Catalyst for generating 3-methyl-3-butene-1-alcohol and application thereof

Abstract

The invention discloses a catalyst for generating 3-methyl-3-butene-1-alcohol and application of the catalyst for generating 3-methyl-3-butene-1-alcohol. The catalyst comprises a carrier component and an active component, the active component comprises phosphate and an auxiliary agent, the auxiliary agent is at least one of cerium oxide or calcium carbonate, and the weight part ratio of the phosphate to the auxiliary agent is (20: 1)-(5: 1). The catalyst disclosed by the invention is applied to a process of generating 3-methyl-3-butene-1-alcohol from isobutene and formaldehyde, has relatively high use stability and keeps relatively good catalytic activity.

Description

Technical Field

[0001] The invention relates to the field of solid base catalysis, and in particular to a catalyst for generating 3-methyl-3-butene-1-ol and application thereof. Background Art

[0002] 3-Methyl-3-butene-1-ol is an important chemical raw material, which can be used to produce citral, L-menthol, ionone, carotenoids, vitamin A, vitamin E, etc. After being converted into 3-methyl-2-butene-1-ol by hydroisomerization reaction, it can be used to produce pyrethroid pesticides. After being converted into isoprene by dehydration reaction, it can be used to synthesize rubber. It can also be used as a raw material for producing a new generation of polycarboxylic acid series high-efficiency water reducer TPEG. Using this high-performance cement water reducer in concrete production and construction can reduce water consumption by more than 30%, increase concrete strength by more than 30%, and reduce cement consumption accordingly, with broad application prospects.

[0003] The preparation method of 3-methyl-3-butene-1-ol from isobutylene and formaldehyde is divided into a thermal condensation reaction without a catalyst and a Prince condensation reaction with a catalyst. Among them, there are two main types of catalysts for the reaction of isobutylene and formaldehyde to generate 3-methyl-3-butene-1-ol, namely acidic catalysts and alkaline catalysts. GB1205397A uses SnCl4 and ZnCl2 catalysts to react isobutylene with formaldehyde to prepare 3-methyl-3-butene-1-ol at 15-100°C. The formaldehyde conversion rate is low and the chloride corrosion is serious. CN102659518A uses SnCl2-supported silicon-aluminum molecular sieves to synthesize 3-methyl-3-butene-1-ol with isobutylene and formaldehyde as raw materials. The yield of the product 3-methyl-3-butene-1-ol is improved, but the highly toxic SnCl2 is still used as a catalyst, which limits its application. US4028424A uses phosphate as a catalyst, and uses polyformaldehyde and isobutylene at 150-200°C to obtain 3-methyl-3-butene-1-ol with a yield of 65%-92% and 3-methyl-2-butene-1-ol with a yield of 1%-6%. The boiling points of the two are close, and the subsequent separation requires high costs. CN107930686A uses a phosphorus silicon aluminum molecular sieve modified with alkaline phosphate, and uses isobutylene and formaldehyde as raw materials. The yield of 3-methyl-3-butene-1-ol relative to formaldehyde is greater than 81%, and the selectivity for the generation of 3-methyl-3-butene-1-ol is greater than 95%. However, the molecular sieve has small pores, and the molecular sieve is rapidly deactivated by carbon deposition under high reaction temperature conditions. CN106582788A uses formaldehyde and isobutylene as starting materials and a modified ZSM-5 molecular sieve as a catalyst to produce 3-methyl-3-butene-1-ol by a Prince condensation reaction in a fixed bed reactor, with a maximum yield of more than 98%, but the reaction conditions are relatively harsh, the pressure is greater than 20MPa, and the equipment requirements are high. Although CN104387234A records that "no acid, alkali, or halogen catalyst is used", according to its specific content, the catalyst used is aluminum alcohol, which is also highly alkaline, so it is still difficult to overcome the disadvantages of existing alkaline catalysts.

[0004] In summary, the existing catalysts for generating 3-methyl-3-butene-1-ol from isobutylene and formaldehyde generally have problems such as difficulty in separation (powdered catalysts or homogeneous catalysts) or low strength of formed catalysts. Therefore, providing a catalyst that is not easy to break and easy to separate from the raw material product has become one of the problems that those skilled in the art need to solve urgently. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a catalyst for generating 3-methyl-3-butene-1-ol and its application. The catalyst of the present invention is applied to the process of generating 3-methyl-3-butene-1-ol from isobutylene and formaldehyde, has higher stability in use, will not be pulverized and broken after long-term use, and maintains good catalytic activity; and is easy to separate from reaction raw materials and products, and has high application value.

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

[0007] Furthermore, the carrier component is derived from at least one of alumina, diaspore and kaolin. Preferably, the alumina is γ-Al2O3 with a particle size of 10-25 μm; the particle size of diaspore is 10-25 μm; and the particle size of kaolin is 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 sodium phosphate and disodium hydrogen phosphate at the same time, wherein the weight ratio of sodium phosphate to disodium hydrogen phosphate is 1:1-1:10, preferably 1:2-1:10.

[0011] Furthermore, the auxiliary agent includes cerium oxide and calcium carbonate at the same time. Cerium oxide and calcium carbonate have a synergistic effect in improving the mechanical strength of the catalyst, the formaldehyde conversion rate and the selectivity of 3-methyl-3-butene-1-ol. Furthermore, the weight ratio of cerium oxide to calcium carbonate is 10:1-1:15, preferably 2:1-1:2.

[0012] Furthermore, the catalyst is cylindrical in shape. Preferably, the cylindrical dimensions are as follows: the diameter of the bottom 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, and more preferably 50.0-100.0 N / cm.

[0014] Furthermore, the catalyst can be prepared by a conventional extrusion molding method in the art. For example, the preparation method of the catalyst comprises the following steps:

[0015] (1) Mixing: Mixing the carrier component and the active component according to the proportion;

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

[0017] (3) Screening: small solid particles are screened through a 10-30 mesh screen;

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

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

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

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

[0022] In order to further improve the mechanical strength of the catalyst, preferably, the present invention provides a method for generating a 3-methyl-3-butene-1-ol catalyst by 3D printing, comprising:

[0023] (S1) mixing acrylic acid, acrylate, dispersant, leveling agent and photocuring agent to obtain a photosensitive resin mixed solution;

[0024] (S2) mixing the first powder and the photosensitive resin mixed solution obtained in step (S1), adding a suspending agent, a first foaming agent and a second powder in sequence, letting the mixture stand, and then adding an anti-sticking agent and a second foaming agent to obtain a printing slurry;

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

[0026] Furthermore, in step (S1), the weight ratio of each substance in the mixed solution is: 20-32 parts of acrylic acid: 8-20 parts of acrylate: 2-10 parts of dispersant: 1.5-7.5 parts of leveling agent: 0.2-2 parts by weight of photocuring agent.

[0027] Further, in step (S1), the acrylate is one or more of 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, dipentaerythritol hexaacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate or ethoxylated trimethylolpropane triacrylate, preferably one or more of 1,6-hexanediol diacrylate, dipropylene glycol diacrylate or trimethylolpropane triacrylate.

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

[0029] Furthermore, in step (S1), the rheological agent is one or both of polydimethylsiloxane and polymethylsiloxane, preferably polydimethylsiloxane.

[0030] Further, in step (S1), the photocuring agent is one or both of a photosensitizer or a photoinitiator, preferably including both a photosensitizer and a photoinitiator, wherein the weight ratio of the photosensitizer: the photoinitiator is 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-isopropylthioxanthone, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone or 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methyl-1-propanone, preferably one or both of 2-isopropylthioxanthone or methyl o-benzoylbenzoate.

[0031] Furthermore, in step (S2), the weight ratio of each material in the printing slurry is 70-90 parts of the first powder: 5-25 parts of the photosensitive resin mixed liquid, and the weight ratio is: 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 mixed solution obtained in (S1) are mixed and ball-milled in a ball mill until uniform, and then 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, diaspore, and kaolin; preferably, the alumina is γ-Al2O3 with a particle size of 10-25 μm; the particle size of the diaspore is 10-25 μm; the particle size of the kaolin is 0.5-2 μm. Further, in step (S2), a pore former can also be introduced, and the pore former can be one or both of carboxymethyl cellulose and starch. The weight percentage of the pore former accounts for 0.3%-3.0% of the first powder.

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

[0035] Further, in step (S2), the first foaming agent and the second foaming agent are each independently selected from a weakly acidic or alkaline water-soluble high-foaming detergent; preferably, the foaming agent is an alkaline water-soluble high-foaming detergent; preferably, the alkaline water-soluble high-foaming detergent is at least one of hydrogen peroxide or sodium bicarbonate powder; more preferably, the alkaline water-soluble high-foaming detergent is sodium bicarbonate powder.

[0036] Furthermore, in step (S2), the anti-sticking agent is one or a mixture of at least two of silicone powder, stearate, paraffin or silicone release agent; preferably, the anti-sticking agent is stearate; more preferably, the anti-sticking agent is magnesium stearate.

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

[0038] Furthermore, the phosphate includes sodium phosphate and disodium hydrogen phosphate at the same time, wherein the weight ratio of sodium phosphate to disodium hydrogen phosphate is 1:1-1:10, preferably 1:2-1:10.

[0039] Furthermore, the auxiliary agent includes cerium oxide and calcium carbonate at the same time. Cerium oxide and calcium carbonate have a synergistic effect in improving the mechanical strength of the catalyst, the formaldehyde conversion rate and the selectivity of 3-methyl-3-butene-1-ol. Furthermore, the weight ratio of cerium oxide to calcium carbonate is 10:1-1:15, preferably 2:1-1:2.

[0040] Further, in step (S2), the first powder and the photosensitive resin mixed liquid are mixed, the suspending agent and the foaming agent are added, the mixture is subjected to low-speed stirring and vacuum dehydrogenation, the second powder is added, the mixture is subjected to high-speed stirring and vacuum dehydrogenation, the mixture is allowed to stand, the anti-adhesive agent and the foaming agent are added, the mixture is subjected to high-speed stirring and vacuum dehydrogenation, and the printing slurry is obtained. The low-speed stirring and high-speed stirring are both conventional operations in the art.

[0041] Furthermore, in step (S2), the second powder is firstly ball-milled and mixed uniformly in a ball mill and then transferred to a mixer for stirring. The ball-milling mixing is a conventional operation in the art.

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

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

[0044] Further, in step (S3), first import the printing model file and set the printing parameters in the computer of the printer, then load the prepared printing slurry into the liquid carrier, initialize the printing platform and the optical machine, and adjust the slurry surface level; based on the printing scheme set by the target model, the printing slurry is laid layer by layer as a 3D printing raw material, scraped flat with a scraper, and selectively exposed layer by layer using an ultraviolet laser or a DLP-UV light source (365nm-405nm), and the solid base catalyst semi-finished product is obtained after the slurry is cured. Further, the post-processing includes cleaning and sintering. Further, the post-processing is to use compressed gas to blow off the shallow paste of the printed catalyst semi-finished product, and then use an ultrasonic 40-60℃ warm water bath for deep cleaning, an oven 80-120℃ drying for 1-5h, and a muffle furnace for degreasing and sintering to obtain a solid base catalyst. Wherein, the degreasing sintering carried out in the muffle furnace has a sintering temperature of 550-650℃ and a holding time of 2-8h.

[0045] Furthermore, 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. Furthermore, the dimensions of the cylindrical catalyst are as follows: the diameter of the bottom circle is 3-5 mm, and the height is 3-5.5 mm.

[0046] The third aspect of the present invention provides an application of the above catalyst in the reaction of isobutylene and formaldehyde to generate 3-methyl-3-butene-1-ol.

[0047] Furthermore, the reaction conditions are as follows: the reaction pressure is 4-10 MPa, the reaction temperature is 170-260° C.; 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 present invention provides a catalyst for generating 3-methyl-3-butene-1-ol from isobutylene and formaldehyde, wherein the active components include phosphate and an auxiliary agent, preferably, the phosphate includes sodium phosphate and disodium hydrogen phosphate at the same time, and the auxiliary agent includes cerium oxide and calcium carbonate at the same time, which has a synergistic effect in improving the mechanical strength of the catalyst, the formaldehyde conversion rate and the selectivity of 3-methyl-3-butene-1-ol.

[0050] The cylindrical catalyst for generating 3-methyl-3-butene-1-ol is usually prepared by extrusion molding process. The inventors have found that the use of 3D printing technology can effectively improve the mechanical strength of the catalyst and further improve the service life of the catalyst. The catalyst prepared by 3D printing technology is applied to the process of generating 3-methyl-3-butene-1-ol from isobutylene and formaldehyde, and the formaldehyde conversion rate and 3-methyl-3-butene-1-ol selectivity are significantly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 The catalyst forming diagram prepared in Example 4;

[0052] Figure 2 This is the catalyst forming diagram prepared in Example 7. DETAILED DESCRIPTION

[0053] The technical solution of the present invention is described in detail below in conjunction with embodiments.

[0054] In the present invention, the formaldehyde conversion rate and the selectivity of the product 3-methyl-3-butene-1-ol are obtained by gas chromatography. The concentrations of the raw material formaldehyde and the product 3-methyl-3-butene-1-ol are determined by configuring standard curves of different concentrations (since a large amount of solution does not participate in the reaction, it is assumed that the volume before and after the reaction remains unchanged).

[0055] In the present invention, the mechanical strength is measured using a DLIII intelligent particle strength tester, and the average value (in N) is taken after 10 tests, and the average value is divided by the length of the cross section of the catalyst particle (in cm), which is the mechanical strength in N / cm.

[0056] In the present invention, the calculation formulas for conversion rate, selectivity and number of recyclable times are:

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

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

[0059] Recyclable times N: Nth formaldehyde conversion rate ≥ 1st formaldehyde conversion rate × 90%;

[0060] Among them, n 甲醛产物 represents the number of moles of formaldehyde generated by the reaction, n 甲醛原料 Indicates the number of moles of formaldehyde added to the reaction, n 3-甲基-3-丁烯-1-醇 represents the number of moles of 3-methyl-3-butene-1-ol produced by the reaction, n 甲醛 Indicates the number of moles of formaldehyde consumed in the reaction.

[0061] In the present invention, during the catalyst preparation process, the ball mill speed is set to 40-180 r / min at low speed, the stirrer speed is set to 500 r / min at low speed, the stirrer speed is set to 1500-2000 r / min at high speed, and the vacuum is 0.5-2 kPa.

[0062] [Example 1]

[0063] 80 parts by weight of diaspore (with a particle size of 10-25 μm) and 20 parts by weight of active components (Na2HPO4·12H2O and CaCO3, with weight parts of 18.4 and 1.6 respectively) are uniformly stirred in a blender at a low speed; 40 parts by weight of water are added to the mixed powder, stirred and kneaded into a paste; dried in the shade at 25°C for 12 hours; passed through a 20-mesh sieve and dried at 100°C for 12 hours; tableted using a rotary tabletting machine; and calcined in a muffle furnace (sintering temperature of 500°C, insulation time of 3 hours) to obtain a cylindrical catalyst.

[0064] [Example 2]

[0065] 80 parts by weight of diaspore (with a particle size of 10-25 μm) and 20 parts by weight of active components (Na2HPO4·12H2O and CeO2, with weight parts of 18.4 and 1.6 respectively) are uniformly stirred in a blender at a low speed; 40 parts by weight of water are added to the mixed powder, stirred and kneaded into a paste; dried in the shade at 25°C for 12 hours; passed through a 20-mesh sieve and dried at 100°C for 12 hours; tableted using a rotary tabletting machine; and calcined in a muffle furnace (sintering temperature of 500°C, insulation time of 3 hours) to obtain a cylindrical catalyst.

[0066] [Example 3]

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

[0068] [Example 4]

[0069] 80 parts by weight of diaspore (with a particle size of 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O, Na2HPO4·12H2O, CaCO3 and CeO2, with weight parts of 4.6, 13.8, 1.0 and 0.6 respectively) are uniformly stirred in a blender at a low speed; 40 parts by weight of water are added to the mixed powder, stirred and kneaded into a paste; dried in the shade at 25°C for 12 hours; passed through a 20-mesh sieve and dried at 100°C for 12 hours; tableted using a rotary tabletting machine; and calcined in a muffle furnace (sintering temperature of 500°C, insulation time of 3 hours) to obtain a cylindrical catalyst.

[0070] [Example 5]

[0071] 80 parts by weight of diaspore (with a particle size of 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O, Na2HPO4·12H2O, CaCO3 and CeO2, with weight parts of 3.5, 14.0, 1.0 and 1.5 respectively) are uniformly stirred in a blender at a low speed; 40 parts by weight of water are added to the mixed powder, stirred and kneaded into a paste; dried in the shade at 25°C for 12 hours; passed through a 20-mesh sieve, dried at 100°C for 12 hours, and formed into tablets using a rotary tabletting machine; and calcined in a muffle furnace (sintering temperature of 500°C, insulation time of 3 hours) to obtain a cylindrical catalyst.

[0072] [Example 6]

[0073] 80 parts by weight of diaspore (with a particle size of 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O, Na2HPO4·12H2O, CaCO3 and CeO2, with weight parts of 4.6, 13.8, 1.5 and 0.1 respectively) are uniformly stirred in a blender at a low speed; 40 parts by weight of water are added to the mixed powder, stirred and kneaded into a paste; dried in the shade at 25°C for 12 hours; passed through a 20-mesh sieve, dried at 100°C for 12 hours, and formed into tablets using a rotary tabletting machine; and calcined in a muffle furnace (sintering temperature of 500°C, insulation time of 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-glycidyloxypropyl trimethoxysilane, 4 parts by weight of polydimethylsiloxane, and 0.4 parts by weight of a mixture of triethanolamine and methyl o-benzoylbenzoate (the weight ratio is 1:15) are stirred in a blender to obtain a photosensitive resin mixed solution;

[0076] (S2) 80 parts by weight of a first powder (diaspore and carboxymethyl cellulose with a particle size of 10-25 μm, in a weight ratio of 40:1) and 12 parts by weight of a photosensitive resin mixed solution are subjected to ball milling and mixing treatment in a ball mill for 5 hours, and then transferred into a blender, 1 part by weight of sodium bentonite and 0.3 parts by weight of NaHCO3 powder are added, and after low-speed stirring and uniform mixing in the blender, vacuumization is evacuated, and then 20 parts by weight of a second powder (Na3PO4·12H2O, Na2HPO4·12H2O, CaCO3 and CeO2, with weight parts of 4.6, 13.8, 1.0 and 0.6, respectively; ball milling and mixing treatment is performed in a ball mill for 3 hours in advance), and after high-speed stirring and uniform mixing, vacuumization is evacuated, and the mixture is allowed to stand at normal pressure for 10 hours, and finally 0.2 parts by weight of magnesium stearate and 0.5 parts by weight of NaHCO3 powder are added, and after high-speed stirring and uniform mixing, vacuumization is evacuated to obtain a printing slurry;

[0077] (S3) importing the printing model file into the computer of the printer, setting the printing parameters, loading the above-prepared printing slurry into the liquid carrier, initializing the printing platform and the optical machine, and adjusting the slurry surface level; according to the printing scheme set by the target model, using the printing slurry as the 3D printing raw material for layer-by-layer laying, scraping with a scraper, and selectively exposing layer by layer using an ultraviolet laser or a DLP-UV light source, and obtaining a solid base catalyst semi-finished product after the slurry is cured;

[0078] The printed solid base catalyst semi-finished product was blown off the shallow layer of paste with compressed gas, and then deeply cleaned with ultrasonic warm water bath at 40°C, dried in an oven at 100°C for 1h, and degreased and sintered in a muffle furnace (sintering temperature 560°C, insulation time 3 hours) to obtain a cylindrical 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-glycidyloxypropyl trimethoxysilane, 4 parts by weight of polydimethylsiloxane, and 0.4 parts by weight of a mixture of triethanolamine and methyl o-benzoylbenzoate (the weight ratio is 1:15) are stirred in a blender to obtain a photosensitive resin mixed solution;

[0081] (S2) 80 parts by weight of the first powder (diaspore 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 mixed solution are subjected to ball milling and mixing treatment in a ball mill for 5 hours, and then transferred into a blender, 1 part by weight of sodium bentonite and 0.3 part by weight of NaHCO3 powder are added, and after low-speed stirring and uniform mixing in the blender, vacuumization is evacuated, and then 20 parts by weight of the second powder (Na3PO4·12H2O, Na2HPO4·12H2O and CaCO3, with weight parts of 4.6, 13.8 and 1.6, respectively; ball milling and mixing treatment is performed in the ball mill for 3 hours in advance), and after high-speed stirring and uniform mixing, vacuumization is evacuated, and the mixture is allowed to stand at normal pressure for 10 hours, and finally 0.2 parts by weight of magnesium stearate and 0.5 parts by weight of NaHCO3 powder are added, and after high-speed stirring and uniform mixing, vacuumization is evacuated to obtain a printing slurry;

[0082] (S3) importing the printing model file into the computer of the printer, setting the printing parameters, loading the above-prepared printing slurry into the liquid carrier, initializing the printing platform and the optical machine, and adjusting the slurry surface level; according to the printing scheme set by the target model, using the printing slurry as the 3D printing raw material for layer-by-layer laying, scraping with a scraper, and selectively exposing layer by layer using an ultraviolet laser or a DLP-UV light source, and obtaining a solid base catalyst semi-finished product after the slurry is cured;

[0083] The printed solid base catalyst semi-finished product was blown off the shallow layer of paste with compressed gas, and then deeply cleaned with ultrasonic warm water bath at 40°C, dried in an oven at 100°C for 1h, and degreased and sintered in a muffle furnace (sintering temperature 560°C, insulation time 3 hours) to obtain a cylindrical 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-glycidyloxypropyl trimethoxysilane, 4 parts by weight of polydimethylsiloxane, and 0.4 parts by weight of a mixture of triethanolamine and methyl o-benzoylbenzoate (the weight ratio is 1:15) are stirred in a blender to obtain a photosensitive resin mixed solution;

[0086] (S2) 80 parts by weight of a first powder (diaspore and carboxymethyl cellulose with a particle size of 10-25 μm, in a weight ratio of 40:1) and 12 parts by weight of a photosensitive resin mixed solution are subjected to ball milling and mixing treatment in a ball mill for 5 hours, and then transferred into a blender, 1 part by weight of sodium bentonite and 0.3 part by weight of NaHCO3 powder are added, and after low-speed stirring and uniform mixing in the blender, vacuumization is evacuated, and then 20 parts by weight of a second powder (Na3PO4·12H2O, Na2HPO4·12H2O and CeO2, with weight parts of 4.6, 13.8 and 1.6, respectively; ball milling and mixing treatment is performed in the ball mill for 3 hours in advance), and after high-speed stirring and uniform mixing, vacuumization is evacuated, and the mixture is allowed to stand at normal pressure for 10 hours, and finally 0.2 parts by weight of magnesium stearate and 0.5 parts by weight of NaHCO3 powder are added, and after high-speed stirring and uniform mixing, vacuumization is evacuated to obtain a printing slurry;

[0087] (S3) importing the printing model file into the computer of the printer, setting the printing parameters, loading the above-prepared printing slurry into the liquid carrier, initializing the printing platform and the optical machine, and adjusting the slurry surface level; according to the printing scheme set by the target model, using the printing slurry as the 3D printing raw material for layer-by-layer laying, scraping with a scraper, and selectively exposing layer by layer using an ultraviolet laser or a DLP-UV light source, and obtaining a solid base catalyst semi-finished product after the slurry is cured;

[0088] The printed solid base catalyst semi-finished product was blown off the shallow layer of paste with compressed gas, and then deeply cleaned with ultrasonic warm water bath at 40°C, dried in an oven at 100°C for 1h, and degreased and sintered in a muffle furnace (sintering temperature 560°C, insulation time 3 hours) to obtain a cylindrical catalyst.

[0089] [Comparative Example 1]

[0090] 80 parts by weight of diaspore (particle size of 10-25 μm) and 20 parts by weight of CaCO3 are stirred evenly in a blender at low speed; 40 parts by weight of water are added to the mixed powder, stirred and kneaded into a paste; dried in the shade at 25°C for 12 hours; sieved through a 20-mesh sieve and dried at 100°C for 12 hours; tableted using a rotary tabletting machine; and calcined in a muffle furnace (sintering temperature of 500°C, insulation time of 3 hours) to obtain a cylindrical catalyst.

[0091] [Comparative Example 2]

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

[0093] [Comparative Example 3]

[0094] 80 parts by weight of diaspore (with a particle size of 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O and Na2HPO4·12H2O, with weight parts of 5.0 and 15.0 respectively) are uniformly stirred in a blender at a low speed; 40 parts by weight of water are added to the mixed powder, stirred and kneaded into a paste; dried in the shade at 25°C for 12 hours; passed through a 20-mesh sieve, dried at 100°C for 12 hours, and formed into tablets using a rotary tabletting machine; and calcined in a muffle furnace (sintering temperature of 500°C, insulation time of 3 hours) to obtain a cylindrical catalyst.

[0095] [Comparative Example 4]

[0096] 80 parts by weight of diaspore (with a particle size of 10-25 μm) and 20 parts by weight of active components (Na3PO4·12H2O, Na2HPO4·12H2O, Ca3(PO4)2 and CeO2, with weight parts of 4.6, 13.8, 1.0 and 0.6 respectively) are uniformly stirred in a blender at a low speed; 40 parts by weight of water are added to the mixed powder, stirred and kneaded into a paste; dried in the shade at 25°C for 12 hours; passed through a 20-mesh sieve, dried at 100°C for 12 hours, and formed into tablets using a rotary tabletting machine; and calcined in a muffle furnace (sintering temperature of 500°C, insulation time of 3 hours) to obtain a cylindrical catalyst.

[0097] Catalyst evaluation

[0098] The evaluation conditions are as follows: 2.4 g of the catalyst obtained in each example, 13.5 g of paraformaldehyde, and 80 g of isobutanol were placed in a 500 mL autoclave, sealed, and nitrogen was introduced to remove the air in the autoclave. The isobutylene metering pump was turned on, the isobutylene feed amount was controlled to be 320 g, the reaction temperature was controlled to be 220 ° C, the reaction pressure was controlled to be 8.0 MPa, the reaction was continued for 4 hours, and the remaining isobutylene and catalyst were removed. After the reaction, the sample was analyzed by gas chromatography to obtain the formaldehyde conversion rate and the selectivity of 3-methyl-3-butene-1-ol. The result data are all average results under this condition, see Table 3.

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

[0100]

[0101]

[0102] Table 2 Catalyst compositions obtained in each example

[0103]

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

[0105]

[0106]

[0107] The above describes the specific implementation of the present invention in detail, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the various technical features being combined in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A catalyst for producing 3-methyl-3-butene-1-ol, the catalyst comprising a carrier component and an active component, the active component comprising a phosphate and an auxiliary agent, the auxiliary agent being at least one of cerium oxide or calcium carbonate, wherein: The weight ratio of phosphate to auxiliary agent is 20:1-5:

1.

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

3. The catalyst 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 catalyst according to claim 1, characterized in that: The phosphate includes sodium phosphate and disodium hydrogen phosphate, wherein the weight ratio of sodium phosphate to disodium hydrogen phosphate is preferably 1:1-1:10, and more preferably 1:2-1:

10.

5. The catalyst according to claim 1, characterized in that: The auxiliary agent includes cerium oxide and calcium carbonate at the same time; wherein the weight ratio of cerium oxide to calcium carbonate is preferably 10:1-1:15, and more preferably 2:1-1:

2.

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

8. The catalyst according to claim 1, characterized in that: The mechanical strength of the catalyst is 40.0-110.0 N / cm, preferably 50.0-100.0 N / cm.

9. Use of the catalyst according to any one of claims 1 to 8 in the reaction of isobutylene and formaldehyde to produce 3-methyl-3-butene-1-ol.

10. The use according to claim 9, characterized in that: The reaction conditions are as follows: The pressure is 4-10MPa, the reaction temperature is 170-260℃; the mass ratio of formaldehyde to isobutanol is 0.05-0.3, The mass ratio of catalyst to formaldehyde is 0.05-0.3.

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