CN103232313A - Extraction and separation method of alkane/olefin - Google Patents
Extraction and separation method of alkane/olefin Download PDFInfo
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- CN103232313A CN103232313A CN2013101631321A CN201310163132A CN103232313A CN 103232313 A CN103232313 A CN 103232313A CN 2013101631321 A CN2013101631321 A CN 2013101631321A CN 201310163132 A CN201310163132 A CN 201310163132A CN 103232313 A CN103232313 A CN 103232313A
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Abstract
The invention discloses an extraction and separation method of alkane/olefin and belongs to the technical field of separation of olefin. The extraction and separation method of alkane/olefin comprises the following steps of: sufficiently contacting and mixing a to-be-separated mixture containing carbon-isotope normal alkane and high-carbon alpha-olefin with an extracting agent; standing, layering and separating, wherein the high-carbon alpha-olefin enters an extracting phase, the carbon-isotope alkane enters the extracting phase for separating. The extracting agent is N-methylpyrrolidone (NMP), N-formyl morpholine (NFM), 1-methylimidazole(1-MI) or gamma-butyrolactone(gamma-BL); and the total volume ratio of the extracting agent to the to-be-separated mixture is 0.25, 0.5, 1.0 or 2.0. The extraction and separation method of the alkane/olefin is simple and environment-friendly.
Description
Technical field
The invention belongs to the separation technology field of alkene, particularly relate to and use particular technology that alpha-olefin is separated from the mixture that contains saturated alkane, say so more specifically the 1-hexene is separated from the mixture that contains normal hexane.
Background technology
High-carbon alpha-olefins such as 1-hexene, 1-octene are organic petrochemical materials important and commonly used, can be used as washing composition, oil dope, tensio-active agent and medicine intermediate etc.They also can be used as the high-quality comonomer and produce high-grade polyolefin resin.Compare with the polyvinyl resin that traditional 1-butylene copolymerization obtains, high density polyethylene(HDPE) (HDPE) and Low Density Polyethylene (LLDPE) by the 1-hervene copolymer all have the former unsurpassable advantage at aspects such as resistance to impact shock, tear strength, tensile strength and stability, and high-carbon alpha-olefins such as 1-hexene, 1-octene replace 1-butylene and the production of propylene copolymer resins is later developing direction.Therefore, they at home and abroad the demand on the market increase year by year and increase rapidly.
At present, the production technique of 1-hexene, 1-octene mainly is ethylene oligomerization method and Fischer-Tropsch synthesis.Two kinds of routes all relate to alpha-olefin with carbon number alkane and other with the separating of carbon number isomers, their boiling point is very approaching, relative volatility belongs to nearly boiling range system close to 1.Common rectificating method is difficult to make the two separation, and energy consumption is high.
At present for high-carbon alpha-olefin with the separating of carbon number alkane, the pertinent literature reported method mainly is extracting rectifying and fractionation by adsorption etc.
Patent CN102452888A discloses a kind of method of separating the 1-hexene from oil from Fischer-Tropsch synthesis.This method obtains C by the cutting light oil fraction
6Cut removes wherein organic oxygen-containing compound with the method for extracting rectifying then; And then separate alkane and the alkene of this carbon number with extraction fractional distillation; Under the effect of catalyzer, remove wherein tertiary carbon alkene with the method for reactive distillation again; Method with precise distillation obtains the 1-hexene at last.Wherein the extraction agent of extracting rectifying separation of alkane and olefin process section is a kind of or CAN among ACN, NMP, the DMF or the binary mixed solvent of NMP and water.Though this method can be isolated the 1-hexene effectively from oil from Fischer-Tropsch synthesis, related process energy consumption is higher and have restrictive factors such as facility investment is big.
Patent CN102452886A has set forth a kind of method by purification 1-octene in the oil from Fischer-Tropsch synthesis.Synthesizing light ends oil with Fischer-Tropsch in its described method is raw material, and cutting obtains C through the secondary cut
8The cut section, the binary azeotropic agent of forming with the second alcohol and water earlier adopts the method for azeotropic distillation to remove wherein sour and other oxygenatedchemicalss then; Pass through alkane and the alkene of this cut section of separation of extracting rectifying again, obtain C
8Alkene is further purified this alkene by precise distillation, obtain meeting the 1-octene product of polymerization-grade requirement.Disclosed processing unit system complex and energy consumption are high.
Patent CN102690161A provides a kind of separation method of benzol-cyclohexane-tetrahydrobenzene.This invention adopts DMAC+N-methyl-2-pyrrolidone (NMP) or gamma-butyrolactone to realize the separation of benzol-cyclohexane-tetrahydrobenzene as the extraction agent extraction fractional distillation.The process system that is applied in this invention utilizes partition wall rectifying principle, uses single tower to realize the function of multitower.Though this extraction and distillation technology has reduced energy consumption to a certain extent, it is not comparatively ideal separation method.
Patent CN101462919A discloses a kind of separation method of alkene absorption.Namely by incoming flow is contacted with sorbent material on the adsorbent bed, sub-argument goes out purification agent alkene from the logistics that comprises one or more alkane selectively.Have a problem when but this method is separated alkene: along with causing that because of the selected sorbent material of the accumulation of more objectionable impuritiess in the incoming flow toxic action increases, the ability of sorbent material will descend, thereby causes the decline of the throughput of whole technology.
Patent CN1738785A has set forth a kind of separation method that separates linear alpha-alkene from stable hydrocarbon.By allowing raw material contact with linear polyaromatic compound and addition reaction takes place with the linear polyaromatic compound-olefin adducts of effective formation, and then isolate alpha-olefin by dissociation.The i.e. related technical process of this invention comprises adduction, reequilibrate, separates, dissociates and later separation, and technology is too complicated, causes cost and energy consumption higher.
In view of the separating technology energy consumption height of above olefin/paraffin, the situation of complex technical process, the separating technology of being badly in need of a kind of effective less energy-consumption of exploitation makes alkene can access cost-effectively with alkane to separate.
Summary of the invention
The present invention is intended to solve existing problem, and a kind of extraction separating method of alkane/olefin is provided, and is especially a kind of from the processing method with extracting and separating high-carbon alpha-olefin the carbon alkane.
Particularly, the wide in range embodiment of the present invention is to isolate the separation method of the solvent extraction (claiming liquid-liquid extraction again) of high-carbon alpha-olefin from comprise the mixed solution with carbon normal paraffin (referring to the normal paraffin identical with the carbonatoms of high-carbon alpha-olefin with the carbon normal paraffin).
Technical scheme of the present invention is: the mixture to be separated that will contain with carbon normal paraffin and high-carbon alpha-olefin fully contacts mixing with extraction agent, standing demix and separating then, wherein high-carbon alpha-olefin enters extraction phase, enters extracting phase with carbon alkane, separates.
Further mixture to be separated not only comprises with carbon normal paraffin and high-carbon alpha-olefin, the organic compound that can also contain other, as with other alkene of high-carbon alpha-olefin same carbon number with other alkane of carbon, be the C that in the industrial production raw material light oil fraction oil is cut fractionation and extracting rectifying and remove the organic oxygen-containing material as mixture to be separated
6Cut.
Used extraction agent is that (γ-BL), the temperature in the liquid-liquid extraction process described in the inventive method is 25 ℃-35 ℃ for N-Methyl pyrrolidone (NMP), N-N-formyl morpholine N-(NFM), 1-Methylimidazole (1-MI) or gamma-butyrolactone; The cumulative volume of extraction agent and mixture to be separated is than (abbreviation is compared)=0.25,0.5,1.0 or 2.0.The extraction time is generally 2h; The phase-splitting time is 1h.
Above-mentioned liquid-liquid extraction is particularly useful for the separation of 1-hexene/normal hexane.
The inventive method is simple, economy, environmental protection.
Specific implementation method
Further specify the present invention in conjunction with the embodiments, but the present invention is not limited to following examples.
Embodiment 1
Mixture to be separated is the mixed solution of the 1-hexene/normal hexane of different ratios, and 1-hexene and normal hexane can arbitrary proportions, and extraction agent is N-N-formyl morpholine N-(NFM);
At first compare (0.25,0.5,1.0) according to difference, the extraction agent NFM that adds certain volume in the mixed solution of 1-hexene and normal hexane, the mixed solution that fills three kinds of materials is put into volumetric flask, again volumetric flask is placed 25 ℃ of water bath with thermostatic control vibrators to shake 2h, leave standstill 1h then.
Change the temperature of vibrator, repeat above experiment.
The extraction results that the extraction selectivity S of the 1-hexene of extraction agent NFM represents under differing temps (25 ℃, 30 ℃, the 35 ℃) condition sees Table 1.
The extraction selectivity of the 1-hexene of extraction agent NFM under table 1 differing temps
w
The 1-hexene% is the molar content of 1-hexene in mixture to be separated; S-NFM is the selectivity of the 1-hexene of extraction agent NFM, i.e. the partition ratio of the partition ratio of 1-hexene in extraction phase/in extracting phase.
The extraction selectivity of 25 ℃ as can be seen from Table 1,30 ℃ and the 35 ℃ 1-hexenes of extraction agent NFM is respectively at 1.3-2.2,1.8-4.1,1.4-3.4, all greater than 1, and the separating effect ideal.
Embodiment 2
Feed liquid is the mixed solution of the 1-hexene/normal hexane of different ratios, and proportionlity wherein is that the molar content of 1-hexene in mixed solution is between 0-1;
Extraction agent is gamma-butyrolactone (γ-BL);
At first compare (0.5,1.0,2.0) according to difference, extraction agent γ-the BL that adds certain volume in the mixed solution of 1-hexene and normal hexane, the mixed solution that fills three kinds of materials is put into the low capacity bottle, again volumetric flask is placed the water bath with thermostatic control vibrator to shake 2h, leave standstill 1h then.Change the temperature of vibrator, repeat above experiment.The extraction results that the extraction selectivity S of the 1-hexene of extraction agent γ-BL represents under differing temps (25 ℃, 30 ℃, the 35 ℃) condition sees Table 2.
The extraction selectivity of the 1-hexene of table 2 differing temps extraction agent γ-BL
25 ℃ as can be seen from Table 2,30 ℃, 35 ℃, the extraction selectivity of extraction agent NFM, NMP, the 1-hexene of γ-BL, 1-MI is respectively at 1.3-2.1,1.5-3.5,1.6-3.4, all greater than 1.
Embodiment 3
(1) raw material light oil fraction oil is carried out fractionation, cutting obtains C
6 +Cut;
(2) C that previous step is obtained
6 +The further fractionation of cut obtains C
6Cut;
(3) C that previous step is obtained
6Carry out extracting rectifying, remove wherein contained organic oxygen-containing compound with polar solvent as extraction agent 1; Wherein used extraction agent 1 can be any in N-Methyl pyrrolidone (NMP), acetonitrile (ACN) or the dimethyl formamide (DMF);
(4) C that previous step is obtained
6Cut carries out liquid-liquid extraction, with C
6Alkane and C
6Alkene separates; Wherein used extraction agent is NMP, N-N-formyl morpholine N-(NFM), 1-Methylimidazole (1-MI) or gamma-butyrolactone (γ-BL); The cumulative volume of extraction agent and mixture to be separated is than (abbreviation is compared)=0.25,0.5,1.0 or 2.0.
Through the resulting C of cutting twice
6Contain alkane, alkene and organic oxygen-containing compound in the cut section simultaneously.Because organic oxygen-containing compound can form a large amount of azeotropes with hydrocarbon, thereby can not remove by simple distillation, utilize the difference of polarity between the hydro carbons of extraction agent 1 and the organic oxygen-containing compound, remove C
6Organic oxygen-containing compound in the cut;
After the liquid-liquid extraction through above-mentioned steps (4), the 1-hexene is in extraction phase, and other fractions are in extracting phase.
Claims (6)
1. the extraction separating method of an alkane/olefin, it is characterized in that, the mixture to be separated that will contain with carbon normal paraffin and high-carbon alpha-olefin fully contacts mixing with extraction agent, standing demix and separating then, wherein high-carbon alpha-olefin enters extraction phase, enter extracting phase with carbon alkane, separate.
2. according to the method for claim 1, it is characterized in that further mixture to be separated not only comprises with carbon normal paraffin and high-carbon alpha-olefin, can also contain with other alkene of high-carbon alpha-olefin same carbon number with other alkane of carbon.
3. according to the method for claim 1, it is characterized in that, is the C that in the industrial production raw material light oil fraction oil is cut fractionation and extracting rectifying and remove the organic oxygen-containing material as mixture to be separated
6Cut.
4. according to the method for claim 1, it is characterized in that, used extraction agent is that (γ-BL), extraction agent compares=0.25,0.5,1.0 or 2.0 with the cumulative volume of mixture to be separated for N-Methyl pyrrolidone (NMP), N-N-formyl morpholine N-(NFM), 1-Methylimidazole (1-MI) or gamma-butyrolactone.
5. according to the method for claim 1, it is characterized in that the temperature in the liquid-liquid extraction process is 25 ℃-35 ℃.
6. according to the described arbitrary method of claim 1-5, it is characterized in that, be particularly useful for the separation of 1-hexene/normal hexane.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152841A (en) * | 2015-09-25 | 2015-12-16 | 中北大学 | Low-temperature-freezing magnetic separation method and device for long-chain alkene and long-chain alkane mixture |
| CN106966852A (en) * | 2016-01-14 | 2017-07-21 | 天津大学 | The method that continuous extraction rectifying separates high-carbon n-alkane and normal olefine |
| CN109012202A (en) * | 2018-09-25 | 2018-12-18 | 河南科技大学 | A kind of method and device using the continuous Olefin/Paraffin Separation of electric field |
| CN109569321A (en) * | 2018-11-14 | 2019-04-05 | 内蒙古伊泰煤基新材料研究院有限公司 | A kind of film and its separation method for alkane separation of olefins |
| CN113087587A (en) * | 2019-12-23 | 2021-07-09 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for separating alkane and olefin by using simulated moving bed |
| CN114478169A (en) * | 2020-11-12 | 2022-05-13 | 国家能源投资集团有限责任公司 | Method and device for separating and purifying 1-hexene from Fischer-Tropsch synthetic oil |
| CN114736091A (en) * | 2021-01-07 | 2022-07-12 | 国家能源投资集团有限责任公司 | Method and apparatus for separating 1-hexene from hydrocarbon stream containing C6 olefins |
| CN114736092A (en) * | 2021-01-07 | 2022-07-12 | 国家能源投资集团有限责任公司 | Process for separating olefins from a mixture of alkanes and olefins |
| CN115612521A (en) * | 2021-07-14 | 2023-01-17 | 国家能源投资集团有限责任公司 | Process for removing oxygenates from a hydrocarbon-containing stream |
| WO2024108672A1 (en) * | 2022-11-24 | 2024-05-30 | 内蒙古伊泰煤基新材料研究院有限公司 | α-OLEFIN EXTRACTANT AND METHOD FOR SEPARATING ALKANES AND α-OLEFINS |
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| US3755154A (en) * | 1969-12-10 | 1973-08-28 | Nissan Chemical Ind Ltd | Separation of hydrocarbons from mixture thereof |
| US4385196A (en) * | 1981-05-18 | 1983-05-24 | Phillips Petroleum Company | Liquid-liquid extraction of low boiling olefin contained in olefin-paraffin mixture using sulfolane-ketone solvent system |
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| US3755154A (en) * | 1969-12-10 | 1973-08-28 | Nissan Chemical Ind Ltd | Separation of hydrocarbons from mixture thereof |
| US4385196A (en) * | 1981-05-18 | 1983-05-24 | Phillips Petroleum Company | Liquid-liquid extraction of low boiling olefin contained in olefin-paraffin mixture using sulfolane-ketone solvent system |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152841B (en) * | 2015-09-25 | 2017-03-01 | 中北大学 | Freezing Magneto separate long-chain olefin and the method and device of paraffins mixture |
| CN105152841A (en) * | 2015-09-25 | 2015-12-16 | 中北大学 | Low-temperature-freezing magnetic separation method and device for long-chain alkene and long-chain alkane mixture |
| CN106966852B (en) * | 2016-01-14 | 2019-10-25 | 天津大学 | The method of continuous extraction rectifying separation high-carbon n-alkane and normal olefine |
| CN106966852A (en) * | 2016-01-14 | 2017-07-21 | 天津大学 | The method that continuous extraction rectifying separates high-carbon n-alkane and normal olefine |
| CN109012202A (en) * | 2018-09-25 | 2018-12-18 | 河南科技大学 | A kind of method and device using the continuous Olefin/Paraffin Separation of electric field |
| CN109569321B (en) * | 2018-11-14 | 2019-11-08 | 内蒙古伊泰煤基新材料研究院有限公司 | A kind of film and its separation method for alkane separation of olefins |
| CN109569321A (en) * | 2018-11-14 | 2019-04-05 | 内蒙古伊泰煤基新材料研究院有限公司 | A kind of film and its separation method for alkane separation of olefins |
| CN113087587A (en) * | 2019-12-23 | 2021-07-09 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for separating alkane and olefin by using simulated moving bed |
| CN114478169A (en) * | 2020-11-12 | 2022-05-13 | 国家能源投资集团有限责任公司 | Method and device for separating and purifying 1-hexene from Fischer-Tropsch synthetic oil |
| CN114736091A (en) * | 2021-01-07 | 2022-07-12 | 国家能源投资集团有限责任公司 | Method and apparatus for separating 1-hexene from hydrocarbon stream containing C6 olefins |
| CN114736092A (en) * | 2021-01-07 | 2022-07-12 | 国家能源投资集团有限责任公司 | Process for separating olefins from a mixture of alkanes and olefins |
| CN114736092B (en) * | 2021-01-07 | 2024-04-02 | 国家能源投资集团有限责任公司 | Process for separating olefins from mixtures of alkanes and olefins |
| CN115612521A (en) * | 2021-07-14 | 2023-01-17 | 国家能源投资集团有限责任公司 | Process for removing oxygenates from a hydrocarbon-containing stream |
| WO2024108672A1 (en) * | 2022-11-24 | 2024-05-30 | 内蒙古伊泰煤基新材料研究院有限公司 | α-OLEFIN EXTRACTANT AND METHOD FOR SEPARATING ALKANES AND α-OLEFINS |
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Application publication date: 20130807 |