CN109574032B - Synthesis method of IM-5 molecular sieve - Google Patents

Synthesis method of IM-5 molecular sieve Download PDF

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CN109574032B
CN109574032B CN201710912671.9A CN201710912671A CN109574032B CN 109574032 B CN109574032 B CN 109574032B CN 201710912671 A CN201710912671 A CN 201710912671A CN 109574032 B CN109574032 B CN 109574032B
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silica gel
solid
solid silica
colloid
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CN109574032A (en
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孙敏
陈俊文
王永睿
贾晓梅
余少兵
慕旭宏
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract

The invention discloses a synthesis method of an IM-5 molecular sieve. The synthesis method comprises the following steps: (1) dissolving inorganic alkali, aluminum source and template agent in water, mixing, preparing and mixingLiquid; (2) under the condition of stirring, the mixed solution is contacted with solid silica gel and mixed to prepare colloid or a solid-liquid mixture; (3) carrying out hydrothermal crystallization on the colloid or the solid-liquid mixture under the crystallization reaction condition; wherein the particle size of the solid silica gel is 40-200 meshes, the bulk density is 360-500g/L, and the specific surface area is 410-520m2The pore volume is 0.88-1.15 mL/g. The synthesis method can effectively inhibit the generation of mixed crystals (such as ZSM-12, mordenite, analcite and alpha-quartz) in the IM-5 molecular sieve by adopting the solid silica gel with specific surface area and pore volume within a specific range as a silicon source, and promotes the IM-5 molecular sieve to have better particle size uniformity.

Description

Synthesis method of IM-5 molecular sieve
Technical Field
The invention relates to a synthesis method of an IM-5 molecular sieve.
Background
The development of petrochemical and fine chemical industries, as well as increasingly stringent requirements for sustainable development and environmental production, have led to an increasing demand for new catalytic materials.
In 1997, Benazzi et al first reported the synthesis of IM-5 molecular sieves. The template agent is 1, 5-bis (N-methylpyrrolidine) pentane bromine salt (MPPBR)2) The silicon source is white carbon black, and the material molar ratio of the synthesis system is 60SiO2：1.7Al2O3：18Na2O：10MPPBr2：3000H2And O. Crystallizing at 170 ℃ for 8-14 days to obtain the pure-phase IM-5 molecular sieve.
From the subsequent research reports, white carbon black is frequently used as a silicon source. But the practical effectiveness of the molecular sieve synthesized by using the white carbon black as the silicon source is limited in industrial application. From literature reports, the molecular sieve is synthesized with high water-silicon ratio (40), so that the single kettle yield is low; the crystallization time is long (10-14d), so that the synthesis efficiency is low; the amount of the template used is large (about 0.15 molar times of silica), and thus the economical efficiency is poor. In addition, ZSM-12, mordenite, analcite and alpha-quartz are easy to be mixed crystals during synthesis, and the crystal grain size of the product is large (usually, the length is more than 300nm, and the width is more than 100nm), which is not favorable for industrial application. Relevant documents are J Catal,2000,189: 382-.
The silicon source is very important for synthesizing the molecular sieve, and the silicon sources with different physicochemical properties have different effects on synthesizing the molecular sieve. All silicon sources capable of synthesizing known silicon-aluminum molecular sieves can be used as silicon sources for synthesizing silicon-aluminum molecular sieves including IM-5, but not all silicon sources can obtain good effect in the synthesis method of the IM-5 molecular sieve, so the silicon sources selected in the synthesis method of the IM-5 molecular sieve have bias. In the above reports, the white carbon black is more preferred, but the white carbon black is used as a silicon source, so that analcime, mordenite and a ZSM-12 mixed crystal phase are easy to appear in the synthesis, and due to the limited practical effectiveness of the white carbon black in the industrial production, researchers try other silicon sources, such as solid silica gel reported in CN 103708491A, wherein the effect of coarse-pore silica gel in the synthesis method is the best, but the application is premised that a template agent precursor is further added in addition to the template agent; moreover, from the SEM image of the product molecular sieve, the morphology regularity of the sample prepared by the method is still to be improved, the grain outline is not clear, and the crystallinity is possibly not high enough. In addition, the influence of a silicon source on the synthesis of the IM-5 molecular sieve is reported in the contemporary chemical industry 2015,44:892-895. in the synthesis method, silica sol is an ideal silicon source, and the IM-5 molecular sieve with larger crystal grains of 300-500nm length and 100-200nm width can be synthesized, but the water-silicon ratio of the synthesis is up to 40. And reports that when silica gel is used as a silicon source, ZSM-12 mixed crystals appear under the synthesis conditions.
The synthesis of IM-5 is difficult to simultaneously meet the matching of a silicon source, a low water-silicon ratio, a low mold-silicon ratio and a shorter crystallization time required by industrial production; in addition, in the prior art, the IM-5 molecular sieve is easy to generate heterocrystal phases such as ZSM-12, mordenite, analcite, alpha-quartz and the like; furthermore, only larger grains IM-5 with a length of >300nm and a width of >100nm are generally prepared. Based on the fact, the IM-5 molecular sieve is synthesized for the first time for nearly 20 years, and no industrial production report is seen yet, so that the wide application of the IM-5 molecular sieve as a catalytic material in industrial production is limited.
Disclosure of Invention
The invention aims to overcome one of the defects in the prior art and provides a synthesis method of an IM-5 molecular sieve, which can inhibit the generation of mixed crystals in the IM-5 molecular sieve and promote the IM-5 molecular sieve to have better particle size uniformity.
In order to achieve the above object, the present invention provides a method for synthesizing an IM-5 molecular sieve, the method comprising: (1) dissolving inorganic alkali, an aluminum source and a template agent in water, and mixing to prepare a mixed solution; (2) under the condition of stirring, contacting the mixed solution with solid silica gel, and mixing to prepare colloid or a solid-liquid mixture; (3) carrying out hydrothermal crystallization on the colloid or the solid-liquid mixture under the crystallization reaction condition; wherein the particle size of the solid silica gel is 40-200 meshes, the bulk density is 360-500g/L, and the specific surface area is 410-520m2The pore volume is 0.88-1.15 mL/g.
By applying the synthesis method of the IM-5 molecular sieve, solid silica gel with specific surface area and pore volume within a specific range is used as a silicon source, so that the generation of mixed crystals (such as ZSM-12, mordenite, analcite, alpha-quartz and the like) in the IM-5 molecular sieve can be effectively inhibited; but also can improve the grain size of the prepared IM-5 molecular sieve and obtain the IM-5 molecular sieve with smaller grain size and better uniformity.
In addition, the IM-5 molecular sieve synthesis method of the invention is favorable for reducing the water-silicon ratio and the mold-silicon ratio in the synthesis process by adopting the solid silica gel with the specific surface area and the pore volume within a specific range as a silicon source, and is favorable for reducing the water content in a crystallization raw material (colloid or solid-liquid mixed liquid) by setting the water-silicon ratio and the mold-silicon ratio within an optimal range, so that the concentration of a template agent is correspondingly improved, the crystallization time is further shortened, the yield of a single kettle is increased, the production efficiency is improved, and the production cost is reduced.
Drawings
FIG. 1 is an X-ray diffraction chart of a raw powder of IM-5 molecular sieve synthesized according to preparation example 1;
FIG. 2 is an SEM image at 500nm of raw IM-5 molecular sieve powder A11 synthesized in example 11 according to the invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a synthesis method of an IM-5 molecular sieve, which comprises the following steps: (1) dissolving inorganic alkali, an aluminum source and a template agent in water, and mixing to prepare a mixed solution; (2) under the condition of stirring, contacting the mixed solution with solid silica gel, and mixing to prepare colloid or a solid-liquid mixture; (3) carrying out hydrothermal crystallization on the colloid or the solid-liquid mixture under the crystallization reaction condition; wherein the particle size of the solid silica gel is 40-200 meshes, the bulk density is 360-500g/L, and the specific surface area is 410-520m2The pore volume is 0.88-1.15 mL/g.
According to the method of the invention, in order to further optimize the crystallinity of the IM-5 molecular sieve and obtain the IM-5 molecular sieve with more uniform grain size,preferably, the particle size of the solid silica gel is 40-180 meshes, the bulk density is 380-500g/L, and the specific surface area is 430-480m2The pore volume is 1.01-1.10 mL/g.
According to the process of the present invention, the solid silica gel preferably has a water content of less than 10% by weight, preferably from 6 to 10% by weight; the pore distribution of the solid silica gel is in the range of 2.5-22.5nm, preferably in the range of 3.5-18 nm.
According to the method of the present invention, in order to reduce the water content in the crystallization raw material (colloid or solid-liquid mixture), increase the concentration of the template agent accordingly, further shorten the crystallization time, and increase the single pot yield, it is preferable that the solid silica gel, the aluminum source, the inorganic base, the template agent and water are fed so that the composition of the colloid or solid-liquid mixture is SiO on a molar basis2：Al2O3：M2O：SDA：H2O100: (0.5-10): (15-30): (6-15): (500-1400), wherein the solid silica gel is SiO2The aluminum source is calculated as Al2O3Calculated as M, the inorganic base2And O, the SDA is the template. More preferably, the composition of the colloid or solid-liquid mixture is SiO in molar terms2：Al2O3：M2O：SDA：H2O＝100：(1-6)：(17.5-25)：(8-12)：(800-1200)。
According to the method of the invention, in the step of mixing and preparing the mixed solution, the selected water is deionized water.
According to the method of the present invention, in the above process of synthesizing the IM-5 molecular sieve, the steps of preparing a colloid or a solid-liquid mixture, stirring, crystallization reaction, hydrothermal crystallization, cooling, washing, filtering, drying, etc. are all conventional steps required in the art for synthesizing the molecular sieve, and related terms are well known to those skilled in the art, for example, the contacting may be slowly adding a solid silicon source to a mixed solution containing an aluminum source. The contact process can be carried out under the condition of stirring, the contact temperature can be +/-20 ℃ at room temperature, and the contact time can be 1-3 hours.
According to the method of the present invention, the hydrothermal crystallization is generally carried out in a crystallization kettle.
According to the method of the present invention, there may be no particular requirement for the crystallization reaction conditions, but in order to improve the production efficiency, it is preferable that the crystallization reaction conditions include: the hydrothermal crystallization temperature is raised to 150 ℃ below zero and 120 ℃ for 1 to 3 days, and then the hydrothermal crystallization temperature is raised to 200 ℃ below zero and 160 ℃ for 2 to 4 days; more preferably, the crystallization reaction conditions include: the hydrothermal crystallization temperature is raised to 140 ℃ for 1 to 3 days, and then raised to 180 ℃ for 170 ℃ and continued for 2 to 4 days.
According to the method, after crystallization is finished, the steps of cooling, washing the mixed solution obtained after crystallization reaction by deionized water (deionized water) and filtering for 3-5 times, and drying at 80-100 ℃ for 12-24 hours to obtain the IM-5 molecular sieve raw powder.
According to the invention, the aluminum source provides Al element necessary for forming a framework for synthesizing the IM-5 molecular sieve, so that substances capable of providing the Al element in a synthesis reaction can be used as the aluminum source, and preferably, the aluminum source is one or more of sodium metaaluminate, aluminum sulfate, aluminum chloride and aluminum nitrate.
According to the invention, a template agent is needed to synthesize the IM-5 molecular sieve, so that the structure guiding effect is achieved, the primary structural unit which is formed by depolymerizing the silicon source and the aluminum source in the colloid system and forms the IM-5 molecular sieve grows around the template agent to form an IM-5 molecular sieve crystal, and preferably, the template agent is biquaternary ammonium salt; preferably, the template agent is 1, 5-bis (N-methylpyrrolidine) pentane bromide.
According to the invention, the inorganic base is a substance used for hydrothermal crystallization synthesis of molecular sieves, which is well known to those skilled in the art, and is preferably sodium hydroxide and/or potassium hydroxide.
The beneficial effects of the synthesis method of the IM-5 molecular sieve of the invention will be further explained by combining specific examples and comparative examples.
The relative concept and calculation of "crystallinity" in the following examples and comparative examples is illustrated below:
relative crystallinity values (r.c.%) were: the sum of the peak areas of five peaks (the 2 theta angles are 22.48 degrees, 23.00 degrees, 23.27 degrees, 24.09 degrees and 24.90 degrees respectively) in the 2 theta interval of 21.0-25.5 degrees of the product A0 synthesized in the preparation example 1 is taken as a reference, and the sum is 100 percent; the ratio of the sum of peak areas of the same five peaks appearing on the XRD spectrum to the sum of peak areas of the five peaks on the XRD spectrum of a0, in percentage, of the products synthesized in the following examples and comparative examples.
Determining the structure of the IM-5 molecular sieve: and (3) determining the prepared molecular sieve raw powder by an XRD analysis method, comparing characteristic peaks with 2 theta angles of 7.60 degrees, 7.76 degrees, 8.85 degrees, 23.09 degrees, 23.42 degrees and 25.07 degrees in the obtained XRD spectrogram with an XRD spectrogram of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption determination', and determining whether the structure is the structure of the IM-5 molecular sieve. XRD analysis adopts a Japanese physical D/MAX-IIIA type diffractometer, and the test conditions are as follows: cu target, Ka radiation, Ni filter, tube voltage 35kV, tube current 35mA, and scanning range 2 theta 4-55 deg.
The particle size and uniformity were observed by scanning electron microscopy SEM in the following examples and comparative examples.
Whether the mixed crystals exist in the following examples and comparative examples is judged by comparing diffraction peaks in XRD diffraction patterns, when the formed XRD drawings are compared with the XRD diffraction patterns in preparation example 1, the IM-5 molecular sieve is considered to have no mixed crystals when no obvious mixed peak appears, and the IM-5 molecular sieve is considered to have mixed crystals when the obvious mixed peak appears.
In the following examples and comparative examples, the specifications and sources of the various reagents used are as follows:
NaOH、AlCl3·6H2O、Al(NO3)3·9H2o is chemically pure and is produced by Beijing chemical plant;
1, 5-bis (N-methylpyrrolidine) pentanedibromide salt (MPPBR)2) The aqueous solution (SDA for short) with the solid content of 58.9 percent by weight is produced by Guangzhou Daojian refining factory;
solid silica gel I with the particle size distribution of 40-120 meshes, the bulk density of 449g/L and the water content of 6.1 wt%; pore distribution 4nm-15nm, specific surface area 452m2The catalyst is produced by China petrochemical Changling catalyst division company;
solid silica gel II with particle size distribution of 40-180 mesh, bulk density of 457g/L, water content of 7.5 wt%, pore distribution of 4-18 nm, specific surface area of 480m2The catalyst is produced by China petrochemical Changling catalyst division, and the pore volume is 1.04 mL/g;
solid silica gel III with particle size distribution of 60-160 mesh, bulk density of 388g/L, water content of 6.3 wt%, pore distribution of 3.5-22.5 nm, and specific surface area of 416m2The catalyst is produced by China petrochemical Changling catalyst division, and the pore volume is 0.962 mL/g;
solid silica gel IV with particle size distribution of 60-180 meshes, bulk density of 405g/L, water content of 10 wt%, pore distribution of 4-21 nm, specific surface area of 422m2The catalyst is produced by China petrochemical Changling catalyst division, and the pore volume is 1.08 mL/g;
solid silica gel V with particle size distribution of 40-200 mesh, bulk density of 368g/L, water content of 8.13 wt%, pore distribution of 3-22 nm, and specific surface area of 404m2(ii) a pore volume of 0.889mL/g, produced by China petrochemical Changling catalyst division;
the solid silica gel VI has the particle size distribution of 30-120 meshes, the bulk density of 357g/L, the water content of 1.8wt percent, the average pore diameter of 11.5nm and the specific surface area of 316m2The pore volume is 0.947mL/g, and the product is produced by Qingdao ocean chemical industry Co.Ltd;
NaAlO2solution of Al2O3The content was 13.64% by weight, Na2The O content was 20.2% by weight, and was produced by ChangLing catalyst division, a China petrochemical Co., Ltd.
Preparation example 1
IM-5 molecular sieves were synthesized according to the methods disclosed in the literature (Synthesis, characterization and catalytic Properties of IM-5and NU-88 molecular sieves; Synthesis, characterization, and catalytic properties of zeolites IM-5and NU-88.Journal of Catalysis 2003: 215151-170).
10.19g of 1, 5-bis (N-methylpyrrolidine) pentane bromide salt aqueous solution, 2.92g of NaOH, 1.1g of Al (NO)3)3·9H2Dissolving O in deionized water, mixing, and adding while stirring6.19g of white carbon black is prepared into milk white colloid, and the molar composition of the latex obtained by mixing is as follows: SiO 22：Al2O3：Na2O：SDA：H2O10: 0.167: 3.65: 1.5: 400 (wherein SDA is 1, 5-bis (N-methylpyrrolidine) pentane bromine salt). The resulting mixture was stirred at room temperature for 24 hours, and the obtained colloid was transferred to a crystallization kettle of 50ml in polytetrafluoroethylene lining, and after rotating and crystallizing at 160 ℃ for 14 days, the rotation speed was 100 rpm. Stopping the crystallization reaction, washing and filtering the product, and drying the product at 80 ℃ overnight to obtain the molecular sieve raw powder A0.
The XRD measurement result of the molecular sieve raw powder A0 is compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the literature, "the pore structure of the IM-5 molecular sieve is determined by catalytic test reaction and hydrocarbon adsorption measurement", and the A0 is determined to be the IM-5 molecular sieve. The XRD measurement results are shown in FIG. 1. The relative crystallinity of molecular sieve crude powder A0 was set to 100%.
Example 1
This example illustrates the synthesis of the IM-5 molecular sieve of the invention.
43.87g NaAlO2The solution, 53.576g of 30 wt% NaOH solution and 127.54g of SDA solution are dissolved in a proper amount of deionized water, evenly mixed, under the condition of stirring, 150g of solid silica gel I is slowly added to prepare milk white colloid, and the stirring is continued for 1 hour. The molar composition of the colloid was: SiO 22：Al2O3：Na2O：SDA：H2O＝100：2.5：17.5：8：900。
Transferring the prepared colloid into a 1L high-pressure reaction kettle with mechanical stirring, crystallizing at 140 ℃ for 2 days, heating to 172 ℃ for crystallization for 3 days, stopping crystallization reaction, washing and filtering the product, and drying at 80 ℃ overnight to obtain the molecular sieve raw powder A1.
XRD test is carried out on the molecular sieve raw powder A1, and the result is compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption determination', so that the A1 is determined to be the IM-5 molecular sieve by comparison. Meanwhile, the particle size distribution of the molecular sieve raw powder A1 is measured, wherein the relative crystallinity result, the mixed crystal comparison result and the particle size distribution result are shown in Table 1.
Example 2
This example illustrates the synthesis of the IM-5 molecular sieve of the invention.
Mixing 29.25g NaAlO2The solution, 74.843g of 30 wt% NaOH solution and 175.35g of SDA solution are dissolved in a proper amount of deionized water, evenly mixed, under the condition of stirring, 150g of solid silica gel I is slowly added to prepare milk white colloid, and the stirring is continued for 1 hour. The molar composition of the colloid was: SiO 22：Al2O3：Na2O：SDA：H2O＝100：1.67：20：11：1000。
Transferring the prepared colloid into a 1L high-pressure reaction kettle with mechanical stirring, crystallizing at 135 deg.C for 2 days, heating to 170 deg.C, crystallizing for 4 days, stopping crystallization reaction, washing and filtering the product, and oven drying at 80 deg.C overnight to obtain molecular sieve raw powder A2.
XRD test is carried out on the molecular sieve raw powder A2, and the result is compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption determination', so that the A2 is determined to be the IM-5 molecular sieve by comparison. Meanwhile, the particle size distribution of the molecular sieve raw powder A2 is measured, wherein the relative crystallinity result, the mixed crystal comparison result and the particle size distribution result are shown in Table 1.
Example 3
This example illustrates the synthesis of the IM-5 molecular sieve of the invention.
19.013gNaAlO2The solution, 89.339g of 30 wt% NaOH solution and 165.80g of SDA solution are dissolved in a proper amount of deionized water, evenly mixed, 130g of solid silica gel I is slowly added under the stirring condition to prepare milk white colloid, and the stirring is continued for 1 hour. The molar composition of the colloid was: SiO 22：Al2O3：Na2O：SDA：H2O＝100：1.25：25：12：1200。
Transferring the prepared colloid into a 1L high-pressure reaction kettle with mechanical stirring, crystallizing at 140 ℃ for 2 days, heating to 180 ℃ for crystallizing for 2 days, stopping the crystallization reaction, washing and filtering the product, and drying at 80 ℃ overnight to obtain the molecular sieve raw powder A3.
XRD test is carried out on the molecular sieve raw powder A3, and the result is compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption determination', so that the A3 is determined to be the IM-5 molecular sieve by comparison. Meanwhile, the particle size distribution of the molecular sieve raw powder A3 is measured, wherein the relative crystallinity result, the mixed crystal comparison result and the particle size distribution result are shown in Table 1.
Examples 4 to 7 and comparative example 1
Wherein the examples are used to illustrate the synthesis of the IM-5 molecular sieve of the invention, and the comparative examples are used to illustrate the synthesis of the IM-5 molecular sieve of the invention with reference to the drawings.
The synthesis of the IM-5 molecular sieve is carried out according to example 1, with the difference that the synthesis is carried out with different solid silica gels, which are compared with the corresponding examples and comparative examples in the following table:
serial number Corresponding solid silica gel Corresponding IM-5 molecular sieve raw powder
Example 4 Solid silica gel II A4
Example 5 Solid silica gel III A5
Example 6 Solid silica gel IV A6
Example 7 Solid silica gel V A7
Comparative example 1 Solid silica gel VI DA1
XRD (X-ray diffraction) tests are carried out on the molecular sieve raw powder A4-A7 and DA1, the measurement results are compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption measurement', and the comparison can determine that both the A4-A7 and the DA1 are the IM-5 molecular sieve. Meanwhile, the particle size distribution of the molecular sieve raw powder A4-A7 and DA1 is measured, wherein the relative crystallinity result, the mixed crystal comparison result and the particle size distribution result are shown in Table 1.
Example 8
Prepared according to the method of example 1, except that the amount of water used is adjusted so that the molar composition of the colloid is: SiO 22：Al2O3：Na2O：SDA：H2O100: 2.5: 17.5: 8: 1500. obtaining molecular sieve raw powder A8.
XRD test is carried out on the molecular sieve raw powder A8, and the result is compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption determination', so that the A8 is determined to be the IM-5 molecular sieve by comparison. Meanwhile, the particle size distribution of the molecular sieve raw powder A8 is measured, wherein the relative crystallinity result, the mixed crystal comparison result and the particle size distribution result are shown in Table 1.
Example 9
Prepared according to the method of example 1, except that the amount of templating agent was adjusted so that the molar composition of the colloid was: SiO 22：Al2O3：Na2O：SDA：H2O100: 2.5: 17.5: 6: 900. obtaining molecular sieve raw powder A9.
XRD test is carried out on the molecular sieve raw powder A9, and the result is compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption determination', so that the A9 is determined to be the IM-5 molecular sieve by comparison. Meanwhile, the particle size distribution of the molecular sieve raw powder A9 is measured, wherein the relative crystallinity result and the mixed crystal comparison result are shown in Table 1.
Example 10
The preparation was carried out in the same manner as in example 1 except that crystallization was carried out at 175 ℃ for 5 days instead of at 140 ℃ for 2 days under crystallization conditions, and then the temperature was raised to 172 ℃ for 3 days. Obtaining molecular sieve raw powder A10.
XRD test is carried out on the molecular sieve raw powder A10, and the result is compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption determination', so that the A10 is determined to be the IM-5 molecular sieve by comparison. Meanwhile, the particle size distribution of the molecular sieve raw powder A10 is measured, wherein the relative crystallinity result, the mixed crystal comparison result and the particle size distribution result are shown in Table 1.
Example 11
IM-5 molecular sieves were synthesized on scale up as in example 1, except that:
87.75kg of NaAlO2Solution 107.152kg of 30 wt% NaOH solution, 255.0kg of SDA solution, 300kg of solid silica gel I instead of 43.87g of NaAlO2Solution 53.576g of 30 wt% NaOH solution, 127.54g of SDA solution and 150g of solid silica gel I, 2m31L autoclave. The molar composition of the colloid was: SiO 22：Al2O3：Na2O：SDA：H2O100: 2.5: 17.5: 8: 900. the crystallization condition is that after crystallization is carried out for 2 days at 140 ℃, the temperature is raised to 172 ℃ for crystallization for 4 days, and the molecular sieve raw powder A11 is obtained.
XRD test is carried out on the molecular sieve raw powder A11, and the result is compared with the XRD spectrum of the IM-5 molecular sieve disclosed in the document 'determination of the pore structure of the IM-5 molecular sieve by catalytic test reaction and hydrocarbon adsorption determination', so that the A11 is determined to be the IM-5 molecular sieve by comparison. Meanwhile, the particle size distribution of the molecular sieve raw powder A11 is measured, as shown in FIG. 2, FIG. 2 is an SEM (scanning electron microscope) spectrum of the molecular sieve raw powder A11 under 500nm, and from FIG. 2, it can be seen that the molecular sieve raw powder A11 has better morphology regularity and clear grain outline, and no other crystals are found; further, the results of relative crystallinity, the results of impurity crystal ratio and the results of particle size distribution are shown in Table 1.
TABLE 1
Example No. 2 Numbering Relative crystallinity value (R.C.)/%) Mixed crystal Particle size distribution (nm × nm)
Preparation example 1 A0 100 Is free of 400-700×100-200
Example 1 A1 105 Is free of 150-250×50-100
Example 2 A2 96 Is free of 150-300×50-100
Example 3 A3 93 Is free of 200-300×50-100
Example 4 A4 103 Is free of 150-250×50-100
Example 5 A5 95 Is provided with -
Example 6 A6 94 Is free of 150-250×50-100
Example 7 A7 77 Is free of 150-250×50-100
Example 8 A8 83 Is free of 200-300×50-150
Example 9 A9 76 Is provided with -
Example 10 A10 73 Is free of 150-250×50-100
Example 11 A11 116 Is free of 200-300×50-100
Comparative example 1 DA1 54 Is provided with -
The experimental data results in table 1 show that the synthesis method of the IM-5 molecular sieve of the present invention can effectively inhibit the formation of heterocrystals (such as ZSM-12, mordenite, analcite, alpha-quartz, etc.) in the IM-5 molecular sieve by using solid silica gel having a specific surface area and a pore volume within a specific range as a silicon source; but also can improve the grain size of the prepared IM-5 molecular sieve and obtain the IM-5 molecular sieve with smaller grain size and better uniformity.
In addition, the IM-5 molecular sieve synthesis method of the invention is favorable for reducing the water-silicon ratio and the mold-silicon ratio in the synthesis process by adopting the solid silica gel with the specific surface area and the pore volume within a specific range as a silicon source, and is favorable for reducing the water content in a crystallization raw material (colloid or solid-liquid mixed liquid) by setting the water-silicon ratio and the mold-silicon ratio within an optimal range, so that the concentration of a template agent is correspondingly improved, the crystallization time is further shortened, the yield of a single kettle is increased, the production efficiency is improved, and the production cost is reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, several simple modifications can be made to the technical solution of the invention, including combinations of the technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (9)

1. A synthesis method of an IM-5 molecular sieve is characterized by comprising the following steps:
(1) dissolving inorganic alkali, an aluminum source and a template agent in water, and mixing to prepare a mixed solution;
(2) under the condition of stirring, contacting the mixed solution with solid silica gel, and mixing to prepare colloid or a solid-liquid mixture;
(3) carrying out hydrothermal crystallization on the colloid or the solid-liquid mixture under the crystallization reaction condition;
wherein the particle size of the solid silica gel is 40-180 meshes, the bulk density is 380-500g/L, and the specific surface area is 430-480m2The pore volume is 1.01-1.10 mL/g;
wherein the solid silica gel, the aluminum source, the inorganic base, the template agent and water are fed so that the colloid or the solid-liquid mixture has a composition of SiO in molar terms2：Al2O3：M2O：SDA：H2O100: (1-6): (17.5-25): (8-12): (800-1200), wherein the solid silica gel is SiO2The aluminum source is calculated as Al2O3Calculated as M, the inorganic base2O, the SDA is the template;
wherein the water content of the solid silica gel is less than 10 wt%, and the pores of the solid silica gel are distributed in the range of 2.5-22.5 nm.
2. The method of claim 1, wherein the solid silica gel has a water content of 6-10 wt%.
3. The method of claim 1, wherein the pores of the solid silica gel are distributed in the range of 3.5-18.0 nm.
4. The method of any one of claims 1 to 3, wherein the crystallization reaction conditions comprise: the hydrothermal crystallization temperature is raised to 150 ℃ below zero and 120 ℃ for 1 to 3 days, and then the hydrothermal crystallization temperature is raised to 200 ℃ below zero and 160 ℃ for 2 to 4 days.
5. The method of claim 4, wherein the crystallization reaction conditions comprise: the hydrothermal crystallization temperature is raised to 140 ℃ for 1 to 3 days, and then raised to 180 ℃ for 170 ℃ and continued for 2 to 4 days.
6. The process of any one of claims 1 to 3, wherein the aluminium source is one or more of sodium metaaluminate, aluminium sulphate, aluminium chloride and aluminium nitrate.
7. The method of any one of claims 1 to 3, wherein the templating agent is a bis-quaternary ammonium salt.
8. The method of claim 7, wherein the templating agent is 1, 5-bis (N-methylpyrrolidine) pentanedium bromide.
9. A process according to any one of claims 1 to 3, wherein the inorganic base is NaOH and/or KOH.
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