CN102701895B - Method for extracting and separating liquid olefin and alkane mixture by adopting functional ionic liquid - Google Patents
Method for extracting and separating liquid olefin and alkane mixture by adopting functional ionic liquid Download PDFInfo
- Publication number
- CN102701895B CN102701895B CN201210191815.3A CN201210191815A CN102701895B CN 102701895 B CN102701895 B CN 102701895B CN 201210191815 A CN201210191815 A CN 201210191815A CN 102701895 B CN102701895 B CN 102701895B
- Authority
- CN
- China
- Prior art keywords
- extraction
- liquid
- group
- charged ion
- positively charged
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a method for separating a liquid olefin and alkane mixture by adopting a functional ionic liquid. In the method, high-purity olefin is separated efficiently from an olefin and alkane mixture with a fractional extraction method by taking a liquid olefin and alkane mixture as a raw material liquid, taking an ion liquid of which cation is substituted by an unsaturated functional group and taking olefin as a washing agent. The method has the advantages of high separating efficiency, low solvent consumption, safety, environment friendliness, easiness for industrial production and the like, and the content of the obtained product olefin is higher than 98 percent.
Description
Technical field
The present invention relates to separation of olefins and purifying, belong to technical field of chemical engineering, be specifically related to a kind of method that adopts functionalized ion liquid extracting and separating from alkene and paraffins mixture to obtain high purity olefin.
Background technology
Alkene is important basic chemical industry raw material, can be used for synthetic polymer and other chemical, and industrial application value is high.Wherein, ethylene industry, as the mainstay industry of petrochemical industry, always occupies critical role in national economy.Ethylene yield and production level are as the sign of weighing a country or regional petrochemical industry industry developmental level.The scale of ethylene production, cost, becomes to produce and stablizes, and quality producies etc. play dominating role to whole petrochemical complex.Hexene also has higher industrial application value, and, shock resistance high by the resin stretched intensity of its prepared PE and lear energy are strong, are the desirable feedstock of Production and Packaging film and agricultural mulch films.
At present, alkene is generally by petrochemical material catalytic pyrolysis preparations such as heavy oil, Sweet natural gas, but cracking obtains, is the mixture of alkane and alkene, and this has affected alkene in industrial application, special in the production of polymer materials, the alkene purity requirement of not enough Production requirement far away.Therefore, the separation of olefin/paraffin has become the committed step of alkene industry.But alkene that carbon number is identical is similar with alkane structure, character approaches, boiling point difference is little, and separating difficulty is large.
The processing method of existing the separation of olefins and alkane has, low-temperature extraction, solvent absorbing, fractionation by adsorption, extracting rectifying, membrane sepn etc.Various technique all has certain effect aspect the separation of olefins and alkane, but due to the singularity of alkene and alkane mixed system, existing separating technology all exists certain deficiency.
In Chinese patent CN1338449A, introduced separation by deep refrigeration and from hydrocarbon-containifirst mixed gas, reclaimed the method for ethene, ethane, but need under low temperature and high pressure, carry out, energy consumption is larger.
U.S. Pat 5460700 is used hexyl acetate, methyl phenyl ketone etc. as entrainment agent, for separation of extractive distillation 1-hexene and hexane, both relative volatilities are increased to 1.35 by 1.07, but the rectifiying plate number needing is 41, still need larger energy requirement, hexyl acetate, methyl phenyl ketone are volatile organic matters simultaneously, while using as entrainment agent, have hexene and the entrainment agent problem of rectifying separation again.
Chinese patent application CN102134177A has introduced a kind of take tetramethylene sulfone as extraction agent separating cyclohexene with the method for hexanaphthene mixed system, and by solvent recovery tower, realizes the recycle of tetramethylene sulfone.
Chinese patent application CN1681754A discloses a kind of method of using polarity extracting agent separation of extractive distillation butylene and butane; polarity extracting agent is anhydrous or the organic solvent that contains 0.1%-20% quality water, comprises dimethyl formamide, N-Methyl pyrrolidone, acetonitrile, furfural, N-formyl morpholine or N,N-DIMETHYLACETAMIDE.
Chinese patent application CN101028987A discloses the device of a kind of separation of extractive distillation propylene and propane, and extraction agent used is containing water-acetonitrile, adopts less reflux ratio and number of theoretical plate, reaches good separating effect and higher product yield.
5069756 of U.S. Pat application ethylene glycol monomethyl ether and propyl carbinol be as azeotropic distillation entrainment agent, or use ethylene glycol monomethyl ether and diacetone alcohol as extracting rectifying entrainment agent separating cyclohexene and hexanaphthene.
Above isolation technique exists separation selectivity low, the little deficiency that waits for the treatment of capacity, and also there is the separation problem of extraction agent and olefin product in the while.For this reason, in separating medium, introduce transition metal, as Ag, Cu etc., utilize the chemical complexing effect existing between metal ion and olefinic double bonds, improved alkene at separating medium, as the sendout on sorbent material, absorption agent, liquid film.Chinese patent application CN1680019A discloses a kind of gac of supported rare earth element compound, for the separation of olefin/paraffin, this sorbent material can significantly improve separation factor, can well be used for the Olefin/Paraffin Separations such as petroleum cracking, catalytic pyrolysis, ethylene oxide production.
Chinese patent application CN101657396A discloses and from C4 hydrocarbon mixture, has separated the technique that obtains 1-butylene, in patent, main use can optionally form sorbent material, X-type zeolite or the y-type zeolite sorbent material of π complexing with alkene, or the X-type of metal ion exchanged or y-type zeolite sorbent material, and in conjunction with distil process, realize the purifying of 1-butylene.
Like this, improving the optionally while separating, also increased the treatment capacity separating, but the easy inactivation of metal ion, production cost is high, has very large deficiency in application.
Meanwhile, ionic liquid is also used to the separation of olefins and alkane, and U.S. Pat 7619129B2 discloses a kind of using the ionic liquid containing alkyl group side chain as liquid film composition, adopts membrane separation technique the separation of olefins and paraffins mixture.In extracting and separating, Chinese patent application CN101148392A has reported and a kind ofly with ionic liquid and organic solvent mixed extractant separation of C 4 hydrocarbon mixtures, has obtained divinyl wherein, realized the purifying of alkene; The ionic liquid that U.S. Pat 2011/0015461A1 discloses a kind of silver ion is for from alkene and paraffins mixture the separation of olefins; U.S. Pat 6623659B2 has shown the effectively Olefin/Paraffin Separation system of ionic liquid that contains IB family metal, wherein separating effect the best of silver ions.
But, due to the volatility of organic solvent, although ionic liquid adds organic solvent can improve alkene rate of mass transfer therein, but caused the separation problem of alkene and solvent, the stability of the ionic liquid of metal ion and the deficiency such as expensive have also limited the ionic liquid of metal ion in the large-scale application of extracting and separating alkene and alkane.
Summary of the invention
Ionic liquid, is that a class is comprised of zwitterion, is the meltbility salt of liquid under room temperature or nearly room temperature condition, at separation field as the green novel separating medium of a class and noticeable.Compared with conventional organic solvents, ionic liquid has some unique character as absorption agent, have very wide liquid temperature scope, almost negligible vapour pressure, non-volatile, non-combustible, organism and inorganics are had to good solubility property, have good thermostability, there is designability simultaneously, can carry out as required functionalized design synthetic, in chemical separating field, have a good application prospect.
Because alkene exists undersaturated carbon-carbon double bond, there is certain π electron effect.The present invention finds: for good the separation of olefins and alkane, on ionic liquid, introduce the functional group with unsaturated group, as cyano group, thiazolinyl, amide group, ester group etc., can improve π-π complexing action of ionic liquid and olefinic double bonds, improve the selectivity separating.
Therefore, the invention provides a kind of functionalized ion liquid on positively charged ion with the unsaturated functional group of single or two replacements that adopts as extraction agent, the alkene of extracting and separating liquid state and the method for paraffins mixture, the method can obtain high purity olefin, and absolute purity can reach more than 98%.
Adopt ion liquid abstraction to separate a method for liquefied olefines and paraffins mixture, comprise the following steps:
1) using liquefied olefines and paraffins mixture as stock liquid, add ionic liquid as extraction agent, using described alkane as washing composition, the alkene in raw material is carried out to fractionation extraction;
Described fractionation extraction is divided into extraction section and washing section, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in alkene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment alkane;
2) extraction liquid is distilled, collect distillate and obtain high-purity alkene, remaining liq is ion liquid abstraction agent, and this extraction agent can be recycled.
Described ionic liquid is comprised of positively charged ion M+ and anion N-two portions;
Described positively charged ion M+ is imidazole type positively charged ion, the pyridine type positively charged ion with monosubstituted group, the piperidines type positively charged ion with monosubstituted group or disubstituted group, the tetramethyleneimine type positively charged ion with monosubstituted group or disubstituted group with monosubstituted group or disubstituted group, have monosubstituted group or disubstituted quaternary phosphine type positively charged ion, have the one in the quaternary ammonium cation of monosubstituted group or disubstituted group;
Described substituted radical has the one in thiazolinyl, cyano group, amide group, ester group at least;
Described anion N-be the one in hexafluoro-phosphate radical, trifluoroacetic acid root, trifluoromethayl sulfonic acid root, ethylsulfonic acid root, dimethyl phosphate radical, diethyl phosphate radical, dihydrogen phosphate, dicyanamide root, three cyanogen methyl roots, four cyanogen borates, two (trifluoromethane sulphonyl) imines root.
Described washing composition is identical with the alkane in raw material, can improve separating effect on the one hand, has avoided on the other hand introducing other material in the raffinate of the enrichment alkane obtaining, and raffinate is without obtaining high purity alkane through processing.
Described extraction agent is selected pure list or difunctionalization ionic liquid, utilize the unsaturated functional group of ionic liquid and specific π-π effect that olefinic double bonds forms, improve alkene and the dissolubility difference of alkane in ionic liquid, realize both high efficiency separation.
Optionally, described substituted radical has C at least
1～C
6straight-chain alkenyl, C
1～C
6straight chain cyano group, C
1～C
6straight chain amide group, C
1～C
6straight chain ester group in one.
Specifically, described monosubstituted group is C
1～C
6straight-chain alkenyl, C
1～C
6straight chain cyano group, C
1～C
6straight chain amide group, C
1～C
6straight chain ester group in one; Two substituted radicals in described disubstituted group are identical, and substituted radical is C
1～C
6straight-chain alkenyl, C
1～C
6straight chain cyano group, C
1～C
6straight chain amide group, C
1～C
6straight chain ester group in one; Or, two substituted radical differences in described disubstituted group, one of them substituted radical is C
1～C
6straight-chain alkenyl, C
1～C
6straight chain cyano group, C
1～C
6straight chain amide group, C
1～C
6straight chain ester group in one, another substituted radical is C
1～C
6straight chained alkyl.
Further, described positively charged ion M+ can select 1-cyanogen propyl group-3-Methylimidazole positively charged ion, 1-acetamido-3-Methylimidazole positively charged ion, N-allyl pyridine positively charged ion, N-acetamido-N-methyl piperidine positively charged ion, 1-ethyl propenoate base-3-Methylimidazole positively charged ion, 1,3-dicyan propyl imidazole positively charged ion, diethyl-dicyan propyl ammonium positively charged ion, 1-allyl group-3-Methylimidazole positively charged ion, 1, the one in 3-diacetylamino glyoxaline cation etc.
Further, described negatively charged ion is the one in hexafluoro-phosphate radical, trifluoromethayl sulfonic acid root, dicyanamide root, three cyanogen methyl roots, four cyanogen borates, two (trifluoromethane sulphonyl) imines root.
In the handled alkene of the present invention and paraffins mixture, alkene molar content is 5%～95%, can be that the liquid hydrocarbon product that alkene obtains is produced in the preparations such as existing supercritical solvent is synthetic, waste polyolefine plastics, through Transformatin impurity and heavy constituent in early stage, main component is the blending ingredients of alkene and alkane.Wherein, under other condition prerequisite as certain in conditions such as the kinds of ionic liquid, when the content of alkene is lower, extracting and separating has obvious selectivity, separate required extraction progression less, can reduce separation costs, when the molar content of alkene is 5%～20% time, the best results of extracting and separating.
In described liquefied olefines and paraffins mixture, alkene is C
5above chain alkene and/or C
5above cyclic olefin, alkane is C
5above chain alkane and/or C
5above cyclic alkane.
Further, in described liquefied olefines and paraffins mixture, alkene is C
5～C
9chain alkene and/or C
5～C
9cyclic olefin, alkane is C
5～C
9chain alkane and/or C
5～C
9cyclic alkane.
In described liquefied olefines and paraffins mixture, the carbonatoms of alkene and alkane can be the same or different, and the effect of extracting and separating is not had a significant effect, and when generally the carbonatoms of alkene and alkane is identical, the difficulty of extracting and separating can increase.
The operating temperature range of described fractionation extraction, at-20 ℃～50 ℃, under high temperature, can make stock liquid volatilization, reduces the ability of extracting and separating; And during low temperature, the viscosity of ionic liquid is too high, has reduced the distribution capability of alkene in ionic liquid.
While carrying out fractionation extraction, consider the factors such as quality product, production cost, the stream ratio between extraction agent, washing composition, stock liquid three is preferably 2～15: 1～5: 1.Stream of the present invention is than the ratio of volumetric flow rate that refers to extraction agent, washing composition, stock liquid three.
Described fractionation extraction adopts existing fractionation extraction equipment, comprises extraction section and washing section, and its structure as shown in Figure 1.Extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of extraction section, flow out the raffinate of enrichment alkane, from the first step of washing section, flow out the extraction liquid that is rich in alkene, collect extraction liquid.Extraction liquid just can obtain high-content olefinic material through simple distil process, realizes the recovery of extraction agent simultaneously.
The present invention adopts high performance liquid chromatography (HPLC) or capillary gas chromatography (GC) to analyze the concentration of alkene and alkane, HPLC concrete analysis condition is: C18 post (4.6 × 250mm, particle diameter 5 μ m, SunFire), 40 ℃ of column temperatures, moving phase is methyl alcohol: acetonitrile: diethylamine=20: 80: 0.2 (v/v/v), flow velocity 0.4ml/min, detector is differential refraction detector.Capillary gas chromatography solid analysis condition: HP-5,30m, column temperature 60-200 ℃, different and different with alkane carbochain according to alkene, detector is fid detector.
Tool of the present invention has the following advantages:
Ionic liquid of the present invention has good thermostability and extremely low vapour pressure, can improve the separating effect of extraction phase as extraction agent, and can be to not polluted by extraction thing; Ionic liquid is not only convenient to recycling simultaneously, and compared with environmental protection, few to the pollution of environment, have broad application prospects;
Functionalized ion liquid of the present invention has unsaturated functional group, can strengthen and the reactive force of alkene unsaturated double-bond, improves the separation selectivity of liquid towards alkene and alkane, thereby reduces the progression of extracting and separating, reduces energy consumption, reduces production costs;
It is extraction agent that the present invention has adopted special functionalized ion liquid, has improved separation efficiency, and the product olefin(e) centent obtaining is higher than 98%.
Accompanying drawing explanation
Fig. 1 is that the present invention adopts ion liquid abstraction to separate the process flow sheet of the method for liquefied olefines and paraffins mixture.
Embodiment
Embodiment 1
Take cyclopentenes and pentamethylene mixture as stock liquid, in stock liquid, cyclopentenes and pentamethylene mol ratio are 1: 1, with cyano group functionalized ion liquid [CPmim] [NTf
2] (1-cyanogen propyl group-3-Methylimidazole two (trifluoromethane sulphonyl) inferior amine salts) be extraction agent, take pentamethylene as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 5: 2.7: 1, at 10 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 19 grades of extraction sections, totally 14 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in cyclopentenes, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment pentamethylene, extraction liquid is separated and obtains cyclopentenes product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of cyclopentenes is 99.2%.
Take 1-octene and octane mixture as stock liquid, in stock liquid, 1-octene and octane mol ratio are 1: 8, with amide group functionalized ion liquid [CONmim] [NTf
2] (1-acetamido-3-Methylimidazole two (trifluoromethane sulphonyl) inferior amine salts) be extraction agent, take octane as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 10: 5: 1, at 40 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 22 grades of extraction sections, totally 16 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in 1-octene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment octane, extraction liquid is separated and obtains 1-octene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of 1-octene is 99.5%.
Embodiment 3
Take 1-hexene and normal hexane mixture as stock liquid, in stock liquid, 1-hexene and normal hexane mol ratio are 1: 1, with thiazolinyl functionalized ion liquid [Apy] [NTf
2] (N-allyl pyridine two (trifluoromethane sulphonyl) inferior amine salts) be extraction agent, take normal hexane as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 6: 2.7: 1, at 20 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 16 grades of extraction sections, totally 10 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in 1-hexene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment normal hexane, extraction liquid is separated and obtains 1-hexene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through GC, analyze, in product, the absolute purity of 1-hexene is 99.1%.
Embodiment 4
Take tetrahydrobenzene and hexanaphthene mixture as stock liquid, in stock liquid, tetrahydrobenzene and hexanaphthene mol ratio are 10: 1, with amide group functionalized ion liquid [P
1, CON] [PF
6] (N-acetamido-N-methyl piperidine hexafluorophosphate) be extraction agent, take hexanaphthene as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 3: 2: 1, at 30 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 26 grades of extraction sections, totally 18 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in tetrahydrobenzene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment hexanaphthene, extraction liquid is separated and obtains tetrahydrobenzene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of tetrahydrobenzene is 98.7%.
Embodiment 5
Take 1-nonene, with just nonane mixture is as stock liquid, in stock liquid, 1-nonene and positive nonane mol ratio are 3: 1, with ester group functionalized ion liquid [AcOxC
2mim] NTf
2(two (trifluoromethane sulphonyl) inferior amine salts of 1-ethyl propenoate base-3-Methylimidazole) are extraction agent, take positive nonane as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 12: 1.5: 1, at 50 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 17 grades of extraction sections, totally 12 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in 1-nonene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of the positive nonane of enrichment, extraction liquid is separated and obtains 1-nonene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of 1-nonene is 99.5%.
Embodiment 6
Take tetrahydrobenzene and hexanaphthene mixture as stock liquid, in stock liquid, tetrahydrobenzene and hexanaphthene mol ratio are 10: 1, with difunctionalization of cyano group ionic liquid [(CP)
2im] [PF
6] (1, 3-dicyan propyl imidazole hexafluorophosphate) be extraction agent, take hexanaphthene as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 3: 2: 1, at 25 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 16 grades of extraction sections, totally 11 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in tetrahydrobenzene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment hexanaphthene, extraction liquid is separated and obtains tetrahydrobenzene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through GC, analyze, in product, the absolute purity of tetrahydrobenzene is 99.7%.
Embodiment 7
Take 1-octene and octane mixture as stock liquid, in stock liquid, 1-octene and octane mol ratio are 1: 5, with difunctionalization of cyano group ionic liquid [N
2,2, cp, cp] [NTf
2] (two (trifluoromethane sulphonyl) inferior amine salts of diethyl-dicyan propyl ammonium, ) be extraction agent, take octane as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 8: 5: 1, at 45 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 20 grades of extraction sections, totally 14 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in 1-octene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment octane, extraction liquid is separated and obtains 1-octene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of 1-octene is 99.0%.
Embodiment 8
Take 1-amylene and Skellysolve A mixture as stock liquid, in stock liquid, 1-amylene and Skellysolve A mol ratio are 2: 1, take thiazolinyl functionalized ion liquid [Amim] [TfO] (1-allyl group-3-Methylimidazole trifluoro-methanyl sulfonate) as extraction agent, take above-mentioned Skellysolve A as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 15: 1.5: 1, at-10 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 21 grades of extraction sections, totally 16 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in 1-amylene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment Skellysolve A, extraction liquid is separated and obtains 1-amylene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of 1-amylene is 98.5%.
Embodiment 9
Take 1-heptene and normal heptane mixture as stock liquid, in stock liquid, 1-heptene and normal heptane mol ratio are 9: 1, with difunctionalization of cyano group ionic liquid [(CP)
2im] [TfO] (1, 3-dicyan propyl imidazole trifluoro-methanyl sulfonate) be extraction agent, take normal heptane as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 4: 2: 1, at 40 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 19 grades of extraction sections, totally 12 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in 1-heptene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment normal heptane, extraction liquid is separated and obtains 1-heptene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of 1-heptene is 99.7%.
Embodiment 10
Take 1-hexene and normal hexane mixture as stock liquid, in stock liquid, 1-hexene and normal hexane mol ratio are 5: 1, with thiazolinyl functionalized ion liquid [Amim] [B (CN)
4] (1-allyl group-3-Methylimidazole four cyanogen borates) be extraction agent, take normal hexane as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 10: 5: 1, at 20 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 20 grades of extraction sections, totally 16 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in 1-hexene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment normal hexane, extraction liquid is separated and obtains 1-hexene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of 1-hexene is 99.7%.
Embodiment 11
Take 1-heptene and normal heptane mixture as stock liquid, in stock liquid, 1-heptene and normal heptane mol ratio are 3: 1, with cyano group functionalized ion liquid [CPmim] [C (CN)
3] (1-cyanogen propyl group-3-Methylimidazole three cyanogen methyl salt) be extraction agent, take normal heptane as washing composition, extraction agent, washing composition, stock liquid three's stream ratio is 8: 2.5: 1, at 40 ℃, in fractionation extraction device, carry out fractionation extraction, specifically as shown in Figure 1, fractionation extraction is divided into extraction section and washing section, wherein, totally 18 grades of extraction sections, totally 12 grades of washing sections, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in 1-heptene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment normal heptane, extraction liquid is separated and obtains 1-heptene product through distillation mode, and reclaim the remaining liq after distillation: ionic liquid.Through HPLC, analyze, in product, the absolute purity of 1-heptene is 99.2%.
Embodiment 12
In stock liquid, 1-heptene and normal heptane mol ratio are 1: 4, and other operates with embodiment 11, wherein, and totally 15 grades of extraction sections, totally 11 grades of washing sections.Through HPLC, analyze, in product, the absolute purity of 1-heptene is 99.5%.
Embodiment 13
In stock liquid, 1-heptene and normal heptane mol ratio are 1: 19, and other operates with embodiment 11, wherein, and totally 13 grades of extraction sections, totally 10 grades of washing sections.Through HPLC, analyze, in product, the absolute purity of 1-heptene is 99.6%.
Claims (7)
1. adopt ion liquid abstraction to separate a method for liquefied olefines and paraffins mixture, it is characterized in that, comprise the following steps:
1) using liquefied olefines and paraffins mixture as stock liquid, add ionic liquid as extraction agent, using described alkane as washing composition, carry out fractionation extraction;
Described liquefied olefines is C
5～C
9chain alkene and/or C
5～C
9cyclic olefin, alkane is C
5～C
9chain alkane and/or C
5～C
9cyclic alkane;
Described fractionation extraction is divided into extraction section and washing section, extraction agent enters fractionation extraction system from the extraction section first step, stock liquid enters fractionation extraction system from the last step of extraction section, washing composition enters fractionation extraction system from the first step of washing section, at extraction section last step, merge stock liquid and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, from the first step of washing section, flow out the extraction liquid that is rich in alkene, collect extraction liquid, from the first step of extraction section, flow out the raffinate of enrichment alkane;
2) extraction liquid is distilled, collect distillate and obtain alkene, remaining liq is ion liquid abstraction agent, and this extraction agent can be recycled;
Described ionic liquid is comprised of positively charged ion M+ and anion N-two portions;
Described positively charged ion M+ is imidazole type positively charged ion, the pyridine type positively charged ion with monosubstituted group, the piperidines type positively charged ion with monosubstituted group or disubstituted group, the tetramethyleneimine type positively charged ion with monosubstituted group or disubstituted group with monosubstituted group or disubstituted group, have monosubstituted group or disubstituted quaternary phosphine type positively charged ion, have the one in the quaternary ammonium cation of monosubstituted group or disubstituted group;
Described monosubstituted group is C
1～C
6straight-chain alkenyl, C
1～C
6straight chain cyano group, C
1～C
6straight chain amide group, C
1～C
6straight chain ester group in one;
Two substituted radicals in described disubstituted group are identical, and substituted radical is C
1～C
6straight-chain alkenyl, C
1～C
6straight chain cyano group, C
1～C
6straight chain amide group, C
1～C
6straight chain ester group in one; Or, two substituted radical differences in described disubstituted group, one of them substituted radical is C
1～C
6straight-chain alkenyl, C
1～C
6straight chain cyano group, C
1～C
6straight chain amide group, C
1～C
6straight chain ester group in one, another substituted radical is C
1～C
6straight chained alkyl;
Described anion N-be the one in hexafluoro-phosphate radical, trifluoroacetic acid root, trifluoromethayl sulfonic acid root, ethylsulfonic acid root, dimethyl phosphate radical, diethyl phosphate radical, dihydrogen phosphate, dicyanamide root, three cyanogen methyl roots, four cyanogen borates, two (trifluoromethane sulphonyl) imines root.
2. method according to claim 1, it is characterized in that, described positively charged ion M+ is 1-cyanogen propyl group-3-Methylimidazole positively charged ion, 1-acetamido-3-Methylimidazole positively charged ion, N-allyl pyridine positively charged ion, N-acetamido-N-methyl piperidine positively charged ion, 1-ethyl propenoate base-3-Methylimidazole positively charged ion, 1,3-dicyan propyl imidazole positively charged ion, diethyl-dicyan propyl ammonium positively charged ion, 1-allyl group-3-Methylimidazole positively charged ion, 1, the one in 3-diacetylamino glyoxaline cation.
3. method according to claim 1, is characterized in that, described negatively charged ion is the one in hexafluoro-phosphate radical, trifluoromethayl sulfonic acid root, dicyanamide root, three cyanogen methyl roots, four cyanogen borates, two (trifluoromethane sulphonyl) imines root.
4. method according to claim 1, is characterized in that, in described liquefied olefines and paraffins mixture, alkene molar content is 5%～95%.
5. method according to claim 4, is characterized in that, in described liquefied olefines and paraffins mixture, alkene molar content is 5%～20%.
6. method according to claim 1, is characterized in that, the temperature of described fractionation extraction is-20 ℃～50 ℃.
7. method according to claim 1, is characterized in that, the stream ratio between extraction agent, washing composition, stock liquid three is 2～15:1～5:1; Described stream is than the ratio of volumetric flow rate that refers to extraction agent, washing composition, stock liquid three.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210191815.3A CN102701895B (en) | 2012-06-12 | 2012-06-12 | Method for extracting and separating liquid olefin and alkane mixture by adopting functional ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210191815.3A CN102701895B (en) | 2012-06-12 | 2012-06-12 | Method for extracting and separating liquid olefin and alkane mixture by adopting functional ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102701895A CN102701895A (en) | 2012-10-03 |
| CN102701895B true CN102701895B (en) | 2014-04-23 |
Family
ID=46895025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210191815.3A Active CN102701895B (en) | 2012-06-12 | 2012-06-12 | Method for extracting and separating liquid olefin and alkane mixture by adopting functional ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102701895B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693454A (en) * | 2016-03-31 | 2016-06-22 | 商云龙 | Method for extracting p-xylene in n-octane by using [Bmim][FeCl4] |
| CN107261765B (en) * | 2017-08-16 | 2020-02-07 | 天津大学 | Method for separating olefins/alkanes using a protic ionic liquid based eutectic solvent |
| CN112691703B (en) * | 2020-12-29 | 2022-08-30 | 天津大学 | Double-salt ionic liquid catalyst for methyl acetate hydrolysis reaction and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4132744A (en) * | 1977-12-12 | 1979-01-02 | Texaco Inc. | Process for separating liquid olefin-paraffin mixtures |
| CN101265152A (en) * | 2007-03-16 | 2008-09-17 | 中国石油大学(北京) | Application of ionic liquid used as solvent in benzene and cyclohexane extraction, rectification and separation |
| CN101417913A (en) * | 2008-11-19 | 2009-04-29 | 烟台大学 | Method for separating butane and butene by using multiple mixed solvent |
| CN101723781A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Solvent for extracting, rectifying and separating styrene from hydrocarbon mixture |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264650A (en) * | 1992-02-11 | 1993-11-23 | Mobil Oil Corporation | Sulfolane purification by hydrocarbon extraction |
-
2012
- 2012-06-12 CN CN201210191815.3A patent/CN102701895B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4132744A (en) * | 1977-12-12 | 1979-01-02 | Texaco Inc. | Process for separating liquid olefin-paraffin mixtures |
| CN101265152A (en) * | 2007-03-16 | 2008-09-17 | 中国石油大学(北京) | Application of ionic liquid used as solvent in benzene and cyclohexane extraction, rectification and separation |
| CN101723781A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Solvent for extracting, rectifying and separating styrene from hydrocarbon mixture |
| CN101417913A (en) * | 2008-11-19 | 2009-04-29 | 烟台大学 | Method for separating butane and butene by using multiple mixed solvent |
Non-Patent Citations (2)
| Title |
|---|
| 新型离子液体用于芳烃、烯烃与烷烃分离的初步研究;朱吉钦等;《化工学报》;20041231;第55卷(第12期);2091-2094 * |
| 朱吉钦等.新型离子液体用于芳烃、烯烃与烷烃分离的初步研究.《化工学报》.2004,第55卷(第12期),2091-2094. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102701895A (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101265152B (en) | Application of ionic liquid used as solvent in benzene and cyclohexane extraction, rectification and separation | |
| CN103435482B (en) | Separation method and separation device of synthesis gas ethylene glycol product | |
| CN1285707C (en) | Naphtha optimized utilization method | |
| CN102701895B (en) | Method for extracting and separating liquid olefin and alkane mixture by adopting functional ionic liquid | |
| CN103232313A (en) | Extraction and separation method of alkane/olefin | |
| CN102718618A (en) | Method for separating high-purity isobutane from four-carbon components of refinery | |
| CN105367368A (en) | Method for preparing high-purity isobutene from C_4 hydrocarbon | |
| CN103664446A (en) | Technology for separating n-hexane-methylcyclopentane through extractive distillation | |
| CN103360201B (en) | The method of recycling vinyl benzene with abstraction distillation from hydrocarbon mixture | |
| CN105503522A (en) | Recycling and refining device for methylbenzene-methyl alcohol/ethyl alcohol and separating method | |
| CN101759520B (en) | Method for extracting, rectifying and separating phenylethylene from hydrocarbon mixture | |
| CN104610022A (en) | Method for separating ethanol-propyl acetate azeotrope through continuous extractive rectification | |
| CN101148392A (en) | Extraction and separation method for hydrocarbons mixture based on ionic liquor | |
| CN101468938B (en) | Composite solvent for extracting, distilling and separating styrene in hydrocarbons mixture, and method therefor | |
| CN102585870A (en) | Method for quickly separating chain hydrocarbon and phenols from medium and low temperature tar | |
| CN113443963A (en) | Method for separating ethanol, ethyl acetate and water by extractive distillation of mixed ionic liquid | |
| CN103360200B (en) | A kind of double solvents of recycling vinyl benzene with abstraction distillation from hydrocarbon mixture and method | |
| CN101781282A (en) | Method for producing high-purity ether used for HPLC | |
| CN101735853B (en) | Heavy paraffin adsorption separation process | |
| CN102311304A (en) | Complex solvent for separating out styrene through extractive distillation and application thereof | |
| CN102276430A (en) | Separation of glycol mono-tertiary-butyl ether and glycol di-tertiary-butyl ether | |
| CN101962311B (en) | Method and device for increasing service life of extractant in hydrofining process of crude benzene | |
| CN1634812A (en) | Method for separating n-alkane from C5 to C6 alkane isomerized products | |
| CN103449949A (en) | Method for separating n-alkanes from low temperature coal tar products | |
| CN1676500A (en) | Method for separating alpha-butylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |