CN106905107A - A kind of method of purification of the HFC-134a of 1,1 dibromo 1,2,2,2 - Google Patents
A kind of method of purification of the HFC-134a of 1,1 dibromo 1,2,2,2 Download PDFInfo
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- CN106905107A CN106905107A CN201710101793.XA CN201710101793A CN106905107A CN 106905107 A CN106905107 A CN 106905107A CN 201710101793 A CN201710101793 A CN 201710101793A CN 106905107 A CN106905107 A CN 106905107A
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- 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
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Abstract
The present invention relates to 1, the method for purification of the HFC-134a of 1 dibromo 1,2,2,2 ", belong to the field of chemical synthesis.1,1 dibromo 1,2,2, the method of purification of 2 HFC-134as, contains 1,2 dibromos 1 in its material, 1,2,2 HFC-134a impurity, the method is extraction fractional distillation, the mass ratio of non-polar solvent mixture of the extractant for benzene or dimethylbenzene and boiling point higher than 80 DEG C, the benzene, meta-xylene or ortho-xylene and non-polar solven is 5:1~1:1.5, extractant is 1 with the mass ratio of material:10‑30.The application uses special mixed extractant, and 0.10% is less than through the content of the HFC-134a of 1,2 dibromo 1,1,2,2 in extracting rectifying product after purification, and extractant residual is less than 50ppm, and the HFC-134a product of 1,1 dibromo 1,2,2,2 meets real requirement.
Description
Technical field
The present invention relates to 1,1- bis- bromo- 1, the method for purification of 2,2,2- HFC-134as, more particularly to from 1,1- bis- bromo- 1,2,
The bromo- 1,2,2,2- tetrafluoros second of 1,1- bis- is purified in the mixture of 2,2- HFC-134as and the bromo- 1,1,2,2- HFC-134as of 1,2- bis-
The method of alkane, belongs to chemical products purification technique field.
Background technology
1,1- bis- bromo- 1,2,2,2- HFC-134as are the highdensity liquid of water white transparency under normal temperature, and low boiling point is non-ignitable, no
It is dissolved in water and is dissolved in alcohols, oils etc. is big with specific impulse, side force is big and high density, the features such as volatile, can be used for meteorology
Aspects such as balloon and deep freeze refrigerator, vacuum leak detector, and can be used for extinguishing chemical, refrigerant and good rocket assist agent and
High-temperature gas lubricant etc..The bromo- 1,2,2,2- HFC-134as of 1,1- bis- have obvious for the polymerisation of liquid fluoroelastomer
Molecular-weight adjusting effect, and be good medicine intermediate.The bromo- 1,2,2,2- HFC-134as of 1,1- bis- with higher
Purity could meet above-mentioned application requirement.However, in current several 1,1- bis- bromo- 1,2,2,2- HFC-134a production methods
In, according to the difference of synthetic route, 1,2- bis- bromo- 1,1,2,2- HFC-134a, a teflurane are also contained to some extent
Deng accessory substance.These accessory substances remove 1,2- bis- bromo- 1, and outside 1,2,2- HFC-134a, other accessory substances are all easy to by common point
Technology is evaporated to be separated off it from the bromo- 1,2,2,2- HFC-134as of 1,1- bis- one by one.Have the bromo- 1,1,2,2- tetrafluoros of 1,2- bis- only
Ethane has the close boiling point (boiling point of the bromo- 1,2,2,2- HFC-134as of 1,1- bis- of 1,2,2,2- HFC-134as bromo- with 1,1- bis-
46-47 DEG C, 1,2- bis- bromo- 1,47.1 DEG C of the boiling point of 1,2,2- HFC-134a), and the relative separation degree of both compounds connects
1 is bordering on, they cannot be only completely separated by common fractionating technology and be reached purification 1,1- bis- bromo- 1,2,2,2- HFC-134as
Purpose.Therefore, 1,1- bis- bromo- 1,2,2,2- HFC-134a products can only be removed by the method for chemical method or special extract rectification
In the bromo- 1,1,2,2- HFC-134as of 1,2- bis-.
The method of special extract rectification has many kinds, but is to take extraction essence for the relatively effective means of this problem are solved
Method is evaporated, extracting rectifying is the 3rd component of addition in separate binary liquid mixture, and the 3rd component is not formed altogether with other components
Boiling thing, but it is different from the molecular force of A in original solution and the components of B two, so as to increase their relative volatility so that component
A and B are separated, wherein the 3rd component referred to as extractant for being added, discharges during rectifying from bottom of towe.
The selection of extractant is most important in extracting rectifying, i.e., in the presence of suitable extractant, 1,1- bis- is bromo-
1,2- bis- bromo- 1 in 1,2,2,2- HFC-134a product, 1,2,2- HFC-134a is separated, to obtain 1, the 1- bis- of high-purity
Bromo- 1,2,2,2- HFC-134as.But so far, also not on separation of extractive distillation reduction by 1,2- bis- bromo- 1,1,2,2-
HFC-134a content obtains the report of the bromo- 1,2,2,2- HFC-134as of 1,1- bis- of high-purity.
The content of the invention
Present invention seek to address that by 1,1- bis- bromo- 1,2,2,2- HFC-134as carry out purifying this problem, the means taken
It is extracting rectifying, extractant is cheap, easily obtains, and weigh residual.
The structural formula of the bromo- 1,2,2,2- HFC-134as of described 1,1- bis- and the bromo- 1,1,2,2- HFC-134as of 1,2- bis- is such as
Formulas I and Formula II：
1,1- bis- bromo- 1, the method for purification of 2,2,2- HFC-134as, 1, the 1- bis- bromo- 1,2,2,2- HFC-134a materials
In contain 1,2- bis- bromo- 1,1,2,2- HFC-134a, the method is extraction fractional distillation, wherein extractant be benzene or dimethylbenzene and boiling
Non-polar solvent mixture of the point higher than 80 DEG C, the benzene or dimethylbenzene are 5 with the mass ratio of non-polar solven:1~1:1.5,
Extractant is 1 with the mass ratio of material:5-30.
Non-polar solven of the boiling point higher than 80 DEG C is carbon tetrachloride or dioxane.
The dimethylbenzene is meta-xylene or ortho-xylene.
The mass ratio of the benzene, meta-xylene or ortho-xylene and non-polar solven is 5:1~3:1.
The extractant is 1 with the mass ratio of the bromo- 1,2,2,2- HFC-134as materials of 1,1- bis-:8-20, extracting rectifying pressure
Power is 0.01~0.2MPa.
The extractant is 1 with the mass ratio of the bromo- 1,2,2,2- HFC-134as materials of 1,1- bis-:8-15, extracting rectifying pressure
Power is 0.03~0.1MPa, and tower bottom of rectifying tower controls 80 DEG C -120 DEG C.
The bromo- 1,1,2,2- HFC-134as contents of the 1,2- bis- are below 5%.
The application use special mixed extractant, tower top 1,1- bis- bromo- 1, the purity of 2,2,2- HFC-134as exists
More than 99.9%, the residual of extractant is below 50ppm.
It is preferably benzene, meta-xylene or ortho-xylene, the mixing with dioxane or carbon tetrachloride to use effect of extracting
Thing not only can obtain 1, the 1- bis- bromo- 1 of high-purity, 2,2,2- HFC-134as, but also be effectively reduced 1,2- as extractant
The residual quantity of extractant in two bromo- 1,1,2,2- HFC-134as products.
The extractant of selection should meet claimed below：Adding a small amount of extractant can just cause the relative volatility of stock blend
Significantly increase；Can be dissolved each other with the original solution of any concentration, to avoid layering, otherwise be difficult to play the effect of extracting rectifying；Extraction
Agent boiling point is more much higher than the boiling point of the other components of mixed liquor, to ensure that he pushes up the purity of component, and is easy to and another component point
From, but boiling point can not be too high, can otherwise cause to be difficult to reclaim；Good stability, etching apparatus, does not obtain easily.
To rectifying column without particular/special requirement, typical rectifying column is used the present invention.In the industrial production, batch-type can be used
Or continous way, according to circumstances can be also taken out using discontinuous and/or the semi continuous that puts into carries out extracting rectifying.
Using the inventive method, through extracting rectifying 1,1- bis- bromo- 1 after purification, 1,2- in 2,2,2- HFC-134a products
Two bromo- 1, the content of 1,2,2- HFC-134a is less than 0.10%, and extractant residual is less than 50ppm, 1,1- bis- bromo- 1,2,2,2- tetra-
Fluoroethane product meets real requirement.
Specific implementation case
Purity detecting instrument：Gas-chromatography
Case study on implementation 1：
From DN25 the stainless head towers of SS304 as rectifying column, length is 2m, load θ ring stainless steel helices.
The bromo- 1,2,2,2- HFC-134as of 1,1- bis- and the bromo- 1,1,2,2- tetrafluoros second of 1,2- bis- are added in 5L tower bottom of rectifying tower
The mixture 1kg of alkane (GC areas ratio is 95/5), is subsequently adding the mixture of 100g benzene and dioxane (mass ratio is 3/1),
Tower bottom of rectifying tower controls 90 DEG C, and tower pressure is 0.05MPa, and maintenance condition is constant, and flow back 2h, overhead extraction, 57 DEG C of collection cuts, gas
Analysis of hplc, as a result see the table below.
Case study on implementation 2：
From DN25 the stainless head towers of SS304 as rectifying column, length is 2m, load θ ring stainless steel helices.
The bromo- 1,2,2,2- HFC-134as of 1,1- bis- and the bromo- 1,1,2,2- tetrafluoros second of 1,2- bis- are added in 5L tower bottom of rectifying tower
The mixture 1kg of alkane (GC areas ratio is 95/5), is subsequently adding the mixture of 120g benzene and dioxane (mass ratio is 3/1),
Tower bottom of rectifying tower controls 100 DEG C, and tower pressure is 0.06MPa, and maintenance condition is constant, and flow back 2h, and overhead extraction, 56.9 DEG C of collections evaporate
Point, as a result gas chromatographic analysis see the table below.
Case study on implementation 3：
From DN25 the stainless head towers of SS304 as rectifying column, length is 2m, load θ ring stainless steel helices.
The bromo- 1,2,2,2- HFC-134as of 1,1- bis- and the bromo- 1,1,2,2- tetrafluoros second of 1,2- bis- are added in 5L tower bottom of rectifying tower
The mixture 1kg of alkane (GC areas ratio is 95/5), is subsequently adding 100g ortho-xylenes mixed with dioxane (mass ratio is 4/1)
Compound, tower bottom of rectifying tower controls 110 DEG C, and tower pressure is 0.06MPa, and maintenance condition is constant, and flow back 2h, overhead extraction, 57 DEG C of collections
As a result cut, gas chromatographic analysis see the table below.
Case study on implementation 4：
From DN25 the stainless head towers of SS304 as rectifying column, length is 2m, load θ ring stainless steel helices.
The bromo- 1,2,2,2- HFC-134as of 1,1- bis- and the bromo- 1,1,2,2- tetrafluoros second of 1,2- bis- are added in 5L tower bottom of rectifying tower
The mixture 1kg of alkane (GC areas ratio is 95/5), is subsequently adding the mixture of 100g benzene and carbon tetrachloride (mass ratio is 3/1),
Tower bottom of rectifying tower controls 90 DEG C, and tower pressure is 0.04MPa, and maintenance condition is constant, and flow back 2h, overhead extraction, 57 DEG C of collection cuts, gas
Analysis of hplc, as a result see the table below.
Case study on implementation 5：
From DN25 the stainless head towers of SS304 as rectifying column, length is 2m, load θ ring stainless steel helices.
The bromo- 1,2,2,2- HFC-134as of 1,1- bis- and the bromo- 1,1,2,2- tetrafluoros second of 1,2- bis- are added in 5L tower bottom of rectifying tower
The mixture 1kg of alkane (GC areas ratio is 95/5), is subsequently adding 120g meta-xylenes mixed with carbon tetrachloride (mass ratio is 4/1)
Compound, tower bottom of rectifying tower controls 90 DEG C, and tower pressure is 0.04MPa, and maintenance condition is constant, and flow back 2h, and overhead extraction, 57 DEG C of collections evaporate
Point, as a result gas chromatographic analysis see the table below.
Case study on implementation 6：
From DN25 the stainless head towers of SS304 as rectifying column, length is 2m, load θ ring stainless steel helices.
The bromo- 1,2,2,2- HFC-134as of 1,1- bis- and the bromo- 1,1,2,2- tetrafluoros second of 1,2- bis- are added in 5L tower bottom of rectifying tower
The mixture 1kg of alkane (GC areas ratio is 95/5), is subsequently adding 80g meta-xylenes mixed with dioxane (mass ratio is 3/1)
Compound, tower bottom of rectifying tower controls 90 DEG C, and tower pressure is 0.05MPa, and maintenance condition is constant, and flow back 2h, and overhead extraction, 57 DEG C of collections evaporate
Point, as a result gas chromatographic analysis see the table below.
Analysis result of the different extractants to rectifying
Claims (7)
1.1,1- bis- bromo- 1, the method for purification of 2,2,2- HFC-134as, 1, the 1- bis- bromo- 1, in 2,2,2- HFC-134a materials
Contain 1,2- bis- bromo- 1,1,2,2- HFC-134a, the method is extraction fractional distillation, wherein extractant is benzene or dimethylbenzene and boiling point
Non-polar solvent mixture higher than 80 DEG C, the benzene or dimethylbenzene are 5 with the mass ratio of non-polar solven:1~1:1.5, extraction
It is 1 that agent is taken with the mass ratio of material:5-30.
2. method of purification according to claim 2, non-polar solven of the boiling point higher than 80 DEG C is carbon tetrachloride or two
The ring of oxygen six.
3. method of purification according to claim 3, the dimethylbenzene is meta-xylene or ortho-xylene.
4. the mass ratio of method of purification according to claim 4, benzene, meta-xylene or ortho-xylene and non-polar solven is
5:1~3:1.
5. according to any described methods of purification of claim 1-4, the extractant and 1,1- bis- bromo- 1,2,2,2- tetrafluoro second
The mass ratio of alkane material is 1:8-20, extracting rectifying pressure is 0.01~0.2MPa.
6. method of purification according to claim 5, the extractant and 1,1- bis- bromo- 1,2,2,2- HFC-134a mixtures
The mass ratio of material is 1:8-15, extracting rectifying pressure is 0.03~0.1MPa, and tower bottom of rectifying tower controls 80 DEG C -120 DEG C.
7. method of purification according to claim 1,1, the 2- bis- bromo- 1,1,2,2- HFC-134a content is below 5%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710101793.XA CN106905107B (en) | 2017-02-24 | 2017-02-24 | Purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane |
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|---|---|---|---|
| CN201710101793.XA CN106905107B (en) | 2017-02-24 | 2017-02-24 | Purification method of 1, 1-dibromo-1, 2,2, 2-tetrafluoroethane |
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| CN106905107A true CN106905107A (en) | 2017-06-30 |
| CN106905107B CN106905107B (en) | 2020-02-18 |
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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 |
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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. |