CN103664502B - A kind of octafluoropropane purification process - Google Patents
A kind of octafluoropropane purification process Download PDFInfo
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- CN103664502B CN103664502B CN201210329041.6A CN201210329041A CN103664502B CN 103664502 B CN103664502 B CN 103664502B CN 201210329041 A CN201210329041 A CN 201210329041A CN 103664502 B CN103664502 B CN 103664502B
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Abstract
The invention discloses a kind of octafluoropropane purification process, comprising: octafluoropropane raw material is carried out normal temperature absorption under normal temperature condition; By the described octafluoropropane raw material that adsorbs through normal temperature at-37 DEG C ~ 10 DEG C, under 0.1 ~ 0.6MPa condition, carry out rectifying; Described octafluoropropane raw material through rectifying is carried out cryogenic absorption at-100 DEG C ~-30 DEG C temperature; Carry out pressurized adsorbent by under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 0.5 ~ 1.5MPa, obtain octafluoropropane product.Adopt the present invention, not only remove most of chloride fluorocarbons impurities in octafluoropropane raw material, and in solution prior art, carbonic acid gas and water remove the inadequate problem of the degree of depth, reduce energy consumption, strengthen the adsorption effect of sorbent material, make octafluoropropane product reach purity more than 99.999%.
Description
Technical field
The present invention relates to gas separation, particularly relate to a kind of octafluoropropane purification process.
Background technology
High-purity octafluoropropane (5N) is mainly used as purgative gas and the etching reagent of semiconductor fabrication, as in plasma etching process, as silicon dioxide film, and the etching gas of phosphorosilicate glass mould.And due to its decomposition efficiency be C
2f
6twice, the load of gas consumption and waste gas treatment equipment can be reduced and reduce the emission measure of greenhouse gases, and as C
2f
6substitute.In recent years, along with the fast development of semicon industry, more and more higher to the purity requirement of the special gas of electronics, high-purity octafluoropropane is the necessary medium of processing super large-scale integration, plays an important role to the development of semicon industry.
By existingly directly to fluoridize, in the thick octafluoropropane prepared of the method such as catalytic fluorination, except air, water, carbonic acid gas, tetrafluoro-methane, also containing chloride fluorocarbons impurities such as a large amount of chlorodifluoromethane, chloropentafluoroethane, Refrigerant 12, R 1216, chlorotrifluoroethylene, 2H-heptafluoro-propane, chloro-tetrafluoroethanes, can by chloride for major part fluorocarbons impurities removing by the method for rectifying, but the carbonic acid gas be difficult in removing octafluoropropane raw material and water, thus be difficult to high-purity octafluoropropane product of acquisition more than 99.999%.
In order to improve octafluoropropane purity, prior art Chinese patent CN1455764A discloses purification process, the Its Preparation Method And Use of octafluoropropane.Described purification process: the thick octafluoropropane containing 10 ~ 10000ppm fluorocarbons impurities is contacted under 250-380 DEG C of high temperature with the impurity decomposing agent be made up of with alkaline earth metal compound ferriferous oxide, then with adsorbent contact, removing impurity, in realize target product, chloride fluorocarbons impurities is reduced to less than 1ppm.But carry out impurity decomposition under 250 DEG C ~ 380 DEG C high temperature, temperature of reaction is high, energy consumption is large, and due to gas at high temperature pressure sharply rise, very high to the requirement of equipment, in order to ensure safety, process flow will inevitably be reduced, thus the production rate that slows down.In addition, while impurity decomposes, also can produce the impurity such as a large amount of carbon monoxide, water, hydrogen, methane, only be difficult to removing by absorption.
Adopt single distillation technology or single adsorption technology to be all difficult to the chloride fluorocarbons impurities in octafluoropropane raw material, CO
2and H
2the volumetric concentration of the impurity such as O reaches standard simultaneously, is difficult to obtain the octafluoropropane product of purity more than 99.999%.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, a kind of octafluoropropane purification process is provided, not only remove most of chloride fluorocarbons impurities in octafluoropropane raw material, and carbonic acid gas and water remove the inadequate problem of the degree of depth in solution prior art, reduce energy consumption, strengthen the adsorption effect of sorbent material, octafluoropropane product is made to reach purity more than 99.999%, simultaneously, avoid bringing energy consumption large because of pyrolytic decomposition impurity, equipment requirements is high, and production efficiency is low, the situation that product purity is not high.
In order to solve the problems of the technologies described above, embodiments provide a kind of octafluoropropane purification process, comprising: octafluoropropane raw material is carried out normal temperature absorption under normal temperature condition;
By the described octafluoropropane raw material that adsorbs through normal temperature at-37 DEG C ~ 10 DEG C, under 0.1 ~ 0.6MPa condition, carry out rectifying;
Described octafluoropropane raw material through rectifying is carried out cryogenic absorption at-100 DEG C ~-30 DEG C temperature;
Carry out pressurized adsorbent by under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 0.5 ~ 1.5MPa, obtain octafluoropropane product.
