METHOD FOR CO-PRODUCING 2,3,3,3-TETRAFLUOROPROPENE AND TRANS-1,3,3,3-TETRAFLUOROPROPENE

Abstract

Disclosed is a method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene, comprising the following steps: preheating a mixture of 1,1,1,2,2-pentachloropropane and 1,1,1,3,3-pentachloropropane together with anhydrous hydrogen fluoride and simultaneously introducing into a first reactor to react in the presence of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 to obtain a first reactor product; directly introducing the first reactor product into a second reactor without separation, and carrying out a catalytic fluorination reaction in the presence of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 to obtain a second reactor product; and separating the second reactor product to obtain the products of 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene. The invention has such advantages that the process is simple and less equipment investment is required; used catalysts have good activity, high selectivity and long total life; and the ratio of the two products can be flexibly adjusted according to market demands.

Claims

1. A method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene, comprising following steps of: (1) preheating a mixture of 1,1,1,2,2-pentachloropropane and 1,1,1,3,3-pentachloropropane together with anhydrous hydrogen fluoride and simultaneously introducing into a first reactor to react in the presence of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 at a reaction temperature of 200-350° C., with a contact time of 1-20 s to obtain a first reactor product, wherein a molar ratio of the anhydrous hydrogen fluoride to the mixture of 1,1,1,2,2-pentachloropropane and 1,1,1,3,3-pentachloropropane is 6-18:1; (2) directly introducing the first reactor product obtained in the step (1) into a second reactor without separation, and carrying out a catalytic fluorination reaction in the presence of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 at a reaction temperature of 250-400° C., with a contact time of 1-35 s to obtain a second reactor product; (3) introducing the second reactor product obtained in the step (2) into a first separation column for separation to obtain a bottom component of a first separation column and hydrogen chloride; (4) introducing the bottom component of the first separation column obtained in the step (3) into a second separation column for separation to obtain an overhead component of the second separation column and a bottom component of the second separation column; (5) washing the overhead component of the second separation column obtained in the step (4) with water and an alkali, drying, and then introducing into a third separation column to obtain an overhead component of the third separation column and a bottom component of the third separation column; (6) introducing the bottom component of the third separation column obtained in the step (5) into a fourth separation column to obtain a 2,3,3,3-tetrafluoropropene product and a bottom component of the fourth separation column; and (7) introducing the bottom component of the fourth separation column obtained in the step (6) into a fifth separation column to obtain a trans-1,3,3,3-tetrafluoropropene product.

2. The method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene according to claim 1, wherein in the step (1), a molar ratio of 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane in the mixture of 1,1,1,2,2-pentachloropropane and 1,1,1,3,3-pentachloropropane is 1:0.05-20.

3. The method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene according to claim 1, wherein in the step (1), the molar ratio of the anhydrous hydrogen fluoride to the mixture of 1,1,1,2,2-pentachloropropane and 1,1,1,3,3-pentachloropropane is 8-15:1, the reaction temperature is 250-300° C., and the contact time is 2-10 s.

4. The method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene according to claim 1, wherein in the step (2), the reaction temperature is 280-330° C., and the contact time is 4-15 s.

5. The method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene according to claim 1, wherein in the step (1), the catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 comprises 0.5-20 wt % of La.sub.2O.sub.3 and 80-99.5 wt % of Cr.sub.2O.sub.3.

6. The method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene according to claim 1, wherein in the step (2), the catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 comprises 1-15 wt % of Ga.sub.2O.sub.3, 3-20 wt % of Y.sub.2O.sub.3 and 65-96 wt % of Cr.sub.2O.sub.3.

7. The method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene according to claim 1, wherein in the step (4), the bottom component of the second separation column is circulated to the first reactor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0042] FIG. 1 is a process flow diagram of the invention.

[0043] As shown in the FIG. 1 refers to vaporizer, 2 refers to first reactor, 3 refers to second reactor, 4 refers to first separation column, 5 refers to second separation column, 6 refers to water washing column, 7 refers to alkali washing column, 8 refers to dryer, 9 refers to third separation column, 10 refers to fourth separation column, 11 refers to fifth separation column, and 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 refer to pipelines.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0044] The process of the invention is as shown in FIG. 1. A first reactor 2 and a second reactor 3 are respectively loaded with different catalysts, and HCC-240ab and HCC-240fa are mixed in a certain ratio, and then mixed with AHF through a vaporizer 1 to be heated and vaporized; the mixture enters the first reactor 2 through a pipeline 12 to have a reaction; the mixture containing HCFO-1233xf, HCFO-1233zd, hydrogen chloride and excessive AHF directly enters the second reactor 3 through pipelines 13, 14 to have a reaction; and the material out of the outlet of the second reactor 3 enters a first separation column 4 through a pipeline 15, and HCl is dry separated from the overhead of the first separation column 4 and stored separately. The material at the bottom of the first separation column 4 enters a second separation column 5 through pipeline 16. A mixture of AHF and a small amount of unreacted HCFO-1233zd and HCFO-1233xf, obtained at the bottom of the second separation column 5 is circulated to the second reactor 3 through pipelines 17, 14 to have a re-reaction; the overhead component of the second separation column 5 is a mixture mainly containing HFO-1234yf and E-HFO-1234ze, and the mixture enters a water washing column 6 for acid removal through a pipeline 18, then enters an alkali washing column 7 for further acid removal through a pipeline 19, then enters a dryer 8 for moisture removal through a pipeline 20, and then enters a third separation column 9 for light component removal through a pipeline 21; and a tiny amount of low-boiling fluorine-containing olefin impurities obtained at the overhead of the third separation column 9 and a material flow of HFO-1234yf and E-HFO-1234ze obtained at the bottom enter a fourth separation column through a pipeline 22. HFO-1234yf produced at the overhead of the fourth separation column and an E-HFO-1234ze-enriched material flow obtained at the bottom enter a fifth separation column through the pipeline 23. When accumulated to a certain amount, E-HFO-1234ze produced at the overhead of the fifth separation column and heavy components obtained at the bottom are recycled or sent to be incinerated.

[0045] The invention is further described in detail below by means of embodiments, but the invention is not limited to the embodiments described.

Embodiment 1

[0046] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 1 wt % of La.sub.2O.sub.3 and 99 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 250° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0047] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 1 wt % of Ga.sub.2O.sub.3, 3 wt % of Y.sub.2O.sub.3 and 96 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 280° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0048] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 250° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 16:1:1, and the contact time is 10 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 280° C., and the contact time is 10 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 2

[0049] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 3 wt % of La.sub.2O.sub.3 and 97 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 250° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0050] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 3 wt % of Ga.sub.2O.sub.3, 5 wt % of Y.sub.2O.sub.3 and 92 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 280° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0051] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 250° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 20:1:1, and the contact time is 7.2 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 280° C., and the contact time is 7.2 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 3

[0052] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 8 wt % of La.sub.2O.sub.3 and 92 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 270° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0053] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 5 wt % of Ga.sub.2O.sub.5, 7 wt % of Y.sub.2O.sub.3 and 88 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 290° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0054] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 270° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 20:1:1, and the contact time is 6 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 290° C., and the contact time is 6 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 4

[0055] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 12 wt % of La.sub.2O.sub.3 and 88 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 270° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0056] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 7 wt % of Ga.sub.2O.sub.7, 9 wt % of Y.sub.2O.sub.3 and 84 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 290° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0057] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 270° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 36:2:1, and the contact time is 4 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 290° C., and the contact time is 4 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 5

[0058] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 16 wt % of La.sub.2O.sub.3 and 84 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 280° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0059] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 9 wt % of Ga.sub.2O.sub.3, 11 wt % of Y.sub.2O.sub.3 and 80 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 300° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0060] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 280° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 20:1:1, and the contact time is 6 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 300° C., and the contact time is 6 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 6

[0061] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 18 wt % of La.sub.2O.sub.3 and 82 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 280° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0062] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 11 wt % of Ga.sub.2O.sub.3, 14 wt % of Y.sub.2O.sub.3 and 75 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 320° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0063] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 280° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 45:2:1, and the contact time is 2 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 320° C., and the contact time is 2 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 7

[0064] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 20 wt % of La.sub.2O.sub.3 and 80 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 300° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0065] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 13 wt % of Ga.sub.2O.sub.3, 17 wt % of Y.sub.2O.sub.3 and 70 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 320° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0066] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 300° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 20:1:1, and the contact time is 4 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 320° C., and the contact time is 4 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 8

[0067] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 10 wt % of La.sub.2O.sub.3 and 90 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 300° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0068] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 15 wt % of Ga.sub.2O.sub.3, 20 wt % of Y.sub.2O.sub.3 and 65 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 330° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0069] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 300° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 45:1:2, and the contact time is 3.6 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 330° C., and the contact time is 3.6 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 9

[0070] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 3 wt % of La.sub.2O.sub.3 and 97 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 300° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0071] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 15 wt % of Ga.sub.2O.sub.3, 20 wt % of Y.sub.2O.sub.3 and 65 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 330° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0072] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 300° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 16:1.9:0.1, and the contact time is 3.6 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 330° C., and the contact time is 4 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

Embodiment 10

[0073] 300 ml of a catalyst La.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing 3 wt % of La.sub.2O.sub.3 and 97 wt % of Cr.sub.2O.sub.3) is loaded into a first reactor, heated to 300° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0074] 300 ml of a catalyst Ga.sub.2O.sub.3—Y.sub.2O.sub.3—Cr.sub.2O.sub.3 (composing l5 wt % of Ga.sub.2O.sub.3, 20 wt % of Y.sub.2O.sub.3 and 65 wt % of Cr.sub.2O.sub.3) is loaded into a second reactor, heated to 330° C., and activated by introducing anhydrous hydrogen fluoride diluted with nitrogen. The flow rate of AHF is 25 g/h, the flow rate of nitrogen is 0.2 L/min, and the activation time is 8 hours.

[0075] After the activation is completed, HCC-240ab, HCC-240fa and hydrogen fluoride are mixed and then introduced in a vaporizer; the vaporized mixture enters the first reactor for reaction after the temperature of the vaporized mixture is slightly lower than the temperature of the first reactor, wherein the temperature of the first reactor is controlled to be 300° C., the molar ratio of anhydrous hydrogen fluoride to 1,1,1,2,2-pentachloropropane to 1,1,1,3,3-pentachloropropane is 16:0.1:1.9, and the contact time is 3.6 s. The material at an outlet of the first reactor is directly sent to the second reactor for reaction, wherein the reaction temperature of the second reactor is 330° C., and the contact time is 4 s. A bypass is connected to the outlet of the first reactor for sampling analysis. The product is washed with water and an alkali before analysis. The composition of the organic product is then analyzed by gas chromatography. The results are shown in Table 1. The product at the outlet of the second reactor was washed with water and alkali, and the composition of the organic product was analyzed by gas chromatography. The results are shown in Table 2.

TABLE-US-00002 TABLE 1 Reaction results of the first reactor HCC-240 Organic composition of the reaction product conversion Embodiments HCC-240ab HCC-240fa HCFO-1233xf HCFO-1233zd E-HFO-1234ze HFO-1234yf rate (%) 1 0 0 50 49.8 0.2 0 100 2 0 0 49.7 49.5 0.5 0.3 100 3 0 0 49.4 47.9 2.1 0.6 100 4 0 0 65.7 31.4 2.0 0.9 100 5 0 0 48.7 46.5 3.5 1.3 100 6 0 0 65.6 30.8 2.6 1.0 100 7 0 0 46.6 44.9 5.1 3.4 100 8 0 0 29.6 60.0 6.6 3.8 100 9 0 0 94.9 4.8 0.2 0.1 100 10 0 0 4.9 93.9 1.1 0 100

TABLE-US-00003 TABLE 2 Reaction results of the second reactor Reaction conditions Reaction HFO-1234yf + temperature Contact Organic composition of the reaction product E-HFO-1234ze Embodiments (° C.) time (s) HCFO-1233xf HCFO-1233zd E-HFO-1234ze HFO-1234yf selectivity (%) 1 280 10 1.3 0.4 49.6 48.7 98.3 2 280 7.2 1.5 0.5 49.5 48.5 98.0 3 290 6 1.2 0.3 49.7 48.8 98.5 4 290 4 1.3 0.2 33.1 65.4 98.5 5 300 6 0.9 0 50.0 49.1 99.1 6 320 2 0.7 0 33.3 66.0 99.3 7 320 4 0.8 0 50.0 49.2 99.2 8 330 3.6 0.6 0 66.6 32.8 99.4 9 330 4 0.3 0 4.9 94.4 99.3 10 330 4 0.2 0 95.0 4.7 99.7