A system for preparing 3-hydroxypropionaldehyde from acrolein hydration and a method for preparing a catalyst

Abstract

The application provides a system for preparing 3-hydroxypropionaldehyde by hydrating propenal and a preparation method of a catalyst, and comprises the following steps: S1: mixing a template agent, an aluminum source, a phosphorus source and a silicon source, adding a vanadium salt, a molybdenum salt and a salt solution of metal X, and obtaining an intermediate catalyst after heating and treatment; S2: mixing the intermediate catalyst, polyethylene glycol, citric acid and silica sol, and obtaining a formed V-Mo-X-SPAO-34 catalyst after drying and calcining. The application has the beneficial effects that: the catalyst prepared in the application has relatively mild reaction conditions in the reaction of preparing 3-hydroxypropionaldehyde by hydrating propenal, the process is simple, the generated by-products are few, and the catalyst is beneficial to large-scale continuous industrial production.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical technology, and in particular relates to a system for preparing 3-hydroxypropional by hydration of acrolein and a method for preparing a catalyst. Background Technology

[0002] With the continuous extension of my country's new materials industry chain, several key industrial chains have achieved rapid development from scratch, from existence to excellence, and from excellence to strength. Among them, PTT polyester is considered a substitute for PET in the industry and represents a high-end polyester consumer market. PTT is also a new product highlighted in the national new materials plan. Its main raw material, PTA, has a large market size and ample supply, which limits the development of the PTT industry due to the availability of 1,3-propanediol. 3-Hydroxypropanal belongs to the hydrocarbon aldehyde class and is a very important chemical intermediate. It is generated in the hydrogenation of acrolein hydration to prepare 1,3-propanediol and in the hydroformylation of ethylene oxide. 3-Hydroxypropanal is soluble in ethanol, acetone, and diethyl ether, readily soluble in water, and chemically highly reactive, readily polymerizing. Therefore, finding a cheap and efficient catalyst for the preparation of 3-hydroxypropanal from acrolein hydration is of paramount importance.

[0003] Patent CN201911229491.6 describes a catalyst for the preparation of 3-hydroxypropanal by propylene hydration, its preparation method, and its application. The catalyst for the propylene hydration to 3-hydroxypropanal reaction is a metal-modified silica-alumina molecular sieve. Applying this catalyst to the propylene hydration to 3-hydroxypropanal reaction can effectively suppress side reactions and improve the selectivity of the target product and the stability of the catalyst. However, this catalyst requires multiple ion exchanges, making the preparation process relatively complex.

[0004] Patent CN201910499885.7 describes a method for preparing 3-hydroxypropional by hydration of acrolein. This method is simple to operate, has a stable process, and the catalyst has high reactivity and very good selectivity. However, the catalyst used in this method is an ionic liquid, which makes separation after the reaction difficult, has high energy consumption, and causes serious catalyst loss. Summary of the Invention

[0005] In view of this, the present invention aims to provide a system and a method for preparing a catalyst for the hydration of acrolein to 3-hydroxypropanal, overcoming the problems of low conversion rate, low selectivity, low yield, difficulty in separation, and serious loss of existing catalysts for the hydration of acrolein to 3-hydroxypropanal.

[0006] A method for preparing a catalyst for the hydration of acrolein to 3-hydroxypropional includes the following steps:

[0007] S1: Mix the template agent, aluminum source, phosphorus source and silicon source, add metal salt solution, and heat and process to obtain intermediate catalyst;

[0008] S2: Mix intermediate catalyst, polyethylene glycol, citric acid and silica sol, and dry and calcine to obtain V-Mo-X-SPAO-34 catalyst.

[0009] Furthermore, the template agent in step S1 includes one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrabutylsodium hydroxide, and tetrabutylammonium bromide;

[0010] The aluminum source in step S1 includes one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, and boehmite.

[0011] The silicon source in step S1 is one or more of tetraethyl silicate, silica sol, and sodium silicate;

[0012] The metal salt solution in step S1 includes one or more soluble salt solutions selected from vanadium, molybdenum, chromium, zirconium, rhodium, and tungsten.

[0013] Preferably, the metal salt solution is a soluble salt solution of vanadium, molybdenum, and X; X is one of chromium, zirconium, rhodium, and tungsten, and the mass ratio of vanadium:molybdenum:X is 1:20:1-30;

[0014] More preferably, the metal salt solution is vanadium, molybdenum, and zirconium, with a vanadium:molybdenum:zirconium mass ratio of 1:20:1-30.

[0015] Further, the molar ratio of aluminum in the aluminum source, phosphorus in the phosphorus source, silicon in the silicon source, metal in the metal salt solution, and template agent is 1:(0.05-2):(0.1-3):(0.1-3):(0.2-2), preferably, the molar ratio is 1:(0.1-1):(0.5-2):(0.5-1.5):(0.4-1).

[0016] Further, in step S1, at room temperature, the template agent is added to the synthesis vessel under stirring, then the aluminum source and phosphorus source are added and stirred evenly, then the silicon source is added dropwise and stirred for a certain period of time, and finally the metal salt solution is added and stirred evenly. The synthesis vessel is then sealed and placed in an oven to crystallize at a certain temperature for a certain period of time.

[0017] Preferably, the stirring time after adding the silicon source is 0.5-3 hours, and more preferably, the stirring time is 0.5-1.5 hours.

[0018] Preferably, the crystallization temperature in the oven is 150-250℃, and more preferably, the crystallization temperature is 170-220℃.

[0019] Preferably, the crystallization time is 12-84 hours, and more preferably, the crystallization time is 24-72 hours.

[0020] Further, in step S1, the intermediate catalyst is obtained by centrifugation, washing, drying, calcination, and grinding after heating;

[0021] Preferably, the roasting temperature is 550-650℃ and the roasting time is 3-12h, more preferably the roasting time is 4-8h.

[0022] Further, in step S2, the catalyst is mixed evenly with polyethylene glycol, citric acid and silica sol, then extruded into strips, dried, calcined, cooled and cut to obtain the shaped V-Mo-X-SPAO-34 catalyst.

[0023] Preferably, the formed V-Mo-X-SPAO-34 catalyst has a length of 4-5 mm and a diameter of 1.5-2.5 mm.

[0024] A method for preparing a catalyst for the hydration of acrolein to 3-hydroxypropanal. The catalyst prepared is used in the preparation of 3-hydroxypropanal.

[0025] A method for preparing a catalyst for the hydration of acrolein to 3-hydroxypropanal includes a hydration reaction system, a light component removal tower, and a heavy component removal tower.

[0026] The bottom of the hydration reaction system is connected to the middle of the light product removal tower via an outlet pipe, and the bottom of the light product removal tower is connected to the heavy product removal tower via a crude product pipe.

[0027] The top of the heavy removal tower is equipped with a discharge pipe for 3-hydroxypropionaldehyde, the product of the light removal tower.

[0028] Furthermore, an acrolein feed pipe and a water feed pipe are provided on one side of the hydration reaction system;

[0029] The top of the light-light-removal tower is connected to the hydration reaction system via an acrolein circulation pipeline, and the acrolein circulation pipeline is equipped with an acrolein circulation pipe.

[0030] The bottom of the deweighting tower is equipped with a discharge pipe for heavy components.

[0031] Furthermore, the acrolein hydration system includes a hydration reactor, which is a series reactor of 1-4 stages, preferably a series reactor of 1-2 stages.

[0032] Preferably, the temperature of the hydration reactor is 20-80℃, and more preferably 30-70℃.

[0033] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0034] Compared with existing technologies, the system for preparing 3-hydroxypropanal by acrolein hydration and the method for preparing the catalyst described in this invention have the following advantages:

[0035] 1. The hydration reactor used in this invention is a 1-4 stage series reactor, which has good reaction effect and low production cost.

