CN102701895A - 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
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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 alkene and separate 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 always occupies critical role as the mainstay industry of petrochemical industry 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 is strong by the resin stretched intensity height of its prepared PE, shock resistance and lear energy, is the desirable feedstock of Production and Packaging film and agricultural mulch films.
At present; Alkene is generally through the preparation of petrochemical material catalytic pyrolysiss such as heavy oil, Sweet natural gas, is the mixture of alkane and alkene yet cracking obtains, and this has influenced the application of alkene in industry; Special in the production of polymer materials, the alkene purity requirement of not enough far away production demand.Therefore, the separation of olefin/paraffin has become the committed step of alkene industry.Yet alkene that carbon number is identical and alkane structural similitude, character are approaching, and boiling point difference is little, and separating difficulty is big.
The process method of existing separation alkene and alkane has, low-temperature extraction, solvent absorbing, fractionation by adsorption, extracting rectifying, membrane sepn etc.Various technologies all have certain effect aspect separation alkene and the alkane, but because the singularity of alkene and alkane mixed system, all there is certain deficiency in existing separating technology.
Introduced separation by deep refrigeration among the Chinese patent CN1338449A and from the hydrocarbon-containifirst mixed gas, reclaimed the method for ethene, ethane, but need under low temperature and high pressure, carry out, energy consumption is bigger.
U.S. Pat 5460700 uses NSC 7323, methyl phenyl ketone etc. as entrainment agent; Be used for extracting rectifying and separate 1-hexene and hexane, both relative volatilities are increased to 1.35 by 1.07, but the rectifiying plate number that needs is 41; Still need bigger energy requirement; NSC 7323, methyl phenyl ketone are volatile organic matters simultaneously, when using as entrainment agent, have hexene and the entrainment agent problem of rectifying separation once more.
It is the method for extraction agent separating cyclohexene and hexanaphthene mixed system with the tetramethylene sulfone that one Chinese patent application CN102134177A has introduced a kind of, and realizes the recycle of tetramethylene sulfone through solvent recovery tower.
One Chinese patent application CN1681754A discloses a kind of method of using the polarity extracting agent extracting rectifying to separate butylene and butane; Polarity extracting agent is anhydrous or contains the organic solvent of 0.1%-20% quality water, comprises N, N-Methyl pyrrolidone, acetonitrile, furfural, N-formyl morpholine or N,N-DIMETHYLACETAMIDE.
One Chinese patent application CN101028987A discloses the device of a kind of extracting rectifying separation of propylene and propane, and used extraction agent is to contain water-acetonitrile, adopts less reflux ratio and number of theoretical plate, reaches separating effect and higher product yield preferably.
U.S. Pat 5069756 application EGME and propyl carbinol perhaps use EGME and diacetone alcohol as extracting rectifying entrainment agent separating cyclohexene and hexanaphthene as the azeotropic distillation entrainment agent.
Above stripping technique exists separation selectivity low, the little deficiency that waits of treatment 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,, utilize the chemical complexing effect that exists between metals ion and the olefinic double bonds, improved alkene at separating medium, like the sendout on sorbent material, absorption agent, the liquid film like Ag, Cu etc.One Chinese patent application CN1680019A discloses a kind of gac of supported rare earth element compound; Be used for the separation of olefin/paraffin; This sorbent material can significantly improve separation factor, can well be used for petroleum cracking, catalytic pyrolysis, ethylene oxide production etc. and separate olefin/paraffin.
One Chinese patent application CN101657396A discloses and from the C4 hydrocarbon mixture, has separated the technology that obtains 1-butylene; Main use can optionally form sorbent material, X type zeolite or the y-type zeolite sorbent material of π complexing in the patent with alkene; Or the X type of metal ion exchanged or y-type zeolite sorbent material, and combine distil process to realize the purifying of 1-butylene.
Like this,, also increased isolating treatment capacity improving the isolating optionally while, but the easy inactivation of metals ion, production cost is high, on using, has very big deficiency.
