CN113967484A - Preparation method of composite solid acid catalyst and application of composite solid acid catalyst in alcohol ether synthesis - Google Patents

Preparation method of composite solid acid catalyst and application of composite solid acid catalyst in alcohol ether synthesis Download PDF

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CN113967484A
CN113967484A CN202111575224.1A CN202111575224A CN113967484A CN 113967484 A CN113967484 A CN 113967484A CN 202111575224 A CN202111575224 A CN 202111575224A CN 113967484 A CN113967484 A CN 113967484A
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acid catalyst
solid acid
composite solid
parts
controlling
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CN113967484B (en
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盛文文
郭华
王良
刘宇
郑遂
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Jiayijia Biotech Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/23—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0228—Coating in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups

Abstract

The invention discloses a preparation method of a composite solid acid catalyst and application thereof in alcohol ether synthesis, belonging to the technical field of catalyst preparation, wherein the preparation method comprises the steps of preparing mixed powder, preparing microspheres, preparing solid-carried acid solution, preparing coated microspheres and carrying out secondary coating; the preparation method of the invention can improve the activity of the catalyst, reduce the reaction temperature, improve the using times of the catalyst and reduce the weight loss of the catalyst in the using process.

Description

Preparation method of composite solid acid catalyst and application of composite solid acid catalyst in alcohol ether synthesis
Technical Field
The invention relates to a preparation method of a composite solid acid catalyst and application thereof in alcohol ether synthesis, belonging to the technical field of catalyst preparation.
Background
The solid acid catalyst is an important catalyst in acid-base catalysts, and the catalytic function is derived from an acid part with catalytic activity on the surface of a solid, and the acid part is called as an acid center. Most of them are oxides or mixed oxides of non-transition elements, and their catalytic performance is different from that of oxide catalysts containing transition elements. The solid acid catalyst comprises: immobilized liquid acid, oxide, sulfide, metal salt, zeolite molecular sieve, heteropoly acid, cation exchange resin, natural clay mineral, solid super acid, etc.
At present, the solid acid catalyst is basically used for synthesizing alcohol ether, ethylene glycol methyl ether in petroleum secondary plant of petrochemical company of the vogue province of 1993 front adopts boron trifluoride diethyl etherate complex catalyst to produce alcohol ether, other manufacturers in China also adopt the same catalyst to produce alcohol ether, then a good effect is obtained by adopting a bentonite-based solid acid catalyst, after the reaction is finished, the kettle liquid is stood for 2 hours, the upper clear liquid is extracted, 5 kilograms of fresh catalyst is supplemented, then the next batch of products are produced, the catalyst can be used for one month repeatedly, then the inactivated catalyst is removed, and the new production cycle is put into again, and later, the catalyst is applied in the Chongqingfeng chemical industry of Liaongyang, Zhanggang solvent plants such as eastern glycollate plant. However, when the catalyst is applied to synthesis of ethylene glycol ethyl ether and butyl ether, the defects of insufficient activity and high reaction temperature exist, in addition, the defect of easy deactivation exists in the solid acid catalyst, although a plurality of methods are developed at present to improve the use times of the solid acid catalyst, the existing solid acid catalyst can be generally used for 20 times, and the catalytic efficiency is greatly reduced when the use times exceed 20 times, and phosphotungstic acid commonly used in synthesis of alcohol ether is dissolved in an organic solvent in the use process, so that the consumption is large in the use process.
Patent CN103934027B discloses a solid acid catalyst and its preparation method and application; the solid acid catalyst is a stable solid acid catalyst obtained by applying active carbon to load metal salt of heteropoly acid and covering a carbon layer on the surface, and can be used for catalyzing vanillyl alcohol and n-butyl alcohol to be etherified under mild conditions to obtain vanillyl alcohol butyl ether. The patent has the following defects: the solid acid catalyst has insufficient activity and is used repeatedly for a few times.
Disclosure of Invention
The invention provides a preparation method of a composite solid acid catalyst and application of the composite solid acid catalyst in alcohol ether synthesis, which can improve the activity of the catalyst, reduce the reaction temperature, improve the use times of the catalyst and reduce the weight loss of the catalyst in the use process.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a process for preparing the composite solid-acid catalyst includes preparing mixed powder, preparing microballs, preparing solid-carried acid liquid, preparing coated microballs and secondary coating.
