阅读说明：本技术 一种提高zsm-11分子筛合成收率的方法及所得烷基化催化剂 (Method for improving synthesis yield of ZSM-11 molecular sieve and obtained alkylation catalyst ) 是由 刘旭光 孔祥友 聂鹏飞 于 2021-08-04 设计创作，主要内容包括：本发明提供一种提高ZSM-11分子筛合成收率的方法及所得烷基化催化剂。该方法由硅源、铝源、无机碱、微孔模板剂、晶体合成助剂(氧化石墨烯)充分混合所得凝胶经静置水热晶化制得ZSM-11分子筛。该合成过程迅速,相同条件下能显著缩短晶化时间,提高合成收率,其合成收率达到66-98％。本发明以氧化石墨烯作为晶化合成助剂,合成所得分子筛中,氧化石墨烯嵌入在所得ZSM-11分子筛中,所得ZSM-11分子筛在催化苯与乙醇的烷基化反应中,表现出优异的稳定性,最低失活速率常数k-(d)(％/h)≤-0.04。(The invention provides a method for improving the synthesis yield of a ZSM-11 molecular sieve and an obtained alkylation catalyst. The method comprises the steps of fully mixing a silicon source, an aluminum source, an inorganic base, a microporous template agent and a crystal synthesis auxiliary agent (graphene oxide) to obtain gel, and standing for hydrothermal crystallization to obtain the ZSM-11 molecular sieve. The synthesis process is rapid, the crystallization time can be obviously shortened under the same conditions, the synthesis yield is improved, and the synthesis yield reaches 66-98%. According to the invention, graphene oxide is used as a crystallization synthesis auxiliary agent to synthesize the obtained molecular sieve, the graphene oxide is embedded in the obtained ZSM-11 molecular sieve, and the obtained ZSM-11 molecular sieve shows excellent stability and lowest inactivation in the alkylation reaction of catalytic benzene and ethanolRate constant k d (％/h)≤‑0.04。)

1. A method for improving the synthesis yield of a ZSM-11 molecular sieve is characterized by comprising the following steps: adding a crystal synthesis auxiliary agent graphene oxide into a ZSM-11 synthesis system.

2. The method of claim 1, wherein a surfactant is added to the ZSM-11 synthesis system to produce a high yield ZSM-11 molecular sieve with a layered packing structure.

3. The method of claim 1, wherein: the particle size of the graphene oxide powder is 0.5-5 mu m, the thickness of the graphene oxide powder is 1-3nm, 4g of graphite oxide is dispersed in 1L of deionized water, and ultrasonic dispersion is carried out until the graphene oxide is completely stripped into a single layer, so that a graphene oxide aqueous solution is obtained.

4. The method of claim 1, wherein: the mol ratio of each material in the ZSM-11 synthesis system is as follows: the silicon source, the aluminum source, the inorganic alkali, the template agent and the deionized water comprise the following components in mole percentage: 1.0 (0.023-0.048): 0.25-0.64): 15; the mass ratio of the graphene oxide to the silicon dioxide is as follows: GO/SiO₂＝0.05-2.5％。

5. The method of claim 1, wherein: the method comprises the following specific steps:

firstly, preparing a precursor synthetic solution:

uniformly mixing a silicon source, an aluminum source, inorganic base, a template agent, deionized water, a crystal growth promoter and a surfactant, adding a crystal synthesis aid graphene oxide, and fully stirring and mixing to form a precursor synthesis solution; wherein the silicon source is SiO₂In amount of (1), an aluminum source (in terms of Al)₂O₃Amount of (d), inorganic base (Me)₂O, Me ═ alkali metal ion in terms of moles of alkali metal ion), template agent, deionized water, surfactant, crystal growth promoter in a molar ratio of 1.0 (0.023 to 0.048): (0.023-0.048): (0.25-0.64): 15: 0.05: (1.0-3.0), graphene oxide and silicon dioxide (SiO)₂) Mass ratio of GO to SiO₂0.05-2.5 wt.%; the silicon source is positive siliconEthyl acetate (TEOS); the aluminum source is sodium aluminate (Na)₂O·Al₂O₃·3H₂O); the inorganic base is sodium hydroxide (Na)₂O·H₂O); the template is tetrabutylammonium hydroxide (TBAOH, 25% aqueous solution); the crystal synthesis auxiliary agent is Graphene Oxide (GO) dispersion liquid (4 g/L); the surfactant is quaternary ammonium salt cellulose; the synthetic auxiliary agent is N-methylpyrrolidone (NMP);

