CN112844482A - Acid-base dual-function heterogeneous catalyst with core-shell structure, preparation method thereof and method for cracking and recycling butyl acrylate heavy component - Google Patents

Acid-base dual-function heterogeneous catalyst with core-shell structure, preparation method thereof and method for cracking and recycling butyl acrylate heavy component Download PDF

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CN112844482A
CN112844482A CN202110046076.8A CN202110046076A CN112844482A CN 112844482 A CN112844482 A CN 112844482A CN 202110046076 A CN202110046076 A CN 202110046076A CN 112844482 A CN112844482 A CN 112844482A
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butyl acrylate
acid
core
catalyst
temperature
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CN112844482B (en
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徐世伟
张宏科
朱子忠
赵越
葛飞
李帅帅
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Wanhua Chemical Group Co Ltd
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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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to an acid-base bifunctional heterogeneous catalyst with a core-shell structure, a preparation method of the acid-base bifunctional heterogeneous catalyst, and a method for cracking and recycling butyl acrylate heavy components. The catalyst is of a core-shell structure and simultaneously loads acid and alkaline active centers. The catalyst is used for catalytically cracking the butyl acrylate heavy component, so that the cracking rate of the butyl acrylate heavy component can be improved, side reactions such as butyl alcohol dehydration acrylic acid and butyl ester polymerization can be inhibited, and the catalyst has the advantages of high cracking rate, high selectivity and high recovery rate. Under the action of the catalyst, butanol and acrylic acid generated by cracking can be continuously catalyzed and esterified to generate butyl acrylate with high conversion rate and high selectivity, side reactions of butanol dehydration to generate dibutyl ether and the like are reduced, and the esterification reaction selectivity is improved.

Description

Acid-base dual-function heterogeneous catalyst with core-shell structure, preparation method thereof and method for cracking and recycling butyl acrylate heavy component
Technical Field
The invention belongs to the technical field of butyl acrylate preparation, and relates to an acid-base bifunctional heterogeneous catalyst with a core-shell structure, a preparation method of the acid-base bifunctional heterogeneous catalyst, and a method for cracking and recovering butyl acrylate heavy components.
Background
With the increase of the productivity of the acrylate, the product competition is gradually intensified. Controlling the unit consumption of acrylate is an important means to reduce costs. A large amount of heavy components are by-produced in the production process of butyl acrylate, the main component is butyl butoxypropionate, and the recovery rate of a heavy component cracker is an important factor influencing the unit consumption of acrylic acid and butanol.
In the production process of butyl acrylate, butyl acrylate and butanol in an esterification reactor can react to generate a byproduct, namely beta-butoxy butyl propionate, the byproduct enters a heavy component cracker along with a heavy component to be recycled, the heavy component mainly comprises beta-butoxy butyl propionate (BPB for short, the content is more than 95%), butyl acrylate (about 2%) and a polymerization inhibitor (phenothiazine and hydroquinone, the content is about 3%), the beta-butoxy butyl propionate can be cracked to generate butyl acrylate and butanol for further recycling under the conditions of catalyst and high temperature after entering the cracker, and the reaction equation is as follows:
main reaction: c4H9C2H4COOC4H9→C2H4COOC4H9+C4H9OH
Side reaction: 2C4H9OH→C4H9-O-C4H9+H2O
At present, homogeneous catalysts such as p-toluenesulfonic acid and the like are mostly adopted in the method for cracking and recovering butyl acrylate heavy components, and beta-butoxy butyl propionate is catalyzed at high temperature to crack to generate butyl acrylate and butanol. The cracking rate and the recovery rate of the homogeneous catalytic cracking are low, and the homogeneous catalyst enters a heavy component storage tank along with the heavy component after the cracking reaction and is stored for sale or is incinerated. During storage, the homogeneous catalyst has strong acidity and strong corrosivity, and causes corrosion to equipment such as storage tanks and pipelines. The problem of tail gas sulfur exceeding standard and the like caused by the sulfur contained in the catalyst in the heavy component incineration treatment. Butanol generated by cracking under the conditions of homogeneous catalyst and high temperature can be dehydrated to generate dibutyl ether, and enters products along with light components, so that the product quality is influenced.
The patent CN102173990A adopts high-temperature cracking and atmospheric distillation to process butyl acrylate heavy components, but the method has low recovery rate and more by-products such as dibutyl ether, and the butyl acrylate can be generated only by returning to an esterification reactor for re-esterification.
In patent CN101932547A, a Michael addition product of sulfonic acid, acrylic acid and ester is mixed with water and cracked and recovered at 150 ℃, and the method has the problems of high corrosion of a homogeneous catalyst to equipment and low cracking and recovery rate of heavy components, and the homogeneous catalyst needs to be separated and has a complex process.
The patent CN102516061A uses atmospheric and vacuum distillation and a screw extruder to process heavy components of acrylic ester, but only can realize the recovery of light components, and can not realize the cracking and esterification processes.
Patent CN106905155A proposes to adopt solid super acidic catalyst schizolysis to retrieve butyl acrylate heavy ends, adds acrylic acid to heavy ends schizolysis raw materials, through pyrolysis and esterification reaction, retrieves the heavy ends and esterifies the butanol that produces simultaneously and produces butyl ester, avoids a large amount of by-products such as butyl ether that generate after dehydration of butanol. But the cracking rate of heavy component BPB is lower, more butyl ether is generated by butanol dehydration side reaction, and the yield of BA is lower.
