CN104557410B - A kind of method of the amylene of high-purity 1 - Google Patents
A kind of method of the amylene of high-purity 1 Download PDFInfo
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- CN104557410B CN104557410B CN201310471735.8A CN201310471735A CN104557410B CN 104557410 B CN104557410 B CN 104557410B CN 201310471735 A CN201310471735 A CN 201310471735A CN 104557410 B CN104557410 B CN 104557410B
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Abstract
A kind of method of the amylene of high-purity 1.Process includes：The raffinate carbon-5 after diolefin and iso-amylene has been separated as raw material rectifying separation removal heavy constituent to extract, and tower top must be enriched with 1 amylene cut, tower reactor discharge heavy constituent；By process 1）The cut for the amylene of enrichment 1 that tower top is obtained carries out precise distillation to remove light component, and tower top obtains C 5 alkane and other light components, and tower reactor obtains 1 amylene crude product；By process 2）The crude product and methanol for obtaining 1 amylene carry out etherification reaction, to remove the butylene of 2 methyl 1 for being difficult to separate in crude product；By process 3）Product feeding treating column carries out purifying to obtain more than 98% 1 amylene after obtained ether.The present invention simplifies technique by modified technique flow, reduces production cost, improves the economy of the amylene technique of high-purity 1.
Description
Technical field
The present invention relates to the separation method of oil C5 fraction, more particularly to pass through the technical process such as precise distillation, etherificate
The method for separating oil C5 fraction high-purity 1- amylenes.
Background technology
The a considerable amount of C5 fractions of process by-product of petroleum cracking ethene, its amount is about the 10% of ethylene yield.At present
The comprehensive utilization of C5 fraction is mainly stripped separation to five cuts, obtains being worth higher isoprene, bicyclic penta 2
The diolefin such as alkene and pentadiene and iso-amylene.The raffinate carbon-5 material for having separated diolefin and iso-amylene through extracting is accounted for
The 10%~15% of C5 fraction raw material.Due to raffinate carbon-5 component boiling point closely, difficulty is separated, fuel oil is typically only used as
Use.For the deep processing of this raffinate carbon-5 material, Chinese patent ZL02145057.9, ZL02145056.0 disclose one kind
Raffinate carbon-5 material is obtained to the mixture of pentane and isopentane by being hydrogenated with entirely, foaming agent, extractant, green refrigeration can be used as
Agent and organic flux etc., this method further increase the value of raffinate carbon-5.But, actually in raffinate carbon-5 material
Containing 10% or so 1- amylenes, it is a kind of useful fine-chemical intermediate, is mainly used in organic synthesis and produces isoamyl two
Alkene, its derivative 1,2- pentanediols are the primary raw materials for preparing new type bactericide propiconazole, it is also possible to make adding for high octane gasoline
Plus agent, its price is significantly larger than pentane and isopentane.
It is directly relatively difficult with the method separation of rectifying because 1- amylenes are close with the boiling point of other light dydrocarbon components.China
Patent ZL200710039674.2 discloses a kind of method for separating C5 fraction extraction 1- amylenes, and this method uses extracting rectifying
Technique, to have extracted the raffinate carbon-5 of diolefin and iso-amylene as raw material, by de- rectifying again, extracting rectifying, stripping, de- light
Rectificating method obtains 95%1- amylene products.Because the technique whole process is complicated, equipment is more, and using extracting rectifying
Method make it that the process energy consumption is higher.
The content of the invention
The invention provides a kind of method of high-purity 1- amylenes, it passes through the technical process such as precise distillation, etherificate
By the method for raffinate carbon-5 fraction seperation high-purity 1- amylenes.Problem to be solved is by modified technique flow, letter
Chemical industry skill, reduces production cost, improves the economy of high-purity 1- amylene techniques.
The following is the detailed technical scheme of the present invention：
A kind of method of high-purity 1- amylenes, the original of the raffinate carbon-5 after diolefin and iso-amylene has been separated to extract
Material, its process includes：
1）Raffinate carbon-5 raw material is through rectifying separation removal heavy constituent, and tower top temperature is 26~32 DEG C, and bottom temperature is 35~
40 DEG C, operating pressure is normal pressure, and reflux ratio is 5~20, and tower top must be enriched with 1- amylene cuts, tower reactor discharge heavy constituent；
2）By process 1）The cut for the enrichment 1- amylenes that tower top is obtained carries out precise distillation to remove light component, operating pressure
Normal pressure, 27~31 DEG C of tower top temperature, 28~34 DEG C of bottom temperature, reflux ratio 20~60, tower top obtains C 5 alkane and other light group
Point, tower reactor obtains 1- amylene crude products；
3）By process 2）The crude product and methanol for obtaining 1- amylenes carry out etherification reaction, are difficult to separate in crude product to remove
2-methyl-1-butene alkene, 2-methyl-1-butene alkene and methanol reaction generation TAME, the complete methanol of unreacted is then in etherification reaction
Water extraction and recovery is used, reaction temperature is 50~80 DEG C, reaction pressure is 0.4~0.8MPa, the reaction time is 4~10h；
4）By process 3）Product feeding treating column is purified after obtained ether.Operating pressure normal pressure, tower top temperature 28~
31 DEG C, 30~35 DEG C of bottom temperature, reflux ratio 10~30, tower top obtains the 1- amylene products of high-purity, and tower reactor must contain TAME things
Material.
Said process 1）Described tower top temperature is preferably 27~30 DEG C, and bottom temperature is preferably 36~39 DEG C, reflux ratio
Preferably 8~15.
Said process 2）Described tower top temperature is preferably 28~31 DEG C, and bottom temperature is preferably 29~33 DEG C, reflux ratio
Preferably 30~50.
Said process 3）Described etherification reaction temperature is preferably 55~70 DEG C, and reaction pressure is preferably 0.5~0.7MPa,
Reaction time is preferably 6~8h.
Said process 4）Described tower top temperature is preferably 29~30.5 DEG C, and bottom temperature is preferably 29~34 DEG C, backflow
Than being preferably 12~20.
By raffinate carbon-5 separate high-purity 1- amylenes method key problem in technology be effectively by component with 1-
The close 2- methyl isophthalic acid butylene of amylene property is removed from component.Inventor has found through substantial amounts of experimental study, with raffinate carbon-5
Cut is that raw material is separated in the technique for producing 1- amylenes, and 2-methyl-1-butene alkene is extremely approached with 1- amylenes boiling point in cut, is used
Conventional rectificating method is difficult to be isolated, and need to consume substantial amounts of energy, influences the economy of technique.And pass through etherification reaction
2-methyl-1-butene alkene generates TAME with methanol reaction afterwards, and TAME property has larger difference with 1- amylenes, using simple
Rectifying mode can just be separated them.
The essence of the present invention is on the basis of existing technology to pass through 2-methyl-1-butene olefinic impurity in 1- amylene crude products
The method generation TAME of etherificate so that it is than being easier to be separated with 1- amylenes, so as to obtain high-purity 1- amylenes.The present invention's
It is a technical advantage that causing 2-methyl-1-butene alkene to change into TAME by simple etherification reaction, so as to simplify with raffinate carbon
Five be waste high-purity 1- amylene techniques, and existing process takes the method for extracting rectifying to separate and produces 1- amylenes, but the work
Skill is because of the method using extracting rectifying, so as to add solvent recovery unit, adds separation costs, and the present invention is using etherificate
Method so that the 2-methyl-1-butene alkene for being difficult to separate with 1- amylenes changes into TAME, and TAME can be directly entered iso-amylene
Production unit, the unnecessary treatment process without producing.Compared compared with extracting rectifying in technique, due to effectively removes
2-methyl-1-butene alkene in raffinate carbon-5 material, the product purity for obtaining 1- amylenes can reach 98% or so.
The present invention is described in further detail below by way of specific embodiment, the receipts of 1- amylenes product in embodiment
Rate is defined as：
Brief description of the drawings
Accompanying drawing 1 is process flow diagram of the invention
Embodiment
Embodiment【1~10】
Accompanying drawing is shown in the technological process of embodiment 1~10, and raw material raffinate carbon-5 cut W1 is that extracting has separated diolefin and different
The oil oil C5 fraction of amylene, it mainly constitutes and is shown in Table 1.
The process condition of each embodiment rectifying column 1,2 and 4, the process condition of methyltertiarvbutyl ether reactor 3 is shown in Table respectively
2 and 3.Material W7 composition is analyzed respectively using gas chromatography, in conjunction with the flow rate calculation 1- amylene yields of each material, knot
Fruit is shown in Table 4.
Table 1.
| Component | Content（Weight %） |
| Isopentane | 16.58 |
| Isosorbide-5-Nitrae pentadiene | 0.26 |
| 1- amylenes | 9.34 |
| 2-methyl-1-butene alkene | 0.63 |
| Pentane | 55.95 |
| 2- amylenes | 13.01 |
| 2- methyl-2-butenes | 3.95 |
| Surplus | 0.28 |
Table 2
Table 3
Table 4
Claims (5)
1. a kind of method for producing 1- amylenes, this method comprises the following steps：
1) to have extracted the raffinate carbon-5 of diolefin and iso-amylene as raw material, raffinate carbon-5 raw material is recombinated through rectifying separation removal
Point, tower top temperature is 26~32 DEG C, and bottom temperature is 35~40 DEG C, and operating pressure is normal pressure, and reflux ratio is 5~20, and tower top is obtained
It is enriched with 1- amylene cuts, tower reactor discharge heavy constituent；
2) by process 1) the obtained cut of enrichment 1- amylenes of tower top carries out precise distillation to remove light component, and operating pressure is normal
Pressure, 27~31 DEG C of tower top temperature, 28~34 DEG C of bottom temperature, reflux ratio 20~60, tower top obtains C 5 alkane and other light components,
Tower reactor obtains 1- amylene crude products；
3) by process 2) obtain the crude products of 1- amylenes and carry out etherification reaction with methanol, to remove the 2- for being difficult to separate in crude product
Methyl isophthalic acid-butylene, 2-methyl-1-butene alkene and methanol reaction generation TAME, the complete methanol of unreacted then uses water in etherification reaction
Extraction and recovery, reaction temperature is 50~80 DEG C, and reaction pressure is 0.4~0.8MPa, and the reaction time is 4~10h；
4) by process 3) product feeding treating column is purified after obtained ether, operating pressure normal pressure, 28~31 DEG C of tower top temperature,
30~35 DEG C of bottom temperature, reflux ratio 10~30, tower top 1- amylene products, tower reactor must contain TAME materials.
2. the method according to claim 1 for producing 1- amylenes, it is characterised in that tower top temperature described in process 1 for 27~
30 DEG C, bottom temperature is 36~39 DEG C, and reflux ratio is 8~15.
3. the method according to claim 1 for producing 1- amylenes, it is characterised in that tower top temperature described in process 2 for 28~
31 DEG C, bottom temperature is 29~33 DEG C, and reflux ratio is 30~50.
4. the method according to claim 1 for producing 1- amylenes, it is characterised in that the etherification reaction temperature described in process 3 is
55~70 DEG C, reaction pressure is 0.5~0.7MPa, and the reaction time is 6~8h.
5. the method according to claim 1 for producing 1- amylenes, it is characterised in that tower top temperature described in process 4 is 29~
30.5 DEG C, bottom temperature is 29~34 DEG C, and reflux ratio is 12~20.
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| CN106478353B (en) * | 2015-08-26 | 2020-03-13 | 中国石油化工股份有限公司 | Method for separating pentene-1 from carbon five byproduct fraction |
| CN106478356B (en) * | 2015-08-26 | 2020-03-13 | 中国石油化工股份有限公司 | Method for separating pentene-1 and pentene-2 from carbon five byproduct fraction |
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| US4629533A (en) * | 1985-01-31 | 1986-12-16 | Phillips Petroleum Company | Isolation of 3-methyl-1-butene from a hydrocarbon stream |
| CN101289362A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
| CN101289360A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 2-amylene by separating C5 distillate of petroleum |
| CN101289363A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
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2013
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| US4629533A (en) * | 1985-01-31 | 1986-12-16 | Phillips Petroleum Company | Isolation of 3-methyl-1-butene from a hydrocarbon stream |
| CN101289362A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
| CN101289360A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 2-amylene by separating C5 distillate of petroleum |
| CN101289363A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
| CN103304382A (en) * | 2012-03-13 | 2013-09-18 | 上海博润石化科技发展有限公司 | Combined process for comprehensively utilizing partial hydrogenation C5 fraction |
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