A catalyst for producing 3-methyl-3-buten-1-ol and use thereof

Abstract

The application discloses a catalyst for generating 3-methyl-3-buten-1-ol and application thereof. The catalyst comprises a carrier component and an active component, the active component comprises a phosphate and an auxiliary agent, the auxiliary agent is at least one of cerium oxide or calcium carbonate, and the weight ratio of the phosphate to the auxiliary agent is 20:1-5:1. The catalyst is applied to a process in which isobutene and formaldehyde generate 3-methyl-3-buten-1-ol, has high use stability, and maintains good catalytic activity.

Description

Technical Field

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

[0002] 3-Methyl-3-buten-1-ol is an important chemical raw material used in the production of citral, L-menthol, ionone, carotenoids, vitamin A, and vitamin E. After hydroisomerization, it is converted to 3-methyl-2-buten-1-ol, which can be used in the production of pyrethroid pesticides. After dehydration, it is converted to isoprene and can be used in the synthesis of rubber. It can also be used as a raw material for the production of the next-generation polycarboxylate superplasticizer TPEG. Using this high-performance cement superplasticizer in concrete production and construction can reduce water consumption by more than 30%, increase concrete strength by more than 30%, and correspondingly reduce cement usage, showing broad application prospects.

[0003] The preparation methods for 3-methyl-3-buten-1-ol from isobutylene and formaldehyde are divided into catalyst-free thermal condensation reactions and catalyst-assisted Prins condensation reactions. The catalysts used for this reaction are mainly of two types: acidic catalysts and basic catalysts. GB1205397A uses SnCl4 and ZnCl2 catalysts to prepare 3-methyl-3-buten-1-ol from isobutylene and formaldehyde at 15–100℃, but the formaldehyde conversion rate is low and chloride corrosion is severe. CN102659518A uses SnCl2-supported silica-alumina molecular sieves to synthesize 3-methyl-3-buten-1-ol from isobutylene and formaldehyde, improving the yield of 3-methyl-3-buten-1-ol; however, it still uses highly toxic SnCl2 as a catalyst, limiting its application. US4028424A uses phosphate as a catalyst to obtain 3-methyl-3-buten-1-ol and 3-methyl-2-buten-1-ol in yields of 65%–92% and 1%–6% respectively from paraformaldehyde and isobutylene at 150–200°C. The two have similar boiling points, requiring high costs for subsequent separation. CN107930686A uses an alkaline phosphate-modified phosphorosilica-alumina molecular sieve with isobutylene and formaldehyde as raw materials, achieving a 3-methyl-3-buten-1-ol yield greater than 81% relative to formaldehyde, with a selectivity for 3-methyl-3-buten-1-ol greater than 95%. However, this molecular sieve has small pores, leading to rapid carbon deposition and deactivation at higher reaction temperatures. CN106582788A uses formaldehyde and isobutylene as starting materials and modified ZSM-5 molecular sieve as catalyst to produce 3-methyl-3-buten-1-ol through a Prins condensation reaction in a fixed-bed reactor, achieving a yield of over 98%. However, the reaction conditions are quite harsh, with pressures exceeding 20 MPa, and the equipment requirements are high. While CN104387234A describes the use of "catalysts without acids, bases, or halogens," its specific content indicates that it uses aluminum alkoxide as the catalyst. This catalyst itself is also highly alkaline, thus failing to overcome the drawbacks of existing alkaline catalysts.

[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 that is not easily broken and can be easily separated 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 generation of 3-methyl-3-buten-1-ol and its application. The catalyst of this invention, applied in the process of isobutylene reacting with formaldehyde to generate 3-methyl-3-buten-1-ol, exhibits higher stability in use, does not pulverize or break down over long-term use, and maintains good catalytic activity; furthermore, its ease of separation from reactants and products makes it highly valuable for application.

[0006] The first aspect of the present invention provides a catalyst for generating 3-methyl-3-buten-1-ol, the catalyst comprising a support component and an active component, the active component comprising a phosphate and an auxiliary agent, wherein the auxiliary agent is at least one of cerium oxide or calcium carbonate, and wherein the weight ratio of the phosphate to the auxiliary agent is 20:1 to 5:1.

[0007] Further, the carrier component is derived from at least one of alumina, gibbsite, and 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.

[0008] Furthermore, the weight ratio of the carrier component to the active component is 70-90:5-20.

[0009] Furthermore, the phosphate is at least one of sodium phosphate, disodium hydrogen phosphate, or dipotassium hydrogen phosphate.

[0010] 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.

[0011] Furthermore, the additive includes both cerium oxide and calcium carbonate. 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. Further, the weight ratio of cerium oxide to calcium carbonate is 10:1 to 1:15, preferably 2:1 to 1:2.

[0012] Furthermore, the catalyst is cylindrical in shape. Preferably, the cylindrical dimensions are as follows: the diameter of the base circle is 3-5 mm, and the height is 3-5.5 mm.

[0013] Furthermore, the mechanical strength of the catalyst is 40.0-110.0 N / cm, more preferably 50.0-100.0 N / cm.

[0014] Furthermore, the catalyst described above can be prepared using extrusion molding methods conventional in the art. For example, the preparation method of the catalyst includes the following steps:

[0015] (1) Mixing: Mix the carrier component and the active component in a certain proportion;

[0016] (2) Kneading: Add an appropriate amount of water to the mixed material and knead it into small solid particles that will not immediately loosen.

[0017] (3) Sieving: Pass the small solid particles through a 10-30 mesh sieve;

[0018] (4) Drying: Dry the sieved solid particles at 80-120℃ for 12-24 hours;

[0019] (5) Molding: The dried solid particles are placed into a pelletizing machine and calcined to obtain a cylindrical shaped catalyst.

[0020] Furthermore, a pore-forming agent may be added during the kneading process. The pore-forming agent is one or more of carboxymethyl cellulose and starch. The weight percentage of the pore-forming agent is 0.3%-3.0% of the carrier component.

[0021] Further, in step (5), the calcination conditions are: temperature 400-650℃, time 1-12 hours.

[0022] To further improve the mechanical strength of the catalyst, preferably, the present invention provides a method for 3D printing to generate a 3-methyl-3-buten-1-ol catalyst, comprising:

[0023] (S1) Mix acrylic acid, acrylate, dispersant, leveling agent and photocuring agent to obtain photosensitive resin mixture;

[0024] (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.

[0025] (S3) The printing slurry obtained in (S2) is loaded into the liquid carrier device, and 3D printing is performed according to the set program. After post-processing, a cylindrical catalyst is obtained.

[0026] 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 UV curing agent.

[0027] 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.

[0028] Further, in step (S1), the dispersant is one or both of 3-aminopropyltriethoxysilane or 3-glycidoxypropyltrimethoxysilane, preferably 3-glycidoxypropyltrimethoxysilane.

[0029] Further, in step (S1), the rheology modifier is one or both of polydimethylsiloxane or polymethylsiloxane, preferably polydimethylsiloxane.

[0030] 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 1:10 to 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 both of 2-isopropylthioxanthonone or methyl phthalobenzoate.

[0031] Further, in step (S2), the weight ratio of each material in the printing slurry is as follows: 70-90 parts of the first powder: 5-25 parts of the photosensitive resin mixture; 0-2.5 parts of the suspending agent: 0.1-2 parts of the first foaming agent: 5-20 parts of the second powder: 0.1-2 parts of the anti-sticking agent: 0.1-1.5 parts of the second foaming agent.

[0032] 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.

[0033] Further, in step (S2), the first powder is a carrier component, selected from at least one of alumina, boehmite, and kaolin; preferably, the alumina is γ-Al2O3 with a particle size of 10-25 μm; the boehmite 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 introduced in step (S2), which may be one or both of carboxymethyl cellulose and starch. The pore-forming agent accounts for 0.3%-3.0% by weight of the first powder.

[0034] Further, in step (S2), the suspending agent is one or more of sodium-based bentonite, lithium-based bentonite, or attapulgite, preferably sodium-based bentonite.

[0035] 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.

[0036] Further, in step (S2), the anti-sticking agent is one or a mixture of at least two 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.

[0037] Further, in step (S2), the second powder is an active component, comprising a phosphate and an additive, wherein the weight ratio of the phosphate to the additive is 20:1 to 5:1. The phosphate is at least one of sodium phosphate, disodium hydrogen phosphate, or dipotassium hydrogen phosphate, and the additive is at least one of cerium oxide or calcium carbonate.

[0038] 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.

[0039] Furthermore, the additive includes both cerium oxide and calcium carbonate. 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. Further, the weight ratio of cerium oxide to calcium carbonate is 10:1 to 1:15, preferably 2:1 to 1:2.

[0040] 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.

[0041] 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.

[0042] Furthermore, in step (S2), the settling is carried out under normal pressure for 8-24 hours.

[0043] Further, in step (S2), the printing paste is a printing slurry or a printing paste.

[0044] 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.

[0045] Further, the mechanical strength of the cylindrical catalyst obtained in step (S3) is 50.0-120.0 N / cm, more preferably 60.0-90.0 N / cm. Further, the cylindrical catalyst has the following dimensions: the diameter of the bottom circle is 3-5 mm, and the height is 3-5.5 mm.

[0046] A third aspect of the present invention provides the application of the above-mentioned catalyst in the reaction of isobutylene and formaldehyde to produce 3-methyl-3-buten-1-ol.

[0047] Furthermore, the reaction conditions are as follows: the reaction pressure is 4-10 MPa, the reaction temperature is 170-260℃; the mass ratio of formaldehyde to isobutanol is 0.05-0.3, and the mass ratio of catalyst to formaldehyde is 0.05-0.3.

[0048] Compared with the prior art, the present invention has the following advantages:

[0049] The catalyst provided by the present invention for the formation of 3-methyl-3-buten-1-ol from isobutylene and formaldehyde includes an active component comprising a phosphate and an auxiliary agent. Preferably, the phosphate comprises both sodium phosphate and disodium hydrogen phosphate, and the auxiliary agent comprises both cerium oxide and calcium carbonate. This catalyst has 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.

[0050] Cylindrical catalysts for the production of 3-methyl-3-buten-1-ol are commonly prepared using extrusion molding. The inventors discovered that 3D printing technology can effectively improve the mechanical strength of the catalyst, further extending its lifespan. When applied to the process of isobutylene reacting with formaldehyde to produce 3-methyl-3-buten-1-ol, the catalyst significantly improves both formaldehyde conversion and the selectivity for 3-methyl-3-buten-1-ol. Attached Figure Description

[0051] Figure 1 The catalyst molding diagram is shown in Example 4.

[0052] Figure 2 The catalyst molding diagram is shown in Example 7. Detailed Implementation

[0053] The technical solution of the present invention will be described in detail below with reference to the embodiments.

[0054] 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 at 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).

[0055] 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.

[0056] In this invention, the formulas for calculating conversion rate, selectivity, and number of reusable cycles are as follows:

[0057] Formaldehyde conversion rate % = (1-n) 甲醛产物 / n 甲醛原料 )×100%;

[0058] 3-Methyl-3-buten-1-ol selectivity % = n 3-甲基-3-丁烯-1-醇 / n 甲醛 ×100%;

[0059] 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%;

[0060] 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.

[0061] In this invention, during the catalyst preparation process, 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 set to 0.5-2 kPa.

[0062]

Example 1

[0063] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of active components (Na2HPO4·12H2O and CaCO3, with weights of 18.4 and 1.6 respectively) were mixed evenly at low speed in a mixer; 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste; the paste was air-dried at 25°C for 12 hours; the paste was then passed through a 20-mesh sieve and dried at 100°C for 12 hours; the paste was then formed into tablets using a rotary tableting machine; and finally calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0064]

Example 2

[0065] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of active components (Na2HPO4·12H2O and CeO2, with weights of 18.4 and 1.6 respectively) were mixed evenly at low speed in a mixer; 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste; the paste was air-dried at 25°C for 12 hours; the paste was then passed through a 20-mesh sieve and dried at 100°C for 12 hours; the paste was then formed into tablets using a rotary tableting machine; and finally calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0066]

Example 3

[0067] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of active components (Na2HPO4·12H2O, CaCO3 and CeO2, with weights of 18.4, 1.0 and 0.6 respectively) were mixed evenly at low speed in a mixer. 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste. The paste was air-dried at 25°C for 12 hours, passed through a 20-mesh sieve, dried at 100°C for 12 hours, and then shaped into tablets using a rotary tableting machine. The tablets were then calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0068]

Example 4

[0069] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O, Na2HPO4·12H2O, CaCO3 and CeO2, with weights of 4.6, 13.8, 1.0 and 0.6 respectively) were mixed evenly at low speed in a mixer; 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste; the paste was air-dried at 25°C for 12 hours; the paste was then passed through a 20-mesh sieve and dried at 100°C for 12 hours; the paste was then formed into tablets using a rotary tableting machine; and finally calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0070]

Example 5

[0071] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O, Na2HPO4·12H2O, CaCO3 and CeO2, with weights of 3.5, 14.0, 1.0 and 1.5 respectively) were mixed evenly at low speed in a mixer. 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste. The paste was air-dried at 25°C for 12 hours, passed through a 20-mesh sieve, dried at 100°C for 12 hours, and then shaped into tablets using a rotary tableting machine. The tablets were then calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0072]

Example 6

[0073] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O, Na2HPO4·12H2O, CaCO3 and CeO2, with weights of 4.6, 13.8, 1.5 and 0.1 respectively) were mixed evenly at low speed in a mixer. 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste. The paste was air-dried at 25°C for 12 hours, passed through a 20-mesh sieve, dried at 100°C for 12 hours, and then shaped into tablets using a rotary tableting machine. The tablets were then calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0074]

Example 7

[0075] (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;

[0076] (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, CaCO3 and CeO2, in 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.

[0077] (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.

[0078] The printed solid alkali 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 cylindrical shaped catalyst.

[0079]

Example 8

[0080] (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;

[0081] (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, Na2HPO4·12H2O and CaCO3, in weights of 4.6, 13.8 and 1.6 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.

[0082] (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.

[0083] The printed solid alkali 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 cylindrical shaped catalyst.

[0084]

Example 9

[0085] (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;

[0086] (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 and CeO2, in weights of 4.6, 13.8 and 1.6 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.

[0087] (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.

[0088] The printed solid alkali 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 cylindrical shaped catalyst.

[0089] Comparative Example 1

[0090] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of CaCO3 were mixed evenly at low speed in a mixer; 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste; the paste was air-dried at 25°C for 12 hours; the paste was then passed through a 20-mesh sieve and dried at 100°C for 12 hours; the paste was then formed into tablets using a rotary tableting machine; and the paste was calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0091] [Comparative Example 2]

[0092] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of CeO2 were mixed evenly at low speed in a mixer; 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste; the paste was air-dried at 25°C for 12 hours; the paste was passed through a 20-mesh sieve and dried at 100°C for 12 hours; the paste was then formed into tablets using a rotary tableting machine; and calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0093] [Comparative Example 3]

[0094] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O and Na2HPO4·12H2O, with weights of 5.0 and 15.0 respectively) were mixed evenly at low speed in a mixer. 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste. The paste was air-dried at 25°C for 12 hours, passed through a 20-mesh sieve, dried at 100°C for 12 hours, and then shaped into tablets using a rotary tableting machine. The tablets were then calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0095] [Comparative Example 4]

[0096] 80 parts by weight of diaspore (particle size 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O, Na2HPO4·12H2O, Ca3(PO4)2 and CeO2, with weights of 4.6, 13.8, 1.0 and 0.6 respectively) were mixed evenly at low speed in a mixer. 40 parts by weight of water were added to the mixed powder, and the mixture was stirred and kneaded into a paste. The paste was then air-dried at 25°C for 12 hours, passed through a 20-mesh sieve, dried at 100°C for 12 hours, and shaped into tablets using a rotary tableting machine. The tablets were then calcined in a muffle furnace (sintering temperature 500°C, holding time 3 hours) to obtain a cylindrical catalyst.

[0097] Catalyst evaluation

[0098] 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, controlling the isobutene feed rate at 320 g, the reaction temperature at 220℃, and the reaction pressure at 8.0 MPa. The reaction was carried out for 4 hours, after which the remaining isobutene and catalyst were removed. The formaldehyde conversion rate and 3-methyl-3-buten-1-ol selectivity were obtained by gas chromatography analysis of the post-reaction samples. The results are averages under these conditions, as shown in Table 3.

[0099] Table 1. Properties of the catalysts obtained in each example.

[0100]

[0101]

[0102] Table 2 Catalyst Composition for Each Example

[0103]

[0104] Table 3 Evaluation results of the catalysts obtained in each example

[0105]

[0106]

[0107] 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. The application of a catalyst for generating 3-methyl-3-buten-1-ol in the reaction of isobutene and formaldehyde to generate 3-methyl-3-buten-1-ol, said catalyst comprising a support component and an active component, said active component comprising a phosphate and an auxiliary agent, said auxiliary agent being cerium oxide and calcium carbonate, wherein, The weight ratio of phosphate to additives is 20:1-5:1, and the weight ratio of cerium oxide to calcium carbonate is 2:1-1:

2.

2. The application according to claim 1, characterized in that: The carrier component is derived from at least one of alumina, gibbsite, and kaolin.

3. The application according to claim 1, characterized in that: The phosphate is at least one of sodium phosphate, disodium hydrogen phosphate, or dipotassium hydrogen phosphate.

4. The application 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.

5. The application according to claim 4, characterized in that: The weight ratio of sodium phosphate to disodium hydrogen phosphate is 1:2 to 1:

10.

6. The application according to claim 1, characterized in that: The weight ratio of the carrier component to the active component is 70-90:5-20.

7. The application according to any one of claims 1-6, characterized in that: The catalyst is cylindrical in shape; the cylindrical dimensions are as follows: diameter 3-5 mm, height 3-5.5 mm.

8. The application according to claim 1, characterized in that: The mechanical strength of the catalyst is 40.0-110.0 N / cm.

9. The application according to claim 8, characterized in that: The mechanical strength of the catalyst is 50.0-100.0 N / cm.

10. The application according to claim 1, characterized in that: The reaction conditions are as follows: reaction pressure is 4-10 MPa, reaction temperature is 170-260℃; the mass ratio of formaldehyde to isobutanol is 0.05-0.3, and the mass ratio of catalyst to formaldehyde is 0.05-0.3.

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