WO2006030656A1

WO2006030656A1 - Method for purifying ethyl chloride and method for producing fluoroethane using same

Info

Publication number: WO2006030656A1
Application number: PCT/JP2005/016155
Authority: WO
Inventors: Hiromoto Ohno; Yukio Nishiyama
Original assignee: Showa Denko K.K.
Priority date: 2004-09-16
Filing date: 2005-08-29
Publication date: 2006-03-23
Also published as: JPWO2006030656A1; JP4953819B2; TW200616930A

Abstract

Disclosed is a method for purifying ethyl chloride wherein a crude ethyl chloride containing a stabilizer and/or moisture is brought into contact with a zeolite having an average pore size of 3-11 Å and/or a carbonaceous material adsorbent having an average pore size of 3.4-11 Å in a liquid phase for reducing the stabilizer and/or moisture contained in the crude ethyl chloride. Also disclosed is a method for producing fluoroethane by using ethyl chloride obtained by such a purification method. The purification method enables to remove stabilizers and moisture contained in ethyl chloride, and can be performed commercially since operations of the process are easy to do.

Description

Method for purifying chlorinated chill and method for producing fluoretane using the same

Technical field

The present invention relates to a method for purifying chlorinated chlor and a fluorochemical using the method.

The present invention relates to a method for producing ethane.

Technical background

Examples of methods for producing ethyl chloride (CH ₃ CH ₂ C 1) include (1) a method in which hydrogen chloride is blown into a mixture of ethyl alcohol and zinc chloride when heated, and (2) a method in which aluminum chloride is used as a catalyst. Methods for adding chlorine to water .. Elementary chemicals (Chemical Dictionary 1 (Kyoritsu Shuppan)) are known.

For example, as a method for purifying crude chlorinated chill, after washing the crude ethyl chloride with concentrated sulfuric acid and water and absorbing it into alcohol, and slightly heating it, the chlorinated chill is easily released, and this is concentrated with concentrated sulfuric acid. There are known methods for drying to obtain ethyl chloride (Chemical Dictionary 1 (Kyoritsu Shuppan)).

In order to ensure the stability and quality of the obtained chilled chill, a stabilizer is generally added, and a stabilizer of about several hundred mass ppm is added. In addition, it is known that chloro chloride is hydrolyzed by moisture and alcohol.

By the way, for example, fluoroeluene (CH ₃ CH ₂ F) produced using chlorinated chill as a raw material is attracting attention as a low-temperature refrigerant, for example, as an etching gas.

As a method for producing fluoretane, the following methods have been conventionally used. Are known.

(1) A method for producing chlorinated fluorinated hydrocarbons by reducing them with hydrogen in the presence of a catalyst (Japanese Patent Laid-Open No. 7-1 2 6 1 9 7), etc. (2) A method for adding hydrogen fluoride to ethylene (Chemical Dictionary 7 (Kyoritsu Publishing)) is known. On the other hand, little is known about the production method of fluoroeluene using fluorination catalyst in the gas phase with ethyl chloride and hydrogen fluoride. For example, the production method using the above (1) is chlorinated fluorination. By excessive hydrogenation reaction or decomposition reaction by reaction of hydrocarbon and hydrogen

, Eight dragon bonbon (HC) class, eight dragon carbon (HCC)

), Chlorofluorocarbons (CFCs), Hydrok □ □ Saturated and unsaturated compounds such as Fluorocarbons (HCFCs) are produced, and separation and purification are extremely difficult. .

The above method (2) uses flammable and explosive range ethylene as a raw material, so that the equipment cost for ensuring safety is large and has an economic problem.

In addition, the method of reacting chloro chloride and hydrogen fluoride as raw materials in the presence of a fluorination catalyst is, for example, when a catalyst mainly composed of trivalent dimethyl oxide is used. Acetylene and ethylene are produced by reactions, etc., and there are problems in safety and economics, leaving technical issues.

As described above, ethyl chloride, which is one of the reaction raw materials, contains a stabilizer to suppress the generation of acid content. For example, as stabilizers, compounds having a single-mouth group include, for example, nitromethane, nitroen, cresol, nitrotoluene, and two-hole fenol.

