阅读说明：本技术 一种三氟甲磺酸的生产装置及方法 (Production device and method of trifluoromethanesulfonic acid ) 是由 林坤 王少波 马朝选 王亚峰 于 2020-12-30 设计创作，主要内容包括：本发明涉及一种三氟甲磺酸的生产装置及方法,属于有机化工技术领域。将甲基磺酰氯水溶液与氟化钾反应,得到的甲基磺酰氟粗品减压蒸馏、相位分离后再次减压蒸馏,得到的甲基磺酰氟纯品与无水氟化氢在电解装置中进行电解,电解后得到的气体冷却后通入氟化钠塔中然后再采用冷阱装置收集,得到的三氟甲磺酰氟与氢氧化钾溶液进行水解反应,反应产物进行萃取分离,重结晶后,得到三氟甲磺酸钾；三氟甲磺酸钾与过量的浓硫酸进行酸解反应,得到的三氟甲磺酸粗品蒸馏后,得到纯化后的三氟甲磺酸。能够快速制备和提纯甲基磺酰氟,并且能对在制备过程中产生的不合格品进行重新氟化,有效提升生产的效率和质量。(The invention relates to a device and a method for producing trifluoromethanesulfonic acid, and belongs to the technical field of organic chemical industry. Reacting a methanesulfonyl chloride aqueous solution with potassium fluoride, carrying out reduced pressure distillation on an obtained methanesulfonyl fluoride crude product, carrying out phase separation, carrying out reduced pressure distillation again, electrolyzing the obtained methanesulfonyl fluoride pure product and anhydrous hydrogen fluoride in an electrolysis device, cooling gas obtained after electrolysis, introducing the cooled gas into a sodium fluoride tower, collecting the gas by using a cold trap device, carrying out hydrolysis reaction on the obtained trifluoromethanesulfonyl fluoride and a potassium hydroxide solution, carrying out extraction separation on a reaction product, and recrystallizing to obtain potassium trifluoromethanesulfonate; and (3) carrying out acidolysis reaction on potassium trifluoromethanesulfonate and excessive concentrated sulfuric acid to obtain a crude trifluoromethanesulfonic acid product, and distilling to obtain the purified trifluoromethanesulfonic acid. The method can rapidly prepare and purify the methanesulfonyl fluoride, can re-fluorinate unqualified products generated in the preparation process, and effectively improves the production efficiency and quality.)

1. A production device of trifluoromethanesulfonic acid is characterized in that: comprises a first potassium fluoride storage tank (1), a methanesulfonyl chloride aqueous solution storage tank (3), a stirrer (5), a first distillation device (7), a phase separation device (10), a second distillation device (11), a methanesulfonyl fluoride storage tank (14), an anhydrous hydrogen fluoride storage tank (15), an electrolysis device (18), a sodium fluoride tower (21), a cold trap device (22) and a potassium hydroxide solution storage tank (23), the device comprises an evaporation device (24), a first absolute ethyl alcohol storage tank (31), an extraction device (27), a filtering device (28), a mixed solution storage tank (30), a second absolute ethyl alcohol storage tank (40), a potassium trifluoromethanesulfonate storage tank (33), a first sulfuric acid storage tank (34), an acidolysis device (35), a third distillation device (36), a silica storage tank (38), a fourth distillation device (39) and a trifluoromethanesulfonic acid storage tank (41);

the device comprises a first potassium fluoride storage tank (1) and a methanesulfonyl chloride aqueous solution storage tank (3), wherein the first potassium fluoride storage tank and the methanesulfonyl chloride aqueous solution storage tank are respectively connected with a stirrer (5), the bottom of the stirrer (5) is connected with one side of a first distillation device (7), the other side of the first distillation device (7) is connected with a phase separation device (10), the bottom of the phase separation device (10) is connected with a second distillation device (11), and the second distillation device (11) is connected with a methanesulfonyl fluoride storage tank (14);

the device comprises a methanesulfonyl fluoride storage tank (14) and an anhydrous hydrogen fluoride storage tank (15), wherein the methanesulfonyl fluoride storage tank and the anhydrous hydrogen fluoride storage tank are respectively connected with an electrolysis device (18), the top of the electrolysis device (18) is provided with a collection cover (17), the top of the collection cover (17) is provided with a condenser (19), the condenser (19) condenses and is connected with one side of a sodium fluoride tower (21) through a condensing pipe (20), and the other side of the sodium fluoride tower (21) is connected with a cold trap device (22);

the cold trap device (22) is also connected with a distillation device (24), the distillation device (24) is also connected with a potassium hydroxide solution storage tank (23) and an extraction device (27), and a filtering device (28), a mixed solution storage tank (30), a lithium trifluoromethanesulfonate storage tank (33), an acidolysis device (35), a third distillation device (36), a fourth distillation device (39) and a trifluoromethanesulfonic acid storage tank (41) are sequentially arranged behind the extraction device (27);

the first absolute ethyl alcohol storage tank (31) is connected with the extraction device (27); the second absolute ethyl alcohol storage tank (40) is connected with the mixed solution storage tank (30); the first sulfuric acid storage tank (34) is connected with an acidolysis device (35); the silica storage tank (38) is connected to the fourth distillation unit.

2. The apparatus for producing trifluoromethanesulfonic acid according to claim 1, characterized in that: the upper end of the stirrer (5) is fixed with a connecting plate (42), the lower end of the connecting plate (42) is rotatably connected with a rotating shaft (43), the lower end of the rotating shaft (43) penetrates through the stirrer (5) and extends out of the stirrer (5) to be connected with a speed regulating mechanism, a connecting piece (52) is installed on one end side wall in the stirrer (5), a bevel gear set (51) and a sleeve (44) are installed on the connecting piece (52), the sleeve (44) is rotatably sleeved on the rotating shaft (43), the bevel gear set (51) consists of three bevel gears, the three bevel gears are sequentially meshed, the rotating shaft (43) and the sleeve (44) are respectively fixedly sleeved on two opposite bevel gears, the rotating shaft (43) and the sleeve (44) can rotate in opposite directions, the lower end of the sleeve (44) is fixed with a transverse plate (53), two ends of the transverse plate (53) are respectively fixed with a connecting rod (46), and the lower end of the connecting rod (, the scraper blade (47) is in contact with the bottom of the stirrer (5), the rotating shaft (43) and the connecting rod (46) are both fixed with stirring blades (45), and the stirring blades (45) on the rotating shaft (43) and the stirring blades (45) on the connecting rod (46) are arranged in a staggered mode.

3. The apparatus for producing trifluoromethanesulfonic acid according to claim 2, characterized in that: the speed regulation mechanism comprises a motor (48), a support (56) and a transmission block (54), the transmission block (54) is fixed at the lower end of a rotating shaft (43), a tapered groove (50) is formed in the transmission block (54), the transmission block (54) is rotatably arranged on one side of the upper end of the support (56), an adaptation mechanism is installed at the lower end of the support (56), the adaptation mechanism is connected with the motor (48), an electric telescopic rod (55) and a vertical rod are installed on the adaptation mechanism, a push plate (58) is rotatably sleeved on the vertical rod, the push plate (58) is fixedly connected with the upper end of the electric telescopic rod (55), a tapered wheel (49) is installed at the upper end of the vertical rod, the tapered wheel (49) is located in the tapered groove (50), the side wall of the tapered wheel (49) is abutted to the side wall in the tapered groove (50), the electric telescopic rod (55) can drive the vertical rod to lift through the push, and the cone-shaped wheel (49) is always in contact with the side wall in the cone-shaped groove (50) through an adaptive mechanism.

4. The apparatus for producing trifluoromethanesulfonic acid according to claim 2, characterized in that: the adaptive mechanism comprises two sliding rods (59) fixed on one side of the lower end of a support (56), sliding plates (60) are sleeved on the two sliding rods (59) in a sliding mode, a U-shaped rod (61) is arranged below a stirrer (5), shaft sleeves are arranged on the U-shaped rod (61) and the sliding plates (60), driving wheels (63) are fixed at the tail ends of output shafts of the two shaft sleeves and a motor (48), the three driving wheels (63) are in transmission connection through a driving belt (64), a first spring (57) is sleeved on the sliding rods (59), two ends of the first spring (57) are respectively fixed on one side, opposite to the support (56) and the sliding plates (60), the lower end of an electric telescopic rod (55) is fixed at the upper end of the sliding plate (60), a vertical rod is sleeved in a sliding mode in a shaft sleeve rotatably connected to the sliding plates (60), a second spring (62) is sleeved on the U-shaped rod (61), one end of the second spring (62) is fixed, the other end of the second spring (62) is fixed on the U-shaped rod (61), when the electric telescopic rod (55) drives the cone pulley (49) to lift, the sliding plate (60) can move, the driving wheel (63) on the sliding plate (60) can move when the sliding plate (60) moves, the second spring (62) can pull the other driving wheel (63) to move, and the driving belt (64) is guaranteed to be always in a tensioning state.

5. The apparatus for producing trifluoromethanesulfonic acid according to claim 1, characterized in that: the first distillation device (7) is also connected with a first impurity storage tank (8).

6. The apparatus for producing trifluoromethanesulfonic acid according to claim 1, characterized in that: the second distillation device (11) is connected with the phase separation device (10) through a first return pipe (12), and a second impurity storage tank (9) is further connected to the phase separation device (10).

7. The apparatus for producing trifluoromethanesulfonic acid according to claim 1, characterized in that: the mixed solution storage tank (30) is connected with the extraction device (27) through a second return pipe (25), and the mixed solution storage tank (30) is further connected with a potassium fluoride solid storage tank (32).

8. The apparatus for producing trifluoromethanesulfonic acid according to claim 1, characterized in that: and a second sulfuric acid storage tank (37) is also connected to the fourth distillation device (39).

9. A production method of trifluoromethanesulfonic acid is characterized in that: the method comprises the following steps:

(1) adding the water solution of methanesulfonyl chloride and potassium fluoride into a stirrer (5) for stirring reaction to obtain a crude product of methanesulfonyl fluoride;

(2) the crude product of the methanesulfonyl fluoride firstly enters a first distillation device (7) for reduced pressure distillation, the collected fraction enters a phase separation device (10) for phase separation, and the lower-layer component enters a second distillation device (11) for reduced pressure distillation again to obtain a pure product of the methanesulfonyl fluoride;

(3) electrolyzing the pure product of the methanesulfonyl fluoride and anhydrous hydrogen fluoride in an electrolysis device (18), wherein the electrolyte is potassium fluoride, cooling the gas obtained after electrolysis, introducing the cooled gas into a sodium fluoride tower (21), and collecting the gas by using a cold trap device (22) to obtain trifluoromethanesulfonyl fluoride;

(4) carrying out hydrolysis reaction on the trifluoromethanesulfonyl fluoride and a potassium hydroxide solution in an evaporation device (24), firstly, extracting and separating a reaction product in an extraction device (27) by using absolute ethyl alcohol, and recrystallizing filtrate collected in a filtering device (28) by using the absolute ethyl alcohol to obtain potassium trifluoromethanesulfonate;

(5) carrying out acidolysis reaction on the potassium trifluoromethanesulfonate and excessive concentrated sulfuric acid in an acidolysis device (35), and obtaining a crude trifluoromethanesulfonic acid after the reaction is finished;

(6) and (3) distilling the crude trifluoromethanesulfonic acid in a third distillation device (36) and a fourth distillation device (39) respectively, and adding silica during distillation in the fourth distillation device (39) to obtain purified trifluoromethanesulfonic acid.

10. The process for producing trifluoromethanesulfonic acid according to claim 9, characterized in that: in the step (1), stirring and reacting at the temperature of 40-80 ℃ for 2-5 h;

in the step (2), the vacuum degree is 400-1000 mmHg and the temperature is 30-80 ℃ during reduced pressure distillation;

in the step (3), the gas obtained after electrolysis is cooled to-40 to-10 ℃, the electrolysis temperature is-15 to 20 ℃, and the voltage is 4 to 12V; the kettle temperature of the cold trap device (22) is-100 to-70 ℃, and the column temperature is-65 to-35 ℃;

in the step (4), the hydrolysis reaction temperature is 70-95 ℃, and the recrystallization temperature is 50-80 ℃;

in the step (6), the vacuum degree is 600-800 mmHg and the temperature is 60-90 ℃ when the mixture is distilled in the third distillation device (36), and the vacuum degree is 500-900 mmHg and the temperature is 40-100 ℃ when the mixture is distilled in the fourth distillation device (39).

Technical Field

The invention relates to a device and a method for producing trifluoromethanesulfonic acid, and belongs to the technical field of organic chemical industry.

Background

The trifluoromethanesulfonic acid belongs to chemical intermediates and organic chemical raw materials/special chemicals, has wide application, and one of the important applications is to prepare lithium trifluoromethanesulfonate, which is one of the important raw materials of a lithium ion battery.

In addition, trifluoromethanesulfonic acid, one of the superacids, is extremely stable to oxidation and reduction and, due to its unique properties, is used in the following fields: in the plastics industry, as oligomerization-polymerization catalysts; the fuel industry, as a protonation catalyst; various fields of the pharmaceutical industry such as nucleosides, antibiotics, steroids, proteins, glycosides; synthesis of herbicides and growth regulators; synthesizing vitamins; sugar industry, etc., whose anhydride is a very strong alkylation catalyst in friedelin (cork triterpene ketone) process, and finally, trifluoromethanesulfonic acid and its derivatives cover a wide range in the field of organic chemical reactions, many chemical reactions and technical processes could not be completed without them, or the gain is very slight, and due to its extremely high functionality, it is considered as a super strong acid of a strong support of the 21 st century fine chemistry industry. At present, the production efficiency of trifluoromethanesulfonic acid is low, and the quality is poor.

Disclosure of Invention

In view of the above, the present invention aims to provide a production apparatus and a production method of trifluoromethanesulfonic acid.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a production device of trifluoromethanesulfonic acid comprises a first potassium fluoride storage tank, a methanesulfonyl chloride aqueous solution storage tank, a stirrer, a first distillation device, a phase separation device, a second distillation device, a methanesulfonyl fluoride storage tank, an anhydrous hydrogen fluoride storage tank, an electrolysis device, a sodium fluoride tower, a cold trap device, a potassium hydroxide solution storage tank, an evaporation device, a first anhydrous ethanol storage tank, an extraction device, a filtration device, a mixed solution storage tank, a second anhydrous ethanol storage tank, a trifluoromethanesulfonic acid potassium storage tank, a first sulfuric acid storage tank, an acidolysis device, a third distillation device, a silica storage tank, a fourth distillation device and a trifluoromethanesulfonic acid storage tank;

the device comprises a first distillation device, a first potassium fluoride storage tank, a second distillation device, a phase separation device, a first potassium fluoride storage tank, a methanesulfonyl chloride aqueous solution storage tank, a stirrer, a second distillation device, a phase separation device, a first distillation device and a second distillation device, wherein the first potassium fluoride storage tank and the methanesulfonyl chloride aqueous solution storage tank are respectively connected with the stirrer;

the device comprises an electrolytic device, a methanesulfonyl fluoride storage tank, an anhydrous hydrogen fluoride storage tank, a condenser, a cold trap device and a water storage tank, wherein the methanesulfonyl fluoride storage tank and the anhydrous hydrogen fluoride storage tank are respectively connected with the electrolytic device;

the cold trap device is also connected with a distillation device, the distillation device is also connected with a potassium hydroxide solution storage tank and an extraction device, and a filtering device, a mixed solution storage tank, a lithium trifluoromethanesulfonate storage tank, an acidolysis device, a third distillation device, a fourth distillation device and a trifluoromethanesulfonic acid storage tank are sequentially arranged behind the extraction device;

the first absolute ethyl alcohol storage tank is connected with the extraction device; the second absolute ethyl alcohol storage tank is connected with the mixed solution storage tank; the first sulfuric acid storage tank is connected with the acidolysis device; the silica storage tank is connected to a fourth distillation unit.

Further, the upper end of agitator is fixed with the connecting plate, the lower extreme of connecting plate rotates and is connected with the pivot, the lower extreme of pivot runs through the agitator and extends to the agitator and be connected with speed adjusting mechanism outward, install the connecting piece on the one end lateral wall in the agitator, install bevel gear group and sleeve pipe on the connecting piece, the sleeve pipe rotates and cup joints in the pivot, bevel gear group comprises three bevel gear, three bevel gear meshes in proper order, pivot and sleeve pipe are fixed the suit respectively on two relative bevel gear wherein, enable pivot and sleeve pipe antiport, sheathed tube lower extreme is fixed with the diaphragm, the both ends of diaphragm are fixed with the connecting rod respectively, the lower extreme of connecting rod is fixed with the scraper blade, bottom in scraper blade and the agitator is inconsistent, all be fixed with the stirring leaf on pivot and the connecting rod, and the stirring leaf on the epaxial stirring leaf of pivot and the connecting rod is.

Further, speed adjusting mechanism includes the motor, support and transmission piece, the transmission piece is fixed at the pivot lower extreme, be equipped with the bell jar on the transmission piece, the transmission piece rotates and sets up in upper end one side of support, adaptation mechanism is installed to the lower extreme of support, adaptation mechanism and motor are connected, install electric telescopic handle and montant in the adaptation mechanism, the push pedal has been cup jointed in the rotation on the montant, push pedal and electric telescopic handle's upper end fixed connection, the cone pulley is installed to the upper end of montant, the cone pulley is located the bell jar, the lateral wall of cone pulley and the lateral wall of bell jar are inconsistent, electric telescopic handle can drive the montant through the push pedal and go up and down, the montant goes up and down to drive the cone pulley, and make the cone pulley inconsistent with the lateral wall.

Further, the adapting mechanism comprises two slide bars fixed on one side of the lower end of the bracket, a sliding plate is sleeved on the two slide bars in a sliding manner, a U-shaped rod is arranged below the stirrer, shaft sleeves are arranged on the U-shaped rod and the sliding plate, driving wheels are fixed at the tail ends of the output shafts of the two shaft sleeves and the motor, the three driving wheels are in transmission connection through a transmission belt, a first spring is sleeved on each slide bar, two ends of the first spring are respectively fixed on one side of the bracket opposite to the sliding plate, the lower end of the electric telescopic rod is fixed at the upper end of the sliding plate, a vertical rod is sleeved in the shaft sleeve which is rotatably connected on the sliding plate in a sliding manner, a second spring is sleeved on each U-shaped rod, one end of the second spring is fixed on the shaft sleeve on the U-shaped rod, the other end of the second spring is fixed on the U-shaped rod, the second spring can pull the other driving wheel to move, and the driving belt is always in a tensioning state.

Furthermore, a first impurity storage tank is connected to the first distillation device.

Further, the second distillation device is connected with the phase separation device through a first return pipe, and the phase separation device is also connected with a second impurity storage tank.

Further, the mixed solution storage tank passes through the second back flow pipe with the extraction device is connected, just still be connected with potassium fluoride solid storage tank on the mixed solution storage tank.

Further, a second sulfuric acid storage tank is connected to the fourth distillation device.

A method for producing trifluoromethanesulfonic acid, comprising the steps of:

(1) adding the water solution of methanesulfonyl chloride and potassium fluoride into a stirrer for stirring reaction to obtain a crude product of methanesulfonyl fluoride;

(2) the crude product of the methanesulfonyl fluoride firstly enters a first distillation device for reduced pressure distillation, the collected fraction enters a phase separation device for phase separation, and the lower component enters a second distillation device for reduced pressure distillation again to obtain a pure product of the methanesulfonyl fluoride;

(3) electrolyzing the pure product of the methanesulfonyl fluoride and anhydrous hydrogen fluoride in an electrolytic device, wherein the electrolyte is potassium fluoride, cooling the gas obtained after electrolysis, introducing the cooled gas into a sodium fluoride tower, and collecting the gas by using a cold trap device to obtain trifluoromethanesulfonyl fluoride;

(4) carrying out hydrolysis reaction on the trifluoromethanesulfonyl fluoride and a potassium hydroxide solution in an evaporation device, firstly, extracting and separating a reaction product in an extraction device by using absolute ethyl alcohol, and recrystallizing filtrate collected in a filtering device by using absolute ethyl alcohol to obtain potassium trifluoromethanesulfonate;

(5) carrying out acidolysis reaction on the potassium trifluoromethanesulfonate and excessive concentrated sulfuric acid in an acidolysis device, and obtaining a crude trifluoromethanesulfonic acid after the reaction is finished;

(6) and distilling the crude trifluoromethanesulfonic acid in a third distillation device and a fourth distillation device respectively, and adding silicon dioxide during distillation in the fourth distillation device to obtain purified trifluoromethanesulfonic acid.

Further, in the step (1), the stirring reaction temperature is 40-80 ℃, and the time is 2-5 hours;

in the step (2), the vacuum degree is 400-1000 mmHg and the temperature is 30-80 ℃ during reduced pressure distillation;

in the step (3), the gas obtained after electrolysis is cooled to-40 to-10 ℃, the electrolysis temperature is-15 to 20 ℃, and the voltage is 4 to 12V; the kettle temperature of the cold trap device is-100 to-70 ℃, and the column temperature is-65 to-35 ℃;

in the step (4), the hydrolysis reaction temperature is 70-95 ℃, and the recrystallization temperature is 50-80 ℃;

in the step (6), the vacuum degree is 600-800 mmHg and the temperature is 60-90 ℃ when distilling in the third distilling device, and the vacuum degree is 500-900 mmHg and the temperature is 40-100 ℃ when distilling in the fourth distilling device.

Advantageous effects

1. The method is convenient for rapidly preparing and purifying the methanesulfonyl fluoride, and can re-fluorinate unqualified products generated in the preparation process, thereby avoiding the possibility of unqualified products and effectively improving the production efficiency and quality;

2. the existing electrolysis equipment is improved, so that the operation of an electrolytic cell is safer and more stable, the stability of electrolytic current can be well ensured, and the electrolytic gas can be treated by condensation, cold trap and distillation technology, so that the purity of the trifluoromethanesulfonyl fluoride product can be effectively improved;

3. through the cooperation of a hydrolysis technology, an acidolysis technology and a distillation technology, the trifluoromethanesulfonyl fluoride product can be well converted into a trifluoromethanesulfonic acid product, and the trifluoromethanesulfonyl fluoride product meets the product quality index of 99.5% and meets the design requirement;

4. when materials are stirred, the stirring efficiency and quality can be effectively ensured, the stirring speed can be well controlled, the materials are conveniently and fully mixed, and the material reaction efficiency and quality are improved;

in conclusion, the invention can well prevent unqualified products in the production of the methanesulfonyl fluoride by improving and optimizing the prior art and equipment, can effectively improve the purity of the trifluoromethanesulfonyl fluoride product, is convenient to convert the trifluoromethanesulfonyl fluoride product into the trifluoromethanesulfonic acid product, meets the product quality index of 99.5%, solves the key technology of trifluoromethanesulfonic acid, and can realize the autonomous production capability.

Drawings

FIG. 1 is a schematic view of the apparatus according to the present invention;

FIG. 2 is a schematic view of the construction of the stirrer according to the present invention;

FIG. 3 is a diagram of a connection structure of the compliant structure of the present invention;

FIG. 4 is a flow chart of a method of the present invention;

wherein, 1-a first potassium fluoride storage tank, 2-a liquid conveying pipe, 3-a methylsulfonyl chloride solution storage tank, 4-a first material conveying pipe, 5-a stirrer, 6-a connecting pipe, 7-a first distillation device, 8-a first impurity storage tank, 9-a second impurity storage tank, 10-a phase separation device, 11-a second distillation device, 12-a first return pipe, 13-a first discharge pipe, 14-a methylsulfonyl fluoride storage tank, 15-an anhydrous hydrogen fluoride storage tank, 16-a second material conveying pipe, 17-a collection cover, 18-an electrolysis device, 19-a condenser, 20-a condenser pipe, 21-a sodium fluoride tower, 22-a cold trap device, 23-a potassium hydroxide solution storage tank, 24-an evaporation device, 25-a second return pipe, 26-a second discharging pipe, 27-an extraction device, 28-a filtering device, 29-a third conveying pipe, 30-a mixed solution storage tank, 31-a first absolute ethyl alcohol storage tank, 32-a KF solid storage tank, 33-potassium trifluoromethanesulfonate storage tank, 34-a first sulfuric acid storage tank, 35-an acid hydrolysis device, 36-a third distillation device, 37-a second sulfuric acid storage tank, 38-a silica storage tank, 39-a fourth distillation device, 40-a second absolute ethyl alcohol storage tank, 41-a trifluoromethanesulfonic acid storage tank, 42-a connecting plate, 43-a rotating shaft, 44-a sleeve, 45-a stirring blade, 46-a connecting rod, 47-a scraping plate, 48-a motor, 49-a cone pulley, 50-a cone pulley, 51-a cone gear set, a conical gear set, 52-connecting piece, 53-transverse plate, 54-transmission block, 55-electric telescopic rod, 56-bracket, 57-first spring, 58-push plate, 59-slide bar, 60-slide plate, 61-U-shaped bar, 62-second spring, 63-transmission wheel and 64-transmission belt.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

A production device of trifluoromethanesulfonic acid comprises a first potassium fluoride storage tank 1, a methanesulfonyl chloride aqueous solution storage tank 3, a stirrer 5, a first distillation device 7, a phase separation device 10, a second distillation device 11, a methanesulfonyl fluoride storage tank 14, an anhydrous hydrogen fluoride storage tank 15, an electrolysis device 18, a sodium fluoride tower 21, a cold trap device 22, a potassium hydroxide solution storage tank 23, an evaporation device 24, a first anhydrous ethanol storage tank 31, an extraction device 27, a filtration device 28, a mixed solution storage tank 30, a second anhydrous ethanol storage tank 40, a potassium trifluoromethanesulfonate storage tank 33, a first sulfuric acid storage tank 34, an acidolysis device 35, a third distillation device 36, a silica storage tank 38, a fourth distillation device 39 and a trifluoromethanesulfonic acid storage tank 41;

wherein, the first potassium fluoride storage tank 1 and the methanesulfonyl chloride aqueous solution storage tank 3 are respectively connected with a stirrer 5, the bottom of the stirrer 5 is connected with one side of a first distillation device 7, the other side of the first distillation device 7 is connected with a phase separation device 10, the bottom of the phase separation device 10 is connected with a second distillation device 11, and the second distillation device 11 is connected with a methanesulfonyl fluoride storage tank 14;

the methanesulfonyl fluoride storage tank 14 and the anhydrous hydrogen fluoride storage tank 15 are respectively connected with an electrolysis device 18, the top of the electrolysis device 18 is provided with a collection cover 17, the top of the collection cover 17 is provided with a condenser 19, the condenser 19 is condensed and connected with one side of a sodium fluoride tower 21 through a condensing pipe 20, and the other side of the sodium fluoride tower 21 is connected with a cold trap device 22;

the cold trap device 22 is also connected with a distillation device 24, the distillation device 24 is also connected with a potassium hydroxide solution storage tank 23 and an extraction device 27, and a filtering device 28, a mixed solution storage tank 30, a lithium trifluoromethanesulfonate storage tank 33, an acidolysis device 35, a third distillation device 36, a fourth distillation device 39 and a trifluoromethanesulfonic acid storage tank 41 are sequentially arranged behind the extraction device 27;

the first absolute ethyl alcohol storage tank 31 is connected with the extraction device 27; the second absolute ethyl alcohol storage tank 40 is connected with the mixed solution storage tank 30; the first sulfuric acid storage tank 34 is connected with an acidolysis device 35; the silica storage tank 38 is connected to a fourth distillation unit.

The upper end of the stirrer 5 is fixed with a connecting plate 42, the lower end of the connecting plate 42 is rotatably connected with a rotating shaft 43, the lower end of the rotating shaft 43 penetrates through the stirrer 5 and extends out of the stirrer 5 to be connected with a speed regulating mechanism, a connecting piece 52 is installed on the side wall of one end in the stirrer 5, a conical gear set 51 and a sleeve 44 are installed on the connecting piece 52, the sleeve 44 is rotatably sleeved on the rotating shaft 43, the conical gear set 51 consists of three conical gears which are sequentially meshed, the rotating shaft 43 and the sleeve 44 are respectively fixedly sleeved on two opposite conical gears so as to enable the rotating shaft 43 and the sleeve 44 to rotate in opposite directions, the lower end of the sleeve 44 is fixed with a transverse plate 53, two ends of the transverse plate 53 are respectively fixed with a connecting rod 46, the lower end of the connecting rod 46 is fixed with a scraper 47, the scraper 47 is abutted to the bottom in the stirrer 5, and, and the stirring blades 45 on the rotating shaft 43 and the stirring blades 45 on the connecting rod 46 are arranged in a staggered manner.

Speed adjusting mechanism includes motor 48, support 56 and transmission piece 54, transmission piece 54 is fixed at pivot 43 lower extreme, be equipped with bell jar 50 on the transmission piece 54, transmission piece 54 rotates the upper end one side that sets up at support 56, adaptation mechanism is installed to the lower extreme of support 56, adaptation mechanism is connected with motor 48, install electric telescopic handle 55 and montant on the adaptation mechanism, the push pedal 58 has been cup jointed in the rotation on the montant, the upper end fixed connection of push pedal 58 and electric telescopic handle 55, cone pulley 49 is installed to the upper end of montant, cone pulley 49 is located bell jar 50, the lateral wall of cone pulley 49 and the lateral wall in the bell jar 50 are inconsistent, electric telescopic handle 55 can drive the montant through push pedal 58 and go up and down, the montant goes up and down to drive cone pulley 49 and goes up and down, and make cone pulley 49 inconsistent with the lateral wall in the.

The adaptive mechanism comprises two slide bars 59 fixed on one side of the lower end of a bracket 56, a sliding plate 60 is sleeved on the two slide bars 59 in a sliding mode, a U-shaped rod 61 is arranged below the stirrer 5, shaft sleeves are arranged on the U-shaped rod 61 and the sliding plate 60, a driving wheel 63 is fixed on the tail ends of the output shafts of the two shaft sleeves and the motor 48, the three driving wheels 63 are in transmission connection through a transmission belt 64, a first spring 57 is sleeved on the slide bar 59, two ends of the first spring 57 are respectively fixed on one opposite side of the bracket 56 and the sliding plate 60, the lower end of an electric telescopic rod 55 is fixed on the upper end of the sliding plate 60, a vertical rod is sleeved in a shaft sleeve rotatably connected on the sliding plate 60 in a sliding mode, a second spring 62 is sleeved on the U-shaped rod 61, one end of the second spring 62 is fixed on the shaft sleeve on the U-shaped rod 61, the other end of the, the sliding plate 60 can move, when the sliding plate 60 moves, the transmission wheel 63 on the sliding plate 60 can move, the second spring 62 can pull the other transmission wheel 63 to move, and the transmission belt 64 is ensured to be in a tensioning state all the time.

The first distillation device 7 is also connected with a first impurity storage tank 8.

The second distillation device 11 is connected with the phase separation device 10 through a first return pipe 12, and a second impurity storage tank 9 is further connected to the phase separation device 10.

The mixed solution storage tank 30 is connected with the extraction device 27 through a second return pipe 25, and a potassium fluoride solid storage tank 32 is further connected to the mixed solution storage tank 30.

A second sulfuric acid storage tank 37 is also connected to the fourth distillation unit 39.

Example 1

As shown in fig. 1-3, a production device of trifluoromethanesulfonic acid, includes agitator 5, and first potassium fluoride storage jar 1 is connected with agitator 5 upper end through first conveying pipeline 4, and methylsulfonyl chloride solution storage jar 3 is connected with agitator 5 upper end through transfer line 2, carries potassium fluoride and methylsulfonyl chloride solution to agitator 5 in as required to mix the liquid and heat and stir, enable fully to take place the reaction between the material.

The upper end of the stirrer 5 is fixed with a connecting plate 42, the lower end of the connecting plate 42 is rotatably connected with a rotating shaft 43, the rotating stability of the rotating shaft 43 can be well guaranteed, the lower end of the rotating shaft 43 penetrates through the stirrer 5 and extends out of the stirrer 5 to be connected with a speed regulating mechanism, and the speed regulating mechanism can well regulate the speed of the rotating shaft 43, so that the stirring efficiency is improved; a connecting piece 52 is arranged on the side wall of one end in the stirrer 5, a bevel gear set 51 and a sleeve 44 are arranged on the connecting piece 52, the sleeve 44 is rotatably sleeved on the rotating shaft 43, the bevel gear set 51 is connected with the rotating shaft 43 and the sleeve 44, the bevel gear set 51 consists of three bevel gears, the three bevel gears are sequentially meshed and fixed in position relation, the rotating shaft 43 and the sleeve 44 are respectively fixedly sleeved on two opposite bevel gears to enable the rotating shaft 43 and the sleeve 44 to rotate reversely, a transverse plate 53 is fixed at the lower end of the sleeve 44, connecting rods 46 are respectively fixed at two ends of the transverse plate 53, a scraping plate 47 is fixed at the lower end of the connecting rod 46, the scraping plate 47 is in contact with the bottom in the stirrer 5, two stirring blades 45 are fixed at two sides of the rotating shaft 43 and at two opposite sides of the two connecting rods 46, and during operation, the scraping plate 47, the stirring blades 45 connected with the connecting rods 46, can stir with high efficiency.

The speed regulation mechanism comprises a transmission block 54 fixed at the lower end of the rotating shaft 43, a conical groove 50 is arranged at the lower end of the transmission block 54, a motor 48 and a support 56 are installed at the lower end of the stirrer 5, the transmission block 54 is rotatably arranged on one side of the upper end of the support 56, an adaptation mechanism is installed at the lower end of the support 56 and is connected with the motor 48, an electric telescopic rod 55 and a vertical rod are installed on the adaptation mechanism, a push plate 58 is rotatably sleeved on the vertical rod, the push plate 58 is fixedly connected with the upper end of the electric telescopic rod 55, a conical wheel 49 is installed at the upper end of the vertical rod, the conical wheel 49 is positioned in the conical groove 50, the side wall of the conical wheel 49 is abutted against the side wall in the conical groove 50, the electric telescopic rod 55 can, and the cone-shaped wheel 49 can be well ensured to be always contacted with the side wall in the cone-shaped groove 50 through the adapting mechanism, and the stability of transmission is ensured.

The adaptive mechanism comprises two slide bars 59 fixed on one side of the lower end of a bracket 56, a sliding plate 60 is sleeved on the two slide bars 59 in a sliding manner, a U-shaped rod 61 is arranged below the stirrer 5, shaft sleeves are arranged on the U-shaped rod 61 and the sliding plate 60, transmission wheels 63 are fixed on the two shaft sleeves and the tail end of an output shaft of a motor 48, the three transmission wheels 63 are in transmission connection through a transmission belt 64, a first spring 57 is sleeved on the slide bar 59, two ends of the first spring 57 are respectively fixed on the opposite sides of the bracket 56 and the sliding plate 60, the lower end of an electric telescopic rod 55 is fixed on the upper end of the sliding plate 60, a vertical rod is sleeved in a shaft sleeve rotatably connected on the sliding plate 60 in a sliding manner, a second spring 62 is sleeved on the U-shaped rod 61, one end of the second spring 62 is respectively fixed on a shaft sleeve slidably arranged on the U-shaped rod 61, the other end of the second, the sliding plate 60 can move, the driving wheel 63 on the sliding plate 60 can move when the sliding plate 60 moves, the second spring 62 can pull the other driving wheel 63 to move, the driving belt 64 is always in a tensioning state, the power transmission stability is guaranteed, the stable operation of the rotating shaft 43 can be guaranteed, and materials can be stirred efficiently.

Connecting pipe 6 is installed to the one end of agitator 5, the one end of connecting pipe 6 is connected with first distillation plant 7, be convenient for distill, can be fine according to the difference of boiling point, isolate impurity, one side of first distillation plant 7 is connected with first impurity storage jar 8 and phase place separator 10 respectively, one side of phase place separator 10 is connected with second impurity storage jar and second distillation plant 11, one side of second distillation plant 11 is connected with first return pipe 12 and first discharge pipe 13, first return pipe 12 and phase place separator 10 are connected, can make unqualified product get into phase place separator 10 once more, separate the function once more, can effectively avoid appearing unqualified product, promote the efficiency and the quality of production.

One end of the first discharging pipe 13 is connected with a methanesulfonyl fluoride storage tank 14, the methanesulfonyl fluoride storage tank 14 and an anhydrous hydrogen fluoride storage tank 15 are respectively connected with an electrolysis device 18 through a second conveying pipe 16, trifluoromethanesulfonyl fluoride is prepared through an electrolysis reaction, and an electrolyte is potassium fluoride. Install on the electrolytic device 18 and collect cover 17, be convenient for effectively collect electrolysis gas to the convenience is handled it, gets rid of impurity in it, and the one end of condenser pipe 20 is run through the setting and is being collected on cover 17, installs condenser 19 on the condenser pipe 20, and the temperature of messenger's condenser pipe 20 that condenser 19 can be fine drops, thereby enables the HF condensation in the electrolysis gas for liquid backward flow to electrolytic device 18 in.

The other end of the condenser pipe 20 is connected with a sodium fluoride tower 21, one end of the sodium fluoride tower 21 is connected with a cold trap device 22, one end of the cold trap device 22 is connected with an evaporation device 24, and the anode and cathode gases in the electrolysis device are not isolated, so that the main component in the electrolysis gas is CF₃SO₂F and H₂The impurities are HF and CF₄、CH₂F₂、CHF₃And F₂SO₂Besides HF, other impurities and H₂Boiling point average ratio CF₃SO₂F is low and the phase difference is more than 30 ℃, therefore, a sodium fluoride tower 21 is adopted to remove HF, and a cold trap device is utilized to remove H₂、F2SO₂、CHF₃、CF₄Equal low boiling point substance, distillation and cold collection of electrolytic gas CF₃SO₂And F.

One side of evaporation plant 24 is connected with KOH solution storage jar 23, extraction device 27 is installed to evaporation plant 24's opposite side, one side of extraction equipment 27 is connected with the second and arranges material pipe 26, the one end that the second was arranged material pipe 26 is connected with first absolute ethyl alcohol storage jar 31, the opposite side of extraction equipment 27 is connected with filter equipment 28, be connected with KF solid storage jar 32 and third conveying pipeline 29 on filter equipment 28, be connected with second back flow pipe 25 on the third conveying pipeline 29, second back flow pipe 25 is connected with extraction equipment 27, the lower extreme of third conveying pipeline 29 is connected with mixed solution storage jar 30.

By utilizing the characteristic that trifluoromethanesulfonyl fluoride is easy to hydrolyze in hot water and alkaline conditions, trifluoromethanesulfonyl fluoride gas is fully contacted with hot excess potassium hydroxide solution for reaction so as to hydrolyze the trifluoromethanesulfonyl fluoride gas into potassium trifluoromethanesulfonate, and then a mixed solution of potassium trifluoromethanesulfonate, potassium fluoride and excess potassium hydroxide generated by the reaction is evaporated and crystallized to obtain mixed crystals of the potassium trifluoromethanesulfonate, the potassium fluoride and the excess potassium hydroxide. And then the different solubility of the compounds in absolute ethyl alcohol is utilized to carry out recrystallization purification, thereby achieving the purpose of purification.

The upper end of the mixed solution storage tank 30 is connected with a second absolute ethyl alcohol storage tank 40, one side of the mixed solution storage tank 30 is connected with a potassium trifluoromethanesulfonate storage tank 33, one side of the potassium trifluoromethanesulfonate storage tank 33 is provided with an acidolysis device 35, the upper end of the acidolysis device 35 is connected with a first sulfuric acid storage tank 34, one side of the acidolysis device 35 is connected with a third distillation equipment 36, one end of the third distillation equipment 36 is connected with a fourth distillation equipment 39, one side of the fourth distillation equipment 39 is connected with a second sulfuric acid storage tank 37 and a silicon dioxide storage tank 38, and one side of the fourth distillation equipment 39 is provided with a trifluoromethanesulfonic acid storage tank 41.

The potassium trifluoromethanesulfonate is acidolyzed into trifluoromethanesulfonic acid by using strong acidity of sulfuric acid through acidolysis equipment. During the reaction, excessive sulfuric acid is added, and silicon dioxide is added to react most of F & lt- & gt with SiF₄Is removed. The acidolysis is carried out with 100% sulfuric acid, so that the water in the reaction process can be removed by utilizing the strong water absorption property. Meanwhile, the residual acid after the reaction is subjected to a reutilization experiment, and the experiment proves that the residual acid can be reutilized once and the yield can reach 77%.

As shown in fig. 4, a method for producing trifluoromethanesulfonic acid, the method comprises the following steps:

(1) adding the water solution of methanesulfonyl chloride and potassium fluoride into a stirrer 5 for stirring reaction to obtain a crude product of methanesulfonyl fluoride;

(2) the crude product of the methanesulfonyl fluoride firstly enters a first distillation device 7 for reduced pressure distillation, the collected fraction enters a phase separation device 10 for phase separation, and the lower component enters a second distillation device 11 for reduced pressure distillation again to obtain a pure product of the methanesulfonyl fluoride;

(3) electrolyzing the pure product of the methanesulfonyl fluoride and anhydrous hydrogen fluoride in an electrolysis device 18, wherein the electrolyte is potassium fluoride, cooling the gas obtained after electrolysis, introducing the cooled gas into a sodium fluoride tower 21, and collecting the gas by using a cold trap device 22 to obtain trifluoromethanesulfonyl fluoride;

(4) carrying out hydrolysis reaction on the trifluoromethanesulfonyl fluoride and a potassium hydroxide solution in an evaporation device 24, firstly, extracting and separating a reaction product in an extraction device 27 by using absolute ethyl alcohol, and recrystallizing filtrate collected in a filtering device 28 by using the absolute ethyl alcohol to obtain potassium trifluoromethanesulfonate;

(5) performing acidolysis reaction on the potassium trifluoromethanesulfonate and excessive concentrated sulfuric acid in an acidolysis device 35, and obtaining a crude trifluoromethanesulfonic acid after the reaction is finished;

(6) and distilling the crude trifluoromethanesulfonic acid in a third distillation device 36 and a fourth distillation device 39 respectively, and adding silica during distillation in the fourth distillation device 39 to obtain purified trifluoromethanesulfonic acid.

Wherein: in the step (1), stirring and reacting at the temperature of 40-80 ℃ for 2-5 h;

in the step (2), the vacuum degree is 400-1000 mmHg and the temperature is 30-80 ℃ during reduced pressure distillation;

in the step (3), the gas obtained after electrolysis is cooled to-40 to-10 ℃, the electrolysis temperature is-15 to 20 ℃, and the voltage is 4 to 12V; the kettle temperature of the cold trap device 22 is-100 to-70 ℃, and the column temperature is-65 to-35 ℃;

in the step (4), the hydrolysis reaction temperature is 70-95 ℃, and the recrystallization temperature is 50-80 ℃;

in the step (6), the vacuum degree is 600-800 mmHg and the temperature is 60-90 ℃ during distillation in the third distillation device 36, and the vacuum degree is 500-900 mmHg and the temperature is 40-100 ℃ during distillation in the fourth distillation device 39.

In the method, methanesulfonyl chloride is fluorinated to generate methanesulfonyl fluoride by using the property of potassium fluoride replacing active chlorine in the sulfonyl chloride, then the methanesulfonyl fluoride and the impurity (mainly water) of the methanesulfonyl fluoride are separated by using the method of reduced pressure distillation, unqualified products are fluorinated again to prepare sufficient amount of electrolytic raw material methanesulfonyl fluoride, the product purity is more than 99%, and the moisture content is less than or equal to 100 ppm.

In the method, most HF escaped from the electrolytic device is condensed into liquid by a low temperature method and flows back to the electrolytic cell, the rest HF is absorbed by the sodium fluoride tower, thus the HF entering the cold trap is little (less than or equal to 2 percent), and finally the purpose of removing HF can be achieved by controlling the temperature and pressure of compressed air during compressed air of the cold trap.

In the method, electrolysis is carried out under normal pressure, and the obtained trifluoromethanesulfonyl fluoride has the purity of more than or equal to 96 percent and the total yield of about 87.5 percent.

In the method, anhydrous ethanol is used for recrystallizing and purifying potassium trifluoromethanesulfonate, so that potassium fluoride is easily separated and removed, but ethanol is firstly subjected to dehydration before ethanol is used, otherwise F in the product^-Hardly reaching the standard, and F is obtained after the treated ethanol is used for recrystallizing and purifying potassium trifluoromethanesulfonate^-The content was only 1.8% before treatment. Recrystallizing and purifying the product potassium trifluoromethanesulfonate F^-The content is less than or equal to 400ppm, and the design requirement is met.

In the process, the distillation conditions under reduced pressure are in particular F^-The removal conditions of the sodium-trifluoromethanesulfonate are studied in a large number, and the obtained trifluoromethanesulfonic acid product is confirmed by qualitative detection of the China center for detecting marine chemical substances, and the impurity content is as follows: f^-About 10ppm, H₂O is about 400ppm, SO₄ ^2-Below 50ppm, the product quality index of 99.5 percent is met.

In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.