As the improvement of such scheme, described by the described octafluoropropane raw material that adsorbs through normal temperature at-37 DEG C ~ 10 DEG C, the step of carrying out rectifying under 0.1 ~ 0.6MPa condition comprises:
The octafluoropropane raw material adsorbed through normal temperature is passed in the first rectifying tower, at-10 DEG C ~ 10 DEG C, under 0.3 ~ 0.6MPa condition, carries out a rectifying;
Described octafluoropropane raw material through a rectifying is passed in Second distillation column, at-37 DEG C ~-10 DEG C, under the condition of 0.1 ~ 0.3MPa, carries out secondary rectifying.
As the improvement of such scheme, in described first rectifying tower, Liquid level is 55% ~ 70%, and emptying flow is 0.1 ~ 2.0Nm
3/ h.
As the improvement of such scheme, the emptying flow of described Second distillation column is 0.5 ~ 2.0Nm
3/ h.
As the improvement of such scheme, in described normal temperature adsorption process, octafluoropropane raw material is passed into the normal temperature adsorber being equiped with the first sorbent material and carry out normal temperature absorption;
Described first sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix;
Described first sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix with the ratio of 1:1 ~ 1:2.
As the improvement of such scheme, in described cryogenic absorption process, described octafluoropropane raw material is passed into the low-temperature adsorber being equiped with the second sorbent material and carries out cryogenic absorption;
Described second sorbent material comprises the second sorbent material a and the second sorbent material b;
Described second sorbent material a is CO
2special adsorbent;
Described second sorbent material b is one in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and 13X molecular sieve or its combination.
As the improvement of such scheme, the step of pressurized adsorbent will be carried out under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 0.5 ~ 1.5MPa, comprising:
Described octafluoropropane raw material after cryogenic absorption is passed into molding machine supercharging, and the air pressure after described supercharging is 0.5 ~ 1.5MPa;
Described octafluoropropane raw material through supercharging is passed in gas purifier and carries out pressurized adsorbent.
As the improvement of such scheme, described gas purifier is equiped with the 3rd sorbent material;
Described 3rd sorbent material is one in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and 13X molecular sieve or its combination.
As the improvement of such scheme, described 3rd sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix;
Described 3rd sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix with the ratio of 1:1 ~ 1:2.
As the improvement of such scheme, the purity of described octafluoropropane product is more than 99.999%;
The CO of described octafluoropropane product
2volumetric concentration≤0.5ppm, H
2o volumetric concentration≤1ppm and containing chlorine fluorine carbon compound foreign body volume concentrations≤1ppm.
Implement the embodiment of the present invention, there is following beneficial effect:
First, the present invention is different from the single distillation technology of prior art or single adsorption technology, adopt the method that distillation technology combines with adsorption technology, the purity of further raising octafluoropropane product, avoid bringing energy consumption large because of pyrolytic decomposition impurity, equipment requirements is high, and production efficiency is low, the situation that product purity is not high.
Secondly, cryogenic absorption technology of the present invention adopts CO
2special adsorbent substitutes common molecular and screens out the CO degassed in body
2, due to CO
2special adsorbent is to CO
2there is highly selective, the CO under the condition of low temperature in selective adsorption octafluoropropane raw material
2, substantially do not adsorb other impurity, solve CO in octafluoropropane
2remove the problem that the degree of depth is inadequate, make CO
2volumetric concentration reaches lower than 0.5ppm effect, and greatly reduces the regeneration times of sorbent material.In addition, because the present invention adopts the technique of low temperature fractionation, the product after rectifying is in low-temperature condition, utilizes gas to be in low-temperature condition and carries out cryogenic absorption, can reduce the energy consumption of low-temperature adsorber.
Because traditional method can remove most of chloride fluorocarbons impurities, but octafluoropropane product prepared by traditional method is difficult to realize CO
2and H
2the volumetric concentration of both O is all less than 1ppm.After adopting the step of pressurized adsorbent, greatly strengthen the adsorptive power of sorbent material, CO can be reduced further
2and H
2o is content in the product, not only controls fluorocarbons impurities volumetric concentration≤1ppm, and realize H
2o≤1ppm and CO
2≤ 0.5ppm, is conducive to octafluoropropane product and reaches purity more than 99.999%.
Finally, the present invention is on the basis of prior art low temperature fractionation, in conjunction with cryogenic absorption technology and pressurized adsorbent technology, purifying is carried out to octafluoropropane gas, not only make containing chlorine fluorine carbon compound foreign body volume concentrations≤1ppm in octafluoropropane product, and make traditional technology be difficult to the CO be separated
2and H
2the volumetric concentration of both O is all less than 1ppm, controls total impurities content at below 10ppm, effectively improve the purity of gas and the purity realizing octafluoropropane product more than 99.999%, meet the requirement for electronics spy gas in semi-conductor and microelectronics industry.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of a kind of octafluoropropane purification process of the present invention;
Fig. 2 is the another schematic flow sheet of a kind of octafluoropropane of the present invention purification process.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the present invention is described in further detail.
Composition graphs 1 and Fig. 2, the present invention discloses a kind of octafluoropropane purification process:
The schematic flow sheet of a kind of octafluoropropane purification process of Fig. 1 the present invention.
S100, carries out normal temperature absorption by octafluoropropane raw material under normal temperature condition.
S101, by the described octafluoropropane raw material that adsorbs through normal temperature at-37 DEG C ~ 10 DEG C, carries out rectifying under 0.1 ~ 0.6MPa condition.
S102, carries out cryogenic absorption by the described octafluoropropane raw material through rectifying at-100 DEG C ~-30 DEG C temperature.
S103, carries out pressurized adsorbent by under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 0.5 ~ 1.5MPa, obtains octafluoropropane product.
Fig. 2 is the another schematic flow sheet of a kind of octafluoropropane of the present invention purification process.
S200, carries out normal temperature absorption by octafluoropropane raw material under normal temperature condition.
Described normal temperature absorption octafluoropropane raw material is passed into the normal temperature adsorber being equiped with the first sorbent material, and carry out normal temperature absorption under normal temperature condition, can remove the CO of a part in octafluoropropane raw material
2, H
2o and C
3f
6deng impurity.
Preferably, described first sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix.
More preferably, described first sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix with the ratio of 1:1 ~ 1:2.
In order to remove the impurity in octafluoropropane raw material further, need to utilize twice distillation technology by the lower-boiling impurity in octafluoropropane raw material and high-boiling-point impurity removing.
S201, passes in the first rectifying tower by the octafluoropropane raw material adsorbed through normal temperature, at-10 DEG C ~ 10 DEG C, carries out a rectifying under 0.3 ~ 0.6MPa condition.
Preferably, in described first rectifying tower, Liquid level is 55% ~ 70%, and emptying flow is 0.1 ~ 2.0Nm
3/ h.
S202, passes in Second distillation column by the described octafluoropropane raw material through a rectifying, at-37 DEG C ~-10 DEG C, carries out secondary rectifying under the condition of 0.1 ~ 0.3MPa.
Preferably, the emptying flow of described Second distillation column is 0.5 ~ 2.0Nm
3/ h.
It should be noted that, the step of described rectifying comprises a rectifying and secondary rectifying.
A described rectifying refers to and passes in the first rectifying tower by described raw material octafluoropropane, at-10 DEG C ~ 10 DEG C, carries out rectifying under 0.3 ~ 0.6MPa condition, keeps liquid level 55% ~ 70% in described first rectifying tower, and emptying flow is 0.1 ~ 2.0Nm
3/ h, removes most N
2, O
2, CO, H
2and CF
4deng lower-boiling impurity.
Described secondary rectifying refers to and passes in Second distillation column by the described octafluoropropane raw material through a rectifying, at-37 DEG C ~-10 DEG C, rectifying is continued under the condition of 0.1 ~ 0.3MPa, after the composition of lower-boiling impurity described in overhead gas is up to standard, extract the octafluoropropane through rectifying from tower top, in secondary rectifying, isolated high-boiling-point impurity is discharged at the bottom of tower.
It should be noted that, the tower top of Second distillation column is provided with stopple coupon, by gas chromatograph, can the volumetric concentration of lower-boiling impurity in on-line checkingi overhead gas.When the volumetric concentration measuring lower-boiling impurity reaches following standard: N
2volumetric concentration≤4ppm, O
2volumetric concentration≤1ppm, CF
4volumetric concentration≤1ppm, H
2volumetric concentration≤1ppm, CO volumetric concentration≤1ppm, will extract octafluoropropane from tower top, and pass into low-temperature adsorber and carry out cryogenic absorption.
It should be noted that, lower-boiling impurity of the present invention and high-boiling-point impurity are all relative to octafluoropropane product.Except octafluoropropane, also there are other materials as N in octafluoropropane raw material
2, O
2, CO, H
2, CF
4, CHClF
2, CCl
2f
2, C
3f
6and CClF
3deng, but for octafluoropropane product, other materials in raw material are all impurity.Wherein, the boiling point of partial impurities lower than the boiling point-36.75 DEG C of octafluoropropane, so be called lower-boiling impurity, similarly, the boiling point of another part impurity higher than the boiling point-36.75 DEG C of octafluoropropane, so be called high-boiling-point impurity.
Following table is each composition boiling point table at normal atmospheric pressure in raw material octafluoropropane:
Each composition boiling point table in table 1 raw material octafluoropropane
| Compound title | Chemical formula | Boiling point/DEG C |
| Nitrogen | N 2 | -195.8 |
| Oxygen | O 2 | -183 |
| Hydrogen | H 2 | -252.87 |
| Carbon monoxide | CO | -191.5 |
| Tetrafluoro-methane | CF 4 | -128.1 |
| Difluorochloromethane | CHClF 2 | -40.83 |
| Octafluoropropane | C 3F 8 | -36.75 |
| Refrigerant 12 | CCl 2F 2 | -29.79 |
| R 1216 | C 3F 6 | -29.6 |
| Trifluorochloroethylene | CClF 3 | -27.85 |
As known from Table 1, described lower-boiling impurity comprises N
2, O
2, CO, H
2, CF
4and CHClF
2, described high-boiling-point impurity comprises CCl
2f
2, C
3f
6and CClF
3.
The method of rectifying is adopted to be difficult to remove the CO in raw material octafluoropropane
2and H
2o, needs to utilize adsorption technology to remove CO further
2and H
2o.
S203, carries out cryogenic absorption by the described octafluoropropane raw material through rectifying at-100 DEG C ~-30 DEG C temperature.
Passed in low-temperature adsorber by described octafluoropropane raw material through rectifying and carry out cryogenic absorption, control temperature, in the scope of-100 DEG C ~-30 DEG C, can remove the CO of in the described octafluoropropane raw material of rectifying more than 70%
2and H
2o.
It should be noted that, cryogenic absorption be utilize sorbent material to the loading capacity of gas with various with temperature different and discrepant characteristic, under the condition of sorbent material adsorption selection, adsorb the impurity composition in mixture at low temperatures, do not discharged by the product gas adsorbed; Intensification or pure air-blowing are washed with these impurity of desorb and sorbent material are regenerated.The principle that the present invention utilizes the loading capacity of sorbent material to increase with the decline of temperature just, makes the CO in the product after described rectifying
2and H
2o by sorbent material selective adsorption, strengthen the adsorption effect of sorbent material, and octafluoropropane can not adsorbed by low-temperature adsorber smoothly, enters next processing step under the condition of low temperature.
In S203 step, described cryogenic absorption described octafluoropropane raw material is passed into the low-temperature adsorber being equiped with the second sorbent material carry out cryogenic absorption;
Described second sorbent material comprises the second sorbent material a and the second sorbent material b;
Described second sorbent material a is CO
2special adsorbent;
Described second sorbent material b is one in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and 13X molecular sieve or its combination.
It should be noted that, CO
2special adsorbent can be in the one in cylindric or granular lithium hydroxide, potassium hydroxide, calcium hydroxide, molecular sieve, silica gel, gac, activated carbon fiber, carbonaceous molecular sieve or its combination.
The present invention adopts CO
2special adsorbent replacement common molecular screens out the CO in octafluoropropane raw material
2, due to CO
2special adsorbent is to CO
2there is highly selective, the CO under the condition of low temperature in selective adsorption octafluoropropane raw material
2, substantially do not adsorb other impurity, solve CO in octafluoropropane
2remove the problem that the degree of depth is inadequate, and greatly reduce the regeneration times of sorbent material.
Molecular sieve is silicate or the silico-aluminate of crystal form, is connected and is formed duct and the cavity system of molecular dimension size (being generally 0.3 ~ 2.0 nm), thus have the characteristic of screening molecule by silicon-oxy tetrahedron or aluminum-oxygen tetrahedron by oxo bridge key.The present invention second sorbent material b is one in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and 13X molecular sieve or its combination, adsorbs the H in octafluoropropane raw material by the second sorbent material b
2o, can remove most H in octafluoropropane raw material
2o.
It is pointed out that the second sorbent material b is not only for adsorbing H
2o, also can be used for CO absorption
2, but in low-temperature adsorber of the present invention, because the second sorbent material a adsorbs the CO of major part in the described octafluoropropane raw material of rectifying
2, therefore, at identical conditions, the second sorbent material b is mainly used in adsorbing the H in the described octafluoropropane raw material of rectifying
2o.
Preferably, the present invention adopts the molecular sieve that 5A and 13X molecular sieve mixes with 1:1 ~ 1:2.
Owing to being the product obtained at-37 DEG C ~ 10 DEG C through the described octafluoropropane raw material of rectifying, being in low-temperature condition when therefore entering low-temperature adsorber, the energy consumption of low-temperature adsorber can be reduced.In addition, the present invention adopts Chinese patent CN201949772 as low-temperature adsorber, and using liquid nitrogen as low-temperature receiver, described low-temperature adsorber can solve the inefficient problem of adsorber mass-and heat-transfer effectively, and can reuse low-temperature receiver, greatly reduces energy consumption.
S204, the described octafluoropropane raw material after cryogenic absorption is passed into molding machine supercharging, and the air pressure after described supercharging is 0.5 ~ 1.5MPa.
Preferably, molding machine pressurized control air pressure is within the scope of 0.8 ~ 1.2MPa.
S205, passes into the described octafluoropropane raw material through supercharging in gas purifier and carries out pressurized adsorbent, obtain described octafluoropropane product.
Similar to the principle of cryogenic absorption, pressurized adsorbent be utilize sorbent material to the loading capacity of gas with various with pressure different and discrepant characteristic, under the condition of sorbent material adsorption selection, under high pressure adsorb the impurity composition in mixture, do not discharged by the octafluoropropane product adsorbed, obtain purity 99.999% octafluoropropane product.
It should be noted that, described gas purifier is equiped with the 3rd sorbent material;
Described 3rd sorbent material is one in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and 13X molecular sieve or its combination.
Preferably, described 3rd sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix.
More preferably, described 3rd sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix with the ratio of 1:1 ~ 1:2.
It should be noted that, by the CO in the described octafluoropropane raw material of cryogenic absorption
2and H
2o under the condition of 0.5 ~ 1.5MPa supercharging can absorb by the 3rd sorbent material, remove CO further
2and H
2o.
The volumetric concentration of the impurity that described octafluoropropane product comprises is N
2volumetric concentration≤2.0ppm, O
2volumetric concentration≤0.5ppm, CF
4volumetric concentration≤0.2ppm, CH
4volumetric concentration≤0.2ppm, CO
2volumetric concentration≤0.5ppm, H
2o volumetric concentration≤1ppm and containing chlorine fluorine carbon compound foreign body volume concentrations≤1ppm.
The volumetric concentration of the impurity that the octafluoropropane product obtained by the present invention comprises, CO
2and H
2o occupies larger proportion in the impurity of product, in other words, how to reduce CO
2and H
2the volumetric concentration of O improves the key of octafluoropropane product purity.But octafluoropropane product prepared by Conventional processing methods is difficult to realize CO
2volumetric concentration≤0.5ppm and H
2o volumetric concentration≤1ppm, after adopting the step of pressurized adsorbent, greatly strengthen the adsorption effect of sorbent material, reduce further CO
2and H
2o is content in the product, is conducive to octafluoropropane product and reaches purity more than 99.999%.
Reach the octafluoropropane product of purity more than 99.999% comprise impurity volumetric concentration can not be greater than 10ppm, and in octafluoropropane product, the volumetric concentration of chloride fluorocarbons impurities is not more than 1ppm, adds N
2, O
2, CF
4, CO
2and H
2the volumetric concentration of O, the volumetric concentration of gained total impurities is not more than 10ppm, and namely product octafluoropropane purity can reach more than 99.999%.
The present invention is set forth further below with specific embodiment
Embodiment 1
Octafluoropropane raw material is passed into be equiped with and carry out normal temperature absorption by 5A and 13X molecular sieve with the normal temperature adsorber that the molecular sieve that 1:1.2 mixes is the first sorbent material; Pass in the first rectifying tower by the octafluoropropane raw material adsorbed through normal temperature, at 0 DEG C, 0.4MPa, emptying flow is 2Nm
3a rectifying is carried out under/h; Pass in Second distillation column by the described octafluoropropane raw material through a rectifying, at-10 DEG C, 0.3MPa, emptying flow is 0.5Nm
3secondary rectifying is carried out under the condition of/h; By under the temperature condition of the described octafluoropropane raw material through rectifying at-75 DEG C, the second sorbent material of employing comprises with CO
2special adsorbent is the second sorbent material a and is the second sorbent material b with 3A molecular sieve, carries out cryogenic absorption; By under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 0.6MPa, 5A molecular sieve is adopted to carry out pressurized adsorbent as the 3rd sorbent material, the octafluoropropane product of final acquisition purity more than 99.999%, the volumetric concentration of the impurity that described octafluoropropane product comprises is CO
2volumetric concentration≤0.3ppm, H
2o volumetric concentration≤0.6ppm.
Embodiment 2
Octafluoropropane raw material is passed into be equiped with and carry out normal temperature absorption by 5A and 13X molecular sieve with the normal temperature adsorber that the molecular sieve that 1:1.5 mixes is the first sorbent material; Pass in the first rectifying tower by the octafluoropropane raw material adsorbed through normal temperature, at 10 DEG C, 0.6MPa, emptying flow is 0.2Nm
3a rectifying is carried out under/h; Pass in Second distillation column by the described octafluoropropane raw material through a rectifying, at-5 DEG C, 0.1MPa, emptying flow is 0.7Nm
3secondary rectifying is carried out under the condition of/h; By under the temperature condition of the described octafluoropropane raw material through rectifying at-55 DEG C, the second sorbent material of employing comprises with CO
2special adsorbent is the second sorbent material a and is the second sorbent material b by 4A and 13X molecular sieve with the molecular sieve that 1:1.2 mixes, and carries out cryogenic absorption; By under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 0.9MPa, the molecular sieve mixed using 1:1 by 5A and 13X molecular sieve is adopted to carry out pressurized adsorbent as the 3rd sorbent material, the octafluoropropane product of final acquisition purity more than 99.999%, the volumetric concentration of the impurity that described octafluoropropane product comprises is CO
2volumetric concentration≤0.5ppm, H
2o volumetric concentration≤0.9ppm.
Embodiment 3
Octafluoropropane raw material is passed into be equiped with and carry out normal temperature absorption by 5A and 13X molecular sieve with the normal temperature adsorber that the molecular sieve that 1:1 mixes is the first sorbent material; Pass in the first rectifying tower by the octafluoropropane raw material adsorbed through normal temperature, at-10 DEG C, 0.5MPa, emptying flow is 1.8Nm
3a rectifying is carried out under/h; Pass in Second distillation column by the described octafluoropropane raw material through a rectifying, at-20 DEG C, 0.2MPa, emptying flow is 1.0Nm
3secondary rectifying is carried out under the condition of/h; By under the temperature condition of the described octafluoropropane raw material through rectifying at-41 DEG C, the second sorbent material of employing comprises with CO
2special adsorbent is the second sorbent material a and is the second sorbent material b with 5A molecular sieve, carries out cryogenic absorption; By under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 1.2MPa, the molecular sieve mixed using 1:1.8 by 5A and 13X molecular sieve is adopted to carry out pressurized adsorbent as the 3rd sorbent material, the octafluoropropane product of final acquisition purity more than 99.999%, the volumetric concentration of the impurity that described octafluoropropane product comprises is CO
2volumetric concentration≤0.4ppm, H
2o volumetric concentration≤0.7ppm.
Embodiment 4
Octafluoropropane raw material is passed into be equiped with and carry out normal temperature absorption by 5A and 13X molecular sieve with the normal temperature adsorber that the molecular sieve that 1:2 mixes is the first sorbent material; Pass in the first rectifying tower by the octafluoropropane raw material adsorbed through normal temperature, at-10 DEG C, 0.3MPa, emptying flow is 1.2Nm
3a rectifying is carried out under/h; Pass in Second distillation column by the described octafluoropropane raw material through a rectifying, at-30 DEG C, 0.15MPa, emptying flow is 2Nm
3secondary rectifying is carried out under the condition of/h; By under the temperature condition of the described octafluoropropane raw material through rectifying at-95 DEG C, the second sorbent material of employing comprises with CO
2special adsorbent is the second sorbent material a and is the second sorbent material b by 5A and 13X molecular sieve with the molecular sieve that 1:1.5 mixes, and carries out cryogenic absorption; By under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 1.2MPa, the molecular sieve mixed using 1:2 by 5A and 13X molecular sieve is adopted to carry out pressurized adsorbent as the 3rd sorbent material, the octafluoropropane product of final acquisition purity more than 99.999%, the volumetric concentration of the impurity that described octafluoropropane product comprises is CO
2volumetric concentration≤0.3ppm, H
2o volumetric concentration≤0.4ppm.
Embodiment 5
Octafluoropropane raw material is passed into be equiped with and carry out normal temperature absorption by 5A and 13X molecular sieve with the normal temperature adsorber that the molecular sieve that 1:2 mixes is the first sorbent material; Pass in the first rectifying tower by the octafluoropropane raw material adsorbed through normal temperature, at-5 DEG C, 0.35MPa, emptying flow is 0.5Nm
3a rectifying is carried out under/h; Pass in Second distillation column by the described octafluoropropane raw material through a rectifying, at-25 DEG C, 0.17MPa, emptying flow is 1.5Nm
3secondary rectifying is carried out under the condition of/h; By under the temperature condition of the described octafluoropropane raw material through rectifying at-32 DEG C, the second sorbent material of employing comprises with CO
2special adsorbent is the second sorbent material a and is the second sorbent material b by 3A and 5A molecular sieve with the molecular sieve that 1:2 mixes, and carries out cryogenic absorption; By under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 1.3MPa, the molecular sieve mixed using 1:1 by 5A and 13X molecular sieve is adopted to carry out pressurized adsorbent as the 3rd sorbent material, the octafluoropropane product of final acquisition purity more than 99.999%, the volumetric concentration of the impurity that described octafluoropropane product comprises is CO
2volumetric concentration≤0.4ppm, H
2o volumetric concentration≤0.7ppm.
Embodiment 6
Octafluoropropane raw material is passed into be equiped with and carry out normal temperature absorption by 5A and 13X molecular sieve with the normal temperature adsorber that the molecular sieve that 1:1.5 mixes is the first sorbent material; Pass in the first rectifying tower by the octafluoropropane raw material adsorbed through normal temperature, at-8 DEG C, 0.4MPa, emptying flow is 0.8Nm
3a rectifying is carried out under/h; Pass in Second distillation column by the described octafluoropropane raw material through a rectifying, at-30 DEG C, 0.24MPa, emptying flow is 1.7Nm
3secondary rectifying is carried out under the condition of/h; By under the temperature condition of the described octafluoropropane raw material through rectifying at-63 DEG C, the second sorbent material of employing comprises with CO
2special adsorbent is the second sorbent material a and is the second sorbent material b by 4A and 5A molecular sieve with the molecular sieve that 1:1.4 mixes, and carries out cryogenic absorption; By under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 1.5MPa, the molecular sieve mixed using 1:1.7 by 5A and 13X molecular sieve is adopted to carry out pressurized adsorbent as the 3rd sorbent material, the octafluoropropane product of final acquisition purity more than 99.999%, the volumetric concentration of the impurity that described octafluoropropane product comprises is CO
2volumetric concentration≤0.5ppm, H
2o volumetric concentration≤0.5ppm.
In order to better compare the octafluoropropane product purity obtained by the present invention and prior art, utilize gas chromatograph to measure the concentration of octafluoropropane product major impurity, concrete measuring method is as follows:
(1) using identical thick octafluoropropane as raw material, the method for embodiment 1 ~ 6 and reference example is adopted to obtain octafluoropropane product;
(2) utilize gas chromatograph to produce to embodiment 1 ~ 6 and reference example the octafluoropropane product foreign body volume concentrations obtained to measure;
(3) experimental data is recorded.
Wherein, above-mentioned reference example is the method utilizing impurity in impurity decomposing agent pyrolytic decomposition octafluoropropane.
Measuring result is as shown in table 2:
The volumetric concentration contrast table of table 2 octafluoropropane product impurity
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Reference example | |
| N 2Volumetric concentration/ppm | 3.0 | 3.5 | 2.0 | 1.8 | 2.2 | 1.5 | 3.6 |
| O 2Volumetric concentration/ppm | 0.7 | 0.8 | 0.6 | 0.4 | 0.4 | 0.3 | 1.0 |
| CF 4Volumetric concentration/ppm | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.3 |
| CH 4Volumetric concentration/ppm | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.5 |
| CO 2Volumetric concentration/ppm | 0.3 | 0.5 | 0.4 | 0.3 | 0.4 | 0.5 | 1.8 |
| H 2O volumetric concentration/ppm | 0.6 | 0.9 | 0.7 | 0.4 | 0.5 | 0.5 | 2.2 |
| Fluorocarbons impurities volumetric concentration/ppm | 1.0 | 0.8 | 0.6 | 0.5 | 0.6 | 0.5 | 0.9 |
As known from Table 2, CO in reference example
2and H
2the volumetric concentration of O is obviously than the CO in embodiment 1 ~ 6
2and H
2the volumetric concentration of O is high, adopts the present invention to carry out purifying to octafluoropropane raw material, controls fluorocarbons impurities volumetric concentration≤1ppm on the one hand, removing CO on the other hand
2and H
2o has unusual effect, CO in octafluoropropane product
2volumetric concentration≤0.5ppm and H
2o volumetric concentration≤1ppm, thus solve impurity CO in the obtained octafluoropropane product of prior art production
2and H
2o removes the inadequate problem of the degree of depth.
In sum, implement the embodiment of the present invention, there is following beneficial effect:
First, the present invention is different from the single distillation technology of prior art or single adsorption technology, adopt the method that distillation technology combines with adsorption technology, the purity of further raising octafluoropropane product, avoid bringing energy consumption large because of pyrolytic decomposition impurity, equipment requirements is high, and production efficiency is low, the situation that product purity is not high.
Secondly, cryogenic absorption technology of the present invention adopts CO
2special adsorbent substitutes common molecular and screens out the CO degassed in body
2, due to CO
2special adsorbent is to CO
2there is highly selective, the CO under the condition of low temperature in selective adsorption octafluoropropane raw material
2, substantially do not adsorb other impurity, solve CO in octafluoropropane
2remove the problem that the degree of depth is inadequate, make CO
2volumetric concentration reaches lower than 0.5ppm effect, and greatly reduces the regeneration times of sorbent material.In addition, because the present invention adopts the technique of low temperature fractionation, the product after rectifying is in low-temperature condition, utilizes gas to be in low-temperature condition and carries out cryogenic absorption, can reduce the energy consumption of low-temperature adsorber.
Because traditional method can remove most of chloride fluorocarbons impurities, but octafluoropropane product prepared by traditional method is difficult to realize CO
2and H
2the volumetric concentration of both O is all less than 1ppm.After adopting the step of pressurized adsorbent, greatly strengthen the adsorptive power of sorbent material, CO can be reduced further
2and H
2o is content in the product, not only controls fluorocarbons impurities volumetric concentration≤1ppm, and realize H
2o≤1ppm and CO
2≤ 0.5ppm, is conducive to octafluoropropane product and reaches purity more than 99.999%.
Finally, the present invention is on the basis of prior art low temperature fractionation, in conjunction with cryogenic absorption technology and pressurized adsorbent technology, purifying is carried out to octafluoropropane gas, not only make containing chlorine fluorine carbon compound foreign body volume concentrations≤1ppm in octafluoropropane product, and make traditional technology be difficult to the CO be separated
2and H
2the volumetric concentration of both O is all less than 1ppm, controls total impurities content at below 10ppm, effectively improve the purity of gas and the purity realizing octafluoropropane product more than 99.999%, meet the requirement for electronics spy gas in semi-conductor and microelectronics industry.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (6)
1. an octafluoropropane purification process, is characterized in that, comprising:
Octafluoropropane raw material is carried out normal temperature absorption under normal temperature condition;
By the described octafluoropropane raw material that adsorbs through normal temperature at-37 DEG C ~ 10 DEG C, under 0.1 ~ 0.6MPa condition, carry out rectifying;
Described octafluoropropane raw material through rectifying is carried out cryogenic absorption at-100 DEG C ~-30 DEG C temperature;
Carry out pressurized adsorbent by under the pressure condition of the described octafluoropropane raw material through cryogenic absorption at 0.5 ~ 1.5MPa, obtain octafluoropropane product;
Described by the described octafluoropropane raw material that adsorbs through normal temperature at-37 DEG C ~ 10 DEG C, the step of carrying out rectifying under 0.1 ~ 0.6MPa condition comprises:
The octafluoropropane raw material adsorbed through normal temperature is passed in the first rectifying tower, at-10 DEG C ~ 10 DEG C, under 0.3 ~ 0.6MPa condition, carries out a rectifying;
Described octafluoropropane raw material through a rectifying is passed in Second distillation column, at-37 DEG C ~-10 DEG C, under the condition of 0.1 ~ 0.3MPa, carries out secondary rectifying;
In described normal temperature adsorption process, octafluoropropane raw material is passed into the normal temperature adsorber being equiped with the first sorbent material and carry out normal temperature absorption;
Described first sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix;
In described cryogenic absorption process, described octafluoropropane raw material is passed into the low-temperature adsorber being equiped with the second sorbent material and carries out cryogenic absorption;
Described second sorbent material comprises the second sorbent material a and the second sorbent material b;
Described second sorbent material a is CO
2special adsorbent;
Described second sorbent material b is one in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and 13X molecular sieve or its combination;
The step of pressurized adsorbent will be carried out under the pressure condition of described octafluoropropane raw material through cryogenic absorption at 0.5 ~ 1.5MPa, comprising:
Described octafluoropropane raw material after cryogenic absorption is passed into molding machine supercharging, and the air pressure after described supercharging is 0.5 ~ 1.5MPa;
Described octafluoropropane raw material through supercharging is passed in gas purifier and carries out pressurized adsorbent;
Described gas purifier is equiped with the 3rd sorbent material;
Described 3rd sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix.
2. octafluoropropane purification process as claimed in claim 1, it is characterized in that, in described first rectifying tower, Liquid level is 55% ~ 70%, and emptying flow is 0.1 ~ 2.0Nm
3/ h.
3. octafluoropropane purification process as claimed in claim 1, it is characterized in that, the emptying flow of described Second distillation column is 0.5 ~ 2.0Nm
3/ h.
4. octafluoropropane purification process as claimed in claim 1, it is characterized in that, described first sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix with the ratio of 1:1 ~ 1:2.
5. the purification process of octafluoropropane as claimed in claim 1, it is characterized in that, described 3rd sorbent material is the molecular sieve that 5A molecular sieve and 13X molecular sieve mix with the ratio of 1:1 ~ 1:2.
6. the purification process of octafluoropropane as described in any one of Claims 1 to 5, it is characterized in that, the purity of described octafluoropropane product is more than 99.999%;
The CO of described octafluoropropane product
2volumetric concentration≤0.5ppm, H
2o volumetric concentration≤1ppm and containing chlorine fluorine carbon compound foreign body volume concentrations≤1ppm.
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| CN104529691B (en) * | 2014-12-30 | 2016-05-04 | 中国船舶重工集团公司第七一八研究所 | The catalysis conversion method of impurity in a kind of perfluoro alkane |
| CN107200675B (en) * | 2016-03-16 | 2019-10-25 | 中昊晨光化工研究院有限公司 | The separation method of perfluoropropane in a kind of perfluoropropene production process |
| CN109956855B (en) * | 2017-12-25 | 2022-04-15 | 中蓝晨光化工研究设计院有限公司 | Preparation method of high-purity perfluoromethyl vinyl ether |
| CN110078583A (en) * | 2019-06-06 | 2019-08-02 | 太仓沪试试剂有限公司 | A kind of purification process of iodoethane |
| CN110483234B (en) * | 2019-08-29 | 2021-12-07 | 浙江博瑞电子科技有限公司 | Method for purifying electronic grade octafluorocyclopentene |
| CN113877313B (en) * | 2021-10-25 | 2022-06-17 | 上海杰视医疗科技有限公司 | Purification device and purification method for medical perfluoropropane |
| CN114367254B (en) * | 2022-01-20 | 2023-05-23 | 中船(邯郸)派瑞特种气体股份有限公司 | Device and method for preparing octafluoropropane from hexafluoropropane |
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