CN110013876A - A method of continuously preparing ethylene oligomer - Google Patents
A method of continuously preparing ethylene oligomer Download PDFInfo
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- CN110013876A CN110013876A CN201810016256.XA CN201810016256A CN110013876A CN 110013876 A CN110013876 A CN 110013876A CN 201810016256 A CN201810016256 A CN 201810016256A CN 110013876 A CN110013876 A CN 110013876A
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The invention discloses a kind of methods for continuously preparing ethylene oligomer, and being sent into the 2nd stage reactor including reaction mass is added continuously to the 1st grade of n grades of tandem reactors, after fully reacting, the reaction was continued, until being delivered to the n-th stage reactor；Wherein, n is more than or equal to 2；Gaseous mixture containing ethylene is added to above-mentioned n-th stage reactor, undissolved gas is overflowed from the top of the n-th stage reactor, n-th grade is back to through condensed liquid condensate, gas component enters (n-1)th grade, repetitive operation is until liquid condensate is back to the 1st grade, gas component enters exhaust system, and ethylene oligomer is prepared.The method is using the inexpensive gaseous mixture containing ethylene, and such as the oil refinery dry gas after being enriched with, using iron series major catalyst, with catalytic activity, high, oligomer is distributed wide feature more than product species.The method has the advantages that low cost, high yield, and existing oil refinery dry gas can be carried out to comprehensive promoted and utilized, biggish economic benefit is generated.
Description
Technical field
The invention belongs to polyethylene preparation technical fields, and in particular to a method of continuously prepare ethylene oligomer.
Background technique
C6Above alpha-olefin raw material important as one kind of petrochemical industry, purposes is very extensive, wherein C6~
C10Alpha-olefin be mainly used as the comonomer of linear low density polyethylene (LLDPE), dosage is maximum, and appreciation potential is maximum, is
The product that the country is most badly in need of at present.C12~C20Alpha-olefin be make surfactant and plasticizer excellent intermediate.C22~
C24Alpha-olefin again be make top-grade lubricating oil raw material etc..C30+ alpha-olefin, can be used as the raw material of specialist additive.
The method that the large-scale production of high alpha-olefin generally uses ethylene oligomerization, such as world-renowned SHOP method, pass through
Transition-metal catalyst (claiming SHOP catalyst) catalysis ethylene oligomerization, prepares C4~C30Or more alpha-olefin mixture, then
The alpha-olefin of each fraction is obtained by rectifying.1998, there is document report pyridine diimine Fe catalyst ethylene neat
Cumulative produces C4~C44Between alpha-olefin, catalytic activity ratio SHOP catalyst it is higher, also more to the selectivity of alpha-olefin
It is high.Then, Chinese Academy of Sciences's chemistry institute and China Petroleum cooperation, have researched and developed Fe catalyst for oligomerization (ZL01109134.7), have had
There is high activity and to the highly selective of alpha-olefin.Currently, in all ethylene oligomerization methods, it is all former using high-purity polymer grade ethylene
Material, this cost of material is high, is unfavorable for the popularization and industrialization of method.
Summary of the invention
In order to improve the deficiencies in the prior art, the object of the present invention is to provide a kind of sides for continuously preparing ethylene oligomer
Method, the method are used as gas raw material using the gaseous mixture (such as the oil refinery dry gas after being enriched with) containing ethylene of low cost, greatly drop
Low cost of material；In addition, the method uses Fe series catalysts, have catalytic activity high, oligomer is distributed width, product species
More features.