[0036] 2. This invention introduces metal ions into SAPO-34 molecular sieve, which significantly improves the conversion rate, selectivity and yield of the catalyst for the preparation of 3-hydroxypropional hydration from acrolein.

[0037] 3. This invention directly introduces metal ions into the traditional SAPO-34 molecular sieve synthesis process to prepare a V-Mo-X-SPAO-34 catalyst, reducing the subsequent ion exchange step of the SAPO-34 molecular sieve and lowering time and labor costs.

[0038] 4. The catalyst prepared in this invention provides a relatively mild reaction condition, a simple process, and few byproducts in the reaction of acrolein hydration to prepare 3-hydroxypropional, which is conducive to large-scale continuous industrial production.

[0039] 5. The formed catalyst is convenient to use in industrial production. Attached Figure Description

[0040] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0041] Figure 1 This is a schematic diagram of the system and catalyst preparation method for the preparation of 3-hydroxypropional by acrolein hydration according to an embodiment of the invention.

[0042] Explanation of reference numerals in the attached figures:

[0043] 1. Acrolein feed pipeline; 2. Water feed pipeline; 3. Liquid discharge pipeline; 4. Acrolein circulation pipeline; 5. Product discharge pipeline; 6. Crude product pipeline; 7. Heavy component discharge pipeline; 8. Product 3-hydroxypropanal discharge pipeline; A. Hydration reaction system; B. Light component removal tower; C. Heavy component removal tower. Detailed Implementation

[0044] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other.

[0045] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0046] A method for preparing a catalyst for the hydration of acrolein to 3-hydroxypropionaldehyde is characterized by the following steps: S1: mixing a template agent, an aluminum source, a phosphorus source, and a silicon source, adding a salt solution of vanadium salt, molybdenum salt, and metal X, and heating to obtain an intermediate catalyst; S2: mixing the intermediate catalyst, polyethylene glycol, citric acid, and silica sol, drying and calcining to obtain the shaped V-Mo-X-SPAO-34 catalyst. The template agent in step S1 includes one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrabutylsodium hydroxide, and tetrabutylammonium bromide. The aluminum source in step S1 includes one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, and boehmite. The silicon source in step S1 is one or more of tetraethyl silicate, silica sol, and sodium silicate; the metal salt solution in step S1 includes one or more soluble salt solutions of chromium, zirconium, rhodium, and tungsten. Preferably, the mass ratio of vanadium:molybdenum:X is 1:20:1-30.

[0047] The molar ratio of aluminum in the aluminum source, phosphorus in the phosphorus source, silicon in the silicon source, metal in the metal salt solution, and template agent is 1:(0.05-2):(0.1-3):(0.1-3):(0.2-2), preferably 1:(0.1-1):(0.5-2):(0.5-1.5):(0.4-1).

[0048] In step S1, at room temperature, the template agent is added to the synthesis vessel while stirring, then the aluminum source and phosphorus source are added and stirred evenly. Next, the silicon source is added dropwise and stirring is continued for a certain period of time. Finally, the metal salt solution is added and stirred evenly. The synthesis vessel is then sealed and placed in an oven to crystallize at a certain temperature for a certain period of time.

[0049] The stirring time after adding the silicon source is 0.5-3h, more preferably 0.5-1.5h; preferably, the crystallization temperature in the oven is 150-250℃, more preferably 170-220℃; the crystallization time is 12-84h, more preferably 24-72h.

[0050] After heating in step S1, the intermediate catalyst is obtained by centrifugation, washing, drying, calcination, and grinding. Preferably, the calcination temperature is 550-650℃ and the calcination time is 3-12h, more preferably the calcination time is 4-8h.

[0051] In step S2, the catalyst is mixed evenly with polyethylene glycol, citric acid, and silica sol, then extruded into strips, dried, calcined, cooled, and cut to obtain the V-Mo-X-SPAO-34 catalyst. Preferably, the formed V-Mo-X-SPAO-34 catalyst has a length of 4-5 mm and a diameter of 1.5-2.5 mm.

[0052] A method for preparing a catalyst for the hydration of acrolein to 3-hydroxypropanal. The catalyst prepared is used in the preparation of 3-hydroxypropanal.

[0053] like Figure 1 As shown, a method for preparing a catalyst for the hydration of acrolein to 3-hydroxypropanal includes a hydration reaction system A, a light product removal tower B, and a heavy product removal tower C. The bottom of the hydration reaction system A is connected to the middle of the light product removal tower B via a liquid outlet pipe 3, and the bottom of the light product removal tower B is connected to the heavy product removal tower C via a crude product pipe 6. The top of the heavy product removal tower C is provided with a 3-hydroxypropanal discharge pipe 8 for the product from the light product removal tower B.

[0054] The hydration reaction system A has an acrolein feed pipe 1 and a water feed pipe 2 on one side; the top of the light component removal tower B is connected to the hydration reaction system A through an acrolein circulation pipe 4, and an acrolein circulation pipe 4 is provided on the acrolein circulation pipe 4; the bottom of the heavy component removal tower C has a heavy component discharge pipe 7. The acrolein hydration system includes a hydration reactor, which is a 1-4 stage series reactor, preferably a 1-2 stage series reactor; preferably, the temperature of the hydration reactor is 20-80℃, more preferably 30-70℃.

[0055] Example 1

[0056] At room temperature, the template agent tetrapropylammonium hydroxide was added to the synthesis vessel under stirring, followed by aluminum sulfate and hypophosphite, and stirred until homogeneous. Next, silica sol was added dropwise, and stirring continued for 0.5 hours. Finally, a vanadium salt soluble solution was added and stirred until homogeneous. The molar ratio of aluminum in aluminum sulfate, phosphorus in hypophosphite, silicon in silica sol, vanadium in vanadium salt, and the template agent tetrapropylammonium hydroxide was 1:0.1:0.8:0.6:0.5. The synthesis vessel was sealed and placed in an oven for crystallization at 180°C for 48 hours. Afterwards, it was centrifuged, washed, and dried, then calcined at 600°C for 5 hours. After cooling, it was ground to obtain the V-SAPO-34 catalyst. 100g of V-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), extruded into strips, dried, calcined, cooled, and cut into appropriate sizes to obtain strip-shaped V-SAPO-34 catalyst. It was used for the hydration reaction of acrolein, with an acrolein conversion rate of 94% and a selectivity of 72% for 3-hydroxypropionaldehyde.

[0057] Example 2

[0058] At room temperature, the template agent tetrapropylammonium hydroxide was added to the synthesis vessel under stirring, followed by aluminum sulfate and hypophosphite, and stirred until homogeneous. Next, silica sol was added dropwise, and stirring continued for 0.5 hours. Finally, a molybdenum salt soluble solution was added and stirred until homogeneous. The molar ratio of aluminum in aluminum sulfate, phosphorus in hypophosphite, silicon in silica sol, molybdenum in molybdenum salt, and the template agent tetrapropylammonium hydroxide was 1:0.1:0.8:0.6:0.5. The synthesis vessel was sealed and placed in an oven for crystallization at 180°C for 48 hours. Afterwards, it was centrifuged, washed, and dried, then calcined at 600°C for 5 hours. After cooling, it was ground to obtain the Mo-SAPO-34 catalyst. 100g of Mo-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), extruded into strips, dried, calcined, cooled, and cut into appropriate sizes to obtain strip-shaped Mo-SAPO-34 catalyst. It was used for the hydration reaction of acrolein, with an acrolein conversion rate of 93% and a selectivity of 66% for 3-hydroxypropionaldehyde.

