CN114455601A - Preparation method and application of molecular sieve - Google Patents

Preparation method and application of molecular sieve Download PDF

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CN114455601A
CN114455601A CN202210178501.3A CN202210178501A CN114455601A CN 114455601 A CN114455601 A CN 114455601A CN 202210178501 A CN202210178501 A CN 202210178501A CN 114455601 A CN114455601 A CN 114455601A
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molecular sieve
acid
drying
preparation
temperature
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CN114455601B (en
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王根林
王刚
郭昊天
丁克鸿
徐林
汪洋
许越
戴业涔
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Jiangsu Yangnong Chemical Group Co Ltd
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Abstract

The invention provides a preparation method and application of a molecular sieve. The preparation method of the molecular sieve comprises the following steps: step S1, mixing raw materials including an organic silicon compound, water and a quaternary ammonium template agent, and carrying out hydrolysis reaction, distillation and crystallization reaction to obtain a molecular sieve precursor; step S2, adjusting the pH of the molecular sieve precursor to 7.0-10.0 by using organic acid, and then performing solid-liquid separation to obtain wet solid and separation liquid; step S3, pre-drying and molding the wet solid to obtain a molded product; step S4, calcining the molded product to obtain the molecular sieve. According to the preparation method, the organic acid is added, the uncrystallized organic silicon is separated out to be used as the binder, and the organic acid can also be used as the extrusion aid, so that the forming strength of the molecular sieve is improved, and the forming process is simplified. The molecular sieve prepared by the preparation method can be used as an efficient catalyst for synthesizing caprolactam by cyclohexanone-oxime gas phase rearrangement, and the catalyst has the advantages of good catalytic activity and high selectivity.

Description

Preparation method and application of molecular sieve
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a preparation method and application of a molecular sieve.
Background
Caprolactam is an important intermediate in the industrial production process of nylon, and Beckmann rearrangement of cyclohexanone oxime is one of the key steps in the production process of caprolactam. At present, the traditional liquid phase rearrangement process using concentrated sulfuric acid as a catalyst is mainly adopted in industry. Although the reaction conditions of the process are mild, and the conversion rate and the selectivity are ideal, a large amount of ammonium sulfate is produced as a byproduct, and equipment corrosion and environmental pollution are easily caused. In order to overcome the defects, attention is paid to a gas-phase Beckmann rearrangement process for catalyzing cyclohexanone oxime by using a solid acid such as a molecular sieve in recent years. However, the reaction temperature required by the gas-phase Beckmann rearrangement process is high, the catalyst stability is poor, the deactivation is rapid, and the selectivity of the catalyst is low.
USP4061724, JP59164617, CN1338427 and the like all report the synthesis method of MFI type silicon molecular sieve, which can be used for the synthesis of caprolactam. However, all the above molecular sieve catalysts have the disadvantages of low catalyst activity, low selectivity and poor stability during the gas phase rearrangement of cyclohexanone oxime, and are difficult to be applied industrially. In order to solve the problems, the composition and the number of acid sites are adjusted by alkali modification, and the shape structure of the MFI-type silicon molecular sieve is optimized to improve the performance of catalyzing cyclohexanone oxime gas-phase Beckmann rearrangement. Although CN1164576 and CN104307556 both modify MFI molecular sieve by means of aliphatic amine and quaternary ammonium base, so that cyclohexanone oxime conversion rate is greater than 99%, and caprolactam selectivity is greater than 95%, they are difficult to form, and even if the catalyst strength after forming is low, the catalyst strength still cannot meet the requirement of industrialization.
Disclosure of Invention
The invention mainly aims to provide a preparation method and application of a molecular sieve, and aims to solve the problems of low forming strength and complex forming process of the molecular sieve in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a molecular sieve, the method comprising: step S1, mixing raw materials including an organic silicon compound, water and a quaternary ammonium template agent, and carrying out hydrolysis reaction, distillation and crystallization reaction to obtain a molecular sieve precursor; step S2, adjusting the pH of the molecular sieve precursor to 7.0-10.0 by using organic acid, and then performing solid-liquid separation to obtain wet solid and separation liquid; step S3, pre-drying and molding the wet solid to obtain a molded product; step S4, calcining the molded product to obtain the molecular sieve.
Further, the organic acid is selected from RCOOH, R (COOH)2、R(COOH)3R is selected from C1～C6Fatty chains or C6～C200The aromatic group, preferably the organic acid, is selected from one or more of formic acid, acetic acid, propionic acid, oxalic acid, 1, 3-malonic acid, benzoic acid, terephthalic acid, phthalic acid, isophthalic acid and trimesic acid.
Further, before crystallization, the mass ratio of the organic silicon compound, water and the quaternary ammonium template agent is controlled to be 1: 10-150: 0.05 to 5.0; preferably, the raw materials also comprise an aluminum source and alkali, the aluminum source is preferably selected from one or more of metaaluminate, aluminate, alumina and aluminum sol, and the aluminum source is further preferably selected from one or more of metaaluminate and potassium metaaluminate; preferably, the alkali is one or more of inorganic alkali and nitrogen-containing organic alkali, more preferably, the alkali is one or more of sodium hydroxide, potassium hydroxide, ammonia water, piperidine, hexamethyleneimine, triethylamine, tetraethylammonium hydroxide and tetrapropylammonium hydroxide, and before crystallization, the mol ratio of the organosilicon compound, the aluminum source, water, the alkali and the quaternary ammonium template agent is controlled to be 1: 0-0.1: 10-150: 0-5.0: 0.05 to 5.0.
Further, the organic silicon compound is selected from silicate ester, preferably the organic silicon compound is selected from one or more of ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate; and/or preferably quaternary ammonium templating agent selected from R1R2R3R4NH4 +B-，R1、R2、R3、R4Each independently represents C1～C4Any one of the aliphatic chains of (1), B-Represents OH-、F-、Br-、Cl-Or I-Further preferably, the quaternary ammonium template is selected from one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium chloride and tetrapropylammonium chloride, and/or the molecular sieve is one or more of an MFI-type zeolite molecular sieve, a Y-type zeolite molecular sieve, a beta-type zeolite molecular sieve, a mordenite molecular sieve or an MWW-type zeolite molecular sieve.
Further, the temperature of the hydrolysis reaction is 20-40 ℃, the time of the hydrolysis reaction is preferably 2-4 h, the temperature of the distillation is preferably 70-100 ℃, the time of the distillation is preferably 1-6 h, the temperature of the crystallization reaction is preferably 150-200 ℃, and the time of the crystallization reaction is preferably 48-72 h.
Furthermore, the pre-drying temperature is 30-100 ℃, the pre-drying temperature is preferably 40-80 ℃, and the pre-drying time is preferably 4-120 h.
Further, the molding is performed by one or more selected from extrusion, tabletting and compression.
Further, before the calcination, the step S4 further includes a drying process of the molded product, wherein the drying temperature is 60 to 140 ℃, and the drying time is 2 to 180 hours.
Further, the calcining temperature is 400-600 ℃, and the calcining time is 1-72 hours.
In order to achieve the above object, according to one aspect of the present invention, there is provided a catalyst for catalyzing cyclohexanone oxime to produce caprolactam, the catalyst comprising the molecular sieve produced by the above production method.
By applying the technical scheme, the preparation method disclosed by the invention has the advantages that the organic acid is added in the process of molding the molecular sieve, so that the uncrystallized organic silicon is separated out to be used as a binder, and the organic acid can also be used as an extrusion aid, so that the forming strength of the molecular sieve is obviously improved, the stability of the molecular sieve in industrial application is ensured, and the loss along with the product in the catalytic reaction and the possible equipment blockage caused by the fact that the molecular sieve is pulverized due to insufficient strength are avoided; meanwhile, the pH is controlled to be 7.0-10.0, the polymerization degree and the charge of the silica sol are adjusted, the forming strength is improved, and the acidity of the catalyst is adjusted and controlled. The preparation method simplifies the forming process, improves the utilization rate of materials, has low production cost and is easy for industrialization. The molecular sieve prepared by the preparation method can be used as an efficient catalyst for synthesizing caprolactam by cyclohexanone-oxime gas phase rearrangement, and the catalyst has the advantages of good catalytic activity and high selectivity.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art, the molecular sieve in the prior art has the problems of low forming strength and complex forming process. In order to solve the problem, the application provides a preparation method and application of a molecular sieve.
