CN112744830B - Titanium-silicon molecular sieve, preparation method thereof and cyclohexanone oxime reaction method - Google Patents

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

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CN112744830B
CN112744830B CN201911051853.7A CN201911051853A CN112744830B CN 112744830 B CN112744830 B CN 112744830B CN 201911051853 A CN201911051853 A CN 201911051853A CN 112744830 B CN112744830 B CN 112744830B
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molecular sieve
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titanium
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silicon source
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CN112744830A (en
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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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Abstract

The invention relates to the field of molecular sieve preparation, in particular to a titanium-silicon molecular sieve, a preparation method thereof and a cyclohexanone oxime 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 molecular sieve Lewis acid amount is 15-30 mu mol/g. The preparation method can synthesize the small-grain stacked titanium-silicon molecular sieve under the conditions of lower template agent dosage and lower water-silicon ratio, reduces the synthesis cost, improves the solid content of the crystallized product of the synthesized molecular sieve, and improves the yield of the single-kettle molecular sieve. The titanium-silicon molecular sieve provided by the invention is used in cyclohexanone oxime reaction, and has higher reaction activity and selectivity.

Description

Titanium-silicon molecular sieve, preparation method thereof and cyclohexanone oxime reaction method
Technical Field
The invention relates to the field of molecular sieve preparation, in particular to a titanium-silicon molecular sieve, a preparation method thereof and a cyclohexanone oxime reaction method.
Background
The titanium-silicon molecular sieve synthesized at present has an MFI structure TS-1, an MEL structure TS-2, an MWW structure MCM-22, a larger pore structure TS-48 and the like.
TS-1 is originally developed and synthesized by EniChem company in Italy, and is a novel titanium-silicon molecular sieve with excellent catalytic selective oxidation performance formed by introducing transition metal titanium into a molecular sieve framework with a ZSM-5 structure, wherein 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-silicon molecular sieve can be used as a catalyst for catalyzing various types of organic oxidation reactions, such as olefin epoxidation, alkane partial oxidation, alcohol oxidation, phenol hydroxylation, cyclic ketone ammoxidation and the like. Because 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 method 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-silicon molecular sieve is taken as an organic matter selective oxidation catalyst, is considered as a milestone in the field of molecular sieve catalysis, and can overcome the defects of complex reaction process, severe conditions, serious environmental pollution and the like of the traditional catalytic oxidation system from the source, so that the titanium-silicon molecular sieve is extremely highly valued by people at present with increasingly strict environmental protection requirements.
In 1983, taramasso reported a method for synthesizing titanium silicalite molecular sieves by hydrothermal crystallization in 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: placing Tetraethoxysilane (TEOS) into nitrogen to protect against CO 2 Slowly adding TPAOH (template agent), then slowly dripping tetraethyl titanate (TEOT), stirring for 1 hr to obtain a reaction mixture containing silicon source, titanium source and organic base, heating, removing alcohol, supplementing water, and heating at 175 deg.CUnder stirring in a raw pressure kettle, crystallizing for 10 days, and then separating, washing, drying and roasting to obtain the TS-1 molecular sieve. However, the titanium insertion skeleton process in the process has a plurality of influencing factors, 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, difficult synthesis and reproduction and the like.
CN1260241a discloses a rearrangement technology of a titanium-silicon molecular sieve, and synthesizes a novel titanium-silicon molecular sieve with a unique hollow structure, so that not only is the reproducibility of synthesizing TS-1 greatly enhanced, but also the size of molecular sieve pores is increased, the mass transfer diffusion rate of reactant molecules in molecular sieve pore channels is greatly improved, and the catalytic performance is increased. The method disclosed in the patent mixes the titanium hydrolysis solution and the synthesized TS-1 molecular sieve uniformly according to the ratio of molecular sieve (g) to Ti (mol) =200-1500:1, and the obtained mixture reacts for 1-8 days at 120-200 ℃ in a reaction kettle, and then is filtered, washed and dried. At present, the HTS molecular sieve is applied to the processes of catalyzing the oxidization of phenol, hydroxylation of cyclohexanone ammoximation and the like to realize industrialization, and has the advantages of mild reaction conditions, high atom utilization rate, simple process, clean and efficient water as a byproduct and the like.
The titanium-silicon molecular sieve synthesized by the prior method mainly takes micropores as main materials, has smaller mesoporous volume, and is not beneficial to mass transfer diffusion in the crystal; and the synthesis difficulty of the molecular sieve is high.
Disclosure of Invention
The invention aims to solve the problems of the prior art that a titanium-silicon molecular sieve mainly takes micropores as main materials, the mesoporous volume is smaller, and the synthesis difficulty is higher, and provides a titanium-silicon molecular sieve, a preparation method thereof and a cyclohexanone oxime 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 at the same time, and the prepared titanium silicalite molecular sieve has higher oxidation activity and selectivity.
The first aspect of the invention provides a titanium silicon 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 molecular sieve Lewis acid amount is 15-30 mu mol/g.
Preferably, the molecular sieve is at 25 ℃, P/P 0 The benzene adsorption amount measured under the conditions of=0.1 and adsorption time of 1 hour is at least 30 mg/g.
The second aspect of the invention provides a method for preparing a titanium silicalite molecular sieve, 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 sol and a 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, in step (1) TiO is used 2 A first liquid titanium source and TiO in step (5) 2 The 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) 2 A first liquid silicon source and SiO in step (5) 2 The 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 used as TiO 2 The total silicon source is calculated as SiO 2 The total titanium source is calculated as TiO 2 First liquid titanium source and TiO 2 Sum of the second liquid titanium sources, the total silicon source being SiO 2 First liquid silicon source of meter, in SiO 2 Second liquid silicon source and SiO 2 Total of solid silicon sources.