In addition, as the compound having a hydroxyl group, phenol, cresol,

2, 6-butyl-p-cresol, aminomethylphenol, etc. If these stabilizers are not included, It lacks qualitative properties, and the generation of acid content due to decomposition proceeds, and hydrolysis occurs due to the contained water.

However, stabilizers and moisture contained in ethyl chloride are undesirable because, for example, they cause deterioration in the activity of the fluorination catalyst used in the production of fluorethan and shorten the catalyst life. It is desirable not to be included.

Therefore, the stabilizer may be removed before the reaction. However, the conventional removal method such as fractional distillation has a problem that the operation is complicated and a large amount of cost is required. Inexpensive invention

The present invention has been made under such a background, and it is possible to remove stabilizers and moisture contained in chlorinated chill, which is easy to operate and industrially feasible. It is an object of the present invention to provide a purification method and a method for producing fluoroethane using the chlorinated chill obtained by this purification method.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has determined that a crude chlorinated chill containing a stabilizer and water or moisture has a mean pore diameter in the range of 3 to 11 A and / or a mean pore diameter. It has been found that the stabilizer and / or water content can be reduced by contacting in a liquid phase with a carbonaceous adsorbent having a range of 3.4 to 11 A. In addition, by reacting hydrogen chloride with a reduced stabilizer with hydrogen fluoride in the gas phase in the presence of a fluorination catalyst, the economy has advantages such as efficient and long catalyst life. The present inventors have found that a typical method for producing fluoretane can be obtained, and have completed the present invention.

Therefore, this invention consists of a matter shown by the following [1]-[14], for example. C 1] Stabilizer and z or moisture-containing crude chlorinated chlorinated zeolite with an average pore size ranging from 3 to 11 A and / or an average pore size ranging from 3.4 to 11 A A method for purifying chlorinated chloride, which is characterized by bringing the carbonaceous adsorbent into contact with a liquid phase and reducing the stabilizer and / or moisture contained in the crude ethyl chloride.

[2] The method for purifying acetyl chloride according to the above [1], wherein the stabilizer is a compound having a nitro group or a hydroxyl group.

[3] The method for purifying chlorinated chill according to the above [1] or [2], wherein the zeolite has a silica-aluminum (SiZAl) ratio of 2 or less.

[4] The above [1] to [3], wherein the zeolite is at least one selected from the group consisting of molecular sieves 4 A, molecular sieves 5 A, molecular sieves 1 OA and molecular sieves 1 3 X. ] The refinement | purification method of chlorinated chill in any one of.

[5] The method for purifying chlorinated chill according to the above [1] or [2], wherein the carbonaceous adsorbent is molecular sieve carbon 4A and / or molecular sieve carbon 5A.

[6] The above [1] to [5], wherein the temperature at which the stabilizer and the crude chlorinated chill containing Z or moisture are brought into contact with the zeolite and / or the carbonaceous adsorbent is in the range of 120 to 60. ] The refinement | purification method of the chloride chloride in any one of.

[7] In any one of the above [1] to [6], the pressure at which the stabilizer and / or crude chlorinated chill containing water is brought into contact with the zeolite and / or the carbonaceous adsorbent is in the range of 0 to IMP a. The method for purifying ethyl chloride as described.

[8] A stabilizer obtained by the purification method according to any one of the above [1] to [7] and Z or chilled chilled chloride with reduced moisture are used as raw materials. A method for producing fluoretane, characterized by being used as

[9] A method for producing fluoretane, comprising the following three steps.

(1) A step of reducing stabilizer and moisture or moisture in the crude ethyl chloride by the purification method according to any one of [1] to [7] above,

(2) a step of mainly obtaining fluorethane by reacting ethyl chloride which has undergone the step of (1) with hydrogen fluoride in the gas phase in the presence of a fluorination catalyst,

(3) The mixed gas containing the fluoroeluene obtained in (2) is separated.

The step of circulating at least a part of the unreacted material to the reaction step (2).

[1 0] A process using chlorinated chill in which the total amount of the stabilizer contained in the ethyl chloride is reduced to 20 mass ppm or less through the process of (1)

(2) A process for producing fluoretane as described in [9] above.

[11] The above using chlorinated chill wherein the total amount of the stabilizer contained in the ethyl chloride after the step (1) is reduced to 10 mass ppm or less.

[10] The method for producing a fluoroelune according to [1 0].

,

[1 2] After the process of (1), the moisture contained in the ethyl chloride

The method for producing fluoretane according to any one of the above [9] to [11], wherein the step (2) is performed using chlorinated chill reduced to 20 mass pPm or less.

[1 3] The fluorination catalyst used in the step (2) is Cu, M n

, Z 、, Pb, Ag, Bi, Co, Fe, Ni, and C, containing at least one element selected from the group consisting of a reaction temperature of 100 to 300 ° C The method for producing fluoroethane as described in any one of [9] to [12] above, which is in the range of

[14] The fluorination catalyst used in the step (2) is a supported catalyst supported on activated carbon, according to any one of the above [9] to [13] Fluoroe evening production method.

According to the present invention, it is possible to efficiently remove a stabilizer and moisture from a stabilizer and / or water-containing chlorinated chloride by a simple method, prevent deterioration of the catalyst, etc., and economically produce fluoretane. The obtained fluorethan can be used as a low temperature refrigerant or etching gas. BEST MODE FOR CARRYING OUT THE INVENTION

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

As described above, for example, (1) a method in which hydrogen chloride is blown into a mixture of ethyl alcohol and zinc chloride when heated, and (2) hydrogen chloride into ethylene using aluminum chloride as a catalyst. However, for the reasons mentioned above, a stabilizer of about several hundred mass P pm is included. It is desirable to reduce this as much as possible before conducting the reaction.

As a result of intensive studies to develop a method for reducing stabilizers contained in cetyl chloride that is easy to operate, economical, and industrially feasible, the present inventor obtained an average of chlorinated chills containing stabilizers. The amount of stabilizer can be reduced by contacting the zeolite with a pore size of 3 to 11 A and / or a carbonaceous adsorbent with an average pore size of 3.4 to 11 A in the liquid phase. I found out that I can do it.

The zeolite used in the method for purifying chlorinated chloride according to the present invention should have an average pore diameter of 3 to 11 A, preferably 3.4 to 10 A. Zeolite 卜 with an average pore size greater than 11 A increases the adsorption amount of chlorinated chloride, and zeolite with an average pore size less than 3 A has a smaller ability to adsorb stabilizers. Yes.

In addition, it is preferable that the zeolite has a Si (silica) A 1 (aluminum) ratio of 2 or less, and when the S i ZA l ratio is greater than 2, the stabilizer may not be selectively adsorbed. . Zeolites include molecular sieves 4 A (MS—4 A), molecular sieves 5 A (MS—5 A), molecular sieves 1 OA (MS— 1 OA) and molecular sieves 1 3 X (S-1 3 X) is preferably at least one selected from the group consisting of By using these zeolites, the water content in ethyl chloride can be reduced at the same time. When heated while containing water, hydrolysis occurs, so it is preferable to reduce the water content. Specifically, the water content in ethyl chloride is preferably 20 mass ppm or less.

Carbonaceous adsorbents preferably have an average pore diameter of 3.4 to 11 A, and carbonaceous adsorbents with an average pore diameter greater than 11 A increase the amount of adsorption of chlorinated chloro chloride. A carbonaceous adsorbent with a pore size smaller than 3.4 A is not preferred because it reduces the ability to adsorb stabilizers. As the carbonaceous adsorbent, molecular sieve force 1 Bon 4 A and Z or molecular sieve carbon 5 A is preferable.

Considering regeneration of the adsorbent, it is preferable to use the zeolite and the carbonaceous adsorbent alone, but they can also be used in combination. The mixing ratio of the zeolite and the carbonaceous adsorbent is not particularly limited, but considering that the moisture in the ethyl chloride is also reduced, the mixing ratio is preferably a ratio rich in zeolite.

As a method of bringing ethyl chloride containing a stabilizer into contact with zeolite and / or a carbonaceous adsorbent in a liquid phase, a known batch or continuous method can be used. Industrially, the adsorbent is preferably distributed continuously on a fixed bed, and the liquid-based space velocity (LHSV) Can be selected appropriately depending on the stabilizer concentration and the amount of chlorinated chill.

Usually, the range of 1 to 80 H r ^-1 is preferable. In addition, in order to industrially implement a method for reducing the stabilizer in chloro chloride, two adsorption towers may be provided, and two towers may be switched to perform continuous purification.

The treatment temperature when purifying chloro chloride in the liquid phase is preferably in the range of 120 to + 60 ° C, more preferably in the range of 0 to 50 ° C. If the treatment temperature is higher than 60 ° C, the equipment cost may increase in terms of the heating and pressure resistance of the equipment, decomposition reactions, etc. may occur. This is not preferable. The pressure is preferably in the range of 0 to I M Pa, more preferably in the range of 0 to 0.6 M Pa. When the pressure is greater than 1 M Pa, it is not economical in terms of the pressure resistance of the equipment.

As described above, by using the purification method of the present invention, the stabilizer and Z or moisture contained in the ethyl chloride can be reduced. The purification method of the present invention is particularly preferably used when the stabilizer is a compound having a nitro group or a hydroxyl group, and examples of the compound having a nitro group include nitromethane, nitrogen, and nitrogen. Examples thereof include resole, nitrotoluene and nitrophenol. Examples of the compound having a hydroxyl group include phenol, cresol, 2,6-dibutyl-p-cresol and aminomethylphenol.

The chlorinated chill containing a stabilizer is brought into contact with the above zeolite and / or the above carbonaceous adsorbent in the liquid phase under the above conditions, and the total amount of the stabilizer is reduced to 20 mass ppm or less. You can get a chill. Preferably, the salt is reduced to 10 mass ppm or less in the total amount of the stabilizer, and further reduced to 5 ppm or less in the total amount of the stabilizer. It is also possible to obtain a chemical ester.

Next, the manufacturing method of the fluoretane of this invention is demonstrated. The method for producing fluoretane of the present invention comprises the following three steps:

(1) a step of reducing the stabilizer and / or moisture in the crude chlorinated chill by the above purification method;

(2) a step of reacting ethyl chloride which has undergone the step of (1) with hydrogen fluoride in the gas phase in the presence of a fluorination catalyst to mainly obtain fluorethane.

(3) The mixed gas containing the fluoroeluene obtained in (2) is separated.

The ethyl chloride obtained through the step (1) is preferably a chloride chill in which the total amount of the compound having a nitro group or a hydroxyl group is reduced to 20 mass ppm or less, and more preferably The total amount of the compound having a nitro group or a hydroxyl group is preferably reduced to 10 mass ppm or less, and particularly preferably the total amount of the compound having a nitro group or a hydroxyl group is reduced to 5 mass ppm or less. Good to have. Producing fluoretane from chlorinated chills with the total amount of compounds having a nitro group and a hydroxyl group reduced to 20 mass ppm or less can increase the life of the catalyst used in the production process and increase efficiency. It is possible to produce a mixture mainly containing fluoretane, both economically and economically.

The catalyst used in the manufacturing process is at least selected from the group consisting of Cu, Mn, Zn, Pb, Ag, Bi, Co, Fe, Ni and the same.

Fluorination catalysts containing one element, which are preferably supported catalysts or bulk catalysts, for example generally halogen exchange reactions

Two

The main component is lumped chromic oxide, which is the catalyst used for this purpose. When a type catalyst or a supported catalyst (for example, one using alumina, aluminum fluoride, etc. as a carrier) is used in this reaction, acetylene or ethylene is produced by the dehalogenation reaction or dehydrogenation reaction as described above. This is not desirable because of problems in terms of sex and economy. In the present invention, it is particularly preferable to use a supported catalyst in which activated charcoal is used as a carrier and the above-mentioned metal is supported thereon, and the metal loading is preferably 1% by mass or more. As an example of preparing such a catalyst, the usual method can be applied. For example, activated carbon is impregnated with an aqueous solution of cobalt chloride, dried, heat-treated in an inert gas, and then reacted. It is preferable to activate with hydrogen fluoride before carrying out. The reaction temperature is preferably from 100 to 350 ° C, more preferably from 150 to 300 ° C. When the reaction temperature is higher than 350 ° C, the amount of acetylene or the like that is a by-product may increase, and when it is lower than 100 ° C, the target reaction may not proceed. The reaction pressure is preferably 0 to 1 MPa, and if it exceeds IMP a, equipment costs such as the pressure resistance of the apparatus increase, which is not economical. The molar ratio of hydrogen fluoride to acetyl chloride (HF / CH ₃ CH ₂ C 1) is preferably 3 to 20; if it exceeds 20, it is not economical due to the increased amount of hydrogen fluoride. It is not economical because its life is short.

The mixture containing fluorethane obtained in the above reaction step is led to a distillation purification step, and at least 90% or more of hydrogen chloride and fluorethane are separated from the top of the column as a low boiling fraction in the distillation purification step. At least 95% of the unreacted hydrogen fluoride and acetyl chloride are separated from the bottom as a high boiling fraction. Hydrogen chloride and fluoretane separated from the top of the column are separated in a separate distillation tower, hydrogen chloride is used for other purposes, and the target fluoretane is purified and recovered as a product. For purification of fluoretane, for example, a process of removing moisture, trace organic impurities, etc. using molecular sieves or carbonaceous adsorbents. Is preferably provided. On the other hand, it is economical to recycle and reuse at least a part of the hydrogen fluoride and chloride chill separated from the tower bottom as they are in the reaction process.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to these Examples.

Raw material example 1

A commercially available chlorinated chill was analyzed with a gas chromatograph (column: complete set of pills / FID). As a stabilizer, nitrogen (CH 3 N 0 ₂ ) contained 2 1 2 mass ppm, and a moisture meter The moisture content was analyzed by Sha type 1) and found to contain 52 mass ppm, and the purity of the salt chill was 99.95 mass%.

Raw material example 2

Analysis of commercially available chloro chloride in the same manner as in raw material example 1 revealed that cresol was included as a stabilizer, its content was 1 38 mass ppm, and moisture was 59 mass ppm. The purity of chlorinated chill was 99.96 mass%.

Catalyst example 1

Activated carbon (Kuraray Chemical Co., Ltd., Kuraray Call 4 GA) is used as the catalyst carrier.

Ferric chloride (FeCl ₃ '6 H ₂ 0) 3 2. Add 58.5 g of pure water to 7 g and heat to 50-60 ° C in a hot water bath to dissolve The solution was cooled to room temperature. To this, 57.977 g of the activated carbon that had been vacuum-dried at 120 ° C. for 3 hours as a pretreatment was crushed to absorb the entire amount of the solution. The wet activated carbon was then dried on a hot water bath at 90 and dried. Thereafter, the dried catalyst was dried in a dryer at 100 ° C. for 3 hours. Next, the catalyst was charged into an Inconel reactor, and the temperature was maintained at 230 ° C. while flowing nitrogen gas, and diluted with nitrogen. The catalyst was prepared by fluorination treatment (activation of the catalyst) under a hydrogen fluoride (HF) stream and then under a 100% hydrogen fluoride stream.

Catalyst example 2

Add 28.5 g of pure water to ferric chloride (FeCl ₃ * .6 H ₂ 0) 2 4. 28 g and cupric chloride (Cu C 1 ₂ ) 8.1 2 g The solution was heated to 50 to 60 ° C. on a hot water bath to dissolve, and the solution was cooled to room temperature. To this, 57.977 g of the activated carbon which had been subjected to the pretreatment shown in Catalyst Example 1 was crushed, and the activated charcoal absorbed the entire amount of the solution. Next, the activated carbon in a wet state was dried on a 90 ° C. hot water bath and dried. Thereafter, the dried catalyst was dried in a dryer at 100 ° C. for 3 hours. Next, the catalyst was filled in an Inconel reactor, and the catalyst was activated under the same conditions and operation as in Catalyst Example 1 to prepare a catalyst.

Example 1

Zeolite [Molecular Sieves 5 A (manufactured by Union Showa Co., Ltd .: average pore size 4.2, Si ZA 1 ratio = 1)] on a stainless steel cylinder with an internal volume of 200 ml After filling with vacuum and vacuum drying, while cooling the cylinder, it was charged with 100 g of chlorinated chill shown in Raw material example 1 and stirred occasionally while maintaining the temperature at 23 ° C (room temperature). After 6 hours, a part of the liquid phase was collected and analyzed with the gas chromatography and moisture meter.

As a result, it was confirmed that nitromethane, which is a stabilizer in ethyl chloride, was reduced to 2 mass ppm, and the water content was 2 mass ppm or less.

Example 2

To a 200 ml stainless steel cylinder, add a carbonaceous adsorbent [ 20 g of molecular sieve carbon 5 A (manufactured by Takeda Pharmaceutical Co., Ltd .: average pore diameter 5 A)] is filled, vacuum dried, and the chilled chill shown in raw material example 2 is cooled while cooling the cylinder. 80 g was charged and stirred occasionally while maintaining the temperature at 23 ° C. (room temperature). After about 5 hours, a part of the liquid phase was taken and analyzed by gas chromatography.

As a result, it was confirmed that cresol, a stabilizer in ethyl chloride, was reduced to 3 mass ppm.

Example 3

Zeolite [Molecular Sieves 13 X (Made by Union Showa Co., Ltd .: average pore size 10 people, Si ZA l ratio = 0.81)] in a stainless steel cylinder with an internal volume of 200 ml 1 5 g and 10 g of the molecular sieve carbon 5 A described in Example 2 were mixed and filled. After vacuum drying, the chloride chill shown in Example 1 of raw material was cooled while cooling the cylinder. The mixture was charged with 0 g, stirred occasionally while maintaining the temperature at 24 (room temperature), and after about 6 hours, a part of the liquid phase was collected and analyzed by the gas chromatography.

As a result, it was confirmed that nitromethane, a stabilizer in ethyl chloride, was reduced to 3 mass ppm.

Comparative Example 1

The same operation and conditions as in Example 2 except that 20 g of carbonaceous adsorbent [activated carbon: granular white sword KL (manufactured by Takeda Pharmaceutical Co., Ltd .: average pore diameter 3 5 A)] was used as the adsorbent. Processed and analyzed.

As a result, cresol, a stabilizer in ethyl chloride, had a mass of 1 28 mass pm, and almost no reduction effect was observed.

Example 4

Fill the stainless steel cylinder with an internal volume of 2 L with 1.9 L of the above molecular sieve 1 3 X, and add 2 3 3 Then, continuous supply was performed at a linear velocity of 2 L / hr in the liquid phase under a pressure of 0.2 MPa. When analysis was performed in the outlet liquid about 3 hours after the start of supply, the stability of nitromethane was reduced to 2 mass ppm, and the water content was 2 mass PPm or less. This exit liquid was collected in a separate container.

Example 5

Inconel with a diameter of 1 inch and a length of lm is filled with 60 ml of the catalyst shown in Catalyst Example 1, and the temperature is 180 ° C and the pressure is 0.2 MPa while flowing nitrogen gas. Then, HF was supplied at 5 5. 3 8 NL / hr, and the supply of nitrogen gas was stopped. Thereafter, the chilled chilly chloride obtained in Example 4 was supplied at 4.6 2 N LZ hr to start the reaction. About 6 hours after the start of the reaction, the acid content in the outlet gas was washed with an alkaline aqueous solution and analyzed by gas chromatography. The results are shown below. CH ₃ CH ₂ F 1 9. 2 2 4 7 CH≡ CH 0. 0 5 2 6 CH ₃ CH ₂ C 1 8 0. 7 1 7 5 Other 0. 0 0 5 2

(Unit: vo 1%) After that, the reaction was continued and analyzed in the same manner as described above after about 100 hours and 20:00 hours. As a result, conversion of chlorinated chill, yield of fluoretane, and selectivity were both Almost the same result as above, almost no deterioration of the catalyst was observed.

Example 6

The reaction was carried out under the same procedures and conditions as in Example 5 except that 80 ml of the catalyst shown in Catalyst Example 2 was charged as the catalyst. After the reaction started, the outlet gas was washed with an alkaline aqueous solution about 5 hours later. Analyzed by totography. The results are shown below.

CH ₃ CH ₂ F 1 9. 4 2 6 1 CH≡ CH 0. 0 4 8 7 CH ₃ CH ₂ C 1 8 0. 5 1 9 7 Other 0. 0 0 5 5

(Unit: vo 1%) Comparative Example 2

Inconel 60 inch reactor with inner diameter 1 inch and length lm is filled with 60 ml of the catalyst shown in Catalyst Example 1, at a temperature of 180 ° and a pressure of 0.2 MPa while flowing nitrogen gas. Then, HF was supplied at 5 5. 3 8 NL / hr, and the supply of nitrogen gas was stopped. Thereafter, ethyl chloride (stabilizer: containing 2 1 2 mass ppm) shown in Raw Material Example 1 was fed at 4.6 2 N L / hr to start the reaction. About 6 hours after the start of the reaction, the outlet gas was washed with an alkaline aqueous solution and analyzed by gas chromatography. The results are shown below.

CH ₃ CH ₂ F 1 9. 0 8 7 8 CH≡ CH 0. 0 5 4 6 CH ₃ CH ₂ C 1 8 0. 8 4 6 8 Other 0. 0 1 0 8

(Unit: v o 1%) Further, the reaction was continued and analyzed in the same manner as described above after about 100 hours. The results are shown below.

C H 3 H 2 F 1 5 7 5 6 8 C H≡ C H 0. 0 4 7 8

C H 3 H 2 C 1 8 4. 1 7 9 2 Other 0. 0 1 6 2

(Unit: V o 1%) As can be seen from the above results, the catalyst is subject to degradation by stabilizers Industrial applicability

INDUSTRIAL APPLICABILITY The present invention is industrially useful because it enables economical production of high-purity fluoretane and uses the obtained fluoretane as a low-temperature refrigerant as an etching gas.

Claims

1. Stabilizer and / or crude chlorinated chill containing water with an average pore size in the range of 3 to 11 A zeolite and Z or average pore size

3.4 Contact with a carbonaceous adsorbent in the range of 4 to 11 A in the liquid phase to reduce the stabilizer and / or moisture contained in the crude salt chill.

A method for purifying ethyl chloride characterized by the following.

2. The method for purifying chlorinated acetyl chloride according to claim 1, wherein the stabilizer is a compound having a 2 □□ group or a hydroxyl group.

3. The ratio of zeolite to aluminum / aluminum (S i Z A 1) ratio is

The method for purifying a salted ethyl ester according to claim 1 or 2, which is 2 or less.

4. The zeolite is molecular sieve 4 A, molecular

The method for purifying chlorinated chill according to any one of claims 1 to 3, wherein the purification method is at least one selected from the group consisting of Sieves 5A, Molecular Sieves 10A, and Molecular Sieves 13X. .

5. The argillaceous adsorbent is molecular thousand scrubbing force bon 4 A and Z or molecular sieving carbon 5 A.

The method for purifying ethyl chloride according to 1 or 2.

6. The temperature at which the crude chilled chloride containing stabilizer and / or moisture is brought into contact with the zeolite and Z or the carbonaceous adsorbent is in a range of 120 to 10 ° C. 2. A method for purifying ethyl chloride as described in 1.

7. The chlorination according to claim 16, wherein the pressure at which the crude chlorinated chill containing a stabilizer and / or water is brought into contact with the zeolite soot and / or the carbonaceous adsorbent is in a range of 0 to 1 MPa. Ethyl purification method ii-.

8. A cheaper product obtained by the purification method according to any one of claims 1 to 7. A method for producing fluoretane, characterized in that it uses as a raw material a fixed agent and Z or chilled chilled chlorine.

9. A process for producing Fluoroetane, which comprises the following three steps.

(1) A step of reducing the stabilizer and / or moisture in the crude chloride by the purification method according to any one of claims 1 to 7,

(3) The mixed gas containing the fluoroeluene obtained in (2) is separated.

10. Process using the chlorinated chill in which the amount of the stabilizer contained in the ethyl chloride after the step (1) is reduced to 20 mass ρ ρ m or less.

The method for producing a fluore evening according to claim 9, wherein 2) is performed.

1 1. The method according to claim 1, wherein the total amount of the stabilizer contained in the ethyl chloride after the step (1) is reduced to 10 mass ρ ρ m or less.

10. A method for producing Fluoro □ evening described in 10.

1 2. After the process (1), the moisture contained in ethyl chloride is 2

The method for producing fluoretane according to any one of claims 9 to 11, wherein the step (2) is carried out using chlorinated chill reduced to 0 mass Ppm or less.

1 3. The fluorination catalyst used in the step (2) is Cu, Mn,

群 A group consisting of n, P b, A g, B i, Co, Fe, N i and C

含み Contains at least one element selected, and the reaction temperature ranges from 100 to 30

The method for producing a fluoroeluent according to any one of claims 9 to 12, which is in the range of 0 ° C.

1 4. The fluoro catalyst according to any one of claims 9 to 13, wherein the fluorination catalyst used in the step (2) is a supported catalyst supported on activated carbon. A method for producing ethane.