scale).
The titanium silicalite molecular sieve provided by the invention has a micropore structure and a crystal boundary mesopore structure, preferably, the pore diameter of micropores is less than 1nm, and the pore diameter (diameter) of mesopores is between 1nm and 5 nm. Specifically, the XRD spectrum of the molecular sieve has diffraction peaks at 2 theta angles of 5-35 degrees, which indicates that the molecular sieve has a micropore structure. In the invention, the volume and the pore size distribution of the mesoporous grain boundary are measured by a low-temperature nitrogen adsorption curve method.
According to a preferred embodiment of the present invention, the amount of Lewis acid of the titanium silicalite is 15 to 30. mu. mol/g, more preferably 20 to 30. mu. mol/g. The acid content of the molecular sieve was determined by pyridine adsorption infrared spectroscopy.
According to a preferred embodiment of the invention, the molecular sieve is at 25 ℃ P/P0The benzene adsorption amount measured under the condition of adsorption time of 1 hour is at least 30 mg/g, preferably 30 to 40 mg/g, ═ 0.1. TheA hysteresis loop exists between the adsorption isotherm and the desorption isotherm of the low temperature nitrogen adsorption of the molecular sieve. Under the same ratio of titanium to silicon, the acid amount and the acid strength of the titanium silicalite molecular sieve provided by the invention are higher than those of the titanium silicalite molecular sieve prepared by the conventional method.
According to the present invention, preferably, the molecular sieve has an MFI structure, an MEL structure, a BEA structure, an MWW structure or an MOR structure.
In a second aspect, the present invention provides a method for preparing a titanium silicalite molecular sieve, the method comprising:
(1) mixing a first liquid titanium source, a first liquid silicon source, an auxiliary agent and a solvent to obtain a first mixture;
(2) aging the first mixture to obtain an aged sol;
(3) heating the aged gel and the solid silicon source to obtain solid gel;
(4) roasting the solid gel to obtain titanium silicon oxide;
(5) and mixing the titanium-silicon oxide, the template agent, a second liquid titanium source, a second liquid silicon source, water and an inorganic ammonium source to obtain a second mixture, and then crystallizing.
In the present invention, the auxiliary in the step (1) is not particularly limited. Preferably, the adjuvant comprises a space filler and/or a stabilizer.
Preferably, the space-filling agent is selected from a silylation agent and/or a water-soluble polymer compound, and more preferably a water-soluble polymer. More preferably, the silylating agent is selected from at least one of trimethylchlorosilane, t-butyldimethylchlorosilane, dimethyldiacetoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and di-t-butyldichlorosilane; the water-soluble high molecular compound is polyacrylamide and/or polyacrylic acid. The weight average molecular weight of the water-soluble polymer compound may be 1000-100000.
Preferably, the stabilizer is selected from at least one of oxalic acid, t-butyl hydroperoxide, cyclohexyl hydroperoxide, hydrogen peroxide and citric acid.
Preferably, the step of(1) The molar ratio of the auxiliary agent to the first liquid silicon source is 0.01-0.1: 1, preferably 0.02-0.07: 1, wherein the first liquid silicon source is SiO2And (6) counting.
In the present invention, the first liquid titanium source in the step (1) and the second liquid titanium source in the step (5) are not particularly limited. Specifically, the first liquid titanium source and the second liquid titanium source are each independently selected from an inorganic liquid titanium source and/or an organic liquid titanium source.
According to a preferred embodiment of the present invention, the inorganic liquid titanium source is selected from at least one of titanium tetrachloride, titanium sulfate and titanyl sulfate, preferably titanium tetrachloride and/or titanyl sulfate.
According to a preferred embodiment of the invention, the organic liquid titanium source is selected from organic acid salts of titanium and/or a titanate, preferably a titanate, selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate, preferably tetraethyl titanate.
According to the invention, preferably, TiO is used in the step (1)2The first liquid titanium source and TiO measured in the step (5)2The molar ratio of the second liquid titanium source is 1: 03-8, preferably 1: 2.5-6.
In the present invention, the first liquid silicon source in step (1) and the second liquid silicon source in step (5) are not particularly limited. In particular, the first and second liquid silicon sources are each independently selected from an inorganic liquid silicon source and/or an organic liquid silicon source.
According to a preferred embodiment of the present invention, the inorganic liquid silicon source is selected from at least one of silicon tetrachloride, sodium silicate and sodium metasilicate, preferably silicon tetrachloride.
Preferably, the organic liquid silicon source is selected from the group consisting of silicon of the formula Si (OR)1)4Of organosilicon esters of, R1Selected from alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms, said alkyl groups being branched or straight chain alkyl groups.
According to a preferred embodiment of the present invention, the silicone grease is selected from at least one of tetramethylsilicate, tetraethyl silicate, tetrabutyl silicate and dimethyldiethylsilicate; preferably at least one of tetramethyl silicate, tetraethyl silicate and tetrapropyl silicate.
According to the invention, step (1) is preferably carried out with SiO2The first liquid silicon source and SiO in step (5)2The molar ratio of the second liquid silicon source is 1: 0.5-8, preferably 1: 2.5-6.