Meanwhile, ionic liquid also is used to separate alkene and alkane, U.S. Pat 7619129B2 disclose a kind of with the ionic liquid that contains alkyl group side chain as the liquid film composition, adopt membrane separation technique to separate alkene and paraffins mixture.On extracting and separating, one Chinese patent application CN101148392A has reported and has a kind ofly obtained divinyl wherein with ionic liquid and organic solvent mixed extractant separation of C 4 hydrocarbon mixtures, realizes the purifying of alkene; U.S. Pat 2011/0015461A1 discloses a kind of argentiferous ionic ionic liquid and has been used for separating alkene from alkene with paraffins mixture; U.S. Pat 6623659B2 has shown that then the ionic liquid that contains IB family metal can effectively separate the olefin/paraffin system, and wherein the separating effect of silver ions is best.
But; Because the volatility of organic solvent; Though adding organic solvent, ionic liquid can improve alkene rate of mass transfer therein; But caused the separation problem of alkene and solvent, the ion liquid stability of metal ion and deficiency such as expensive have also limited the large-scale application of the ionic liquid of metal ion at extracting and separating alkene and alkane.
Summary of the invention
Ionic liquid is one type and is made up of zwitterion, under room temperature or nearly room temperature condition, is the meltbility salt of liquid, at separation field as one type of novel separating medium of green and noticeable.Compare with conventional organic solvents, ionic liquid has some unique character as absorption agent, has very wide liquid temperature scope; Almost negligible vp, non-volatile, not flammable; Organism and inorganics are had good solubility property, good thermostability is arranged, have designability simultaneously; It is synthetic to carry out functionalized design as required, has a good application prospect in the chemical separating field.
Because there is undersaturated carbon-carbon double bond in alkene, has certain πDian Zixiaoying.The present invention finds: in order well to separate alkene and alkane; On ionic liquid, introduce functional group with unsaturated group; Like cyanic acid, thiazolinyl, carboxamido-group, ester group etc., can improve the π-π complexing action of ionic liquid and olefinic double bonds, improve isolating selectivity.
Therefore; The invention provides a kind of functionalized ion liquid that has the unsaturated functional group of single or two replacement on the positively charged ion that adopts as extraction agent; The alkene that extracting and separating is liquid and the method for paraffins mixture, this method can obtain high purity olefin, and absolute purity can reach more than 98%.
A kind of method that adopts ion liquid abstraction to separate liquefied olefines and paraffins mixture may further comprise the steps:
1) with liquefied olefines and paraffins mixture as liquid stock, add ionic liquid as extraction agent, as washing composition, the alkene in the raw material is carried out fractionation extn with said alkane;
Described fractionation extn is divided into extraction section and washing section; Extraction agent gets into the fractionation extn system from the extraction section first step; Liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together; Extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in alkene from the first step of washing section, collect extraction liquid, flow out the raffinate of enrichment alkane from the first step of extraction section;
2) extraction liquid is distilled, collect distillate and obtain high-purity alkene, remaining liq is the ion liquid abstraction agent, and this extraction agent can be recycled.
Described ionic liquid is made up 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 single substituted radical, the piperidines type positively charged ion with single substituted radical or disubstituted group, the tetramethyleneimine type positively charged ion with single substituted radical or disubstituted group with single substituted radical or disubstituted group, have single substituted radical or disubstituted De quaternary phosphine type positively charged ion, have a kind of in the quaternary ammonium cation of single substituted radical or disubstituted group;
Described substituted radical has a kind of in thiazolinyl, cyanic acid, carboxamido-group, the ester group at least;
A kind of in hexafluoro-phosphate radical, trifluoroacetic acid root, trifluoromethayl sulfonic acid root, ethylsulfonic acid root, dimethyl-phosphate radical, diethylammonium phosphate radical, dihydrogen phosphate, dicyanamide root, three cyanogen methyl roots, four cyanogen borates, two (trifluoromethane sulphonyl) imines root of described anion N-be.
Described washing composition is identical with alkane in the raw material, can improve separating effect on the one hand, has avoided in the raffinate of the enrichment alkane that obtains, introducing other material on the other hand, and raffinate need not promptly to obtain high purity alkane through handling.
Described extraction agent is selected pure list or difunctionalization ionic liquid for use; Specific π-π the effect that utilizes ion liquid unsaturated functional group and olefinic double bonds to form; Improve alkene and the dissolubility difference of alkane in ionic liquid, realize both high efficiency separation.
Optional, described substituted radical has C at least
1～C
6Straight-chain alkenyl, C
1～C
6Straight chain cyanic acid, C
1～C
6Straight chain carboxamido-group, C
1～C
6The straight chain ester group in a kind of.
Specifically, described single substituted radical is C
1～C
6Straight-chain alkenyl, C
1～C
6Straight chain cyanic acid, C
1～C
6Straight chain carboxamido-group, C
1～C
6The straight chain ester group in a kind of; Two substituted radicals in the described disubstituted group are identical, and substituted radical is C
1～C
6Straight-chain alkenyl, C
1～C
6Straight chain cyanic acid, C
1～C
6Straight chain carboxamido-group, C
1～C
6The straight chain ester group in a kind of; Perhaps, two substituted radical differences in the described disubstituted group, one of them substituted radical is C
1～C
6Straight-chain alkenyl, C
1～C
6Straight chain cyanic acid, C
1～C
6Straight chain carboxamido-group, C
1～C
6The straight chain ester group in a kind of, 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 for use; 3-dicyan propyl imidazole positively charged ion, diethylammonium-dicyan propyl ammonium positively charged ion, 1-allyl group-3-Methylimidazole positively charged ion, 1, a kind of in the 3-diacetylamino glyoxaline cation etc.
Further, described negatively charged ion is a kind of in hexafluoro-phosphate radical, trifluoromethayl sulfonic acid root, dicyanamide root, three cyanogen methyl roots, four cyanogen borates, two (trifluoromethane sulphonyl) imines root.
The alkene molar content is 5%～95% in handled alkene of the present invention and the paraffins mixture; Can be that the liquid hydrocarbon product that alkene obtains is produced in preparations such as existing supercritical solvent is synthetic, waste polyolefine plastics; Removals impurity and heavy constituent through early stage are handled, and staple is the blending ingredients of alkene and alkane.Wherein, Under the certain prerequisite of conditions such as other condition such as ion liquid kind, when the content of alkene hanged down, extracting and separating had obvious selectivity; It is less to separate required extraction progression; Can reduce separation costs, when the molar content of alkene 5%～20% the time, the best results of extracting and separating.
In described liquefied olefines and the 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 the 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.
The carbonatoms of alkene and alkane can be the same or different in described liquefied olefines and the paraffins mixture, and to the not obviously influence of effect of extracting and separating, the difficulty of extracting and separating can increase when the carbonatoms of general alkene and alkane was identical.
The operating temperature range of described fractionation extn under the high temperature, can make the liquid stock volatilization at-20 ℃～50 ℃, reduces the ability of extracting and separating; And during low temperature, ion liquid viscosity is too high, has reduced the distribution capability of alkene in ionic liquid.
When carrying out fractionation extn, take all factors into consideration factors such as quality product, production cost, the stream ratio between extraction agent, washing composition, the liquid stock three is preferably 2～15: 1～5: 1.Stream of the present invention is than the ratio of the volumetric flow rate that refers to extraction agent, washing composition, liquid stock three.
Existing fractionation extn equipment is adopted in described fractionation extn, comprises extraction section and washing section, and its structure is as shown in Figure 1.Extraction agent gets into the fractionation extn system from the extraction section first step; Liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together; Extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the raffinate of enrichment alkane from the first step of extraction section, flow out the extraction liquid that is rich in alkene, collect extraction liquid from the first step of washing section.Extraction liquid just can obtain the high-content olefinic material through simple distil process, realizes the recovery of extraction agent simultaneously.
The present invention adopts HPLC (HPLC) or capillary gas chromatography (GC) to analyze the concentration of alkene and alkane; HPLC concrete analysis condition is: and the 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 are differential refraction detector.Capillary gas chromatography solid analysis condition: HP-5,30m, column temperature 60-200 ℃, different with the alkane carbochain and different according to alkene, detector is a fid detector.
The present invention has following advantage:
Ionic liquid of the present invention has good thermostability and extremely low vp, can improve the separating effect of extraction phase as extraction agent, and can be to not polluted by the collection thing; Ionic liquid not only is convenient to recycling simultaneously, and than 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 the reactive force with the alkene unsaturated double-bond, improves the separation selectivity of liquid towards alkene and alkane, thereby reduces the progression of extracting and separating, the minimizing 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 that obtains is higher than 98%.
Description of drawings
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
With cyclopentenes and pentamethylene mixture is liquid stock, and cyclopentenes and pentamethylene mol ratio are 1: 1 in the liquid stock, with cyanic acid functionalized ion liquid [CPmim] [NTf
2] (1-cyanogen propyl group-3-Methylimidazole two (trifluoromethane sulphonyl) inferior amine salts) be extraction agent, is washing composition with the pentamethylene, extraction agent, washing composition, liquid stock three's stream ratio is 5: 2.7: 1; In the fractionation extn device, carry out fractionation extn under 10 ℃, specifically as shown in Figure 1, fractionation extn is divided into extraction section and washing section; Wherein, totally 19 grades of extraction sections, totally 14 grades of washing sections; Extraction agent gets into the fractionation extn system from the extraction section first step; Liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together; Extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in cyclopentenes from the first step of washing section, collect extraction liquid, flow out the raffinate of enrichment pentamethylene from the first step of extraction section; Extraction liquid separated obtaining the cyclopentenes product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of cyclopentenes is 99.2% in the product.
With 1-octene and octane mixture is liquid stock, and 1-octene and octane mol ratio are 1: 8 in the liquid stock, with carboxamido-group functionalized ion liquid [CONmim] [NTf
2] (1-acetamido-3-Methylimidazole two (trifluoromethane sulphonyl) inferior amine salts) be extraction agent, is washing composition with the octane, extraction agent, washing composition, liquid stock three's stream ratio is 10: 5: 1; In the fractionation extn device, carry out fractionation extn under 40 ℃, specifically as shown in Figure 1, fractionation extn is divided into extraction section and washing section; Wherein, totally 22 grades of extraction sections, totally 16 grades of washing sections; Extraction agent gets into the fractionation extn system from the extraction section first step; Liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together; Extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in the 1-octene from the first step of washing section, collect extraction liquid, flow out the raffinate of enrichment octane from the first step of extraction section; Extraction liquid separated obtaining the 1-octene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of 1-octene is 99.5% in the product.
Embodiment 3
With 1-hexene and normal hexane mixture is liquid stock, and 1-hexene and normal hexane mol ratio are 1: 1 in the liquid stock, with thiazolinyl functionalized ion liquid [Apy] [NTf
2] (N-allyl pyridine two (trifluoromethane sulphonyl) inferior amine salts) be extraction agent, is washing composition with the normal hexane, extraction agent, washing composition, liquid stock three's stream ratio is 6: 2.7: 1; In the fractionation extn device, carry out fractionation extn under 20 ℃, specifically as shown in Figure 1, fractionation extn is divided into extraction section and washing section; Wherein, totally 16 grades of extraction sections, totally 10 grades of washing sections; Extraction agent gets into the fractionation extn system from the extraction section first step, and liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section; Merge liquid stock at the extraction section last step and get into extraction section together, extraction phase carries out multi-stage counter current extraction mutually with washing, is rich in the extraction liquid of 1-hexene from the first step outflow of washing section; Collect extraction liquid, flow out the raffinate of enrichment normal hexane from the first step of extraction section; Extraction liquid separated obtaining 1-hexene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through GC, the absolute purity of 1-hexene is 99.1% in the product.
Embodiment 4
With tetrahydrobenzene and hexanaphthene mixture is liquid stock, and tetrahydrobenzene and hexanaphthene mol ratio are 10: 1 in the liquid stock, with carboxamido-group functionalized ion liquid [P
1, CON] [PF
6] (N-acetamido-N-methyl piperidine hexafluorophosphate) be extraction agent, is washing composition with the hexanaphthene, extraction agent, washing composition, liquid stock three's stream ratio is 3: 2: 1; In the fractionation extn device, carry out fractionation extn under 30 ℃, specifically as shown in Figure 1, fractionation extn is divided into extraction section and washing section; Wherein, totally 26 grades of extraction sections, totally 18 grades of washing sections; Extraction agent gets into the fractionation extn system from the extraction section first step, and liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section; Merge liquid stock at the extraction section last step and get into extraction section together, extraction phase carries out multi-stage counter current extraction mutually with washing, is rich in the extraction liquid of tetrahydrobenzene from the first step outflow of washing section; Collect extraction liquid, flow out the raffinate of enrichment hexanaphthene from the first step of extraction section; Extraction liquid separated obtaining the tetrahydrobenzene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of tetrahydrobenzene is 98.7% in the product.
