Summary of the invention
The purpose of this invention is to provide that a kind of process method is simple, less energy consumption, quality is good, cost is low trifluoromethyl sulfonic acid fluoride CF
3SO
2The method of F separation and purification.
The technical scheme that realizes above-mentioned purpose is: a kind of trifluoromethyl sulfonic acid fluoride CF
3SO
2The method of F separation and purification is with methanesulfonyl fluoride CH
3SO
2F electrochemical fluorination reaction gas-phase product is a raw material, and said method steps is following:
(1) cooling condensation: with methanesulfonyl fluoride CH
3SO
2The condensation of lowering the temperature of F electrochemical fluorination gas-phase product makes the hydrogen fluoride HF in the gas phase be condensed into liquid phase;
(2) solution-air is separated: will go up material that step cooling condensation obtains and carry out solution-air and separate, liquid-phase fluorination hydrogen HF goes further to handle the back and recycles, and gas phase gets into next step;
(3) washing: will go up the gaseous phase materials that obtains of step and carry out the carbonate aqueous solution washing, the material after the washing gets into next step;
(4) solution-air is separated: will go up material that a step obtains and carry out solution-air and separate, liquid phase is gone further processing, and gas phase gets into next step;
(5) dehydrate: will go up in the gaseous phase materials that obtains of step and add dewatering agent, and dehydrate;
(6) gas-solid separation: the material that will go up after a step dewaters carries out gas-solid separation, and solid phase is gone further processing, and gas phase gets into next step;
(7) deep cooling but: will go up material that a step obtains gas phase and carry out deep cooling and but get into next step in the back;
(8) solution-air is separated: will go up material that a step obtains and carry out solution-air and separate, gas phase is hydrogen H
2Go further processing, liquid phase is the product trifluoromethyl sulfonic acid fluoride CF that separation and purification obtains
3SO
2F.
Further, the service temperature of the first step cooling condensation is-20 ℃~0 ℃, and the operation absolute pressure is 0.1MPa~1.0MPa.
Further, the described washing lotion of the 3rd step washing is Na
2CO
3, NaHCO
3, K
2CO
3Or KHCO
3In the aqueous solution any one.
Further, to dehydrate described dewatering agent be Na the 5th step
2SO
4, P
2O
5, in activated carbon, zeyssatite or the molecular sieve any one.
Further, the 7th step, deep cooled service temperature was-80 ℃~-40 ℃, and working pressure is 0.1MPa~1.0MPa.
Trifluoromethyl sulfonic acid fluoride CF of the present invention
3SO
2The principle of F separation and purification is: (1) utilizes trifluoromethyl sulfonic acid fluoride CF
3SO
2The difference of the boiling point (19 ℃) of F boiling point (21 ℃) and hydrogen fluoride HF through the refrigerative method, makes hydrogen fluoride HF liquefaction, separates through solution-air then, and product is separated with hydrogen fluoride, turns back to the electrochemical fluorination systemic circulation through liquefaction hydrogen fluoride HF and uses; (2) the indissoluble liquid that utilizes the trifluoromethyl sulfonic acid fluoride is in water, and difficult hydrolysis, the difference that hydrogen fluoride HF dissolves easily in water, and the operation through washing separates with a spot of hydrogen fluoride HF product with other water miscible impurity; (3) utilize trifluoromethyl sulfonic acid fluoride CF
3SO
2F is prone to liquefaction (boiling point-21 ℃), hydrogen H
2The characteristics of difficult liquefaction through deep cooled method, make trifluoromethyl sulfonic acid fluoride CF
3SO
2F liquefaction is refining.
Realize that the main technique equipment that the present invention needs is: cooling apparatus, straining installation etc.
Adopt the benefit of technique scheme to be: (1), make full use of the singularity of product, operational path is short, and technology is simple, consuming little energy, production cost is low, has improved the security of technological process; (2), realized cleaning production, be convenient to suitability for industrialized production, the no three wastes produce, cleaning, environmental protection, various by products can be recycled, this has practiced thrift cost greatly; (3), adopt the product methyl fluoride sulfonic acid fluoride CF of process method separation and purification of the present invention
3SO
2The F quality is good, yield is high.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation.
Main technique equipment is: cooling apparatus and straining installation etc.
Embodiment one
As shown in the figure, a kind of trifluoromethyl sulfonic acid fluoride CF
3SO
2The method of F separation and purification is with methanesulfonyl fluoride CH
3SO
2F electrochemical fluorination reaction gas-phase product is a raw material, and said method steps is following:
(1) cooling condensation: in indirect cooling heat exchanger, will mainly contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F, hydrogen fluoride HF and hydrogen H
2Methanesulfonyl fluoride CH
3SO
2The condensation of lowering the temperature of F electrochemical fluorination gas-phase product, the operation absolute pressure is 0.8MPa, is cooled to-9 ℃, makes the hydrogen fluoride HF in the gas phase be condensed into liquid phase;
(2) solution-air is separated: in gas-liquid separator, HF removes to turn back to CH with liquid-phase fluorination hydrogen
3SO
2Recycle in the reaction of F electrochemical fluorination, contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Gas phase get into next step;
(3) washing: will go up the gaseous phase materials that obtains of step through in the bubbling absorption unit, through the yellow soda ash Na of 0.1mol/L
2CO
3The aqueous solution, washing are removed the hydrogen fluoride HF and other impurity of gaseous phase materials trace, and the material after the washing gets into next step;
(4) solution-air is separated: in gas-liquid separator, HF removes to turn back to CH with liquid-phase fluorination hydrogen
3SO
2Recycle in the reaction of F electrochemical fluorination, contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Gas phase get into next step;
(5) dehydrate: will go up the gaseous phase materials that obtains of step is the dewatering drying device of filler through the 4A molecular sieve, sloughs the water in the gaseous phase materials;
(6) gas-solid separation: the gaseous phase materials gas phase through dehydrating gets into next step;
(7) deep cooling but: in indirect cooling heat exchanger, with trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Carry out deep cooling but, the operation absolute pressure is 1.0MPa, is cooled to-40 ℃, makes the trifluoromethyl sulfonic acid fluoride CF in the gas phase
3SO
2F is cooled to liquid phase;
(8) solution-air is separated: will go up material that a step obtains and carry out solution-air and separate, gas phase is hydrogen H
2Go further processing, liquid phase is the product trifluoromethyl sulfonic acid fluoride CF that separation and purification obtains
3SO
2F.
Embodiment two
As shown in the figure, a kind of trifluoromethyl sulfonic acid fluoride CF
3SO
2The method of F separation and purification is with methanesulfonyl fluoride CH
3SO
2F electrochemical fluorination reaction gas-phase product is a raw material, and said method steps is following:
(1) cooling condensation: in indirect cooling heat exchanger, will mainly contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F, hydrogen fluoride HF and hydrogen H
2Methanesulfonyl fluoride CH
3SO
2The condensation of lowering the temperature of F electrochemical fluorination gas-phase product, the operation absolute pressure is 0.5MPa, is cooled to-15 ℃, makes the hydrogen fluoride HF in the gas phase be condensed into liquid phase;
(2) solution-air is separated: in gas-liquid separator, HF removes to turn back to CH with liquid-phase fluorination hydrogen
3SO
2Recycle in the reaction of F electrochemical fluorination, contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Gas phase get into next step;
(3) washing: will go up the gaseous phase materials that obtains of step through in the filler absorption unit, through the sodium hydrogencarbonate NaHCO of 0.2mol/L
3The aqueous solution, washing are removed the hydrogen fluoride HF and other impurity of gaseous phase materials trace, and the material after the washing gets into next step;
(4) solution-air is separated: the gas material of removing the micro-hydrogen fluoride HF of gaseous phase materials and other impurity through washing gets into next step, and liquid phase is gone further processing, and gas phase gets into next step;
(5) dehydrate: will go up the gaseous phase materials that obtains of step is that the activated carbon of 1mm is the dewatering drying device of filler through equivalent diameter, sloughs the water in the gaseous phase materials;
(6) gas-solid separation: the gaseous phase materials gas phase through dehydrating gets into next step;
(7) deep cooling but: in indirect cooling heat exchanger, with trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Carry out deep cooling but, the operation absolute pressure is 0.5MPa, is cooled to-60 ℃, makes the trifluoromethyl sulfonic acid fluoride CF in the gas phase
3SO
2F is cooled to liquid phase;
(8) solution-air is separated: will go up material that a step obtains and carry out solution-air and separate, gas phase is hydrogen H
2Go further processing, liquid phase is the product trifluoromethyl sulfonic acid fluoride CF that separation and purification obtains
3SO
2F.
Embodiment three
As shown in the figure, a kind of trifluoromethyl sulfonic acid fluoride CF
3SO
2The method of F separation and purification is with methanesulfonyl fluoride CH
3SO
2F electrochemical fluorination reaction gas-phase product is a raw material, and said method steps is following:
(1) cooling condensation: in indirect cooling heat exchanger, will mainly contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F, hydrogen fluoride HF and hydrogen H
2Methanesulfonyl fluoride CH
3SO
2The condensation of lowering the temperature of F electrochemical fluorination gas-phase product, the operation absolute pressure is 0.1MPa, is cooled to-20 ℃, makes the hydrogen fluoride HF in the gas phase be condensed into liquid phase;
(2) solution-air is separated: in gas-liquid separator, HF removes to turn back to CH with liquid-phase fluorination hydrogen
3SO
2Recycle in the reaction of F electrochemical fluorination, contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Gas phase get into next step;
(3) washing: will go up the gaseous phase materials that obtains of step through the bubbling absorption unit, process is carried out the salt of wormwood K of 0.1mol/L
2CO
3The aqueous solution, washing are removed the hydrogen fluoride HF and other impurity of gaseous phase materials trace, and the material after the washing gets into next step;
(4) solution-air is separated: the gas material of removing the micro-hydrogen fluoride HF of gaseous phase materials and other impurity through washing gets into next step, and liquid phase is gone further processing, and gas phase gets into next step;
(5) dehydrate: will go up the gaseous phase materials that obtains of step is that the zeyssatite of 1mm is the dewatering drying device of filler through equivalent diameter, sloughs the water in the gaseous phase materials;
(6) gas-solid separation: the gaseous phase materials gas phase through dehydrating gets into next step;
(7) deep cooling but: in indirect cooling heat exchanger, with trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Carry out deep cooling but, the operation absolute pressure is 0.2MPa, is cooled to-70 ℃, makes the trifluoromethyl sulfonic acid fluoride CF in the gas phase
3SO
2F is cooled to liquid phase;
(8) solution-air is separated: will go up material that a step obtains and carry out solution-air and separate, gas phase is hydrogen H
2Go further processing, liquid phase is the product trifluoromethyl sulfonic acid fluoride CF that separation and purification obtains
3SO
2F.
Embodiment four
As shown in the figure, a kind of trifluoromethyl sulfonic acid fluoride CF
3SO
2The method of F separation and purification is with methanesulfonyl fluoride CH
3SO
2F electrochemical fluorination reaction gas-phase product is a raw material, and said method steps is following:
(1) cooling condensation: in indirect cooling heat exchanger, will mainly contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F, hydrogen fluoride HF and hydrogen H
2Methanesulfonyl fluoride CH
3SO
2The condensation of lowering the temperature of F electrochemical fluorination gas-phase product, the operation absolute pressure is 0.1MPa, is cooled to-20 ℃, makes the hydrogen fluoride HF in the gas phase be condensed into liquid phase;
(2) solution-air is separated: in gas-liquid separator, HF removes to turn back to CH with liquid-phase fluorination hydrogen
3SO
2Recycle in the reaction of F electrochemical fluorination, contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Gas phase get into next step;
(3) washing: will go up the gaseous phase materials that obtains of step through the filler absorption unit, through the saleratus KHCO of 0.2mol/L
3The aqueous solution, washing are removed the hydrogen fluoride HF and other impurity of gaseous phase materials trace, and the material after the washing gets into next step;
(4) solution-air is separated: the gas material of removing the micro-hydrogen fluoride HF of gaseous phase materials and other impurity through washing gets into next step, and liquid phase is gone further processing, and gas phase gets into next step;
(5) dehydrate: will go up the gaseous phase materials that obtains of step is the Na of 1mm through equivalent diameter
2SO
4Be the dewatering drying device of filler, slough the water in the gaseous phase materials;
(6) gas-solid separation: the gaseous phase materials gas phase through dehydrating gets into next step;
(7) deep cooling but: in indirect cooling heat exchanger, with trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Carry out deep cooling but, the operation absolute pressure is 0.1MPa, is cooled to-80 ℃, makes the trifluoromethyl sulfonic acid fluoride CF in the gas phase
3SO
2F is cooled to liquid phase;
(8) solution-air is separated: will go up material that a step obtains and carry out solution-air and separate, gas phase is hydrogen H
2Go further processing, liquid phase is the product trifluoromethyl sulfonic acid fluoride CF that separation and purification obtains
3SO
2F.
Embodiment five
As shown in the figure, a kind of trifluoromethyl sulfonic acid fluoride CF
3SO
2The method of F separation and purification is with methanesulfonyl fluoride CH
3SO
2F electrochemical fluorination reaction gas-phase product is a raw material, and said method steps is following:
(1) cooling condensation: in indirect cooling heat exchanger, will mainly contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F, hydrogen fluoride HF and hydrogen H
2Methanesulfonyl fluoride CH
3SO
2The condensation of lowering the temperature of F electrochemical fluorination gas-phase product, the operation absolute pressure is 1.0MPa, is cooled to 0 ℃, makes the hydrogen fluoride HF in the gas phase be condensed into liquid phase;
(2) solution-air is separated: in gas-liquid separator, HF removes to turn back to CH with liquid-phase fluorination hydrogen
3SO
2Recycle in the reaction of F electrochemical fluorination, contain trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Gas phase get into next step;
(3) washing: will go up the gaseous phase materials that obtains of step through the filler absorption unit, through the saleratus KHCO of 0.2mol/L
3The aqueous solution, washing are removed the hydrogen fluoride HF and other impurity of gaseous phase materials trace, and the material after the washing gets into next step;
(4) solution-air is separated: the gas material of removing the micro-hydrogen fluoride HF of gaseous phase materials and other impurity through washing gets into next step, and liquid phase is gone further processing, and gas phase gets into next step;
(5) dehydrate: will go up the gaseous phase materials that obtains of step is the P of 1mm through equivalent diameter
2O
5Be the dewatering drying device of filler, slough the water in the gaseous phase materials;
(6) gas-solid separation: the gaseous phase materials gas phase through dehydrating gets into next step;
(7) deep cooling but: in indirect cooling heat exchanger, with trifluoromethyl sulfonic acid fluoride CF
3SO
2F and hydrogen H
2Carry out deep cooling but, the operation absolute pressure is 0.8MPa, is cooled to-50 ℃, makes the trifluoromethyl sulfonic acid fluoride CF in the gas phase
3SO
2F is cooled to liquid phase;
(8) solution-air is separated: will go up material that a step obtains and carry out solution-air and separate, gas phase is hydrogen H
2Go further processing, liquid phase is the product trifluoromethyl sulfonic acid fluoride CF that separation and purification obtains
3SO
2F.
Remove the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.