JP2006257019A - Method for producing 1,1-difluoroethene and 1,1,1-trifluoroethane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method capable of producing 1,1-difluoroethene and 1,1,1-trifluoroethane together. <P>SOLUTION: 1-Chloro-1,1-difluoroethane is heated in the presence of a catalyst in a first reaction area (1) to provide a first reaction mixture and at least one of a first fraction containing 1,1-difluoroethene, a second fraction containing 1,1,1-trifluoroethane, a third fraction containing 1-chloro-1-fluoroethene and a fourth fraction containing 1,1-dichloroethene is separated from the first reaction mixture and at least one of the third and fourth fraction is fed to a second reaction area (5) and at least one of 1-chloro-1-fluoroethene and 1,1-dichloroethene is heated in the presence of a catalyst together with hydrogen fluoride in the second reaction area (5) to provide a second reaction mixture and a fifth fraction containing 1,1,1-trifluoroethane is separated from the second reaction mixture. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing 1,1-difluoroethene (or vinylidene fluoride, hereinafter referred to as R-1132a) and 1,1,1-trifluoroethane (hereinafter referred to as R-143a).

  Conventionally, as a method for producing R-1132a, a method of thermally decomposing 1-chloro-1,1-difluoroethane (hereinafter referred to as R-142b) has been used.

British Patent No. 1265245 Francis H. Walker, 1 other, “Dehydrohalogenation of 1,1,1-Trihaloethanes”, Journal of Organic Chemistry ( Journal of Organic Chemistry), October 1965, vol. 30, p. 3284-3285 A. Hess, et al., "CH3CF3-nCln haloalkanes and CH2 = CF2-nCln haloolefins on γ-alumina: CH3CF3-nCln haloalkanes and CH2 = CF2-nCln halo -olefins on-alumina catalysts: reactions, kinetics and adsorption), Journal of Fluorine Chemistry, 1995, Vol. 74, p. 27-35

  In addition to the conventional methods as described above, R-142b is known to produce R-1132a also by a dehydrochlorination reaction in the presence of a catalyst (for example, Patent Document 1, Non-Patent Documents 1 and 2). checking). R-142b can generate R-143a by halogen exchange (Cl is exchanged with F) and / or hydrofluorination of R-1132a generated from R-142b (see, for example, Non-Patent Document 2). )

  R-113a is useful as a raw material for producing fluororubber, and R-143a is a compound in which R-143a is 1,1,1,2,2-pentafluoroethane (R-125) and 1,1 , 1,2-tetrafluoroethane (R-134a) is useful as a component of a mixed refrigerant (R-404A) mixed together. However, a production method for producing R-1132a and R-142b together has not been known so far.

  An object of this invention is to provide the novel manufacturing method which can co-produce R-1132a and R-143a.

According to a first aspect of the present invention, there is provided a process for producing 1,1-difluoroethene (R-1132a) and 1,1,1-trifluoroethane (R-143a),
(A) 1-chloro-1,1-difluoroethane (R-142b) is reacted in the first reaction zone by heating in the presence of a catalyst to obtain a first reaction mixture,
(B) a first fraction containing 1,1-difluoroethene (R-1132a), a second fraction containing 1,1,1-trifluoroethane (R-143a), and 1-chloro from the first reaction mixture; Separating at least one of the third fraction containing -1-fluoroethene (R-1131a) and the fourth fraction containing 1,1-dichloroethene (R-1130a), preferably both, and the third and third Sending at least one of the four fractions, preferably both to the second reaction zone,
(C) In the second reaction zone, at least one of 1-chloro-1-fluoroethene (R-1131a) and 1,1-dichloroethene (R-1130a), preferably both in the presence of a catalyst together with hydrogen fluoride. Reacting by heating to obtain a second reaction mixture, and (d) separating a fifth fraction comprising 1,1,1-trifluoroethane (R-143a) from the second reaction mixture, which comprises Provides a process for obtaining 1,1-difluoroethene (R-1132a) in the first fraction and 1,1,1-trifluoroethane (R-143a) in the second and fifth fractions. Is done.

  According to the production method of the present invention according to the first aspect, R-1132a and R-143a can be produced together. Furthermore, in the production method of the present invention, two reaction zones are provided. In the first reaction zone, R-132b and R-143a are produced using R-142b as a raw material, and in the second reaction zone, a secondary reaction zone is formed in the first reaction zone. Since R-143a can be produced by using at least one of R-1131a and R-1130a produced as a product, preferably both as raw materials, efficiently producing R-1132a and R-143a Can do.

  In the production method of the present invention, the separation in step (b) and the separation in step (d) can be carried out by separate distillation operations.

  In one embodiment of the invention, step (d) comprises from the second reaction mixture a sixth fraction comprising 1-chloro-1-fluoroethene (R-1131a) and 1,1-dichloroethene (R-1130a). Separating at least one, preferably both, of the seventh fraction and returning it to the second reaction zone. Thereby, at least one of R-1131a and R-1130a contained in the second reaction mixture, preferably both can be reused as a raw material in the second reaction zone to produce R-143a. Can be manufactured more efficiently.

  In one embodiment of the invention, step (b) comprises separating an eighth fraction comprising 1-chloro-1,1-difluoroethane (R-142b) from the first reaction mixture and returning it to the first reaction zone. You can leave. Alternatively or additionally, step (d) separates the ninth fraction containing 1-chloro-1,1-difluoroethane (R-142b) from the second reaction mixture and returns it to the first reaction zone. May include. Thereby, R-1132a and R-143a can be produced by reusing R-142b contained in at least one of the first reaction mixture and the second reaction mixture, preferably R-142b, as a raw material in the first reaction zone. Therefore, R-1132a and R-143a can be manufactured more efficiently.

According to a second aspect of the present invention, there is provided a process for producing 1,1-difluoroethene (R-1132a) and 1,1,1-trifluoroethane (R-143a),
(E) 1-chloro-1,1-difluoroethane (R-142b) is reacted in the first reaction zone by heating in the presence of a catalyst to obtain a first reaction mixture,
(F) In the second reaction zone, at least one of 1-chloro-1-fluoroethene (R-1131a) and 1,1-dichloroethene (R-1130a), preferably both together with hydrogen fluoride in the presence of a catalyst. Reacting by heating to obtain a second reaction mixture; and (g) a tenth fraction comprising 1,1-difluoroethene (R-1132a) from the first reaction mixture and the second reaction mixture; An eleventh fraction containing 1-trifluoroethane (R-143a), a twelfth fraction containing 1-chloro-1-fluoroethene (R-1131a) and a first fraction containing 1,1-dichloroethene (R-1130a). Separating at least one of the 13 fractions, preferably both, and preferably at least one of the twelfth and thirteenth fractions. Or sending both to the second reaction zone, thereby obtaining 1,1-difluoroethene (R-1132a) in the tenth fraction and 1,1,1-trifluoro in the eleventh fraction. A process for obtaining ethane (R-143a) is provided.

  According to the production method of the present invention according to the second aspect, the same effects as those of the production method of the present invention according to the first aspect can be obtained, and in addition, the first reaction mixture and the second reaction mixture can be obtained. Since the separation operation is made common, the manufacturing method can be further simplified, and the equipment cost and the manufacturing cost can be further reduced.

  In the production method of the present invention, the separation in the step (g) can be carried out by a distillation operation.

  In one embodiment of the present invention, step (g) comprises separating the 14th fraction comprising 1-chloro-1,1-difluoroethane (R-142b) from the first reaction mixture and the second reaction mixture, and May include returning to As a result, R-1132a and R-143a can be produced by reusing R-142b contained in the first reaction mixture and the second reaction mixture as raw materials in the first reaction zone. -143a can be manufactured more efficiently.

  Through the first and second aspects, the production method of the present invention can be used before the first reaction mixture is subjected to the separation operation (between steps (a) and (b) and between steps (e) and (g). ) May further comprise removing hydrogen chloride and hydrogen fluoride from the first reaction mixture. In addition, the production method of the present invention can be used to remove chloride from the second reaction mixture before separation from the second reaction mixture (between steps (c) and (d) and between steps (f) and (g)). It may further comprise removing hydrogen and hydrogen fluoride.

  The catalyst that can be used in the present invention is a reaction that generates R-1132a and R-143a from R-142b in the first reaction zone, and R-143a from R-1131a and / or R-1130a in the second reaction zone. What is necessary is just to catalyze the reaction to be carried out. The same catalyst or different catalysts may be used in the first reaction zone and the second reaction zone, or one or more catalysts may be used in the same reaction zone.

（式中、

は金属塩化物の標準生成エンタルピー（ｋJ・ｍｏｌ^−１）、ｎは金属塩化物中の塩素原子数）で定義されるＸの値が１３５〜４００ｋJ・ｍｏｌ^−１の範囲内である少なくとも１種の金属を含んで成るものを用いることができる。Ｘの値が１３５〜４００ｋJ・ｍｏｌ^−１の範囲内である金属としては、例えば以下の表１を参照して、Ｍｇ、Ａｌ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、ＺｒおよびＩｎなどが挙げられる。第１反応域においては、Ｃａ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、ＺｎおよびＩｎからなる群から選択される少なくとも１種の金属を含んで成る触媒を用いることが好ましい。第２反応域においては、Ｍｇ、Ａｌ、Ｔｉ、Ｖ、Ｃｒ、ＣｕおよびＺｒからなる群から選択される少なくとも１種の金属を含んで成る触媒を用いることが好ましい。

Such catalysts include the following formula:

(Where

Is at least one of the values of X defined by the standard enthalpy of formation of metal chloride (kJ · mol ⁻¹ , n is the number of chlorine atoms in the metal chloride) within the range of 135 to 400 kJ · mol ⁻¹ It is possible to use a material comprising any of these metals. As a metal whose X value is in the range of 135 to 400 kJ · mol ⁻¹ , for example, referring to Table 1 below, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, In, etc. are mentioned. In the first reaction zone, it is preferable to use a catalyst comprising at least one metal selected from the group consisting of Ca, Mn, Fe, Co, Ni, Zn and In. In the second reaction zone, it is preferable to use a catalyst comprising at least one metal selected from the group consisting of Mg, Al, Ti, V, Cr, Cu and Zr.

  The catalyst may be obtained by supporting the above metal on a support such as activated carbon, or may be a compound containing the above metal, for example, activated alumina. However, the present invention is not limited to these, and the above metals can be used alone as a catalyst.

  The production method of the present invention as described above is preferably carried out continuously, but in the production method according to the first aspect, the fraction containing R-1131a or R-1130a is not returned to the second reaction zone, and R If the fraction containing -142b is not returned to the first reaction zone, it may be carried out batchwise.

  According to the present invention, a novel production method capable of co-producing R-1132a and R-143a is provided. In the production method of the present invention, two reaction zones are provided, and by-products generated in the first reaction zone are used in the second reaction zone, so that R-1132a and R-143a can be efficiently produced.

(Embodiment 1)
The present embodiment relates to the manufacturing method of the present invention according to the first aspect described above. Hereinafter, the manufacturing method of this embodiment is demonstrated, referring FIG.

First, R-142b is supplied to the first reactor 1 in which a catalyst has been put in advance, and R-142b is heated in the presence of the catalyst in the first reaction zone defined by the first reactor 1. As a result, R-142b (CClF ₂ —CH ₃ ) is converted into R-1132a (CF ₂ ═CH ₂ ) and R-143a (CF ₃ —CH ₃ ), for example, by the following reactions (I) and (IIa) or (IIb): ) To generate each.

Here, HF consumed in the reactions (IIa) and (IIb) is a side reaction that generates R-1131a (CC1F = CH ₂ ) and R-1130a (CCl ₂ = CH ₂ ), for example, the following reaction (IIIa) And (IIIb).

  Therefore, the first reaction mixture obtained in the first reactor 1 is not only the target products R-1132a and R-143a, but also unreacted R-142b and by-products R-1131a, R- 1130a, including HCl and HF.

  The heating temperature in the first reaction zone is selected so that the above reaction can proceed. Although the temperature depends on the pressure condition, when the pressure control is not particularly performed, the temperature is, for example, about 250 to 450 ° C., preferably about 300 to 400 ° C.

  The material and form of the catalyst used in the first reaction zone are the selectivity of the target product R-1132a and the selectivity of R-143a, the conversion rate of R-142b, the separation between the reaction mixture and the catalyst, and You may select suitably considering cost etc. The material of the catalyst is not limited to these, but for example, Ca, Mn, Fe, Co, Ni, Zn, and In are preferable. Such a catalyst can be used by being supported on a carrier, and the selectivity and conversion rate may differ depending on the material of the carrier. The support material is preferably activated carbon.

