Production device and method of mannitol carbonate sulfate

Abstract

The invention provides a production device and method of mannitol carbonate sulfate. The production device comprises a sulfonylation reaction kettle, a solvent evaporation kettle D, an intermediate product three-in-one kettle, an oxidation reaction kettle, a phase splitting kettle, a dehydration tank, a solvent evaporation kettle E and a product three-in-one kettle. The method comprises the following steps: adding thionyl chloride, mannitol carbonate and a solvent I into a sulfonylation reaction kettle, feeding the reacted material into a solvent evaporation kettle D, evaporating and recovering excessive thionyl chloride and solvent I, feeding the residue into an intermediate product three-in-one kettle for washing, filtering and drying, and feeding the obtained solid into an oxidation reaction kettle for oxidation reaction. Reaction liquid enters a phase splitting kettle for phase splitting, an oil phase enters a solvent evaporation kettle E after being dehydrated by a dehydration tank, a solid enters a product three-in-one kettle after a solvent is evaporated, and a final product is obtained after washing, filtering and drying. According to the method, continuous and green preparation of MCS is achieved through solvent recycling and a mild and efficient two-step process, the product yield is larger than 92%, the purity is higher than 99.5%, and the method has industrial application value.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lithium ion battery additives, more particularly, to a production device and method of mannitol carbon sulfate. BACKGROUND

[0002] Mannitol carbon sulfate (MCS for short) is a new type of sulfate lithium ion battery electrolyte additive. Studies have shown that MCS can form a stable and dense solid-state electrolyte interface (SEI) film on the electrode surface, significantly improving the cycle life and rate performance of the battery. This additive performs excellently in terms of interface stability and high-voltage compatibility, and has good high and low temperature performance, suitable for wide temperature range working environment. In addition, MCS can effectively inhibit the decomposition reaction of common carbonate solvents such as dimethyl carbonate and ethylene carbonate, reducing the gas production phenomenon of the battery during the cycle process, thereby improving the safety performance of the battery.

[0003] In summary, MCS has significant advantages in improving the high-voltage performance, wide temperature adaptability, cycle stability and safety of lithium ion batteries, and shows broad application prospects.

[0004] However, the existing synthesis process still has many limitations. For example, CN 120441561 A discloses a preparation method of mannitol carbon sulfate, but uses an organic base with a higher price as a catalyst, resulting in a high production cost; CN 118598869 A discloses a synthesis method and application of a sulfate compound, but its synthesis steps are long and complex, and the yield is low. Due to the complicated process route, unsatisfactory total yield and other factors, the current research on MCS is still mainly in the laboratory stage, and there is no patent report on its large-scale production device.

[0005] In view of the above problems, the present application provides a production device and method of mannitol carbon sulfate, aiming to realize efficient, low-cost and continuous production of MCS, and promote its industrial application in the field of lithium battery materials, in order to overcome the deficiencies in current practical applications. SUMMARY

[0006] The purpose of the present application is to provide a production device and method of mannitol carbon sulfate, aiming to solve the problems mentioned in the background art.

[0007] The present application is achieved, a kind of production device of mannitol carbonic acid sulfate ester, including sulfonylation reaction kettle, solvent evaporation kettle D, intermediate product three-in-one processing kettle, oxidation reaction kettle, phase separation kettle, dehydration tank, solvent evaporation kettle E and product three-in-one processing kettle;The feed inlet of the sulfonylation reaction kettle is used to add sulfoxyl chloride, mannitol carbonate and solvent one, the sulfonylation reaction kettle is equipped with stirrer, and is connected with reaction condenser and reflux tank, and the discharge port of the sulfonylation reaction kettle is connected with the feed inlet of solvent evaporation kettle D;The solvent evaporation kettle D is equipped with condensing device, for evaporating and recycling the excessive sulfoxyl chloride and solvent one in reaction, and the discharge port of the solvent evaporation kettle D is connected with the feed inlet of intermediate product three-in-one processing kettle;The intermediate product three-in-one processing kettle has integrated functions of washing, filtering and drying, and is provided with an interface connected with vacuum system, and the solid material outlet of the intermediate product three-in-one processing kettle is connected with the feed inlet of oxidation reaction kettle;The oxidation reaction kettle is equipped with stirrer and heat exchange structure, for reaction temperature control, and the discharge port of the oxidation reaction kettle is connected with the feed inlet of phase separation kettle;The bottom of the phase separation kettle is provided with water phase outlet and oil phase outlet, and the oil phase outlet of the phase separation kettle is connected with the inlet of dehydration tank;The dehydration tank is loaded with dehydration molecular sieve, and the outlet of the dehydration tank is connected with the feed inlet of solvent evaporation kettle E;The solvent evaporation kettle E is equipped with stirrer and condensing device, and the solid material outlet of the solvent evaporation kettle E is connected with the feed inlet of product three-in-one processing kettle;The product three-in-one processing kettle has washing, filtering and drying functions, and is provided with an interface connected with vacuum system, and the solid material outlet of the product three-in-one processing kettle is used to output mannitol carbonic acid sulfate ester product.

[0008] Optionally, the reaction condenser connected with the sulfonylation reaction kettle is provided with non-condensable gas discharge port;The solvent evaporation kettle D is also equipped with stirrer, for material stirring and dispersing;The vacuum system connected with the intermediate product three-in-one processing kettle is used for pressure reduction operation in drying process, and the washing wastewater discharged from the liquid material outlet of the intermediate product three-in-one processing kettle is transported to subsequent processing procedure;The heat exchange structure of the oxidation reaction kettle is jacket or half-tube heat exchange structure, for heating or cooling in reaction process.

[0009] Optionally, the water phase outlet of the phase separation kettle is configured with conductivity online monitoring system, and the conductivity online monitoring system and the cut-off valves of oil phase outlet and water phase outlet realize interlock control, the oil phase inlet of the phase separation kettle is located in the upper part or middle part of the phase separation kettle, and the water phase discharged from the water phase outlet of the phase separation kettle is discharged into subsequent processing section as salt-containing wastewater.

[0010] Optionally, the dehydration molecular sieve in the dehydration tank is 4A molecular sieve or 5A type molecular sieve, for removing trace water in oil phase deeply;The liquid material discharged from the product three-in-one processing kettle is washing liquid, and the washing liquid is transported to subsequent procedure for solvent recovery.

[0011] Optionally, the outlet of the oxidation reactor is connected to the inlet of the phase separator through a filter, which is a basket filter, for separation and recovery of the catalyst.

[0012] Optionally, a solvent recovery tank is further included, and all evaporated solvents are transported to the solvent recovery tank for centralized treatment and recycling.

[0013] Another object of the present application is to provide a production method of mannitol carbonate sulfate, which uses the production device of mannitol carbonate sulfate.

[0014] 1) Sulfurylation reaction process: mannitol carbonate, solvent I and thionyl chloride are put into a sulfurylation reactor in a mass ratio of 1:(5-20):(1.2-3), and stirred at 40-70°C for 4-48 hours; after the reaction is completed, the excess thionyl chloride is evaporated and recovered, and the material is transferred to a solvent evaporation tank D to evaporate solvent I at 40-90°C, and the recovered solvent I is recycled; the solid material after evaporation of solvent I is transferred to an intermediate product three-in-one treatment tank for water washing, filtration and drying treatment to obtain pure intermediate D;

[0015] 2) Oxidation reaction process: intermediate D, solvent II and catalyst are added into an oxidation reactor in a mass ratio of 1:(5-20):(0.001-0.05), stirred and dispersed for 0.5-1 hour, and then an oxidizing agent is slowly added, and the mass ratio of intermediate D to the oxidizing agent is 1:(5-10), and the reaction is stirred at 5-50°C for 1-5 hours; after the reaction is completed, the reaction liquid is subjected to solid-liquid separation through a filter, the separated catalyst is recycled, and the liquid phase is transported to a phase separator for oil-water separation; the oil phase after phase separation is transported to a dehydration tank for dehydration, the dehydrated oil phase is transferred to a solvent evaporation tank E for distillation recovery of solvent II under reduced pressure at 40-90°C, the recovered solvent II is recycled, and the residual solid is transferred to a product three-in-one treatment tank for washing, filtration and drying treatment to obtain mannitol carbonate sulfate product, and the total yield of mannitol carbonate sulfate is greater than 92%, and the purity is greater than 99.5%.

[0016] Optionally, the solvent I in step 1) is selected from one or more of ethyl acetate, acetonitrile, dimethyl carbonate and dichloromethane; the water washing process is: water is added in an amount of 5-10 times the mass of intermediate D, and stirred for 1-4 hours after adding water to fully remove water-soluble impurities, which include by-product d and residual salts, and the structure of the by-product d is a compound containing two hydrophilic hydroxyl groups; the drying treatment conditions are: a drying temperature of 50-80°C, and a system pressure controlled at 1-20 kPa(A), and the reduced pressure drying is realized through a vacuum system connected to the intermediate product three-in-one treatment tank.

[0017] Optionally, the solvent in step 2) is selected from one or more of ethyl acetate, acetonitrile, dimethyl carbonate and dichloromethane; the catalyst is titanium silicalite or ruthenium trichloride, and the oxidant is aqueous sodium hypochlorite or hydrogen peroxide, and when the oxidant is aqueous sodium hypochlorite, the effective chlorine content is 10%; when the oil-water separation is performed in a phase separation kettle, the conductivity of the water phase is 50-200 S / m, and the conductivity of the oil phase is 10-50 mS / m; when the water phase is initially separated, the water phase is discharged by opening the water phase cut-off valve, and when the conductivity of the water phase outlet is reduced to below 100 mS / m, the water phase valve is closed and the oil phase valve is opened to discharge the oil phase; the dehydration tank is provided with 4A molecular sieves or 5A molecular sieves, and the trace amount of water in the dehydrated oil phase is deeply removed; the washing process of the product three-in-one treatment kettle is as follows: dichloromethane is used as a washing agent, the amount of the washing agent is 5-10 times the mass of the solid material, and after the feeding, the stirring is performed for 1-4 hours to sufficiently wash and remove the residual impurities; the drying process conditions of the product three-in-one treatment kettle are as follows: the drying temperature is 50-80 DEG C, the system pressure is controlled to be 1-20 kPa (A), and the vacuum system connected to the product three-in-one treatment kettle is used to realize the reduced-pressure drying.

[0018] Optionally, the intermediate D generated in the sulfonylation reaction in step 1) is mannitol chlorosulfite carbonate, the main product generated in the oxidation reaction in step 2) is mannitol sulfate carbonate, and the by-product e is a compound containing a specific structure; and the organic mother liquor such as a washing liquid and a distillation condensate is uniformly transported to a solvent recovery system and is resourcefully utilized after treatment.

[0019] The production device and method for mannitol sulfate carbonate provided by the application have the following beneficial effects:

[0020] The application first constructs a complete set of devices suitable for the large-scale production of MCS, and the overall structure is simple, the investment is low, the operation is convenient, the degree of automation is high, and the continuous and industrial operation is easy to realize, thereby filling the blank of production equipment in the field; through distillation, the solvent in the sulfonylation and oxidation processes is efficiently recovered and recycled, the raw material consumption and production cost are greatly reduced, the reaction conditions are mild, the energy consumption is low, the safety is good, and the green and low-carbon concept is met; the process flow is simple and efficient, the equipment utilization rate is high, the material loss is small, the product yield and purity are excellent, the total yield of MCS is greater than 92%, and the purity is higher than 99.5%, thereby meeting the high-quality requirements of high-end lithium ion battery electrolyte additives.

[0021] In summary, the application first provides a complete set of production devices and methods for mannitol sulfate carbonate, which are simple in structure, low in cost and high in degree of automation, and through solvent recycling and a mild and efficient two-step process, the continuous and green preparation of MCS is realized, the product yield is greater than 92%, the purity is higher than 99.5%, and the application has significant industrial application value.

[0022] Other features of the present application, and its particular advantages, will become apparent to those skilled in the art from the following detailed description, taken in combination with the appended drawings, in which: BRIEF DESCRIPTION OF DRAWINGS

[0023] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the application and, together with the description, serve to explain the principles of the application.

[0024] Figure 1 The structure schematic diagram of the production device of mannitol carbonic acid sulfate provided by the embodiment of the present application.

[0025] In the figure: 1, sulfonylation reaction kettle; 2, solvent evaporation kettle D; 3, intermediate three-in-one processing kettle; 4, oxidation reaction kettle; 5, phase separation kettle; 6, dehydration tank; 7, solvent evaporation kettle E; 8, product three-in-one processing kettle. DETAILED DESCRIPTION

[0026] Various exemplary embodiments of the present application will now be described in detail with reference to the figures. It should be noted that the relative arrangements, numerical expressions, and values of components and steps set forth in these embodiments are not limiting to the scope of the present application unless otherwise specifically stated.

[0027] The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the scope of the application its application or uses.

[0028] Techniques, methods, and apparatus known to those of ordinary skill in the relevant art can not be discussed in detail herein. However, where appropriate, such techniques, methods, and apparatus should be considered as being part of the specification.

[0029] In all of the examples shown and discussed herein, any specific values should be interpreted as merely exemplary and not as a limitation. Thus, other examples of exemplary embodiments can have different values.

[0030] It should be noted that like reference numerals and letters refer to like items in the following drawings, and thus, once an item is defined in one drawing, it need not be discussed further in subsequent drawings.

[0031] The following first specifically describes a production device and method of mannitol carbonic acid sulfate according to an embodiment of the present application in combination with the accompanying drawings.

[0032] The present application is applicable to the production of mannitol carbonic acid sulfate by taking mannitol carbonate as the main raw material.

[0033] Mannitol carbonate (MC for short), is a new type of organic intermediate, which is mainly obtained by ester exchange of dimethyl carbonate (DMC) and D-mannitol (DM for short), and its structural formula is shown in the following figure:

[0034]

[0035] The present application takes MC as the main raw material, and obtains the target product MCS through two-step reaction. The present application mainly involves two reactions of sulfonylation and oxidation, and the specific reactions are shown as follows:

[0036]

[0037] In combination with the reaction process, the MCS synthesized by the present application mainly has one or more of the following impurities:

[0038]

[0039] As shown in Figure 1 , a production device for mannitol carbonate sulfate provided by one embodiment of the present application includes a sulfonylation reaction kettle 1, a solvent evaporation kettle D 2, an intermediate product three-in-one treatment kettle 3, an oxidation reaction kettle 4, a phase separation kettle 5, a dehydration tank 6, a solvent evaporation kettle E 7, and a product three-in-one treatment kettle 8.

[0040] The feeding port of the sulfonylation reaction kettle 1 is used for adding thionyl chloride, mannitol carbonate (MC), and solvent one; the sulfonylation reaction kettle 1 is provided with a stirrer, and is connected with a reaction condenser and a reflux tank, wherein the condenser is provided with a non-condensable gas discharge port.

[0041] The discharging port of the sulfonylation reaction kettle 1 is connected with a feeding port of the solvent evaporation kettle D 2; the solvent evaporation kettle D 2 is provided with a stirrer, and is provided with a condensing device; the solvent evaporation kettle D 2 is used for evaporating and recycling the excessive thionyl chloride and solvent one in the reaction.

[0042] The discharging port of the solvent evaporation kettle D 2 is connected with a feeding port of the intermediate product three-in-one treatment kettle 3; the intermediate product three-in-one treatment kettle 3 has the functions of washing, filtering, and drying in one, and one interface is connected with a vacuum system, which is used for pressure reduction operation in the drying process.

[0043] The solid material outlet of the intermediate product three-in-one treatment kettle 3 is connected with the feeding port of the oxidation reaction kettle 4, and the liquid material outlet of the intermediate product three-in-one treatment kettle 3 discharges washing wastewater to a subsequent treatment process.

[0044] The oxidation reaction kettle 4 is provided with a stirrer, and is provided with a jacket or a semi-tube heat exchange structure, which is used for heating or cooling control in the reaction process.

[0045] The discharging port of the oxidation reaction kettle 4 is connected with the feeding port of the phase separation kettle 5 through a filter (preferably a basket filter), which is used for separation and recovery of the catalyst.

[0046] The oil phase outlet of the phase separation kettle 5 is also connected with the inlet of the dewatering tank 6, and the outlet of the dewatering tank 6 is connected with one feeding port of the solvent evaporation kettle E7.

[0047] The bottom of the phase separation kettle 5 is provided with an oil phase outlet and a water phase outlet (the oil phase inlet is located at the upper part or the middle part), the water phase outlet is provided with an on-line conductivity monitoring system, and is connected with the shut-off valves of the oil phase outlet and the water phase outlet to realize interlocking control and automatic liquid separation.

[0048] The oil phase separated by the phase separation kettle 5 is transported to the dewatering tank 6, and the water phase is discharged into a subsequent treatment section as salt-containing wastewater.

[0049] The dewatering tank 6 is internally provided with dewatering molecular sieves, preferably 4A or 5A type molecular sieves, for deeply removing trace water in the oil phase.

[0050] The solvent evaporation kettle E7 is provided with a stirrer and a condensing device.

[0051] The solid material outlet of the solvent evaporation kettle E7 is connected with the feeding port of the product three-in-one treatment kettle 8.

[0052] The product three-in-one treatment kettle 8 also has washing, filtering and drying functions, and is provided with an interface connected with a vacuum system.

[0053] The solid material outlet of the product three-in-one treatment kettle 8 obtains the final product MCS, and the liquid material (washing liquid) discharged from the product three-in-one treatment kettle 8 is transported to a subsequent process for solvent recovery.

[0054] The device further comprises a solvent recovery kettle, and all evaporated solvents are transported to the solvent recovery kettle for centralized treatment and recycling.

[0055] As shown in Figure 1 An embodiment of the present application further provides a production method of mannitol carbonic sulfuric ester, which is produced by using the above device and is suitable for preparing MCS by taking mannitol carbonate (MC) as a main raw material. The specific process flow is as follows:

[0056] 1. Sulfonylation reaction process

[0057] MC, solvent I and thionyl chloride are put into the sulfonylation reaction kettle 1 according to the mass ratio of 1:(5-20):(1.2-3), and are stirred and reacted at 40-70℃ for 4-48 hours to perform sulfonylation reaction.

[0058] After the reaction is completed, the excessive thionyl chloride is evaporated from the top of the reaction kettle and is recycled.

[0059] The main product generated in the reaction is the intermediate D (mannitol carbonic chlorosulfinic ester):

[0060]

[0061] Byproduct d is easily soluble in water due to its two hydrophilic hydroxyl groups, and can be effectively removed by subsequent water washing. Byproduct d is shown in the following figure:

[0062]

[0063] Preferably, the solvent one is selected from one or more of ethyl acetate, acetonitrile, dimethyl carbonate (DMC), dichloromethane, and more preferably DMC.

[0064] After the reaction is completed, the material is transferred to a solvent evaporation kettle D2, and the solvent one is evaporated at 40-90°C. The recovered solvent can be recycled.

[0065] After the solvent one is evaporated, the solid material is transferred to an intermediate product three-in-one processing kettle 3 for water washing, filtration, and drying treatment.

[0066] During the water washing process, the amount of water added is 5-10 times the mass of the intermediate D. After adding water, stirring is performed for 1-4 hours to fully remove water-soluble impurities (such as byproduct d and residual salts). Subsequently, filtration is performed, and the filter cake is retained for subsequent reactions, and the filtrate is discharged as waste water into the subsequent treatment section.

[0067] The filter cake is dried under vacuum conditions, the drying temperature is 50-80°C, and the system pressure is controlled at 1-20 kPa (A). After drying is completed, the obtained pure intermediate D is transported to an oxidation reaction kettle 4 for the next step of oxidation reaction.

[0068] 2. Oxidation reaction process

[0069] Intermediate D from the previous step, solvent two, and catalyst are added to the oxidation reaction kettle 4 in a mass ratio of 1:(5-20):(0.001-0.05), and stirring and dispersion are performed for 0.5-1 hour to ensure uniform mixing of the materials. Subsequently, the oxidizing agent is slowly added, and the mass ratio of intermediate D to oxidizing agent is 1:(5-10), and the oxidation reaction is started.

[0070] The reaction temperature is controlled at 5-50°C, and the reaction time is maintained for 1-5 hours. During the reaction, the temperature is regulated through a jacket or a half pipe to ensure smooth reaction.

[0071] The main product of the oxidation reaction is mannitol carbonate sulfate (MCS):

[0072]

[0073] After the reaction is completed, the system contains the target product MCS, unreacted solvent, catalyst, and a small amount of byproducts. The main byproduct is e:

[0074]

[0075] The solvent two is selected from one or more of ethyl acetate, acetonitrile, dimethyl carbonate (DMC), dichloromethane, preferably DMC, which has good solubility and process compatibility.

[0076] The catalyst is a titanium-silicon molecular sieve or ruthenium trichloride, preferably a titanium-silicon molecular sieve. The catalyst has high catalytic activity and selectivity, and is easy to recover and regenerate, and can be recycled.

[0077] The oxidizing agent is an aqueous sodium hypochlorite solution or hydrogen peroxide, preferably a sodium hypochlorite solution with an effective chlorine content of 10%, which has a mild reaction and good controllability, and is conducive to improving the selectivity and yield of the product.

[0078] After the oxidation reaction is completed, the reaction liquid is subjected to solid-liquid separation through a filter (preferably a basket filter):

[0079] The solid component is the catalyst, which can be recycled after treatment; the liquid phase is transported to a phase separation kettle 5 for oil-water separation.

[0080] During the phase separation, the water phase has a large density due to the presence of a large amount of inorganic salt (mainly sodium chloride), and is located in the lower layer; the organic phase (oil phase) has a small density and is located in the upper layer. To achieve precise separation, an online conductivity monitoring device is provided at the water phase outlet of the phase separation kettle, and is interlocked with the shut-off valves at the oil phase and water phase outlets for control.

[0081] The water phase has a high conductivity of about 50-200 S / m, while the oil phase has a low conductivity of about 10-50 mS / m. During separation, the water phase shut-off valve is first opened to discharge the high-conductivity salt water phase from the bottom to a subsequent wastewater treatment process. When the conductivity of the water phase outlet is reduced to below 100 mS / m, the system automatically determines that the oil-water interface is close to the outlet, and then closes the water phase valve and opens the oil phase valve to transport the organic phase (containing MCS) to a dehydration tank 6 for dehydration treatment.

[0082] The dehydration tank 6 is provided with a molecular sieve dehydrating agent, preferably 4A or 5A molecular sieve, which can effectively remove trace amounts of water in the organic phase.

[0083] The dehydrated oil phase material is transferred to a solvent evaporation kettle E7, which is subjected to vacuum distillation at 40-90°C to recover the solvent two. The recovered solvent can be recycled for use in the oxidation process.

[0084] The residual solid enters a product three-in-one treatment kettle 8, which is subjected to purification treatment using dichloromethane as a washing agent. The amount of washing agent is 5-10 times the mass of the solid material. After feeding, the mixture is stirred for 1-4 hours to fully wash and remove residual impurities, and then filtered.

[0085] The filter cake was dried under vacuum at a temperature of 50–80°C and a system pressure controlled at 1–20 kPa(A). The resulting solid was the high-purity target product—mannitol sulfate (MCS).

[0086] Organic mother liquors such as washing liquid and distillation condensate are uniformly transported to the solvent recovery system, where they are processed and utilized as resources.

[0087] The quality indicators of the MCS products produced by this process are as follows:

[0088] Overall yield: 92%–97.1%; purity: 99.51%–99.95% (as determined by HPLC). This indicates that the method has advantages such as high yield, high purity, and good process stability, and is suitable for large-scale production of high-quality MCS.

[0089] Example 1

[0090] like Figure 1 As shown, an embodiment of the present invention provides a production apparatus for mannitol carbonate sulfate, including a sulfonation reactor 1, a solvent evaporation reactor D2, an intermediate product three-in-one processing reactor 3, an oxidation reactor 4, a phase separation reactor 5, a dehydration tank 6, a solvent evaporation reactor E7, and a product three-in-one processing reactor 8.

[0091] The feed inlet of the sulfonation reactor 1 is used to add thionyl chloride, mannitol carbonate (MC) and solvent 1; the sulfonation reactor 1 is equipped with a stirrer and connected to a reaction condenser and a reflux tank, wherein the condenser is provided with a non-condensable gas discharge port.

[0092] The outlet of the sulfonation reactor 1 is connected to one inlet of the solvent evaporation reactor D2; the solvent evaporation reactor D2 is equipped with a stirrer and a condenser, and is used to evaporate and recover excess thionyl chloride and solvent 1 in the reaction.

[0093] The outlet of the solvent evaporator D2 is connected to one inlet of the intermediate product three-in-one processing vessel 3; the intermediate product three-in-one processing vessel 3 has integrated functions of washing, filtering and drying, and one of its interfaces is connected to a vacuum system for depressurization during the drying process.

[0094] The solid material outlet of the intermediate product three-in-one processing vessel 3 is connected to the feed inlet of the oxidation reaction vessel 4, and the washing wastewater discharged from the liquid material outlet of the intermediate product three-in-one processing vessel 3 is transported to the subsequent processing steps.

[0095] The oxidation reactor 4 is equipped with a stirrer and a jacketed or semi-tube heat exchange structure for heating or cooling control during the reaction process.

[0096] The outlet of the oxidation reactor 4 is connected to the inlet of the phase separation reactor 5 through a filter (preferably a basket filter) for separation and recovery of the catalyst.

[0097] The oil phase outlet of the phase separation reactor 5 is also connected to the inlet of the dehydration tank 6, and the outlet of the dehydration tank 6 is connected to one inlet of the solvent evaporation reactor E7.

[0098] The phase separation reactor 5 is provided with an oil phase inlet at the upper or middle part and a water phase outlet at the bottom, and the water phase outlet is provided with an online conductivity monitoring system and is connected to the shut-off valves of the oil phase and water phase outlets for interlocking control to realize automatic separation.

[0099] The oil phase separated by the phase separation reactor 5 is transported to the dehydration tank 6, and the water phase is discharged as salt-containing wastewater into a subsequent treatment section.

[0100] The dehydration tank 6 is provided with 4A molecular sieves for deep removal of trace water in the oil phase.

[0101] The solvent evaporation reactor E7 is provided with a stirrer and a condensing device.

[0102] The solid material outlet of the solvent evaporation reactor E7 is connected to the inlet of the product three-in-one treatment reactor 8.

[0103] The product three-in-one treatment reactor 8 also has washing, filtering and drying functions and is provided with an interface connected to a vacuum system.

[0104] The solid material outlet of the product three-in-one treatment reactor 8 obtains the final product MCS, and the liquid material (washing liquid) discharged from the product three-in-one treatment reactor 8 is transported to a subsequent process for solvent recovery.

[0105] The device further comprises a solvent recovery reactor, and all evaporated solvents are transported to the solvent recovery reactor for centralized treatment and recycling.

[0106] As shown in Figure 1 An embodiment of the present application also provides a production method of mannitol carbonic sulfuric ester, which is produced by using the above device and is suitable for preparing MCS by using mannitol carbonate (MC) as the main raw material. The specific process flow is as follows:

[0107] 1. Sulfurylation reaction process

[0108] MC, solvent I and thionyl chloride are put into the sulfurylation reactor 1 at a mass ratio of 1:5:1.2, and sulfurylation reaction is carried out under the condition of 40℃ for 48 hours.

[0109] After the reaction is completed, the excess thionyl chloride is evaporated from the top of the reactor and recycled.

[0110] The main product of the reaction is intermediate D (mannitol chlorosulfite) :

[0111]

[0112] By-product d is easily soluble in water due to its two hydrophilic hydroxyl groups, and can be effectively removed by subsequent water washing. By-product d is shown in the following figure:

[0113]

[0114] Preferably, the solvent one is selected from dichloromethane.

[0115] After the reaction is completed, the material is transferred to a solvent evaporation kettle D2, and the solvent one is evaporated at 40°C. The recovered solvent can be recycled.

[0116] After the solvent one is evaporated, the solid material is transferred to an intermediate three-in-one processing kettle 3 for water washing, filtration and drying treatment.

[0117] During the water washing process, the amount of water added is 5 times the mass of intermediate D. After adding water, stirring is performed for 4 hours to fully remove water-soluble impurities (such as by-product d and residual salts). Subsequently, filtration is performed, and the filter cake is retained for subsequent reactions, and the filtrate is discharged as waste water into the subsequent treatment section.

[0118] The filter cake is dried under vacuum conditions, and the drying temperature is 50°C, and the system pressure is controlled at 5 kPa (A). After drying is completed, the obtained pure intermediate D is transported to an oxidation reaction kettle 4 for the next step of oxidation reaction.

[0119] 2. Oxidation reaction process

[0120] Intermediate D from the previous step, solvent two, and catalyst are added to the oxidation reaction kettle 4 in a mass ratio of 1:5:0.001, and stirring and dispersion are performed for 0.5-1 hours to ensure uniform mixing of the materials. Subsequently, the oxidizing agent is slowly added, and the mass ratio of intermediate D to oxidizing agent is 1:5, and the oxidation reaction is started.

[0121] The reaction temperature is controlled at 5°C, and the reaction time is maintained for 5 hours. During the reaction, the temperature is adjusted through a jacket or a half pipe to ensure smooth reaction.

[0122] The main product of the oxidation reaction is mannitol carbonate sulfite (MCS) :

[0123]

[0124] After the reaction is completed, the system contains the target product MCS, unreacted solvent, catalyst, and a small amount of by-products. The main by-product is e:

[0125]

[0126] The solvent two is selected from ethyl acetate, which has good solubility and process compatibility.

[0127] The catalyst is a titanium-silicon molecular sieve. The catalyst has high catalytic activity and selectivity, is easy to recover and regenerate, and can be recycled.

[0128] The oxidizing agent is hydrogen peroxide, which has mild reaction and good controllability, and is conducive to improving the selectivity and yield of the product.

[0129] After the oxidation reaction is completed, the reaction liquid is subjected to solid-liquid separation through a filter (preferably a basket filter):

[0130] The solid component is the catalyst, which can be recycled after treatment; the liquid phase is transported to a phase separation kettle 5 for oil-water separation.

[0131] During the phase separation, the water phase contains a large amount of inorganic salt (mainly sodium chloride), and has a high density, so it is located in the lower layer; the organic phase (oil phase) has a small density, and is located in the upper layer. In order to achieve accurate separation, an online conductivity monitoring device is arranged at the water phase outlet of the phase separation kettle, and is interlocked with the cut-off valves at the oil phase and water phase outlets.

[0132] The conductivity of the water phase is relatively high, about 50-200 S / m, and the conductivity of the oil phase is relatively low, about 10-50 mS / m. During the separation, the water phase cut-off valve is first opened, and the high-conductivity salt water phase is discharged from the bottom and sent to the subsequent wastewater treatment process. When the conductivity of the water phase outlet is reduced to below 100 mS / m, the system automatically determines that the oil-water interface has approached the outlet, and then the water phase valve is closed and the oil phase valve is opened, so that the organic phase (containing MCS) is transported to a dehydration tank 6 for dehydration treatment.

[0133] The dehydration tank 6 is provided with 5A molecular sieve, which can effectively remove the trace amount of water in the organic phase.

[0134] The dehydrated oil phase material is transferred to a solvent evaporation kettle E7, which is subjected to reduced pressure distillation at 80°C to recover the solvent two. The recovered solvent can be recycled in the oxidation process.

[0135] The residual solid enters a product three-in-one treatment kettle 8, which is subjected to purification treatment using dichloromethane as a washing agent. The amount of the washing agent is 5 times the mass of the solid material. After the material is added, it is stirred for 4 hours to sufficiently wash and remove the residual impurities, and then filtration is performed.

[0136] The filter cake is dried under vacuum conditions, and the drying temperature is 50°C, and the system pressure is controlled at 20 kPa (A). After the drying is completed, the obtained solid is the high-purity target product, i.e., mannitol carbonate sulfate (MCS).

[0137] The organic mother liquor such as washing liquid and distillation condensate is uniformly transported to a solvent recovery system, and is realized resource utilization after treatment.

[0138] The quality index of the MCS product prepared by the process is as follows:

[0139] The total yield is 92.1%, and the purity is 99.51% (determined by HPLC). It is shown that the method has the advantages of high yield, high purity and good process stability, and is suitable for large-scale production of high-quality MCS.

[0140] Example 2

[0141] As shown in Figure 1 Fig. 1, a device for producing mannitol carbonic acid sulfate provided by one embodiment of the present application comprises a sulfonylation reaction kettle 1, a solvent evaporation kettle D 2, an intermediate product three-in-one treatment kettle 3, an oxidation reaction kettle 4, a phase separation kettle 5, a dehydration tank 6, a solvent evaporation kettle E 7 and a product three-in-one treatment kettle 8.

[0142] The feeding port of the sulfonylation reaction kettle 1 is used for adding thionyl chloride, mannitol carbonate (MC) and solvent one; the sulfonylation reaction kettle 1 is provided with a stirrer, and is connected with a reaction condenser and a reflux tank, wherein the condenser is provided with a non-condensable gas discharge port.

[0143] The discharging port of the sulfonylation reaction kettle 1 is connected with a feeding port of the solvent evaporation kettle D 2; the solvent evaporation kettle D 2 is provided with a stirrer, and is provided with a condensing device; the solvent evaporation kettle D 2 is used for evaporating and recovering the excessive thionyl chloride and solvent one in the reaction.

[0144] The discharging port of the solvent evaporation kettle D 2 is connected with a feeding port of the intermediate product three-in-one treatment kettle 3; the intermediate product three-in-one treatment kettle 3 has the functions of washing, filtering and drying integration, wherein one interface is connected with a vacuum system, and is used for pressure reduction operation in the drying process.

[0145] The solid material outlet of the intermediate product three-in-one treatment kettle 3 is connected with the feeding port of the oxidation reaction kettle 4, and the liquid material outlet of the intermediate product three-in-one treatment kettle 3 is connected with a subsequent treatment process.

[0146] The oxidation reaction kettle 4 is provided with a stirrer, and is provided with a jacket or a semi-tube heat exchange structure, which is used for heating or cooling control in the reaction process.

[0147] The discharging port of the oxidation reaction kettle 4 is connected with the feeding port of the phase separation kettle 5 through a filter (preferably a basket filter), which is used for separation and recovery of the catalyst.

[0148] The oil phase outlet of the phase separation kettle 5 is also connected with the inlet of the dehydration tank 6, and the outlet of the dehydration tank 6 is connected with a feeding port of the solvent evaporation kettle E 7.

[0149] The bottom of the phase separation kettle 5 is provided with a water phase outlet and an oil phase outlet (the oil phase inlet is located at the upper part or the middle part), the water phase outlet is configured with an online conductivity monitoring system, and is connected with the shut-off valves of the oil phase outlet and the water phase outlet to realize interlocking control and automatic liquid separation.

[0150] The oil phase separated by the phase separation kettle 5 is transported to the dehydration tank 6, and the water phase is discharged into a subsequent treatment section as salt-containing wastewater.

[0151] The dehydration tank 6 is internally provided with 5A type molecular sieves for deeply removing trace water in the oil phase.

[0152] The solvent evaporation kettle E7 is provided with a stirrer and a condensing device.

[0153] The solid material outlet of the solvent evaporation kettle E7 is connected with the feed inlet of the product three-in-one treatment kettle 8.

[0154] The product three-in-one treatment kettle 8 also has washing, filtering and drying functions, and is provided with an interface connected with a vacuum system.

[0155] The solid material outlet of the product three-in-one treatment kettle 8 obtains the final product MCS, and the liquid material (washing liquid) discharged from the product three-in-one treatment kettle 8 is transported to a subsequent process for solvent recovery.

[0156] The device further comprises a solvent recovery kettle, and all evaporated solvents are transported to the solvent recovery kettle for centralized treatment and recycling.

[0157] As shown in Figure 1 An embodiment of the present application further provides a production method of mannitol carbonic sulfuric ester, which is produced by using the above device and is suitable for preparing MCS by taking mannitol carbonate (MC) as a main raw material. The specific process flow is as follows:

[0158] 1. Sulfurylation reaction process

[0159] MC, solvent I and thionyl chloride are put into the sulfurylation reaction kettle 1 according to a mass ratio of 1:10:1.5, and sulfurylation reaction is carried out under the condition of 60℃ and stirring for 20 hours.

[0160] After the reaction is completed, the excessive thionyl chloride is evaporated from the top of the reaction kettle and recycled.

[0161] The main product generated in the reaction is the intermediate D (mannitol carbonic chlorosulfite):

[0162]

[0163] The by-product d is easily dissolved in water due to containing two hydrophilic hydroxyl groups, and can be effectively removed through subsequent water washing. The by-product d is shown in the following figure:

[0164]

[0165] Preferably, the solvent one is selected from dimethyl carbonate (DMC).

[0166] After the reaction is completed, the material is transferred to a solvent evaporation kettle D2, and the solvent one is evaporated at 80°C. The recovered solvent can be recycled.

[0167] After the solvent one is evaporated, the solid material is transferred to an intermediate three-in-one processing kettle 3 for water washing, filtration, and drying treatment.

[0168] During the water washing process, the amount of water added is 8 times the mass of the intermediate D. After adding water, stirring is performed for 2 hours to fully remove water-soluble impurities (such as byproduct d and residual salts). Subsequently, filtration is performed, and the filter cake is retained for subsequent reactions, and the filtrate is discharged as waste water into the subsequent treatment section.

[0169] The filter cake is dried under vacuum conditions, with a drying temperature of 60°C and a system pressure controlled at 10 kPa (A). After drying is completed, the obtained pure intermediate D is transported to an oxidation reaction kettle 4 for the next step of oxidation reaction.

[0170] 2. Oxidation reaction process

[0171] Intermediate D from the previous step, solvent two, and catalyst are added to the oxidation reaction kettle 4 in a mass ratio of 1:10:0.05, and stirring and dispersion are performed for 0.5-1 hours to ensure uniform mixing of the materials. Subsequently, the oxidizing agent is slowly added, and the mass ratio of intermediate D to oxidizing agent is 1:8, and the oxidation reaction is started.

[0172] The reaction temperature is controlled at 40°C, and the reaction time is maintained for 3 hours. During the reaction, temperature regulation is performed through a jacket or a half pipe to ensure smooth reaction.

[0173] The main product of the oxidation reaction is mannitol carbonate sulfate (MCS):

[0174]

[0175] After the reaction is completed, the system contains the target product MCS, unreacted solvent, catalyst, and a small amount of byproduct. The main byproduct is e:

[0176]

[0177] The solvent two is selected from dimethyl carbonate (DMC), which has good solubility and process compatibility.

[0178] The catalyst is ruthenium trichloride. This catalyst has high catalytic activity and selectivity, is easy to recover and regenerate, and can be recycled.

[0179] The oxidant is sodium hypochlorite solution with effective chlorine content of 10%, the reaction is mild and controllable, and is conducive to improving the selectivity and yield of the product.

[0180] After the completion of the oxidation reaction, the reaction liquid is subjected to solid-liquid separation through a filter (preferably a basket filter):

[0181] The solid component is a catalyst, which can be recycled after treatment; the liquid phase is transported to a phase separation kettle 5 for oil-water separation.

[0182] During the phase separation, the water phase containing a large amount of inorganic salt (mainly sodium chloride) has a relatively large density and is located in the lower layer; the organic phase (oil phase) has a relatively small density and is located in the upper layer. To achieve accurate separation, an online conductivity monitoring device is arranged at the water phase outlet of the phase separation kettle, and is interlocked with the shut-off valves at the oil phase and water phase outlets for control.

[0183] The conductivity of the water phase is relatively high, about 50-200 S / m, while the conductivity of the oil phase is relatively low, about 10-50 mS / m. During the separation, the water phase shut-off valve is first opened to discharge the high-conductivity salt water phase from the bottom to the subsequent wastewater treatment process. When the conductivity of the water phase outlet is reduced to below 100 mS / m, the system automatically determines that the oil-water interface has approached the outlet, and then closes the water phase valve and opens the oil phase valve to transport the organic phase (containing MCS) to a dehydration tank 6 for dehydration treatment.

[0184] The dehydration tank 6 is provided with 5A molecular sieve to effectively remove trace amounts of water in the organic phase.

[0185] The dehydrated oil phase material is transferred to a solvent evaporation kettle E7, which is subjected to reduced pressure distillation at 80°C to recover solvent II. The recovered solvent can be recycled for use in the oxidation process.

[0186] The residual solid is introduced into a product three-in-one treatment kettle 8, which is subjected to purification treatment using dichloromethane as a washing agent, and the amount of the washing agent is 8 times the mass of the solid material. After the addition, the mixture is stirred for 2 hours to sufficiently wash and remove residual impurities, and then is subjected to filtration.

[0187] The filter cake is dried under vacuum conditions, and the drying temperature is 70°C and the system pressure is controlled at 10 kPa (A). After the completion of the drying, the obtained solid is high-purity target product, i.e., mannitol carbonic sulfuric ester (MCS).

[0188] The organic mother liquor such as washing liquid and distillation condensate is uniformly transported to a solvent recovery system, which is treated to realize resource utilization.

[0189] The quality indicators of the MCS product prepared by the process are as follows:

[0190] Total yield: 97.1%; purity: 99.95% (determined by HPLC). The method has the advantages of high yield, high purity, good process stability, etc., and is suitable for large-scale production of high-quality MCS.

[0191] Example 3

[0192] As shown in the drawings, a device for producing mannitol carbonate sulfate provided by one embodiment of the application includes a sulfonylation reactor 1, a solvent evaporation reactor D 2, an intermediate product three-in-one treatment reactor 3, an oxidation reactor 4, a phase separation reactor 5, a dehydration tank 6, a solvent evaporation reactor E 7, and a product three-in-one treatment reactor 8. Figure 1 The feed inlet of the sulfonylation reactor 1 is used to add thionyl chloride, mannitol carbonate (MC), and solvent one. The sulfonylation reactor 1 is equipped with a stirrer and connected to a reaction condenser and a reflux tank, wherein the condenser is provided with a non-condensable gas discharge port.

[0193] The discharge outlet of the sulfonylation reactor 1 is connected to a feed inlet of the solvent evaporation reactor D 2. The solvent evaporation reactor D 2 is provided with a stirrer and equipped with a condensing device. The solvent evaporation reactor D 2 is used to evaporate and recover excess thionyl chloride and solvent one in the reaction.

[0194] The discharge outlet of the solvent evaporation reactor D 2 is connected to a feed inlet of the intermediate product three-in-one treatment reactor 3. The intermediate product three-in-one treatment reactor 3 has integrated functions of washing, filtering, and drying, wherein one interface is connected to a vacuum system for pressure reduction operation in the drying process.

[0195] The solid material outlet of the intermediate product three-in-one treatment reactor 3 is connected to the feed inlet of the oxidation reactor 4, and the liquid material outlet of the intermediate product three-in-one treatment reactor 3 discharges washing wastewater to a subsequent treatment process.

[0196] The oxidation reactor 4 is equipped with a stirrer and provided with a jacket or a semi-tube heat exchange structure for heating or cooling control during the reaction.

[0197] The discharge outlet of the oxidation reactor 4 is connected to the feed inlet of the phase separation reactor 5 through a filter (preferably a basket filter) for separation and recovery of the catalyst.

[0198] The oil phase outlet of the phase separation reactor 5 is also connected to the inlet of the dehydration tank 6, and the outlet of the dehydration tank 6 is connected to a feed inlet of the solvent evaporation reactor E 7.

[0199] The bottom of the phase separation reactor 5 is provided with a water phase outlet and an oil phase outlet (the oil phase inlet is located at the upper part or the middle part). The water phase outlet is configured with an online conductivity monitoring system and is interlocked with the shut-off valves of the oil phase and water phase outlets to realize automatic liquid separation.

[0200] ​

[0201] The oil phase separated from the phase separation kettle 5 is transported to a dehydration tank 6, and the water phase is discharged as salt-containing wastewater into a subsequent treatment section.

[0202] A 5A molecular sieve is installed in the dehydration tank 6 for deep removal of trace water in the oil phase.

[0203] The solvent evaporation kettle E7 is equipped with a stirrer and a condensing device.

[0204] The solid material outlet of the solvent evaporation kettle E7 is connected to the feed inlet of a product three-in-one treatment kettle 8.

[0205] The product three-in-one treatment kettle 8 also has washing, filtering and drying functions, and is provided with an interface connected to a vacuum system.

[0206] The solid material outlet of the product three-in-one treatment kettle 8 obtains the final product MCS, and the liquid material (washing liquid) discharged from the product three-in-one treatment kettle 8 is transported to a subsequent process for solvent recovery.

[0207] The device further comprises a solvent recovery kettle, and all evaporated solvents are transported to the solvent recovery kettle for centralized treatment and recycling.

[0208] As shown in Figure 1 An embodiment of the present application also provides a production method of mannitol carbonic sulfuric ester, which is produced by using the above device and is suitable for preparing MCS by using mannitol carbonate (MC) as a main raw material. The specific process flow is as follows:

[0209] 1. Sulfurylation reaction process

[0210] MC, solvent I and thionyl chloride are put into the sulfurylation reaction kettle 1 according to a mass ratio of 1:20:3, and sulfurylation reaction is performed under the condition of 70℃ and stirring for 48 hours.

[0211] After the reaction is completed, the excessive thionyl chloride is evaporated from the top of the reaction kettle and recycled.

[0212] The main product generated in the reaction is the intermediate D (mannitol carbonic chlorosulfinic ester):

[0213]

[0214] The by-product d is easily dissolved in water due to containing two hydrophilic hydroxyl groups, and can be effectively removed through subsequent water washing. The by-product d is shown in the following figure:

[0215]

[0216] Preferably, the solvent I is selected from dimethyl carbonate (DMC).

[0217] The reaction completed material is transferred to solvent evaporation kettle D2, and solvent 1 is evaporated at 90°C. The recovered solvent can be recycled.

[0218] The solid material after evaporation of solvent 1 is transferred to the intermediate three-in-one processing kettle 3 for water washing, filtration and drying treatment.

[0219] During the water washing process, the amount of water added is 10 times the mass of the intermediate D. After adding water, stirring is performed for 4 hours to fully remove water-soluble impurities (such as byproduct d and residual salts). Subsequently, filtration is performed, and the filter cake is retained for subsequent reactions, and the filtrate is discharged as waste water into the subsequent treatment section.

[0220] The filter cake is dried under vacuum conditions, and the drying temperature is 80°C, and the system pressure is controlled at 1 kPa (A). After drying is completed, the obtained pure intermediate D is transported to the oxidation reaction kettle 4 for the next step of oxidation reaction.

[0221] 2. Oxidation reaction process

[0222] Intermediate D from the previous step, solvent 2, and catalyst are added to the oxidation reaction kettle 4 in a mass ratio of 1:20:0.05, and stirring and dispersion are performed for 0.5-1 hours to ensure uniform mixing of the materials. Subsequently, the oxidizing agent is slowly added, and the mass ratio of intermediate D to oxidizing agent is 1:10, and the oxidation reaction is started.

[0223] The reaction temperature is controlled at 50°C, and the reaction time is maintained for 2 hours. During the reaction, temperature regulation is performed through a jacket or a half pipe to ensure smooth reaction.

[0224] The main product of the oxidation reaction is mannitol carbon sulfate (MCS):

[0225]

[0226] After the reaction is completed, the system contains the target product MCS, unreacted solvent, catalyst, and a small amount of byproduct. The main byproduct is e:

[0227]

[0228] The solvent 2 is selected from dimethyl carbonate (DMC), which has good solubility and process compatibility.

[0229] The catalyst is a titanium-silicon molecular sieve. The catalyst has high catalytic activity and selectivity, is easy to recover and regenerate, and can be recycled.

[0230] The oxidizing agent is a sodium hypochlorite solution with an effective chlorine content of 10%, which is mild and controllable, and is conducive to improving the selectivity and yield of the product.

[0231] After the oxidation reaction is completed, the reaction liquid is subjected to solid-liquid separation through a filter (preferably a basket filter):

[0232] The solid component is a catalyst, which can be recycled after treatment; the liquid phase is transported to a phase separation kettle 5 for oil-water separation.

[0233] In the phase separation process, the water phase contains a large amount of inorganic salt (mainly sodium chloride), and has a relatively large density, so it is located in the lower layer; the organic phase (oil phase) has a relatively small density, and is located in the upper layer. To achieve accurate separation, an online conductivity monitoring device is arranged at the water phase outlet of the phase separation kettle, and is interlocked with the shut-off valves at the oil phase and water phase outlets for control.

[0234] The water phase has a relatively high conductivity of about 50-200 S / m, while the oil phase has a relatively low conductivity of about 10-50 mS / m. During separation, the water phase shut-off valve is first opened, and the high-conductivity salt water phase is discharged from the bottom and sent to a subsequent wastewater treatment process. When the conductivity at the water phase outlet is reduced to below 100 mS / m, the system automatically determines that the oil-water interface has approached the outlet, and then closes the water phase valve and opens the oil phase valve, so that the organic phase (containing MCS) is transported to a dehydration tank 6 for dehydration treatment.

[0235] The dehydration tank 6 is provided with 5A molecular sieves, which can effectively remove trace amounts of water in the organic phase.

[0236] The dehydrated oil phase material is transferred to a solvent evaporation kettle E7, which is subjected to reduced pressure distillation at 90°C to recover solvent II. The recovered solvent can be recycled for use in the oxidation process.

[0237] The residual solid is introduced into a product three-in-one treatment kettle 8, which is subjected to purification treatment using dichloromethane as a washing agent. The amount of washing agent is 10 times the mass of the solid material. After the material is added, stirring is performed for 4 hours to sufficiently wash and remove residual impurities, and then filtration is performed.

[0238] The filter cake is dried under vacuum conditions, and the drying temperature is 80°C, and the system pressure is controlled at 20 kPa (A). After drying is completed, the obtained solid is high-purity target product, i.e., mannitol carbonate sulfate (MCS).

[0239] The washing liquid and distillation condensate and other organic mother liquor are uniformly transported to a solvent recovery system, which is subjected to treatment to realize resource utilization.

[0240] The quality indicators of the MCS product prepared by the process are as follows:

[0241] The total yield is 95.5%, and the purity is 99.95% (determined by HPLC). It is shown that the method has the advantages of high yield, high purity, good process stability, and the like, and is suitable for large-scale production of high-quality MCS.

[0242] Example 4

[0243] As Figure 1 shown in the figure, a device for producing mannitol carbonate sulfate according to an embodiment of the present application comprises a sulfonylation reactor 1, a solvent evaporation reactor D 2, an intermediate product three-in-one treatment reactor 3, an oxidation reactor 4, a phase separation reactor 5, a dehydration tank 6, a solvent evaporation reactor E 7, and a product three-in-one treatment reactor 8.

[0244] The feed inlet of the sulfonylation reactor 1 is used to add thionyl chloride, mannitol carbonate (MC), and solvent one; the sulfonylation reactor 1 is equipped with a stirrer and connected to a reaction condenser and a reflux tank, wherein the condenser is provided with a non-condensable gas discharge port.

[0245] The discharge outlet of the sulfonylation reactor 1 is connected to a feed inlet of the solvent evaporation reactor D 2; the solvent evaporation reactor D 2 is provided with a stirrer and equipped with a condensing device, and the solvent evaporation reactor D 2 is used to evaporate and recover excess thionyl chloride and solvent one in the reaction.

[0246] The discharge outlet of the solvent evaporation reactor D 2 is connected to a feed inlet of the intermediate product three-in-one treatment reactor 3; the intermediate product three-in-one treatment reactor 3 has integrated functions of washing, filtering, and drying, and one interface is connected to a vacuum system for pressure reduction operation during the drying process.

[0247] The solid material outlet of the intermediate product three-in-one treatment reactor 3 is connected to the feed inlet of the oxidation reactor 4, and the liquid material outlet of the intermediate product three-in-one treatment reactor 3 discharges washing wastewater to a subsequent treatment process.

[0248] The oxidation reactor 4 is equipped with a stirrer and provided with a jacket or a semi-tube heat exchange structure for heating or cooling control during the reaction.

[0249] The discharge outlet of the oxidation reactor 4 is connected to the feed inlet of the phase separation reactor 5 through a filter (preferably a basket filter) for separation and recovery of the catalyst.

[0250] The oil phase outlet of the phase separation reactor 5 is also connected to the inlet of the dehydration tank 6, and the outlet of the dehydration tank 6 is connected to a feed inlet of the solvent evaporation reactor E 7.

[0251] The phase separation reactor 5 is provided with a water phase outlet and an oil phase outlet (the oil phase inlet is located at the upper part or the middle part), the water phase outlet is configured with an online conductivity monitoring system, and is connected to the shut-off valves of the oil phase and water phase outlets to realize interlocking control and automatic separation.

[0252] The oil phase separated by the phase separation reactor 5 is transported to the dehydration tank 6, and the water phase is discharged as salt-containing wastewater to a subsequent treatment section.

[0253] The dehydration tank 6 is installed with 5A molecular sieves for deep removal of trace water in the oil phase.

[0254] The solvent evaporation kettle E7 is equipped with a stirrer and a condensing device.

[0255] The solid material outlet of the solvent evaporation kettle E7 is connected with the feed inlet of the product three-in-one processing kettle 8.

[0256] The product three-in-one processing kettle 8 also has washing, filtering and drying functions, and is provided with an interface connected with a vacuum system.

[0257] The solid material outlet of the product three-in-one processing kettle 8 obtains the final product MCS, and the liquid material (washing liquid) discharged from the product three-in-one processing kettle 8 is transported to a subsequent process for solvent recovery.

[0258] The device further comprises a solvent recovery kettle, and all evaporated solvents are transported to the solvent recovery kettle for centralized treatment and recycling.

[0259] As shown in Figure 1 An embodiment of the present application further provides a production method of mannitol carbonic sulfuric ester, which is produced by using the above device and is suitable for preparing MCS by taking mannitol carbonate (MC) as a main raw material. The specific process flow is as follows:

[0260] 1. Sulfurylating reaction process

[0261] MC, solvent I and thionyl chloride are put into the sulfurylating reaction kettle 1 according to a mass ratio of 1:15:2, and sulfurylating reaction is carried out under the condition of 50℃ and stirring for 48 hours.

[0262] After the reaction is completed, the excessive thionyl chloride is evaporated from the top of the reaction kettle and recycled.

[0263] The main product generated in the reaction is intermediate D (mannitol carbonic chlorosulfite):

[0264]

[0265] The by-product d is easily dissolved in water due to containing two hydrophilic hydroxyl groups, and can be effectively removed through subsequent water washing. The by-product d is shown in the following figure:

[0266]

[0267] Preferably, the solvent I is selected from dimethyl carbonate (DMC).

[0268] After the reaction is completed, the material is transferred to the solvent evaporation kettle D2, and the solvent I is evaporated at 70℃. The recycled solvent can be recycled.

[0269] After the solvent I is evaporated, the solid material is transferred to the intermediate three-in-one processing kettle 3 for water washing, filtering and drying treatment.

[0270] During the water washing process, the amount of water added is 9 times the mass of intermediate D. After adding water, stirring is performed for 3 hours to ensure that water-soluble impurities (such as byproduct d and residual salts) are fully removed. Subsequently, a filtration operation is performed, and the filter cake is retained for use in subsequent reactions, and the filtrate is discharged as waste water to a subsequent treatment section.

[0271] The filter cake is dried under vacuum conditions, with a drying temperature of 60°C and a system pressure controlled at 5 kPa (A). After drying is completed, the obtained pure intermediate D is transported to the oxidation reaction kettle 4 for use in the next step of the oxidation reaction.

[0272] 2. Oxidation reaction process

[0273] Intermediate D from the previous step, solvent II, and catalyst are added to the oxidation reaction kettle 4 in a mass ratio of 1:15:0.001, and stirring is performed for 0.5-1 hours to ensure uniform mixing of the materials. Subsequently, the oxidizing agent is slowly added, and the mass ratio of intermediate D to oxidizing agent is 1:6, and the oxidation reaction is started.

[0274] The reaction temperature is controlled at 10°C, and the reaction time is maintained for 5 hours. During the reaction, temperature control is performed through a jacket or half-pipe to ensure smooth progress of the reaction.

[0275] The main product of the oxidation reaction is mannitol carbonic sulfuric ester (MCS):

[0276]

[0277] After the reaction is completed, the system contains the target product MCS, unreacted solvent, catalyst, and a small amount of byproducts. The main byproduct is e:

[0278]

[0279] The solvent II is selected from ethyl acetate, which has good solubility and process compatibility.

[0280] The catalyst is ruthenium trichloride. This catalyst has high catalytic activity and selectivity, and is easy to recover and regenerate, and can be recycled.

[0281] The oxidizing agent is a sodium hypochlorite solution with an effective chlorine content of 10%, which is mild and has good controllability, and is conducive to improving the selectivity and yield of the product.

[0282] After the oxidation reaction is completed, the reaction liquid is subjected to solid-liquid separation through a filter (preferably a basket filter):

[0283] The solid component is the catalyst, which can be recycled after treatment; the liquid phase is transported to the phase separation kettle 5 for oil-water separation.

[0284] In the phase separation process, the water phase contains a large amount of inorganic salt (mainly sodium chloride), and has a large density, so it is located in the lower layer; the organic phase (oil phase) has a small density, and is located in the upper layer. In order to realize accurate separation, an online conductivity monitoring device is arranged at the water phase outlet of the phase separation kettle, and is interlocked with the cut-off valves at the oil phase and water phase outlets for control.

[0285] The conductivity of the water phase is relatively high, about 50-200 S / m, and the conductivity of the oil phase is relatively low, about 10-50 mS / m. In the separation process, first, the water phase cut-off valve is opened, and the high-conductivity salt water phase is discharged from the bottom and sent to the subsequent wastewater treatment process. When the conductivity of the water phase outlet is reduced to below 100 mS / m, the system automatically determines that the oil-water interface is close to the outlet, and then the water phase valve is closed and the oil phase valve is opened, so that the organic phase (containing MCS) is transported to the dehydration tank 6 for dehydration treatment.

[0286] The dehydration tank 6 is provided with 5A type molecular sieve, which can effectively remove the trace amount of water in the organic phase.

[0287] The dehydrated oil phase material is transferred to the solvent evaporation kettle E7, and is subjected to reduced pressure distillation at 80 DEG C, so that the solvent II is recovered. The recovered solvent can be recycled in the oxidation process.

[0288] The residual solid enters the product three-in-one treatment kettle 8, and is subjected to purification treatment by using dichloromethane as a washing agent. The amount of the washing agent is 8 times the mass of the solid material. After the material is added, stirring is performed for 2 hours, so that the residual impurities are removed, and then filtration is performed.

[0289] The filter cake is dried under vacuum condition, the drying temperature is 60 DEG C, and the system pressure is controlled at 15 kPa (A). After the drying is completed, the obtained solid is high-purity target product, i.e., mannitol carbonate sulfate (MCS).

[0290] The washing liquid and distillation condensate and other organic mother liquor are uniformly transported to a solvent recovery system, and are subjected to treatment, so that resource utilization is realized.

[0291] The quality indexes of the MCS product prepared by the process are as follows:

[0292] The total yield is 96.3%, and the purity is 99.78% (determined by HPLC). It is shown that the method has the advantages of high yield, high purity and good process stability, and is suitable for large-scale production of high-quality MCS.

[0293] The production device and method of mannitol carbonate sulfate provided in the above embodiments of the application have the following main advantages:

[0294] 1) The first complete device suitable for large-scale production of mannitol carbonate sulfate (MCS) is constructed. The device has simple overall structure, low equipment investment, convenient operation, high automation, and is easy to realize continuous and industrial operation, filling the technical gap of MCS in the field of production equipment.

[0295] 2) Efficient recovery and recycling of solvents is achieved. The solvents used in sulfonylation and oxidation reactions can be recovered by distillation and reused, significantly reducing raw material consumption and production cost; at the same time, the reaction conditions are mild (room temperature to moderate temperature), the energy consumption is low, and the process safety is high, which meets the production concept of green and low carbon.

[0296] 3) The process is simple and efficient, and the product yield and purity are excellent. The two-step synthesis route is adopted, the equipment utilization rate is high, the material loss is small, and the whole process operation is continuous and stable. The conversion rate of mannitol carbonate (MC) is high, the total yield of the target product MCS is more than 92%, the purity is higher than 99.5%, and the product quality meets the application requirements of high-end lithium battery materials.

[0297] Although some specific embodiments of the present application have been described in detail through examples, those skilled in the art should understand that the above examples are only for illustration, not for limiting the scope of the present application. Those skilled in the art should understand that the above embodiments can be modified without departing from the scope and spirit of the present application. The scope of the present application is defined by the appended claims.

Claims

1. A device for producing mannitol carbonic sulfuric ester, comprising a sulfonylation reactor (1), a solvent evaporation reactor D (2), an intermediate product three-in-one treatment reactor (3), an oxidation reactor (4), a phase separation reactor (5), a dehydration tank (6), a solvent evaporation reactor E (7), and a product three-in-one treatment reactor (8), characterized in that: a feeding port of the sulfonylation reactor (1) is used for adding thionyl chloride, mannitol carbonate, and solvent I; the sulfonylation reactor (1) is provided with a stirrer, and is connected with a reaction condenser and a reflux tank; and a discharging port of the sulfonylation reactor (1) is connected with a feeding port of the solvent evaporation reactor D (2); the solvent evaporation reactor D (2) is provided with a condensing device, which is used for evaporating and recycling excess thionyl chloride and solvent I in the reaction; a discharging port of the solvent evaporation reactor D (2) is connected with a feeding port of the intermediate product three-in-one treatment reactor (3); the intermediate product three-in-one treatment reactor (3) has integrated functions of washing, filtering, and drying, and is provided with an interface connected with a vacuum system; a solid material outlet of the intermediate product three-in-one treatment reactor (3) is connected with a feeding port of the oxidation reactor (4); the oxidation reactor (4) is provided with a stirrer and a heat exchange structure, which is used for controlling the reaction temperature; a discharging port of the oxidation reactor (4) is connected with a feeding port of the phase separation reactor (5); the phase separation reactor (5) is provided with a water phase outlet and an oil phase outlet at the bottom; an oil phase outlet of the phase separation reactor (5) is connected with an inlet of the dehydration tank (6); the dehydration tank (6) is provided with a dehydration molecular sieve; an outlet of the dehydration tank (6) is connected with a feeding port of the solvent evaporation reactor E (7); the solvent evaporation reactor E (7) is provided with a stirrer and a condensing device; a solid material outlet of the solvent evaporation reactor E (7) is connected with a feeding port of the product three-in-one treatment reactor (8); the product three-in-one treatment reactor (8) has functions of washing, filtering, and drying, and is provided with an interface connected with a vacuum system; and a solid material outlet of the product three-in-one treatment reactor (8) is used for outputting a mannitol carbonic sulfuric ester product. An incondensable gas discharge port is arranged on the reaction condenser connected with the sulfonylation reactor (1); the solvent evaporation reactor D (2) is also provided with a stirrer, which is used for stirring and dispersing the materials; the vacuum system connected with the intermediate product three-in-one treatment reactor (3) is used for pressure reduction operation in the drying process; and the washing wastewater discharged from a liquid material outlet of the intermediate product three-in-one treatment reactor (3) is transported to a subsequent treatment process; the heat exchange structure of the oxidation reactor (4) is a jacket or a half-pipe heat exchange structure, which is used for heating or cooling in the reaction process; the water phase outlet of the phase separation reactor (5) is configured with an online conductivity monitoring system, which is interlocked with the cut-off valves of the oil phase outlet and the water phase outlet; the oil phase inlet of the phase separation reactor (5) is located at the upper part or the middle part of the phase separation reactor (5); and the water phase discharged from the water phase outlet of the phase separation reactor (5) is discharged into a subsequent treatment section as salt-containing wastewater; and the dehydration molecular sieve in the dehydration tank (6) is a 4A molecular sieve or a 5A molecular sieve, which is used for deeply removing trace water in the oil phase. ​ ​ ​ ​ ​ ​ ​ 2. The apparatus for producing mannitol carbonic acid sulfate according to claim 1, characterized by, ​ ​ ​ ​ 3. The apparatus for producing mannitol carbonic acid sulfate ester according to claim 2, characterized by, ​ ​ 4. The apparatus for producing mannitol carbonic acid sulfate ester according to claim 3, characterized by, ​ The liquid material discharged from the product three-in-one processing kettle (8) is a washing liquid, which is transported to a subsequent process for solvent recovery.

5. The apparatus for producing mannitol carbonic acid sulfate according to claim 4, wherein The discharge port of the oxidation kettle (4) is connected with the feed port of the phase separation kettle (5) through a filter, which is a basket filter, used for separation and recovery of the catalyst, and the separated catalyst can be recycled after treatment.

6. The apparatus for producing mannitol carbonic acid sulfate ester according to claim 5, characterized by, A solvent recovery kettle is further included, and all the evaporated solvents are transported to the solvent recovery kettle for centralized treatment and recycling.

7. A method for producing mannitol carbonate sulfate using the apparatus for producing mannitol carbonate sulfate according to any one of claims 1 to 6, characterized by, The method comprises the following steps: 1) Sulfurylation reaction process: mannitol carbonate, solvent I and thionyl chloride are put into a sulfurylation reaction kettle (1) according to a mass ratio of 1:(5-20):(1.2-3), and stirred and reacted at 40-70℃ for 4-48 hours; after the reaction is completed, the excessive thionyl chloride is evaporated and recovered, the material is transferred to a solvent evaporation kettle D (2), and solvent I is evaporated at 40-90℃; the recovered solvent I is recycled; the solid material after evaporation of solvent I is transferred to an intermediate product three-in-one processing kettle (3) for water washing, filtration and drying treatment, to obtain pure intermediate D; 2) Oxidation reaction process: intermediate D, solvent II and catalyst are added into an oxidation kettle (4) according to a mass ratio of 1:(5-20):(0.001-0.05), stirred and dispersed for 0.5-1 hour, and then an oxidizing agent is slowly added, and the mass ratio of intermediate D to the oxidizing agent is 1:(5-10), and the reaction is stirred at 5-50℃ for 1-5 hours; after the reaction is completed, the reaction liquid is subjected to solid-liquid separation through a filter, the separated catalyst is recycled, and the liquid phase is transported to a phase separation kettle (5) for oil-water separation; the oil phase after phase separation is transported to a dehydration tank (6) for dehydration, the dehydrated oil phase is transferred to a solvent evaporation kettle E (7), and solvent II is recovered by distillation under reduced pressure at 40-90℃; the recovered solvent II is recycled; the residual solid is transferred to a product three-in-one processing kettle (8) for washing, filtration and drying treatment, to obtain mannitol carbonate sulfate product, and the total yield of mannitol carbonate sulfate is greater than 92%, and the purity is greater than 99.5%.

8. The method for producing mannitol carbonic acid sulfate ester according to claim 7, characterized by, The solvent I in step 1) is selected from one or more of ethyl acetate, acetonitrile, dimethyl carbonate and dichloromethane; The water washing process is as follows: water is added in an amount of 5-10 times the mass of intermediate D, and stirred for 1-4 hours after adding water, so that water-soluble impurities are fully removed, the water-soluble impurities including by-product d and residual salts, and the structure of the by-product d is a compound containing two hydrophilic hydroxyl groups; The drying treatment conditions are as follows: the drying temperature is 50-80℃, and the system pressure is controlled at 1-20 kPa (A), and the vacuum system connected with the intermediate product three-in-one processing kettle (3) is used for reducing pressure drying.

9. The method for producing mannitol carbonic acid sulfate ester according to claim 8, characterized by, The solvent II in step 2) is selected from one or more of ethyl acetate, acetonitrile, dimethyl carbonate and dichloromethane; The catalyst is titanium-silicon molecular sieve or ruthenium trichloride; The oxidizing agent is sodium hypochlorite aqueous solution or hydrogen peroxide, and when the oxidizing agent is sodium hypochlorite aqueous solution, the effective chlorine content is 10%. The water phase conductivity is 50-200 S / m and the oil phase conductivity is 10-50 mS / m when the phase separation kettle (5) separates oil and water; the water phase cut-off valve is opened to discharge the water phase at the initial stage of separation, and the water phase valve is closed and the oil phase valve is opened to discharge the oil phase when the water phase outlet conductivity is reduced to below 100 mS / m; The dehydration tank (6) is provided with 4A molecular sieve or 5A molecular sieve, and trace water in the dehydrated oil phase is deeply removed; The washing process of the product three-in-one treatment kettle (8) is as follows: dichloromethane is used as a washing agent, the washing agent is used in an amount of 5-10 times the mass of the solid material, and stirring is performed for 1-4 hours after feeding to sufficiently wash and remove residual impurities; The drying process conditions of the product three-in-one treatment kettle (8) are as follows: the drying temperature is 50-80 DEG C, the system pressure is controlled to be 1-20 kPa (A), and vacuum drying is realized through the vacuum system connected to the product three-in-one treatment kettle (8).

10. The method for producing mannitol carbonic acid sulfate ester according to claim 9, characterized by, The intermediate D generated in the sulfonylation reaction in step 1) is mannitol chlorosulfite carbonate; The main product generated in the oxidation reaction in step 2) is mannitol sulfate carbonate, and the by-product is by-product e, which is a compound containing a specific structure, and the organic mother liquor such as washing liquid and distillation condensate is uniformly transported to a solvent recovery system and is realized resource utilization after treatment.

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