CN106588551A - Separation method of 1-hexylene namely ethylene oligomerization product - Google Patents
Separation method of 1-hexylene namely ethylene oligomerization product Download PDFInfo
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Abstract
The invention relates to a separation method of 1-hexylene namely an ethylene oligomerization product. The separation method comprises the following steps: introducing an ethylene oligomerization product (I) into a flash tank to carry out flash evaporation, introducing the liquid discharge (II) from the flash tank into a dehydrogenation tower, introducing the liquid discharge (III) from the dehydrogenation tower into a C6 separation tower to obtain a 1-hexylene product; subjecting the gas discharge (IV) from the flash tank to gas-liquid separation through condensation, introducing obtained gas (V) into a C4 separation tower; subjecting the gas discharge (VI) from the dehydrogenation tower to gas-liquid separation through condensation, introducing obtained gas (VII) into the C4 separation tower; carrying out rectification in the C4 separation tower, and obtaining 1-hexylene isomers from the bottom of the C4 separation tower. The provided method realizes high efficient separation of ethylene oligomerization products; a rectification tower for separating 1-hexylene isomers is not needed, and the mass percentage of obtained 1-hexylene product can reach 99.4%.
Description
Technical field
The present invention relates to ethylene oligomerization field, and in particular to for a kind of 1- hexenes for ethylene oligomerization product
Separation method.More particularly relate to a kind of isomer of 1- hexenes in removal ethylene oligomerization product, mainly side chain
Alpha-olefin, so as to ensure the separation method of 1- hexene product qualities.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry, can inexpensively by oligomerisation reaction
Small-numerator olefin be changed into high value-added product, such as 1- hexenes and 1- octenes.Wherein, 1- hexenes are
The important comonomer of production LLDPE and HDPE, is also the raw material of some fine chemicals.1- hexenes are total to
Poly- LLDPE resins compared with the copolymer of 1-butylene, its tensile strength, impact strength, tear resistance
It is all substantially excellent with property durable in use, it is particularly suitable for the agricultural mulch films such as packaging film and greenhouse, canopy room.But 1- oneself
Alkene has extremely strict requirements to its product purity when in use.
The continuous prodution process that a kind of ethylene oligomerization prepares low-carbon alpha-alkene is reported in CN1160700A.
Using a kind of zirconium quaternary system catalyst, under specific reaction condition, by catalyst solution, ethylene raw material gas
And quencher is continuously added to respectively corresponding course of reaction, oligomerization product draws product through continuous rectification.Simultaneously
Reaction actual conditions is also indicated that, the catalyst is higher to the selectivity of carbon alkene below 10, but its catalysis activity
It is not high.
Ethylene oligomerization production method above all lays particular emphasis on the research of ethylene oligomerization production technology and catalyst, but
It is similar to other patents, what reaction was substantially carried out in ordinary high pressure reactor.CN100339342C is situated between
Continued a kind of method of the separation and purification 1- hexenes from ethylene tripolymer.It is using two rectifying column generations connected
For it is traditional it is three tower cascade connected complete the refined of 1- hexenes in ethylene trimerization technique, a side line is employed on stream
Discharging tower, de- weight and de- light function is focused on and realize on a rectifying column, reduces production cost and device
Investment.
In the production process that ethylene oligomerization produces alpha-olefin, branched alpha-olefin isomer is usually contained,
Isomer is mainly 4-methyl-1-pentene, and into follow-up piece-rate system the product quality of 1- hexenes can be affected.By
Require to reach more than 99.2% (quality percentage) in 1- hexene products run-of-the-mill, it is most both at home and abroad to report all
It is that product is drawn using the separation method of continuous rectification, when the separation of isomer is processed using the refined rectification of increase
The method of tower.Individually increase the refined rectifying column of 1- hexenes be used for 1- hexenes and isomer 4-methyl-1-pentene point
From, although 1- hexene product qualities are can guarantee that, but because the branched alpha-olefin of carbon six more connects with the boiling point of 1- hexenes
Closely, especially the boiling point of 1- hexenes and isomer 4-methyl-1-pentene differs less than 10 DEG C, not only increases and sets
Standby investment, and because rectifying column separates necessary big reflux operation, energy consumption is also inevitable larger.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, of the invention to provide a kind of dividing for 1- hexenes for ethylene oligomerization product
From method, by controlling flash tank and the condenser temperature above lightness-removing column, and using material under different temperatures
Saturated vapor pressure, makes most of 1- hexenes isomer, such as 4-methyl-1-pentene, be introduced into the knockout tower of carbon six it
It is front just with flash tank and lightness-removing column gas phase discharging extraction enter the knockout tower of carbon four, using ethylene, butylene and
1- hexene isomers boiling point difference is larger, carries out further rectification separation, and isomer is discharged into production system, from
And ensure that the content of isomer does not affect the quality of the 1- hexene products that 1- hexene knockout towers isolate.