The purpose of the present invention is what is be achieved through the following technical solutions:
A method of ethylene oligomer continuously being prepared, described method includes following steps:
(1) iron series major catalyst shown in organic solvent, co-catalyst and formula 1 is added continuously to n grades of tandem reactions
The 1st grade of device, reaction mass form solution system in reactor, and reaction mass stop is delivered to n grades of series connection after a certain period of time
The 2nd grade of formula reactor；It repeats the above steps, until reaction mass is delivered to n-th grade of n grades of tandem reactors；Wherein,
N is more than or equal to 2；
In formula 1, R1-R9It is identical or different, it is independently from each other H, C1-C4Alkyl, C1-C4Alkoxy, replace or
Unsubstituted phenyl；The substituent group is C1-C4Alkyl, halogen, the C containing halogen1-C4Alkyl；Of the substituent group
Number is 1-3；
R10-R11It is identical or different, it is independently from each other C1-C4Alkyl, substituted or unsubstituted phenyl；The substitution
Base is C1-C4Alkyl, halogen, the C containing halogen1-C4Alkyl；The number of the substituent group is 1-3；
R ' and R " is identical or different, is independently from each other methyl, ethyl or n-propyl；
(2) gaseous mixture containing ethylene is added to n-th grade of above-mentioned n grades of tandem reactor, gas passes through distribution grid
Dissolution enters solution system, and undissolved gas is overflowed from the top of n-th grade of tandem reactor, into condenser, through condensing
Liquid condensate afterwards is back to n-th grade of n grades of tandem reactors, and it is anti-to enter n grades of tandems through condensed gas component
(n-1)th grade for answering device；It repeats the above steps, until being back to the 1st of n grades of tandem reactors through condensed liquid condensate
Grade, enters exhaust system through condensed gas component, ethylene oligomer is prepared.
According to the present invention, the method also includes following steps:
(3) reaction mass being prepared in n-th grade of the n grade tandem reactor of step (2) is sent into intermediate storage tank,
Carry out condensation process twice；
(4) reaction mass after condensation process twice in the intermediate storage tank of step (3) is sent into centrifugal separation system,
Solid-Liquid Separation is carried out, ethylene oligomer is prepared.
According to the present invention, the step (1) specifically:
(1) iron series major catalyst shown in organic solvent, co-catalyst and formula 1 is added continuously to n grades of tandem reactions
The 1st grade of device, reaction mass form solution system in reactor, and reaction mass stops after a certain period of time, will by delivery pump
Material is delivered to the 2nd grade of n grades of tandem reactors；It repeats the above steps, until material is delivered to n grades of strings by delivery pump
N-th grade of connection formula reactor；Wherein, n 3-6.
According to the present invention, the condensation process twice of the step (3) specifically: first time condensation process, condensation temperature
Control is being higher than 0 DEG C, and condensed liquid condensate is back to intermediate storage tank, and uncondensable gas carries out at second of condensation
Reason, condensation temperature control at 0 DEG C hereinafter, by obtained liquid condensate condensed again separate and recover, other are not cold
Solidifying gas enters exhaust system.
According to the present invention, the step (3) and step (4) specifically:
(3) reaction mass being prepared in n-th grade of the n grade tandem reactor of step (2) is sent by pressure difference
Intermediate storage tank carries out first time condensation process, and condensation temperature control is being greater than 0 DEG C to less than is being equal between 40 DEG C, for the first time
Condensed liquid condensate is back to intermediate storage tank, and incondensable gas carries out second of condensation process, condensation temperature control
At 0 DEG C hereinafter, second condensed liquid condensate (mainly including butylene etc.) separates and recovers, by other incondensable gases into
Enter exhaust system；
(4) reaction mass after condensation process twice in the intermediate storage tank of step (3) is pumped into centrifugation through conveying
Separation system carries out Solid-Liquid Separation, wherein solid powder is transferred to drying device, is granulated after dry, liquid phase enters knockout tower
It is fractionated.
Preferably, in formula 1, R1-R6And R8It is identical or different, it is independently from each other H, C1-C4Alkyl, C1-C4Alkane
Oxygroup, substituted or unsubstituted phenyl；The substituent group is C1-C4Alkyl, halogen, the C containing halogen1-C4Alkyl；Institute
The number for stating substituent group is 1-3；R7And R9Selected from H；R10-R11Selected from methyl；R ' and R " is identical or different, is independently from each other
Methyl, ethyl or n-propyl.
According to the present invention, compound shown in formula 1 is selected from as shown in following formula 1a, formula 1b and formula 1c:
According to the present invention, ethylene contents are greater than 20vol.% in the gaseous mixture, it is preferable that ethylene contains in the gaseous mixture
Amount is within the scope of 50-99.5vol.%；Contain the impurity for hindering polymerization, such as CO, acetylene, alcohol, mercaptan etc. in the gaseous mixture
Content at ppm to ppb grades, meet the Active pharmaceutical of catalyst.