According to the invention, the molar ratio of the total titanium source to the total silicon source is preferably 0.005-0.05: 1, more preferably 0.008-0.035: 1, for example 0.01-0.03: 1 or 0.01-0.025: 1 or 0.015-0.025: 1, wherein the total titanium source is TiO2The total silicon source is SiO2The total titanium source is TiO2A first liquid titanium source and in TiO2The total sum of the second liquid titanium source and the total silicon source is SiO2First liquid silicon source in terms of SiO2Second liquid silicon source and SiO2The sum of the calculated solid silicon sources.
Preferably in SiO2The total liquid silicon source and SiO in step (3)2The molar ratio of the solid silicon source is 1: 1-9, preferably 1: 2-8. In the invention, the high proportion of solid silicon source is used, so that the production cost can be reduced, and in addition, the solid content of the crystallized product of the titanium-silicon molecular sieve can be improved, thereby improving the output of single synthesis under the condition that the synthesis reaction kettle is not changed.
In the present invention, the solid silicon source in the step (3) is not particularly limited. Specifically, the solid silicon source may be a high-purity silica solid or powder, and preferably, the solid silicon source is white carbon and/or high-purity silica gel, preferably white carbon. Preferably, the SiO in the solid silicon source is based on dry weight2The content is not less than 99.99 weight percent, and the total mass content of Fe, Al and Na impurities is less than 10 ppm; for example SiO2The content is 99.99 to 100% by weight, and usually more than 99.99 and less than 100% by weight.
According to a specific embodiment of the present invention, SiO is contained in the silica gel2The content is 99.99 wt.% or more, for example, 99.9 or more9 to less than 100 wt%, and the mass content of Fe, Al and Na impurities is less than 10 ppm.
According to a specific embodiment of the invention, the white carbon black has a specific surface area of 50-400m2The dry basis weight of the white carbon black is taken as a reference, and SiO in the white carbon black2The content is 99.99 wt.% or more, for example, 99.99 wt.% or more and less than 100 wt.%, and the mass content of Fe, Al and Na impurities is less than 10 ppm.
According to the present invention, the white carbon black can be commercially available or can be prepared according to the existing method, for example, according to the method provided by CN200910227646.2, and the present invention is not particularly limited herein.
In the present invention, the kind and amount of the solvent used in the step (1) are not particularly limited. The first liquid titanium source, the first liquid silicon source and the auxiliary agent may be dissolved in the solvent. Specifically, the solvent is selected from water and/or alcohol (preferably alcohol with 1-5C atoms), such as water and/or ethanol.
The embodiment of mixing in step (1) in the present invention is not particularly limited, as long as the first liquid titanium source, the first liquid silicon source, the auxiliary agent and the solvent are uniformly mixed. Preferably, the mixing is carried out under stirring conditions, for example in a magnetic stirrer, for a period of time ranging from 1 to 20 hours.
According to the invention, the aging conditions are selected in a wide range, and preferably, the aging conditions in step (2) include: the aging temperature is 20-65 ℃, preferably 20-50 ℃; the aging time is 1 to 60 hours, preferably 2 to 50 hours, more preferably 3 to 30 hours, for example 3 to 15 hours.
According to a specific embodiment of the present invention, the aging in step (2) refers to allowing the first mixture in step (1) to stand at 20-65 ℃ for 1-60 hours, wherein the aging process preferably does not require stirring, and the first mixture is allowed to stand under the aging conditions.
According to the present invention, the heating conditions are selected in a wide range, and preferably, the heating conditions in step (3) include: under the closed condition, the heating temperature is 50-500 ℃, and preferably 250-500 ℃; the heating time is 1 to 30 hours, preferably 1 to 20 hours.
According to a specific embodiment of the present invention, the heating in step (3) refers to heating the aged sol and the solid silicon source in step (2) at 50-500 ℃ for 1-30 hours, so that the aged sol is completely converted into a solid gel, wherein the heating may be performed in a closed autoclave, which is not described herein in detail.
According to a preferred embodiment of the present invention, before the solid gel is calcined in step (4), the solid gel is further filtered and washed. Wherein, the filtration and washing are conventional means well known to those skilled in the art, and the detailed description of the present invention is omitted.
In the present invention, the baking is not particularly limited. Specifically, the roasting conditions in the step (4) include: in an oxygen-containing atmosphere, the roasting temperature is 100-500 ℃, preferably 250-480 ℃, and further preferably 350-450 ℃; the calcination time is 1 to 20 hours, preferably 2 to 10 hours, and more preferably 2 to 8 hours. In the present invention, the oxygen-containing atmosphere is not particularly limited, and it is sufficient that only oxygen required for calcination can be supplied, and it may be pure oxygen or a mixed gas of oxygen and other gases.
In the present invention, the template in the step (5) is not particularly limited. The appropriate template can be selected according to the structure of the desired synthesized molecular sieve (MFI structure, MEL structure, BEA structure, MWW structure or MOR structure). Preferably, the template is selected from at least one of an organic quaternary ammonium compound, a long-chain alkyl ammonium compound and an organic amine, and further preferably, the template comprises the organic quaternary ammonium compound, the long-chain alkyl ammonium compound and optionally the organic amine.
Preferably, the organic quaternary ammonium compound is an organic quaternary ammonium base and/or an organic quaternary ammonium salt. Further preferably, the organic quaternary ammonium base is selected from at least one of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and tetraethylammonium hydroxide, and the organic quaternary ammonium salt is selected from at least one of tetrapropylammonium bromide, tetrabutylammonium bromide, tetraethylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium chloride and tetraethylammonium chloride.
According to a preferred embodiment of the present invention, the titanium silicalite molecular sieve obtained by the preparation method has an MFI structure, and the organic quaternary ammonium compound is at least one selected from the group consisting of tetrapropylammonium hydroxide, tetrapropylammonium chloride and tetrapropylammonium bromide.
According to a preferred embodiment of the present invention, the titanium silicalite molecular sieve obtained by the preparation method has a MEL structure, and the organic quaternary ammonium compound is at least one selected from tetrabutylammonium hydroxide, tetrabutylammonium bromide and tetrabutylammonium chloride.
According to a preferred embodiment of the present invention, the titanium silicalite molecular sieve obtained by the preparation method has a BEA structure, and the organic quaternary ammonium compound is at least one selected from tetraethylammonium hydroxide, tetraethylammonium bromide and tetraethylammonium chloride.
Preferably, the long-chain alkylammonium compound has the formula R2N(R3)3X, wherein R2Is alkyl with 12-18 carbon atoms, R3Is H or an alkyl radical having 1 to 4 carbon atoms, X is a monovalent anion, for example OH-、Cl-、Br-. Specifically, when X is OH-When the long-chain alkyl ammonium compound is a basic long-chain alkyl ammonium compound; when X is Cl-When the long-chain alkyl ammonium compound is long-chain alkyl ammonium chloride; when X is Br-When the alkyl ammonium compound is a long-chain alkyl ammonium bromide compound, the long-chain alkyl ammonium bromide compound is a long-chain alkyl ammonium bromide compound.
According to a preferred embodiment of the present invention, the basic long-chain alkylammonium compound is selected from at least one of dodecyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide and octadecyltrimethylammonium hydroxide.
According to a preferred embodiment of the invention, the long-chain alkyl ammonium chloride is selected from at least one of dodecyl ammonium chloride, tetradecyl ammonium chloride, hexadecyl ammonium chloride and octadecyl ammonium chloride.
According to a preferred embodiment of the invention, the long chain alkyl ammonium bromide is selected from at least one of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide.
According to the present invention, preferably, the organic amine is at least one of an aliphatic amine, an alcohol amine, and an aromatic amine; the fatty amine has a general formula of R4(NH2)nWherein R is4Is an alkyl or alkylene group having 1 to 4 carbon atoms, n ═ 1 or 2; the alcohol amine has the general formula of (HOR)5)mNH(3-m)Wherein R is5Is alkyl having 1 to 4 carbon atoms, m is 1, 2 or 3; the aromatic amine is an amine having one aromatic substituent.
According to a preferred embodiment of the present invention, the aliphatic amine is at least one selected from the group consisting of ethylamine, n-butylamine, butanediamine and hexamethylenediamine.
According to a preferred embodiment of the present invention, the alcohol amine is at least one selected from the group consisting of monoethanolamine, diethanolamine and triethanolamine.
According to a preferred embodiment of the present invention, the aromatic amine is at least one selected from aniline, toluidine and p-phenylenediamine.
According to the present invention, preferably, the molar ratio of the organic quaternary ammonium compound to the total silicon source is 0.04-0.45: 1, and the molar ratio of the long-chain alkyl ammonium compound to the total silicon source is 0.04-0.45: 1; the molar ratio of the organic amine to the total silicon source is 0-0.4: 1.
Preferably, the molar ratio of the template to the total silicon source is 0.08-0.6: 1, preferably 0.1-0.3: 1, more preferably 0.1-0.25: 1, and even more preferably 0.1-0.2: 1.
According to the present invention, preferably, the molar ratio of the water to the total silicon source in step (5) is 5-100: 1. In the method provided by the invention, the small-grain stacked titanium silicalite molecular sieve can be synthesized under high solid content, so that the using amount of water is reduced, the single-kettle yield is improved, namely more molecular sieves are synthesized under the same synthesis reactor volume, and the molar ratio of the water to the total silicon source in the step (5) is preferably 5-80: 1 or 5-50: 1 or 6-30: 1 or 6-20: 1 or 6-15: 1.
Preferably, the molar ratio of the inorganic ammonium source in step (5) to the first liquid titanium source in step (1) is 0.01-5: 1, preferably 0.01-4: 1, and more preferably 0.01-0.5: 1, and the inorganic ammonium source is NH4 +The first liquid titanium source is TiO2And (6) counting.
In the present invention, the inorganic ammonium source in the step (5) is not particularly limited. In particular, the inorganic ammonium source is selected from inorganic ammonium salts and/or aqueous ammonia, preferably aqueous ammonia. The inorganic ammonium salt is preferably at least one selected from the group consisting of ammonium chloride, ammonium nitrate and ammonium sulfate.
In the invention, the inorganic ammonium source is added, so that the oxidation activity of the titanium silicalite molecular sieve is improved, the utilization rate of the titanium source (higher framework titanium-silicon ratio under the condition of the same titanium source usage) is improved, and the usage amount of the titanium source is reduced.
