CN106905107B - Purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane - Google Patents
Purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane Download PDFInfo
- Publication number
- CN106905107B CN106905107B CN201710101793.XA CN201710101793A CN106905107B CN 106905107 B CN106905107 B CN 106905107B CN 201710101793 A CN201710101793 A CN 201710101793A CN 106905107 B CN106905107 B CN 106905107B
- Authority
- CN
- China
- Prior art keywords
- tetrafluoroethane
- dibromo
- xylene
- tower
- mass ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
- C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane, belonging to the field of chemical synthesis. The method for purifying the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane comprises the steps of extracting and rectifying 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane impurities in materials, wherein the extracting agent is benzene or a mixture of xylene and a nonpolar solvent with a boiling point higher than 80 ℃, the mass ratio of the benzene, the m-xylene or the o-xylene to the nonpolar solvent is 5: 1-1: 1.5, and the mass ratio of the extracting agent to the materials is 1: 10-30. The content of 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane in the product after extraction, rectification and purification by adopting a specially selected mixed extracting agent is less than 0.10 percent, the residue of the extracting agent is less than 50ppm, and the product of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane meets the practical requirement.
Description
Technical Field
The invention relates to a purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane, in particular to a method for purifying 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane from a mixture of the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane and the 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane, and belongs to the technical field of purification of chemical products.
Background
The 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane is colorless, transparent and high-density liquid at normal temperature, is low in boiling point, non-combustible, insoluble in water, soluble in alcohols, oils and the like, has the characteristics of large specific impulse, large lateral force, high density, volatility and the like, can be used for meteorological balloons, low-temperature refrigerators, vacuum leak detectors and the like, and can be used for fire extinguishing agents, refrigerants, good rocket boosting agents, high-temperature gas lubricants and the like. The 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane has an obvious molecular weight regulating effect on the polymerization reaction of the liquid fluoroelastomer and is a good medical intermediate. The 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane has a high purity so as to meet the application requirements. However, in several current methods for producing 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane, by-products such as 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane and monobromo tetrafluoroethane are contained to various degrees depending on the synthetic route. These by-products, except for 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane, can be easily separated from 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane by ordinary fractionation techniques. Only 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane has a boiling point close to that of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane (the boiling point of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane is 46 to 47 ℃ and the boiling point of 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane is 47.1 ℃) and the relative separation degree of these two compounds is close to 1, and it is impossible to completely separate them by a common fractionation technique and purify 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane. Therefore, 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane in the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane product can only be removed by chemical means or by means of special rectification.
There are many methods for special rectification, however, an effective means for solving the problem is to adopt extractive rectification, i.e. adding a third component into the separated binary mixed solution, the third component does not form an azeotrope with other components, but has a different molecular force from the two components A and B in the original solution, so as to increase the relative volatility of the components A and B, and the components A and B are separated, wherein the added third component is called an extracting agent and is discharged from the bottom of the tower during rectification.
The choice of the extractant is most important in extractive rectification, i.e. the 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane in the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane product is separated off in the presence of a suitable extractant to obtain high purity 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane. However, until now, there has been no report on extractive distillation separation for reducing the content of 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane to obtain high-purity 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane.
Disclosure of Invention
The invention aims to solve the problem of purifying 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane, and adopts the means of extraction and rectification, wherein the extractant is low in price, easy to obtain and residual in a weighing way.
The structural formulas of the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane and the 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane are shown as a formula I and a formula II:
the method for purifying the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane is an extractive distillation method, wherein the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane material contains the 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane, an extracting agent is a mixture of benzene or xylene and a nonpolar solvent with a boiling point higher than 80 ℃, the mass ratio of the benzene or xylene to the nonpolar solvent is 5: 1-1: 1.5, and the mass ratio of the extracting agent to the material is 1: 5-30.
The nonpolar solvent with the boiling point higher than 80 ℃ is carbon tetrachloride or dioxane.
The xylene is meta-xylene or ortho-xylene.
The mass ratio of the benzene, the m-xylene or the o-xylene to the nonpolar solvent is 5: 1-3: 1.
The mass ratio of the extracting agent to the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane material is 1:8-20, and the extraction and rectification pressure is 0.01-0.2 MPa.
The mass ratio of the extracting agent to the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane material is 1:8-15, the extraction and rectification pressure is 0.03-0.1 MPa, and the tower kettle of the rectification tower is controlled at 80-120 ℃.
The content of the 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane is less than 5 percent.
The method adopts a specially selected mixed extracting agent, the purity of the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane at the tower top is more than 99.9 percent, and the residue of the extracting agent is less than 50 ppm.
The mixture of benzene, m-xylene or o-xylene and dioxane or carbon tetrachloride with good extraction effect is used as an extractant, so that high-purity 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane can be obtained, and the residual amount of the extractant in 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane products can be effectively reduced.
The extractant chosen should meet the following requirements: the relative volatility of the original components can be obviously increased by adding a small amount of the extracting agent; can be mutually dissolved with the original solution with any concentration to avoid layering, otherwise, the effect of extraction and rectification is difficult to be played; the boiling point of the extractant is much higher than that of other components of the mixed solution so as to ensure the purity of other components and is easy to separate from other components, but the boiling point is not too high, otherwise, the extractant is difficult to recover; good stability, no corrosion to equipment and easy acquisition.
The invention has no special requirement on the rectifying tower, and the typical rectifying tower is used. In industrial production, extractive distillation may be carried out batchwise or continuously, or, as the case may be, discontinuously, or discontinuously.
By adopting the method, the content of the 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane in the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane product after extraction, rectification and purification is less than 0.10 percent, the residue of the extracting agent is less than 50ppm, and the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane product meets the practical requirement.
Detailed description of the preferred embodiments
A purity detection instrument: gas chromatography
Example 1:
a SS304 stainless steel tower of DN25 is used as a rectifying tower, the length is 2m, and a theta ring stainless steel packing is filled.
1kg of a mixture of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane and 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane (the GC area ratio is 95/5) is added into a tower bottom of a 5L rectifying tower, then 100g of a mixture of benzene and dioxane (the mass ratio is 3/1) is added, the tower bottom of the rectifying tower is controlled at 90 ℃, the tower pressure is 0.05MPa, the conditions are maintained unchanged, the mixture is refluxed for 2 hours, extracted from the tower top, fractions are collected at 57 ℃, and the results are analyzed by gas chromatography and are shown in the table below.
Example 2:
a SS304 stainless steel tower of DN25 is used as a rectifying tower, the length is 2m, and a theta ring stainless steel packing is filled.
1kg of a mixture of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane and 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane (the GC area ratio is 95/5) is added into a tower bottom of a 5L rectifying tower, then 120g of a mixture of benzene and dioxane (the mass ratio is 3/1) is added, the tower bottom of the rectifying tower is controlled at 100 ℃, the tower pressure is 0.06MPa, the conditions are maintained unchanged, the mixture is refluxed for 2h, the mixture is extracted from the tower top, fractions are collected at 56.9 ℃, and the results are shown in the following table after gas chromatographic analysis.
Example 3:
a SS304 stainless steel tower of DN25 is used as a rectifying tower, the length is 2m, and a theta ring stainless steel packing is filled.
1kg of a mixture of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane and 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane (the GC area ratio is 95/5) is added into a tower bottom of a 5L rectifying tower, then 100g of a mixture of o-xylene and dioxane (the mass ratio is 4/1) is added, the tower bottom of the rectifying tower is controlled at 110 ℃, the tower pressure is 0.06MPa, the conditions are maintained unchanged, the mixture is refluxed for 2h, extracted from the tower top, fractions are collected at 57 ℃, and the results are shown in the following table after gas chromatographic analysis.
Example 4:
a SS304 stainless steel tower of DN25 is used as a rectifying tower, the length is 2m, and a theta ring stainless steel packing is filled.
