CN113880057B - Clean production process of difluoro sulfimide - Google Patents
Clean production process of difluoro sulfimide Download PDFInfo
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Abstract
The invention relates to the technical field of production of difluoro-sulfonyl imide, in particular to a clean production process of difluoro-sulfonyl imide. The clean production process of the difluoro sulfimide uses an intermittent reaction kettle as a pre-reaction device, a micro-channel reactor as a main reaction device, and the micro-channel reactor comprises a first temperature zone and a second temperature zone which are connected in series, wherein the two temperature zones comprise a plurality of reaction modules connected in series; firstly adding sulfamic acid, sulfur trioxide and thionyl chloride into an intermittent reaction kettle for reaction to obtain a pre-reaction liquid, then pumping the pre-reaction liquid into a first temperature zone for reaction to obtain a dichloro reaction liquid, simultaneously pumping the dichloro reaction liquid and hydrogen fluoride liquid into a second temperature zone for reaction to obtain a difluoro reaction liquid, and carrying out reduced pressure rectification to obtain a high-purity difluoro sulfimide product. The invention is based on a micro-channel reactor, and the high-purity bis-fluorosulfonyl imide product is obtained through the efficient fluoridation of hydrogen fluoride and the rectification and purification from the synthesis of bis-chlorosulfonyl imide.
Description
Technical Field
The invention relates to the technical field of production of difluoro-sulfonyl imide, in particular to a clean production process of difluoro-sulfonyl imide.
Background
The lithium ion battery has the excellent characteristics of high working voltage, high energy density, long cycle life, capability of rapid charge and discharge and the like, is widely applied to the fields of various mobile electrical appliances, automobiles and the like at present, and is developing into the electric energy storage field of wind energy and solar energy, and the related manufacturing industry is facing the expansion of productivity and technical level and the improvement of pressure.
The most widely used lithium salt of electrolyte in the current lithium battery is lithium hexafluorophosphate, which has small radius of fluorine atom and PF 6 - Proper radius, good ionic conductivity and electrochemical stability, but has the defects of weak high temperature resistance, easy decomposition when meeting water, and the initiation of decomposition to generate HF gas at 60-80 ℃. The lithium bis (fluorosulfonyl) imide salt has good thermal stability and chemical stabilityStability, and unique excellent properties of electrode material compatibility, low viscosity, low melting point, high conductivity, etc., are considered to be possible to replace LiPF 6 Is a new generation of lithium ion battery electrolyte.
The production scheme for lithium bis-fluorosulfonyl imide generally comprises: synthesizing dichlor sulfimide, fluoro and salifying. The fluoro working section is the step with the highest technical difficulty, and the technical level of the fluoro working section not only directly influences the quality of the final product, but also determines the technological indexes such as safety, environmental protection and the like. The main current domestic fluoro process is divided into two kinds of fluoride salt process and hydrogen fluoride process.
Patent CN106006586B discloses a method for preparing potassium bis (fluorosulfonyl) imide, which takes bis (chlorosulfonyl) imide and hydrogen fluoride as raw materials to complete fluorination reaction under the action of a catalyst, and the main problems of the process are dangerousness and low efficiency. The fluorination reaction is one of the national specified dangerous processes, the intermittent production process has extremely high danger, and the policy encourages development and popularization of the microchannel continuous flow process and improves the intrinsic safety of the process. Because the reaction is a gas-liquid two-phase reaction of hydrogen fluoride gas and dichlorsulfimide, the mass transfer efficiency in the traditional reaction kettle is extremely low, the reaction time is as long as 10-25 hours, the production cost is increased, and the danger coefficient is also increased.
Patent CN101747242B discloses a method for preparing alkali metal salt of difluoro-sulfonyl imide, which uses dichloro-sulfonyl imide and antimony trifluoride as raw materials to carry out fluorination reaction. The process has the advantages of high process safety, but the problems of rare metal resource consumption, byproduct fluorine-containing antimony chloride waste salt and the like are also outstanding, and other similar processes using fluoride salt as a fluoride reagent have similar problems. Although the technology still occupies a main production line in China, the technology should be replaced gradually under the development trend of green chemical industry and clean technology.
In summary, in the context of the rapid expansion of market demands, the development of the level of technology of bis-fluoro-sulfonyl imide is also urgent, and the problems of process safety and cleanliness need to be solved more perfectly.
Disclosure of Invention
The invention aims to solve the technical problems that: the clean production process of the difluoro sulfimide is based on a micro-channel reactor, and the high-purity difluoro sulfimide product is obtained through high-efficiency fluoro reaction of hydrogen fluoride and rectification purification from the synthesis of the dichloro sulfimide.
The clean production process of the bisfluorosulfonyl imide uses an intermittent reaction kettle as a pre-reaction device and a microchannel reactor as a main reaction device, wherein the microchannel reactor comprises a first temperature zone and a second temperature zone which are connected in series, and the two temperature zones comprise a plurality of reaction modules connected in series; the method comprises the following steps:
(1) Adding sulfamic acid, sulfur trioxide and thionyl chloride into an intermittent reaction kettle, starting stirring, and reacting at a certain temperature and pressure to obtain a pre-reaction solution;
(2) The pre-reaction liquid is pumped into a reaction module of a first temperature zone of the microchannel reactor for reaction, and dichloro reaction liquid is obtained from an outlet;
(3) The method comprises the steps that dichloro reaction liquid enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out from a lower liquid outlet and is pumped into a reaction module in a second temperature zone, and hydrogen fluoride liquid is pumped into the reaction module in the second temperature zone for reaction, so that difluoro reaction liquid is obtained from an outlet;
(4) The difluoro reaction feed liquid enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and is discharged to a fluorine-chlorine separation condenser, the reaction liquid flows out from a lower liquid outlet, and the reaction liquid is pumped into a rectifying tower for reduced pressure rectification, so that a high-purity difluoro sulfimide product is obtained.
In the step (1), the molar ratio of sulfamic acid, sulfur trioxide and thionyl chloride is 1:1 (2-2.5).
In the step (1), the reaction temperature is 90-120 ℃, the reaction pressure is 0.1-0.7MPa, and the reaction time is 1-6h.
In the step (2), the first temperature zone is provided with 4-10 modules connected in series, the reaction (residence) time of the single module is 5-15s, and the total reaction (residence) time of the temperature zone is 20-150s.
In the step (2), the reaction temperature of the first temperature zone is 120-150 ℃ and the reaction pressure is 0.5-1.5MPa.
In the step (3), the molar ratio of the hydrogen fluoride to the sulfamic acid in the step (1) is (2-10): 1.
In the step (3), the second temperature zone is provided with 4-10 modules connected in series, the reaction (residence) time of the single module is 2-6s, and the reaction (residence) time of the temperature zone is 8-60s.
In the step (3), the reaction temperature of the second temperature zone is 90-120 ℃ and the reaction pressure is 0.5-1.2MPa.
In the step (4), the gas is mixed gas of hydrogen chloride and hydrogen fluoride, and the mixed gas enters a fluorine-chlorine separation condenser to be separated to obtain hydrogen fluoride liquid which is recycled for the reaction in the step (3).
In the step (4), the pressure of the vacuum rectification is 2-5mmHg, and the collection temperature of the difluoro sulfimide fraction is 112-115 ℃.
As a preferable scheme, the clean production process of the difluoro sulfimide comprises the following steps:
(1) Adding quantitative sulfamic acid, sulfur trioxide and thionyl chloride into an intermittent reaction kettle, controlling the temperature to be 90-120 ℃, starting stirring, regulating and controlling the pressure in the kettle to be 0.1-0.7MPa by adopting a back pressure valve, and reacting for 1-6h;
(2) Pumping the pre-reaction liquid into a reaction module of a first temperature zone of a microchannel reactor through a transfer pump, wherein the reaction temperature is 120-150 ℃, the reaction pressure is 0.5-1.5MPa, 4-10 modules are connected in series in the temperature zone, the reaction (residence) time of a single module is 5-15s, and the reaction (residence) time of the temperature zone is 20-150s;
(3) The method comprises the steps that dichloro reaction feed liquid flows out of a first temperature zone, enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out of a lower liquid outlet, is pumped into a reaction module of a second temperature zone through a transfer pump, and simultaneously hydrogen fluoride liquid is pumped into the reaction module for mixed reaction, wherein the reaction temperature is 90-120 ℃, the reaction pressure is 0.5-1.2MPa, 4-10 modules are connected in series in the temperature zone, the reaction (residence) time of a single module is 2-6s, and the reaction (residence) time of the temperature zone is 8-60s;
(4) The difluoro reaction feed liquid flows out of the continuous flow reactor, enters a gas-liquid separation tank, the gas is discharged from an upper gas outlet and goes to a fluorine-chlorine separation condenser, the reaction liquid flows out of a lower liquid outlet, and is pumped into a rectifying tower through a transfer pump for reduced pressure rectification, so that a high-purity difluoro sulfimide product is obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) The continuous flow production process of the difluoro-sulfonyl imide is developed based on a micro-channel reactor, and the blank of the continuous flow process in the difluoro-sulfonyl imide production industry is filled;
(2) The fluorination process belongs to a national specified 'dangerous process', and the traditional process method has great safety risk, the reaction liquid holdup is reduced to below 1kg by adopting the microchannel reactor, the intrinsic safety is greatly improved, the mass transfer and heat transfer effects of gas-liquid two phases in a reaction system are greatly improved by adopting the microchannel reactor, and dangerous accidents caused by heat accumulation are prevented;
(3) According to the invention, sulfur trioxide is adopted to replace chlorosulfonic acid in the traditional process to synthesize the intermediate dichloro sulfonyl imide, so that the reactivity and the raw material utilization rate are improved, most of the reaction in the section is finished by adopting pre-reaction, then the reaction temperature and the reaction pressure are improved by using a microchannel reactor, the residual reaction is rapidly finished, and the production efficiency is remarkably improved;
(4) The intermediate dichloro sulfimide and hydrogen fluoride are in gas-liquid two phases in the traditional reaction process, and the microchannel reactor used in the invention can obviously improve the mass transfer efficiency of the gas-liquid two phases, thereby not only reducing the use amount of the hydrogen fluoride, but also greatly shortening the fluorination reaction time;
(5) Compared with the fluoride salt fluorination process, the process has the advantages that no fluoride waste salt is generated, and the process has higher cleanliness; compared with the hydrogen fluoride fluorination process of the traditional batch process, the method does not need to use a catalyst, avoids the introduction of impurities and the generation of three wastes, has higher product purity, and can recycle and recycle excessive hydrogen fluoride.
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.
The purity detection method of the product difluoro sulfimide comprises the following steps:
(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) And F, measuring: diluting a sample with dilute alkaline water, heating for full hydrolysis, and potentiometric titration to measure the content of fluorine ions by using a fluorine electrode;
(3) If F%/N% >2, the sample purity is calculated as N%; if F%/N% < 2, the sample purity is calculated as F%.
Example 1
The clean production process of the difluoro sulfimide adopts an intermittent reaction kettle as a pre-reaction device and a micro-channel reactor as a main reaction device, wherein the micro-channel reactor comprises a first temperature zone and a second temperature zone which are connected in series, and the two temperature zones comprise 6 reaction modules connected in series; the method comprises the following steps:
(1) 97.1g (1 mol) sulfamic acid, 273.7g (2.3 mol) thionyl chloride and 80g (1 mol) sulfur trioxide are added into a batch reactor, the temperature is controlled at 110 ℃, stirring is started, the pressure in the reactor is regulated and controlled to be 0.4MPa by a back pressure valve, and the reaction is carried out for 3 hours;
(2) Feeding the pre-reaction liquid into a reaction module of a first temperature zone of a microchannel reactor at 49.2g/min through a transfer pump, wherein the reaction temperature is 135 ℃, the reaction pressure is 0.75MPa, the temperature zone is provided with 6 modules connected in series, the reaction (residence) time of a single module is 10s, and the reaction (residence) time of the temperature zone is 60s;
(3) The method comprises the steps that dichloro reaction liquid flows out of a first temperature zone, enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out of a lower liquid outlet, the reaction liquid is pumped into a reaction module of a second temperature zone through a transfer pump, hydrogen fluoride liquid is pumped into the reaction module, the mol ratio of hydrogen fluoride in the reaction liquid to sulfamic acid in the step (1) is 6:1, the total flow rate of two materials is 98.4g/min, the reaction temperature is 105 ℃, the reaction pressure is 0.8MPa, 6 series modules are arranged in the temperature zone, the reaction (residence) time of a single module is 5s, and the reaction (residence) time of the temperature zone is 30s;
(4) The difluoro reaction feed liquid flows out of the continuous flow reactor, enters a gas-liquid separation tank, the gas is discharged from an upper gas outlet and goes to a fluorine-chlorine separation condenser, the reaction liquid flows out from a lower liquid outlet, the reaction liquid is pumped into a rectifying tower through a transfer pump, and the fraction at 112-115 ℃ is collected under the pressure of 2-5mmHg, so that the high-purity difluoro sulfimide product is obtained, the product yield is 94.05%, and the product purity is 99.9%.
Example 2
The clean production process of the difluoro sulfimide adopts an intermittent reaction kettle as a pre-reaction device and a micro-channel reactor as a main reaction device, wherein the micro-channel reactor comprises a first temperature zone and a second temperature zone which are connected in series, and the two temperature zones comprise 4 reaction modules connected in series; the method comprises the following steps:
(1) 97.1g (1 mol) sulfamic acid, 238g (2.0 mol) thionyl chloride and 80g (1 mol) sulfur trioxide are added into a batch reactor, the temperature is controlled at 90 ℃, stirring is started, the pressure in the reactor is regulated and controlled to be 0.2MPa by a back pressure valve, and the reaction is carried out for 1h;
(2) The pre-reaction liquid is pumped into a reaction module of a first temperature zone of a microchannel reactor at 49.2g/min through a transfer pump, the reaction temperature is 120 ℃, the reaction pressure is 0.5MPa, the temperature zone is provided with 4 modules connected in series, the reaction (residence) time of a single module is 5s, and the reaction (residence) time of the temperature zone is 20s;
(3) The method comprises the steps that dichloro reaction liquid flows out of a first temperature zone, enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out of a lower liquid outlet, the reaction liquid is pumped into a reaction module of a second temperature zone through a transfer pump, hydrogen fluoride liquid is pumped into the reaction module, the mol ratio of the hydrogen fluoride in the reaction liquid to sulfamic acid in the step (1) is 2:1, the total flow rate of two materials is 98.4g/min, the reaction temperature is 90 ℃, the reaction pressure is 0.5MPa, 4 series modules are arranged in the temperature zone, the reaction (residence) time of a single module is 2s, and the reaction (residence) time of the temperature zone is 8s;
(4) The difluoro reaction feed liquid flows out of the continuous flow reactor, enters a gas-liquid separation tank, the gas is discharged from an upper gas outlet and goes to a fluorine-chlorine separation condenser, the reaction liquid flows out from a lower liquid outlet, the reaction liquid is pumped into a rectifying tower through a transfer pump, and the fraction at 112-115 ℃ is collected under the pressure of 2-5mmHg, so that the high-purity difluoro sulfimide product is obtained, the product yield is 90.6%, and the product purity is 98.5%.
Example 3
The clean production process of the difluoro sulfimide adopts an intermittent reaction kettle as a pre-reaction device and a micro-channel reactor as a main reaction device, wherein the micro-channel reactor comprises a first temperature zone and a second temperature zone which are connected in series, and the two temperature zones comprise 10 reaction modules connected in series; the method comprises the following steps:
(1) 97.1g (1 mol) sulfamic acid, 297.5g (2.5 mol) thionyl chloride and 80g (1 mol) sulfur trioxide are added into a batch reactor, the temperature is controlled at 120 ℃, stirring is started, the pressure in the reactor is regulated and controlled to be 0.7MPa by a back pressure valve, and the reaction is carried out for 6 hours;
(2) The pre-reaction liquid is pumped into a reaction module of a first temperature zone of a microchannel reactor at 49.2g/min through a transfer pump, the reaction temperature is 150 ℃, the reaction pressure is 1.5MPa, the temperature zone is provided with 10 modules connected in series, the reaction (residence) time of a single module is 10s, and the reaction (residence) time of the temperature zone is 100s;
(3) The method comprises the steps that dichloro reaction liquid flows out of a first temperature zone, enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out of a lower liquid outlet, the reaction liquid is pumped into a reaction module of a second temperature zone through a transfer pump, hydrogen fluoride liquid is pumped into the reaction module, the mol ratio of hydrogen fluoride in the reaction liquid to sulfamic acid in the step (1) is 10:1, the total flow rate of two materials is 98.4g/min, the reaction temperature is 120 ℃, the reaction pressure is 1.2MPa, 10 modules are connected in series in the temperature zone, the reaction (residence) time of a single module is 5s, and the reaction (residence) time of the temperature zone is 50s;
(4) The difluoro reaction feed liquid flows out of the continuous flow reactor, enters a gas-liquid separation tank, the gas is discharged from an upper gas outlet and goes to a fluorine-chlorine separation condenser, the reaction liquid flows out from a lower liquid outlet, the reaction liquid is pumped into a rectifying tower through a transfer pump, and the fraction at 112-115 ℃ is collected under the pressure of 2-5mmHg, so that the high-purity difluoro sulfimide product is obtained, the product yield is 96.1%, and the product purity is 99.5%.
Example 4
The clean production process of the bisfluorosulfonyl imide uses an intermittent reaction kettle as a pre-reaction device and a micro-channel reactor as a main reaction device, wherein the micro-channel reactor comprises a first temperature zone and a second temperature zone which are connected in series, and each of the two temperature zones comprises 8 and 6 reaction modules connected in series; the method comprises the following steps:
(1) 97.1g (1 mol) sulfamic acid, 273.7g (2.3 mol) thionyl chloride and 80g (1 mol) sulfur trioxide are added into a batch reactor, the temperature is controlled to be 100 ℃, stirring is started, and the pressure in the reactor is regulated and controlled to be 0.3MPa by adopting a back pressure valve for 3 hours of reaction;
(2) The pre-reaction liquid is pumped into a reaction module of a first temperature zone of a microchannel reactor at 49.2g/min through a transfer pump, the reaction temperature is 130 ℃, the reaction pressure is 0.6MPa, the temperature zone is provided with 8 modules connected in series, the reaction (residence) time of a single module is 10s, and the reaction (residence) time of the temperature zone is 80s;
(3) The method comprises the steps that dichloro reaction liquid flows out of a first temperature zone, enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out of a lower liquid outlet, the reaction liquid is pumped into a reaction module of a second temperature zone through a transfer pump, hydrogen fluoride liquid is pumped into the reaction module, the mol ratio of hydrogen fluoride in the reaction liquid to sulfamic acid in the step (1) is 8:1, the total flow rate of two materials is 98.4g/min, the reaction temperature is 105 ℃, the reaction pressure is 0.8MPa, 6 series modules are arranged in the temperature zone, the reaction (residence) time of a single module is 5s, and the reaction (residence) time of the temperature zone is 30s;
(4) The difluoro reaction feed liquid flows out of the continuous flow reactor, enters a gas-liquid separation tank, the gas is discharged from an upper gas outlet and goes to a fluorine-chlorine separation condenser, the reaction liquid flows out from a lower liquid outlet, the reaction liquid is pumped into a rectifying tower through a transfer pump, and the fraction at 112-115 ℃ is collected under the pressure of 2-5mmHg, so that the high-purity difluoro sulfimide product is obtained, the product yield is 95.0%, and the product purity is 99.8%.
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 98.0%.
107.5g (0.5 mol) of dichloro-sulphonyl-imine liquid and 0.1g of antimony pentachloride catalyst are added into a tetrafluoro reaction bottle, the temperature is raised to 100-105 ℃, HF gas is slowly introduced under stirring for 24g, the temperature is reduced to room temperature after the reaction is carried out for 20 hours, the reaction liquid is rectified, and fractions with 112-115 ℃ are collected under the pressure of 2-5mmHg, thus 92.45g of comparative example product is obtained, the yield is 88%, and the purity is 98.0%.
Comparative example 2
The comparative example also uses an intermittent reaction kettle as a pre-reaction device, and a microchannel reactor as a main reaction device, wherein the batch reaction kettle comprises a first temperature zone and a second temperature zone which are connected in series, and each temperature zone comprises 2 reaction modules connected in series;
(1) 97.1g (1 mol) sulfamic acid, 238g (2.0 mol) thionyl chloride and 80g (1 mol) sulfur trioxide are added into a batch reactor, the temperature is controlled at 90 ℃, stirring is started, the pressure in the reactor is regulated and controlled to be 0.2MPa by a back pressure valve, and the reaction is carried out for 1h;
(2) The pre-reaction liquid is pumped into a reaction module of a first temperature zone of a microchannel reactor at 49.2g/min through a transfer pump, the reaction temperature is 120 ℃, the reaction pressure is 0.5MPa, the temperature zone is provided with 2 modules connected in series, the reaction (residence) time of a single module is 5s, and the reaction (residence) time of the temperature zone is 10s;
(3) The method comprises the steps that dichloro reaction liquid flows out of a first temperature zone, enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out of a lower liquid outlet, the reaction liquid is pumped into a reaction module of a second temperature zone through a transfer pump, hydrogen fluoride liquid is pumped into the reaction module, the mol ratio of the hydrogen fluoride in the reaction liquid to sulfamic acid in the step (1) is 2:1, the total flow rate of two materials is 98.4g/min, the reaction temperature is 90 ℃, the reaction pressure is 0.5MPa, 2 series modules are arranged in the temperature zone, the reaction (residence) time of a single module is 2s, and the reaction (residence) time of the temperature zone is 4s;
(4) The difluoro reaction feed liquid flows out of the continuous flow reactor, enters a gas-liquid separation tank, the gas is discharged from an upper gas outlet and goes to a fluorine-chlorine separation condenser, the reaction liquid flows out from a lower liquid outlet, the reaction liquid is pumped into a rectifying tower through a transfer pump, and the fraction at 112-115 ℃ is collected under the pressure of 2-5mmHg, so that the high-purity difluoro sulfimide product is obtained, the product yield is 81.6%, and the product purity is 96.5%.
Comparative example 3
The comparative example does not adopt a pre-reaction device, and directly enters a microchannel reactor as a reaction device, and comprises a first temperature zone and a second temperature zone which are connected in series, wherein each temperature zone comprises 4 reaction modules connected in series;
(1) 97.1g (1 mol) sulfamic acid, 238g (2.0 mol) thionyl chloride and 80g (1 mol) sulfur trioxide are added into a pre-mixer and stirred uniformly;
(2) The premixed feed liquid is pumped into a reaction module of a first temperature zone of a microchannel reactor through a feed transfer pump at 49.2g/min, wherein the reaction temperature is 120 ℃, the reaction pressure is 0.5MPa, the temperature zone is provided with 4 modules connected in series, the reaction (residence) time of a single module is 5s, and the reaction (residence) time of the temperature zone is 20s;
(3) The method comprises the steps that dichloro reaction liquid flows out of a first temperature zone, enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out of a lower liquid outlet, the reaction liquid is pumped into a reaction module of a second temperature zone through a transfer pump, hydrogen fluoride liquid is pumped into the reaction module, the mol ratio of the hydrogen fluoride in the reaction liquid to sulfamic acid in the step (1) is 2:1, the total flow rate of two materials is 98.4g/min, the reaction temperature is 90 ℃, the reaction pressure is 0.5MPa, 4 series modules are arranged in the temperature zone, the reaction (residence) time of a single module is 2s, and the reaction (residence) time of the temperature zone is 8s;
(4) The difluoro reaction feed liquid flows out of the continuous flow reactor, enters a gas-liquid separation tank, the gas is discharged from an upper gas outlet and goes to a fluorine-chlorine separation condenser, the reaction liquid flows out from a lower liquid outlet, the reaction liquid is pumped into a rectifying tower through a transfer pump, and the fraction at 112-115 ℃ is collected under the pressure of 2-5mmHg, so that the high-purity difluoro sulfimide product is obtained, the product yield is 75.3%, and the product purity is 96.2%.
Claims (7)
1. A clean production process of difluoro sulfimide is characterized in that: the method comprises the steps of using an intermittent reaction kettle as a pre-reaction device and a micro-channel reactor as a main reaction device, wherein the micro-channel reactor comprises a first temperature zone and a second temperature zone which are connected in series, and each of the two temperature zones comprises a plurality of reaction modules connected in series; the method comprises the following steps:
(1) Adding sulfamic acid, sulfur trioxide and thionyl chloride into an intermittent reaction kettle, starting stirring, and reacting at a certain temperature and pressure to obtain a pre-reaction solution;
(2) The pre-reaction liquid is pumped into a reaction module of a first temperature zone of the microchannel reactor for reaction, and dichloro reaction liquid is obtained from an outlet;
(3) The method comprises the steps that dichloro reaction liquid enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a tail gas treatment system, reaction liquid flows out from a lower liquid outlet and is pumped into a reaction module in a second temperature zone, and hydrogen fluoride liquid is pumped into the reaction module in the second temperature zone for reaction, so that difluoro reaction liquid is obtained from an outlet;
(4) The difluoro reaction feed liquid enters a gas-liquid separation tank, gas is discharged from an upper gas outlet and goes to a fluorine-chlorine separation condenser, the reaction liquid flows out from a lower liquid outlet, and the reaction liquid is pumped into a rectifying tower for reduced pressure rectification, so that a high-purity difluoro sulfimide product is obtained;
in the step (1), the molar ratio of sulfamic acid to sulfur trioxide to thionyl chloride is 1:1 (2-2.5);
in the step (1), the reaction temperature is 90-120 ℃, the reaction pressure is 0.1-0.7MPa, and the reaction time is 1-6h;
in the step (2), 4-10 modules are arranged in series in the first temperature zone;
in the step (3), 4-10 modules are arranged in the second temperature zone in series;
in the step (4), the gas is mixed gas of hydrogen chloride and hydrogen fluoride, and the mixed gas enters a fluorine-chlorine separation condenser to be separated to obtain hydrogen fluoride liquid which is recycled for the reaction in the step (3).
2. The clean production process of bis-fluorosulfonyl imide according to claim 1, wherein: in step (2), the reaction residence time of the single module is 5-15s, and the total reaction residence time of the temperature zone is 20-150s.
3. The clean production process of bis-fluorosulfonyl imide according to claim 1, wherein: in the step (2), the reaction temperature of the first temperature zone is 120-150 ℃ and the reaction pressure is 0.5-1.5MPa.
4. The clean production process of bis-fluorosulfonyl imide according to claim 1, wherein: in the step (3), the molar ratio of the hydrogen fluoride to the sulfamic acid in the step (1) is (2-10): 1.
5. The clean production process of bis-fluorosulfonyl imide according to claim 1, wherein: in step (3), the reaction residence time of the single module is 2 to 6s, and the total reaction residence time of the temperature zone is 8 to 60s.
6. The clean production process of bis-fluorosulfonyl imide according to claim 1, wherein: in the step (3), the reaction temperature of the second temperature zone is 90-120 ℃ and the reaction pressure is 0.5-1.2MPa.
7. The clean production process of bis-fluorosulfonyl imide according to claim 1, wherein: in the step (4), the pressure of the vacuum rectification is 2-5mmHg, and the collection temperature of the difluoro sulfimide fraction is 112-115 ℃.
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