CN110642265B - Method for synthesizing ZSM-5 molecular sieve with framework containing heteroatom - Google Patents
Method for synthesizing ZSM-5 molecular sieve with framework containing heteroatom Download PDFInfo
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Abstract
The invention relates to a method for synthesizing a ZSM-5 molecular sieve with a framework containing heteroatoms. The technical scheme is as follows: the synthesis method of the ZSM-5 molecular sieve with the framework containing the heteroatom sequentially comprises the following steps: a) obtaining a mixture I containing a silicon source, an aluminum source, a heteroatom metal source and water; b) obtaining a mixture II containing the mixture I and an organic amine template agent, wherein the pH value of the mixture II is 5-9; c) adjusting the pH value of the mixture II to 10-11.5 by using a pH regulator to obtain a mixture III; d) crystallizing the mixture III in a crystallization kettle to obtain a mixture IV; e) and (3) carrying out solid-liquid separation on the mixture IV to obtain the ZSM-5 molecular sieve with the framework containing the heteroatom, and can be used for industrial production of the ZSM-5 molecular sieve with the framework containing the heteroatom.
Description
Technical Field
The invention relates to a method for synthesizing a ZSM-5 molecular sieve with a framework containing heteroatoms.
Background
The microporous zeolite molecular sieve is an inorganic crystal containing silicon, aluminum and the like, has a framework with pore channels which contain regular and ordered arrangement and have similar molecular size, and is widely applied in the fields of catalysis, ion exchange, separation and the like, in particular to a ZSM-5 molecular sieve. The ZSM-5 zeolite is a cross channel system formed by 10-membered rings and has three-dimensional channels. In the early 70 s of the last century, the synthesis method of the ZSM-5 molecular sieve was first reported in the United states patent USP 3702866. Since then, ZSM-5 molecular sieves have been widely used in alkylation, isomerization, disproportionation, selective cracking, and gasoline synthesis from methanol, among other reactions. The heteroatom is adopted to replace aluminum in the framework, and the acidity of the molecular sieve is changed. In practical application, the diffusion of molecules in the molecular sieve is limited due to the similar pore diameter and the molecular size, and the number of the diffused pore channels is closely related to the pore diameter and the diffusion rate of the molecules. The smaller the molecular sieve grain, the better the molecular diffusion effect.
The traditional synthetic method of the heteroatom ZSM-5 molecular sieve is a complex synthetic method, and under the alkaline condition, a compound containing aluminum and silicon is synthesized under the hydrothermal condition. In CN1608990A, tetrapropylammonium bromide or ammonium hydroxide thereof is used as a template to synthesize the heteroatom molecular sieve by a conventional method. Uniformly mixing the adopted heteroatom source alkali metal salt, sodium hydroxide, template agent and water, dripping a silicon source, uniformly stirring to obtain sol, wherein the water-silicon ratio is more than 50, aging is required for 1-2 days at room temperature, the temperature is 80-120 ℃ for 3-10 days, and performing suction filtration, washing to neutrality and drying. Because the heteroatom precipitation is prevented in the synthesis process, the gelling process is very long, the water-silicon ratio is high, the dripping speed is controlled, the heteroatom is uniformly distributed, and the synthesis scale cannot be enlarged.
ZL89108240.9 adopts gas phase transfer method to prepare ZSM-5 molecular sieve, firstly mixes a certain amount of aluminum sulfate, sodium silicate, sodium hydroxide and deionized water in a certain order, filters and washes to obtain amorphous gel. With Ethylenediamine (EDA), triethylamine (Et)3A) And reacting for 5-7 days at 453-473K by using a mixed solution of water and water as a template agent to prepare ZSM-5 molecular sieve powder. ZSM-5 containing no heteroatom is synthesized by the method. ZSM-5 molecular sieves containing heteroatoms are very difficult.
In ZL98110744.3, a quaternary ammonium salt or quaternary ammonium base is used as a template agent to hydrothermally synthesize the heteroatom ZSM-5 molecular sieve. The method adopts two templates, at least contains quaternary ammonium salt or quaternary ammonium base, and also adopts a second organic amine template, although the mother liquor recycling method is adopted to reduce the dosage of the template, the dosage of the template is still larger, a large amount of waste liquor is still generated in the subsequent washing of a molecular sieve filter cake and needs to be treated, and the synthesis is more complex.
The heteroatom synthesis method provided by ZL00133567.7 adopts relatively complex ZSM-5 molecular sieve containing Fe heteroatom, which is synthesized by using NaY, silica gel and the like as silicon sources and organic amine ethylamine or tetrapropylamino compound as a template agent. The method synthesizes the conventional molecular sieve with larger grains, and is difficult to synthesize the nano heteroatom molecular sieve.
The invention relates to a method for synthesizing a ZSM-5 molecular sieve with a framework containing heteroatoms, which mainly solves the problems of difficult synthesis and low single-kettle yield of the ZSM-5 molecular sieve with the framework containing the heteroatoms in the prior art.
Disclosure of Invention
The invention relates to a method for synthesizing a ZSM-5 molecular sieve with a framework containing heteroatoms, which mainly solves the problem of difficult synthesis of the ZSM-5 molecular sieve with the framework containing the heteroatoms in the prior art. The novel synthesis method of the ZSM-5 molecular sieve with the framework containing the heteroatom has the advantages of simplicity and strong operability.
The technical scheme adopted by the invention is as follows:
the synthesis method of the ZSM-5 molecular sieve with the framework containing the heteroatom sequentially comprises the following steps:
a) obtaining a mixture I containing a silicon source, an aluminum source, a heteroatom metal source and water, wherein the silicon source is SiO2The aluminum source is calculated as Al2O3Counting heteroatom metal source as M2OnThe molar ratio of each substance is SiO2:Al2O3:M2On:H2O ═ a: b: 1: c, wherein n represents the valence state of the heteroatom metal, and the value range of n is 2-6; the value range of a is 10-9000, the value range of b is 0-30, and the value range of c is 100-90000;
b) obtaining a mixture II containing the mixture I and an organic amine template agent, wherein the pH value of the mixture II is 5-9;
c) adjusting the pH value of the mixture II to 10-11.5 by using a pH regulator to obtain a mixture III;
d) crystallizing the mixture III in a crystallization kettle to obtain a mixture IV;
e) carrying out solid-liquid separation on the mixture IV to obtain a ZSM-5 molecular sieve with a framework containing heteroatoms;
the heteroatom metal includes at least one selected from the group consisting of iron-based metals, group IIIA metals, group IVA metals and group VB metals.
In the above technical solution, the silicon source used is preferably at least one of silica sol, water glass, silica gel and silicate.
In the above technical solution, the aluminum source used is preferably at least one of aluminum sulfate, aluminum nitrate, aluminum hydroxide and sodium aluminate.
In the above-mentioned embodiment, the iron-based metal is preferably at least one selected from Fe, Co and Ni.
In the above technical solution, the group IIIA metal is preferably Ga; the group IVA metal is preferably Ge; the group VB metal is preferably selected from V.
In the technical scheme, the organic amine preferably contains 1-20 carbon number of aliphatic amine in the molecule. Such as but not limited to one or more of cyclohexylamine, alkylamine, dialkylamine, trialkylamine, and tetraalkylammonium compounds. Wherein the tetraalkylammonium compound can be a quaternary ammonium base or a quaternary ammonium salt. Wherein the quaternary ammonium salt can be a halide or sulfate which can be a quaternary ammonium. Among them, the alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms.
In the above technical scheme, the value range of a is preferably 12-200.
In the technical scheme, the value range of b is preferably 0.1-20.
In the technical scheme, the value range of c is preferably 400-8000.
In the above technical scheme, the organic amine: SiO 22The molar ratio is preferably 0.0001-0.5; more preferably 0.01 to 0.3.
In the technical scheme, ZSM-5 seed crystals can be optionally added in the step b) and/or the step c). Wherein the seed crystal preferably takes up silicon source (silicon source is SiO)2Calculated) is more than 0 and less than 5 percent.
In the technical scheme, the preferable pH value of the mixture II is 5-8.
In the above technical solution, the pH adjusting agent in step c) may be at least one selected from sodium hydroxide, potassium hydroxide and ammonia.
In the above technical solution, the regulator in step c) preferably includes at least ammonia, for example, the regulator is ammonia or a mixture of the pH regulator ammonia and other pH regulators.
We have surprisingly found that ammonia has a strong crystallite-reducing effect when ammonia-containing substances are used as pH modifiers in step c), resulting in a heteroatom-containing ZSM-5 molecular sieve of 50-190 nm; in contrast, when the conventional NaOH or KOH is used as the pH regulator, the obtained ZSM-5 containing the heteroatom has crystal grains far larger than those of the former, and is 650-4000 nm ZSM-5 molecular sieve containing the heteroatom. We have also surprisingly found that ammonia as a pH modifier does not have a significant effect on the reduction of crystallites when preparing conventional aluminosilicate molecular sieves.
When the regulator is selected from ammonia, the ammonia can be pure ammonia or ammonia solution, and when ammonia water (ammonia water solution) is adopted, the concentration of the ammonia water can be but is not limited to 1-14 mol/L. In a specific embodiment, when a pH adjuster in the form of aqueous ammonia is used, the concentration of aqueous ammonia is generally 5 mol/liter for convenience of the same ratio.
In the above technical solution, the crystallization temperature is preferably 100-.
In the technical scheme, the crystallization time is preferably 4-150 h.
The novel synthesis method of the ZSM-5 molecular sieve with the framework containing the heteroatom has the advantages of simple method and strong operability. Particularly, when the pH value is 5-9 and the pH value is adjusted to 10-11.5 by taking ammonia as a pH adjusting agent in the step c), the ZSM-5 molecular sieve with the nanometer-scale framework and the heteroatom is obtained.
The invention is further illustrated by the following examples:
Detailed Description
[ example 1 ]
Aluminum sulfate octadecahydrate, ferric sulfate, water, 2 g of sodium chloride and 6 g of sulfuric acid are dissolved to prepare solution. 120.0g of water glass (containing 21.2 mass percent of silicon dioxide and 6.5 mass percent) is weighed. And (3) gelatinizing the two solutions under strong stirring, adding 50.0 g of tetrapropylammonium bromide solution containing 10.0 g of tetrapropylammonium bromide after gelatinizing, uniformly stirring until the pH value is 7.5, adding seed crystals, and then adjusting the pH value to 11.0 by using 5 mol/L ammonia water. Crystallizing at 140 deg.C under sealed condition for 90 hr. Obtaining the Fe-AlZSM-5 molecular sieve with the grain size of 120 nm.
For comparison, the main process conditions and experimental results are shown in Table 1
[ example 2 ]
Aluminum sulfate octadecahydrate, ferric sulfate, water, 2 g of sodium chloride and 6 g of sulfuric acid are dissolved to prepare solution. 120.0g of water glass (containing 21.2 mass percent of silicon dioxide and 6.5 mass percent) is weighed. And (3) gelatinizing the two solutions under strong stirring, adding 50.0 g of tetrapropylammonium bromide solution containing 10.0 g of the gelatinized solution, uniformly stirring to obtain a pH value of 7.5, and then adjusting the pH value to 10.5 by using 5 mol/L NaOH. Crystallizing at 140 deg.C under sealed condition for 90 hr. Obtaining the Fe-AlZSM-5 molecular sieve with the crystal grain of 1500 nm.
[ example 3 ]
Dissolving the aluminum sulfate octadecahydrate, the ammonium vanadate and the water to prepare a solution. 50 g of silica sol (containing 40 w% silica) was weighed out. And (3) gelatinizing the two mixed solutions under strong stirring, adding 50.0 g of an ethylamine solution containing 4.0 g of the mixture after gelatinizing, uniformly stirring the mixture until the pH value is 8.0, and then adjusting the pH value to 10.5 by using 5 mol/L ammonia water. Crystallizing at 150 deg.C under sealed condition for 60 hr. Obtaining the V-AlZSM-5 molecular sieve with the grain size of 150 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 4 ]
Dissolving the aluminum sulfate octadecahydrate, the ammonium vanadate and the water to prepare a solution. 240 g of silica sol (containing 40 w% silica) is weighed. And (3) gelatinizing the two mixed solutions under strong stirring, adding 50.0 g of an ethylamine solution containing 4.0 g of the mixture after gelatinizing, uniformly stirring the mixture, wherein the pH value is 8.0, and then adjusting the pH value to 10.5 by using a sodium hydroxide aqueous solution of 5 mol/L. Crystallizing at 150 deg.C under sealed condition for 60 hr. Obtaining the V-AlZSM-5 molecular sieve with the crystal grain of 1900 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 5 ]
Dissolving sodium germanate, water and tetrapropyl ammonium bromide to prepare a solution. 240 g of silica sol (containing 40 w% silica) is weighed. The two mixtures are stirred vigorously to form gel, the pH value is 7.5, and then the pH value is adjusted to 10.5 by using 5 mol/L ammonia water. Crystallizing at 180 deg.C under sealed condition for 40 hr. The Ge-ZSM-5 molecular sieve with crystal grains of 90nm is obtained.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 6 ]
