System and method for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone

Abstract

The present invention discloses a system and method for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone, and relates to the technical field of lithium battery additive synthesis. The system comprises: a raw material liquid bottle, wherein a dichloromethane solution of vinyl sulfite is stored in the raw material liquid bottle; an ozone generator, wherein the ozone generator is connected to an oxygen storage bottle and is used to oxidize the oxygen from the oxygen storage bottle into ozone; a micro-reaction plate, wherein the feed port of the micro-reaction plate is respectively connected to the raw material liquid bottle and the ozone generator; and a receiving bottle, wherein the receiving bottle is connected to the discharge port of the micro-reaction plate. The system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone of the present invention has a simple structure, does not generate wastewater or waste residue during the reaction process, is beneficial to energy conservation and environmental protection, and can achieve a full reaction through micro-reaction, which is beneficial to improving the reaction effect and yield, with the yield reaching over 90%.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium battery additive synthesis, and in particular to a system and method for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone. Background Art

[0002] Ethylene sulfate is a common additive in lithium-ion battery electrolytes. Its main functions include: 1) improving the battery's high-temperature cycling, high-temperature storage, and low-temperature discharge performance; 2) reducing battery expansion after high-temperature storage, reducing capacity decay and internal resistance; 3) inhibiting the decline in the battery's initial capacity and increasing the initial discharge capacity; and 4) enhancing the stability of the graphite anode and improving battery cycling performance. Furthermore, in the field of organic synthesis, it is primarily used as a hydroxyethylation reagent in organic synthesis, a pharmaceutical intermediate, and a raw material for the synthesis of antihypertensive drugs.

[0003] Currently, synthetic diethylene sulfate (DTD) is generally prepared using ethylene sulfite (ES) as a raw material, ruthenium trichloride as a catalyst, and sodium hypochlorite as an oxidant. However, this process still has the following problems:

[0004] (1) The amount of wastewater after sodium hypochlorite oxidation is large.

[0005] (2) After the organic phase and the aqueous phase are separated, sodium sulfate or magnesium sulfate needs to be added for drying, which produces a large amount of waste residue.

[0006] (3) The introduction of water into the system increases the difficulty of later refining.

[0007] (4) Ruthenium trichloride is expensive, which greatly increases the cost.

[0008] Therefore, it is an urgent problem to be solved by the present invention to provide a system and method for preparing vinyl sulfate with simple equipment and energy conservation. Summary of the Invention

[0009] The present invention provides a system and method for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone, aiming to solve the problems of high cost and energy loss in the above-mentioned background technology.

[0010] In order to achieve the above technical objectives, the present invention mainly adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone, comprising:

[0012] A raw material liquid bottle, wherein a dichloromethane solution of vinyl sulfite is stored in the raw material liquid bottle;

[0013] an ozone generator connected to an oxygen storage bottle and configured to oxidize oxygen from the oxygen storage bottle into ozone;

[0014] A micro-reaction plate, wherein the feed ports of the micro-reaction plate are respectively connected to the raw material liquid bottle and the ozone generator;

[0015] A receiving bottle is connected to the discharge port of the micro reaction plate.

[0016] In a preferred embodiment of the present invention, the raw material liquid bottle is connected to the feed port of the micro reaction plate via a first pipeline, and a feed metering pump is provided on the first pipeline.

[0017] In another preferred embodiment of the present invention, the ozone generator is connected to the feed port of the micro-reaction plate via a second pipeline, and a flow meter is provided on the second pipeline.

[0018] As a further improvement of the present invention, a water bath circulator is further included, wherein the water inlet and the water outlet of the water bath circulator are both connected to the micro reaction plate, and are used to provide heat to the micro reaction plate.

[0019] Preferably, the micro reaction plate is configured as one or more micro reaction plates connected in series.

[0020] As a further improvement of the present invention, the micro-reaction plate includes a reaction plate body and micro-reaction channels arranged in the reaction plate body and arranged in a spiral manner. A plurality of arc-shaped mixing holes are evenly spaced and connected at the upper part of the micro-reaction channels. A plurality of arc-shaped buffer holes are connected at one end of the arc-shaped mixing hole away from the micro-reaction channel. One end of the buffer hole is set as a liquid inlet end, and the other end is set as an elastic end.

[0021] Furthermore, the elastic end is made of expanded polytetrafluoroethylene elastic band.

[0022] Furthermore, the width of the liquid inlet end of the buffer hole is narrower than the width of the elastic end, and each of the elastic ends is located on the arc of the same circle, and the center of the circle is located in the arc-shaped mixing hole.

[0023] In a second aspect, the present invention further provides a method for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone, using the system described in the first aspect, and mainly comprising the following steps:

[0024] S1: dissolving the raw material vinyl sulfite in dichloromethane to prepare a dichloromethane solution of vinyl sulfite;

[0025] S2: ozone is prepared online using an ozone generator;

[0026] S3: Adding a dichloromethane solution of vinyl sulfite and ozone in a certain proportion into a micro-reaction plate for reaction to prepare vinyl sulfate.

[0027] In a preferred embodiment of the present invention, the mass ratio of vinyl sulfite to dichloromethane is 10:1, the ozone concentration is 10%, the molar ratio of vinyl sulfite to ozone is 1:1.2, and the reaction temperature is -10°C.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone of the present invention has a simple structure and does not generate wastewater or waste residue during the reaction process, which is beneficial to energy conservation and environmental protection.

[0030] (2) The present invention adopts a new micro-reaction plate, which can ensure that vinyl sulfite and ozone are fully contacted and mixed, thereby achieving a full reaction, which is beneficial to improving the reaction effect and yield;

[0031] (3) The present invention uses ozone as a strong oxidant. Currently, it is widely used in wastewater treatment and urban tap water treatment, but the concentration is relatively low, below 1%. Its actual use in organic synthesis is rare, and the concentration of ozone used in chemical synthesis is around 10%. Under such high concentration conditions, ozone is extremely unstable, and after the ozone reaction, it generates oxygen. The mixed system with the reaction solvent is an explosive mixture, which is quite dangerous. In addition, the temperature of traditional ozone batch reactions is below -50°C, which places extremely high demands on equipment and consumes a lot of energy. The present invention uses ozone online preparation equipment to reduce the flammability and explosion risks in the ozone oxidation process. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a schematic structural diagram of a system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone according to Example 1 of the present invention;

[0033] Figure 2 Schematic diagram of the structure of the micro-reaction channel in the micro-reaction plate in Example 2 of the present invention;

[0034] Figure 3 This is an enlarged view of point A in Example 2 of the present invention. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of this application more clearly understood, the present application is further described in detail below with reference to the following examples. It should be understood that the specific examples described herein are merely for the purpose of explaining this application and are not intended to limit this application. Reagents not described in detail in this application are all conventional reagents and can be obtained from commercial channels; methods not specifically described in detail are all conventional experimental methods and can be obtained from the prior art.

[0036] It should be noted that the terms "first", "second", etc. in the description and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence, nor do they play a substantial limiting role on the subsequent technical features. It should be understood that the numbers used in this way can be interchanged where appropriate, so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0037] Example 1

[0038] like Figure 1 A system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone is shown, comprising:

[0039] A raw material liquid bottle 1, wherein a dichloromethane solution of vinyl sulfite is stored in the raw material liquid bottle 1; the raw material liquid bottle 1 is connected to the feed port of the micro reaction plate 4 via a first pipeline 5, and a feed metering pump 6 is provided on the first pipeline 5, and the amount of the dichloromethane solution of vinyl sulfite entering the feed port of the micro reaction plate 4 is controlled by the feed metering pump 6;

[0040] An ozone generator 2 is connected to an oxygen storage bottle 3 and is used to oxidize oxygen from the oxygen storage bottle 3 into ozone. The ozone generator 2 is connected to the feed port of the micro-reaction plate 4 via a second pipeline 7. A flow meter 8 is provided on the second pipeline 7 to control the amount of ozone entering the feed port of the micro-reaction plate 4.

[0041] A micro-reaction plate 4, wherein the feed ports of the micro-reaction plate 4 are respectively connected to the raw material liquid bottle 1 and the ozone generator 2; when the dichloromethane solution of ethylene sulfite and ozone enter the micro-reaction plate 4 in proportion, a full reaction is carried out in the micro-reaction plate 4;

[0042] A receiving bottle 10 is connected to the discharge port of the micro-reaction plate 4. After the dichloromethane solution of vinyl sulfite and ozone fully react through the micro-reaction plate 4, the resulting vinyl sulfate flows out of the discharge port of the micro-reaction plate 4 and is received by the receiving bottle 10, completing the vinyl sulfate preparation process.

[0043] In the process of the reaction between the dichloromethane solution of vinyl sulfite and ozone, in order to control the reaction temperature, the system of the present invention further includes a water bath circulator 9, the water inlet and outlet of which are both connected to the micro reaction plate 4, for providing heat to the micro reaction plate 4. Preferably, in the present invention, anhydrous ethanol is circulated in the water bath circulator 9, and the compressor in the water bath circulator 9 is used for cooling, so that the temperature of the micro reaction plate 4 is controlled at about -10°C, which is convenient for the reaction.

[0044] In the present invention, the micro-reaction plate 4 can be provided as a single plate or as multiple micro-reaction plates 4 connected in series. The liquid holding capacity of a single micro-reaction plate is 20 mL. The number of micro-reaction plates is adaptively adjusted according to the total amount of solution. In the present invention, two micro-reaction plates are preferably used. Without further limitation, the reaction solution is allowed to complete the reaction within the micro-reaction plate for a residence time of 1-5 minutes.

[0045] Example 2

[0046] It is basically the same as Example 1, except that Figure 2 、 Figure 3 As shown, the micro-reaction plate 4 in the present invention includes a reaction plate body and a micro-reaction channel 12 arranged in the reaction plate body and spirally arranged. Preferably, the diameter of the micro-reaction channel 12 is 1 mm, and a plurality of arc-shaped mixing holes 13 are evenly spaced and connected at the upper part of the micro-reaction channel 12. The arc-shaped mixing hole 13 is connected to one end away from the micro-reaction channel 12 and is connected to a plurality of arc-shaped buffer holes 14. One end of the buffer hole 14 is set as a liquid inlet end, and the other end is set as an elastic end 15.

[0047] After the reaction liquid enters the micro-reaction channel 12 of the micro-reaction plate 4, it will pass through the arc-shaped mixing hole 13 during its flow. Due to the effect of inertia, the reaction liquid in the arc-shaped mixing hole 13 further flows from the liquid inlet end into the arc-shaped buffer hole 14 until it reaches the elastic end 15 of the arc-shaped buffer hole 14. Then, under the elastic action of the elastic end 15, the reaction liquid refluxes from the liquid inlet end back to the arc-shaped mixing hole 13. The reaction liquids in multiple directions all realize this elastic action, re-mix and react in the arc-shaped mixing hole 13, and then flow into the micro-reaction channel 12, which can fully ensure that the reaction of ozone and the dichloromethane solution of ethylene sulfite is complete.

[0048] In the present invention, the elastic end 15 is made of expanded polytetrafluoroethylene elastic band. Of course, it can also be other elastic components that do not interact with ozone, vinyl sulfite, dichloromethane and vinyl sulfite, and no further limitation is made here.

[0049] Furthermore, to ensure mixing efficiency and reaction rate, the width of the liquid inlet end of the buffer hole 14 in the present invention is narrower than that of the elastic end, and each of the elastic ends 15 is located on the arc of the same circle, the center of which is located within the arc-shaped mixing hole 13. When two arc-shaped buffer holes 14 are provided, they form a rabbit-ear-like structure with the arc-shaped mixing hole 13. When multiple arc-shaped buffer holes 14 are provided, such as 4, 5, 6 or more, they form a semicircular petal-like structure.

[0050] Example 3

[0051] The system of Example 1 or Example 2 is used to carry out a reaction for synthesizing vinyl sulfate.

[0052] The main steps are as follows:

[0053] S1: dissolving the raw material vinyl sulfite in dichloromethane to prepare a dichloromethane solution of vinyl sulfite; wherein the mass ratio of vinyl sulfite to dichloromethane is 10:1;

[0054] S2: Using an ozone generator to prepare ozone online; its effective concentration is controlled at about 10%;

[0055] S3: Add the dichloromethane solution of vinyl sulfite and ozone in proportion to a micro-reaction plate, and react at normal pressure and a reaction temperature of -10°C to prepare vinyl sulfate, wherein the molar ratio of vinyl sulfite to ozone is 1:1.2.

[0056] Comparative Example

[0057] The conventional method for preparing vinyl sulfate using vinyl sulfite (ES) as a raw material, ruthenium trichloride as a catalyst, and sodium hypochlorite as an oxidant was used as a control group. The systems of Examples 1 and 2 of the present invention were used as experimental groups to prepare vinyl sulfate. The yields of vinyl sulfate among the three groups were compared. The results are shown in the following table.

[0058] Group Control Group Example 1 Example 2 Yield (%) 83% 91% 98%

[0059] The above is only a preferred specific implementation method of the present application, but the scope of protection of the present application is not limited thereto. Any changes or replacements that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed in this application should be covered by the scope of protection of the present application.

Claims

1. A system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone, characterized in that: include: A raw material liquid bottle, wherein a dichloromethane solution of vinyl sulfite is stored in the raw material liquid bottle; an ozone generator connected to an oxygen storage bottle and configured to oxidize oxygen from the oxygen storage bottle into ozone; A micro-reaction plate, wherein the feed ports of the micro-reaction plate are respectively connected to the raw material liquid bottle and the ozone generator; A receiving bottle connected to the discharge port of the micro reaction plate; The micro-reaction plate comprises a reaction plate body and micro-reaction channels arranged in a spiral pattern within the reaction plate body. A plurality of arc-shaped mixing holes are evenly spaced and connected to the upper portion of the micro-reaction channels. An end of the arc-shaped mixing hole away from the micro-reaction channels is connected to a plurality of arc-shaped buffer holes. One end of the buffer hole is configured as a liquid inlet end, and the other end is configured as an elastic end. The elastic end is made of expanded polytetrafluoroethylene elastic band; The width of the liquid inlet end of the buffer hole is narrower than that of the elastic end, and each of the elastic ends is located on the arc of the same circle, and the center of the circle is located in the arc-shaped mixing hole.

2. The system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone according to claim 1, characterized in that: The raw material liquid bottle is connected to the feed port of the micro reaction plate through a first pipeline, and a feed metering pump is provided on the first pipeline.

3. The system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone according to claim 1, characterized in that: The ozone generator is connected to the feed port of the micro-reaction plate through a second pipeline, and a flow meter is provided on the second pipeline.

4. The system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone according to claim 1, characterized in that: It also includes a water bath circulator, the water inlet and the water outlet of the water bath circulator are both connected to the micro reaction plate, and are used to provide heat to the micro reaction plate.

5. The system for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone according to claim 1, characterized in that: The micro reaction plate is configured as one or more micro reaction plates connected in series.

6. A method for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone, characterized in that: The system according to any one of claims 1 to 5 comprises the following steps: S1: dissolving the raw material vinyl sulfite in dichloromethane to prepare a dichloromethane solution of vinyl sulfite; S2: ozone is prepared online using an ozone generator; S3: Adding a dichloromethane solution of vinyl sulfite and ozone in a certain proportion into a micro-reaction plate for reaction to prepare vinyl sulfate.

7. The method for preparing vinyl sulfate by oxidizing vinyl sulfite with ozone according to claim 6, characterized in that: The mass ratio of vinyl sulfite to dichloromethane is 10:1, the ozone concentration is 10%, the molar ratio of vinyl sulfite to ozone is 1:1.2, and the reaction temperature is -10°C.

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