Embodiment 5
Is liquid stock with the 1-nonene with positive nonane mixture, and the 1-nonene is 3: 1 with positive nonane mol ratio in the liquid stock, 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, are washing composition with positive nonane, and extraction agent, washing composition, liquid stock three's stream ratio is 12: 1.5: 1; In the fractionation extn device, carry out fractionation extn under 50 ℃, specifically as shown in Figure 1, fractionation extn is divided into extraction section and washing section; Wherein, totally 17 grades of extraction sections, totally 12 grades of washing sections; Extraction agent gets into the fractionation extn system from the extraction section first step; Liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together; Extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in the 1-nonene from the first step of washing section, collect extraction liquid, flow out the raffinate of the positive nonane of enrichment from the first step of extraction section; Extraction liquid separated obtaining 1-nonene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of 1-nonene is 99.5% in the product.
Embodiment 6
With tetrahydrobenzene and hexanaphthene mixture is liquid stock, and tetrahydrobenzene and hexanaphthene mol ratio are 10: 1 in the liquid stock, with difunctionalization of cyanic acid ionic liquid [(CP)
2Im] [PF
6] (1,3-dicyan propyl imidazole hexafluorophosphate) be extraction agent, is washing composition with the hexanaphthene; Extraction agent, washing composition, liquid stock three's stream ratio is 3: 2: 1, in the fractionation extn device, carries out fractionation extn under 25 ℃, and is specifically as shown in Figure 1; Fractionation extn is divided into extraction section and washing section, wherein, and totally 16 grades of extraction sections; Totally 11 grades of washing sections, extraction agent gets into the fractionation extn system from the extraction section first step, and liquid stock gets into the fractionation extn system from the last step of extraction section; Washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together, and extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in tetrahydrobenzene from the first step of washing section, collect extraction liquid, flow out the raffinate of enrichment hexanaphthene from the first step of extraction section; Extraction liquid separated obtaining the tetrahydrobenzene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through GC, the absolute purity of tetrahydrobenzene is 99.7% in the product.
Embodiment 7
With 1-octene and octane mixture is liquid stock, and 1-octene and octane mol ratio are 1: 5 in the liquid stock, with difunctionalization of cyanic acid ionic liquid [N
2,2, cp, cp] [NTf
2] (diethylammonium-dicyan propyl ammonium two (trifluoromethane sulphonyl) inferior amine salts) be extraction agent, is washing composition with the octane; Extraction agent, washing composition, liquid stock three's stream ratio is 8: 5: 1, in the fractionation extn device, carries out fractionation extn under 45 ℃, and is specifically as shown in Figure 1; Fractionation extn is divided into extraction section and washing section, wherein, and totally 20 grades of extraction sections; Totally 14 grades of washing sections, extraction agent gets into the fractionation extn system from the extraction section first step, and liquid stock gets into the fractionation extn system from the last step of extraction section; Washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together, and extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in the 1-octene from the first step of washing section, collect extraction liquid, flow out the raffinate of enrichment octane from the first step of extraction section; Extraction liquid separated obtaining the 1-octene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of 1-octene is 99.0% in the product.
Embodiment 8
With 1-amylene and Skellysolve A mixture is liquid stock, and 1-amylene and Skellysolve A mol ratio are 2: 1 in the liquid stock, is extraction agent with thiazolinyl functionalized ion liquid [Amim] [TfO] (1-allyl group-3-Methylimidazole trifluoro-methanyl sulfonate); With above-mentioned Skellysolve A is washing composition, and extraction agent, washing composition, liquid stock three's stream ratio is 15: 1.5: 1, in the fractionation extn device, carries out fractionation extn under-10 ℃; Specifically as shown in Figure 1, fractionation extn is divided into extraction section and washing section, wherein; Totally 21 grades of extraction sections, totally 16 grades of washing sections, extraction agent gets into the fractionation extn system from the extraction section first step; Liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together; Extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in the 1-amylene from the first step of washing section, collect extraction liquid, flow out the raffinate of enrichment Skellysolve A from the first step of extraction section; Extraction liquid separated obtaining 1-amylene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of 1-amylene is 98.5% in the product.
Embodiment 9
With 1-heptene and normal heptane mixture is liquid stock, and 1-heptene and normal heptane mol ratio are 9: 1 in the liquid stock, with difunctionalization of cyanic acid ionic liquid [(CP)
2Im] [TfO] (1,3-dicyan propyl imidazole trifluoro-methanyl sulfonate) is extraction agent, is washing composition with the normal heptane; Extraction agent, washing composition, liquid stock three's stream ratio is 4: 2: 1, in the fractionation extn device, carries out fractionation extn under 40 ℃, and is specifically as shown in Figure 1; Fractionation extn is divided into extraction section and washing section, wherein, and totally 19 grades of extraction sections; Totally 12 grades of washing sections, extraction agent gets into the fractionation extn system from the extraction section first step, and liquid stock gets into the fractionation extn system from the last step of extraction section; Washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together, and extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in the 1-heptene from the first step of washing section, collect extraction liquid, flow out the raffinate of enrichment normal heptane from the first step of extraction section; Extraction liquid separated obtaining 1-heptene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of 1-heptene is 99.7% in the product.
Embodiment 10
With 1-hexene and normal hexane mixture is liquid stock, and 1-hexene and normal hexane mol ratio are 5: 1 in the liquid stock, with thiazolinyl functionalized ion liquid [Amim] [B (CN)
4] (1-allyl group-3-Methylimidazole four cyanogen borates) be extraction agent, is washing composition with the normal hexane, extraction agent, washing composition, liquid stock three's stream ratio is 10: 5: 1; In the fractionation extn device, carry out fractionation extn under 20 ℃, specifically as shown in Figure 1, fractionation extn is divided into extraction section and washing section; Wherein, totally 20 grades of extraction sections, totally 16 grades of washing sections; Extraction agent gets into the fractionation extn system from the extraction section first step, and liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section; Merge liquid stock at the extraction section last step and get into extraction section together, extraction phase carries out multi-stage counter current extraction mutually with washing, is rich in the extraction liquid of 1-hexene from the first step outflow of washing section; Collect extraction liquid, flow out the raffinate of enrichment normal hexane from the first step of extraction section; Extraction liquid separated obtaining 1-hexene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of 1-hexene is 99.7% in the product.
Embodiment 11
With 1-heptene and normal heptane mixture is liquid stock, and 1-heptene and normal heptane mol ratio are 3: 1 in the liquid stock, with cyanic acid functionalized ion liquid [CPmim] [C (CN)
3] (1-cyanogen propyl group-3-Methylimidazole three cyanogen methyl salt) be extraction agent, is washing composition with the normal heptane, extraction agent, washing composition, liquid stock three's stream ratio is 8: 2.5: 1; In the fractionation extn device, carry out fractionation extn under 40 ℃, specifically as shown in Figure 1, fractionation extn is divided into extraction section and washing section; Wherein, totally 18 grades of extraction sections, totally 12 grades of washing sections; Extraction agent gets into the fractionation extn system from the extraction section first step, and liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section; Merge liquid stock at the extraction section last step and get into extraction section together, extraction phase carries out multi-stage counter current extraction mutually with washing, is rich in the extraction liquid of 1-heptene from the first step outflow of washing section; Collect extraction liquid, flow out the raffinate of enrichment normal heptane from the first step of extraction section; Extraction liquid separated obtaining 1-heptene product through the distillation mode, and reclaim the remaining liq after the distillation: ionic liquid.Analyze through HPLC, the absolute purity of 1-heptene is 99.2% in the product.
Embodiment 12
1-heptene and normal heptane mol ratio are 1: 4 in liquid stock, and other is operated with embodiment 11, wherein, and totally 15 grades of extraction sections, totally 11 grades of washing sections.Analyze through HPLC, the absolute purity of 1-heptene is 99.5% in the product.