Based on the problems of low recovery rate of a homogeneous catalyst, high selectivity of a byproduct dibutyl ether and equipment corrosion caused by the homogeneous catalyst in the conventional method for cracking the butyl acrylate heavy component, a new method for cracking the butyl acrylate heavy component needs to be found, so that the cracking rate of the heavy component is improved, side reactions are reduced, and the problems of equipment corrosion and difficult recovery of the catalyst are solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel acid-base bifunctional heterogeneous catalyst with a core-shell structure and a preparation method thereof. The catalyst is used for catalytically cracking the butyl acrylate heavy component, so that the cracking rate of the butyl acrylate heavy component can be improved, side reactions such as butyl alcohol dehydration acrylic acid and butyl ester polymerization can be inhibited, and the catalyst has the advantages of high cracking rate, high selectivity and high recovery rate. Under the action of the catalyst, butanol and acrylic acid generated by cracking can be continuously catalyzed and esterified to generate butyl acrylate with high conversion rate and high selectivity, side reactions of butanol dehydration to generate dibutyl ether and the like are reduced, and the esterification reaction selectivity is improved.
The catalyst is of a core-shell structure, and simultaneously supports an acidic active center and a basic active center, the preparation method comprises the steps of adopting a mesoporous material as a core layer carrier, loading a large number of Al atoms on a skeleton of the mesoporous material through a grafting method to obtain an ordered mesoporous silicon material with stronger acidity, then carrying out alkali modification through an impregnation method by adopting N-tert-butylacrylamide, complexing with silicon hydroxyl on the surface of the mesoporous material, loading the basic active center on the core layer carrier through complexing to obtain a core layer structure simultaneously supporting the acidic active center and the basic active center, and then coating a shell layer containing the strong acid center on the surface of the core layer structure through a hydrothermal synthesis method to form the acid-base dual-function core-shell structure heterogeneous catalyst, wherein the shell layer of the catalyst is provided with the strong acid active center, and the core layer is provided with the acidic active center and the basic active center.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of an acid-base bifunctional heterogeneous catalyst with a core-shell structure, which comprises the following steps:
(1) preparing a core layer mesoporous material loaded with an acidic active center by a grafting method: dissolving P123 (polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer) in hydrochloric acid, adding butanol, uniformly mixing, adding aluminum isopropoxide and Tetraethoxysilane (TEOS), uniformly mixing, then carrying out crystallization reaction, adjusting the pH value of a system to 7.5-8.5 by using ammonia water after crystallization is finished, and carrying out constant-temperature hydrothermal treatment to obtain a core-layer mesoporous material (Al-KIT-6) loaded with an acidic active center;
(2) The core layer mesoporous material adopts an impregnation method to complex and load an alkaline active center: roasting and activating the nuclear mesoporous material loaded with the acidic active center prepared in the step (1), then adding the nuclear mesoporous material into acetonitrile solution of N-tert-butylacrylamide for soaking, taking out and drying to obtain the nuclear mesoporous material (Al-KIT-6-NH) loaded with the acidic active center and the alkaline active center simultaneously2)；
(3) The core layer mesoporous material is coated with a mesoporous structure shell material loaded with a strong acid active center by a hydrothermal synthesis method: dispersing the core layer mesoporous material loaded with the acidic and alkaline active centers prepared in the step (2) in water, adding Cetyl Trimethyl Ammonium Bromide (CTAB) for full dissolution, and then adding Tetraethoxysilane (TEOS) and ammonium paratungstate (H)8N2O4W), cerium nitrate hexahydrate (Ce (NO)3)3·6H2O), hydrothermal reacting until the system is gel, standing, filtering, washing, drying, and adding ammonium sulfate ((NH)4)2SO4) And ammonium fluoride (NH)4F) The acid-base bifunctional core-shell structure heterogeneous catalyst is obtained by soaking in the composite aqueous solution, taking out, drying and roasting.
In the preparation method, in the step (1), the mass ratio of P123 to tetraethoxysilane, aluminum isopropoxide, hydrochloric acid (calculated by HCl in the solution) and butanol (namely P123: TEOS: AiPO: HCl: BuOH) is 1: (10-100): (1-5): (0.5-2): (1-2), preferably 1: (30-90): (2-3): (0.5-1): (1-1.5).
Preferably, the hydrochloric acid concentration is 1 to 5 wt%, preferably 1 to 2 wt%.
The preparation method comprises the step (1), wherein the crystallization reaction is carried out at the temperature of 100-150 ℃, preferably at the temperature of 100-120 ℃; the time is 12-24h, preferably 20-24 h.
In the preparation method of the invention, in the step (1), when the pH value of the system is adjusted by ammonia water after crystallization is finished, the concentration of the ammonia water is preferably 10-20 wt%, and preferably 15-20 wt%.
The preparation method comprises the step (1), wherein the constant-temperature hydrothermal treatment is carried out at the temperature of 90-120 ℃, preferably at the temperature of 100-.
In the preparation method, after the constant-temperature hydrothermal treatment is completed in step (1), conventional post-treatment processes such as washing, filtering, drying, extracting and the like are further included, in some examples, the post-treatment method adopted by the invention is preferably that reaction liquid after the constant-temperature hydrothermal treatment is washed, filtered and dried, then extracted by using an ethanol-hydrochloric acid solution, and dried again to obtain solid powder, namely the core layer mesoporous material loaded with the acidic active center;
wherein in the extraction process, the dosage of the extractant ethanol-hydrochloric acid solution is calculated by adding a mixed solution of 145-155mL of ethanol and 3-4g of 37% HCl into each 1g of solid sample;
wherein the drying operation temperature is 100-120 ℃, and the time is 10-12 h.
In the step (2), the roasting activation is carried out in an air atmosphere at the temperature of 500-600 ℃, preferably 520-540 ℃; the time is 4-8h, preferably 4-6 h.
In the preparation method, in the step (2), the impregnation process is carried out for 2-12h, preferably 2-4 h; the dipping solution adopted in the dipping process is the acetonitrile solution of the N-tertiary butyl acrylamide, and the concentration is 0.1-1mol/L, preferably 0.1-0.5 mol/L;
preferably, the amount of the impregnation liquid is such that every 1g of the sample is impregnated with 25 to 30ml of the N-t-butylacrylamide acetonitrile solution.
