CN103508830A - Method for separating alkanes and olefin in etherification C4 fractions - Google Patents
Method for separating alkanes and olefin in etherification C4 fractions Download PDFInfo
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- CN103508830A CN103508830A CN201210202476.4A CN201210202476A CN103508830A CN 103508830 A CN103508830 A CN 103508830A CN 201210202476 A CN201210202476 A CN 201210202476A CN 103508830 A CN103508830 A CN 103508830A
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- cut
- acetic acid
- butyl acetate
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Abstract
The invention discloses a method for separating alkanes and olefin in etherification C4 fractions. The method comprises the following steps: 1, allowing the etherification C4 fractions to contact with acetic acid under the action of a catalyst to obtain sec-butyl acetate, and separating out C4 alkanes; and 2, cracking sec-butyl acetate to obtain acetic acid and n-butene. The method, which is characterized in that the acetic acid completely reacts with butylene in the etherification C4 fractions to generate sec-butyl acetate and obtain the C4 alkanes and sec-butyl acetate is cracked to obtain widely used n-butene, realizes the separation of the alkanes from the etherification C4 fractions, the complete separation of the alkanes from olefins and the obtaining of widely used n-butene through a simple technology.
Description
Technical field
The present invention relates to petrochemical industry.Further, the present invention relates to C after a kind of separated ether
4butane in cut and the method for alkene.
Background technology
Along with the variation of petrochemical industry resource general layout, the more and more valuable ，Dan of the C-4-fraction of ethylene plant and refinery China is at present to C
4the utilization of product insufficient, utilizing at present maximum is iso-butylene and the divinyl in carbon four products.In refinery casing head, not containing divinyl, can directly carry out etherification reaction, in ethylene plant's C-4-fraction, contain approximately 45% divinyl, need to will after Butadiene Extraction, carry out again etherification reaction.The technology of producing at present methyl tertiary butyl ether (MTBE) is very ripe, there is ether-based device in each petroleum chemical enterprise, by mixed c 4 cut, react and prepare methyl tertiary butyl ether with methyl alcohol, the basic complete reaction of iso-butylene, after remaining ether, C-4-fraction is the mixture of alkane and monoolefine, wherein monoolefine is valuable industrial chemicals, but is not fully used.Major cause is that these six kinds of product boiling points differ very little, is difficult to separation.The boiling point of each component is as shown in table 1.
Table 1
| Carbon four | Boiling point (℃) |
| Trimethylmethane | －11.73 |
| Iso-butylene | －6.9 |
| 1-butylene | －6.26 |
| Normal butane | －0.5 |
| Trans-2-butene | 0.88 |
| Cis-2-butene | 3.74 |
CN 1139560C discloses a kind of method of separating butane and butylene, utilizes dimethyl formamide and composition thereof, adopts method separating butane and the butylene of extracting rectifying.
CN 1170793C discloses a kind of method of separating butane and butylene, utilizes methylethylketone series mixed solvent, adopts method separating butane and the butylene of extracting rectifying.
CN 1709841A discloses a kind of method of separating butane and butylene, utilizes acetonitrile series mixed solvent, adopts method separating butane and the butylene of extracting rectifying.
The separation method of traditional extracting rectifying is invested greatly, cost is high.Extraction agent is dimethyl formamide, N-formyl morpholine N-, methyl-2-pyrrolidone, acetonitrile equal solvent, and these extraction agents at high temperature easily decompose, and not only affect quality product, and increases the loss of extraction agent.
Summary of the invention
The problems such as the investment existing in prior art is large, cost is high in order to solve, the easy decomposition of solvent, the invention provides a kind of by C after Reaction Separation ether
4the method of alkene and alkane in cut, has that technique is simple, a separating effect advantage completely.
The invention provides C after a kind of separated ether
4in cut, the method for butane and alkene, comprises
Step I: under the effect of catalyzer, by C after ether
4cut contacts with acetic acid, obtains 2-butyl acetate, and isolates C
4alkane;
Step II: the 2-butyl acetate obtaining in step I is carried out to cracking and obtain acetic acid and n-butene.
According to method provided by the invention, C after described ether
4cut refers to the C utilizing from ethylene plant and refinery
4c after iso-butylene synthesize methyl tert-butyl ether in cut
4cut.C after described ether
4cut is mainly the mixture of alkane and monoolefine, and its main component comprises Trimethylmethane, normal butane, 1-butylene, t-2-butylene, c-2-butylene.
In aforesaid method, in described step I, by C after ether
4when cut contacts under the effect of catalyzer with acetic acid, C after ether
4alkene and acetic acid reaction in cut obtain 2-butyl acetate, C after ether
4alkene in cut is fallen by complete reaction, and C after ether
4alkane in cut do not participate in reaction, from reactive system, discharge, thus from ether C
4in cut, separation has obtained C
4alkane.C after ether
4the selectivity that alkene in cut and acetic acid reaction generate 2-butyl acetate is greater than 99%, in a specific embodiment, and in described step I, C after acetic acid/ether
4the mol ratio of the C 4 olefin of cut is 1 ~ 1.5, C after ether
4weight space velocity 1 ~ the 3h of C-4-fraction
-1.
In aforesaid method, in described step II, 2-butyl acetate cracking obtains acetic acid and n-butene (1-butylene).N-butene has use value very widely, and acetic acid can recycle, as is back to step I.In a specific embodiment, in described step II, temperature is 400 ℃, and pressure is 0.05 ~ 0.1MPa, the air speed 1 ~ 3h of 2-butyl acetate
-1.
In aforesaid method, in described step I and step II, in reactor, carry out.Described reactor is selected from tubular reactor and tower reactor.In a specific embodiment of aforesaid method, in described step I, reactor top temperature is 30 ~ 80 ℃, and at the bottom of reactor, temperature is 110 ~ 200 ℃, and pressure is 0.5 ~ 2.5MPa.
In aforesaid method, described catalyzer is strong acidic ion resin.In a specific embodiment, described catalyzer is selected from H type and macropore strong acid cation resin.
By method provided by the invention, utilize acetic acid by C after ether
4butylene complete reaction in cut generates 2-butyl acetate, and obtains C
4alkane; 2-butyl acetate is carried out to scission reaction, can obtain broad-spectrum n-butene.By method provided by the invention, by simple technique, just realized C after ether
4the separation of alkane in cut, alkane and separation of olefins are complete, and have obtained having the n-butene of extensive use.
Accompanying drawing explanation
Fig. 1 is according to the process flow sheet of method provided by the invention embodiment.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated, but does not form any limitation of the invention.
Fig. 1 is process flow sheet according to an embodiment of the invention.Acetic acid 4 enters reactor 1 from the top of reactor 1, C after ether
4cut 5 passes into reactor 1, C from the bottom of reactor 1
4alkane 6 is discharged from the top of reactor 1, the 2-butyl acetate product 7 obtaining enters cracking reactor 2 and carries out cracking from flow out reactor 1 bottom, the n-butene 11 that cracking obtains flows out from cracking reactor 2 tops, and the acetic acid 4 that cracking obtains is from discharge the bottom of cracking reactor 2, can be recycled, can reenter reactor 2 and participate in reaction.
Embodiment 1
Acetic acid raw material is the Glacial acetic acid that purity is greater than 99.5%, and reactor 1 use consists of C after the ether of Trimethylmethane 44.19%, normal butane 13.23%, 1-butylene 13.76%, t-2-butylene 16.55%, iso-butylene 0.1%, c-2-butylene 11.75%
4cut.
Catalyzer adopts macropore strong acid phenylethylene resin cation (R.C.), and the trade mark is NKC-9, by 50 grams of catalyst packings well after integral body pack in reactor.
Step I: reactor top temperature is 50 ℃, at the bottom of reactor, temperature is 180 ℃, pressure is 1.0MPa, C after acetic acid and ether
4the mol ratio of the C 4 olefin in cut is 1.1, C after ether
4the weight space velocity 3h of cut
-1.Acetic acid enters from reactor 1 portion of returning back to top with volume pump, C after ether
4cut enters from reactor 1 bottom by liquid mass flow meter.
Step II: reactor top temperature is 30 ℃, at the bottom of reactor, temperature is 450 ℃, pressure is 0.05MPa, 2-butyl acetate air speed 1h
-1.Reactor 1 liquid product enters from reactor 2 tops with volume pump.
Reaction result is in Table 2 and table 3.
Embodiment 2
Acetic acid raw material is the Glacial acetic acid that purity is greater than 99.5%, and reactor 1 use consists of C after the ether of Trimethylmethane 0.25%, normal butane 20.45%, 1-butylene 5.11%, t-2-butylene 43.72%, iso-butylene 0.12%, c-2-butylene 30.17%
4cut.
Catalyzer adopts macropore strong acid phenylethylene resin cation (R.C.), and the trade mark is NKC-9, by 50 grams of catalyst packings well after integral body pack in reactor.
Step I: reactor top temperature is 50 ℃, at the bottom of reactor, temperature is 150 ℃, pressure is 1.0MPa, C after acetic acid and ether
4the mol ratio of the C 4 olefin in cut is 1.1, C after ether
4the weight space velocity 2h of cut
-1.Acetic acid enters from reactor 1 top with volume pump, C after ether
4cut enters from reactor 1 bottom by liquid mass flow meter.
Step II: reactor top temperature is 30 ℃, at the bottom of reactor, temperature is 450 ℃, pressure is 0.05MPa, 2-butyl acetate air speed 1h
-1.Reactor 1 liquid product enters from reactor 2 tops with volume pump.Reaction result is in Table 2 and table 3.
The test-results of table 2 step I
| Project | Embodiment 1 | Embodiment 2 |
| Reactor top temperature ℃ | 70 | 65 |
| Temperature ℃ at the bottom of reactor | 180 | 180 |
| Reaction pressure on top surface MPa | 1.0 | 1.0 |
| Acetic acid/butylene mol ratio | 1.1 | 1.1 |
| Carbon four air speed h -1 | 3 | 2 |
| 2-butyl acetate selectivity | 99.2 | 99.5 |
| Reactor top C 4Olefin(e) centent | Do not measure | Do not measure |
The test-results of table 3 step II
| Project | Embodiment 1 | Embodiment 2 |
| Reactor top temperature ℃ | 30 | 30 |
| Reactor still temperature ℃ | 450 | 450 |
| Reactor top pressure MPa | 0.05 | 0.05 |
| 2-butyl acetate air speed h -1 | 1 | 1 |
| Reactor top C 4Determination of Alkane Content | Do not measure | Do not measure |
From table 2 and table 3, data can draw, by method provided by the invention, and can be effectively separated C after ether
4alkene in cut and alkane, separating effect is complete.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, but should be understood to word wherein used, be descriptive and explanatory vocabulary, rather than limited vocabulary.Can in the scope of the claims in the present invention, to the present invention, modify in accordance with regulations, and within not deviating from scope and spirit of the present invention, the present invention be revised.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Claims (8)
1. C after a separated ether
4in cut, the method for butane and alkene, comprises
Step I: under the effect of catalyzer, by C after ether
4cut contacts with acetic acid, obtains 2-butyl acetate, and isolates C
4alkane;
Step II: the 2-butyl acetate obtaining in step I is carried out to cracking and obtain acetic acid and n-butene.
2. method according to claim 1, is characterized in that, in step I, and C after acetic acid/ether
4the mol ratio of the C 4 olefin in cut is 1 ~ 1.5, C after ether
4cut weight space velocity 1 ~ 3h
-1.
3. method according to claim 1, is characterized in that, in step II, temperature is that 400 ℃, pressure are 0.05 ~ 0.1MPa, 2-butyl acetate air speed 1 ~ 3h
-1.
4. according to the method described in any one in claim 1 ~ 3, it is characterized in that, in described step I and step II, in reactor, carry out.
5. method according to claim 4, is characterized in that, described reactor is selected from tubular reactor and tower reactor.
6. according to the method described in any one in claim 1 ~ 5, it is characterized in that, in described step I, reactor top temperature is that temperature is that 110 ~ 200 ℃, pressure are 0.5 ~ 2.5MPa at the bottom of 30 ~ 80 ℃, reactor.
7. according to the method described in any one in claim 1 ~ 6, it is characterized in that, described catalyzer is strong acidic ion resin.
8. method according to claim 7, is characterized in that, the catalyzer in described step I is selected from H type and macropore strong acid cation resin.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152833A (en) * | 2015-07-22 | 2015-12-16 | 珠海飞扬新材料股份有限公司 | Method for preparing n-butene |
| CN109096036A (en) * | 2018-08-09 | 2018-12-28 | 天津大学 | The method and apparatus of 1- decene is separated from Fischer-Tropsch synthesis oil using coupling reaction and separation technique |
| CN109096035A (en) * | 2018-07-17 | 2018-12-28 | 天津大学 | Utilize the method and apparatus of kinetics differential separation alkane and alkene |
| CN109180413A (en) * | 2018-08-09 | 2019-01-11 | 天津大学 | The method and apparatus of 1- hexene is separated from Fischer-Tropsch synthesis oil using coupling reaction and separation technique |
| CN109265307A (en) * | 2018-08-09 | 2019-01-25 | 天津大学 | The method and apparatus of 1- octene is separated from Fischer-Tropsch synthesis oil using coupling reaction and separation technique |
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| CN101012145A (en) * | 2006-12-26 | 2007-08-08 | 南京石油化工股份有限公司 | Method of separating butane-1 from C4 fraction |
| CN101143819A (en) * | 2007-10-16 | 2008-03-19 | 胡先念 | Method for preparing sec-butyl acetate |
| CN102344334A (en) * | 2011-07-27 | 2012-02-08 | 天津市泰旭物流有限公司 | Method for preparing isobutylene by using etherification method |
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| CN101012145A (en) * | 2006-12-26 | 2007-08-08 | 南京石油化工股份有限公司 | Method of separating butane-1 from C4 fraction |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152833A (en) * | 2015-07-22 | 2015-12-16 | 珠海飞扬新材料股份有限公司 | Method for preparing n-butene |
| CN109096035A (en) * | 2018-07-17 | 2018-12-28 | 天津大学 | Utilize the method and apparatus of kinetics differential separation alkane and alkene |
| CN109096036A (en) * | 2018-08-09 | 2018-12-28 | 天津大学 | The method and apparatus of 1- decene is separated from Fischer-Tropsch synthesis oil using coupling reaction and separation technique |
| CN109180413A (en) * | 2018-08-09 | 2019-01-11 | 天津大学 | The method and apparatus of 1- hexene is separated from Fischer-Tropsch synthesis oil using coupling reaction and separation technique |
| CN109265307A (en) * | 2018-08-09 | 2019-01-25 | 天津大学 | The method and apparatus of 1- octene is separated from Fischer-Tropsch synthesis oil using coupling reaction and separation technique |
| CN109180413B (en) * | 2018-08-09 | 2021-07-27 | 天津大学 | Method and device for separating 1-hexene from Fischer-Tropsch synthetic oil by using reaction separation coupling process |
| CN109265307B (en) * | 2018-08-09 | 2021-07-30 | 天津大学 | Method and device for separating 1-octene from Fischer-Tropsch synthetic oil by using reaction separation coupling process |
| CN109096036B (en) * | 2018-08-09 | 2021-08-31 | 天津大学 | Method and device for separating 1-decene from Fischer-Tropsch synthetic oil by using reaction separation coupling process |
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