阅读说明：本技术 一种形貌可控kl分子筛的合成方法及应用 (Synthesis method and application of KL molecular sieve with controllable morphology ) 是由 王树元 高亚 徐丹 朱地 赵保峰 宋安刚 冯翔宇 于 2021-09-27 设计创作，主要内容包括：本发明属于分子筛催化技术领域,具体涉及一种形貌可控KL分子筛的合成方法及应用,为了解决现有技术中烷基芳烃产物在KL分子筛中的扩散速率受到极大的限制的问题,所述合成方法包括：将铝源和钾源混合制备前驱体；而后将硅源和分子筛改性剂混合液加入所述前驱体溶液得到初始溶胶,持续搅拌老化、晶化和焙烧,即得到KL分子筛；通过调节分子筛改性剂的种类或硅源与分子筛改性剂的添加比例调节KL分子筛的形貌。该分子筛可以改善烷基芳烃产物在分子筛孔道中的扩散速率,采用原子层沉积负载Pt等金属制备烷烃芳构化催化剂,在正构烷烃芳构化反应中有效减少二次氢解副反应的发生,具有优异的烷烃重整制芳烃性能。(The invention belongs to the technical field of molecular sieve catalysis, and particularly relates to a synthesis method and application of a KL molecular sieve with a controllable morphology, aiming at solving the problem that the diffusion rate of an alkyl aromatic hydrocarbon product in the KL molecular sieve is greatly limited in the prior art, the synthesis method comprises the following steps: mixing an aluminum source and a potassium source to prepare a precursor; then adding the mixed solution of a silicon source and a molecular sieve modifier into the precursor solution to obtain initial sol, and continuously stirring, aging, crystallizing and roasting to obtain a KL molecular sieve; the morphology of the KL molecular sieve is adjusted by adjusting the type of the molecular sieve modifier or the adding ratio of the silicon source to the molecular sieve modifier. The molecular sieve can improve the diffusion rate of alkyl aromatic hydrocarbon products in molecular sieve pore passages, and the atomic layer deposition loading Pt and other metals are adopted to prepare the alkane aromatization catalyst, so that secondary hydrogenolysis side reaction is effectively reduced in the normal alkane aromatization reaction, and the molecular sieve has excellent performance of preparing aromatic hydrocarbon by alkane reforming.)

1. A synthetic method of a KL molecular sieve with a controllable morphology is characterized by comprising the following steps: mixing an aluminum source and a potassium source to prepare a precursor; then adding the mixed solution of a silicon source and a molecular sieve modifier into the precursor solution to obtain initial sol, and continuously stirring, aging, crystallizing and roasting to obtain a KL molecular sieve; the morphology of the KL molecular sieve is adjusted by adjusting the type of the molecular sieve modifier or the adding ratio of the silicon source to the molecular sieve modifier.

2. The method for synthesizing a KL molecular sieve with controllable morphology according to claim 1, wherein the molecular sieve modifier is n-butylamine, propylamine, 1,2, 6-hexanetriol, 1, 5-pentanediol, ethanol, n-propanol, isopropanol, n-butanol, cyclohexane, diethyl ether, triethylene or tributylphosphine.

3. The method for synthesizing a KL molecular sieve with controllable morphology according to claim 1, wherein the molar ratio of the silicon source to the molecular sieve modifier is 1: 0.1-100; or the aluminum source is aluminum sulfate or aluminum hydroxide; or, the potassium source is potassium hydroxide, potassium nitrate, potassium silicate, or potassium sulfate; or, the silicon source is silicon dioxide sol, potassium silicate or sodium silicate.

4. The method for synthesizing a KL molecular sieve with controllable morphology according to claim 1, wherein the method specifically comprises the following steps: (1) mixing an aluminum source, a potassium source and water to obtain a mixed solution 1, and continuously stirring for 5-50min at normal temperature; (2) mixing a silicon source, water and a molecular sieve modifier to obtain a mixed solution 2, and continuously stirring for 5-50min at normal temperature; (3) adding the mixed solution 2 into the mixed solution 1, and continuously stirring for 2-20h at room temperature.

5. The method for synthesizing KL molecular sieve with controllable morphology as claimed in claim 4, wherein the molar ratio of the aluminum source, the potassium source and the water in the mixed solution 1 is 1 (5-20): (500) -1500; or, in the mixed solution 2, the mole ratio of the silicon source to the molecular sieve modifier is 1 (100) -200: 0.1-100; or, the crystallization time is 3-7 days, and the temperature is 130-; or, the roasting time is 4h, and the temperature is 450-600 ℃.