[0059] Example 3

[0060] At room temperature, the template agent tetrapropylammonium hydroxide was added to the synthesis vessel under stirring, followed by aluminum sulfate and hypophosphite, and stirred until homogeneous. Next, silica sol was added dropwise, and stirring continued for 0.5 h. Finally, a molybdenum salt soluble solution was added and stirred until homogeneous. The molar ratio of aluminum in aluminum sulfate, phosphorus in hypophosphite, silicon in silica sol, zirconium in zirconium salt, and the template agent tetrapropylammonium hydroxide was 1:0.1:0.8:0.6:0.5. The synthesis vessel was sealed and placed in an oven for crystallization at 180 °C for 48 h. Afterwards, the solution was centrifuged, washed, dried, and then calcined at 600 °C for 5 h. After cooling, it was ground to obtain the Zr-SAPO-34 catalyst. 100g of Zr-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), then extruded into strips. After drying, calcination, and cooling, the mixture was cut into appropriate sizes to obtain strip-shaped Zr-SAPO-34 catalyst. It was used in the acrolein hydration reaction, achieving an acrolein conversion rate of 92% and a 3-hydroxypropionaldehyde selectivity of 68%.

[0061] Example 4;

[0062] At room temperature, the template agent tetrapropylammonium hydroxide was added to the synthesis vessel under stirring, followed by aluminum sulfate and hypophosphite, and stirred until homogeneous. Next, silica sol was added dropwise, and stirring continued for 0.5 h. Finally, a molybdenum salt soluble solution was added and stirred until homogeneous. The molar ratio of aluminum in aluminum sulfate, phosphorus in hypophosphite, silicon in silica sol, vanadium (vanadium salt), molybdenum (molybdenum salt), and the template agent tetrapropylammonium hydroxide was 1:0.1:0.8:0.6:0.5. The synthesis vessel was sealed and placed in an oven for crystallization at 180 °C for 48 h. Afterwards, the solution was centrifuged, washed, dried, and then calcined at 600 °C for 5 h. After cooling, it was ground to obtain the V-Mo-SAPO-34 catalyst. 100g of V-Mo-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), then extruded into strips. After drying, calcination, and cooling, the mixture was cut into appropriate sizes to obtain strip-shaped V-Mo-SAPO-34 catalyst. When used in the acrolein hydration reaction, the acrolein conversion rate was 94%, and the selectivity for 3-hydroxypropionaldehyde was 81%.

[0063] Example 5

[0064] At room temperature, the template agent tetrapropylammonium hydroxide was added to the synthesis vessel under stirring, followed by aluminum sulfate and hypophosphite, and stirred until homogeneous. Next, silica sol was added dropwise, and stirring continued for 0.5 h. Finally, a molybdenum salt soluble solution was added and stirred until homogeneous. The molar ratio of aluminum in aluminum sulfate, phosphorus in hypophosphite, silicon in silica sol, vanadium (vanadium salt), chromium (chromium salt), and the template agent tetrapropylammonium hydroxide was 1:0.1:0.8:0.6:0.5. The synthesis vessel was sealed and placed in an oven for crystallization at 180 °C for 48 h. Afterwards, the solution was centrifuged, washed, dried, and then calcined at 600 °C for 5 h. After cooling, it was ground to obtain the V-Zr-SAPO-34 catalyst. 100g of V-Zr-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), then extruded into strips. After drying, calcination, and cooling, the mixture was cut into appropriate sizes to obtain strip-shaped V-Zr-SAPO-34 catalyst. It was used in the acrolein hydration reaction, achieving an acrolein conversion rate of 93% and a 3-hydroxypropionaldehyde selectivity of 76%.

[0065] Example 6

[0066] At room temperature, the template agent tetrapropylammonium hydroxide was added to the synthesis vessel under stirring, followed by aluminum sulfate and hypophosphite, and stirred until homogeneous. Next, silica sol was added dropwise, and stirring continued for 0.5 h. Finally, a molybdenum salt soluble solution was added and stirred until homogeneous. The molar ratio of aluminum in aluminum sulfate, phosphorus in hypophosphite, silicon in silica sol, (molybdenum in molybdenum salt, chromium in chromium salt), and the template agent tetrapropylammonium hydroxide was 1:0.1:0.8:0.6:0.5. The synthesis vessel was sealed and placed in an oven for crystallization at 180 °C for 48 h. Afterwards, the solution was centrifuged, washed, dried, and then calcined at 600 °C for 5 h. After cooling, it was ground to obtain the Mo-Zr-SAPO-34 catalyst. 100g of Mo-Zr-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), then extruded into strips. After drying, calcination, and cooling, the mixture was cut into appropriate sizes to obtain strip-shaped Mo-Zr-SAPO-34 catalyst. It was used in the acrolein hydration reaction, achieving an acrolein conversion rate of 93% and a 3-hydroxypropionaldehyde selectivity of 80%.

[0067] Example 7

[0068] At room temperature, the template agent tetrapropylammonium hydroxide was added to the synthesis vessel under stirring, followed by aluminum sulfate and hypophosphite, and stirred until homogeneous. Next, silica sol was added dropwise, and stirring continued for 0.5 h. Finally, soluble salt solutions of vanadium salt, molybdenum salt, and metallic chromium were added and stirred until homogeneous. The molar ratio of aluminum in aluminum sulfate, phosphorus in hypophosphite, silicon in silica sol, vanadium (vanadium salt), molybdenum (molybdenum salt), and chromium (chromium salt) to the template agent tetrapropylammonium hydroxide was 1:0.1:0.8:(0.6):0.5. The synthesis vessel was sealed and placed in an oven for crystallization at 180 °C for 48 h. Afterwards, the solution was centrifuged, washed, dried, and then calcined at 600 °C for 5 h. After cooling, it was ground to obtain the V-Mo-Cr-SPAO-34 catalyst. 100g of V-Mo-Cr-SPAO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), then extruded into strips. After drying, calcination, and cooling, the mixture was cut into appropriate sizes to obtain strip-shaped V-Mo-Cr-SPAO-34 catalyst. This catalyst was used in the acrolein hydration reaction, achieving an acrolein conversion rate of 96% and a 3-hydroxypropionaldehyde selectivity of 92%.

[0069] Example 8

[0070] At room temperature, the template agent tetrapropylammonium bromide was added to the synthesis vessel under stirring, followed by aluminum nitrate and phosphorous acid, and stirred until homogeneous. Then, tetraethyl silicate was added dropwise and stirring was continued for 1 hour. Finally, a solution of vanadium salt, molybdenum salt, and soluble zirconium salt was added and stirred until homogeneous. The molar ratio of aluminum in aluminum nitrate, phosphorus in phosphorous acid, silicon in tetraethyl silicate, vanadium in vanadium salt, molybdenum in molybdenum salt, and zirconium in zirconium salt to the template agent tetrapropylammonium bromide was 1:0.5:1.5:(1):0.6. The synthesis vessel was sealed and placed in an oven for crystallization at 200°C for 72 hours. Afterward, the mixture was centrifuged, washed, and dried, and then calcined at 580°C for 6 hours. After cooling, it was ground to obtain the V-Mo-Zr-SAPO-34 catalyst. 100g of V-Mo-Zr-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), then extruded into strips. After drying, calcination, and cooling, the mixture was cut into appropriate sizes to obtain strip-shaped V-Mo-Zr-SAPO-34 catalyst. This catalyst was used in the acrolein hydration reaction, achieving an acrolein conversion rate of 96% and a 3-hydroxypropionaldehyde selectivity of 96%.

[0071] Example 9

[0072] At room temperature, the template agent tetrabutylammonium hydroxide was added to the synthesis vessel under stirring, followed by sodium aluminate and phosphoric acid, and stirred until homogeneous. Tetraethyl silicate was then added dropwise, and stirring continued for 1.5 hours. Finally, a soluble salt solution of vanadium salt, molybdenum salt, and rhodium was added and stirred until homogeneous. The molar ratio of aluminum in sodium aluminate, phosphorus in phosphoric acid, silicon in tetraethyl silicate, vanadium in vanadium salt, molybdenum in molybdenum salt, and rhodium in rhodium salt to the template agent tetrabutylammonium hydroxide was 1:0.8:1:(1.5):0.8. The synthesis vessel was sealed and placed in an oven for crystallization at 190°C for 36 hours. Afterwards, the mixture was centrifuged, washed, and dried, then calcined at 550°C for 7 hours. After cooling, it was ground to obtain the V-Mo-Rh-SAPO-34 catalyst. 100g of V-Mo-Rh-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), then extruded into strips. After drying, calcination, and cooling, the mixture was cut into appropriate sizes to obtain strip-shaped V-Mo-Rh-SAPO-34 catalyst. This catalyst was used in the acrolein hydration reaction, achieving an acrolein conversion rate of 93% and a 3-hydroxypropionaldehyde selectivity of 95%.

[0073] Example 10

[0074] At room temperature, the template agent tetrabutylammonium bromide was added to the synthesis vessel under stirring, followed by the addition of boehmite and metaphosphoric acid, and stirred until homogeneous. Sodium silicate was then added dropwise, and stirring continued for 1 hour. Finally, a solution of soluble vanadium salt, molybdenum salt, and tungsten salt was added and stirred until homogeneous. The molar ratio of aluminum in the boehmite, phosphorus in the metaphosphoric acid, silicon in the sodium silicate, vanadium in the vanadium salt, molybdenum in the molybdenum salt, and tungsten in the tungsten salt, to the template agent tetrabutylammonium bromide was 1:0.4:0.7:(0.8):0.4. The synthesis vessel was sealed and placed in an oven for crystallization at 220°C for 60 hours. Afterwards, the mixture was centrifuged, washed, and dried, then calcined at 650°C for 8 hours. After cooling, it was ground to obtain the V-Mo-W-SAPO-34 catalyst. 100g of V-Mo-W-SAPO-34 catalyst was mixed evenly with 0.2g of polyethylene glycol 2000, 3g of citric acid, and 20g of silica sol (SiO2 content 30%), then extruded into strips. After drying, calcination, and cooling, the mixture was cut into appropriate sizes to obtain strip-shaped V-Mo-W-SAPO-34 catalyst. This catalyst was used in the acrolein hydration reaction, achieving an acrolein conversion rate of 95% and a 3-hydroxypropionaldehyde selectivity of 92%.

[0075] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing catalyst V-Mo-X-SPAO-34 for the hydration of acrolein to 3-hydroxypropanal, characterized in that: Includes the following steps: S1: Mix the template agent, aluminum source, phosphorus source and silicon source, add vanadium salt, molybdenum salt and metal X salt solution, heat and process to obtain intermediate catalyst; S2: Mix intermediate catalyst, polyethylene glycol, citric acid, and silica sol, and dry and calcine to obtain V-Mo-X-SPAO-34 catalyst; The metal salt solution in step S1 includes one or more soluble salt solutions selected from vanadium, molybdenum, chromium, zirconium, rhodium, and tungsten. Vanadium salts, molybdenum salts, and metal X salts are soluble salt solutions; X is one of chromium, zirconium, rhodium, and tungsten, and the mass ratio of vanadium:molybdenum:X is 1:20:(1-30). The molar ratio of aluminum in the aluminum source, phosphorus in the phosphorus source, silicon in the silicon source, metal in the metal salt solution, and template agent is 1:(0.05-2):(0.1-3):(0.1-3):(0.2-2).

2. The preparation method according to claim 1, characterized in that: The template agent in step S1 includes one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrabutylsodium hydroxide, and tetrabutylammonium bromide; The aluminum source in step S1 includes one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, and boehmite. The silicon source in step S1 is one or more of tetraethyl silicate, silica sol, and sodium silicate.

3. The preparation method according to claim 2, characterized in that: The metal salt solution contains vanadium, molybdenum, and zirconium, with a vanadium:molybdenum:zirconium mass ratio of 1:20:1-30.

4. The preparation method according to claim 1, characterized in that: The molar ratio of aluminum in the aluminum source, phosphorus in the phosphorus source, silicon in the silicon source, metal in the metal salt solution, and template agent is 1:(0.1-1):(0.5-2):(0.5-1.5):(0.4-1).

5. The preparation method according to claim 1, characterized in that: In step S1, at room temperature, the template agent is added to the synthesis vessel while stirring. Then, aluminum source and phosphorus source are added and stirred evenly. Next, silicon source is added dropwise and stirring is continued for a certain period of time. Finally, metal salt solution is added and stirred evenly. The synthesis vessel is sealed and placed in an oven for crystallization at a certain temperature for a certain period of time.

6. The preparation method according to claim 5, characterized in that: After adding the silicon source, continue stirring for 0.5-3 hours.

7. The preparation method according to claim 5, characterized in that: After adding the silicon source, continue stirring for 0.5-1.5 hours.

8. The preparation method according to claim 5, characterized in that: The crystallization temperature in the oven is 150-250℃.

9. The preparation method according to claim 5, characterized in that: The crystallization temperature in the oven is 170-220℃.

10. The preparation method according to claim 5, characterized in that: The crystallization time is 12-84 hours.

11. The preparation method according to claim 5, characterized in that: The crystallization time is 24-72 hours.

12. The preparation method according to claim 1, characterized in that: The intermediate catalyst is obtained by heating, centrifuging, washing, drying, calcining, and grinding.

13. The preparation method according to claim 10, characterized in that: The roasting temperature is 550-650℃, and the roasting time is 3-12h.

14. The preparation method according to claim 10, characterized in that: The roasting time is 4-8 hours.

15. The preparation method according to claim 1, characterized in that: In step S2, the intermediate catalyst is mixed evenly with polyethylene glycol, citric acid and silica sol, then extruded into strips, dried, calcined, cooled and cut to obtain V-Mo-X-SPAO-34 catalyst.

16. The preparation method according to claim 15, characterized in that: The shaped V-Mo-X-SPAO-34 catalyst has a length of 4-5 mm and a diameter of 1.5-2.5 mm.

17. The catalyst prepared by the method according to any one of claims 1-16 is used in the preparation of 3-hydroxypropanal.

18. A system for preparing 3-hydroxypropanal using a catalyst prepared by the method according to any one of claims 1-16, characterized in that: This includes the hydration reaction system, the light component removal tower, and the heavy component removal tower; The bottom of the hydration reaction system is connected to the middle of the light product removal tower via an outlet pipe, and the bottom of the light product removal tower is connected to the heavy product removal tower via a crude product pipe. The top of the heavy removal tower is equipped with a discharge pipe for 3-hydroxypropionaldehyde, the product of the light removal tower.

19. The system for preparing 3-hydroxypropanal according to claim 18, characterized in that: The hydration reaction system has an acrolein feed pipe and a water feed pipe on one side; The top of the light-weight removal tower is connected to the hydration reaction system via an acrolein circulation pipeline; the acrolein circulation pipeline is equipped with an acrolein circulation pipe. The bottom of the deweighting tower is equipped with a discharge pipe for heavy components.

20. The system for preparing 3-hydroxypropanal according to claim 18, characterized in that: The acrolein hydration system includes a hydration reactor, which is a series reactor consisting of 1-4 stages.

21. The system for preparing 3-hydroxypropanal according to claim 20, characterized in that: The hydration reactor is a 1-2 stage series reactor.

22. The system for preparing 3-hydroxypropanal according to claim 20, characterized in that: The temperature of the hydration reactor is 20-80℃.

23. The system for preparing 3-hydroxypropanal according to claim 20, characterized in that: The temperature of the hydration reactor is 30-70℃.

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