Method for producing 1-chloro-3,3,3-trifluoropropene

Abstract

A method for manufacturing 1-chloro-3,3,3-trifluoropropene (1230zd) is provided. The method includes contacting a halogenated hydrocarbon compound having a carbon number of 3 and represented by a general formula (1) with a metal catalyst in a gas phase.
CF.sub.aCl.sub.3-aCH.sub.2CHF.sub.bCl.sub.2-b(1) In the formula, a is an integer from 0 to 2, b is 1 or 2 when a=0, b is 0 or 1 when a=1, and b is 0 when a=2.

Claims

1. A method for manufacturing 1-chloro-3,3,3-trifluoropropene, the method comprising contacting a halogenated hydrocarbon compound and represented by a general formula (1) with a metal catalyst in a gas phase:
CF.sub.aCl.sub.3-aCH.sub.2CHF.sub.bCl.sub.2-b(1), wherein the reaction is carried out in the presence of at least one fluorocarbon compound selected from the group consisting of 1,3,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane, wherein hydrogen fluoride is not supplied in the reaction, wherein a temperature of the reaction is equal to or higher than 230 C., and wherein, in the formula, a is an integer from 0 to 2, b is 1 or 2 when a=0, b is 0 or 1 when a=1, and b is 0 when a=2.

2. The method according to claim 1, wherein the reaction is carried out in the presence of 1,1,1,3,3-pentachloropropane.

3. The method according to claim 1, wherein the fluorocarbon compound is 1,3,3,3-tetrafluoropropene or 1,1,1,3,3-pentafluoropropane.

4. The method according to claim 1, wherein the metal catalyst includes at least one metal selected from the group consisting of aluminum, vanadium, chromium, titanium, magnesium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tin, antimony, zinc, lanthanum, tantalum, and tungsten.

5. The method according to claim 4, wherein the metal catalyst is an oxide of the metal, an oxyhalide of the metal, or a halide of the metal.

6. The method according to claim 4, wherein the metal catalyst is a supported catalyst or a non-supported catalyst, and a support of the supported catalyst is carbon, an oxide of the metal, an oxyhalide of the metal, or a halide of the metal.

7. The method according to claim 1, wherein the metal catalyst includes at least a fluorine atom.

8. The method according to claim 1, wherein the reaction is carried out in the presence of chlorine.

9. The method according to claim 1, wherein the reaction is carried out in the presence of a filler.

10. The method according to claim 9, wherein the filler is at least one material selected from the group consisting of carbon, plastics, ceramics, and a metal.

11. The method according to claim 1, wherein 1,1,3,3-tetrachloropropene, 1,3-dichloro-3,3-difluoropropene, or 1,3,3-trichloro-3-fluoropropene is formed in addition to 1-chloro-3,3,3-trifluoropropene in the reaction.

Description

EXAMPLES

(1) Hereinafter, an embodiment according to the present invention is explained in detail using Examples. The embodiments of the present invention are not limited to the Examples.

(2) In the present specification, the term FID % means an area percentage of a chromatogram obtained by a gas chromatography analysis using an FID as a detector.

Preparation Example 1

Preparation of Fluorinated Activated Alumina

(3) Activated alumina (300 g, KHS-46 manufactured by Sumitomo Chemical Co., Ltd, particle size of 4 to 6 mm and a specific surface area of 155 m.sup.2/g) was weighted out, and powder adhered on its surface was washed out with water. To the washed alumina was slowly added 1150 g of 10 wt % hydrofluoric acid, and the mixture was stirred and then kept standing for 4 hours. After washing with water, the activated alumina was filtered, dried at a normal temperature overnight, and then dried in an electric furnace at 200 C. for 2 hours. Into a reaction tube made of stainless steel (SUS 316) and having an internal diameter of 1 inch and a length of 40 cm was added 150 mL of the dried alumina, and the temperature of the reaction tube was increased to 200 C. in the electric furnace while allowing nitrogen to flow therethrough at a flow rate of 150 cc/sec and then allowing hydrogen fluoride to flow therethrough at a flow rate of 0.1 g/min together with nitrogen. Since the temperature increases as the hydrogen fluoride treatment proceeds, the flow rates of nitrogen and hydrogen fluoride were adjusted to prevent the inner temperature from exceeding 400 C. When the heat generation was completed, the flow rate of nitrogen was dropped to 30 cc/sec, the set temperature of the electric furnace was increased by 50 C. every 30 minutes to a final temperature of 400 C., and then this state was maintained for two hours. The activated alumina subjected to the fluorinating treatment (hereinafter, also referred to as a catalyst 1) was prepared in this way.

Preparation Example 2

Preparation of Fluorinated Chromium-Supporting Alumina Catalyst

(4) To an Erlenmeyer flask was added a 20 wt % aqueous solution of chromium chloride, and 100 mL of the activated alumina subjected to the fluorinating treatment and prepared in the Preparation Example 1 was soaked and kept therein for 3 hours. This alumina was filtered and dried at 70 C. under a reduced pressure using a rotary evaporator. Into a cylinder-shaped reaction tube made of stainless steel (SUS 316), having an internal diameter of 1 inch and a length of 40 cm, and equipped with an electric furnace was charged with 100 mL of this chromium-supporting alumina, and the temperature was increased to 200 C. while allowing nitrogen to flow therethrough. When no more water outflow was observed, nitrogen gas and hydrogen fluoride were simultaneously supplied at flow rates of 150 cc/sec and 0.1 g/sec, respectively, and the flow rates of nitrogen and hydrogen fluoride were adjusted so that the inner temperature does not exceed 400 C. When the hot spot caused by the fluorination of the charged chromium-supporting alumina reached an outlet terminal of the reaction tube, the flow rate of nitrogen was reduced to 30 cc/sec, the set temperature of the electric furnace was increased by 50 C. every 30 minutes to the final temperature of 400 C., and then this state was maintained for 2 hours. The chromium-supporting alumina subjected to the fluorinating treatment (hereinafter, also referred to as a catalyst 2) was prepared in this way.

Preparation Example 3

Preparation of Fluorinated Chromium-Supporting Activated Carbon

(5) To an Erlenmeyer flask was added a 20 wt % aqueous solution of chromium chloride, and 100 mL of activated carbon was soaked and maintained therein for 3 hours. This activated carbon was filtered and dried at 70 C. under a reduced pressure using a rotary evaporator. Into a cylinder-shaped reaction tube made of stainless steel (SUS 316), having an internal diameter of 1 inch and a length of 40 cm, and equipped with an electric furnace was charged with 100 mL of the obtained chromium-supporting activated carbon, and the temperature was increased to 200 C. while allowing nitrogen to flow therethrough. When no more water outflow was observed, nitrogen gas and hydrogen fluoride were simultaneously supplied at flow rates of 150 cc/sec and 0.1 g/sec, respectively, and the flow rates of nitrogen and hydrogen fluoride were adjusted so that the inner temperature does not exceed 400 C. When the hot spot caused by the fluorination of the charged chromium-supporting activated carbon reached an outlet terminal of the reaction tube, the flow rate of nitrogen was reduced to 30 cc/sec, the set temperature of the electric furnace was increased by 50 C. every 30 minutes to the final temperature of 400 C., and then this state was maintained for 2 hours. The chromium-supporting activated carbon subjected to the fluorinating treatment (hereinafter, also referred to as a catalyst 3) was prepared in this way.

Example 1-1

(6) Into a cylinder-shaped reaction tube made of stainless steel (SUS 316), having an internal diameter of 1 inch and a length 40 cm, and equipped with an electric furnace was charged with 50 mL of the catalyst prepared in the Preparation Example 1, and the internal temperature of the reaction tube was increased to 300 C. while allowing nitrogen gas to flow therethrough at a flow rate of approximately 30 cc/min. After that, the supply of nitrogen was stopped, and vaporized 1,3,3-trichloro-1,1-difluoropropane (242fa, purity of 96.7 FID %, the same is applied below) and 1,1,1,3,3-pentafluoropropane (245fa, purity of 99.9 FID %, the same is applied below) were introduced into the reaction tube (molar ratio of 242fa/245fa=1/1, contact time of 60 seconds). When the flow rate became stable, 500 mL of a water trap cooled with ice water was disposed at an outlet of the reaction tube, by which the organic substances were recovered and a by-produced acid component was absorbed for approximately 100 minutes. The gas passing through the water trap was recovered by a dry ice trap disposed next to the water trap, and the recovered materials in the water trap and the dry ice trap were mixed. The composition of the organic substances obtained by removing an acid from the recovered materials was analyzed with a gas chromatography. The result is shown in Table 1.

Examples 1-2 to 1-4

(7) The same operations were carried out as those of the Example 1-1 except that the internal temperatures of the reaction tubes were respectively set to be 200 C., 250 C., and 350 C.

Example 2-1

(8) The same operations were carried out as those of the Example 1-1 except that 1,1,3,3-tetrachloro-1-fluoropropane (241fa, purity of 98.2 FID %, the same is applied below) was introduced instead of 1,3,3-trichloro-1,1-difluoropropane (242fa).

Examples 2-2 to 2-4

(9) The same operations were carried out as those of the Example 2-1 except that the internal temperatures of the reaction tubes were respectively set to be 200 C., 250 C., and 350 C.

Example 3-1

(10) The same operations were carried out as those of the Example 1-1 except that 1,1,1,3-tetrafluoropropene (1234ze, purity of 99.9 FID %, the same is applied below) was introduced instead of 1,1,1,3,3-pentafluoropropane (245fa).

Example 3-2

(11) The same operations were carried out as those of the Example 1-1 except that 100 mL of the catalyst prepared in the Preparation Example 1 was charged, 1,1,1,3-tetrafluoropropene (1234ze) was introduced instead of 1,1,1,3,3-pentafluoropropane (245fa), and chlorine was introduced (molar ratio of 242fa/1234ze/chlorine=1/0.5/0.02, contact time of 60 seconds).

(12) The obtained crude product, 800 g, was separated and purified with a normal-pressure distillation tower in which 10 stages of Heli Packs No. 2 were charged to obtain a 95 g of an initial fraction (the temperature of the tower top was 5-19 C., 17.0 FID % of 1234ze, 6.0 FID % of 245fa, and 77.0 FID % of 1233zd(E)), 600 g of a second fraction (the temperature of the tower top was 19.0-19.2 C., 99.9 FID % of 1233zd(E)), 60 g of a third fraction (the temperature of the tower top was 39.0 to 39.2 C., 99.5 FID % of 1233zd(Z)), and 40 g of residue mainly including 1230za.

(13) Next, the same operations as those of the Example 1-1 were performed except that the aforementioned initial fraction (a ratio of 242fa/amount of the introduced initial fraction=1/4.3, a contact time of 60 seconds) was introduced instead of 245fa.

Example 3-3

(14) The same operations were carried out as those of the Example 1-1 except that 1,1,1,3,3-pentafluoropropane (245fa) was not introduced.

Example 3-4

(15) The same operations were carried out as those of the Example 1-1 except that 1,1,3,3-tetrachloro-1-fluoropropane (241fa) was introduced instead of 1,3,3-trichloro-1,1-difluoropropane (242fa) and 1,1,1,3,3-pentafluoropropane (245fa) was not introduced.

Example 3-5

(16) The same operations were carried out as those of the Example 1-1 except that 1,1,3,3-tetrachloro-1-fluoropropane (241fa) was introduced instead of 1,3,3-trichloro-1,1-difluoropropane (242fa) and 1,3,3,3-tetrafluoropropene (1234ze) was introduced instead of 1,1,1,3,3-pentafluoropropane (245fa).

Example 4-1

(17) The same operations were carried out as those of the Example 1-1 except that 50 mL of the catalyst prepared in the Preparation Example 2 was charged instead of the catalyst prepared in the Preparation Example 1.

Example 4-2

(18) The same operations were carried out as those of the Example 1-1 except that 50 mL of the catalyst prepared in the Preparation Example 3 was charged instead of the catalyst prepared in the Preparation Example 1.

Example 5-1

(19) The same operations as those of the Example 1-1 were performed except that 242fa and 1,1,3,3-tetrachloro-1-fluoropropane (241fa) were introduced (molar ratio of 241fa/242fa/245fa=1.1/1.5/1.8, a contact time of 60 seconds) instead of 1,3,3-trichloro-1,1-difluoropropane (242fa).

Referential Example 1

(20) The same operations as those of the Example 1-1 were performed except that 50 mL of activated carbon was charged instead of the catalyst prepared in the Preparation Example, 1, 1,1,1,3,3-pentafluoropropane (245fa) was not introduced, and the internal temperature of the reaction tube was set to 250 C.

Referential Example 2

(21) The same operations as those of the Example 1-1 were performed except that 50 mL of activated carbon was charged instead of the catalyst prepared in the Preparation Example 1, 1,1,3,3-tetrachloro-1-fluoropropane (241fa) was introduced instead of 1,3,3-trichloro-1,1-difluoropropane (242fa), and the internal temperature of the reaction tube was set to 200 C.

(22) The results of the Examples and the Referential Examples are summarized in Table 1. In Table 1, - means that no substance was detected.

(23) TABLE-US-00001 Reaction Raw Raw Temperature Organic Composition (FID %) Samples Material 1 Material 2 Catalyst ( C.) 1234zeE 245fa 1234zeZ Examples 1-1 242fa 245fa 1 300 1.3 0.7 0.3 1-2 242fa 245fa 1 200 6.1 17 1 1-3 242fa 245fa 1 250 4 10.7 0.8 1-4 242fa 245fa 1 350 0.9 0.5 0.1 2-1 241fa 245fa 1 300 2.8 1.7 0.5 2-2 241fa 245fa 1 200 9 15 1 2-3 241fa 245fa 1 250 6.8 13.6 1.5 2-4 241fa 245fa 1 350 1.5 1 0.1 3-1 242fa 1234ze 1 300 4 0.9 0.7 3-2 242fa Initial 1 300 0.6 0.2 0.1 fraction 3-3 242fa 1 300 3-4 241fa 1 300 3-5 241fa 1234ze 1 300 7.5 0.1 1.7 4-1 242fa 245fa 2 300 0.5 10 0.1 4-2 242fa 245fa 3 300 0.4 10.3 0.1 5-1 242fa + 241fa 245fa 1 300 2.1 1.2 0.4 Referential 1 242fa 250 Example 2 241fa 200 Organic Composition (FID %) Raw Samples 1233zdE 1233zdZ 1232zd 1231zd 1230za Material1 Examples 1-1 83.1 10 1.1 <0.1 1.9 <0.1 1-2 20.5 2.6 8.1 <0.1 17 26.1 1-3 71.2 7.1 1.2 <0.1 3.4 <0.1 1-4 84.2 11 1 <0.1 1.1 <0.1 2-1 76.9 9 3.5 0.3 4.2 <0.1 2-2 19.5 3 1 1 27 22 2-3 63.1 5.9 2 0.4 5.8 0.2 2-4 82.1 10 2.3 0.1 1.5 <0.1 3-1 82.7 9.5 0.4 <0.1 0.9 <0.1 3-2 88.5 10 0.2 <0.1 0.1 <0.1 3-3 56.1 6.1 4.2 <0.1 30.3 2.5 3-4 31.3 3.2 2.1 0.1 63.2 <0.1 3-5 71.3 9.1 1.9 <0.1 6.5 <0.1 4-1 67.9 8.5 5.6 <0.1 2.9 3 4-2 69.1 11.5 4.4 <0.1 1.3 2.1 5-1 80.1 10 2.2 0.1 3.3 <0.1 Referential 1 0.8 0.2 93 <0.1 2.3 2.1 Example 2 <0.1 <0.1 9.1 48 20.2 12

(24) As is clearly revealed from Table 1, it was proven that implementation of the method according to the present embodiment makes it possible to highly selectively manufacture 1233zd in a high yield from the halogenated hydrocarbon compound having a carbon number of 3 and represented by the general formula (1).

INDUSTRIAL APPLICABILITY

(25) The use of a halogenated hydrocarbon compound, which is readily available and has a carbon number of 3, as a raw material allows a chlorofluoropropene having a low GWP and applicable in a variety of usages to be manufactured in an industrial scale.

(26) Hereinafter, examples of other embodiments are additionally noted.

(27) 1. A method for manufacturing 1,1,3,3-tetrachloropropene (1230za), the method including contacting a halogenated hydrocarbon compound having a carbon number of 3 and represented by a general formula (1) with a metal catalyst in a gas phase.
CF.sub.aCl.sub.3-aCH.sub.2CHF.sub.bCl.sub.2-b(1)
In the formula, a is an integer from 0 to 2, b is an integer from 0 to 2 when a=0, b is an integer from 0 to 1 when a=1, and b is 0 when a=2.

(28) 2. The method described in 1, where at least one kind of fluorocarbon compound selected from 1,3,3,3-tetrafluoropropene (1234ze), 1,1,3,3-tetrafluoropropene (1234zc), and 1,1,1,3,3-pentafluoropropane (245fa) is supplied in the reaction.

(29) 3. The method described in 1 or 2, where the halogenated hydrocarbon compound having a carbon number of 3 and represented by the general formula (1) is at least one kind of compound selected from 1,1,3,3-tetrachloro-1-fluoropropane (241fa), 1,1,1,3-tetrachloro-3-fluoropropane (241fb), 1,3,3-trichloro-1,1-difluoropropane (242fa), 1,1,3-trichloro-1,3-difluoropropane (242fb), and 1,1,1-trichloro-3,3-difluoropropane (242fc).

(30) 4. The method described in 2 or 3, where the fluorocarbon compound is 1,3,3,3-tetrafluoropropene (1234ze) or 1,1,1,3,3-pentafluoropropane (245fa).

(31) 5. The method described in any of 1 to 4, where the metal catalyst includes at least one kind of metal selected from aluminum, vanadium, chromium, titanium, magnesium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tin, antimony, zinc, lanthanum, tantalum, and tungsten.

(32) 6. The method described in 5, where the metal catalyst is an oxide of the metal, an oxyhalide of the metal, or a halide of the metal.

(33) 7. The method described in 5 or 6,

(34) where the metal catalyst is a supported catalyst or a non-supported catalyst, and

(35) a support of the supported catalyst is carbon, an oxide of the metal, an oxyhalide of the metal, or a halide of the metal.

(36) 8. The method described in any of 1 to 7, where the metal catalyst includes at least a fluorine atom.

(37) 9. The method described in any of 1 to 8, where a reaction temperature is 100 C. to 500 C. in the reaction.

(38) 10. The method described in any of 1 to 9, where hydrogen fluoride is not substantially supplied in the reaction.

(39) 11. The method described in any of 1 to 10, where the reaction is carried out in the presence of chlorine.

(40) 12. The method described in any of 1 to 11, where the reaction is carried out in the absence of a metal catalyst.

(41) 13. The method described in any of 1 to 12, where the reaction is carried out in the presence of a filler.

(42) 14. The method described in 13, where a material of the filler is at least one kind of material selected from carbon, plastics, ceramics, and a metal.

(43) 15. The method described in any of 1 to 14, where 1-chloro-3,3,3-trifluoropropene (1233zd), 1,3-dichloro-3,3-difluoropropene (1232zd), or 1,3,3-trichloro-3-fluoropropene (1231zd) is formed in addition to 1,1,3,3-tetrachloropropene (1230za) in the reaction.