Embodiment 13
1-heptene and normal heptane mol ratio are 1: 19 in liquid stock, and other is operated with embodiment 11, wherein, and totally 13 grades of extraction sections, totally 10 grades of washing sections.Analyze through HPLC, the absolute purity of 1-heptene is 99.6% in the product.
Claims (10)
1. a method that adopts ion liquid abstraction to separate liquefied olefines and paraffins mixture is characterized in that, may further comprise the steps:
1) with liquefied olefines and paraffins mixture as liquid stock, add ionic liquid as extraction agent, as washing composition, carry out fractionation extn with said alkane;
Described fractionation extn is divided into extraction section and washing section; Extraction agent gets into the fractionation extn system from the extraction section first step; Liquid stock gets into the fractionation extn system from the last step of extraction section, and washing composition gets into the fractionation extn system from the first step of washing section, merges liquid stock at the extraction section last step and gets into extraction section together; Extraction phase carries out multi-stage counter current extraction mutually with washing; Flow out the extraction liquid that is rich in alkene from the first step of washing section, collect extraction liquid, flow out the raffinate of enrichment alkane from the first step of extraction section;
2) extraction liquid is distilled, collect distillate and obtain alkene, remaining liq is the ion liquid abstraction agent, and this extraction agent can be recycled;
Described ionic liquid is made up 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 single substituted radical, the piperidines type positively charged ion with single substituted radical or disubstituted group, the tetramethyleneimine type positively charged ion with single substituted radical or disubstituted group with single substituted radical or disubstituted group, have single substituted radical or disubstituted De quaternary phosphine type positively charged ion, have a kind of in the quaternary ammonium cation of single substituted radical or disubstituted group; Described substituted radical has a kind of in thiazolinyl, cyanic acid, carboxamido-group, the ester group at least;
A kind of in hexafluoro-phosphate radical, trifluoroacetic acid root, trifluoromethayl sulfonic acid root, ethylsulfonic acid root, dimethyl-phosphate radical, diethylammonium phosphate radical, dihydrogen phosphate, dicyanamide root, three cyanogen methyl roots, four cyanogen borates, two (trifluoromethane sulphonyl) imines root of described anion N-be.
2. method according to claim 1 is characterized in that, described single substituted radical is C
1～C
6Straight-chain alkenyl, C
1～C
6Straight chain cyanic acid, C
1～C
6Straight chain carboxamido-group, C
1～C
6The straight chain ester group in a kind of;
Two substituted radicals in the described disubstituted group are identical, and substituted radical is C
1～C
6Straight-chain alkenyl, C
1～C
6Straight chain cyanic acid, C
1～C
6Straight chain carboxamido-group, C
1～C
6The straight chain ester group in a kind of; Perhaps, two substituted radical differences in the described disubstituted group, one of them substituted radical is C
1～C
6Straight-chain alkenyl, C
1～C
6Straight chain cyanic acid, C
1～C
6Straight chain carboxamido-group, C
1～C
6The straight chain ester group in a kind of, another substituted radical is C
1～C
6Straight chained alkyl.
3. 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, diethylammonium-dicyan propyl ammonium positively charged ion, 1-allyl group-3-Methylimidazole positively charged ion, 1, a kind of in the 3-diacetylamino glyoxaline cation.
4. method according to claim 1 is characterized in that, described negatively charged ion is a kind of in hexafluoro-phosphate radical, trifluoromethayl sulfonic acid root, dicyanamide root, three cyanogen methyl roots, four cyanogen borates, two (trifluoromethane sulphonyl) imines root.
5. method according to claim 1 is characterized in that, in described liquefied olefines and the 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.
6. according to claim 1 or 5 described methods, it is characterized in that in described liquefied olefines and the 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.
7. according to claim 1 or 5 described methods, it is characterized in that the alkene molar content is 5%～95% in described liquefied olefines and the paraffins mixture.
8. method according to claim 7 is characterized in that, the alkene molar content is 5%～20% in described liquefied olefines and the paraffins mixture
9. method according to claim 1 is characterized in that, the temperature of described fractionation extn is-20 ℃～50 ℃.
10. method according to claim 1 is characterized in that, the stream ratio between extraction agent, washing composition, the liquid stock three is 2～15: 1～5: 1.
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