CN110467193B - Titanium-silicon molecular sieve, preparation method and application thereof - Google Patents

Titanium-silicon molecular sieve, preparation method and application thereof Download PDF

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CN110467193B
CN110467193B CN201811301616.7A CN201811301616A CN110467193B CN 110467193 B CN110467193 B CN 110467193B CN 201811301616 A CN201811301616 A CN 201811301616A CN 110467193 B CN110467193 B CN 110467193B
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molecular sieve
preparing
titanium
titanium silicalite
silicalite molecular
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CN110467193A (en
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王利国
周俊雅
李会泉
贺鹏
曹妍
牛鑫
陈家强
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Lianhong New Materials Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C—CHEMISTRY; METALLURGY
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention provides a titanium-silicon molecular sieve, a preparation method and application thereof, wherein the method comprises the following steps: (1) Mixing an aqueous solution of a titanium source, a silicon source and a microporous pore-forming agent with a mesoporous pore-forming agent; obtaining a reaction mixture; (2) Carrying out hydrothermal crystallization on the reaction mixture to obtain a reaction product; and (3) roasting the reaction product to obtain the titanium-silicon molecular sieve. The method reduces the cost of the template agent, is friendly to the environment, effectively solves the problem of diffusion of reactants, and the obtained titanium-silicon molecular sieve has excellent catalytic performance in the reaction of preparing the m-xylylenediamine by the carbonylation of the m-xylylenediamine.

Description

Titanium-silicon molecular sieve, preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, relates to a titanium-silicon molecular sieve, a preparation method and application thereof, and in particular relates to a titanium-silicon molecular sieve with a porous structure, a preparation method thereof and application thereof in preparation of m-xylylene dicarbamate.
Background
Titanium-silicon molecular sieves have been shown to play an important role in many fields such as petrochemical industry, industrial catalysis, etc. Due to the unique MFI topological structure and the catalytic performance brought by the introduction of titanium atoms, the catalyst can realize high-efficiency catalysis of selective oxidation reaction under mild conditions. However, the active center of the traditional titanium-silicon molecular sieve is positioned on the wall of the micropore, and organic molecules with larger sizes cannot diffuse into the micropore.
In order to solve the above problems, researchers have developed a large number of methods for synthesizing porous titanium silicalite molecular sieves, mainly focusing on hydrothermal synthesis, gas phase crystallization, dry gel conversion, etc. As CN105197956B discloses a preparation method of TS-1 titanium silicalite molecular sieve, the method comprises the following steps: 1) Hydrolysis: in terms of mole ratio, according to SiO in the silicon source 2 TiO in titanium source 2 Template agent H 2 Preparing a reaction mixture solution with the ratio of O of 1 (0.01-0.08) to 0.05-0.4) to 10-25, and hydrolyzing the reaction mixture at 20-70 ℃ for 3-5 hours; wherein the template agent is tetrapropylammonium hydroxide; 2) Alcohol expelling: heating the reaction mixture obtained in the step 1) to 70-95 ℃, removing alcohol for 2-6 hours, and adding deionized water in the alcohol removing process to ensure that the concentration change value of the template agent in the reaction mixture solution is within +/-10%; 3) Crystallization: the hydrothermal crystallization temperature is 175-200 ℃, the hydrothermal crystallization time is 2-4 hours, and the crystallization can be carried out under the static condition or the stirring condition; 4) Filtering, washing, drying and roasting the crystallized product obtained in the previous step, filtering, washing, drying and roasting at 500-600 ℃ for 3-6 hours to obtain the TS-1 titanium silicalite molecular sieve, wherein in the step 2), the concentration of tetrapropylammonium hydroxide is 5-10wt%. Among the methods, the formation of templatesThis control is a common problem. Since literature reports successful preparation of porous Beta molecular sieves using poly (diallyl dimethyl ammonium chloride) quaternary ammonium salt as a template, organic surfactants have been widely used as soft templates for the preparation of porous molecular sieves. Compared with the hard template commonly used in early synthesis, the soft template is usually an organic surfactant, has the advantages of strong structure and acid controllability, and mainly comprises alkyl quaternary ammonium salt containing a multi-quaternary ammonium group and an amphiphilic organosilicon surfactant. However, the soft template has the problems of high price and high cost. Therefore, the development of a template agent low-cost or recyclable titanium-silicon molecular sieve preparation process has important significance.
At present, the traditional production process of m-xylylenediamine diisocyanate adopts a m-xylylenediamine phosgenation low-temperature salification method, a small amount of m-chloromethyl benzyl isocyanate is generated in the reaction process, and the method adopts highly toxic phosgene, so that the method has great danger in the use, transportation and storage processes. The existing researchers improve the phosgene method and design a production route for synthesizing isophthalamide diisocyanate by triphosgene, but triphosgene, namely di (trichloromethyl) carbonate, still has certain toxicity and is poor in environmental friendliness. Therefore, finding new green synthetic routes is a necessary trend in the technological development.
The route for preparing the isocyanate intermediate dicarbamate by the carbonylation of organic diamine and preparing the diisocyanate by a pyrolysis method has been reported for a long time, but the reaction conditions are harsh, and the catalyst has the problems of difficult recovery, difficult preparation and the like. With the development of catalyst preparation technology and the advent of new catalysts in recent years, this route has achieved efficient preparation of a variety of diisocyanates. The application of the route in the production of the m-xylylenediamine diisocyanate is mainly divided into two steps, namely the synthesis of an intermediate m-xylylenediamine carbamate and the pyrolysis of the intermediate to prepare the m-xylylenediamine diisocyanate. In the process of preparing the key intermediate m-xylylenediamine carbamate, the development of a high-efficiency catalyst is a key for practical application.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a titanium silicon molecular sieve, a preparation method and application thereof, wherein the method uses amino acid and derivatives thereof which can be recovered by a simple method to partially replace expensive pore-forming agent tetrapropylammonium hydroxide, so that the problem of diffusion of reactants is effectively solved; the prepared titanium-silicon porous molecular sieve has excellent catalytic effect when being applied to the preparation of m-xylylenediamine.
To achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a titanium silicalite molecular sieve, the method comprising the steps of:
(1) Mixing an aqueous solution of a titanium source, a silicon source and a microporous pore-forming agent with a mesoporous pore-forming agent; obtaining a reaction mixture;
(2) Carrying out hydrothermal crystallization on the reaction mixture to obtain a reaction product;
(3) And roasting the reaction product to obtain the titanium-silicon molecular sieve.
The method uses the amino acid and the derivative thereof which can be recovered by a simple method to partially replace the expensive pore-forming agent tetrapropylammonium hydroxide, thereby effectively solving the problem of reactant diffusion. The preparation method has the advantages of low cost and good environment friendliness, and provides a new thought for preparing the titanium-silicon molecular sieve.
The mixing in the step (1) specifically comprises the following steps: firstly, mixing a titanium source and a silicon source to obtain a first mixture; then mixing the first mixture with an aqueous solution of a microporous pore-forming agent to obtain a second mixture; and mixing the second mixture with the mesoporous pore-forming agent. The use of such a mixing sequence can reduce the hydrolysis of titanium and effectively inhibit the formation of anatase.
The mixing of the titanium source and the silicon source comprises the following steps: in an ice water bath environment, a silicon source is added to a titanium source. The hydrolysis of titanium is controlled by low temperature to reduce the formation of anatase.
Preferably, the addition is in the form of a drop.
Preferably, the dropping speed is 0.5 to 1.5mL/min, such as 0.5mL/min, 0.6mL/min, 0.7mL/min, 0.8mL/min, 0.9mL/min, 1.0mL/min, 1.1mL/min, 1.2mL/min, 1.3mL/min, 1.4mL/min, 1.5mL/min, etc., preferably 0.6 to 1.2mL/min, further preferably 1mL/min.
Preferably, the mixing of the titanium source and the silicon source is performed under stirring.
Preferably, the stirring time is 0.2 to 1.2 hours, such as 0.3 hours, 0.4 hours, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1.0 hours, 1.1 hours or 1.2 hours, etc., preferably 0.5 to 1 hour, further preferably 0.8 to 1 hour.
Preferably, the stirring speed is 50 to 350rpm, such as 60rpm, 80rpm, 100rpm, 120rpm, 140rpm, 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, 320rpm or 340rpm, etc., preferably 100 to 300rpm, further preferably 150 to 200rpm.
Preferably, the titanium source is selected from any one or a combination of at least two of titanium tetrachloride, tetraethyl titanate, tetrapropyl titanate or tetrabutyl titanate. Typical but non-limiting combinations are titanium tetrachloride and tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate.
Preferably, the silicon source is selected from any one or a combination of at least two of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate or silica gel. Typical but non-limiting combinations are methyl orthosilicate and ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate and silica gel.
Preferably, the mixing of the first mixture with the aqueous solution of the microporous spacing agent comprises the steps of: an aqueous solution of a microporosity pore former is added to the first mixture in an ice water bath environment.
Preferably, the addition is in the form of a drop.
Preferably, the dropping speed is 0.5 to 1.5mL/min, such as 0.5mL/min, 0.6mL/min, 0.7mL/min, 0.8mL/min, 0.9mL/min, 1.0mL/min, 1.1mL/min, 1.2mL/min, 1.3mL/min, 1.4mL/min, 1.5mL/min, etc., preferably 0.6 to 1.2mL/min, further preferably 1mL/min.
Preferably, the mixing of the first mixture with the aqueous solution of the microporous spacing agent is performed under stirring.
Preferably, the stirring time is 0.2 to 1.2 hours, such as 0.3 hours, 0.4 hours, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1.0 hours, 1.1 hours or 1.2 hours, etc., preferably 0.5 to 1 hour, further preferably 0.8 to 1 hour.
Preferably, the stirring speed is 50 to 350rpm, such as 60rpm, 80rpm, 100rpm, 120rpm, 140rpm, 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, 320rpm or 340rpm, etc., preferably 100 to 300rpm, further preferably 150 to 200rpm.
Preferably, the microporous pore former is selected from tetraalkylammonium hydroxide, preferably any one or a combination of at least two of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide. Typical but non-limiting combinations are for example tetramethylammonium hydroxide and tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
Preferably, the mixing of the second mixture with the mesoporous pore former comprises the following steps: and adding a mesoporous pore-forming agent into the second mixture under stirring.
Preferably, the stirring time is 0.2 to 1.2 hours, such as 0.3 hours, 0.4 hours, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1.0 hours, 1.1 hours or 1.2 hours, etc., preferably 0.5 to 1 hour, further preferably 0.8 to 1 hour.
Preferably, the stirring speed is 50 to 350rpm, such as 60rpm, 80rpm, 100rpm, 120rpm, 140rpm, 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, 320rpm or 340rpm, etc., preferably 100 to 300rpm, further preferably 150 to 200rpm.
Preferably, the mesoporous pore-forming agent is selected from amino acids and/or derivatives of amino acids, preferably any one or a combination of at least two of lysine, lysine hydrochloride, l-carnitine fumarate or l-carnitine tartrate. Typical but non-limiting combinations are lysine and lysine hydrochloride, l-carnitine and l-carnitine fumarate, lysine hydrochloride and l-carnitine tartrate.
Step (1) SiO in the silicon source 2 TiO in titanium source 2 The molar ratio of the microporous pore-forming agent, the mesoporous pore-forming agent and water is 1 (0.001-0.1): 0.001-5): 0.001-1): 5-400, such as 1:0.002:0.005:0.003:10, 1:0.005:0.05:0.04:50,1:0.02:0.1:0.05:100, 1:0.05:1:0.01:200, 1:0.08:2:0.07:300, 1:0.09:4:0.1:350, or 1:0.05:3:0.7:380, etc.
The temperature of the hydrothermal crystallization in the step (2) is 160-210 ℃, such as 170 ℃, 180 ℃, 190 ℃, 200 ℃, and the like, preferably 180-200 ℃.
Preferably, the time of the hydrothermal crystallization is 12-48h, such as 15h, 18h, 20h, 25h, 30h, 35h, 40h or 45h, etc., preferably 16-40 h.
The temperature of the firing in the step (3) is 400 to 800 ℃, such as 420 ℃, 450 ℃, 480 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 750 ℃, etc., preferably 500 to 700 ℃, and more preferably 550 to 650 ℃.
Preferably, the roasting time in step (3) is 4-24 hours, such as 5 hours, 8 hours, 10 hours, 18 hours, 20 hours or 22 hours, etc., preferably 10-20 hours.
Preferably, the reaction product is further subjected to pretreatment before the roasting in the step (3), wherein the pretreatment comprises solid-liquid separation, washing and drying.
As a preferable technical scheme, the preparation method of the titanium silicalite molecular sieve comprises the following steps:
(1) Mixing a titanium source and a silicon source under the conditions of ice-water bath and stirring to obtain a first mixture; maintaining the ice water bath and stirring conditions, and adding an aqueous solution of the microporous pore-forming agent into the first mixture to obtain a second mixture; removing the ice water bath, and adding a mesoporous pore-forming agent into the second mixture to obtain a reaction mixture; wherein SiO in the silicon source 2 TiO in titanium source 2 The molar ratio of the microporous pore-forming agent to the mesoporous pore-forming agent to the water is 1 (0.001-0.1): 0.001-5): 0.001-1): 5-400; the micropore pore-forming agent is selected from tetraalkylammonium hydroxide; the mesoporous pore-forming agent is selected from amino acid and/or derivatives of amino acid;
(2) Carrying out hydrothermal crystallization on the reaction mixture at 160-210 ℃ for 12-48h to obtain a reaction product;
(3) And (3) carrying out solid-liquid separation, washing and drying on the reaction product, and roasting for 4-24 hours at 400-800 ℃ to obtain the titanium-silicon molecular sieve.
The invention also provides the titanium silicalite molecular sieve prepared by the preparation method, and the titanium silicalite molecular sieveThe aperture is 1-2 mu m; specific surface area of 40-600 m 2 /g。
The invention also provides a method for preparing m-xylylenediamine carbamate by the carbonylation of m-xylylenediamine, which uses the titanium-silicon molecular sieve as a catalyst. Namely, the invention also provides the application of the titanium silicalite molecular sieve.
The prepared titanium-silicon porous molecular sieve has excellent catalytic effect when being applied to the preparation of m-xylylenediamine.
The method for preparing m-xylylenediamine by carbonylation of m-xylylenediamine comprises the following steps: in an inert atmosphere, taking carbamate and m-xylylenediamine as raw materials or urea and m-phenylenediamine as raw materials, taking alcohol as a solvent, taking a titanium-silicon molecular sieve as a catalyst, and heating to react to obtain the m-xylylenediamine.
Preferably, the inert atmosphere is selected from nitrogen atmosphere, inert gas atmosphere, and the like.
Preferably, the reaction is carried out in an autoclave.
Preferably, the carbamate is any one or a combination of at least two of methyl carbamate, ethyl carbamate, propyl carbamate and butyl carbamate.
Preferably, the molar ratio of m-xylylenediamine to carbamate is 1 (5-20), such as 1:6, 1:8, 1:10, 1:12, 1:15, or 1:18, etc.
Preferably, the molar ratio of m-phenylenediamine to urea is 1 (5-20), such as 1:6, 1:8, 1:10, 1:12, 1:15, or 1:18, etc.
Preferably, the alcohol is selected from any one or a combination of at least two of methanol, ethanol, propanol or butanol. Typical but non-limiting combinations are methanol and ethanol, methanol and butanol, ethanol, propanol and butanol.
Preferably, the molar ratio of the alcohol to m-xylylenediamine is (8-40): 1, such as 10:1, 12:1, 18:1, 20:1, 25:1, 30:1 or 36:1, etc
Preferably, the mass ratio of the catalyst to m-xylylenediamine is (0.001-1): 1, such as 0.003:1, 0.005:1, 0.008:1, 0.01:1, 0.03:1, 0.04:1, 0.07:1, or 0.09:1, etc.
Preferably, the temperature of the reaction is 180-260 ℃, such as 190 ℃, 200 ℃, 220 ℃, 230 ℃, 250 ℃, etc.
Preferably, the reaction time is 0.5 to 12 hours, such as 1 hour, 2 hours, 3 hours, 5 hours, 8 hours, 10 hours, etc.
As a preferred technical scheme, the method for preparing m-xylylenediamine by carbonylation of m-xylylenediamine comprises the following steps:
in an inert atmosphere, taking carbamate and m-xylylenediamine as raw materials or urea and m-phenylenediamine as raw materials, taking alcohol as a solvent, taking a titanium-silicon molecular sieve as a catalyst, and reacting for 0.5-12h at 180-260 ℃ to obtain m-xylylenediamine; wherein, the mol ratio of the m-xylylenediamine to the carbamate or urea is 1 (5-20); the molar ratio of the alcohol to the m-xylylenediamine is (8-40): 1; the mass ratio of the catalyst to m-xylylenediamine is (0.001-1): 1.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the titanium-silicon molecular sieve, the recoverable organic matters such as the amino acid and the derivative thereof are used as pore-forming agents, so that expensive traditional template agents are partially replaced, the cost of the template agents is reduced, and the problem of diffusion of reactants is effectively solved.
The titanium-silicon molecular sieve provided by the invention has excellent catalytic performance in the reaction of preparing m-xylylenediamine carbamate by the carbonylation of m-xylylenediamine, wherein the conversion rate of the m-xylylenediamine is more than 99%, and the yield of the m-xylylenediamine carbamate is more than 90% under the preferable condition.
The preparation method of the titanium-silicon molecular sieve provided by the invention has the advantages of lower cost and environmental friendliness, and simultaneously provides an application new idea for preparing the m-xylylene carbamate by using the titanium-silicon molecular sieve catalyst.
Drawings
FIG. 1 is an X-ray diffraction pattern of sample 1 prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of sample 1 prepared in example 1 of the present invention.
FIG. 3 is a low power transmission electron micrograph of sample 1 prepared in example 1 of the present invention.
FIG. 4 is a high power projection electron microscope image of sample 1 prepared in example 1 of the present invention.
FIG. 5 is an infrared test chart of sample 1 and L-lysine after washing with water according to example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
Example 1
A preparation method of a titanium-silicon molecular sieve comprises the following steps:
(1) 13.2mL of tetraethyl orthosilicate was slowly added to 0.72g of tetrabutyl titanate under ice-water bath and stirring conditions, stirred for 30 minutes, then 25mL of tetrapropylammonium hydroxide aqueous solution (25 wt%) was added dropwise in a stirred state, and stirred for 12 hours; removing the ice water bath, adding 3.46-g L-lysine into the reaction mixture, and stirring for 3 hours to obtain a clear solution;
(2) Transferring the clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing at 170 ℃ for 48 hours to obtain a reaction product;
(3) And centrifuging, washing, separating, drying the reaction product, roasting the dried sample at 550 ℃ for 6 hours, and naturally cooling to room temperature to obtain the porous titanium silicalite molecular sieve sample 1.
The area ratio of mesopores to micropores in this sample was 21% by BET test.
Fig. 1 is an X-ray diffraction pattern of sample 1 prepared in example 1, showing characteristic peaks of MFI topology at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, and double diffraction peaks of 24.3 ° and 29.4 ° become single diffraction peaks, which is considered as strong evidence of Ti entering the framework. FIG. 2 is a scanning electron microscope image of sample 1, showing the synthesized titanium-siliconThe molecular sieve has uniform size, higher crystallinity and unique appearance. Fig. 3 and fig. 4 are respectively a low power transmission electron microscope image and a high power transmission electron microscope image of sample 1 in example 1, regular lattice fringes can be observed, and certain inter-crystalline pore channels are formed, which are beneficial to the diffusion and adsorption of reactants. FIG. 5 is an infrared test chart of sample 1 and L-lysine after washing with water, and it can be seen that the characteristic peak of L-lysine (1421 cm -1 And 1204cm -1 ) Substantially disappeared, indicating that L-lysine could be recovered by simple water washing.
Example 2
A preparation method of a titanium-silicon molecular sieve comprises the following steps:
(1) 13.2mL of tetraethyl orthosilicate was slowly added to 0.72g of tetrabutyl titanate under ice-water bath and stirring conditions, stirred for 30 minutes, and then 12.5mL of tetrapropylammonium hydroxide aqueous solution (25 wt%) was added dropwise in a stirred state, and stirred for 12 hours; removing the ice water bath, adding 3.81g of L-carnitine into the reaction mixture, and stirring for 3 hours to obtain a clear solution;
(2) Transferring the clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 48 hours at 180 ℃ to obtain a reaction product;
(3) And centrifuging the reaction product, washing with water, separating, drying, roasting the dried sample at 550 ℃ for 6 hours, and naturally cooling to room temperature to obtain the porous titanium silicalite molecular sieve sample 2.
The sample 2 was subjected to an X-ray diffraction test, and the test result showed that characteristic peaks of MFI topology appear at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, and double diffraction peaks of 24.3 ° and 29.4 ° become single diffraction peaks.
And (3) carrying out scanning electron microscope test on the sample 2, wherein the test structure is as follows: the synthesized titanium-silicon molecular sieve has uniform size, higher crystallinity and unique appearance.
And carrying out transmission electron microscope test on the sample 2, wherein the test result is as follows: sample 2 has regular lattice fringes, and forms certain inter-crystalline pore canal, which is beneficial to the diffusion and adsorption of reactants.
Example 3
A preparation method of a titanium-silicon molecular sieve comprises the following steps:
(1) 13.2mL of tetraethyl orthosilicate was slowly added to 0.72g of tetrabutyl titanate under ice-water bath and stirring conditions, stirred for 30 minutes, and then 12.5mL of tetrapropylammonium hydroxide aqueous solution (25 wt%) was added dropwise in a stirred state, and stirred for 12 hours; removing the ice water bath, adding 3.46g of L-carnitine tartrate to the reaction mixture, and stirring for 3 hours to obtain a clear solution;
(2) Transferring the clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 48 hours at 180 ℃ to obtain a reaction product;
(3) And centrifuging the reaction product, washing with water, separating, drying, roasting the dried sample at 550 ℃ for 6 hours, and naturally cooling to room temperature to obtain the porous titanium silicalite molecular sieve sample 3.
The sample 3 was subjected to an X-ray diffraction pattern test, and the test result showed that characteristic peaks of MFI topology appear at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, and double diffraction peaks of 24.3 ° and 29.4 ° become single diffraction peaks.
And (3) carrying out scanning electron microscope test on the sample 3, wherein the test structure is as follows: the synthesized titanium-silicon molecular sieve has uniform size, higher crystallinity and unique appearance.
And carrying out transmission electron microscope test on the sample 3, wherein the test result is as follows: sample 3 has regular lattice fringes, and forms certain inter-crystalline pore canal, which is beneficial to the diffusion and adsorption of reactants.
Example 4
A preparation method of a titanium-silicon molecular sieve comprises the following steps:
(1) Slowly adding propyl orthosilicate into titanium tetrachloride under the conditions of ice-water bath and stirring, stirring for 30 minutes, then dropwise adding tetraethyl ammonium hydroxide aqueous solution under the stirring state, and stirring for 12 hours; removing the ice water bath, adding the L-carnitine fumarate into the reaction mixture, and stirring for 3 hours to obtain a clear solution; siO in silicon source 2 TiO in titanium source 2 The molar ratio of the microporous pore-forming agent to the mesoporous pore-forming agent to the water is SiO 2 :TiO 2 Microporous pore-forming agent: mesoporous pore-forming agent: solvent = 1:0.001:5:0.001:400;
(2) Transferring the clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 12 hours at 210 ℃ to obtain a reaction product;
(3) And centrifuging, washing, separating, drying the reaction product, roasting the dried sample at 400 ℃ for 24 hours, and naturally cooling to room temperature to obtain the porous titanium silicalite molecular sieve sample 4.
The sample 4 was subjected to an X-ray diffraction pattern test, and the test result showed that characteristic peaks of MFI topology appear at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, and double diffraction peaks of 24.3 ° and 29.4 ° become single diffraction peaks.
And carrying out scanning electron microscope test on the sample 4, wherein the test structure is as follows: the synthesized titanium-silicon molecular sieve has uniform size, higher crystallinity and unique appearance.
And carrying out transmission electron microscope test on the sample 4, wherein the test result is as follows: sample 4 has regular lattice fringes and forms certain inter-crystalline pore canal, which is beneficial to the diffusion and adsorption of reactants.
Example 5
A preparation method of a titanium-silicon molecular sieve comprises the following steps:
(1) Slowly adding silica gel into tetrapropyl titanate under the conditions of ice-water bath and stirring, stirring for 30 minutes, then dropwise adding a tetramethyl ammonium hydroxide aqueous solution under the stirring state, and stirring for 12 hours; removing the ice water bath, adding lysine hydrochloride into the reaction mixture, and stirring for 3 hours to obtain a clear solution; siO in silicon source 2 TiO in titanium source 2 The molar ratio of the microporous pore-forming agent to the mesoporous pore-forming agent to the water is SiO 2 :TiO 2 Microporous pore-forming agent: mesoporous pore-forming agent: solvent = 1:0.1:0.001:1:5;
(2) Transferring the clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing at 160 ℃ for 48 hours to obtain a reaction product;
(3) And centrifuging the reaction product, washing with water, separating, drying, roasting the dried sample at 800 ℃ for 4 hours, and naturally cooling to room temperature to obtain the porous titanium silicalite molecular sieve sample 5.
The sample 5 was subjected to an X-ray diffraction pattern test, and the test result showed that characteristic peaks of MFI topology appear at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, and double diffraction peaks of 24.3 ° and 29.4 ° become single diffraction peaks.
And (3) carrying out scanning electron microscope test on the sample 5, wherein the test structure is as follows: the synthesized titanium-silicon molecular sieve has uniform size, higher crystallinity and unique appearance.
And carrying out transmission electron microscope test on the sample 5, wherein the test result is as follows: sample 5 has regular lattice fringes and forms certain inter-crystalline channels, which are beneficial to the diffusion and adsorption of reactants.
Example 6
A preparation method of a titanium-silicon molecular sieve comprises the following steps:
(1) Slowly adding methyl orthosilicate and ethyl orthosilicate (the mol ratio is 2:1) into tetrapropyl titanate and tetramethyl titanate (the mol ratio is 1:1) under the conditions of ice-water bath and stirring, stirring for 30 minutes, then dropwise adding an aqueous solution of tetrabutylammonium hydroxide and tetramethylammonium hydroxide (the mol ratio of tetrabutylammonium hydroxide to tetramethylammonium hydroxide is 1:2) under the stirring state, and stirring for 12 hours; removing the ice water bath, adding L-carnitine tartrate and L-carnitine (molar ratio is 3:2) into the reaction mixture, and stirring for 3 hours to obtain a clear solution; siO in silicon source 2 TiO in titanium source 2 The molar ratio of the microporous pore-forming agent to the mesoporous pore-forming agent to the water is SiO 2 :TiO 2 Microporous pore-forming agent: mesoporous pore-forming agent: solvent = 1:0.05:3:0.5:200;
(2) Transferring the clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 30 hours at 200 ℃ to obtain a reaction product;
(3) And centrifuging the reaction product, washing with water, separating, drying, roasting the dried sample at 600 ℃ for 20 hours, and naturally cooling to room temperature to obtain the porous titanium silicalite molecular sieve sample 6.
The sample 6 was subjected to an X-ray diffraction pattern test, and the test result showed that characteristic peaks of MFI topology appear at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, and double diffraction peaks of 24.3 ° and 29.4 ° become single diffraction peaks.
And (3) carrying out scanning electron microscope test on the sample 6, wherein the test structure is as follows: the synthesized titanium-silicon molecular sieve has uniform size, higher crystallinity and unique appearance.
The transmission electron microscope test is carried out on the sample 6, and the test result is as follows: sample 6 has regular lattice fringes and forms certain inter-crystalline pore canal, which is beneficial to the diffusion and adsorption of reactants.
Application example 1
A process for preparing isophthalate by the carbonylation of m-xylylenediamine comprising:
1.36g of m-xylylenediamine, 4.45g of ethyl carbamate, 7.8g of ethanol and 0.2g of sample 1 are taken and added into a 50mL high-pressure reaction kettle, nitrogen is introduced, leakage detection is carried out, the temperature is raised to 200 ℃ under the protection of normal-pressure nitrogen after ventilation, after reaction for 8 hours, sampling is carried out, and gas chromatography is carried out for analysis.
The result shows that the conversion rate of the m-xylylenediamine is more than 99%, and the yield of the m-xylylenediamine is 97.7%.
Application example 2
A process for preparing isophthalate by the carbonylation of m-xylylenediamine comprising:
urea and m-xylylenediamine are used as raw materials, methanol is used as a solvent, a sample 3 is used as a catalyst, the materials are added into a high-pressure reaction kettle, nitrogen is introduced, leakage detection is carried out, the temperature is raised to 180 ℃ under the protection of normal-pressure nitrogen after ventilation, and after reaction for 12 hours, sampling is carried out and gas chromatography is carried out for analysis; wherein, the molar ratio of the m-xylylenediamine to the urea is 1:5; the molar ratio of methanol to m-xylylenediamine is 40:1; the mass ratio of the catalyst to the m-xylylenediamine is 1:1.
The result shows that the conversion rate of the m-xylylenediamine is more than 99%, and the yield of the m-xylylenediamine is 91.3%.
Application example 3
A process for preparing isophthalate by the carbonylation of m-xylylenediamine comprising:
butyl carbamate and m-xylylenediamine are used as raw materials, butanol is used as a solvent, a sample 5 is used as a catalyst, the materials are added into a high-pressure reaction kettle, nitrogen is introduced, leakage detection is carried out, the temperature is raised to 260 ℃ under the protection of normal-pressure nitrogen after ventilation, after reaction for 0.5h, sampling is carried out, and gas chromatography is carried out for analysis; wherein, the mol ratio of the m-xylylenediamine to the butyl carbamate is 1:20; the molar ratio of butanol to m-xylylenediamine is 8:1; the mass ratio of the catalyst to the m-xylylenediamine was 0.001:1.
The result shows that the conversion rate of the m-xylylenediamine is more than 99%, and the yield of the m-xylylenediamine is 90.1%.
Application example 4
A process for preparing isophthalate by the carbonylation of m-xylylenediamine comprising:
taking propyl carbamate and m-xylylenediamine as raw materials, propanol as a solvent and a sample 2 as a catalyst, adding the materials into a high-pressure reaction kettle, introducing nitrogen, detecting leakage, heating to 230 ℃ under the protection of normal-pressure nitrogen after ventilation, reacting for 10 hours, and sampling and entering gas chromatography for analysis; wherein, the mol ratio of the m-xylylenediamine to the propyl carbamate is 1:10; the molar ratio of propanol to m-xylylenediamine is 20:1; the mass ratio of the catalyst to m-xylylenediamine was 0.5:1.
The result shows that the conversion rate of the m-xylylenediamine is more than 99%, and the yield of the m-xylylenediamine is 95.4%.
Comparative example 1
A preparation method of a titanium silicalite molecular sieve was the same as in example 1 except that the L-lysine in the step (1) was replaced with tetrapropylammonium hydroxide. Sample 7 of the porous titanium silicalite molecular sieve was prepared.
The area ratio of mesopores to micropores in this sample was 13% by BET test.
The sample 7 was subjected to an X-ray diffraction test, and the test result showed that characteristic peaks of MFI topology appear at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, and double diffraction peaks of 24.3 ° and 29.4 ° become single diffraction peaks.
And carrying out scanning electron microscope test on the sample 7, wherein the test structure is as follows: the sample size is uniform, the crystallinity is higher, and the particle size is 200-400nm.
The transmission electron microscope test is carried out on the sample 7, and the test result is as follows: sample 7 had regular lattice fringes, but no significant intergranular channels.
Comparative example 2
A preparation method of a titanium silicalite molecular sieve was the same as in example 1 except that L-lysine in the step (1) was replaced with starch. Sample 8 of the porous titanium silicalite molecular sieve was prepared.
The area ratio of mesopores to micropores in this sample was 35% by BET test.
The sample 8 was subjected to an X-ray diffraction test, and the test result showed that characteristic peaks of MFI topology appear at 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °, and double diffraction peaks of 24.3 ° and 29.4 ° become single diffraction peaks, but crystallinity is slightly reduced.
And (3) carrying out scanning electron microscope test on the sample 8, wherein the test structure is as follows: the sample size is uniform, and the particle size is 350-550nm.
The transmission electron microscope test is carried out on the sample 8, and the test result is as follows: sample 8 has regular lattice fringes and forms certain inter-crystalline channels, which are beneficial to the diffusion and adsorption of reactants.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (58)

1. A method for preparing a titanium silicalite molecular sieve, which is characterized by comprising the following steps:
(1) Mixing an aqueous solution of a titanium source, a silicon source and a microporous pore-forming agent with a mesoporous pore-forming agent; obtaining a reaction mixture;
(2) Carrying out hydrothermal crystallization on the reaction mixture to obtain a reaction product;
(3) Roasting the reaction product to obtain a titanium-silicon molecular sieve; the mixing in step (1)Comprising the following steps: firstly, mixing a titanium source and a silicon source to obtain a first mixture; then mixing the first mixture with an aqueous solution of a microporous pore-forming agent to obtain a second mixture; mixing the second mixture with a mesoporous pore-forming agent; the mixing of the titanium source and the silicon source comprises the following steps: adding a silicon source into a titanium source in an ice water bath environment; the mesoporous pore-forming agent is selected from amino acid and/or derivatives of amino acid; the micropore pore former is selected from tetraalkylammonium hydroxide; the mesoporous pore-forming agent is any one or a combination of at least two of lysine, lysine hydrochloride, L-carnitine fumarate or L-carnitine tartrate; step (1) SiO in the silicon source 2 TiO in titanium source 2 The molar ratio of the microporous pore-forming agent to the mesoporous pore-forming agent to water is 1 (0.001-0.1) (0.001-5) (0.001-1) (5-400), and the titanium-silicon molecular sieve is of an MFI topological structure.
2. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the addition is in the form of dropwise addition.
3. The method for preparing a titanium silicalite molecular sieve according to claim 2, wherein the dropping speed is 0.5-1.5 mL/min.
4. The method for preparing a titanium silicalite molecular sieve according to claim 3, wherein the dropping speed is 0.6-1.2 mL/min.
5. The method for preparing a titanium silicalite molecular sieve according to claim 4, wherein the dropping speed is 1mL/min.
6. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the mixing of the titanium source and the silicon source is performed under stirring.
7. The method for preparing a titanium silicalite molecular sieve according to claim 6, wherein the stirring time is 0.2-1.2 hours.
8. The method for preparing a titanium silicalite molecular sieve according to claim 7, wherein the stirring time is 0.5 to 1h.
9. The method for preparing a titanium silicalite molecular sieve according to claim 8, wherein the stirring time is 0.8-1 h.
10. The method for preparing a titanium silicalite molecular sieve according to claim 6, wherein the stirring speed is 50-350 rpm.
11. The method for preparing a titanium silicalite molecular sieve according to claim 10, wherein the stirring speed is 100-300 rpm.
12. The method for preparing a titanium silicalite molecular sieve according to claim 11, wherein the stirring speed is 150-200 rpm.
13. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the titanium source is selected from any one or a combination of at least two of titanium tetrachloride, tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
14. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the silicon source is selected from any one or a combination of at least two of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, and silica gel.
15. The method of preparing a titanium silicalite molecular sieve according to claim 1, wherein the mixing of the first mixture with the aqueous solution of the microporosity pore former comprises the steps of: an aqueous solution of a microporosity pore former is added to the first mixture in an ice water bath environment.
16. The method for preparing a titanium silicalite molecular sieve according to claim 15, wherein said adding is in the form of dropwise addition.
17. The method for preparing a titanium silicalite molecular sieve according to claim 16, wherein the dropping speed is 0.5-1.5 mL/min.
18. The method for preparing a titanium silicalite molecular sieve according to claim 17, wherein the dropping speed is 0.6-1.2 mL/min.
19. The method for preparing a titanium silicalite molecular sieve according to claim 18, wherein the dropping speed is 1mL/min.
20. The method of claim 1, wherein the mixing of the first mixture with the aqueous solution of the microporous pore former is performed under stirring.
21. The method for preparing a titanium silicalite molecular sieve according to claim 20, wherein the stirring time is 0.2-1.2 hours.
22. The method for preparing a titanium silicalite molecular sieve according to claim 21, wherein the stirring time is 0.5 to 1h.
23. The method for preparing a titanium silicalite molecular sieve according to claim 22, wherein the stirring time is preferably 0.8-1 h.
24. The method for preparing a titanium silicalite molecular sieve according to claim 20, wherein the stirring speed is 50-350 rpm.
25. The method for preparing a titanium silicalite molecular sieve according to claim 24, wherein the stirring speed is 100-300 rpm.
26. The method for preparing a titanium silicalite molecular sieve according to claim 25, wherein the stirring speed is 150-200 rpm.
27. The method for preparing a titanium silicalite according to claim 1, wherein the micropore agent is any one or a combination of at least two of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.
28. The method of preparing a titanium silicalite molecular sieve according to claim 1, wherein the mixing of the second mixture with the mesoporous pore former comprises the steps of: and adding a mesoporous pore-forming agent into the second mixture under stirring.
29. The method for preparing a titanium silicalite molecular sieve according to claim 28, wherein said stirring time is 0.2-1.2 hours.
30. The method for preparing a titanium silicalite molecular sieve according to claim 29, wherein said stirring time is 0.5-1 h.
31. The method for preparing a titanium silicalite molecular sieve according to claim 30, wherein the stirring time is 0.8-1 h.
32. The method for preparing a titanium silicalite molecular sieve according to claim 28, wherein the stirring speed is 50-350 rpm.
33. The method for preparing a titanium silicalite molecular sieve according to claim 32, wherein the stirring speed is 100-300 rpm.
34. The method for preparing a titanium silicalite molecular sieve according to claim 33, wherein said stirring speed is 150-200 rpm.
35. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the hydrothermal crystallization temperature in the step (2) is 160-210 ℃.
36. The method for preparing a titanium silicalite molecular sieve according to claim 35, wherein the hydrothermal crystallization temperature in step (2) is 180-200 ℃.
37. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the hydrothermal crystallization time is 12-48 hours.
38. The method for preparing a titanium silicalite molecular sieve according to claim 37, wherein the hydrothermal crystallization time is 16-40 hours.
39. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the temperature of the calcination in step (3) is 400-800 ℃.
40. The method of preparing a titanium silicalite molecular sieve according to claim 39, wherein said calcination in step (3) is carried out at a temperature of 500-700 ℃.
41. The method of preparing a titanium silicalite according to claim 40, wherein the calcination temperature in step (3) is 550-650 ℃.
42. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the calcination time in step (3) is 4 to 24 hours.
43. The method of preparing a titanium silicalite molecular sieve according to claim 42, wherein said calcination in step (3) is carried out for a period of 10 to 20 hours.
44. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the reaction product is further subjected to pretreatment before the calcination in step (3), wherein the pretreatment comprises solid-liquid separation, washing and drying.
45. The method for preparing a titanium silicalite molecular sieve according to claim 1, wherein the method comprises the steps of:
(1) Mixing a titanium source and a silicon source under the ice water bath environment and stirring condition to obtain a first mixture; maintaining the ice water bath and stirring conditions, and adding an aqueous solution of the microporous pore-forming agent into the first mixture to obtain a second mixture; removing the ice water bath, and adding a mesoporous pore-forming agent into the second mixture to obtain a reaction mixture; wherein SiO in the silicon source 2 TiO in titanium source 2 The molar ratio of the microporous pore-forming agent to the mesoporous pore-forming agent to the water is 1 (0.001-0.1): 0.001-5): 0.001-1): 5-400; the micropore pore-forming agent is selected from tetraalkylammonium hydroxide; the mesoporous pore-forming agent is any one or a combination of at least two of lysine, lysine hydrochloride, L-carnitine fumarate or L-carnitine tartrate;
(2) Carrying out hydrothermal crystallization on the reaction mixture at 160-210 ℃ for 12-48h to obtain a reaction product;
(3) And (3) carrying out solid-liquid separation, washing and drying on the reaction product, and roasting for 4-24 hours at 400-800 ℃ to obtain the titanium-silicon molecular sieve.
46. A titanium silicalite molecular sieve prepared according to the process of any one of claims 1 to 45, characterized by a specific surface area of 400 to 600m 2 /g。
47. A process for preparing m-xylylenediamine by carbonylation of m-xylylenediamine, which comprises using the titanium silicalite of claim 46 as a catalyst.
48. The method of claim 47, wherein the method for producing isophthalcarbamate by the carbonylation of m-xylylenediamine comprises: in an inert atmosphere, taking carbamate and m-xylylenediamine as raw materials or urea and m-phenylenediamine as raw materials, taking alcohol as a solvent, taking a titanium-silicon molecular sieve as a catalyst, and heating to react to obtain the m-xylylenediamine.
49. The method of claim 48, wherein the inert atmosphere is selected from a nitrogen atmosphere or an inert gas atmosphere.
50. The process of claim 48 wherein the reaction is carried out in an autoclave.
51. The method of claim 48, wherein the carbamate is selected from any one or a combination of at least two of methyl carbamate, ethyl carbamate, propyl carbamate, and butyl carbamate.
52. The method of claim 49, wherein the molar ratio of m-xylylenediamine to carbamate is 1 (5-20).
53. The process according to claim 48, wherein the molar ratio of m-phenylenediamine to urea is from 1 (5-20).
54. The method of claim 48, wherein the alcohol is selected from any one or a combination of at least two of methanol, ethanol, propanol, or butanol.
55. The method according to claim 48, wherein the molar ratio of the alcohol to m-xylylenediamine is (8-40): 1.
56. The method according to claim 48, wherein the mass ratio of the catalyst to m-xylylenediamine is (0.001-1): 1.
57. The method of claim 48, wherein the temperature of the reaction is 180-260 ℃.
58. The method of claim 48, wherein the reaction time is 0.5 to 12 hours.
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