Method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene

Abstract

This invention discloses a method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene. This method includes inputting the mixed gases of hydrogen fluoride and 1,1,1,3,3-pentachloropropane together with 1,1,2,3-tetrachloropropene into a first reactor for a reaction to obtain a reaction product; directly inputting the reaction product into a second reactor to perform a reaction in the presence of a catalyst; separating hydrogen chloride from the obtained product; obtaining 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene respectively after water washing, alkaline washing, drying and rectifying. This invention has the advantages of flexible production, simple process, small investment, low energy consumption and high conversion rate.

Claims

1. A method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene, the method comprising: (a) preheating and then directing hydrogen fluoride and 1,1,1,3,3-pentachloropropane into a first reactor in a molar ratio of 9:1-15:1, wherein the first reactor comprises an upper section filled with an aluminum oxide supported chromium metal catalyst and a lower section filled with a chromic oxide supported indium metal catalyst, wherein the hydrogen fluoride and the 1,1,1,3,3-pentachloropropane are reacted in the upper section of the first reactor at a temperature of 200-400 C. and at an air flow rate of 300-1,000 h.sup.1, and a product from the upper section enters the lower section of the first reactor to continuously react with the 1,1,2,3-tetrachloropropane to obtain a first reaction product of the first reactor, wherein a molar ratio of the 1,1,2,3-tetrachloropropane to the hydrogen fluoride in the lower section of the first reactor is 3:9-5:9; (b) directly directing the first reaction product of the first reactor into a second reactor to perform a reaction catalysed by a catalyst at a temperature of 250-450 C. and at an air flow rate of 500-1,500 h.sup.1 to obtain a second reaction product of the second reactor; (c) separating the second reaction product of the second reactor in a hydrogen chloride tower to obtain a first tower bottom fraction and a first tower top fraction, which is hydrogen chloride that is refined to obtain hydrochloric acid; (d) removing hydrogen fluoride and hydrogen chloride from the first tower bottom fraction of the hydrogen chloride tower by sequentially passing the first tower bottom fraction through a water washing tower, an alkaline washing tower and a drying tower to obtain a substance; (e) directing the substance into a first rectifying tower to obtain a second tower bottom fraction and a second tower top fraction; (f) directing the second tower bottom fraction of the first rectifying tower into a second rectifying tower to obtain 1-chloro-3,3,3-trifluoropropene and a third tower top fraction; and (g) directing the second tower top fraction of the first rectifying tower into a third rectifying tower to obtain 2,3,3,3-tetrafluoropropene at the top of the third rectifying tower and 1,3,3,3-tetrafluoropropene at the bottom of the third rectifying tower.

2. The method of claim 1, further comprising circulating the third top fraction from the second rectifying tower to the second reactor.

3. The method of claim 1, wherein the molar ratio is 9:1-12:1, the temperature is 250-320 C. and the air flow rate is 500-800 h.sup.1 for the hydrogen fluoride and the 1,1,1,3,3-pentachloropropane reacted in step (a).

4. The method of claim 1, wherein the temperature is 300-400 C. and the air flow rate is 800-1,200 h.sup.1 for the reaction in step (b).

5. The method of claim 1, wherein the loading amount of chromium in the aluminum oxide supported chromium metal catalyst is 5-15 wt % in step (a).

6. The method of claim 1, wherein the loading amount of indium in the aluminum oxide supported indium metal catalyst is 3-10 wt % in step (a).

7. The method of claim 1, wherein the catalyst in the second reactor comprises 70-80 wt % of chromium oxide, 10-15 wt % of magnesium oxide, and 5-15 wt % of zinc oxide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a process flowchart of this invention.

(2) As shown in the FIGURE, 1preheater; 2first reactor; 3second reactor; 4hydrogen chloride tower; 5water washing tower; 6alkaline washing tower; 7drying tower; 8first rectifying tower; 9second rectifying tower; 10third rectifying tower; 1121 pipelines.

DESCRIPTION OF THE EMBODIMENTS

(3) The process flow of this invention can be seen in FIG. 1. The first reactor is divided into two sections, namely an upper section and a lower section, each filled with a different catalyst. Raw materials, hydrogen fluoride and HCC-240fa, are input in a certain molar ratio into a preheater 1 via a pipeline 11 to be preheated, and then enter the top of the upper section of a first reactor 2 via a pipeline 12. 1,1,2,3-tetrachloropropene is input into the lower section of the first reactor 2, and a mixture of HFO-1233zd, HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained after reaction. The mixture is directly input into a second reactor 3 via a pipeline 13 without separation. After reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained and enters a hydrogen chloride tower 4 via a pipeline 14 to obtain a tower bottom fraction and an tower top fraction. The tower top fraction of the hydrogen chloride tower 4 is hydrogen chloride, and the hydrogen chloride is separately refined to obtain hydrochloric acid. The tower bottom fraction enters a water washing tower 5 via a pipeline 15 to be washed with water, then enters an alkaline washing tower 6 via a pipeline 16 to be washed with alkali, next enters a drying tower 7 via a pipeline 17 to be dried to obtain a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf and HFO-1233zd. The mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf and HFO-1233zd enters a first rectifying tower 8 via a pipeline 18 to obtain a tower bottom fraction and an tower top fraction. The tower top fraction of the first rectifying tower 8 includes HFO-1234yf and HFO-1234ze, and enters a third rectifying tower 10 via a pipeline 21. A product HFO-1234yf is obtained at the top of the third rectifying tower 10, and a product HFO-1234ze is obtained in the tower bottom of the third rectifying tower 10. The tower bottom fraction of the first rectifying tower 8 enters a second rectifying tower 9 via a pipeline 19 to be separated to obtain a tower bottom fraction and an tower top faction of the second rectifying tower 9. The fraction at the top of the second rectifying tower 9 mainly includes HCFO-1233xf and carries a small amount of HFO-1233zd, and is circulated to enter the second reactor. A product HFO-1233zd is obtained in the tower bottom of the second rectifying tower 9.

(4) This invention is described in further detail in conjunction with embodiments. However, this invention is not merely limited to the following embodiments.

Embodiment 1

(5) First, 100 mL of Cr.sub.2O.sub.3/In catalyst (3 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al.sub.2O.sub.3/Cr catalyst (10 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 80% of chromic oxide, 10% of magnesium oxide, and 10% of zinc oxide) is placed into a second reactor.

(6) Then, the first reactor is heated to a temperature of 350 C., while HF and nitrogen gas are input to perform activation for 50 hours at an HF flow rate of 100 g/h and a nitrogen flow rate of 1.5 L/min. The second reactor is heated to a temperature of 350 C., while HF and nitrogen gas are input to perform activation for 40 hours at an HF flow rate of 100 g/h and a nitrogen flow rate of 1.5 L/min. In this way, the activation of the catalysts in the two reactors is completed. The first reactor and the second reactor are heated, a temperature increase rate is 1 C./min from room temperature to 150 C., and a temperature increase rate is 0.5 C./min when the temperature is above 150 C.

(7) Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 9:1. The temperature of the upper section of the first reactor is controlled to be 280 C., the air flow rate is controlled to be 500 h.sup.1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 1 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 300 C., and the air flow rate is 800 h.sup.1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 1 after gas chromatography analysis.

(8) TABLE-US-00001 TABLE 1 Composition of Organics at the reactor exit in Embodiment 1 Reactor/ HFO- HFO- HFO- HCFO- fraction 1234yf 1234ze 1233zd 1233xf Others First reactor 0 1.5 55 43.4 0.1 (%) Second reactor 22.5 28.6 18.5 30.3 0.1 (%)

Embodiment 2

(9) First, 100 mL of Cr.sub.2O.sub.3/In catalyst (5 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al.sub.2O.sub.3/Cr catalyst (15 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 70% of chromic oxide, 15% of magnesium oxide, and 15% of zinc oxide) is placed into a second reactor.

(10) The activation method of the catalysts is the same as that in Embodiment 1.

(11) Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 10:1. The temperature of the upper section of the first reactor is controlled to be 300 C., the air flow rate is controlled to be 600 h.sup.1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 5:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 2 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 320 C., and the air flow rate is 800 h.sup.1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 2 after gas chromatography analysis.

(12) TABLE-US-00002 TABLE 2 Composition of Organics at the reactor exit in Embodiment 2 Reactor/ HFO- HFO- HFO- HCFO- fraction 1234yf 1234ze 1233zd 1233xf Others First reactor 0 1.8 46.9 51.2 0.1 (%) Second reactor 25.8 31.6 17.1 25.3 0.2 (%)

Embodiment 3

(13) First, 100 mL of Cr.sub.2O.sub.3/In catalyst (10 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al.sub.2O.sub.3/Cr catalyst (5 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 80% of chromic oxide, 12% of magnesium oxide, and 8% of zinc oxide) is placed into a second reactor.

(14) The activation method of the catalysts is the same as that in Embodiment 1.

(15) Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 15:1. The temperature of the upper section of the first reactor is controlled to be 320 C., the air flow rate is controlled to be 1000 h.sup.1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 3:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 3 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 350 C., and the air flow rate is 1200 h.sup.1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 3 after gas chromatography analysis.

(16) TABLE-US-00003 TABLE 3 Composition of Organics at the reactor exit in Embodiment 3 Reactor/ HFO- HFO- HFO- HCFO- fraction 1234yf 1234ze 1233zd 1233xf Others First reactor 0 2.7 38.6 58.5 0.2 (%) Second reactor 31.3 29.4 16.6 22.6 0.1 (%)

Embodiment 4

(17) First, 100 mL of Cr.sub.2O.sub.3/In catalyst (8 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al.sub.2O.sub.3/Cr catalyst (8 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 80% of chromic oxide, 15% of magnesium oxide, and 5% of zinc oxide) is placed into a second reactor.

(18) The activation method of the catalysts is the same as that in Embodiment 1.

(19) Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 12:1. The temperature of the upper section of the first reactor is controlled to be 400 C., the air flow rate is controlled to be 300 h.sup.1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 4 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 400 C., and the air flow rate is 500 h.sup.1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 4 after gas chromatography analysis.

(20) TABLE-US-00004 TABLE 4 Composition of Organics at the reactor exit in Embodiment 4 Reactor/ HFO- HFO- HFO- HCFO- fraction 1234yf 1234ze 1233zd 1233xf Others First reactor 0 3.1 44.5 52.3 0.1 (%) Second reactor 28.6 25.3 18.2 27.8 0.1 (%)

Embodiment 5

(21) First, 100 mL of Cr.sub.2O.sub.3/In catalyst (6 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al.sub.2O.sub.3/Cr catalyst (10 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 80% of chromic oxide, 10% of magnesium oxide, and 10% of zinc oxide) is placed into a second reactor.

(22) The activation method of the catalysts is the same as that in Embodiment 1.

(23) Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 10:1. The temperature of the upper section of the first reactor is controlled to be 300 C., the air flow rate is controlled to be 500 h.sup.1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 5 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 330 C., and the air flow rate is 600h.sup.1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 5 after gas chromatography analysis.

(24) TABLE-US-00005 TABLE 5 Composition of Organics at the reactor exit in Embodiment 5 Reactor/ HFO- HFO- HFO- HCFO- fraction 1234yf 1234ze 1233zd 1233xf Others First reactor 0 1.0 52.8 46.1 0.1 (%) Second reactor 15.3 22.5 31.2 31 0 (%)

Embodiment 6

(25) First, 100 mL of Cr.sub.2O.sub.3/In catalyst (8 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al.sub.2O.sub.3/Cr catalyst (10 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 75% of chromic oxide, 15% of magnesium oxide, and 10% of zinc oxide) is placed into a second reactor.

(26) The activation method of the catalysts is the same as that in Embodiment 1.

(27) Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 9:1. The temperature of the upper section of the first reactor is controlled to be 300 C., the air flow rate is controlled to be 600 h.sup.1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 6 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 300 C., and the air flow rate is 700 h.sup.1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 6 after gas chromatography analysis.

(28) TABLE-US-00006 TABLE 6 Composition of Organics at the reactor exit in Embodiment 6 Reactor/ HFO- HFO- HFO- HCFO- fraction 1234yf 1234ze 1233zd 1233xf Others First reactor 0 1.2 48.5 50.2 0.1 (%) Second reactor 20.1 25.3 20.4 34 0.2 (%)