According to the present invention, the gross pressure of the gaseous mixture containing ethylene is within the scope of 0.1-10MPa.
According to the present invention, the gaseous mixture is the mixing that the ethylene contents that oil refinery dry gas is enriched with are 60vol.% or more
Gas.
According to the present invention, the conversion ratio of ethylene is greater than 90% in the gaseous mixture.
According to the present invention, the temperature of the polymerization reaction is 60-100 DEG C.
According to the present invention, the residence time of the reaction mass every stage reactor in n grades of tandem reactors is 20 points
Clock -200 minutes.
According to the present invention, the co-catalyst is selected from methylaluminoxane.
According to the present invention, the molar ratio of the co-catalyst and iron series major catalyst shown in formula 1 is 2000:1-50:1.
According to the present invention, it is organic to be selected from alkanes organic solvent, olefines organic solvent or aromatic hydrocarbons for the organic solvent
At least one of solvent, such as at least one in n-hexane, hexamethylene, petroleum ether, toluene, dimethylbenzene or hexene -1
Kind.
According to the present invention, the organic solvent is also selected from the liquid ethylene oligomerisation alkene that above-mentioned polymerization reaction is prepared
Hydrocarbon mixture.
According to the present invention, the fusing point for the ethylene oligomer being prepared is between 40-125 DEG C.
According to the present invention, the carbon number distribution for the ethylene oligomer being prepared is concentrated mainly on C4-C300Between, wherein C4-
C24Shared mass ratio is between 50-70wt%.
Beneficial effects of the present invention:
The present invention provides a kind of method for continuously preparing ethylene oligomer, the method is using low cost containing ethylene
Gaseous mixture greatly reduces cost of material if the oil refinery dry gas after being enriched with is as gas raw material；In addition, the method uses iron
Owner's catalyst has catalytic activity high, and oligomer is distributed wide feature more than product species.In short, the method have it is low at
Originally, the advantages of high yield, existing oil refinery dry gas can be carried out to comprehensive promoted and utilized, biggish economic benefit is generated.
Detailed description of the invention
Fig. 1 is process flow chart described in a preferred embodiment of the invention.
In attached drawing, R201-R203 represents series connection autoclave stirred reactor, and E201-E203 represents condenser, C301 represent from
Scheming, D301 represent intermediate storage tank, and D302 represents liquefied mixture storage tank, and DR301 represents drier.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1
As shown in Figure 1, as follows using the technique of thtee-stage shiplock reactor continuous production ethylene oligomer:
(1) by hexamethylene (250L/min), co-catalyst methylaluminoxane (10% toluene solution, 1L/min) and such as formula 1a
Shown in the toluene solution (1mmol/L, 1L/min) of iron series major catalyst be added continuously to 10m according to flow3The R201 of volume
In；
(2) by the gaseous mixture (other components are mainly 13wt% ethane and 2wt% propane) containing 85wt% ethylene, pressure
For 4MPa, flow 2350Kg/h, it is continuously added to R203 reactor, gas enters solution system by distribution grid dissolution, from
R203 reactor top is overflowed, and into condenser E203, liquid condensate passes back into R203 reactor, is come out in condenser E203
Gas enters R202 reactor, and gas enters solution system by distribution grid dissolution, overflows from R202 reactor top, into condensation
Device E202, liquid condensate pass back into R202 reactor, and the gas come out in condenser E202 enters R201 reactor, gas warp
It crosses distribution grid to dissolve into solution system, be overflowed from R201 reactor top, into condenser E201, liquid condensate is passed back into
R201 reactor, the gas come out in condenser E201 enter exhaust system；Ethylene cyclisation in the gas that condenser E201 comes out
Rate reaches 95%.The temperature of R201 to R203 controls between 60-90 DEG C, and residence time of the logistics in each reactor be
20min。
(3) reaction mass enters intermediate storage tank D301 from R203 reactor, carries out first time condensation process, condensation temperature
Control is greater than 0 DEG C to less than equal to 40 DEG C, and condensed liquid condensate is back to intermediate storage tank, incondensable gas for the first time
Second of condensation process is carried out, condensation temperature control is at 0 DEG C hereinafter, second of condensed liquid condensate butylene separates back
It receives, other incondensable gases enter exhaust system；
(4) intermediate storage tank D301 material enters centrifugal separation system C301 through delivery pump, by solid liquid phase in mixed material into
Row separation, solid powder are transferred to drying device DR301, are granulated after dry, and liquid phase enters storage tank D302, are transported to point from D302
It is fractionated from tower.
