CN107537559B - Titanium-silicon-containing molecular sieve catalyst and preparation method and application thereof - Google Patents
Titanium-silicon-containing molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of titanium-silicon molecular sieves, and particularly provides a preparation method of a titanium-silicon-containing molecular sieve catalyst, which comprises the following steps: (1) contacting a discharging agent with an organic compound to obtain a contacted product, wherein the organic compound is selected from one or more of sulfone, ketone and amide, and the discharging agent is the discharging agent of a reaction device which takes a titanium silicalite molecular sieve as a catalyst active component; (2) in the presence of an aqueous solvent, mixing the contacted product with an alkali source, and then carrying out hydrothermal treatment. The invention provides a catalyst obtained by the method. The invention provides the application of the catalyst in oxidation reaction. The relative crystallinity and micropore specific surface area of the titanium-silicon molecular sieve in the discharging agent are recovered, and the organic compound can be recycled by simple separation, thereby reducing the pollution of the preparation process to the environment. The invention does not need to be regenerated at high temperature, effectively saves energy consumption and is very suitable for industrial application.
Description
Technical Field
The invention relates to a titanium-silicon-containing molecular sieve catalyst, a preparation method and application thereof.
Background
Titanium silicalite is a new heteroatom molecular sieve developed in the beginning of the eighties of the last century. TS-1 with MFI structure, TS-2 with MEL structure, TS-48 with larger pore structure, etc. have been synthesized. The molecular sieve has excellent selective oxidation performance and higher catalytic activity for a plurality of organic oxidation reactions, such as olefin epoxidation, aromatic hydrocarbon hydroxylation, cyclohexanone oximation, alcohol oxidation and the like, and has good application prospect when being used as a redox type molecular sieve catalyst.
Wherein the TS-1 molecular sieve is a novel titanium silicalite molecular sieve with excellent catalytic selective oxidation performance formed by introducing a transition metal element titanium into a molecular sieve framework with a ZSM-5 structure. TS-1 not only has the catalytic oxidation effect of titanium, but also has the shape-selective effect and excellent stability of ZSM-5 molecular sieve. As the TS-1 molecular sieve can adopt the pollution-free low-concentration hydrogen peroxide as the oxidant in the oxidation reaction of the 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, thereby having great industrial application prospect. However, the titanium silicalite molecular sieves generally have poor catalytic performance after a period of operation, and exhibit deactivation. The reason for the deactivation may be due to impurities or reaction by-products introduced during the synthesis of the molecular sieve accumulating in the pores of the catalyst, blocking the pores, etc.
Disclosure of Invention
The invention aims to provide a method for preparing a titanium-containing silicon molecular sieve catalyst, which is different from the prior art, not only saves energy consumption and cost, but also greatly reduces the pollution of the preparation process to the environment.
To achieve the foregoing objective and in accordance with a first aspect of the present invention, there is provided a method for preparing a titanium-containing silicon molecular sieve catalyst, the method comprising:
(1) contacting a discharging agent with an organic compound to obtain a contacted product, wherein the organic compound is selected from one or more of sulfone, ketone and amide, and the discharging agent is the discharging agent of a reaction device which takes a titanium silicalite molecular sieve as a catalyst active component;
(2) in the presence of an aqueous solvent, mixing the contacted product with an alkali source, and then carrying out hydrothermal treatment.
According to a second aspect of the present invention there is provided a catalyst obtainable by the process according to the present invention.
According to a third aspect of the invention there is provided the use of a catalyst according to the invention in an oxidation reaction.
According to the preparation method provided by the invention, the relative crystallinity and micropore specific surface area of the titanium silicalite molecular sieve serving as an active component in the discharging agent are recovered, the activity and activity stability are good, and the discharging agent can basically reach the activity when fresh.
According to the method, the used organic compound can be recycled through simple separation, and the pollution of the preparation process to the environment is greatly reduced.
The invention can basically and completely recover the activity, the crystallinity and the micropore specific surface area of the prepared catalyst without regenerating at high temperature, effectively saves energy consumption and is very suitable for industrial application.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
As described above, the present invention provides a method for preparing a titanium-containing silicon molecular sieve catalyst, which comprises: (1) contacting a discharging agent with an organic compound to obtain a contacted product, wherein the organic compound is selected from one or more of sulfone, ketone and amide, and the discharging agent is the discharging agent of a reaction device which takes a titanium silicalite molecular sieve as a catalyst active component; (2) in the presence of an aqueous solvent, the contacted product alkali sources are mixed and then subjected to hydrothermal treatment.
The process according to the invention, carried out according to the preceding scheme, achieves the objects of the invention, and organic compounds satisfying the aforementioned requirements can be used in the present invention, and for the present invention, it is preferred that the organic compound is one or more of a sulfoxide, a cyclic sulfone, an alkanone and an amide.
More preferably, according to the process of the present invention, the organic compound is one or more of dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
In the present invention, the discharging agent of the reaction device using the titanium silicalite molecular sieve as the catalyst active component may be a discharging agent discharged from various devices using the titanium silicalite molecular sieve as the catalyst active component, the discharging agent may be a discharging agent in a device using the titanium silicalite molecular sieve as the catalyst directly, or a discharging agent discharged from a device using the titanium silicalite molecular sieve as the formed catalyst active component (the catalyst is a formed catalyst, and may further include a substrate, a binder, and the like).
In the present invention, the discharging agent may be, for example, a discharging agent discharged from an oxidation reaction apparatus in which a titanium silicalite is used as a catalyst active component. The oxidation reaction may be various oxidation reactions, for example, the discharging agent of the reaction apparatus using the titanium silicalite molecular sieve as the active component of the catalyst may be one or more of a discharging agent of an ammoximation reaction apparatus, a discharging agent of a hydroxylation reaction apparatus and a discharging agent of an epoxidation reaction apparatus, specifically, may be one or more of a discharging agent of a cyclohexanone ammoximation reaction apparatus, a discharging agent of a phenol hydroxylation reaction apparatus and a discharging agent of a propylene epoxidation reaction apparatus, and preferably, the discharging agent is a catalyst that is deactivated in an alkaline environment, and therefore, for the present invention, it is preferable that the discharging agent is a discharging agent of a cyclohexanone ammoximation reaction apparatus (such as deactivated titanium silicalite TS-1, powdery, and having a particle size of 100-500 nm).
In the present invention, the discharging agent is a deactivated catalyst whose activity cannot be restored to 50% of the initial activity by a conventional regeneration method such as solvent washing or calcination (the initial activity is the average activity of the catalyst within 1 hour under the same reaction conditions; for example, in the actual cyclohexanone oximation reaction, the initial activity of the catalyst is generally 95% or more).
The activity of the discharging agent varies depending on its source. In general, the activity of the discharging agent may be 5-95% of the activity when fresh (i.e., the activity of the fresheners). Preferably, the activity of the discharging agent may be 50% or less of the activity when fresh, and more preferably, the activity of the discharging agent may be 10 to 40% of the activity when fresh. The activity of the freshener is generally above 90%, usually above 95%.
In the present invention, the discharging agent may be derived from an industrial deactivator or a deactivated catalyst after reaction in a laboratory.
In the invention, the discharging agent of each device is respectively measured by adopting the reaction of each device, and the discharging agent is the discharging agent provided that the activity of the discharging agent is lower than that of the fresh agent in the same device under the same reaction condition. As mentioned above, it is preferred that the activity of the discharging agent is less than 50% of the activity of the fresh agent.
In the present invention, taking the discharging agent of the cyclohexanone ammoximation reaction device as an example, the activity is measured by the following method:
taking a TS-1 molecular sieve (prepared by the method described in Zeolite, 1992, Vol.12: 943-950), TiO22.1%) was placed in a 100mL slurry bed reactor with continuous feed and membrane separation means, and a mixture of water and 30 wt% hydrogen peroxide (water to hydrogen peroxide volume ratio of 10: 9) a mixture of cyclohexanone and tert-butanol was added at a rate of 10.5mL/h (the volume ratio of cyclohexanone to tert-butanol was 1: 2.5) adding 36 wt% ammonia water at the speed of 5.7mL/h, simultaneously adding the three material flows, continuously discharging at the corresponding speed, maintaining the reaction temperature at 80 ℃, sampling the product after the reaction is stable, analyzing the liquid phase composition by using a gas chromatography method every 1 hour, calculating the conversion rate of cyclohexanone by using the following formula, and taking the conversion rate as the activity of the titanium-silicon molecular sieve. Conversion of cyclohexanone [ (molar amount of cyclohexanone charged-molar amount of unreacted cyclohexanone)/molar amount of cyclohexanone charged]× 100%, where the 1h result is taken as the initial activity.
According to the method of the present invention, the titanium silicalite molecular sieve in the discharging agent can be at least one of a titanium silicalite molecular sieve of MFI structure (such as TS-1), a titanium silicalite molecular sieve of MEL structure (such as TS-2), a titanium silicalite molecular sieve of BEA structure (such as Ti-Beta), a titanium silicalite molecular sieve of MWW structure (such as Ti-MCM-22), a titanium silicalite molecular sieve of two-dimensional hexagonal structure (such as Ti-MCM-41 and Ti-SBA-15), a titanium silicalite molecular sieve of MOR structure (such as Ti-MOR), a titanium silicalite molecular sieve of TUN structure (such as Ti-TUN) and a titanium silicalite molecular sieve of other structure (such as Ti-ZSM-48). Preferably, the titanium silicalite molecular sieve is one or more of a titanium silicalite molecular sieve with an MFI structure, a titanium silicalite molecular sieve with an MEL structure and a titanium silicalite molecular sieve with a BEA structure, more preferably the titanium silicalite molecular sieve with the MFI structure, and more preferably the titanium silicalite molecular sieve with the MFI structure is a titanium silicalite molecular sieve with hollow structure grains, and the radial length of a cavity part of the hollow structure is 5-300 nm.
According to the method, the discharging agent of the reaction device taking the titanium silicalite molecular sieve as the active component of the catalyst is preferably the discharging agent of an ammoximation reaction device; preferably, the titanium silicalite molecular sieve is of an MFI structure, and the activity of the discharging agent is less than 50% of the activity of the discharging agent in a fresh state.
According to the process of the present invention, preferably in step (1), the temperature of the contacting is lower than the boiling point of the organic compound, preferably 20 to 250 ℃ lower than the boiling point of the organic compound, and the contacting temperature differs depending on the use of different organic compounds. Such as dimethylsulfoxide, sulfolane, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, at standard pressures, having boiling points of 189 deg.C, 285 deg.C, 202 deg.C, 153 deg.C and 96 deg.C, respectively.
According to the process of the invention, the boiling point of the organic compound refers to the boiling point of the single organic compound used. If a plurality of organic compounds are used, the boiling point is based on the lowest boiling point.
The pressure of the contact in the step (1) is not particularly required, and is preferably 0.001-1.0 MPa.
According to the method of the present invention, it is preferable that the contacting in the step (1) is performed in the presence of ammonia, and the mass ratio of ammonia to the organic compound is (0.0001 to 0.1): 1. according to the technical scheme, the preparation time can be saved, and the catalytic effect of the catalyst can be further improved.
Wherein, ammonia can be introduced in the form of liquid ammonia, aqueous solution or gas. The concentration of ammonia as an aqueous solution (i.e., aqueous ammonia) is not particularly limited and may be conventionally selected, for example, from 1 to 36% by weight.
According to the method of the present invention, the ratio of the above-mentioned organic compound to the discharging agent is not particularly limited as long as the object of the present invention can be achieved. From the viewpoint of convenience of operation and saving of raw materials, it is preferable that in the step (1), the mass ratio of the organic compound to the discharging agent is (0.5 to 100): 1, more preferably (2-50):1, more preferably (5-25): 1.
according to the method of the present invention, the contacted product in step (1) may be a mixture obtained by direct contact, or may be a contacted solid product obtained by separation, and the solid product may be dried or not dried to perform step (2), preferably dried, and the drying conditions include: the temperature is 80-300 ℃, the drying time is based on the drying to constant weight, and the drying time can be specifically adjusted according to the requirement. Wherein the separating step generally comprises: filtering, washing and the like. And are not described in detail herein.
According to the method of the present invention, it is preferable that in the step (2), the hydrothermal treatment conditions include: the pH value is 8-14, preferably 10-13.
According to the method of the present invention, it is preferable that in the step (2), the hydrothermal treatment conditions include: the temperature is 120-200 ℃, preferably 150-170 ℃.
According to the method of the present invention, it is preferable that in the step (2), the hydrothermal treatment conditions include: the pressure is 0-3MPa, the time is 0.5-72h, and the pressure is gauge pressure.
According to the method of the invention, in the step (2), the mass ratio of the contacted product to the alkali source is (1-100): 1.
according to a preferred embodiment of the present invention, step (2) is carried out in the presence of a noble metal source, preferably the mass ratio of the product after contact to the noble metal source on a dry basis is (20-1000): 1, preferably (20-50): 1.
according to the method of the present invention, it is preferable that the noble metal source is one or more of an oxide of a noble metal, a halide of a noble metal, a carbonate of a noble metal, a nitrate of a noble metal, an ammonium nitrate salt of a noble metal, an ammonium chloride salt of a noble metal, a hydroxide of a noble metal, and a complex of a noble metal, for example, one or more of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag, and Au; preferably, the noble metal is Pd, Ag, Au and/or Pt, and in the case of palladium, the noble metal source is selected from one or more of palladium oxide, palladium carbonate, palladium chloride, palladium nitrate, palladium ammonium nitrate, palladium ammine chloride, palladium acetate, palladium hydroxide, a palladium complex, palladium acetate and palladium acetylacetonate.
According to the method of the present invention, the kind of the alkali source can be selected from a wide range, and can be an organic alkali source and/or an inorganic alkali source, such as one or more of urea, ammonia, an alkali metal compound, an alkaline earth metal compound, a quaternary ammonium alkali compound, an aliphatic amine compound and an aliphatic alcohol amine compound.
In the invention, the quaternary ammonium base can be various organic quaternary ammonium bases, and the aliphatic amine can be various NH3In which at least one hydrogen is substituted with an aliphatic hydrocarbon group (preferably an alkyl group), which may be a variety of NH3Wherein at least one hydrogen is substituted with a hydroxyl-containing aliphatic hydrocarbon group (preferably an alkyl group).
Specifically, the quaternary ammonium base may be a quaternary ammonium base represented by formula II, the aliphatic amine may be an aliphatic amine represented by formula III, and the aliphatic alcohol amine may be an aliphatic alcohol amine represented by formula IV:
in the formula II, R5、R6、R7And R8Each is C1-C4Alkyl of (2) including C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a), for example: r5、R6、R7And R8Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R9(NH2)n(formula III)
In the formula III, n is an integer of 1 or 2. When n is 1, R9Is C1～C6Alkyl of (2) including C1～C6Straight chain alkyl of (2) and C3-C6Branched alkyl radicals of (2), e.g. methyl, ethyl, n-propyl, isopropyl, n-butylAlkyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl. When n is 2, R9Is C1-C6Alkylene of (2) including C1-C6Linear alkylene of (A) and (C)3-C6Such as methylene, ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene.
(HOR10)mNH(3-m)(formula IV)
In the formula IV, m are R10Are the same or different and are each C1-C4Alkylene of (2) including C1-C4Linear alkylene of (A) and (C)3-C4Branched alkylene groups of (a), such as methylene, ethylene, n-propylene and n-butylene; m is 1, 2 or 3.
According to a preferred embodiment of the present invention, the alkali source is one or more of ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylenediamine, monoethanolamine, diethanolamine and triethanolamine. Various cases such as a mixture of tetraethylammonium hydroxide and n-butylamine, a mixture of ethylenediamine and tetrapropylammonium hydroxide, a mixture of di-n-propylamine and tetrapropylammonium hydroxide, a mixture of tetraethylammonium hydroxide and tetrapropylammonium hydroxide, and a mixture of hexamethylenediamine and tetrapropylammonium hydroxide can be used in the present invention, and there is no particular requirement for the mixing ratio.
According to the method of the present invention, preferably the method of the present invention further comprises: recovering a solid product from the hydrothermally treated product, wherein the step of recovering the solid product generally comprises: filtration, washing, etc., steps, which are well known to those skilled in the art, are not described in detail herein.
According to the method of the present invention, preferably the method further comprises: and blowing the solid product after the hydrothermal treatment in an inert atmosphere at the temperature of 100-300 ℃ for 0.1-10h, wherein the inert atmosphere is a nitrogen atmosphere or an air atmosphere.
According to the method of the present invention, preferably the method further comprises: before the step (1), the discharging agent is contacted with a modifying solution containing nitric acid and at least one peroxide for modification treatment, and in the modification treatment, the molar ratio of the discharging agent as a raw material to the peroxide in terms of titanium silicalite molecular sieves is 1: (0.01-5), preferably 1: (0.05-3), more preferably 1: (0.1-2), the molar ratio of the peroxide to the nitric acid is 1: (0.01-50), preferably 1: (0.1-20), more preferably 1: (0.2-10), more preferably 1: (0.5-5), particularly preferably 1: (0.6-3.5), wherein the titanium silicalite molecular sieve is calculated by silicon dioxide.
According to the method of the present invention, it is preferable that the concentrations of the peroxide and the nitric acid in the modification liquid are each 0.1 to 50% by weight, preferably 0.5 to 25% by weight, and more preferably 5 to 15% by weight; wherein the peroxide is selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, peracetic acid, and perpropionic acid.
According to the method of the present invention, it is preferable that in the modification treatment, a discharging agent as a raw material is contacted with the modification solution at a temperature of 10 to 350 ℃, preferably 20 to 300 ℃, more preferably 50 to 250 ℃, and further preferably 60 to 200 ℃, the contact being performed in a vessel having a pressure of 0 to 5MPa, the pressure being a gauge pressure, and the duration of the contact being 1 to 10 hours, preferably 3 to 5 hours.
The invention provides a catalyst obtained by the method.
The invention provides the application of the catalyst in oxidation reaction.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the comparative examples and examples, the reagents used were all commercially available chemically pure reagents.
The discharging agents of the following examples and comparative examples were obtained as follows, and the activity of titanium silicalite molecular sieves (including titanium silicalite discharging agents, and titanium silicalite fresheners) was measured by the following method.
Taking a TS-1 molecular sieve (prepared by the method described in Zeolite, 1992, Vol.12: 943-950), TiO22.1% by mass and a relative crystallinity of 100%) was placed in a 100mL slurry bed reactor with continuous feed and membrane separation means, and a mixture of water and 30 wt% of hydrogen peroxide (the volume ratio of water to hydrogen peroxide was 10: 9) a mixture of cyclohexanone and tert-butanol was added at a rate of 10.5mL/h (the volume ratio of cyclohexanone to tert-butanol was 1: 2.5) adding 36 wt% ammonia water at the speed of 5.7mL/h, simultaneously adding the three material flows, continuously discharging at the corresponding speed, maintaining the reaction temperature at 80 ℃, sampling the product after the reaction is stable, analyzing the liquid phase composition by using a gas chromatography method every 1 hour, calculating the conversion rate of cyclohexanone by using the following formula, and taking the conversion rate as the activity of the titanium-silicon molecular sieve. Conversion of cyclohexanone [ (molar amount of cyclohexanone charged-molar amount of unreacted cyclohexanone)/molar amount of cyclohexanone charged]×100％。
The cyclohexanone conversion, measured for the first time, i.e. 1h, was its initial activity, which was 99.5%. After a period of about 168 hours, the cyclohexanone conversion rate is reduced from the initial 99.5% to 50%, the catalyst is separated and regenerated by roasting (roasting at 570 ℃ for 4 hours in an air atmosphere), and then the catalyst is continuously used in the cyclohexanone ammoximation reaction, and the step is repeatedly carried out until the activity after regeneration is lower than 50% of the initial activity, at which time, the inactivated ammoximation catalyst sample is used as the discharging agent of the invention, and the discharging agents SH-1 (the activity is 50%, the relative crystallinity is 87%), SH-2 (the activity is 40%, the relative crystallinity is 75%), SH-3 (the activity is 25%, the relative crystallinity is 68%), and SH-4 (the activity is 10%, and the relative crystallinity is 54%) are sequentially obtained according to the method.
Wherein, the X-ray diffraction (XRD) phase diagram of the discharging agent sample is measured on a Siemens D5005 type X-ray diffractometer, the crystallinity of the sample relative to the reference sample is expressed by the ratio of the sum of diffraction intensities (peak heights) of five-finger diffraction characteristic peaks of the sample and the reference sample between 2 theta of 22.5 degrees to 25.0 degrees, the crystallinity of the fresh agent sample is 100 percent, and the relative crystallinity of each discharging agent sample is calculated.
In the invention, the specific surface area of the micropores adopts N2And (4) determining by a constant-temperature adsorption-desorption method.
Example 1
Under the condition of normal pressure and 90 ℃, dimethyl sulfoxide and a discharging agent (SH-1) are mixed and contacted for 5.5 hours, wherein the weight ratio of the discharging agent to the dimethyl sulfoxide is 1: filtering and washing the mixture to obtain a contacted solid product, and drying the contacted solid product at 180 ℃ to constant weight;
mixing the dried solid with an ammonia water solution, and carrying out hydrothermal treatment at the pH of 10 and the temperature of 170 ℃ for 15h, wherein the mass ratio of the solid to ammonia is 50: 1, filtering, washing with water, drying (120 ℃) to constant weight, and recovering to obtain the molecular sieve A, wherein the activity, the relative crystallinity and the micropore specific surface area are shown in table 1 (the activity determination method is consistent with the method and the step for determining the fresh agent, and the cyclohexanone conversion rate determined in the 1h is taken as the activity).
Example 2
Mixing and contacting dimethyl sulfoxide and a discharging agent (SH-2) for 7.5 hours at the normal pressure of 80 ℃, wherein the weight ratio of the discharging agent to the dimethyl sulfoxide is 1: 5, filtering and washing to obtain a contacted solid product, and then drying at 180 ℃ to constant weight;
and then mixing the dried solid with an ammonia water solution, and carrying out hydrothermal treatment at the temperature of 150 ℃ for 12h at the pH of 10, wherein the mass ratio of the solid to ammonia is 20: 1, filtering, washing with water, drying (120 ℃) to constant weight, and recovering to obtain the molecular sieve B, wherein the activity, the relative crystallinity and the micropore specific surface area are shown in table 1.
Example 3
Mixing and contacting N-methyl pyrrolidone and a discharging agent (SH-3) for 15h under the condition of normal pressure and 60 ℃, wherein the weight ratio of the discharging agent to the N-methyl pyrrolidone is 1: 25, filtering and washing to obtain a contacted solid product, and then drying at 180 ℃ to constant weight;
mixing the dried solid with a diethanolamine aqueous solution, and carrying out hydrothermal treatment for 6h at the temperature of 150 ℃ and the pH value of 11, wherein the mass ratio of the solid to the diethanolamine is 80: 1, filtering, washing with water, drying (120 ℃) to constant weight to obtain the molecular sieve C, wherein the activity, the relative crystallinity and the micropore specific surface area are shown in Table 1 (the activity determination method is consistent with the method and the step for determining the fresh agent, and the cyclohexanone conversion rate determined in the 1h is taken as the activity).
Example 4
Mixing and contacting N, N-dimethylformamide, liquid ammonia and an unloading agent (SH-4) for 2.5 hours at the normal pressure and the temperature of 90 ℃, wherein the weight ratio of the unloading agent to the N, N-dimethylformamide is 1: 15, the mass ratio of the liquid ammonia to the N, N-dimethylformamide is 0.005: 1, filtering and washing to obtain a contacted solid product, and then drying at 180 ℃ to constant weight;
mixing the dried solid with a mixed aqueous solution of hexamethylene diamine and tetrapropylammonium hydroxide, and carrying out hydrothermal treatment at the pH of 13 and the temperature of 150 ℃ for 0.5h, wherein the mass ratio of the solid to the hexamethylene diamine to the tetrapropylammonium hydroxide is 100: 10: and 10, drying the obtained solid product in an air atmosphere at 200 ℃ for 3h to obtain the molecular sieve D, wherein the activity, the relative crystallinity and the micropore specific surface area are shown in Table 1 (the activity determination method is consistent with the method and the step for determining the freshness agent, and the cyclohexanone conversion rate determined in the 1h is taken as the activity).
Example 5
A catalyst was prepared according to the method of example 1 to obtain molecular sieve E, except that the discharging agent was modified as follows before contacting with the organic compound, and the remaining steps were the same:
mixing the discharging agent (SH-1) with HNO3(HNO310%) and an aqueous solution of hydrogen peroxide (the mass concentration of hydrogen peroxide is 7.5%), stirring the obtained mixture in a closed container at 70 ℃ for 5 hours, cooling the obtained reaction mixture to room temperature, filtering, and drying the obtained solid-phase substance at 120 ℃ to constant weight to obtain the modified discharging agent. Wherein the discharging agent is SiO2The molar ratio of the discharging agent to the hydrogen peroxide is 1: 0.1.
example 6
A catalyst was prepared according to the method of example 2 to obtain molecular sieve F except that the discharging agent was modified as follows before contacting with the organic compound:
will discharge agent(SH-2) and a composition containing HNO3(HNO310%) and an aqueous solution of hydrogen peroxide (the mass concentration of hydrogen peroxide is 5%), stirring the obtained mixture in a closed container at 120 ℃ for 4 hours, cooling the obtained reaction mixture to room temperature, filtering, and drying the obtained solid-phase substance at 120 ℃ to constant weight to obtain the modified discharging agent. Wherein the discharging agent is SiO2The molar ratio of the discharging agent to the hydrogen peroxide is 1: 0.4.
example 7
A catalyst was prepared according to the method of example 3 to obtain molecular sieve G except that the discharging agent was modified as follows before contacting with the organic compound:
mixing the discharging agent (SH-3) with HNO3(HNO315%) and an aqueous solution of hydrogen peroxide (the mass concentration of hydrogen peroxide is 8%), stirring the obtained mixture in a closed container at 150 ℃ for reaction for 3 hours, cooling the obtained reaction mixture to room temperature, filtering, and drying the obtained solid-phase substance at 120 ℃ to constant weight to obtain the modified discharging agent. Wherein the discharging agent is SiO2The molar ratio of the discharging agent to the hydrogen peroxide is 1: 2.
example 8
A catalyst was prepared according to the method of example 4, except that the contacting of the organic compound with the stripping agent was not carried out in the presence of ammonia, as follows:
mixing and contacting N, N-dimethylformamide with an unloading agent (SH-4) for 15h under the condition of normal pressure and 90 ℃, wherein the weight ratio of the unloading agent to the N, N-dimethylformamide is 1: 15, filtering and washing to obtain a contacted solid product, and then drying at 180 ℃ to constant weight;
mixing the dried solid with a mixed aqueous solution of hexamethylene diamine and tetrapropylammonium hydroxide, and carrying out hydrothermal treatment at the pH of 13 and the temperature of 150 ℃ for 0.5h, wherein the mass ratio of the solid to the hexamethylene diamine to the tetrapropylammonium hydroxide is 100: 10: and 10, drying the obtained solid product in an air atmosphere at 200 ℃ for 3H to obtain the molecular sieve H, wherein the activity, the relative crystallinity and the micropore specific surface area are shown in the table 1 (the activity determination method is consistent with the method and the step for determining the fresh agent, and the cyclohexanone conversion rate determined in the 1H is taken as the activity).
Example 9
A catalyst was prepared by following the procedure of example 4, except that the step (2) was carried out in the presence of a noble metal source as follows:
mixing and contacting N, N-dimethylformamide, liquid ammonia and an unloading agent (SH-4) for 2.5 hours at the normal pressure and the temperature of 90 ℃, wherein the weight ratio of the unloading agent to the N, N-dimethylformamide is 1: 15, the mass ratio of the liquid ammonia to the N, N-dimethylformamide is 0.005: 1, filtering and washing to obtain a contacted solid product, and then drying at 180 ℃ to constant weight;
mixing the dried solid, palladium chloride and mixed aqueous solution of hexamethylene diamine and tetrapropylammonium hydroxide, and carrying out hydrothermal treatment at the pH of 13 and the temperature of 150 ℃ for 0.5h, wherein the mass ratio of the solid to the hexamethylene diamine to the tetrapropylammonium hydroxide is 100: 10: 10, the mass ratio of the solid to the palladium chloride is 100: and 5, drying the obtained solid product in an air atmosphere at 200 ℃ for 3h to obtain the molecular sieve I, wherein the activity, the relative crystallinity and the micropore specific surface area are shown in the table 1 (the activity determination method is consistent with the method and the step for determining the fresh agent, and the cyclohexanone conversion rate determined in the 1h is taken as the activity).
Example 10
A catalyst was prepared by following the procedure of example 4, except that the step (2) was carried out in the presence of a noble metal source as follows:
mixing and contacting N, N-dimethylformamide, liquid ammonia and an unloading agent (SH-4) for 2.5 hours at the normal pressure and the temperature of 90 ℃, wherein the weight ratio of the unloading agent to the N, N-dimethylformamide is 1: 15, the mass ratio of the liquid ammonia to the N, N-dimethylformamide is 0.005: 1, filtering and washing to obtain a contacted solid product, and then drying at 150 ℃ to constant weight;
mixing the dried solid, platinum nitrate, a mixed aqueous solution of hexamethylene diamine and tetrapropylammonium hydroxide, and carrying out hydrothermal treatment at the temperature of 150 ℃ for 0.5h at the pH of 13, wherein the mass ratio of the solid to the hexamethylene diamine to the tetrapropylammonium hydroxide is 100: 5: 25, the mass ratio of the solid to the platinum nitrate is 100: and 5, drying the obtained solid product in an air atmosphere at 200 ℃ for 3h to obtain the molecular sieve J, wherein the activity, the relative crystallinity and the micropore specific surface area are shown in the table 1 (the activity determination method is consistent with the method and the step for determining the fresh agent, and the cyclohexanone conversion rate determined in the 1h is taken as the activity).
Example 11
A catalyst was prepared according to the method of example 4, with the main difference that step (2) was carried out in the presence of a noble metal source, as follows:
mixing and contacting N, N-dimethylformamide, liquid ammonia and an unloading agent (SH-4) for 2.5 hours at the normal pressure and the temperature of 90 ℃, wherein the weight ratio of the unloading agent to the N, N-dimethylformamide is 1: 15, the mass ratio of the liquid ammonia to the N, N-dimethylformamide is 0.005: 1, filtering and washing to obtain a contacted solid product, and then drying at 150 ℃ to constant weight;
mixing the dried solid, palladium acetate, mixed aqueous solution of hexamethylene diamine and tetrapropylammonium hydroxide, and carrying out hydrothermal treatment at the pH of 14 and the temperature of 170 ℃ for 0.5h, wherein the mass ratio of the solid to the hexamethylene diamine to the tetrapropylammonium hydroxide is 100: 15: 25, the mass ratio of the solid to the platinum nitrate is 100: and 2, drying the obtained solid product at 200 ℃ for 3h in an air atmosphere to obtain the molecular sieve K, wherein the activity, the relative crystallinity and the micropore specific surface area are shown in Table 1 (the activity determination method is consistent with the method and the step for determining the fresh agent, and the cyclohexanone conversion rate determined in the 1h is taken as the activity).
TABLE 1
| Examples | Sample (I) | Activity, a | Relative degree of crystallinity,% | Specific surface area of micropores, m2/g |
| 1 | A | 94.5 | 96 | 361 |
| 2 | B | 95.3 | 98 | 353 |
| 3 | C | 95.6 | 99 | 368 |
| 4 | D | 96.5 | 100 | 361 |
| 5 | E | 97.2 | 99 | 378 |
| 6 | F | 98.3 | 99 | 380 |
| 7 | G | 98.9 | 100 | 385 |
| 8 | H | 94.5 | 97 | 358 |
| 9 | I | 99.9 | 100 | 381 |
| 10 | J | 99.8 | 99 | 382 |
| 11 | K | 99.5 | 100 | 379 |
| Fresh agent | 99.5 | 100 | 376 |
As can be seen from the data in Table 1, the titanium-silicon-containing molecular sieve catalyst obtained by the preparation method provided by the invention has better catalytic performance compared with the catalyst obtained by the roasting or acid washing and roasting method in the prior art, and the crystallinity and the micropore specific surface area are basically and completely recovered. Particularly, a small amount of ammonia is introduced when the catalyst is contacted with an organic compound, so that the effect of the prepared catalyst can be further improved, and the contact time can be greatly shortened.
The results of the method of the invention show that the method can basically and completely recover the activity, crystallinity and micropore specific surface area of the prepared catalyst without regeneration at high temperature, effectively save energy consumption and is very suitable for industrial application.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (25)
1. A method for preparing a titanium-containing silicon molecular sieve catalyst is characterized by comprising the following steps:
(1) contacting a discharging agent with an organic compound to obtain a contacted product, wherein the organic compound is selected from one or more of sulfone, ketone and amide, and the discharging agent is the discharging agent of a reaction device which takes a titanium silicalite molecular sieve as a catalyst active component;
(2) in the presence of a water-containing solvent, mixing the contacted product with an alkali source, and then carrying out hydrothermal treatment;
in the step (1), the contacting is carried out in the presence of ammonia, and the mass ratio of ammonia to the organic compound is (0.0001-0.1): 1;
in the step (2), the hydrothermal treatment conditions include: the pH value is 8-14, the temperature is 120-200 ℃, the pressure is 0-3MPa, the time is 0.5-72h, and the pressure is gauge pressure;
the step (2) is carried out in the presence of a noble metal source, and the mass ratio of the contacted product to the noble metal source is (20-1000) in dry weight: 1.
2. the production method according to claim 1, wherein the organic compound is one or more of dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.
3. The preparation method according to claim 1, wherein the discharging agent of the reaction device using the titanium silicalite molecular sieve as the catalyst active component is a discharging agent of an ammoximation reaction device.
4. The process of claim 1, wherein the titanium silicalite molecular sieve is of the MFI structure and the activity of the discharging agent is less than 50% of the activity when fresh.
5. The production method according to any one of claims 1 to 4, wherein the contacting temperature in step (1) is lower than the boiling point of the organic compound.
6. The production method according to any one of claims 1 to 4, wherein the contacting temperature is 20 to 250 ℃ lower than the boiling point of the organic compound.
7. The production method according to any one of claims 1 to 4, wherein in step (1), the mass ratio of the organic compound to the discharging agent is (0.5 to 100): 1.
8. the production method according to any one of claims 1 to 4, wherein, in the step (2),
the mass ratio of the product after contact to the alkali source is (1-100) by dry weight: 1,
the alkali source is one or more of ammonia water, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylenediamine, monoethanolamine, diethanolamine and triethanolamine.
9. The production method according to any one of claims 1 to 4, wherein the noble metal source is one or more of an oxide of a noble metal, a halide of a noble metal, a carbonate of a noble metal, a nitrate of a noble metal, a hydroxide of a noble metal, and a complex of a noble metal, and the noble metal is one or more of Ru, Rh, Pd, Os, Ir, Pt, Ag, and Au.
10. The production method according to any one of claims 1 to 4, wherein the method further comprises: and blowing the solid product after the hydrothermal treatment for 0.1-10h at the temperature of 100-300 ℃ in a nitrogen atmosphere or an air atmosphere.
11. The production method according to any one of claims 1 to 4, wherein the method further comprises: before the step (1), the discharging agent is contacted with a modifying solution containing nitric acid and at least one peroxide for modification treatment, and in the modification treatment, the molar ratio of the discharging agent as a raw material to the peroxide in terms of titanium silicalite molecular sieves is 1: (0.01-5), the molar ratio of the peroxide to the nitric acid is 1: (0.01-50), wherein the titanium silicalite molecular sieve is calculated by silicon dioxide.
12. The preparation method according to claim 11, wherein in the modification treatment, the molar ratio of the discharging agent as the raw material to the peroxide in terms of the titanium silicalite molecular sieve is 1: (0.05-3), and the molar ratio of the peroxide to the nitric acid is 1: (0.1-20), wherein the titanium silicalite molecular sieve is calculated by silicon dioxide.
13. The preparation method according to claim 11, wherein in the modification treatment, the molar ratio of the discharging agent as the raw material to the peroxide in terms of the titanium silicalite molecular sieve is 1: (0.1-2), the molar ratio of the peroxide to the nitric acid is 1: (0.2-10), wherein the titanium silicalite molecular sieve is calculated by silicon dioxide.
14. The production method according to claim 11, wherein, in the modification treatment, the molar ratio of the peroxide to the nitric acid is 1: (0.5-5).
15. The production method according to claim 11, wherein, in the modification treatment, the molar ratio of the peroxide to the nitric acid is 1: (0.6-3.5).
16. The production method according to claim 11, wherein the concentrations of the peroxide and the nitric acid in the modification liquid are each 0.1 to 50 wt%; wherein the peroxide is selected from one or more of hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, peroxyacetic acid and peroxypropionic acid.
17. The production method according to claim 11, wherein the concentrations of the peroxide and the nitric acid in the modification liquid are each 0.5 to 25% by weight.
18. The production method according to claim 11, wherein the concentrations of the peroxide and the nitric acid in the modification liquid are each 5 to 15% by weight.
19. The production method according to claim 11, wherein in the modification treatment, a discharging agent as a raw material is contacted with the modification solution at a temperature of 10 to 350 ℃, the contact is performed in a vessel having a pressure of 0 to 5MPa, the pressure is a gauge pressure, and the duration of the contact is 1 to 10 hours.
20. The production method according to claim 11, wherein in the modification treatment, a discharging agent as a raw material is brought into contact with the modification liquid at a temperature of 20 to 300 ℃.
21. The production method according to claim 11, wherein in the modification treatment, a discharging agent as a raw material is brought into contact with the modification liquid at a temperature of 50 to 250 ℃.
22. The production method according to claim 11, wherein in the modification treatment, a discharging agent as a raw material is brought into contact with the modification liquid at a temperature of 60 to 200 ℃.
23. The production method according to claim 11, wherein, in the modification treatment, the duration of the contact is 3 to 5 hours.
24. A catalyst prepared by the process of any one of claims 1 to 23.
25. Use of a catalyst according to claim 24 in an oxidation reaction.
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