KR100197153B1 - Method of separating dichloro difluoromethane from difluoromethane mixture - Google Patents
Method of separating dichloro difluoromethane from difluoromethane mixture Download PDFInfo
- Publication number
- KR100197153B1 KR100197153B1 KR1019950000924A KR19950000924A KR100197153B1 KR 100197153 B1 KR100197153 B1 KR 100197153B1 KR 1019950000924 A KR1019950000924 A KR 1019950000924A KR 19950000924 A KR19950000924 A KR 19950000924A KR 100197153 B1 KR100197153 B1 KR 100197153B1
- Authority
- KR
- South Korea
- Prior art keywords
- difluoromethane
- dichlorodifluoromethane
- mixture
- composition
- distillation
- Prior art date
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
Abstract
본 발명은 디클로로디플루오로메탄을 함유하는 디플루오로메탄 혼합물을 증류하여 디클로로디플루오로메탄을 상기 혼합물에서의 조성보다 농축된 조성으로 탑정으로 제거하는 것으로 이루어지는, 디플루오로메탄으로부터 디클로로디플루오로메탄을 제거하는 방법에 관한 것이다.The present invention consists in distilling a difluoromethane mixture containing dichlorodifluoromethane to remove dichlorodifluoromethane to the top in a more concentrated composition than the composition in the mixture, dichlorodifluoro from difluoromethane. It relates to a method for removing romethane.
Description
본 발명은 디플루오로메탄과 디클로로디플루오로메탄 혼합물로부터 디클로로디플루오로메탄을 제거하는 방법에 관한 것이다.The present invention relates to a process for removing dichlorodifluoromethane from a mixture of difluoromethane and dichlorodifluoromethane.
염화불화탄소류는 냉매, 폼 분출제, 세척용매 등으로 광범위하게 사용되고 있으나, 이들이 오존층을 파괴하고 지구 온난화의 원인이 되는 것으로 밝혀짐에 따라 사용이 억제되고 있으며, 이들의 대체물을 찾고자 하는 연구가 활발히 진행되고 있다.Chlorinated fluorocarbons are widely used as refrigerants, foam blowing agents, cleaning solvents, etc., but they have been suppressed as they are found to destroy the ozone layer and cause global warming. It is actively underway.
디플루오로메탄은 염소를 포함하고 있지 않기 때문에 오존층을 파괴시키지 않으므로 클로로디플루오로메탄의 유망한 대체물질중의 하나로 알려져 있다. 디플루오로메탄은 염소를 포함하는 메탄 화합물, 예를 들면 디클로로메탄, 클로로디플루오로메탄, 디클로로디플루오로메탄 등을 원료로 하여 제조될 수 있다.Since difluoromethane does not contain chlorine and thus does not destroy the ozone layer, it is known as one of the promising alternatives to chlorodifluoromethane. Difluoromethane can be produced from methane compounds containing chlorine, for example, dichloromethane, chlorodifluoromethane, dichlorodifluoromethane and the like.
그러나 반응 생성물 중에서 디플루오로메탄 외에도 여러 가지 불순물이 포함되어 있다. 불순물에는 플루오로메탄이나 트리풀루오로메탄과 같이 디플루오로메탄보다 저비점인 염화불화탄소계 화합물과, 클로로플루오로메탄, 클로로디플루오로메탄, 클로로메탄 또는 디클로로디플루오로메탄과 같이 디플루오로메탄보다 고비점인 화합물들이 있으며, 대부분의 염화불화탄소계 물질은 끓는 점 차이를 이용한 증류나 흡착(유럽특허출원 92302424.4) 등의 방법에 의해 제거될 수 있다.However, in addition to difluoromethane, the reaction product contains various impurities. Impurities include chlorinated fluorocarbon compounds having a lower boiling point than difluoromethane, such as fluoromethane and trifluoromethane, and difluorine, such as chlorofluoromethane, chlorodifluoromethane, chloromethane or dichlorodifluoromethane. There are compounds having a higher boiling point than romethane, and most chlorofluorocarbon-based materials can be removed by a method such as distillation or adsorption (European patent application 92302424.4) using a boiling point difference.
증류에 의해 불순물을 제거하는 경우, 디플루오로메탄보다 저비점인 화합물은 증류탑의 탑정으로 제거되고, 디플루오로메탄보다 고비점인 화합물은 증류탑의 탑저에서 제거된다.When impurities are removed by distillation, compounds having a lower boiling point than difluoromethane are removed to the top of the distillation column, and compounds having a higher boiling point than difluoromethane are removed from the bottom of the distillation column.
그러나 본 발명자들은 디플루오로메탄보다 고비점인 디클로로디플루오로메탄은 디플루오로메탄과 끓는 점 차이가 상당히 큼에도 불구하고(대기압에서의 끓는 점이 디플루오로메탄은 -52℃이고, 디클로로디플루오로메탄은 -30℃이다) 디플루오로메탄과 최저공비혼합물을 형성하므로 다른 고비점 불순물과 같이 증류에 의해 탑저로 제거되지 않음을 알게 되었다.However, the inventors found that dichlorodifluoromethane, which has a higher boiling point than difluoromethane, has a significant difference in boiling point from difluoromethane (when boiling at atmospheric pressure, difluoromethane is -52 ° C, and dichlorodi Fluoromethane forms the lowest azeotrope with difluoromethane, so it is found that it is not removed to the bottom by distillation like other high boiling impurities.
디클로로디플루오로메탄을 함유하는 디플루오로메탄을 증류하는 경우, 디플루오로메탄보다 끌는 점이 높은 디클로로디플루오로메탄이 탑정으로 농축되며 또한 순수한 디플루오로메탄이 있을 때보다 디클로로디플루오로메탄이 탑정으로 농축되었을 때 탑정 온도가 더 낮은 값을 나타낸다. 이 두 결과로부터 디플루오로메탄과 디클로로디플루오로메탄은 최저공비혼합물을 형성한다는 것이 확인되었다.When difluoromethane containing dichlorodifluoromethane is distilled off, dichlorodifluoromethane, which has a higher drag point than difluoromethane, is concentrated to the top and dichlorodifluoromethane than when there is pure difluoromethane. When concentrated to this column, the tower temperature shows a lower value. From these two results, it was confirmed that difluoromethane and dichlorodifluoromethane form the lowest azeotrope.
본 발명은 디클로로디플루오로메탄을 함유하는 디플루오로메탄 혼합물을 증류하여 디클로로디플루오로메탄을 상기 혼합물에서의 조성보다 농축된 조성으로 탑정으로 제거하는 것으로 이루어지는, 디플루오로메탄로부터 디클로로디플루오로메탄을 제거하는 방법을 제공한다.The present invention consists in distilling a difluoromethane mixture containing dichlorodifluoromethane to remove dichlorodifluoromethane to the top in a more concentrated composition than the composition in the mixture, dichlorodifluoro from difluoromethane. Provided are methods for removing romethane.
본 발명에 따른 방법에서 디클로로디플루오로메탄은 디플루오로메탄과의 공비혼합물 형태로 제거될 수 있다.In the process according to the invention dichlorodifluoromethane can be removed in the form of an azeotrope with difluoromethane.
본 발명에 따르면 디클로로디플루오로메탄 등의 불순물을 함유하는 디플루오로메탄을 증류장치를 사용하여 증류하면 디클로로디플루오로메탄은 최초의 농도보다 농축된 조성으로, 또는 디플루오로메탄과 최저공비 혼합물을 형성하여 탑정으로 농축되므로 탑저에서 디클로로디플루오로메탄을 포함하지 않는 디플루오로메탄을 얻을 수 있다.According to the present invention, when difluoromethane containing impurities such as dichlorodifluoromethane is distilled using a distillation apparatus, dichlorodifluoromethane is concentrated in the composition than the initial concentration, or at the lowest azeotropy ratio with difluoromethane. Since the mixture is formed and concentrated to the top, difluoromethane without dichlorodifluoromethane can be obtained at the bottom.
즉, 증류탑으로 공급되는, 디클로로디플루오로메탄을 함유하는 디플루오로메탄중의 디클로로디플루오로메탄의 조성이 공비혼합물에서의 디클로로디플루오로메탄의 조성보다 낮을 경우, 증류탑 상부에서 환류되는 액중의 디클로로디플루오로메탄 조성은 원료 혼합물(증류탑으로 공급되는 혼합물) 중의 조성보다 높아질 수 있으므로 최대공비조성까지 디클로로디플루오로메탄을 농축시킬 수 있으며, 따라서 탑저에서는 디클로로디플루오로메탄을 함유하지 않는 정제된 디플루오로메탄을 얻을 수 있다.That is, when the composition of dichlorodifluoromethane in difluoromethane containing dichlorodifluoromethane supplied to the distillation column is lower than the composition of dichlorodifluoromethane in the azeotrope, the liquid refluxed at the top of the distillation column The dichlorodifluoromethane composition of can be higher than the composition in the raw material mixture (mixture supplied to the distillation column), so that the dichlorodifluoromethane can be concentrated up to the maximum azeotropic composition, so that the column bottom does not contain dichlorodifluoromethane. Purified difluoromethane can be obtained.
본 발명에 따라 디클로로디플루오로메탄을 제거하는 공정의 압력은 0 내지 30kg/㎠G가 좋으며, 4 내지 20kg/㎠G가 바람직하다. 본 발명의 방법에는 통상적으로 사용되는 어떤 증류 장치도 사용될 수 있으며, 연속 증류뿐 아니라 회분식 증류에 의해서도 가능하다.According to the present invention, the pressure of the process for removing dichlorodifluoromethane is preferably 0 to 30 kg / cm 2 G, and preferably 4 to 20 kg / cm 2 G. Any distillation apparatus conventionally used may be used in the process of the present invention, and not only by continuous distillation but also by batch distillation.
디플루오로메탄과 디클로로디플루오로메탄의 공비 조성은 압력에 따라 변하며, 예를 들어 7.1kg/㎠G 압력하에서 증류하면 공비혼합물의 조성은 디플루오로메탄 87몰%, 디클로로디플루오로메탄 13몰%이고, 이러한 공비 조성에서의 온도는 -1℃이다. 12.0kg/㎠G 압력하에서의 공비 조성은 디플루오로메탄 89몰%, 디클로로디플루오로메탄 11몰%이고, 이 공비 조성에서의 온도는 15℃이다.The azeotropic composition of difluoromethane and dichlorodifluoromethane varies with pressure, for example, when distilled under 7.1 kg / cm 2 G pressure, the composition of the azeotrope is 87 mol% difluoromethane, dichlorodifluoromethane 13 Mol% and the temperature at this azeotropic composition is -1 ° C. The azeotropic composition at 12.0 kg / cm 2 G pressure is 89 mol% difluoromethane and 11 mol% dichlorodifluoromethane, and the temperature at this azeotropic composition is 15 ° C.
또한 본 발명에 따른 디클로로디플루오로메탄을 제거 방법에 의해 디플루오로메탄보다 저비점인 불순물도 또한 제거될 수 있다.In addition, impurities having a lower boiling point than difluoromethane may also be removed by the method for removing dichlorodifluoromethane according to the present invention.
아래의 실시예는 본 발명을 더욱 자세히 설명하기 위한 것이며, 본 발명의 범위를 제한하고자 하는 것은 아니다.The following examples are intended to illustrate the invention in more detail, and are not intended to limit the scope of the invention.
[실시예 1]Example 1
직경 41mm, 높이 3m인 스테인레스 스틸로 제작된 충전 증류탑(충전물 : 니트메쉬)에서 실험을 실시하였다. 증류탑을 진공으로 만든 후 디플루오로메탄을 2900g( 55.8몰) 주입하고 재비기를 가열하여 전환류의 조건에서 증류하였다. 탑정 압력이 7.1kg/㎠G일 때 탑정 온도는 0℃였다. 여기에 디클로로디플루오로메탄 95g(1.3몰)을 재비기로 주입하여 정상상태에 도달한 후 탑정압력이 7.1kg/㎠G일 때 탑정온도는 -1℃였다. 탑정으로부터 가스시료를 채취해 가스크로마토그라피로 분석한 결과 디플루오로메탄 87몰%, 디클로로디플루오로메탄 13몰%였다.The experiment was carried out in a packed distillation column (filled material: knit mesh) made of stainless steel having a diameter of 41 mm and a height of 3 m. After the distillation column was vacuumed, 2900 g (55.8 mol) of difluoromethane was injected and the reboiler was heated to distill under the conditions of the conversion flow. The tower temperature was 0 ° C. when the tower pressure was 7.1 kg / cm 2 G. After distilling 95 g (1.3 mol) of dichlorodifluoromethane into the reboiler to reach a steady state, the tower top temperature was -1 ° C when the tower top pressure was 7.1 kg / cm 2 G. Gas samples were collected from the column top and analyzed by gas chromatography, and 87 mol% of difluoromethane and 13 mol% of dichlorodifluoromethane were obtained.
[실시예 2]Example 2
실시예 1의 증류탑에 디클로로디플루오로메탄 32g(0.3몰)을 더 주입하고 실시예 1과 동일한 조건에서 증류하였다. 탑정의 압력이 7.1kg/㎠G일 때 탑정온도는 -1℃였으며 탑정으로부터 약 2m까지의 증류탑 온도는 탑정온도와 같았다. 탑정으로부터 가스시료를 채취해 가스크로마토그라피로 분석한 결과 디플루오로메탄 87몰%, 디클로로디플루오로메탄 13몰%였다.32 g (0.3 mol) of dichlorodifluoromethane was further injected into the distillation column of Example 1, and distilled under the same conditions as in Example 1. When the pressure of the column top was 7.1kg / cm 2 G, the tower top temperature was -1 ° C and the distillation column temperature from the tower top to about 2m was equal to the tower top temperature. Gas samples were collected from the column top and analyzed by gas chromatography, and 87 mol% of difluoromethane and 13 mol% of dichlorodifluoromethane were obtained.
[실시예 3]Example 3
실시예 2의 혼합물을 탑정압력이 12.0kg/㎠G일 때 전환류시키면서 증류하였다. 정상상태에 도달하였을 때 탑정 온도는 15℃였고 탑정으로부터 가스시료를 채취해 가스크로마토그라피로 분석한 결과 디플루오로메탄 89몰%, 디클로로디플루오로메탄 11몰%였다.The mixture of Example 2 was distilled off with divert flow when the column top pressure was 12.0 kg / cm 2 G. When the steady state was reached, the top temperature was 15 ° C. Gas samples were collected from the top and analyzed by gas chromatography, and 89 mol% of difluoromethane and 11 mol% of dichlorodifluoromethane were obtained.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950000924A KR100197153B1 (en) | 1995-01-20 | 1995-01-20 | Method of separating dichloro difluoromethane from difluoromethane mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950000924A KR100197153B1 (en) | 1995-01-20 | 1995-01-20 | Method of separating dichloro difluoromethane from difluoromethane mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR960029297A KR960029297A (en) | 1996-08-17 |
| KR100197153B1 true KR100197153B1 (en) | 1999-06-15 |
Family
ID=19406982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019950000924A KR100197153B1 (en) | 1995-01-20 | 1995-01-20 | Method of separating dichloro difluoromethane from difluoromethane mixture |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100197153B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432816A (en) * | 2013-07-29 | 2013-12-11 | 南京工业大学 | Recovery method and recovery device of waste cleaning solvent |
-
1995
- 1995-01-20 KR KR1019950000924A patent/KR100197153B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432816A (en) * | 2013-07-29 | 2013-12-11 | 南京工业大学 | Recovery method and recovery device of waste cleaning solvent |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960029297A (en) | 1996-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2007091762A (en) | Method for separating hfc-32 and hfc-125 | |
| KR100338277B1 (en) | Method of removing hydrogen fluoride | |
| EP0782557A1 (en) | Purification process for hexafluoroethane products | |
| EP0743933B1 (en) | Process for separating pentafluoroethane from a mixture comprising halogenated hydrocarbons and chloropentafluoroethane | |
| US7396485B2 (en) | Azeotrope-like compositions of difluoromethane | |
| EP1370624B1 (en) | Azeotrope-like composition of 1,1,1,3,3-pentafluoropropane and 1-chloro-1,1,3,3,3-pentafluoropropane | |
| CA2576181A1 (en) | Azeotrope-like compositions of 1,1,1,3,3-pentachloropropane and carbon tetrachloride | |
| EP0743934B1 (en) | Process for separating pentafluoroethane from a mixture comprising halogenated hydrocarbons and chloropentafluoroethane | |
| US5514251A (en) | Process for the removal of water from a solution by azeotropic distillation and process for the production of a hydrofluoroalkane | |
| EP0696267B1 (en) | AZEOTROPIC AND AZEOTROPE-LIKE COMPOSITIONS AND A PROCESS FOR SEPARATING HCl AND HALOCARBONS | |
| KR100197153B1 (en) | Method of separating dichloro difluoromethane from difluoromethane mixture | |
| EP1425076B1 (en) | Azeotrope-like compositions of 1,1,1,3,3-pentafluorobutane and hydrogen fluoride | |
| JP3892037B2 (en) | Method for purifying pentafluoroethane | |
| JPH05320077A (en) | Azeotropic mixture of pentafluoroethane with pentafluorochloroethane and method for separating pentafluorochloroethane | |
| US3658657A (en) | Separation and recovery of 1,1,1-trichloroethane by extractive distillation | |
| KR100244058B1 (en) | Process for purifying fluoroethanes and chlorofluoroethanes | |
| US7141094B2 (en) | Azeotrope-like compositions of iodine heptafluoride and hydrogen fluoride | |
| JP2004529198A (en) | Azeotropic composition and method for separating pentafluoroethane and hydrogen chloride | |
| JPH0471911B2 (en) | ||
| RU2178779C2 (en) | Hexafluoropropylene recovery process | |
| KR100603655B1 (en) | A Method for Separating Stream Comprising Chlorine and Difluoromethane | |
| JP2001342007A (en) | Hydrogen fluoride separation method | |
| JPH111446A (en) | Azeotropic mixture of perfluoroalkyl iodide with hydrogen fluoride, and separation and purification of perfluoroalkyl iodide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| AMND | Amendment | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application | ||
| J201 | Request for trial against refusal decision | ||
| B701 | Decision to grant | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20040130 Year of fee payment: 6 |
|
| LAPS | Lapse due to unpaid annual fee |