Synthesis device and preparation method suitable for pentaerythritol bicyclic sulfate

Abstract

The synthesis device comprises a reaction kettle, an external circulation device and a micropacked bed reactor, a stirrer and an ejector are arranged in the reaction kettle, the external circulation device comprises a circulation pump and a circulation tank, the inlet end of the circulation pump is communicated with the lower end of the reaction kettle, and the outlet end of the circulation tank is communicated with the lower end of the micropacked bed reactor. The outlet end of the circulating pump is communicated with the lower end part of the circulating tank, the upper end part of the circulating tank is communicated with the ejector, and the micro-packed bed reactor comprises a reaction pipeline fixedly communicated with the lower end part of the reaction kettle and a glass spring filler filled in the reaction pipeline. According to the synthesis device, the stirrer in the reaction kettle is matched with the external circulation device and is combined with the micro-packed bed reactor to further enhance the two-phase mixing effect, so that residual materials are fully reacted, the reaction efficiency, the product yield and the purity are remarkably improved, the subsequent product purification pressure is greatly relieved, and the production cost is reduced. The method has a great cost advantage for large-scale industrial production.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a synthesis apparatus and preparation method suitable for pentaerythritol bicyclic sulfate. Background Technology

[0002] Pentaerythritol dicyclic sulfate is a novel electrolyte additive for lithium-ion batteries. It can construct a more stable SEI (solid electrolyte interface) protective layer on the surfaces of the positive and negative electrodes, effectively improving the battery's charge-discharge performance, high-temperature stability, and cycle life. It shows significant application potential in suppressing battery overcharge and over-discharge sensitivity and mitigating the risk of high-temperature thermal runaway. Furthermore, this compound also demonstrates potential value in pharmaceutical intermediates, heat-resistant coatings, and specialty polymer additives.

[0003] Currently, its synthetic routes can be mainly divided into the following categories: Transesterification: Using pentaerythritol and dimethyl sulfate as raw materials, synthesis is carried out under the action of a catalyst. The dimethyl sulfate used in this process is highly toxic, and the reaction conditions are harsh (requiring high-temperature reflux at 150℃), resulting in low synthesis efficiency and poor environmental friendliness. Substitution reaction: Using pentaerythritol and sulfonamide compounds as reactants, relying on specific layered bimetallic hydroxides or aluminum-magnesium spinel catalysts. This route has limited raw material sources and high costs, restricting its large-scale application. Sulfonation-ring-closing method: Using sulfur trioxide Lewis base complexes as sulfonating agents, the reaction is carried out under inert gas protection. Raw material costs are high, post-processing steps are cumbersome, and industrialization efficiency is low. Metathesis exchange method: Using silyl ether and sulfonyl fluoride gas as raw materials, although the route is simple, the raw material costs are high, toxicity is high, and the hazards are prominent, making industrial scale-up difficult. Catalytic oxidation method: Using pentaerythritol sulfite as a precursor, the target product is prepared through an oxidation reaction. This route has advantages such as high atom economy and fewer steps, making it one of the most promising paths for industrialization.

[0004] In catalytic oxidation, existing processes often use noble metal catalysts such as ruthenium trichloride and sodium hypochlorite as oxidants, and carry out the process in a traditional batch reactor. This process has significant bottlenecks: the oxidant sodium hypochlorite is unstable and easily decomposes, introducing impurities; the batch reactor suffers from uneven mixing of the two phases and low mass transfer efficiency, resulting in long reaction cycles, incomplete conversion, increased byproducts, and difficulty in subsequent separation and purification. Summary of the Invention

[0005] The purpose of this invention is to provide a synthesis apparatus suitable for pentaerythritol dicyclic sulfate, which can ensure that the reaction proceeds fully, reduce the decomposition rate of sodium hypochlorite, reduce the generation of impurities, and improve the overall reaction efficiency, and is especially suitable for large-scale industrial production of pentaerythritol dicyclic sulfate.

[0006] Another object of the present invention is to provide a method for preparing pentaerythritol bicyclic sulfate using the above-described synthetic apparatus.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides an apparatus suitable for the synthesis of pentaerythritol bicyclic sulfate, comprising a reaction vessel, an external circulation device, and a micro-packed bed reactor. The reaction vessel is equipped with a stirrer and an ejector located at the upper part of its interior. The external circulation device includes a circulation pump and a circulation tank. The inlet of the circulation pump is connected to the lower end of the reaction vessel, and the outlet of the circulation pump is connected to the lower end of the circulation tank. The upper end of the circulation tank is connected to the ejector. The micro-packed bed reactor includes a reaction pipe fixedly connected to the lower end of the reaction vessel and glass spring packing filled within the reaction pipe.

[0008] The mixing effect is improved by stirring inside the reactor, ensuring uniform heating. The liquid is broken into fine droplets by external circulation spraying, which greatly increases the contact area between the two phases, thereby improving mass transfer efficiency and accelerating the reaction rate. The mixing effect between the two phases is further enhanced by the micro-packed bed reactor, allowing the residual materials to react fully. As a result, the reaction efficiency, product yield and purity are significantly improved, and the pressure of subsequent product purification is greatly relieved. This has a great cost advantage for large-scale industrial production.

[0009] In some embodiments, the agitator is a ribbon agitator. A ribbon agitator can promote axial up-and-down convection circulation of materials, forming a spiral flow, thereby significantly improving mixing uniformity, effectively enhancing the heating uniformity of various locations within the reactor, and preventing localized overheating.

[0010] Furthermore, the shaft of the ribbon agitator extends along the axis of the reactor.

[0011] In some embodiments, the reactor is equipped with a heat preservation component to facilitate stabilizing the reaction temperature and ensure the reaction effect.

[0012] In some embodiments, the circulating storage tank is equipped with a heat insulation component to further prevent an increase in impurity content due to sudden temperature changes.

[0013] In some embodiments, the liquid outlet diameter of the injector is 5 to 20 mm, for example 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 16 mm, 17 mm, 18 mm, 19 mm or 20 mm.

[0014] In some embodiments, the reaction pipeline is equipped with a heat insulation component to further prevent the increase of impurity content due to temperature changes.

[0015] In some embodiments, the reaction pipeline is a polytetrafluoroethylene pipe, a titanium pipe, or a nickel pipe, which has good structural stability and strong corrosion resistance.

[0016] In some embodiments, the inner diameter of the reaction conduit is 1 to 10 cm, for example, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm or 10 cm.

[0017] In some embodiments, the specifications of the glass spring packing are not particularly limited, and existing glass spring packings in the art can be used. For example, the inner diameter of the glass spring packing is preferably 3-8 mm, such as 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, or 8 mm. The length of the glass spring packing is preferably 6-20 mm, such as 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 16 mm, 17 mm, 18 mm, 19 mm, or 20 mm.

[0018] In some embodiments, there is no particular limitation on the amount of glass spring packing, as long as it is sufficient to fill the reaction channel.

[0019] In some embodiments, the reaction conduit is spiral-shaped, which facilitates further homogenization of the two phases during the flow process.

[0020] In some embodiments, a switch is provided at the connection between the reactor and the reaction pipeline, and the switch remains closed until the sodium hypochlorite solution has been completely fed in.

[0021] In some embodiments, the synthesis apparatus further includes a first tank for loading a pentaerythritol dicyclic sulfate ester solution, a second tank for loading a catalyst solution, and a third tank for loading a sodium hypochlorite solution.

[0022] Furthermore, the first storage tank and the third storage tank are equipped with heat insulation components.

[0023] Furthermore, the first storage tank, the second storage tank, and the third storage tank are respectively connected to the reactor via pipelines equipped with feed pumps and check valves.

[0024] More preferably, the first storage tank is connected to a first pipeline equipped with a first feed pump and a first check valve, the second storage tank is connected to a first pipeline equipped with a second feed pump and a second check valve, and the third storage tank is connected to a third pipeline equipped with a third feed pump and a third check valve. The first pipeline, the second pipeline, and the third pipeline are each connected to a mixing pipe, which is connected to the reactor. During feeding, the pentaerythritol dicyclic sulfate ester solution and the catalyst solution can be fed simultaneously and premixed in the mixing pipe.

[0025] In some embodiments, the synthesis apparatus further includes a separatory tank connected to the reaction pipeline.

[0026] Furthermore, the upper end of the reaction pipe is connected to the lower end of the reaction vessel, and the lower end of the reaction pipe is connected to the upper end of the separator.

[0027] The second aspect of the present invention provides a method for preparing pentaerythritol dicyclic sulfate, wherein the pentaerythritol dicyclic sulfate is prepared using the synthesis apparatus described above, wherein a pentaerythritol dicyclic sulfate ester solution, a catalyst solution and a sodium hypochlorite solution are first introduced into the reaction vessel for reaction, and the resulting mixture is then passed through the micro-packed bed reactor for further reaction.

[0028] In some embodiments, the mass concentration of the pentaerythritol bicyclic sulfate solution is 5% to 10%, for example 5%, 6%, 7%, 8%, 9% or 10%.

[0029] In some embodiments, the solvent for the pentaerythritol bicyclic sulfate solution is acetonitrile and / or dimethyl carbonate.

[0030] In some embodiments, the temperature of the pentaerythritol dicyclic sulfate ester solution is 30~60°C, for example 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, or 60°C. In actual operation, the temperature of the first storage tank can be set accordingly.

[0031] In some embodiments, the catalyst solution is a ruthenium trichloride solution with a mass concentration of 0.1% to 1%, for example, the concentration of the ruthenium trichloride solution is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%.

[0032] In some embodiments, the solvent for the catalyst solution is acetonitrile and / or water. The catalyst solution can be stored at room temperature.

[0033] In some embodiments, the available chlorine content of the sodium hypochlorite solution is 6% to 10%, specifically 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%.

[0034] In some embodiments, the temperature of the sodium hypochlorite solution is 5~20°C, for example 5°C, 10°C, 15°C or 20°C, to prevent the decomposition of sodium hypochlorite. In actual operation, the temperature of the third storage tank can be set accordingly.

[0035] In some embodiments, the mass ratio of pentaerythritol bicyclic sulfate ester to catalyst is 1:(0.00001~0.0001), for example 1:0.00001, 1:0.00002, 1:0.00003, 1:0.00004, 1:0.00005, 1:0.00006, 1:0.00007, 1:0.00008, 1:0.00009 or 1:0.0001.

[0036] In some embodiments, the mass ratio of pentaerythritol bicyclic sulfate ester to sodium hypochlorite is 1:(0.5~0.9), for example 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85 or 1:0.9.

[0037] In some embodiments, the reaction temperature in the reactor is 30 to 60°C, for example 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, or 60°C.

[0038] In some embodiments, the stirring speed of the stirrer is 150~450 r / min.

[0039] In some embodiments, the nozzle diameter of the injector is 5-20 mm.

[0040] In some embodiments, the temperature in the circulation tank is 30~60°C, for example 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C.

[0041] In some embodiments, the reaction time in the reactor is 1 to 2 hours, for example 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, or 2 hours.

[0042] In some embodiments, the residence time in the micro-filled bed reactor is 0.2 to 0.5 h, for example 0.2 h, 0.25 h, 0.3 h, 0.35 h, 0.4 h, 0.45 h or 0.5 h.

[0043] According to some specific embodiments, a pentaerythritol dicyclic sulfate ester solution and a catalyst solution are introduced into the reaction vessel and mixed evenly. Then, a sodium hypochlorite solution is introduced and reacted at 20~60°C. The feeding time of the sodium hypochlorite solution is controlled to be 1~2 hours. After the sodium hypochlorite solution feeding is completed, the mixture in the reaction vessel is continuously introduced into the micro-packed bed reactor. The residence time of the mixture in the micro-packed bed reactor is controlled to be 0.2~0.5 hours. The reaction liquid flowing out of the micro-packed bed reactor is allowed to stand and separate into layers in a separatory tank to obtain an organic phase.

[0044] Furthermore, the temperature of the first storage tank is set to 30~60℃, the temperature of the third storage tank is set to 5~20℃, the temperature of the reactor and the circulation tank is set to 30~60℃, the outer wall of the reaction pipeline is fitted with a heat insulation layer, the stirrer in the reactor always maintains a stirring speed of 150~400r / min, and the liquid outlet diameter of the ejector is 5~20mm.

[0045] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art: The synthesis apparatus of this invention improves the mixing effect and ensures uniform heating through an in-vessel stirrer. Combined with external circulation jetting, it breaks the liquid into fine droplets for mixing, significantly increasing the contact area between the two phases, thereby improving mass transfer efficiency and accelerating the reaction rate. Combined with a micro-packed bed reactor, it further enhances the two-phase mixing effect, allowing residual materials to react fully. As a result, the reaction efficiency, product yield, and purity are all significantly improved, and the pressure of subsequent product purification is greatly reduced. It has a great cost advantage for large-scale industrial production. Attached Figure Description

[0046] Figure 1 This is a schematic diagram of the apparatus for synthesizing pentaerythritol bicyclic sulfate in Example 1; Figure 2 This is a partial cross-sectional schematic diagram of the apparatus for synthesizing pentaerythritol bicyclic sulfate in Example 1; Figure 3 The GC spectrum of the pentaerythritol bicyclic sulfate product in Example 3 is shown below. 1. Reactor; 111. Motor; 112. Feed inlet; 113. First jacket; 114. Heat medium outlet; 115. Ribbon agitator; 116. Triangular support frame; 117. Heat medium inlet; 118. Discharge outlet; 119. External circulation inlet; 120. Ejector; 121. External circulation outlet; 2. Circulation pump; 3. Circulation tank; 4. Micro-packed bed reactor; 41. Reaction pipeline; 42. Glass spring packing; 5. Separator; 61. First storage tank; 611. First feed pump; 612. First check valve; 613. Second jacket; 62. Second storage tank; 621. Second feed pump; 622. Second check valve; 63. Third storage tank; 631. Third feed pump; 632. Third check valve; 633. Third jacket; 64. Mixing pipe. Detailed Implementation

[0047] The present invention will be further described below with reference to embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific applications, and the implementation conditions not specified are conventional conditions in this industry.

[0048] Unless otherwise specified, the raw materials used in the following examples and comparative examples are all commercially available products.

[0049] Example 1: This example provides an apparatus suitable for the synthesis of pentaerythritol bicyclic sulfate, such as... Figure 1 and Figure 2 As shown, it includes a first storage tank 61, a second storage tank 62, a third storage tank 63, a reaction vessel 1, an external circulation device, a micro-packed bed reactor 4, and a separatory tank 5.

[0050] Specifically, the first storage tank 61 is used to load a pentaerythritol dicyclic sulfate ester solution, the second storage tank 62 is used to load a catalyst solution, and the third storage tank 63 is used to load a sodium hypochlorite solution. The first storage tank 61 is connected to a first pipeline equipped with a first feed pump 611 and a first check valve 612; the second storage tank 62 is connected to a first pipeline equipped with a second feed pump 621 and a second check valve 622; and the third storage tank 63 is connected to a third pipeline equipped with a third feed pump 631 and a third check valve 632. The first, second, and third pipelines are each connected to a mixing pipe 64, which is connected to the reactor 1. The outer wall of the first storage tank 61 is covered with a second jacket 613 for heat insulation, and the outer wall of the third storage tank 63 is covered with a third jacket 633 for heat insulation.

[0051] Specifically, the upper end of the reactor 1 is provided with a feed inlet 112 and an external circulation inlet 119, and the lower end is provided with a discharge outlet 118 and an external circulation outlet 121. A ribbon agitator 115 is installed inside the reactor 1, with its motor 111 located outside the top of the reactor 1. The shaft of the ribbon agitator 115 extends along the axis of the reactor 1. The feed inlet 112 of the reactor 1 is connected to a mixing pipe. An ejector 120 is installed inside the reactor 1, and it is connected to the external circulation inlet 119. In this embodiment, the outlet diameter of the ejector 120 is 8 mm. A first jacket 113 for heating and heat preservation is fitted onto the outer wall of the reactor 1. The first jacket 113 has a cavity for introducing a heat medium. The upper end of the first jacket 113 is provided with a heat medium outlet 114, and the lower end of the first jacket 113 is provided with a heat medium inlet 117. The reactor 1 is also provided with a triangular support frame 116 for support.

[0052] Specifically, the external circulation device includes a circulation pump 2 and a circulation tank 3. The inlet of the circulation pump 2 is connected to the external circulation outlet 121 of the reactor 1 via a pipe, and the outlet of the circulation pump 2 is connected to the inlet of the circulation tank 3 via a pipe. The outlet of the circulation tank 3 is connected to the external circulation inlet 119 of the reactor 1 via a pipe. The inlet of the circulation tank 3 is located at its lower end near one end, and the outlet is located at its upper end near the other end. The outer wall of the circulation tank 3 is also fitted with an insulation layer for heat preservation.

[0053] Specifically, the micro-packed bed reactor 4 is detachably connected to the reactor 1, and a switch at the connection point is provided to control the connection or closure between the two. The micro-packed bed reactor 4 includes a reaction pipe 41 fixedly connected to the lower end of the reactor 1 and glass spring packing 42 filled inside the reaction pipe 41. The reaction pipe 41 is spiral-shaped and can be made of polytetrafluoroethylene, titanium, or nickel, and can be replaced as needed. In this embodiment, the inner diameter of the reaction pipe 41 is 4 cm. The glass spring packing 42 fills the reaction pipe 41. The glass spring packing 42 is a commercially available product with an inner diameter of 3-8 mm and a length of 6-20 mm. An insulation layer is fitted on the outer wall of the reaction pipe 41.

[0054] Specifically, the upper end of the reaction pipe 41 is connected to the outlet 118 of the reaction vessel 1, and the lower end of the reaction pipe 41 is connected to the top inlet of the separator 5.

[0055] Example 2: This example provides a method for preparing pentaerythritol bicyclic sulfate using the synthesis apparatus of Example 1, as detailed below: The first storage tank 61 contains a 10% pentaerythritol dicyclic sulfate solution, using acetonitrile as the solvent, and is set at a temperature of 40°C. The second storage tank 62 contains a 0.8% ruthenium trichloride solution, also using acetonitrile. The third storage tank 63 contains a 6% sodium hypochlorite solution with an available chlorine content, and is set at a temperature of 10°C. The feed mass ratio of pentaerythritol dicyclic sulfate to ruthenium trichloride and sodium hypochlorite is 1:0.00005:0.82. The reaction pipe 41 of the micro-packed bed reactor 4 uses polytetrafluoroethylene tubing with an insulation layer. The temperature of the reactor 1 and the circulation tank 3 is set at 50°C. The stirring speed of the spiral ribbon agitator 115 inside the reactor 1 is set at 350 r / min.

[0056] The first feed pump 611, the first check valve 612, the second feed pump 621, and the second check valve 622 are opened. The pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution are premixed in the mixing pipe 64 and then stirred and mixed in the reactor 1. After all the pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution have been introduced into the reactor 1, the third feed pump 631 and the third check valve 632 are opened, and the sodium hypochlorite solution is started to be fed. The feeding time of the sodium hypochlorite solution is controlled to be 1.5 hours. During the feeding of the sodium hypochlorite solution, the external circulation pump 2 is turned on for external circulation. Under the action of the ribbon agitator 115 and the external circulation device, the mixing effect of the aqueous phase and the acetonitrile phase is significantly improved, and the materials react at 50°C. After the sodium hypochlorite solution is fed, the outlet 118 of reactor 1 is opened. The mixture flows through the micro-packed bed reactor 4 for a second, thorough reaction, and then enters the separator 5 for separation. The residence time of the mixture in the micro-packed bed reactor 4 is 0.3 hours. The acetonitrile phase obtained after separation, after testing, shows a raw material conversion rate of 99.99% and a product selectivity of 97.46%. The acetonitrile phase is post-processed to obtain pentaerythritol dicyclic sulfate product, with a 1H NMR spectrum of [missing information]. 1 HNMR (400 MHz, DMSO- d 6 δ=4.92 (s, 8H), total product yield was 92.6%, GC purity was 99.64%, chloride ion content was 2ppm, and acid value (calculated as HF) was 10ppm.

[0057] Example 3: This example provides another method for preparing pentaerythritol dicyclic sulfate using the synthesis apparatus of Example 1. The first storage tank 61 contains a 10% (w / w) pentaerythritol dicyclic sulfate ester solution, using acetonitrile as the solvent, and is kept at a temperature of 30°C. The second storage tank 62 contains a 1% (w / w) ruthenium trichloride solution, using water as the solvent. The third storage tank 63 contains a 6% (w / w) sodium hypochlorite solution, and is kept at a temperature of 15°C. The feed mass ratio of pentaerythritol dicyclic sulfate ester to ruthenium trichloride and sodium hypochlorite is 1:0.00005:0.82. The reaction pipe 41 of the micro-packed bed reactor 4 is a titanium tube with an insulation layer. The temperature of the reactor 1 and the circulation tank 3 is set to 40°C. The stirring speed of the spiral ribbon agitator 115 inside the reactor 1 is set to 400 r / min.

[0058] The first feed pump 611, the first check valve 612, the second feed pump 621, and the second check valve 622 are opened. The pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution are premixed in the mixing pipe 64 and then stirred and mixed in the reactor 1. After all the pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution have been introduced into the reactor 1, the third feed pump 631 and the third check valve 632 are opened, and the sodium hypochlorite solution is started to be fed. The feeding time of the sodium hypochlorite solution is controlled to be 2 hours. During the feeding of the sodium hypochlorite solution, the external circulation pump 2 is opened for external circulation. Under the action of the ribbon agitator 115 and the external circulation device, the mixing effect of the aqueous phase and the acetonitrile phase is significantly improved, and the materials react at 40°C. After the sodium hypochlorite solution is fed, the outlet 118 of reactor 1 is opened. The mixture flows through the micro-packed bed reactor 4 for a second, thorough reaction, and then enters the separator 5 for separation. The residence time of the mixture in the micro-packed bed reactor 4 is 0.3 hours. The acetonitrile phase obtained after separation, after testing, shows a raw material conversion rate of 99.99% and a product selectivity of 96.48%. The acetonitrile phase is then post-treated to obtain pentaerythritol dicyclic sulfate product, with a total product yield of 91.7%, a GC purity of 99.56%, a chloride ion content of 2 ppm, and an acid value (calculated as HF) of 9 ppm.

[0059] Example 4: This example provides another method for preparing pentaerythritol dicyclic sulfate using the synthesis apparatus of Example 1. The first storage tank 61 contains a 5% (w / w) pentaerythritol dicyclic sulfate ester solution, using dimethyl carbonate as the solvent, and is kept at a temperature of 50°C. The second storage tank 62 contains a 0.8% (w / w) ruthenium trichloride solution, using water as the solvent. The third storage tank 63 contains a 6% (w / w) sodium hypochlorite solution, and is kept at a temperature of 20°C. The feed mass ratio of pentaerythritol dicyclic sulfate ester to ruthenium trichloride and sodium hypochlorite is 1:0.00003:0.82. The reaction pipe 41 of the micro-packed bed reactor 4 uses nickel pipe with an insulation layer. The temperature of the reactor 1 and the circulation tank 3 is set to 60°C. The stirring speed of the spiral ribbon agitator 115 inside the reactor 1 is set to 300 r / min.

[0060] The first feed pump 611, the first check valve 612, the second feed pump 621, and the second check valve 622 are opened. The pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution are premixed in the mixing pipe 64 and then stirred and mixed in the reactor 1. After all the pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution have been introduced into the reactor 1, the third feed pump 631 and the third check valve 632 are opened, and the sodium hypochlorite solution is started to be fed. The feeding time of the sodium hypochlorite solution is controlled to be 1 hour. During the feeding of the sodium hypochlorite solution, the external circulation pump 2 is opened for external circulation. Under the action of the ribbon agitator 115 and the external circulation device, the mixing effect of the aqueous phase and the dimethyl carbonate phase is significantly improved, and the materials react at 60°C. After the sodium hypochlorite solution is fed, the outlet 118 of reactor 1 is opened. The mixture flows through the micro-packed bed reactor 4 for a second, thorough reaction, and then enters the separator 5 for separation. The residence time of the mixture in the micro-packed bed reactor 4 is 0.3 hours. The dimethyl carbonate phase obtained after separation is tested and found to have a raw material conversion rate of 99.91% and a product selectivity of 95.19%. The dimethyl carbonate phase is then post-processed to obtain pentaerythritol dicyclic sulfate product with a total product yield of 91.3%, a GC purity of 99.51%, a chloride ion content of 1 ppm, and an acid value (calculated as HF) of 8 ppm.

[0061] Example 5: This example provides another method for preparing pentaerythritol dicyclic sulfate using the synthesis apparatus of Example 1. The first storage tank 61 contains an 8% (w / w) pentaerythritol dicyclic sulfate ester solution, using acetonitrile as the solvent, and is kept at a temperature of 40°C. The second storage tank 62 contains a 1% (w / w) ruthenium trichloride solution, also using acetonitrile as the solvent. The third storage tank 63 contains a 6% (w / w) sodium hypochlorite solution, and is kept at a temperature of 10°C. The feed mass ratio of pentaerythritol dicyclic sulfate ester to ruthenium trichloride and sodium hypochlorite is 1:0.0001:0.82. The reaction pipe 41 of the micro-packed bed reactor 4 uses a nickel pipe with an insulation layer. The temperature of the reactor 1 and the circulation tank 3 is set to 50°C. The stirring speed of the spiral ribbon agitator 115 inside the reactor 1 is set to 400 r / min.

[0062] The first feed pump 611, the first check valve 612, the second feed pump 621, and the second check valve 622 are opened. The pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution are premixed in the mixing pipe 64 and then stirred and mixed in the reactor 1. After all the pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution have been introduced into the reactor 1, the third feed pump 631 and the third check valve 632 are opened, and the sodium hypochlorite solution is started to be fed. The feeding time of the sodium hypochlorite solution is controlled to be 1.5 hours. During the feeding of the sodium hypochlorite solution, the external circulation pump 2 is turned on for external circulation. Under the action of the ribbon agitator 115 and the external circulation device, the mixing effect of the aqueous phase and the acetonitrile phase is significantly improved, and the materials react at 50°C. After the sodium hypochlorite solution is fed, the outlet 118 of reactor 1 is opened. The mixture flows through the micro-packed bed reactor 4 for a second, thorough reaction, and then enters the separator 5 for separation. The residence time of the mixture in the micro-packed bed reactor 4 is 0.4 hours. The acetonitrile phase obtained after separation is tested and found to have a raw material conversion rate of 100% and a product selectivity of 98.61%. The acetonitrile phase is then post-processed to obtain pentaerythritol dicyclic sulfate product with a total product yield of 93.7%, a GC purity of 99.84%, a chloride ion content of 2 ppm, and an acid value (calculated as HF) of 11 ppm.

[0063] Example 6: This example provides another method for preparing pentaerythritol dicyclic sulfate using the synthesis apparatus of Example 1. The first storage tank 61 contains a 10% (w / w) pentaerythritol dicyclic sulfate ester solution, using acetonitrile as the solvent, and is kept at a temperature of 50°C. The second storage tank 62 contains a 0.8% (w / w) ruthenium trichloride solution, also using acetonitrile. The third storage tank 63 contains a 10% (w / w) sodium hypochlorite solution, and is kept at a temperature of 5°C. The feed mass ratio of pentaerythritol dicyclic sulfate ester to ruthenium trichloride and sodium hypochlorite is 1:0.00005:0.66. The reaction pipe 41 of the micro-packed bed reactor 4 is a titanium tube with an insulation layer. The temperature of the reactor 1 and the circulation tank 3 is set to 60°C. The stirring speed of the spiral ribbon agitator 115 inside the reactor 1 is set to 150 r / min.

[0064] The first feed pump 611, the first check valve 612, the second feed pump 621, and the second check valve 622 are opened. The pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution are premixed in the mixing pipe 64 and then stirred and mixed in the reactor 1. After all the pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution have been introduced into the reactor 1, the third feed pump 631 and the third check valve 632 are opened, and the sodium hypochlorite solution is started to be fed. The feeding time of the sodium hypochlorite solution is controlled to be 1 hour. During the feeding of the sodium hypochlorite solution, the external circulation pump 2 is opened for external circulation. Under the action of the ribbon agitator 115 and the external circulation device, the mixing effect of the aqueous phase and the acetonitrile phase is significantly improved, and the materials react at 60°C. After the sodium hypochlorite solution is fed, the outlet 118 of reactor 1 is opened. The mixture flows through the micro-packed bed reactor 4 for a second, thorough reaction, and then enters the separator 5 for separation. The residence time of the mixture in the micro-packed bed reactor 4 is 0.2 hours. The acetonitrile phase obtained after separation, after testing, shows a raw material conversion rate of 99.99% and a product selectivity of 92.35%. The acetonitrile phase is then post-treated to obtain pentaerythritol dicyclic sulfate product, with a total product yield of 87.7%, a GC purity of 99.52%, a chloride ion content of 2 ppm, and an acid value (calculated as HF) of 10 ppm.

[0065] Example 7: This example provides another method for preparing pentaerythritol dicyclic sulfate using the synthesis apparatus of Example 1. The first storage tank 61 contains a 5% (w / w) pentaerythritol dicyclic sulfate ester solution, using acetonitrile as the solvent, and is kept at a temperature of 30°C. The second storage tank 62 contains a 0.5% (w / w) ruthenium trichloride solution, also using acetonitrile. The third storage tank 63 contains a 10% (w / w) sodium hypochlorite solution, and is kept at a temperature of 15°C. The feed mass ratio of pentaerythritol dicyclic sulfate ester to ruthenium trichloride and sodium hypochlorite is 1:0.00001:0.7. The reaction pipe 41 of the micro-packed bed reactor 4 is a titanium tube with an insulation layer. The temperature of the reactor 1 and the circulation tank 3 is set to 30°C. The stirring speed of the spiral ribbon agitator 115 inside the reactor 1 is set to 250 r / min.

[0066] The first feed pump 611, the first check valve 612, the second feed pump 621, and the second check valve 622 are opened. The pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution are premixed in the mixing pipe 64 and then stirred and mixed in the reactor 1. After all the pentaerythritol dicyclic sulfate ester solution and the ruthenium trichloride solution have been introduced into the reactor 1, the third feed pump 631 and the third check valve 632 are opened, and the sodium hypochlorite solution is started to be fed. The feeding time of the sodium hypochlorite solution is controlled to be 2 hours. During the feeding of the sodium hypochlorite solution, the external circulation pump 2 is opened for external circulation. Under the action of the ribbon agitator 115 and the external circulation device, the mixing effect of the aqueous phase and the acetonitrile phase is significantly improved, and the materials react at 30°C. After the sodium hypochlorite solution is fed, the outlet 118 of reactor 1 is opened. The mixture flows through the micro-packed bed reactor 4 for a second, thorough reaction, and then enters the separator 5 for separation. The residence time of the mixture in the micro-packed bed reactor 4 is 0.5 h. The acetonitrile phase obtained after separation, after testing, shows a raw material conversion rate of 99.86% and a product selectivity of 93.14%. The acetonitrile phase is then post-treated to obtain pentaerythritol dicyclic sulfate product, with a total product yield of 88.4%, a GC purity of 99.57%, a chloride ion content of 2 ppm, and an acid value (calculated as HF) of 11 ppm.

[0067] Comparative Example 1: This comparative example provides a method for preparing pentaerythritol dicyclic sulfate using a batch glass reactor. Specifically, an acetonitrile solvent with a mass concentration of 8% pentaerythritol dicyclic sulfate ester is added to the reactor, followed by a 1% ruthenium trichloride aqueous solution. The mixture is stirred at 350 r / min and heated to 40°C. A sodium hypochlorite solution with an effective chlorine content of 6% is then added dropwise. The mass ratio of pentaerythritol dicyclic sulfate ester to ruthenium trichloride and sodium hypochlorite is 1:0.0001:0.82. The sodium hypochlorite solution is added dropwise over a period of 6 hours. After the addition is complete, the mixture is kept at the desired temperature for 30 minutes to complete the reaction. The reaction solution is then transferred to a separatory tank 5 for separation to obtain the acetonitrile phase. The raw material conversion rate is 98.77%, and the product selectivity is 85.49%.

[0068] As can be seen from the above examples and comparative examples, the preparation of pentaerythritol dicyclic sulfate using the synthesis apparatus of Example 1 has the advantages of simplicity, continuity, and high efficiency, and is suitable for industrial production. The synthesis apparatus, through the ribbon stirrer 115, the external circulation jet system, and the micro-packed bed reactor 4, effectively enhances the mixing effect of the liquid-liquid two phases, ensuring complete reaction of the materials. It also boasts high reaction efficiency, short reaction time, reduced decomposition of sodium hypochlorite, and effectively improved the utilization rate of sodium hypochlorite, resulting in high-yield, high-quality pentaerythritol dicyclic sulfate.

[0069] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. An apparatus suitable for the synthesis of pentaerythritol bicyclic sulfate, characterized in that: It includes a reaction vessel, an external circulation system, and a micro-packed bed reactor. The reactor is equipped with a stirrer, and an injector is located in the upper part of the reactor interior. The external circulation device includes a circulation pump and a circulation tank. The inlet end of the circulation pump is connected to the lower end of the reaction vessel, the outlet end of the circulation pump is connected to the lower end of the circulation tank, and the upper end of the circulation tank is connected to the ejector. The micro-filled bed reactor includes a reaction pipe fixedly connected to the lower end of the reactor vessel and glass spring packing filled in the reaction pipe.

2. The synthesis apparatus according to claim 1, characterized in that: The agitator is a ribbon agitator.

3. The synthesis apparatus according to claim 1, characterized in that: The reactor is equipped with a heat preservation component; And / or, the circulating storage tank is equipped with a heat insulation component; And / or, the reaction pipeline is equipped with a heat insulation component.

4. The synthesis apparatus according to claim 1, characterized in that: The reaction pipeline is a polytetrafluoroethylene pipe, a titanium pipe, or a nickel pipe; And / or, the inner diameter of the reaction pipe is 1~10cm; And / or, the inner diameter of the glass spring packing is 3~8mm; And / or, the length of the glass spring packing is 6~20mm.

5. The synthesis apparatus according to claim 1, characterized in that: The reaction conduit is spiral-shaped; And / or, a switch is provided at the connection between the reactor and the reaction pipeline.

6. The synthesis apparatus according to claim 1, characterized in that: It also includes a first storage tank for loading pentaerythritol dicyclic sulfate ester solution, a second storage tank for loading catalyst solution, and a third storage tank for loading sodium hypochlorite solution.

7. The synthesis apparatus according to claim 6, characterized in that: The first storage tank and the third storage tank are equipped with insulation components; And / or, the first storage tank, the second storage tank and the third storage tank are respectively connected to the reactor through pipelines equipped with feed pumps and check valves.

8. The synthesis apparatus according to claim 1, characterized in that: It also includes a separatory tank connected to the reaction pipeline.

9. The synthesis apparatus according to claim 8, characterized in that: The upper end of the reaction pipe is connected to the lower end of the reaction vessel, and the lower end of the reaction pipe is connected to the upper end of the separator.

10. A method for preparing pentaerythritol bicyclic sulfate, characterized in that: The pentaerythritol bicyclic sulfate is prepared using the synthesis apparatus according to any one of claims 1 to 9. The pentaerythritol bicyclic sulfate ester solution, the catalyst solution, and the sodium hypochlorite solution are first introduced into the reaction vessel for reaction, and the resulting mixture is then passed through the micro-packed bed reactor for further reaction.

11. The preparation method according to claim 10, characterized in that: The pentaerythritol dicyclic sulfate ester solution has a mass concentration of 5% to 10%; and / or, the solvent of the pentaerythritol dicyclic sulfate ester solution is acetonitrile and / or dimethyl carbonate; and / or, the temperature of the pentaerythritol dicyclic sulfate ester solution is 30 to 60°C. And / or, the catalyst solution is a ruthenium trichloride solution with a mass concentration of 0.1% to 1%; and / or, the solvent of the catalyst solution is acetonitrile and / or water; And / or, the available chlorine content of the sodium hypochlorite solution is 6%~10%; and / or, the temperature of the sodium hypochlorite solution is 5~20℃; And / or, the mass ratio of the pentaerythritol bicyclic sulfate ester to the catalyst is 1:(0.00001~0.0001). And / or, the mass ratio of the pentaerythritol bicyclic sulfate ester to sodium hypochlorite is 1:(0.5~0.9).

12. The preparation method according to claim 10, characterized in that: The reaction temperature in the reactor is 30~60℃; And / or, the temperature in the circulating tank is 30~60℃; And / or, the reaction time in the reactor is 1 to 2 hours; And / or, the residence time in the micro-filled bed reactor is 0.2 to 0.5 h.

13. The preparation method according to any one of claims 10 to 12, characterized in that: The pentaerythritol dicyclic sulfate ester solution and the catalyst solution are introduced into the reactor and mixed evenly. Then, sodium hypochlorite solution is introduced and reacted at 20-60°C. The feeding time of sodium hypochlorite solution is controlled at 1-2 hours. After the sodium hypochlorite solution is fed, the mixture in the reactor is continuously introduced into the micro-packed bed reactor. The residence time of the mixture in the micro-packed bed reactor is controlled at 0.2-0.5 hours. The reaction liquid flowing out of the micro-packed bed reactor is allowed to stand and separate into layers in a separatory tank to obtain the organic phase.

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