CN113800486B - Production process of dichloro-sulfonyl imide - Google Patents
Production process of dichloro-sulfonyl imide Download PDFInfo
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- CN113800486B CN113800486B CN202111073013.8A CN202111073013A CN113800486B CN 113800486 B CN113800486 B CN 113800486B CN 202111073013 A CN202111073013 A CN 202111073013A CN 113800486 B CN113800486 B CN 113800486B
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
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- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/096—Amidosulfonic acid; Salts thereof
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- C01B21/00—Nitrogen; Compounds thereof
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the technical field of production of dichloro sulfonyl imide, in particular to a production process of dichloro sulfonyl imide. The production process of the dichloro sulfonyl imide comprises the following steps: adding sulfamic acid and thionyl chloride into a reaction kettle until solids are completely dissolved, then adding sulfur trioxide into the reaction kettle at a constant speed, heating to 90-120 ℃ after the sulfur trioxide is added, continuing to react for 5-10h, recovering to normal pressure, starting a condensate outlet valve of a condenser, continuing to react for 1-3h until no condensate flows out of the condenser, and performing reduced pressure rectification to obtain the target product of the dichloro-sulphonyl imine. Compared with the original chlorosulfonic acid method process, the method reduces the hydrogen chloride waste gas amount by 1/3, and the sulfur dioxide tail gas of the process can be recycled and reused in a thionyl chloride production device, so that the three-waste yield is further reduced, and the method belongs to an innovative process meeting the development requirements of the green chemical industry.
Description
Technical Field
The invention relates to the technical field of production of dichloro sulfonyl imide, in particular to a production process of dichloro sulfonyl imide.
Background
With the continuous increase of the market demand of novel electrolyte difluoro-sulfonyl imide of lithium battery in recent years, the production process of raw material dichloro-sulfonyl imide is also more important, and the further production of difluoro-sulfonyl imide by performing fluorine-chlorine halogen exchange on the dichloro-sulfonyl imide is the most valuable production method at present.
The mainstream production process of the bischlorosulfonimide comprises two types: the method is to synthesize the dichloro sulfonyl imide by taking sulfamic acid, thionyl chloride and chlorosulfonic acid as raw materials, and the reaction flow is as follows:
for example, patent CN101747242B discloses a preparation method of bis-chlorosulfonyl imide, which comprises a synthesis process of bis-chlorosulfonyl imide, wherein sulfamic acid, thionyl chloride and chlorosulfonic acid are used as raw materials, the raw materials react for 20-24 hours at a high temperature of 110-130 ℃, and then the raw materials are rectified to obtain the bis-chlorosulfonyl imide, the reaction equation is as follows, the process is widely applied due to the advantage of lower production cost, but each 1 molecule of product is produced, namely 2 molecules of sulfur dioxide and 3 molecules of hydrogen chloride, so that the atomic utilization rate of the process is low, and the number of by-products three wastes is high, and the development trend of clean and environment-friendly in the fine chemical industry is violated. The process has long reaction period, high reaction temperature, high energy consumption, more side reactions and a plurality of problems, so that the process needs to be optimized and upgraded.
The other is to synthesize the dichloro sulfonyl imide by taking chlorosulfonic acid and chlorosulfonyl isocyanate as raw materials, and the reaction flow is as follows:
for example, patent CN1606447288B discloses a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the synthesis process of bis (chlorosulfonyl) imide. The method takes chlorosulfonic acid and chlorosulfonyl isocyanate as raw materials, and the reaction is carried out at a high temperature of 120-140 ℃ under the action of a catalyst, and the distillation is carried out to obtain the dichlorosulfonylimide, wherein the reaction equation is as follows, the method has the advantages of no byproduct gas of sulfur dioxide and hydrogen chloride, high atom utilization rate, but the same outstanding problem, the chlorosulfonyl isocyanate raw materials are prepared from cyanogen chloride and sulfur trioxide, the cyanogen chloride has extremely high toxicity and high price, the use cost of the chlorosulfonyl isocyanate raw materials is overhigh, and the market profit space of the dichlorosulfonylimide is reduced, so that the method is difficult to use on a large scale.
In summary, the existing production process of the bis-chlorosulfonyl imide has the problems of large amount of three wastes, multiple side reactions, high raw material cost and the like, and along with the development of the lithium battery industry and the bis-fluorosulfonyl imide electrolyte, higher requirements are also put forward on the product quality of the bis-chlorosulfonyl imide, and development of a novel production process with advantages is needed to solve the problems.
Disclosure of Invention
The invention aims to solve the technical problems that: compared with the original chlorosulfonic acid method, the production process of the dichlorsulfimide reduces the hydrogen chloride waste gas by 1/3, and the sulfur dioxide tail gas of the process can be recycled and reused to a thionyl chloride production device, thereby further reducing the three-waste yield, and belonging to an innovative technology meeting the development requirements of the green chemical industry.
The invention relates to a production process of dichlor sulfimide, which takes sulfamic acid, thionyl chloride and sulfur trioxide as raw materials, and the dichlor sulfimide is prepared by reacting at 40-70 ℃ and then at 90-120 ℃.
The production process of the dichloro sulfonyl imide comprises the following steps:
(1) Adding sulfamic acid and thionyl chloride into a reaction kettle, and starting a stirring and condenser reflux device until all solids are dissolved;
(2) And then adding sulfur trioxide into a reaction kettle at a constant speed at the temperature of 40-70 ℃, heating to 90-120 ℃ after the addition of the sulfur trioxide is finished, continuing to react for 5-10h, recovering to normal pressure, starting a condensate outlet valve of a condenser, continuing to react for 1-3h until no condensate flows out of the condenser, and performing reduced pressure rectification to obtain the target product, namely the dichloro-sulfonyl imide.
Wherein, the mol ratio of sulfamic acid, sulfur trioxide and thionyl chloride is 1:1 (2-2.5);
in the step (1), the pressure in the reaction kettle is controlled to be 0.1-0.7MPa, and the temperature is controlled to be 40-70 ℃.
In the step (2), the addition time of the sulfur trioxide is controlled to be 1-6 hours.
In the step (2), the condensate is excessive thionyl chloride, and the condensate is recycled after flowing out of the condenser.
In the step (2), the reduced pressure rectification pressure is 5-10 mmHg, and the temperature of the target product dichloro sulfonyl imide fraction is 90-105 ℃.
In the step (2), sulfur dioxide and hydrogen chloride tail gas generated in the reaction process are absorbed by a multi-stage absorption tower to obtain byproduct hydrochloric acid aqueous solution and sulfur dioxide gas, and the sulfur dioxide is recycled and reused in the thionyl chloride production process.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the traditional process, the invention does not use chlorosulfonic acid with higher cost, innovatively develops the sulfur trioxide process, reduces the cost of raw materials, improves the reactivity, improves the utilization rate of the raw materials and shortens the reaction period;
(2) Compared with the traditional chlorosulfonic acid process, the sulfur trioxide route process reduces 1/3 of byproduct hydrogen chloride gas, and the process greatly reduces the treatment pressure of production tail gas due to the low added value and high treatment cost of the byproduct hydrogen chloride, thereby belonging to a cleaner and more economic new process;
(3) According to the invention, on the basis of adopting the sulfur trioxide process, the reaction process parameters are further optimized and divided into two reaction stages of low temperature and high temperature, compared with the high temperature reaction of the traditional process, the side reaction probability of the process is greatly reduced, the purity of the product obtained after rectification is higher and can reach more than 99.8%, and the process is suitable for the production of the difluoro sulfonimide lithium for the downstream lithium battery.
Detailed Description
The invention is further described below in conjunction with specific embodiments, which should not be construed as limiting the scope of the invention, as many insubstantial modifications and adaptations of the invention to those skilled in the art may become apparent to those in light of the foregoing disclosure.
Example 1
Adding 97.1g (1 mol) sulfamic acid and 273.7g (2.3 mol) thionyl chloride into a reaction kettle, starting stirring, starting a condenser reflux device, controlling the temperature to 55 ℃, setting the back pressure valve pressure to 0.4MPa, adding 80g (1 mol) sulfur trioxide into the reaction kettle at a constant speed for 3 hours after the solid is completely dissolved, heating to 110 ℃ after the sulfur trioxide is added, continuing to react for 7.5 hours, recovering to normal pressure, starting a condensate outlet valve of the condenser, continuing to react for 2 hours, until no condensate flows out from the condenser, starting reduced pressure rectification, and collecting the fraction at 90-105 ℃ to obtain 212.4g of the product of the bischlorosulfimide liquid, wherein the reaction yield is 99.1% and the product purity is 99.9%.
Example 2
Adding 97.1g (1 mol) sulfamic acid and 238g (2.0 mol) thionyl chloride into a reaction kettle, starting stirring, starting a reflux device of a condenser, controlling the temperature to 40 ℃, setting the back pressure valve pressure to 0.1MPa, adding 80g (1 mol) sulfur trioxide into the reaction kettle at a constant speed for 1h after the solid is completely dissolved, heating to 90 ℃ for continuous reaction for 5h after the sulfur trioxide is added, recovering to normal pressure, starting a condensate outlet valve of the condenser, continuing to react for 1h until no condensate flows out from the condenser, starting reduced pressure rectification, and collecting a fraction at 90-105 ℃ to obtain 205.5g of the dichlorosulfimide liquid with the reaction yield of 96.0% and the product purity of 99.8%.
Example 3
Adding 97.1g (1 mol) sulfamic acid and 297.5g (2.5 mol) thionyl chloride into a reaction kettle, starting stirring, starting a condenser reflux device, controlling the temperature to be 70 ℃, setting the back pressure valve pressure to be 0.7MPa, adding 80g (1 mol) sulfur trioxide into the reaction kettle at a constant speed within 6 hours after the solid is completely dissolved, heating to 120 ℃ for continuous reaction for 10 hours after the sulfur trioxide is added, recovering to normal pressure, starting a condensate outlet valve of the condenser, continuing the reaction for 3 hours until no condensate flows out from the condenser, starting reduced pressure rectification, and collecting fractions at 90-105 ℃ to obtain 211.0g of the dichlorosulfimide liquid with the reaction yield of 98.5% and the product purity of 99.9%.
Example 4
Adding 97.1g (1 mol) sulfamic acid and 273.7g (2.3 mol) thionyl chloride into a reaction kettle, starting stirring, starting a condenser reflux device, controlling the temperature to be 70 ℃, setting the back pressure valve pressure to be 0.7MPa, adding 80g (1 mol) sulfur trioxide into the reaction kettle at a constant speed within 1h after the solid is completely dissolved, heating to 110 ℃ for continuous reaction for 10h after the sulfur trioxide is added, recovering to normal pressure, starting a condensate outlet valve of the condenser, continuing to react for 1h until no condensate flows out from the condenser, starting reduced pressure rectification, and collecting the fraction at 90-105 ℃ to obtain 210.0g of the dichloro sulfonyl imide liquid with the reaction yield of 98% and the product purity of 99.9%.
Comparative example 1
97.1g (1 mol) sulfamic acid, 273.7g (2.3 mol) thionyl chloride and 117g (1 mol) chlorosulfonic acid are added into a reaction kettle, stirring is started, a condenser reflux device is started, the temperature is controlled to be 130 ℃, the reaction is carried out for 24 hours, excessive thionyl chloride is distilled off under normal pressure, the distillation is carried out under reduced pressure, the fraction at 90-105 ℃ is collected, 192.2g of dichlorosulfimide liquid is obtained, the reaction yield is 88%, and the product purity is 98.1%.
Comparative example 2
97.1g (1 mol) sulfamic acid, 273.7g (2.3 mol) thionyl chloride and 80g (1 mol) sulfur trioxide are added into a reaction kettle, stirring is started, a condenser reflux device is started, the temperature is controlled to be 130 ℃, the reaction is carried out for 24 hours, excessive thionyl chloride is distilled off under normal pressure, the distillation is carried out under reduced pressure, the fraction at 90-105 ℃ is collected, 201g of dichlorosulfimide liquid is obtained, the reaction yield is 92.0%, and the product purity is 98.0%.
The purities of the products of examples 1-4 and comparative examples 1-2 were examined by potentiometric titration, and the analytical methods were as follows:
(1) And (3) measuring N: adding water into the sample for full hydrolysis, titrating with sodium nitrite solution, and taking starch potassium iodide as an indicator;
(2) Measuring Cl: and (3) fully hydrolyzing the sample with glacial alkaline water, and measuring the content of chloride ions by using silver nitrate as a titration solution and potentiometric titration.
(3) If Cl%/N% >2, the sample purity is calculated as N%; if Cl%/N% < 2, the sample purity is calculated as Cl%.
The technical advantages of examples 1-4 and comparative examples 1-2 are shown in Table 1.
TABLE 1 comparison of technical advantages of examples 1-4 and comparative examples 1-2 results
| Numbering device | Reaction temperature, DEG C | Reaction time, h | Yield of reaction, percent | Purity of the product% | 1mol of three wastes of product, g |
| Example 1 | 55、110 | 12.5 | 99.1 | 99.9 | 83.7 |
| Example 2 | 40、90 | 7 | 96.0 | 99.8 | 90.6 |
| Example 3 | 70、120 | 19 | 98.5 | 99.9 | 85.1 |
| Example 4 | 70、110 | 12 | 98.0 | 99.9 | 86.1 |
| Comparative example 1 | 130 | 24 | 88.0 | 98.0 | 140.9 |
| Comparative example 2 | 130 | 24 | 92.0 | 98.1 | 100.1 |
As can be seen from Table 1, in comparative example 1, sulfamic acid, thionyl chloride and chlorosulfonic acid are used as raw materials, and the bischlorosulfimide is synthesized at high temperature.
Claims (4)
1. A production process of dichloro sulfonyl imide is characterized in that: the method comprises the following steps:
(1) Adding sulfamic acid and thionyl chloride into a reaction kettle, and starting a stirring and condenser reflux device until all solids are dissolved;
(2) Then adding sulfur trioxide into a reaction kettle at a constant speed at the temperature of 40-70 ℃, controlling the adding time of the sulfur trioxide to be 1-6h, heating to 90-120 ℃ after the adding of the sulfur trioxide is finished, continuing to react for 5-10h, recovering to normal pressure, starting a condensate outlet valve of a condenser, continuing to react for 1-3h until no condensate flows out of the condenser, and performing reduced pressure rectification to obtain a target product of dichloro sulfonyl imide;
the molar ratio of sulfamic acid, sulfur trioxide and thionyl chloride is 1:1 (2-2.5);
in the step (1), the pressure in the reaction kettle is controlled to be 0.1-0.7MPa, and the temperature is controlled to be 40-70 ℃.
2. The production process of the bischlorosulfonimide according to claim 1, wherein the process is characterized by: in the step (2), the condensate is excessive thionyl chloride, and the condensate is recycled after flowing out of the condenser.
3. The production process of the bischlorosulfonimide according to claim 1, wherein the process is characterized by: in the step (2), the reduced pressure rectification pressure is 5-10 mmHg, and the temperature of the target product dichloro sulfonyl imide fraction is 90-105 ℃.
4. The production process of the bischlorosulfonimide according to claim 1, wherein the process is characterized by: in the step (2), sulfur dioxide and hydrogen chloride tail gas generated in the reaction process are absorbed by a multi-stage absorption tower to obtain byproduct hydrochloric acid aqueous solution and sulfur dioxide gas, and the sulfur dioxide is recycled and reused in the thionyl chloride production process.
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| CN115159480A (en) * | 2022-06-24 | 2022-10-11 | 森松（江苏）重工有限公司 | Production system of bis (chlorosulfonyl) imide |
| CN115215306B (en) * | 2022-06-29 | 2024-03-08 | 山东凯盛新材料股份有限公司 | Preparation method and preparation equipment of high-purity dichloro sulfonyl imide |
| CN115304039B (en) * | 2022-10-10 | 2022-12-06 | 山东海科新源材料科技股份有限公司 | Purification device and method for bis (chlorosulfonyl) imide |
| CN115594157A (en) * | 2022-11-09 | 2023-01-13 | 荣成青木高新材料有限公司（Cn） | Preparation method of bis (chlorosulfonyl) imide |
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