Preparation method of butyl acrylate synthesis catalyst
By using an acidic molecular sieve-supported heteropolyacid and metal catalyst in the synthesis of butyl acrylate, the problems of equipment corrosion and low activity were solved, the reaction efficiency and product purity were improved, and a highly efficient and stable catalytic effect was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- WANHUA CHEM GRP CO LTD
- Filing Date
- 2025-12-17
- Publication Date
- 2026-04-21
AI Technical Summary
Existing catalysts in the synthesis of butyl acrylate suffer from problems such as equipment corrosion, numerous side reactions, low catalytic activity, and low single-pass conversion rate, resulting in low production efficiency and product purity.
A catalyst was prepared by loading heteropolyacids and metals onto acidic molecular sieves, followed by acid treatment, calcination, and molding processes. This process increased the specific surface area and active sites, suppressed side reactions, and improved catalytic activity and selectivity.
It improves the reactivity and selectivity of butyl acrylate synthesis, reduces byproduct generation, extends equipment life, and lowers production costs and energy consumption.
Smart Images
Figure BDA0005743523820000031 
Figure BDA0005743523820000032
Abstract
Description
Technical Field
[0001] This application relates to the field of catalyst technology, and more specifically, to a method for preparing a catalyst for the synthesis of butyl acrylate. Background Technology
[0002] Butyl acrylate, as a key acrylate monomer, possesses unique chemical properties and a wide range of applications, playing an indispensable role in numerous industrial fields such as coatings, adhesives, and textile auxiliaries. In the coatings industry, butyl acrylate is a crucial raw material for preparing high-performance acrylic resin coatings. Its addition significantly improves the flexibility, weather resistance, and adhesion of coatings, enabling them to maintain good performance under various harsh environments and extending the service life of coated objects. In the adhesives field, adhesives synthesized with butyl acrylate exhibit advantages such as high bonding strength, fast curing speed, and good water resistance, and are widely used in packaging, construction, and automotive industries, providing reliable solutions for product assembly and fixation. In textile auxiliaries, butyl acrylate can be used to prepare textile finishing agents, imparting softness, wrinkle resistance, and water resistance to textiles, thereby enhancing their quality and added value.
[0003] Currently, the synthesis of butyl acrylate mainly involves the esterification reaction of acrylic acid and n-butanol. The traditional sulfuric acid-catalyzed esterification method was a widely used process in the past. Although sulfuric acid has strong acidity and catalytic activity, enabling rapid reaction, it also brings serious equipment corrosion problems: sulfuric acid reacts chemically with the metal materials in the reaction equipment, significantly shortening the equipment's lifespan and increasing replacement costs and maintenance difficulties. Furthermore, sulfuric acid catalysis can trigger a series of side reactions, generating various byproducts. The presence of these byproducts not only reduces the purity of butyl acrylate, increasing the difficulty and cost of product purification, but also may cause environmental pollution.
[0004] To overcome the shortcomings of sulfuric acid catalysis, researchers have developed a cation exchange resin catalytic process. Cation exchange resins, as solid acid catalysts, offer advantages such as non-corrosiveness to equipment and ease of separation and recovery, reducing environmental pollution and equipment wear during production to some extent. However, this process still has significant drawbacks. The acidic centers of cation exchange resins are relatively uniformly distributed, resulting in limited catalytic activity and a low single-pass conversion rate of acrylic acid to n-butanol, typically only between 50% and 60%. To achieve higher yields, multiple cyclic reactions are required, which not only increases energy consumption and time costs but also reduces production efficiency.
[0005] In recent years, researchers have been exploring novel catalysts to improve the synthesis efficiency and product quality of butyl acrylate. For example, catalysts such as tungsten-antimony heteropolyacids and niobium-zirconium composite oxides have been applied to the synthesis of acrylates; however, these catalysts still suffer from drawbacks such as low activity, low space velocity, and insufficient selectivity. Therefore, developing a highly efficient, stable, and environmentally friendly catalyst for the synthesis of butyl acrylate is of significant practical importance. Summary of the Invention
[0006] The purpose of this invention is to provide a method for preparing a catalyst for the synthesis of butyl acrylate, wherein the obtained catalyst can effectively improve the reactivity and selectivity of the synthesis of butyl acrylate by the esterification of acrylic acid and butanol.
[0007] The present invention includes:
[0008] A method for preparing a catalyst for the synthesis of butyl acrylate includes the following steps:
[0009] S1. The active component of the acidic molecular sieve is subjected to acid treatment to obtain the first product;
[0010] S2. Load the first product with heteropoly acid and calcine it to obtain the second product;
[0011] S3. Load the second product with metal and calcine it to obtain the third product;
[0012] S4. The third product is mixed with a binder and then subjected to molding to obtain the catalyst.
[0013] In a preferred embodiment, in step S1, the acidic molecule is selected from one or more of HZSM-5, HMOR, and HZSM-23; the specific surface area is 300-500 m². 2 / g.
[0014] The acid used for acid treatment is preferably one or more of hydrochloric acid, citric acid, and nitric acid, and the concentration of the acid solution is 0.1–3 mol / L, preferably 0.1–1 mol / L;
[0015] The amount of acid used is 1 to 50 mL, preferably 1 to 20 mL, relative to 1 g of the acidic molecular sieve active component.
[0016] The acid treatment conditions are as follows: under stirring, the temperature is 10-100℃ and the time is 8-24h, preferably, the temperature is 20-50℃ and the time is 10-20h;
[0017] Optionally, the solid product obtained from acid treatment is filtered and dried at 50–200°C for 10–20 h to obtain the first product.
[0018] In a preferred embodiment, in step S2, the heteropoly acid is preferably one or more of phosphotungstic acid or phosphomolybdic acid;
[0019] The mass ratio of the heteropolyacid to the first product is 0.01 to 0.5:1, preferably 0.1 to 0.5:1, and more preferably 0.2 to 0.4:1;
[0020] Optionally, the loading method can be a mixing method or an impregnation method. The mixing method involves: mixing the first product with heteropoly acid in a specific ratio until homogeneous, then compressing the mixture into tablets. After tableting, the tablets are crushed, with a particle size preferably of 20-40 mesh. The crushed particles are then calcined at 350-650℃ (preferably 450-600℃) for 10-20 hours to obtain the second product. The impregnation method involves: preparing a heteropoly acid solution with a concentration of 0.1-2 wt%, immersing the proportionally weighed first product in the solution for 10-20 hours, drying it at 90-200℃ after impregnation, and then calcining it at 350-650℃ (preferably 450-600℃) for 10-20 hours to obtain the second product.
[0021] In a preferred embodiment, in step S3, the metal is preferably one or more of magnesium, calcium, or lanthanum;
[0022] The metal precursor is preferably one or more of acetate, nitrate or chloride;
[0023] The loading of the metal element to the mass ratio of the second product is 0.01 to 1:1, preferably 0.01 to 0.1:1;
[0024] Optionally, the metal element loading method can be either a mixing method or an impregnation method. The mixing method involves: mixing the second product and the precursor in a specific ratio until homogeneous, then compressing the mixture into tablets. After tableting, the tablets are crushed, with the particle size preferably between 20 and 40 mesh. The crushed particles are then calcined at 350–650°C (preferably 450–600°C) for 10–20 hours to obtain the third product. The impregnation method involves: preparing the precursor into a solution with a concentration of 0.1–2 wt%, immersing the proportionally weighed second product in the solution for 10–20 hours, drying it at 90–120°C after impregnation, and then calcining it at 350–650°C (preferably 450–600°C) for 10–20 hours to obtain the third product.
[0025] In a preferred embodiment, in step S4, the adhesive is one or more of alumina and silicon dioxide;
[0026] The mass ratio of the adhesive to the third product is 0.01 to 0.5:1, preferably 0.1 to 0.5:1;
[0027] Optionally, the molding method is extrusion molding, during which a molding aid is added. The molding aid is one or more of nitric acid solution and citric acid solution. The concentration of the molding aid is optionally 1-3 wt%, and the amount added relative to 1 g of the third product is 1-20 ml, preferably 1-8 ml. The extruded catalyst is then pelletized, and after pelleting, it is calcined at 350-650℃ (preferably 450-600℃) for 10-20 h to obtain the finished catalyst.
[0028] The catalyst is used in the reaction of esterification of acrylic acid and butanol to synthesize butyl acrylate.
[0029] In a preferred embodiment, the reaction conditions of the catalyst include: a reaction temperature of 80–150°C, a pressure of 10–80 kPa (absolute pressure), and a reaction time of 1–10 h.
[0030] The beneficial effects of this invention are as follows:
[0031] Acid treatment of molecular sieves increases their specific surface area and exposes more active sites; loading heteropolyacids further increases the number of active sites, effectively improving the activity of the catalyst; loading of metal elements effectively suppresses the occurrence of side reactions and improves the selectivity of the catalyst. Detailed Implementation
[0032] To facilitate understanding of the present invention, the following description, in conjunction with embodiments, will further illustrate the invention. It should be understood that the following embodiments are merely for a better understanding of the invention and do not imply that the invention is limited to these embodiments.
[0033] Catalyst performance was evaluated using the following calculation method:
[0034] The activity of the catalyst is determined according to X AA To calculate:
[0035]
[0036] The selectivity of the catalyst is determined according to Y BA To calculate:
[0037]
[0038] Example 1
[0039] Take HZSM-5 molecular sieve (SiO2 / Al2O3 = 150, specific surface area 410 m²) 210g of magnesium acetate was mixed with 100ml of 0.1mol / L hydrochloric acid solution and stirred at 25℃ for 15h. After filtration, the mixture was dried at 150℃ for 10h to obtain product one. 4g of phosphotungstic acid was thoroughly mixed with 10g of product one, compressed into tablets, crushed, and sieved to obtain 20-40 mesh particles. The tablets were then calcined at 500℃ for 10h to obtain product two. 0.92g of magnesium acetate was thoroughly mixed with 10g of product two, compressed into tablets, crushed, and sieved to obtain 20-40 mesh particles. The tablets were then calcined at 500℃ for 10h to obtain product three. 3g of alumina was thoroughly mixed with 10g of product three, and 50ml of 1% nitric acid aqueous solution was added. After thorough mixing, the mixture was extruded and pelletized, and then calcined at 500℃ for 10h to obtain catalyst C-1.
[0040] Example 2
[0041] Take 10g of HZSM-5 molecular sieve used in Example 1, add 30ml of 0.5mol / L nitric acid solution, and stir at 25℃ for 10h. After filtration, dry at 120℃ for 10h to obtain product one. Take 2g of phosphomolybdic acid, mix it thoroughly with product one, compress it into tablets, crush and sieve it to obtain 20-40 mesh particles, and then calcine it at 600℃ for 15h to obtain product two. Take 1.7g of lanthanum nitrate and 10g of product two, mix them thoroughly, compress them into tablets, crush and sieve them to obtain 20-40 mesh particles, and then calcine them at 600℃ for 15h to obtain product three. Take 2g of silicon dioxide and 10g of product three, mix them thoroughly, add 50ml of 1% nitric acid aqueous solution, mix thoroughly, extrude and granulate, and then calcine at 600℃ for 15h to obtain catalyst C-2.
[0042] Example 3
[0043] HZSM-23 molecular sieve (SiO2 / Al2O3 = 120, specific surface area 382 m²) was used. 2 10g of magnesium acetate was added to 150ml of 0.2mol / L citric acid solution and stirred at 25℃ for 18h. After filtration, the product was dried at 150℃ for 10h to obtain product one. 3g of phosphotungstic acid was taken, thoroughly mixed with product one, compressed into tablets, crushed, and sieved to obtain 20-40 mesh particles, and then calcined at 500℃ for 10h to obtain product two. 1g of magnesium acetate was taken and thoroughly mixed with 10g of product two, compressed into tablets, crushed, and sieved to obtain 20-40 mesh particles, and then calcined at 500℃ for 10h to obtain product three. 3g of alumina was taken and thoroughly mixed with 10g of product three, 70ml of 3% citric acid aqueous solution was added, thoroughly mixed, extruded, and pelletized, and then calcined at 500℃ for 10h to obtain catalyst C-3.
[0044] Example 4
[0045] Take 10g of HZSM-5 molecular sieve used in Example 1, add 100ml of 0.1mol / L nitric acid solution, and stir at 25℃ for 15h. After filtration, dry at 150℃ for 10h to obtain product one. Take 4g of phosphomolybdic acid, prepare an aqueous solution with a concentration of 0.4wt%, disperse product one in the solution and impregnate for 10h, then dry at 120℃ and calcine at 500℃ for 10h to obtain product two. Take 1g of magnesium acetate, prepare an aqueous solution with a concentration of 0.1wt%, disperse 10g of product two in the solution and impregnate for 10h, then dry at 120℃ and calcine at 500℃ for 10h to obtain product three. Take 3g of alumina and 10g of product three and mix thoroughly, add 50ml of 1% nitric acid aqueous solution, mix thoroughly, extrude and granulate, then calcine at 500℃ for 10h to obtain catalyst C-4.
[0046] Example 5
[0047] HMOR molecular sieve (SiO2 / Al2O3 = 120, specific surface area 394 m²) was used. 2 10g of magnesium oxide was added to 100ml of 0.1mol / L nitric acid solution and stirred at 25℃ for 10h. After filtration, it was dried at 150℃ for 10h to obtain product one. 3g of phosphotungstic acid was taken, thoroughly mixed with product one, compressed into tablets, crushed and sieved to obtain 20-40 mesh particles, and then calcined at 500℃ for 10h to obtain product two. 1g of magnesium acetate was taken and thoroughly mixed with 10g of product two, compressed into tablets, crushed and sieved to obtain 20-40 mesh particles, and then calcined at 500℃ for 10h to obtain product three. 3g of alumina was taken and thoroughly mixed with 10g of product three, 50ml of 1% citric acid aqueous solution was added, thoroughly mixed, extruded and granulated, and then calcined at 500℃ for 10h to obtain catalyst C-5.
[0048] Comparative Example 1
[0049] Take 10g of HZSM-5 molecular sieve used in Example 1, add 100ml of 0.1mol / L nitric acid solution, and stir at 25℃ for 10h. After filtration, dry at 150℃ for 10h to obtain product one. Take 3g of alumina and mix thoroughly with 10g of product one, add 50ml of 1% nitric acid aqueous solution, mix thoroughly, extrude and granulate, and then calcine at 500℃ for 10h to obtain catalyst D-1.
[0050] Comparative Example 2
[0051] Take 10g of HZSM-5 molecular sieve used in Example 1, add 100ml of 0.1mol / L nitric acid solution, and stir at 25℃ for 10h. After filtration, dry at 150℃ for 10h to obtain product one. Take 4g of phosphomolybdic acid, mix it thoroughly with product one, compress it into tablets, crush and sieve it to obtain 20-40 mesh particles, and then calcine at 500℃ for 10h to obtain product two. Take 3g of alumina and 10g of product two, mix them thoroughly, add 50ml of 1% nitric acid aqueous solution, mix thoroughly, extrude and granulate, and then calcine at 500℃ for 10h to obtain catalyst D-2.
[0052] Comparative Example 3
[0053] 10g of HZSM-5 molecular sieve used in Example 1 was added to 100ml of 0.1mol / L nitric acid solution and stirred at 25℃ for 10h. After filtration, the product was dried at 150℃ for 10h to obtain product one. 1g of lanthanum nitrate was thoroughly mixed with 10g of product one, compressed into tablets, crushed, and sieved to obtain 20-40 mesh particles, which were then calcined at 500℃ for 10h to obtain product two. 3g of alumina was thoroughly mixed with 10g of product two, and 50ml of 1% nitric acid aqueous solution was added. After thorough mixing, the mixture was extruded and granulated, and then calcined at 500℃ for 10h to obtain catalyst C-2.
[0054] Experimental Example
[0055] This example evaluates the performance of the catalysts prepared in Examples 1-5 and Comparative Examples 1-3. In a small batch stirred tank apparatus, 10 g of catalyst, 50 g of acrylic acid, and 50 g of butanol were added. The reaction temperature was 100 °C, the reaction pressure was 50 kPa (absolute pressure), and the reaction time was 4 h. The reaction results are shown in Tables 1 and 2.