It is as follows that ethylene oligomer analyzes result: C4-C24Account for oligomer total amount 70.5wt%, C24+Account for oligomer total amount
29.5wt%, the melting range for the ethylene oligomer being prepared is between 40-123 DEG C.
Embodiment 2
As shown in Figure 1, as follows using the technique of thtee-stage shiplock reactor continuous production ethylene oligomer:
(1) C that will be prepared in embodiment 14-C24Mixed liquor (250L/min), co-catalyst methylaluminoxane (10%
Toluene solution, 1L/min) and the iron series major catalyst as shown in formula 1b toluene solution (1mmol/L, 1L/min) according to flow
It is added continuously to 10m3In the R201 of volume；
(2) by the gaseous mixture (other components are mainly 13wt% ethane and 2wt% propane) containing 70wt% ethylene, pressure
For 4MPa, flow 2850Kg/h, it is continuously added to R203 reactor, gas enters solution system by distribution grid dissolution, from
R203 reactor top is overflowed, and into condenser E203, liquid condensate passes back into R203 reactor, is come out in condenser E203
Gas enters R202 reactor, and gas enters solution system by distribution grid dissolution, overflows from R202 reactor top, into condensation
Device E202, liquid condensate pass back into R202 reactor, and the gas come out in condenser E202 enters R201 reactor, gas warp
It crosses distribution grid to dissolve into solution system, be overflowed from R201 reactor top, into condenser E201, liquid condensate is passed back into
R201 reactor, the gas come out in condenser E201 enter exhaust system；Ethylene cyclisation in the gas that condenser E201 comes out
Rate reaches 97%.The temperature of R201 to R203 controls between 60-90 DEG C, and residence time of the logistics in each reactor be
20min。
(3) reaction mass enters intermediate storage tank D301 from R203 reactor, carries out first time condensation process, condensation temperature
Control is greater than 0 DEG C to less than equal to 40 DEG C, and condensed liquid condensate is back to intermediate storage tank, incondensable gas for the first time
Second of condensation process is carried out, condensation temperature control is at 0 DEG C hereinafter, second of condensed liquid condensate butylene separates back
It receives, other incondensable gases enter exhaust system；
(4) intermediate storage tank D301 material enters centrifugal separation system C301 through delivery pump, by solid liquid phase in mixed material into
Row separation, solid powder are transferred to drying device DR301, are granulated after dry, and liquid phase enters storage tank D302, are transported to point from D302
It is fractionated from tower.
It is as follows that ethylene oligomer analyzes result: C4-C24Account for oligomer total amount 62wt%, C24+Oligomer total amount 38wt% is accounted for,
The melting range for the ethylene oligomer being prepared is at 40-123 DEG C.