In the present invention, the crystallization is not particularly limited. Preferably, the crystallization conditions in step (5) include: the crystallization temperature is 110-200 ℃, preferably 140-180 ℃, and further preferably 160-180 ℃; the crystallization pressure is autogenous pressure, and the crystallization time is 2 to 480 hours, preferably 0.5 to 10 days, for example, 1 to 6 days, and more preferably 1 to 3 days.
According to one embodiment of the invention, the crystallization may be carried out in a stainless steel stirred tank. The temperature rise for crystallization can be carried out in a one-stage temperature rise manner or a multi-stage temperature rise manner, and the temperature rise rate can be carried out according to the existing crystallization temperature rise method, for example, 0.5-1 ℃/min.
According to a preferred embodiment of the present invention, the crystallization conditions include: crystallizing at 100-.
According to the invention, the method can also comprise recovering titanium silicalite from the product obtained by crystallization in the step (5). The method for recovering the titanium silicalite molecular sieve can be the existing method, and comprises the steps of filtering, washing and roasting a crystallized product or filtering, washing, drying and roasting the crystallized product. The purpose of filtration is to separate the crystallized small-grain stacked titanium-silicon molecular sieve from the crystallization mother liquor, and the purpose of washing is to wash off the silicon-containing template adsorbed on the surface of the molecular sieve particles, for example, the molecular sieve-water weight ratio of 1: 1-20 (1-20) such as 1: 1-15 can be mixed and washed at room temperature to 50 ℃, and then filtered or rinsed with water. The drying is to remove most of the water in the molecular sieve to reduce the water evaporation amount during calcination, and the drying temperature can be 100-200 ℃. The purpose of calcination is to remove the template in the molecular sieve, for example, the calcination temperature is 350-650 ℃, and the calcination time is 2-10 hours. The titanium silicalite molecular sieve provided by the invention is obtained by recovery.
According to the invention, preferably, the method further comprises a step (6), said step (6) comprising: and (4) mixing the solid product obtained in the step (5), organic base and water, and then carrying out second crystallization.
Preferably, the conditions of the second crystallization include: the second crystallization temperature is 110-200 ℃, more preferably 150-200 ℃; the second crystallization time is 0.5 to 10 days, more preferably 1 to 8 days.
According to a preferred embodiment of the present invention, the solid product obtained in step (5), an organic base and water are mixed and subjected to a second crystallization. The obtained titanium-silicon molecular sieve with small crystal grain stacked shape has a hollow structure, which is called as molecular sieve rearrangement in the invention. Preferably, the organic base is reacted with the solid product obtained in step (5) (in SiO)2In terms of molar ratio) of 0.02 to 0.5: 1, more preferably 0.02 to 0.2: 1. Preferably, the water is mixed with the solid product (in SiO)2In terms of molar ratio) of 2 to 50: 1, more preferably 2 to 30: 1, for example 2 to 20: 1, preferably 5 to 10: 1. The organic base may be organic amine and/or organic quaternary ammonium base, and the organic amine and the organic quaternary ammonium base are defined as above, which is not described herein again.
Specifically, the method can also comprise recovering titanium silicalite molecular sieves from the product obtained by crystallization in the step (6). Generally comprises filtering, washing, drying and then roasting the crystallized product, and the recovery method can be referred to the step (5), and the invention is not described herein.
In the present invention, the rearrangement of the molecular sieve step (6) may be performed once or may be repeated a plurality of times. Through rearrangement treatment, the small-grain stacked titanium silicalite molecular sieve with a more obvious mesoporous structure is obtained, and the rearranged titanium silicalite molecular sieve has larger pore volume and specific surface area.
In a third aspect, the invention provides a cyclohexanone oximation reaction method, which comprises contacting cyclohexanone, ammonia and hydrogen peroxide with the titanium silicalite molecular sieve provided by the invention under oximation reaction conditions.
The cyclohexanone oximation reaction method according to the present invention is not particularly limited in the oximation reaction conditions, and can be carried out under conventional conditions. Specifically, the oximation reaction conditions comprise: the reaction temperature is 40-120 ℃, preferably 50-100 ℃, the reaction pressure is 0-5MPa, preferably 0.1-3MPa, and the volume space velocity is 5-15h-1Preferably 5-10h-1。
In the present invention, it is preferred that the molar ratio of cyclohexanone, ammonia and hydrogen peroxide is 1: 0.2-5, preferably 1: 1-3.
The contacting may be carried out in a solvent or in the absence of a solvent. The solvent may be one or more of alcohol, ketone, nitrile, ether, ester and water. Specific examples of the solvent may include, but are not limited to, at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetone, butanone, methyl t-butyl ether, acetonitrile, and water. Preferably, the solvent is at least one of methanol, acetone, t-butanol and water. The amount of the solvent used in the present invention is not particularly limited, and may be selected conventionally. Generally, the solvent may be used in an amount of 10 to 5000 parts by weight, preferably 50 to 4000 parts by weight, more preferably 50 to 2000 parts by weight, relative to 100 parts by weight of cyclohexanone.
The present invention will be described in detail below by way of examples.
SEM electron microscope experiments were performed on Hitachi S4800 high resolution cold field emission scanning electron microscope.
TEM electron microscopy experiments were carried out on a transmission electron microscope of the type Tecnai F20G 2S-TWIN, from FEI, equipped with an energy filtration system GIF2001 from Gatan, with an attached X-ray energy spectrometer. The electron microscope sample is prepared on a micro-grid with the diameter of 3mm by adopting a suspension dispersion method.
XRD measurement method: x-ray diffraction (XRD) crystallography of the sample was performed on a Siemens D5005X-ray diffractometer using a CuK alpha radiation source
Figure BDA0002253707820000151
Tube voltage 40kV, tube current 40mA, scanning speed 0.5 °/min, scanning range 2 θ is 4-40 °.
The characterization method of the low-temperature nitrogen adsorption curve was performed on a Micromeritics ASAP-2010 static nitrogen adsorption apparatus manufactured by Quantachrome.
The pore volume was measured by a nitrogen adsorption capacity method according to the BJH calculation method (see petrochemical analysis method (RIPP test method), RIPP151-90, scientific Press, 1990).
The acid content of the titanium silicalite molecular sieve is measured by pyridine absorption infrared spectroscopy.
The particle size of the molecular sieve particles and the particle size of the crystal grains of the titanium silicalite molecular sieve are obtained by transmission electron microscope detection (measured by a TEM scale).
In the following examples, room temperature was 25 ℃ unless otherwise specified.
The sources of the raw materials used in the examples and comparative examples are as follows:
tetrabutyl titanate, analytically pure, chemical reagents of the national pharmaceutical group, ltd.
Titanium tetrachloride, analytically pure, chemical reagents of the national drug group, ltd.
Tetrapropylammonium hydroxide, available from Guangdong chemical plant.
Tetraethyl silicate, analytically pure, chemical reagents of the national pharmaceutical group, ltd.
Ammonia, analytically pure, concentration 20% by weight.
White carbon black, Zhejiang Juhua group product, model AS-150; a solid content of more than 95% by weight, a silica content of more than 99.99% by weight on a dry basis, the total content of iron, sodium and AlThe amount is less than 10ppm, and the specific surface area is 195m2/g。
Other reagents are not further described, and are all commercial products and analytically pure.
The gas chromatograph is purchased from Agilent company and is model 6890, and the analytical chromatographic column is an FFAP column.
Examples 1 to 12 of the present invention are made of SiO2The total silicon source usage was fixed at 0.2 mol.
Example 1
(1) Tetrabutyl titanate (a first liquid titanium source), tetraethyl silicate (TEOS, a first liquid silicon source), polyacrylic acid (weight average molecular weight of 5000) powder and 3g of water are sequentially added into a 500mL beaker, put on a magnetic stirrer with heating and stirring functions, mixed uniformly and stirred at room temperature for 4 hours to obtain a first mixture.
(2) And standing the first mixture at room temperature for 12 hours for aging treatment to obtain an aged sol.
(3) Adding white carbon black powder (solid silicon source) into the aged sol under stirring, and heating in a closed autoclave at 500 ℃ for 5 hours to obtain solid gel.
(4) Washing the solid gel with deionized water for 3 times, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain TiO2-SiO2White oxide.
(5) Mixing the titanium silicon oxide, 25.05 wt% tetrapropylammonium hydroxide aqueous solution (TPAOH), hexadecyl trimethyl ammonium hydroxide (MSDS), tetrabutyl titanate (second liquid titanium source), tetraethyl silicate (TEOS, second liquid silicon source), 20 wt% ammonia water and water to obtain a second mixture, then transferring the second mixture into a stainless steel closed reaction kettle, crystallizing the second mixture at the constant temperature of 175 ℃ for 48 hours to obtain a crystallized sample, filtering and washing the crystallized sample, drying the crystallized sample at the temperature of 120 ℃ for 24 hours, and roasting the crystallized sample at the temperature of 550 ℃ for 6 hours to obtain the titanium silicon molecular sieve S-1 with small crystal grain stacking shape, wherein the titanium silicon molecular sieve S-1 has an MFI structure.
The SEM and TEM photographs of the titanium silicalite S-1 are shown in figures 1 and 2, and the XRD analysis spectrum is shown in figure 8.
As can be seen from fig. 1 and 2, the molecular sieve particles are formed by stacking crystal grains having a particle size of 20 to 50 nm. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Example 2
(1) Titanium tetrachloride, tetraethyl silicate (TEOS), tert-butyl hydroperoxide and 10g of ethanol were sequentially added to a 500mL beaker, placed on a magnetic stirrer with heating and stirring functions, mixed uniformly and stirred at room temperature for 10 hours to obtain a first mixture.
(2) And standing the first mixture at 37 ℃ for 24 hours for aging treatment to obtain an aged sol.
(3) Adding white carbon black powder into the aged sol under stirring, and heating in a sealed autoclave at 450 ℃ for 4 hours to obtain solid gel.
(4) Washing the solid gel with deionized water for 3 times, and roasting in a muffle furnace at 450 ℃ for 4 hours to obtain TiO2-SiO2White oxide.
(5) Mixing the titanium silicon oxide, 25.05 weight percent tetrapropylammonium hydroxide aqueous solution (TPAOH), hexadecyl trimethyl ammonium hydroxide (MSDS), tetrabutyl titanate, tetraethyl silicate (TEOS), 20 weight percent ammonia water and water to obtain a second mixture, then transferring the second mixture into a stainless steel closed reaction kettle, crystallizing at the constant temperature of 160 ℃ for 72 hours to obtain a crystallized sample, filtering and washing the crystallized sample, drying the crystallized sample at 120 ℃ for 24 hours, and roasting the crystallized sample at 550 ℃ for 6 hours to obtain the titanium silicon molecular sieve S-2 with small crystal grain stacking shape, wherein the titanium silicon molecular sieve S-2 has an MFI structure.
The SEM image and the TEM image of the titanium silicalite molecular sieve S-2 are similar to those of the titanium silicalite molecular sieve S-1, and an XRD analysis spectrogram is shown in FIG. 8.
The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Example 3
Taking the titanium silicalite molecular sieve S-2 prepared in the example 2 as a matrix, taking 6g of the sample and a TPAOH aqueous solution with the weight percent of 22.05 to mix, uniformly stirring, crystallizing for 3 days at 150 ℃ in a closed reaction kettle, filtering, washing, drying for 24 hours at 120 ℃, and roasting for 6 hours at 550 ℃ to obtain the hollow small-grain stacked titanium silicalite molecular sieve S-3 with an MFI structure.
The TEM photograph of the titanium silicalite S-3 is shown in FIG. 3. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Examples 4 to 7
Titanium silicalite molecular sieves were prepared according to the procedure of example 1, with the components and synthesis conditions of the titanium silicalite molecular sieves shown in table 1, to obtain small-grained stacked titanium silicalite molecular sieves S-4 to S-7. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Example 8
The titanium silicalite molecular sieve was prepared according to the method of example 1, except that in step (5), the titanium silicalite molecular sieve was first crystallized at 120 ℃ for 1 day and then crystallized at 170 ℃ for 2 days, the composition and synthesis conditions of the titanium silicalite molecular sieve are shown in table 1, and the titanium silicalite molecular sieve S-8 with small stacked grains was obtained. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Example 9
Preparing a titanium silicalite molecular sieve with an MEL structure. Referring to the method according to example 1, the composition and synthesis conditions of the titanium silicalite molecular sieve are shown in table 1 by changing the mixture ratio and the template, and the titanium silicalite molecular sieve S-9 with stacked small grains is obtained. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Example 10
Preparing the titanium silicalite molecular sieve with BEA structure. Referring to the method of example 1, the composition and synthesis conditions of the titanium silicalite molecular sieve are shown in table 1 by changing the mixture ratio and the template, and the titanium silicalite molecular sieve S-10 with stacked small grains is obtained. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Example 11
The procedure of example 1 was followed except that the aging temperature was 75 ℃ to obtain titanium silicalite S-11. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Example 12
The procedure of example 1 was followed, except that polyacrylic acid was replaced with an equimolar amount of trimethylchlorosilane, to obtain titanium silicalite molecular sieve S-12. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Comparative example 1
Mixing 22.5g tetraethyl silicate with 7g tetrapropylammonium hydroxide, adding 59.8g deionized water, and uniformly mixing; then hydrolyzing for 1h at 60 ℃ to obtain a hydrolysis solution of tetraethyl silicate. To the above solution was slowly dropped a solution composed of 1.1g of titanium tetrachloride and 5g of isopropyl alcohol under vigorous stirring, and the mixture was stirred at 75 ℃ for 3 hours to obtain a clear and transparent colloid. And then the colloid is moved into a stainless steel closed reaction kettle and crystallized for 3 days at the constant temperature of 170 ℃, thus obtaining the conventional titanium silicalite molecular sieve D-1.
The SEM and TEM photographs of the titanium silicalite D-1 are shown in FIGS. 4 and 5, and the XRD analysis spectrum is shown in FIG. 8. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Comparative example 2
Mixing 22.5g tetraethyl silicate with 9g tetrapropyl ammonium hydroxide, adding 64.5g deionized water, and uniformly mixing; then hydrolyzing for 1h at 60 ℃ to obtain a hydrolysis solution of tetraethyl silicate. To the above solution was slowly dropped a solution composed of 0.6g of titanium tetrachloride and 7g of isopropyl alcohol under vigorous stirring, and the mixture was stirred at 75 ℃ for 7 hours to obtain a clear and transparent colloid. And then the colloid is moved into a stainless steel closed reaction kettle and crystallized for 3 days at the constant temperature of 170 ℃ to obtain the conventional titanium silicalite molecular sieve.
Then titanium tetrachloride, anhydrous isopropanol, tetrapropylammonium hydroxide and deionized water are uniformly mixed according to the molar ratio of 1: 15: 2.4: 350, and are hydrolyzed for 30 minutes at the temperature of 45 ℃ under normal pressure to obtain a hydrolyzed solution of titanium tetrachloride. And (2) uniformly mixing the prepared titanium silicalite molecular sieve with the hydrolysis solution of titanium tetrachloride according to the ratio of the molecular sieve (g) to the Ti (mol) of 600: 1, uniformly stirring for 12 hours at normal temperature (25 ℃), finally placing the dispersed suspension into a stainless steel reaction kettle, and standing for 3 days at 165 ℃ to obtain the rearranged titanium silicalite molecular sieve D-2.
