阅读说明：本技术 用于生产反式-1-氯-3,3,3-三氟丙烯的工艺 (Process for producing trans-1-chloro-3, 3, 3-trifluoropropene ) 是由 B.科利尔 A.皮加莫 N.布鲁萨德利 于 2019-07-16 设计创作，主要内容包括：本发明涉及用于生产反式-1-氯-3,3,3-三氟丙烯的工艺,其包括如下步骤：i)提供反应器,所述反应器包括盖子、底部、连接所述底部和所述盖子的侧壁、至少一个反应物供应管线和至少一个用于抽出所形成产物的管线,所述反应器进一步包含液相A；ii)提供被加热至从100℃至170℃的温度T1的包括氢氟酸的物流B和提供包括1,1,3,3-四氯丙烯和/或1,3,3,3-四氯丙烯的物流C；所述物流B和所述物流C经由所述至少一个反应物供应管线对所述反应器进行供应；iii)在所述液相A中使所述物流B与所述物流C反应以形成包括反式-1-氯-3,3,3-三氟丙烯的物流D。本发明特征在于步骤iii)于在50℃和110℃之间的温度T2下进行,和所述温度T1和所述温度T2之间的以绝对值计的温度差大于30℃。(The present invention relates to a process for the production of trans-1-chloro-3, 3, 3-trifluoropropene comprising the steps of: i) providing a reactor comprising a lid, a bottom, a side wall connecting the bottom and the lid, at least one reactant supply line and at least one line for withdrawing the formed product, the reactor further comprising a liquid phase a; ii) providing a stream B comprising hydrofluoric acid heated to a temperature T1 of from 100 ℃ to 170 ℃ and providing a stream C comprising 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene; said stream B and said stream C supply said reactor via said at least one reactant supply line; iii) reacting said stream B with said stream C in said liquid phase A to form a stream D comprising trans-1-chloro-3, 3, 3-trifluoropropene. The invention is characterized in that step iii) is carried out at a temperature T2 between 50 ℃ and 110 ℃ and in that the temperature difference between the temperature T1 and the temperature T2 in absolute terms is greater than 30 ℃.)

1. A process for the production of trans-1-chloro-3, 3, 3-trifluoropropene comprising the steps of:

i) providing a reactor comprising a lid, a bottom, a side wall connecting the bottom and the lid, at least one reactant supply line and at least one line for withdrawing the formed product, the reactor further comprising a liquid phase a;

ii) providing a stream B comprising hydrofluoric acid heated to a temperature T1 of from 100 ℃ to 170 ℃ and providing a stream C comprising 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene; said stream B and said stream C supply said reactor via said at least one reactant supply line;

iii) reacting said stream B with said stream C in said liquid phase A to form a stream D comprising trans-1-chloro-3, 3, 3-trifluoropropene;

is characterized in that

Step iii) is carried out at a temperature T2 between 50 ℃ and 110 ℃, and

the temperature difference in absolute value between the temperature T1 and the temperature T2 is greater than or equal to 30 ℃.

2. The process as claimed in claim 1, characterized in that said reactor also comprises heating means capable of heating said liquid phase A; the temperature of the heating device is T3; the temperature T3 is higher than the temperature T2 and the temperature T3 is less than 120 ℃.

3. The process as claimed in any of the preceding claims, characterized in that the liquid phase a provided in step i) is heated to a temperature T4 of between 50 ℃ and 110 ℃ before carrying out step iii); preferably, the temperature T4 is equal to the temperature T2.

4. The process as claimed in any of the preceding claims, characterized in that the liquid phase A is a low HF liquid phase.

5. The process as claimed in the preceding claim, characterized in that the liquid phase a low in HF is a liquid phase comprising less than 15% by weight of HF, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferentially less than 6% by weight of HF, in particular less than 5% by weight of HF, more in particular less than 4% by weight of HF, preferably less than 2% by weight of HF, based on the total weight of the liquid phase.

6. The process as claimed in any one of the preceding claims, characterized in that the temperature T2 is between 60 ℃ and 105 ℃, preferably between 70 ℃ and 100 ℃, more preferentially between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃.

7. The process as claimed in any of the preceding claims, characterized in that the temperature T1 is between 120 ℃ and 170 ℃, in particular between 125 ℃ and 165 ℃, more particularly between 125 ℃ and 155 ℃.

8. The process as claimed in any of the preceding claims 2 to 7, characterized in that the temperature T3 is less than 115 ℃, preferably less than 110 ℃, more preferably less than 105 ℃, in particular less than 100 ℃.

9. The process as claimed in any one of the preceding claims, characterized in that said stream D also comprises at least one of the by-products chosen from: 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene, and cis-1-chloro-3, 3, 3-trifluoropropene; and, in said stream D, the total molar content of said at least one of said by-products is less than 5 mol%.

10. The process according to any of the preceding claims, characterized in that the molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is greater than 95 mol%.

11. The process as claimed in any of the preceding claims, characterized in that step iii) is carried out at a pressure between 5 and 20 bar absolute, preferably between 10 and 18 bar absolute.

Technical Field

The present invention relates to the production of hydrochlorofluoroolefins. More particularly, the present invention relates to the production of 1-chloro-3, 3, 3-trifluoropropene.

Background

3,3, 3-trifluoro-1-chloropropene, or alternatively 1-chloro-3, 3, 3-trifluoropropene (HCFO-1233zd), exists in the form of two isomers: the cis isomer, i.e., Z-3,3, 3-trifluoro-1-chloropropene (HCFO-1233zdZ), and the trans isomer, i.e., E-3,3, 3-trifluoro-1-chloropropene (HCFO-1233 zdE). They have different boiling points, 18.5 ℃ for the trans compound and 39.5 ℃ for the cis compound, respectively.

Fluids based on E-3,3, 3-trifluoro-1-chloropropene (HCFO-1233zdE) have found numerous applications in a wide variety of industrial fields, particularly as heat transfer fluids, propellants, blowing agents, gaseous dielectrics, monomeric or polymeric media, support fluids (support fluids), abrasives, desiccants, and fluids for energy production equipment.

The manufacture of HCFO-1233zdE is accompanied by numerous byproducts having boiling points close to that of HCFO-1233 zdE. This results in a relatively complex and expensive purification step. The difficulties encountered during the purification of HCFO-1233zdE often result in significant losses of the target product. In addition, the by-products can form azeotropic compositions with HCFO-1233zdE, making separation by simple distillation very difficult, or even impossible.

US5877359 discloses a process for making HCFO-1233zdE from 1,1,3, 3-tetrachloropropene in the liquid phase and in the absence of a catalyst. US9643903 also discloses a process for fluorinating 1,1,3, 3-tetrachloropropene in the liquid phase and in the absence of a catalyst in a HF-rich medium. A process for fluorinating 1,1,3, 3-tetrachloropropene to give 1-chloro-3, 3, 3-trifluoropropene is also known from U.S. Pat. No. 9255045.

Typically, the fluorination reaction is carried out at the following temperatures: which requires heating the reactor to a temperature significantly above the target reaction temperature. The high temperature of the reactor wall locally produces an increase in the production of by-products such as cis-1-chloro-3, 3, 3-trifluoropropene or the production of per-fluorinated products such as 1,1,1,3, 3-pentafluoropropane or 1,3,3, 3-tetrafluoropropene.

There is a need for an efficient process for the production of trans-1-chloro-3, 3, 3-trifluoropropene that minimizes the production of by-products or over-fluorinated products.

Disclosure of Invention

The applicant has surprisingly observed that preheating the starting raw materials, in particular hydrofluoric acid, to a temperature significantly higher than the reaction temperature makes it possible to limit the heating of the reactor.

The present invention provides a process for the production of trans-1-chloro-3, 3, 3-trifluoropropene comprising the steps of:

i) providing a reactor comprising a lid, a bottom, a side wall connecting the bottom and the lid, at least one reactant supply line and at least one line for withdrawing the formed product, the reactor further comprising a liquid phase a;

ii) providing a stream B comprising hydrofluoric acid heated to a temperature T1 of from 100 ℃ to 170 ℃ and providing a stream C comprising 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene; said stream B and said stream C supply said reactor via said at least one reactant supply line;

iii) reacting said stream B with said stream C in said liquid phase A to form a stream D comprising trans-1-chloro-3, 3, 3-trifluoropropene;

is characterized in that

Step iii) is carried out at a temperature T2 between 50 ℃ and 110 ℃, and

the temperature difference in absolute value between the temperature T1 and the temperature T2 is greater than or equal to 30 ℃.

According to a preferred embodiment, the reactor further comprises heating means capable of heating the liquid phase a; the temperature of the heating device is T3; the temperature T3 is higher than the temperature T2 and the temperature T3 is less than 120 ℃.

According to a preferred embodiment, the liquid phase a provided in step i) is heated to a temperature T4 between 50 ℃ and 110 ℃ before carrying out step iii); preferably, the temperature T4 is equal to the temperature T2.

According to a preferred embodiment, the liquid phase a is a low HF liquid phase.

According to a preferred embodiment, the low HF liquid phase is a liquid phase comprising less than 15 wt.% HF, advantageously less than 10 wt.% HF, preferably less than 8 wt.% HF, more preferentially less than 6 wt.% HF, in particular less than 5 wt.% HF, more in particular less than 4 wt.% HF, advantageously less than 2 wt.% HF, based on the total weight of the liquid phase.

According to a preferred embodiment, the temperature T2 is between 60 ℃ and 105 ℃, preferably between 70 ℃ and 100 ℃, more preferentially between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃.

According to a preferred embodiment, the temperature T1 is between 120 ℃ and 170 ℃, in particular between 125 ℃ and 165 ℃, more particularly between 125 ℃ and 155 ℃.

According to a preferred embodiment, the temperature T3 is less than 115 ℃, preferably less than 110 ℃, more preferably less than 105 ℃, in particular less than 100 ℃.

According to a preferred embodiment, said stream D further comprises at least one by-product selected from the group consisting of: 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene, and cis-1-chloro-3, 3, 3-trifluoropropene; and, in said stream D, the total molar content of said at least one of said by-products is less than 5 mol%.

According to a preferred embodiment, the molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is more than 95 mol%.

According to a preferred embodiment, step iii) is carried out at a pressure between 5 and 20 bar absolute (bara), preferably between 10 and 18 bar absolute.

Detailed Description

The present invention relates to a process for the production of trans-1-chloro-3, 3, 3-trifluoropropene. In particular, the process is carried out in a reactor comprising: a lid, a bottom, a side wall connecting the bottom and the lid, at least one reactant supply line and at least one line for withdrawing a formed product.

In addition, the reactor comprises a liquid phase a. The liquid phase A is a low HF liquid phase or an HF-rich liquid phase.

The low HF liquid phase a is a liquid phase comprising less than 15 wt% HF, advantageously less than 10 wt% HF, preferably less than 8 wt% HF, more preferentially less than 6 wt% HF, in particular less than 5 wt% HF, more in particular less than 4 wt% HF, preferably less than 2 wt% HF, based on the total weight of the liquid phase.

The HF-rich liquid phase a is a liquid phase comprising more than 20 wt.% HF, advantageously more than 25 wt.% HF, preferably more than 30 wt.% HF, more preferentially more than 35 wt.% HF, in particular more than 40 wt.% HF, more in particular more than 45 wt.% HF, preferably more than 50 wt.% HF, based on the total weight of the liquid phase.

Preferably, the liquid phase a is a low HF liquid phase. In particular, the liquid phase a comprises at least 10 wt% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, based on the total weight of the starting composition. Advantageously, the starting composition comprises at least 15 wt% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, preferably at least 20 wt% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, more preferably at least 25 wt% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, especially at least 30 wt% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, more especially at least 35 wt% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, preferably at least 40 wt% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, advantageously at least 45% by weight of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, preferably at least 50% by weight of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, and particularly preferably at least 55% by weight of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, based on the total weight of the liquid phase a.

Preferably, the liquid phase a comprises at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at least 95 wt%, or at least 99 wt% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, based on the total weight of the liquid phase a.

The present process therefore comprises a step i) of providing a reactor comprising a lid, a bottom, a side wall connecting the bottom and the lid, at least one reactant supply line and at least one line for withdrawing the product formed, the reactor further comprising a liquid phase a.

Stream B used in the present process comprises hydrofluoric acid. The term "hydrofluoric acid" as used herein encompasses hydrofluoric acid and anhydrous hydrofluoric acid. Preferably, the hydrofluoric acid comprises less than 1000ppm water, advantageously less than 800ppm water, preferably less than 600ppm water, more preferentially less than 400ppm water, in particular less than 200ppm water, more in particular less than 100ppm water, preferably less than 50ppm water.

Preferably, the flow B comprises at least 50% by weight of hydrofluoric acid, advantageously at least 60% by weight of hydrofluoric acid, preferably at least 70% by weight of hydrofluoric acid, more preferentially at least 80% by weight of hydrofluoric acid, in particular at least 90% by weight of hydrofluoric acid, more in particular at least 95% by weight of hydrofluoric acid, preferably at least 99% by weight of hydrofluoric acid, based on the total weight of said flow B.

Preferably, stream B is heated to a temperature T1 of from 100 ℃ to 170 ℃. Stream B is heated before introducing it into the reactor. The heating of stream B can be performed by various means such as electric heat tracing (electric heat tracing), i.e., the reactant supply line containing stream B is covered with an electric resistance, a heat exchanger or a jacket placed around the reactant supply line containing stream B. The jacket contains a heat transfer fluid such as steam, pressurized hot water, or oil.

Stream C used in the present process comprises 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene. Preferably, the stream comprises at least 50 wt.% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, advantageously at least 60 wt.% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, preferably at least 70 wt.% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, more preferably at least 80 wt.% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, in particular at least 90 wt.% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, more in particular at least 95 wt.% of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, preferably at least 99% by weight of 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene, based on the total weight of the stream C.

The stream B and the stream C are supplied to the reactor via one or more reactant supply lines. Optionally, said stream B or said stream C may be mixed prior to introduction into said reactor. Optionally injecting said stream B and/or said stream C into said liquid phase a present in said reactor.

Preferably, said streams B and C are contacted in the liquid phase. The reaction between hydrofluoric acid and 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene allows the formation of a stream D comprising trans-1-chloro-3, 3, 3-trifluoropropene. Preferably, stream D is a gas stream.

Accordingly, the present invention provides a process for the production of trans-1-chloro-3, 3, 3-trifluoropropene comprising the steps of:

i) providing a reactor comprising a lid, a bottom, a side wall connecting the bottom and the lid, at least one reactant supply line and at least one line for withdrawing the formed product, the reactor further comprising a liquid phase a;

ii) providing a stream B comprising hydrofluoric acid heated to a temperature T1 of from 100 ℃ to 170 ℃ and providing a stream C comprising 1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene; said stream B and said stream C supply said reactor via said at least one reactant supply line;

iii) reacting said stream B with said stream C in said liquid phase A to form a stream D comprising trans-1-chloro-3, 3, 3-trifluoropropene.

Preferably, step iii) is carried out at a temperature T2 of between 50 ℃ and 150 ℃, advantageously between 50 ℃ and 140 ℃, preferably between 50 ℃ and 130 ℃, more preferentially between 50 ℃ and 120 ℃, in particular between 50 ℃ and 110 ℃. More particularly, step iii) is carried out at a temperature T2 of between 60 ℃ and 105 ℃, preferably between 70 ℃ and 100 ℃, more preferentially between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃.

According to a preferred embodiment, the temperature difference in absolute value between the temperature T1 and the temperature T2 is greater than or equal to 30 ℃. The temperature difference in absolute value between the temperature T1 and the temperature T2 may be greater than or equal to 32 ℃, or greater than or equal to 34 ℃, or greater than or equal to 36 ℃, or greater than or equal to 38 ℃, or greater than or equal to 40 ℃, or greater than or equal to 42 ℃, or greater than or equal to 44 ℃, or greater than or equal to 46 ℃, or greater than or equal to 48 ℃, or greater than or equal to 50 ℃.

Preferably, the temperature difference in absolute value between the temperature T1 and the temperature T2 is between 30 ℃ and 80 ℃, advantageously between 33 ℃ and 75 ℃, preferably between 35 ℃ and 70 ℃, in particular between 35 ℃ and 65 ℃, more particularly between 35 ℃ and 60 ℃.

According to a preferred embodiment, the reactor further comprises heating means capable of heating the liquid phase a. The heating means may heat the side walls of the reactor or directly heat the liquid phase a. For example, the heating means may be a double jacket placed around the side wall of the reactor, a coil placed in the reactor and in contact with the liquid phase a, or a recirculation loop with a heat exchanger placed outside the reactor. The coils and jacket contain a heat transfer fluid such as steam, pressurized hot water, or oil. The heating means make it possible to fix the temperature T3.

Preferably, the temperature T3 is higher than the temperature T2. In addition, the temperature T3 is less than 120 ℃, advantageously less than 115 ℃, preferably less than 110 ℃, more preferably less than 105 ℃, in particular less than 100 ℃.

According to a preferred embodiment, the liquid phase a supplied in step i) is heated to a temperature T4 of between 50 ℃ and 150 ℃ before carrying out step iii). Preferably, the liquid phase a is heated to a temperature T4 of between 50 ℃ and 140 ℃, preferably between 50 ℃ and 130 ℃, more preferentially between 50 ℃ and 120 ℃, in particular between 50 ℃ and 110 ℃. More particularly, the liquid phase a is heated to a temperature T4 of between 60 ℃ and 105 ℃, preferably between 70 ℃ and 100 ℃, more preferentially between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃. In particular, the liquid phase a is heated to a temperature T4 equal to the temperature T2.

According to a preferred embodiment, the temperature T1 is between 120 ℃ and 170 ℃, advantageously between 125 ℃ and 165 ℃, preferably between 125 ℃ and 155 ℃.

According to a preferred embodiment, the temperature difference in absolute value between the temperature T3 and the temperature T2 is less than or equal to 30 ℃, in particular less than or equal to 25 ℃, more particularly less than or equal to 20 ℃.

Preferably, the temperature T1 is between 120 ℃ and 170 ℃, in particular between 125 ℃ and 165 ℃, more particularly between 125 ℃ and 155 ℃; the temperature T2 is between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃; the temperature T3 is greater than T2 and less than 120 ℃, advantageously less than 115 ℃, preferably less than 110 ℃, more preferentially less than 105 ℃, in particular less than 100 ℃; and the temperature T4 is between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃.

In particular, the temperature T1 is between 120 ℃ and 170 ℃, in particular between 125 ℃ and 165 ℃, more particularly between 125 ℃ and 155 ℃; the temperature T2 is between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃; the temperature T3 is greater than T2 and less than 120 ℃, advantageously less than 115 ℃, preferably less than 110 ℃, more preferentially less than 105 ℃, in particular less than 100 ℃; the temperature T4 is between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃; and the temperature difference in absolute value between the temperature T3 and the temperature T2 is less than or equal to 30 ℃, in particular less than or equal to 25 ℃, more in particular less than or equal to 20 ℃.

More particularly, the temperature T1 is between 120 ℃ and 170 ℃, in particular between 125 ℃ and 165 ℃, more particularly between 125 ℃ and 155 ℃; the temperature T2 is between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃; the temperature T3 is greater than T2 and less than 120 ℃, advantageously less than 115 ℃, preferably less than 110 ℃, more preferentially less than 105 ℃, in particular less than 100 ℃; the temperature T4 is between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃; a temperature difference in absolute value between the temperature T3 and the temperature T2 of less than or equal to 30 ℃, in particular less than or equal to 25 ℃, more in particular less than or equal to 20 ℃; and the temperature difference in absolute values between the temperature T1 and the temperature T2 is between 30 ℃ and 80 ℃, advantageously between 33 ℃ and 75 ℃, preferably between 35 ℃ and 70 ℃, in particular between 35 ℃ and 65 ℃, more particularly between 35 ℃ and 60 ℃.

Preferably, the temperature T1 is between 120 ℃ and 170 ℃, in particular between 125 ℃ and 165 ℃, more particularly between 125 ℃ and 155 ℃; the temperature T2 is between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃; the temperature T3 is greater than T2 and less than 120 ℃, advantageously less than 115 ℃, preferably less than 110 ℃, more preferentially less than 105 ℃, in particular less than 100 ℃; the temperature T4 is between 80 ℃ and 100 ℃, in particular between 85 ℃ and 95 ℃, more particularly between 88 ℃ and 92 ℃; a temperature difference in absolute value between the temperature T3 and the temperature T2 of less than or equal to 30 ℃, in particular less than or equal to 25 ℃, more in particular less than or equal to 20 ℃; the temperature difference in absolute values between the temperature T1 and the temperature T2 is between 30 ℃ and 80 ℃, advantageously between 33 ℃ and 75 ℃, preferably between 35 ℃ and 70 ℃, in particular between 35 ℃ and 65 ℃, more particularly between 35 ℃ and 60 ℃; and temperature T4 is equal to temperature T2.

According to a preferred embodiment, said stream D further comprises at least one by-product selected from the group consisting of: 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene, and cis-1-chloro-3, 3, 3-trifluoropropene. Preferably, in said stream D, the total molar content of 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene and cis-1-chloro-3, 3, 3-trifluoropropene is less than 5 mol%. In particular, in said stream D, the total molar content of 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene and cis-1-chloro-3, 3, 3-trifluoropropene is less than 4.9 mol%. More particularly, in said stream D, the total molar content of 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene and cis-1-chloro-3, 3, 3-trifluoropropene is less than 4.8 mol%. Preferably, in said stream D, the total molar content of 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene and cis-1-chloro-3, 3, 3-trifluoropropene is less than 4.7 mol%. Advantageously, in said stream D, the total molar content of 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene and cis-1-chloro-3, 3, 3-trifluoropropene is less than 4.6 mol%. Preferably, in said stream D, the total molar content of 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene and cis-1-chloro-3, 3, 3-trifluoropropene is less than 4.5 mol%. Particularly preferably, in said stream D, the total molar content of 1,1,1,3, 3-pentafluoropropane, cis/trans-1, 3,3, 3-tetrafluoropropene and cis-1-chloro-3, 3, 3-trifluoropropene is less than 4.4 mol%.

The molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is more than 95 mol%. Advantageously, the molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is greater than 95.1 mol%. Preferably, the molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is more than 95.2 mol%. More preferably, the molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is more than 95.3 mol%. In particular, the molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is preferably greater than 95.4 mol%. More particularly, the molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is greater than 95.5 mol%. Preferably, the molar content of trans-1-chloro-3, 3, 3-trifluoropropene in said stream D is more than 95.6 mol%. Said molar content being expressed on the basis of the organic compounds present in the stream under consideration. Stream D may also comprise HCl and HF. The molar contents mentioned above are the molar contents obtained at the outlet of the reactor, i.e. before purification.

Step i) is preferably carried out in the absence of a catalyst.

Step i) may alternatively be carried out in the presence of a catalyst. The catalyst may be TiCl₄Or SbCl₅A catalyst. The catalyst may also be an ionic liquid. Ionic liquids which may be suitable are lewis acid derivatives based on aluminium, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron. The term "ionic liquid" refers to a non-aqueous salt (salt) that is the ionic nature of a liquid at moderate temperatures (preferably below 120 ℃). The ionic liquid is preferably produced by a reaction between an organic salt and an inorganic compound. The ionic liquid is preferably reacted with the general formula Y via at least one halogen or oxyhalogen Lewis acid based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron⁺A^-Reaction of a salt, wherein A^-Denotes a halide anion (bromide, iodide, and preferably chloride or fluoride) or hexafluoroantimonate (SbF)₆ ^-) And Y⁺Is represented by quaternary ammonium, quaternary phosphoniumOr a tertiary sulfonium cation. The aluminum, titanium, niobium, tantalum, antimony, nickel, zinc or iron based halogen lewis acids may be chlorine, bromine, fluorine or mixed derivatives, such as chlorofluoroic acid. Mention may more particularly be made of chlorides, fluorides or chlorofluorides having the formula:

TiCl_xF_ywherein x + y is 4 and 0. < = x.< =4

TaCl_xF_yWherein x + y is 5 and 0. < = x.< =5

NbCl_xF_yWherein x + y is 5 and 0. < = x.< =5

SnCl_xF_yWherein x + y is 4 and 1£x£4

SbCl_xF_yWherein x + y is 5 and 0. < = x.< =5

AlCl_xF_yWherein x + y is 3 and 0. < = x.< =3

NiCl_xF_yWherein x + y is 2 and 0. < = x.< =2

FeCl_xF_yWherein x + y is 3 and 0. < = x.< =3

As examples of such compounds, the following compounds may be mentioned: TiCl (titanium dioxide)₄、TiF₄、TaCl₅、TaF₅、NbCl₅、NbF₅、SbCl₅、SbCl₄F、SbCl₃F₂、SbCl₂F₃、SbClF₄、SbF₅And mixtures thereof. The following compounds are preferably used: TiCl (titanium dioxide)₄、TaCl₅+TaF₅、NbCl₅+NbF₅、SbCl₅、SbFCl₄、SbF₂Cl₃、SbF₃Cl₂、SbF₄Cl、SbF₅And SbCl₅+SbF₅. Antimony-based compounds are more particularly preferred. As examples of oxyhalogen Lewis acids which can be used according to the invention, mention may be made of TiOCl₂、TiOF₂And SbOCl_xF_y(x + y ═ 3). In salt Y⁺A^-In (b) cation Y⁺May correspond to one of the following general formulae: r¹R²R³R⁴N⁺、R¹R²R³R⁴P⁺、R¹R²R³S⁺Wherein the symbol R¹To R⁴Identical or different, each represents a saturated or unsaturated, cyclic or acyclic, or aromatic hydrocarbon, chlorocarbon, fluorohydrocarbon, chlorofluorocarbon or fluorohydrocarbon group having from 1 to 10 carbon atoms, in which one or more of these groups may also contain one or more heteroatoms such as N, P, S or O. Ammonium, ammonium,Or sulfonium cation Y⁺May also form part of a saturated or unsaturated, or aromatic, heterocyclic ring having 1 to 3 nitrogen, phosphorus or sulfur atoms, and may correspond to one or the other of the following general formulaeThe method comprises the following steps:

wherein R is¹And R²As previously defined. Wherein the formula comprises two or three ammonium groups,Or salts of sulfonium sites may also be suitably employed. As salt Y⁺A^-As examples of (A) there may be mentioned tetraalkylammonium chlorides and fluorides, tetraalkylammonium chlorides and fluoridesChlorides and fluorides, and trialkylsulfonium chlorides and fluorides, alkylpyridinesChlorides and fluorides, dialkylimidazolesChlorides, fluorides and bromides, and trialkylimidazolesChlorides and fluorides. Trimethylsulfonium fluoride or chloride, N-ethylpyridineChlorides or fluorides, N-butylpyridinesChloride or fluoride, 1-ethyl-3-methylimidazoleChloride or fluoride, and 1-butyl-3-methylimidazoleChlorides or fluorides being more particularly mentionedHeavy. The ionic liquid may be prepared in a manner known per se by reacting a halogen or haloxylewis acid with an organic salt Y⁺A^-Are prepared by appropriate mixing. Reference is made in particular to the process described in document WO 01/81353. The catalyst may alternatively be trifluoromethanesulfonic acid or trifluoroacetic acid as set out in US 6166274.

Step iii) is preferably carried out at a pressure of 5-20 bar absolute (bara), preferably at a pressure of 10-18 bar absolute, more particularly 12-18 bar absolute.

Preferably, the HF/[1,1,3, 3-tetrachloropropene and/or 1,3,3, 3-tetrachloropropene ] molar ratio at the reactor inlet is between 5 and 10, more preferably between 5 and 7, in particular between 5 and 6.

The process preferably further comprises the steps of: (iv) at least one step of treating stream D to obtain a stream E comprising E-1-chloro-3, 3, 3-trifluoropropene, HCl, HF and Z-1-chloro-3, 3, 3-trifluoropropene, and a stream F comprising essentially HF (for example at least 50 wt%, preferably at least 70 wt% HF); (v) at least one step of recovering the hydrochloric acid in stream E to obtain stream G of HCl and stream H comprising E-1-chloro-3, 3, 3-trifluoropropene, HCl, HF, and Z-1-chloro-3, 3, 3-trifluoropropene; (vi) at least one step of purifying the stream H obtained from step (v) to obtain E-1233zd preferably having a purity not less than 98% by weight, advantageously not less than 99% by weight, and very advantageously not less than 99.9% by weight.

Prior to the purification step, the stream H obtained in step (v) is preferably subjected to at least one separation step to obtain: a stream comprising predominantly HF (e.g., at least 90 wt.%, preferably at least 98 wt.%, and advantageously at least 99 wt.% HF), which can be recycled to the reactor; and streams comprising E-1-chloro-3, 3, 3-trifluoropropene, HCl, HF, and Z-1-chloro-3, 3, 3-trifluoropropene. This separation step is preferably a decantation, carried out at a temperature advantageously comprised between-50 and 50 ℃, preferably between-20 ℃ and 10 ℃.

The treatment step (iv) is preferably a reflux column, advantageously carried out at a temperature between 30 and 120 ℃ to obtain the stream F, which is recycled to the reactor.

The recovery of HCl in step (v) is preferably obtained by a distillation column equipped with a bottom reboiler and a top reflux system. The temperature at the bottom is advantageously between 20 and 110 ℃. The temperature at the top is advantageously between-50 and 0 ℃. The distillation of HCl is typically carried out at a pressure between 7 and 25 bar.

According to one embodiment, the purification step (vi) preferably comprises at least one distillation step and advantageously at least two distillation steps. According to a preferred embodiment, the purification step (vi) comprises at least one step of washing with water and/or by means of an alkaline solution, a drying step, and at least one distillation step. The purpose of this distillation step is to remove light products as well as heavy products, which can be partly recycled to the reactor, depending on whether they are recyclable or not.

The process is preferably carried out continuously.

Examples

The apparatus used consisted of a liquid phase reactor with a capacity of 60 liters, jacketed, made of 316L stainless steel. With means for measuring temperature, pressure, and liquid level. The reactants may be supplied via a dip tube, while the product stream (circulation) formed is passed through a 5 m reflux column before being condensed at the top of the column. The column is packed with structured metal packing, which allows the low boiling products to be separated, while the raw materials, intermediate compounds and unreacted HF fall back into the reactor. A pressure regulating valve applies an operating pressure to the assembly. An on-line take-off system allows sampling of the outgoing gas stream, which is directed to the gas chromatograph. The reactants are supplied continuously and the products are analyzed and collected continuously.

Example 1 (according to the invention)

An amount of 25 liters of liquid phase a comprising 1,1,3, 3-tetrachloropropene was introduced into the reactor. The HF supply was preheated using a jacket supplied with superheated steam. The temperature T1 was 130 ℃. The liquid phase a was preheated to 90 ℃, i.e. to a temperature T4 of 90 ℃, using electrical tracing (electrical tracing). The reactor jacket was then supplied with hot water using a boiler. The temperature T3 of the wall was 95 ℃. The reaction temperature T2 (the temperature of the liquid phase during the fluorination reaction in this case) was 90 ℃. The pressure regulation is adjusted to 15 bar absolute. The molar ratio between HF and 1,1,3, 3-tetrachloropropene was 6. The gas stream composition results are given in table 1.

Example 2 (according to the invention)

The procedure of example 1 was reproduced, wherein the temperature of the HF entering the reactor was 123 ℃ (T1). The temperature T3 was 97 ℃. The temperature T2 and the temperature T4 were 90 ℃. The reactor was heated in the same manner as before. The molar ratio between HF and 1,1,3, 3-tetrachloropropene was 6. The gas stream composition results are given in table 1.

Example 3 (comparative)

The procedure of example 1 was reproduced, wherein the temperature of the HF entering the reactor was 117 ℃ (T1). The temperature T3 was 100 ℃. The temperature T2 and the temperature T4 were 90 ℃. The reactor was heated in the same manner as before. The molar ratio between HF and 1,1,3, 3-tetrachloropropene was 6. The gas stream composition results are given in table 1.

TABLE 1

	F1233zd-E (mol%)	F1233zdZ + F1234ze +245fa (mol%)
			Example 1 (invention)	95.4	4.31
Example 2 (invention)	95.4	4.33
			Example 3 (comparative)	94.4	5.10

The values mentioned represent the molar contents of the components mentioned in the gas stream obtained at the outlet of the reactor, expressed on the basis of the organic compounds present in the reactor, i.e. without taking into account the HCl content and the HF content of this stream.

The results detailed in table 1 show that the process according to the invention produces fewer reaction by-products and per-fluorinated products. The heating of the hydrofluoric acid combined with the temperature control of the reactor wall allows for a more efficient process for the production of trans-1-chloro-3, 3, 3-trifluoropropene.