CN109437224B - Synthesis method of heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve - Google Patents
Synthesis method of heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve Download PDFInfo
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Abstract
The invention discloses a synthetic method of a heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve, which comprises the following steps: uniformly mixing a metal source, a silicon source, an organic template agent, a complexing agent, a mineralizer and water, heating and stirring by adopting microwave or ultrasonic waves for reaction, and then sequentially carrying out hydrothermal crystallization and purification treatment on the reaction mixture to obtain HBMZ zeolite molecular sieve raw powder; then, mixing HBMZ zeolite molecular sieve raw powder and an acid solution sufficiently to react to obtain an acid treatment product; and finally, carrying out high-temperature roasting treatment on the acid treatment product to obtain the HBMZ zeolite molecular sieve. The heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve prepared by the invention has unique bird nest-shaped micron cavity structure characteristics, and the high-exposed metal active sites and the overhead ultrathin nanosheets are beneficial to the diffusion of reactant molecules and product molecules and the formation of intermediates in the catalytic reaction process, so that an ideal reaction site is provided for the occurrence of catalytic reaction.
Description
Technical Field
The invention relates to the technical field of inorganic chemical synthesis, in particular to a synthetic method of a heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve.
Background
With the continuous development of nanotechnology, the concept of nanoreactors is gradually proposed and rapidly becomes a research hotspot in the fields of energy storage, chemical synthesis and biomedicine. Different porous materials and other functional nano materials are integrated on the nanometer size, so that the composite porous functional material with different nano structures is obtained. Researchers have constructed novel multifunctional porous materials, such as yolk-shell structured porous materials, core-shell structured porous materials, hollow structured porous materials, three-dimensional assembled porous materials, and the like. The hollow microsphere is a porous material with a hollow structure, has a diameter ranging from nanometer to hundreds of micrometers, is hollow inside, and is a material with a special structure. Compared with solid spheres or non-spherical particles with the same size, the hollow microspheres have the advantages of low density, large specific surface area and the like, so that the hollow microspheres have wide application prospects as a novel functional material, such as light fillers, separation materials, controlled release capsules, artificial cells, microelectronic elements, high-selectivity catalysts and carriers thereof and the like.
The hollow microsphere is generally prepared by a hard template, and the principle is that a core-shell structure is formed on the surface of the template through deposition or chemical reaction, and the template is further removed through high-temperature calcination or a chemical method to obtain the hollow microsphere. However, the hard template method has an influence on the shell structure or product properties during the template removal process, and the preparation method is a multi-step complex process. Although the soft template method does not need strict control conditions, the hollow microspheres obtained by the soft template method have wide particle size distribution, complex system components and relatively poor controllability.
In the prior art, Chinese patent with publication number CN 107954437 discloses a preparation method of an AITQ-24 zeolite molecular sieve, which adopts choline hydroxide as an organic template agent according to choline hydroxide/YO2＝0.1～1.0，X2O3/YO2＝0～0.1，H2O/YO2The porous crystalline zeolite molecular sieve material ITQ-24 is obtained by a method of carrying out hydrothermal crystallization on a mixture at a temperature of 100-200 ℃ for 24-350 hours, wherein Y is at least one tetravalent element, and X is at least one trivalent element. Although the ITQ-24 molecular sieve synthesized by the technical scheme has a stable structure, the cost is high by adopting choline hydroxide as an organic template.
Chinese patent with publication number CN 108529641A discloses a zeolite molecular sieve with multi-stage pore channels and a preparation method thereof, the method comprises the steps of mixing and stirring uniformly a silicon source, an aluminum source and water, and then dropwise adding an organic quaternary ammonium salt template agent and continuously stirring to obtain aluminosilicate gel; (ii) a Transferring the aluminosilicate gel into a hydrothermal reaction kettle, and carrying out hydrothermal crystallization for 3-30 days at the temperature of 100-175 ℃; and cooling the product obtained in the step two to room temperature, performing centrifugal separation, washing the obtained precipitate with deionized water, performing centrifugal separation again, and drying to obtain the zeolite molecular sieve. Although the zeolite molecular sieve prepared by the method has a multi-stage pore channel structure, the preparation process of the material is complicated, and the preparation time is 3-30 days.
However, the research on the next step of directly preparing the micron cavity reactor type zeolite molecular sieve with the bird nest-shaped crystal structure containing the heteroatom is still less under the condition without the hard template, and the application of the micron cavity reactor type zeolite molecular sieve in the aspect of catalytic reaction is limited.
Disclosure of Invention
The invention aims to provide a synthetic method of a heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve, the synthetic process of the preparation method is simple, the production cost is low, a plurality of zeolite molecular sieve crystal materials are synthesized by adding different heteroatoms, the repeatability is good, and the large-scale production and application of the micron cavity reactor type zeolite molecular sieve are facilitated.
In order to achieve the above purpose, the synthesis method of the heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve provided by the invention comprises the following steps: uniformly mixing a metal source, a silicon source, an organic template agent, a complexing agent, a mineralizer and water, heating and stirring by adopting microwave or ultrasonic waves for reaction, and then sequentially carrying out hydrothermal crystallization and purification treatment on the reaction mixture to obtain HBMZ zeolite molecular sieve raw powder; then, mixing HBMZ zeolite molecular sieve raw powder and an acid solution fully for reaction, and then filtering, washing and drying the mixture in sequence to obtain an acid treatment product; and finally, carrying out high-temperature roasting treatment on the acid treatment product to obtain the HBMZ zeolite molecular sieve.
In a preferred embodiment, the metal source, the silicon source, the organic template, the complexing agent, the mineralizer and the water are in a molar ratio of (0.0001-0.05): (0.2-10): (0.1-10): (0.002-0.1): (0.02-3): (1-200).
As a preferred embodiment, the metal source is selected from one or more of tin salt, aluminum salt, zirconium salt, zinc salt, lanthanum salt, vanadium salt, titanium salt, iron salt, cobalt salt, manganese salt, copper salt, and chromium salt.
As a preferred embodiment, the tin salt is tin tetrachloride, dimethyltin dichloride; the aluminum salt is sodium metaaluminate and aluminum isopropoxide; the zirconium salt is zirconium nitrate; the zinc salt is zinc acetate; the lanthanum salt is lanthanum nitrate; the vanadium salt is ammonium metavanadate; the titanium salt is tetrabutyl titanate and titanium tetrachloride; the ferric salt is ferric chloride; the cobalt salt is cobalt acetate; the manganese salt is manganese acetate; the copper salt is copper sulfate; the chromium salt is chromium nitrate.
As a preferred embodiment, the silicon source is selected from one or more of silica sol, fumed silica, silica gel, ethyl orthosilicate; the organic template agent is selected from one or more of 4-hydroxypiperidine, piperidine, 4-amino-2, 2,6, 6-tetramethylpiperidine, hexamethyleneimine and hexamethylenetetramine.
As a preferred embodiment, the complexing agent is selected from one or more of diethanolamine, triethanolamine, tartaric acid; one or more of the mineralizer potassium chloride, boric acid and sodium borate.
Preferably, the microwave or ultrasonic heating and stirring reaction time is 0.5-8 h, the microwave or ultrasonic power is 300-1200W in the reaction process, and the radiation heating temperature is 50-100 ℃; the hydrothermal crystallization treatment is specifically hydrothermal crystallization at 120-180 ℃ for 48-360 h.
Preferably, the HBMZ zeolite molecular sieve raw powder and the acid solution are fully mixed and reacted for 10 to 20 hours at the temperature of 70 to 90 ℃; the weight ratio of the HBMZ zeolite molecular sieve raw powder to the acid solution is 1 (5-100); the molar concentration of the acidic solution is 0.1-10 mol/L;
the acid solution is formed by mixing inorganic acid and organic acid according to the molar ratio of 1: 3-3: 1, wherein the inorganic acid is one or more of nitric acid, phosphoric acid and hydrochloric acid; the organic acid is selected from one or more of malonic acid, n-butyric acid, succinic acid and n-valeric acid.
Preferably, the high-temperature roasting treatment is carried out for 5-10 hours at 450-550 ℃.
As a preferred embodiment, the method for synthesizing the heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve specifically comprises the following steps:
1) preparation of HBMZ zeolite molecular sieve raw powder
The preparation method comprises the following steps of (1) mixing a metal source, a silicon source, an organic template, a complexing agent, a mineralizer and water according to a molar ratio of (0.0001-0.05): (0.2-10): (0.1-10): (0.002-0.1): (0.02-3): (1-200) uniformly mixing, heating and stirring by using microwave or ultrasonic waves for reaction for 0.5-8 h, wherein the power of the microwave or ultrasonic waves is 300-1200W in the reaction process, the radiation heating temperature is 50-100 ℃, then performing hydrothermal crystallization on the reaction mixture at the temperature of 120-180 ℃ for 48-360 h, and finally performing purification treatment to obtain HBMZ zeolite molecular sieve raw powder;
2) acid treatment
Fully mixing and reacting the HBMZ zeolite molecular sieve raw powder obtained in the step 1) with an acid solution according to a molar ratio of 1: 3-3: 1, and then sequentially filtering, washing and drying to obtain an acid treatment product;
3) roasting treatment
Roasting the acid treatment product obtained in the step 2) for 5-10 hours at the temperature of 450-550 ℃ to obtain the HBMZ zeolite molecular sieve.
Compared with the prior art, the invention has the following advantages:
firstly, the invention adopts microwave or ultrasonic wave auxiliary heating pre-reaction and hydrothermal crystallization modes to control the hydrolysis of metal salt, and the micron cavity reactor type zeolite molecular sieve with excellent performance can be obtained by crystallization in a hydrothermal reaction kettle after fully and uniformly mixing, has simple synthesis process and low production cost, synthesizes various zeolite molecular sieve crystal materials by adding different heteroatoms, has good repeatability, and is beneficial to the large-scale production and application of the micron cavity reactor type zeolite molecular sieve.
Secondly, the HBMZ molecular sieve prepared by the invention has a complete and novel crystalline structure, the material has a unique nest-shaped micron cavity structure characteristic, the high-exposed metal active site and the overhead ultrathin nanosheet layer are beneficial to the diffusion of reactant molecules and product molecules and the formation of intermediates in the catalytic reaction process, an ideal reaction site is provided for the occurrence of catalytic reaction, the molecular sieve material containing the heteroatom can catalyze the epoxidation reaction of linear olefin with high activity, and long online time can be realized.
Thirdly, the method has simple process, no special equipment requirement and easy industrial production, and can synthesize the zeolite molecular crystal materials of the same type containing different metal heteroatoms by one-step crystallization under the combined action of similar organic template agents and complexing agents.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve prepared in accordance with the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
Example 1
1) Preparation of HBMZ zeolite molecular sieve raw powder
The metal in the metal salt in molar ratio: SiO in silicon source2: organic template agent: complexing agent: mineralizing agent: water 0.0067: 1.0: 1.5: 0.02: 1.35: 25, adding a metal source into an aqueous solution of an organic template agent, uniformly stirring by magnetic force, adding a silicon source, uniformly stirring by magnetic force, adding a complexing agent to obtain a reaction mixed solution, heating and stirring by microwave for 4 hours, reacting at the microwave power of 500W and the radiant heating temperature of 80 ℃ in the reaction process, then carrying out hydrothermal crystallization on the reaction mixture at the temperature of 170 ℃ for 84 hours, filtering, washing and drying to obtain the HBMZ zeolite molecular sieve raw powder. The metal source is tin tetrachloride, the silicon source is fumed silica, the organic template is piperidine, the complexing agent is triethanolamine, and the mineralizer is boric acid.
2) Acid treatment
Mixing HBMZ zeolite molecular sieve raw powder obtained in the step 1) with an acid solution with the molar concentration of 3mol/L according to the weight ratio of 1: 40 preparing a reaction mixture, wherein the acid solution is prepared by mixing hydrochloric acid and malonic acid according to the molar ratio of 3:1, treating at 80 ℃ for 15 hours, and filtering, washing and drying once to obtain an acid treatment product.
3) Roasting treatment
Roasting the product obtained in the step 2) at 500 ℃ for 10h to obtain the product, namely the HBMZ zeolite molecular sieve.
Example 2
The procedure was as in example 1 except that:
dimethyl tin dichloride according to molar ratio: silica sol: 4-hydroxypiperidine: diethanolamine: potassium chloride: water 0.02: 2.0: 2.0: 0.05: 1.0: 60, uniformly mixing; microwave reaction is carried out for 3 hours, the microwave power is 600W, the heating temperature is 90 ℃, and hydrothermal crystallization is carried out for 120 hours at 160 ℃.
Example 3
The procedure was as in example 1 except that:
according to molar ratio, sodium metaaluminate: silica gel: hexamethyleneimine: triethanolamine: sodium borate: water 0.01: 3.0: 5.0: 0.1: 2.0: 80, uniformly mixing; microwave reaction is carried out for 2 hours, the microwave power is 800W, the heating temperature is 95 ℃, and hydrothermal crystallization is carried out for 96 hours at 170 ℃.
Example 4
The procedure was as in example 1 except that:
and (3) according to molar ratio of aluminum isopropoxide: ethyl orthosilicate: hexamethylenetetramine: tartaric acid: boric acid: water 0.05: 5.0: 3.0: 0.05: 2.5: 100, uniformly mixing; microwave reaction is carried out for 0.5h, the microwave power is 700W, the heating temperature is 90 ℃, and hydrothermal crystallization is carried out for 360h at 120 ℃.
Example 5
The procedure was as in example 1 except that:
according to molar ratio, n-butyl titanate: fumed silica: piperidine: triethanolamine: boric acid: water 0.0375: 1.0: 1.5: 0.1: 1.34: 25, uniformly mixing; microwave reaction is carried out for 4 hours, the microwave power is 500W, the heating temperature is 70 ℃, and hydrothermal crystallization is carried out for 84 hours at 170 ℃.
Example 6
The procedure was as in example 1 except that:
according to the molar ratio of titanium tetrachloride: silica sol: hexamethyleneimine: triethanolamine: sodium borate: water 0.035: 1.0: 2.0: 0.05: 1.4: 40, uniformly mixing; microwave reaction for 4h, microwave power 1000W, heating temperature 100 ℃, and hydrothermal crystallization for 144h at 160 ℃.
Example 7
The procedure was as in example 1 except that:
according to molar ratio, lanthanum nitrate: fumed silica: piperidine: tartaric acid: potassium chloride: water 0.01: 1.5: 1.6: 0.02: 1.4: 40, uniformly mixing; microwave reaction is carried out for 1h, the microwave power is 1000W, the heating temperature is 100 ℃, and hydrothermal crystallization is carried out for 120h at 170 ℃.
Example 8
The procedure was as in example 1 except that:
zinc acetate according to molar ratio: ethyl orthosilicate: piperidine: triethanolamine: boric acid: water 0.02: 1.0: 1.0: 0.05: 1.0: 25, uniformly mixing; microwave reaction for 4h, microwave power of 800W, heating temperature of 90 ℃, and hydrothermal crystallization for 144h at 170 ℃.
Example 9
The procedure was as in example 1 except that:
according to molar ratio, sodium metaaluminate: fumed silica: 4-amino-2, 2,6, 6-tetramethylpiperidine: triethanolamine: boric acid: water 0.01: 1.0: 1.5: 0.05: 1.3: 405 uniformly mixing; ultrasonic reaction is carried out for 7 hours, the ultrasonic power is 300W, the heating temperature is 50 ℃, and hydrothermal crystallization is carried out for 288 hours at 170 ℃.
Example 10
The procedure was as in example 1 except that:
and (3) according to molar ratio of aluminum isopropoxide: silica sol: hexamethyleneimine: triethanolamine: sodium borate: water 0.0067: 1.0: 1.5: 0.1: 1.4: 60, uniformly mixing; ultrasonic reaction is carried out for 8 hours, the ultrasonic power is 500W, the heating temperature is 90 ℃, and hydrothermal crystallization is carried out for 240 hours at 140 ℃.
Example 11
The procedure was as in example 1 except that:
according to molar ratio, zirconium nitrate: fumed silica: piperidine: triethanolamine: boric acid: water 0.0133: 1.0: 1.5: 0.05: 1.3: 40, uniformly mixing; ultrasonic reaction is carried out for 4 hours, the ultrasonic power is 600W, the heating temperature is 90 ℃, and hydrothermal crystallization is carried out for 90 hours at 180 ℃.
Example 12
The procedure was as in example 1 except that:
molar ratio of ammonium metavanadate: fumed silica: piperidine: triethanolamine: boric acid: water 0.0001: 1.0: 1.5: 0.08: 1.4: 40, uniformly mixing; microwave reaction for 1h, microwave power of 1200W, heating temperature of 100 ℃, hydrothermal crystallization for 90h at 170 ℃.
Example 13
The procedure was as in example 1 except that:
according to mol ratio, ferric chloride: fumed silica: piperidine: diethanolamine: potassium chloride: water 0.0067: 0.2: 0.1: 0.06: 1.2: 25, uniformly mixing; microwave reaction is carried out for 2 hours, the microwave power is 1000W, the heating temperature is 90 ℃, and hydrothermal crystallization is carried out for 144 hours at 160 ℃.
Example 14
The procedure was as in example 1 except that:
and (3) according to molar ratio of cobalt acetate: fumed silica: piperidine: diethanolamine: potassium chloride: water 0.0375: 1.0: 2.0: 0.05: 1.5: 40, uniformly mixing; microwave reaction is carried out for 4 hours, the microwave power is 500W, the heating temperature is 90 ℃, and hydrothermal crystallization is carried out for 240 hours at 170 ℃.
Example 15
The procedure was as in example 1 except that:
manganese acetate in molar ratio: fumed silica: piperidine: diethanolamine: potassium chloride: water 0.0375: 1.0: 2.0: 0.08: 1.5: 40, uniformly mixing; microwave reaction is carried out for 8 hours, the microwave power is 400W, the heating temperature is 80 ℃, and hydrothermal crystallization is carried out for 144 hours at 150 ℃.
Example 16
The procedure was as in example 1 except that:
according to molar ratio, copper nitrate: fumed silica: piperidine: triethanolamine: potassium chloride: water 0.0375: 1.0: 1.5: 0.05: 1.5: 40, uniformly mixing; microwave reaction is carried out for 4 hours, the microwave power is 500W, the heating temperature is 90 ℃, and hydrothermal crystallization is carried out for 168 hours at 170 ℃.
Example 17
The procedure was as in example 1 except that:
according to molar ratio, chromium nitrate: fumed silica: piperidine: triethanolamine: potassium chloride: water 0.02: 10.0: 10.0: 0.1: 1.5: 200, uniformly mixing; microwave reaction for 3h, microwave power of 700W, heating temperature of 95 ℃, hydrothermal crystallization for 192h at 170 ℃.
Example 18
The procedure was as in example 1 except that:
mixing HBMZ zeolite molecular sieve raw powder with an acid solution with the molar concentration of 2mol/L according to the weight ratio of 1: 10 preparing a reaction mixture, mixing the acid solution with nitric acid and n-butyric acid solution according to the molar ratio of 2:1, and treating at 90 ℃ for 10 hours;
example 19
The procedure was as in example 1 except that:
mixing HBMZ zeolite molecular sieve raw powder with an acid solution with the molar concentration of 2mol/L according to the weight ratio of 1: 5 preparing a reaction mixture, mixing the acid solution with nitric acid and n-butyric acid solution according to a molar ratio of 2:1, and treating at 90 ℃ for 24 hours.
Example 20
The procedure was as in example 1 except that:
mixing HBMZ zeolite molecular sieve raw powder with an acid solution with the molar concentration of 6mol/L according to the weight ratio of 1: 70 preparing a reaction mixture, wherein the acid solution is prepared by mixing phosphoric acid and succinic acid solution according to the molar ratio of 1:1 and treating for 8 hours at 97 ℃.
Example 21
The procedure was as in example 1 except that:
mixing HBMZ zeolite molecular sieve raw powder with an acid solution with the molar concentration of 10mol/L according to the weight ratio of 1: 50 preparing a reaction mixture, mixing the acid solution with a nitric acid solution and an n-valeric acid solution according to a molar ratio of 1:2, and treating at 70 ℃ for 12 hours.
Example 22
The procedure was as in example 1 except that:
mixing HBMZ zeolite molecular sieve raw powder with an acid solution with the molar concentration of 5mol/L according to the weight ratio of 1: 100 preparing a reaction mixture, wherein the acid solution is prepared by mixing hydrochloric acid and malonic acid solution according to a molar ratio of 1:3, and treating for 24 hours at 60 ℃;
example 23
The procedure was as in example 1 except that:
mixing HBMZ zeolite molecular sieve raw powder with an acid solution with the molar concentration of 6mol/L according to the weight ratio of 1: 40 preparing a reaction mixture, mixing the acid solution with nitric acid and succinic acid solution according to the molar ratio of 2:1, and treating for 24 hours at 80 ℃.
Example 24
The procedure was as in example 1 except that:
and roasting the acid treatment product at 400 ℃ for 20h to obtain the product HBMZ zeolite molecular sieve.
Example 25
The procedure was as in example 1 except that:
and roasting the acid treatment product at 550 ℃ for 10h to obtain the product HBMZ zeolite molecular sieve.
Example 26
The procedure was as in example 1 except that:
and roasting the acid treatment product at 600 ℃ for 5h to obtain the product HBMZ zeolite molecular sieve.
Effect example 1: scanning electron microscopy
Scanning Electron microscope the measurement was carried out on a JSM-6510A scanning electron microscope manufactured by Japan Electron Ltd. The scanning voltage of the tungsten lamp is 30Kv, the diameter of a sample to be detected can be amplified to 150mm, and an EDS (X-ray energy spectrometer) module is additionally arranged.
As can be seen from FIG. 1, the HBMZ zeolite molecular sieve prepared by the invention is a hollow sphere material which is composed of uniform nanosheets and grows in an interlaced mode. The HBMZ zeolite molecular sieve crystal of the invention has a uniform, complete and novel crystal structure: the size of a single crystal is about 3 x 5 microns, and the size of a tiny cavity containing one micron is about 2 x 4 microns; the material is formed by the staggered co-growth of single-, double-and multi-cell-thick nanosheet crystals, a sample comprises a single nanosheet layer with the thickness of 2.5nm, a double nanosheet layer with the thickness of 5.0nm and a multi-nanosheet layer with the thickness of more than 5.0nm, and the micron cavity reactor is spontaneously assembled.
Effect example 2 epoxidation catalytic Effect of Linear olefin with Hydrogen peroxide
And (2) uniformly mixing 20.0g of the HBMZ zeolite molecular sieve prepared in the example 1 and 10.0g of auxiliary agent aluminum oxide, adding 80.0g of water, grinding and mixing to obtain a wet mass, processing the wet mass into a strip-shaped catalyst by using a catalyst forming machine to obtain the formed catalyst, drying in the shade at room temperature, and drying in a drying oven to obtain the strip-shaped HBMZ zeolite molecular sieve catalyst.
The method comprises the steps that HBMZ molecular sieve catalysts are filled in a parallel flow type trickle fixed bed from 1/10 at the upper end to 1/10 at the lower end in a segmented mode, theta ring fillers are filled between two adjacent sections of the HBMZ molecular sieve catalysts, the length of each strip catalyst is 3-5 mm, and the diameter of each strip catalyst is 2-3 mm; the length of the theta ring packing is 2-5 mm, and the diameter of the theta ring packing is 2-3 mm; the filling height of each section of HBMZ molecular sieve catalyst and theta ring packing is 2-3 cm.
At 55 ℃ and normal pressure, uniformly mixed liquid of chloropropene (with the mass concentration of 14.5 percent), acetonitrile and hydrogen peroxide (with the molar weight ratio of chloropropene to hydrogen peroxide of 1.4:1) flows out of a mixed liquid storage, and is metered by a liquid metering pump to be at 0.75ml/ml cat.h-1Introducing from the upper end of a cocurrent trickle fixed bed; the reaction product flows out from the lower end, and is sequentially condensed at low temperature by a condensing pipe and separated by a liquid component separator to obtain the epoxide product. The cocurrent trickle fixed bed reactor is used for collecting waste liquid generated by reaction. The conversion rate of the chloropropene raw material is regularly monitored by a GC and hydrogen peroxide content detector and controlled in>72 percent, the utilization rate of hydrogen peroxide is more than or equal to 99 percent, the selectivity of the product epoxide is controlled to be more than or equal to 99 percent, and the online service life of the catalyst is more than 10000 h.
The above description is only an embodiment of the present invention, and it should be noted that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.
Claims (6)
1. A synthetic method of a heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve is characterized by comprising the following steps: uniformly mixing a metal source, a silicon source, an organic template agent, a complexing agent, a mineralizer and water, heating and stirring by adopting microwave or ultrasonic waves for reaction, and then sequentially carrying out hydrothermal crystallization and purification treatment on the reaction mixture to obtain HBMZ zeolite molecular sieve raw powder; then, mixing HBMZ zeolite molecular sieve raw powder and an acid solution fully for reaction, and then filtering, washing and drying the mixture in sequence to obtain an acid treatment product; finally, carrying out high-temperature roasting treatment on the acid treatment product to obtain the HBMZ zeolite molecular sieve;
the metal source, the silicon source, the organic template, the complexing agent, the mineralizing agent and the water are in a molar ratio of (0.0001-0.05): (0.2-10): (0.1-10): (0.002-0.1): (0.02-3): (1-200);
the microwave or ultrasonic heating and stirring reaction time is 0.5-8 h, the microwave or ultrasonic power is 300-1200W in the reaction process, and the radiation heating temperature is 50-100 ℃; the hydrothermal crystallization treatment is specifically hydrothermal crystallization at 120-180 ℃ for 48-360 h;
fully mixing and reacting the HBMZ zeolite molecular sieve raw powder and an acid solution for 10-20 hours at the temperature of 70-90 ℃; the weight ratio of the HBMZ zeolite molecular sieve raw powder to the acid solution is 1 (5-100); the molar concentration of the acidic solution is 0.1-10 mol/L;
the acid solution is formed by mixing inorganic acid and organic acid according to the molar ratio of 1: 3-3: 1, wherein the inorganic acid is one or more of nitric acid, phosphoric acid and hydrochloric acid; the organic acid is selected from one or more of malonic acid, n-butyric acid, succinic acid and n-valeric acid;
the high-temperature roasting treatment is specifically roasting treatment for 5-10 hours at the temperature of 450-550 ℃.
2. The method for synthesizing the heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve of claim 1, wherein said metal source is selected from one or more of the group consisting of tin salts, aluminum salts, zirconium salts, zinc salts, lanthanum salts, vanadium salts, titanium salts, iron salts, cobalt salts, manganese salts, copper salts, and chromium salts.
3. The method for synthesizing the heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve of claim 2, wherein said tin salt is tin tetrachloride, dimethyltin dichloride; the aluminum salt is sodium metaaluminate and aluminum isopropoxide; the zirconium salt is zirconium nitrate; the zinc salt is zinc acetate; the lanthanum salt is lanthanum nitrate; the vanadium salt is ammonium metavanadate; the titanium salt is tetrabutyl titanate and titanium tetrachloride; the ferric salt is ferric chloride; the cobalt salt is cobalt acetate; the manganese salt is manganese acetate; the copper salt is copper sulfate; the chromium salt is chromium nitrate.
4. The method for synthesizing the heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve of claim 1, wherein said silicon source is selected from the group consisting of one or more of silica sol, fumed silica, silica gel, ethyl orthosilicate; the organic template agent is selected from one or more of 4-hydroxypiperidine, piperidine, 4-amino-2, 2,6, 6-tetramethylpiperidine, hexamethyleneimine and hexamethylenetetramine.
5. The method for synthesizing the heteroatom-containing microcavity reactor type HBMZ zeolite molecular sieve of claim 1, wherein said complexing agent is selected from one or more of diethanolamine, triethanolamine, tartaric acid; one or more of the mineralizer potassium chloride, boric acid and sodium borate.
6. The method for synthesizing the heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve of claim 1, specifically comprising the steps of:
1) preparation of HBMZ zeolite molecular sieve raw powder
The preparation method comprises the following steps of (1) mixing a metal source, a silicon source, an organic template, a complexing agent, a mineralizer and water according to a molar ratio of (0.0001-0.05): (0.2-10): (0.1-10): (0.002-0.1): (0.02-3): (1-200) uniformly mixing, heating and stirring by using microwave or ultrasonic waves for reaction for 0.5-8 h, wherein the power of the microwave or ultrasonic waves is 300-1200W in the reaction process, the radiation heating temperature is 50-100 ℃, then performing hydrothermal crystallization on the reaction mixture at the temperature of 120-180 ℃ for 48-360 h, and finally performing purification treatment to obtain HBMZ zeolite molecular sieve raw powder;
2) acid treatment
Fully mixing and reacting the HBMZ zeolite molecular sieve raw powder obtained in the step 1) with an acid solution according to a molar ratio of 1: 3-3: 1, and then sequentially filtering, washing and drying to obtain an acid treatment product;
3) roasting treatment
Roasting the acid treatment product obtained in the step 2) for 5-10 hours at the temperature of 450-550 ℃ to obtain the HBMZ zeolite molecular sieve.
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