The preparation method comprises the step (2) of drying at the temperature of 80-100 ℃ for 5-8 h.
In the preparation method, in the step 3), the dispersion concentration of the core-layer mesoporous material loaded with the acidic and alkaline active centers in water is 0.02-0.05 g/mL;
the mass ratio of the core-layer mesoporous material loaded with the acidic and alkaline active centers to the cetyl trimethyl ammonium bromide and the tetraethoxysilane is 1: 1-2: 1-2, preferably 1: 1-1.5: 1-1.4;
the mass ratio of the core layer mesoporous material loaded with the acidic and alkaline active centers to the ammonium paratungstate and the cerium nitrate hexahydrate is 1: 0.28-1.4: 0.03 to 0.5, preferably 1: 0.28-0.84: 0.03-0.30.
In the preparation method, in the step 3), the hydrothermal reaction is carried out in a constant-temperature water bath under stirring, and the reaction temperature is 50-80 ℃, preferably 60-70 ℃; stirring for 1-4h, preferably 1-2h until the system is gelatinous, and standing for 1-4h, preferably 1-2 h;
the stirring speed is 100-.
In the preparation method, in the step 3), the time of the impregnation process is 2-12h, preferably 4-6 h; the impregnation process adopts equal-volume impregnation, and the impregnation liquid adopted in the impregnation process is a composite aqueous solution of ammonium sulfate and ammonium fluoride, wherein the total mass of the aqueous solution is 100 wt%, the ammonium sulfate is 3-7 wt%, and the ammonium fluoride is 0.74-3.7 wt%.
In the preparation method, step 3), the filtration, washing, drying and roasting are conventional operations in the field, and in some examples, the method preferably adopted after the standing is finished is to cool the system to room temperature, pump-filter, wash the system to neutrality by using distilled water and absolute ethyl alcohol, and then dry the system;
the drying temperature is 100-120 ℃, and the drying time is 2-4 h;
the roasting temperature is 400-600 ℃, preferably 480-580 ℃, and more preferably 500-560 ℃; the time is 2-12h, preferably 4-8 h.
The invention also provides the acid-base bifunctional heterogeneous catalyst with the core-shell structure, which is prepared by the method.
The catalyst comprises an internal core-layer structure (Al-KIT-6-NH)2) The nuclear layer structure takes a mesoporous material as a framework, the mesoporous material is loaded with an acidic active center Al through grafting, and is loaded with a basic active center NH through complexing2-O-Si；
The shell structure is coated outside the core layer structure, the shell structure takes a mesoporous material as a framework, the mesoporous material is doped with tungsten oxide and cerium oxide, and a strong acid active center SO is loaded on the mesoporous material4 2-、 F-1、WO3And CeO2。
The particle size of the catalyst is 150-200 mu m; specific surface area of 400-2G, preferably 700-850m2/g；
The pore diameter of the shell layer is 50-200nm, preferably 50-120nm, and the total acid amount is 0.4-0.9mmol/g, preferably 0.7-0.85 mmol/g;
the pore diameter of the nuclear layer is 4-12nm, preferably 6-10nm, and the total acid amount is 0.4-0.7mmol/g, preferably 0.4-0.55 mmol/g; the total alkali amount of the core layer is 0.5-4mmol/g, preferably 0.5-1.5 mmol/g;
preferably, the mass ratio of the core layer to the shell layer is 2-10:1, preferably 2-4.5: 1.
The catalyst of the invention, wherein the Si/Al molar ratio is between 10 and 100, preferably between 20 and 50; the molar ratio of W to Ce is 1-20:1, preferably 5-10: 1; f-1/SO4 2-The molar ratio is 1:1-10, preferably 1: 1.5-4.
In the shell structure of the catalyst, the load of W is 0.5-4mmol/g, preferably 0.5-2 mmol/g; the loading amount of Ce is 0.1-0.4mmol/g, preferably 0.1-0.2 mmol/g.
Meanwhile, the invention also provides application of the acid-base bifunctional core-shell structure heterogeneous catalyst prepared by the method in cracking recovery of butyl acrylate heavy components.
According to the application, the method for cracking and recycling the heavy component of the butyl acrylate is provided, the method takes the byproduct heavy component of the butyl acrylate as a raw material, adopts the acid-base bifunctional core-shell structure heterogeneous catalyst, performs cracking reaction at a certain temperature and under a certain pressure to generate the butyl acrylate and butanol, simultaneously adds a certain amount of acrylic acid into a reaction system, and performs esterification reaction with the butanol generated by cracking at the temperature and under the action of the acid-base bifunctional core-shell structure heterogeneous catalyst to obtain the butyl acrylate.
In the method, the butyl acrylate byproduct heavy component comprises 95-97% of beta-butoxy butyl propionate, 0.5-2% of butyl acrylate and 1-3% of polymerization inhibitor by taking the total mass as 100%; the polymerization inhibitor mainly comprises phenothiazine, hydroquinone and the like.
In the process of the present invention, the amount of the catalyst is 2 to 20%, preferably 2 to 12%, more preferably 2 to 5% by mass of the butyl acrylate by-product heavy component.
In the method, the cracking reaction temperature is 120-220 ℃, preferably 140-190 ℃; the pressure is 40 to 100Kpa (absolute), preferably 60 to 90Kpa (absolute), and the reaction time is 2 to 12 hours, preferably 4 to 8 hours.
In the method, the addition amount of the acrylic acid is 1-40%, preferably 2-25%, and more preferably 10-25% of the mass of the butyl acrylate byproduct heavy component;
in the method, the esterification reaction and the cracking reaction are carried out simultaneously, and the reaction conditions are the same, namely the temperature is 120-220 ℃, and the temperature is preferably 140-190 ℃; the pressure is 40 to 100Kpa (absolute), preferably 60 to 90Kpa (absolute), and the reaction time is 2 to 12 hours, preferably 4 to 8 hours.
In the method, the cracking rate of the butyl acrylate byproduct heavy component (BPB) can reach more than 94 percent, and the selectivity can reach more than 95 percent. Butyl alcohol and acrylic acid generated by cracking are subjected to esterification reaction to obtain butyl acrylate, so that the side reaction of butyl alcohol dehydration to generate butyl ether is reduced, the cracking reaction selectivity is obviously improved, the conversion rate of the esterification reaction can reach more than 90% under the conditions of the catalyst and the cracking reaction, and the selectivity can reach more than 98%; based on the finally obtained butyl acrylate, the recovery rate of the butyl acrylate byproduct heavy component (BPB) can reach 75 percent.
Compared with the prior art, the method has the beneficial effects that:
(1) according to the invention, the heterogeneous catalyst is adopted to catalyze and crack the butyl acrylate heavy component, so that the problems of post-system corrosion caused by the fact that the homogeneous catalyst enters a post-system along with the heavy component and the problem of over standard sulfur in the burning treatment of the heavy component are avoided.
(2) The catalyst adopts a core-shell structure acid-base bifunctional catalyst, a core layer introduces a large amount of Al into a pore channel through pH value adjustment to form an acid active center, the core layer is subjected to alkali modification by using N-tert-butylacrylamide through an impregnation method, and the N-tert-butylacrylamide and silicon hydroxyl on the surface of a mesoporous material are subjected to complexation reaction to generate a basic active center NH2the-O-Si is more alkaline than the aminopropyl active center generated by a grafting method, and can effectively inhibit the butanol dehydration side reaction.
(3) Catalyst shell miningAttaching a mesoporous material shell by hydrothermal synthesis method, and introducing WO into the mesoporous material skeleton3-CeO2The tungsten oxide and the cerium oxide are used as strong acid active centers to enhance the acidity in the pore channel, and simultaneously form steric hindrance between the core layer and the shell layer to change the skeleton structure of the mesoporous material, adjust the pore channel structure of the mesoporous and increase the aperture. Simultaneously, sulfate and fluoride ions are introduced to the surface of the nuclear layer through impregnation and are attached to the surface of the mesoporous material to form SO4 2--F-1The preparation method of the invention leads the strong acid active center WO3-CeO2/SO4 2--F-1The catalyst is uniformly distributed on the surface and in the framework of the shell mesoporous material, so that the catalytic activity and efficiency of cracking butyl butoxypropionate are effectively improved.
(4) Meanwhile, the acrylic acid and butyl acrylate are easy to polymerize to generate macromolecular polymers, the recovery rate is reduced, and the reaction liquid is sticky; on the other hand, the core layer has both an acid site and a basic site, so that the steric hindrance is not favorable for the existence of free radicals required for the polymerization of acrylic acid, thereby further inhibiting the polymerization of acrylic acid and butyl ester.
(5) The catalyst has dual catalytic functions of cracking and esterification, the core layer of the catalyst adopts an acid-base double-activity center, the esterification reaction is high in conversion rate and selectivity, the activity of a butanol dehydration side reaction in the cracking reaction process can be reduced while the esterification reaction is catalyzed efficiently, the generation of butyl ether is reduced, and the recovery rate of a butyl acrylate byproduct heavy component is remarkably improved.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The following table 1 shows the information of the main raw materials used in the examples of the present invention, and if not specifically described, the other raw materials are all common raw materials purchased from the market:
table 1 main material information
Name of raw materials Composition specification Manufacturer of the product
Butyl acrylate byproduct heavy component - Wanhua chemistry
Acrylic acid Analytical purity Bailingwei Tech Co Ltd
Sodium hydroxide Analytical purity SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Anhydrous ethanol Analytical purity SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Cetyl trimethyl ammonium Bromide Reagent grade SHANGHAI TITAN TECHNOLOGY Co.,Ltd.
Tetraethoxysilane Reagent grade SHANGHAI TITAN TECHNOLOGY Co.,Ltd.
P123 Reagent grade SHANGHAI TITAN TECHNOLOGY Co.,Ltd.
Hydrochloric acid (HCl 38%) Analytical purity Bailingwei Tech Co Ltd
N-tert-butylacrylamide Analytical purity Bailingwei Tech Co Ltd
Butanol Analytical purity SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Methylene dichloride Analytical purity SHANGHAI TITAN TECHNOLOGY Co.,Ltd.
Aqueous ammonia Analytical purity SHANGHAI TITAN TECHNOLOGY Co.,Ltd.
Isopropanol (I-propanol) Analytical purity Chemical industry of Xilong
Tungsten ammonium oxide pentahydrate Analytical purity Chemical industry of Xilong
Cerium nitrate hexahydrate Analytical purity Chemical industry of Xilong
Ammonium sulfate Analytical purity Chemical industry of Xilong
Ammonium fluoride Analytical purity Chemical industry of Xilong
The embodiment of the invention adopts a main analytical instrument and a test method which comprise the following steps:
1. structural characterization of the catalyst: an XRD-6000X-ray diffractometer of Shimadzu corporation in Japan is adopted, CuKa radiation is adopted, the tube voltage is 40kv, the tube current is 30mA, the step length is 0.02 degrees, the scanning speed is 4 degrees/min, and the scanning range is 5-50 degrees.
2. Infrared spectrum of the catalyst: measured by a MODEL205 Fourier infrared spectrometer, the scanning range is 400-400cm-1Characteristic peak of infrared absorption.
3. Total acid amount of catalyst: measured by a TPRO1100 model catalyst Performance Analyzer from thermoelectricity corporation, USA. The carrier gas was He and detector TCD detected a current of 150 mA. Preheating a sample, treating the sample in an atmosphere of 540 ℃, reducing the temperature to 120 ℃ and adsorbing NH3Until saturation, then carrying out temperature programmed desorption (the temperature rise rate is 10 ℃/min), and recording NH3-TPD curve.
4. The catalyst comprises the following elements: and (4) measuring the content of the elements in the catalyst by using an X-ray energy spectrometer.
And an SRS3400X fluorescence spectrometer is adopted for measuring the silicon-aluminum content of the catalyst.
Nuclear magnetic resonance was used to test the silicon to aluminum ratio of the catalyst core layer: SiMASNMR experiments were performed using a Bru KER DRX400 model, using a MASBBO 4mm probe and ZrO2 sample tubes at room temperature and 4kHz rotation speed. The AlMASNMR experiments were performed on a BrukeMSC-400 spectrometer. The resonance frequency was 104.2MHz27, the AlMASNMR spectrum was sampled with a single pulse, the pulse width was 0.6. mu.s (. pi./12), the accumulation interval was 0.5s, the number of accumulations was 5000, and the number of revolutions of the MAS rotation was 4 kHz.
5. And (3) carrying out qualitative analysis on the reaction product: adopting a Shimadzu QP-2010 gas chromatograph-mass spectrometer, and adopting a programmed heating method: the column temperature was 80 deg.C, the initial retention time was 2min, the temperature was raised to 220 deg.C at a rate of 20 deg.C/min, and the final temperature was retained for 2 min.
6. Quantitative analysis of reaction products: LC-20AT high performance liquid chromatography is adopted, and the operation conditions are as follows: mobile phase butanol: buffer solution (KH)2PO4/H3PO4) 1:9, column XDB-C18(250mm × 4.6mm × 5.0 μ M), ultraviolet detector (SPD-M20A), column box temperature 30 ℃, detection wavelength 210mm, flow rate 1.0ml/min, internal standard method for quantification.
Example 1
The preparation method of the acid-base bifunctional heterogeneous catalyst (cat1) with the core-shell structure comprises the following specific steps:
1) preparing a core layer mesoporous material loaded with an acidic active center by a grafting method: in a constant-temperature water bath at 35 ℃, 4g of P123 is dissolved in 152g of hydrochloric acid solution with the concentration of 1.5 wt%, the mixture is stirred until the solution is clear, then 4g of butanol is added, the mixture is stirred for one hour, 8g of aluminum isopropoxide (AlPO) is added, and then 120g of TEOS is added dropwise, and the mixture is stirred and mixed uniformly. The obtained mixture is put into a reaction kettle to be crystallized for 24 hours at the temperature of 100 ℃. After crystallization, the pH value of the system is adjusted to 7.5 by using ammonia water with the concentration of 20% at room temperature, and then the system is subjected to hydrothermal treatment at the constant temperature of 90 ℃ for 20 hours. Then, washing and filtering, drying at 100 ℃, extracting the template agent by using an ethanol-hydrochloric acid solution (a mixed solution of 150mL of ethanol and 3.8g of 37% HCl is added into 1g of a sample) at 100 ℃, and drying at 100 ℃ for 10h to obtain the core-layer mesoporous material (Al-KIT-6) loaded with the acidic active center.
2) The core layer mesoporous material adopts an impregnation method to complex and load alkaliSexual activity center: roasting 5g of Al-KIT-6 in the air atmosphere at 600 ℃ for 4h for activation, soaking in 125ml of acetonitrile solution of N-tert-butylacrylamide with the concentration of 0.1mol/L for 12h, and drying at 100 ℃ for 5h to obtain the nuclear mesoporous material (Al-KIT-6-NH) loaded with both acidic and alkaline active centers2)。
3) The core layer mesoporous material is coated with a mesoporous structure shell material loaded with a strong acid active center by a hydrothermal synthesis method: 5g of Al-KIT-6-NH are taken2The powder was dispersed in 100mL (dispersion concentration: 0.05g/mL) of distilled water, 6.75g of CTAB was added thereto and stirred in a constant temperature water bath at 50 ℃ for 10min to be sufficiently dissolved, and then 8.1g of TEOS was added thereto along with 2.84g of H8N2O4W、0.62gCe(NO3)3·6H2O (the molar ratio of W to Ce is 7:1), stirring at the speed of 100-250r/min, carrying out hydrothermal reaction for 4h until the system is gelatinous, and standing in a beaker for 2 h. Taking out, cooling, filtering, washing with distilled water and anhydrous ethanol to neutrality, and drying at 100 deg.C for 2 hr. The obtained powder is added with (NH)4)2SO4And NH4Soaking the F compound aqueous solution (3 wt% of ammonium sulfate and 0.74 wt% of ammonium fluoride) for 2h in the same volume, and drying at 120 ℃ for 4 h. And (3) roasting the dried product in a muffle furnace at 580 ℃ for 4 hours to obtain the acid-base bifunctional heterogeneous catalyst cat1 with the core-shell structure. The characterization results of the catalyst are shown in table 5 below.
Examples 2 to 4
The acid-base bifunctional heterogeneous catalyst with the core-shell structure (cat2-cat4) is prepared, the preparation method refers to example 1, on the basis of example 1, the reaction conditions of step 1) are adjusted, and the steps 2) and 3) are not changed, the specific operation conditions are shown in table 2, and the acid-base bifunctional heterogeneous catalyst with the core-shell structure (cat2-cat4) is obtained. The characterization results of the catalyst are shown in table 5 below.
Table 2 examples 2-4 reaction conditions
Figure BDA0002897181680000141
Examples 5 to 7
The acid-base bifunctional heterogeneous catalyst with the core-shell structure (cat5-cat7) is prepared, the preparation method refers to example 1, on the basis of example 1, the reaction conditions of step 2) are adjusted, and the steps 1) and 3) are not changed, the specific operation conditions are shown in table 3, and the acid-base bifunctional heterogeneous catalyst with the core-shell structure (cat 4-cat 7) is obtained. The characterization results of the catalyst are shown in table 5 below.
Table 3 examples 5-7 reaction conditions
Figure BDA0002897181680000142
Figure BDA0002897181680000151
Examples 8 to 10
The acid-base bifunctional heterogeneous catalyst with a core-shell structure (cat8-cat10) is prepared, referring to example 1, the reaction conditions of step 3), steps 1) and 2) are adjusted to be unchanged on the basis of example 1, and the specific operation conditions are shown in table 4, so that the acid-base bifunctional heterogeneous catalyst with a core-shell structure (cat8-cat10) is obtained. The characterization results of the catalyst are shown in table 5 below.
Table 4 examples 8-10 reaction conditions
Figure BDA0002897181680000152
TABLE 5 characterization results of the catalysts cat1-cat10 prepared in examples 1-10
Figure BDA0002897181680000153
Figure BDA0002897181680000161
Example 11
Cracking and recovering butyl acrylate heavy components:
the raw material butyl acrylate byproduct heavy component comprises 95 percent of beta-butoxy butyl propionate, 2 percent of butyl acrylate and 3 percent of polymerization inhibitor (phenothiazine and hydroquinone) by taking the total mass as 100 percent.
The catalyst cat1 prepared in example 1 was used for the deep cleavage of the heavy components of butyl acrylate: the catalyst cat1 was added in a mass fraction of 2% based on the amount of the butyl acrylate by-product heavy component starting material, and acrylic acid in an amount of 10% based on the mass of the butyl acrylate by-product heavy component was added to the reaction system, followed by reaction at 180 ℃ under a pressure of 90Kpa (absolute) for 5 hours, followed by sampling and analysis, and the results are shown in Table 7 below.
Examples 12 to 20
Cracking and recovering butyl acrylate heavy components:
the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The catalysts cat2-cat10 prepared in examples 2-10 were used for the deep cleavage of the heavy components of butyl acrylate: referring to example 11, on the basis of example 11, the reaction conditions were adjusted, the specific operating conditions are shown in table 6, and the results of sampling analysis after the reaction was completed are shown in table 7 below.
TABLE 6 examples 11-20 reaction conditions
Figure BDA0002897181680000171
Comparative example 1:
cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
Referring to example 11, the same mass of homogeneous catalyst methanesulfonic acid was used instead of cat1 to perform the deep cracking reaction of butyl acrylate heavy components, the other conditions were the same, and samples were taken after the reaction was completed and analyzed, and the results are shown in table 7 below.
Comparative example 2:
referring to the preparation method of the example 1, the step 1) for preparing Al-KIT-6 is omitted, the Y-type molecular sieve is directly used in the step 2) instead of Al-KIT-6, and other conditions are the same, so that the catalyst is prepared.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above mentioned catalyst cat1 was used to carry out the deep cracking reaction of heavy components of butyl acrylate, the other conditions were the same, and the results of the analysis by sampling after the reaction were as shown in Table 7 below.
Comparative example 3:
the catalyst was prepared by following the procedure of example 1, replacing the acetonitrile solution of N-t-butylacrylamide in step 2) with the same amount of acetonitrile solution of aminopropyltriethoxysilane at the same concentration, and obtaining the catalyst under the same conditions.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above catalyst is used to replace cat1 for the deep cracking reaction of butyl acrylate heavy component, the other conditions are the same, and the results of sampling and analyzing after the reaction are shown in the following table 7. Comparative example 4:
cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
Referring to example 11, the same mass of core-layer mesoporous material (Al-KIT-6) loaded with acidic active centers prepared in example 1 was used instead of cat1 to perform the deep cracking reaction of butyl acrylate heavy components, the other conditions were the same, and after the reaction, samples were taken for analysis, and the results are shown in table 7 below.
Comparative example 5:
method referring to example 11, the same mass of core-layer mesoporous material (Al-KIT-6-NH) loaded with both acidic and basic active centers prepared in example 1 was used2) The catalyst cat1 was replaced to carry out the deep cracking reaction of the heavy components of butyl acrylate under the same conditions, and the results of the analysis by sampling after the reaction were as shown in Table 7 below.
Comparative example 6:
preparing a catalyst: directly loading WO by using a core-layer mesoporous material loaded with acid-base double components3-CeO2/SO4 2--F-1The method comprises the following steps: 5g of core-layer mesoporous material loaded with acid-base double components is soaked in 100ml of the materialDipping in an acidic solvent (3 wt% of ammonium sulfate, 0.74 wt% of ammonium fluoride, 1.4 wt% of ammonium paratungstate and 0.5 wt% of cerium nitrate hexahydrate) for 2h, drying at 120 ℃ for 10h, and then roasting in a muffle furnace at 560 ℃ for 4h in an air atmosphere to obtain the catalyst.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above catalyst is used to replace cat1 for the deep cracking reaction of butyl acrylate heavy component, the other conditions are the same, and the results of sampling and analyzing after the reaction are shown in the following table 7. Comparative example 7:
the catalyst was prepared according to the method of example 1, without adding Ce (NO) in step 3)3)3·6H2And O, preparing the catalyst under the same other conditions.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above catalyst is used to replace cat1 for the deep cracking reaction of butyl acrylate heavy component, the other conditions are the same, and the results of sampling and analyzing after the reaction are shown in the following table 7. Comparative example 8:
preparation of the catalyst according to the method of example 1, (NH) in step 3)4)2SO4And NH4Replacing the composite aqueous solution of F with same (NH)4)2SO4The catalyst is prepared from the aqueous solution with the same concentration and other conditions.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above catalyst is used to replace cat1 for the deep cracking reaction of butyl acrylate heavy component, the other conditions are the same, and the results of sampling and analyzing after the reaction are shown in the following table 7. Comparative example 9:
referring to the step 3) of the embodiment 1, the shell material is independently adopted to synthesize the mesoporous material, and W/Ce and F are loaded-1/SO4 2-And the loading is not changed, thus obtaining the catalyst.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above catalyst is used to replace cat1 for the deep cracking reaction of butyl acrylate heavy component, the other conditions are the same, and the results of sampling and analyzing after the reaction are shown in the following table 7.
