CN106573878A - Extraction solvent for extractive distillation and method for separating hydrocarbons using the same - Google Patents

Extraction solvent for extractive distillation and method for separating hydrocarbons using the same Download PDF

Info

Publication number
CN106573878A
CN106573878A CN201580015895.9A CN201580015895A CN106573878A CN 106573878 A CN106573878 A CN 106573878A CN 201580015895 A CN201580015895 A CN 201580015895A CN 106573878 A CN106573878 A CN 106573878A
Authority
CN
China
Prior art keywords
hydrocarbon
propionic acid
acid amide
extractant
positive
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.)
Pending
Application number
CN201580015895.9A
Other languages
Chinese (zh)
Inventor
藤冈东洋藏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Publication of CN106573878A publication Critical patent/CN106573878A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

An extractive solvent for extractive distillation represented by general formula (1) used for separating any one of (a) to (c) from a hydrocarbon mixture containing at least two selected from saturated aliphatic hydrocarbons (a), unsaturated aliphatic hydrocarbons (b), and aromatic hydrocarbons (c) by extractive distillation, and a method for separating hydrocarbons using the same. R1：C1~6Linear/branched/cyclic alkyl; r2,3：C1~6Straight/branched alkyl; n: 0 to 2.

Description

The separation method of the extractant of extractive distillation and the hydro carbons using the solvent
Technical field
The present invention relates to the separation method of the extractant of extractive distillation and the hydro carbons using the solvent.
Background technology
Extractive distillation is important dividing as the means that target component is separated from hydrocarbon mixture, in chemical industrial field From method.
For example, as plastics, chemical fibre etc. the aromatic compounds such as the benzene,toluene,xylene of important source material by from Separate so as to manufacture in the raw materials such as crude oil, Petroleum, modified Petroleum.However, exist in these raw materials being separated with conduct The boiling point of the aromatic compounds of target saturated hydrocarbons, unsaturated hydrocarbons closely, thus by simple distillation it is refined be difficult to into Row is separated, and to use extractive distillation.
Extractive distillation is referred to be added as the ternary solvent for extraction to the mixture containing at least 2 kinds compositions (hereinafter also referred to " extractant ") is so that answering the relative volatility of detached composition to change and being carried out point by distillation From method.That is, extractant must be the solvent respectively for each composition in mixture with different affinitys.
As such extractant, from from the viewpoint of versatility etc., in the past using METHYLPYRROLIDONE (with Down also referred to as " NMP "), N,N-dimethylformamide (hereinafter also referred to " DMF ") etc..
In recent years, the NMP being commonly used as extractant is gradually under a cloud genotoxicity, Europe chemistry to people Product management board (ECHA) is appointed as NMP based on REACH regulations on June 20th, 2011 to assert candidate substances (SVHC).
Additionally, DMF is in international chemicals safety card, and (ICSC is numbered：0457) show in, for a long time or repeatedly exposure can be to liver It is dirty to produce impact, function damage is produced sometimes, it also specifies thing by the regulation that Japanese MHLW is appointed as being related to carcinogenecity Matter.
From such background, for extractant, on the basis of the performance for expeditiously separating target component, go back High security is gradually required, the solvent of NMP, DMF for consumingly needing to substitute the worry for having unhealthful.
The separation method of monocyclic hydrocarbon mixture is disclosed in patent documentation 1 and 2, it is characterised in that from comprising saturation Separated by extractive distillation in the mixture of at least two monocyclic hydrocarbons in monocyclic hydrocarbon, unsaturated monocyclic hydrocarbon and aromatic monocyclic hydrocarbon and satisfied In the method for monocyclic hydrocarbon or unsaturated monocyclic hydrocarbon, as extractant respectively using phosphotriester and dipropylene glycol.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Application 62-123135 publication
Patent documentation 2：Japanese Unexamined Patent Application 62-123136 publication.
The content of the invention
The invention problem to be solved
In the technology of patent documentation 1, although having obtained separation high than ever as extractant by using phosphotriester Efficiency, but as representational phosphotriester trimethyl phosphate international chemicals safety card (ICSC number：0686) quilt in Point out to be possible to cause the impact and genetic factor damage to nervous system, set out from a security point, its existing problem.
In the technology of patent documentation 2, although using dipropylene glycol as extractant, dipropylene glycol has solvent skin Skin toxicity, is noted in recent years danger (the international chemicals safety card with contact atopic dermatitis：ICSC is numbered：1055), It is investigated and avoids used in chemicals etc..
Present invention aim at, there is provided the extractant of the high extractive distillation of safe, extraction efficiency, and use The separation method of the hydro carbons of the solvent.
The means to solve the problem
The present inventor go out from a security point through furtheing investigate repeatedly in order to realize object defined above as a result, being found that Send out using not being restricted and be not investigated using the specific compound for limiting that to can serve as the extraction efficiency in extractive distillation excellent Different, safe extractant, so as to complete the present invention.
That is, the present invention provides following [1] ~ [8].
[1] extractant of extractive distillation, it is used for from containing selected from saturated aliphatic hydrocarbon (a), aliphatic unsaturated hydrocarbon (b) The method of any one in (a) ~ (c) is separated by extractive distillation in hydrocarbon mixture with aromatic hydrocarbon (c) at least two, It uses following formulas (1) to represent：
[changing 1]
In formula, R1It is straight chain, side chain or cyclic alkyl that carbon number is 1 ~ 6, R2And R3It is independently of one another that carbon number is 1 ~ 6 straight chain or branched alkyl, n is 0 ~ 2 integer.
[2] extractant according to above-mentioned [1], wherein, in aforementioned hydrocarbon mixture, aforementioned (a) composition and aforementioned (b) The mass ratio [(a)/(b)] of composition is 20/80 ~ 95/5.
[3] extractant according to above-mentioned [1] or [2], wherein, in aforementioned hydrocarbon mixture, aforementioned (a) composition with it is front The mass ratio [(a)/(c)] for stating (c) composition is 20/80 ~ 95/5.
[4] separation method of hydrocarbon mixture, it is from containing selected from saturated aliphatic hydrocarbon (a), aliphatic unsaturated hydrocarbon (b) and virtue The method of any one being somebody's turn to do in (a) ~ (c) is separated by extractive distillation in the hydrocarbon mixture of at least two in race's hydrocarbon (c), its In, as extractant, using the extractant any one of above-mentioned [1] ~ [3].
[5] separation method of the hydrocarbon mixture according to above-mentioned [4], wherein, aforementioned (a) ~ (c) be carbon number for 4 ~ 10 hydrocarbon.
[6] separation method of the hydrocarbon mixture according to above-mentioned [4] or [5], wherein, aforementioned hydrocarbon mixture and aforementioned extraction The mol ratio for taking solvent is 1:0.5~1:10.
[7] separation method of the hydrocarbon mixture according to any one of above-mentioned [4] ~ [6], wherein, aforementioned extractant It is the mixture of compound and other solvents represented with aforementioned formula (1).
[8] separation method of the hydrocarbon mixture according to above-mentioned [7], wherein, the compound represented with aforementioned formula (1) It is 0.1 with the mol ratio of other polar solvents:0.9~1:0.
Invention effect
The present invention can provide the extractant of the high extractive distillation of safe, extraction efficiency, and using the solvent The separation method of hydro carbons.
Description of the drawings
Fig. 1：Show the figure of the extractive distillation device used in embodiment.
Specific embodiment
[extractant]
The extractant of the present invention is used for from containing in saturated aliphatic hydrocarbon (a), aliphatic unsaturated hydrocarbon (b) and aromatic hydrocarbon (c) At least two hydrocarbon mixture in by extractive distillation separate should be in (a) ~ (c) the method for any one, it uses following formulas (1) represent：
[changing 2]
In formula, R1It is straight chain, side chain or cyclic alkyl that carbon number is 1 ~ 6, R2And R3It is independently of one another that carbon number is 1 ~ 6 straight chain or branched alkyl, n is 0 ~ 2 integer.
In aforementioned formula (1), from from the viewpoint of the viewpoint and safety for improving extraction efficiency, R1Carbon number be 1 ~ 6, preferably 1 ~ 5, more preferably 1 ~ 4.Additionally, by making R1Carbon number within the above range, used in extractive distillation Afterwards, extractant can be at a lower temperature refined, therefore becomes the excellent extractant of energy efficiency.
Additionally, from the same viewpoint, R1For straight chain, side chain or cyclic alkyl, preferably straight chain or side chain The alkyl of alkyl, more preferably straight chain.
As the specific example of aforementioned linear alkyl, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl and just can be enumerated Hexyl etc..
As the specific example of aforementioned branched alkyl, isopropyl, sec-butyl, isobutyl group, the tert-butyl group, 2- methyl can be enumerated Butyl, 3- methyl butyls, isopentyl, 2- ethyl propyls, neopentyl etc..
As the specific example of aforementioned cyclic alkyl, cyclopenta, cyclohexyl etc. can be enumerated.
Wherein, from from the viewpoint of viewpoint, the viewpoint of distillation extraction solvent and the safety for improving extraction efficiency, preferred first Base, ethyl, n-pro-pyl, normal-butyl, more preferably methyl, normal-butyl.
In aforementioned formula (1), from from the viewpoint of the viewpoint and safety for improving extraction efficiency, R2And R3Carbon number It is each independently 1 ~ 6, preferably 1 ~ 3, more preferably 1 ~ 2, more preferably 1.Additionally, by making R2And R3Carbon atom Number within the above range, used in extractive distillation after, can refine extractant at a lower temperature, therefore become energy dose-effect The excellent extractant of rate.
From from the viewpoint of raising extraction efficiency, R2And R3It is each independently straight or branched alkyl, preferably straight chain alkane Base.
As the specific example of aforementioned linear alkyl, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, just can be enumerated Hexyl etc..
As the specific example of aforementioned branched alkyl, isopropyl, sec-butyl, isobutyl group, the tert-butyl group, 2- methyl can be enumerated Butyl, 3- methyl butyls, isopentyl, 2- ethyl propyls, neopentyl etc..
Wherein, from from the viewpoint of viewpoint, the viewpoint of distillation extraction solvent and the safety for improving extraction efficiency, preferred first Base, ethyl, n-pro-pyl, more preferably methyl, ethyl, further preferred methyl.
In aforementioned formula (1), from improve extraction efficiency from the viewpoint of, n for 0 ~ 2 integer, preferably 1 ~ 2 integer, More preferably 2.
As the specific example of the compound represented by formula (1), such as R2And R3For the compound of methyl, can be with Enumerate 3- methoxyl group-N, N- dimethylpropionamides, 3- ethyoxyl-N, N- dimethylpropionamides, 3- positive propoxy-N, N- dimethyl Propionic acid amide., 3- isopropoxy-N, N- dimethylpropionamides, 3- n-butoxy-N, N- dimethylpropionamides, 3- sec-butoxy-N, N- dimethylpropionamides, 3- tert-butoxy-N, N- dimethylpropionamides, 3- n-pentyloxy-N, N- dimethylpropionamides, 3- rings penta Epoxide-N, N- dimethylpropionamide, 3- positive hexyloxy-N, N- dimethylpropionamides, 3- cyclohexyloxy-N, N- dimethylpropionamides Deng.
As R2And R3Compound represented by the formula (1) of ethyl, can enumerate such as 3- methoxyl groups-N, N- diethyls Base propionic acid amide., 3- ethyoxyl-N, N- diethyl propionamides, 3- positive propoxy-N, N- diethyl propionamides, 3- isopropoxy-N, N- diethyl propionamides, 3- n-butoxy-N, N- diethyl propionamides, 3- sec-butoxy-N, the tertiary fourth of N- diethyl propionamides, 3- Epoxide-N, N- diethyl propionamide, 3- n-pentyloxy-N, N- diethyl propionamides, 3- cyclopentyloxy-N, N- diethyl propionyl Amine, 3- positive hexyloxy-N, N- diethyl propionamides, 3- cyclohexyloxy-N, N- diethyl propionamides etc..
As R2And R3Compound represented by the formula (1) of n-pro-pyl, can enumerate such as 3- methoxyl groups-N, N- bis- N-pro-pyl propionic acid amide., 3- ethyoxyl-N, N- diη-propyl propionic acid amide .s, 3- positive propoxy-N, N- diη-propyl propionic acid amide .s, 3- isopropyls Epoxide-N, N- diη-propyl propionic acid amide., 3- n-butoxy-N, N- diη-propyl propionic acid amide .s, 3- sec-butoxy-N, N- diη-propyls Propionic acid amide., 3- tert-butoxy-N, N- diη-propyl propionic acid amide .s, 3- n-pentyloxy-N, N- diη-propyl propionic acid amide .s, the oxygen of 3- rings penta Base-N, N- diη-propyl propionic acid amide., 3- positive hexyloxy-N, N- diη-propyl propionic acid amide .s, 3- cyclohexyloxy-N, N- diη-propyls third Amide etc..
As R2And R3Compound represented by the formula (1) of isopropyl, can enumerate such as 3- methoxyl groups-N, N- bis- Isopropyl propionic acid amide., 3- ethyoxyl-N, N- diisopropyl propionic acid amide .s, 3- positive propoxy-N, N- diisopropyl propionic acid amide .s, 3- isopropyls Epoxide-N, N- diisopropyl propionic acid amide., 3- n-butoxy-N, N- diisopropyl propionic acid amide .s, 3- sec-butoxy-N, N- diisopropyls Propionic acid amide., 3- tert-butoxy-N, N- diisopropyl propionic acid amide .s, 3- n-pentyloxy-N, N- diisopropyl propionic acid amide .s, the oxygen of 3- rings penta Base-N, N- diisopropyl propionic acid amide., 3- positive hexyloxy-N, N- diisopropyl propionic acid amide .s, 3- cyclohexyloxy-N, N- diisopropyls third Amide etc..
As R2And R3In any one be the compound of ethyl and another one represented by the formula (1) of methyl, can enumerate Such as 3- methoxyl groups-N, N- Methylethyl propionic acid amide., 3- ethyoxyl-N, N- Methylethyl propionic acid amide .s, 3- positive propoxy-N, N- first Base ethyl propionamide, 3- isopropoxy-N, N- Methylethyl propionic acid amide .s, 3- n-butoxy-N, N- Methylethyl propionic acid amide .s, 3- are secondary Butoxy-N, N- Methylethyl propionic acid amide., 3- tert-butoxy-N, N- Methylethyl propionic acid amide .s, 3- n-pentyloxy-N, N- methyl second Base propionic acid amide., 3- cyclopentyloxy-N, N- Methylethyl propionic acid amide .s, 3- positive hexyloxy-N, N- Methylethyl propionic acid amide .s, 3- hexamethylene oxygen Base-N, N- Methylethyl propionic acid amide. etc..
As R2And R3In any one be the compound of n-pro-pyl and another one represented by the formula (1) of methyl, Ke Yiju Go out such as 3- methoxyl groups-N, N- methyl-propyl propionic acid amide .s, 3- ethyoxyl-N, N- methyl-propyl propionic acid amide .s, 3- positive propoxy-N, N- Methyl-propyl propionic acid amide., 3- isopropoxy-N, N- methyl-propyl propionic acid amide .s, 3- n-butoxy-N, N- methyl-propyl propionic acid amide .s, 3- Sec-butoxy-N, N- methyl-propyl propionic acid amide., 3- tert-butoxy-N, N- methyl-propyl propionic acid amide .s, 3- n-pentyloxy-N, N- methyl Propyl propanamide, 3- cyclopentyloxy-N, N- methyl-propyl propionic acid amide .s, 3- positive hexyloxy-N, N- methyl-propyl propionic acid amide .s, 3- hexamethylenes Epoxide-N, N- methyl-propyl propionic acid amide. etc..
As R2And R3In any one be the compound of n-pro-pyl and another one represented by the formula (1) of ethyl, Ke Yiju Go out such as 3- methoxyl groups-N, N- ethyl propyl propionic acid amide .s, 3- ethyoxyl-N, N- ethyl propyl propionic acid amide .s, 3- positive propoxy-N, N- Ethyl propyl propionic acid amide., 3- isopropoxy-N, N- ethyl propyl propionic acid amide .s, 3- n-butoxy-N, N- ethyl propyl propionic acid amide .s, 3- Sec-butoxy-N, N- ethyl propyl propionic acid amide., 3- tert-butoxy-N, N- ethyl propyl propionic acid amide .s, 3- n-pentyloxy-N, N- ethyls Propyl propanamide, 3- cyclopentyloxy-N, N- ethyl propyl propionic acid amide .s, 3- positive hexyloxy-N, N- ethyl propyl propionic acid amide .s, 3- hexamethylenes Epoxide-N, N- ethyl propyl propionic acid amide. etc..
As R2And R3Compound represented by the formula (1) of normal-butyl, can enumerate such as 3- methoxyl groups-N, N- bis- Butyl propionic acid amide., 3- ethyoxyl-N, N- dibutyl propionic acid amide .s, 3- positive propoxy-N, N- dibutyl propionic acid amide .s, 3- isopropoxies- N, N- dibutyl propionic acid amide., 3- n-butoxy-N, N- dibutyl propionic acid amide .s, 3- sec-butoxy-N, N- dibutyl propionic acid amide .s, uncle 3- Butoxy-N, N- dibutyl propionic acid amide., 3- n-pentyloxy-N, N- dibutyl propionic acid amide .s, 3- cyclopentyloxy-N, N- dibutyl propionyl Amine, 3- positive hexyloxy-N, N- dibutyl propionic acid amide .s, 3- cyclohexyloxy-N, N- dibutyl propionic acid amide .s etc..
As R2And R3Compound represented by the formula (1) of n-heptyl, can enumerate such as 3- methoxyl groups-N, N- bis- Heptyl propionic acid amide., 3- ethyoxyl-N, N- diheptyl propionic acid amide .s, 3- positive propoxy-N, N- diheptyl propionic acid amide .s, 3- isopropoxies- N, N- diheptyl propionic acid amide., 3- n-butoxy-N, N- diheptyl propionic acid amide .s, 3- sec-butoxy-N, N- diheptyl propionic acid amide .s, uncle 3- Butoxy-N, N- diheptyl propionic acid amide., 3- n-pentyloxy-N, N- diheptyl propionic acid amide .s, 3- cyclopentyloxy-N, N- diheptyl propionyl Amine, 3- positive hexyloxy-N, N- diheptyl propionic acid amide .s, 3- cyclohexyloxy-N, N- diheptyl propionic acid amide .s etc..
As R2And R3Compound represented by the formula (1) of n-hexyl, can enumerate such as 3- methoxyl groups-N, N- bis- Hexyl propionic acid amide., 3- ethyoxyl-N, N- dihexyl propionic acid amide .s, 3- positive propoxy-N, N- dihexyl propionic acid amide .s, 3- isopropoxies- N, N- dihexyl propionic acid amide., 3- n-butoxy-N, N- dihexyl propionic acid amide .s, 3- sec-butoxy-N, N- dihexyl propionic acid amide .s, uncle 3- Butoxy-N, N- dihexyl propionic acid amide., 3- n-pentyloxy-N, N- dihexyl propionic acid amide .s, 3- cyclopentyloxy-N, N- dihexyl propionyl Amine, 3- positive hexyloxy-N, N- dihexyl propionic acid amide .s, 3- cyclohexyloxy-N, N- dihexyl propionic acid amide .s etc..
Wherein, it is excellent from from the viewpoint of viewpoint, the viewpoint of distillation regeneration extractant and the safety for improving extraction efficiency Select 3- methoxyl group-N, N- dimethylpropionamides, 3- n-butoxy-N, N- dimethylpropionamides.
Compound represented by above-mentioned formula (1) can be used alone one kind, it is also possible to and with two or more.
[hydrocarbon mixture]
Contain selected from saturated aliphatic hydrocarbon (a), unsaturation for the hydrocarbon mixture of the extractive distillation of the extractant using the present invention In aliphatic hydrocarbon (b) and aromatic hydrocarbon (c) at least two.
(saturated aliphatic hydrocarbon (a))
As saturated aliphatic hydrocarbon (a), the saturated aliphatic hydrocarbon of ring-type or chain can be enumerated.
As the specific example of the saturated aliphatic hydrocarbon of ring-type, it may be preferred to enumerate Pentamethylene., hexamethylene, hexahydrotoluene, 1,2- dimethyl cyclohexanes, 1,3- dimethyl cyclohexanes, 1,4- dimethyl cyclohexanes, cyclooctane, cyclodecane, cyclododecane, first Cyclopentane, ethyl cyclohexane, diethyl cyclohexane, ethyl cyclopentane etc..
As the specific example of the saturated aliphatic hydrocarbon of chain, it may be preferred to enumerate pentane, 2- methybutanes, 2,2- diformazans Base propane, normal hexane, 2- methylpentanes, 3- methylpentanes, 2,2- dimethylbutanes, 2,3- dimethylbutanes, 3- ethylbutanes, Normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2,2- dimethyl pentanes, 2,3- dimethyl pentanes, 2,4- dimethyl pentanes, 3- Ethylpentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,2- dimethylhexanes, 2,3- dimethyl oneself Alkane, 3,3- dimethylhexanes, 3,4- dimethylhexanes, 3- ethyl hexanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- first Base octane, 2,2- dimethylhexanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2,5- dimethylhexanes, 3- ethyl hexyls Alkane, 4- ethyl hexanes, n-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,2- dimethyl-octas Alkane, 2,3- dimethyl octanes, 2,4- dimethyl octanes, 2,5- dimethyl octanes, 2,6- dimethyl octanes, 2,7- dimethyl-octas Alkane, trimethyl octane etc..
As the carbon number of aforementioned saturated aliphatic hydrocarbon (a), preferably 4 ~ 10, more preferably 5 ~ 8, more preferably 6 ~ 7, it is still more preferably 6.If the carbon number of aforementioned saturated aliphatic hydrocarbon (a) is within the above range, can be expeditiously Separated.
(aliphatic unsaturated hydrocarbon (b))
As aliphatic unsaturated hydrocarbon (b), the aliphatic unsaturated hydrocarbon of ring-type or chain can be enumerated.
As the specific example of the aliphatic unsaturated hydrocarbon of ring-type, it may be preferred to enumerate cyclopentenes, cyclohexene, methyl cyclohexane Alkene, dimethylcyclohexenes, cyclo-octene, cyclodecene, cyclododecene, ethyl-cyclohexene, methyl cyclopentene, ethylcyclopentene, ring penta Diene, cyclohexadiene, methyl cyclohexadiene, cycloheptadiene, cyclooctane alkene, cyclodecadiene, the carbon diene of ring 12 etc..
As the aliphatic unsaturated hydrocarbon of chain, internal olefin or terminal olefine can be enumerated, they can have in 1 intramolecular One or more unsaturated bonds.Further, in the case of with multiple unsaturated bonds, they can be conjugated can not also be total to Yoke.
As the specific example of the aliphatic unsaturated hydrocarbon of chain, it may be preferred to enumerate n-pentene, 2- n-pentenes, 3- positive penta Alkene, 2- methyl butenes, 2,2- dimethyl allenes, n-hexylene, 2- n-hexylenes, 3- n-hexylenes, 2- methylpentenes, 3- methylpentenes, 2,2- neohexenes, 2,3- neohexenes, 3- ethyl butylene, nhepene, 2- methylhexenes, 3- methylhexenes, 2,2- bis- Methylpentene, 2,3- dimethyl pentenes, 2,4- dimethyl pentenes, 3- ethylpentenes, positive octene, 2- methyl heptenyls, 3- methyl heptan Alkene, 4- methyl heptenyls, 2,2- dimethyhexenes, 2,3- dimethyhexenes, 3,3- dimethyhexenes, 3,4- dimethyhexenes, 3- Ethyl hexene, positive nonene, 2- methyl octenes, 3- methyl octenes, 4- methyl octenes, 2,2- dimethyhexenes, 2,3- dimethyl oneself Alkene, 2,4- dimethyhexenes, 2,5- dimethyhexenes, 3- ethyl hexenes, 4- ethyl hexenes, positive decene, 2- methyl nonenes, 3- first Base nonene, 4- methyl nonenes, 5- methyl nonenes, 2,2- dimethyl octenes, 2,3- dimethyl octenes, 2,4- dimethyl octenes, 2, 5- dimethyl octenes, 2,6- dimethyl octenes, 2,7- dimethyl octenes, trimethyl octene, the positive pentadienes of 1,3-, 1,4- positive penta 2 The positive hexadiene of alkene, 1,3-, the positive hexadienes of 1,4-, the positive hexadienes of 1,5-, the positive heptadiene of 1,3-, the positive heptadiene of 1,4-, 1,5- positive heptan The positive heptadiene of diene, 1,6-, the positive heptadiene of 2,4-, the positive hexadienes of 1,3-, the positive hexadienes of 1,4-, the positive hexadienes of 1,5-, 1,6- are just The positive hexadiene of hexadiene, 1,7-, the positive hexadienes of 2,4-, the positive hexadienes of 2,5-, the positive hexadienes of 2,6-, the positive nonadienes of 1,2-, 1,3- Positive nonadiene, the positive nonadienes of 1,4-, the positive nonadienes of 1,5-, the positive nonadienes of 1,6-, the positive nonadienes of 1,7-, the positive nonadienes of 1,8-, 2, The positive nonadienes of 4-, the positive nonadienes of 2,5-, the positive nonadienes of 2,6-, the positive nonadienes of 2,7-, the positive nonadienes of 3,5-, the positive nonadienes of 3,6-, The positive decadinene of 1,3-, the positive decadinene of 1,4-, the positive decadinene of 1,5-, the positive decadinene of 1,6-, the positive decadinene of 1,7-, the 1,8- positive last of the ten Heavenly stems two The positive decadinene of alkene, 1,9-, the positive decadinene of 2,4-, the positive decadinene of 2,5-, the positive decadinene of 2,6-, the positive decadinene of 2,7-, the 2,8- positive last of the ten Heavenly stems The positive decadinene of diene, 3,5-, the positive decadinene of 3,6-, the positive decadinene of 3,7-, the positive decadinene of 4,6- etc..
As the carbon number of aliphatic unsaturated hydrocarbon (b), preferably 4 ~ 10, more preferably 5 ~ 8, more preferably 6 ~ 7, Still more preferably it is 6.If the carbon number of aforementioned aliphatic unsaturated hydrocarbon (b) is within the above range, can be expeditiously Separated.
(aromatic hydrocarbon (c))
As aromatic hydrocarbon (c), it may be preferred to enumerate benzene, toluene, o-Dimethylbenzene, meta-xylene, xylol, ethylbenzene, diethyl in ground Base benzene, isopropylbenzene, trimethylbenzene etc..
As the carbon number of aromatic hydrocarbon (c), preferably 6 ~ 10, more preferably 6 ~ 8, more preferably 6 ~ 7, more enter one Step is preferably 6.If the carbon number of foregoing aromatic hydrocarbon (c) is within the above range, can expeditiously be separated.
Wherein, preferably comprise the saturated aliphatic hydrocarbon (a) of ring-type and the aliphatic unsaturated hydrocarbon (b) of ring-type hydrocarbon mixture or The hydrocarbon mixture of the aliphatic unsaturated hydrocarbon (b) containing ring-type and aromatic hydrocarbon (c), further preferably carbon number are 6 ~ 10 ring-type Saturated aliphatic hydrocarbon (a) and carbon number be the hydrocarbon mixture of the aliphatic unsaturated hydrocarbon (b) of 6 ~ 10 ring-type or former containing carbon Subnumber is the aliphatic unsaturated hydrocarbon (b) of 6 ~ 10 ring-type and the hydrocarbon mixture of the aromatic hydrocarbon (c) that carbon number is 6 ~ 10, further Preferably comprise the aliphatic unsaturated hydrocarbon of saturated aliphatic hydrocarbon (a) and carbon number for 6 ~ 8 ring-type of the ring-type that carbon number is 6 ~ 8 The hydrocarbon mixture of (b) or the aliphatic unsaturated hydrocarbon (b) containing the ring-type that carbon number is 6 ~ 8 and the virtue that carbon number is 6 ~ 8 The hydrocarbon mixture of race's hydrocarbon (c), further preferably carbon number are the saturated aliphatic hydrocarbon (a) and carbon atom of 6 or 7 ring-type Number is the hydrocarbon mixture or the unsaturation containing the ring-type that carbon number is 6 or 7 of the aliphatic unsaturated hydrocarbon (b) of 6 or 7 ring-type Aliphatic hydrocarbon (b) and carbon number are the hydrocarbon mixture of 6 or 7 aromatic hydrocarbon (c).
Aforementioned (a) ~ (c) compositions can have carbonyl, ether, hydroxyl, carboxylic in the range of the effect of the without prejudice to present invention The substituent groups such as base.
As long as contain selected from saturated aliphatic hydrocarbon for the hydrocarbon mixture of the extractive distillation of the extractant using the present invention A the hydrocarbon mixture of at least two in (), aliphatic unsaturated hydrocarbon (b) and aromatic hydrocarbon (c) then has no particular limits, can include Composition beyond above-mentioned (a) ~ (c).
Additionally, aforementioned hydrocarbon mixture is preferably and contains saturated aliphatic hydrocarbon from from the viewpoint of expeditiously being separated The hydrocarbon mixture or the hydrocarbon mixture containing saturated aliphatic hydrocarbon (a) He aromatic hydrocarbon (c) of (a) and aliphatic unsaturated hydrocarbon (b).
In hydrocarbon mixture containing saturated aliphatic hydrocarbon (a) and aliphatic unsaturated hydrocarbon (b), aforementioned (a) composition and aforementioned (b) into Point mass ratio [(a)/(b)] from from the viewpoint of expeditiously being separated and preferably 20/80 ~ 95/5, more preferably 40/ 60 ~ 90/10, more preferably 60/40 ~ 80/20.
In hydrocarbon mixture containing saturated aliphatic hydrocarbon (a) and aromatic hydrocarbon (c), the matter of aforementioned (a) composition and aforementioned (c) composition Amount than [(a)/(c)] from from the viewpoint of expeditiously being separated and preferably 20/80 ~ 95/5, more preferably 40/60 ~ 90/ 10, more preferably 60/40 ~ 80/20.
[separation method of hydro carbons]
The separation method of the hydro carbons of the present invention is from containing selected from saturated aliphatic hydrocarbon (a), aliphatic unsaturated hydrocarbon (b) and aromatic hydrocarbon The method of any one being somebody's turn to do in (a) ~ (c) is separated by extractive distillation in the hydrocarbon mixture of at least two in (c), wherein, make For extractant, using the extractant of the present invention.
The saturated aliphatic hydrocarbon (a) of separation method, aliphatic unsaturated hydrocarbon (b), aromatic hydrocarbon (c) for the present invention and contain Their hydrocarbon mixture is identical with what is enumerated in the explanation item of above-mentioned extractant, and suitable mode is also identical.
(extractant)
The present invention separation method by using the present invention extractant as extractant, can be in the situation of high security Under with high extraction efficiency separate target component.
Additionally, when separating the hydrocarbon mixture comprising Multiple components, in the range of the effect for not hindering the present invention, can make With the mixture with other solvents such as such as polar solvent.
[other polar solvents]
As other polar solvents, it is possible to use the aliphatic di-nitrile compounds such as the sulphones such as such as sulfolane, adiponitrile, N- first The dialkyl sulphoxides such as lactone compound, the dimethyl sulfoxides such as the N- alkylpyrrolidone compounds such as base ketopyrrolidine, gamma-butyrolacton Compound etc..In these other polar solvents, set out from a security point, preferably and with the lactone chemical combination such as gamma-butyrolacton Thing and water.
For the usage amount of these other extractants, from from the viewpoint of extraction efficiency and cost, aforementioned formula (1) institute The compound of expression is preferably 0.1 with the mol ratio of other polar solvents:0.9~1:0, more preferably 0.3:0.7~1:0, enter one Step is preferably 0.5:0.5~1:0.
(extraction conditionss)
Hereinafter, each condition of the separation method for being used to implement the present invention is illustrated.
[mixing ratio of extractant and hydrocarbon mixture]
As the usage amount of extractant, from from the viewpoint of raising extraction efficiency, the mol ratio of hydrocarbon mixture and extractant Example is preferably 1:0.5~1:10, more preferably 1:0.75~1:7, more preferably 1:1~1:5, it is still more preferably 1:1~ 1:2。
It is 1 by making the molar ratio of the extractant relative to hydrocarbon mixture in the present invention:More than 0.5, can improve The separation efficiency of target hydrocarbon, by being 1:Less than 10, the size of distilling apparatus can be suppressed, the recovery of solvent can be reduced Expense.
[extraction mode]
As for implement the present invention separation method mode, it is possible to use known mode, batch distillation or Any one of continuous way distillation, can suitably select according to purpose.
[extraction equipment]
As the device of the separation method for being used to implement the present invention, it is possible to use the known distilling apparatus such as distillation column come real Apply.
When implementing the separation method of the present invention with multisection type continuous still tower, for introduction segment and the raw material of extractant Supply section between hop count, between the hop count between tower top and the introduction segment of extractant and bottom of towe and the supply section of raw material Hop count, the relation of purity, the response rate of composition etc. can be distillated with pre research and suitably be selected.
[extraction temperature and pressure]
The temperature for implementing the separation method of the present invention can be according to suitably being selected with being separated into the boiling point etc. of the composition of target.This Outward, the pressure for implementing the separation method of the present invention can be any one of normal pressure, pressurization, decompression, it may be considered that extraction efficiency Suitably to determine.
Embodiment
Hereinafter, the present invention, but the present invention are further illustrated not by any restriction of these embodiments by embodiment.
Embodiment 1
As shown in figure 1, being separately added in table 1 to being provided with the 1L glass containers of Dropping funnel and two way cock (cock C) Shown extractant and hydrocarbon compound (a and b), obtain mixture, and the Dropping funnel is provided with condensing tube and with sampling With cock (cock A).At this moment, the cock (cock B) of Dropping funnel is opened, is entered in the way of backflow is returned in glass container Row is arranged, and with magnetic stirring apparatuss and stirrer stirring inside and the oil bath that heats up, makes mixture flow back.
Then, the temperature of oil bath is adjusted and maintained so that the drop fallen from cooling tube reaches 1 second about 2 ~ 3 drop.About 1 After hour, the cock (cock B) of Dropping funnel is closed, distillate is collected in Dropping funnel.During distillate accumulation about 1mL, make The distillate in Dropping funnel is gathered from sampling cock (cock A) with syringe, in the same way from being installed on glass system Two way cock (cock C) collection bottom liquid on container.
Liquid to gathering carries out gas chromatographic analysiss (detector), calculates the concentration (quality %) of hexamethylene, cyclohexene, Relative volatility α ab is calculated by following formula.
αab=(Y(a)/X(a))/(Y(b)/X(b))。
Y (a) and Y (b) are respectively hydrocarbon compound a and hydrocarbon compound b phases under vapor liquid equilibrium state in gas phase (distillate) For hydrocarbon compound a and the molar fraction of the total amount of hydrocarbon compound b.
The hydrocarbon compound a and hydrocarbon compound b that X (a) and X (b) are respectively in liquid phase under vapor liquid equilibrium state (bottom liquid) is relative In hydrocarbon compound a and the molar fraction of the total amount of hydrocarbon compound b.
Embodiment 2 ~ 3, comparative example 1 ~ 4
In embodiment 1, used extractant, distillation and their use are changed as described in Tables 1 and 2 Amount, in addition, by method similarly to Example 1 lock out operation is carried out.
By the relative volatility calculated in each embodiment and comparative example together with the information of the safety for being related to extractant In being shown in table 1 and table 2.Should illustrate, the MSDS that the following supplier's distribution of information reference of safety are related in Tables 1 and 2 (changes Learn Material Safety tables of data), represented with the benchmark described in table.
3- methoxyl group-N, N- dimethylpropionamides：Idemitsu Kosen Co., Ltd.
3- n-butoxy-N, N- dimethylpropionamides：Idemitsu Kosen Co., Ltd.
METHYLPYRROLIDONE：Wako Pure Chemical Industries, Ltd.
N,N-dimethylformamide：Wako Pure Chemical Industries, Ltd.
Dipropylene glycol：Asahi Glass Co., Ltd
Trimethyl phosphate：Tama Chemicals Co., Ltd.
N- N-formyl morpholine Ns：Wako Pure Chemical Industries, Ltd..
[table 1]
。
[table 2]
。
From table 1 ~ 2, by 3- methoxyl group-N, N- dimethylpropionamides, 3- n-butoxy-N, N- dimethylpropionamides etc. When compound represented by formula (1) is used for extractant, can be from containing aliphatic unsaturated hydrocarbon or aromatic hydrocarbon and saturated fat Saturated hydrocarbons are optionally distillated in the hydrocarbon compound of race's hydrocarbon, at the same can optionally concentrate in the liquid of bottom aliphatic unsaturated hydrocarbon, Aromatic hydrocarbon, can be utilized as the extractant of extractive distillation.And understand, the compound represented by these formulas (1) Compared with the NMP for using in the past, show high relative volatility and safety is also excellent, therefore the extractant of the present invention It is extractant safe, that extraction efficiency is high.

Claims (8)

1. the extractant of extractive distillation, it is used for from containing selected from saturated aliphatic hydrocarbon (a), aliphatic unsaturated hydrocarbon (b) and virtue The method of any one being somebody's turn to do in (a) ~ (c) is separated by extractive distillation in the hydrocarbon mixture of at least two in race's hydrocarbon (c), its use Following formulas (1) represent：
[changing 1]
In formula, R1It is straight chain, side chain or cyclic alkyl that carbon number is 1 ~ 6, R2And R3It is independently of one another that carbon number is 1 ~ 6 straight chain or branched alkyl, n is 0 ~ 2 integer.
2. extractant according to claim 1, wherein, in the hydrocarbon mixture, (a) composition and (b) into The mass ratio [(a)/(b)] for dividing is 20/80 ~ 95/5.
3. extractant according to claim 1 and 2, wherein, in the hydrocarbon mixture, (a) composition and (c) The mass ratio [(a)/(c)] of composition is 20/80 ~ 95/5.
4. the separation method of hydrocarbon mixture, it is from containing selected from saturated aliphatic hydrocarbon (a), aliphatic unsaturated hydrocarbon (b) and aromatic hydrocarbon The method of any one being somebody's turn to do in (a) ~ (c) is separated by extractive distillation in the hydrocarbon mixture of at least two in (c), wherein, make For extractant, the extractant according to any one of claim 1 ~ 3 is used.
5. the separation method of hydrocarbon mixture according to claim 4, wherein, it is 4 ~ 10 that (a) ~ (c) is carbon number Hydrocarbon.
6. the separation method of the hydrocarbon mixture according to claim 4 or 5, wherein, the hydrocarbon mixture is molten with the extraction The mol ratio of agent is 1:0.5~1:10.
7. the separation method of the hydrocarbon mixture according to any one of claim 4 ~ 6, wherein, the extractant is described The compound represented with formula (1) and the mixture of other solvents.
8. the separation method of hydrocarbon mixture according to claim 7, wherein, the compound that the use formula (1) represents with The mol ratio of other polar solvents is 0.1:0.9~1:0.
CN201580015895.9A 2014-03-28 2015-03-25 Extraction solvent for extractive distillation and method for separating hydrocarbons using the same Pending CN106573878A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014-069968 2014-03-28
JP2014069968 2014-03-28
PCT/JP2015/059103 WO2015147046A1 (en) 2014-03-28 2015-03-25 Extraction solvent for extractive distillation and method for separating hydrocarbons using same

Publications (1)

Publication Number Publication Date
CN106573878A true CN106573878A (en) 2017-04-19

Family

ID=54195557

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580015895.9A Pending CN106573878A (en) 2014-03-28 2015-03-25 Extraction solvent for extractive distillation and method for separating hydrocarbons using the same

Country Status (4)

Country Link
JP (1) JPWO2015147046A1 (en)
CN (1) CN106573878A (en)
TW (1) TW201600497A (en)
WO (1) WO2015147046A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112271400A (en) * 2020-09-01 2021-01-26 广州天赐高新材料股份有限公司 Novel application of amide compound
CN114751826A (en) * 2022-04-21 2022-07-15 厦门大学 Extraction and rectification method for separating ethyl acetate and methylcyclohexane azeotrope

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023248810A1 (en) * 2022-06-24 2023-12-28 株式会社カネカ Polyamic acid composition, polyimide production method, laminate production method, and electronic device production method

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3914303A (en) * 1972-09-01 1975-10-21 Cpc International Inc Preparation of N,N-dialkylacylamides
JP4377594B2 (en) * 2003-02-19 2009-12-02 出光興産株式会社 Process for producing β-alkoxypropionamides
JP5601075B2 (en) * 2010-08-04 2014-10-08 株式会社リコー Ink jet ink, ink cartridge, ink jet recording method, ink jet recording apparatus, and ink recorded matter
JP2013189411A (en) * 2012-03-15 2013-09-26 Kohjin Holdings Co Ltd METHOD FOR PRODUCING N-SUBSTITUTED-β-ALKOXYPROPIONIC ACID AMIDE

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112271400A (en) * 2020-09-01 2021-01-26 广州天赐高新材料股份有限公司 Novel application of amide compound
CN114751826A (en) * 2022-04-21 2022-07-15 厦门大学 Extraction and rectification method for separating ethyl acetate and methylcyclohexane azeotrope
CN114751826B (en) * 2022-04-21 2023-02-28 厦门大学 Extractive distillation method for separating ethyl acetate and methylcyclohexane azeotrope

Also Published As

Publication number Publication date
JPWO2015147046A1 (en) 2017-04-13
TW201600497A (en) 2016-01-01
WO2015147046A1 (en) 2015-10-01

Similar Documents

Publication Publication Date Title
EP0679708B1 (en) Single column extractive distillation for the separation of aromatic hydrocarbons from a hydrocarbon mixture
KR101440637B1 (en) Method for separating a c4 fraction by means of extractive distillation using a selective solvent
US11731922B2 (en) Method for separating aromatic hydrocarbon using extractive distillation
CN106573878A (en) Extraction solvent for extractive distillation and method for separating hydrocarbons using the same
CN103360201B (en) The method of recycling vinyl benzene with abstraction distillation from hydrocarbon mixture
US8282816B2 (en) Extractive distillation process and system
KR20120030382A (en) Fractional extraction of butadiene
TWI615378B (en) Flexible butadiene extraction process
US20140216915A1 (en) Apparatus for removing a contaminant from a solvent separation process
US3844902A (en) Combination of extractive distillation and liquid extraction process for separation of a hydrocarbon feed mixture
CN104193575A (en) Device and method for extracting, distilling and separating propane and propylene
US10266463B2 (en) Process for recovering isoprene from pyrolysis gasoline
US9656929B2 (en) Co-extraction systems for separation and purification of butadiene and isoprene
US4693810A (en) Process for the separation of hydrocarbons from a mixed feedstock
CN114425180A (en) Improved eutectic solvent, preparation method thereof and application of improved eutectic solvent in separation of polycyclic aromatic hydrocarbon
CN101468938A (en) Double solvent for extracting, distilling and separating styrene in hydrocarbons mixture
CN102140369A (en) Preparation method of aromatic rubber oil
US3617535A (en) Recovery of aromatic hydrocarbons from hydrocarbon mixtures by selective extraction and/or extractive distillation
US20100300939A1 (en) Process for Removing a Contaminant from an Aromatic Selective Solvent
CN107779220B (en) A kind of gasoline processing method
CN103360200A (en) Composite solvent and method for extracting, rectifying and recovering styrene from hydrocarbon mixture
US2652439A (en) Hydrocarbon separation
CN109694744A (en) The method of the recovery method and crude lube stock oil dewaxing of crude lube stock oil dewaxing solvent
US8747622B2 (en) Aromatics-recovery process
KR102049312B1 (en) Method for providing a purified crude gaseous c4 fraction as an input stream for an extractive distillation using a selective solvent

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170419

WD01 Invention patent application deemed withdrawn after publication