CN114425438B - Preparation method of titanium-containing catalyst, titanium-containing catalyst and method for preparing epoxy compound - Google Patents
Preparation method of titanium-containing catalyst, titanium-containing catalyst and method for preparing epoxy compound Download PDFInfo
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- CN114425438B CN114425438B CN202010999873.3A CN202010999873A CN114425438B CN 114425438 B CN114425438 B CN 114425438B CN 202010999873 A CN202010999873 A CN 202010999873A CN 114425438 B CN114425438 B CN 114425438B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
A process for preparing a titanium-containing catalyst, comprising the steps of: (1) Mixing an amorphous silicon source, a titanium source and an alkaline aqueous solution for heat treatment to prepare a titanium silicate gel, and mixing the titanium silicate gel with a titanium silicon molecular sieve, an auxiliary agent and an ammonium salt for molding to obtain a molded catalyst; (2) Treating the formed catalyst for 0.5-3h under the conditions of externally applied pressure, externally added water, apparent pressure of 0.01-1.0 MPa and temperature of 100-300 ℃; (3) And (3) adding a liquid with the pH value more than 9 into the molded catalyst obtained by the treatment in the step (2) at the apparent pressure of 0.01-1.0 MPa and the temperature of 300-600 ℃ for at least 0.5h to obtain the titanium-containing catalyst. The invention has simple operation flow, and the titanium silicon molecular sieve grain of the titanium-containing catalyst has a plurality of mesoporous pores of 4-20nm, and has excellent catalytic performance in olefin epoxidation reaction.
Description
Technical Field
The present invention relates to a method for preparing a catalyst, a catalyst and an application thereof, and more particularly, to a method for preparing a titanium-containing catalyst, a titanium-containing catalyst and a method for preparing an epoxy compound.
Background
The epoxy compound has active epoxy bond, so that the epoxy compound can be used for preparing various important chemicals, and is closely related to daily life of people, thereby having important effect. Wherein, the propylene oxide is mainly used for producing chemicals such as polyurethane, propylene glycol and the like, and the domestic productivity reaches 300 ten thousand tons/year. The titanium-silicon molecular sieve is adopted to catalyze the one-step reaction of propylene and hydrogen peroxide to prepare propylene oxide, and the production process is clean and favored because of few reaction steps, wherein the high-activity titanium-containing catalyst is the focus of the research of propylene epoxidation to prepare propylene oxide.
The preparation of high-activity titanium-containing catalysts involves two main aspects, namely the preparation of high-activity titanium-silicon molecular sieves and the preparation of high-performance molded catalysts. CN1301599a discloses a titanium-silicon molecular sieve with an intragranular hollow structure, which has excellent performance in olefin epoxidation reaction due to its unique structure. CN101274922a further discloses a method for performing propylene epoxidation reaction by using the titanium-silicon molecular sieve raw powder described in CN1301599a as a catalyst and a shaped titanium-containing catalyst. The raw powder is used for reaction, so that engineering problems are brought to separation of products and catalysts, the titanium-silicon molecular sieve content in the molding method is only 70%, the propylene oxide selectivity is 72.5%, and the catalytic performance is required to be further improved.
CN102441430a discloses a method for forming titanium-containing catalyst by using amorphous silicon dioxide as binder to form hollow titanium-silicon molecular sieve of CN1132699C, the hydrogen peroxide conversion rate of the catalyst obtained by forming the method can reach 96.7%, and propylene oxide selectivity can reach 95.0%.
The preparation method of the high-performance titanium-silicon molecular sieve is complex, so that the preparation of the titanium-containing catalyst has higher overall energy consumption and lower economical efficiency. How to shorten the preparation flow of olefin epoxidation titanium-containing catalyst and prepare high-performance epoxidation catalyst at the same time is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a titanium-containing catalyst, wherein the titanium-containing catalyst has a plurality of mesoporous pores of 4-20nm in titanium-silicon molecular sieve grains and has good olefin epoxidation catalytic performance. Compared with the existing preparation method, the preparation process is simpler, the template agent in the molecular sieve crystal can be effectively utilized, and meanwhile, small-size mesopores in the molecular sieve crystal can be generated, so that the catalytic performance is improved.
It is a further object of the present invention to provide a titanium-containing catalyst prepared by the process of the present invention.
It is a further object of the present invention to provide the use of said molecular sieves.
In order to achieve one of the objects of the present invention, the present invention provides a process for producing a titanium-containing catalyst, characterized in that the process comprises the steps of:
(1) Mixing an amorphous silicon source, a titanium source and an alkaline aqueous solution for heat treatment to prepare a titanium silicate gel, and mixing the titanium silicate gel with a titanium silicon molecular sieve, an auxiliary agent and an ammonium salt for molding to obtain a molded catalyst;
(2) Treating the formed catalyst for 0.5-3h under the conditions of externally applied pressure, externally added water, apparent pressure of 0.01-1.0 MPa and temperature of 100-300 ℃;
(3) And (3) adding a liquid with the pH value more than 9 into the molded catalyst obtained by the treatment in the step (2) at the apparent pressure of 0.01-1.0 MPa and the temperature of 300-600 ℃ for at least 0.5h to obtain the titanium-containing catalyst.
In order to achieve the second object of the present invention, the present invention provides a titanium-containing catalyst prepared according to the method of the present invention.
In order to achieve the third object of the invention, the invention provides the application of the titanium-containing catalyst in olefin epoxidation catalytic reaction.
The preparation method of the titanium-containing catalyst provided by the invention has the advantages of simple process, easiness in implementation and good effect, and can effectively utilize the molecular sieve intragranular template agent to generate a small-size mesoporous structure. The titanium-containing catalyst provided by the invention has good effect in olefin epoxidation catalytic oxidation reaction, and has high catalytic activity, high hydrogen peroxide conversion rate, high propylene oxide selectivity and high hydrogen peroxide effective utilization rate when being used for preparing propylene oxide by propylene epoxidation.
Drawings
Fig. 1 is a TEM image of the titanium silicalite molecular sieve obtained in comparative example 1.
FIG. 2 is a TEM image of a titanium silicalite molecular sieve in the titanium-containing catalyst obtained in example 1.
Detailed Description
The invention provides a preparation method of a titanium-containing catalyst, which is characterized by comprising the following steps:
(1) Mixing an amorphous silicon source, a titanium source and an alkaline aqueous solution for heat treatment to prepare a titanium silicate gel, and mixing the titanium silicate gel with a titanium silicon molecular sieve, an auxiliary agent and an ammonium salt for molding to obtain a molded catalyst;
(2) Treating the formed catalyst for 0.5-3h under the conditions of externally applied pressure, externally added water, apparent pressure of 0.01-1.0 MPa and temperature of 100-300 ℃;
(3) And (3) adding a liquid with the pH value more than 9 into the molded catalyst obtained by the treatment in the step (2) at the apparent pressure of 0.01-1.0 MPa and the temperature of 300-600 ℃ for at least 0.5h to obtain the titanium-containing catalyst. .
In the method of the present invention, the titanium silicalite molecular sieve in step (1) may have a structure of AEL, AFI, AFN, BEC, CFI, CHA, CON, EUO, FAU, FER, IMF, LTA, MER, MFI, MEL, MOR, MWW, RHO, TON, BEA, EWT, or two-dimensional hexagonal phase, and preferably has an MFI structure.
In the method of the present invention, the titanium silicalite molecular sieve in the step (1) may be a titanium silicalite molecular sieve which does not contain organic matters after being baked, or may be a titanium silicalite molecular sieve containing organic matters such as a template agent, and preferably a titanium silicalite molecular sieve containing a template agent. The titanium-silicon molecular sieve containing the template agent is prepared by adopting a hydrothermal synthesis method or a rearrangement method, and is filtered, dried and removed without roasting. In the titanium-silicon molecular sieve containing the template agent, the content of the template agent is preferably 1-30% of the weight of the molecular sieve.
The template agent comprises an organic amine compound, such as aliphatic amine, aromatic amine, alcohol amine, organic quaternary ammonium base, organic quaternary ammonium salt and/or long-chain alkyl ammonium compound.
The organic amine can be one or more of fatty amine, aromatic amine and alcohol amine, and the fatty amine (or fatty amine compound) is represented by R 1 (NH 2 ) n Wherein R is 1 Is an alkyl or alkylene group having 1 to 8 carbon atoms,n=1 or 2; the general formula of the alcohol amine (or alcohol amine compound) is written as (HOR) 2 ) m NH (3-m) Wherein R is 2 Is an n-or iso-alkyl group having 1 to 8 carbon atoms, m=1, 2 or 3. The fatty amine comprises one or more of ethylamine, n-propylamine, n-butylamine, butanediamine, hexamethylenediamine, cyclopentylamine and cyclohexylamine. The aromatic amine refers to an amine with one aromatic substituent, and can be one or more of aniline, amphetamine, p-phenylenediamine and toluidine. The alcohol amine can be, for example, one or more of monoethanolamine, diethanolamine, and triethanolamine.
The organic quaternary ammonium base comprises one or more selected from tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or tetraethylammonium hydroxide; the organic quaternary ammonium salt comprises one or more selected from tetrapropylammonium bromide, tetrabutylammonium bromide, tetraethylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride.
The general formula of the long-chain alkyl ammonium compound is R 3 NH 3 X or R 3 N(R 4 ) 3 X, wherein R is 3 Represents an n-or iso-alkyl group having 12 to 18 carbon atoms, R 4 Represents an n-or iso-alkyl group having 1 to 4 carbon atoms; x represents a monovalent anion, which may be OH - 、Cl - 、Br - The method comprises the steps of carrying out a first treatment on the surface of the When X is OH - When the present invention is referred to as basic long chain alkyl ammonium compounds; the long chain alkyl ammonium compound may be one or more of octadecyl trimethyl ammonium hydroxide, octadecyl trimethyl ammonium bromide, octadecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium hydroxide, hexadecyl ammonium chloride, tetradecyl trimethyl ammonium bromide, tetradecyl ammonium chloride, tetradecyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium bromide, and dodecyl ammonium chloride.
The amorphous silicon source in the step (1) of the method comprises silica sol and organic silicon ester. The silica sol comprises acidic silica sol and alkaline silica sol, and the content of the silica sol is preferably 5-40% by weight of silicon dioxide. The organic silicon ester comprises organic silicon compounds with alkoxy groups, including one or more of tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate, trimethoxy chlorosilane, triethoxyphenyl silane and triethoxypropenyl silane. The amorphous silicon source is preferably an organosilicon ester, more preferably tetraethyl silicate.
In the method of the present invention, the titanium source in step (1) includes one or more of organic titanium esters, titanium tetrachloride, titanium trichloride, and titanium sulfate, preferably organic titanium esters, more preferably tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate.