  Then, the obtained first reaction mixture is taken out from the first reactor 1, and hydrogen chloride (HCl) and hydrogen fluoride (HF) are removed from the first reaction mixture. Removal of hydrogen chloride and hydrogen fluoride can be carried out, for example, by adding water to the first reaction mixture and transferring HCl and HF in the first reaction mixture into the aqueous phase. However, when HF is contained in a relatively large amount in the reaction mixture, it is preferable to remove HF by bringing sulfuric acid into contact with the reaction mixture and absorbing HF with sulfuric acid.

  Thereafter, the first reaction mixture from which HCl and HF have been removed is placed in the first distillation column 3 and subjected to a distillation separation operation. R-1132a, R-143a, R-1131a, R-142b, and R-1130a are separated into fractions (preferably consisting essentially of the components) containing each of them as a main component by the difference in boiling points. To take out from the first distillation column 3. The R-1132a fraction and the R-143a fraction are target substance fractions. The fraction of R-1131a and the fraction of R-1130a are sent to the 2nd reactor 5 which put the catalyst beforehand. On the other hand, the fraction of R-142b is returned to the first reactor 1 for reuse.

In addition to the above R-1131a fraction and R-1130a fraction, the second reactor 5 is supplied with the above R-1131a fraction and R-1130a fraction separated by the second distillation column 7 described later. Also, hydrogen fluoride (HF) is supplied. Then, R-1131a and R-1130a are heated together with HF in the presence of a catalyst in the second reaction zone defined by the second reactor 5. As a result, R-1131a (CCIF = CH ₂ ) and R-1130a (CCl ₂ = CH ₂ ) produce R-143a (CF ₃ —CH ₃ ), for example, through the following reactions (IV) and (V), respectively. To do.

_{Here, R-142b (CClF 2 -CH} 3) as an intermediate product may also be generated.

  Therefore, the second reaction mixture obtained in the second reactor 5 is not only R-143a which is one of the target products, but also unreacted R-1131a, R-1130a and HF, and HCl which is a by-product. As well as the intermediate product R-142b.

  The heating temperature in the second reaction zone is selected so that the above reaction can proceed. Although the temperature depends on the pressure condition, when pressure control is not particularly performed, the temperature is, for example, about 100 to 300 ° C., preferably about 150 to 250 ° C.

  The material and form of the catalyst used in the second reaction zone include the selectivity of the target product R-143a, the conversion rate of R-1131a and R-1130a, the separability between the reaction mixture and the catalyst and the cost. You may select suitably in consideration. The material of the catalyst is not limited to these, but for example, Mg, Ti, V, Cr, Cu and Zr are preferable. Such a catalyst can be used by being supported on a carrier, and the selectivity and conversion rate may differ depending on the material of the carrier. The support material is preferably activated carbon. It is also preferable to use Al in the form of activated alumina.

  Then, the obtained second reaction mixture is taken out from the second reactor 5, and hydrogen fluoride (HF) and hydrogen chloride (HCl) are removed from the second reaction mixture. The removal of hydrogen chloride and hydrogen fluoride can be carried out in the same manner as when removing from the first reaction mixture, but the second reaction mixture contains a larger amount of HF than the first reaction mixture, and the second reaction mixture contains sulfuric acid. It is preferable to remove HF by bringing HF into contact and absorbing HF with sulfuric acid.

  Thereafter, the second reaction mixture from which HF and HCl have been removed is placed in the second distillation column 7 and subjected to a distillation separation operation. The second distillation is carried out by separating the fractions containing R-143a, R-1131a, R-142b, and R-1130a as the main components (preferably a fraction substantially composed of the components). Remove from Tower 7. The fraction of R-143a is the target substance fraction. The fraction of R-1131a and the fraction of R-1130a are returned to the second reactor 5 for reuse. On the other hand, the fraction of R-142b is returned to the first reactor 1 for reuse.

  Such a manufacturing method of this embodiment is continuously implemented.

  According to this embodiment, it is possible to co-produce R-1132a and R-143a by obtaining them in separate fractions.

(Embodiment 2)
This embodiment is a modification of the first embodiment. Hereinafter, the manufacturing method of this embodiment is demonstrated, referring FIG. In FIG. 2, the same members or elements as those shown in FIG. 1 are denoted by the same reference numerals, and the same as those in the first embodiment unless otherwise specified.

  In the present embodiment, a tank 9 is provided, in which the fraction of R-1131a and the fraction of R-1130a taken out from the first distillation column 3 and the second distillation column 7 are placed, and a mixture containing R-1130a and R-1131a Is supplied from the tank 9 to the second distillation column 7.

  According to the manufacturing method of the present embodiment, in addition to the effects described in the first embodiment, a substance to be supplied to the second distillation column 7 can be stored once and sent to the second distillation column 7 at an appropriate flow rate. .

(Embodiment 3)
This embodiment relates to the manufacturing method of the present invention according to the second aspect described above. Hereinafter, the manufacturing method of this embodiment is demonstrated, referring FIG. In FIG. 3, the same members or elements as those shown in FIG. 1 are denoted by the same reference numerals, and are the same as those in the first embodiment unless otherwise specified.

  In the present embodiment, a common distillation column 11 is provided instead of the first distillation column 3 and the second distillation column 7, and the second reaction mixture taken out from the second reactor 5 is taken out from the first reactor. Together with the mixture, hydrogen chloride (HCl) and hydrogen fluoride (HF) are removed therefrom, and the mixture is put into a common distillation column 11 and subjected to a distillation separation operation.

  According to the present embodiment, in addition to the effects described in the first embodiment, the hydrogen chloride and hydrogen fluoride removing operation and the distillation separation operation of the first reaction mixture and the second reaction mixture are made common, so that the production method is It can be further simplified, and the equipment cost and the manufacturing cost can be further reduced.

  As mentioned above, although three embodiment of this invention was described, this invention is not limited to these, Various modification | change is possible. For example, in the above embodiment, R-1131a and R-1130a are separated from the first reaction mixture and supplied to the second reaction zone, but only one of them may be separated and supplied to the second reaction zone. . In the above embodiment, HF and HCl are removed from the first reaction mixture and the second reaction mixture, respectively, but these are not essential to the present invention as long as the desired fraction can be appropriately separated from the reaction mixture. May be omitted. In addition, in Embodiments 1 to 3, the R-142b fraction was reused, and in Embodiments 1 and 2, the R-1131a fraction and the R-1130a fraction were reused. Is not essential to the present invention and may be omitted.

  In this example, the reaction in the first reaction zone was conducted and tested in the presence of three materials generally used as catalyst supports.

First, activated alumina, zeolite 13X (manufactured by Kishida Chemical Co., Ltd., Molecular Sieve 13X (1/16 pellets)) and activated carbon were respectively added to the reactor, and the reactor temperature was about 300 ° C. As a reference, an empty reactor was prepared and heated in the same manner.
And R-142b and nitrogen gas were continuously flowed to each reactor by volume flow ratio about 60:40. The flow rate was such that the carrier weight per unit flow rate would be at an equivalent level in each reactor.
After the process was stabilized, the reaction mixture exiting the reactor was sampled over a period of time. Note that the pressure in the reactor was not particularly controlled throughout the process.
The composition of the reaction mixture was examined by analyzing the organic composition in the obtained reaction mixture sample by gas chromatography. Table 2 shows each composition ratio of R-1132a and R-143a in the reaction mixture. Moreover, the conversion rate of R-142b and each selectivity of R-1132a and R-143a were calculated | required from the analysis value, and it shows in Table 2 collectively.

  Referring to Table 2, when activated carbon is used among these three types of materials, the selectivity of each of R-1132a and R-143a is high. Therefore, as a support material for the catalyst used in the first reaction zone, It was found that activated carbon is preferable. This is also supported by the results of Examples 2 and 3. Further, since activated carbon has a high selectivity for R-143a, it is considered that it can be preferably used as a support material for the catalyst used in the second reaction zone by appropriately adjusting the reaction conditions.

  In addition, when activated alumina was used, it was found that the sum of the composition ratios of R-1132a and R-143a was high, and thus activated alumina itself could be used as a catalyst. In this case, since the selectivity of R-143a is higher than that of R-1132a, it is considered that activated alumina is suitable for the catalyst used in the second reaction zone. This is supported by the results of Example 3.

  In this example, the reaction was conducted in the first reaction zone in the presence of a material in which various metals were supported on activated carbon.

First, Mg, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Ru, Rh, Pd, In, Ba, and Pt are added to the activated carbon similar to that used in Example 1. Each supported catalyst was prepared. The metal loading (based on the weight of the carrier, the same applies hereinafter) was 0.5 to 36% by weight. The obtained catalyst was put in each reactor, and the reactor temperature was about 300 ° C.
And R-142b and nitrogen gas were continuously flowed to each reactor by volume flow ratio about 60:40. The flow rate was such that the carrier weight per unit flow rate would be at an equivalent level in each reactor.
After the process was stabilized, the reaction mixture exiting the reactor was sampled over a period of time. Note that the pressure in the reactor was not particularly controlled throughout the process.
The composition of the reaction mixture was examined by analyzing the organic composition in the obtained reaction mixture sample by gas chromatography. Table 3 shows each composition ratio of R-1132a and R-143a in the reaction mixture. Moreover, the conversion rate of R-142b and each selectivity of R-1132a and R-143a were calculated | required from the analysis value, and it shows in Table 3 collectively.

  Based on the results in Table 3, in the case of using Mg, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr and In supported on activated carbon, R- It has been found that the sum of the composition ratios of 1132a and R-143a exceeds 20 mol%, and therefore they are suitable for use as a catalyst. Further, among these, when Ca, Mn, Fe, Ni, Zn and In are used, the composition ratio of R-1132a and thus the selectivity is relatively high, which is suitable for the catalyst used in the first reaction zone. it is conceivable that. On the other hand, when Mg, Ti, V, Cr, Cu and Zr are used, the composition ratio of R-1132a and thus the selectivity is low, and the composition ratio of R-143a and thus the selectivity is relatively high. It is considered suitable for the catalyst used in the reaction zone.

  In this example, the reaction in the first reaction zone and the second reaction zone was carried out to obtain a first reaction mixture and a second reaction mixture, respectively.

(First reaction mixture)
First, 276 cm ³ (Zn supported amount: 11 wt%) of Zn supported on activated carbon similar to that used in Example 1 was put in the reactor, and the reactor temperature was set to about 300 ° C.
And R-142b was continuously flowed to the reactor at a flow rate of about 975 cm ³ / min (converted to 0 ° C. and 0.1 MPa).
After the process for carrying out the reaction in the first reaction zone was stabilized as described above, the first reaction mixture exiting the reactor was sampled over 8 hours. Note that the pressure in the reactor was not particularly controlled throughout the process.
The feed rate of R-142b during sampling was about 2 kg.
The organic composition (that is, the composition excluding HF and HCl) in the obtained first reaction mixture sample was analyzed by gas chromatography. The results are shown in Table 4.

(Second reaction mixture)
First, about 276 cm ³ of an activated alumina catalyst similar to that used in Example 1 was placed in the reactor, and the reactor temperature was about 200 ° C.
Then, R-1131a, R-1130a, and HF were continuously flowed into the reactor at flow rates of about 146 cm ³ / min, about 20 cm ³ / min, and about 1004 cm ³ / min (converted to 0 ° C. and 0.1 MPa), respectively.
After the process of performing the reaction in the second reaction zone as described above was stabilized, the second reaction mixture exiting the reactor was sampled over 8 hours. Note that the pressure in the reactor was not particularly controlled throughout the process.
The feed rates of R-1131a, R-1130a and HF during sampling were about 0.3 kg, about 0.04 kg and about 0.4 kg, respectively.
The organic composition (that is, the composition excluding HF and HCl) in the obtained second reaction mixture sample was analyzed by gas chromatography. The results are shown in Table 4.

  From Table 4, it can be seen that the first reaction mixture contains R-1132a and R-143a as the target products and R-1131a and R-1130a to be sent to the second reaction zone, and that the second reaction mixture is the target product. It was confirmed to contain some R-143a. In addition, the first reaction mixture and the second reaction mixture are confirmed to contain R-142b, which can be reused for the reaction in the first reaction zone. The second reaction mixture is also confirmed to contain R-1131a and R-1130a, which can be reused for the reaction in the second reaction zone.

It is a schematic diagram for demonstrating the manufacturing method in one embodiment of this invention. It is a schematic diagram for demonstrating the manufacturing method in another embodiment of this invention. It is a schematic diagram for demonstrating the manufacturing method in another embodiment of this invention.

Explanation of symbols

1 First reactor (first reaction zone)
3 First distillation column 5 Second reactor (second reaction zone)
7 Second distillation column 9 Tank 11 Common distillation column

Claims (13)

A process for producing 1,1-difluoroethene and 1,1,1-trifluoroethane,
(A) 1-chloro-1,1-difluoroethane is reacted in the first reaction zone by heating in the presence of a catalyst to obtain a first reaction mixture,
(B) a first fraction containing 1,1-difluoroethene from the first reaction mixture, a second fraction containing 1,1,1-trifluoroethane, and a third fraction containing 1-chloro-1-fluoroethene. And at least one of the fourth fractions comprising 1,1-dichloroethene and sending at least one of the third and fourth fractions to the second reaction zone,
(C) reacting at least one of 1-chloro-1-fluoroethene and 1,1-dichloroethene with hydrogen fluoride in the presence of a catalyst in the second reaction zone to obtain a second reaction mixture; And (d) separating a fifth fraction comprising 1,1,1-trifluoroethane from the second reaction mixture, thereby obtaining 1,1-difluoroethene in the first fraction, and second And a process for obtaining 1,1,1-trifluoroethane in the fifth fraction.   The production method according to claim 1, wherein the separation in step (b) and the separation in step (d) are carried out by separate distillation operations.   Step (d) separates at least one of the sixth fraction containing 1-chloro-1-fluoroethene and the seventh fraction containing 1,1-dichloroethene from the second reaction mixture and returning it to the second reaction zone. The manufacturing method of Claim 1 or 2 containing.   Process according to any of claims 1 to 3, wherein step (b) comprises separating the eighth fraction comprising 1-chloro-1,1-difluoroethane from the first reaction mixture and returning it to the first reaction zone. Method.   Process according to any of claims 1 to 4, wherein step (d) comprises separating the ninth fraction comprising 1-chloro-1,1-difluoroethane from the second reaction mixture and returning it to the first reaction zone. Method. A process for producing 1,1-difluoroethene and 1,1,1-trifluoroethane,
(E) 1-chloro-1,1-difluoroethane is reacted in the first reaction zone by heating in the presence of a catalyst to obtain a first reaction mixture,
(F) reacting at least one of 1-chloro-1-fluoroethene and 1,1-dichloroethene with hydrogen fluoride in the presence of a catalyst in the second reaction zone to obtain a second reaction mixture; And (g) a tenth fraction containing 1,1-difluoroethene from the first reaction mixture and the second reaction mixture, an eleventh fraction containing 1,1,1-trifluoroethane, and 1-chloro-1-fluoro. Separating at least one of the twelfth fraction containing ethene and the thirteenth fraction containing 1,1-dichloroethene and sending at least one of the twelfth and thirteenth fractions to the second reaction zone, thereby 1,1-difluoroethene is obtained in the 10th fraction and 1,1,1-trifluoro in the 11th fraction A production method for obtaining ethane.   The production method according to claim 6, wherein the separation in the step (g) is carried out by a distillation operation.   Step (g) comprises separating the fourteenth fraction comprising 1-chloro-1,1-difluoroethane from the first reaction mixture and the second reaction mixture and returning them to the first reaction zone. Manufacturing method.   The production method according to claim 1, further comprising removing hydrogen chloride and hydrogen fluoride from the first reaction mixture before subjecting the first reaction mixture to a separation operation.   The production method according to claim 1, further comprising removing hydrogen chloride and hydrogen fluoride from the second reaction mixture before subjecting the second reaction mixture to a separation operation. The catalyst is

(Where

Includes a metal having a value of X defined by the standard enthalpy of formation of metal chloride (kJ · mol ⁻¹ , n is the number of chlorine atoms in the metal chloride) within the range of 135 to 400 kJ · mol ^−1. The manufacturing method in any one of Claims 1-10 which consists of these.   The production method according to claim 11, wherein the catalyst used in the first reaction zone comprises at least one metal selected from the group consisting of Ca, Mn, Fe, Co, Ni, Zn and In.   The production method according to claim 11, wherein the catalyst used in the second reaction zone comprises at least one metal selected from the group consisting of Mg, Al, Ti, V, Cr, Cu and Zr.

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