In one exemplary embodiment of the present application, there is provided a method of preparing a molecular sieve, the method comprising: step S1, mixing raw materials including an organic silicon compound, water and a quaternary ammonium template agent, and carrying out hydrolysis reaction, distillation and crystallization reaction to obtain a molecular sieve precursor; step S2, adjusting the pH of the molecular sieve precursor to 7.0-10.0 by using organic acid, and then performing solid-liquid separation to obtain wet solid and separation liquid; step S3, pre-drying and molding the wet solid to obtain a molded product; step S4, calcining the molded product to obtain the molecular sieve.
According to the preparation method, the organic acid is added in the process of molding the molecular sieve, so that the uncrystallized organic silicon is separated out to be used as a binder, and the organic acid can also be used as an extrusion aid, so that the molding strength of the molecular sieve is obviously improved, the stability of the molecular sieve in industrial application is ensured, and the loss along with a product in a catalytic reaction and possible equipment blockage caused by the fact that the molecular sieve is pulverized due to insufficient strength are avoided; meanwhile, the pH is controlled to be 7.0-10.0, the polymerization degree and the charge of the silica sol are adjusted, the forming strength is improved, and the acidity of the catalyst is adjusted and controlled. The preparation method simplifies the forming process, improves the utilization rate of materials, has low production cost and is easy for industrialization. The molecular sieve prepared by the preparation method can be used as an efficient catalyst for synthesizing caprolactam by cyclohexanone-oxime gas phase rearrangement, and the catalyst has the advantages of good catalytic activity and high selectivity.
The organic acid is selected to adjust the pH value of the molecular sieve precursor, and the main reasons are that the anions of sulfuric acid and hydrochloric acid in the inorganic acid are difficult to remove, the oxidizing property of the nitrate anions is strong, the pyrolysis process can react with organic components, and the catalyst is locally overheated, so that the strength of the catalyst is low. The organic acid can be used for adjusting the pH value mildly, does not cause the introduced acid to cause excessive damage to the formed crystals, and does not introduce other anions which are difficult to remove. To further facilitate the dispersion of the organic acid in the molecular sieve precursor, optimizing its efficiency of pH adjustment, in some embodiments, the organic acid is selected from RCOOH, R (COOH)2、R(COOH)3R is selected from C1～C6Fatty chains or C6～C200An aromatic group, preferably an organic acid selected from formic acid, acetic acid, propionic acid, oxalic acid, 1, 3-malonic acid, benzoic acid,One or more of terephthalic acid, phthalic acid, isophthalic acid and trimesic acid. The organic acids are small molecular acids, so that the organic acids are easier to disperse in the molecular sieve precursor, and the pH value adjusting efficiency is improved.
The process of step S1 of the present application may be performed by conventional hydrolysis and crystallization processes in the prior art when forming molecular sieves. As in the prior art, the hydrolysis reaction produces alcohol, which is removed by distillation. In some embodiments, the molar ratio of organosilicon compound, water, and quaternary ammonium templating agent is controlled to be 1: 10-150: 0.05 to 5.0. During the alcohol removal by distillation, water was added to the system to achieve the above ratio.
When the molecular sieve is a silicon-aluminum molecular sieve, the raw materials also comprise an aluminum source and a base, in some embodiments, the aluminum source is preferably selected from one or more of metaaluminate, aluminate, alumina and aluminum sol, and the aluminum source is further preferably selected from one or more of sodium metaaluminate and potassium metaaluminate; the alkali is preferably one or more of inorganic alkali and nitrogen-containing organic alkali, and more preferably one or more of sodium hydroxide, potassium hydroxide, ammonia water, piperidine, hexamethyleneimine, triethylamine, tetraethylammonium hydroxide and tetrapropylammonium hydroxide. Before crystallization, controlling the molar ratio of an organic silicon compound, an aluminum source, water, alkali and a quaternary ammonium template agent to be 1: 0-0.1: 10-150: 0-5.0: 0.05 to 5.0. During the alcohol removal by distillation, water was added to the system to achieve the above ratio.
In some embodiments, the organosilicon compound is selected from an orthosilicate, preferably the organosilicon compound is selected from one or more of ethyl orthosilicate, propyl orthosilicate, or butyl orthosilicate; preferably the quaternary ammonium templating agent is selected from R1R2R3R4NH4 +B-，R1、R2、R3、R4Each independently represents C1～C4Any one of the aliphatic chains of (1), B-Represents OH-、F-、Br-、Cl-Or I-Further preferably, the quaternary ammonium template is selected from tetraethylammonium hydroxideOne or more of tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium chloride and tetrapropylammonium chloride. And adjusting the pore structure of the formed molecular sieve by using the added quaternary ammonium template. Correspondingly, the preferred molecular sieve is one or more of MFI type zeolite molecular sieve, Y type zeolite molecular sieve, beta type zeolite molecular sieve, mordenite molecular sieve or MWW zeolite molecular sieve.
The above step S1 can refer to the conditions of hydrolysis and crystallization in the prior art. In some embodiments, the temperature of the hydrolysis reaction is preferably 20-40 ℃, and the time of the hydrolysis reaction is preferably 2-4 h; preferably, the distillation temperature is 70-100 ℃, and the distillation time is 1-6 h; preferably, the temperature of the crystallization reaction is 150-200 ℃, and the time of the crystallization reaction is 48-72 hours, so as to improve the crystallinity.
The purpose of the pre-drying is mainly to facilitate the subsequent molding, so that the pre-drying conditions are not too severe, and reference can be made to the pre-drying conditions in the prior art. In some embodiments, the pre-drying temperature is 30-100 ℃, preferably the pre-drying temperature is 40-80 ℃, and preferably the pre-drying time is 4-120 h. Under the pre-drying condition, the volatilization of water can be accelerated, and the loss of the added organic acid is avoided.
The manner of molding is not particularly limited, and in some embodiments, the manner of molding is selected from one or more of extrusion, tableting, and compression. Forming corresponding rod-shaped molded products, sheet-shaped molded products, spherical molded products, and the like.
In some embodiments, before the calcining, the step S4 further includes drying the molded article at a temperature of 60 to 140 ℃ for 2 to 180 hours. The drying pretreatment before calcination avoids the problem that the mechanical strength is reduced due to the fact that moisture is quickly volatilized caused by direct high-temperature calcination so that cracks are generated on the surface of a molded product.
The calcination is to remove the template from the molecular sieve. In some embodiments, the temperature of the calcination is controlled to be 400 to 600 ℃, and the calcination time is 1 to 72 hours. So as to ensure the thoroughness of the removal of the template agent and the complete removal of the organic acid by pyrolysis and oxidation during the calcination.
In another exemplary embodiment of the present application, a catalyst for catalyzing cyclohexanone oxime to produce caprolactam is provided, wherein the catalyst comprises the molecular sieve produced by the above-mentioned production method.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
In the following examples, the end of catalyst life is considered when a 3% decrease in one of the cyclohexanone oxime conversion and caprolactam selectivity relative to the corresponding value of the reaction plateau is considered as catalyst deactivation.
Example 1
Mixing 416g of ethyl orthosilicate, 200g of 40 wt% tetrapropyl ammonium hydroxide aqueous solution and 160g of ultrapure water, hydrolyzing for 3h at room temperature, then distilling to remove alcohol, controlling the distillation temperature to be 70-90 ℃, controlling the distillation time to be 3h, continuously supplementing 80g of water in the alcohol removal process, wherein the alcohol removal rate is over 70%, then transferring the colloid into a high-pressure kettle, heating to 170 ℃, and crystallizing for 72h to obtain a molecular sieve precursor; after crystallization reaction, dripping 39.2g of acetic acid into the molecular sieve precursor under the condition of mechanical stirring, adjusting the pH value to 8.43, and filtering; pre-drying the filtered wet filter cake, wherein the pre-drying temperature is 60 ℃, the pre-drying time is 6 hours, and the weight loss rate is 4.3%; kneading and extruding the materials to form
Figure BDA0003519728540000052
Is cylindrical and is dried for 24 hours at the temperature of 120 ℃; calcining the dried extruded product at 500 ℃ for 8h to obtain the finished product of the catalyst Silicalite-1, and testing the mechanical strength of the product to be 97N/cm by a tensile tester.
Preparing 20 wt% cyclohexanone-oxime ethanol solution, using nitrogen as carrier gas, and its space velocity is 0.8h-1The cyclohexanone oxime/ethanol solution is mixed with ammonia and subjected to rearrangement reaction on a 360 ℃ bed layer under the action of the finished product catalyst Silicalite-1 to generate caprolactam, the conversion rate of the cyclohexanone oxime is 99.0 percent, the selectivity of the caprolactam is 95.2 percent and the service life of the catalyst is 640 hours through quantitative determination of GC internal standard.
Examples 2 to 4
Spherical molecular sieves (average pore diameter of 27.5nm and pore volume of 0.9 cm) are respectively obtained by changing the mould on the basis of example 13Per g, specific surface area 375m2G, sphere diameter 0.2mm), cylindrical molecular sieve (average pore diameter 49.7nm, pore volume 4.8cm3Per g, specific surface area 402m2A diameter of 1.6mm and a length of 1.5mm in terms of a/g ratio, and a circular ring type (average pore diameter of 36.3nm, pore volume of 2.4 cm)3(ii)/g, specific surface area 251m2(g), inner diameter 1.1mm, outer diameter 2.3mm, length 2.0mm), the mechanical strength is shown in Table 1:
TABLE 1
Figure BDA0003519728540000051
Examples 5 to 14
The mechanical strength of the catalysts prepared in examples 5 to 14, in which the kind of acid, pH, and loss on drying ratio were changed on the basis of example 1, are shown in table 2.
Example 15
Mixing 416g of ethyl orthosilicate, 16.4g of sodium metaaluminate, 26.6g of tetrapropylammonium bromide, 400g of sodium hydroxide and 360g of ultrapure water, hydrolyzing at room temperature for 2h, then distilling at 100 ℃ for 6h, heating to 80 ℃ for removing alcohol for 3h at constant temperature, wherein the alcohol removal rate is over 70%, then transferring the colloid into a high-pressure kettle, heating to 150 ℃ and crystallizing for 48h to obtain a molecular sieve precursor; after crystallization reaction, 308.7g of acetic acid is dripped into the molecular sieve precursor under the condition of mechanical stirring, the pH is adjusted to 9.5, and filtration is carried out; pre-drying the filtered wet filter cake at 30 ℃ for 120h, wherein the weight loss rate is 8.0%; kneading and extruding the materials to form
Figure BDA0003519728540000062
Then drying for 180 hours at 60 ℃; and calcining the dried extruded product at 500 ℃ for 8h to obtain the finished catalyst.
Example 16
Taking 83.5g of ethyl orthosilicateMixing ester, 1000g of 40 wt% tetrapropyl ammonium hydroxide aqueous solution and 480g of ultrapure water, hydrolyzing for 4h at room temperature, distilling at 70 ℃ for 1h, heating to 80 ℃ for removing alcohol for 3h at constant temperature until the alcohol removal rate reaches more than 70%, transferring the colloid into a high-pressure kettle, heating to 200 ℃ and crystallizing for 72h to obtain a molecular sieve precursor; after crystallization reaction, 297.6g of acetic acid is dripped into the molecular sieve precursor under the condition of mechanical stirring, the pH is adjusted to 9.6, and filtration is carried out; pre-drying the filtered wet filter cake, wherein the pre-drying temperature is 100 ℃, the pre-drying time is 4 hours, and the weight loss rate is 18.4%; kneading and extruding the materials to form
Figure BDA0003519728540000061
Then drying for 2 hours at 140 ℃; and calcining the dried extruded product at 500 ℃ for 8h to obtain the finished catalyst.
Example 17
In contrast to example 5, the temperature of the predrying was 120 ℃.
Example 18
In contrast to example 5, the pH was adjusted to 7 with formic acid, the amount of formic acid used being 93.1 g.
Example 19
In contrast to example 5, the pH was adjusted to 10 with formic acid, the amount of formic acid used being 17.8 g.
Comparative example 1
Taking 650g of tetraethoxysilane, hydrolyzing with 530g of water and 700g of 25 percent tetrapropyl ammonium hydroxide aqueous solution by mass fraction for one hour, heating to 70 ℃, removing alcohol at constant temperature for 2 hours, transferring the colloid into a high-pressure kettle, heating to 170 ℃, crystallizing for 60 hours, filtering, washing, drying, and roasting at 550 ℃ for 5 hours to obtain the all-silicon ZSM-5 zeolite molecular sieve. 50g of 25 mass percent tetrapropylammonium hydroxide aqueous solution, 30g of diethylamine and 30g of dimethyldiethoxysilane are dissolved in 500g of water to obtain mixed aqueous solution, 150g of the synthesized all-silicon ZSM-5 zeolite molecular sieve is placed in the mixed aqueous solution, modified at 190 ℃ for 48h, filtered, washed and dried. Mixing the modified zeolite molecular sieve with 100g of silica gel, adding 150mL of 1N nitric acid, kneading, extruding into a phi 1.6 multiplied by 2mm shape, drying at 120 ℃, and roasting the extruded product at 550 ℃ for 5 hours to obtain the finished catalyst.
Comparative example 2
75g of 40% (SiO) was added to 100g of deionized water2Weight) of silica sol, stirring, adding 0.38g of boric acid, adding 7g of tetrapropylammonium bromide (TPABr) template agent, finally adding 6g of ammonium fluoride, stirring for 1 hour, placing into a 500mL crystallization kettle, standing and crystallizing for 24 hours at 180 ℃ under autogenous pressure, cooling, filtering, washing, and drying a filter cake at 120 ℃ to obtain 30.5g of a B-ZSM-5 molecular sieve product. 10g of B-ZSM-5 molecular sieve is taken and 10.8g of 40% (SiO) is added2Weight) silica sol as a binder, kneading uniformly, extruding into strips, granulating, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 3 hours to obtain a catalyst finished product A.
Treating 10g of the molecular sieve with 0.1N hydrochloric acid at 80 deg.C for 2h, at pH of 1.2, filtering, washing, oven drying, and adding 10.8g of 40% (SiO)2Weight) silica sol as a binder, kneading uniformly, extruding and molding, granulating, drying at 120 ℃ for 2 hours, and roasting at 550 ℃ for 3 hours to obtain a catalyst finished product B.
Comparative example 3
In contrast to example 5, the pH was adjusted to 2.5 using formic acid, the amount of formic acid used being 193.0 g.
Comparative example 4
In contrast to example 5, the pH was adjusted to 4.5 using formic acid, the amount of formic acid used being 115.6 g.
The mechanical strength of the catalysts prepared in comparative examples 1 to 4 is shown in table 2.
TABLE 2
Figure BDA0003519728540000071
Figure BDA0003519728540000081
Figure BDA0003519728540000091
The molecular sieve is too low in strength and easy to break and pulverize, and the pressure drop of a bed layer can be increased in the production process, so that the pressure of a system is increased, and the device cannot stably run. The data of the examples show that the strength of the obtained molecular sieve is greater than 85N/cm, is obviously improved compared with that before the regulation of the organic acid, and is suitable for industrial production; in the catalysis process, the raw material has higher conversion rate and selectivity at a high level, and particularly the service life of the catalyst is obviously prolonged, so that the strength change of the molecular sieve is proved to be beneficial to prolonging the service life of the catalyst. Moreover, compared with the process of firstly preparing the molecular sieve and then adding the binder for molding in the prior art, the catalyst has the advantages of short preparation flow, simple steps, high material utilization rate and higher catalyst preparation efficiency; meanwhile, the water-based paint is more stable in the using process, and has longer service life due to less loss. Of course, one skilled in the art can further perform a further acid modification or base modification of the high strength molecular sieves of the present application to further extend the catalyst life.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: according to the preparation method, the composition and the number of the acid sites are adjusted by using the quaternary ammonium template agent, so that the stability of the molecular sieve is improved, and the organic acid is added in the process of molding the molecular sieve, so that the uncrystallized organic silicon is separated out to be used as a binder, and the organic acid is used as an extrusion aid, so that the forming strength of the molecular sieve is obviously improved; meanwhile, the pH is controlled to be 7.0-10.0, the polymerization degree and the charge of the silica sol can be adjusted, the forming strength is improved, and the acidity of the catalyst is adjusted and controlled. The preparation method simplifies the forming process, improves the utilization rate of materials, has low production cost and is easy for industrialization. The molecular sieve prepared by the preparation method can be used as a high-efficiency catalyst for synthesizing caprolactam by cyclohexanone-oxime gas phase rearrangement, and the catalyst has the advantages of good catalytic activity and high selectivity.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for preparing a molecular sieve, the method comprising:
step S1, mixing raw materials including an organic silicon compound, water and a quaternary ammonium template agent, and carrying out hydrolysis reaction, distillation and crystallization reaction to obtain a molecular sieve precursor;
step S2, adjusting the pH of the molecular sieve precursor to 7.0-10.0 by using organic acid, and then carrying out solid-liquid separation to obtain wet solid and separation liquid;
step S3, pre-drying and molding the wet solid to obtain a molded product;
and step S4, calcining the molded product to obtain the molecular sieve.
2. The process according to claim 1, wherein the organic acid is selected from RCOOH, R (COOH)2、R(COOH)3R is selected from C1～C6Fatty chains or C6～C200And (b) an aromatic group, preferably the organic acid is selected from one or more of formic acid, acetic acid, propionic acid, oxalic acid, 1, 3-malonic acid, benzoic acid, terephthalic acid, phthalic acid, isophthalic acid and trimesic acid.
3. The method according to claim 1, wherein before the crystallization, the molar ratio of the organosilicon compound, the water and the quaternary ammonium template is controlled to be 1: 10-150: 0.05 to 5.0;
preferably, the raw materials also comprise an aluminum source and an alkali, the aluminum source is selected from one or more of metaaluminate, aluminate, alumina and aluminum sol, and the aluminum source is further selected from one or more of metaaluminate and potassium metaaluminate; preferably, the alkali is one or more of inorganic alkali and nitrogen-containing organic alkali, further preferably, the alkali is one or more selected from sodium hydroxide, potassium hydroxide, ammonia water, piperidine, hexamethyleneimine, triethylamine, tetraethylammonium hydroxide and tetrapropylammonium hydroxide, and before the crystallization, the molar ratio of the organosilicon compound, the aluminum source, the water, the alkali and the quaternary ammonium template is controlled to be 1: 0-0.1: 10-150: 0-5.0: 0.05 to 5.0.
4. The method according to any one of claims 1 to 3, wherein the organosilicon compound is selected from the group consisting of orthosilicates, preferably one or more of ethyl, propyl or butyl orthosilicate; and/or the quaternary ammonium template is selected from R1R2R3R4NH4 +B-，R1、R2、R3、R4Each independently represents C1～C4Any one of the aliphatic chains of (1), B-Represents OH-、F-、Br-、Cl-Or I-Further preferably, the quaternary ammonium template is selected from one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium chloride and tetrapropylammonium chloride, and/or the molecular sieve is one or more of an MFI-type zeolite molecular sieve, a Y-type zeolite molecular sieve, a beta-type zeolite molecular sieve, a mordenite molecular sieve or an MWW-type zeolite molecular sieve.
5. The preparation method according to claim 1, wherein the temperature of the hydrolysis reaction is 20-40 ℃, the time of the hydrolysis reaction is preferably 2-4 h, the temperature of the distillation is preferably 70-100 ℃, the time of the distillation is preferably 1-6 h, the temperature of the crystallization reaction is preferably 150-200 ℃, and the time of the crystallization reaction is preferably 48-72 h.
6. The preparation method according to claim 1, wherein the temperature of the pre-drying is 30-100 ℃, preferably the temperature of the pre-drying is 40-80 ℃, and preferably the time of the pre-drying is 4-120 h.
7. The method of claim 1, wherein the molding is performed by one or more selected from extrusion, tabletting, and compression.
8. The method according to claim 1, wherein the step S4 further comprises a step of drying the molded article before the calcination, wherein the drying temperature is 60 to 140 ℃, and the drying time is 2 to 180 hours.
9. The preparation method according to claim 1, wherein the calcination temperature is 400 to 600 ℃, and the calcination time is 1 to 72 hours.
10. A catalyst for catalyzing cyclohexanone oxime to prepare caprolactam, wherein the catalyst comprises the molecular sieve prepared by the preparation method of any one of claims 1 to 9.
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