CN101479220A - Process for producing high-purity hexafluoropropylene and cleaning gas - Google Patents

Abstract

A process for industrially advantageously producing high-purity hexafluoropropylene; and a use of this high-purity hexafluoropropylene, specifically, a cleaning gas for removing deposits in a semiconductor manufacturing apparatus or liquid-crystal manufacturing apparatus. In the process for high-purity hexafluoropropylene production, crude hexafluoropropylene produced by the pyrolysis of chlorodifluoromethane is purified to thereby produce high-purity hexafluoropropylene. It comprises: a step (1) in which the crude hexafluoropropylene is brought into contact with an adsorbent comprising a zeolite having an average micropore diameter of 3.4-11 AA and/or a carbonaceous adsorbent having an average micropore diameter of 3.5-11 AA to reduce the content of chlorine compounds and/or hydrocarbons in the crude hexafluoropropylene; and a step (2) in which the hexafluoropropylene obtained in the step (1) is distilled to reduce the content of low-boiling ingredients therein.

Description

Method for producing high-purity hexafluoropropylene and purge gas

technical field

The invention relates to a method for producing high-purity hexafluoropropylene. In particular, it relates to a method for producing hexafluoropropylene which can be ideally used for removing deposits in semiconductor manufacturing equipment or liquid crystal manufacturing equipment, and uses of high-purity hexafluoropropylene.

Background technique

Hexafluoropropylene (hereinafter sometimes referred to as "CF ₃ CF=CF ₂ " or "FC-1216") is used, for example, as a purge gas in semiconductor device manufacturing processes, as a raw material for octafluoropropane (C ₃ F ₈ ), etc. . As its production method, the following methods are known, for example:

(1) A method obtained as a by-product in the process of producing tetrafluoroethylene (CF ₂ =CF ₂ ) through thermal decomposition of chlorodifluoromethane (CHClF ₂ ) represented by the following formula,

2CHClF ₂ +H ₂ O→CF ₂ ＝CF ₂ +CF ₃ CF＝CF ₂

(2) A method obtained by thermally decomposing polytetrafluoroethylene, or passing tetrafluoroethylene over platinum under reduced pressure and high temperature, etc.,

(3) A method of chlorofluorinating and dehalogenating propane, propylene, or partially halogenated C3 acyclic hydrocarbons (JP-A-4-145033 Gazette),

etc. However, in many cases, hexafluoropropylene contains various impurities such as saturated compounds such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrocarbons (HCs), and unsaturated compounds. These impurities are difficult to separate from hexafluoropropene by distillation operations.

Therefore, in order to obtain hexafluoropropylene with higher purity, these impurities must be removed as much as possible. In particular, for chlorofluorocarbons and hydrochlorofluorocarbons which are chlorine-containing compounds, in addition to the purpose of highly purifying hexafluoropropylene, from the viewpoint of preventing the destruction of the ozone layer, etc., it is necessary to prevent contamination in semiconductor manufacturing equipment or liquid crystal manufacturing equipment. From the viewpoint of internal contamination (the etching chamber is contaminated by chlorine-containing compounds), it is necessary to remove compounds that are difficult to separate by ordinary distillation.

However, among these impurities, there are also compounds that are very difficult to separate from hexafluoropropene because they form an azeotrope or an azeotrope-like mixture with hexafluoropropene. For example, chlorofluoroethylene (CH ₂ ＝CClF), chlorotrifluoroethylene (CF ₂ ＝CClF), dichlorodifluoromethane (CCl ₂ F ₂ ), etc., form azeotropic mixtures because their boiling point is close to that of hexafluoropropylene Or azeotropic mixture, so it is a very difficult compound to separate and purify.

1,1,1,2-tetrafluoroethane (CF ₃ CH ₂ F) and pentafluoroethane (CF ₃ CHF ₂ ), which are important compounds as a cooling medium, are known as methods for purifying impurities such as the following: The above methods: a method of purifying by extractive distillation; a method of removing impurities by a dehalogenation hydrogenation reaction using hydrogen, etc. in the presence of a catalyst.

In addition, in order to highly purify saturated compounds such as nitrogen trifluoride (NF ₃ ) and hexafluoroethane (CF ₃ CF ₃ ) used as purge gas, and to reduce such chlorine-containing compounds (purification), it has been proposed and implemented Various methods were used to achieve high purity.

On the other hand, as a method using hexafluoropropylene as a purge gas, for example,

(1) Plasma CVD reaction chamber cleaning method and plasma etching method (Japanese Unexamined Patent Publication No. 9-296271),

(2) Etching gas and cleaning gas (JP-A-10-27781),

(3) Cleaning method and substrate processing device in the processing chamber (JP-A-2005-26409),

etc. However, there are still problems and problems regarding impurities in hexafluoropropylene, especially regarding the purification method and high purity of chlorine-containing compounds that are pollution sources.

Patent Document 1: Japanese Unexamined Patent Publication No. 4-145033

Patent Document 2: Japanese Unexamined Patent Publication No. 9-296271

Patent Document 3: Japanese Unexamined Patent Application Publication No. H10-27781

Patent Document 4: JP-A-2005-26409

Contents of the invention

The present invention will solve the problems of the above-mentioned prior art, and its purpose is to provide an advantageous industrial production method of high-purity hexafluoropropylene, and provide the purposes of this high-purity hexafluoropropylene, specifically, its purpose is to provide a method for removing Cleaning gas for deposits in semiconductor manufacturing equipment or liquid crystal manufacturing equipment.

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, found that high-purity hexafluoropropylene can be obtained by combining the steps of making the chlorine-containing compound and/or or hydrocarbon crude hexafluoropropylene with an average pore size of 3.4 ~11 of zeolites and/or a mean pore size of 3.5 ~11 The process of contacting the adsorbent of the carbonaceous adsorbent, thereby reducing the content of chlorine-containing compounds and/or hydrocarbons, and the distillation purification process.

That is, the present invention consists of the following [1] to [15].

[11] A method for producing high-purity hexafluoropropylene, comprising purifying crude hexafluoropropylene produced through thermal decomposition of chlorodifluoromethane to produce high-purity hexafluoropropylene, comprising the following step (1) and process (2),

Step (1): Make the crude hexafluoropropylene and the average pore diameter of 3.4 ~11 of zeolites and/or a mean pore size of 3.5 ~11 The adsorbent contact of the carbonaceous adsorbent, thereby reducing the content of chlorinated compounds and/or hydrocarbons in the crude hexafluoropropylene;

Step (2): The content of low boiling point components in the hexafluoropropylene obtained in step (1) is reduced by distillation.

[2] The method for producing high-purity hexafluoropropene according to the above [1], wherein the chlorine-containing compound is at least one compound represented by the general formula C _v H _x Cl _y F _z , in the above general formula, v is an integer of 1 to 4, x is an integer of 0 to 2, y is an integer of 1 to 3, z is an integer of 1 to 6, and 2v≦x+y+z≦2v+2.

[3] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the chlorine-containing compound is selected from dichlorodifluoromethane, dichlorofluoromethane, chlorodifluoromethane, chlorofluoroethylene, chlorine At least one of trifluoroethylene, chlorotetrafluoroethane, chloropentafluoroethane, and chlorohexafluoropropane.

[4] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the hydrocarbon is at least one selected from propylene, cyclopropane and propane.

[5] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the zeolite is a zeolite having a silica/aluminum ratio of 2.0 or less.

[6] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the low boiling point component is at least one selected from nitrogen, oxygen, carbon monoxide and carbon dioxide.

[7] The method for producing high-purity hexafluoropropylene described in [1] above, wherein crude hexafluoropropylene produced by thermally decomposing chlorodifluoromethane is distilled to reduce the content of high-boiling-point components in the crude hexafluoropropylene , and then supplied to the step (1).

[8] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the chlorine-containing compound content in the high-purity hexafluoropropylene obtained in the step (2) is 20 ppm or less by volume.

[9] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the hydrocarbon content in the high-purity hexafluoropropylene obtained in the step (2) is 30 ppm or less by volume.

[10] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the content of low boiling point components in the high-purity hexafluoropropylene obtained in the step (2) is 20 ppm or less by volume.

[11] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the purity of the high-purity hexafluoropropylene obtained in the step (2) is 99.99% by volume or more.

[12] The method for producing high-purity hexafluoropropylene according to the above [1], wherein the high-purity hexafluoropropylene is used as a purge gas for removing deposits in semiconductor manufacturing equipment or liquid crystal manufacturing equipment .

[13] A purge gas for removing deposits in semiconductor or liquid crystal manufacturing equipment, wherein the content of chlorine-containing compounds is 20 ppm or less by volume, the content of hydrocarbons is 30 ppm or less by volume, and the content of low boiling point components is 20 ppm or less by volume. High-purity hexafluoropropene having a purity of 99.99% by volume or less is 20 ppm or less.

[14] The purge gas according to the above [13], wherein the high-purity hexafluoropropylene is produced by the method of any one of the above-mentioned [1] to [12].

[15] A cleaning method for removing deposits in semiconductor manufacturing equipment or liquid crystal manufacturing equipment at a temperature in the range of 50 to 500° C. and a pressure in the range of 0.05 to 1 MPa using the cleaning gas described in the above [13].

According to the present invention, high-purity hexafluoropropylene can be efficiently produced by a simple method, and the obtained high-purity hexafluoropropylene can be ideally used as plasma for removing deposits in semiconductor manufacturing equipment or liquid crystal manufacturing equipment. Body purge gas.

Detailed ways

Hereinafter, preferred embodiments of the present invention will be described in detail.

The method for producing high-purity hexafluoropropylene of the present invention is a method for producing high-purity hexafluoropropylene by purifying crude hexafluoropropylene. Specifically, the following steps (1) and (2) are included: (1) make the above-mentioned crude hexafluoropropylene and ~11 of zeolites and/or a mean pore size of 3.5 ~11 The carbonaceous adsorbent of the carbonaceous adsorbent is contacted with the adsorbent, thereby reducing the operation of the content of chlorine-containing compounds and/or hydrocarbons in the crude hexafluoropropylene; The process of boiling point component content.

Crude hexafluoropropylene used in the present invention is produced as a by-product when tetrafluoroethylene is produced through thermal decomposition of chlorodifluoromethane, and contains chlorine-containing compounds such as chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs) Various impurities such as saturated compounds and unsaturated compounds such as hydrocarbons and hydrocarbons (HC).

As above-mentioned chlorine-containing compound, can enumerate general formula C _v H _x Cl _y F _z (in formula, v is the integer of 1～4, x is the integer of 0～2, y is the integer of 1～3, z is 1～ Integer of 6, 2v≦x+y+z≦2v+2), crude hexafluoropropylene contains 1 or 2 or more of these compounds. Specific examples of the compound represented by the above general formula include dichlorodifluoromethane (CCl ₂ F ₂ ), dichloromonofluoromethane (CHCl ₂ F), chlorodifluoromethane (CHClF ₂ ), chlorofluoroethylene ( CH ₂ =CClF), chlorotrifluoroethylene (CF ₂ =CClF), chlorotetrafluoroethane (CF ₃ CHClF), chloropentafluoroethane (CF ₃ CClF ₂ ) and chlorohexafluoropropane (CF ₃ CHFCClF ₂ ) wait. The content of the chlorine-containing compound in crude hexafluoropropylene is preferably 0.05% by volume or less.

Examples of the hydrofluorocarbons include difluoroethylene (CHF=CHF), tetrafluoroethane (CF ₃ CH ₂ F), trifluoropropene (CF ₃ CH=CH ₂ ), fluoropropene (CH ₃ CF= CH ₂ ) etc. The content of the hydrofluorocarbons in the crude hexafluoropropylene is preferably 0.05% by volume or less.

Examples of the hydrocarbons include propylene (CH ₂ =CHCH ₃ ), cyclopropane (C ₃ H ₆ ), propane (CH ₃ CH ₂ CH ₃ ), and the like. The content of the above hydrocarbons in crude hexafluoropropylene is preferably 0.05% by volume or less.

The adsorbent used in the present invention is that (1) the average pore diameter is 3.4 ~11 Zeolite, (2) average pore size is 3.5 ~11 carbonaceous adsorbent, or (3) a mixture of the above-mentioned zeolite and the above-mentioned carbonaceous adsorbent. A zeolite having an average pore diameter within the above range is excellent in the effect of reducing the impurity content in crude hexafluoropropylene. In addition, a carbonaceous adsorbent having an average pore diameter within the above-mentioned range is excellent in the effect of reducing the impurity content in crude hexafluoropropylene. Furthermore, from the viewpoint of further enhancing the effect of reducing the impurity content, a zeolite having a silica/aluminum ratio of 2.0 or less is more preferable.

更优选为

的平均细孔径的沸石。如果是平均细孔径大于

的沸石，则有时六氟丙烯的吸附量增多，如果是平均细孔径小于

的沸石，则有时吸附含氯化合物、烃类的能力减小。That is, the zeolite used in the method for producing high-purity hexafluoropropylene of the present invention preferably has

more preferably

average pore diameter of zeolites. If the average pore diameter is greater than

The zeolite, sometimes the adsorption capacity of hexafluoropropylene increases, if the average pore size is less than

If the zeolite is used, the ability to adsorb chlorine-containing compounds and hydrocarbons may decrease.

In addition, the Si (silicon dioxide)/Al (aluminum) ratio of the zeolite is preferably 2.0 or less. When the Si/Al ratio exceeds 2, chlorine-containing compounds and hydrocarbons may not be selectively adsorbed. The zeolite is preferably selected from molecular sieve 4A (MS-4A, manufactured by Union Showa Co., Ltd.), molecular sieve 5A (MS-5A, manufactured by Union Showa Co., Ltd.), molecular sieve 10X (MS-10A, manufactured by Union Showa Co., Ltd.), and molecular sieve 13X. (MS-13X, manufactured by Union Showa Co., Ltd.).

On the other hand, activated carbon and carbon molecular sieves are known as carbonaceous adsorbents. Activated carbon is made of coconut shell, coal, wood, etc., and is activated by a special treatment called activation to make the raw material generate fine pores after high-temperature carbonization. It has a wide range of uses as an excellent adsorbent, but in In the production method of the present invention, it is preferable to use a carbon molecular sieve which is a molecular sieve activated carbon whose pore diameter is highly controlled.

的平均细孔径的吸附剂，如果是平均细孔径大于

的碳质吸附剂，则有时六氟丙烯的吸附量增多，如果是平均细孔径小于

的碳质吸附剂，则有时吸附含氯化合物、烃类的能力减小。作为碳质吸附剂，优选碳分子筛4A(例如武田药品工业株式会社制造)或碳分子筛5A(例如武田药品工业株式会社制造)，它们也可以并用。The carbonaceous adsorbent preferably has

The average pore size of the adsorbent, if the average pore size is greater than

Carbonaceous adsorbents, sometimes the adsorption capacity of hexafluoropropylene increases, if the average pore size is less than

If the carbonaceous adsorbent is used, the ability to adsorb chlorine-containing compounds and hydrocarbons may decrease. As the carbonaceous adsorbent, carbon molecular sieve 4A (for example, manufactured by Takeda Pharmaceutical Co., Ltd.) or carbon molecular sieve 5A (for example, manufactured by Takeda Pharmaceutical Co., Ltd.) is preferable, and these may be used in combination.

In addition, in the above-mentioned adsorbent containing the above-mentioned zeolite and the carbonaceous adsorbent, the mixing ratio of the zeolite and the carbonaceous adsorbent is not particularly limited, and can be appropriately set according to the type and content of impurities in the crude hexafluoropropylene.

As described above, in the present invention, the content of chlorine-containing compounds and/or hydrocarbons is reduced by bringing the above-mentioned adsorbent into contact with crude hexafluoropropylene. The state of the crude hexafluoropropylene when the adsorbent is in contact with the crude hexafluoropropylene is not particularly limited, for example, it may be a method of contacting the crude hexafluoropropylene in a gaseous state, a method of contacting in a gas-liquid mixed state, or a method of contacting in a liquid state. Any method among the methods, but the method of contacting in a liquid state is efficient, so it is preferable.

The method of contacting the adsorbent with crude hexafluoropropylene is not particularly limited, and known methods such as batch method and continuous method can be used, for example. Generally, in industry, for example, two fixed-bed adsorption towers are installed, and when one reaches adsorption saturation, it is replaced and regenerated. In addition, the conditions of the contact treatment are not particularly limited, but the treatment temperature is preferably low temperature, for example, preferably in the temperature range of -50 to 50°C, and more preferably in the temperature range of -20 to 30°C. In addition, when the crude hexafluoropropylene is brought into contact with the liquid state, the treatment pressure is not particularly limited as long as it can maintain the liquid state, and is not particularly limited when the crude hexafluoropropylene is brought into contact with the gaseous state, but is preferably The range of 0.05MPa～1MPa.

The crude hexafluoropropylene may also be introduced into a distillation column to remove low-boiling point components (low-boiling point fractions) and high-boiling point components (high-boiling point fractions) before being contacted with the adsorbent. However, in this case, it may be mixed with Low-boiling components from the adsorbent, low-boiling components must be removed again. Therefore, in the production method according to the present invention, after (1) bringing the crude hexafluoropropylene into contact with the adsorbent, (2) distilling the hexafluoropropylene obtained in the step (1) to reduce The process of content of low boiling point components. In addition, it is preferable to reduce the high-boiling point components in the crude hexafluoropropylene before the above-mentioned contact step (1), and it is preferable to have a step in the present invention, that is, to distill the crude hexafluoropropylene before the above-mentioned contact step (1), thereby Reduce the content of high boiling point components in crude hexafluoropropylene.

Nitrogen, oxygen, carbon monoxide, carbon dioxide, and mixtures of two or more of these are mentioned as said low boiling point component.

In this way, after the crude hexafluoropropylene is brought into contact with the above-mentioned adsorbent, the content of chlorine-containing compounds, hydrocarbons, and low boiling point components can be reduced by distillation, and high-purity hexafluoropropylene having a purity of 99.99% by volume or higher can be obtained. The content of chlorine-containing compounds in the high-purity hexafluoropropylene is preferably 20 ppm or less by volume, more preferably 10 ppm or less by volume, and the content of hydrocarbons is preferably 30 ppm or less by volume, more preferably 20 ppm or less by volume, The content of low boiling point components is preferably 20 ppm or less by volume, more preferably 10 ppm or less by volume.

Such high-purity hexafluoropropylene can be used as a cleaning gas for removing deposits in semiconductor manufacturing equipment or liquid crystal manufacturing equipment. At this time, high-purity hexafluoropropylene may be used alone, or at least one diluent gas selected from He, Ar, N ₂ , Ne, Kr, and oxygen-containing compounds may be added according to cleaning conditions. Examples of the oxygen-containing compound include O ₂ , CO, CO ₂ , NO, N ₂ O, OF ₂ , COF ₂ and the like. The addition amount of these diluent gases is preferably 40% by volume or less.

When cleaning a semiconductor manufacturing device using the above-mentioned cleaning gas, it may be cleaned under plasma conditions or may be cleaned under plasma-free conditions. In the case of cleaning under plasma conditions, the excitation source is not particularly limited as long as it can excite plasma from the above-mentioned cleaning gas, but it is preferable to use a microwave excitation source because the cleaning efficiency is good. In addition, the temperature range and pressure range of the purge gas of the present invention are not particularly limited as long as they can generate plasma, but the temperature range is preferably 50-500°C, and the pressure range is preferably 0.05-1 MPa. On the other hand, in the case of cleaning under plasma-free conditions, the cleaning gas is introduced into the chamber, and the pressure in the chamber is preferably set to a range of 0.05 to 1 MPa, and at least part of the chamber and the cleaning gas, or any One side is heated to the range of 150-500° C. to activate the cleaning gas, so that the semiconductor manufacturing device can be cleaned by etching and removing the deposits from the chamber and other areas where the deposits have accumulated.

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by these examples.

Preparation Example 1

When tetrafluoroethylene is produced from chlorodifluoromethane (CHClF ₂ ) via thermal decomposition (thermal decomposition temperature: 600° C.), the product is distilled twice to recover tetrafluoroethylene, and crude hexafluoropropylene is obtained. The crude hexafluoropropylene was analyzed by gas chromatography ["GC-14A" manufactured by Shimadzu Corporation, column: Porapack-Q (6m) manufactured by Shimadzu Corporation, measurement temperature: 80 to 200°C]. The results are shown in Table 1.

Example 1

)混合并填充到容积1000ml的不锈钢制圆筒中，进行真空干燥。接着，一边对圆筒进行冷却，一边向其中填充约550g上述制备例1所得的粗六氟丙烯，在室温下时常搅拌，填充约12小时后回收液相部分[工序(1)]。用气相色谱[(株)岛津制作所制造“GC-14A”，柱：(株)岛津制作所制造Porapack-Q(6m)，测定温度：80～200℃]分析该液相部分。将结果示于表1。80 g of molecular sieve 13X (manufactured by Union Showa Co., Ltd.: average pore diameter 10 , the ratio of silica/aluminum=0.81) and 70g of carbonaceous adsorbent (carbon molecular sieve 5A, manufactured by Takeda Pharmaceutical Co., Ltd.: average pore diameter

) were mixed and filled into a stainless steel cylinder with a capacity of 1000 ml, and vacuum-dried. Next, while cooling the cylinder, about 550 g of the crude hexafluoropropylene obtained in Preparation Example 1 above was filled thereinto, stirred constantly at room temperature, and the liquid phase was recovered after filling for about 12 hours [step (1)]. The liquid phase was analyzed by gas chromatography ["GC-14A" manufactured by Shimadzu Corporation, column: Porapack-Q (6m) manufactured by Shimadzu Corporation, measurement temperature: 80 to 200°C]. The results are shown in Table 1.

Next, the liquid phase obtained in the above step (1) is introduced into a distillation column, the low boiling point component (low boiling point fraction) is taken out from the top of the distillation column, and the liquid phase is recovered from the bottom of the distillation column [step (2)]. The liquid phase was analyzed by gas chromatography ["GC-14A" manufactured by Shimadzu Corporation, column: Porapack-Q (6m) manufactured by Shimadzu Corporation, measurement temperature: 80 to 200°C]. The results are shown in Table 1.

Reference example 1

30 g of molecular sieve 13X (manufactured by Union Showa Co., Ltd.: average pore diameter 10 , the ratio of silica/aluminum=0.81) was filled in a stainless steel cylinder with a volume of 200 ml, and vacuum-dried. Next, while cooling the cylinder, about 70 g of the crude hexafluoropropylene obtained in Preparation Example 1 above was filled thereinto, stirred constantly at room temperature, and the liquid phase was recovered after filling for about 12 hours. The liquid phase was analyzed by gas chromatography ["GC-14A" manufactured by Shimadzu Corporation, column: Porapack-Q (6m) manufactured by Shimadzu Corporation, measurement temperature: 80 to 200°C]. The results are shown in Table 1.

Reference example 2

20 g of carbonaceous adsorbent (carbon molecular sieve 5A, manufactured by Takeda Pharmaceutical Co., Ltd.: average pore diameter 5 ) was filled in a stainless steel cylinder with a capacity of 200 ml, and vacuum-dried. Next, while cooling the cylinder, about 60 g of the crude hexafluoropropylene obtained in Preparation Example 1 above was filled thereinto, stirred constantly at room temperature, and the liquid phase was recovered after filling for about 12 hours. The liquid phase was analyzed by gas chromatography ["GC-14A" manufactured by Shimadzu Corporation, column: Porapack-Q (6m) manufactured by Shimadzu Corporation, measurement temperature: 80 to 200°C]. The results are shown in Table 1.

[Table 1]

(Unit: volume %)

Claims (15)

1. the manufacture method of a high purity R 1216 is that the thick R 1216 that will produce via the chlorodifluoromethane thermolysis carries out purifying, thereby makes the method for high purity R 1216, comprises following operation (1) and operation (2),

Operation (1): making described thick R 1216 is 3.4 with containing average fine pore

～11

Zeolite and/or average fine pore be 3.5

～11

The sorbent material contact of carbonaceous adsorbent, thereby reduce the chlorine-containing compound in the thick R 1216 and/or the content of hydro carbons;

Operation (2): by distilling the content of the low boiling point component in the R 1216 that reduces operation (1) gained.

2. the manufacture method of high purity R 1216 according to claim 1, described chlorine-containing compound are general formula C _vH _xCl _yF _zAt least a kind of shown compound, in the above-mentioned general formula, v is 1～4 integer, and x is 0～2 integer, and y is 1～3 integer, and z is 1～6 integer, 2v≤x+y+z≤2v+2.

3. the manufacture method of high purity R 1216 according to claim 1, described chlorine-containing compound are at least a kind that is selected from Refrigerant 12, Dichloromonofluoromethane, chlorodifluoromethane, chlorine vinyl fluoride, chlorotrifluoroethylene, chloro-tetrafluoroethane, chloropentafluoroethane and the chlorine HFC-236fa.

4. the manufacture method of high purity R 1216 according to claim 1, described hydro carbons are at least a kind that is selected from propylene, cyclopropane and the propane.

5. the manufacture method of high purity R 1216 according to claim 1, described zeolite are that the ratio of silicon-dioxide/aluminium is the zeolite below 2.0.

6. the manufacture method of high purity R 1216 according to claim 1, described low boiling point component are to be selected from least a in nitrogen, oxygen, carbon monoxide and the carbonic acid gas.

7. the manufacture method of high purity R 1216 according to claim 1, the thick R 1216 that will produce via the chlorodifluoromethane thermolysis distills, thereby reduces the high boiling point component content in the thick R 1216, is supplied to described operation (1) then.

8. the manufacture method of high purity R 1216 according to claim 1, the chlorine-containing compound content by volume in the high purity R 1216 of described operation (2) gained is below the 20ppm.

9. the manufacture method of high purity R 1216 according to claim 1, the hydrocarbon content by volume in the high purity R 1216 of described operation (2) gained is below the 30ppm.

10. the manufacture method of high purity R 1216 according to claim 1, the content by volume of the low boiling point component in the high purity R 1216 of described operation (2) gained is below the 20ppm.

11. the manufacture method of high purity R 1216 according to claim 1, the purity of the high purity R 1216 of described operation (2) gained is more than the 99.99 volume %.

12. the manufacture method of high purity R 1216 according to claim 1, described high purity R 1216 uses as being used to remove semiconductor-fabricating device sedimental purgative gas interior or that the liquid crystal manufacturing installation is interior.

13. a sedimental purgative gas that is used to remove in semi-conductor or the liquid crystal manufacturing installation is that chlorine-containing compound content by volume is that 20ppm is following, the hydrocarbon content by volume is that 30ppm is following and low boiling point component content by volume is below the 20ppm and purity is the above high purity R 1216s of 99.99 volume %.

14. purgative gas according to claim 13, described high purity R 1216 are to use each the high purity R 1216 of method manufacturing of claim 1～12.

15. a purging method uses the described purgative gas of claim 13, under the pressure of the temperature of 50～500 ℃ of scopes, 0.05～1MPa scope, removes in the semiconductor-fabricating device or the settling in the liquid crystal manufacturing installation.