Dissolving sodium germanate, water and tetrapropyl ammonium bromide to prepare a solution. 120 g of silica sol (containing 40 w% silica) was weighed. The two mixtures are stirred vigorously to form a gel, the pH value is 7.5, and then the pH value is adjusted to 10.5 by using 5 mol/L sodium hydroxide aqueous solution. Crystallizing at 180 deg.C under sealed condition for 40 hr. The Ge-ZSM-5 molecular sieve with crystal grain of 1600nm is obtained.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 7 ]
Cobalt sulfate, water and 1 g of sulfuric acid are dissolved to prepare a solution. The silica sol (containing 40 w% silica) was weighed to 120 g. The two mixed solutions are stirred strongly, and the pH value of the gel is 5.0. The aqueous tetrapropylammonium hydroxide solution (30% in content) was stirred for 1 hour, and then the pH was adjusted to 10.5 with 5 mol/L aqueous ammonia. Crystallizing at 200 deg.C in a sealed condition for 35 hr. Obtaining the Co-ZSM-5 molecular sieve with the crystal grain of 80 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 8 ]
Cobalt sulfate, water and 1 g of sulfuric acid are dissolved to prepare a solution. The silica sol (containing 40 w% silica) was weighed to 120 g. The two mixed solutions are stirred strongly, and the pH value of the gel is 5.0. The aqueous tetrapropylammonium hydroxide solution (30% in) was stirred for 1 hour and then adjusted to pH10.5 with 5 mol/l aqueous sodium hydroxide solution. Crystallizing at 200 deg.C in a sealed condition for 35 hr. Obtaining the Co-ZSM-5 molecular sieve with the crystal grain of 900 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 9 ]
Aluminum nitrate, nickel sulfate, water and 1 g of sulfuric acid are dissolved to prepare a solution. The silica gel was weighed and dissolved with sodium hydroxide to obtain 120 g (containing 40 w% silica). The two mixed solutions are stirred strongly to form gel, and then ZSM-5 seed crystal is added. An aqueous tetrapropylammonium hydroxide solution (containing 30%) was added thereto, and the mixture was stirred for 1 hour at pH 8.0, then adjusted to pH10.5 with 5 mol/l aqueous ammonia, and stirred for 1 hour. Crystallizing at 140 deg.C under sealed condition for 100 hr. Obtaining the Ni-AlZSM-5 molecular sieve with the crystal grain of 50 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 10 ]
Aluminum nitrate, nickel sulfate, water and 1 g of sulfuric acid are dissolved to prepare a solution. The silica gel was weighed and dissolved with sodium hydroxide to obtain 120 g (containing 40 w% silica). The two mixed solutions are stirred strongly to form gel, and then ZSM-5 seed crystal is added. Tetrapropylammonium hydroxide aqueous solution (30% in content) was added, and stirred for 1 hour at pH 8.0, then adjusted to pH10.5 with 1 mol/l KOH, and stirred for 1 hour. Crystallizing at 140 deg.C under sealed condition for 100 hr. Obtaining the Ni-AlZSM-5 molecular sieve with the crystal grain of 650 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 11 ]
Dissolving the aluminum sulfate octadecahydrate, the bismuth nitrate and the water to prepare a solution. 180 g of ethyl orthosilicate is weighed and water (containing 40 w% of silicon dioxide) is added. The two mixed solutions are stirred strongly to form gel, then tripropylamine is added, ZSM-5 seed crystal is added and stirred for 2 hours, the pH value is 8.5, then the pH value is adjusted to 10.5 by using ammonia water of 5 mol/L and stirred for 3 hours. Crystallizing at 180 deg.C under sealed condition for 40 hr. The Bi-AlZSM-5 molecular sieve with the crystal grain of 190nm is obtained.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 12 ]
Aluminum sulfate octadecahydrate, bismuth nitrate, water and 1 g of sulfuric acid are dissolved to prepare a solution. 180 g of ethyl orthosilicate is weighed and water (containing 40 w% of silicon dioxide) is added. The two mixed solutions are stirred strongly to form gel, then tripropylamine 3.0 g is added, ZSM-5 seed crystal is added and stirred for 2 hours, the pH value is 8.5, then 5 mol/L sodium hydroxide aqueous solution is used for adjusting the pH value to 10.5, and the stirring is carried out for 3 hours. Crystallizing at 180 deg.C under sealed condition for 40 hr. Obtaining the Bi-AlZSM-5 molecular sieve with the grain size of 4000 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 13 ]
Ferric sulfate, water, dipropyl ammonium bromide and 1 g concentrated sulfuric acid are dissolved to prepare a solution. 180 g of water glass (containing 21% silica, 6.5%) are weighed out. The two solutions are stirred strongly to form gel, then ZSM-5 seed crystal is added, the pH is 9.0, and then the pH is adjusted to 10.5 by 5 mol/L ammonia water. Crystallizing at 150 deg.C under sealed condition for 150 hr. Obtaining the Fe-ZSM-5 molecular sieve with the grain size of 150 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 14 ]
Ferric sulfate, water, 1 g dipropylammonium bromide and 1 g concentrated sulfuric acid are dissolved to prepare a solution. 180 g of water glass (containing 21% silica, 6.5%) are weighed out. The two solutions are stirred vigorously to form gel, then ZSM-5 seed crystal is added, the pH is 9.0, and then 5 mol/L potassium hydroxide aqueous solution is used for adjusting the pH to 10.5. Crystallizing at 150 deg.C under sealed condition for 150 hr. Obtaining the Fe-ZSM-5 molecular sieve with crystal grain of 1500 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ examples 15 to 21 ]
Aluminum sulfate octadecahydrate, ferric sulfate, water and 6 g of sulfuric acid are dissolved to prepare solution. 120 g of water glass (weight content: 25.8% of silicon dioxide and 7.0% of sodium oxide) is weighed. The two solutions are stirred vigorously to form gel, then seed crystal is added, the pH value is 7.5, and then the pH value is adjusted to 10.5 by using 5 mol/L ammonia water. Crystallizing at a specified temperature for a specified time. Obtaining the Fe-AlZSM-5 molecular sieve. For comparison, the main process conditions and experimental results are listed in table 1.
[ example 22 ]
Tin sulfate, water, tetrapropylammonium bromide and 9 g of concentrated sulfuric acid are dissolved to prepare a solution. 180 g of water glass (containing 21% silicon dioxide and 6.5%) and sodium aluminate are weighed. The two solutions are stirred strongly to form gel, then ZSM-5 seed crystal is added, the pH is 9.0, and then the pH is adjusted to 10.5 by 5 mol/L ammonia water solution. Crystallizing at 170 deg.C under sealed condition for 60 hr. Obtaining the Sn-ZSM-5 molecular sieve with crystal grains of 1500 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ example 23 ]
Gallium nitrate, water, tetrapropyl ammonium bromide and 9 g of concentrated sulfuric acid are dissolved to prepare a solution. 180 g of water glass (containing 21% silica, 6.5%) are weighed out. The two solutions are stirred strongly to form gel, the pH value is 9.0, then the pH value is adjusted to 10.5 by using 5 mol/L ammonia water solution, and then ZSM-5 crystal seeds are added. Crystallizing at 170 deg.C under sealed condition for 60 hr. Obtaining the Ga-ZSM-5 molecular sieve with crystal grain of 1500 nm.
For comparison, the main process conditions and experimental results are listed in table 1.
[ COMPARATIVE EXAMPLE 1 ]
Aluminum sulfate octadecahydrate, water, 2 g of sodium chloride and 6 g of sulfuric acid are dissolved to prepare a solution. 120.0g of water glass (containing 21.2 mass percent of silicon dioxide and 6.5 mass percent) is weighed. And (3) gelatinizing the two solutions under strong stirring, adding 50.0 g of tetrapropylammonium bromide solution containing 10.0 g of tetrapropylammonium bromide after gelatinizing, uniformly stirring until the pH value is 7.5, adding seed crystals, and then adjusting the pH value to 11.0 by using 5 mol/L ammonia water. Crystallizing at 140 deg.C under sealed condition for 90 hr. The AlZSM-5 molecular sieve with the crystal grain of 2200nm is obtained.
For comparison, the main process conditions and experimental results are shown in Table 1
[ COMPARATIVE EXAMPLE 2 ]
Aluminum sulfate octadecahydrate, water, 2 g of sodium chloride and 6 g of sulfuric acid are dissolved to prepare a solution. 120.0g of water glass (containing 21.2 mass percent of silicon dioxide and 6.5 mass percent) is weighed. And (3) gelatinizing the two solutions under strong stirring, adding 50.0 g of tetrapropylammonium bromide solution containing 10.0 g of the colloid after gelatinizing, uniformly stirring, wherein the pH value is 7.5, adding seed crystals, and then adjusting the pH value to 11.0 by using 5 mol/L NaOH. Crystallizing at 140 deg.C under sealed condition for 90 hr. The AlZSM-5 molecular sieve with crystal grains of 2800nm is obtained.
For comparison, the main process conditions and experimental results are shown in Table 1
Table 1 (wait for)
TABLE 1 (continuation)
Claims (10)
1. The synthesis method of the ZSM-5 molecular sieve with the framework containing the heteroatom sequentially comprises the following steps:
a) obtaining a mixture I containing a silicon source, an aluminum source, a heteroatom metal source and water, wherein the silicon source is SiO2The aluminum source is calculated as Al2O3Counting heteroatom metal source as M2OnThe molar ratio of each substance is SiO2:Al2O3:M2On:H2O ═ a: b: 1: c, wherein n represents the valence state of the heteroatom metal, and the value range of n is 2-6; the value range of a is 10-9000, the value range of b is 0-30, and the value range of c is 100-90000;
b) obtaining a mixture II containing the mixture I and an organic amine template agent, wherein the pH value of the mixture II is 5-9;
c) adjusting the pH value of the mixture II to 10-11.5 by using a pH regulator to obtain a mixture III;
d) crystallizing the mixture III in a crystallization kettle to obtain a mixture IV;
e) carrying out solid-liquid separation on the mixture IV to obtain a ZSM-5 molecular sieve with a framework containing heteroatoms;
the heteroatom metal comprises at least one selected from iron group metals, IIIA group metals, IVA group metals and VB group metals;
step c) the pH adjusting agent comprises at least ammonia.
2. The method for synthesizing the ZSM-5 molecular sieve having a framework containing the heteroatom as claimed in claim 1, wherein the silicon source used is at least one of silica sol, water glass, silica gel and silicate ester.
3. The method for synthesizing the ZSM-5 molecular sieve having a framework containing the heteroatom, as claimed in claim 1, wherein the aluminum source used is at least one of aluminum sulfate, aluminum nitrate, aluminum hydroxide and sodium aluminate.
4. The method for synthesizing the ZSM-5 molecular sieve having a framework containing the heteroatom as claimed in claim 1, wherein the iron-based metal is at least one selected from Fe, Co and Ni.
5. The method for synthesizing the ZSM-5 molecular sieve with the framework containing the heteroatom as claimed in claim 1, wherein the organic amine contains aliphatic amine with carbon number of 1-20 in the molecule.
6. The method for synthesizing the ZSM-5 molecular sieve with the framework containing the heteroatom as claimed in claim 1, wherein a is in a range of 12 to 200.
7. The synthesis method of the framework heteroatom-containing ZSM-5 molecular sieve of claim 1, characterized in that the organic amine: SiO 22The molar ratio is 0.0001 to 0.5.
8. The synthesis method of the framework heteroatom-containing ZSM-5 molecular sieve as claimed in claim 1, characterized in that ZSM-5 seed crystals are added in step b) and/or step c).
9. The method of synthesizing a framework heteroatom-containing ZSM-5 molecular sieve as claimed in claim 1, characterized in that in step c) the pH adjusting agent is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonia, and at least comprises ammonia.
10. The method for synthesizing the ZSM-5 molecular sieve with a framework containing the heteroatom as claimed in claim 1, wherein the crystallization temperature is 100-250 ℃.
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| US4952385A (en) * | 1987-03-02 | 1990-08-28 | Georgia Tech Research Corp. | Ferrisilicate molecular sieve and use as a catalyst |
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| EP0037982A1 (en) * | 1980-04-16 | 1981-10-21 | Bayer Ag | Method of making shaped crystalline aluminosilicates catalysts |
| US4952385A (en) * | 1987-03-02 | 1990-08-28 | Georgia Tech Research Corp. | Ferrisilicate molecular sieve and use as a catalyst |
| CN101279746A (en) * | 2007-04-02 | 2008-10-08 | 南京工业大学 | Method for fast synthesizing ZSM-5 molecular sieve by variable temperature crystallization method |
| CN101538051A (en) * | 2009-05-06 | 2009-09-23 | 北京化工大学 | Method for preparing ZSM-5 zeolite catalyst |
| CN103121695A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Synthetic method of molecular sieve ZSM-5 (zeolite socony mobil-5) with heteroatom-containing frame |
| CN103936026A (en) * | 2014-04-03 | 2014-07-23 | 南京工业大学 | Method for synthesizing ZSM-5 molecular sieve |
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