CN114736092A - Process for separating olefins from a mixture of alkanes and olefins - Google Patents
Process for separating olefins from a mixture of alkanes and olefins Download PDFInfo
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- CN114736092A CN114736092A CN202110028156.0A CN202110028156A CN114736092A CN 114736092 A CN114736092 A CN 114736092A CN 202110028156 A CN202110028156 A CN 202110028156A CN 114736092 A CN114736092 A CN 114736092A
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 140
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 127
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000926 separation method Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 50
- 238000000605 extraction Methods 0.000 claims description 34
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000002798 polar solvent Substances 0.000 claims description 18
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 2
- 230000032798 delamination Effects 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 43
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention relates to the field of alkane and alkene separation, and discloses a method for separating alkene from a mixture of alkane and alkene, (1) the mixture containing alkane and alkene is firstly mixed with an extracting agent and then extracted, and an extract phase A containing the extracting agent, alkene and a small part of alkane and a raffinate phase a containing most of alkane are obtained through separation; (2) carrying out second mixing on the extract phase A and an alkane separating agent, then layering, and separating to obtain a lower-layer mixed solution B containing olefin, the extracting agent and the alkane separating agent and an upper-layer mixed solution B containing alkane; (3) and (4) rectifying the extract phase B, and separating to obtain an olefin product. The method for separating the olefin from the mixture of the alkane and the olefin, provided by the invention, has the advantages of no need of heating, low energy consumption and simple flow, and can obtain the olefin product with the purity of more than 99 percent by utilizing the extracting agent and the alkane separating agent to separate the mixture containing the alkane and the olefin.
Description
Technical Field
The invention relates to the technical field of alkane and alkene separation, in particular to a method for separating alkene from a mixture of alkane and alkene.
Background
The product of the coal-based Fischer-Tropsch synthesis oil generally contains 50 wt% to 70 wt% of alpha-olefin and also contains a lot of alkanes with the same carbon number as the olefins. The alpha-olefin in the coal-based synthetic oil is particularly odd-numbered olefin which cannot be produced in the petrochemical industry, and the olefin can be used as a high-quality comonomer and is more likely to provide infinite possibility for downstream polymerization to obtain a new performance product. If the alpha-olefin can be separated, the economic benefit of the coal-based synthetic oil can be improved, the performance of downstream products can be greatly improved, and the continuous and healthy development of the coal chemical industry in China can be promoted.
However, because the difference between the boiling points of the olefin and the alkane is small, it is difficult to completely separate the alkane and the olefin by rectification or extraction, especially to completely separate the alkane and the olefin with similar or same carbon number.
At present, the separation of olefin and alkane is mainly carried out by traditional extraction, rectification or extractive rectification process. However, because the boiling point difference between the olefins and the alkanes with similar or identical carbon numbers is very small, the separation of the olefins and the alkanes is not thorough by adopting the traditional extraction, and the separation cost by adopting the rectification process and the extractive rectification process is very high, the using amount of the solvent is large, the recovery is difficult, and the requirements of the current social development are not met. Although current technology also enables separation of olefins and alkanes, there is still a need to explore more efficient, energy efficient separation methods.
CN103232313A describes a simple extraction method which can realize the separation of alkane and olefin. The method adopts a single-component polar extraction agent, such as N-methylpyrrolidone (NMP), N-formyl morpholine (NFM) and 1-methylimidazole (1-MI), to be fully contacted and mixed with a mixture of alkane and alkene with the same carbon number to be separated, and then the mixture is stood for layering and separation. However, in this process, complete separation of the same carbon number alkanes and alkenes is not achieved.
Therefore, it is desirable to provide a method for separating olefin from a mixture of alkane and olefin, which is simple in operation, low in energy consumption and high in separation efficiency.
Disclosure of Invention
The invention aims to overcome the problems of high energy consumption or incomplete separation of alkane and olefin in the prior art, and provides a method for separating olefin from a mixture of alkane and olefin, which has the advantages of simple operation, low energy consumption and high separation efficiency, and the purity of the separated olefin is more than 99%.
