CN115504912A - Method for preparing high-purity trifluoromethanesulfonic anhydride by using batch distillation kettle - Google Patents
Method for preparing high-purity trifluoromethanesulfonic anhydride by using batch distillation kettle Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity trifluoromethanesulfonic anhydride in an intermittent distillation kettle, which comprises the following steps: carrying out heat treatment and reduced pressure distillation on the crude trifluoromethanesulfonic anhydride in a first purification kettle to obtain a first kettle residue, a first front fraction, a first middle fraction and a first rear fraction; and introducing the first kettle residue, the first front fraction and the first rear fraction into a second purification kettle for heat treatment and reduced pressure distillation to obtain second kettle residue, a second front fraction, a second middle fraction and a second rear fraction, refluxing the obtained second middle fraction into the first purification kettle, mixing with the obtained crude trifluoromethanesulfonic anhydride for heat treatment and reduced pressure distillation to finally obtain a fine trifluoromethanesulfonic acid product. The method solves the problem that impurities with different boiling points generated by side reactions are difficult to purify in the anhydride reaction process, greatly improves the product purity, and solves the problem that other components contain a small amount of products and are difficult to recover by a way of batch vacuum distillation and multi-stage purification.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for preparing high-purity trifluoromethanesulfonic anhydride in an intermittent distillation kettle.
Background
Trifluoromethanesulfonic anhydride is an important reagent for drug synthesis, and is used for trifluoromethanesulfonylation reaction in organic chemistry, and is generally used for protection of amino and hydroxyl groups or a precursor of synthetic coupling reaction. Trifluoromethanesulfonic anhydride is widely used in pharmaceutical industry as an intermediate, such as nucleoside, antibiotic, steroid, protein, glycoside, vitamin, etc., and is a novel catalyst for efficient Friedel-Crafts alkylation and cyclohexane alkylation reaction, for example, the national new medicine epristeride compound needs the reagent trifluoromethanesulfonic anhydride.
The trifluoromethanesulfonic anhydride can be prepared by a variety of methods, including the chloride reaction of trifluoromethanesulfonic acid with phosphorus, the mixed anhydride method, and the reaction of trifluoromethanesulfonic acid with phosphorus pentoxide.
1) Chloride reaction of triflic acid with phosphorus
Reacting trifluoromethanesulfonic acid with phosphorus pentachloride, wherein the temperature of the added raw material is not more than 40 ℃, the reaction temperature is controlled to be 20-80 ℃, so that a mixture containing trifluoromethanesulfonic anhydride can be obtained, and further distillation is carried out, so that trifluoromethanesulfonic anhydride can be obtained, and the chemical equation is as follows: 2CF 3 SO 3 H+PCl 5 →(CF 3 SO 2 ) 2 O+POCl 3 +2HCl。
Mixing trifluoromethanesulfonic acid with phosphorus trichloride, adding Cl2 equal to PCl3, preferably at a temperature of not more than 40 ℃, reacting at 20-80 ℃, and distilling the product to obtain trifluoromethanesulfonic anhydride with higher purity, wherein the chemical equation is as follows: 2CF 3 SO 3 H+PCl 5 →(CF 3 SO 2 ) 2 O+POCl 3 +2HCl。
2) Mixed anhydride process
Reacting trifluoromethanesulfonic acid or its derivative with ketene, carbonyl acid or its derivative under certain conditions to produce mixed anhydride containing trifluoromethanesulfonyl and carbonyl, wherein the molecular formula is CF 3 SO 2 -O-CO-R. It decomposes to some extent to give trifluoromethanesulfonic anhydride.
Trifluoromethanesulfonyl chloride with trifluoromethanesulfonate (CF) 3 SO 3 M, M = Li, na, K) reaction can also produce trifluoromethanesulfonic anhydride, the chemical equation being: CF (compact flash) 3 SO 2 Cl+CF 3 SO 3 M——→(CF 3 SO 2 ) 2 O+MCl。
3) In the presence of trifluoromethanesulfonic acid and phosphorus pentoxide, the trifluoromethanesulfonic anhydride is dehydrated to generate trifluoromethanesulfonic anhydride, and the chemical formula is as follows: 6CF 3 SO 3 H+P 2 O 5 ——→3(CF 3 SO 2 ) 2 O+2H 3 PO 4
The method for preparing the trifluoromethanesulfonic anhydride is mild in reaction and high in yield, and becomes a main method for industrially producing the trifluoromethanesulfonic anhydride at present.
The crude trifluoromethanesulfonic anhydride can be obtained by the above preparation method, but the main content is low, the impurity content is high, the requirement of the market on high purity can not be met for a long time, and further purification is needed.
Chinese patent CN 201310410009.5 discloses a purification method of trifluoromethanesulfonic anhydride, which comprises: 1) Introducing the crude trifluoromethanesulfonic anhydride into a distillation kettle, and heating and fully refluxing for 1-5h; 2) Adjusting the reflux ratio when the kettle temperature reaches 50-65 ℃ and collecting fractions; 3) And finishing the distillation when the temperature of the distillation kettle is more than 120 ℃. The method adjusts the reflux ratio to control different discharge fractions, has large control difficulty, has no liquid disturbance device in an intermittent distillation kettle, causes the product purity to be lower than 99.7 percent due to uneven heating of internal materials, and has the advantages of quick kettle temperature rise and low product yield along with the change of the residual weight and components of the materials in the kettle in the distillation process.
Chinese patent CN202010672255.8 discloses a preparation process of trifluoromethanesulfonic anhydride, which comprises: 1) Mixing and stirring trifluoromethanesulfonic acid and phosphorus pentoxide, and performing reduced pressure distillation to discharge; 2) And putting the obtained crude product into a distillation kettle, vacuumizing, heating, decompressing and distilling to obtain a refined trifluoromethanesulfonic anhydride. The process method adopts a simple distillation means to purify the trifluoromethanesulfonic anhydride, and has the advantages of low purity, low distillation vacuum, high discharging speed and high impurity content.
Chinese patent CN201910769924.0 discloses a preparation method of trifluoromethanesulfonic anhydride, wherein trifluoromethanesulfonate and excessive trifluoromethanesulfonyl fluoride are reacted under the action of a catalyst to prepare the anhydride, the process has the advantages of multiple steps for preparing the trifluoromethanesulfonyl fluoride, high requirement on the purity of the trifluoromethanesulfonyl fluoride, high pressure in the reaction process, easiness in vaporization of the trifluoromethanesulfonyl fluoride, vacuum loss and low conversion rate. The obtained trifluoromethanesulfonic anhydride is subjected to simple reduced pressure distillation only in one step, and the purity of the final product is difficult to further improve.
The existing production process adopts a common intermittent distillation mode, impurities such as trifluoromethyl trifluoromethanesulfonate, sulfur dioxide, hydrogen fluoride, sulfuric acid, pyrophosphoric acid and the like generated in the anhydride reaction process have more residues, high-purity trifluoromethanesulfonic anhydride is difficult to prepare only by single simple distillation, and fractions obtained by distillation contain part of trifluoromethanesulfonic anhydride products and cannot be effectively purified.
Therefore, we have proposed a method for preparing trifluoromethanesulfonic anhydride in high purity in a batch still to solve the above problems.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing high-purity trifluoromethanesulfonic anhydride in a batch still, aiming at the defects of the prior art. The method adopts a mode of batch vacuum distillation and multi-stage purification of the component parts, thereby not only solving the problem that impurities with different boiling points generated by side reactions are difficult to purify in the anhydride reaction process, greatly improving the product purity, but also solving the problem that the rest components contain a small amount of products and are difficult to recover.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing high-purity trifluoromethanesulfonic anhydride by using a batch still is characterized by comprising the following steps:
s1, adding a crude trifluoromethanesulfonic anhydride product into a first purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen; after the heat treatment is finished, carrying out reduced pressure distillation, adjusting the pressure of the first purification kettle to-0.06 MPa, then gradually heating the first purification kettle, and when the temperature of the first purification kettle is less than 60 ℃, obtaining a first front fraction; when the temperature of the first purifying kettle is 60 ℃, a first middle distillate is discharged; when the temperature of the first purification kettle is 130 ℃, discharging a first back fraction, and when the temperature of the first purification kettle is 160 ℃, stopping discharging to obtain a first kettle residue, a first front fraction, a first middle fraction and a first back fraction;
s2, introducing the first kettle residue, the first front fraction and the first rear fraction obtained in the S1 into a second purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen; after the heat treatment is finished, carrying out reduced pressure distillation, adjusting the pressure of the second purification kettle to-0.06 MPa, then gradually heating the second purification kettle, and when the temperature of the second purification kettle is less than 60 ℃, discharging a second front fraction; when the temperature of the second purification kettle is 60 ℃, a second middle distillate is discharged; when the temperature of the second purification kettle is 130 ℃, discharging a second rear fraction, and when the temperature of the second purification kettle is 160 ℃, stopping discharging to obtain a second kettle residue, a second front fraction, a second middle fraction and a second rear fraction;
s3, refluxing the second middle fraction obtained in the S2 to the first purification kettle to mix with the newly added crude trifluoromethanesulfonic anhydride, performing heat treatment again, stirring in the heat treatment process, and introducing nitrogen; after the heat treatment is finished, carrying out reduced pressure distillation to obtain kettle residue, front fraction, middle fraction and back fraction, wherein the middle fraction is a refined trifluoromethanesulfonic anhydride;
and the second front fraction and the second rear fraction obtained in the S2 are all refluxed to the second purification kettle for cyclic reaction. .
Preferably, the temperature of the heat treatment in S1 is 25-30 ℃, the time is 8-10 h, and the pressure is-0.04 MPa.
Preferably, the purity of the nitrogen in S1, S2 and S3 is 99.99%, and the flow rate is 0.8m 3 /h～1m 3 H; the stirring frequency is 10HZ.
Preferably, the temperature of the heat treatment in S2 is 25-35 ℃, the time is 3-8 h, and the pressure is-0.04 MPa.
Preferably, the mass ratio of the second middle distillate to the newly added crude trifluoromethanesulfonic anhydride in S3 is 1: (1.5-2).
Preferably, the heat treatment in S3 is the same as the heat treatment step in S1, and the reduced pressure distillation in S3 is the same as the reduced pressure distillation step in S1.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the modes of stirring, nitrogen-blowing heat treatment and reduced pressure distillation, and effectively removes light and heavy component impurities by performing two-stage heat treatment and reduced pressure distillation purification through fraction classification to obtain a product with higher purity, and each component in the distillation process adopts different treatment modes to be effectively recycled, and the product yield can reach more than 92%. Is superior to the similar indexes in the industry, has good economic value and social value, and is easy to popularize in the industry.
2. The invention carries out twice heat treatment and twice reduced pressure distillation on the crude trifluoromethanesulfonic anhydride, mainly separates components with different boiling points, and can separate other components except for the trifluoromethanesulfonic anhydride from the anhydride through twice heat treatment by experiment groping, thereby achieving higher recovery effect, reducing loss and preparing for improving the purity of the anhydride. If the process is one-time heat treatment and one-time distillation, the loss of the trifluoromethanesulfonic anhydride product is large, and the purity cannot reach more than 99.5%.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
The method for preparing high-purity trifluoromethanesulfonic anhydride by using a batch still in this example comprises the following steps:
s1, adding a crude trifluoromethanesulfonic anhydride product with the mass of 2100kg into a first purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen with the flow of 1m 3 H; after the heat treatment is finished, carrying out reduced pressure distillation, adjusting the pressure of the first purification kettle to-0.06 MPa, gradually heating the first purification kettle, and when the temperature of the first purification kettle is less than 60 ℃, obtaining a first front fraction; when the temperature of the first purifying kettle is 60 ℃, a first middle distillate is obtained; when the temperature of the first purification kettle is 130 ℃, discharging a first rear fraction, and when the temperature of the first purification kettle is 160 ℃, stopping discharging to obtain first kettle residue, a first front fraction, a first middle fraction and a first rear fraction; the discharging proportion of the first front fraction is 20%, the discharging proportion of the first middle fraction is 65%, and the discharging proportion of the first back fraction is 10%;
the temperature of the heat treatment is 30 ℃, the time is 8 hours, and the pressure is-0.04 MPa; the purity of the nitrogen is 99.99 percent; the stirring frequency is 10HZ; the total mass of the first still residue, the first front fraction and the first back fraction is 630kg;
the first front cut contained 50% trifluoromethanesulfonic anhydride, 35% trifluoromethyl ester, and 15% other impurities; the first kettle residue contains 35% of trifluoromethanesulfonic anhydride, 55% of sulfuric acid, 7% of phosphoric acid and 3% of fluorosulfonic acid; the first later fraction contains 85% of trifluoromethanesulfonic anhydride and 15% of sulfuric acid; the first middle distillate contains 98% of trifluoromethanesulfonic anhydride and 2% of other impurities;
s1, removing light components such as trifluoromethyl trifluoromethanesulfonate, sulfur dioxide, hydrogen fluoride, carbon dioxide and the like in a crude trifluoromethanesulfonic anhydride product;
s2, introducing the first kettle residue, the first front fraction and the first rear fraction obtained in the S1 into a second purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen, wherein the heat treatment temperature is 30 ℃, the time is 8 hours, and the pressure is-0.04 MPa; after the heat treatment is finished, adjusting the pressure of the second purification kettle to be-0.06 MPa, adjusting the discharge speed to be 30kg/h, discharging middle distillate when the temperature of the second purification kettle is 60 ℃, switching the discharge of the rear distillate when the temperature of the second purification kettle is 130 ℃, and stopping the discharge when the temperature is 160 ℃ to obtain second kettle residue, a second front fraction, a second middle fraction and a second rear fraction;
the purity of the nitrogen is 99.99 percent, and the flow rate is 1m 3 H; the stirring frequency is 10HZ; and (3) detection: the content of trifluoromethanesulfonic anhydride in the second middle distillate was 97.84%;
the second front cut contains 20% trifluoromethanesulfonic anhydride, 75% trifluoromethyl ester and 5% other impurity components; the second kettle residue contains 5% of trifluoromethanesulfonic anhydride, 85% of sulfuric acid and 10% of phosphoric acid; the second later fraction contains 75% trifluoromethanesulfonic anhydride and 25% sulfuric acid;
s3, refluxing the second middle fraction obtained in the S2 into the first purification kettle, mixing the second middle fraction with the newly added crude trifluoromethanesulfonic anhydride for heat treatment, stirring in the heat treatment process, and introducing nitrogen, wherein the heat treatment temperature is 30 ℃, the time is 8h, and the pressure is-0.04 MPa; after the heat treatment is finished, closing the nitrogen, carrying out reduced pressure distillation, wherein the pressure of the first purification kettle is-0.06 MPa during the reduced pressure distillation, then gradually heating the first purification kettle, and when the temperature of the first purification kettle is lower than 60 ℃, discharging front fraction; when the temperature of the first purifying kettle is 60 ℃, middle distillate is discharged; when the temperature of the first purification kettle is 130 ℃, discharging the rear fraction, when the temperature of the first purification kettle is 160 ℃, stopping discharging to obtain kettle residue, front fraction, middle fraction and rear fraction, controlling the discharging proportion of the front fraction to be 10%, the discharging proportion of the middle fraction to be 80%, the discharging proportion of the rear fraction to be 5%, and the balance to be kettle residue; the middle fraction is a refined trifluoromethanesulfonic anhydride product;
and the mass ratio of the second middle distillate to the newly added crude trifluoromethanesulfonic anhydride is 1:2; the purity of the nitrogen is 99.99 percent, and the flow rate is 1m 3 H; the stirring frequency is 10HZ; the reduced pressure distillation is the same as the reduced pressure distillation step in S1; the second front fraction and the second back fraction obtained in the S2 flow back to the second purification kettle for cyclic reaction;
transferring the first kettle residue, the second kettle residue and the kettle residue obtained in the S1, the S2 and the S3 into a recovery tank for storage, cooling the jacket refrigerating fluid of the recovery tank, and maintaining negative pressure of-0.04 MPa in the tank through vacuum to be used as a raw material of a reaction process.
The crude trifluoromethanesulfonic anhydride used in this example contained 90.5% trifluoromethanesulfonic anhydride and 407ppm F - 2467ppm of SO 4 2- (ii) a The indexes of the detected fine trifluoromethanesulfonic anhydride product obtained in this example are shown in table 1;
table 1: index of production of trifluoromethanesulfonic anhydride obtained in example 1
Example 2
The method for preparing high-purity trifluoromethanesulfonic anhydride by using a batch still in this example comprises the following steps:
s1, adding 3000kg of crude trifluoromethanesulfonic anhydride product into a first purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen with the flow of 0.8m 3 H; after the heat treatment is finished, carrying out reduced pressure distillation, adjusting the pressure of the first purification kettle to-0.06 MPa, gradually heating the first purification kettle, and when the temperature of the first purification kettle is lower than 60 ℃, obtaining a first front fraction; when the temperature of the first purifying kettle is 60 ℃, a first middle distillate is discharged; when the temperature of the first purification kettle is 130 ℃, discharging a first back fraction, and when the temperature of the first purification kettle is 160 ℃, stopping discharging to obtain a first kettle residue, a first front fraction, a first middle fraction and a first back fraction; the fraction ratio of the first front cut is 20%, the fraction ratio of the first middle cut is 65%, and the fraction ratio of the first back cut is 10%;
the temperature of the heat treatment is 25 ℃, the time is 10 hours, and the pressure is-0.04 MPa; the purity of the nitrogen is 99.99 percent; the stirring frequency is 10HZ; the total mass of the first still residue, the first front fraction and the first back fraction is 900kg;
the first front cut contains trifluoromethanesulfonic anhydride, trifluoromethyl ester and impurities; the first kettle residue contains trifluoromethanesulfonic anhydride, sulfuric acid, phosphoric acid and fluorosulfonic acid; the first after-cut fraction contains trifluoromethanesulfonic anhydride and sulfuric acid; the first middle distillate contains trifluoromethanesulfonic anhydride and other impurities;
s2, introducing the first kettle residue, the first front fraction and the first rear fraction obtained in the S1 into a second purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen, wherein the heat treatment temperature is 35 ℃, the time is 3 hours, and the pressure is-0.04 MPa; after the heat treatment is finished, adjusting the pressure of the second purification kettle to-0.06 MPa, controlling the discharge speed to be 30kg/h, discharging middle distillate when the temperature of the second purification kettle is 60 ℃, switching the discharge of rear distillate when the temperature of the second purification kettle is 130 ℃, and stopping the discharge when the temperature is 160 ℃ to obtain second kettle residue, second front distillate, second middle distillate and second rear distillate;
the purity of the nitrogen is 99.99 percent, and the flow rate is 0.8m 3 H; the stirring frequency is 10HZ; the mass of the second middle distillate obtained is 800kg; through detection: the content of trifluoromethanesulfonic anhydride in the second middle distillate was 98.68%; the second front cut fraction contains trifluoromethanesulfonic anhydride, trifluoromethyl ester and other impurities; the second kettle residue contains trifluoromethanesulfonic anhydride, sulfuric acid and phosphoric acid; the second later fraction contains trifluoromethanesulfonic anhydride and sulfuric acid;
s3, refluxing the second middle fraction obtained in the S2 into the first purification kettle, mixing the second middle fraction with the newly added crude trifluoromethanesulfonic anhydride for heat treatment, stirring in the heat treatment process, and introducing nitrogen, wherein the heat treatment temperature is 25 ℃, the time is 10 hours, and the pressure is-0.04 MPa; closing nitrogen after the heat treatment is finished, carrying out reduced pressure distillation, wherein the pressure of the first purification kettle is-0.06 MPa during the reduced pressure distillation, then gradually heating the first purification kettle, and when the temperature of the first purification kettle is less than 60 ℃, discharging front fraction; when the temperature of the first purification kettle is 60 ℃, middle distillate is discharged; when the temperature of the first purification kettle is 130 ℃, discharging the rear fraction, when the temperature of the first purification kettle is 160 ℃, stopping discharging to obtain kettle residue, front fraction, middle fraction and rear fraction, controlling the discharging proportion of the front fraction to be 5%, the discharging proportion of the middle fraction to be 85%, the discharging proportion of the rear fraction to be 5% and the balance to be kettle residue; the middle fraction is a refined trifluoromethanesulfonic anhydride product;
the mass ratio of the reflux of the first middle distillate and the newly added crude trifluoromethanesulfonic anhydride is 1:1.5; the purity of the nitrogen is 99.99 percent, and the flow rate is 0.8m 3 H; the stirring frequency is 10HZ; the reduced pressure distillation is the same as the reduced pressure distillation step in S1; the second front fraction and the second back fraction obtained in the S2 flow back to the second purification kettle for cyclic reaction;
transferring the first kettle residue, the second kettle residue and the kettle residue obtained in the S1, the S2 and the S3 into a recovery tank for storage, cooling refrigerating fluid in a jacket of the recovery tank, and maintaining negative pressure of-0.04 MPa in the tank through vacuum to be used as a raw material of a reaction process.
The crude trifluoromethanesulfonic anhydride used in this example contained 91.5% trifluoromethanesulfonic anhydride and 358ppm F - 3261ppm SO 4 2- ) (ii) a The indexes of the detected refined trifluoromethanesulfonic anhydride product obtained in this example are shown in table 2;
table 2: index of production of trifluoromethanesulfonic anhydride obtained in example 2
Example 3
The method for preparing high-purity trifluoromethanesulfonic anhydride by using a batch still in this example comprises the following steps:
s1, adding 2100kg of crude trifluoromethanesulfonic anhydride product into a first purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen with the flow of 0.9m 3 H; after the heat treatment is finished, carrying out reduced pressure distillation, adjusting the pressure of the first purification kettle to-0.06 MPa, gradually heating the first purification kettle, and when the temperature of the first purification kettle is lower than 60 ℃, obtaining a first front fraction; when the temperature of the first purifying kettle is 60 ℃, dischargingA first middle distillate fraction; when the temperature of the first purification kettle is 130 ℃, discharging a first rear fraction, and when the temperature of the first purification kettle is 160 ℃, stopping discharging to obtain first kettle residue, a first front fraction, a first middle fraction and a first rear fraction; the fraction ratio of the first front cut is 20%, the fraction ratio of the first middle cut is 65%, and the fraction ratio of the first back cut is 10%;
the temperature of the heat treatment is 27 ℃, the time is 9h, and the pressure is-0.04 MPa; the purity of the nitrogen is 99.99%; the stirring frequency is 10HZ; the total mass of the first still residue, the first front fraction and the first back fraction is 630kg;
the first front cut contains trifluoromethanesulfonic anhydride, trifluoromethyl ester and impurities; the first kettle residue contains trifluoromethanesulfonic anhydride, sulfuric acid, phosphoric acid and fluorosulfonic acid; the first after-cut fraction contains trifluoromethanesulfonic anhydride and sulfuric acid; the first middle distillate contains trifluoromethanesulfonic anhydride and other impurities;
s2, introducing the first kettle residue, the first front fraction and the first rear fraction obtained in the S1 into a second purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen, wherein the heat treatment temperature is 32 ℃, the time is 6 hours, and the pressure is-0.04 MPa; after the heat treatment is finished, adjusting the pressure of the second purification kettle to-0.06 MPa, controlling the discharge speed to be 30kg/h, discharging middle distillate when the temperature of the second purification kettle is 60 ℃, switching the discharge of rear distillate when the temperature of the second purification kettle is 130 ℃, and stopping the discharge when the temperature is 160 ℃ to obtain second kettle residue, second front distillate, second middle distillate and second rear distillate;
the purity of the nitrogen is 99.99 percent, and the flow rate is 0.9m 3 H; the stirring frequency is 10HZ; the mass of the second middle distillate is 700kg; through detection: the trifluoromethanesulfonic anhydride content of the second middle distillate was 97.34%; the second front cut fraction contains trifluoromethanesulfonic anhydride, trifluoromethyl ester and other impurities; the second kettle residue contains trifluoromethanesulfonic anhydride, sulfuric acid and phosphoric acid; the second later fraction contains trifluoromethanesulfonic anhydride and sulfuric acid;
s3, refluxing the second middle distillate obtained in the S2 into the first purification kettle, mixing the second middle distillate with the newly added crude trifluoromethanesulfonic anhydride, performing heat treatment, stirring in the heat treatment process, and introducing nitrogen, wherein the heat treatment temperature is 27 ℃, the time is 9 hours, and the pressure is-0.04 MPa; closing nitrogen after the heat treatment is finished, carrying out reduced pressure distillation, wherein the pressure of the first purification kettle is-0.06 MPa during the reduced pressure distillation, then gradually heating the first purification kettle, and when the temperature of the first purification kettle is less than 60 ℃, discharging front fraction; when the temperature of the first purifying kettle is 60 ℃, middle distillate is discharged; when the temperature of the first purification kettle is 130 ℃, discharging the rear fraction, when the temperature of the first purification kettle is 160 ℃, stopping discharging to obtain kettle residue, front fraction, middle fraction and rear fraction, controlling the discharging proportion of the front fraction to be 10%, the discharging proportion of the middle fraction to be 80%, the discharging proportion of the rear fraction to be 5%, and the balance to be kettle residue; the middle fraction is a refined trifluoromethanesulfonic anhydride;
and the mass ratio of the first middle distillate to the newly added crude trifluoromethanesulfonic anhydride is 1:1.7; the purity of the nitrogen is 99.99 percent, and the flow rate is 0.9m 3 H; the stirring frequency is 10HZ; the reduced pressure distillation is the same as the reduced pressure distillation step in S1; the second front fraction and the second back fraction obtained in the S2 flow back to the second purification kettle for circular reaction;
transferring the first kettle residue, the second kettle residue and the kettle residue obtained in the S1, the S2 and the S3 into a recovery tank for storage, cooling refrigerating fluid in a jacket of the recovery tank, and maintaining negative pressure of-0.04 MPa in the tank through vacuum to be used as a raw material of a reaction process.
The crude trifluoromethanesulfonic anhydride used in this example contained 90.8% trifluoromethanesulfonic anhydride and 397ppm F - 3164ppm of SO 4 2- ) (ii) a The indexes of the detected refined trifluoromethanesulfonic anhydride product obtained in this example are shown in table 3;
table 3: index for Trifluoromethanesulfonic anhydride product obtained in example 3
At present, the quality index of trifluoromethanesulfonic anhydride in the industry is shown in table 4;
TABLE 4 trifluoromethanesulfonic anhydride quality index (trade)
As can be seen, the refined trifluoromethanesulfonic anhydride products obtained in examples 1-3 all meet the above quality specifications.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. A method for preparing high-purity trifluoromethanesulfonic anhydride by using a batch still is characterized by comprising the following steps:
s1, adding a crude trifluoromethanesulfonic anhydride product into a first purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen; after the heat treatment is finished, carrying out reduced pressure distillation, adjusting the pressure of the first purification kettle to-0.06 MPa, then gradually heating the first purification kettle, and when the temperature of the first purification kettle is less than 60 ℃, obtaining a first front fraction; when the temperature of the first purifying kettle is 60 ℃, a first middle distillate is discharged; when the temperature of the first purification kettle is 130 ℃, discharging a first rear fraction, and when the temperature of the first purification kettle is 160 ℃, stopping discharging to obtain first kettle residue, a first front fraction, a first middle fraction and a first rear fraction;
s2, introducing the first kettle residue, the first front fraction and the first rear fraction obtained in the S1 into a second purification kettle for heat treatment, stirring in the heat treatment process, and introducing nitrogen; after the heat treatment is finished, carrying out reduced pressure distillation, adjusting the pressure of the second purification kettle to-0.06 MPa, then gradually heating the second purification kettle, and when the temperature of the second purification kettle is less than 60 ℃, discharging a second front fraction; when the temperature of the second purification kettle is 60 ℃, a second middle distillate is discharged; when the temperature of the second purification kettle is 130 ℃, discharging a second rear fraction, and when the temperature of the second purification kettle is 160 ℃, stopping discharging to obtain a second kettle residue, a second front fraction, a second middle fraction and a second rear fraction;
s3, refluxing the second middle distillate obtained in the S2 to the first purification kettle to be mixed with the newly added crude trifluoromethanesulfonic anhydride, performing heat treatment again, stirring in the heat treatment process, and introducing nitrogen; after the heat treatment is finished, carrying out reduced pressure distillation to obtain kettle residue, front fraction, middle fraction and back fraction, wherein the middle fraction is a refined trifluoromethanesulfonic anhydride;
and the second front fraction and the second back fraction obtained in the S2 are all refluxed into the second purification kettle for cyclic reaction.
2. The method for preparing high-purity trifluoromethanesulfonic anhydride according to claim 1, wherein the temperature of the heat treatment in S1 is 25-30 ℃, the time is 8-10 h, and the pressure is-0.04 MPa.
3. The method for preparing high-purity trifluoromethanesulfonic anhydride according to claim 1, wherein the purity of nitrogen in S1, S2 and S3 is 99.99% and the flow rate is 0.8m 3 /h～1m 3 H; the stirring frequency is 10HZ.
4. The method for preparing high-purity trifluoromethanesulfonic anhydride according to claim 1, wherein the temperature of the heat treatment in S2 is 30-35 ℃, the time is 3-8 h, and the pressure is-0.04 MPa.
5. The process according to claim 1, wherein the mass ratio of the second middle distillate and the newly added crude trifluoromethanesulfonic anhydride in S3 is 1: (1.5-2).
6. The method of claim 2, wherein the heat treatment in S3 is the same as the heat treatment in S1, and the reduced pressure distillation in S3 is the same as the reduced pressure distillation in S1.
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| JP2022139965A (en) * | 2021-03-12 | 2022-09-26 | 旭化成株式会社 | Method for producing fluorine-containing vinyl sulfonic acid fluoride or fluorine-containing vinyl sulfonate, and method for separating the same |
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