Preferably in SiO 2 Counting the total liquid silicon source and SiO in step (3) 2 Said fixing of the meterThe molar ratio of the bulk silicon source is 1:1-9, preferably 1:2-8.
Preferably, the molar ratio of the templating 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 from 5 to 100:1.
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.
The third aspect of the invention provides a titanium-silicon 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 oxime reaction conditions, wherein the titanium silicalite molecular sieve is the titanium silicalite molecular sieve provided by the invention.
According to the preparation method of the titanium-silicon molecular sieve, provided by the invention, the expensive liquid silicon source is partially replaced by the relatively cheap and easily obtained solid silicon source, so that the waste emission in the molecular sieve production process can be reduced, the raw material cost is saved, and meanwhile, the high-performance small-grain stacked titanium-silicon molecular sieve material is obtained, and the prepared molecular sieve has higher oxidation activity. The preparation method of the titanium-silicon molecular sieve provided by the invention can synthesize the small-grain stacked titanium-silicon molecular sieve material under the conditions of lower template dosage and lower water-silicon ratio, can reduce the synthesis cost of the titanium-silicon molecular sieve material, improves the solid content of the crystallized product of the synthesized molecular sieve, and improves the yield of the single-kettle molecular sieve. The titanium-silicon molecular sieve prepared by the preparation method provided by the invention is used in cyclohexanone oxime reaction, and has higher reaction activity and selectivity.
Drawings
FIG. 1 is an SEM photograph of a 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 a Ti-MFI molecular sieve obtained by the rearrangement treatment of example 3;
FIG. 4 is an SEM photograph of a 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 and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of 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 molecular sieve Lewis acid amount is 15-30 mu mol/g.
According to the invention, the molecular sieve particles of the titanium-silicon molecular sieve are formed by stacking crystal grains with the particle size of 20-50nm and are obtained through transmission electron microscopy detection.
According to the present invention, the molecular sieve particles of the titanium silicalite molecular sieve and the grain size of the crystal grains are obtained by transmission electron microscopy (measured by a TEM scale).
The molecular sieve particles of the titanium-silicon molecular sieve provided by the invention contain rich grain boundaries, and the grain boundaries not only strengthen the mass transfer diffusion of reactant and product molecules, but also improve the Lewis acid content of framework titanium species. The molecular sieve particles of the titanium silicon molecular sieve provided by the invention have an average grain boundary size of 1-5nm and a grain boundary mesoporous volume of 0.1-0.5mL/g.
According to a preferred embodiment of the invention, the molar ratio of titanium to silicon in the molecular sieve is from 0.005 to 0.04:1, preferably from 0.01 to 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 mesoporous volume of 0.1 to 0.2mL/g.
According to a preferred embodiment of the invention, the molecular sieve has a micropore volume of from 0.15 to 0.18mL/g.
In the present invention, the grain boundary refers to an interface between grains having the same structure but different orientations, and a contact interface between grains is called a grain boundary. The grain boundary size refers to the distance between grains, and is obtained by transmission electron microscopy (measured by a TEM ruler).
The titanium-silicon molecular sieve provided by the invention has a microporous structure and also has a grain boundary mesoporous structure, preferably, the aperture of the micropores is smaller than 1nm, and the aperture (diameter) of the mesopores is between 1 and 5 nm. Specifically, the XRD spectrum of the molecular sieve has diffraction peaks at angles of 5-35 degrees 2 theta, which indicates that a microporous structure exists in the molecular sieve. In the invention, the grain boundary mesoporous volume and the pore size distribution are measured by adopting a low-temperature nitrogen adsorption curve method.
According to a preferred embodiment of the present invention, the Lewis acid amount of the titanium silicalite molecular sieve is 15 to 30. Mu. Mol/g, more preferably 20 to 30. Mu. Mol/g. The acid content of the molecular sieve is measured by pyridine adsorption infrared spectrum.
According to a preferred embodiment of the invention, the molecular sieve is at 25℃P/P 0 The benzene adsorption amount measured under the conditions of 1 hour adsorption time is at least 30 mg/g, preferably 30-40 mg/g=0.1. A hysteresis loop exists between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption of the molecular sieve. Under the same titanium-silicon ratio, the acid quantity and the acid strength of the titanium-silicon molecular sieve provided by the invention are higher than those of the titanium-silicon molecular sieve prepared by the conventional method.
According to the present invention, preferably, the molecular sieve has an MFI structure, a MEL structure, a BEA structure, an MWW structure, or a MOR structure.
The second aspect of the invention provides a method for preparing a titanium silicalite molecular sieve, 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 sol and a 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 agent in the step (1) is not particularly limited. Preferably, the auxiliary agent 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 high molecular compound, and more preferably a water-soluble high molecular polymer. More preferably, the silylating agent is selected from at least one of trimethylchlorosilane, t-butyldimethylchlorosilane, dimethyldiacetoxysilane, N-phenyl-3-aminopropyl trimethoxysilane 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 to 100000.
Preferably, the stabilizer is at least one selected from 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 from 0.01 to 0.1:1, preferably from 0.02 to 0.07:1, wherein the first liquid silicon source is in the form of SiO 2 And (5) counting.
In the present invention, the first liquid titanium source in step (1) and the second liquid titanium source in 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 and/or titanates, preferably titanates, selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate, preferably tetraethyl titanate.
According to the present invention, preferably, tiO is used in the step (1) 2 A first liquid titanium source and TiO in step (5) 2 The 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. Specifically, the first liquid silicon source and the second liquid silicon source 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 organo-liquid silicon source is selected from the group consisting of silicon having the general formula Si (OR 1 ) 4 The organosilicon ester of R 1 Selected 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 at least one selected from the group consisting of tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate and dimethyl diethyl silicate; preferably at least one of tetramethyl silicate, tetraethyl silicate and tetrapropyl silicate.
According to the present invention, preferably, siO is used in the step (1) 2 A first liquid silicon source and SiO in step (5) 2 The molar ratio of the second liquid silicon source is 1:0.5-8, preferably 1:2.5-6.
Preferably, according to the present invention, the molar ratio of total titanium source to total silicon source is from 0.005 to 0.05:1, more preferably from 0.008 to 0.035:1, such as from 0.01 to 0.03:1 or from 0.01 to 0.025:1 or from 0.015 to 0.025:1, wherein,the total titanium source is TiO 2 The total silicon source is calculated as SiO 2 The total titanium source is TiO 2 First liquid titanium source and TiO 2 The sum of the second liquid titanium sources is calculated, and the total silicon source is expressed as SiO 2 First liquid silicon source of meter, in SiO 2 Second liquid silicon source and SiO 2 Total of solid silicon sources.
Preferably in SiO 2 Counting the total liquid silicon source and SiO in step (3) 2 The molar ratio of the solid silicon source is 1:1-9, preferably 1:2-8. In the invention, the high-proportion solid silicon source is used, so that the production cost can be reduced, and the solid content of the titanium-silicon molecular sieve crystallization product can be increased, thereby increasing the yield of single synthesis under the condition that the synthesis reaction kettle is unchanged.
In the present invention, the solid silicon source in step (3) is not particularly limited. Specifically, the solid silicon source may be a high purity silica solid or powder, preferably, the solid silicon source is white carbon black and/or high purity silica gel, preferably white carbon black. Preferably, the SiO in the solid silicon source is based on dry weight 2 The content is not less than 99.99 wt%, and the total mass content of Fe, al and Na impurities is less than 10ppm; for example SiO 2 The content is 99.99-100 wt%, usually more than 99.99 and less than 100 wt%.
According to one embodiment of the invention, siO in the silica gel 2 The content is 99.99 wt% or more, for example, 99.99 wt% or more and 100 wt% or less, and the mass content of Fe, al and Na impurities is less than 10ppm.
According to one specific embodiment of the invention, the specific surface area of the white carbon black is 50-400m 2 Per gram, based on the dry weight of the white carbon black, of SiO 2 The content is 99.99 wt% or more, for example, 99.99 wt% or more and 100 wt% or less, and the mass content of Fe, al and Na impurities is less than 10ppm.
According to the present invention, the white carbon black is commercially available or can be prepared according to a conventional method, for example, according to the method provided in CN200910227646.2, and the present invention is not particularly limited herein.
In the present invention, the kind and amount of the solvent in the step (1) are not particularly limited. As long as the first liquid titanium source, the first liquid silicon source, and the auxiliary agent are dissolved in the solvent. In particular, the solvent is selected from water and/or alcohols (preferably alcohols having 1 to 5C atoms), for example water and/or ethanol.
The specific embodiment of the mixing in the step (1) is not particularly limited in the present invention, 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, the stirring time being from 1 to 20 hours.
According to the present invention, the conditions for the aging are selected widely, and preferably, the conditions for the aging in step (2) include: the aging temperature is 20-65deg.C, preferably 20-50deg.C; 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 one embodiment of the present invention, the aging in step (2) means that the first mixture in step (1) is allowed to stand at 20-65 ℃ for 1-60 hours, wherein the aging process is preferably performed without stirring, and the first mixture is allowed to stand under the aging conditions.
According to the present invention, the heating conditions are widely selected, and preferably, the heating conditions in step (3) include: under airtight condition, the heating temperature is 50-500 ℃, preferably 250-500 ℃; the heating time is 1 to 30 hours, preferably 1 to 20 hours.
According to one embodiment of the present invention, heating in the step (3) means that the aged sol and the solid silicon source in the step (2) are heated at 50-500 ℃ for 1-30 hours, so that the aged sol is completely converted into solid gel, wherein the heating treatment can be performed in a closed autoclave, and the present invention is not described herein in detail.
According to a preferred embodiment of the present invention, the step (4) of filtering and washing the solid gel is further included before the solid gel is baked. Wherein, the filtration and washing are conventional means well known to those skilled in the art, and the present invention is not described herein in detail.
In the present invention, the firing is not particularly limited. Specifically, the conditions of the firing in 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. The oxygen-containing atmosphere in the present invention is not particularly limited, and may be pure oxygen or a mixed gas of oxygen and other gases, and is preferably air from the viewpoint of economy, as long as oxygen gas required for calcination can be provided.
In the present invention, the template in step (5) is not particularly limited. The suitable templating agent may be selected according to the structure of the molecular sieve desired to be synthesized (MFI structure, MEL structure, BEA structure, MWW structure or MOR structure). Preferably, the templating agent 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 templating agent includes 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. 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 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 the group consisting of 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 the group consisting of tetraethylammonium hydroxide, tetraethylammonium bromide and tetraethylammonium chloride.
Preferably, the long chain alkyl ammonium compound has the formula R 2 N(R 3 ) 3 X, wherein R is 2 Is alkyl with 12-18 carbon atoms, R 3 Is H or alkyl having 1-4 carbon atoms, X is a monovalent anion, e.g. OH - 、Cl - 、Br - . In particular, when X is OH - In the process, the long-chain alkyl ammonium compound is a basic long-chain alkyl ammonium compound; when X is Cl - In the process, the long-chain alkyl ammonium compound is long-chain alkyl ammonium chloride; when X is Br - In the case of long-chain alkylammonium bromide, the long-chain alkylammonium compound is long-chain alkylammonium bromide.
According to a preferred embodiment of the present invention, the basic long-chain alkyl ammonium compound is selected from at least one of dodecyl trimethyl ammonium hydroxide, tetradecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide and octadecyl trimethyl ammonium hydroxide.
According to a preferred embodiment of the present 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 present 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 aliphatic amine, alcohol amine and aromatic amine; the general formula of the fatty amine is R 4 (NH 2 ) n Wherein R is 4 Is an alkyl or alkylene group having 1 to 4 carbon atoms, n=1 or 2; the alcohol amine has a general formula (HOR) 5 ) m NH (3-m) Wherein R is 5 Is an alkyl group having 1 to 4 carbon atoms, m=1, 2 or 3; the aromatic amine is an amine having one aromatic substituent.
According to a preferred embodiment of the present invention, the fatty amine is selected from at least one of ethylamine, n-butylamine, butanediamine and hexamethylenediamine.
According to a preferred embodiment of the present invention, the alcohol amine is selected from at least one of monoethanolamine, diethanolamine and triethanolamine.
According to a preferred embodiment of the present invention, the aromatic amine is selected from at least one of 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 templating agent to the total silicon source is from 0.08 to 0.6:1, preferably from 0.1 to 0.3:1, more preferably from 0.1 to 0.25:1, and even more preferably from 0.1 to 0.2:1.
According to the invention, preferably, the molar ratio of the water to the total silicon source in step (5) is from 5 to 100:1. In the method provided by the invention, the small-grain stacked titanium-silicon molecular sieve can be synthesized under high solid content, so that the use amount of water can be reduced, the yield of a single kettle is improved, namely more molecular sieves are synthesized under the same synthesis reactor volume, and the molar ratio of 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 from 0.01 to 5:1, preferably from 0.01 to 4:1, further preferably from 0.01 to 0.5:1, the inorganic ammonium source being in NH 4 + The first liquid titanium source is TiO 2 And (5) counting.
In the present invention, the inorganic ammonium source in step (5) is not particularly limited. Specifically, 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-silicon molecular sieve is improved, the utilization rate of the titanium source (the titanium-silicon ratio of a skeleton is higher under the condition of the same use amount of the titanium source) is improved, and the use 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 110-200deg.C, preferably 140-180deg.C, and further preferably 160-180deg.C; 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 performed in a stainless steel stirred tank. The crystallization temperature rise can be carried out in a one-stage temperature rise mode or a multi-stage temperature rise mode, 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 100-130deg.C (preferably 110-130deg.C) for 0.5-1.5 days, and crystallizing at 160-180deg.C for 1-3 days.
According to the invention, the method may further comprise recovering the titanium silicalite molecular sieve from the product obtained by crystallization in 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 small-grain stacked titanium-silicon molecular sieve obtained by crystallization from the crystallization mother liquor, and the purpose of washing is to wash away the silicon-containing template agent adsorbed on the surfaces of molecular sieve particles, for example, the molecular sieve and water can be mixed and washed at the temperature of room temperature to 50 ℃, the weight ratio of the molecular sieve to the water is 1:1-20, for example, 1:1-15, and then filtered or leached by water. The purpose of drying is to remove most of the moisture in the molecular sieve to reduce the amount of moisture evaporation during calcination, and the drying temperature may be 100-200 ℃. The purpose of calcination is to remove the templating agent from the molecular sieve, for example, at a temperature of 350-650 c for a period of 2-10 hours. The titanium silicalite molecular sieve provided by the invention is obtained through recovery.
According to the present invention, preferably, the method further comprises a step (6), the step (6) comprising: mixing the solid product obtained in the step (5), organic base and water, and then performing second crystallization.
Preferably, the conditions of the second crystallization include: the second crystallization temperature is 110-200deg.C, more preferably 150-200deg.C; 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 to perform the second crystallization. The obtained small-grain stacked titanium-silicon molecular sieve has a hollow structure, and is called molecular sieve rearrangement in the invention. Preferably, the organic base is combined with the solid product obtained in step (5) (in the form of SiO 2 Calculated as a mole ratio) of 0.02-0.5:1, more preferably 0.02-0.2:1. Preferably, the water is mixed with the solid product (in SiO 2 Calculated as a molar ratio) is 2-50:1, more preferably 2-30:1, for example 2-20:1, preferably 5-10:1. The organic base may be an organic amine and/or an organic quaternary ammonium base, and the limitation of the organic amine and the organic quaternary ammonium base is as described above, and the present invention is not described herein.
Specifically, the method may further comprise recovering the titanium silicalite molecular sieve from the product obtained by crystallization in step (6). Typically comprising filtering, washing, drying and then calcining the crystallized product, reference is made to the recovery method described in step (5), which is not described in detail herein.
In the present invention, the rearrangement of the molecular sieve step (6) may be performed once or repeated several times. Through rearrangement treatment, the small-grain stacked titanium-silicon molecular sieve with more obvious mesoporous structure is obtained, and the rearranged titanium-silicon molecular sieve has larger pore volume and specific surface area.
In a third aspect, the present invention provides a process for the oximation of cyclohexanone, which comprises contacting cyclohexanone, ammonia and hydrogen peroxide with a titanium silicalite molecular sieve according to the present invention under oximation reaction conditions.
According to the inventionThe method for the oximation of cyclohexanone is not particularly limited, and the oximation reaction conditions may be carried out under conventional conditions. Specifically, the oximation reaction conditions include: 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 -1 Preferably 5-10h -1 。
In the present invention, the molar ratio of cyclohexanone, ammonia and hydrogen peroxide is preferably 1:0.2-5:0.2-5, preferably 1:1-3:1-3.
The contacting may be performed 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 conventionally selected. 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 by examples.
SEM electron microscopy experiments were performed on a high resolution cold field emission scanning electron microscope in hitachi S4800.
TEM electron microscope experiments were carried out on a Tecnai F20G 2S-TWIN transmission electron microscope from FEI company, equipped with an energy filter system GIF2001 from Gatan company, with an X-ray spectrometer attached. 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) pattern measurement of the sample was performed on a Siemens D5005X-ray diffractometer with a source of CuK alphaTube voltage 40kV, tube current 40mA, scan speed 0.5 °/min, scan range 2θ=4-40 °.
The characterization of the low temperature nitrogen adsorption curve was performed on a model Micromeritics ASAP-2010 static nitrogen adsorber manufactured by Quantachrome company.
The pore volume was measured by the nitrogen adsorption capacity method according to BJH calculation method (see petrochemical analysis method (RIPP test method), RIPP151-90, published by science Press, 1990).
The acid content of the titanium-silicon molecular sieve is measured by pyridine adsorption infrared spectrum.
The particle size of the molecular sieve particles of the titanium-silicon molecular sieve is obtained by transmission electron microscopy (measured by a TEM scale).
In the examples below, 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, national pharmaceutical chemicals limited.
Titanium tetrachloride, analytically pure, national pharmaceutical group chemical reagent limited.
Tetrapropylammonium hydroxide, a chemical plant is available in Guangdong.
Tetraethyl silicate, analytically pure, national medicine group chemical reagent limited.
Ammonia, analytically pure, concentration 20% by weight.
White carbon black, zhejiang macro group product, model AS-150; the solid content is more than 95 weight percent, the silicon dioxide content in dry basis is more than 99.99 weight percent, the total content of iron, sodium and Al is less than 10ppm, and the specific surface area is 195m 2 /g。
Other reagents, not further described, were commercially available and analytically pure.
The gas chromatograph was purchased from Agilent company under the trade designation 6890 gas chromatograph, and the analytical chromatographic column was an FFAP column.
In the embodiment of the invention, 1 to 12 are prepared by SiO 2 The amount of the total silicon source was fixed at 0.2mol.
Example 1
(1) Tetrabutyl titanate (first liquid titanium source), tetraethyl silicate (TEOS, first liquid silicon source), polyacrylic acid (weight average molecular weight 5000) powder, and 3g of water were sequentially added to a 500mL beaker, placed on a magnetic stirrer with heating and stirring functions, uniformly mixed, 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 TiO 2 -SiO 2 White oxide.
(5) The titanium silicon oxide, a tetrapropylammonium hydroxide aqueous solution (TPAOH) with a concentration of 25.05 wt%, cetyltrimethylammonium hydroxide (MSDS), tetrabutyltitanate (second liquid titanium source), tetraethyl silicate (TEOS, second liquid silicon source), ammonia water with a concentration of 20 wt% and water are mixed to obtain a second mixture, and then the second mixture is transferred into a stainless steel closed reaction kettle to be crystallized for 48 hours at a constant temperature of 175 ℃ to obtain a crystallized sample, filtered and washed, dried at 120 ℃ for 24 hours, and baked at 550 ℃ for 6 hours to obtain a titanium silicon molecular sieve S-1 with an MFI structure in a small grain stack shape.
SEM and TEM photographs of the titanium silicalite molecular sieve S-1 are shown in fig. 1 and 2, and XRD analysis spectra are shown in fig. 8.
As can be seen from fig. 1 and 2, the molecular sieve particles are formed by stacking grains having a particle size of 20-50 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Example 2
(1) Titanium tetrachloride, tetraethyl silicate (TEOS), t-butyl hydroperoxide, and 10g of ethanol were sequentially added to a 500mL beaker, and mixed well on a magnetic stirrer with heating and stirring functions, 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 closed 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 TiO 2 -SiO 2 White oxide.
(5) The titanium silicon oxide, a tetrapropylammonium hydroxide aqueous solution (TPAOH) with a concentration of 25.05 wt%, cetyltrimethylammonium hydroxide (MSDS), tetrabutyl titanate, tetraethyl silicate (TEOS), ammonia water with a concentration of 20 wt% and water are mixed to obtain a second mixture, and then the second mixture is transferred into a stainless steel closed reaction kettle, crystallized at a constant temperature of 160 ℃ for 72 hours to obtain a crystallized sample, filtered, washed, dried at 120 ℃ for 24 hours, and calcined at 550 ℃ for 6 hours to obtain a small-grain stacked titanium silicon molecular sieve S-2 with an MFI structure.
The SEM and TEM images of the titanium silicalite molecular sieve S-2 are similar to those of the titanium silicalite molecular sieve S-1, and the XRD analysis spectrum is shown in figure 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Example 3
The titanium silicon molecular sieve S-2 prepared in the embodiment 2 is adopted as a matrix, 6g of the sample is mixed with 22.05 wt% of TPAOH water solution, stirred uniformly, crystallized for 3 days at 150 ℃ in a closed reaction kettle, filtered, washed, dried for 24 hours at 120 ℃, and baked for 6 hours at 550 ℃ to obtain the hollow small-grain stacked titanium silicon molecular sieve S-3 which has an MFI structure.
TEM photograph of the titanium silicalite molecular sieve 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Examples 4 to 7
Titanium silicalite molecular sieves were prepared as in example 1, with the titanium silicalite molecular sieves composition and synthesis conditions shown in Table 1, to give small-grain stacked titanium silicalite molecular sieves S-4 through 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Example 8
Titanium silicalite molecular sieves were prepared as in example 1, except that in step (5) they were crystallized at 120℃for 1 day and then at 170℃for 2 days, the composition and synthesis conditions of the titanium silicalite molecular sieves being shown in Table 1, to give a small-grain stacked titanium silicalite molecular sieve S-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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Example 9
Preparing the titanium silicalite molecular sieve with MEL structure. With reference to the procedure of example 1, the composition and the template agent were changed, and the composition and synthesis conditions of the titanium silicalite molecular sieve are shown in Table 1, to obtain a small-grain stacked titanium silicalite molecular sieve S-9. 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Example 10
Preparing the titanium silicalite molecular sieve with BEA structure. The composition and the template agent of the titanium silicalite molecular sieve were changed by the method of reference example 1, and the composition and synthesis conditions of the titanium silicalite molecular sieve are shown in Table 1, to obtain a small-grain stacked titanium silicalite molecular sieve S-10. 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content 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 a titanium silicalite molecular sieve 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Comparative example 1
22.5g of tetraethyl silicate and 7g of tetrapropylammonium hydroxide are mixed, 59.8g of deionized water is added for uniform mixing; then hydrolyzing for 1h at 60 ℃ to obtain a hydrolysis solution of the tetraethyl silicate. A solution of 1.1g of titanium tetrachloride and 5g of isopropyl alcohol was slowly dropped into the above solution under vigorous stirring, and the mixture was stirred at 75℃for 3 hours to give a clear and transparent colloid. And transferring the colloid into a stainless steel closed reaction kettle, and crystallizing for 3 days at the constant temperature of 170 ℃ to obtain the conventional titanium-silicon molecular sieve D-1.
SEM and TEM photographs of the titanium silicalite molecular sieve D-1 are shown in FIG. 4 and FIG. 5, and XRD analysis spectra are 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Comparative example 2
22.5g of tetraethyl silicate is mixed with 9g of tetrapropylammonium hydroxide, and 64.5g of deionized water is added for uniform mixing; then hydrolyzing for 1h at 60 ℃ to obtain a hydrolysis solution of the tetraethyl silicate. A solution of 0.6g of titanium tetrachloride and 7g of isopropyl alcohol was slowly dropped into the above solution under vigorous stirring, and the mixture was stirred at 75℃for 7 hours to give a clear and transparent colloid. And transferring the colloid into a stainless steel closed reaction kettle, and crystallizing for 3 days at the constant temperature of 170 ℃ to obtain the conventional titanium-silicon molecular sieve.
And uniformly mixing titanium tetrachloride, anhydrous isopropanol, tetrapropylammonium hydroxide and deionized water according to the molar ratio of 1:15:2.4:350, and hydrolyzing at the temperature of 45 ℃ for 30 minutes under normal pressure to obtain a hydrolysis solution of titanium tetrachloride. Uniformly mixing the prepared titanium silicalite molecular sieve with the hydrolysis solution of titanium tetrachloride according to the molecular sieve (g) to Ti (mol) =600:1, uniformly stirring for 12 hours at normal temperature (25 ℃), and finally placing the dispersed suspension into a stainless steel reaction kettle and standing for 3 days at 165 ℃ to obtain the rearrangement-treated titanium silicalite molecular sieve D-2.
SEM and TEM photographs of the titanium silicalite molecular sieve D-2 are shown in FIG. 6 and FIG. 7, and XRD analysis spectra are 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Comparative example 3
The procedure of example 1 was followed except that aqueous ammonia (inorganic ammonium source) was not added, to obtain titanium silicalite molecular sieve D-3. The average grain size of the molecular sieve grains, and 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Comparative example 4
The procedure of example 1 was followed except that aqueous ammonia (inorganic ammonium source) was not added and aging was not conducted, to obtain titanium silicalite molecular sieve D-4. 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content 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 molecular sieve 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 listed in table 2. The micropore volume, mesopore volume, benzene adsorption and Lewis acid content of the molecular sieve are shown in Table 2.
Test case
The titanium silicalite molecular sieves prepared in examples 1 to 12 and comparative examples 1 to 5 above were used as catalysts for cyclohexanone oxime reaction to carry out oxime reaction.
According to the mass ratio of titanium silicalite molecular sieve to tertiary butanol (solvent) to 25 weight percent ammonia water=1:7.5:7.5 (wherein the weight of the ammonia water is NH 3 Meter) are evenly stirred and mixed in a slurry bed, the temperature is raised to 78 ℃, and the dosage of the titanium silicalite molecular sieve is 3g. Then, at this temperature, 30% by weight of hydrogen peroxide was added at a rate of 6mL/h, a mixture of cyclohexanone and t-butanol (volume ratio of cyclohexanone to t-butanol: 1:2.5) was added at a rate of 8.6mL/h, and at the same time, 25% by weight of aqueous ammonia solution was added at a rate of 6mL/h, the volume space velocity was 7.92h -1 . The three materials are added simultaneously, and simultaneously, the materials are continuously discharged at a corresponding speed, the concentration of each material after the reaction is quantitatively analyzed by using a gas chromatograph 3 hours after the reaction is stabilized, and the cyclohexanone conversion rate and the cyclohexanone oxime selectivity are calculated, and the specific results are shown in Table 2.
The cyclohexanone conversion and cyclohexanone oxime selectivity were calculated according to the following formulas, respectively:
TABLE 1
Table 1, below
Note that: TPABr is tetrapropylammonium bromide, CTMAB is hexadecyltrimethylammonium bromide, DTAB is dodecyltrimethylammonium hydroxide, MSDS is hexadecyltrimethylammonium hydroxide, TBAOH is tetrabutylammonium hydroxide, and TEAOH is tetraethylammonium hydroxide.
TABLE 2
As can be seen from the data in Table 2, the titanium silicalite molecular sieve provided by the invention can obtain more excellent catalytic performance than the conventional titanium silicalite molecular sieve by using the titanium silicalite molecular sieve as a catalyst for cyclohexanone oxime reaction.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (50)

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 molecular sieve Lewis acid amount is 15-30 mu mol/g;
wherein, the titanium silicalite molecular sieve is prepared by the following method:
(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 sol and a solid silicon source to obtain solid gel; (4) Roasting the solid gel to obtain titanium silicon oxide; (5) 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;
Wherein the auxiliary agent comprises a space filling agent and/or a stabilizing agent, and the space filling agent is at least one selected from a silanization reagent, polyacrylamide and polyacrylic acid; the stabilizer is at least one selected from oxalic acid, tert-butyl hydroperoxide, cyclohexyl hydroperoxide, hydrogen peroxide and citric acid.
2. The molecular sieve of claim 1, wherein the molar ratio of titanium to silicon in the molecular sieve is 0.005-0.04:1.
3. the molecular sieve according to claim 2, wherein the molar ratio of titanium to silicon in the molecular sieve is 0.01-0.035:1.
4. the molecular sieve of claim 2, wherein the molecular sieve particles have an average grain boundary size of 1-3nm and a grain boundary mesoporous volume of 0.1-0.2mL/g.
5. The molecular sieve of claim 1, wherein the molecular sieve is at 25 ℃, P/P 0 The benzene adsorption amount measured under the conditions of=0.1 and adsorption time of 1 hour is at least 30 mg/g.
6. The molecular sieve of claim 5, wherein the molecular sieve has an MFI structure, a MEL structure, a BEA structure, a MWW structure, or a MOR structure.
7. A method for preparing a titanium silicalite molecular sieve, 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 sol and a solid silicon source to obtain solid gel;
(4) Roasting the solid gel to obtain titanium silicon oxide;
(5) 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;
wherein the auxiliary agent comprises a space filling agent and/or a stabilizing agent, and the space filling agent is at least one selected from a silanization reagent, polyacrylamide and polyacrylic acid; the stabilizer is at least one selected from oxalic acid, tert-butyl hydroperoxide, cyclohexyl hydroperoxide, hydrogen peroxide and citric acid.
8. The process of claim 7, wherein the molar ratio of the auxiliary agent to the first liquid silicon source in step (1) is 0.01-0.1:1, wherein the first liquid silicon source is SiO 2 And (5) counting.
9. The process of claim 7, wherein the molar ratio of the promoter to the first liquid silicon source in step (1) is from 0.02 to 0.07:1, wherein the first liquid silicon source is SiO 2 And (5) counting.
10. The method of claim 7, wherein the first and second liquid titanium sources are each independently selected from an inorganic liquid titanium source and/or an organic liquid titanium source.
11. The method of manufacturing of claim 10, wherein the first and second liquid silicon sources are each independently selected from an inorganic liquid silicon source and/or an organic liquid silicon source.
12. The preparation method according to claim 10, wherein the solid silicon source in the step (3) is white carbon black and/or silica gel.
13. The process according to claim 10, wherein TiO is used in the step (1) 2 A first liquid titanium source and TiO in step (5) 2 The molar ratio of the second liquid titanium source is 1:0.5-8。
14. the process according to claim 10, wherein TiO is used in the step (1) 2 A first liquid titanium source and TiO in step (5) 2 The molar ratio of the second liquid titanium source is 1:2.5-6.
15. The process according to claim 10, wherein SiO is used in step (1) 2 A first liquid silicon source and SiO in step (5) 2 The molar ratio of the second liquid silicon source is 1:0.5-8.
16. The process according to claim 10, wherein SiO is used in step (1) 2 A first liquid silicon source and SiO in step (5) 2 The molar ratio of the second liquid silicon source is 1:2.5-6.
17. The method of claim 10, wherein the molar ratio of total titanium source to total silicon source is 0.005-0.05:1, wherein the total titanium source is TiO 2 The total silicon source is calculated as SiO 2 The total titanium source is TiO 2 First liquid titanium source and TiO 2 The sum of the second liquid titanium sources is calculated, and the total silicon source is expressed as SiO 2 First liquid silicon source of meter, in SiO 2 Second liquid silicon source and SiO 2 Total of solid silicon sources.
18. The preparation method according to claim 10, wherein SiO is used as a material 2 Total liquid silicon source and SiO in step (3) 2 The mole ratio of the solid silicon source is 1:1-9; the total liquid silicon source is SiO 2 First liquid silicon source and SiO 2 A second liquid silicon source.
19. The preparation method according to claim 10, wherein SiO is used as a material 2 Total liquid silicon source and SiO in step (3) 2 The solid of the meterThe molar ratio of the silicon source is 1:2-8; the total liquid silicon source is SiO 2 First liquid silicon source and SiO 2 A second liquid silicon source.
20. The production method according to claim 7, wherein the aging condition in step (2) comprises: the aging temperature is 20-65 ℃; the aging time is 1-60 hours.
21. The method of claim 20, wherein the aging conditions in step (2) include: the aging temperature is 20-50 ℃; the aging time is 2-50 hours.
22. The production method according to claim 20, wherein the heating condition in step (3) comprises: heating to 50-500 deg.c under sealed condition; the heating time is 1-30 hours.
23. The production method according to claim 20, wherein the heating condition in step (3) comprises: under the airtight condition, the heating temperature is 250-500 ℃; the heating time is 1-20 hours.
24. The production method according to claim 20, wherein the conditions of the firing in step (4) include: roasting at 100-500 deg.c in oxygen atmosphere; the roasting time is 1-20 hours.
25. The production method according to claim 20, wherein the conditions of the firing in step (4) include: roasting at 250-480 deg.c in oxygen atmosphere; the roasting time is 2-10 hours.
26. The method of any one of claims 17-25, wherein the templating agent in step (5) comprises an organic quaternary ammonium compound, a long chain alkyl ammonium compound, and optionally an organic amine.
27. The process of claim 26, wherein the organic quaternary ammonium compound is an organic quaternary ammonium base and/or an organic quaternary ammonium salt.
28. The process of claim 26, wherein the long chain alkyl ammonium compound has the formula R 2 N(R 3 ) 3 X, wherein R is 2 Is alkyl with 12-18 carbon atoms, R 3 Is H or alkyl with 1-4 carbon atoms, X is monovalent anion.
29. The method of claim 26, wherein the organic amine is one or more of a fatty amine, an alcohol amine, and an aromatic amine; the general formula of the fatty amine is R 4 (NH 2 ) n Wherein R is 4 Is an alkyl or alkylene group having 1 to 4 carbon atoms, n=1 or 2; the alcohol amine has a general formula (HOR) 5 ) m NH (3-m) Wherein R is 5 Is an alkyl group having 1 to 4 carbon atoms, m=1, 2 or 3; the aromatic amine is an amine having one aromatic substituent.
30. The method of claim 26, wherein the molar ratio of the organic quaternary ammonium compound to the total silicon source is 0.04-0.45:1, the molar ratio of the long-chain alkyl ammonium compound to the total silicon source is 0.04-0.45:1, a step of; the molar ratio of the organic amine to the total silicon source is 0-0.4:1.
31. the method of claim 30, wherein the molar ratio of the templating agent to the total silicon source is 0.08-0.6:1.
32. The method of claim 30, wherein the molar ratio of the templating agent to the total silicon source is 0.1-0.3:1.
33. the method of claim 30, wherein the molar ratio of the templating agent to the total silicon source is 0.1-0.25:1.
34. the method of any one of claims 17-25, wherein the molar ratio of water to the total silicon source in step (5) is from 5 to 100:1.
35. the method of claim 34, wherein the molar ratio of water to the total silicon source in step (5) is from 5 to 50:1.
36. the method of claim 34, wherein the molar ratio of water to the total silicon source in step (5) is from 6 to 30:1.
37. the method of claim 34, wherein 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, the inorganic ammonium source is prepared by NH 4 + The first liquid titanium source is TiO 2 And (5) counting.
38. The method of claim 34, wherein 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 4:1, the inorganic ammonium source is prepared by NH 4 + The first liquid titanium source is TiO 2 And (5) counting.
39. The method of claim 34, wherein 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 0.5:1, the inorganic ammonium source is prepared by NH 4 + The first liquid titanium source is TiO 2 And (5) counting.
40. The production method according to any one of claims 7 to 25, wherein the crystallization condition in step (5) comprises: the crystallization temperature is 110-200 ℃, the crystallization pressure is autogenous pressure, and the crystallization time is 2-480 hours.
41. The process of claim 40, wherein the crystallization time is 0.5 to 10 days.
42. The process according to claim 40, wherein the crystallization temperature is 140 to 180 ℃.
43. The process according to claim 40, wherein the crystallization temperature is 160 to 180 ℃.
44. The process of claim 40, wherein the crystallization conditions include: crystallizing at 100-130deg.C for 0.5-1.5 days, and crystallizing at 160-180deg.C for 1-3 days.
45. The method of any one of claims 7-25, wherein the method further comprises step (6), said step (6) comprising: mixing the solid product obtained in the step (5), organic base and water, and then performing second crystallization.
46. The process of claim 45, wherein the second crystallization conditions comprise: the second crystallization temperature is 110-200 ℃; the second crystallization time is 0.5-10 days.
47. The process of claim 45, wherein the second crystallization conditions comprise: the second crystallization temperature is 150-200 ℃; the second crystallization time is 1-8 days.
48. The process according to claim 45, wherein the process further comprises drying and calcining the solid product obtained in step (5) and/or the second crystallized product obtained in step (6).
49. The titanium silicalite molecular sieve of any one of claims 7-48.
50. A process for the oximation of cyclohexanone, which comprises contacting cyclohexanone, ammonia and hydrogen peroxide with a titanium silicalite under oximation conditions, wherein the titanium silicalite is according to any one of claims 1-6 and 49.
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