In order to achieve the above object, the present invention provides a method for separating an alkene from a mixture of an alkane and the alkene, the method comprising the steps of:
(1) the method comprises the following steps of firstly mixing a mixture containing alkane and olefin with an extracting agent, then extracting, and separating to obtain an extraction phase A containing the extracting agent, the olefin and a small part of alkane, and a raffinate phase a containing a large part of alkane;
(2) carrying out second mixing on the extract phase A and an alkane separating agent, then layering, and separating to obtain a lower-layer mixed solution B containing olefin, the extracting agent and the alkane separating agent and an upper-layer mixed solution B containing alkane;
(3) and rectifying the extract phase B, and separating to obtain an olefin product.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
1) the method for separating the olefin from the mixture of the alkane and the olefin, provided by the invention, has the advantages of no need of heating, low energy consumption and simple flow, and the extraction agent and the alkane separating agent are used for separating the mixture containing the alkane and the olefin, so that the olefin with the purity of more than 99 percent can be obtained;
2) according to the method for separating the olefin from the mixture of the alkane and the olefin, the used extracting agent and the alkane separating agent can be recycled, so that the production cost is saved, and the method is suitable for industrial popularization;
3) the method for separating the olefin from the mixture of the alkane and the olefin, provided by the invention, can separate the alkane and the olefin in the mixture of the alkane and the olefin containing a plurality of carbon numbers in the wide-cut section at one time to obtain a high-purity mixed olefin product, and can separate the mixture of the alkane and the olefin containing one carbon number to obtain the high-purity olefin, so that the application range is wide.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The present invention provides a process for separating an alkene from a mixture of an alkane and an alkene, the process comprising the steps of:
(1) the method comprises the following steps of firstly mixing a mixture containing alkane and olefin with an extracting agent, then extracting, and separating to obtain an extraction phase A containing the extracting agent, the olefin and a small part of alkane, and a raffinate phase a containing a large part of alkane;
(2) carrying out second mixing on the extract phase A and an alkane separating agent, then layering, and separating to obtain a lower-layer mixed solution B containing olefin, the extracting agent and the alkane separating agent and an upper-layer mixed solution B containing alkane;
(3) and rectifying the lower-layer mixed solution B, and separating to obtain an olefin product.
In the step (1):
in a preferred embodiment, the mixture containing alkane and alkene is a mixture containing a plurality of alkanes and alkenes with the same carbon number or a mixture containing one alkane and alkene with the same carbon number.
In the present invention, the carbon number of the alkane or alkene is not particularly limited, and may be C5-C12, preferably C5-C10. The structure of the alkane in the present invention is not particularly limited, and the alkane may be a straight-chain alkane, or may be a branched or cyclic alkane, and is preferably a straight-chain alkane. The structure of the olefin is not particularly limited in the present invention, and the olefin may be an α -olefin or an internal olefin, and is preferably an α -olefin.
The invention can separate the alkane and the olefin with a plurality of same carbon numbers in the wide fraction section at one time to obtain a high-purity mixed olefin product. For example, a complex alkylene mixture naphtha is separated to obtain a high-purity mixed olefin, and then the high-purity mixed olefin obtained by further separation can obtain olefin products with various carbon numbers, such as pentene, hexene, heptene, octene, nonene, decene and the like, or can obtain an olefin combination, such as pentene + hexene and the like, according to actual production needs. Or separating a mixture containing an alkane and an alkene with the same carbon number to obtain the alkene with high purity, for example, separating 1-hexene/n-hexane to obtain 1-hexene with high purity; 1-heptene/n-heptane can be separated to obtain high purity 1-heptene.
In a preferred embodiment, the mixture containing alkane and alkene is a mixture containing one alkane and alkene with the same carbon number, preferably a mixture containing one alkane and alpha-alkene with the same carbon number, further preferably a mixture containing one alkane and alpha-alkene with the same carbon number and with the carbon number of 5-12, such as 5-10, and more preferably a mixture containing 1-hexene and n-hexane.
In a preferred embodiment, the present invention is not particularly limited as to the source of the mixture of alkanes and alkenes, preferably a Fischer-Tropsch light oil with or without deoxygenation to remove oxygenates from the coal chemical production.
In a preferred embodiment, the extractant is a weakly polar solvent or a built extractant, wherein the built extractant comprises the weakly polar solvent and a strongly polar solvent;
in a preferred embodiment, the weakly polar solvent is selected from at least one of γ -butyrolactone, N-methylpyrrolidone, N-dimethylformamide, N-formylmorpholine, morpholine, dimethylsulfoxide, acetonitrile; preferably at least one selected from the group consisting of gamma-butyrolactone, N-methylpyrrolidone, N-dimethylformamide, N-formylmorpholine and dimethylsulfoxide; the strongly polar solvent is selected from alcohols and/or water, preferably water.