1kg of a mixture of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane and 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane (the GC area ratio is 95/5) is added into a tower bottom of a 5L rectifying tower, then 100g of a mixture of benzene and carbon tetrachloride (the mass ratio is 3/1) is added, the tower bottom of the rectifying tower is controlled at 90 ℃, the tower pressure is 0.04MPa, the condition is maintained unchanged, the reflux is carried out for 2h, the tower top is extracted, fractions are collected at 57 ℃, and the results are analyzed by gas chromatography and are shown in the following table.
Example 5:
a SS304 stainless steel tower of DN25 is used as a rectifying tower, the length is 2m, and a theta ring stainless steel packing is filled.
1kg of a mixture of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane and 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane (the GC area ratio is 95/5) is added into a tower bottom of a 5L rectifying tower, then 120g of a mixture of m-xylene and carbon tetrachloride (the mass ratio is 4/1) is added, the tower bottom of the rectifying tower is controlled at 90 ℃, the tower pressure is 0.04MPa, the condition is maintained unchanged, the mixture is refluxed for 2h, the distillate is extracted from the tower top, and the distillate is collected at 57 ℃ and subjected to gas chromatography analysis, wherein the results are shown in the following table.
Example 6:
a SS304 stainless steel tower of DN25 is used as a rectifying tower, the length is 2m, and a theta ring stainless steel packing is filled.
1kg of a mixture of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane and 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane (the GC area ratio is 95/5) is added into a tower bottom of a 5L rectifying tower, then 80g of a mixture of m-xylene and dioxane (the mass ratio is 3/1) is added, the tower bottom of the rectifying tower is controlled at 90 ℃, the tower pressure is 0.05MPa, the conditions are maintained unchanged, the mixture is refluxed for 2 hours, extracted from the tower top, fractions are collected at 57 ℃, and the results of gas chromatographic analysis are shown in the table below.
Analysis results of different extractants on rectification
Claims (6)
- The method for purifying the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane is an extraction rectification method, wherein an extracting agent is a mixture of benzene or xylene and a nonpolar solvent with a boiling point higher than 80 ℃, the mass ratio of the benzene or xylene to the nonpolar solvent is 5: 1-1: 1.5, the mass ratio of the extracting agent to the material is 1:5-30, and the nonpolar solvent with the boiling point higher than 80 ℃ is carbon tetrachloride or dioxane.
- 2. The purification process according to claim 1, wherein the xylene is m-xylene or o-xylene.
- 3. The purification method according to claim 2, wherein the mass ratio of the benzene, m-xylene or o-xylene to the nonpolar solvent is 5:1 to 3: 1.
- 4. The purification method according to any one of claims 1 to 3, wherein the mass ratio of the extracting agent to the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane material is 1:8-20, and the extractive distillation pressure is 0.01-0.2 MPa.
- 5. The purification method according to claim 4, wherein the mass ratio of the extracting agent to the 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane mixed material is 1:8-15, the extractive distillation pressure is 0.03-0.1 MPa, and the tower bottom of the distillation tower is controlled at 80-120 ℃.
