Solid acid-binding agent as well as preparation method and application thereof

Abstract

The invention provides a solid acid-binding agent as well as a preparation method and application thereof. The structure of the solid acid-binding agent is shown in the specification. According to the prepared solid acid-binding agent, hydrogen chloride in the reaction can be removed without triethylamine, the subsequent processes of centrifugation, triethylamine recovery and the like are omitted, the solid acid-binding agent can be recycled, and the obvious cost advantage is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, in particular to a solid acid binding agent and a preparation method and application thereof. BACKGROUND

[0002] The current industrial production process of vinylene carbonate mainly adopts the triethylamine and chloroethylene carbonate route: CEC (chloroethylene carbonate) is removed of hydrogen chloride in a reaction kettle under the catalysis of triethylamine with DMC (dimethyl carbonate) as a solvent. The solution containing solid triethylamine hydrochloride is filtered by centrifugation, and then the solution is introduced into a desolventizing tower, a crude distillation tower, a rectification tower and a crystallizer to obtain qualified vinylene carbonate product. The triethylamine used as an acid binding agent has the problems of strong basicity in reaction, multiple side reactions and low product yield. Moreover, the recovery of the generated triethylamine hydrochloride needs to consume a large amount of liquid caustic for neutralization, generates waste brine, and the recovery process is complicated, high in cost and great in environmental protection pressure.

[0003] The current industrial route of vinylene carbonate has the following disadvantages: (1) the process route is complicated, involves the operation of various solid materials, cannot realize automatic and continuous production, and has high safety risk; (2) the overall reaction yield of the product is not high, a large amount of chlorine-containing solid hazardous waste, acid gas and tar are generated in the production process, the treatment cost is high, and the environmental protection pressure is great; (3) the vinylene carbonate synthesized by the route contains a large amount of by-products and chlorides, which makes the subsequent separation and purification difficult, and repeated rectification and crystallization are needed to reach a content of 99.995%. Therefore, the prior art needs to be further developed. SUMMARY

[0004] In view of the various deficiencies of the prior art, in order to solve the above problems, a solid acid binding agent and a preparation method and application thereof are provided. The following technical solutions are provided: The present application provides a solid acid binding agent, the structure of which is shown as follows: .

[0005] In addition, the present application also provides a preparation method of the solid acid binding agent, and the preparation steps are as follows: (1) first Mannich reaction: in an alcohol solution, add ethylenediamine and polyformaldehyde, control the pH value to be 1-3, react at 30-50 DEG C for 2-3 h, then increase the temperature to 60-90 DEG C, drop add aniline solution, after the drop addition is completed, heat for 14-16 h; (2) second Mannich reaction: after the first Mannich reaction, continue to add polyformaldehyde at a reduced temperature, control the pH value to be 1-3, react at 30-50 DEG C for 2-3 h, then increase the temperature to 60-90 DEG C, drop add aniline solution, after the drop addition is completed, heat for 14-16 h; (3) after the second Mannich reaction is completed, filter at a reduced temperature to obtain the solid acid binding agent.

[0006] Further, the molar ratio of the reaction raw material ethylenediamine, paraformaldehyde and aniline in the first Mannich reaction is 1: (2.3-2.5): 1.

[0007] Further, the pH value in the first Mannich reaction is controlled by using hydrochloric acid solution and is 1-3.

[0008] Further, in the first Mannich reaction, the dropping time of the aniline solution is 2-3h, and the solvent of the aniline solution is an alcohol solvent.

[0009] Further, the molar ratio of the reaction raw material ethylenediamine, paraformaldehyde and aniline in the first Mannich reaction is 1: (2.3-2.5): 1.

[0010] Further, the pH value in the first Mannich reaction is controlled by using hydrochloric acid solution and is 1-3.

[0011] Further, in the first Mannich reaction, the dropping time of the aniline solution is 2-3h, and the solvent of the aniline solution is an alcohol solvent.

[0012] The application also provides an application of the solid acid-binding agent, which is used to remove hydrogen chloride in the synthesis of vinylene carbonate to obtain vinylene carbonate.

[0013] Further, the solid acid-binding agent is filled into a filler tower after being pressed and crushed, and the vinyl chloride carbonate and diethyl carbonate are mixed and then punched into the filler tower to stay for 3-5min, and the solid acid-binding agent can be recycled by being treated at high temperature to release hydrogen chloride.

[0014] Beneficial effects: 1. The application prepares a new type of solid acid-binding agent, which can remove hydrogen chloride in the reaction without using triethylamine, so that subsequent processes such as centrifugation and triethylamine recovery are saved, and the solid acid-binding agent can be recycled by being treated at high temperature to release hydrogen chloride, which has obvious cost advantage.

[0015] 2. The use of the solid acid-binding agent in the synthesis of vinylene carbonate can reduce the side reaction in the synthesis of vinylene carbonate, increase the content of the reaction solution and reduce impurities, so that high-purity vinylene carbonate can be obtained through simple rectification, which is simple in operation, low in cost, and green and environmentally friendly. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is a reaction schematic diagram of the preparation of the solid acid-binding agent. DETAILED DESCRIPTION

[0017] In order for the personnel in the art to better understand the technical solutions of the present application, the technical solutions of the present application are clearly and completely described below in combination with the embodiments of the present application, and other similar embodiments obtained by the personnel in the art without creative labor on the basis of the embodiments in the present application shall all belong to the scope of protection of the present application.

[0018] According to the embodiments of the present application, a solid acid-binding agent is provided, and the structure is shown as follows: .

[0019] The present application prepares a new type of solid acid-binding agent, which can remove hydrogen chloride in the reaction without using triethylamine, thereby saving subsequent centrifugation, triethylamine recovery and other processes, and the solid acid-binding agent can be recycled after hydrogen chloride is resolved by high temperature treatment, thereby having obvious cost advantage.

[0020] The preparation method of the solid acid-binding agent is shown as follows: Figure 1 The preparation steps are as follows: (1) first Mannich reaction: in an alcohol solution, ethylenediamine and polyformaldehyde are added, the pH value is controlled to be 1-3, and reaction is carried out at 30-50 DEG C for 2-3 h, then the temperature is increased to 60-90 DEG C, and aniline solution is added dropwise, after the dropwise addition is completed, the temperature is kept for 14-16 h; (2) second Mannich reaction: after the first Mannich reaction, polyformaldehyde is continuously added after cooling, the pH value is controlled to be 1-3, and reaction is carried out at 30-50 DEG C for 2-3 h, then the temperature is increased to 60-90 DEG C, and aniline solution is added dropwise, after the dropwise addition is completed, the temperature is kept for 14-16 h; (3) after the second Mannich reaction is completed, the temperature is decreased, and the solid acid-binding agent is obtained by filtration. The present application synthesizes a solid acid-binding agent by using simple raw materials such as polyformaldehyde, ethylenediamine and aniline, the solid acid-binding agent is used for synthesis of vinylene carbonate, the solid acid-binding agent can be regenerated in situ after use, the production process is simplified, the production cost is reduced, the use of triethylamine is avoided in the synthesis process of vinylene carbonate, subsequent centrifugation, triethylamine recovery and other processes are saved, and the production adopts a continuous packed column reaction, only two packed columns are needed for regeneration by switching back and forth, the solid acid-binding agent can be recycled, and obvious cost advantage is obtained.

[0021] The solid acid-binding agent can be recycled, and is regenerated by high-temperature dehydrochlorination gas method, the solid acid-binding agent is washed twice by using diethyl carbonate, then heated to 130-150 DEG C under vacuum condition, most of the adsorbed hydrogen chloride is resolved in the form of gas, then washed by using 2-3% alkali solution after cooling to displace the residual hydrogen chloride, and the regenerated solid acid-binding agent after activation can be recycled.

[0022] In order to improve the use effect and life of the solid acid-binding agent, in the synthesis of vinylene carbonate, the raw material chloroethylene carbonate is purified by rectification to remove tar, dichloroethylene carbonate and other impurities, the content of chloroethylene carbonate is ≥98%, the mass ratio of chloroethylene carbonate to diethyl carbonate is 1: (2-4), the reaction temperature is 70-90℃, and the residence time of the reaction material in the tower is ≥2min.

[0023] Example 1 A glass four-necked flask with stirring and thermometer is prepared, and under the condition of nitrogen protection, 60.1g of ethylenediamine (1mol) and 69g of polyformaldehyde (2.3mol) are weighed into 300ml of methanol, stirring is started, a small amount of concentrated hydrochloric acid is added to adjust the pH value to 1, and the reaction is carried out at 35℃ for 3h. After the reaction is completed, the temperature is raised to 65℃, 93.1g of aniline (1mol) is dissolved in 300ml of ethanol solvent, and the prepared aniline ethanol solution is slowly added to the four-necked flask, the dropping time is 3h, after the dropping is completed, the temperature is slowly raised to reflux state, and the reaction is continued for 15h. After the reaction is completed, the temperature is lowered to 35℃, 69g of polyformaldehyde solid and a small amount of hydrochloric acid are added to control the pH value to 1, and the reaction is carried out at 35℃ for 3h. Then the temperature is raised to 65℃, 93.1g of aniline (1mol) is dissolved in 300ml of methanol solvent, and the prepared aniline methanol solution is slowly added to the four-necked flask, the dropping time is 3h, after the dropping is completed, the temperature is slowly raised to reflux state, and the reaction is continued for 15h. After the temperature is lowered to 35℃, the solid material 273.0g is obtained by filtering and drying. After the solid is pressed into tablets by a tablet press at 20MPa, it is added to a filler column with jacketed cooling water, 90g of chloroethylene carbonate (purity 98.6%) is weighed and added to 180g of diethyl carbonate to form a solution, the solution is heated to 75℃, and then pumped into the filler column through a metering pump, the residence time of the solution is controlled to 3-5min. After the reaction is completed, 234.9g of solution is obtained, the content of vinylene carbonate is 22.1%, and the yield is 83.33%.

[0024] Example 2 Prepare a glass four-necked flask with stirring and thermometer, under the condition of nitrogen protection, respectively take 60.1g ethylenediamine (1mol), 75g polyformaldehyde (2.5mol) into 300ml ethanol, open the stirring, add a small amount of concentrated hydrochloric acid to adjust the pH value to 3.0, react at 50℃ for 3h, after the reaction is completed, warm up to 75℃, take 93.1g aniline and dissolve it in methanol solvent, slowly add it into the four-necked flask, the dropping time is 2h, after the dropping is completed, slowly warm up to the reflux state, continue to react for 16h, then cool down, continue to add 75g polyformaldehyde (2.5mol) solid and a small amount of hydrochloric acid to adjust the pH value to 3.0, control the reaction temperature at 50℃ for 3h, then warm up to 75℃, take 93.1g aniline (1mol) and dissolve it in 300ml ethanol solvent, slowly add the aniline ethanol solution into the four-necked flask, the dropping time is 2h, after the dropping is completed, react for 16h under the condition of refluxing, after the reaction is completed, filter and dry to obtain 281.3g solid material. After the secondary solid is granulated into tablets by tablet press at 20MPa, add it into the filler column with jacketed cooling water, take 90g chloroethylenecarbonate (purity 98.6%) and add it into 180g diethyl carbonate to form a solution, warm up the solution to 75℃, then pump it into the filler column, control the solution residence time to be 3-5min, after the reaction is completed, obtain 226.3g solution, the detection of vinylene carbonate content is 24.4%, the yield is 88.86%.

[0025] Example 3 A glass four-necked flask with stirring and thermometer was prepared, and 60.1 g of ethylenediamine (1 mol) and 72 g of polyformaldehyde (2.4 mol) were weighed into 300 ml of ethylene glycol under the condition of nitrogen protection, and a small amount of concentrated hydrochloric acid was added to adjust the pH value to 2. The reaction was carried out at 30°C for 2 h. After the reaction was completed, the temperature was increased to 90°C. 93.1 g of aniline (1 mol) was dissolved in 300 ml of ethanol solvent, and was slowly added to the four-necked flask. The dropping time was 3 h. After the dropping was completed, the temperature was slowly increased to the reflux state. The reaction was continued for 14 h. Then, the temperature was decreased, and 69 g of polyformaldehyde solid and a small amount of hydrochloric acid were added to control the pH value to 2. The reaction was carried out at 30°C for 2 h. Then, the temperature was increased to 90°C. 93.1 g of aniline (1 mol) was dissolved in 300 ml of ethylene glycol solvent, and was slowly added to the four-necked flask. The dropping time was 3 h. After the dropping was completed, the reaction was carried out at the reflux state for 14 h. After the reaction was completed, filtration and drying were carried out to obtain 275.5 g of solid material. The solid material was pressed into tablets by a tablet press at 20 MPa, and was then added to a filler column with jacketed cooling water. 90 g of chloroethylene carbonate (purity 98.6%) was weighed, and was added to 180 g of diethyl carbonate to prepare a solution. The solution was heated to 75°C, and was pumped into the filler column by a metering pump. The residence time of the solution was controlled to be 3-5 min. After the reaction was completed, 235.7 g of a solution was obtained. The content of vinylene carbonate was 23.2%, and the yield was 86.75%.

[0026] Example 4 The used solid acid-binding agent in Example 1 was washed twice with solvent diethyl carbonate, and was vacuum degassed (1 KPa absolute pressure) at 140°C for 2 h. Then, the solid acid-binding agent was washed once with 2% NaOH aqueous solution, and was used after vacuum drying. 90 g of chloroethylene carbonate (purity 98.6%) was weighed, and was added to 180 g of diethyl carbonate to prepare a solution. The solution was heated to 75°C, and was pumped into the filler column with the activated solid acid-binding agent by a metering pump. The residence time of the solution was controlled to be 3-5 min. After the reaction was completed, 236.3 g of a solution was obtained. The content of vinylene carbonate was 21.2%, and the yield was 80.41%.

[0027] Example 5 The used solid acid-binding agent in Example 2 was washed twice with solvent diethyl carbonate, and was vacuum degassed (1 KPa absolute pressure) at 140°C for 2 h. Then, the solid acid-binding agent was washed once with 2% NaOH aqueous solution, and was used after vacuum drying. 90 g of chloroethylene carbonate (purity 98.6%) was weighed, and was added to 180 g of diethyl carbonate to prepare a solution. The solution was heated to 75°C, and was pumped into the filler column with the activated solid acid-binding agent by a metering pump. The residence time of the solution was controlled to be 3-5 min. After the reaction was completed, 228.32 g of a solution was obtained. The content of vinylene carbonate was 23.2%, and the yield was 85.02%.

[0028] Example 6 The solid acid binding agent used in Example 3 was washed twice with solvent diethyl carbonate, heated to 140°C and vacuum degassed (1 KPa absolute pressure) for 2 hours, then washed once with 2% NaOH aqueous solution and dried in vacuum before use. 90 g of chloroethylene carbonate (purity 98.6%) was weighed into 180 g of diethyl carbonate to form a solution, which was warmed to 75°C and pumped through a packed column of the activated solid acid binding agent at a residence time of 3-5 minutes. The reaction was terminated and the solution was obtained in a yield of 238.5 g with a content of 23.3% of vinylene carbonate, a yield of 87.95%.

[0029] Comparative Example 1 A glass four-necked flask with stirring and thermometer was prepared under nitrogen protection, 60.1 g of ethylenediamine (1 mol) and 72 g of polyformaldehyde (2.4 mol) were weighed into 300 ml of methanol, and stirring was started. The reaction was carried out at 30°C for 2 hours. After the reaction was completed, the temperature was increased to 65°C, 93.1 g of aniline (1 mol) was dissolved in methanol and slowly added dropwise into the flask, the dropwise addition time was 3 hours. After the dropwise addition was completed, the temperature was slowly increased to reflux, and the reaction was continued for 14 hours. After cooling, 69 g of polyformaldehyde solid was added, and the reaction was carried out at 30°C for 2 hours. Then the temperature was increased to 65°C, 93.1 g of aniline (1 mol) was dissolved in ethanol and slowly added dropwise, the dropwise addition time was 3 hours. After the dropwise addition was completed, the reaction was carried out at reflux for 16 hours. After the heat preservation was completed, no solid was precipitated in the reaction solution, and gas chromatography was used to detect that the reaction solution contained a large amount of unreacted aniline and hexanediamine.

[0030] Comparative Example 2 A glass four-necked flask with stirring and thermometer was prepared under nitrogen protection, 60.1 g of ethylenediamine (1 mol) and 72 g of polyformaldehyde (2.4 mol) were weighed into 300 ml of methanol, and stirring was started. The reaction was carried out at 30°C for 2 hours. After the reaction was completed, the temperature was increased to 65°C, 93.1 g of aniline (1 mol) was dissolved in methanol and slowly added dropwise into the flask, the dropwise addition time was 3 hours. After the dropwise addition was completed, the temperature was slowly increased to reflux, and the reaction was continued for 14 hours. After cooling, 69 g of polyformaldehyde solid was added, and the reaction was carried out at 30°C for 2 hours. Then the temperature was increased to 65°C, 93.1 g of aniline (1 mol) was dissolved in ethanol and slowly added dropwise, the dropwise addition time was 3 hours. After the dropwise addition was completed, the reaction was carried out at reflux for 16 hours. After the heat preservation was completed, no solid was precipitated in the reaction solution, and gas chromatography was used to detect that the reaction solution contained a large amount of unreacted aniline and hexanediamine.

[0031] Comparative Example 3 A glass four-necked flask with stirring and thermometer was prepared, 60.1 g of ethylenediamine (1 mol) and 84 g of polyformaldehyde (2.8 mol) were added into 300 ml of methanol under the condition of nitrogen protection, stirring was started, a small amount of concentrated hydrochloric acid was added to adjust the pH value to 2, and the reaction was carried out at 30°C for 2 h. After the reaction was completed, the temperature was increased to 65°C, 93.1 g of aniline (1 mol) was dissolved in ethanol solvent, and the aniline solution was slowly added to the four-necked flask, the dropping time was 3 h, after the addition was completed, the temperature was slowly increased to reflux state, and the reaction was continued for 14 h. After the temperature was lowered, 84 g of polyformaldehyde solid and a small amount of hydrochloric acid were added to control the pH value to 2, and the reaction was carried out at 30°C for 2 h. Then the temperature was increased to 65°C, 93.1 g of aniline (1 mol) was dissolved in ethanol solvent, and the aniline solution was slowly added, the dropping time was 3 h, after the addition was completed, the reaction was carried out at reflux state for 14 h. After the temperature was lowered, the reaction solution was filtered and dried to obtain 286.8 g of solid material. The solid was granulated into tablets by a tablet press at 20 MPa, and then added to a filler column with jacketed cooling water. 90 g of chloroethylene carbonate (purity 98.6%) was added into 180 g of diethyl carbonate to form a solution, the solution was heated to 75°C, and then pumped into the filler column, the residence time of the solution was controlled to be 3-5 min. After the reaction was completed, 260.3 g of solution was obtained, the content of vinylene carbonate was 4.3%, and the yield was 17.7%.

[0032] Comparative Example 4 A glass four-necked flask with stirring and thermometer was prepared, 60.1 g of ethylenediamine (1 mol) and 84 g of polyformaldehyde (2.8 mol) were added into 300 ml of methanol under the condition of nitrogen protection, stirring was started, a small amount of concentrated hydrochloric acid was added to adjust the pH value to 2, and the reaction was carried out at 30°C for 2 h. After the reaction was completed, the temperature was increased to 65°C, 93.1 g of aniline (1 mol) was dissolved in ethanol solvent, and the aniline solution was slowly added to the four-necked flask, the dropping time was 3 h, after the addition was completed, the temperature was slowly increased to reflux state, and the reaction was continued for 14 h. After the temperature was lowered, 84 g of polyformaldehyde solid and a small amount of hydrochloric acid were added to control the pH value to 2, and the reaction was carried out at 30°C for 2 h. Then the temperature was increased to 65°C, 93.1 g of aniline (1 mol) was dissolved in ethanol solvent, and the aniline solution was slowly added, the dropping time was 3 h, after the addition was completed, the reaction was carried out at reflux state for 14 h. After the temperature was lowered, the reaction solution was filtered and dried to obtain 286.8 g of solid material. The solid was granulated into tablets by a tablet press at 20 MPa, and then added to a filler column with jacketed cooling water. 90 g of chloroethylene carbonate (purity 98.6%) was added into 180 g of diethyl carbonate to form a solution, the solution was heated to 75°C, and then pumped into the filler column, the residence time of the solution was controlled to be 3-5 min. After the reaction was completed, 260.3 g of solution was obtained, the content of vinylene carbonate was 4.3%, and the yield was 17.7%.

[0033] Comparative Example 5 No solid acid binding agent of the present application was added to the filler column, 90 g of chloroethylene carbonate (purity 98.6%) was added into 180 g of diethyl carbonate to form a solution, the solution was heated to 75°C, and then pumped into the filler column, the residence time of the solution was controlled to be 3-5 min. After the reaction was completed, no target product was detected.

[0034] Furthermore, it should be understood that although the specification is described in terms of embodiments, not every embodiment includes only one independent technical solution, and the specification is described in this way only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A solid acid binding agent, characterized in that, The structure is shown as follows: 。 2. A process for the preparation of the solid acid binding agent of claim 1, characterized in that, The preparation steps are as follows: (1) the first Mannich reaction is carried out: in an alcohol solution, ethylenediamine and paraformaldehyde are added, the pH value is controlled to be 1-3, and reaction is carried out at 30-50°C for 2-3h, then the temperature is increased to 60-90°C, aniline solution is added dropwise, after the dropwise addition is completed, the reaction is carried out at constant temperature for 14-16h; (2) the second Mannich reaction is carried out: after the first Mannich reaction, paraformaldehyde is continuously added at a reduced temperature, the pH value is controlled to be 1-3, and reaction is carried out at 30-50°C for 2-3h, then the temperature is increased to 60-90°C, aniline solution is added dropwise, after the dropwise addition is completed, the reaction is carried out at constant temperature for 14-16h; (3) the second Mannich reaction is carried out at a reduced temperature, and a solid acid-binding agent is obtained by filtration.

3. The method of preparing a solid acid-binding agent according to claim 2, characterized in that, In the first Mannich reaction, the molar ratio of the reaction raw materials ethylenediamine, paraformaldehyde and aniline is 1:(2.3-2.5):

1.

4. The method of preparing a solid acid-binding agent according to claim 2, characterized by, In the first Mannich reaction, hydrochloric acid solution is used to control the pH value to be 1-3.

5. The method of preparing a solid acid-binding agent according to claim 2, characterized by, In the first Mannich reaction, the dropwise addition time of the aniline solution is 2-3h, and the solvent of the aniline solution is an alcohol solvent.

6. The method of preparing a solid acid-binding agent according to claim 2, characterized by, In the second Mannich reaction, the molar ratio of paraformaldehyde and aniline is (2.3-2.5):

1.

7. The method of preparing a solid acid-binding agent according to claim 2, characterized by, In the second Mannich reaction, hydrochloric acid solution is used to control the pH value to be 1-3.

8. The method of preparing a solid acid binding agent according to claim 2, characterized in that, In the second Mannich reaction, the dropwise addition time of the aniline solution is 2-3h, and the solvent of the aniline solution is an alcohol solvent.

9. Use of a solid acid-binding agent, characterized in that The solid acid-binding agent of claim 1 is used to remove hydrogen chloride in the synthesis of vinylene carbonate, and vinylene carbonate is obtained.

10. Use of a solid acid-binding agent according to claim 9, characterized in that After the solid acid-binding agent is pressed into tablets, broken, and filled into a packed column, chloroethylene carbonate and diethyl carbonate are mixed and then punched into the packed column to stay for 3-5min.

Images