secondly, synthesizing liquid crystal by the precursor:

placing the precursor synthetic liquid obtained in the first step into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and performing static crystallization for 6-72h at the temperature of 160-175 ℃;

step three, obtaining a product:

and cooling the product, and then centrifuging, washing, drying and removing the template agent to obtain the ZSM-11 molecular sieve.

6. The method of claim 1, wherein: the GO embedding efficiency in the product is more than or equal to 90 percent, the synthesis yield of the added GO under the same reaction condition is at least 3 percent higher than that of the ZSM-11 molecular sieve without the added GO, and the crystallization time under the same yield condition is at least shortened by more than 20 percent.

7. An alkylation catalyst, characterized in that it is obtained by a process according to any one of claims 1 to 6.

8. Use of a ZSM-11 molecular sieve, obtained by the process of any of claims 1-6, as an alkylation catalyst; deactivation rate constant k in the catalytic alkylation of benzene with ethanol_d(％/h)≤-0.04。

9. The use according to claim 8, characterized in that the process of catalyzing the alkylation of benzene with ethanol is: firstly, activating the ZSM-11 molecular sieve obtained by the method of any one of claims 1 to 6 to obtain an acidic ZSM-11 molecular sieve, loading 1.5g of the acidic ZSM-11 molecular sieve into a die, placing the die into a tablet press after the die is installed, adjusting the pressure to 10MPa, maintaining the pressure for 3min, taking out the pressed molecular sieve sheet from the die, and placing the molecular sieve sheet into an agate mortar; then, gently grinding the molecular sieve sheet; sieving the grinded molecular sieve particles to obtain particles of 40-60 meshes; filling 0.35g of sieved particles into a quartz tube with the inner diameter of 8mm, and after the whole reactor is assembled, detecting leakage at a joint to ensure that the whole system is complete in tightness; then opening the gas flow to 40mL/min, heating the temperature of the reaction furnace to 350 ℃, adjusting the temperature of a vaporizer to 80 ℃, activating for 10 hours, and then mixing the components in a molar ratio of benzene: ethanol ═ 1: 1 at a speed of 0.05mL/min, feeding the raw materials into a reaction device;

in the reaction process, the whole reaction temperature is stabilized at 350 ℃; after each reaction for 2 hours, a sample was taken, and the content of each component in the product was analyzed by a gas chromatograph/mass spectrometer.

Technical Field

The invention belongs to the technical field of catalytic chemistry, and particularly relates to a method for improving the synthesis yield of a ZSM-11 molecular sieve and an obtained product.

Background

ZSM-11 was the molecular sieve first developed by Mobil corporation in the early 70 s of the 20 th century, and belongs to the Pentasil type of zeoliteStone, with MEL topology. ZSM-11 belongs to tetragonal system, and has the unit cell parameters as follows: α is 90.000 °, β is 90.000 °, γ is 90.000 °, and the skeleton density isThe pore channels of the ZSM-11 molecular sieve are formed by intersecting oval ten-membered ring two-dimensional straight pore channels (0.51nm multiplied by 0.55 nm). The ZSM-11 molecular sieve has a very unique lattice structure, the silicon-aluminum ratio in a crystal framework is high, and the surface of the crystal has obvious hydrophobic effect and strong acidity, so that the ZSM-11 molecular sieve is an important adsorbent and a good shape-selective acid catalyst. It can be used for toluene-methanol alkylation, meta-xylene isomerization and toluene disproportionation reaction, and benzene and ethylene and ethanol alkylation reaction, etc.

At present, the method for preparing the ZSM-11 molecular sieve is mainly a hydrothermal synthesis method. The hydrothermal synthesis method is to disperse the raw materials of silicon source, aluminum source, template agent, etc. in water, and crystallize for a certain time under the condition of usually higher than 373K and more than one atmospheric pressure to obtain the molecular sieve. The method has the advantages of simple operation and easy implementation. However, in the synthesis process, the synthesis solution is required to form local supersaturation to generate crystal nucleus, and the molecular sieve is formed by continuous growth, mutual fusion and crosslinking. The required heat is provided by conventional external convection or conduction at a slow heating rate (<10K/min), and the traditional heating technology causes that some synthetic samples can be mixed with amorphous phase products and mixed crystals, so that the hydrothermal method preparation process has the problems of long preparation period, high cost, low yield, easy generation of ZSM-5 mixed crystals and the like. Therefore, researchers have been working on the rapid, precise synthesis of ZSM-11 molecular sieves. For example, chinese patent 201810919992.6 discloses a method for promoting synthesis of ZSM-11 molecular sieves, which employs addition of a crystal growth promoter to shorten the crystallization time by dynamic crystallization, but this method can only achieve the highest relative crystallinity after 80 hours of crystallization in fig. 1, and relies on a rotary heating device, which is not favorable for later industrial production, and the obtained ZSM-11 has a low synthesis yield, and the utilization rate of raw materials and the synthesis capacity need to be further improved. Aiming at the existing synthesis method, a preparation method of the ZSM-11 molecular sieve with simpler operation, higher synthesis speed and higher synthesis yield is urgently needed to be developed.

Disclosure of Invention

The invention aims to provide a method for improving the synthesis yield of a ZSM-11 molecular sieve, which can improve the utilization rate of raw materials by adding a crystal synthesis auxiliary agent graphene oxide into a synthesis system, can further shorten the crystallization time under the same reaction condition, and obviously improve the synthesis yield, and the synthesized ZSM-11 molecular sieve has the advantages of short crystallization time, high crystallinity, large specific surface area, high synthesis yield and the like.

In order to achieve the purpose, the invention adopts the technical scheme that:

a method for improving the synthesis yield of a ZSM-11 molecular sieve is characterized in that graphene oxide is introduced into a synthesis system of the ZSM-11 molecular sieve as a crystal synthesis auxiliary agent. Graphene oxide is an oxide of graphene, is a carbon material having a layered structure, and has a surface rich in oxygen-containing functional groups, such as hydroxyl groups, epoxy groups, and carboxyl groups, after oxidation. In the ZSM-11 molecular sieve synthesis gel, graphene oxide can adsorb components such as a template agent, a silicon precursor and the like, and can act synergistically with the components in a static reaction system, so that the synthesis of the molecular sieve can be accelerated, the synthesis rate of the molecular sieve is improved, and meanwhile, the higher synthesis yield of the molecular sieve can be ensured.

The method for improving the synthesis yield of the ZSM-11 molecular sieve comprises the following specific steps:

firstly, preparing a precursor synthetic solution:

uniformly mixing a silicon source, an aluminum source, inorganic base, a template agent, deionized water, a crystal growth promoter and a surfactant, adding a crystal synthesis aid graphene oxide, and fully stirring and mixing to form a precursor synthesis solution; wherein the silicon source is SiO₂In amount of (1), an aluminum source (in terms of Al)₂O₃Amount of (d), inorganic base (Me)₂O, Me is an alkali metal ion, as alkali metalThe mole number of ions), the mole ratio of the template agent, the deionized water, the surfactant and the crystal growth promoter is 1.0 (0.023-0.048): (0.023-0.048): (0.25-0.64): 15: 0.05: (1.0-3.0), graphene oxide and silicon dioxide (SiO)₂) Mass ratio of GO to SiO₂0.05-2.5 wt.%; the silicon source is Tetraethoxysilane (TEOS); the aluminum source is sodium aluminate (Na)₂O·Al₂O₃·3H₂O); the inorganic base is sodium hydroxide (Na)₂O·H₂O); the template is tetrabutylammonium hydroxide (TBAOH, 25% aqueous solution); the crystal synthesis auxiliary agent is Graphene Oxide (GO) dispersion liquid (4 g/L); the surfactant is quaternary ammonium cellulose; the synthetic auxiliary agent is N-methylpyrrolidone (NMP);

secondly, synthesizing liquid crystal by the precursor:

placing the precursor synthetic liquid obtained in the first step into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and performing static crystallization for 6-72h at the temperature of 160-175 ℃;

step three, obtaining a product:

and cooling the product, and then centrifuging, washing, drying and removing the template agent to obtain the ZSM-11 molecular sieve.

The mass ratio of the graphene oxide to the silicon dioxide is preferably: GO/SiO₂0.07%, 0.12%, 0.17%, 0.18%, 1.0%, 1.7%, 1.8%, etc. may be used.

The crystal synthesis auxiliary agent is Graphene Oxide (GO) dispersion liquid (4g/L), and the preparation method comprises the following steps: dispersing 4g of graphite oxide in 1L of deionized water, and performing ultrasonic dispersion for 24 hours; the surfactant is quaternary ammonium salt cellulose (such as JR-400).

The invention also protects the application of the ZSM-11 molecular sieve, and the molecular sieve is activated by the specific process: by the ion exchange technology, sodium ions in the ZSM-11 molecular sieve synthesized by the method can be replaced by other cations, so that the acidic ZSM-11 molecular sieve is obtained and is applied to the alkylation reaction process of benzene and ethanol.

The activated molecular sieve is used in the alkylation reaction of benzene and ethanol, and the specific process is as follows: firstly, 1.5g of acidic ZSM-11 molecular sieve is filled into a die, after the die is installed, the die is put into a tablet machine, the pressure is adjusted to 10MPa, and after the pressure is maintained for 3min, the molecular sieve sheet is taken out of the die and put into an agate mortar. Then, the molecular sieve pieces were gently ground. And sieving the grinded molecular sieve particles to obtain particles of 40-60 meshes. And (3) filling 0.35g of the catalyst particles into a quartz tube with the inner diameter of 8mm, and after the whole reactor is assembled, detecting leakage at a joint to ensure that the whole system is complete in tightness. Then opening the gas flow to 40mL/min, heating the temperature of the reaction furnace to 350 ℃, adjusting the temperature of a vaporizer to 80 ℃, activating for 10 hours, and then mixing the components in a molar ratio of benzene: ethanol ═ 1: 1 was fed to the reaction apparatus at a rate of 0.05 mL/min. During the reaction, the entire reaction temperature was stabilized at 350 ℃. After each reaction for 2 hours, a sample was taken, and the content of each component in the product was analyzed by a gas chromatograph/mass spectrometer.

And simultaneously adding a surfactant into a ZSM-11 synthesis system to prepare the high-yield ZSM-11 molecular sieve with the layered stack structure.

The GO embedding efficiency in the product is more than or equal to 90 percent, the synthesis yield of the added GO under the same reaction condition is at least 3 percent higher than that of the ZSM-11 molecular sieve without the added GO, and the crystallization time under the same yield condition is at least shortened by more than 20 percent.

Compared with the prior art, the invention has the beneficial effects that:

the method is simple and easy to realize, and compared with the conventional ZSM-11 molecular sieve, the method improves the synthesis yield of the molecular sieve, accelerates the synthesis speed of the molecular sieve and improves the catalytic performance of the molecular sieve. By adopting the technology of the invention, under the same crystallization time, the yield of the ZSM-11 molecular sieve is increased, for example, the highest yield of added GO can reach 98%, and under the same conditions, the yield of added GO is only 92%. Furthermore, in the case of obtaining similar yields (91-92%), such as example 4 and comparative example 1, the crystallization time required for the GO-added ZSM-11 molecular sieve was reduced by 48 h. The yield calculation method comprises the following steps: actual yield ═ M_ZSM-11/M_SiO2)*100％，M_ZSM-11The mass of the ZSM-11 molecular sieve finally obtained; m_SiO2Adding SiO into the reaction system₂The mass of (c); the embedding efficiency calculation method comprises the following steps: embedding efficiency ═ W_GO-ZSM-11/W_GO)*100％,W_GO-ZSM-11Is the mass entering the molecular sieve; w_GOThe mass of GO added to the reaction system. The deactivation rate constant of the ZSM-11 molecular sieve without the graphene oxide is generally-0.122%/h, and the molecular sieve prepared by the method can obviously reduce the deactivation rate.

The method creatively further improves the synthesis yield of the ZSM-11 molecular sieve and obviously shortens the synthesis time of the ZSM-11 molecular sieve for the first time in a mode of adding the graphene oxide. Meanwhile, the cationic surfactant is introduced, so that the crystal molecular sieve in the shape of a sphere-like accumulation can be obtained under the high-temperature reaction condition, and the catalytic reaction is favorably carried out. In addition, graphene oxide has specificity to the ZSM-11 molecular sieve, the molecular sieve synthesis gel can be attached to the surface of the graphene oxide through interaction force, and finally the graphene oxide can be embedded into the molecular sieve, so that the utilization rate of raw materials is improved, and the synthesis time of the molecular sieve is shortened.

Drawings

FIG. 1 is an XRD spectrum of the molecular sieve obtained in example 1;

FIG. 2 is an SEM photograph of the molecular sieve obtained in example 1.

Detailed Description

The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention.

Example 1

Under stirring conditions, 150.8g tetrabutylammonium hydroxide (25% aqueous solution), 0.676g sodium hydroxide (96.0 wt.% NaOH), 2.08g sodium aluminate (more than or equal to 90 wt.%), 133.64g azomethylpyrrolidone (more than or equal to 99 wt.%), 89g ethyl orthosilicate (more than or equal to 99 wt.%), and a surfactant were sequentially added to a beaker in the above order, and after hydrolysis at 75 ℃ for two hours, a homogeneous mixed sol was formed. Then, adding 7mL of graphene aqueous solution (4g of graphite oxide is dispersed in 1L of deionized water, ultrasonic dispersion is carried out for 24h, the particle size of graphite oxide powder is required to be 0.5-5 μm, the thickness is required to be 1-3nm, the graphite oxide powder is stripped into a single layer under the action of ultrasonic dispersion and is easily embedded into a molecular sieve), and fully mixing the graphite oxide powder and the molecular sieve to obtain a precursor synthetic solution. Pouring the obtained precursor synthetic solution into a reaction kettle, sealing the reaction kettle, and standing and crystallizing for 72 hours at 175 ℃.

The molar composition of the raw material mixture in this example was: 1.0SiO₂:0.023Al₂O₃:0.048Na₂O:0.64TBAOH:15H₂O0.05 JR-400 (cationic hydroxyethylcellulose) 3.0NMP and GO/SiO₂(mass ratio) 0.1%.

The reaction was quenched with tap water and centrifuged to obtain a solid product. Then washing with deionized water to neutrality. Drying at 70 ℃ overnight to obtain molecular sieve raw powder. After the template agent is removed, the yield of the molecular sieve is measured to be 98%. The ZSM-11 type molecular sieve prepared by the method is subjected to repeated experiments for three times, and the yield error of the prepared molecular sieve is not more than 2%.

XRD characterization and analysis (see figure 1) shows that the obtained product is ZSM-11 molecular sieve. SEM analysis, see figure 2, shows particle size of 2.5-3.5 μm, and is composed of 20-100nm grains, and no distinct GO phase (graphene oxide). This indicates that GO is embedded in the ZSM-11 molecular sieve.

Comparative example 1

The steps and raw materials of the comparative example are the same as those of example 1, except that graphene oxide is not added in the preparation process. After crystallization by standing at 175 ℃ for 72 hours, the ZSM-11 yield was measured to be 92%, and the yield was substantially constant with the time of crystallization, which was the maximum yield.

This comparative example illustrates the slow synthesis rate without addition of graphene oxide, compared to the synthesis yield of 98% in example 1.

Example 2

The steps and raw materials in this example are the same as example 1, except that 3.5mL of graphene oxide aqueous solution, GO/SiO₂(mass ratio) 0.05%, and the yield of ZSM-11 was 95%.

The synthesis yield of the example and the example 1 is increased compared with that of the comparative example 1, which shows that the synthesis of the ZSM-11 can be promoted by adding the graphene oxide under the same conditions.

Example 3

Under stirring conditions, 150.8g tetrabutylammonium hydroxide (25% aqueous solution), 0.676g sodium hydroxide (96.0 wt.% NaOH), 2.08g sodium aluminate (more than or equal to 90 wt.%), 133.64g azomethylpyrrolidone (more than or equal to 99 wt.%), 89g ethyl orthosilicate (more than or equal to 99 wt.%), and a surfactant were sequentially added to a beaker in the above order, and after hydrolysis at 75 ℃ for two hours, a homogeneous mixed sol was formed. Then, 35.2mL of graphene aqueous solution (4g of graphite oxide is dispersed in 1L of deionized water, ultrasonic dispersion is carried out for 24h, the particle size of graphite oxide powder is required to be 0.5-5 μm, the thickness is required to be 1-3nm, the graphite oxide powder is stripped into a single layer under the action of ultrasonic dispersion and is easily embedded into a molecular sieve) is added into the mixed sol, and the precursor synthetic solution is fully mixed to obtain the precursor synthetic solution. Pouring the obtained precursor synthetic solution into a reaction kettle, sealing the reaction kettle, and standing and crystallizing at 175 ℃ for 60 hours.

The molar composition of the raw material mixture in this example was: 1.0SiO₂:0.023Al₂O₃:0.048Na₂O:0.64TBAOH:15H₂O0.05 JR-400 (cationic hydroxyethylcellulose) 3.0NMP and GO/SiO₂(mass ratio) 0.5%.

The reaction was quenched with tap water and centrifuged to obtain a solid product. Then washing with deionized water to neutrality. Drying at 70 ℃ overnight to obtain molecular sieve raw powder. After the template agent is removed, the yield of the molecular sieve is measured to be 92%. The ZSM-11 type molecular sieve prepared by the method is subjected to repeated experiments for three times, and the yield error of the prepared molecular sieve is not more than 2%. The XRD and SEM analysis results of the obtained ZSM-11 molecular sieve are similar to those of example 1.

Compared with the comparative example 1, the reaction raw materials and conditions are the same, except that the maximum yield of the ZSM-11 can be achieved by adding more graphene oxide and crystallizing at 175 ℃ for 60 hours, and the time for achieving the maximum yield is obviously shortened compared with the comparative example 1, and the result shows that the addition of the graphene oxide can promote the synthesis of the ZSM-11.

Comparative example 2

The steps and raw materials of the comparative example are the same as those of example 3, except that graphene oxide is not added in the preparation process. After standing crystallization at 175 ℃ for 60h, the ZSM-11 yield was measured to be 86%, which compared to the 92% synthesis yield in example 3, illustrates the slow synthesis rate of ZSM-11 without added graphene oxide.

Examples 4 to 7

The steps and raw materials of examples 4-7 are the same as example 3, except that the crystallization time is 24h, 12h, 9h and 6h, respectively, and the corresponding ZSM-11 yields are 91%, 89%, 79% and 66%, respectively. This example examines the synthesis yields at different crystallization times. The ZSM-11 type molecular sieve prepared by the method is subjected to repeated experiments for three times, and the yield error of the prepared molecular sieve is not more than 2%. The XRD results of the resulting ZSM-11 molecular sieve were similar to those of example 1.

Comparative examples 3 to 6

The steps and raw materials of the comparative example are the same as those of examples 4 to 7, except that graphene oxide is not added in the preparation process. The crystallization times of comparative examples 3 to 6 were set to correspond to those of examples 4 to 7, and comparative examples 2 to 6 were set to 60h, 24h, 12h, 9h, and 6h, respectively, and the corresponding yields of ZSM-11 were 86%, 82%, 77%, 72%, and 56%, respectively.

The comparison between the comparative examples 3 to 6 and the examples 4 to 7 shows that the crystallization yield of the graphene under the same reaction condition is remarkably improved under different crystallization time conditions under the same crystallization time, and the synthesis speed of the graphene is not increased. The method can enable the reaction system to reach the maximum yield as soon as possible, obviously shortens the crystallization reaction time, and promotes the synthesis of the ZSM-11 molecular sieve.

Example 8

The steps and materials of this example were the same as example 3 except that the crystallization temperature was 160 ℃ and the crystallization time was 72 hours. ZSM-11 was metered in a yield of 83%. The ZSM-11 type molecular sieve prepared by the method is subjected to repeated experiments for three times, and the yield error of the prepared molecular sieve is not more than 2%.

Comparative example 7

The procedure and materials of this comparative example were the same as those of example 8 except that no graphene oxide was added and the yield of ZSM-11 was 80%. This comparative example illustrates the slow synthesis rate of ZSM-11 without the addition of graphene oxide.

Example 9

This example synthesizes a ZSM-5 type molecular sieve, the procedure is the same as example 1 except that the templating agent TBAOH is replaced by TPAOH, and the yield of ZSM-5 is measured to be 68%.

Comparative example 8

The procedure is as in example 9 except that no graphene oxide is added and the yield of the ZSM-5 is 70%. Compared with the synthesis yield of 68% in example 9, the synthesis yield is not obviously affected by adding the graphene oxide in the synthesis process of the ZSM-5 molecular sieve, and even the synthesis of the molecular sieve is inhibited.

Example 10

This example synthesizes a molecular sieve of type TS-1 by the following procedure. Firstly, weighing 55g of ultrapure water and 48.8g of TPAOH, adding the ultrapure water and the TPAOH into a beaker, putting the beaker filled with a mixed solution of water and a template agent into a constant-temperature water bath kettle, heating the beaker in a stirring water bath to 80 ℃, dropwise adding 16g of half silicon source tetraethoxysilane into the mixed solution, and fully stirring the mixture; heating at constant temperature for 1h, cooling the system to 0 ℃, and stirring vigorously; mixing 1.8g of titanium source titanium sulfate and 3.5g of complexing agent hydrogen peroxide in an ice-water bath, adding 5ml of deionized water, and dropwise adding the obtained titanium source solution into silica sol after dissolving into a uniform solution; hydrolyzing in ice water bath for 20 minutes, heating to 80 ℃, dropping 16g of the other half silicon source, and hydrolyzing and distilling alcohol to ensure that the final molar composition is TEOS: TPAOH: ti (SO)₄)₂: ultrapure water: h₂O₂1:0.4:0.05:20: 0.15; thereafter, 2.5mL of an aqueous graphene solution was added to the above mixed sol and thoroughly mixed. And (3) putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out static hydrothermal crystallization for 72 hours at 175 ℃ under a sealed condition. The reaction was quenched with tap water and centrifuged to obtain a solid product. Then washing with deionized water to neutrality. Drying at 70 ℃ overnight to obtain molecular sieve raw powder. After the template agent is removed, the yield of the molecular sieve is 76%. The TS-1 type molecular sieve prepared by the method is subjected to a repeatability experiment, the repeatability experiment is repeated three times, and the yield error of the prepared molecular sieve is not more than 2%.

Comparative example 9

The specific implementation steps are the same as those in example 10, except that graphene oxide is not added, and the yield of the measured TS-1 is 76%. Compared with the synthesis yield of 76% in example 10, the synthesis yield of TS-1 is not promoted by adding graphene oxide in the synthesis process of the TS-1 molecular sieve.

The molecular sieves prepared in the above embodiments and comparative examples are all subjected to repeated experiments for three times, and the yield error of the prepared molecular sieve is not more than 2%. XRD is also carried out for characterization, and corresponding molecular sieve samples can be obtained.

TABLE 1 statistics of data

As can be seen from the data in table 1, example 1 is the same as the specific procedure of comparative example 1, except that no GO is added to comparative example 1. The yield of example 1 is higher than that of comparative example 1, and the result shows that the synthesis of ZSM-11 can be promoted by adding GO in the synthesis system. Example 2 the same as example 1 except that 3.5mL of graphene oxide solution was added in example 2, the yield was higher than that of comparative example 1, and the result shows that different amounts of GO can promote the synthesis of ZSM-11. Example 3 is the same as the specific procedure of comparative example 1, except that the GO is added in example 3, and the yield of 60h of crystallization in example 3 is the same as the yield of 72h of crystallization in comparative example 1. Comparative example 2 is the same as example 3 except that comparative example 2 does not have GO added and comparative example 2 yields significantly lower than example 3, the results above show that the addition of GO can promote crystallization.

Examples 4-7 are the same as the specific procedure of example 3 except that the crystallization time is different in examples 4-7, comparative examples 3-6 are the same as the specific procedure of corresponding examples 4-7 except that GO is not added in comparative examples 3-6, and the yield of examples 4-7 is higher than that of corresponding comparative examples 3-6. Comparing example 4 with comparative example 1, the crystallization time required for example 4 with GO addition was shorter, with similar yields (91-92%). The same results were obtained for comparative example 6 and comparative example 4, with a shorter crystallization time for example 6 with the addition of GO, in case of obtaining similar yields (77-79%). Therefore, the yield of the ZSM-11 molecular sieve can be remarkably improved by judging the addition of GO, and the synthesis speed of the ZSM-11 molecular sieve is accelerated.

Example 8 was the same as the specific procedure of example 1 except that the crystallization temperature of example 18 was lowered to 160 deg.c, which resulted in a decrease in product yield, indicating that the crystallization temperature had a significant effect on product yield. Comparative example 7, with no GO addition, had a further reduction in yield, indicating that the addition of GO helped to increase the yield of ZSM-11.

In order to investigate whether the graphene oxide has a promoting effect on the synthesis yield of other types of molecular sieves, ZSM-5 type molecular sieves and TS-1 type molecular sieves are synthesized respectively in the patent. Example 9 and comparative example 8 examine the effect of graphene oxide on the synthesis yield of ZSM-5. Comparative example 8 is the same as the specific procedure of example 9 except that no graphene oxide is added in comparative example 8. The results show that the synthesis yield of ZSM-5 of comparative example 8 is slightly higher than that of ZSM-5 of example 9, and the above results show that the synthesis yield of ZSM-5 cannot be improved by adding graphene oxide. Example 10 and comparative example 9 examine the effect of graphene oxide on the synthesis yield of a TS-1 type molecular sieve. Comparative example 9 is the same as example 10 except that no graphene oxide was added in comparative example 9. Comparative example 9 was the same as the synthesis yield in example 20, and the above results show that the addition of graphene oxide did not improve the synthesis yield of TS-1. Different types of molecular sieves have different synthesis raw materials and different pore channel structures, so that the interaction force between graphene and synthesis gel is different, the graphene oxide and the ZSM-11 molecular sieve have specific matching property, the synthesis of the ZSM-11 molecular sieve can be obviously promoted, the synthesis yield is improved, the reaction time is shortened, and the catalyst more beneficial to alkylation catalytic reaction is obtained.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.