Comparative example 10
The catalyst was prepared by the method of reference example 1 without adding H in step 3)8N2O4W, and obtaining the catalyst under the same other conditions.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above catalyst is used to replace cat1 for the deep cracking reaction of butyl acrylate heavy component, the other conditions are the same, and the results of sampling and analyzing after the reaction are shown in the following table 7.
Comparative example 11
Preparation of the catalyst according to the method of example 1, (NH) in step 3)4)2SO4And NH4Replacing the composite aqueous solution of F with NH4And (4) preparing the catalyst by using the aqueous solution with the concentration of F under the same other conditions.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above catalyst is used to replace cat1 for the deep cracking reaction of butyl acrylate heavy component, the other conditions are the same, and the results of sampling and analyzing after the reaction are shown in the following table 7.
Comparative example 12
Referring to the preparation method of the embodiment 1, after crystallization in the step 1), pH value adjustment is not carried out by using ammonia water, a template agent is directly extracted to obtain a mesoporous material KIT-6, and the subsequent preparation steps 2) and 3) are the same as those of the embodiment 1, so that a catalyst with a nuclear layer without aluminum is obtained, and the catalyst is prepared under the same other conditions.
Cracking and recovering butyl acrylate heavy components: the raw material butyl acrylate by-produced recombinant was the same as in example 11.
The method refers to example 11, the same mass of the above catalyst is used to replace cat1 for the deep cracking reaction of butyl acrylate heavy component, the other conditions are the same, and the results of sampling and analyzing after the reaction are shown in the following table 7.
In the above examples 11 to 20 and comparative examples 1 to 12, the cracking rate of the heavy component BPB, the recovery rate of butyl acrylate, the conversion rate and yield of the esterification reaction, and the selectivity of the by-product dibutyl ether were calculated by sampling analysis after the completion of the reaction, and the specific calculation formula was as follows:
BPB cleavage% (% M (residual BPB in the starting material after BPB-reaction) in the sample)/M (BPB in the starting material)
Percent recovery of butyl acrylate (% M (butyl acrylate in sample after reaction)/M (raw material)%
Conversion of esterification%
Percent esterification yield (% M (actual amount of butyl acrylate produced by esterification)/M (theoretical amount of butyl acrylate produced by esterification)%
The results are shown in Table 7 below.
TABLE 7 analysis of results of examples 11 to 20 and comparative examples 1 to 12
Figure BDA0002897181680000221

Claims (10)

1. A preparation method of an acid-base bifunctional heterogeneous catalyst with a core-shell structure is characterized by comprising the following steps:
(1) dissolving P123 in hydrochloric acid, adding butanol, uniformly mixing, adding aluminum isopropoxide and ethyl orthosilicate, uniformly mixing, then carrying out crystallization reaction, adjusting the pH value of the system to 7.5-8.5 by using ammonia water after crystallization is finished, and carrying out constant-temperature hydrothermal treatment to obtain a core-layer mesoporous material loaded with an acidic active center;
(2) roasting and activating the core layer mesoporous material loaded with the acidic active center prepared in the step (1), then adding the core layer mesoporous material into an acetonitrile solution of N-tert-butyl acrylamide for dipping, taking out and drying to obtain the core layer mesoporous material loaded with the acidic active center and the alkaline active center simultaneously;
(3) dispersing the core layer mesoporous material loaded with the acidic and alkaline active centers prepared in the step (2) in water, adding hexadecyl trimethyl ammonium bromide to fully dissolve, then adding ethyl orthosilicate, ammonium paratungstate and cerous nitrate hexahydrate to perform hydrothermal reaction, standing until the system is in a gel state, then filtering, washing and drying, adding the obtained product into a composite aqueous solution of ammonium sulfate and ammonium fluoride to be soaked, taking out the obtained product, drying and roasting to obtain the acid-base bifunctional core-shell structure heterogeneous catalyst.
2. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the P123 to the ethyl orthosilicate, the aluminum isopropoxide, the hydrochloric acid (calculated as HCl therein) and the butanol is 1: (10-100): (1-5): (0.5-2): (1-2), preferably 1: (30-90): (2-3): (0.5-1): (1-1.5).
Preferably, the hydrochloric acid concentration is 1 to 5 wt%, preferably 1 to 2 wt%.
The crystallization reaction is carried out at the temperature of 100-150 ℃, preferably at the temperature of 100-120 ℃; the time is 12-24h, preferably 20-24 h; and/or
When the pH value of the system is adjusted by ammonia water after crystallization is finished, the concentration of the adopted ammonia water is preferably 10-20 wt%, and is preferably 15-20 wt%; and/or
The constant-temperature hydrothermal treatment is carried out at the temperature of 90-120 ℃, preferably at the temperature of 100-.
3. The preparation method according to claim 1 or 2, wherein in the step (1), after the constant-temperature hydrothermal treatment is completed, the constant-temperature hydrothermal treatment comprises washing, filtering, drying and post-extraction treatment;
the post-treatment method is preferably that the reaction solution after constant-temperature hydrothermal treatment is washed, filtered and dried, then extracted by ethanol-hydrochloric acid solution and dried again to obtain solid powder;
wherein in the extraction process, the dosage of the extractant ethanol-hydrochloric acid solution is calculated by adding a mixed solution of 145-155mL of ethanol and 3-4g of 37% HCl into each 1g of solid sample;
wherein the drying operation temperature is 100-120 ℃, and the time is 10-12 h.
4. The method according to any one of claims 1 to 3, wherein in step (2), the calcination activation is carried out in an air atmosphere at a temperature of 500-600 ℃, preferably 520-540 ℃; the time is 4 to 8 hours, preferably 4 to 6 hours; and/or
The dipping process is carried out for 2-12h, preferably 2-4 h; the dipping solution adopted in the dipping process is the acetonitrile solution of the N-tertiary butyl acrylamide, and the concentration is 0.1-1mol/L, preferably 0.1-0.5 mol/L;
preferably, the dosage of the impregnation liquid is that every 1g of sample is immersed in 25-30ml of the acetonitrile solution of the N-tertiary butyl acrylamide; and/or
And drying at 60-80 ℃ for 5-8 h.
5. The preparation method according to any one of claims 1 to 4, wherein in the step 3), the dispersion concentration of the core layer mesoporous material loaded with the acidic and basic active centers in water is 0.02 to 0.05 g/mL;
the mass ratio of the core-layer mesoporous material loaded with the acidic and alkaline active centers to the cetyl trimethyl ammonium bromide and the tetraethoxysilane is 1: 1-2: 1-2, preferably 1: 1-1.5: 1-1.4;
the mass ratio of the core layer mesoporous material loaded with the acidic and alkaline active centers to the ammonium paratungstate and the cerium nitrate hexahydrate is 1: 0.28-1.4: 0.03 to 0.5, preferably 1: 0.28-0.84: 0.03-0.30; and/or
The hydrothermal reaction is carried out in a constant-temperature water bath under stirring, and the reaction temperature is 50-80 ℃, preferably 60-70 ℃; stirring for 1-4h, preferably 1-2h until the system is gelatinous, and standing for 1-4h, preferably 1-2 h;
the stirring speed is 100-; and/or
The dipping process is carried out for 2-12h, preferably 4-6 h; the impregnation process is equal-volume impregnation; the dipping solution adopted in the dipping process is the compound aqueous solution of ammonium sulfate and ammonium fluoride, and the composition of the compound aqueous solution is that the total mass of the aqueous solution is 100 wt%, the ammonium sulfate is 3-7 wt%, and the ammonium fluoride is 0.74-3.7 wt%; and/or
The drying temperature is 100-120 ℃, and the drying time is 2-4 h;
the roasting temperature is 400-600 ℃, preferably 480-580 ℃, and more preferably 500-560 ℃; the time is 2-12h, preferably 4-8 h.
6. The acid-base bifunctional heterogeneous catalyst with a core-shell structure, which is prepared by the method of any one of claims 1 to 5, is characterized in that the catalyst comprises an internal core-layer structure, the core-layer structure takes a mesoporous material as a framework, the mesoporous material is loaded with an acidic active center Al through grafting, and is loaded with a basic active center NH through complexing2-O-Si；
The shell structure is coated outside the core layer structure, the shell structure takes a mesoporous material as a framework, the mesoporous material is doped with tungsten oxide and cerium oxide, and a strong acid active center SO is loaded on the mesoporous material4 2-、F-1、WO3And CeO2。
7. The catalyst as claimed in claim 6, wherein the catalyst has a particle size of 150-200 μm; specific surface area of 400-2G, preferably 700-850m2/g；
The pore diameter of the shell layer is 50-200nm, preferably 50-120nm, and the total acid amount is 0.4-0.9mmol/g, preferably 0.7-0.85 mmol/g;
the pore diameter of the nuclear layer is 4-12nm, preferably 6-10nm, and the total acid amount is 0.4-0.7mmol/g, preferably 0.4-0.55 mmol/g; the total alkali amount of the core layer is 0.5-4mmol/g, preferably 0.5-1.5 mmol/g; and/or
The mass ratio of the core layer to the shell layer of the catalyst is 2-10:1, preferably 2-4.5: 1;
wherein the Si/Al molar ratio is between 10 and 100, preferably between 20 and 50; the molar ratio of W to Ce is 1-20:1, preferably 5-10: 1; f-1/SO4 2-The molar ratio is 1:1-10, preferably 1: 1.5-4;
in the shell, the load of W is 0.5-4mmol/g, preferably 0.5-2 mmol/g; the loading amount of Ce is 0.1-0.4mmol/g, preferably 0.1-0.2 mmol/g.
8. Use of the acid-base bifunctional core-shell structured heterogeneous catalyst prepared by the method of any one of claims 1 to 5 or the acid-base bifunctional core-shell structured heterogeneous catalyst of claim 6 or 7 in cracking recovery of a butyl acrylate heavy component.
9. A method for cracking and recycling butyl acrylate heavy components is characterized in that butyl acrylate by-product heavy components are taken as raw materials, an acid-base bifunctional core-shell structure heterogeneous catalyst prepared by the method of any one of claims 1 to 5 or the acid-base bifunctional core-shell structure heterogeneous catalyst of claim 6 or 7 is adopted to carry out cracking reaction to generate butyl acrylate and butanol, meanwhile, a certain amount of acrylic acid is added into a reaction system, and esterification reaction is carried out on the acrylic acid and the butanol generated by cracking to obtain the butyl acrylate.
10. The method according to claim 9, wherein the butyl acrylate byproduct heavy component comprises 95-97% of beta-butoxypropionic acid butyl ester, 0.5-2% of butyl acrylate and 1-3% of polymerization inhibitor by taking the total mass as 100%; and/or
The dosage of the catalyst is 2-20%, preferably 2-12%, more preferably 2-5% of the mass of the butyl acrylate byproduct heavy component; and/or
The cracking reaction temperature is 120-220 ℃, and preferably 140-190 ℃; the pressure is 40-100Kpa (absolute), preferably 60-90Kpa (absolute), and the reaction time is 2-12h, preferably 4-8 h; and/or
The addition amount of the acrylic acid is 1-40%, preferably 2-25%, more preferably 10-25% of the mass of the butyl acrylate byproduct heavy component; and/or
The esterification reaction is carried out at the temperature of 120-220 ℃, preferably at the temperature of 140-190 ℃; the pressure is 40-100Kpa (absolute), preferably 60-90Kpa (absolute), and the time is 2-12h, preferably 4-8 h.
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