CN109516472B - Synthesis method of Ga isomorphous substituted nano GaZSM-22 molecular sieve - Google Patents
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Abstract
A method for synthesizing Ga isomorphous substituted nanometer GaZSM-22 molecular sieve relates to a method for synthesizing nanometer GaZSM-22 molecular sieve. The invention aims to solve the problem that the size of the GaZSM-22 molecular sieve prepared by the existing method is large. The synthesis method comprises the following steps: firstly, preparing mixed gel; secondly, crystallization: obtaining the Ga isomorphous substituted nanometer GaZSM-22 molecular sieve. Has the advantages that: the rod-shaped nanocrystal has the particle size of 20-50 nm, the crystal grain length of 50-100 nm, the silicon-gallium ratio of 25-45: 1, and no aluminum atom in a molecular sieve framework. The method is mainly used for synthesizing the nano GaZSM-22 molecular sieve by substituting Ga isomorphous.
Description
Technical Field
The invention relates to a synthesis method of a Ga isomorphous substituted nanometer GaZSM-22 molecular sieve.
Background
The zeolite molecular sieve is a microporous crystal material with the characteristics of regular pore structure, larger specific surface area, stronger acidity, higher stability and the like, is one of the most important shape-selective catalysts and carriers in modern petrochemical industry, and is widely applied to industrial production processes of catalysis, adsorption, ion exchange and the like. The ZSM-22 molecular sieve is a microporous zeolite molecular sieve with TON topological structure developed by Mobil corporation in the last 80 century, and has one-dimensional linear non-crossed straight channel with ten-membered ring opening and pore diameter of 0.45nm x 0.55 nm. Due to the proper pore structure and acidity, ZSM-22 molecular sieves have been widely used in the petrochemical fields of catalytic dewaxing of lubricating oil, alkylation of aromatic hydrocarbons, preparation of olefins from methanol, and the like, and particularly Pt/ZSM-22 bifunctional catalysts prepared by using ZSM-22 molecular sieves as carriers show good catalytic performance in the hydroisomerization reaction of normal paraffins (Journal of Catalysis,2001,203, 213-231).
The normal alkane component in the diesel oil and gasoline distillate is converted into isoparaffin through hydrogenation isomerization reaction, so that the low-temperature flow property of the diesel oil or the octane value of the gasoline can be effectively improved, and the quality of the fuel oil is further improved. Then, the ZSM-22 aluminosilicate molecular sieve has strong acidity, the crystal size of the molecular sieve synthesized by the traditional hydrothermal method is large, the length of a rod-shaped crystal grain reaches 1-3 mu m, and the diffusion of a carbonium ion intermediate and an isomerization reaction product is seriously inhibited, so that the cracking reaction is accelerated, and the yield of an isomer product is low. On the other hand, a large amount of organic template is used in the process of synthesizing the ZSM-22 molecular sieve by adopting the traditional hydrothermal method, the crystallization time is long, the preparation cost is high, the waste gas generated by decomposing the organic template in the roasting process can cause pollution to the environment, and the application of the ZSM-22 molecular sieve is limited to a certain extent.
The Ga isomorphous substituted GaZSM-22 molecular sieve is a GaZSM-22 molecular sieve which is prepared by adding gallium oxide or salt containing Ga in the process of preparing mixed gel and synthesizing a molecular sieve framework Al by Ga in one step, the molecular sieve not only can keep the original framework structure of the molecular sieve by ZSM-22, but also can obviously weaken the acid strength of the molecular sieve because Ga is introduced into the molecular sieve framework, thereby effectively inhibiting the occurrence of side reactions such as cracking and the like, improving the catalytic reaction performance and reducing the carbon deposition inactivation rate of the molecular sieve. Ga isomorphously substituted ZSM-22 molecular sieves were first synthesized by Indian scholars, Reddy et al (Zeolite,1994,14, 290-. The authors synthesized a series of GaZSM-22 molecular sieves with different Si/Ga ratios by using gallium sulfate as a gallium source, and demonstrated the existence of framework gallium, but the crystal size of the synthesized GaZSM-22 molecular sieve was about 1 μm.
Disclosure of Invention
The invention aims to solve the problem that the Ga isomorphous substituted ZSM-22 molecular sieve prepared by the existing method has overlarge particle size, and provides a synthesis method of the Ga isomorphous substituted nano GaZSM-22 molecular sieve.
A synthesis method of Ga isomorphous substituted nanometer GaZSM-22 molecular sieve is specifically completed according to the following steps:
firstly, preparing mixed gel:
a. weighing 1 part of gallium trioxide, 50-90 parts of silicon source, 15-27 parts of 1, 6-hexanediamine, 10-18 parts of potassium hydroxide and 1750-3150 parts of deionized water in parts by mole; dividing 1750-3150 parts of deionized water into four parts according to the volume ratio of 3:4:3:2, and sequentially preparing deionized water I, deionized water II, deionized water III and deionized water IV;
b. mixing 10-18 parts of potassium hydroxide weighed in the step one with deionized water I to prepare a potassium hydroxide solution;
c. mixing 1 part of the gallium trioxide weighed in the step one with deionized water II to obtain gallium trioxide suspension, dropwise adding the gallium trioxide suspension into the potassium hydroxide solution obtained in the step one under the condition of stirring, and dissolving to obtain solution A;
d. mixing 15-27 parts of 1, 6-hexamethylene diamine weighed in the step one with deionized water III to obtain a 1, 6-hexamethylene diamine solution; adding a 1, 6-hexamethylene diamine solution into the solution A obtained in the step one c under the condition of stirring to obtain a solution B;
e. mixing 50-90 parts of silicon source weighed in the step one with deionized water IV to obtain a silicon source suspension, dropwise adding the silicon source suspension into the solution B obtained in the step one under the stirring condition, and stirring for 1-3 hours to obtain mixed gel;
secondly, crystallization: and (3) placing the mixed gel in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, dynamically crystallizing for 10-48 h at the temperature of 145-185 ℃ and at the rotating speed of 60-180 r/min, cooling to 25 ℃, then sequentially centrifuging, washing and drying, then placing in a muffle furnace, and roasting for 3-20 h at the temperature of 500-700 ℃ to obtain the Ga in-situ isomorphous substituted nano GaZSM-22 molecular sieve.
The invention has the beneficial effects that:
the Ga isomorphous substituted nano GaZSM-22 molecular sieve synthesized by the method is pure silicate gallate, the framework of the molecular sieve does not contain aluminum atoms, and the silicon-gallium ratio of the framework is only 25-45: 1.
Secondly, the invention takes gallium oxide as a gallium source, synthesizes the nanometer GaZSM-22 molecular sieve substituted by Ga in-situ isomorphous into rod-shaped nanometer crystals, the particle size is 20nm to 50nm, and the length of the crystal grains is 50nm to 100 nm.
And thirdly, the dosage of the organic template used in the synthesis of the Ga isomorphous substituted nano GaZSM-22 molecular sieve is obviously reduced, the dosage of the template is only 1/5-1/10 of the dosage of the traditional method, the crystallization time is greatly shortened, and the dosage is only 1/6-1/2 of the traditional hydrothermal method, so that the problems of high production cost of the molecular sieve, environmental pollution and the like caused by high price and high toxicity of the organic template are effectively solved.
The grain size of the Ga isomorphous substituted nano GaZSM-22 molecular sieve synthesized by the method is obviously reduced compared with that of the ZSM-22 molecular sieve synthesized by the traditional hydrothermal method, the acid strength is obviously weakened, the Ga isomorphous substituted nano GaZSM-22 molecular sieve can be used as a catalyst, the diffusion performance of reactants and products in a molecular sieve pore channel can be obviously improved, the accessibility of an active site of the catalyst is improved, the cracking reaction of an isomerization product is effectively inhibited, and the yield of a target product of the hydroisomerization reaction is obviously improved.
Drawings
FIG. 1 is an XRD spectrum of a GaZSM-22 molecular sieve obtained in example 1;
FIG. 2 is an SEM image of the GaZSM-22 molecular sieve obtained in example 1;
FIG. 3 is a Ga nuclear magnetic spectrum of the GaZSM-22 molecular sieve obtained in example 1;
FIG. 4 is an XRD spectrum of the GaZSM-22 molecular sieve obtained in example 2;
FIG. 5 is an SEM image of the GaZSM-22 molecular sieve obtained in example 2;
FIG. 6 is a Ga nuclear magnetic spectrum of the GaZSM-22 molecular sieve obtained in example 2;
Detailed Description
The first embodiment is as follows: the embodiment is a synthesis method of a Ga isomorphous substituted nanometer GaZSM-22 molecular sieve, which is specifically completed by the following steps:
firstly, preparing mixed gel:
a. weighing 1 part of gallium trioxide, 50-90 parts of silicon source, 15-27 parts of 1, 6-hexanediamine, 10-18 parts of potassium hydroxide and 1750-3150 parts of deionized water in parts by mole; dividing 1750-3150 parts of deionized water into four parts according to the volume ratio of 3:4:3:2, and sequentially preparing deionized water I, deionized water II, deionized water III and deionized water IV;
b. mixing 10-18 parts of potassium hydroxide weighed in the step one with deionized water I to prepare a potassium hydroxide solution;
c. mixing 1 part of the gallium trioxide weighed in the step one with deionized water II to obtain gallium trioxide suspension, adding the gallium trioxide suspension into the potassium hydroxide solution obtained in the step one under the condition of stirring, and dissolving to obtain solution A;
d. mixing 15-27 parts of 1, 6-hexamethylene diamine weighed in the step one with deionized water III to obtain a 1, 6-hexamethylene diamine solution; adding a 1, 6-hexamethylene diamine solution into the solution A obtained in the step one c under the condition of stirring to obtain a solution B;
e. mixing 50-90 parts of silicon source weighed in the step one with deionized water IV to obtain a silicon source suspension, adding the silicon source suspension into the solution B obtained in the step one under the condition of stirring, and stirring for 1-3 hours to obtain mixed gel;
secondly, crystallization: and (3) placing the mixed gel in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, dynamically crystallizing for 10-48 h at the temperature of 145-185 ℃ and at the rotating speed of 60-180 r/min, cooling to 25 ℃, then sequentially centrifuging, washing and drying, then placing in a muffle furnace, and roasting for 3-20 h at the temperature of 500-700 ℃ to obtain the Ga in-situ isomorphous substituted nano GaZSM-22 molecular sieve.
The second embodiment is as follows: the present embodiment differs from the first embodiment in that: in the first step a, the atomic ratio of Si in the silicon source to Ga in the gallium sesquioxide is 25-45: 1. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step a, the silicon source is silica sol with the mass fraction of 20.0-40.0%. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: and in the second step, dynamic crystallization is carried out for 12 to 36 hours at the temperature of 155 to 165 ℃ and at the rotating speed of 80 to 120 r/min. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the centrifugation condition in the second step is centrifugation for 5min to 10min at the rotating speed of 3000r/min to 5000 r/min. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and the washing condition in the second step is that the washing is carried out for 3-5 times by using secondary deionized water. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and drying for 12 hours at the temperature of 100-120 ℃ in the drying treatment condition in the second step. The rest is the same as the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the Ga in-situ isomorphous substituted nanometer GaZSM-22 molecular sieve in the step two is a rod-shaped nanometer crystal, the particle size is 20nm to 50nm, and the length of the crystal grain is 50nm to 100 nm. The rest is the same as the first to seventh embodiments.
The following tests were carried out to confirm the effects of the present invention
Example 1: a synthesis method of Ga isomorphous substituted nanometer GaZSM-22 molecular sieve is specifically completed according to the following steps:
firstly, preparing mixed gel:
a. 1.511g of potassium hydroxide and 10.022g of deionized water are mixed to prepare a potassium hydroxide solution;
b. mixing 0.179g of gallium trioxide with 13.363g of deionized water to obtain gallium trioxide suspension, adding the gallium trioxide suspension into the potassium hydroxide solution obtained in the step one a under the condition of stirring, and dissolving to obtain a solution A;
c. mixing 3.000g of 1, 6-hexamethylenediamine with 10.022g of deionized water to obtain a 1, 6-hexamethylenediamine solution; adding a 1, 6-hexamethylene diamine solution into the solution A obtained in the step one B under the stirring condition to obtain a solution B;
d. 18.721g of silica sol with the mass fraction of 27.6% and 6.682g of deionized water are mixed to obtain a silicon source suspension, the silicon source suspension is added into the solution B obtained in the step one c under the stirring condition, and the mixture is stirred to obtain mixed gel;
secondly, crystallization: and (3) placing the mixed gel in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, dynamically crystallizing for 15 hours at the temperature of 160 ℃ and the rotating speed of 60r/min, cooling to 25 ℃, then sequentially centrifuging, washing and drying, then placing in a muffle furnace, and roasting for 10 hours at the temperature of 600 ℃ to obtain the Ga in-situ isomorphous substituted nano GaZSM-22 molecular sieve.
The centrifugation condition in the second step of the example 1 is centrifugation for 10min at the rotating speed of 4000r/min, the washing condition is washing for 4 times by using secondary deionized water, and the drying treatment condition is drying for 12h at the temperature of 110 ℃.
The GaZSM-22 molecular sieve obtained in example 1 had a Si/Ga ratio of 45 (atomic ratio).
Fig. 1 is an XRD spectrum of the GaZSM-22 molecular sieve obtained in example 1, and from fig. 1, characteristic diffraction peaks corresponding to TON topology are found at 8.15 °, 20.35 °, 24.61 °, 25.69 ° and 35.6 ° 2 θ, and no diffraction peaks of other hetero-crystalline phases are found, indicating that pure-phase GaZSM-22 molecular sieve is synthesized in example 1.
FIG. 2 is an SEM image of the GaZSM-22 molecular sieve obtained in example 1, and it can be seen from FIG. 2 that the GaZSM-22 molecular sieve obtained in example 1 is a bouquet-like aggregate formed by rod-like small crystal grains, and the diameter of each crystal grain is 20 to 50nm and the length dimension is 50 to 100 nm.
FIG. 3 is a Ga nuclear magnetic spectrum of the GaZSM-22 molecular sieve obtained in example 1, and it can be seen from FIG. 3 that a resonance signal peak attributed to a four-coordinate framework Ga species appears in the vicinity of 160ppm, indicating that Ga is introduced into the molecular sieve framework.
Example 2: a synthesis method of Ga isomorphous substituted nanometer GaZSM-22 molecular sieve is specifically completed according to the following steps:
firstly, preparing mixed gel:
a. mixing 1.623g of potassium hydroxide and 9.996g of deionized water to prepare a potassium hydroxide solution;
b. mixing 0.231g of gallium trioxide with 13.328g of deionized water to obtain gallium trioxide suspension, adding the gallium trioxide suspension into the potassium hydroxide solution obtained in the step one a under the condition of stirring, and dissolving to obtain a solution A;
c. mixing 3.000g of 1, 6-hexamethylenediamine with 9.996g of deionized water to obtain a 1, 6-hexamethylenediamine solution; adding a 1, 6-hexamethylene diamine solution into the solution A obtained in the step one B under the stirring condition to obtain a solution B;
d. 18.721g of silica sol with the mass fraction of 27.6% and 6.664g of deionized water are mixed to obtain a silicon source suspension, the silicon source suspension is added into the solution B obtained in the step one c under the stirring condition, and the mixture is stirred to obtain mixed gel;
secondly, crystallization: and (3) placing the mixed gel in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, dynamically crystallizing for 15 hours at the temperature of 160 ℃ and the rotating speed of 60r/min, cooling to 25 ℃, then sequentially centrifuging, washing and drying, then placing in a muffle furnace, and roasting for 10 hours at the temperature of 600 ℃ to obtain the Ga in-situ isomorphous substituted nano GaZSM-22 molecular sieve.
The centrifugation condition in the second step of the example 2 is centrifugation for 10min at the rotating speed of 4000r/min, the washing condition is washing for 4 times by using secondary deionized water, and the drying treatment condition is drying for 12h at the temperature of 110 ℃.
The GaZSM-22 molecular sieve obtained in example 2 had a Si/Ga of 35 (atomic ratio).
Fig. 4 is an XRD spectrum of the GaZSM-22 molecular sieve obtained in example 2, and from fig. 4, characteristic diffraction peaks corresponding to TON topology are found at 8.15 °, 20.35 °, 24.61 °, 25.69 ° and 35.6 ° 2 θ, and no diffraction peak of other hetero-crystalline phases is found, indicating that pure-phase GaZSM-22 molecular sieve is synthesized in example 2.
FIG. 5 is an SEM image of the GaZSM-22 molecular sieve obtained in example 2, and it can be seen from FIG. 5 that the GaZSM-22 molecular sieve obtained in example 2 is a bouquet-like aggregate formed by rod-like small crystal grains, and the diameter of each crystal grain is 20 to 50nm and the length dimension is 50 to 100 nm.
FIG. 6 is a Ga nuclear magnetic spectrum of the GaZSM-22 molecular sieve obtained in example 2, and it can be seen from FIG. 6 that a resonance signal peak attributed to a four-coordinate framework Ga species appears in the vicinity of 160ppm, indicating that Ga is introduced into the molecular sieve framework.
Example 3: a synthesis method of Ga isomorphous substituted nanometer GaZSM-22 molecular sieve is specifically completed according to the following steps:
firstly, preparing mixed gel:
a. mixing 1.623g of potassium hydroxide and 9.727g of deionized water to prepare a potassium hydroxide solution;
b. mixing 0.231g of gallium trioxide with 12.969g of deionized water to obtain gallium trioxide suspension, adding the gallium trioxide suspension into the potassium hydroxide solution obtained in the step one a under the condition of stirring, and dissolving to obtain a solution A;
c. mixing 3.000g of 1, 6-hexamethylenediamine with 9.727g of deionized water to obtain a 1, 6-hexamethylenediamine solution; adding a 1, 6-hexamethylene diamine solution into the solution A obtained in the step one B under the stirring condition to obtain a solution B;
d. mixing 20.000g of silica sol with the mass fraction of 25.9% with 6.485g of deionized water to obtain a silicon source suspension, adding the silicon source suspension into the solution B obtained in the step one c under the stirring condition, and stirring to obtain mixed gel;
secondly, crystallization: and (3) placing the mixed gel in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, dynamically crystallizing for 24 hours at the temperature of 150 ℃ and the rotating speed of 60r/min, cooling to 25 ℃, then sequentially centrifuging, washing and drying, then placing in a muffle furnace, and roasting for 10 hours at the temperature of 600 ℃ to obtain the Ga in-situ isomorphous substituted nano GaZSM-22 molecular sieve.
The centrifugation condition in the second step of example 3 is centrifugation for 10min at the rotation speed of 4000r/min, the washing condition is washing for 4 times by using secondary deionized water, and the drying treatment condition is drying for 12h at the temperature of 110 ℃.
The GaZSM-22 molecular sieve obtained in example 3 had a Si/Ga of 35 (atomic ratio).
Example 4: a synthesis method of Ga isomorphous substituted nanometer GaZSM-22 molecular sieve is specifically completed according to the following steps:
firstly, preparing mixed gel:
a. 1.511g of potassium hydroxide and 10.022g of deionized water are mixed to prepare a potassium hydroxide solution;
b. mixing 0.179g of gallium trioxide with 13.363g of deionized water to obtain gallium trioxide suspension, adding the gallium trioxide suspension into the potassium hydroxide solution obtained in the step one a under the condition of stirring, and dissolving to obtain a solution A;
c. mixing 3.000g of 1, 6-hexamethylenediamine with 10.022g of deionized water to obtain a 1, 6-hexamethylenediamine solution; adding a 1, 6-hexamethylene diamine solution into the solution A obtained in the step one B under the stirring condition to obtain a solution B;
d. 18.721g of silica sol with the mass fraction of 27.6% and 6.682g of deionized water are mixed to obtain a silicon source suspension, the silicon source suspension is added into the solution B obtained in the step one c under the stirring condition, and the mixture is stirred to obtain mixed gel;
secondly, crystallization: and (3) placing the mixed gel in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, dynamically crystallizing for 12 hours at the temperature of 160 ℃ and the rotating speed of 80r/min, cooling to 25 ℃, then sequentially centrifuging, washing and drying, then placing in a muffle furnace, and roasting for 10 hours at the temperature of 600 ℃ to obtain the Ga in-situ isomorphous substituted nano GaZSM-22 molecular sieve.
