CN103508830B - Method for separating alkanes and olefin in etherification C4 fractions - Google Patents
Method for separating alkanes and olefin in etherification C4 fractions Download PDFInfo
- Publication number
- CN103508830B CN103508830B CN201210202476.4A CN201210202476A CN103508830B CN 103508830 B CN103508830 B CN 103508830B CN 201210202476 A CN201210202476 A CN 201210202476A CN 103508830 B CN103508830 B CN 103508830B
- Authority
- CN
- China
- Prior art keywords
- reactor
- ether
- cut
- acetic acid
- butyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 and a kind of be separated C after ether
4butane in cut and the method for alkene.
Background technology
Along with the change of fossil resources general layout, the C-4-fraction of ethylene plant and refinery is more and more valuable, but China is at present to C
4the utilization of product is also insufficient, and utilizing maximum is at present iso-butylene in carbon four product and divinyl.Not containing divinyl in refinery casing head, directly can carry out etherification reaction, containing the divinyl of about 45% in ethylene plant's C-4-fraction, need to carry out etherification reaction again by after Butadiene Extraction.The technology of current production methyl tertiary butyl ether (MTBE) is very ripe, there is ether-based device in each petroleum chemical enterprise, reacted by mixed c 4 cut and methyl alcohol and prepare methyl tertiary butyl ether, 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 point differences are very little, is difficult to be separated.The boiling point of each component is as shown in table 1.
Table 1
| Carbon four | Boiling point (DEG C) |
| 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 investment of traditional extracting rectifying is large, 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
For solving the problems such as the investment existed in prior art is large, cost is high, solvent easily decomposes, 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, separating effect advantage completely.
The invention provides and a kind of be separated C after 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 obtained in step I is carried out cracking and obtains acetic acid and n-butene.
According to method provided by the invention, C after described ether
4cut refers to the C utilized 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 in cut and acetic acid reaction obtain 2-butyl acetate, C after ether
4alkene in cut is fallen by complete reaction, and C after ether
4alkane in cut does not participate in reaction, discharges from reactive system, thus from C after ether
4be separated in cut and obtain 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, in described step I, and 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 widely, and acetic acid then can recycle, as being back to step I.In a specific embodiment, in described step II, temperature is 400 DEG C, and pressure is 0.05 ~ 0.1MPa, the air speed 1 ~ 3h of 2-butyl acetate
-1.
In aforesaid method, carry out in the reactor in described step I and step II.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 DEG C, and temperature at the bottom of reactor is 110 ~ 200 DEG C, 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 Macroporous strongly acid cation exchange 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 scission reaction, broad-spectrum n-butene can be obtained.By method provided by the invention, just achieve C after ether by simple technique
4the separation of alkane in cut, alkane and separation of olefins completely, and obtain the n-butene with extensive use.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of an embodiment according to method provided by the invention.
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 obtained enters cracking reactor 2 after flowing out bottom reactor 1 and carries out cracking, the n-butene 11 that cracking obtains flows out from cracking reactor 2 top, and the acetic acid 4 that cracking obtains is after the bottom discharge of cracking reactor 2, can be recycled, reactor 2 can be reentered and participate in reaction.
Embodiment 1
Acetic acid raw material is the Glacial acetic acid that purity is greater than 99.5%, reactor 1 C after the ether consisting 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 rear overall loading reactor.
Step I: reactor top temperature is 50 DEG C, temperature at the bottom of reactor is 180 DEG C, and 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 volume pump enters from reactor 1 portion of returning back to top, C after ether
4cut is entered bottom reactor 1 by liquid mass flow meter.
Step II: reactor top temperature is 30 DEG C, temperature at the bottom of reactor is 450 DEG C, and pressure is 0.05MPa, 2-butyl acetate air speed 1h
-1.Reactor 1 liquid product volume pump enters from reactor 2 top.
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%, reactor 1 C after the ether consisting 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 rear overall loading reactor.
Step I: reactor top temperature is 50 DEG C, temperature at the bottom of reactor is 150 DEG C, and 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 volume pump enters from reactor 1 top, C after ether
4cut is entered bottom reactor 1 by liquid mass flow meter.
Step II: reactor top temperature is 30 DEG C, temperature at the bottom of reactor is 450 DEG C, and pressure is 0.05MPa, 2-butyl acetate air speed 1h
-1.Reactor 1 liquid product volume pump enters from reactor 2 top.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 DEG C | 70 | 65 |
| Temperature DEG C at the bottom of reactor | 180 | 180 |
| Reaction pressure on top surface MPa | 1.0 | 1.0 |
| Acetic acid/butene molar 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 DEG C | 30 | 30 |
| Reactor still temperature DEG C | 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, effectively can be separated C after ether
4alkene in cut and alkane, separating effect is complete.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (7)
1. C after a separation ether
4the method of butane and alkene in cut, comprising:
Step I: under the effect of catalyzer, by C after ether
4cut contacts with acetic acid, C after ether
4alkene complete reaction in cut, obtains 2-butyl acetate, and isolates C
4alkane, described catalyzer is strong acidic ion resin;
Step II: the 2-butyl acetate obtained in step I is carried out cracking and obtains 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 400 DEG C, pressure is 0.05 ~ 0.1MPa, 2-butyl acetate air speed 1 ~ 3h
-1.
4. according to the method in claims 1 to 3 described in any one, it is characterized in that, carry out in the reactor in described step I and step II.
5. method according to claim 4, is characterized in that, described reactor is selected from tubular reactor and tower reactor.
6. method according to claim 4, is characterized in that, in described step I, reactor top temperature is 30 ~ 80 DEG C, temperature at the bottom of reactor is 110 ~ 200 DEG C, pressure is 0.5 ~ 2.5MPa.
7. according to the method in claim 1-3 described in any one, it is characterized in that, the catalyzer in described step I is selected from H type and Macroporous strongly acid cation exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210202476.4A CN103508830B (en) | 2012-06-15 | 2012-06-15 | Method for separating alkanes and olefin in etherification C4 fractions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210202476.4A CN103508830B (en) | 2012-06-15 | 2012-06-15 | Method for separating alkanes and olefin in etherification C4 fractions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103508830A CN103508830A (en) | 2014-01-15 |
| CN103508830B true CN103508830B (en) | 2015-05-13 |
Family
ID=49892318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210202476.4A Active CN103508830B (en) | 2012-06-15 | 2012-06-15 | Method for separating alkanes and olefin in etherification C4 fractions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103508830B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152833B (en) * | 2015-07-22 | 2017-08-08 | 珠海飞扬新材料股份有限公司 | A kind of 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 |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-06-15 CN CN201210202476.4A patent/CN103508830B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 混合C4分离制高纯度1-丁烯;黄荣南 等;《兰化科技》;19950630;第13卷(第2期);122-127，132 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103508830A (en) | 2014-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103508830B (en) | Method for separating alkanes and olefin in etherification C4 fractions | |
| CN100358852C (en) | Process for the preparation of tert.-butanol | |
| CN101475429A (en) | Method for comprehensive utilization of cracking C4 | |
| CN104557478A (en) | Method for preparing tert-butyl ether | |
| CN103304382A (en) | Combined process for comprehensively utilizing partial hydrogenation C5 fraction | |
| CN104262117A (en) | Method for preparing dihydric alcohol mono-t-butyl ether | |
| CN103965003A (en) | Production method of butadiene | |
| CN103785482B (en) | A kind of deactivating process for the treatment of of olefin isomerization catalyst | |
| CN106554275A (en) | A kind of method comprehensively utilized by C-4-fraction after ether | |
| CN102633588A (en) | Method for preparing high-purity isobutene from raffinate C4 by means of separation | |
| CN103508884B (en) | One utilizes C after ether 4cut prepares the method for 2-butyl acetate | |
| CN104672046B (en) | Method of increasing ethylene and propylene yields by freshening C-4 olefins in catalytic cracking or pyrolysis process after separation | |
| CN103772117A (en) | Method for preparing butadiene through multistage adiabatic oxidative dehydrogenation of butylene | |
| CN106554251A (en) | A kind of method that C-4-fraction prepares sec-butyl alcohol and ethanol after utilization ether | |
| CN103086830B (en) | Production method of butadiene | |
| CN103508885B (en) | One utilizes C after ether 4cut prepares the method for 2-butyl acetate | |
| CN102603452A (en) | Method for preparing isoalkenes through isomerizing linear alkenes | |
| CN102442976B (en) | Method for epoxidizing olefinic hydrocarbon | |
| CN107286983A (en) | The method of C 4 olefin oligomerisation gasoline component | |
| CN107286984B (en) | The method of n-butene gasoline component coproduction isobutene | |
| CN102336624A (en) | Method for preparing isobutene with tertiary butanol method | |
| CN103787843B (en) | A kind of method preparing tert amyl methyl ether(TAME) | |
| CN107537568A (en) | A kind of method of modifying of cationic ion-exchange resin and the method for preparing tert amyl methyl ether(TAME) | |
| CN107602328B (en) | Pre-separation process for byproduct carbon four of MTO device | |
| CN102267854A (en) | Method for preparing isobutylene by virtue of sulfuric acid extraction method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |