Method for co-producing low-carbon foaming agents

Abstract

The invention discloses a method for co-operating low-carbon foaming agents, comprising: preheating 1,1,1,3,3-pentachloropropane and hydrogen fluoride and then introducing into a reactor to have a reaction in the presence of a catalyst to obtain a reaction product, and separating and purifying to obtain the following low-carbon foaming agent products: trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, cis-1-chloro-3,3,3-trifluoropropene. The invention has the advantages of simple process, environmental friendliness, high production efficiency and low cost.

Claims

1. A method for co-producing low-carbon foaming agents, comprising following steps of: (1) preheating 1,1,1,3,3-pentachloropropane and hydrogen fluoride, introducing the 1,1,1,3,3-pentachloropropane and the hydrogen fluoride into a reactor, and reacting the 1,1,1,3,3-pentachloropropane and the hydrogen fluoride in the presence of a catalyst to obtain a reaction product, wherein a ratio of the 1,1,1,3,3-pentachloropropane and the hydrogen fluoride is 1:10-40, a temperature of the reaction is 150-400 C., a pressure of the reaction is 0.1-2.0 MPa, and a material space velocity of the reaction is 10-1000 h.sup.1; (2) introducing the reaction product obtained in the Step (1) into a recycle column to obtain a recycle column overhead fraction and a recycle column bottom component; (3) introducing the recycle column overhead fraction obtained in the Step (2) into a hydrogen chloride separation column to obtain a hydrogen chloride separation column overhead fraction and a hydrogen chloride separation column bottom component; (4) introducing the hydrogen chloride separation column bottom component obtained in the Step (3) and an extractant into an extraction column for extraction to obtain an extraction column overhead component and an extraction column bottom component; and (5) alkaline washing the extraction column bottom component obtained in the Step (4) and then rectifying to obtain following low-carbon foaming agent products: trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and cis-1-chloro-3,3,3-trifluoropropene, wherein in the Step (1), the catalyst is Cr.sub.2O.sub.3/Zn, and wherein a load of Zn in the Cr.sub.2O.sub.3/Zn is 1-10 wt %.

2. The method for co-producing low-carbon foaming agents according to claim 1, wherein in the Step (2), the recycle column bottom component is recycled to the reactor.

3. The method for co-producing low-carbon foaming agents according to claim 1, wherein in the Step (4), the extraction column overhead component is introduced into a hydrogen fluoride recovery column for separation to obtain an overhead fraction and a bottom component, the overhead fraction is recycled to the reactor and the bottom component is recycled to the extraction column.

4. The method for co-producing low-carbon foaming agents according to claim 1, wherein in the Step (4), the extractant is water.

5. The method for co-producing low-carbon foaming agents according to claim 1, wherein in the Step (4), a molar ratio of the hydrogen chloride separation column bottom component to the extractant is 1:0.1-2.5.

6. The method for co-producing low-carbon foaming agents according to claim 1, wherein in the Step (4), a temperature of the extraction column is 0-28 C. and a pressure of the extraction column is 0.1-1.0 MPa.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 is a process flow diagram of the invention.

(2) As shown in the FIGURE, 1 refers to reactor, 2 refers to recycle column, 3 refers to hydrogen chloride separation column, 4 refers to hydrogen fluoride recovery column, 5 refers to extraction column, 6 refers to alkaline washing column, 7 refers to first rectification column, 8 refers to second rectification column, 9 refers to third rectification column, and 10 refers to fourth rectification column.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(3) The process of the invention is as shown in FIG. 1. 1,1,1,3,3-pentachloropropane and hydrogen fluoride are preheated and then introduced into a reactor 1 to have a reaction in the presence of a catalyst to obtain a mixture containing 1,1,1,3,3-pentafluoropropane, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, cis-1-chloro-3,3,3-trifluoropropene, trans-1-chloro-3,3,3-trifluoropropene, hydrogen chloride, unconverted raw materials 1,1,1,3,3-pentachloropropane and hydrogen fluoride. The mixture obtained in the reactor 1 is introduced into a recycle column 2, and the recycle column 2 overhead fraction is a mixture containing 1,1,1,3,3-pentafluoropropane, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, cis-1-chloro-3,3,3-trifluoropropene, trans-1-chloro-3,3,3-trifluoropropene, hydrogen chloride and a small amount of hydrogen fluoride; the recycle column 2 bottom component is a mixture of 1,1,1,3,3-pentachloropropane and hydrogen fluoride, and the mixture of 1,1,1,3,3-pentachloropropane and hydrogen fluoride obtained at the bottom of the recycle column 2 is recycled to the reactor 1. The recycle column 2 overhead fraction is introduced into a hydrogen chloride separation column 3, and the hydrogen chloride separation column 3 overhead fraction is hydrogen chloride; the hydrogen chloride separation column 3 bottom component is a mixture containing 1,1,1,3,3-pentafluoropropane, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, cis-1-chloro-3,3,3-trifluoropropene, trans-1-chloro-3,3,3-trifluoropropene and a small amount of hydrogen fluoride. The hydrogen chloride separation column 3 bottom component and the extractant are introduced into an extraction column 5 for extraction, and the extraction column 5 overhead component is a mixture of hydrogen fluoride and the extractant and is introduced into a hydrogen fluoride recovery column 4 for separation, and the hydrogen fluoride recovery column 4 overhead fraction is hydrogen fluoride and is recycled to the reactor 1, and the hydrogen fluoride recovery column 4 bottom component is the extractant and is recycled to an extraction column 5; and the hydrogen fluoride recovery column 4 bottom component is a mixture of 1,1,1,3,3-pentafluoropropane, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, cis-1-chloro-3,3,3-trifluoropropene and trans-1-chloro-3,3,3-trifluoropropene. The extraction column bottom component is introduced into an alkaline washing column 6 for alkaline washing, and then sequentially passes through a first rectification column 7, a second rectification column 8, a third rectification column 9, and a fourth rectification column 10 for rectification; a trans-1,3,3,3-tetrafluoropropene product is obtained at the overhead of the first rectification column 7, and a cis-1,3,3,3-tetrafluoropropene product is obtained at the overhead of the second rectification column 8, a 1,1,1,3,3-pentafluoropropane product is obtained at the overhead of the rectification column 9, a trans-1-chloro-3,3,3-trifluoropropene product is obtained at the overhead of the fourth rectification column 10, and a cis-1-chloro-3,3,3-trifluoropropene product is obtained at the bottom of the four rectification column.

(4) The invention is further described in detail below by means of embodiments, but the invention is not limited to the embodiments described.

Embodiment 1

(5) 100 ml of a catalyst Cr.sub.2O.sub.3/In (load of In is 3 wt %) is loaded into a reactor, then the reactor is heated to 350 C., HF and nitrogen are introduced for activation, wherein the HF flow rate is 100 g/h, the nitrogen flow rate is 1.5 L/min, and the activation time is 50 hours.

(6) Then, the feed reaction is started, and HF and R-240fa are preheated and then introduced into the reactor. The molar ratio of HF to R-240fa is 10:1, the reactor temperature is controlled to 150 C., the reaction pressure is 0.3 MPa, the space velocity is 100 h.sup.1, the molar ratio of the hydrogen chloride separation column bottom component to the extractant is 1:0.1, the temperature of the extraction column is 25 C., and the pressure of the extraction column is 0.1 MPa. The organic composition of the outlet product of the reactor is analyzed by sampling and gas chromatography, as shown in Table 1. Through analysis of samples from an extraction column bottom discharge pipeline, the hydrogen fluoride content is 0.1%.

(7) TABLE-US-00001 TABLE 1 Outlet Organic Composition of the Reactor in Embodiment 1 Component R- R- R- R- R- 1234ze(E) 1234ze(Z) 245fa 1233zd(E) 1233zd(Z) Content (%) 1.74 0.43 0.17 81.39 15.76

Embodiment 2

(8) 100 ml of a catalyst Cr.sub.2O.sub.3/Zn (load of Zn is 3 wt %) is loaded into a reactor, then the reactor is heated to 350 C., HF and nitrogen are introduced for activation, wherein the HF flow rate is 100 g/h, the nitrogen flow rate is 1.5 L/min, and the activation time is 50 hours.

(9) Then, the feed reaction is started, and HF and R-240fa are preheated and then introduced into the reactor. The molar ratio of HF to R-240fa is 15:1, the reactor temperature is controlled to 200 C., the reaction pressure is 0.5 MPa, the space velocity is 300 h.sup.1, the molar ratio of the hydrogen chloride separation column bottom component to the extractant is 1:1.0, the temperature of the extraction column is 15 C., and the pressure of the extraction column is 0.5 MPa. The organic composition of the outlet product of the reactor is analyzed by sampling and gas chromatography, as shown in Table 2. Through analysis of samples from an extraction column bottom discharge pipeline, the hydrogen fluoride content is 0.05%.

(10) TABLE-US-00002 TABLE 2 Outlet Organic Composition of the Reactor in Embodiment 2 Component R- R- R- R- R- 1234ze(E) 1234ze(Z) 245fa 1233zd(E) 1233zd(Z) Content (%) 0.6 0.1 0.1 82.39 16.34

Embodiment 3

(11) 100 ml of a catalyst Cr.sub.2O.sub.3/In (load of In is 5 wt %) is loaded into a reactor, then the reactor is heated to 350 C., HF and nitrogen are introduced for activation, wherein the HF flow rate is 100 g/h, the nitrogen flow rate is 1.5 L/min, and the activation time is 50 hours.

(12) Then, the feed reaction is started, and HF and R-240fa are preheated and then introduced into the reactor. The molar ratio of HF to R-240fa is 20:1, the reactor temperature is controlled to 250 C., the reaction pressure is 0.8 MPa, the space velocity is 500 h.sup.1, the molar ratio of the hydrogen chloride separation column bottom component to the extractant is 1:0.5, the temperature of the extraction column is 10 C., and the pressure of the extraction column is 0.3 MPa. The organic composition of the outlet product of the reactor is analyzed by sampling and gas chromatography, as shown in Table 3. Through analysis of samples from an extraction column bottom discharge pipeline, the hydrogen fluoride content is 0.08%.

(13) TABLE-US-00003 TABLE 3 Outlet Organic Composition of the Reactor in Embodiment 3 Component R- R- R- R- R- 1234ze(E) 1234ze(Z) 245fa 1233zd(E) 1233zd(Z) Content (%) 4.11 7.89 83.12 2.05 2.83

Embodiment 4

(14) 100 ml of a catalyst Cr.sub.2O.sub.3/Zn (load of Zn is 7 wt %) is loaded into a reactor, then the reactor is heated to 350 C., HF and nitrogen are introduced for activation, wherein the HF flow rate is 100 g/h, the nitrogen flow rate is 1.5 L/min, and the activation time is 50 hours.

(15) Then, the feed reaction is started, and HF and R-240fa are preheated and then introduced into the reactor. The molar ratio of HF to R-240fa is 25:1, the reactor temperature is controlled to 300 C., the reaction pressure is 1.0 MPa, the space velocity is 800 h.sup.1, the molar ratio of the hydrogen chloride separation column bottom component to the extractant is 1:2.0, the temperature of the extraction column is 0 C., and the pressure of the extraction column is 1.0 MPa. The organic composition of the outlet product of the reactor is analyzed by sampling and gas chromatography, as shown in Table 4. Through analysis of samples from an extraction column bottom discharge pipeline, the hydrogen fluoride content is 0.01%.

(16) TABLE-US-00004 TABLE 4 Outlet Organic Composition of the Reactor in Embodiment 4 Component R- R- R- R- R- 1234ze(E) 1234ze(Z) 245fa 1233zd(E) 1233zd(Z) Content (%) 0.97 2.03 96.5 0.2 0.3

Embodiment 5

(17) 100 ml of a catalyst Cr.sub.2O.sub.3/In (load of In is 7 wt %) is loaded into a reactor, then the reactor is heated to 350 C., HF and nitrogen are introduced for activation, wherein the HF flow rate is 100 g/h, the nitrogen flow rate is 1.5 L/min, and the activation time is 50 hours.

(18) Then, the feed reaction is started, and HF and R-240fa are preheated and then introduced into the reactor. The molar ratio of HF to R-240fa is 30:1, the reactor temperature is controlled to 350 C., the reaction pressure is 1.5 MPa, the space velocity is 1000 h.sup.1, the molar ratio of the hydrogen chloride separation column bottom component to the extractant is 1:1.2, the temperature of the extraction column is 12 C., and the pressure of the extraction column is 0.5 MPa. The organic composition of the outlet product of the reactor is analyzed by sampling and gas chromatography, as shown in Table 5. Through analysis of samples from an extraction column bottom discharge pipeline, the hydrogen fluoride content is 0.07%.

(19) TABLE-US-00005 TABLE 5 Outlet Organic Composition of the Reactor in Embodiment 5 Component R- R- R- R- R- 1234ze(E) 1234ze(Z) 245fa 1233zd(E) 1233zd(Z) Content (%) 85.12 7.88 4.21 2.01 0.78

Embodiment 6

(20) 100 ml of a catalyst Cr.sub.2O.sub.3/Zn (load of Zn is 5 wt %) is loaded into a reactor, then the reactor is heated to 350 C., HF and nitrogen are introduced for activation, wherein the HF flow rate is 100 g/h, the nitrogen flow rate is 1.5 L/min, and the activation time is 50 hours.

(21) Then, the feed reaction is started, and HF and R-240fa are preheated and then introduced into the reactor. The molar ratio of HF to R-240fa is 40:1, the reactor temperature is controlled to 400 C., the reaction pressure is 1.7 MPa, the space velocity is 900 h.sup.1, the molar ratio of the hydrogen chloride separation column bottom component to the extractant is 1:1.5, the temperature of the extraction column is 5 C., and the pressure of the extraction column is 0.7 MPa. The organic composition of the outlet product of the reactor is analyzed by sampling and gas chromatography, as shown in Table 6. Through analysis of samples from an extraction column bottom discharge pipeline, the hydrogen fluoride content is 0.03%.

(22) TABLE-US-00006 TABLE 6 Outlet Organic Composition of the Reactor in Embodiment 6 Component R- R- R- R- R- 1234ze(E) 1234ze(Z) 245fa 1233zd(E) 1233zd(Z) Content (%) 94.85 3.25 1.45 0.35 0.1