In a preferred embodiment, the alcohol may be selected from mono-or polyols, preferably mono-alcohols, more preferably C1-C4 mono-alcohols, preferably C2-C3 mono-alcohols, such as ethanol.
In order to further improve the extraction separation efficiency of alkane and alkene, in a preferred embodiment, the extractant is preferably a compound extractant of the weak polar solvent and a strong polar solvent; wherein the mass ratio of the weak polar solvent to the strong polar solvent is 10-1000:1, preferably 5-100:1, and more preferably 8-30: 1.
In a further preferred embodiment, the built extractant is selected from at least one of gamma-butyrolactone + water, N-methylpyrrolidone + water, N-dimethylformamide + water, N-formylmorpholine + water, and dimethylsulfoxide + water.
In a preferred embodiment, the separation coefficient β of the olefin in the extractant is > 1.3, preferably β > 1.5, more preferably β > 1.9 at 25 ℃.
Wherein the separation coefficient β is (olefin content in the extract phase/paraffin content in the extract phase)/(olefin content in the raffinate phase/paraffin content in the raffinate phase).
In a preferred embodiment, the mass ratio of the extractant to the mixture comprising alkane and alkene is 0.1 to 15:1, preferably 0.5 to 5:1, more preferably 1 to 2.5: 1.
In a preferred embodiment, the first mixing mode of the extractant and the mixture containing alkane and alkene is not particularly limited, and the mixing mode can be performed at room temperature by means of the difference of gravity and buoyancy, and can also be performed by means of mechanical assistance such as shaking, stirring, shaking and the like. The invention does not specially limit the mixing time of extraction, and the specific mixing time can be adjusted according to the mixing mode and the treatment capacity.
In a preferred embodiment, in step (1), the extraction is carried out at room temperature, and the extraction temperature may be in the range of 5 to 40 ℃, preferably 10 to 30 ℃. The extraction time is not specially limited, and the specific extraction time can be adjusted according to the treatment capacity.
In a preferred embodiment, after the extraction is finished, an extract phase a containing the extractant, the olefin and a small part of the alkane is obtained, and a raffinate phase a containing a large part of the alkane is obtained. Wherein, the content of the extracting agent in the extract phase A is 81-93 wt%, preferably 83-89 wt% based on 100% of the total amount of the extract phase A; the olefin content is from 6 to 14% by weight, preferably from 9 to 12.5% by weight; the alkane content is 1 to 5 wt%, preferably 2 to 4.5 wt%.
In the step (2):
in a preferred embodiment, the alkane separating agent is an alkene or a mixture of alkenes, preferably the same alkene as the alkene to be separated.
In the present invention, the alkene to be separated refers to an alkene in a mixture comprising an alkane and an alkene. The inventor researches and creatively discovers that: the extraction phase A is homogeneous mixed liquid of extractant-alkene-alkane, the polarity of the extractant and the alkene is large, the polarity of the alkane is small, after the alkane separating agent with large polarity is added into the extraction phase A, the original polarity balance in the extraction phase A can be broken, so that the newly added alkane separating agent gradually replaces the alkane to enter the extraction phase A to form homogeneous solution of the extractant-alkene-alkane separating agent, and the alkane with small polarity is separated from the homogeneous mixed liquid of the extractant-alkene-alkane and enters the upper layer of the homogeneous solution of the extractant-alkene-alkane separating agent, so that the mixed liquid is subjected to phase splitting, and the alkane can be separated from the extraction phase A.
In order to reduce the difficulty of the separation operation of the subsequent extractant, namely the alkene-alkane separating agent, and simplify the separation process, the alkane separating agent is preferably the same as the alkene to be separated. When the olefin to be separated in the mixture comprising the alkane and the olefin comprises a plurality of olefins, the alkane separating agent is at least one of the plurality of olefins to be separated, and can be a single olefin or a mixture of the plurality of olefins. When the alkane separating agent is a mixture of a plurality of olefins, the invention does not make special requirements on the specific mixing proportion of the plurality of olefins in the mixture. For example, when separating a mixture of 1-heptene, 1-hexene/n-heptane, and n-hexane, the alkane separating agent may be 1-hexene, 1-heptene, or a mixture of 1-hexene and 1-heptene in any ratio.
In a preferred embodiment, the mass ratio of the alkane separating agent to the extract phase a is 0.01 to 15:1, preferably 0.02 to 5:1, more preferably 0.05 to 0.5:1, and even more preferably 0.06 to 0.15: 1.
In a preferred embodiment, the second mixing mode of the alkane separating agent and the extract phase A is not particularly limited, and the alkane separating agent and the extract phase A can be mixed by means of gravity and buoyancy difference, or by means of mechanical assistance such as shaking, stirring, shaking and the like. The mixing time of the alkane separating agent and the extract phase A is not specially limited, and the specific mixing time can be adjusted according to the mixing mode and the treatment capacity.
In a preferred embodiment, the delamination is performed at room temperature, wherein the room temperature is not particularly limited in the present invention, and may be 5 to 40 ℃, preferably 10 to 30 ℃.
In a preferred embodiment, the layering comprises standing and separating. The standing time is not particularly limited, and the specific standing time can be adjusted according to the treatment capacity.
In a preferred embodiment, after the completion of the standing, a liquid separation operation is performed to obtain a lower mixed liquid B containing olefins, an extracting agent and an alkane separating agent, and an upper mixed liquid B containing alkanes;
in a preferred embodiment, the step (2) further includes repeating the layering operation on the obtained lower mixed liquid B until the alkane content in the obtained lower mixed liquid B is less than or equal to 0.15%, preferably less than or equal to 0.07%.
Wherein, after repeated operation for many times, the alkane in the extract phase A can be basically and completely removed, and the lower mixed liquid B which hardly contains the alkane is obtained.
In the step (3):
the distillation operation conditions in the step (3) are not specially limited, and the distillation operation can be carried out according to the prior art, and the normal pressure distillation can be preferably used. Here, the normal pressure in the present invention means 0.1 MPa.
Since the alkane separating agent is also an alkene, in the present invention, the alkene product separated in step (3) includes not only the alkene to be separated from the mixture comprising the alkane and the alkene, but also the alkane separating agent added. When the alkane separating agent is preferably the same as the alkene to be separated in the mixture containing alkane and alkene, the lower mixed liquid B is subjected to a rectification operation, and high-purity alkene and extracting agent can be obtained. Wherein, the high-purity olefin product obtained by rectification comprises the olefin to be separated and the added alkane separating agent. The obtained extractant can be recycled, the production cost can be saved, and the method is suitable for industrial popularization. When the alkane separating agent is the alkene different from the alkene to be separated, the lower mixed liquid B is rectified, and the obtained alkene product can be the alkene product to be separated and the single alkane separating agent. Wherein, the obtained extracting agent and the alkane separating agent can be recycled.
In a preferred embodiment, the purity of the isolated olefin is above 99 wt%, preferably above 99.7 wt%.
In a preferred embodiment, the extractant is isolated with a purity of 99 wt.%, preferably above 99.5 wt.%.
In a preferred embodiment, the operations of step (1) and step (2) may be repeated a plurality of times in order to further increase the amount of alkene separated from the mixture comprising alkane and alkene.
The present invention will be described in detail below by way of examples.
Example 1
(1) 30g of a mixture with 70 wt% of 1-hexene and 30 wt% of n-hexane is fully mixed and contacted with 40g of gamma-butyrolactone + water compound extractant C1 (the gamma-butyrolactone content is 90 wt%), extraction is carried out: shaking for 1min at 20 ℃, standing for 15min, and separating liquid to obtain an extract phase; wherein, the obtained extraction phase has 11.5 wt% of 1-hexene, 2.5 wt% of n-hexane, 77.5 wt% of gamma-butyrolactone and 8.5 wt% of water.
(2) And (2) fully mixing and contacting 45g of the extraction phase separated from the step (1) with 5g of 1-hexene serving as an alkane separating agent, and layering: shaking for 2min at 20 ℃, standing for 10min, and separating liquid to obtain lower layer mixed liquid; the obtained lower layer mixed liquid is subjected to three times of layering operation, wherein the composition and the content of the lower layer mixed liquid obtained after each time of layering are shown in table 1:
table 1:
(3) and (3) rectifying the lower layer mixed liquid separated after the third liquid separation operation in the step (2), wherein the purity of the obtained 1-hexene is 99.8 wt% and the purity of the obtained extractant is 99.8 wt% at the distillation temperature of 62-65 ℃.
Example 2
(1) Fully mixing and contacting 30g of a mixture with 70 wt% of 1-hexene and 30 wt% of n-hexane with 45g of a compound extractant C2 (with 95 wt% of dimethyl sulfoxide) of dimethyl sulfoxide and water, and extracting: shaking for 2min at 20 ℃, standing for 10min, and separating liquid to obtain an extract phase; in the obtained extraction phase, the content of 1-hexene was 12.1 wt%, the content of n-hexane was 2.3 wt%, the content of dimethyl sulfoxide was 81.3 wt%, and the content of water was 4.3 wt%; .
(2) And (2) fully mixing and contacting 50g of the extraction phase obtained by separation in the step (1) with 6g of 1-hexene serving as an alkane separating agent, and demixing: shaking for 2min at 20 ℃, standing for 10min, and separating liquid to obtain lower layer mixed liquid; repeating the layering operation for three times on the obtained lower layer mixed liquid, wherein the composition and the content of the lower layer mixed liquid obtained after each time of layering are shown in table 2;
table 2:
(3) and (3) rectifying the lower layer mixed liquid separated after the third liquid separation operation in the step (2), wherein the purity of the obtained 1-hexene is 99.8 wt% and the purity of the obtained extractant is 99.6 wt% at the distillation temperature of 62-65 ℃.
Example 3
(1) 20g of a mixture with 70 wt% of 1-hexene and 30 wt% of N-hexane is fully mixed and contacted with 40g of a compound extracting agent C3 (with 93 wt% of N-methylpyrrolidone) of N-methylpyrrolidone and water for extraction: shaking for 1min at 20 ℃, standing for 10min, and separating liquid to obtain an extract phase; wherein, in the obtained extraction phase, the content of 1-hexene, N-hexane and N-methylpyrrolidone is 9.0 wt%, 4.2 wt%, 83.3 wt% and 3.5 wt%, respectively.
(2) And (2) fully mixing and contacting 44g of the extraction phase separated in the step (1) with 5g of 1-hexene serving as an alkane separating agent, and layering: shaking for 2min at 20 ℃, standing for 10min, and separating liquid to obtain lower layer mixed liquid; repeating the layering operation for three times on the obtained lower layer mixed liquid, wherein the composition and the content of the lower layer mixed liquid obtained after each time of layering are shown in table 3;
table 3:
(3) and (3) rectifying the lower layer mixed liquid separated after the third liquid separation operation in the step (2), wherein the purity of the obtained 1-hexene is 99.7 wt% and the purity of the obtained extractant is 99.6 wt% at the distillation temperature of 62-65 ℃.
Example 4
(1) 100g of a mixture having the composition shown in Table 4 was thoroughly mixed and contacted with 120g N-formylmorpholine + water complex extractant C4 (the content of N-formylmorpholine is 95 wt%), extraction was carried out: shaking at 20 deg.C for 1min, standing for 15min, and separating to obtain extract phase; the composition and content of the extract phase obtained are shown in Table 5.
TABLE 4
| Component/wt.% | C5 | C6 | C7 | C8 | C9 | C10 |
| N-alkanes | 4.86 | 5.45 | 4.65 | 4.85 | 4.99 | 0.96 |
| N-olefins | 12.28 | 13.80 | 13.56 | 14.64 | 15.04 | 4.92. |
TABLE 5
(2) And (2) fully mixing and contacting 136g of the extraction phase separated in the step (1) with 10g of 1-hexene serving as an alkane separating agent, and layering: shaking at 20 deg.C for 2min, standing for 10min, and separating to obtain lower layer mixed solution; repeating the layering operation for three times on the obtained lower layer mixed liquid, wherein the composition and the content of the lower layer mixed liquid obtained after each time of layering are shown in table 6;
table 6:
(3) and (3) rectifying the lower layer mixed liquid separated after the third liquid separation operation in the step (2), wherein the purity of the obtained normal olefins is more than 99 wt% at the distillation temperature of 62-172 ℃.
Example 5
(1) 60g of a mixture with a 1-hexene content of 70 wt% and an n-hexane content of 30 wt% was thoroughly mixed and contacted with 35g N-formylmorpholine extractant C5 for extraction: shaking for 1min at 20 ℃, standing for 15min, and separating liquid to obtain an extract phase; wherein, the obtained extraction phase has a 1-hexene content of 10.5 wt%, a N-hexane content of 3.5 wt% and a N-formylmorpholine content of 86 wt%.
(2) And (2) fully mixing and contacting 40g of the extraction phase separated from the step (1) with 4g of 1-hexene serving as an alkane separating agent, and demixing: shaking for 2min at 20 ℃, standing for 10min, and separating liquid to obtain lower layer mixed liquid; the obtained lower layer mixed liquid is subjected to three times of layering operation, wherein the composition and the content of the lower layer mixed liquid obtained after each time of layering are shown in table 1:
table 7:
(3) and (3) rectifying the lower layer mixed liquid separated after the third liquid separation operation in the step (2), wherein the purity of the obtained 1-hexene is 99.8 wt% and the purity of the obtained extractant is 99.6 wt% at the distillation temperature of 62-65 ℃.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A process for separating an alkene from a mixture of an alkane and an alkene, the process comprising the steps of:
(1) extracting after first mixing a mixture containing alkane and alkene with an extracting agent, and separating to obtain an extract phase A containing the extracting agent, the alkene and a small part of alkane and a raffinate phase a containing a large part of alkane;
(2) carrying out second mixing contact on the extract phase A and an alkane separating agent, then layering, and separating to obtain a lower-layer mixed solution B containing olefin, the extracting agent and the alkane separating agent and an upper-layer mixed solution B containing alkane;
(3) and rectifying the lower-layer mixed liquor B, and separating to obtain an olefin product.
2. The separation method according to claim 1, wherein in the step (1), the mixture containing alkane and alkene is a mixture containing a plurality of alkanes and alkenes with the same carbon number or a mixture containing one alkane and alkene with the same carbon number;
preferably, the mixture comprising alkanes and alkenes is a mixture comprising alkanes and alkenes of one and the same carbon number, more preferably a mixture of 1-hexene and n-hexane.
3. The separation method according to claim 1 or 2, wherein the extractant is a weakly polar solvent or a built extractant, wherein the built extractant comprises the weakly polar solvent and a strongly polar solvent;
preferably, the weakly polar solvent is selected from at least one of γ -butyrolactone, N-methylpyrrolidone, N-dimethylformamide, N-formylmorpholine, morpholine, dimethyl sulfoxide, acetonitrile, preferably from at least one of γ -butyrolactone, N-methylpyrrolidone, N-dimethylformamide, N-formylmorpholine and dimethyl sulfoxide; the strongly polar solvent is selected from alcohols and/or water, preferably water.
4. The separation method according to claim 3, wherein in the compound extractant of the weak polar solvent and the strong polar solvent, the mass ratio of the weak polar solvent to the strong polar solvent is 10-1000:1, preferably 50-100:1, and more preferably 8-30: 1.
5. The separation process according to any one of claims 1 to 4, wherein the mass ratio of the extractant to the mixture comprising alkane and alkene is from 0.1 to 15:1, preferably from 0.5 to 5: 1;
preferably, the extraction is performed at room temperature.
6. The separation process according to claim 5, wherein the extractant content in the extract phase A is 81-93 wt%, preferably 83-89 wt%; the olefin content is from 6 to 14% by weight, preferably from 9 to 12.5% by weight; the alkane content is 1 to 5 wt%, preferably 2 to 4.5 wt%.
7. The separation process according to any one of claims 1 to 6, wherein in step (2) the alkane separating agent is an alkene or a mixture of alkenes, preferably the same alkene as the alkene to be separated.
8. The separation process according to claim 1, wherein the mass ratio of the alkane separating agent to the extract phase a is 0.01-15:1, preferably 0.06-0.15: 1;
preferably, the delamination is performed at room temperature.
9. The separation method according to claim 8, wherein the step (2) further comprises repeating the layering operation on the obtained lower layer mixed liquor B until the mass content of alkane in the obtained lower layer mixed liquor B is less than or equal to 0.15%, preferably less than or equal to 0.07%.
10. The separation method according to claim 1, wherein in the step (3), the rectification is atmospheric rectification.
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