[0056] Table 1
[0057] catalyst C-1 C-2 C-3 C-4 C-5 <![CDATA[X AA ]]> 95.4 94.7 94.0 96.6 95.7 <![CDATA[Y BA ]]> 96.1 97.2 96.6 97.6 96.7
[0058] Table 2
[0059] catalyst D-1 D-2 D-3 <![CDATA[X AA ]]> 67.1 85.2 71.1 <![CDATA[Y BA ]]> 90.4 80.7 85.0
[0060] It is readily understood that the above embodiments are merely illustrative examples for clear explanation and do not imply that the invention is limited thereto. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A method for preparing a catalyst for the synthesis of butyl acrylate, characterized in that, Includes the following steps: S1. The active component of the acidic molecular sieve is subjected to acid treatment to obtain the first product; S2. Load the first product with a heteropoly acid to obtain the second product; S3. Load the second product with a metal element to obtain the third product; S4. The third product is mixed with a binder and then subjected to molding to obtain the catalyst.
2. The method according to claim 1, characterized in that, In step S1, the acidic molecules are selected from one or more of HZSM-5, HMOR, and HZSM-23.
3. The method according to claim 1 or 2, characterized in that, In step S1, the acid is selected from one or more of hydrochloric acid, nitric acid, and citric acid, and the concentration of the acid solution is 0.01 to 3 mol / L, preferably 0.1 to 1 mol / L; Preferably, the amount of acid solution used is 1 to 50 mL relative to 1 g of the acidic molecular sieve active component, more preferably 1 to 20 mL.
4. The method according to any one of claims 1-3, characterized in that, The acid treatment conditions described in step S1 are as follows: Under stirring, the temperature is 10–100°C and the time is 8–24 h, preferably 20–50°C and the time is 10–20 h; Optionally, the solid product obtained from acid treatment is filtered and dried at 50–200°C for 10–20 h to obtain the first product.
5. The method according to claim 1, characterized in that, In step S2, the heteropolyacid is selected from one or more of phosphotungstic acid or phosphomolybdic acid; Preferably, the mass ratio of heteropolyacid to the first product is 0.01 to 0.5:1, more preferably 0.1 to 0.5:
1.
6. The method according to claim 1 or 5, characterized in that, In step S2, the loading method is either a mixing method or an impregnation method. The mixing method involves mixing the first product with heteropoly acid in a certain proportion, then compressing the mixture into tablets. After tableting, the tablets are crushed, with the particle size of the crushed particles preferably being 20-40 mesh. The crushed particles are then calcined at 350-650°C for 10-20 hours to obtain the second product. The impregnation method involves preparing a solution of heteropoly acid with a concentration of 0.1-2 wt%. The first product, weighed according to the proportion, is immersed in the solution for 10-20 hours. After impregnation, the product is dried at 90-200°C and then calcined at 350-650°C for 10-20 hours to obtain the second product.
7. The method according to claim 1, characterized in that, In step S3, the metallic element is one or more of magnesium, calcium, or lanthanum; Preferably, the mass ratio of the loading of the metal element to the second product is 0.01 to 1:1, more preferably 0.01 to 0.1:1; Preferably, the loading method of the metal element is either a mixing method or an impregnation method. The mixing method involves: mixing the second product with the metal element precursor evenly, then pressing the mixture into tablets, followed by crushing. The particle size of the crushed particles is preferably 20-40 mesh. The crushed particles are then calcined at 350-650°C for 10-20 hours to obtain the third product. The impregnation method involves: preparing the metal element precursor into a solution with a concentration of 0.1-2 wt%, immersing the second product in the solution for 10-20 hours, drying it at 90-120°C after impregnation, and then calcining it at 350-650°C for 10-20 hours to obtain the third product. Preferred precursors for metal elements are acetates, nitrates, or chlorides.
8. The method according to claim 1, characterized in that, In step S4, the adhesive is one or more of alumina and silicon dioxide; Preferably, the mass ratio of the adhesive to the third product is 0.01 to 0.5:1, more preferably 0.1 to 0.5:
1.
9. The method according to claim 1 or 8, characterized in that, In step S4, the molding method is extrusion molding. A molding aid is added during the molding process. The molding aid is one or more of nitric acid solution and citric acid solution. The concentration of the molding aid can be 1-3 wt%. The amount of molding aid added relative to 1g of the third product is 1-20ml. The catalyst after extrusion is granulated and then calcined at 350-650℃ for 10-20h to obtain the finished catalyst.
10. The use of the catalyst prepared by the method according to any one of claims 1 to 9 for the synthesis of butyl acrylate by esterification of acrylic acid and butanol; Preferred conditions: reaction temperature is 80–150℃, pressure is absolute pressure 10–80 kPa, and time is 1–10 h.