In the method of the present invention, the alkaline aqueous solution in the step (1) may be an aqueous solution having a pH of 10-14 and containing an organic base or an inorganic base, where the organic base or the inorganic base refers to a compound that is alkaline in water, and includes an organic amine compound, for example, aliphatic amine, aromatic amine, alcohol amine, and organic quaternary ammonium base, and the alkaline inorganic substance may be one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, and ammonia water. Organic quaternary ammonium bases and aqueous ammonia are preferred. More preferably one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, aqueous ammonia.
In the method of the invention, the auxiliary agent in the step (1) comprises one or more of sesbania powder, starch, polyalcohol and nanocellulose, wherein the polyalcohol is preferably a compound with at least two hydroxyl groups and C2-C6, and can be, for example, ethylene glycol, propylene glycol, glycerol, glyceraldehyde, pentaerythritol, pentanediol, hexanediol, dihydroxyacetone, fructose, glucose and the like.
In the method of the present invention, the ammonium salt in the step (1) is an organic ammonium salt or an inorganic ammonium salt, including one or more of ammonium acetate, ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium sulfate, ammonium bisulfate, ammonium phosphate, monoammonium phosphate, ammonium fluoride, and ammonium fluorosilicate, preferably one or more of ammonium acetate, ammonium carbonate, ammonium phosphate, and ammonium fluoride.
According to the method of the present invention, the heat treatment in the step (1) comprises treatment at 50-100 ℃ for 0.5-5 hours.
According to the method disclosed by the invention, the silicon-titanium gel in the step (1) comprises the following components in mole: amorphous silicon source (calculated as silica), titanium source (calculated as titania), water 1: (0.05-0.30): (3-10), preferably 1: (0.1-0.25): (4-8). The weight ratio of the titanium-silicon molecular sieve to the silicon-titanium gel to the auxiliary agent to the ammonium salt is preferably 100: (3-20): (1-6): (0.1-2), more preferably 100: (5-15): (1-4): (0.5-1.5).
In the method, the forming in the step (1) comprises rolling ball forming, kneading and extruding to form the strip. The titanium-containing catalyst which is formed by rolling ball forming and extrusion molding is more suitable for the application in a fixed bed reactor. The preparation method of the titanium-containing catalyst can obtain the titanium-containing catalyst with more excellent performance formed by rolling balls or extruding strips.
In the process of the present invention, in the step (2), the apparent pressure is preferably 0.1 to 0.6MPa, more preferably 0.2 to 0.4MPa, the treatment temperature is preferably 150 to 200℃and the treatment time is preferably 1 to 2 hours. In the step (3), the apparent pressure is preferably 0.2 to 0.7MPa, more preferably 0.3 to 0.5MPa, the treatment temperature is preferably 400 to 550℃and the treatment time is preferably 3 to 6 hours. The two-step treatment of the steps (2) and (3) is preferably carried out continuously by changing the temperature and switching materials.
In the method of the invention, in the step (3), the liquid with the pH value of more than 9 is preferably ammonia water or aqueous solution of organic amine. The mass fraction of the alkaline substance in the liquid is preferably 1% -28%, more preferably 5% -20%. The organic amine is preferably organic quaternary ammonium base and/or fatty amine, the organic quaternary ammonium base can be one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide, and the fatty amine (or fatty amine compound) has a general formula of R 1 (NH 2 ) n Wherein R is 1 Represents an alkyl or alkylene group having 1 to 8 carbon atoms, n=1 or 2, and may be, for example, one or more of ethylamine, n-propylamine, n-butylamine, butanediamine, hexamethylenediamine, cyclopentylamine, cyclohexylamine. The pH value of the liquid is more than 9The body is further preferably aqueous ammonia.
In the method of the present invention, the step (2) and the step (3) comprise contacting water and a liquid with a pH value of > 9 with the shaped catalyst at the temperature and the pressure respectively, or contacting the liquid with the shaped catalyst after vaporizing. Preferably, this comprises heating said water and a liquid having a pH > 9 to vaporise and contacting the resulting gas with a shaped catalyst. The contacting includes static contacting, and fluid contacting through titanium silicalite. The amount of the water used in the step (2) is preferably (0.1-2) g water/(g catalyst-min), more preferably (0.3-0.8) g water/(g catalyst-min); the amount of the liquid having a pH of > 9 used in the step (3) is preferably (0.1-2) g of liquid/(g of catalyst. Min), more preferably (0.6-1.4) g of liquid/(g of catalyst. Min)
The titanium-containing catalyst can be partially or completely removed from the titanium-silicon molecular sieve template agent through the preparation method of the invention, the roasting can be omitted, and the titanium-containing catalyst treated in the steps (2) and (3) can be further roasted in an oxygen-containing atmosphere. The titanium-containing catalyst treated in the steps (2) and (3) may be washed and/or dried and then calcined. The calcination can be carried out under oxygen-enriched or oxygen-depleted conditions, the calcination temperature is preferably 300-800 ℃, and the calcination time is preferably 0.5-12h.
In order to maintain the high catalytic performance of the titanium-containing catalyst, the preparation method of the invention can further comprise the steps of alkaline washing the titanium-containing catalyst prepared by the method with an ammonia water solution and acid washing with an acid solution containing hydrogen peroxide. The pH value of the ammonia water solution is preferably 9-14, more preferably 10-12, the titanium-containing catalyst accounts for preferably 1-10, more preferably 3-7 weight percent of the ammonia water solution, and the alkaline washing is preferably performed at 40-90 ℃ for 10-120min, more preferably at 60-80 ℃ for 30-90min. The pH value of the acid solution containing hydrogen peroxide is preferably 1-6, more preferably 2-4, and the weight percentage of hydrogen peroxide is preferably 0-5, more preferably 0.3-3. In the alkaline washing, the titanium-containing catalyst is preferably 1 to 10% by weight, more preferably 3 to 7% by weight, based on the aqueous ammonia solution. The acid washing is preferably conducted at 40 to 90℃for 10 to 120 minutes, more preferably at 60 to 80℃for 30 to 90 minutes.
According to the preparation method provided by the invention, the template agent in the molecular sieve crystal can be fully utilized for carrying out intra-crystal reaming, the titanium-containing catalyst is characterized by TEM, and a plurality of 4-20nm mesopores are arranged in the titanium-silicon molecular sieve crystal grain of the titanium-containing catalyst, and the small-size mesopore structure is favorable for improving the catalytic performance of the titanium-silicon molecular sieve.
The invention also provides a titanium-containing catalyst which is characterized by being prepared by the preparation method. The titanium-containing catalyst can be further mixed with other catalysts, cocatalysts, structure assistants, electronic assistants, binders, inert carriers and the like mechanically, by kneading, tabletting, extruding, spraying, rolling ball forming, oil column forming and other methods to prepare the catalytic mixture containing the titanium-containing catalyst, and the weight percentage of the titanium-containing catalyst in the catalytic mixture is preferably more than 10%.
The invention further provides an application of the titanium-containing catalyst in preparing an epoxy compound by olefin epoxidation, namely a method for preparing the epoxy compound by olefin epoxidation.
The epoxidation reaction conditions include hydrogen peroxide: olefins: the solvent molar ratio is preferably 1: (0.5-10): (2-30), more preferably 1: (2-5): (5-15), the reaction temperature is preferably 10-80 ℃, more preferably 30-50 ℃, the reaction pressure is preferably 0.1-5MPa gauge pressure, and the reaction liquid hourly space velocity is preferably 0.1-8h-1. The solvent is preferably water or alcohol, ester or nitrile with 1-6 carbon atoms. Preferably, the olefin is propylene, i.e., propylene is epoxidized to produce propylene oxide.
The application provided by the invention can be carried out in a plurality of reactors such as a kettle type reactor, a slurry bed reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a micro-channel reactor and the like; the reaction raw materials and the titanium-containing catalyst can be fed at one time, intermittently and continuously; separation of the product from the catalyst may be achieved in a variety of ways, for example, separation of the product and recovery and reuse of the catalyst may be achieved by sedimentation, filtration, centrifugation, evaporation, membrane separation, etc.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the following examples and comparative examples:
the content of the template agent in the molecular sieve is measured by a thermogravimetric method, and the weight loss from the temperature of more than 200 ℃ of the weight loss curve to the time when the weight loss curve is stable is calculated as the template agent content of the molecular sieve.
The high-resolution morphology analysis of the molecular sieve is characterized by adopting a TEM method.
The starting materials used in the examples and comparative examples were analytically pure reagents unless otherwise specified.
The amount of hydrogen peroxide is titrated and analyzed by adopting a sodium thiosulfate method. The reaction product is analyzed by gas chromatography, and the analysis result is quantified by an external standard method. Wherein, the analysis conditions of the chromatograph are: agilent-6890 chromatograph, HP-5 capillary chromatographic column, sample injection amount 0.5 μl, sample inlet temperature 280 ℃. The column temperature was maintained at 100deg.C for 2min, then raised to 250deg.C at 15 ℃/min and maintained for 10min. FID detector, detector temperature 300 ℃.
Examples and comparative examples:
hydrogen peroxide conversion (%) = (number of moles of hydrogen peroxide in raw material-number of moles of hydrogen peroxide in product)/number of moles of hydrogen peroxide in raw material×100%
Epoxy compound selectivity (%) =moles of epoxy compound formed in the product/moles of olefin consumed to form all the products×100%
Effective utilization rate (%) of hydrogen peroxide=mole number of hydrogen peroxide consumed for generating all products/(mole number of hydrogen peroxide in raw material-mole number of hydrogen peroxide in product) ×100%
Preparation example 1
The preparation example is used for preparing the TS-1-A molecular sieve containing the template agent.
About 3/4 of the tetrapropylammonium hydroxide (TPAOH, 20 wt%) solution was added to the tetraethyl orthosilicate (TEOS) solution to give a pH of about 13The liquid mixture is then added dropwise, with vigorous stirring, to the liquid mixture obtained, the desired amount of n-butyl titanate [ Ti (OBu) ] 4 ]Is stirred for 15 minutes. Finally, the remaining TPAOH was slowly added to the mixture and stirred at 348-353K for about 3 hours to give a chemical composition of 0.02TiO 2 ∶SiO 2 ∶0.36TPA∶35H 2 O sol, crystallizing at 443K for 3 days, filtering the obtained solid, washing with distilled water, and drying at 373K for 5 hours to obtain molecular sieve sample with the number of TS-1-A.
The weight loss of TS-1-A measured by thermogravimetric method at 200-600deg.C is 15%.
Preparation example 2
The preparation example is used for preparing the TS-1-B molecular sieve containing the template agent.
The difference from preparation example 1 is that a TiO having a chemical composition of 0.008 is obtained 2 ∶SiO 2 ∶0.36TPA∶35H 2 O sol and molecular sieve sample number is TS-1-B.
The weight loss of TS-1-B measured by thermogravimetric method at 200-600deg.C is 12%.
Comparative example 1
This comparative example illustrates the preparation of TS-1-C without templating agent using air calcination.
Roasting TS-1-A at 550 ℃ under the condition of air atmosphere and normal pressure for 6 hours to remove the template agent, wherein the molecular sieve sample number is TS-1-C. The weight loss of the treated molecular sieve at 200-600 ℃ is 0 by adopting a thermogravimetric method. The TEM characterization result of the molecular sieve is shown in figure 1, and the molecular sieve has no obvious mesoporous structure in the crystal.
Comparative example 1
The comparative example illustrates that TS-1-D is prepared by molding and roasting a titanium-silicon molecular sieve containing a template agent.
Tetraethyl silicate (calculated as silica), tetraethyl titanate (calculated as titania), and aqueous tetrapropylammonium hydroxide solution (calculated as water) having a pH of 14 were mixed in a molar ratio of 1:0.05:10, mixing and treating at 80 ℃ for 3 hours to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium chloride according to the weight ratio of 100:3:6:0.1 mixing to form a rolling ball, wherein the auxiliary agent is sesbania powder and propylene glycol according to the weight ratio of 1:2. And roasting the formed catalyst at 550 ℃ under normal pressure in an air atmosphere for 6 hours to remove the template agent, wherein the sample number of the catalyst is TS-1-D. The weight loss of the treated catalyst at 200-600 ℃ is 0 as measured by a thermogravimetric method.
Example 1
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-F using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetraethyl titanate (calculated as titanium dioxide) and tetrapropylammonium hydroxide aqueous solution with pH value of 14 (calculated as water) are mixed according to a mole ratio of 1:0.05:10, mixing and treating at 80 ℃ for 3 hours to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium chloride according to the weight ratio of 100:3:6:0.1 mixing to form a rolling ball, wherein the auxiliary agent is sesbania powder and propylene glycol according to the weight ratio of 1:2.
And secondly, introducing water into the formed catalyst under the condition of 120 ℃ and N2 back pressure of 0.45MPa, generating a water vapor atmosphere, and treating for 2.5 hours, wherein the rate of introducing water is 0.1g of liquid/(g of catalyst.min).
And thirdly, continuously introducing ammonia water with the mass fraction of 10% under the conditions of 350 ℃ and N2 back pressure of 0.2Mpa, wherein the pH value of the solution is 14, the introducing rate is 0.3g of liquid/(g of catalyst.min), and the treatment time is 4h.
The weight loss of the treated catalyst was 0.4% at 200-600 c as measured by thermogravimetry. Roasting at 550 ℃ for 6 hours under normal pressure and air atmosphere to remove residual template agent, wherein the sample number of the catalyst is TS-1-F. The TEM result of the titanium-silicon molecular sieve of the crushed titanium-containing catalyst is shown in figure 2, and the existence of a plurality of mesoporous structures of 4-20nm in the crystal of the molecular sieve can be seen.
Example 2
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-G using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetraisopropyl titanate (calculated as titanium dioxide) and ammonia water with the pH value of 14 (calculated as water) are mixed according to the mole ratio of 1:0.09:9, mixing and treating for 4 hours at 60 ℃ to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium bicarbonate according to the weight ratio of 100:4:5:0.4 mixing and rolling ball forming, wherein the auxiliary agent is sesbania powder and fructose according to the weight ratio of 1: 1.5.
And secondly, introducing water into the formed catalyst at 230 ℃ and under the condition of N2 back pressure of 0.5MPa, generating a water vapor atmosphere for 3 hours, wherein the rate of introducing water is 0.2g of liquid/(g of catalyst.min).
And thirdly, continuously introducing 15% ammonia water by mass under the conditions of 380 ℃ and N2 back pressure of 0.6Mpa, wherein the pH value of the solution is 14, the introducing rate is 0.4g of liquid/(g of catalyst.min), and the treatment time is 4h.
The weight loss of the treated catalyst was 0.3% at 200-600 c as measured by thermogravimetry. Roasting at 550 ℃ for 6 hours under normal pressure and air atmosphere to remove residual template agent, wherein the sample number of the catalyst is TS-1-G. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 3
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-H using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetrabutyl titanate (calculated as titanium dioxide) and tetrabutyl ammonium hydroxide aqueous solution with a pH value of 14 (calculated as water) are mixed according to a mole ratio of 1:0.05:3, mixing and treating for 2 hours at 70 ℃ to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, ethylene glycol and ammonium sulfate according to the weight ratio of 100:20:5:2 mixing and rolling ball forming. And secondly, introducing water into the formed catalyst at the temperature of 280 ℃ and the back pressure of N2 of 0.6MPa, generating a water vapor atmosphere, and treating for 3 hours, wherein the rate of introducing water is 0.9g of liquid/(g of catalyst.min). And thirdly, continuously introducing ammonia water with the mass fraction of 20% under the conditions of 600 ℃ and N2 back pressure of 0.25Mpa, wherein the pH value of the solution is 14, the introducing rate is 1.8g of liquid/(g of catalyst.min), and the treatment time is 5h.
The weight loss of the treated catalyst was 0.4% at 200-600 c as measured by thermogravimetry. Roasting at 550 ℃ for 6 hours under normal pressure and air atmosphere to remove residual template agent, wherein the sample number of the catalyst is TS-1-H. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 4
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-I using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetraethyl titanate (calculated as titanium dioxide) and tetraethyl ammonium hydroxide aqueous solution with a pH value of 13 (calculated as water) are mixed according to a mole ratio of 1:0.3:10, mixing and treating at 60 ℃ for 3 hours to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium dihydrogen phosphate according to the weight ratio of 100:16:6:1.6 mixing and kneading, and then extruding strips to form, wherein the auxiliary agent is starch and hexanediol according to the weight ratio of 1: 3.
And secondly, introducing water into the formed catalyst under the condition of 140 ℃ and N2 back pressure of 0.15MPa, generating a water vapor atmosphere, and treating for 2.5 hours, wherein the rate of introducing water is 1.2g of liquid/(g of catalyst.min).
And thirdly, continuously introducing 15% ammonia water by mass under the conditions of 30 ℃ and N2 back pressure of 0.6Mpa, wherein the pH value of the solution is 14, the introducing rate is 1.5g of liquid/(g of catalyst.min), and the treatment time is 3h.
The weight loss of the treated catalyst was 0.3% at 200-600 c as measured by thermogravimetry. Roasting at 550 ℃ for 6 hours under normal pressure and air atmosphere to remove residual template agent, wherein the sample number of the catalyst is TS-1-I. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 5
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-J using the process of the present invention.
In the first step, a silica sol (30% in terms of silica), titanium sulfate (in terms of titanium dioxide) and an aqueous tetrapropylammonium hydroxide solution (in terms of water) having a pH of 13 are mixed in a molar ratio of 1:0.05:3, mixing and treating for 4 hours at 90 ℃ to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium nitrate according to the weight ratio of 100:4:5:0.3 mixing and performing rolling ball molding, wherein the auxiliary agent is starch and glyceraldehyde according to the weight ratio of 1: 1.5.
And secondly, introducing water into the formed catalyst at 260 ℃ under the condition of N2 back pressure of 0.5MPa, generating a water vapor atmosphere, and treating for 3 hours, wherein the rate of introducing water is 0.85g of liquid/(g of catalyst.min).
And thirdly, continuously introducing propylamine with the mass fraction of 28% under the conditions of 350 ℃ and N2 back pressure of 0.25Mpa, wherein the pH value of the solution is measured to be 13, the introducing rate is 0.4g of liquid/(g of catalyst.min), and the treatment time is 4h. The weight loss of the treated catalyst was 0.4% at 200-600 c as measured by thermogravimetry. Roasting at 550 ℃ for 6 hours under normal pressure and air atmosphere to remove residual template agent, wherein the sample number of the catalyst is TS-1-J. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 6
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-K using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetrabutyl titanate (calculated as titanium dioxide) and an aqueous ammonia solution (calculated as water) with a pH value of 13 are mixed according to a mole ratio of 1:0.09:9, mixing and treating at 60 ℃ for 5 hours to obtain the titanium silicate gel, and then mixing TS-1-A, the titanium silicate gel, an auxiliary agent and ammonium bisulfate according to the weight ratio of 100:18:6:1.8 mixing to form a rolling ball, wherein the auxiliary agent is sesbania powder and glycerin according to the weight ratio of 1: 2.5.
And secondly, introducing water into the formed catalyst under the conditions of 220 ℃ and N2 back pressure of 0.7MPa, generating a water vapor atmosphere, and treating for 2.5 hours, wherein the rate of introducing water is 0.25g of liquid/(g of catalyst.min).
And thirdly, continuously introducing ammonia water with the mass fraction of 25% under the conditions of 600 ℃ and N2 back pressure of 0.7Mpa, wherein the pH value of the solution is 14, the introducing rate is 2g of liquid/(g of catalyst.min), and the treatment time is 3h.
The weight loss of the treated catalyst was 0.3% at 200-600 c as measured by thermogravimetry. Roasting at 550 ℃ for 6 hours under normal pressure and air atmosphere to remove residual template agent, wherein the sample number of the catalyst is TS-1-K. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 7
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-L using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetraisopropyl titanate (calculated as titanium dioxide) and an aqueous ammonia solution (calculated as water) with a pH value of 14 are mixed according to a mole ratio of 1:0.1:4, mixing and treating for 4 hours at 70 ℃ to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium acetate according to the weight ratio of 100:5:1:0.5, mixing and kneading, and then extruding to form strips, wherein the auxiliary agent is sesbania powder and pentaerythritol according to the weight ratio of 1: 3.
And secondly, introducing water into the formed catalyst under the conditions of 200 ℃ and N2 back pressure of 0.2MPa, generating a water vapor atmosphere, and treating for 1.5 hours, wherein the rate of introducing water is 0.3g of liquid/(g of catalyst.min).
And thirdly, continuously introducing 15% ammonia water by mass under the conditions of 400 ℃ and N2 back pressure of 0.3Mpa, wherein the pH value of the solution is 14, the introducing rate is 1g of liquid/(g of catalyst.min), and the treatment time is 4h.
The weight loss of the treated catalyst measured by thermogravimetric method was 0.1% at 200-600 ℃. Roasting at 550 ℃ for 6 hours under normal pressure and air atmosphere to remove residual template agent, wherein the sample number of the catalyst is TS-1-L. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 8
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-M using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetrabutyl titanate (calculated as titanium dioxide) and tetrapropylammonium hydroxide aqueous solution with pH value of 14 (calculated as water) are mixed according to a mole ratio of 1:0.25:8, mixing and treating for 4 hours at 80 ℃ to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium carbonate according to the weight ratio of 100:10:4:1.5 mixing and performing rolling ball molding, wherein the auxiliary agent is starch and dihydroxyacetone according to the weight ratio of 1: 1.5.
And secondly, introducing water into the formed catalyst under the condition of 150 ℃ and N2 back pressure of 0.3MPa, generating a water vapor atmosphere for treatment for 1.5 hours, wherein the rate of introducing water is 0.5g of liquid/(g of catalyst.min).
And thirdly, continuously introducing ammonia water with the mass fraction of 5% under the conditions of 450 ℃ and N2 back pressure of 0.3Mpa, wherein the pH value of the solution is 14, the introducing rate is 1.2g of liquid/(g of catalyst.min), and the treatment time is 6h.
The weight loss of the treated catalyst measured by thermogravimetric method was 0.1% at 200-600 ℃. Roasting at 550 ℃ for 6 hours under normal pressure and air atmosphere to remove residual template agent, wherein the sample number of the catalyst is TS-1-M. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 9
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-N using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetraethyl titanate (calculated as titanium dioxide) and tetraethyl ammonium hydroxide aqueous solution with pH value of 14 (calculated as water) are mixed according to a mole ratio of 1:0.15:6, mixing and treating at 80 ℃ for 3 hours to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium phosphate according to the weight ratio of 100:15:3:1 mixing and rolling ball forming, wherein the auxiliary agent is starch and glycerin according to the weight ratio of 1:2.
And secondly, introducing water into the formed catalyst under the conditions of 200 ℃ and N2 back pressure of 0.2MPa, generating a water vapor atmosphere, and treating for 1.5 hours, wherein the rate of introducing water is 0.8g of liquid/(g of catalyst.min).
And thirdly, continuously introducing ammonia water with the mass fraction of 20% under the conditions of 550 ℃ and N2 back pressure of 0.45Mpa, wherein the pH value of the solution is 14, the introducing rate is 0.6g of liquid/(g of catalyst.min), and the treatment time is 4h.
The weight loss of the treated catalyst measured by thermogravimetric method was 0.1% at 200-600 ℃. The catalyst sample number is TS-1-N. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 10
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-O using the process of the present invention.
In the first step, tetraethyl silicate (calculated as silicon dioxide), tetrabutyl titanate (calculated as titanium dioxide) and tetrabutyl ammonium hydroxide aqueous solution with a pH value of 14 (calculated as water) are mixed according to a mole ratio of 1:0.2:5, mixing and treating for 4 hours at 60 ℃ to obtain the silicon-titanium adhesive, and then mixing TS-1-A, the silicon-titanium adhesive, an auxiliary agent and ammonium fluoride according to the weight ratio of 100:8:2:0.7, mixing and rolling ball forming, wherein the auxiliary agent is sesbania powder and glucose according to the weight ratio of 1: 1.5.
And secondly, introducing water into the formed catalyst under the condition of 150 ℃ and N2 back pressure of 0.4MPa, generating a water vapor atmosphere for treatment for 1.5 hours, wherein the rate of introducing water is 0.4g of liquid/(g of catalyst.min).
And thirdly, continuously introducing ammonia water with the mass fraction of 10% under the conditions of 500 ℃ and N2 back pressure of 0.5Mpa, wherein the pH value of the solution is 14, the introducing rate is 1.4g of liquid/(g of catalyst.min), and the treatment time is 5h.
The weight loss of the treated catalyst measured by thermogravimetric method was 0.1% at 200-600 ℃. The catalyst sample number is TS-1-O. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that a plurality of mesoporous structures of 4-20nm exist in the molecular sieve crystal.
Example 11
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-P using the process of the present invention.
Mixing TS-1-N with ammonia water solution with pH value of 11 according to mass fraction of catalyst for 5%, treating at 60deg.C for 60min, separating catalyst, further mixing with nitric acid solution with pH value of 2 and containing 2% hydrogen peroxide according to mass fraction of molecular sieve for 3%, treating at 80deg.C for 60min, and separating catalyst. Sample number is TS-1-P.
TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that numerous mesoporous structures of 4-20nm still exist in the crystal of the molecular sieve.
Example 12
This example illustrates the preparation of a shaped titanium-containing catalyst TS-1-Q using the process of the present invention.
Mixing TS-1-O with ammonia water solution with pH value of 10 according to mass fraction of catalyst, treating at 80deg.C for 60min, separating catalyst, further mixing with hydrochloric acid solution with pH value of 3 and containing 1% hydrogen peroxide according to mass fraction of molecular sieve for 5%, treating at 60deg.C for 60min, and separating catalyst. Sample number is TS-1-Q. TEM results of the crushed titanium-silicon molecular sieve of the titanium-containing catalyst show that numerous mesoporous structures of 4-20nm still exist in the crystal of the molecular sieve.
Evaluation comparative example 1, evaluation examples 1 to 12
The catalyst was used for propylene epoxidation to propylene oxide according to the following procedure.
Filling a catalyst into a fixed bed reactor, and then mixing hydrogen peroxide, propylene and methanol according to a molar ratio of 1:2:7, introducing a catalyst bed, controlling the reaction temperature to 40 ℃, controlling the reaction pressure to 2MPa, controlling the weight hourly space velocity of the reaction materials to 2h < -1 >, and sampling and analyzing after the reaction is stably carried out for 2h. The results are shown in Table 1.
TABLE 1
As can be seen from examples 1-12, comparative example 1 and comparative example 1, the titanium-containing catalyst provided by the invention has the advantages of simple process, easy implementation, good effect, effective utilization of the intramolecular template agent in the molecular sieve crystal and production of small-size mesoporous structure.
As can be seen from evaluation examples 1-12, evaluation comparative example 1 and evaluation comparative example 1, the titanium-containing catalyst provided by the invention has the characteristics of high catalytic activity, high raw material conversion rate, high propylene oxide selectivity and high hydrogen peroxide effective utilization rate when being used for preparing propylene oxide by propylene epoxidation.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination of the various embodiments of the present disclosure may be made without departing from the spirit of the present disclosure, which should also be considered as the disclosure of the present invention.
Claims (15)
1. A process for preparing a titanium-containing catalyst, comprising the steps of:
(1) Mixing an amorphous silicon source, a titanium source and an alkaline aqueous solution for heat treatment to prepare a titanium silicate gel, and mixing the titanium silicate gel with a titanium silicon molecular sieve, an auxiliary agent and an ammonium salt for molding to obtain a molded catalyst; the titanium silicalite molecular sieve contains a template agent, wherein the content of the template agent accounts for 1-30% of the weight of the titanium silicalite molecular sieve; the auxiliary agent is one or more selected from sesbania powder, starch, polyalcohol and nanocellulose;
(2) Treating the formed catalyst for 0.5-3h under the conditions of externally applied pressure, externally added water, apparent pressure of 0.01-1.0 MPa and temperature of 100-300 ℃; the water is preheated and vaporized, and the generated gas is contacted with the formed catalyst;
(3) And (3) adding a liquid with the pH value more than 9 into the molded catalyst obtained by the treatment in the step (2) at the apparent pressure of 0.01-1.0 MPa and the temperature of 300-600 ℃ for at least 0.5h to obtain the titanium-containing catalyst.
2. The method of claim 1, wherein the shaping of step (1) comprises ball shaping, kneading followed by extrusion.
3. The method of claim 1, wherein the amorphous silicon source of step (1) comprises a silica sol or an organosilicon ester; the titanium source comprises organic titanium ester, titanium tetrachloride, titanium trichloride and titanium sulfate; the alkaline aqueous solution is an aqueous solution containing organic alkali or inorganic alkali and having a pH value of 10-14; the ammonium salt is organic ammonium salt or inorganic ammonium salt, and the heat treatment comprises the treatment for 0.5-5h at 50-100 ℃.
4. The method of claim 1, wherein in the titanium silicalite of step (1), the molar ratio of the amorphous silicon source, the titanium source and the water is 1: (0.05-0.30): (3-10) wherein the amorphous silicon source is calculated as silicon dioxide and the titanium source is calculated as titanium dioxide; the weight ratio of the titanium-silicon molecular sieve to the silicon-titanium gel to the auxiliary agent to the ammonium salt is 100: (3-20): (1-6): (0.1-2).
5. The method of claim 1, wherein the apparent pressure in step (2) is 0.1-0.6MPa and the apparent pressure in step (3) is 0.2-0.7MPa.
6. The process of claim 1 wherein the titanium silicalite of step (1) has an MFI structure.
7. The method according to claim 1, wherein the liquid with the pH value of more than 9 in the step (3) is aqueous ammonia or aqueous solution of organic amine, and the mass fraction of the alkaline substance in the liquid is 1-28%.
8. The process of claim 1 wherein step (3) comprises pre-heating said liquid having a pH > 9 to vaporize and contacting the resulting gas with a shaped catalyst.
9. The process according to claim 1, wherein in the steps (2) and (3), the water or the liquid having a pH of > 9 is used in an amount of (0.1-2) g/(g shaped catalyst. Min), respectively.
10. The method of claim 1, further comprising calcining the shaped catalyst in an oxygen-containing atmosphere.
11. The method of claim 10, further comprising subjecting the titanium-containing catalyst to alkali wash and acid wash.
12. The method according to claim 11, wherein the titanium-containing catalyst is subjected to alkali washing with an aqueous ammonia solution and is subjected to acid washing with an acid solution containing hydrogen peroxide.
13. A titanium-containing catalyst, characterized in that it is prepared by the process according to any one of claims 1 to 12.
14. A process for the preparation of an epoxide by epoxidation of an olefin, characterized in that an olefin, hydrogen peroxide and a solvent are contacted under epoxidation reaction conditions in the presence of the titanium-containing catalyst of claim 13 to obtain a product comprising an epoxide.
15. The process of claim 14 wherein said olefin is propylene.
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| JPH11165074A (en) * | 1997-12-01 | 1999-06-22 | Mitsubishi Gas Chem Co Inc | Production of titanosilicate-carrying catalyst and production of organic compound using the same by hydrogen peroxide |
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| CN110655091A (en) * | 2019-10-18 | 2020-01-07 | 延长中科（大连）能源科技股份有限公司 | Preparation method of mordenite molecular sieve |
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| JPH11165074A (en) * | 1997-12-01 | 1999-06-22 | Mitsubishi Gas Chem Co Inc | Production of titanosilicate-carrying catalyst and production of organic compound using the same by hydrogen peroxide |
| CN105854742A (en) * | 2016-04-07 | 2016-08-17 | 中国天辰工程有限公司 | High-performance titanium-silicon molecular sieve catalyst and extrusion molding method thereof |
| CN109721066A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method |
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