The SEM and TEM photographs of the titanium silicalite D-2 are shown in FIGS. 6 and 7, and the XRD analysis spectrum is shown in FIG. 8. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Comparative example 3
The procedure of example 1 was followed, except that ammonia (inorganic ammonium source) was not added, to obtain titanium silicalite D-3. The average grain size of the molecular sieve grains, the average grain boundary size, are listed in table 2. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Comparative example 4
Titanium silicalite D-4 was obtained following the procedure of example 1, except that no ammonia (inorganic ammonium source) was added and no aging was performed. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Comparative example 5
The procedure of example 1 was followed, except that the solid silicon source in step (3) was added to step (1), to obtain titanium silicalite D-5. The average particle size of the molecular sieve grains, the average particle size of the molecular sieve particles, and the average grain boundary size are shown in table 2. The micropore volume, mesopore volume, benzene adsorption amount and Lewis acid amount of the molecular sieve are shown in Table 2.
Test example
The titanium silicalite molecular sieves prepared in the above examples 1 to 12 and comparative examples 1 to 5 were used as catalysts for cyclohexanone oximation reaction to carry out oximation reaction.
According to the mass ratio of titanium silicon molecular sieve to tertiary butanol (solvent) to 25 wt% ammonia water (wherein, the weight of the ammonia water is NH)3Metering) is evenly stirred and mixed in a slurry bed, the temperature is raised to 78 ℃, and the dosage of the titanium silicalite molecular sieve is 3 g. Then 30 weight percent hydrogen peroxide is added at the temperature at the rate of 6mL/h, a mixture of cyclohexanone and tert-butyl alcohol is added at the rate of 8.6mL/h (the volume ratio of the cyclohexanone to the tert-butyl alcohol is 1: 2.5), and simultaneously 25 weight percent ammonia water solution is added at the rate of 6mL/h, and the volume space velocity is 7.92h-1. The three materials are added simultaneously, and are discharged continuously at corresponding speed, 3 hours after the reaction is stable, a gas chromatograph is used for carrying out quantitative analysis on the concentration of each substance after the reaction, the cyclohexanone conversion rate and the cyclohexanone oxime selectivity are calculated, and specific results are shown in table 2.
The conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime are respectively calculated according to the following formulas:
Figure BDA0002253707820000221
Figure BDA0002253707820000222
TABLE 1
Figure BDA0002253707820000231
TABLE 1
Figure BDA0002253707820000241
Note: TPABr is tetrapropylammonium bromide, CTMAB is cetyltrimethylammonium bromide, DTAB is dodecyltrimethylammonium hydroxide, MSDS is cetyltrimethylammonium hydroxide, TBAOH is tetrabutylammonium hydroxide, TEAOH is tetraethylammonium hydroxide.
TABLE 2
Figure BDA0002253707820000251
According to the data in table 2, it can be seen that, compared with the existing titanium silicalite molecular sieve, the titanium silicalite molecular sieve provided by the invention can be used as a catalyst for cyclohexanone oximation reaction, and more excellent catalytic performance can be obtained.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (14)

1. The titanium-silicon molecular sieve is characterized in that the molecular sieve particles are formed by stacking crystal grains with the particle size of 20-50nm, the particle size of the molecular sieve particles is 500-1000nm, the average grain boundary size of the molecular sieve particles is 1-5nm, the grain boundary mesoporous volume is 0.1-0.5mL/g, and the Lewis acid content of the molecular sieve is 15-30 mu mol/g.
2. The molecular sieve of claim 1, wherein the molar ratio of titanium to silicon in the molecular sieve is from 0.005 to 0.04: 1, preferably 0.01-0.035: 1;
preferably, the average grain boundary size of the molecular sieve particles is 1-3nm, and the mesoporous volume of the grain boundary is 0.1-0.2 mL/g.
3. The molecular sieve of claim 1, wherein the molecular sieve is at 25 ℃, P/P0(ii) an adsorbed benzene amount of at least 30 mg/g as measured at an adsorption time of 1 hour, 0.1;
preferably, the molecular sieve has an MFI structure, an MEL structure, a BEA structure, an MWW structure or an MOR structure.
4. A method for preparing a titanium silicalite molecular sieve, the method comprising:
(1) mixing a first liquid titanium source, a first liquid silicon source, an auxiliary agent and a solvent to obtain a first mixture;
(2) aging the first mixture to obtain an aged sol;
(3) heating the aged gel and the solid silicon source to obtain solid gel;
(4) roasting the solid gel to obtain titanium silicon oxide;
(5) and mixing the titanium-silicon oxide, the template agent, a second liquid titanium source, a second liquid silicon source, water and an inorganic ammonium source to obtain a second mixture, and then crystallizing.
5. The production method according to claim 4, wherein the auxiliary in step (1) comprises a space-filling agent and/or a stabilizer;
preferably, the space-filling agent is selected from a silylating agent and/or a water-soluble polymer compound;
preferably, the space-filling agent is selected from at least one of a silylating agent, polyacrylamide, and polyacrylic acid;
preferably, the stabilizer is selected from at least one of oxalic acid, t-butyl hydroperoxide, cyclohexyl hydroperoxide, hydrogen peroxide and citric acid;
preferably, the molar ratio of the auxiliary agent to the first liquid silicon source in step (1) is 0.01-0.1: 1, preferably 0.02 to 0.07: 1, wherein the first liquid silicon source is SiO2And (6) counting.
