CN101148392A - Extraction and separation method for hydrocarbons mixture based on ionic liquor - Google Patents
Extraction and separation method for hydrocarbons mixture based on ionic liquor Download PDFInfo
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- CN101148392A CN101148392A CNA200710176767XA CN200710176767A CN101148392A CN 101148392 A CN101148392 A CN 101148392A CN A200710176767X A CNA200710176767X A CN A200710176767XA CN 200710176767 A CN200710176767 A CN 200710176767A CN 101148392 A CN101148392 A CN 101148392A
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Abstract
The present invention is C4 hydrocarbon mixture extracting and separating process. Ionic liquid additive is introduced to form one new type of composite extractant for extracting and separating C4 hydrocarbon mixture with 1, 3-butadiene as the main component. Introducing the ionic liquid additive into the extractant can increase the total dissolubility of C4 hydrocarbon mixture in the extractant, raising the hydrocarbon selectivity and relative volatility, and thus raise the extracting and separating effect obviously. In addition, the added ionic liquid has very low vapor pressure and high boiling point, and thus convenient recovery and reuse.
Description
Technical field
C among the present invention
4The separation method of hydrocarbon mixture relates to and a kind ofly belongs to the extraction and separation technology field based on ion liquid novel extraction agent, specifically, relates to from C
4The method of extracting and separating divinyl in the blending ingredients.
Background technology
1,3-butadiene (common name divinyl, down together) is a kind of important petrochemical complex basic organic material and synthetic rubber monomer, is C
4One of most important component in the cut, the status in the petrochemical complex olefin feedstock is only second to ethene and propylene.Owing to contain conjugated diolefine in its molecule, can replace, reaction such as addition, cyclisation and polymerization, make it have purposes widely at aspects such as synthetic rubber and organic syntheses, can synthesize multiple rubber products such as cis-1,4-polybutadiene rubber (BR), styrene-butadiene rubber(SBR) (SBR), paracril, SBS elastomer (SBS), acrylonitrile-butadiene-styrene (ABS) (ABS) resin, can be used for producing adiponitrile, hexanediamine, nylon 66,1 in addition, organic chemical industry's product such as 4-butyleneglycol and as caking agent, gasoline dope etc., purposes is very extensive.
At present, the source of world's divinyl mainly contains two kinds, and a kind of is from refinery C
4The cut dehydrogenation obtains, and this method only adopts in some butane, the resourceful a few countries of butylene at present.Another is the mixed C from the ethylene cracker by-product
4Extracting obtains in the cut, and this method is cheap, preponderates economically, is the present main source of divinyl in the world.92% divinyl employing C is arranged in the world at present approximately
4Extraction process is produced, and the divinyl of China all adopts C
4Extraction process is produced.Present industrial common method has N methylpyrrolidone process (NMP method), acetonitrile method (ACN method), dimethyl formamide method (DMF method) etc.
These extraction agents can improve mutual selectivity of hydrocarbons and relative volatility, therefore, industrially adopt them for a long time, but present development trend is to develop the better extraction agent of separating effect to improve extraction efficiency, cuts down the consumption of energy as extraction agent always.C
4The modification of extracting extraction agent not only has realistic meaning for the production of divinyl, and equally also has important reference and promotional value for the extracting rectifying separation of hydro carbons system.
Reported among the Chinese patent CN200480022303 that ionic liquid is applied to as entrainment agent that fractionation by distillation is narrow boils or the processing method of azeotropic mixture, but at C
4In the technology of hydrocarbon mixture extracting rectifying separation of butadiene research is not arranged; Report in the Japanese Patent 97 (clear and 52 years)-24685 adds a kind of glycols compound in original acetonitrile extraction rectification technique solvent, can increase mixed C to a certain extent
4Each material of solubleness in extraction system and hydro carbons relative volatility each other.But owing to the existence of water, reduced mixed C on the one hand in this kind of extractants
4Solubleness in extraction system can cause ACN hydrolysis, etching apparatus on the other hand.
Based on above present Research, consider that simultaneously ionic liquid as a kind of novel green solvent, has some peculiar properties: 1) can be by designing ion liquid yin, yang ion part to reach needed certain specific character; 2) almost do not have vapour pressure, non-volatile, nonflammable, be difficult for oxidation, adjustable viscosity, good thermostability; 3) stable to water and air, be convenient to manipulation, be easy to reclaim; 4) many organic compound and metal ion all there are good solubility, a non-water, two-phase system that polarity is adjustable can be provided.Ionic liquid at room temperature can be advantageously applied to liquid-liquid extraction, liquid-phase micro-extraction, solid-phase microextraction, supercritical CO as extraction solvent (organic phase, i.e. extraction phase, hydrophobic phase)
2Extraction.Therefore, the present invention mainly forms in the acetonitrile at traditional extraction agent, introduces ionic liquid and is the extraction additive, and its extracting and separating effect is significantly improved, and ionic liquid can have broad application prospects so that reclaim and recycle simultaneously.
Summary of the invention
It is a kind of to C that this invention provides
4Hydrocarbon mixture carries out isolating method.The feature of this separation method is, is primary solvent with the acetonitrile, forms the novel extraction agent to wherein adding a certain amount of ion liquid addictive, to being the C of main component with the divinyl
4Hydrocarbon mixture carries out extractive distillation, and divinyl is effectively separated.
Because the ionic liquid that uses in this invention has improved hydrocarbons relative volatility and solubleness each other to a certain extent, therefore be used.
As this type of ion liquid material example, select to list following: 1-ethyl-3-Methylimidazole bromine salt ([Emim] [Br]), 1-butyl-3-Methylimidazole bromine salt ([Bmim] [Br]), 1-hexyl-3-Methylimidazole bromine salt ([Hmim] [Br]), 1-octyl group-3-Methylimidazole bromine salt ([Omim] [Br]), 1-decyl-3-Methylimidazole bromine salt ([Dmim] [Br]), 1-butyl-3-Methylimidazole hexafluorophosphate ([Bmim] [PF
6]), 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim] [BF
4]), 1-ethyl-3-Methylimidazole trifluoroacetate ([Bmim] [CF
3COO]) etc. glyoxaline ion liquid; Pyridines ionic liquids such as N-3-bromine ammonium propyl group pyridinium tribromide salt; Two glyoxaline ion liquids such as two imidazoles bromine salt; Two season such as phosphine bromine salt in two season phosphonium salt class ionic liquid; Alcamines ionic liquids such as thanomin acetate; Quaternary ammonium ionic liquids such as benzyltrimethylammonium hydroxide acetylsalicylic acid or the like.More than enumerate each material, only select wherein a kind of getting final product when operating usually for use, but also can select for use two or more ionic liquids to form multifunctional assistant as required if any specific demand.
In this invention, ion liquid usage quantity situation is as follows: in the ordinary course of things, ionic liquid can account for 1～50% of extraction agent total amount, and best situation is 10～25% of a total amount.As the chief component of extraction agent, acetonitrile accounts for 50～99% of total amount greatly at the content of extraction agent, and best situation is 70～90% of a total amount.If ethane nitrile content is lower than at 50% o'clock, hydro carbons for the solubility property of extraction agent and relative volatility together with the time descend.Vapor liquid equilibrium temperature of reaction 293～373K wherein, pressure 0.10～10MPa.
Embodiment:
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and deionized water earlier, stir.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Embodiment 2
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and EmimBr earlier, stir.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Embodiment 3
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and BmimBr earlier, stir.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Embodiment 4
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and C earlier
6MimBr stirs.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Embodiment 5
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and C earlier
8MimBr stirs.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Embodiment 6
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and BmimCl earlier, stir.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Embodiment 7
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and BmimPF earlier
6, stir.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Embodiment 8
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and HmimBF earlier
4, stir.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Embodiment 9
Before the experiment, in the balanced reaction still, add a certain proportion of acetonitrile and BmimBF earlier
4, stir.Vacuumizing repeatedly three times, to guarantee the vacuum tightness in the still. the weight ratio by hydrocarbon compound and extraction agent is 1: 7 feeding C in the still then
4Hydrocarbon at pressure 0.20MPa, under the temperature 303K condition, stirs the sufficiently long time until vapor liquid equilibrium.Get gas phase after the balance and form employing gas chromatographic analysis and calculating, its result is as shown in table 1.
Result among the embodiment is as follows:
Wherein in the table 1: the 1-n-butene; 2-1,3 divinyl; The anti-butylene of 3-; The 4-maleic; The 5-Trimethylmethane.
C under the different extraction agent effects of table 1
4Relative volatility between component
| Embodiment | Extraction agent kind/wt% | Relative volatility | Equilibrium temperature/K | The phase state | |||
| α 12 | α 32 | α 42 | α 52 | ||||
| 1 | Acetonitrile 90+ water 10 | 2.082 | 1.668 | 1.192 | 4.714 | 303 | 1 phase |
| 2 | Acetonitrile 90+EmimBr 10 | 2.301 | 1.727 | 1.209 | 5.985 | 303 | 1 phase |
| 3 | Acetonitrile 90+BmimBr 10 | 2.097 | 1.641 | 1.196 | 4.784 | 302.8 | 1 phase |
| 4 | Acetonitrile 90+C 6mimBr 10 | 2.127 | 1.681 | 1.163 | 6.086 | 302.8 | 1 phase |
| 5 | Acetonitrile 90+C 8mimBr 10 | 2.123 | 1.685 | 1.190 | 5.005 | 302.7 | 1 phase |
| 6 | Acetonitrile 90+BmimCl 10 | 2.148 | 1.698 | 1.196 | 5.142 | 303 | 1 phase |
| 7 | Acetonitrile 90+BmimPF 610 | 2.280 | 1.699 | 1.223 | 5.910 | 303 | 1 phase |
| 8 | Acetonitrile 90+HmimBF 410 | 2.100 | 1.676 | 1.199 | 4.759 | 302.7 | 1 phase |
| 9 | Acetonitrile 90+BmimBF 410 | 2.184 | 1.704 | 1.238 | 5.429 | 303 | 1 phase |
Claims (5)
1. extraction separating method based on ion liquid hydrocarbon mixture is characterized in that adopting the composite extractant that is formed by main extraction agent and one or more ion liquid addictives, to being the C of main component with the 1,3-butadiene
4Hydrocarbon mixture carries out extracting and separating, thereby divinyl is separated effectively.
2. a kind of extraction separating method based on ion liquid hydrocarbon mixture according to claim 1 is characterized in that extracting and separating C
4The employed composite extractant of hydrocarbon mixture is made of main extraction agent and additive mixing, and main extraction agent accounts for 50～99% of gross weight, and additive accounts for 1～50% of gross weight.
3. a kind of extraction separating method based on ion liquid hydrocarbon mixture according to claim 1 is characterized in that the isolating temperature range 293～373K of extracting rectifying, pressure range 0.10～10MPa.
4. according to claim 2, additive contains the imidazoles of different side chain carbon numbers, pyridines, quaternary ammonium salt, alcamines, quaternary phosphonium ionic liquid for one or more in the composite extractant.
5. according to claim 2, main extraction agent is acetonitrile (ACN), dimethyl formamide (DMF) or N-Methyl pyrrolidone (NMP) in the composite additive.
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| CNA200710176767XA CN101148392A (en) | 2007-11-02 | 2007-11-02 | Extraction and separation method for hydrocarbons mixture based on ionic liquor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101813685A (en) * | 2010-04-20 | 2010-08-25 | 长安大学 | Method for determining residual erythrocin in environment by hydrophobic ionic liquid |
| CN102146012A (en) * | 2011-03-03 | 2011-08-10 | 中国科学院过程工程研究所 | Method for producing butadiene based on ionic liquid complex solvent |
| CN102452882A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Mixed solvent based on ionic liquid and used for C5 separation |
| CN102850170A (en) * | 2011-06-29 | 2013-01-02 | 中国石油化工股份有限公司 | Ionic liquid-based mixed solvent for C 5 separation |
| CN101417913B (en) * | 2008-11-19 | 2013-01-16 | 烟台大学 | Method for separating butane and butene by using multiple mixed solvent |
| CN103897720A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for separating reforming raffinate oil by extractive distillation with composite solvent |
| CN105693454A (en) * | 2016-03-31 | 2016-06-22 | 商云龙 | Method for extracting p-xylene in n-octane by using [Bmim][FeCl4] |
| CN108290085A (en) * | 2015-11-24 | 2018-07-17 | 环球油品公司 | Vertical separator for ionic-liquid catalyst effluent |
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2007
- 2007-11-02 CN CNA200710176767XA patent/CN101148392A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417913B (en) * | 2008-11-19 | 2013-01-16 | 烟台大学 | Method for separating butane and butene by using multiple mixed solvent |
| CN101813685A (en) * | 2010-04-20 | 2010-08-25 | 长安大学 | Method for determining residual erythrocin in environment by hydrophobic ionic liquid |
| CN102452882A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Mixed solvent based on ionic liquid and used for C5 separation |
| CN102452882B (en) * | 2010-10-19 | 2014-02-05 | 中国石油化工股份有限公司 | Mixed solvent based on ionic liquid and used for C5 separation |
| CN102146012A (en) * | 2011-03-03 | 2011-08-10 | 中国科学院过程工程研究所 | Method for producing butadiene based on ionic liquid complex solvent |
| CN102850170B (en) * | 2011-06-29 | 2015-12-16 | 中国石油化工股份有限公司 | A kind of carbon five separation mixed solvent based on ionic liquid |
| CN102850170A (en) * | 2011-06-29 | 2013-01-02 | 中国石油化工股份有限公司 | Ionic liquid-based mixed solvent for C 5 separation |
| CN103897720A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for separating reforming raffinate oil by extractive distillation with composite solvent |
| CN103897720B (en) * | 2012-12-27 | 2016-02-10 | 中国石油天然气股份有限公司 | A kind of method of complex solvent extraction rectifying separation reforming raffinate oil |
| CN108290085A (en) * | 2015-11-24 | 2018-07-17 | 环球油品公司 | Vertical separator for ionic-liquid catalyst effluent |
| US10654033B2 (en) | 2015-11-24 | 2020-05-19 | Uop Llc | Vertical separation vessel for ionic liquid catalyzed effluent |
| CN108290085B (en) * | 2015-11-24 | 2021-06-25 | 环球油品公司 | Vertical separator for ionic liquid catalyst effluent |
| CN105693454A (en) * | 2016-03-31 | 2016-06-22 | 商云龙 | Method for extracting p-xylene in n-octane by using [Bmim][FeCl4] |
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Open date: 20080326 |