CN107641816B - Continuous electrochemical reaction device and method for continuously oxidizing thioether substrate into sulfone - Google Patents
Continuous electrochemical reaction device and method for continuously oxidizing thioether substrate into sulfone Download PDFInfo
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Abstract
The invention provides a continuous electrochemical reaction device and a method for continuously oxidizing thioether substrates into sulfone. The continuous electrochemical reaction device comprises a continuous electrochemical reactor and a temperature control device, wherein the continuous electrochemical reactor comprises a reactor body, the reactor body is provided with a reaction cavity, a central electrode and a peripheral electrode are arranged in the reaction cavity, and the peripheral electrode is arranged around the central electrode; the temperature control device is arranged around the reactor body. A central electrode and a peripheral electrode are arranged in a reaction cavity of the continuous electrochemical reactor, the peripheral electrode is arranged around the central electrode, and the unit volume of the reactor has a larger heat exchange area, so that the material has higher reaction efficiency. The continuous flowing reactor has the advantages of high reactant flow speed in the reactor, short treatment time, high reaction efficiency and less side reaction. Not only the reaction is stable compared with batch reaction, but also the temperature control is simple and the operation is convenient, and the volume of the equipment is reduced.
Description
Technical Field
The invention relates to the field of electrochemical reaction, in particular to a continuous electrochemical reaction device and a method for continuously oxidizing thioether substrates into sulfone.
Background
Organic electrosynthesis has significant advantages over traditional organic synthesis: (1) the electrochemical reaction is realized by electron gain and loss of reactants on the electrode, and other reagents are not added in principle, so that the material consumption is reduced, and the environmental pollution is reduced; (2) the selectivity is very high, side reactions are reduced, the product purity and yield are high, and the product separation and purification work is greatly simplified; (3) the reaction is carried out at normal temperature and normal pressure or low pressure, which is very beneficial to saving energy and reducing equipment investment; (4) the process flow is simple, and the reaction is easy to control.
Most of the existing electrochemical reactors are batch-type electrochemical reactors. After a certain amount of reactants (electrolyte) are fed into the simple intermittent electrochemical reactor at regular time, reaction products are discharged after a certain reaction time. It is clear that as the electrochemical and accompanying chemical reactions proceed, the reactants are depleted, their concentrations are reduced, the products are formed, and the product concentrations are increased (assuming here that the concentration distribution of reactants and products is uniform throughout the reactor and the same reaction time for each reactant). The operation of a batch electrochemical reactor is labor intensive and is generally suitable only for small scale production or for intermittent product supply.
Taking the oxidation of thioether substrates to sulfones as an example, the existing oxidation reaction usually uses a chemical oxidant, such as hydrogen peroxide to obtain sulfones with high yield and conversion rate under the catalysis of sodium tungstate. The inorganic peroxide oxone realizes the oxidation of a-amino thioether substrate, the chromium trioxide/catalyzed periodic acid oxidizes a series of aryl thioether substrates to obtain the sulfone and the sulfoxide at room temperature or low temperature with higher yield and conversion rate, and the molybdenum peroxide derivative catalyst realizes the oxidation of a series of aliphatic or aromatic thioether substrates with higher selectivity and yield to obtain the sulfone or sulfoxide product. Kazuhiko reported that oxidation of various aromatic and aliphatic thioether substrates using oxidized mercury/iodine gave sulfone products in higher yields. The chemical oxidant is generally more in use equivalent, and the post-treatment brings more harm of three wastes and heavy metal pollution.
In the last 70 s, a groove-type reactor was developed, graphite as an anode and aluminum as a cathode to oxidize dimethyl sulfide substrate into sulfone by electrochemical oxidation under acidic conditions, thereby obtaining high yield and ideal current efficiency. However, in the subsequent electrochemical development, it is almost rare in the case of industrial application.
The intermittent operation has the defects of auxiliary time, large equipment specification required by batch amplification, low heat exchange efficiency, long reaction period, low production efficiency, large occupied area and the like, and meanwhile, the intermittent operation is in large-scale production, and the direct current of hundreds of amperes is used, so that the equipment cost and the safety risk of operation are increased. Meanwhile, intermittent operation is easy to cause local reaction nonuniformity and more side reactions, so that the product quality is unstable.
Disclosure of Invention
The invention mainly aims to provide a continuous electrochemical reaction device and a method for continuously oxidizing a thioether substrate into sulfone, so as to solve the problem of low electrochemical reaction efficiency in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a continuous electrochemical reaction apparatus comprising a continuous electrochemical reactor including a reactor body having a reaction chamber in which a central electrode and a peripheral electrode are disposed, and a temperature control device; the temperature control device is arranged around the reactor body.
Further, the reactor body comprises: the reactor comprises a reactor side wall, a reactor upper cover and a reactor lower cover, wherein the reactor side wall, the reactor upper cover and the reactor lower cover enclose a reaction cavity, the reactor upper cover covers the top of the reactor side wall, and the reactor lower cover covers the bottom of the reactor side wall.
Further, the side wall of the reactor is connected with the upper cover of the reactor through an upper flange, and the side wall of the reactor is connected with the lower cover of the reactor through a lower flange.
Further, the reactor body further comprises: the reactor comprises a raw material inlet and a product outlet, wherein the raw material inlet is positioned at the lower half part of the side wall of the reactor; the product outlet is located in the upper half of the reactor sidewall.
Further, the reactor body further comprises: the inert gas inlet is positioned at the upper half part of the side wall of the reactor and is positioned above the product outlet; the tail gas outlet is positioned at the upper half part of the side wall of the reactor and is positioned above the inert gas inlet.
Further, the continuous electrochemical reactor further comprises: and the inert gas flowmeter is communicated with the inert gas inlet.
Further, the temperature control device is a temperature control jacket, and the temperature control jacket comprises a jacket cavity arranged around the continuous electrochemical reactor, and a jacket inlet and a jacket outlet arranged on the side wall of the jacket cavity.
Further, the jacket inlet is located in the lower half of the side wall of the jacket cavity, and the jacket outlet is located in the upper half of the side wall of the jacket cavity.
Further, the continuous electrochemical reaction device also comprises a temperature measuring device, and the temperature measuring device is connected with the product outlet.
Further, the material of the central electrode and the peripheral electrode is selected from any one of the following materials: graphite, Pt, Cu, Ag, Zn, Pb, Au, Fe, Ti, Ni, alloy or metal oxide, the metal oxide being PbO2、CuO、Ag2O、Fe2O3、TiO2Or NiO; the material of the side wall of the reactor is metal material, polytetrafluoroethylene, PP or metal material sprayed with polytetrafluoroethylene, and the metal material is iron or stainless steel.
Further, the shape of the central electrode is a rod or a net; the peripheral electrode is in the form of a sheet or mesh.
Furthermore, the distance between the central electrode and the peripheral electrode is 0.1-5 cm.
Furthermore, the distance between the central electrode and the peripheral electrode is 0.5-3 cm.
Further, a separator is disposed between the central electrode and the peripheral electrode.
Further, the reaction chamber is the cylinder, and the draw ratio of reaction chamber is 3 ~ 300: 1.
further, the length-diameter ratio of the reaction cavity is 10-100: 1.
furthermore, the continuous electrochemical reaction device also comprises an electrolytic reaction power supply which is electrically connected with the central electrode and the peripheral electrode, and the electrolytic reaction power supply is a direct current voltage-stabilizing current-stabilizing reaction power supply.
Further, the continuous electrochemical reactor is a plurality of continuous electrochemical reactors, and the plurality of continuous electrochemical reactors are arranged in series or in parallel.
Furthermore, the continuous electrochemical reaction device also comprises a raw material device and a raw material power conveying device, wherein the raw material device is communicated with the continuous electrochemical reactor through the raw material power conveying device.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for continuous oxidation of a thioether substrate to a sulfone, which comprises continuously feeding the thioether substrate to any one of the above continuous electrochemical reaction apparatuses for oxidation.
Further, the method comprises sampling and detecting at the product outlet of the continuous electrochemical reaction device to control the molar ratio of the raw material to the product of the thioether substrate to be less than 1%.
Furthermore, the central electrode in the continuous electrochemical reaction device is a graphite electrode, and the peripheral electrode is zinc or copper.
By applying the technical scheme of the invention, the central electrode and the peripheral electrode are arranged in the reaction cavity of the continuous electrochemical reactor, the peripheral electrode is arranged around the central electrode, the unit volume of the reactor has larger heat exchange area, so that materials have higher reaction efficiency in the continuous electrochemical reactor, the reaction materials continuously enter, reaction products are continuously discharged, and the continuous flowing reactor ensures that reactants flow fast in the reactor, has short treatment time, improves the reaction efficiency and reduces side reactions. Not only the reaction is stable compared with batch reaction, but also the temperature control is simple and the operation is convenient, and the volume of the equipment is reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic view illustrating a structure of a continuous electrochemical reaction apparatus according to a preferred embodiment of the present invention; and
fig. 2 is a schematic view illustrating a structure of a continuous electrochemical reaction apparatus according to another preferred embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. a continuous electrochemical reactor; 13. a center electrode; 14. a peripheral electrode;
11. a reactor body; 111. a reaction chamber; 112. a reactor sidewall; 113. an upper cover of the reactor; 114. a lower cover of the reactor;
115. a raw material inlet; 116. a product outlet; 117. an inert gas inlet; 118. a tail gas outlet; 12. an inert gas flow meter;
20. a temperature control device; 201. a jacket inlet; 202. a jacket outlet;
30. a temperature measuring device; 101. an upper flange; 102. a lower flange;
40. a raw material device; 50. a raw material power conveying device; 60. and (4) an electrolytic reaction power supply.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As mentioned in the background, the current electrochemical reaction has a problem of low reaction efficiency, and in order to improve the situation, in an exemplary embodiment of the present application, there is provided a continuous electrochemical reaction apparatus, as shown in fig. 1, comprising: the continuous electrochemical reactor 10 comprises a reactor body 11, the reactor body 11 is provided with a reaction cavity 111, a central electrode 13 and a peripheral electrode 14 are arranged in the reaction cavity 111, and the peripheral electrode 14 is arranged around the central electrode 13; the temperature control device 20 is disposed around the reactor body 11.
The continuous electrochemical reaction device that this application provided sets up central electrode 13 and peripheral electrode 14 in continuous electrochemical reactor 10's reaction chamber 111, and make peripheral electrode 14 set up around central electrode 13, unit reactor volume has great heat transfer area, make the material make in continuous electrochemical reactor 10 have faster reaction efficiency, reaction material gets into in succession, reaction product is continuous to be discharged, this kind of reactor of continuous flow makes reactant flow rate in the reactor fast, the processing time is short, improve reaction efficiency, reduce side reaction. Not only the reaction is stable compared with batch reaction, but also the temperature control is simple and the operation is convenient, and the volume of the equipment is reduced.
The specific structure of the continuous electrochemical reactor 10 described above can be suitably modified based on the structure of the existing electrochemical reactor. In a preferred embodiment of the present application, the reactor body 11 comprises: the reactor comprises a reactor side wall 112, a reactor upper cover 113 and a reactor lower cover 114, wherein the reactor side wall 112, the reactor upper cover 113 and the reactor lower cover 114 enclose a reaction cavity 111, the reactor upper cover 113 covers the top of the reactor side wall 112, and the reactor lower cover 114 covers the bottom of the reactor side wall 112. The reactor of this structure is assembled and is dismantled all conveniently.
In the preferred embodiment, the connection manner of the side wall 112 and the upper and lower covers 113 and 114 is not limited as long as the continuous electrochemical reaction can be achieved. In a preferred embodiment of the present application, the reactor sidewall 112 and the reactor upper cover 113 are connected by the upper flange 101, and the reactor sidewall 112 and the reactor lower cover 114 are connected by the lower flange 102. The flange connection enables the reactor upper cover 113 and the reactor lower cover 114 to be connected with the reactor side wall 112 more tightly and have higher tightness.
The reactant in the continuous electrochemical reactor 10 continuously enters the reactor, and the product is continuously discharged from the reactor, so that the continuous electrochemical reactor 10 further comprises a raw material inlet 115 and a product outlet 116, and the specific arrangement positions of the raw material inlet 115 and the product outlet 116 can be reasonably arranged according to actual needs. In a preferred embodiment of the present application, the reactor body 11 further comprises a raw material inlet 115 and a product outlet 116, the raw material inlet 115 being located in the lower half of the reactor side wall 112; the product outlet 116 is located in the upper half of the reactor sidewall 112. The arrangement of the material inlet 115 at the bottom and the product outlet 116 at the top can help to make the material react sufficiently and then be discharged.
In order to further improve the safety and stability of the continuous electrochemical reaction apparatus, in a preferred embodiment of the present application, the reactor body 11 further includes an inert gas inlet 117 and a tail gas outlet 118, wherein the inert gas inlet 117 is located at the upper half of the reactor sidewall 112 and above the product outlet 116; the off-gas outlet 118 is located in the upper half of the reactor sidewall 112 and above the inert gas inlet 117. The spacing between the inert gas inlet 117 and the product outlet 116 is determined based on the flow rate of the electrolytically evolved gas to more fully dilute the electrolytically generated gas (typically hydrogen or oxygen). The off-gas outlet 118 is located at the uppermost position of the reaction chamber 111, and there is a sufficient distance between the inert gas inlet 117 and the off-gas outlet 118 so that there is sufficient space for the gas to be diluted. Continuous feeding, continuous ejection of compact especially relates to the reaction of gas production, can derive gas effectively, avoids the gas accumulation, improves security and reaction efficiency.
In order to monitor the amount of inert gas introduced into the continuous electrochemical reactor 10 in real time, in a preferred embodiment of the present application, the electrochemical reactor further comprises an inert gas flow meter 12, the inert gas flow meter 12 being in communication with the inert gas inlet 117.
In the continuous electrochemical reactor 10, the structure and form of the temperature control device 20 are not particularly limited, and are all suitable for the present application as long as suitable reaction temperature conditions can be provided for the continuous electrochemical reactor 10. In a preferred embodiment of the present application, the temperature control device 20 is a temperature-controlled jacket, which comprises a jacket cavity disposed around the electrochemical reactor, and a jacket inlet 201 and a jacket outlet 202 disposed on the sidewall of the jacket cavity. The reaction jacket is arranged, so that the temperature condition of the continuous reactor can be more conveniently and directly regulated and controlled.
The specific positions of the jacket inlet 201 and the jacket outlet 202 are not limited as long as the media in the jacket can be effectively utilized for temperature control. In a preferred embodiment of the present application, the jacket inlet 201 is located in the lower half of the jacket cavity side wall and the jacket outlet 202 is located in the upper half of the jacket cavity side wall. Through the lower inlet and the upper outlet, the heat exchange can be fully carried out with the materials in the continuous electrochemical reactor 10, and the temperature control efficiency is high.
In order to regulate the temperature control device 20 more accurately in order to control the temperature of the continuous electrochemical reactor 10 more accurately. In a preferred embodiment of the present application, as shown in fig. 2, the continuous electrochemical reaction apparatus further comprises a temperature measuring device 30, and the temperature measuring device 30 is connected to the product outlet 116. The temperature measuring device 30 is arranged at the product outlet 116, so that the temperature in the reactor can be accurately known in real time, and the reaction temperature condition can be adjusted and monitored.
In the continuous electrochemical reactor 10, the material of the center electrode 13 and the peripheral electrode 14 is not particularly limited as long as the electrochemical reaction can be performed. In a preferred embodiment of the present application, the material of the central electrode 13 and the peripheral electrode 14 is selected from any one of the following materials: graphite, Pt, Cu, Ag, Zn, Pb, Au, Fe, Ti, Ni, alloys or oxides of the above metals; the material of the side wall 112 of the reactor is metal, teflon, PP or metal coated with teflon.
The specific electrode materials used for the above-mentioned various electrode materials vary according to the electrochemical reaction. When the metal oxide is used as an electrode, it means PbO2、CuO、Ag2O、Fe2O3、TiO2And NiO, etc. Accordingly, the material of the sidewall 112 of the reactor can be selected according to the actual requirement, for example, it can be a metal material, such as iron or stainless steel. The reactor side wall 112 itself made of a metal material may be used as an electrode. It may also be a non-metallic material such as polytetrafluoroethylene or PP. Or a metal material sprayed with polytetrafluoroethylene.
In the continuous electrochemical reactor 10, there is no particular limitation on the shape of the central electrode 13 and the peripheral electrode 14, and in a preferred embodiment of the present invention, the central electrode 13 is in the shape of a rod or a net; the peripheral electrode 14 is in the form of a sheet or mesh. The mesh is similar to a screen window, but the holes and the size are set according to requirements, and the mesh can also be set to be in a specific shape.
The electrode spacing is one of the important parameters to be considered in the design of electrochemical reactors, and can affect the efficiency of the electrode reaction. In a preferred embodiment of the present application, the distance between the central electrode 13 and the peripheral electrode 14 is 0.1-5 cm. In another preferred embodiment of the present application, the distance between the central electrode 13 and the peripheral electrode 14 is 0.5-3 cm. The electrode spacing in the preferable range is small, the electrolytic voltage is reduced, the energy consumption is reduced, and the reaction efficiency is high under the same electric energy.
In a preferred embodiment of the present application, a membrane is arranged between the central electrode 13 and the peripheral electrode 14. The arrangement of the diaphragm helps to avoid product mixing in two-stage production, prevents side reactions and secondary reactions from occurring to influence product purity, yield and current efficiency, and avoids dangers and safety accidents (such as gas mixing explosion).
The specific shape of the continuous electrochemical reactor 10 is not particularly limited since it has no influence on the reaction. In a preferred embodiment of the present application, the reaction chamber 111 is a cylinder, and the length-diameter ratio of the reaction chamber 111 is 3 to 300: 1. in another preferred embodiment of the present application, the length-to-diameter ratio of the reaction chamber 111 is 10 to 100: 1. the length-diameter ratio of the reaction cavity 111 is controlled within the range, so that the reaction cavity has the beneficial effects of avoiding back mixing, reducing side reactions and the like.
The continuous electrochemical reaction device takes part in electrochemical reaction, and therefore, the continuous electrochemical reaction device is also required to be connected with a power supply. In a preferred embodiment of the present application, the continuous electrochemical reaction apparatus further comprises an electrolysis reaction power supply 60 electrically connected to the central electrode 13 and the peripheral electrode 14, and the electrolysis reaction power supply 60 is a direct current voltage-stabilized current-stabilized reaction power supply. The direct current voltage-stabilizing current-stabilizing reaction power supply has high stability, so that the reaction condition is relatively stable.
In practical applications, a plurality of continuous electrochemical reactors 10 may be used according to different electrochemical reaction requirements. In a preferred embodiment of the present application, the continuous electrochemical reactor 10 is provided in plurality, and a plurality of continuous electrochemical reactors 10 are arranged in series or in parallel.
The continuous electrochemical reactor 10 of the continuous electrochemical reaction apparatus can perform a continuous electrochemical reaction by continuously feeding and continuously discharging. Various modes for realizing continuous feeding and continuous discharging are available, for example, a power conveying device can be arranged at the raw material inlet 115, and a material extraction power device can also be arranged at the product outlet 116. In summary, a continuous electrochemical reaction of the material within the electrochemical reactor is achieved by the pressure difference between the feed inlet 115 and the product outlet 116. In a preferred embodiment of the present application, the continuous electrochemical reaction apparatus further comprises a raw material device 40 and a raw material power transmission device 50, wherein the raw material device 40 is communicated with the continuous electrochemical reactor 10 through the raw material power transmission device 50.
In another exemplary embodiment of the present application, a method for the continuous oxidation of a thioether substrate to a sulfone is provided, comprising continuously feeding the thioether substrate to any one of the above continuous electrochemical reaction apparatuses for oxidation. The continuous method greatly improves the reaction efficiency of the continuous oxidation of the thioether substrate into the sulfone.
In the above method for continuously oxidizing a thioether-based substrate to sulfone, the reaction termination conditions are the same as those of the conventional batch reaction. Specifically, in a preferred embodiment of the present application, the method further comprises sampling at the product outlet of the continuous electrochemical reaction device to control the molar ratio of the raw material to the product of the thioether substrate to be less than 1%. In actual operation, the continuous reaction system is stabilized when the molar ratio of the raw material to the product is less than 1% by detecting the molar ratio of the raw material in the effluent liquid at the product outlet and continuously adjusting the flow rate parameter and the current density parameter of the raw material continuously fed into the continuous electrochemical reaction device according to the ratio. In the continuous production process, the molar ratio of the raw materials in the product liquid is discontinuously detected at the product outlet and controlled within the ratio range, so that the stability of the reaction system is monitored in real time, the unicity of the continuous reaction product is ensured, and the generation of byproducts is reduced. The specific way of monitoring the molar ratio of the substrate raw materials in the product can be carried out by mass spectrometry.
In order to further improve the efficiency of the continuous oxidation reaction of the thioether substrate to the sulfone, in a preferred embodiment of the present application, the central electrode in the continuous electrochemical reaction device is a graphite electrode, and the peripheral electrode is zinc or copper. The electrode type has high electrochemical reaction efficiency for the continuous oxidation of the thioether substrate into the sulfone.
The advantageous effects of the present application will be further described with reference to specific examples.
Examples 1 to 6: oxidation of thioether substrates to sulfones
The information on the continuous electrochemical reactions of examples 1 to 6 is shown in table 1 below, in which the central electrode is a graphite electrode and the peripheral electrode is a zinc electrode.
Example 1
Dissolving 500g of raw materials in 10L of 0.4M HCl aqueous solution, injecting 0.4M HCl electrolyte in advance to fill an electrolytic cell, electrifying a direct current of 19.8A, using a peristaltic pump to pump the materials into a reactor at the speed of 13.3mL/min, sequentially passing through three reactors connected in series, and sampling and detecting at an outlet end after 50min, wherein the molar ratio of the raw materials to the products is less than 1%. The current efficiency is 60 percent, and the product separation yield is 95 percent.
Example 2
Dissolving 500g of raw material in 10L of 0.4M HCl aqueous solution, injecting 0.4M HCl electrolyte in advance, filling the electrolytic cell, and electrifying with 48.4A DC current with current density of 70mA/cm2And the mixture is pumped into a reactor at the speed of 32.5mL/min by using a peristaltic pump, and sequentially passes through three reactors connected in series, after 50min, sampling and detecting at an outlet end, wherein the molar ratio of the raw material to the product is less than 1%. The current efficiency is 58 percent, and the product separation yield is 92 percent.
Example 3
Dissolving 500g of raw material in 10L of 0.4M HCl aqueous solution, injecting 0.4M HCl electrolyte in advance, filling the electrolytic cell, and electrifying with 11A DC current with current density of 70mA/cm2And was fed to the reverse at a rate of 7.39mL/min using a peristaltic pumpThree reactors connected in series are sequentially arranged in the reactor, and after 50min, sampling detection is carried out at the outlet end, so that the molar ratio of the raw materials to the product is less than 1%. The current efficiency is 52 percent, and the product separation yield is 86 percent.
Example 4
Dissolving 500g of raw material in 10L of 0.4M HCl aqueous solution, injecting 0.4M HCl electrolyte in advance, filling the electrolytic cell, and electrifying 88A DC with current density of 70mA/cm2And the mixture is pumped into a reactor at the speed of 59.1mL/min by using a peristaltic pump, and sequentially passes through three reactors connected in series, after 50min, sampling and detecting at an outlet end, wherein the molar ratio of the raw material to the product is less than 1%. The current efficiency is 55 percent, and the product separation yield is 88 percent.
The procedures of examples 5 and 6 were similar to those of the above examples, and the specific reaction conditions and effects are shown in Table 1.
Table 1:
comparative example:
adding 10g thioether substrate and 100mL 0.4M HCl solution into 150mL open electrolytic cell, stirring, and placing graphite electrode 15 x 5cm in the electrolytic cell2Two pieces with an immersion liquid portion area of 12 x 5cm2The current density is 70mA/cm2The current is 4.2A, the reaction system is tracked until the molar ratio of the raw materials to the product is less than 1%, the electrolysis time is 4.3h, the current efficiency is 50%, and the post-treatment separation yield is 85%.
It can be seen that the continuous electrochemical reactor is operated continuously, the reactants enter the reactor continuously, the products are discharged continuously, and the composition of the electrolyte varies with its spatial position in the reactor, with the same residence time for each reactant, resulting in high reaction efficiency.
From the above description, it can be seen that the continuous electrochemical reaction apparatus of the present application of the present invention described above achieves the following technical effects: (1) the unit reactor volume has larger heat exchange area, and is particularly suitable for the reaction with larger heat effect; (2) the flow speed of reactants in the reactor is fast, the processing time is short, and the volume of equipment is greatly reduced; (3) the electrode spacing is small, and the small electrode spacing reduces the electrolytic voltage, thereby reducing the energy consumption; (4) the reactor adopts tubular electrodes, can be used singly or in combination according to requirements, and has convenient operation and management and strong flexibility; (5) simple structure, reduced fixed and operating cost, small floor area and reduced investment cost.
Continuous feeding, continuous ejection of compact especially relates to the reaction of gas production, derives gas effectively, avoids the gas accumulation, and the security is high, and reaction efficiency is high. The device is continuous and efficient, the volume and the occupied area of the device are reduced, the operation time is saved, and the labor intensity is reduced; the defects of unstable product quality and the like caused by uneven local reaction and more side reactions are avoided; compared with intermittent operation, the method has the advantages of small reaction system, easy temperature control and high safety.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. A continuous electrochemical reaction device, comprising:
a continuous electrochemical reactor (10) comprising a reactor body (11), the reactor body (11) having a reaction chamber (111), a central electrode (13) and a peripheral electrode (14) being disposed within the reaction chamber (111), the peripheral electrode (14) being disposed around the central electrode (13); and
a temperature control device (20), the temperature control device (20) being disposed around the reactor body (11);
the reactor body (11) further comprises:
an inert gas inlet (117), the inert gas inlet (117) being located at an upper half of the reactor sidewall (112) and above the product outlet (116); and
a tail gas outlet (118), the tail gas outlet (118) being located at an upper half of the reactor sidewall (112) and above the inert gas inlet (117);
the distance between the central electrode (13) and the peripheral electrode (14) is 0.5-3 cm, and the length-diameter ratio of the reaction cavity (111) is 10-100: 1.
2. continuous electrochemical reaction device according to claim 1, characterized in that said reactor body (11) comprises: the reactor comprises a reactor side wall (112), a reactor upper cover (113) and a reactor lower cover (114), wherein the reactor side wall (112), the reactor upper cover (113) and the reactor lower cover (114) enclose the reaction cavity (111), the reactor upper cover (113) covers the top of the reactor side wall (112), and the reactor lower cover (114) covers the bottom of the reactor side wall (112).
3. The continuous electrochemical reaction device according to claim 2, characterized in that the reactor side wall (112) and the reactor upper cover (113) are connected by an upper flange (101).
4. The continuous electrochemical reaction device according to claim 2, characterized in that the reactor side wall (112) and the reactor lower cover (114) are connected by a lower flange (102).
5. The continuous electrochemical reaction device according to claim 2, characterized in that the reactor body (11) further comprises:
a feedstock inlet (115), the feedstock inlet (115) being located in a lower half of the reactor sidewall (112); and
a product outlet (116), the product outlet (116) being located at an upper half of the reactor sidewall (112).
6. The continuous electrochemical reaction device according to claim 1, characterized in that the continuous electrochemical reactor (10) further comprises: an inert gas flow meter (12), the inert gas flow meter (12) in communication with the inert gas inlet (117).
7. Continuous electrochemical reaction device according to claim 1 or 2, characterized in that the temperature control device (20) is a temperature controlled jacket comprising a jacket cavity arranged around the continuous electrochemical reactor (10) and a jacket inlet (201) and a jacket outlet (202) arranged on the jacket cavity side wall.
8. The continuous electrochemical reaction device according to claim 7, wherein the jacket inlet (201) is located at a lower half of the side wall of the jacket cavity, and the jacket outlet (202) is located at an upper half of the side wall of the jacket cavity.
9. The continuous electrochemical reaction device according to claim 4, further comprising a temperature measuring device (30), wherein the temperature measuring device (30) is connected to the product outlet (116).
10. The continuous electrochemical reaction device according to claim 2, wherein the material of the central electrode (13) and the peripheral electrode (14) is selected from any one of the following: graphite, Pt, Cu, Ag, Zn, Pb, Au, Fe, Ti, Ni, alloy or metal oxide, wherein the metal oxide is PbO2、CuO、Ag2O、Fe2O3、TiO2Or NiO; the material of reactor lateral wall (112) is the metal material of metal material, polytetrafluoroethylene, PP or spraying polytetrafluoroethylene, the metal material is iron or stainless steel.
11. The continuous electrochemical reaction device according to claim 1 or 2, characterized in that the central electrode (13) is shaped as a rod or a net; the peripheral electrode (14) is sheet-shaped or net-shaped.
12. Continuous electrochemical reaction device according to claim 1 or 2, characterized in that a separator is arranged between the central electrode (13) and the peripheral electrode (14).
13. The continuous electrochemical reaction device according to claim 1 or 2, further comprising an electrolysis reaction power supply (60) electrically connected to the central electrode (13) and the peripheral electrode (14), wherein the electrolysis reaction power supply (60) is a direct current voltage and current stabilization reaction power supply.
14. Continuous electrochemical reaction device according to claim 1 or 2, characterized in that said continuous electrochemical reactor (10) is in plurality, a plurality of said continuous electrochemical reactors (10) being arranged in series or in parallel.
15. The continuous electrochemical reaction device according to claim 1 or 2, further comprising:
a raw material device (40); and
the raw material power conveying device (50), and the raw material device (40) is communicated with the continuous electrochemical reactor (10) through the raw material power conveying device (50).
16. A method for the continuous oxidation of a thioether substrate to a sulfone, comprising continuously feeding the thioether substrate to a continuous electrochemical reaction apparatus according to any one of claims 1 to 15 for oxidation.
17. The method of claim 16, further comprising sampling the product outlet of the continuous electrochemical reaction apparatus to control the molar ratio of raw materials to product of the thioether substrate to be less than 1%.
18. The method according to claim 16, wherein the central electrode (13) in the continuous electrochemical reaction device is a graphite electrode and the peripheral electrode (14) is zinc or copper.
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| CN201710668033.7A CN107641816B (en) | 2017-08-07 | 2017-08-07 | Continuous electrochemical reaction device and method for continuously oxidizing thioether substrate into sulfone |
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| CN201710668033.7A CN107641816B (en) | 2017-08-07 | 2017-08-07 | Continuous electrochemical reaction device and method for continuously oxidizing thioether substrate into sulfone |
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| CN107641816B true CN107641816B (en) | 2020-01-24 |
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| CN110106515B (en) * | 2019-06-03 | 2020-04-28 | 南京工业大学 | Method for preparing sulfone compound by using electrochemical microchannel technology |
| CN110656346B (en) * | 2019-11-07 | 2021-02-02 | 南京工业大学 | Method for continuously preparing 2-aryl-3-halogenated-benzothiophene compound by using electrochemical microchannel reaction device |
| CN115896830A (en) * | 2023-02-16 | 2023-04-04 | 凯莱英生命科学技术(天津)有限公司 | Reaction kettle and electrochemical reaction device with same |
| CN117448853B (en) * | 2023-10-12 | 2024-06-21 | 大连理工大学 | Tubular continuous parallel-flow carbon dioxide electro-reduction combined oxygen production reactor and operation method thereof |
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