A catalyst for synthesizing 3-methyl-3-buten-1-ol and preparation and application thereof

Abstract

The application discloses a catalyst for synthesizing 3-methyl-3-buten-1-ol and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: (S1) mixing acrylic acid, acrylic ester, a dispersing agent, a leveling agent and a photocuring agent to obtain a photosensitive resin mixture; (S2) mixing the first powder and the photosensitive resin mixture obtained in the step (S1), sequentially adding a suspending agent, a foaming agent and the second powder, standing, and then adding an anti-sticking agent and the foaming agent to obtain a printing slurry; (S3) loading the printing slurry obtained in the step (S2) into a carrier liquid device, performing 3D printing according to a set program, and performing post-processing to obtain a catalyst with a three-dimensional cuboid grid skeleton structure. The catalyst has high mechanical strength and long service life, is used in a process in which isobutylene and formaldehyde generate 3-methyl-3-buten-1-ol, and the formaldehyde conversion rate and the 3-methyl-3-buten-1-ol selectivity are greatly improved.

Description

Technical Field

[0001] This invention relates to the field of solid base catalysis, specifically to a catalyst for the synthesis of 3-methyl-3-buten-1-ol and its preparation and application. Background Technology

[0002] Isopentenol, chemically known as 3-methyl-2-butenol, is an important organic intermediate used in the production of various fine chemicals and pharmaceuticals, including citral, floral fragrances, and vitamin A. The traditional method for producing isopentenol is the isoprene process, which uses isoprene as a raw material and involves oxidation, acetylation, and saponification with an alkaline solution. This method has a long process route, consumes a large amount of raw materials, produces many byproducts, has high production costs, and causes significant pollution.

[0003] In recent years, the method for preparing isopentenol from isobutylene and formaldehyde via 3-methyl-3-buten-1-ol has become a research hotspot. This method has a simple process flow, few byproducts, abundant raw material sources, low production cost, and virtually no pollution, thus showing great development potential. CN109317212A discloses a catalyst for the synthesis of 3-methyl-3-buten-1-ol, its preparation method, and its uses. This catalyst is composed of attapulgite-modified metal silicate salts supported on amine compounds and strong base compounds. CN111068754A discloses a modified molecular sieve catalyst for 3-methyl-3-buten-1-ol and its preparation method. This catalyst uses molecular sieves as the parent material and is modified by steam washing, acid washing, and alkaline phosphate composite modification. It can be used in the reaction of isobutylene and formaldehyde to synthesize 3-methyl-3-buten-1-ol. CN107930686A discloses a method for the synthesis of 3-methyl-3-buten-1-ol, a catalyst, and its preparation method. The preparation method of the catalyst used for the synthesis of 3-methyl-3-buten-1-ol includes: calcining aluminosilicate molecular sieves at 300-600℃ for 3.5-5 hours, followed by isotropic impregnation in an alkaline phosphate solution, aging, drying, and calcining. However, the above catalysts are generally unformed powders or the strength of the formed catalyst particles is not high, making it difficult to meet the requirements of liquid-solid separation in continuous production.

[0004] In summary, existing catalysts for the production of 3-methyl-3-buten-1-ol from isobutylene and formaldehyde generally suffer from problems such as difficulty in separation (powdered catalysts or homogeneous catalysts) or low strength of molded catalysts. Therefore, providing a catalyst with higher strength, less brittleness, and easier separation from the raw materials and products has become one of the urgent problems to be solved by those skilled in the art. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a catalyst for the synthesis of 3-methyl-3-buten-1-ol, its preparation, and its application. The catalyst of this invention, applied in the reaction of isobutylene and formaldehyde to produce 3-methyl-3-buten-1-ol, exhibits higher mechanical strength, further extending the catalyst's lifespan. It is also easily separated from the reactants and products, significantly improving the formaldehyde conversion rate and the selectivity of 3-methyl-3-buten-1-ol.

[0006] The first aspect of this invention provides a method for preparing a catalyst for synthesizing 3-methyl-3-buten-1-ol, comprising: (S1) Mix acrylic acid, acrylate, dispersant, leveling agent and photocuring agent to obtain photosensitive resin mixture; (S2) Mix the first powder and the photosensitive resin mixture obtained in step (S1), add the suspending agent, the first foaming agent and the second powder in sequence, let stand, and then add the anti-sticking agent and the second foaming agent to obtain the printing slurry. (S3) The printing slurry obtained in step (S2) is loaded into the liquid carrier device, and 3D printing is performed according to the set program. After post-processing, the catalyst is obtained.

[0007] Further, in step (S1), the weight ratio of each substance in the mixture is: 20-32 parts acrylic acid: 8-20 parts acrylate: 2-10 parts dispersant: 1.5-7.5 parts leveling agent: 0.2-2 parts light curing agent.

[0008] Further, in step (S1), the acrylate is one or more of 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, dipentaerythritol hexaacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, or ethoxylated trimethylolpropane triacrylate, preferably one or more of 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, or trimethylolpropane triacrylate, and more preferably includes both dipropylene glycol diacrylate and trimethylolpropane triacrylate, wherein the weight ratio of dipropylene glycol diacrylate to trimethylolpropane triacrylate is preferably 1-2.5:1-1.5.

[0009] Further, in step (S1), the dispersant is one or both of 3-aminopropyltriethoxysilane or 3-glycidoxypropyltrimethoxysilane, preferably 3-glycidoxypropyltrimethoxysilane.

[0010] Further, in step (S1), the leveling agent is one or both of polydimethylsiloxane or polymethylsiloxane, preferably polydimethylsiloxane.

[0011] Further, in step (S1), the photocuring agent is one or both of a photosensitizer and a photoinitiator, preferably including both a photosensitizer and a photoinitiator, wherein the weight ratio of photosensitizer to photoinitiator is preferably 1:10-1:100. Further, the photosensitizer is one or more of ethyl 4-dimethylaminobenzoate, triethylamine, ethyl-p-dimethylaminobenzoate, or triethanolamine, preferably one or more of triethylamine or triethanolamine; the photoinitiator is one or more of 2-isopropylthioxanthonone, methyl phthalobenzoate, 2,4-diethylthioxanthonone, or 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methyl-1-propanone, preferably one or more of 2-isopropylthioxanthonone or methyl phthalobenzoate.

[0012] Further, in step (S2), the weight ratio of each material in the printing slurry is as follows: 70-90 parts of first powder: 5-25 parts of photosensitive resin mixture: 0-2.5 parts of suspending agent: 0.1-2 parts of first foaming agent: 5-20 parts of second powder: 0.1-2 parts of anti-sticking agent: 0.1-1.5 parts of second foaming agent.

[0013] Furthermore, in step (S2), the first powder and the photosensitive resin mixture obtained in (S1) are first ball-milled and mixed evenly in a ball mill before being transferred to a mixer for stirring. The ball milling mixing is a conventional operation in the art.

[0014] Further, in step (S2), the first powder is at least one of alumina, gibbsite, or kaolin; preferably, the alumina is γ-Al2O3 with a particle size of 10-25 μm; the gibbsite has a particle size of 10-25 μm; and the kaolin has a particle size of 0.5-2 μm. Further, a pore-forming agent may also be added in step (S2), which may be one or more of carboxymethyl cellulose and starch; the pore-forming agent accounts for 0.3%-3.0% of the weight of the first powder.

[0015] Further, in step (S2), the suspending agent is one or more of sodium-based bentonite, lithium-based bentonite, or attapulgite, preferably sodium-based bentonite.

[0016] Further, in step (S2), the first foaming agent and the second foaming agent are each independently selected from weakly acidic or alkaline water-soluble high-foaming cleaners; preferably, the foaming agent is an alkaline water-soluble high-foaming cleaner; preferably, the alkaline water-soluble high-foaming cleaner is at least one of hydrogen peroxide or sodium bicarbonate powder; more preferably, the alkaline water-soluble high-foaming cleaner is sodium bicarbonate powder.

[0017] Further, in step (S2), the anti-sticking agent is at least one of silicone powder, stearate, paraffin wax or organosilicon release agent; preferably, the anti-sticking agent is stearate; more preferably, the anti-sticking agent is magnesium stearate.

[0018] Further, in step (S2), the second powder comprises a phosphate; preferably, the second powder comprises a phosphate and an additive, wherein the weight ratio of the phosphate to the additive is 20:1-5:1. Further, the phosphate is at least one of sodium phosphate or disodium hydrogen phosphate, and the additive is at least one of cerium oxide or calcium carbonate.

[0019] Furthermore, the phosphate includes both sodium phosphate and disodium hydrogen phosphate, wherein the weight ratio of sodium phosphate to disodium hydrogen phosphate is 1:1 to 1:10, preferably 1:2 to 1:10.

[0020] Furthermore, the additive comprises both cerium oxide and calcium carbonate, wherein cerium oxide and calcium carbonate have a synergistic effect in improving the mechanical strength of the catalyst, as well as the formaldehyde conversion rate and the selectivity of 3-methyl-3-buten-1-ol. Furthermore, the weight ratio of cerium oxide to calcium carbonate is 10:1 to 1:15, preferably 2:1 to 1:2.

[0021] Further, in step (S2), the first powder and photosensitive resin mixture are mixed, a suspending agent and a washing agent are added, and the mixture is stirred at low speed and dehydrogenated under vacuum. The second powder is then added, stirred at high speed and dehydrogenated under vacuum, and allowed to stand. An anti-sticking agent and a washing agent are then added, and the mixture is stirred at high speed and dehydrogenated under vacuum to obtain the printing slurry. The low-speed stirring and high-speed stirring are both conventional operations in the art.

[0022] Furthermore, in step (S2), the second powder is first ball-milled and mixed evenly in a ball mill before being transferred to a mixer for stirring. The ball milling and mixing is a conventional operation in the art.

[0023] Furthermore, in step (S2), the settling is carried out under normal pressure for 8-24 hours.

[0024] Further, in step (S2), the printing paste is a printing slurry or a printing paste.

[0025] Further, in step (S3), the printing model file is first imported into the printer's computer, printing parameters are set, the prepared printing slurry is loaded into the liquid carrier device, the printing platform and optical engine are initialized, and the slurry level is adjusted. Based on the printing scheme set for the target model, the printing slurry is used as a 3D printing material and laid layer by layer, leveled with a scraper, and selectively exposed layer by layer using an ultraviolet laser or DLP-UV light source (365nm-405nm). After the slurry solidifies, a solid alkali catalyst semi-finished product is obtained. Further, the post-processing includes cleaning and sintering. Further, the post-processing involves blowing off the shallow layer of paste from the printed catalyst semi-finished product with compressed gas, then deep cleaning with an ultrasonic 40-60℃ warm water bath, drying in an oven at 80-120℃ for 1-5 hours, and degreasing and sintering in a muffle furnace to obtain a solid alkali catalyst. The degreasing and sintering in the muffle furnace is carried out at a sintering temperature of 550-650℃ for a holding time of 2-8 hours.

[0026] A second aspect of the present invention provides a catalyst for the synthesis of 3-methyl-3-buten-1-ol prepared by the above method.

[0027] Furthermore, the mechanical strength of the catalyst is 20-120 N / cm, more preferably 25-40 N / cm.

[0028] Furthermore, the catalyst has a three-dimensional cuboid mesh framework structure, wherein the height of the catalyst is 2-12 mm, the length is 2-12 mm, the width is 2-12 mm, and the porosity of the catalyst is 21.5%-95.1%.

[0029] Furthermore, in the catalyst, the basic unit grid skeleton structure of the three-dimensional cuboid grid skeleton structure is a cuboid skeleton structure, preferably a cube skeleton structure, the side length of the basic unit grid skeleton structure is 200-800μm, and the diameter of the cross-section of the skeleton is 50-600μm.

[0030] Furthermore, in the catalyst, the cross-section of the three-dimensional cuboid mesh skeleton structure is preferably rectangular, square, or circular, and more preferably circular.

[0031] Furthermore, in the catalyst, the basic unit grid skeleton structure is the same in the three-dimensional cuboid grid skeleton structure.

[0032] A third aspect of the present invention provides a method for synthesizing 3-methyl-3-buten-1-ol, comprising: reacting formaldehyde with isobutene under the catalysis of the above-mentioned catalyst to obtain 3-methyl-3-buten-1-ol.

[0033] Furthermore, the reaction conditions include: a reaction pressure of 4-10 MPa and a reaction temperature of 170-260 °C.

[0034] Furthermore, the reaction conditions also include: a mass ratio of formaldehyde to isobutanol of 0.05-0.3, and a mass ratio of catalyst to formaldehyde of 0.05-0.3.

[0035] Compared with the prior art, the present invention has the following advantages: In existing technologies, catalyst preparation commonly uses extrusion molding, but the resulting catalysts have low mechanical strength (5-20 N / cm). The inventors discovered that by using 3D printing technology and simultaneously controlling the composition and ratio of the printing slurry, an integral catalyst with a three-dimensional cuboid mesh framework structure can be prepared, which can effectively improve the mechanical strength of the catalyst and further extend its service life. When applied to the process of isobutylene reacting with formaldehyde to produce 3-methyl-3-buten-1-ol, the formaldehyde conversion rate and the selectivity of 3-methyl-3-buten-1-ol are significantly improved.

[0036] This invention uses 3D printing technology to prepare a three-dimensional cuboid mesh framework catalyst. The promoter and phosphate, and even more so CaCO3 and CeO2, mutually promote each other in improving formaldehyde conversion rate, 3-methyl-3-buten-1-ol selectivity and pressure strength. Attached Figure Description

[0037] Figure 1 This is a schematic diagram of the basic unit cubic framework structure in the catalyst of this invention. Detailed Implementation

[0038] The technical solution of the present invention will be described in detail below with reference to the embodiments.

[0039] In this invention, gas chromatography was used to analyze the formaldehyde conversion rate and the selectivity of the product 3-methyl-3-buten-1-ol. By configuring standard curves of different concentrations, the concentrations of the raw material formaldehyde and the product 3-methyl-3-buten-1-ol were determined (since a large amount of solution does not participate in the reaction, it is assumed that the volume remains unchanged before and after the reaction).

[0040] In this invention, mechanical strength is measured using a DLIII type intelligent particle strength tester. The test is performed 10 times and the average value (in N) is taken. The average value is then divided by the length of the cross-section of the catalyst particle (in cm) to obtain the mechanical strength, which is in N / cm.

[0041] In this invention, the formulas for calculating conversion rate, selectivity, and number of reusable cycles are as follows: Formaldehyde conversion rate % = (1-n) 甲醛产物 / n 甲醛原料 ) × 100%; 3-Methyl-3-buten-1-ol selectivity % = n 3-甲基-3-丁烯-1-醇 / n甲醛 ×100%; Number of times it can be reused N: The formaldehyde conversion rate of the Nth time is ≥ the formaldehyde conversion rate of the first time × 90%; Where, n 甲醛产物 n represents the number of moles of formaldehyde produced in the reaction. 甲醛原料 n represents the number of moles of formaldehyde added in the reaction. 3-甲基-3-丁烯-1-醇 n represents the number of moles of 3-methyl-3-buten-1-ol produced in the reaction. 甲醛 This indicates the number of moles of formaldehyde consumed in the reaction.

[0042] In this invention, during the preparation of each catalyst, the ball mill speed is set to a low speed of 40-180 r / min, the stirrer speed is set to a low speed of 500 r / min, the stirrer speed is set to a high speed of 1500-2000 r / min, and the vacuum is 0.5-2 kPa.

[0043] In this invention, each catalyst exhibits a three-dimensional cuboid mesh framework structure, wherein the catalyst has a length of 4 mm, a width of 4 mm, and a height of 5 mm. The basic unit constituting the three-dimensional cuboid mesh framework structure is a cubic framework structure with a side length of 300 μm and a circular cross-section with a diameter of 240 μm. The porosity of the catalyst is 50%.

[0044]

Example 1

[0045] (S1) 24 parts by weight of acrylic acid, 12 parts by weight of acrylate (the weight ratio of dipropylene glycol diacrylate to trimethylolpropane triacrylate is 2:1), 3 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, 4 parts by weight of polydimethylsiloxane, 0.4 parts by weight of triethanolamine and methyl phthalate (weight ratio is 1:15) are stirred evenly in a mixer to obtain a photosensitive resin mixture; (S2) 80 parts by weight of the first powder (hydrazine and carboxymethyl cellulose with a particle size of 10-25 μm, in a weight ratio of 40:1) and 12 parts by weight of the above-obtained photosensitive resin mixture were ball-milled for 5 hours and then transferred to a mixer. 1 part by weight of sodium bentonite and 0.3 parts by weight of NaHCO3 powder were added. After mixing at low speed in the mixer and then vacuuming, 20 parts by weight of the second powder (Na3PO4·12H2O and Na2HPO4·12H2O, in weights of 5 and 15 respectively; pre-mixed by ball milling for 3 hours) were added. After mixing at high speed and then vacuuming, the mixture was allowed to stand at normal pressure for 10 hours. Finally, 0.2 parts by weight of magnesium stearate and 0.5 parts by weight of NaHCO3 powder were added. After mixing at high speed and then vacuuming, the printing slurry was obtained. (S3) Import the printing model file into the printer's computer, set the printing parameters, load the above-prepared printing slurry into the liquid carrier, initialize the printing platform and optical engine, and adjust the slurry level; according to the printing scheme set by the target model (three-dimensional cuboid mesh skeleton structure), use the above-prepared printing slurry as the 3D printing material to lay it layer by layer, scrape it flat with a scraper, and use ultraviolet laser or DLP-UV light source to selectively expose it layer by layer. After the slurry is solidified, a solid alkali catalyst semi-finished product is obtained. The printed solid base catalyst semi-finished product was blown off with compressed gas to remove the shallow paste, then deeply cleaned with ultrasonic 40℃ warm water bath, dried in an oven at 100℃ for 1 hour, and degreased and sintered in a muffle furnace (sintering temperature 560℃, holding time 3 hours) to obtain a three-dimensional cuboid mesh framework structure catalyst.

[0046]

Example 2

[0047]

Example 3

[0048]

Example 4

[0049]

Example 5

[0050]

Example 6

[0051]

Example 7

[0052]

Example 8

[0053]

Example 9

[0054]

Comparative Example 1

[0055] [Comparative Example 2] (S1) 24 parts by weight of acrylic acid, 12 parts by weight of acrylate (the weight ratio of dipropylene glycol diacrylate to trimethylolpropane triacrylate is 2:1), 3 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, 4 parts by weight of polydimethylsiloxane, 0.4 parts by weight of a mixture of triethanolamine and methyl phthalate (the weight ratio is 1:15) are stirred evenly in a mixer to obtain a photosensitive resin mixture. (S2) 80 parts by weight of the first powder (hydrazine and carboxymethyl cellulose with a particle size of 10-25 μm, in a weight ratio of 40:1) and 12 parts by weight of the photosensitive resin mixture were ball-milled for 5 hours and then transferred to a mixer. 1 part by weight of sodium bentonite and 0.3 parts by weight of NaHCO3 powder were added. After mixing at low speed in the mixer and then vacuuming, 20 parts by weight of the second powder (CeO2; pre-mixed by ball milling for 3 hours) were added. After mixing at high speed and then vacuuming, the mixture was allowed to stand at normal pressure for 10 hours. Finally, 0.2 parts by weight of magnesium stearate and 0.5 parts by weight of NaHCO3 powder were added. After mixing at high speed and then vacuuming, the printing slurry was obtained. (S3) Import the printing model file into the printer's computer, set the printing parameters, load the above-prepared printing slurry into the liquid carrier, initialize the printing platform and optical engine, and adjust the slurry level; according to the printing scheme set for the target model, use the printing slurry as the 3D printing material to lay it layer by layer, scrape it flat, and use ultraviolet laser or DLP-UV light source to selectively expose it layer by layer. After the slurry is solidified, a solid alkali catalyst semi-finished product is obtained. The printed solid base catalyst semi-finished product was blown off with compressed gas to remove the shallow paste, then deeply cleaned with ultrasonic 40℃ warm water bath, dried in an oven at 100℃ for 1 hour, and degreased and sintered in a muffle furnace (sintering temperature 560℃, holding time 3 hours) to obtain a three-dimensional cuboid mesh framework structure catalyst.

[0056] [Comparative Example 3] (S1) 24 parts by weight of acrylic acid, 12 parts by weight of acrylate (the weight ratio of dipropylene glycol diacrylate to trimethylolpropane triacrylate is 2:1), 3 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, 4 parts by weight of polydimethylsiloxane, 0.4 parts by weight of a mixture of triethanolamine and methyl phthalate (the weight ratio is 1:15) are stirred evenly in a mixer to obtain a photosensitive resin mixture. (S2) 80 parts by weight of the first powder (hydrazine and carboxymethyl cellulose with a particle size of 10-25 μm, in a weight ratio of 40:1) and 12 parts by weight of the photosensitive resin mixture were ball-milled for 5 hours and then transferred to a mixer. 1 part by weight of sodium bentonite and 0.3 parts by weight of NaHCO3 powder were added. After mixing at low speed in the mixer and then vacuuming, 20 parts by weight of the second powder (Na3PO4·12H2O, Na2HPO4·12H2O, Ca3(PO4)2 and CeO2, with weights of 4.6, 13.8, 1.0 and 0.6 respectively; pre-mixed by ball milling for 3 hours) were added. After mixing at high speed and then vacuuming, the mixture was allowed to stand at normal pressure for 10 hours. Finally, 0.2 parts by weight of magnesium stearate and 0.5 parts by weight of NaHCO3 powder were added. After mixing at high speed and then vacuuming, the printing slurry was obtained. (S3) Import the printing model file into the printer's computer, set the printing parameters, load the above-prepared printing slurry into the liquid carrier, initialize the printing platform and optical engine, and adjust the slurry level; according to the printing scheme set for the target model, use the printing slurry as the 3D printing material to lay it layer by layer, scrape it flat, and use ultraviolet laser or DLP-UV light source to selectively expose it layer by layer. After the slurry is solidified, a solid alkali catalyst semi-finished product is obtained. The printed solid base catalyst semi-finished product was blown off with compressed gas to remove the shallow paste, then deeply cleaned with ultrasonic 40℃ warm water bath, dried in an oven at 100℃ for 1 hour, and degreased and sintered in a muffle furnace (sintering temperature 560℃, holding time 3 hours) to obtain a three-dimensional cuboid mesh framework structure catalyst.

[0057] Table 1 Mechanical strength of the catalysts obtained in each example Example 1 26.1 Example 2 28.7 Example 3 29.5 Example 4 30.6 Example 5 32.6 Example 6 33.9 Example 7 25.4 Example 8 26.7 Example 9 24.5 Comparative Example 1 16.1 Comparative Example 2 17.4 Comparative Example 3 27.3

[0058] Catalyst evaluation

[0059] The evaluation conditions were as follows: A 500 mL high-pressure reactor was used. 2.4 g of the catalyst obtained in each example, 13.5 g of paraformaldehyde, and 80 g of isobutanol were placed in the reactor, sealed, and nitrogen was introduced to purge air from the reactor. The isobutene metering pump was turned on, and the isobutene feed rate was controlled at 320 g. The reaction temperature was controlled at 220 ℃, and the reaction pressure was controlled at 8.0 MPa. The reaction was carried out for 4 h, and the remaining isobutene and catalyst were removed. The formaldehyde conversion rate and 3-methyl-3-buten-1-ol selectivity of the samples after the reaction were analyzed by gas chromatography. The results are averages under these conditions, as shown in Table 2.

[0060] Table 2 Evaluation results of the catalysts obtained in each case Example 1 93.1 91.6 4 Example 2 93.6 94.2 4 Example 3 92.5 92.1 5 Example 4 95.2 94.5 7 Example 5 96.0 94.0 8 Example 6 95.7 94.6 7 Example 7 94.4 93.3 6 Example 8 94.6 91.9 7 Example 9 94.1 90.9 5 Comparative Example 1 73.6 90.0 3 Comparative Example 2 21.8 62.0 5 Comparative Example 3 92.0 91.1 5 The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a catalyst for the synthesis of 3-methyl-3-buten-1-ol, comprising: (S1) Mix acrylic acid, acrylate, dispersant, leveling agent and photocuring agent to obtain photosensitive resin mixture; (S2) Mix the first powder and the photosensitive resin mixture obtained in step (S1), add the suspending agent, the first foaming agent and the second powder in sequence, let stand, and then add the anti-sticking agent and the second foaming agent to obtain the printing slurry. (S3) The printing slurry obtained in step (S2) is loaded into the liquid carrier device, and 3D printing is performed according to the set program. After post-processing, the catalyst is obtained. In step (S2), the weight ratio of each material in the printing slurry is as follows: 70-90 parts of first powder: 5-25 parts of photosensitive resin mixture: 0-2.5 parts of suspending agent: 0.1-2 parts of first foaming agent: 5-20 parts of second powder: 0.1-2 parts of anti-sticking agent: 0.1-1.5 parts of second foaming agent; the first powder is at least one of alumina, gibbsite, and kaolin; the suspending agent is one or more of sodium-based bentonite, lithium-based bentonite, or attapulgite; the... The first and second foaming agents are each independently selected from weakly acidic or alkaline water-soluble high-foaming cleaning agents; the anti-sticking agent is at least one of silicone powder, stearate, paraffin wax, or organosilicon release agent; the second powder includes phosphate and additives, wherein the weight ratio of phosphate to additive is 20:1-5:1; the phosphate is at least one of sodium phosphate or disodium hydrogen phosphate, and the additive is cerium oxide and calcium carbonate, wherein the weight ratio of cerium oxide to calcium carbonate is 2:1-1:

2.

2. The preparation method according to claim 1, characterized in that: In step (S1), the weight ratio of each substance in the mixture is: 20-32 parts acrylic acid: 8-20 parts acrylate: 2-10 parts dispersant: 1.5-7.5 parts leveling agent: 0.2-2 parts light curing agent.

3. The preparation method according to claim 1 or 2, characterized in that: In step (S1), the acrylate is one or more of the following: 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, dipentaerythritol hexaacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, or ethoxylated trimethylolpropane triacrylate.

4. The preparation method according to claim 3, characterized in that: The acrylate is one or more of 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, or trimethylolpropane triacrylate.

5. The preparation method according to claim 4, characterized in that: The acrylate includes both dipropylene glycol diacrylate and trimethylolpropane triacrylate, wherein the weight ratio of dipropylene glycol diacrylate to trimethylolpropane triacrylate is 1-2.5:1-1.

5.

6. The preparation method according to claim 1 or 2, characterized in that: In step (S1), the dispersant is one or both of 3-aminopropyltriethoxysilane or 3-glycidoxypropyltrimethoxysilane; And / or, in step (S1), the leveling agent is one or both of polydimethylsiloxane or polymethylsiloxane.

7. The preparation method according to claim 6, characterized in that: In step (S1), the dispersant is 3-glycidoxypropyltrimethoxysilane; And / or, in step (S1), the leveling agent is polydimethylsiloxane.

8. The preparation method according to claim 1 or 2, characterized in that: In step (S1), the photocuring agent is one or both of photosensitizers and photoinitiators; And / or, the photosensitizer is one or more of ethyl 4-dimethylaminobenzoate, triethylamine, ethyl-p-dimethylaminobenzoate, or triethanolamine; And / or, the photoinitiator is one or more of 2-isopropylthioxanthonone, methyl o-benzoylbenzoate, 2,4-diethylthioxanthonone, or 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methyl-1-propanone.

9. The preparation method according to claim 8, characterized in that: In step (S1), the photocuring agent includes both a photosensitizer and a photoinitiator, wherein the weight ratio of photosensitizer to photoinitiator is 1:10 to 1:

100. And / or, the photosensitizer is one or more of triethylamine or triethanolamine; And / or, the photoinitiator is one or more of 2-isopropylthioxanthone or methyl benzoate.

10. The preparation method according to claim 1, characterized in that: In step (S2), a pore-forming agent is also added, wherein the pore-forming agent is one or more of carboxymethyl cellulose and starch; And / or, the pore-forming agent accounts for 0.3%-3.0% of the weight of the first powder; And / or, in step (S2), the suspending agent is sodium-based bentonite; And / or, in step (S2), the first foaming agent and the second foaming agent are each independently alkaline, water-soluble, high-foaming cleaning agents; the alkaline, water-soluble, high-foaming cleaning agent is at least one of hydrogen peroxide or sodium bicarbonate powder; And / or, in step (S2), the anti-sticking agent is magnesium stearate.

11. The preparation method according to claim 10, characterized in that: The alkaline, water-soluble, high-foaming cleaning agent is sodium bicarbonate powder.

12. The preparation method according to claim 1, characterized in that: The phosphate includes both sodium phosphate and disodium hydrogen phosphate, wherein the weight ratio of sodium phosphate to disodium hydrogen phosphate is 1:1 to 1:

10.

13. The preparation method according to claim 12, characterized in that: The weight ratio of sodium phosphate to disodium hydrogen phosphate is 1:2 to 1:

10.

14. The preparation method according to claim 1, characterized in that: In step (S3), the post-processing includes blowing off the shallow layer of paste from the printed catalyst semi-finished product with compressed gas, then deep cleaning with ultrasonic 40-60℃ warm water bath, drying at 80-120℃ for 1-5 hours, and degreasing and sintering at 550-650℃ for 2-8 hours.

15. A catalyst for the synthesis of 3-methyl-3-buten-1-ol prepared by any of the preparation methods described in claims 1-14.

16. The catalyst according to claim 15, characterized in that: The mechanical strength of the catalyst is 20-120 N / cm; And / or, the catalyst has a three-dimensional cuboid mesh framework structure, wherein the catalyst has a height of 2-12 mm, a length of 2-12 mm, a width of 2-12 mm, and a porosity of 21.5%-95.1%.

17. The catalyst according to claim 16, characterized in that: In the catalyst, the basic unit grid skeleton structure of the three-dimensional cuboid grid skeleton structure is a cuboid skeleton structure, the side length of the basic unit grid skeleton structure is 200-800μm, and the diameter of the cross-section of the skeleton is 50-600μm.

18. The catalyst according to claim 17, characterized in that: The basic unit mesh skeleton structure of the three-dimensional cuboid mesh skeleton structure is a cube skeleton structure.

19. A method for synthesizing 3-methyl-3-buten-1-ol, comprising: Formaldehyde and isobutylene are reacted under the catalysis of any one of the catalysts described in claims 15-18 to obtain 3-methyl-3-buten-1-ol.

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