The centrifugation in the second step of example 4 is carried out for 10min at the rotation speed of 4000r/min, the washing is carried out for 4 times by using secondary deionized water, and the drying treatment is carried out for 12h at the temperature of 110 ℃.
The Si/Ga of the GaZSM-22 molecular sieve obtained in example 4 was 45 (atomic ratio).
Claims (8)
1. A method for synthesizing Ga isomorphous substituted nanometer GaZSM-22 molecular sieve is characterized by comprising the following steps:
firstly, preparing mixed gel:
a. weighing 1 part of gallium trioxide, 50-90 parts of silicon source, 15-27 parts of 1, 6-hexanediamine, 10-18 parts of potassium hydroxide and 1750-3150 parts of deionized water in parts by mole; dividing 1750-3150 parts of deionized water into four parts according to the volume ratio of 3:4:3:2, and sequentially preparing deionized water I, deionized water II, deionized water III and deionized water IV;
b. mixing 10-18 parts of potassium hydroxide weighed in the step one with deionized water I to prepare a potassium hydroxide solution;
c. mixing 1 part of the gallium trioxide weighed in the step one with deionized water II to obtain gallium trioxide suspension, adding the gallium trioxide suspension into the potassium hydroxide solution obtained in the step one under the condition of stirring, and dissolving to obtain solution A;
d. mixing 15-27 parts of 1, 6-hexamethylene diamine weighed in the step one with deionized water III to obtain a 1, 6-hexamethylene diamine solution; adding a 1, 6-hexamethylene diamine solution into the solution A obtained in the step one c under the condition of stirring to obtain a solution B;
e. mixing 50-90 parts of silicon source weighed in the step one with deionized water IV to obtain a silicon source suspension, adding the silicon source suspension into the solution B obtained in the step one under the condition of stirring, and stirring for 1-3 hours to obtain mixed gel;
secondly, crystallization: and (3) placing the mixed gel in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, dynamically crystallizing for 10-48 h at the temperature of 145-185 ℃ and at the rotating speed of 60-180 r/min, cooling to 25 ℃, then sequentially centrifuging, washing and drying, then placing in a muffle furnace, and roasting for 3-20 h at the temperature of 500-700 ℃ to obtain the Ga in-situ isomorphous substituted nano GaZSM-22 molecular sieve.
2. The method for synthesizing Ga isomorphous substituted nanometer GaZSM-22 molecular sieve according to claim 1, wherein in step one a, the atomic ratio of Si in the silicon source to Ga in the gallium sesquioxide is 25-45: 1.
3. The method for synthesizing the Ga isomorphous substituted nanometer GaZSM-22 molecular sieve according to claim 2, wherein the silicon source in the first step a is silica sol with a mass fraction of 20.0-40.0%.
4. The method for synthesizing Ga isomorphous substituted nanometer GaZSM-22 molecular sieve according to claim 1, wherein the dynamic crystallization is carried out for 12 to 36 hours in the second step under the conditions that the temperature is 155 to 165 ℃ and the rotating speed is 80 to 120 r/min.
5. The method for synthesizing Ga isomorphous substituted nanometer GaZSM-22 molecular sieve according to claim 1, wherein the centrifugation in the second step is performed at a rotation speed of 3000r/min to 5000r/min for 5min to 10 min.
6. The method for synthesizing the Ga isomorphous substituted nanometer GaZSM-22 molecular sieve according to claim 5, wherein the washing condition in the second step is that washing is carried out 3-5 times by using twice deionized water.
7. The method for synthesizing the Ga isomorphous substituted nanometer GaZSM-22 molecular sieve according to claim 6, wherein the drying treatment in the second step is carried out for 12 hours at a temperature of 100-120 ℃.
8. The method according to claim 1, wherein the Ga isomorphously substituted nanometer GaZSM-22 molecular sieve in the second step is a rod-shaped nanocrystal with a particle size of 20nm to 50nm and a grain length of 50nm to 100 nm.
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