Composite stirring set and reactor comprising same
Through the design of the composite stirring set, the uneven dispersion and scratching problems of catalysts are solved, and efficient hydrogenation reaction is achieved, reducing energy consumption and improving safety.
Patent Information
- Application Number
- CN202422401114.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-30
- Publication Date
- 2025-08-08
- Estimated Expiration
- 2034-09-30
AI Technical Summary
The uneven dispersion of catalysts, local accumulation and scratching of the reactor walls in existing hydrogenation reactors leads to low reaction efficiency, high energy consumption and high safety risks.
A composite stirring set is adopted, including baffle type, self-priming type and axial flow stirrer. The agitating shaft is driven to enhance the mass transfer effect of the three-phase reaction of gas-liquid-solid, avoid catalyst aggregation and scratching, and improve mixing uniformity.
Significantly improve reaction speed and efficiency, reduce reaction temperature, reduce energy consumption, improve operational safety, and avoid catalyst settlement and wall scratches.
Smart Images
Figure CN223197030U_ABST
Abstract
Description
Technical Field
[0001] The present application relates to a composite stirring kit and a reactor comprising the kit, in particular to a catalytic hydrogenation reactor. Background Art
[0002] Hydrogenation reactors are commonly used in chemical reactions, widely used in fields such as petrochemicals, pharmaceuticals, food, and materials science. Hydrogenation reactions typically involve three-phase reactions involving solids, liquids, and gases using metal catalysts. Metal catalysts have poor dispersion in the reaction solvent, and existing stirring methods can only achieve good mixing in localized areas, but struggle to evenly disperse the catalyst throughout the reaction system. The catalyst tends to settle to the bottom of the reactor, limiting its active surface area and resulting in inadequate contact between the reactants and the catalyst, thus reducing reaction efficiency.
[0003] Existing technologies solve the above-mentioned mass transfer problem by increasing the temperature. On the one hand, increasing the temperature increases the activity of the catalyst, and on the other hand, it reduces the viscosity of the solvent and increases the dispersion of the catalyst in the solvent. Although increasing the temperature can improve the dispersion and mixing efficiency of the catalyst in the reaction system and reduce the risk of local accumulation of the catalyst due to uneven stirring, it also promotes the acceleration of the reaction rate and increases the occurrence of side reactions. This may not only reduce the selectivity and purity of the target product, but also increase the uncertainty and control difficulty of the reaction process. These challenges are particularly prominent under high temperature and high pressure conditions where the viscosity of the solvent and reactants changes significantly with temperature and pressure. In addition, high-temperature reactions not only consume a lot of energy, but also pose safety risks under high-pressure conditions. Utility Model Content
[0004] The inventors of the present application have discovered that in catalytic hydrogenation reactions, there are not only the aforementioned problems of uneven dispersion and localized accumulation of solid catalysts, but also the problem that metal catalysts easily aggregate and scrape the reactor wall.
[0005] The present application provides a novel composite stirring kit and a reactor comprising the kit, in particular a catalytic hydrogenation reactor.
[0006] Specifically, this application relates to:
[0007] (1) A composite stirring set, characterized in that the set includes a baffle stirrer, a self-priming stirrer and an axial flow stirrer, wherein the self-priming stirrer and the axial flow stirrer are arranged on the same stirring shaft, and the stirring shaft is a hollow shaft with a gas suction port opened on the shaft.
[0008] (2) The composite stirring set according to (1) above is characterized in that the baffle stirrer is connected to the stirring shaft and is driven by the stirring shaft.
[0009] (3) The composite stirring set according to (1) or (2) above is characterized in that the baffle-type stirrer is cylindrical and has 2 to 6 baffles.
[0010] (4) A reactor, characterized in that the reactor comprises the composite stirring set described in any one of (1) to (3) above.
[0011] (5) The reactor according to (4) above is characterized in that the height of the baffle-type agitator is at least 1 / 2, more preferably at least 2 / 3, of the height of the reactor body.
[0012] (6) The reactor according to (4) or (5) above is characterized in that the axial flow agitator is arranged at the end of the agitator shaft, and the end of the agitator shaft extends into the vicinity of the bottom of the reactor.
[0013] (7) The reactor according to any one of (4) to (6) above is characterized in that the self-priming agitator is arranged at a position 1 / 3 to 2 / 3 of the height of the reactor body from the bottom of the reactor.
[0014] (8) The reactor according to any one of (4) to (7) above, characterized in that the reactor is a catalytic hydrogenation reactor.
[0015] (9) The reactor according to any one of (4) to (8) above, characterized in that the reactor is used for the following catalytic hydrogenation reaction:
[0016]
[0017] Where R is C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 6-20 Aryl, C 6-20 Aryl-C 1-10 Alkyl, C 6-20 Aryl-C 2-10 Alkenyl, C 6-20 Aryl-C 2-10 Alkynyl, C 6-20 Heteroaryl-C 1-10 Alkyl, C 6-20 Heteroaryl-C 2-10 Alkenyl, C 6-20 Heteroaryl-C 2-10 Alkynyl, wherein the alkyl, alkenyl, alkynyl, aryl, heteroaryl are optionally substituted by 1 or more halogen, C 1-6 Alkyl, halogenated C 1-6 Substitution of alkyl groups;
[0018] Preferably R is C1-6 Alkyl, C 6-20 Aryl-C 1-6 Alkyl or C 6-20 Heteroaryl-C 1-6 Alkyl, more preferably R is phenyl-C 1-6 Alkyl or pyridyl-C 1-6 Alkyl, wherein phenyl or pyridyl is optionally substituted by 1 or 2 or more selected from halogen, C 1-6 Alkyl, halogenated C 1-6 The alkyl group is substituted with a substituent.
[0019] (10) The reactor according to (9) above is characterized in that the reactor is used for the following catalytic hydrogenation reaction:
[0020]
[0021] (11) The reactor according to (9) or (10) above is characterized in that the temperature inside the reactor is controlled at 10 to 50°C, preferably at room temperature to 40°C.
[0022] The composite stirring kit and reactor of the present application significantly enhance the gas-liquid mass transfer and liquid-solid mass transfer in the gas-liquid-solid three-phase reaction system, improving the dispersion and suspension of solids in the reaction system, avoiding the undesirable problem of catalyst aggregation and scraping, and ensuring full contact between reactants and catalyst, thereby significantly improving reaction speed and efficiency. At the same time, the composite stirring kit and reactor of the present application also enable reactions to be carried out at lower temperatures, reducing energy consumption and improving the convenience and safety of reaction operations. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is a schematic structural diagram of a specific embodiment of the reactor of the present application.
[0024] Figure 2 This is a schematic structural diagram of a specific embodiment of the baffle agitator used in the composite stirring set of this application.
[0025] Figure 3 This is a structural diagram of a specific embodiment of the composite stirring set of the present application.
[0026] Figure 4 This is a comparison chart of the hydrogen absorption curves of Example 1, Comparative Examples 2 and 4 of the present application.
[0027] Figure 5 This is a photo of the catalyst dispersion state during the stirring reaction process of Comparative Example 4 of this application.
[0028] Description of reference numerals:
[0029] 1. Stirring motor; 2. Air inlet valve; 3. Air outlet valve; 4. Stirring shaft; 5. Baffle agitator; 6. Self-priming agitator; 7. Axial flow agitator; 8. Sampling port; 9. Feed port; 10: Baffle; 11: Gas suction port. DETAILED DESCRIPTION
[0030] The composite stirring set and reactor of the present application are described in more detail below with reference to the accompanying drawings, but the present application is not limited thereto. Any modifications and changes that do not depart from the scope of the present application fall within the scope of the present application.
[0031] like Figure 3 As shown, the composite stirring set of the present application includes a baffle stirrer 5 , a self-priming stirrer 6 , and an axial flow stirrer 7 .
[0032] Due to centrifugal force, the metal catalyst can be knocked against the inner wall of the reactor during stirring. If the metal catalyst clumps together, it can scratch and damage the reactor's inner wall. The baffled agitator 5 acts as a flow barrier, preventing the solid catalyst from contacting the reactor's inner wall, thereby avoiding scratches and damage. It also increases turbulence, ensuring uniform mixing and further turbulent suspension of the catalyst, increasing liquid-solid mass transfer and improving mixing efficiency.
[0033] The total height of the baffled agitator 5 is determined by the height of the reactor body. To better prevent solids such as the catalyst in the reaction system from agglomerating and scraping the inner walls of the reactor, the total height of the baffled agitator 5 should be at least 1 / 2, preferably at least 2 / 3, of the height of the reactor body. More preferably, the baffled agitator 5 should be substantially the same height as the reactor body.
[0034] The baffle agitator 5 may have 2 to 6, preferably 2 to 4, baffles 10. The baffles 10 may be arranged vertically or substantially vertically to the inner wall of the reactor.
[0035] The baffle stirrer 5 is preferably cylindrical. As long as the reactor can accommodate it and the operation convenience allows, the closer the diameter of the baffle stirrer 5 is to the inner diameter of the reactor, the better.
[0036] The baffled agitator 5 can be connected to the agitator shaft 4 and driven to rotate by the agitator shaft 4. The baffled agitator 5 can also be placed independently in the reactor and driven to rotate by the liquid flow rotation force caused by the stirring of the self-priming agitator 6 and the axial flow agitator 7.
[0037] The self-priming agitator 6 and the axial flow agitator 7 are arranged on the same agitator shaft 4. The agitator shaft 4 is a hollow shaft with a gas suction port 11, preferably a gas suction port 11 is opened on the shaft at a height corresponding to the upper part of the reactor. The agitator motor 1 provides power to drive the agitator to rotate through the agitator shaft 4.
[0038] The gas suction port 11 is located above the reactant liquid level, sucking the gas in the upper space of the reactor, and then dispersed into the liquid through the rotation and stirring of the self-priming stirrer 6, thereby increasing gas-liquid mass transfer.
[0039] The axial flow agitator 7 is preferably located at the end of the agitator shaft 4, which extends into the vicinity of the bottom of the reactor. The axial flow agitator 7 increases the axial flow of the material, suspending solids such as the catalyst at the bottom of the reactor, preventing solid sedimentation, increasing liquid-solid mass transfer, and further enhancing the mixing effect.
[0040] The axial flow agitator 7 is preferably a propeller or a screw propeller. The propeller and the screw propeller may have two to six blades, preferably three blades.
[0041] The self-priming agitator 6 is arranged on the upper part of the axial flow agitator 7, and preferably the height from the bottom of the reactor is 1 / 3 to 2 / 3 of the height of the reactor body.
[0042] The self-priming stirrer 6 self-primes and redisperses the gas, increases gas-liquid mass transfer, and forms an effective gas-liquid mixing. The self-priming stirrer 6 is preferably a 3-6 port self-priming stirrer.
[0043] The composite stirring kit and reactor of the present application can be widely used in gas-liquid-solid three-phase reactions, and specific examples include but are not limited to catalytic hydrogenation reactions.
[0044] Catalytic hydrogenation reactions typically involve high reaction system viscosity and low solid catalyst dispersion, leading to the aforementioned issues of uneven solid catalyst dispersion and localized accumulation. Furthermore, catalytic hydrogenation reactions are typically conducted under high pressure. The method of increasing temperature to reduce viscosity to promote dispersion not only increases energy consumption but also raises new concerns regarding operational ease and safety risks associated with high-temperature, high-pressure reactions.
[0045] The inventors of the present application have discovered that the composite stirring kit and reactor of the present application can significantly improve the mass and heat transfer effects in the reaction system.
[0046] When the inventors used the composite stirring assembly and reactor described herein to conduct the following catalytic hydrogenation reaction, they found that the hydrogen absorption rate and reaction were significantly accelerated, reaching hydrogen absorption equilibrium within 3 hours and completing the reaction after 5 hours. Furthermore, the inventors unexpectedly discovered that the reaction temperature could be significantly reduced from the original high temperature of over 70°C without affecting the reaction rate and efficiency.
[0047]
[0048] The above reaction is one of the intermediate steps in the preparation of fluopyram by catalytic hydrogenation.
[0049] When a metal catalyst is used in the above-mentioned reaction, carrying out the reaction in a reactor with a composite stirring set according to the present application can effectively eliminate the problem of scraping the inner wall of the reactor after the catalyst aggregates. The metal catalyst can be listed, but is not limited to, a monometallic catalyst, a bimetallic catalyst, a supported metal catalyst, and a special promoter metal catalyst. Examples of monometallic catalysts include, but are not limited to, palladium, platinum, nickel, cobalt, etc. Examples of bimetallic catalysts include, but are not limited to, Ru / Co, Ni / MgO, etc. Examples of supported catalysts include, but are not limited to, Ni / SiO2, etc. Examples of special promoter metal catalysts include, but are not limited to, Raney-type catalysts, such as Raney cobalt, Raney nickel, Raney copper, etc.
[0050] Those skilled in the art can reasonably foresee that the composite stirring set and reactor of the present application can be used to implement the following cyanide catalytic hydrogenation reaction:
[0051]
[0052] Where R is C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 6-20 Aryl, C 6-20 Aryl-C 1-10 Alkyl, C 6-20 Aryl-C 2-10 Alkenyl, C 6-20 Aryl-C 2-10 Alkynyl, C 6-20 Heteroaryl-C 1-10 Alkyl, C 6-20 Heteroaryl-C 2-10 Alkenyl, C 6-20 Heteroaryl-C 2-10 Alkynyl, wherein the alkyl, alkenyl, alkynyl, aryl, heteroaryl are optionally substituted by 1 or more halogen, C 1-6 Alkyl, halogenated C 1-6 Substitution of alkyl groups;
[0053] Preferably R is C 1-6 Alkyl, C 6-20 Aryl-C 1-6 Alkyl or C 6-20 Heteroaryl-C 1-6 Alkyl, more preferably R is phenyl-C 1-6 Alkyl or pyridyl-C 1-6 Alkyl, wherein phenyl or pyridyl is optionally substituted by 1 or 2 or more selected from halogen, C 1-6 Alkyl, halogenated C 1-6 The alkyl group is substituted with a substituent.
[0054] Example
[0055] The present invention is described in detail below with reference to the embodiments.
[0056] In the examples and comparative examples of the present application, the detection conditions were as follows by high performance liquid chromatography:
[0057] The instrument was an Agilent 1100LC liquid chromatograph with a UV detector; the chromatographic column was Kromasil 100-5-C18, 4.6×250 mm; the mobile phase was acetonitrile:water = 6:4 (v:v) with 0.1% formic acid added; the column temperature was 30°C; the flow rate was 1.0 mL / min; and the wavelength was 210 nm.
[0058] Example 1
[0059] This embodiment uses the reactor of the present application with a composite stirring set, wherein the baffle agitator 5 has 4 baffles, and the height is basically the same as the reactor body, the self-priming agitator 6 is a 6-port self-priming agitator, and the axial flow agitator 7 is a three-fold blade axial flow agitator.
[0060] 20g 2- (3- chloro -5- (trifluoromethyl) pyridin-2-yl) acetonitrile is dissolved in 200mL methanol, then 6g Raney's cobalt Ra-Co catalyst is added in solution, solution is added in reactor by feed port 9, and it is ensured that the air tightness of feed bin and connecting pipeline, then open air inlet valve 2, be passed through nitrogen and carry out gas replacement three times, then be passed through hydrogen and carry out gas replacement three times, it is ensured that the hydrogen initial pressure filled is greater than the pressure in the kettle, the last time hydrogen filling pressure is to about 3MPa. Open and stir, react at room temperature. Stirring process catalyst is uniformly dispersed, and suspended state is good, and there is no problem of gathering scraping wall. Observe the pressure change on pressure gauge, treat that pressure is constant after extending 1h, sample by sampling port 8, reaction solution color is yellow-green, and high performance liquid chromatography detects and confirms that raw material conversion is complete, reacts 5h in total.
[0061] Comparative Example 1
[0062] The reactor used in this comparative example is only equipped with an axial flow stirrer 7, and the other structures are the same as those of the reactor in Example 1.
[0063] 20g of 2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)acetonitrile was dissolved in 200mL of methanol, and then 6g of Raney cobalt Ra-Co catalyst was added to the solution. The solution was added to the reactor through the feed port 9, and the air tightness of the feed bin and the connecting pipe was ensured. Subsequently, the air inlet valve 2 was opened, and nitrogen was introduced for gas replacement three times, followed by hydrogen for gas replacement three times. The final hydrogen pressure was filled to about 3MPa. Stirring was started, the temperature was raised to 70°C for reaction, and after the pressure remained constant, the reaction was extended for 1h. A sample was taken through the sampling port 8. The reaction liquid was yellow-green in color. High-performance liquid chromatography confirmed that the raw material conversion rate exceeded 99%, and the conversion was basically complete. The total reaction time was 17h.
[0064] Comparative Example 2
[0065] The reactor used in this comparative example is the same as that in comparative example 1.
[0066] 20 g of 2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)acetonitrile was dissolved in 200 mL of methanol, and then 6 g of Raney cobalt Ra-Co catalyst was added to the solution. The solution was added to the reactor through the feed port 9, and the air tightness of the feeding bin and the connecting pipe was ensured. The air inlet valve 2 was opened, and nitrogen was introduced for gas replacement three times, and then hydrogen was introduced for gas replacement three times. The hydrogen pressure was filled to about 3 MPa for the last time. Stirring was started and the reaction was carried out at room temperature. The pressure change on the pressure gauge was observed. After the pressure remained unchanged, the reaction was extended for 1 hour. Sampling was taken through the sampling port 8. The color of the reaction liquid was orange. High-performance liquid chromatography confirmed that the raw material was not completely converted, with about 4.3% remaining. The total reaction time was 10 hours.
[0067] Comparative Example 3
[0068] This comparative example used a reactor equipped with a magnetic stirrer.
[0069] 4g of 2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)acetonitrile was dissolved in 40mL of methanol, and then 1.2g of Raney cobalt Ra-Co catalyst was added to the solution. The solution was added to the reactor through the feed port 9, and the airtightness of the feed bin and the connecting pipe was ensured. Subsequently, the air inlet valve 2 was opened, and nitrogen was introduced for gas replacement three times, followed by hydrogen for gas replacement three times. The final hydrogen pressure was increased to about 3MPa. Stirring was started, and the temperature was raised to 70°C for reaction. The pressure change on the pressure gauge was observed. After the pressure remained constant, the reaction was extended for 1 hour. A sample was taken through the sampling port 8. The reaction liquid was yellow-green in color. High-performance liquid chromatography confirmed that the raw material conversion rate was less than 98%, and the conversion was not complete. The total reaction time was 8.5 hours.
[0070] Comparative Example 4
[0071] The reactor used in this comparative example does not have a baffle stirrer 5, and other structures are the same as the reactor in Example 1.
[0072] 20g 2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)acetonitrile was dissolved in 200mL methanol, and then 6g Raney cobalt Ra-Co catalyst was added to the solution. The solution was added to the reactor through the feed port 9, and the air tightness of the feed bin and the connecting pipe was ensured. The air inlet valve 2 was opened, and nitrogen was introduced for gas replacement three times, and then hydrogen was introduced for gas replacement three times. The hydrogen pressure was filled to about 3MPa for the last time, and stirring was started. The reaction was carried out at room temperature. During the stirring process, the catalyst was unevenly dispersed, a large amount of aggregation occurred, and scraping problems (such as Figure 5 Observe the pressure change on the pressure gauge. After the pressure remains constant, continue the reaction for 1 hour. Sampling is taken through sampling port 8. The reaction liquid is orange-yellow. High-performance liquid chromatography (HPLC) analysis confirms that the conversion rate of the raw material is less than 99%, indicating incomplete conversion. The total reaction time is 8.5 hours.
[0073] The above examples and comparative examples are as follows:
[0074]
[0075] The conversion rate is calculated as follows:
[0076]
[0077] Among them, S 产物 represents the product peak area; S 原料 represents the raw material peak area.
[0078] The pressure probe in the reactor is connected to an external pressure display (pressure gauge) to record the pressure display value and prepare the hydrogen absorption rate curve. The hydrogen absorption rate curves of Example 1 and Comparative Example 2 and Comparative Example 4 are shown in FIG. Figure 4 As shown. Figure 4 It can be seen from the hydrogen absorption rate curve that under the same conditions, the reaction using the three-composite stirring device of the present application is faster and smoother than that of Comparative Example 2 and Comparative Example 4.
[0079] Industrial Applicability
[0080] The composite stirring kit and reactor of the present application can be widely used in gas-liquid-solid three-phase reactions such as the preparation of fluopyram intermediates. They can greatly improve the dispersion in the reaction system, prevent solids such as catalysts from aggregating and scraping the wall, enhance mass and heat transfer, and reduce the reaction temperature. This eliminates the need for heating required in traditional catalytic hydrogenation reactions, reduces energy consumption, and improves production safety and controllability, thus having high industrial practical value.
Claims
1. A composite stirring set, characterized in that: The set includes a baffle stirrer, a self-priming stirrer and an axial flow stirrer, wherein the self-priming stirrer and the axial flow stirrer are arranged on the same stirring shaft, and the stirring shaft is a hollow shaft with a gas suction port opened on the shaft.
2. The composite stirring set according to claim 1, characterized in that: The baffle stirrer is connected to the stirring shaft and is driven by the stirring shaft.
3. The composite stirring set according to claim 1 or 2, characterized in that: The baffle-type agitator is cylindrical and has 2 to 6 baffles.
4. The composite stirring set according to claim 1 or 2, characterized in that: The axial flow agitator is a propeller or a screw propeller.
5. Reactor, characterized in that The reactor comprises the composite stirring set according to any one of claims 1 to 4.
6. The reactor according to claim 5, characterized in that The height of the baffle agitator is more than 1 / 2 of the height of the reactor body.
7. The reactor according to claim 5 or 6, characterized in that The axial flow stirrer is arranged at the end of the stirring shaft, and the end of the stirring shaft extends into the vicinity of the bottom of the reactor.
8. The reactor according to claim 5 or 6, characterized in that The self-priming agitator is arranged at a position where the height from the bottom of the reactor is 1 / 3 to 2 / 3 of the height of the reactor body.
9. The reactor according to claim 5 or 6, characterized in that The reactor is a catalytic hydrogenation reactor.