6. The production method according to claim 4, wherein the first liquid titanium source and the second liquid titanium source are each independently selected from an inorganic liquid titanium source and/or an organic liquid titanium source;
preferably, the first and second liquid silicon sources are each independently selected from an inorganic liquid silicon source and/or an organic liquid silicon source;
preferably, the solid silicon source in the step (3) is white carbon black and/or silica gel;
preferably, TiO is used in step (1)2The first liquid titanium source and TiO measured in the step (5)2The molar ratio of the second liquid titanium source is 1: 0.5 to 8, preferably 1: 2.5-6;
preferably, SiO is used in step (1)2The first liquid silicon source and SiO in step (5)2The molar ratio of the second liquid silicon source is 1: 0.5 to 8, preferably 1: 2.5-6;
preferably, the molar ratio of the total titanium source to the total silicon source is 0.005-0.05: 1, wherein the total titanium source is TiO2The total silicon source is SiO2The total titanium source is TiO2A first liquid titanium source and in TiO2The total sum of the second liquid titanium source and the total silicon source is SiO2First liquid silicon source in terms of SiO2Second liquid silicon source and SiO2The sum of the counted solid silicon sources;
preferably in SiO2The total liquid silicon source and SiO in step (3)2The molar ratio of the solid silicon source is 1: 1-9, preferably 1: 2-8.
7. The production method according to claim 4, wherein the aging conditions in step (2) include: the aging temperature is 20-65 ℃, preferably 20-50 ℃; the aging time is 1 to 60 hours, preferably 2 to 50 hours;
preferably, the heating conditions in step (3) include: under the closed condition, the heating temperature is 50-500 ℃, and preferably 250-500 ℃; the heating time is 1 to 30 hours, preferably 1 to 20 hours;
preferably, the roasting conditions in step (4) include: in an oxygen-containing atmosphere, the roasting temperature is 100-500 ℃, and preferably 250-480 ℃; the calcination time is 1 to 20 hours, preferably 2 to 10 hours.
8. The production method according to any one of claims 4 to 7, wherein the templating agent in step (5) comprises an organic quaternary ammonium compound, a long-chain alkyl ammonium compound, and optionally an organic amine;
preferably, the organic quaternary ammonium compound is an organic quaternary ammonium base and/or an organic quaternary ammonium salt;
preferably, the long-chain alkylammonium compound has the formula R2N(R3)3X, wherein R2Is alkyl with 12-18 carbon atoms, R3Is H or alkyl with 1-4 carbon atoms, and X is monovalent anion;
preferably, the organic amine is one or more of aliphatic amine, alcohol amine and aromatic amine; the fatty amine has a general formula of R4(NH2)nWherein R is4Is an alkyl or alkylene group having 1 to 4 carbon atoms, n ═ 1 or 2; the alcohol amine has the general formula of (HOR)5)mNH(3-m)Wherein R is5Is alkyl having 1 to 4 carbon atoms, m is 1, 2 or 3; the aromatic amine is an amine having one aromatic substituent.
9. The method of claim 8, wherein the molar ratio of the organic quaternary ammonium compound to the total silicon source is from 0.04 to 0.45: 1, the molar ratio of the long-chain alkyl ammonium compound to the total silicon source is 0.04-0.45: 1; the molar ratio of the organic amine to the total silicon source is 0-0.4: 1;
preferably, the molar ratio of the template agent to the total silicon source is 0.08-0.6: 1, preferably 0.1 to 0.3: 1, more preferably 0.1 to 0.25: 1.
10. the production method according to any one of claims 4 to 9, wherein the molar ratio of the water to the total silicon source in step (5) is 5 to 100: 1, preferably 5 to 50: 1, more preferably 6 to 30: 1;
preferably, the molar ratio of the inorganic ammonium source in step (5) to the first liquid titanium source in step (1) is from 0.01 to 5: 1, preferably 0.01 to 4: 1, more preferably 0.01 to 0.5: 1, the inorganic ammonium source is NH4 +The first liquid titanium source is TiO2And (6) counting.
11. The production method according to any one of claims 4 to 10, wherein the crystallization conditions in step (5) include: the crystallization temperature is 110-;
preferably, the crystallization temperature is 140-180 ℃, and more preferably 160-180 ℃;
preferably, the crystallization conditions include: crystallizing at 100-130 deg.C for 0.5-1.5 days, and crystallizing at 160-180 deg.C for 1-3 days.
12. The production method according to any one of claims 4 to 11, wherein the method further comprises a step (6), and the step (6) comprises: mixing the solid product obtained in the step (5), organic alkali and water, and then carrying out second crystallization;
preferably, the conditions of the second crystallization include: the second crystallization temperature is 110-200 ℃, preferably 150-200 ℃; the second crystallization time is 0.5-10 days, preferably 1-8 days;
preferably, the method further comprises drying and calcining the solid product obtained in step (5) and/or the second crystallized product obtained in step (6).
13. The titanium silicalite molecular sieve prepared by the preparation method of any one of claims 4 to 12.
14. A cyclohexanone oxime reaction process comprising contacting cyclohexanone, ammonia, and hydrogen peroxide with a titanium silicalite molecular sieve under oximation reaction conditions, wherein the titanium silicalite molecular sieve is the titanium silicalite molecular sieve of any one of claims 1-3 and 13.
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