- 6. The purification method according to claim 1, wherein the content of 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane is 5% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710101793.XA CN106905107B (en) | 2017-02-24 | 2017-02-24 | Purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710101793.XA CN106905107B (en) | 2017-02-24 | 2017-02-24 | Purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106905107A CN106905107A (en) | 2017-06-30 |
| CN106905107B true CN106905107B (en) | 2020-02-18 |
Family
ID=59208651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710101793.XA Active CN106905107B (en) | 2017-02-24 | 2017-02-24 | Purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106905107B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4748284A (en) * | 1981-10-21 | 1988-05-31 | Montedison S.P.A. | Process for preparing 1,1-dihalo-1,2,2,2-tetrafluoroethanes |
| CN1143945A (en) * | 1994-03-11 | 1997-02-26 | 纳幕尔杜邦公司 | Separating and removing impurities from tetrafluoroethanes by using extractive distillation |
| US5922175A (en) * | 1997-02-04 | 1999-07-13 | Elf Atochem S.A. | Purification of chlorotetraflouroethane by extractive distillation |
| CN101134710A (en) * | 2006-08-29 | 2008-03-05 | 中昊晨光化工研究院 | Method for reclaiming octafluorocyclobutane from residual liquid of tetrafluoroethylene manufacturing process |
-
2017
- 2017-02-24 CN CN201710101793.XA patent/CN106905107B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4748284A (en) * | 1981-10-21 | 1988-05-31 | Montedison S.P.A. | Process for preparing 1,1-dihalo-1,2,2,2-tetrafluoroethanes |
| CN1143945A (en) * | 1994-03-11 | 1997-02-26 | 纳幕尔杜邦公司 | Separating and removing impurities from tetrafluoroethanes by using extractive distillation |
| US5922175A (en) * | 1997-02-04 | 1999-07-13 | Elf Atochem S.A. | Purification of chlorotetraflouroethane by extractive distillation |
| CN101134710A (en) * | 2006-08-29 | 2008-03-05 | 中昊晨光化工研究院 | Method for reclaiming octafluorocyclobutane from residual liquid of tetrafluoroethylene manufacturing process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106905107A (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7858813B2 (en) | Process for the rectification of mixtures of high-boiling air-and/or temperature-sensitive useful products | |
| US3847756A (en) | Recovery of diethyl ether from an olefin hydration product stream by extractive distillation with water | |
| CN106966866B (en) | Method for separating butanone-isopropanol-ethanol azeotrope through three-tower pressure swing distillation | |
| SU559641A3 (en) | The method of cleaning and drying monocarboxylic acids " | |
| CA2965476C (en) | Breaking a methanol/methyl methacrylate azeotrope using pressure swing distillation | |
| CN106905107B (en) | Purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane | |
| CN106478339B (en) | Method for separating cyclopentane and 2, 2-dimethylbutane | |
| JPS5625130A (en) | Purification of high melting point compound | |
| US4012289A (en) | N-Butane/acetone separation using sulfolane | |
| RU2673663C2 (en) | Method of separation of ethylbenzene | |
| CN106518618A (en) | Method for continuously extracting, rectificating and separating isopropanol-isopropyl ether azeotrope by mixed solvent | |
| CN108299161B (en) | Method for removing water in 2-methyl-3-butyne-2-alcohol and entrainer | |
| CN107954826B (en) | Refining method of trans-1-chloro-3, 3, 3-trifluoropropene | |
| CN106831338B (en) | Preparation method of high-purity difluoroethanol | |
| EP2637998B1 (en) | Process for refining crude acetyls mixture | |
| US3157693A (en) | Recovery of acrylic acid esters by water wahing and fractionation | |
| CN102311304A (en) | Complex solvent for separating out styrene through extractive distillation and application thereof | |
| CN104529697B (en) | A kind of method that reclaims high-purity octafluorocyclobutane from monochlorodifluoromethane cracking raffinate | |
| JP6941615B2 (en) | Method for removing or recovering 2-alkoxyethanol, and method for producing (2-alkoxyethyl) vinyl ether | |
| CN108864126B (en) | Method for continuously and hierarchically rectifying eucalyptus oil | |
| CN107954859B (en) | Method for separating acrylic acid/triisobutene azeotrope | |
| CN114315792A (en) | Method for enriching thianaphthene from mixture of thianaphthene and naphthalene by solvent crystallization coupled extraction rectification method | |
| CN106831340B (en) | Preparation method of high-purity trifluoroethanol | |
| CN103360219B (en) | A kind of synthetic method of high-purity propofol | |
| US3620030A (en) | Method of purifying vinyl fluoride contaminated with impurities by distillation in the presence of carbon dioxide or trifluoromethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210603 Address after: 362000 west side of 11 / F, youth building, 288 Tian'an North Road, Fengze District, Quanzhou City, Fujian Province Patentee after: Quanzhou Yuji New Material Technology Co.,Ltd. Address before: 100081 room 808, science and technology building, no.683, zone 2, No.5 Zhongguancun South Street, Haidian District, Beijing Patentee before: BEIJING YUJI SCIENCE AND TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |