CN107954826B - Refining method of trans-1-chloro-3, 3, 3-trifluoropropene - Google Patents
Refining method of trans-1-chloro-3, 3, 3-trifluoropropene Download PDFInfo
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Abstract
The invention provides a refining method of trans-1-chloro-3, 3, 3-trifluoropropene. The method uses hydrocarbon compounds as an extracting agent, and removes the impurity cis-1, 3,3, 3-tetrafluoropropene in a trans-1-chloro-3, 3, 3-trifluoropropene crude product by extractive distillation. The invention provides a continuous and efficient refining method of trans-1-chloro-3, 3, 3-trifluoropropene.
Description
Technical Field
The invention relates to a refining method of trans-1-chloro-3, 3, 3-trifluoropropene, in particular to a method for removing impurities cis-1, 3,3, 3-tetrafluoropropene in a trans-1-chloro-3, 3, 3-trifluoropropene crude product by extractive distillation.
Background
The trans-1-chloro-3, 3, 3-trifluoropropene (E-HCFO-1233zd) has Ozone Depletion Potential (ODP) close to 0 and greenhouse effect potential (GWP) of 7.0, is excellent in environmental protection performance, is considered as a fourth generation fluorocarbon foaming agent by the international society, and has good development prospect. In addition, E-HCFO-1233zd is also widely used as a solvent, a propellant, a fire extinguishing agent, and a dry etching agent.
In the 1,1,1,3, 3-pentachloropropane route, in the presence or absence of a catalyst, E-HCFO-1233zd is prepared through a fluorination reaction, and a series of intermediate fluorides and byproducts are generated, wherein the boiling points of E-HCFO-1233zd (19 ℃) and Z-HFO-1234ze (9 ℃) are close, an azeotrope or an approximate azeotrope is easily formed, the separation of the two is difficult to realize by the conventional rectification technology, and in addition, the two are both olefins and cannot be removed by using a chlorination reaction mode.
Chinese patent CN1320109A adopts X-type zeolite adsorbent, and adsorbs and removes various impurities in the E-HCFO-1233zd crude product under pressure at 0-3 ℃, such as trans-1, 3,3, 3-tetrafluoropropene (E-HFO-1234ze), 1,3,3, 3-pentafluoropropane (HFC-245fa), Z-HFO-1234ze and the like. When the method is used for batch treatment of impurities in the crude product, the crude product needs to be kept stand for a long time (24 hours) at low temperature (-20 ℃); when the impurities are continuously treated, the content of the impurity Z-HFO-1234ze is increased to more than 0.1 percent only after 89 min. To obtain a good adsorption effect, the adsorbent must be regenerated. Therefore, this method has problems such as long treatment period, non-continuity, and low efficiency.
Disclosure of Invention
The invention aims to overcome the defects in the background technology and provide a continuous and efficient refining method of trans-1-chloro-3, 3, 3-trifluoropropene.
In order to realize the purpose of the invention, the invention uses hydrocarbon compounds as an extracting agent to remove the impurity cis-1, 3,3, 3-tetrafluoropropene in the crude trans-1-chloro-3, 3, 3-trifluoropropene product by extractive distillation. The extractant selected in the invention is specifically selected from n-hexane, cyclohexane, n-heptane, n-pentane, toluene, xylene, styrene or dicyclopentadiene.
The principle of extractive distillation is to separate Z-HFO-1234ze from E-HCFO-1233zd by adding said extractant to significantly change the relative volatility of the two. The relative volatility (. alpha.) of Z-HFO-1234ze to E-HCFO-1233zd is defined herein as follows:
in order to obtain the relative volatility alpha of Z-HFO-1234ze and E-HCFO-1233zd after the extractant is added, the invention adopts a 300ml reaction kettle experiment measurement with a gas phase and liquid phase sampling valve, and the specific steps are as follows: the reaction vessel was charged with 160g of extractant and a 20g Z-HFO-1234ze/E-HCFO-1233zd mixture (where the E-HCFO-1233zd content was 98.0 wt%); immersing the reaction kettle in a constant-temperature oil bath at 55 ℃, stirring the materials by magnetic force to fully mix the materials, taking a gas phase sample and a liquid phase sample when the materials in the reaction kettle reach gas-liquid phase balance, and analyzing and determining the composition content of each phase by gas chromatography. The relative volatility alpha value is calculated according to the relative volatility definition formula, and the related experiment results are shown in table 1.
TABLE 1 alpha values after addition of extractant
As can be seen from Table 1, the relative volatility of Z-HFO-1234ze with respect to E-HCFO-1233zd was changed by adding an extractant which is either a non-polar or a weakly polar solvent, and alpha was changed from 1.25 without the extractant to significantly more than 1, so that Z-HFO-1234ze was more volatile, i.e. the impurity Z-HFO-1234ze could be separated from the top of the column by extractive distillation.
As can be seen from Table 1, the preferred extractant is a hydrocarbon compound, and the particularly preferred extractant is n-heptane. In addition, the extractant may be used alone, or two or more of them may be used in combination.
When the extraction agent of the present invention is used for extractive distillation and purification of E-HCFO-1233zd, it can be carried out by using a conventional distillation column, such as a plate column, a sieve plate column or a packed column. The design parameters and operating conditions of the rectifying tower are changed along with the selection of the extracting agent and the change of the raw material composition, and the design parameters and the operating conditions can be properly selected for achieving the separation purpose. When the extractant is used for extraction and rectification, two towers of an extraction lightness-removing tower and an extraction and rectification tower can be adopted for operation:
(1) feeding the E-HCFO-1233zd crude product from the middle part of the extraction and lightness-removing tower, feeding an extracting agent from the upper part of the extraction and lightness-removing tower, extracting the E-HCFO-1233zd to the bottom of the extraction and lightness-removing tower by using the extracting agent to form E-HCFO-1233 zd-enriched extract liquid as bottom fraction, feeding the E-HCFO-1233zd enriched extract liquid into an extraction and rectification tower, and obtaining Z-HFO-1234ze fraction at the top of the extraction and recovery tower; (2) the extraction rectifying tower separates the E-HCFO-1233zd from the extractant, the E-HCFO-1233zd product is obtained at the tower top, the extractant is obtained at the tower bottom, and the extractant is circulated to the extraction lightness-removing tower.
The invention removes the impurity cis-1, 3,3, 3-tetrafluoropropene in the trans-1-chloro-3, 3, 3-trifluoropropene crude product by extractive distillation, wherein the extractant is a hydrocarbon compound, and comprises the following steps:
(1) feeding a raw material trans-1-chloro-3, 3, 3-trifluoropropene crude product from the middle part of an extraction and lightness-removing tower, feeding an extracting agent from the upper part of the extraction and lightness-removing tower, wherein the mass ratio of the extracting agent to the raw material is 3-20: 1, the tower top fraction is cis-1, 3,3, 3-tetrafluoropropene, the tower bottom fraction is trans-1-chloro-3, 3, 3-trifluoropropene and the extracting agent, and the raw material enters an extraction and rectification tower; the tower operating conditions were: the operation pressure of the tower is 100-300 kPa, the temperature of the top of the tower is 9.3-41.2 ℃, the temperature of the bottom of the tower is 40.2-158 ℃, and the reflux ratio is 0.5-5;
(2) the material at the bottom of the extraction and lightness-removing tower enters an extraction and rectification tower, the tower top fraction is a trans-1-chloro-3, 3, 3-trifluoropropene product, and the tower bottom fraction is an extractant, and the material is recycled in the extraction and lightness-removing tower; the operation pressure of the tower is 50-200 kPa, the temperature of the top of the tower is 1.0-37.7 ℃, the temperature of the bottom of the tower is 98.0-145.0 ℃, and the reflux ratio is 4.5-20. The extractant is n-hexane, cyclohexane, n-heptane, n-pentane, toluene, xylene, styrene or dicyclopentadiene, and particularly preferred is n-heptane.
A preferred E-HCFO-1233zd refining method using n-heptane as extractant includes the following steps:
(1) taking a crude product of E-HCFO-1233zd as a raw material, wherein the content of E-HCFO-1233zd is 98.0-99.0 wt%, the content of Z-HFO-1234ze is 0.1-2.0 wt%, taking n-heptane as an extracting agent, feeding the extracting agent from the upper part of an extraction and lightness-removing tower, feeding the raw material from the middle part of the extraction and lightness-removing tower, the mass ratio of the extracting agent to the raw material is 5: 1-10: 1, dividing the top fraction of the extraction and lightness-removing tower into Z-HFO-1234ze, and allowing the fraction in the bottom of the tower to be E-HCFO-1233zd and the extracting agent to enter an extraction and rectification tower; the extraction conditions of the extraction lightness-removing column are as follows: the operation pressure of the tower is 100-200 kPa, the temperature of the top of the tower is 9.3-28.4 ℃, the temperature of the bottom of the tower is 40.2-63.1 ℃, and the reflux ratio is 0.5-5;
(2) the top fraction of the extraction and rectification tower is E-HCFO-1233zd, the bottom fraction of the tower is an extractant, and the extractant is circulated to the extraction and lightness-removing tower; the operating conditions of the extractive distillation column are as follows: the operation pressure of the tower is 100-200 kPa, the temperature of the top of the tower is 17.9-37.7 ℃, the temperature of the bottom of the tower is 98.0-123.3 ℃, and the reflux ratio is 4.5-20.
The raw material trans-1-chloro-3, 3, 3-trifluoropropene crude product is a trans-1-chloro-3, 3, 3-trifluoropropene crude product which is obtained by carrying out chemical reaction on 1,1,1,3, 3-pentachloropropane and hydrogen fluoride serving as raw materials and carrying out pretreatment on the raw materials. The invention has the advantages that: E-HCFO-1233zd and Z-HFO-1234ze are effectively separated by the screened special extracting agent and the refining process of the extraction lightness-removing column and the extraction rectifying column, so that the E-HCFO-1233zd with the purity of 99.9 percent can be continuously and efficiently refined.
Drawings
FIG. 1 is a flow chart of a purification process of trans-1-chloro-3, 3, 3-trifluoropropene.
The reference numerals in fig. 1 have the following meanings: t1-extractive lightness-removing column; t2-extractive distillation column; 1-trans-1-chloro-3, 3, 3-trifluoropropene crude product; 2-T1 overhead; 3-T1 column bottoms; 4-T2 overhead; 5-T2 column bottoms.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The extraction lightness-removing column T1 and the extraction rectification column T2 are both packed columns, the diameter of the column is phi 25mm, phi 3 multiplied by 3 theta ring stainless steel packing is filled in the column, and the height of a packing layer is 4 m. The rectification material 1 is a crude product of E-HCFO-1233zd, wherein the content of E-HCFO-1233zd is 99.0 wt%, and the content of Z-HFO-1234ze is 1.0 wt%. Feeding a material 1 from the middle part of an extraction and light-ends removal tower T1 at a flow rate of 100g/h, feeding a T2 tower bottom distillate 5 (namely a circulating extractant, n-heptane) from the upper part of a T1 tower at a flow rate of 500g/h, feeding a T1 tower top distillate 2 of Z-HFO-1234ze, and feeding a T1 tower bottom distillate 3 of E-HCFO-1233zd and the extractant into an extraction and rectification tower T2. The overhead 4 from T2 was E-HCFO-1233zd and the bottoms 5 from T2 was extractant returned to T1, the column operating conditions are shown in Table 2. The purity of E-HCFO-1233zd from T2 overhead 4 was 99.9% as determined by gas chromatography, i.e., the purity of E-HCFO-1233zd was increased from 99.0% to 99.9% by extractive distillation.
Table 2 column operating conditions in example 1
| Rectifying tower | T1 | T2 |
| Operating pressure/kPa (A) | 100 | 200 |
| Overhead temperature/. degree.C | 9.3 | 37.7 |
| Column bottom temperature/. degree.C | 40.2 | 123.3 |
| Reflux ratio | 0.5 | 4.5 |
Example 2
Example 2 was operated similarly to example 1 except that the operating parameters of the rectification columns T1 and T2 were different and are shown in Table 3. The E-HCFO-1233zd purity of T2 overhead 4 was 99.9% as determined by gas chromatography.
Table 3 column operating conditions in example 2
| Rectifying tower | T1 | T2 |
| Operating pressure/kPa (A) | 200 | 100 |
| Overhead temperature/. degree.C | 28.4 | 17.9 |
| Column bottom temperature/. degree.C | 63.1 | 98.0 |
| |
5 | 20 |
Example 3
Example 3 was conducted in a similar manner to example 1 except that the composition of feed 1 was changed to E-HCFO-1233zd98.0 wt% and Z-HFO-1234ze 2.0 wt%, the extractant flow rate was adjusted to 1000g/h, the operating parameters are shown in Table 4, and the E-HCFO-1233zd purity of T2 overhead 4 as determined by gas chromatography was 99.9%.
Table 4 column operating conditions in example 3
| Rectifying tower | T1 | T2 |
| Operating pressure/kPa (A) | 200 | 100 |
| Overhead temperature/. degree.C | 28.4 | 17.9 |
| Column bottom temperature/. degree.C | 63.1 | 98.0 |
| |
5 | 20 |
Example 4
Example 4 was conducted in a similar manner to example 1 except that the composition of feed 1 was changed to E-HCFO-1233zd99.5 wt% and Z-HFO-1234ze 0.5 wt%, the operating parameters are shown in Table 5, and the purity of E-HCFO-1233zd at T2 overhead 4 was 99.9% as determined by gas chromatography.
Table 5 column operating conditions in example 4
| Rectifying tower | T1 | T2 |
| Operating pressure/kPa (A) | 200 | 100 |
| Overhead temperature/. degree.C | 28.4 | 17.9 |
| Column bottom temperature/. degree.C | 63.1 | 98.0 |
| |
1 | 10 |
Example 5
The procedure of example 5 was similar to that of example 1 except that the extractant was changed to xylene, the extractant flow rate was adjusted to 300g/h, the operating parameters of the rectification columns T1 and T2 were different as shown in Table 6, and the purity of E-HCFO-1233zd at the overhead 4 of T2 as measured by gas chromatography was 99.9%.
Table 6 column operating conditions in example 5
| Rectifying tower | T1 | T2 |
| Operating pressure/kPa (A) | 300 | 50 |
| Overhead temperature/. degree.C | 41.2 | 1.0 |
| Column bottom temperature/. degree.C | 158 | 114.5 |
| |
1 | 10 |
Example 6
Example 6 was conducted in a similar manner to example 1 except that the extractant was changed to styrene, the extractant flow rate was adjusted to 2000g/h, the operating parameters are shown in Table 7, and the purity of E-HCFO-1233zd at T2 overhead 4 was 99.9% as determined by gas chromatography.
Table 7 column operating conditions in example 6
| Rectifying tower | T1 | T2 |
| Operating pressure/kPa (A) | 200 | 100 |
| Overhead temperature/. degree.C | 28.4 | 17.9 |
| Column bottom temperature/. degree.C | 149 | 145 |
| |
1 | 10 |
Claims (2)
1. A refining method of trans-1-chloro-3, 3, 3-trifluoropropene is characterized in that cis-1, 3,3, 3-tetrafluoropropene which is an impurity in a crude product of the trans-1-chloro-3, 3, 3-trifluoropropene is removed by extractive distillation, wherein an extracting agent is a hydrocarbon compound, and the refining method comprises the following steps:
(1) feeding a raw material trans-1-chloro-3, 3, 3-trifluoropropene crude product from the middle part of an extraction and lightness-removing tower, feeding an extracting agent from the upper part of the extraction and lightness-removing tower, wherein the mass ratio of the extracting agent to the raw material is 3-20: 1, the tower top fraction is cis-1, 3,3, 3-tetrafluoropropene, the tower bottom fraction is trans-1-chloro-3, 3, 3-trifluoropropene and the extracting agent, and the raw material enters an extraction and rectification tower; the tower operating conditions were: the operation pressure of the tower is 100-300 kPa, the temperature of the top of the tower is 9.3-41.2 ℃, the temperature of the bottom of the tower is 40.2-158 ℃, and the reflux ratio is 0.5-5;
(2) the material at the bottom of the extraction and lightness-removing tower enters an extraction and rectification tower, the tower top fraction is a trans-1-chloro-3, 3, 3-trifluoropropene product, and the tower bottom fraction is an extractant, and the material is recycled in the extraction and lightness-removing tower; the operation pressure of the tower is 50-200 kPa, the temperature of the top of the tower is 1.0-37.7 ℃, the temperature of the bottom of the tower is 98.0-145.0 ℃, and the reflux ratio is 4.5-20;
the extracting agent is n-hexane, cyclohexane, n-heptane, n-pentane, toluene, xylene, styrene or dicyclopentadiene.
2. The method for purifying trans-1-chloro-3, 3, 3-trifluoropropene according to claim 1, comprising the steps of:
(1) taking a trans-1-chloro-3, 3, 3-trifluoropropene crude product as a raw material, taking n-heptane as an extracting agent, feeding the extracting agent from the upper part of an extraction and lightness-removing tower, feeding the raw material from the middle part of the extraction and lightness-removing tower, wherein the mass ratio of the extracting agent to the raw material is 5-10: 1, the top fraction of the extraction and lightness-removing tower is cis-1, 3,3, 3-tetrafluoropropene, the bottom fraction of the extraction and lightness-removing tower is trans-1-chloro-3, 3, 3-trifluoropropene and the extracting agent, and the raw material enters an extraction and rectification tower; the operating conditions of the extraction lightness-removing tower are as follows: the operation pressure of the tower is 100-200 kPa, the temperature of the top of the tower is 9.3-28.4 ℃, the temperature of the bottom of the tower is 40.2-63.1 ℃, and the reflux ratio is 0.5-5;
(2) the top fraction of the extraction and rectification tower is E-HCFO-1233zd, the bottom fraction of the tower is an extractant, and the extractant is circulated to the extraction and lightness-removing tower; the operating conditions of the extractive distillation column are as follows: the operation pressure of the tower is 100-200 kPa, the temperature of the top of the tower is 17.9-37.7 ℃, the temperature of the bottom of the tower is 98.0-123.3 ℃, and the reflux ratio is 4.5-20;
the raw material trans-1-chloro-3, 3, 3-trifluoropropene crude product is obtained by taking 1,1,1,3, 3-pentachloropropane and hydrogen fluoride as raw materials, carrying out chemical reaction and carrying out pretreatment.
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Citations (4)
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|---|---|---|---|---|
| US6120652A (en) * | 1997-03-11 | 2000-09-19 | Central Glass Company | Method for purifying crude 1,1,1,3,3-pentafluoropropane |
| CN101768046A (en) * | 2008-12-30 | 2010-07-07 | 浙江蓝天环保高科技股份有限公司 | HFC-245fa refining method |
| CN102307831A (en) * | 2009-02-03 | 2012-01-04 | 中央硝子株式会社 | Method of purifying (Z)-1-chloro-3,3,3-trifluoropropene |
| CN102844285A (en) * | 2010-02-18 | 2012-12-26 | 霍尼韦尔国际公司 | Integrated process and methods of producing (e)-1-chloro-3,3,3-trifluoropropene |
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- 2017-12-01 CN CN201711247649.3A patent/CN107954826B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6120652A (en) * | 1997-03-11 | 2000-09-19 | Central Glass Company | Method for purifying crude 1,1,1,3,3-pentafluoropropane |
| CN101768046A (en) * | 2008-12-30 | 2010-07-07 | 浙江蓝天环保高科技股份有限公司 | HFC-245fa refining method |
| CN102307831A (en) * | 2009-02-03 | 2012-01-04 | 中央硝子株式会社 | Method of purifying (Z)-1-chloro-3,3,3-trifluoropropene |
| CN102844285A (en) * | 2010-02-18 | 2012-12-26 | 霍尼韦尔国际公司 | Integrated process and methods of producing (e)-1-chloro-3,3,3-trifluoropropene |
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