Fixed bed reactor for bearing emulsion droplet catalyst

Abstract

The invention belongs to the technical field of chemical equipment, and particularly relates to a fixed bed reactor for bearing an emulsion droplet catalyst, the fixed bed reactor comprises a reactor main body, and connecting flanges are arranged at the upper end and the lower end of the reactor main body; a quick-open type cover plate is connected to the connecting flange, and a liquid inlet spraying device is arranged on the quick-open type cover plate at the upper end; a conical closing opening is formed in the lower end of the reactor main body, a filter screen is arranged at the lower end of the conical closing opening, a plurality of layers of catalyst bearing assemblies are arranged in the reactor main body, and hydrophobic screens in the filter screen and the catalyst bearing assemblies are subjected to chemical modification treatment. According to the invention, the filter screen and the hydrophobic screen are arranged and are chemically modified, so that the fixed bed reactor has hydrophobicity, the emulsion catalyst can be filled in the fixed bed reactor, and long-term stable existence under a flowing condition is realized, so that efficient and continuous reaction of a two-phase system is realized.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical equipment, and in particular relates to a fixed bed reactor for carrying an emulsion catalyst. Background Art

[0002] With the rapid development of the modern chemical industry, the pursuit of efficient, green and sustainable chemical reaction processes has become the core driving force for the progress of the industry. Fixed-bed reactors, as an important technical device in the chemical industry, have played a pivotal role in catalytic reactions due to their simple structure, convenient operation and easy control of reaction conditions. However, despite their excellent performance in treating gas-solid and liquid-solid catalytic reactions, traditional fixed-bed reactors have been unable to achieve the growing demand for continuous treatment of complex multiphase systems, especially oil / water, oil / ionic liquid, gas / liquid and other two-phase catalytic systems. Especially when it comes to the application of homogeneous catalysts and biocatalysts, these catalysts often require a liquid environment and are difficult to apply in fixed beds.

[0003] In recent years, Pickering emulsion, as an innovative reaction medium, has provided a new idea for solving the above problems with its excellent stability and environmental compatibility. Pickering emulsion uses solid particles as emulsifiers. These solid particles can form a dense monolayer film at the oil-water interface, effectively preventing the aggregation of emulsion droplets and significantly improving the stability of the emulsion. More importantly, by encapsulating homogeneous catalysts or biocatalysts inside Pickering emulsion droplets, not only the efficient dispersion and stable storage of the catalyst is achieved, but also the subsequent separation and recovery of the catalyst is greatly facilitated, which has far-reaching significance for reducing production costs, improving resource utilization and reducing environmental pollution.

[0004] However, the integration of Pickering emulsion technology into the design of fixed-bed reactors in order to achieve efficient continuous reactions in two-phase catalytic systems still faces a series of technical difficulties and challenges. The primary problem is how to ensure that the Pickering emulsions can be stably filled in the fixed-bed reactor to prevent the Pickering emulsions from flowing out of the reactor during the flow process. In addition, how to design a reasonable reactor structure and flow field distribution to ensure that the reaction liquid can pass through the reactor evenly at a stable flow rate to ensure the efficient catalytic reaction is also a key technical point that needs to be solved.

[0005] At present, fixed-bed catalytic reactors in industry are mainly designed to be filled with solid catalysts. For the innovative technology of directly filling Pickering emulsions, there is still a lack of relevant technical solutions and practical application cases. Therefore, the development of a new fixed-bed reactor that can stably fill Pickering emulsions is not only a major innovation in existing reactor technology, but also a major step in promoting the chemical industry to develop in a greener, more efficient and sustainable direction. Summary of the invention

[0006] In view of the above problems, the present invention provides a fixed bed reactor for supporting an emulsion catalyst.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] A fixed bed reactor for carrying an emulsion catalyst comprises a reactor body, wherein connecting flanges are arranged at the upper and lower ends of the reactor body; a quick-opening cover is connected to the connecting flange, and a liquid inlet spray device is arranged on the quick-opening cover at the upper end; a conical closing is arranged at the lower end of the reactor body, and a filter is arranged at the lower end of the conical closing, so as to realize the filling of the emulsion catalyst; a plurality of layers of catalyst carrying components are arranged inside the reactor body, so as to realize the multi-layer distribution of the emulsion catalyst, and the filter and the hydrophobic screen in the catalyst carrying component are chemically modified to make them hydrophobic, so as to ensure the stable filling of the emulsion catalyst.

[0009] Furthermore, the reactor body is made of any one of quartz, glass or stainless steel, and is cylindrical in shape with an inner diameter of 2 to 50 cm and a height of 5 to 200 cm.

[0010] Furthermore, the height of the tapered opening is 1 to 20 cm, and the diameter of the lower end of the tapered opening is 1 to 35 cm.

[0011] Furthermore, the filter screen is made of any one of quartz, stainless steel or quartz sand, the filter screen has a diameter of 0.8 to 33 cm, a thickness of 0.2 to 0.5 cm, and a pore size of 10 to 100 μm.

[0012] Furthermore, the catalyst supporting assembly includes a hydrophobic screen obtained through chemical modification, and a sealing ring is arranged on the circumferential surface of the hydrophobic screen to achieve sealing between the hydrophobic screen and the inner wall of the reactor body.

[0013] Furthermore, a plurality of supporting legs are evenly arranged on the upper surface of the hydrophobic screen, and supporting holes corresponding to the supporting legs are arranged on the lower surface of the hydrophobic screen. Adjacent catalyst supporting assemblies are assembled together through the cooperation of the supporting legs and the supporting holes, and the hydrophobic screen located at the bottom is supported by a tapered closing.

[0014] Furthermore, the chemical modification is to place the filter or hydrophobic screen in any one of the organic solvents selected from toluene, ethanol and octane, and then add any one of the hydrophobic silanes selected from methyltrimethoxysilane, dichlorodimethylsilane, tetramethylsilane, methyltriethoxysilane, n-octadecyltriethoxysilane and octyltrimethoxysilane, and any one of the organic bases selected from n-hexylamine or triethylamine, and heat at 60 to 120° C. for 4 to 8 hours.

[0015] Furthermore, the number of layers of the catalyst supporting assembly is 0-20.

[0016] Furthermore, the two connecting flanges are fixedly connected by four studs.

[0017] Furthermore, the diameter of the liquid inlet spray device is 1 to 40 cm.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] The present invention is different from the conventional fixed bed reactor filled with solid catalysts. By providing a filter screen and a hydrophobic screen and chemically modifying them to make them hydrophobic, the emulsion catalyst can be filled in the fixed bed reactor and can exist stably for a long time under flow conditions, thereby realizing efficient and continuous reaction of the two-phase system.

[0020] The present invention provides multiple layers of hydrophobic screens in the reactor body to buffer and intercept the flow rate of the reaction liquid, thereby effectively ensuring the stability of the flow rate of the reaction liquid.

[0021] The present invention can realize a series reaction process of multi-step catalytic reactions by arranging multiple layers of hydrophobic screens in the reactor body;

[0022] The present invention fixes the Pickering emulsion or the catalyst prepared based on the Pickering emulsion through a fixed bed reactor, and is suitable for various chemical reactions and biocatalytic reactions, including oxidation, reduction, esterification, acylation, etc., and provides a high-efficiency and stable reaction equipment for continuous production in the chemical industry. It has broad application prospects and important practical value in the fields of chemical industry, fine chemicals, pharmaceuticals, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a structural schematic diagram of the present invention;

[0024] Figure 2 This is a schematic structural diagram of a catalyst-carrying assembly of the present invention;

[0025] In the figure, there are a reactor body 1, a connecting flange 2, a quick-opening cover plate 3, a liquid inlet spray device 4, a conical closing 5, a filter screen 6, a catalyst supporting assembly 7, a stud 8, a hydrophobic screen 701, a sealing ring 702, a support leg 703, and a support hole 704. DETAILED DESCRIPTION

[0026] In order to further illustrate the technical solution of the present invention, the present invention is further described below through embodiments.

[0027] Example 1

[0028] like Figure 1 to Figure 2 As shown, a fixed bed reactor for carrying an emulsion catalyst comprises a reactor body 1, wherein the reactor body 1 is made of quartz, is cylindrical in shape, has an inner diameter of 30 cm, and is 60 cm in height; a connecting flange 2 is provided at the upper and lower ends of the reactor body 1, and the two connecting flanges 2 are fixedly connected by four studs 8; a quick-opening cover plate 3 is connected to the connecting flange 2, and a liquid inlet spray device 4 is provided on the quick-opening cover plate 3 at the upper end, and the diameter of the liquid inlet spray device 4 is 10 cm; a conical closing 5 is provided at the lower end of the reactor body 1, and the height of the conical closing 5 is 5 cm The diameter of the lower end of the conical closing 5 is 25 cm. A filter screen 6 is arranged at the lower end of the conical closing 5 for filling the emulsion catalyst. The material of the filter screen 6 is any one of quartz, stainless steel or quartz sand. The diameter of the filter screen 6 is 24 cm, the thickness is 0.3 cm, and the pore size of the filter screen 6 is 40 μm. Several layers of catalyst supporting components 7 are arranged inside the reactor body 1 to realize the multi-layer distribution of the emulsion catalyst. The filter screen 6 and the hydrophobic screen 701 in the catalyst supporting component 7 are chemically modified to make them hydrophobic to ensure the stable filling of the emulsion catalyst. The number of layers of the catalyst supporting assembly 7 is 15, and the catalyst supporting assembly 7 includes a hydrophobic screen 701 obtained by chemical modification. A sealing ring 702 is arranged on the circumferential surface of the hydrophobic screen 701, which is used to achieve the sealing between the hydrophobic screen 701 and the inner wall of the reactor body 1. A plurality of supporting legs 703 are evenly arranged on the upper surface of the hydrophobic screen 701, and supporting holes 704 corresponding to the supporting legs 703 are arranged on the lower surface of the hydrophobic screen 701. Adjacent catalyst supporting assemblies 7 are assembled together by matching the supporting legs 703 with the supporting holes 704, and the hydrophobic screen 701 located at the bottom is supported by a tapered closing mouth 5.

[0029] The chemical modification is to place the filter 6 or the hydrophobic mesh 701 in toluene, then add methyltrimethoxysilane and n-hexylamine, and heat at 60° C. for 4 hours.

[0030] CALB enzyme was immobilized on Pickering emulsions to prepare a catalyst with a size of 50 microns for transesterification chiral resolution reaction; the reaction was carried out continuously for 4000 hours, the conversion rate was greater than 49%, and the ee values ​​of the generated chiral alcohols and chiral esters were both greater than 95%.

[0031] Example 2

[0032] like Figure 1 to Figure 2 As shown, a fixed bed reactor for carrying an emulsion catalyst comprises a reactor body 1, wherein the reactor body 1 is made of glass, is cylindrical in shape, has an inner diameter of 15 cm, and is 50 cm in height; a connecting flange 2 is provided at the upper and lower ends of the reactor body 1, and the two connecting flanges 2 are fixedly connected by four studs 8; a quick-opening cover plate 3 is connected to the connecting flange 2, and a liquid inlet spray device 4 is provided on the quick-opening cover plate 3 at the upper end, and the diameter of the liquid inlet spray device 4 is 8 cm; a conical closing mouth 5 is provided at the lower end of the reactor body 1, and the conical closing mouth 5 The height of the reactor body 1 is 5 cm, the diameter of the lower end of the tapered opening 5 is 10 cm, and a filter screen 6 is arranged at the lower end of the tapered opening 5 for filling the emulsion catalyst. The filter screen 6 is made of stainless steel, has a diameter of 8 cm, a thickness of 0.2 cm, and a pore size of 20 μm. Several layers of catalyst supporting components 7 are arranged inside the reactor body 1 for realizing multi-layer distribution of the emulsion catalyst. The filter screen 6 and the hydrophobic screen 701 in the catalyst supporting component 7 are both chemically modified to make them hydrophobic to ensure stable filling of the emulsion catalyst. The number of layers of the catalyst supporting assembly 7 is 10, and the catalyst supporting assembly 7 includes a hydrophobic screen 701 obtained by chemical modification. A sealing ring 702 is arranged on the circumferential surface of the hydrophobic screen 701, which is used to achieve the sealing between the hydrophobic screen 701 and the inner wall of the reactor body 1. A plurality of supporting legs 703 are evenly arranged on the upper surface of the hydrophobic screen 701, and supporting holes 704 corresponding to the supporting legs 703 are arranged on the lower surface of the hydrophobic screen 701. Adjacent catalyst supporting assemblies 7 are assembled together by matching the supporting legs 703 with the supporting holes 704, and the hydrophobic screen 701 located at the bottom is supported by a tapered closing mouth 5.

[0033] The chemical modification is to place the filter 6 or the hydrophobic mesh 701 in ethanol, then add octyltrimethoxysilane and triethylamine, and heat at 80° C. for 6 hours.

[0034] Ketoreductase and coenzyme were immobilized on Pickering emulsions to prepare catalysts with a size of 30 microns for ketone reduction reaction; the reaction was continued for 350 hours, the conversion rate was greater than 90%, and the ee value of the generated chiral alcohol was greater than 98%.

[0035] Example 3

[0036] like Figure 1 to Figure 2 As shown, a fixed bed reactor for carrying an emulsion catalyst comprises a reactor body 1, wherein the reactor body 1 is made of stainless steel, is cylindrical in shape, has an inner diameter of 40 cm, and is 150 cm in height, and is provided with connecting flanges 2 at both the upper and lower ends of the reactor body 1, and the two connecting flanges 2 are fixedly connected by four studs 8; a quick-opening cover plate 3 is connected to the connecting flange 2, and a liquid inlet spray device 4 is provided on the quick-opening cover plate 3 at the upper end, and the diameter of the liquid inlet spray device 4 is 25 cm; a conical closing mouth 5 is provided at the lower end of the reactor body 1, and the conical closing mouth 5 The height of the reactor body 1 is 10 cm, the diameter of the lower end of the tapered opening 5 is 25 cm, and a filter screen 6 is arranged at the lower end of the tapered opening 5 for filling the emulsion catalyst. The material of the filter screen 6 is quartz sand, the diameter of the filter screen 6 is 23 cm, the thickness is 0.2 cm, and the pore size of the filter screen 6 is 20 μm; several layers of catalyst supporting components 7 are arranged inside the reactor body 1 for realizing multi-layer distribution of the emulsion catalyst, and the filter screen 6 and the hydrophobic screen 701 in the catalyst supporting component 7 are chemically modified to make them hydrophobic to ensure stable filling of the emulsion catalyst. The number of layers of the catalyst supporting assembly 7 is 20, and the catalyst supporting assembly 7 includes a hydrophobic screen 701 obtained by chemical modification. A sealing ring 702 is arranged on the circumferential surface of the hydrophobic screen 701, which is used to achieve the sealing between the hydrophobic screen 701 and the inner wall of the reactor body 1. A plurality of supporting legs 703 are evenly arranged on the upper surface of the hydrophobic screen 701, and supporting holes 704 corresponding to the supporting legs 703 are arranged on the lower surface of the hydrophobic screen 701. Adjacent catalyst supporting assemblies 7 are assembled together by matching the supporting legs 703 with the supporting holes 704, and the hydrophobic screen 701 located at the bottom is supported by a tapered closing mouth 5.

[0037] The chemical modification is to place the filter 6 or the hydrophobic mesh 701 in octane, then add dichlorodimethylsilane and n-hexylamine, and heat at 120° C. for 8 hours.

[0038] The transaminase and coenzyme were immobilized on Pickering emulsions to prepare a catalyst with a size of 30 microns for ketone reduction reaction; the reaction was carried out continuously for 300 hours, the conversion rate was greater than 90%, and the ee value of the generated chiral alcohol was greater than 98%.

[0039] Example 4

[0040] like Figure 1 to Figure 2 As shown, a fixed bed reactor for carrying an emulsion catalyst comprises a reactor body 1, wherein the reactor body 1 is made of glass, is cylindrical in shape, has an inner diameter of 50 cm, and is 200 cm in height, and is provided with connecting flanges 2 at both the upper and lower ends of the reactor body 1, and the two connecting flanges 2 are fixedly connected by four studs 8; a quick-opening cover plate 3 is connected to the connecting flange 2, and a liquid inlet spray device 4 is provided on the quick-opening cover plate 3 at the upper end, and the diameter of the liquid inlet spray device 4 is 35 cm; a conical closing mouth 5 is provided at the lower end of the reactor body 1, and the conical closing mouth 5 has a diameter of 35 cm. The height is 20 cm, the diameter of the lower end of the tapered opening 5 is 35 cm, and a filter screen 6 is arranged at the lower end of the tapered opening 5 for filling the emulsion catalyst. The material of the filter screen 6 is stainless steel, the diameter of the filter screen 6 is 33 cm, the thickness is 0.5 cm, and the pore size of the filter screen 6 is 100 μm; several layers of catalyst supporting components 7 are arranged inside the reactor body 1 to realize the multi-layer distribution of the emulsion catalyst, and the filter screen 6 and the hydrophobic screen 701 in the catalyst supporting component 7 are chemically modified to make them hydrophobic to ensure the stable filling of the emulsion catalyst. The catalyst supporting assembly 7 has two layers, and includes a hydrophobic screen 701 obtained through chemical modification. A sealing ring 702 is arranged on the circumferential surface of the hydrophobic screen 701 for sealing the hydrophobic screen 701 with the inner wall of the reactor body 1. A plurality of supporting legs 703 are evenly arranged on the upper surface of the hydrophobic screen 701, and supporting holes 704 corresponding to the supporting legs 703 are arranged on the lower surface of the hydrophobic screen 701. Adjacent catalyst supporting assemblies 7 are assembled together through the cooperation of the supporting legs 703 and the supporting holes 704, and the hydrophobic screen 701 at the bottom is supported by a tapered closing opening 5.

[0041] The chemical modification is to place the filter 6 or the hydrophobic mesh 701 in toluene, then add n-octadecyltriethoxysilane and triethylamine, and heat at 60° C. for 4 hours.

[0042] The acid catalyst and the base catalyst are respectively immobilized in Pickering emulsions, and the size of the prepared catalysts is 1 mm. The catalyst supporting component 7 has two layers, which are filled with the base catalyst and the acid catalyst respectively, and an acid-base series reaction is carried out; the reaction is continuously carried out for 120 hours, and the conversion rate is greater than 90%.

[0043] The above shows and describes the main features and advantages of the present invention. It is obvious to those skilled in the art that the present invention is not limited to the details of the above exemplary embodiments, and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes that fall within the meaning and scope of the equivalent elements of the claims are included in the present invention.

[0044] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A fixed bed reactor for supporting an emulsion catalyst, characterized in that: The invention comprises a reactor body (1), wherein connecting flanges (2) are arranged at the upper and lower ends of the reactor body (1); a quick-opening cover plate (3) is connected to the connecting flange (2), and a liquid inlet spray device (4) is arranged on the quick-opening cover plate (3) at the upper end; a conical closing opening (5) is arranged at the lower end of the reactor body (1), and a filter screen (6) is arranged at the lower end of the conical closing opening (5) for filling an emulsion catalyst; and a plurality of layers of catalyst supporting components (7) are arranged inside the reactor body (1) for realizing multi-layer distribution of the emulsion catalyst, and the filter screen (6) and the hydrophobic screen (701) in the catalyst supporting component (7) are both chemically modified to have hydrophobicity, so as to ensure stable filling of the emulsion catalyst.

2. A fixed bed reactor for supporting an emulsion catalyst according to claim 1, characterized in that: The reactor body (1) is made of any one of quartz, glass or stainless steel and is cylindrical in shape with an inner diameter of 2 to 50 cm and a height of 5 to 200 cm.

3. A fixed bed reactor for supporting an emulsion catalyst according to claim 2, characterized in that: The height of the conical closing opening (5) is 1 to 20 cm, and the diameter of the lower end of the conical closing opening (5) is 1 to 35 cm.

4. A fixed bed reactor for supporting an emulsion catalyst according to claim 3, characterized in that: The material of the filter screen (6) is any one of quartz, stainless steel or quartz sand, the diameter of the filter screen (6) is 0.8 to 33 cm, the thickness is 0.2 to 0.5 cm, and the pore size of the filter screen (6) is 10 to 100 μm.

5. A fixed bed reactor for supporting an emulsion catalyst according to claim 1, characterized in that: The catalyst supporting assembly (7) comprises a hydrophobic screen (701) obtained by chemical modification, and a sealing ring (702) is arranged on the circumferential surface of the hydrophobic screen (701) for achieving sealing between the hydrophobic screen (701) and the inner wall of the reactor body (1).

6. A fixed bed reactor for supporting an emulsion catalyst according to claim 5, characterized in that: A plurality of support legs (703) are evenly arranged on the upper surface of the hydrophobic screen (701), and support holes (704) corresponding to the support legs (703) are arranged on the lower surface of the hydrophobic screen (701). The adjacent catalyst supporting assemblies (7) are assembled together through the cooperation of the support legs (703) and the support holes (704), and the hydrophobic screen (701) located at the bottom is supported by a tapered closing opening (5).

7. A fixed bed reactor for supporting an emulsion catalyst according to claim 1, characterized in that: The chemical modification is to place the filter (6) or the hydrophobic screen (701) in any one of the organic solvents selected from toluene, ethanol and octane, then add any one of the hydrophobic silanes selected from methyltrimethoxysilane, dichlorodimethylsilane, tetramethylsilane, methyltriethoxysilane, n-octadecyltriethoxysilane and octyltrimethoxysilane, and any one of the organic bases selected from n-hexylamine and triethylamine, and heat at 60 to 120° C. for 4 to 8 hours.

8. A fixed bed reactor for supporting an emulsion catalyst according to claim 1, characterized in that: The number of layers of the catalyst supporting assembly (7) is 0-20.

9. A fixed bed reactor for supporting an emulsion catalyst according to claim 1, characterized in that: The two connecting flanges (2) are fixedly connected via four studs (8).

10. A fixed bed reactor for supporting an emulsion catalyst according to claim 1, characterized in that: The diameter of the liquid inlet spraying device (4) is 1 to 40 cm.

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