6. The method for synthesizing a KL molecular sieve with controllable morphology according to any one of claims 1 to 5, wherein the molecular sieve modifier is n-butylamine, propylamine, 1,2, 6-hexanetriol or 1, 5-pentanediol, and the molar ratio of the silicon source to the molecular sieve modifier is 1:0.1-100 to obtain a cylindrical KL molecular sieve;

or the molecular sieve modifier is ethanol, n-propanol, isopropanol or n-butanol, and the molar ratio of the silicon source to the molecular sieve modifier is 1:0.1-100 to obtain a coin-shaped KL molecular sieve;

or the molecular sieve modifier is cyclohexane, diethyl ether, triethylene or tributylphosphine, and the molar ratio of the silicon source to the molecular sieve modifier is 1:0.1-100 to obtain the double-cone KL molecular sieve.

7. A KL molecular sieve is characterized by being prepared by adopting the synthesis method of the KL molecular sieve with the controllable morphology according to claim 6, wherein the morphology of the KL molecular sieve is a cylindrical KL molecular sieve, a coin-shaped KL molecular sieve or a double-cone-shaped KL molecular sieve; preferably, the KL molecular sieve is a coin-shaped KL molecular sieve.

8. A catalyst, characterized in that the catalyst uses the KL molecular sieve of claim 7 as a carrier, and the supported metal is at least one of Pt, Pd, Fe, Sn, Co or Zn.

9. A method for preparing a catalyst, which is characterized in that atomic layer deposition is adopted to load metal on the KL molecular sieve in the claim 7.

10. Use of the KL molecular sieve of claim 7 and/or the catalyst of claim 8 and/or the catalyst of claim 9 for the preparation of aromatics by reforming alkanes.

Technical Field

The invention belongs to the technical field of molecular sieve catalysis, and particularly relates to a synthesis method and application of a KL molecular sieve with a controllable morphology.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

Light aromatics such as benzene, toluene and xylene (BTX) are used as basic organic chemical raw materials and have important position in the fields of fine chemical industry and petrochemical industry. BTX aromatic hydrocarbon is mainly prepared by catalytic reforming, and the catalyst used in the reaction process mainly comprises Pt/Al catalyst commonly used in industry₂O₃A catalyst system. Researches find that the Pt loaded KL molecular sieve catalyst has higher catalyst activator aromatic hydrocarbon selectivity for catalytically reforming long linear alkane containing carbon number C6-C8 to generate light aromatic hydrocarbon.

Pt/KL is a well-known monofunctional catalytic system, and alkane reacts on an active site completely provided by metal Pt, so that cracking and isomerization reactions caused by acidity are avoided. Although the catalyst has excellent catalytic performance, the aromatization performance of the Pt/KL catalyst on high-carbon alkane (such as n-octane) is poor due to the diffusion limitation of the one-dimensional linear pore channel structure of the KL molecular sieve. The morphology and grain size regulation, pore structure optimization, framework composition regulation and the like of the KL molecular sieve have important influence on the catalytic performance of the KL molecular sieve, and the limitation of molecular sieve pores on the diffusion rate of products and reactants can be improvedWhile optimizing the metallic function of Pt. The patent CN108033462A adopts a hydrothermal synthesis method, and a KL molecular sieve with a hierarchical pore structure is prepared by adding polyethylene glycol (PEG), so that the mesoporous size can be regulated and controlled within the range of 2-7 nm, the diffusion speed of reactants and products in a pore channel is improved, secondary side reaction of the products is avoided, and the yield of aromatic hydrocarbon is improved. Patent CN106395851A by adding Ba²⁺The KL molecular sieve containing Ba heteroatom is prepared by ions, and the KL molecular sieve is favorable for the diffusion of reactants and products in the pore channels of the KL molecular sieve due to the smaller grain size, and has obviously improved yield of C8 aromatic hydrocarbon in the aromatization reaction of normal paraffin. The catalyst of the modified KL molecular sieve loaded with metal Pt has better catalytic effect.

However, the inventors found that the diffusion rate of the alkylaromatic hydrocarbon product in the existing KL molecular sieve is greatly limited, and byproducts are easily generated in the alkane aromatization reaction, thereby reducing the performance of alkane reforming for preparing aromatic hydrocarbon. Therefore, how to solve the above problems becomes a key to improve the effect of producing aromatics by reforming alkanes.

Disclosure of Invention

In order to solve the defects of the prior art, the invention provides a synthesis method and application of a KL molecular sieve with a controllable shape, the molecular sieve presents different shape structures (such as coin-shaped) and can improve the diffusion rate of alkyl aromatic hydrocarbon products in a molecular sieve pore channel, and the alkane aromatization catalyst is prepared by loading metals such as Pt and the like through atomic layer deposition, so that the secondary hydrogenolysis side reaction is effectively reduced in the normal alkane aromatization reaction, and the excellent performance of preparing aromatic hydrocarbon through alkane reforming is realized.

Specifically, the invention is realized by the following technical scheme:

in a first aspect of the present invention, a method for synthesizing a KL molecular sieve with controllable morphology includes: mixing an aluminum source and a potassium source to prepare a precursor; then adding the mixed solution of a silicon source and a molecular sieve modifier into the precursor solution to obtain initial sol, and continuously stirring, aging, crystallizing and roasting to obtain a KL molecular sieve; the morphology of the KL molecular sieve is adjusted by adjusting the type of the molecular sieve modifier or the adding ratio of the silicon source to the molecular sieve modifier.

In the second aspect of the invention, the KL molecular sieve is prepared by adopting the synthesis method of the KL molecular sieve with the controllable morphology, and the morphology of the KL molecular sieve is a cylindrical KL molecular sieve, a coin-shaped KL molecular sieve or a biconical KL molecular sieve; preferably, the KL molecular sieve is a coin-shaped KL molecular sieve.

In a third aspect of the present invention, the KL molecular sieve is used as a carrier of the catalyst, and the supported metal is at least one of Pt, Pd, Fe, Sn, Co, or Zn.

In the fourth aspect of the present invention, a preparation method of the catalyst is to load metal on the KL molecular sieve by atomic layer deposition.

In the fifth aspect of the present invention, the KL molecular sieve and/or the catalyst and/or the preparation method of the catalyst are/is applied to a reaction for preparing aromatic hydrocarbon by alkane reforming.

One or more embodiments of the present invention have the following advantageous effects:

(1) the molecular sieve modifier is added under the in-situ synthesis condition to regulate the crystallization process of the KL molecular sieve, so that the aim of regulating the morphology of the molecular sieve is fulfilled.

(2) By modulating aluminum source (aluminum sulfate) and adding molecular sieve modifiers (ethanol and isopropanol), the growth of the KL molecular sieve in the [001] direction can be controlled, so that the coin-shaped KL molecular sieve is obtained, the molecular sieve can effectively reduce diffusion barrier of reactant and product molecules in a molecular sieve pore channel, the reaction rate and the product selectivity are improved, and side reactions are reduced.

(3) The drop site of metal on the KL molecular sieve is controlled by adopting atomic layer deposition, the drop site of active metal can be regulated and controlled at the atomic level, and the activity and the utilization rate of the metal are further improved. KL molecular sieves with different shapes have larger influence on the position and electronic properties of metal, and the prepared catalyst has better catalytic activity and aromatic selectivity when used for alkane reforming.

(4) The obtained coin-shaped KL molecular sieve can reduce the diffusion process of a metal precursor in the atomic layer deposition process, is favorable for obtaining a molecular sieve loaded metal catalyst with more uniform dispersion, and can obtain more electrons from molecular sieve coordinated K ions because highly dispersed metal is more fully contacted with molecular sieve pore channels, and metal in an electron-rich state is more favorable for the alkane reforming process so as to obtain the catalyst with higher activity and product selectivity.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:

figure 1 is an SEM photograph of comparative example 1 for the preparation of a conventional KL molecular sieve.

Figure 2 is an XRD pattern of comparative example 1 for preparing a conventional KL molecular sieve.

Fig. 3 is an SEM photograph of example 1 for preparing a cylindrical KL molecular sieve.

Figure 4 is an XRD pattern of example 1 for preparing cylindrical KL molecular sieve.

Figure 5 is an SEM photograph of the coin-shaped KL molecular sieve prepared in example 2.

Figure 6 is an XRD pattern of the KL molecular sieve coin-like prepared in example 2.

Fig. 7 is an SEM photograph of the double-tapered KL molecular sieve prepared in example 3.

Figure 8 is an XRD pattern of the double-tapered KL molecular sieve prepared in example 3.

Fig. 9 is an SEM photograph of the coin-shaped KL molecular sieve prepared in example 4.

Figure 10 is an XRD pattern of the KL molecular sieve coin-like prepared in example 4.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

At present, the diffusion rate of alkyl aromatic hydrocarbon products in the existing KL molecular sieve is greatly limited, byproducts are easily generated in alkane aromatization reaction, and the performance of preparing aromatic hydrocarbon by alkane reforming is reduced. Therefore, the invention provides a synthesis method and application of the KL molecular sieve.

In one or more embodiments of the present invention, a method for synthesizing a KL molecular sieve with controllable morphology includes: mixing an aluminum source and a potassium source to prepare a precursor; then adding the mixed solution of a silicon source and a molecular sieve modifier into the precursor solution to obtain initial sol, and continuously stirring, aging, crystallizing and roasting to obtain a KL molecular sieve; the morphology of the KL molecular sieve is adjusted by adjusting the type of the molecular sieve modifier or the adding ratio of the silicon source to the molecular sieve modifier.

In order to control the morphology of the KL molecular sieve, the molecular sieve modifier is n-butylamine, propylamine, 1,2, 6-hexanetriol, 1, 5-pentanediol, ethanol, n-propanol, isopropanol, n-butanol, cyclohexane, diethyl ether, triethylene or tributylphosphine.

The morphology of the KL molecular sieve can be adjusted by adjusting the type of the KL molecular sieve, and meanwhile, in order to more accurately and efficiently prepare the KL molecular sieve with higher purity and specific morphology, the molar ratio of the silicon source to the molecular sieve modifier is 1:0.1-100, and the molar ratio is in the range, so that the morphology of the KL molecular sieve can be conveniently adjusted.

The aluminum source is aluminum sulfate or aluminum hydroxide, and the potassium source is potassium hydroxide, potassium nitrate, potassium silicate or potassium sulfate. The selection of the aluminum source and the potassium source may be such that a precursor solution can be obtained. The silicon source is chosen more conventionally as a silica sol, potassium silicate or sodium silicate.

Specifically, the synthesis method specifically comprises the following steps: (1) mixing an aluminum source, a potassium source and water to obtain a mixed solution 1, and continuously stirring for 5-50min at normal temperature; (2) mixing a silicon source, water and a molecular sieve modifier to obtain a mixed solution 2, and continuously stirring for 5-50min at normal temperature; (3) adding the mixed solution 2 into the mixed solution 1, and continuously stirring for 2-20h at room temperature.

Further, in the mixed solution 1, the molar ratio of the aluminum source to the potassium source to the water is 1 (5-20): 500-1500); or, in the mixed solution 2, the mole ratio of the silicon source to the molecular sieve modifier is 1 (0.1-100); or, the crystallization time is 3-7 days, and the temperature is 130-; or, the roasting time is 4h, and the temperature is 450-600 ℃.

Preferably, for the adjustment of specific KL molecular sieves with different morphologies, the molecular sieve modifier is n-butylamine, propylamine, 1,2, 6-hexanetriol or 1, 5-pentanediol, and the molar ratio of the silicon source to the molecular sieve modifier is 1:0.1-100 to obtain a cylindrical KL molecular sieve;

or the molecular sieve modifier is ethanol, n-propanol, isopropanol or n-butanol, and the molar ratio of the silicon source to the molecular sieve modifier is 1:0.1-100 to obtain a coin-shaped KL molecular sieve;

or the molecular sieve modifier is cyclohexane, diethyl ether, triethylene or tributylphosphine, and the molar ratio of the silicon source to the molecular sieve modifier is 1:0.1-100 to obtain the double-cone KL molecular sieve.

In one or more embodiments of the invention, the KL molecular sieve is prepared by adopting the synthesis method of the KL molecular sieve with the controllable morphology, and the morphology of the KL molecular sieve is a cylindrical KL molecular sieve, a coin-shaped KL molecular sieve or a biconical KL molecular sieve; preferably, the KL molecular sieve is a coin-shaped KL molecular sieve, the coin-shaped KL molecular sieve can reduce the diffusion process of a metal precursor in the atomic layer deposition process, a more uniformly dispersed molecular sieve-loaded metal catalyst can be obtained, highly dispersed metal is more fully contacted with a molecular sieve pore channel, more electrons can be obtained from the molecular sieve coordinated K ions, and the metal in an electron-rich state is more beneficial to the generation of an alkane reforming process, so that the catalyst with higher activity and product selectivity can be obtained.

In one or more embodiments of the present invention, a catalyst is prepared by using the KL molecular sieve as a carrier, and the supported metal is at least one of Pt, Pd, Fe, Sn, Co, or Zn. The cylindrical, coin-shaped or biconical KL molecular sieve is used as a carrier, so that pore channel blockage is avoided, and the dispersion uniformity of metal on the molecular sieve is improved.

In one or more embodiments of the invention, atomic layer deposition is adopted to load metal on the KL molecular sieve, the KL molecular sieve based on the morphology is taken as a carrier, the atomic layer deposition technology is utilized to realize the placement of the metal on the molecular sieve, the uniformity of the metal placement is controlled, the metal accumulation is avoided, the occurrence of subsequent reaction side reactions is reduced, and the selectivity of products is improved.

In one or more embodiments of the present invention, the KL molecular sieve and/or the catalyst and/or the preparation method of the catalyst are applied to a reaction for preparing aromatic hydrocarbons by alkane reforming, and the KL molecular sieve based on the above morphology facilitates the alkane reforming process to occur, so as to obtain a catalyst with higher activity and product selectivity.

The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.

Example 1

88.56g of KOH were added to 852g H₂Stirring in O until clear, and taking 11.3g of Al (OH)₃Adding the solution into the KOH solution, and continuously stirring for 5min to obtain a solution 1; 290.4g of silica Sol (SiO) was taken₂40% content) was added to 193.92g H₂To O, 2g of n-butylamine (CH) was added dropwise under stirring₃(CH₂)₃NH₂) After the dripping is finished, continuously stirring for 5min to obtain a solution 2; adding the solution 2 to the solution 1 and stirring at room temperature for 16 h; transferring the mixed solution to a crystallization kettle for crystallization for 72 hours at 150 ℃; after cooling to room temperature, washing the mixed solution to neutrality, and then centrifuging; drying the solid obtained after centrifugation at 120 ℃ for 12h, finally roasting in a muffle furnace at 500 ℃ for 4h,the cylindrical KL molecular sieve is obtained, the XRD pattern is shown in figure 4, and the SEM morphology picture is shown in figure 3.

Dissolving the cylindrical KL molecular sieve synthesized in the embodiment 1 in ethanol, uniformly dispersing the dissolved cylindrical KL molecular sieve on a quartz plate, drying the mixture in air at room temperature for 2 hours, and transferring the mixture to a reaction chamber of atomic layer deposition equipment, wherein the ALD deposition parameters are as follows: the temperature of the reaction cavity is 220 ℃, and the platinum source adopts trimethyl-methyl cyclopentadiene platinum (MeCpPtMe)₃) As precursor, a temperature of 65 ℃ was used, O₃As the oxidizing agent, high-purity nitrogen gas having a flow rate of 50sccm was used as the carrier gas at room temperature. First MeCpPtMe was performed₃The pulse time of (1) was 0.5s, the deposition time was 60s, the purge time was 100s, and then O was performed₃The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100 s. After 4 consecutive Pt cycles, the Pt/KL catalyst is obtained.

Example 2

88.56g of KOH were added to 852g H₂Stirring in O until the mixture is clear, and taking 48.24g of Al₂(SO₄)₃·18H₂Adding O into the KOH solution, and continuously stirring for 5min to obtain a solution 1; 290.4g of silica Sol (SiO) was taken₂Content of 30%) was added to 193.92g H₂To O, 266.4g of ethanol (CH) was added dropwise with stirring₃CH₂OH), continuously stirring for 15min after the dripping is finished to obtain a solution 2; adding the solution 2 into the solution 1, and continuously stirring at room temperature for 20 hours; transferring the mixed solution to a crystallization kettle for crystallization for 72 hours at 170 ℃; after cooling to room temperature, washing the mixed solution to neutrality, and then centrifuging; the solid obtained after centrifugation is dried at 120 ℃ overnight and finally calcined in a muffle furnace at 500 ℃ for 4h to obtain the coin-shaped KL molecular sieve, wherein XRD (X-ray diffraction) is shown in figure 6, and SEM (scanning electron microscope) is shown in figure 5.

The coin-shaped KL molecular sieve prepared in example 2 was dissolved in ethanol and then uniformly dispersed on a quartz plate, and was dried in air at room temperature for 2 hours and then transferred to a reaction chamber of an atomic layer deposition apparatus, where the ALD deposition parameters were set as follows: the temperature of the reaction cavity is 220 ℃, palladium hexafluoroacetylacetone is used as a metal precursor, the use temperature is 70 ℃, formaldehyde is used as an oxidant, the use temperature is room temperature, and the carrier gas is high-purity nitrogen with the flow rate of 50 sccm. Firstly, go on sixThe pulse time of palladium fluoroacetylacetonate was 0.5s, the deposition time was 20s, the purge time was 40s, and then the pulse time of formaldehyde was 1s, the reaction time was 20s, and the purge time was 40 s. After continuously repeating the Pd circulation for 2 times, the Pd/KL catalyst is obtained. Followed by deposition of Pt, MeCpPtMe₃The pulse time of (1) was 0.5s, the deposition time was 60s, the purge time was 100s, and then O was performed₃The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100 s. After 4 Pt cycles are continuously repeated, the PdPt/KL catalyst is obtained.

Example 3

88.56g of KOH were added to 852g H₂Stirring in O until the mixture is clear, and taking 48.24g of Al₂(SO₄)₃·18H₂Adding O into the KOH solution, and continuously stirring for 5min to obtain a solution 1; 290.4g of silica Sol (SiO) was taken₂40% content) was added to 193.92g H₂To O, 70g of cyclohexane (C) was added dropwise under stirring₆H₁₂) After the dripping is finished, continuously stirring for 5min to obtain a solution 2; adding the solution 2 into the solution 1, and continuously stirring at room temperature for 6 hours; transferring the mixed solution to a crystallization kettle for crystallization at 175 ℃ for 24 hours; after cooling to room temperature, washing the mixed solution to neutrality, and then centrifuging; and drying the solid obtained after centrifugation at 120 ℃ overnight, and finally roasting the solid in a muffle furnace at 500 ℃ for 4 hours to obtain the double-cone KL molecular sieve, wherein XRD (X-ray diffraction) is shown in figure 8, and SEM (scanning electron microscope) is shown in figure 7.

The double-cone KL molecular sieve prepared in the embodiment 3 is dissolved in ethanol and then uniformly dispersed on a quartz plate, the quartz plate is dried in air at room temperature for 2 hours and then transferred to a reaction chamber of atomic layer deposition equipment, and the ALD deposition parameters are set as follows: the temperature of the reaction cavity is 200 ℃, diethyl zinc is adopted as a metal precursor, the using temperature is room temperature, and H₂O is an oxidant, the using temperature is room temperature, and the carrier gas is high-purity nitrogen with the flow rate of 50 sccm. Firstly, the pulse time of diethyl zinc is 0.02s, the deposition time is 10s, the purging time is 25s, and then H is carried out₂The pulse time for O was 0.1s, the reaction time was 10s, and the purge time was 30 s. After continuously repeating the Zn circulation for 5 times, Zn/KL catalyst is obtained. Followed by deposition of Pt, MeCpPtMe₃The pulse time of (a) is 0.5s,deposition time 60s, purge time 100s, followed by O₃The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100 s. After continuously repeating the Pt circulation for 6 times, the ZnPt/KL catalyst is obtained.

Example 4

72.56g of KOH were added to 750g H₂Stirring in O until the mixture is clear, and taking 44.45g of Al₂(SO₄)₃·18H₂Adding O into the KOH solution, and continuously stirring for 5min to obtain a solution 1; 275.6g of silica Sol (SiO)₂Content of 30%) was added to 185g H₂To O, 95g of isopropyl alcohol (C) was added dropwise with stirring₃H₇OH), continuously stirring for 5min after the dripping is finished to obtain a solution 2; adding the solution 2 to the solution 1 and stirring at room temperature for 16 h; transferring the mixed solution to a crystallization kettle for crystallization for 72 hours at 150 ℃; after cooling to room temperature, washing the mixed solution to neutrality, and then centrifuging; and drying the solid obtained after centrifugation at 120 ℃ overnight, and finally roasting the solid in a muffle furnace at 500 ℃ for 4 hours to obtain the ultrathin coin-shaped KL molecular sieve, wherein XRD (X-ray diffraction) of the KL molecular sieve is shown in figure 10, and SEM (scanning electron microscope) of the KL molecular sieve is shown in figure 9.

Dissolving the ultra-thin coin-shaped KL prepared in the embodiment 4 in ethanol, uniformly dispersing the dissolved ethanol on a quartz plate, drying the solution in air at room temperature for 2 hours, and transferring the solution to a reaction chamber of atomic layer deposition equipment, wherein the ALD deposition parameters are as follows: the temperature of the reaction cavity is 220 ℃, ferrocene is adopted as a metal precursor, the use temperature is 95 ℃, and O₃As the oxidizing agent, high-purity nitrogen gas having a flow rate of 50sccm was used as the carrier gas at room temperature. Firstly carrying out H, the pulse time of ferrocene is 0.5s, the deposition time is 20s, the purging time is 40s₂The pulse time for O was 1s, the reaction time was 20s, and the purge time was 40 s. And continuously repeating the Fe circulation for 4 times to obtain the Fe/KL catalyst. Followed by deposition of Pt, MeCpPtMe₃The pulse time of (1) was 0.5s, the deposition time was 60s, the purge time was 100s, and then O was performed₃The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100 s. After 4 Pt cycles were repeated successively, a FePt/KL catalyst was obtained.

Comparative example 1

Weighing 22.6g Al (OH)₃Dissolving in 400g deionized water, weighing 93.2g KOH, dissolving in 275g deionized water, transferring the two solutions into a three-neck flask, heating to 100 ℃ under the condition of stirring, and cooling to room temperature after the solution is clear. Then, 334g of silica Sol (SiO) was added dropwise to the above-mentioned transparent solution with stirring₂30 percent of mixed solution and 100g of deionized water, fully stirring the mixed solution after the dropwise addition to obtain molecular sieve initial sol, transferring the molecular sieve initial sol into a crystallization kettle, placing the crystallization kettle into a 180 ℃ oven for 22 hours, then cooling the molecular sieve initial sol to room temperature, carrying out suction filtration, washing the molecular sieve to be neutral with the deionized water, transferring the molecular sieve initial sol into a 120 ℃ oven for drying for 12 hours, and finally roasting the molecular sieve initial sol in a muffle furnace for 4 hours at 500 ℃ to obtain a conventional KL molecular sieve carrier, wherein an SEM picture is shown in figure 1, XRD is shown in figure 2, and the molecular sieve with the morphology is not beneficial to regulation and control of metal placement and has poor catalytic performance.

Dissolving the conventional KL molecular sieve prepared in the comparative example in ethanol, uniformly dispersing the dissolved conventional KL molecular sieve on a quartz plate, drying the solution in air at room temperature for 2 hours, and transferring the solution to a reaction chamber of atomic layer deposition equipment, wherein the ALD deposition parameters are as follows: the temperature of the reaction cavity is 220 ℃, and the platinum source adopts trimethyl-methyl cyclopentadiene platinum (MeCpPtMe)₃) As precursor, a temperature of 65 ℃ was used, O₃As the oxidizing agent, high-purity nitrogen gas having a flow rate of 50sccm was used as the carrier gas at room temperature. First MeCpPtMe was performed₃The pulse time of (1) was 0.5s, the deposition time was 60s, the purge time was 100s, and then O was performed₃The pulse time of (2) was 1s, the reaction time was 60s, and the purge time was 100 s. After 6 Pt cycles were repeated successively, a Pt/KL catalyst was obtained.

Example 5

Evaluation of reaction Performance

The atomic layer deposition technology described in comparative example 1 and examples 1-4 was used to prepare Pt and its Pt-containing bimetallic supported KL molecular sieve supported catalysts with different morphologies, and n-heptane was used as the raw material to evaluate its aromatization performance in a fixed bed microreactor. Mass airspeed WHSV of 1h^-1Reaction temperature 450 ℃ and H₂The reaction pressure was 0.1MPa, all products were analyzed by on-line chromatography, and the results are shown in Table 1.

As can be seen from the data in the table, the coin-shaped KL molecular sieve loaded Pt-M (Pd, Fe) bimetallic catalyst shows higher catalytic activity and aromatic selectivity for heptane aromatization.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.