An embodiment of the invention is to provide a kind of separation side of the 1- hexenes for ethylene oligomerization product
Method, comprises the following steps：
1) ethylene oligomerization product I is passed through into flash tank carries out flash distillation, and the liquid phase discharging II flowed out from flash tank enters
Enter lightness-removing column；
2) the liquid phase discharging III for flowing out from lightness-removing column is passed through in the knockout tower of carbon six, obtains 1- hexene products；
3) the gas phase discharging IV flowed out from flash tank carries out gas-liquid separation by condensation, and gas phase V for obtaining is passed through
The knockout tower of carbon four；
4) the gas phase discharging VI flowed out from lightness-removing column carries out gas-liquid separation by condensation, and gas phase VII for obtaining is led to
In entering the knockout tower of carbon four；
5) by rectification in the knockout tower of carbon four, bottom of towe obtains 1- hexene isomers.
According to the present invention provide method, can directly from isolated purity in the knockout tower of carbon six 99.2% with
On, preferably more than 99.4% 1- hexene products, and the bottom of towe in the knockout tower of carbon four obtains 1- hexene isomers.
In other words, 1- hexenes isomer is separated from the knockout tower of carbon four, so as to without the need for again to obtaining in the knockout tower of carbon six
To material further separated, so as to 1- hexenes be opened with its isomer separation, obtain highly purified 1-
Hexene.The technological process that the present invention is provided, simple, short flow process, energy consumption and material consumption it is low, and reduce equipment throwing
Money, with broad application prospect.
In a preferred embodiment of the present invention, in the step 3) in, the temperature of the condensation is
30-80 DEG C, preferred 30-60 DEG C, more preferably 40-60 DEG C.According to the present invention, by the way that the gas phase of flash tank is gone out
Material IV condensations at said temperatures, the 1- comprising most unreacting ethylene, 1-butylene and a part
Hexene isomer is separated as gas phase V, is passed through the knockout tower of carbon four.In a specific example, institute
State step 3) in condensed liquid phase then can return to flash tank, with liquid phase material in tank into lightness-removing column carrying out
It is further to separate, improve the response rate.In a preferred embodiment, the step 3) in condensation temperature
Degree, preferably 40 DEG C.
In another preferred embodiment of the present invention, in the step 4) in, the temperature of the condensation is
- 5-15 DEG C, preferred 0-10 DEG C.According to the present invention, in the step 4) in, steamed by the tower top by lightness-removing column
Vapour VI is condensed at said temperatures, and a part includes remaining ethylene, butylene and most 1- hexenes isomery
Body is separated as gas phase VII, is passed through the knockout tower of carbon four.In a specific example, in the step
It is rapid 4) in, another part is as liquid-phase reflux to lightness-removing column.
In another preferred embodiment of the present invention, in the step 1) in, the flash tank pressure is
3.2-3.6MPa, flash tank temperature is 100-120 DEG C.Reactant liquor enters flash tank, and flash distillation gaseous phase materials are condensed
After device condensation, gas-liquid separation is carried out, gaseous phase materials enter the knockout tower of carbon four；Liquid phase material returns flash tank, with
Original liquid phase material in flash tank enters lightness-removing column.
In another preferred embodiment of the present invention, the pressure of the lightness-removing column is 0.5-0.8MPa, preferably
For 0.6MPa, column bottom temperature is 218-225 DEG C, and preferably 220.7 DEG C, tower top temperature is 60-70 DEG C, preferably
66.2℃.It is preferred that gas phase VII is passed through in the knockout tower of carbon four after compression.The liquid phase material that flash tank comes is entered
In tower, separate through lightness-removing column, the condensed device condensation of top gaseous phase, a part returns tower as backflow, another
Part goes out tower and enters the knockout tower of carbon four Jing after compressor compression；Lightness-removing column bottom of towe liquid phase material goes out tower into six points of carbon
From tower.
In another preferred embodiment of the present invention, the pressure of the knockout tower of the carbon four is 3.0-3.2MPa,
Column bottom temperature is 190-195 DEG C, and tower top temperature is -10.0 DEG C to -9.0 DEG C.It is described in a specific example
The knockout tower of carbon four is can be with the sieve-plate tower of side take-off.In a specific embodiment, the knockout tower of the carbon four
The number of plates be 45 to 60.Wherein, the flitch number of the side take-off is the 26 to 30th block of plate.Gas phase V
Pass through rectification in the knockout tower of the carbon four with gas phase VII, ethylene flows out from tower top, and 1-butylene goes out as side line
Material flows out from the knockout tower of carbon four, and the bottom of towe in the knockout tower of carbon four obtains the isomer of 1- hexenes.
In another preferred embodiment of the present invention, by by the overhead vapours VI of lightness-removing column in the temperature
The lower condensation of degree, a part is comprising remaining ethylene, butylene and most 1- hexenes isomer as gas phase VII
It is separated, then is compressed under the pressure of 3.2-3.5MPa, the pressure for making gas phase VII reaches four points of carbon
The knockout tower of carbon four is entered after the stress level of tower.
In another preferred embodiment of the present invention, the pressure of the knockout tower of carbon six is 0.1-1.0MPa, bottom of towe
Temperature is 180-210 DEG C, and tower top temperature is 70-100 DEG C.According to the present invention, from the thing that lightness-removing column bottom of towe flows out
Expect to enter the knockout tower of carbon six, after the condensed device condensation of gas phase that carbon six separates column overhead, part conduct is returned
Under flow liquid is returned in tower, and another part is the 1- hexene products for obtaining, and the liquid phase of the knockout tower bottom of towe of carbon six is entered
One separative element, wherein the gas phase temperature that column overhead is separated according to carbon six, the temperature of condensation can be
60-70℃.In a specific example, the purity of the 1- hexenes obtained from the knockout tower of carbon six is 99.4%, from
And can further be separated, it becomes possible to directly use.
In another preferred embodiment of the present invention, the solvent of the ethylene oligomerization product is toluene or diformazan
Benzene.
In a preferred embodiment of the present invention, the ethylene oligomerization product by phenanthroline iron complex,
Triethyl aluminum, the ethylene oligomerization reaction of the catalyst system and catalyzing catalysis of accelerator composition are obtained.
The method that the present invention is provided, by simple technological process, realizes the high efficiency separation of oligomerizing ethylene product,
It is not required to individually increase rectifying column to separate 1- hexene isomers, it is not only simple to operate, it is easy to control, it is whole to separate
Process is more stable, while construction investment can be saved, reduces operating cost and energy consumption.
According to the isolated 1- hexene products of method that the present invention is provided, quality percentage reaches 99.2%, excellent
More than 99.4% is selected, meets product quality requirement, with preferable prospects for commercial application and economic worth.
Description of the drawings
Accompanying drawing 1 shows one of the invention separation process figure preferred embodiment.
Accompanying drawing 2 shows the separation process figure of a comparative example.
Specific embodiment
Following embodiments are only used for that the present invention is described in detail, it will be appreciated that the scope of the present invention is not
It is limited to following embodiments.
Below in conjunction with the accompanying drawings of 1 couple of present invention is preferred embodiment further described.
Ethylene oligomerization product I is passed through into flash tank carries out flash distillation, and the pressure of flash tank is 3.2-3.6MPa, temperature
For 100-120 DEG C.The liquid phase discharging II flowed out from flash tank enters lightness-removing column.
The gas phase discharging IV flowed out from flash tank is (different including unreacted ethylene, butylene, 1- hexenes and 1- hexenes
Structure body etc.) gas-liquid separation is carried out by condensation, condensation temperature is 30-80 DEG C, and gas phase V for obtaining is passed through carbon four
Knockout tower (tower of abbreviation carbon four in figure), the liquid-phase reflux for obtaining is to flash tank.The liquid phase flowed out from flash tank goes out
Material II enters lightness-removing column.
The pressure of lightness-removing column is 0.5-0.8MPa, and column bottom temperature is 218-225 DEG C, and tower top temperature is 60-70 DEG C.
The liquid phase discharging III flowed out from lightness-removing column is passed through in the knockout tower of carbon six (tower of abbreviation carbon six in figure), six points of carbon
It is 0.1-1.0MPa from the pressure of tower, column bottom temperature is 180-210 DEG C, and tower top temperature is 70-100 DEG C.From carbon
Six separation column overheads steam gas phase discharging it is condensed after isolate qualified 1- hexene product (1- hexene mass hundred
Point rate separates the gas phase that column overhead is steamed more than 99.2%) according to carbon six, the temperature of condensation can at 60-70 DEG C,
Its liquid phase discharging enters next separative element from bottom of towe.
Steam from lightness-removing column tower top gaseous phase materials VI (including remaining ethylene and 1-butylene, a part of 1- oneself
Alkene and most 1- hexenes isomer) condensed by condenser, condensation temperature is -5-15 DEG C, condensed liquid
Lightness-removing column is back to as backflow, gas phase VII obtained after condensation is entered after compressor compresses, is passed through carbon
In four knockout towers, for example, it is compressed to after 3.2-3.5MPa, is passed through the knockout tower of carbon four.
The pressure of the knockout tower of carbon four for example can be 3.0-3.2MPa, and column bottom temperature for example can be 190-195 DEG C, tower
Top temperature can be for example -10.0 to -9.0 DEG C, and its number of plates for example can be between 45-60.From the knockout tower tower of carbon four
Top separates ethylene, and side take-off 1-butylene (such as can be in 26-30 block plates), bottom of towe produces 1- hexene isomers,
Predominantly 4-methyl-1-pentene.
Embodiment 1
By ethylene oligomerization product 32254.708kg/h (wherein containing ethylene 6450.603kg/h, butylene 1137.455
Kg/h, 1- hexene 1078.694kg/h, 1- hexene isomer 27.654kg/h, it is higher than 1- hexenes that remaining is boiling point
Solvent and other product) be passed through flash tank and carry out flash distillation, the pressure of flash tank is 3.5MPa, and temperature is
110 DEG C, the liquid phase discharging flowed out from flash tank enters lightness-removing column.
From flash tank flow out gas phase discharging (wherein containing ethylene 4528.301kg/h, butylene 377.785kg/h,
1- hexene 102.231kg/h, 1- hexene isomer 3.721kg/h, octene 4.242kg/h) by condensing into circulation of qi promoting
Liquid is separated, and condensation temperature is 40 DEG C, and the gas phase for obtaining is 4862.715kg/h (wherein containing ethylene 4502.524
Kg/h, butylene 312.396kg/h, 1- hexene 45.824kg/h, 1- hexene isomer 1.971kg/h) it is passed through carbon
Four towers, the liquid-phase reflux for obtaining is to flash tank.The liquid phase discharging flowed out from flash tank enters lightness-removing column, altogether
27391.993kg/h (wherein containing ethylene 1948.079kg/h, butylene 825.059kg/h, 1- hexenes 1032.870
Kg/h, 1- hexene isomer 25.683kg/h, remaining is solvent and other product of the boiling point higher than 1- hexenes,
Such as octene).
The pressure 0.6MPa of lightness-removing column, column bottom temperature is 220.7 DEG C, and tower top temperature is 66.2 DEG C.From lightness-removing column
Middle outflow liquid phase discharging 24580.141kg/h (1- hexene 1014.191kg/h, 1- hexene isomer 5.648kg/h,
Remaining is solvent and other product of the boiling point higher than 1- hexenes) enter the knockout tower of carbon six from lightness-removing column bottom of towe.Carbon
The pressure of six knockout towers is 0.15MPa, and column bottom temperature is 190 DEG C, and tower top temperature is 73.8 DEG C.From six points of carbon
From the condensed rear separation of gas phase discharging that column overhead is steamed, condensation temperature is 67 DEG C, obtains mass content and is more than
99.4% 1- hexene product 1019.829kg/h (1- hexene 1014.188kg/h, 1- hexenes isomer 5.641
kg/h)。
The gaseous phase materials steamed from lightness-removing column tower top are condensed by condenser, and condensation temperature is 3.5 DEG C, after condensation
Liquid phase be back to lightness-removing column as backflow, the discharging of the gas phase that obtains after condensation for 2811.852kg/h (wherein
Containing ethylene 1948.079kg/h, butylene 825.059kg/h, 1- hexene 18.679kg/h, 1- hexene isomers
20.035kg/h), Jing compressors are pressurized to 3.5MPa, in being passed through the knockout tower of carbon four.
The pressure of the knockout tower of carbon four is 3.2MPa, and column bottom temperature is 192 DEG C, and tower top temperature is -9.1 DEG C, column plate
Number is 60, and side line is produced from the 30th block of plate.The ethylene of tower top discharges as 6450.585kg/h, the butylene of side line
Discharge as 1137.445kg/h, bottom of towe discharging contains 1- hexene 64.493kg/h, 1- hexene isomer 21.9kg/h.
Embodiment 2
By ethylene oligomerization product 32254.708kg/h (wherein containing ethylene 6450.603kg/h, butylene 1137.455
Kg/h, 1- hexene 1078.694kg/h, 1- hexene isomer 27.654kg/h, it is higher than 1- hexenes that remaining is boiling point
Solvent and other product) be passed through flash tank and carry out flash distillation, the pressure of flash tank is 3.5MPa, and temperature is
120 DEG C, the liquid phase discharging flowed out from flash tank enters lightness-removing column.
From flash tank flow out gas phase discharging (wherein containing ethylene 4538.301kg/h, butylene 379.785kg/h,
1- hexene 104.231kg/h, 1- hexene isomer 4.721kg/h, octene 4.942kg/h) by condensing into circulation of qi promoting
Liquid is separated, and condensation temperature is 50 DEG C, and the gas phase for obtaining is 4878.687kg/h (wherein containing ethylene 4510.751
Kg/h, butylene 318.275kg/h, 1- hexene 47.679kg/h, 1- hexene isomer 1.982kg/h) it is passed through carbon
Four towers, the liquid-phase reflux for obtaining is to flash tank.The liquid phase discharging flowed out from flash tank enters lightness-removing column, altogether
27376.021kg/h (wherein containing ethylene 1939.852kg/h, butylene 819.180kg/h, 1- hexenes 1031.015
Kg/h, 1- hexene isomer 25.672kg/h, remaining is solvent and other product of the boiling point higher than 1- hexenes).
The pressure 0.6MPa of lightness-removing column, column bottom temperature is 220.7 DEG C, and tower top temperature is 66.2 DEG C.From lightness-removing column
Middle outflow liquid phase discharging 24577.854kg/h (1- hexene 1011.872kg/h, 1- hexene isomer 5.680kg/h,
Remaining is solvent and other product of the boiling point higher than 1- hexenes) enter the knockout tower of carbon six from lightness-removing column bottom of towe.Carbon
The pressure of six knockout towers is 0.15MPa, and column bottom temperature is 190 DEG C, and tower top temperature is 73.8 DEG C.From six points of carbon
From the condensed rear separation of gas phase discharging that column overhead is steamed, condensation temperature is 67 DEG C, obtains mass content and is more than
99.4% 1- hexene product 1017.541kg/h (1- hexene 1011.869kg/h, 1- hexenes isomer 5.672
kg/h)。
The gaseous phase materials steamed from lightness-removing column tower top are condensed by condenser, and condensation temperature is 0 DEG C, condensed
Liquid phase returns tower top as backflow, and the gas phase discharging obtained after condensation (wherein contains ethylene for 2798.167kg/h
1939.852kg/h, butylene 819.180kg/h, 1- hexene 19.143kg/h, 1- hexene isomer 19.992kg/h),
Again Jing compressors are pressurized to 3.5MPa, in being passed through the knockout tower of carbon four.
The pressure of the knockout tower of carbon four is 3.2MPa, and column bottom temperature is 192 DEG C, and tower top temperature is -9.1 DEG C.Tower top
Ethylene discharging be 6450.6kg/h, side line butylene discharging be 1137.451kg/h.Tower top discharging contains 1-
Hexene 66.82kg/h, 1- hexene isomer 21.971kg/h.
Embodiment 3
By ethylene oligomerization product 32254.708kg/h (wherein containing ethylene 6450.603kg/h, butylene 1137.455
Kg/h, 1- hexene 1078.694kg/h, 1- hexene isomer 27.654kg/h, it is higher than 1- hexenes that remaining is boiling point
Solvent and other product) be passed through flash tank and carry out flash distillation, the pressure of flash tank is 3.5MPa, and temperature is
100 DEG C, the liquid phase discharging flowed out from flash tank enters lightness-removing column.
From flash tank flow out gas phase discharging (wherein containing ethylene 4526.301kg/h, butylene 374.785kg/h,
1- hexene 102.031kg/h, 1- hexene isomer 3.421kg/h, octene 4.2kg/h) gas-liquid is carried out by condensation
Separate, condensation temperature be 60 DEG C, the gas phase for obtaining be 4894.784kg/h (wherein containing ethylene 4519.439kg/h,
Butylene 323.439kg/h, 1- hexene 49.915kg/h, 1- hexene isomer 1.991kg/h) tower of carbon four is passed through,
The liquid-phase reflux for obtaining is to flash tank.The liquid phase discharging flowed out from flash tank enters lightness-removing column, and totally 27359.924
Kg/h (wherein containing ethylene 1931.164kg/h, butylene 814.016kg/h, 1- hexene 1028.779kg/h, 1-
Hexene isomer 25.663kg/h, remaining is solvent and other product of the boiling point higher than 1- hexenes).
The pressure 0.6MPa of lightness-removing column, column bottom temperature is 220.7 DEG C, and tower top temperature is 66.2 DEG C.From lightness-removing column
Middle outflow liquid phase discharging 24574.926kg/h (1- hexene 1009.021kg/h, 1- hexene isomer 5.603kg/h,
Remaining is solvent and other product of the boiling point higher than 1- hexenes) enter the knockout tower of carbon six from lightness-removing column bottom of towe.Carbon
The pressure of six knockout towers is 0.15MPa, and column bottom temperature is 190 DEG C, and tower top temperature is 73.8 DEG C.From six points of carbon
From the condensed rear separation of gas phase discharging that column overhead is steamed, condensation temperature is 67 DEG C, obtains mass content and is more than
99.4% 1- hexene product 1014.611kg/h (1- hexene 1009.018kg/h, 1- hexenes isomer 5.593
kg/h)。
The gaseous phase materials steamed from lightness-removing column tower top are condensed by condenser, and condensation temperature is 10 DEG C, condensed
Liquid phase returns tower top as backflow, and the gas phase discharging obtained after condensation (wherein contains ethylene for 2784.998kg/h
1931.164kg/h, butylene 814.016kg/h, 1- hexene 19.758kg/h, 1- hexene isomer 20.06kg/h),
Again Jing compressors are pressurized to 3.5MPa, in being passed through the knockout tower of carbon four.
The pressure of the knockout tower of carbon four is 3.2MPa, and column bottom temperature is 192 DEG C, and tower top temperature is -9.1 DEG C.Tower top
Ethylene discharging be 6449.588kg/h, side line butylene discharging be 1137.449kg/h, tower top discharging contain 1-
Hexene 69.67kg/h, 1- hexene isomer 22.029kg/h.
Comparative example 1
According to the separation process separating ethene oligomerization product of accompanying drawing 2.By ethylene oligomerization product 32254.708kg/h
(wherein containing ethylene 6450.603kg/h, butylene 1137.455kg/h, 1- hexene 1078.694kg/h, 1- oneself
Alkene isomer 27.654kg/h, remaining is solvent and other product of the boiling point higher than 1- hexenes) it is passed through flash distillation
Tank carries out flash distillation, and the pressure of flash tank is 3.5MPa, and temperature is 110 DEG C.
From flash tank flow out gas phase discharging (wherein containing ethylene 4528.302kg/h, butylene 377.788kg/h,
1- hexene 102.23kg/h, 1- hexene isomer 3.719kg/h) gas-liquid separation, condensation temperature are carried out by condensation
For -5 DEG C, the gas phase for obtaining be 4521.226kg/h (wherein containing ethylene 4238.611kg/h, butylene 281.168
Kg/h, 1- hexene 1.345kg/h, 1- hexene isomer 0.102kg/h) tower of carbon four is passed through, the liquid phase for obtaining is returned
It flow to flash tank.The liquid phase discharging flowed out from flash tank enters lightness-removing column, and common 27733.482kg/h (wherein contains
There are ethylene 2211.992kg/h, butylene 856.287kg/h, 1- hexene 1077.349kg/h, 1- hexene isomers
27.552kg/h, remaining is solvent and other product of the boiling point higher than 1- hexenes).
The pressure 0.6MPa of lightness-removing column, column bottom temperature is 205 DEG C, and tower top temperature is 35 DEG C.Flow from lightness-removing column
Go out liquid phase discharging 24665.203kg/h (1- hexene 1077.349kg/h, 1- hexene isomer 27.552kg/h,
Remaining is solvent and other product of the boiling point higher than 1- hexenes) enter the knockout tower of carbon six from lightness-removing column bottom of towe.Carbon
The pressure of six knockout towers is 0.15MPa, and column bottom temperature is 190 DEG C, and tower top temperature is 73.8 DEG C.From six points of carbon
1- hexene material 1104.895kg/h (the 1- hexenes 1077.347 of mass content 97.5% are isolated from column overhead
Kg/h, 1- hexene isomer 27.548kg/h) isolate 1- of the mass content more than 99.2% into the treating column of carbon six
Hexene product.76 pieces of the six treating column number of plates of carbon, reboiler 836345.731KJ/hr, reflux ratio 133.
The gaseous phase materials steamed from lightness-removing column tower top are condensed by condenser, and condensation temperature is -20 DEG C, and liquid phase is made
Tower top is returned for backflow, the gas phase discharging obtained after condensation is 3068.279kg/h (wherein containing ethylene 2211.992
Kg/h, butylene 856.287kg/h), then Jing after compressor is pressurized to 3.5MPa, in the knockout tower of carbon four.
Can be drawn by the contrast of embodiment 1-3 and comparative example 1, compared with comparative example 1, according to the application
The method of offer not only eliminates processing step, also shortens technological process, has saved equipment investment and corresponding
Energy consumption, under the premise of separated ethylene oligomerization product component proportioning identical, the 1- hexenes of embodiment 1-3 are produced
Quality percentage ratio is more than product obtained in comparative example 1.It is simple and easy to operate according to the method that the application is provided,
Technological process is short, reduces production cost.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to this
Bright any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that its
In word used be descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation at this
The present invention is modified in the range of invention claim, and without departing substantially from the scope of the present invention and essence
The present invention is revised in god.Although the present invention described in it is related to specific method, material and reality
Example is applied, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, the present invention is expansible
To other all methods and applications with identical function.
Claims (10)
1. a kind of separation method of the 1- hexenes for ethylene oligomerization product, comprises the following steps：
1) ethylene oligomerization product I is passed through into flash tank carries out flash distillation, and the liquid phase discharging II flowed out from flash tank enters
Enter lightness-removing column；
2) the liquid phase discharging III for flowing out from lightness-removing column is passed through in the knockout tower of carbon six, obtains 1- hexene products；
3) the gas phase discharging IV flowed out from flash tank carries out gas-liquid separation by condensation, and gas phase V for obtaining is passed through
The knockout tower of carbon four；
4) the gas phase discharging VI flowed out from lightness-removing column carries out gas-liquid separation by condensation, and gas phase VII for obtaining is led to
In entering the knockout tower of carbon four；
5) by rectification in the knockout tower of carbon four, bottom of towe obtains 1- hexene isomers.
2. separation method according to claim 1, it is characterised in that in the step 3) in, it is described
The temperature of condensation is 30-80 DEG C, preferred 30-60 DEG C, more preferably 40-60 DEG C.
3. separation method according to claim 1 and 2, it is characterised in that in the step 4) in,
The temperature of the condensation is -5-15 DEG C, preferred 0-10 DEG C.
4. the separation method according to any one of claim 1-3, it is characterised in that in the step 1)
In, the flash tank pressure is 3.2-3.6MPa, and flash tank temperature is 100-120 DEG C.
5. the separation method according to any one of claim 1-4, it is characterised in that the lightness-removing column
Pressure is 0.5-0.8MPa, and preferred gas phase VII is passed through in the knockout tower of carbon four after compression.
6. the separation method according to any one of claim 1-5, it is characterised in that in the step 3)
In, the liquid phase obtained after gas-liquid separation is back to flash tank；And/or, in the step 4) in, gas-liquid separation
Liquid phase afterwards is back to lightness-removing column.
7. the separation method according to any one of claim 1-6, it is characterised in that the carbon four is separated
The pressure of tower is 3.0-3.2MPa, and column bottom temperature is 190-195 DEG C, and tower top temperature is -10.0 DEG C to -9.0 DEG C.
8. the separation method according to any one of claim 1-7, it is characterised in that the carbon four is separated
Tower is the sieve-plate tower of side take-off, and its number of plates is between 45 to 60.
9. separation method according to claim 8, it is characterised in that the side line of the knockout tower of the carbon four goes out
Flitch is 26-30 block plates, and lateral line discharging is 1-butylene.
10. the separation method according to any one of claim 1-9, it is characterised in that the knockout tower of carbon four
Tower top discharging be ethylene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107151195A (en) * | 2016-03-02 | 2017-09-12 | 中国石油化工股份有限公司 | The method that catalyst and polyethylene are removed in ethylene oligomerization production alpha-olefin technique |
| CN115108878A (en) * | 2022-06-24 | 2022-09-27 | 中国五环工程有限公司 | Separation method for ethylene oligomerization product and catalyst |
| CN115106037A (en) * | 2022-08-04 | 2022-09-27 | 山东京博石油化工有限公司 | Device and process for producing alpha-olefin by continuous ethylene selective oligomerization |
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| CN1160700A (en) * | 1996-03-21 | 1997-10-01 | 抚顺石油化工公司研究院 | Continuous ethylene oligomerization process preparing straight-chain low-carbon alpha-alkene |
| CN1609083A (en) * | 2003-10-17 | 2005-04-27 | 中国石油化工股份有限公司北京燕山分公司研究院 | Method of separating refined 1-hexene from ethylene tripolymer |
| CN101734991A (en) * | 2008-11-07 | 2010-06-16 | 中国石油化工股份有限公司 | Method for improving content of 1-hexene in hexene materials |
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| CN1609083A (en) * | 2003-10-17 | 2005-04-27 | 中国石油化工股份有限公司北京燕山分公司研究院 | Method of separating refined 1-hexene from ethylene tripolymer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107151195A (en) * | 2016-03-02 | 2017-09-12 | 中国石油化工股份有限公司 | The method that catalyst and polyethylene are removed in ethylene oligomerization production alpha-olefin technique |
| CN115108878A (en) * | 2022-06-24 | 2022-09-27 | 中国五环工程有限公司 | Separation method for ethylene oligomerization product and catalyst |
| CN115108878B (en) * | 2022-06-24 | 2023-12-01 | 中国五环工程有限公司 | Separation method for ethylene oligomerization products and catalysts |
| CN115106037A (en) * | 2022-08-04 | 2022-09-27 | 山东京博石油化工有限公司 | Device and process for producing alpha-olefin by continuous ethylene selective oligomerization |
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