The preparation method comprises the following steps of preparing mixed powder by mixing bentonite, zeolite powder and boron nitride according to a mass ratio of 3-6: 1, ball milling after uniformly mixing, and controlling the ball-material ratio in the ball milling process to be 20-30: 1, the rotating speed is 400-500rpm, the ball milling time is 3-4h, and mixed powder is obtained after the ball milling is finished.
The preparation method comprises the steps of uniformly mixing mixed powder, citric acid, acetic acid and chitin to obtain primary mixed liquid, controlling the temperature of the primary mixed liquid to be 50-60 ℃, then slowly dropwise adding a cross-linking liquid into the primary mixed liquid while carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 20-30kHz, controlling the dropwise adding time to be 30-40min, continuing the ultrasonic oscillation for 20-30min after the dropwise adding is finished to obtain mixed liquid, carrying out spray drying on the mixed liquid, controlling the temperature of an air inlet to be 110-120 ℃ and the temperature of an air outlet to be 70-80 ℃ in the spray drying process, and obtaining the microspheres after the spray drying is finished.
Wherein the mass ratio of the mixed powder, the citric acid, the acetic acid and the chitin is 25-30: 10-15: 15-20: 3-5.
Wherein the mass ratio of the primary mixed solution to the cross-linking solution is 1: 1.5-2.
The cross-linking liquid comprises the following components in parts by weight: 30-35 parts of diethyl ether, 15-20 parts of glutaraldehyde, 5-8 parts of zwitterionic polyacrylamide and 1-2 parts of ethyl acrylate.
The preparation method of the immobilized acid solution comprises the steps of adding nano activated carbon, aluminum chloride, polyvinyl alcohol 1788 and nano alumina into 1.5-2% by mass of phosphotungstic acid aqueous solution, and then stirring at the temperature of 50-60 ℃ for 2-2.5 hours at the stirring speed of 200-250rpm to obtain the immobilized acid solution.
Wherein, the mass ratio of phosphotungstic acid aqueous solution, nano activated carbon, aluminum chloride and polyvinyl alcohol 1788 to nano alumina is 30-35: 10-15: 3-5: 7-10: 15-20.
The particle size of the nano activated carbon is 80-100 nm.
The particle size of the nano alumina is 50-80 nm.
Preparing the coated microspheres by mixing the immobilized acid solution and the microspheres in a mass ratio of (2-3): 1, uniformly mixing, performing microwave oscillation, controlling the intensity of the microwave oscillation to be 50-70W, controlling the time of the microwave oscillation to be 30-40min, performing high-pressure treatment after the microwave oscillation is finished, controlling the temperature of the high-pressure treatment to be 65-70 ℃, the pressure of the high-pressure treatment to be 80-100MPa, and the time of the high-pressure treatment to be 10-15min, obtaining a wrapping liquid after the high-pressure treatment is finished, and then performing vacuum spray drying on the wrapping liquid, controlling the vacuum degree in the vacuum spray drying process to be 0.01-0.02MPa, controlling the air inlet temperature to be 110-.
And in the secondary coating, coating the microspheres and the acid gel according to a mass ratio of 1: 3-4, uniformly mixing, freezing, spray-drying, controlling the temperature of a spray freezing air inlet of the freezing spray-drying to be-20 to-10 ℃, the temperature of an air outlet to be-30 to-20 ℃, the temperature of a cold trap to be-60 to-50 ℃, the spray pressure to be 20-30bar, and obtaining the composite solid acid catalyst after the freezing spray-drying is finished.
The acidic gel comprises the following components in parts by weight: 30-35 parts of deionized water, 10-12 parts of hyaluronic acid, 7-10 parts of alginic acid, 3-5 parts of xanthan gum, 2-4 parts of acetic acid and 1-2 parts of poly (diallyldimethylammonium chloride).
The molecular weight of the hyaluronic acid is 1000-3000 kDa.
The application of the composite solid acid catalyst in alcohol ether synthesis is characterized by adding absolute ethyl alcohol and the composite solid acid catalyst into a reaction kettle, mixing, vacuumizing the reaction kettle until the vacuum degree is 60-80Pa, introducing nitrogen into the reaction kettle, controlling the gas pressure of the introduced nitrogen to be 0.06-0.08MPa, controlling the temperature of the reaction kettle to be 40-50 ℃, controlling the stirring speed to be 200-300rpm, then adding ethylene oxide, controlling the adding time of the ethylene oxide to be 1-1.5h, and continuing to react for 1.5-2h after the addition is finished to obtain ethylene glycol ether.
Wherein the molar ratio of the absolute ethyl alcohol to the ethylene oxide is 1-1.06: 1.
Wherein the mass ratio of the composite solid acid catalyst to the absolute ethyl alcohol is 43.33-46: 1.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the composite solid acid catalyst prepared by the invention, high-pressure treatment is carried out in the step of coating microspheres, and the solid acid catalyst is coated for the second time, so that the catalytic activity can be improved, the reaction temperature can be reduced, and the reaction temperature of absolute ethyl alcohol and ethylene oxide can be reduced to 40-50 ℃;
(2) according to the composite solid acid catalyst prepared by the invention, through ultrasonic oscillation in the microsphere preparation step, high-pressure treatment in the microsphere wrapping step and secondary wrapping of the solid acid catalyst, the yield and purity of ethylene glycol ethyl ether in the reaction of absolute ethyl alcohol and ethylene oxide can be improved, the yield of ethylene glycol ethyl ether is improved to 89.6-91.5%, and the purity is improved to 87.2-90.4%;
(3) the composite solid acid catalyst prepared by the invention can improve the using times of the catalyst by carrying out high-pressure treatment in the step of coating microspheres and carrying out secondary coating on the solid acid catalyst, and after the composite solid acid catalyst prepared by the invention is repeatedly used for 30 times, the yield of ethylene glycol ethyl ether can still reach 88.7-91.1%;
(4) the composite solid acid catalyst prepared by the invention can reduce the weight loss in the using process of the catalyst by carrying out high-pressure treatment in the step of coating microspheres and carrying out secondary coating on the solid acid catalyst, and after the composite solid acid catalyst prepared by the invention is repeatedly used for 30 times, the mass loss of ethylene glycol ethyl ether is 4.6-8%.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A preparation method of a composite solid acid catalyst comprises the following steps:
1. preparing mixed powder: mixing bentonite, zeolite powder and boron nitride according to a mass ratio of 6:1, ball milling after uniformly mixing, and controlling the ball-material ratio in the ball milling process to be 30: 1, the rotating speed is 500rpm, the ball milling time is 3h, and mixed powder is obtained after the ball milling is finished.
2. Preparing microspheres: uniformly mixing the mixed powder, citric acid, acetic acid and chitin to obtain a primary mixed solution, controlling the temperature of the primary mixed solution to 50 ℃, then slowly dropwise adding a cross-linking solution into the primary mixed solution while performing ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 20kHz, the dropwise adding time to be 30min, continuing the ultrasonic oscillation for 20min after the dropwise adding is finished to obtain a mixed solution, performing spray drying on the mixed solution, controlling the temperature of an air inlet to be 110 ℃, the temperature of an air outlet to be 70 ℃ in the spray drying process, and finishing the spray drying to obtain the microspheres.
Wherein the mass ratio of the mixed powder, the citric acid, the acetic acid and the chitin is 25: 10: 15: 3.
wherein the mass ratio of the primary mixed solution to the cross-linking solution is 1: 1.5.
the cross-linking liquid comprises the following components in parts by weight: 30 parts of diethyl ether, 15 parts of glutaraldehyde, 5 parts of zwitterionic polyacrylamide and 1 part of ethyl acrylate.
3. Preparing solid-carried acid solution: adding nano activated carbon, aluminum chloride, polyvinyl alcohol 1788 and nano alumina into 1.5 mass percent of phosphotungstic acid aqueous solution, and then stirring at the temperature of 50 ℃ and the stirring speed of 200rpm for 2-2.5h to obtain the immobilized acid solution.
Wherein, phosphotungstic acid aqueous solution, nano activated carbon, aluminum chloride and polyvinyl alcohol 1788, the mass ratio of nano alumina is 30: 10: 3: 7: 15.
the particle size of the nano activated carbon is 80 nm.
The particle size of the nano alumina is 50 nm.
4. Preparing a coating microsphere: carrying out solid-carried acid solution and microspheres according to a mass ratio of 2: 1, uniformly mixing, performing microwave oscillation, controlling the intensity of the microwave oscillation to be 50W, controlling the time of the microwave oscillation to be 30min, performing high-pressure treatment after the microwave oscillation is finished, controlling the temperature of the high-pressure treatment to be 65 ℃, the pressure of the high-pressure treatment to be 80MPa, controlling the time of the high-pressure treatment to be 10min, obtaining a wrapping liquid after the high-pressure treatment is finished, then performing vacuum spray drying on the wrapping liquid, controlling the vacuum degree in the vacuum spray drying process to be 0.01MPa, the air inlet temperature to be 110 ℃, the air outlet temperature to be 60 ℃, and obtaining the wrapping microspheres after the vacuum spray drying is finished.
5. Secondary packaging: coating the microspheres and the acid gel according to a mass ratio of 1: 3, uniformly mixing, freezing, spraying and drying, controlling the temperature of a spray freezing air inlet of the freezing spray drying to be-20 ℃, the temperature of an air outlet of the freezing spray drying to be-30 ℃, the temperature of a cold trap to be-60 ℃, and the spraying pressure to be 20bar, and obtaining the composite solid acid catalyst after the freezing spray drying is finished.
The acidic gel comprises the following components in parts by weight: 30 parts of deionized water, 10 parts of hyaluronic acid, 7 parts of alginic acid, 3 parts of xanthan gum, 2 parts of acetic acid and 1 part of poly (diallyldimethylammonium chloride).
The molecular weight of the hyaluronic acid is 1000 kDa.
Example 2
A preparation method of a composite solid acid catalyst comprises the following steps:
1. preparing mixed powder: mixing bentonite, zeolite powder and boron nitride according to a mass ratio of 5: 1, ball milling after uniformly mixing, and controlling the ball-material ratio in the ball milling process to be 25: 1, the rotating speed is 450rpm, the ball milling time is 3.5h, and mixed powder is obtained after the ball milling is finished.
2. Preparing microspheres: uniformly mixing the mixed powder, citric acid, acetic acid and chitin to obtain a primary mixed solution, controlling the temperature of the primary mixed solution to 55 ℃, then slowly dropwise adding a cross-linking solution into the primary mixed solution while performing ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 25kHz, the dropwise adding time to be 35min, continuing the ultrasonic oscillation for 25min after the dropwise adding is finished to obtain a mixed solution, performing spray drying on the mixed solution, controlling the temperature of an air inlet to be 115 ℃ and the temperature of an air outlet to be 75 ℃ in the spray drying process, and finishing the spray drying to obtain the microspheres.
Wherein the mass ratio of the mixed powder, the citric acid, the acetic acid and the chitin is 27: 12: 17: 4.
wherein the mass ratio of the primary mixed solution to the cross-linking solution is 1: 1.7.
the cross-linking liquid comprises the following components in parts by weight: 32 parts of diethyl ether, 17 parts of glutaraldehyde, 7 parts of zwitterionic polyacrylamide and 1.5 parts of ethyl acrylate.
3. Preparing solid-carried acid solution: adding nano activated carbon, aluminum chloride, polyvinyl alcohol 1788 and nano alumina into 1.7 mass percent of phosphotungstic acid aqueous solution, and then stirring at 55 ℃ and a stirring speed of 220rpm for 2.2 hours to obtain the solid-carried acid solution.
Wherein, phosphotungstic acid aqueous solution, nano activated carbon, aluminum chloride and polyvinyl alcohol 1788, the mass ratio of nano alumina is 32: 12: 4: 9: 17.
the particle size of the nano activated carbon is 90 nm.
The particle size of the nano alumina is 70 nm.
4. Preparing a coating microsphere: carrying out solid-carried acid solution and microspheres according to the mass ratio of 2.5: 1, uniformly mixing, performing microwave oscillation, controlling the intensity of the microwave oscillation to be 60W, controlling the time of the microwave oscillation to be 35min, performing high-pressure treatment after the microwave oscillation is finished, controlling the temperature of the high-pressure treatment to be 67 ℃, the pressure of the high-pressure treatment to be 90MPa, controlling the time of the high-pressure treatment to be 12min, obtaining a wrapping liquid after the high-pressure treatment is finished, then performing vacuum spray drying on the wrapping liquid, controlling the vacuum degree in the vacuum spray drying process to be 0.01MPa, the air inlet temperature to be 115 ℃, the air outlet temperature to be 65 ℃, and obtaining the wrapping microspheres after the vacuum spray drying is finished.
5. Secondary packaging: coating the microspheres and the acid gel according to a mass ratio of 1: 3.5, after uniformly mixing, carrying out freeze spray drying, controlling the temperature of a spray freezing air inlet of the freeze spray drying to be-15 ℃, the temperature of an air outlet to be-25 ℃, the temperature of a cold trap to be-55 ℃, and the spray pressure to be 25bar, and finally obtaining the composite solid acid catalyst after the freeze spray drying.
The acidic gel comprises the following components in parts by weight: 32 parts of deionized water, 11 parts of hyaluronic acid, 8 parts of alginic acid, 4 parts of xanthan gum, 3 parts of acetic acid and 1.5 parts of poly (diallyldimethylammonium chloride).
The molecular weight of the hyaluronic acid is 2000 kDa.
Example 3
A preparation method of a composite solid acid catalyst comprises the following steps:
1. preparing mixed powder: mixing bentonite, zeolite powder and boron nitride according to a mass ratio of 6:1, ball milling after uniformly mixing, and controlling the ball-material ratio in the ball milling process to be 30: 1, the rotating speed is 500rpm, the ball milling time is 4 hours, and mixed powder is obtained after the ball milling is finished.
2. Preparing microspheres: uniformly mixing the mixed powder, citric acid, acetic acid and chitin to obtain a primary mixed solution, controlling the temperature of the primary mixed solution to 60 ℃, then slowly dropwise adding a cross-linking solution into the primary mixed solution while performing ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 30kHz, the dropwise adding time to be 40min, continuing the ultrasonic oscillation for 30min after the dropwise adding is finished to obtain a mixed solution, performing spray drying on the mixed solution, controlling the temperature of an air inlet to be 120 ℃, the temperature of an air outlet to be 80 ℃ in the spray drying process, and finishing the spray drying to obtain the microspheres.
Wherein the mass ratio of the mixed powder, the citric acid, the acetic acid and the chitin is 30: 15: 20: 5.
wherein the mass ratio of the primary mixed solution to the cross-linking solution is 1: 2.
the cross-linking liquid comprises the following components in parts by weight: 35 parts of diethyl ether, 20 parts of glutaraldehyde, 8 parts of zwitterionic polyacrylamide and 2 parts of ethyl acrylate.
3. Preparing solid-carried acid solution: adding nano activated carbon, aluminum chloride, polyvinyl alcohol 1788 and nano alumina into 2 mass percent phosphotungstic acid aqueous solution, and then stirring at the stirring speed of 250rpm for 2.5 hours at the temperature of 60 ℃ to obtain the solid-carried acid solution.
Wherein, phosphotungstic acid aqueous solution, nano activated carbon, aluminum chloride and polyvinyl alcohol 1788, and the mass ratio of nano alumina is 35: 15: 5: 10: 20.
the particle size of the nano activated carbon is 100 nm.
The particle size of the nano alumina is 80 nm.
4. Preparing a coating microsphere: carrying out solid-carried acid solution and microspheres according to the mass ratio of 3: 1, uniformly mixing, performing microwave oscillation, controlling the intensity of the microwave oscillation to be 70W, controlling the time of the microwave oscillation to be 40min, performing high-pressure treatment after the microwave oscillation is finished, controlling the temperature of the high-pressure treatment to be 70 ℃, the pressure of the high-pressure treatment to be 100MPa, controlling the time of the high-pressure treatment to be 15min, obtaining a wrapping liquid after the high-pressure treatment is finished, then performing vacuum spray drying on the wrapping liquid, controlling the vacuum degree in the vacuum spray drying process to be 0.02MPa, the air inlet temperature to be 120 ℃, the air outlet temperature to be 70 ℃, and obtaining wrapping microspheres after the vacuum spray drying is finished.
5. Secondary packaging: coating the microspheres and the acid gel according to a mass ratio of 1: 4, uniformly mixing, freezing, spraying and drying, controlling the temperature of a spray freezing air inlet of the freezing and spraying drying to be-10 ℃, the temperature of an air outlet to be-20 ℃, the temperature of a cold trap to be-50 ℃, the spraying pressure to be 30bar, and obtaining the composite solid acid catalyst after the freezing and spraying drying.
The acidic gel comprises the following components in parts by weight: 35 parts of deionized water, 12 parts of hyaluronic acid, 10 parts of alginic acid, 5 parts of xanthan gum, 4 parts of acetic acid and 2 parts of poly (diallyldimethylammonium chloride).
The molecular weight of the hyaluronic acid is 3000 kDa.
Comparative example 1
The preparation method of the composite solid acid catalyst described in example 1 is adopted, and the difference is that: and in the step 2, replacing ultrasonic oscillation with mechanical oscillation in the step of preparing the microspheres, and controlling the frequency of the mechanical oscillation to be 20 kHz.
Comparative example 2
The preparation method of the composite solid acid catalyst described in example 1 is adopted, and the difference is that: and (4) omitting high-pressure treatment in the step of preparing the coating microspheres, namely obtaining the coating liquid after microwave oscillation is finished.
Comparative example 3
The preparation method of the composite solid acid catalyst described in example 1 is adopted, and the difference is that: the 5 th secondary wrapping step is omitted.
Example 4
Adding 46kg of absolute ethyl alcohol into a reaction kettle, adding 1kg of the compound solid acid catalyst prepared in the embodiment 1, vacuumizing the reaction kettle until the vacuum degree is 60Pa, introducing nitrogen into the reaction kettle, controlling the gas pressure of the introduced nitrogen to be 0.06MPa, controlling the temperature of the reaction kettle to be 40 ℃ and the stirring speed to be 200rpm, then adding 44kg of ethylene oxide, controlling the adding time of the ethylene oxide to be 1h, and continuing to react for 1.5h after the addition is finished to obtain the ethylene glycol ether. The yield of ethylene glycol ethyl ether was 90.4% and the purity was 90.4%.
After the compound solid acid catalyst prepared by the preparation method of the embodiment is reused for 30 times, the yield of the ethylene glycol ethyl ether can still reach 89.1%; after repeated use for 30 times, the mass of the residual composite solid acid catalyst is 0.92kg, and the mass loss is 8%.
Example 5
Adding 50kg of absolute ethyl alcohol into a reaction kettle, adding 1.1kg of the composite solid acid catalyst prepared in the embodiment 2, vacuumizing the reaction kettle until the vacuum degree is 70Pa, introducing nitrogen into the reaction kettle, controlling the gas pressure of the introduced nitrogen to be 0.07MPa, controlling the temperature of the reaction kettle to be 45 ℃ and the stirring speed to be 250rpm, then adding 45kg of ethylene oxide, controlling the adding time of the ethylene oxide to be 1.2h, and continuing to react for 1.7h after the addition is finished to obtain the ethylene glycol ether. The yield of ethylene glycol ethyl ether was 91.5% and the purity was 88.7%.
After the compound solid acid catalyst prepared by the preparation method of the embodiment is reused for 30 times, the yield of the ethylene glycol ethyl ether can still reach 91.1%; after the composite solid acid catalyst is repeatedly used for 30 times, the mass of the residual composite solid acid catalyst is 1.05kg, and the mass loss is 4.6%.
Example 6
Adding 52kg of absolute ethyl alcohol into a reaction kettle, adding 1.2kg of the composite solid acid catalyst prepared in the embodiment 3, vacuumizing the reaction kettle until the vacuum degree is 80Pa, introducing nitrogen into the reaction kettle, controlling the gas pressure of the introduced nitrogen to be 0.08MPa, controlling the temperature of the reaction kettle to be 50 ℃ and the stirring speed to be 300rpm, then adding 47kg of ethylene oxide, controlling the adding time of the ethylene oxide to be 1.5h, and continuing to react for 2h after the addition is finished to obtain the ethylene glycol ether. The yield of ethylene glycol ethyl ether was 89.6% and the purity was 87.2%.
After the compound solid acid catalyst prepared by the preparation method of the embodiment is reused for 30 times, the yield of the ethylene glycol ethyl ether can still reach 88.7%; after repeated use for 30 times, the mass of the residual composite solid acid catalyst is 1.11kg, and the mass loss is 7.5%.
Comparative example 4
Adding 46kg of absolute ethyl alcohol into a reaction kettle, adding 1kg of the composite solid acid catalyst prepared in the comparative example 1, vacuumizing the reaction kettle until the vacuum degree is 60Pa, introducing nitrogen into the reaction kettle, controlling the gas pressure of the introduced nitrogen to be 0.06MPa, controlling the temperature of the reaction kettle to be 40 ℃ and the stirring speed to be 200rpm, then adding 44kg of ethylene oxide, controlling the adding time of the ethylene oxide to be 1h, and continuing to react for 1.5h after the addition is finished to obtain the ethylene glycol ether. The yield of ethylene glycol ethyl ether was 82.4% and the purity was 82.4%.
After the prepared composite solid acid catalyst is reused for 30 times according to the preparation method of the embodiment, the yield of the ethylene glycol ethyl ether is 81.5%; after repeated use for 30 times, the mass of the residual composite solid acid catalyst is 0.9kg, and the mass loss is 10%.
Comparative example 5
Adding 50kg of absolute ethyl alcohol into a reaction kettle, adding 1.1kg of the composite solid acid catalyst prepared in the comparative example 2, vacuumizing the reaction kettle until the vacuum degree is 70Pa, introducing nitrogen into the reaction kettle, controlling the gas pressure of the introduced nitrogen to be 0.07MPa, controlling the temperature of the reaction kettle to be 45 ℃ and the stirring speed to be 250rpm, then adding 45kg of ethylene oxide, controlling the adding time of the ethylene oxide to be 1.2h, and continuing to react for 1.7h after the addition is finished to obtain the ethylene glycol ether. The yield of ethylene glycol ethyl ether was 86.4% and the purity was 83.7%.
After the prepared composite solid acid catalyst is reused for 30 times according to the preparation method of the embodiment, the yield of the ethylene glycol ethyl ether is 50.7%; after repeated use for 30 times, the mass of the residual composite solid acid catalyst is 0.56kg, and the mass loss is 49.1%.
Comparative example 6
Adding 52kg of absolute ethyl alcohol into a reaction kettle, adding 1.2kg of the composite solid acid catalyst prepared in the comparative example 3, vacuumizing the reaction kettle until the vacuum degree is 80Pa, introducing nitrogen into the reaction kettle, controlling the gas pressure of the introduced nitrogen to be 0.08MPa, controlling the temperature of the reaction kettle to be 50 ℃ and the stirring speed to be 300rpm, then adding 47kg of ethylene oxide, controlling the adding time of the ethylene oxide to be 1.5h, and continuing to react for 2h after the addition is finished to obtain the ethylene glycol ether. The yield of ethylene glycol ethyl ether was 76.9% and the purity was 74.8%.
After the prepared composite solid acid catalyst is reused for 30 times according to the preparation method of the embodiment, the yield of the ethylene glycol ethyl ether is 45.2%; after the composite solid acid catalyst is repeatedly used for 30 times, the mass of the residual composite solid acid catalyst is 0.46kg, and the mass loss is 61.7%.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: 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.

Claims (8)

1. A preparation method of a composite solid acid catalyst is characterized by comprising the steps of preparing mixed powder, preparing microspheres, preparing solid acid carrying liquid, preparing coated microspheres and carrying out secondary coating;
the preparation method comprises the following steps of preparing mixed powder by mixing bentonite, zeolite powder and boron nitride according to a mass ratio of 3-6: 1, ball milling is carried out after uniform mixing, and mixed powder is obtained after ball milling is finished;
the preparation method comprises the steps of preparing microspheres, uniformly mixing mixed powder, citric acid, acetic acid and chitin to obtain primary mixed liquid, controlling the temperature of the primary mixed liquid to be 50-60 ℃, then slowly dropwise adding a cross-linking liquid into the primary mixed liquid while carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 20-30kHz, controlling the dropwise adding time to be 30-40min, continuing the ultrasonic oscillation for 20-30min after the dropwise adding is finished to obtain mixed liquid, carrying out spray drying on the mixed liquid, and finishing the spray drying to obtain the microspheres;
preparing the coated microspheres by mixing the immobilized acid solution and the microspheres in a mass ratio of (2-3): 1, uniformly mixing, performing microwave oscillation, controlling the intensity of the microwave oscillation to be 50-70W, controlling the time of the microwave oscillation to be 30-40min, performing high-pressure treatment after the microwave oscillation is finished, controlling the temperature of the high-pressure treatment to be 65-70 ℃, the pressure of the high-pressure treatment to be 80-100MPa, and the time of the high-pressure treatment to be 10-15min, obtaining a wrapping liquid after the high-pressure treatment is finished, and then performing vacuum spray drying on the wrapping liquid, controlling the vacuum degree in the vacuum spray drying process to be 0.01-0.02MPa, controlling the air inlet temperature to be 110-;
and in the secondary coating, coating the microspheres and the acid gel according to a mass ratio of 1: 3-4, uniformly mixing, freezing, spray-drying, controlling the temperature of a spray freezing air inlet of the freezing spray-drying to be-20 to-10 ℃, the temperature of an air outlet to be-30 to-20 ℃, the temperature of a cold trap to be-60 to-50 ℃, the spray pressure to be 20-30bar, and obtaining the composite solid acid catalyst after the freezing spray-drying is finished.
2. The preparation method of the composite solid acid catalyst according to claim 1, wherein the mass ratio of the mixed powder, the citric acid, the acetic acid and the chitin is 25-30: 10-15: 15-20: 3-5.
3. The preparation method of the composite solid acid catalyst according to claim 1, wherein the mass ratio of the primary mixed solution to the crosslinking solution is 1: 1.5-2.
4. The preparation method of the composite solid acid catalyst according to claim 1, wherein the composition of the crosslinking solution comprises, in parts by weight: 30-35 parts of diethyl ether, 15-20 parts of glutaraldehyde, 5-8 parts of zwitterionic polyacrylamide and 1-2 parts of ethyl acrylate.
5. The preparation method of the composite solid acid catalyst as claimed in claim 1, wherein the preparation of the immobilized acid solution comprises adding nano activated carbon, aluminum chloride, polyvinyl alcohol 1788 and nano alumina into 1.5-2% by mass of phosphotungstic acid aqueous solution, and stirring at 50-60 ℃ and at a stirring speed of 200-250rpm for 2-2.5h to obtain the immobilized acid solution.
6. The preparation method of the composite solid acid catalyst according to claim 5, wherein the mass ratio of the phosphotungstic acid aqueous solution, the nano activated carbon, the aluminum chloride, the polyvinyl alcohol 1788 and the nano alumina is 30-35: 10-15: 3-5: 7-10: 15-20.
7. The preparation method of the composite solid acid catalyst according to claim 1, wherein the composition of the acidic gel comprises, in parts by weight: 30-35 parts of deionized water, 10-12 parts of hyaluronic acid, 7-10 parts of alginic acid, 3-5 parts of xanthan gum, 2-4 parts of acetic acid and 1-2 parts of poly (diallyldimethylammonium chloride).
8. The application of the composite solid acid catalyst prepared by the method of claim 1 in alcohol ether synthesis is characterized in that absolute ethyl alcohol and the composite solid acid catalyst are added into a reaction kettle to be mixed, the reaction kettle is vacuumized to the vacuum degree of 60-80Pa, then nitrogen is introduced into the reaction kettle, the gas pressure of the introduced nitrogen is controlled to be 0.06-0.08MPa, the temperature of the reaction kettle is controlled to be 40-50 ℃, the stirring speed is controlled to be 200-phase stirring 300rpm, then ethylene oxide is added, the adding time of the ethylene oxide is controlled to be 1-1.5h, and the reaction is continued for 1.5-2h after the addition is finished to obtain ethylene glycol ether;
wherein the molar ratio of the absolute ethyl alcohol to the ethylene oxide is 1-1.06: 1;
wherein the mass ratio of the composite solid acid catalyst to the absolute ethyl alcohol is 43.33-46: 1.
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