Embodiment 3
As shown in Figure 1, as follows using the technique of thtee-stage shiplock reactor continuous production ethylene oligomer:
(1) C that will be prepared in embodiment 14-C24Mixed liquor (250L/min), co-catalyst methylaluminoxane (10% toluene
Solution, 1L/min) and the toluene solution (1mmol/L, 1L/min) of the iron series major catalyst as shown in formula 1c it is continuous according to flow
It is added to 10m3In the R201 of volume；
(2) by the gaseous mixture (other components are mainly 13wt% ethane and 2wt% propane) containing 60wt% ethylene, pressure
For 4MPa, flow 3150Kg/h, it is continuously added to R203 reactor, gas enters solution system by distribution grid dissolution, from
R203 reactor top is overflowed, and into condenser E203, liquid condensate passes back into R203 reactor, is come out in condenser E203
Gas enters R202 reactor, and gas enters solution system by distribution grid dissolution, overflows from R202 reactor top, into condensation
Device E202, liquid condensate pass back into R202 reactor, and the gas come out in condenser E202 enters R201 reactor, gas warp
It crosses distribution grid to dissolve into solution system, be overflowed from R201 reactor top, into condenser E201, liquid condensate is passed back into
R201 reactor, the gas come out in condenser E201 enter exhaust system；Ethylene cyclisation in the gas that condenser E201 comes out
Rate reaches 98%.The temperature of R201 to R203 controls between 60-90 DEG C, and residence time of the logistics in each reactor be
20min。
(3) reaction mass enters intermediate storage tank D301 from R203 reactor, carries out first time condensation process, condensation temperature
Control is greater than 0 DEG C to less than equal to 40 DEG C, and condensed liquid condensate is back to intermediate storage tank, incondensable gas for the first time
Second of condensation process is carried out, condensation temperature control is at 0 DEG C hereinafter, second of condensed liquid condensate butylene separates back
It receives, other incondensable gases enter exhaust system；
(4) intermediate storage tank D301 material enters centrifugal separation system C301 through delivery pump, by solid liquid phase in mixed material into
Row separation, solid powder are transferred to drying device DR301, are granulated after dry, and liquid phase enters storage tank D302, are transported to point from D302
It is fractionated from tower.
It is as follows that ethylene oligomer analyzes result: C4-C24Account for oligomer total amount 53wt%, C24+Oligomer total amount 47wt% is accounted for,
The melting range for the ethylene oligomer being prepared is at 40-123 DEG C.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of method for continuously preparing ethylene oligomer, which is characterized in that described method includes following steps:
(1) iron series major catalyst shown in organic solvent, co-catalyst and formula 1 is added continuously to n grades of tandem reactors
1st grade, reaction mass forms solution system in reactor, and it is anti-that reaction mass stop is delivered to n grades of tandems after a certain period of time
The 2nd grade for answering device；It repeats the above steps, until reaction mass is delivered to n-th grade of n grades of tandem reactors；Wherein, n is big
In equal to 2；
In formula 1, R1-R9It is identical or different, it is independently from each other H, C1-C4Alkyl, C1-C4Alkoxy, replace or do not take
The phenyl in generation；The substituent group is C1-C4Alkyl, halogen, the C containing halogen1-C4Alkyl；The number of the substituent group is
1-3；
R10-R11It is identical or different, it is independently from each other C1-C4Alkyl, substituted or unsubstituted phenyl；The substituent group is
C1-C4Alkyl, halogen, the C containing halogen1-C4Alkyl；The number of the substituent group is 1-3；
R ' and R " is identical or different, is independently from each other methyl, ethyl or n-propyl；
(2) gaseous mixture containing ethylene is added to n-th grade of above-mentioned n grades of tandem reactor, gas is dissolved by distribution grid
Into solution system, undissolved gas is overflowed from the top of n-th grade of tandem reactor, into condenser, through condensed
Liquid condensate is back to n-th grade of n grades of tandem reactors, enters n grades of tandem reactors through condensed gas component
(n-1)th grade；It repeats the above steps, until it is back to the 1st grade of n grades of tandem reactors through condensed liquid condensate,
Enter exhaust system through condensed gas component, ethylene oligomer is prepared.
2. the method according to claim 1, wherein the method also includes following steps:
(3) reaction mass being prepared in n-th grade of the n grade tandem reactor of step (2) is sent into intermediate storage tank, carried out
Condensation process twice；
(4) reaction mass after condensation process twice in the intermediate storage tank of step (3) is sent into centrifugal separation system, carried out
Ethylene oligomer is prepared in Solid-Liquid Separation.
3. method according to claim 1 or 2, which is characterized in that the step (1) specifically:
(1) iron series major catalyst shown in organic solvent, co-catalyst and formula 1 is added continuously to n grades of tandem reactors
1st grade, reaction mass forms solution system in reactor, and reaction mass stops after a certain period of time, by delivery pump by material
It is delivered to the 2nd grade of n grades of tandem reactors；It repeats the above steps, until material is delivered to n grades of tandems by delivery pump
N-th grade of reactor；Wherein, n 3-6.
4. method according to any one of claim 1-3, which is characterized in that the condensation process twice of the step (3)
Specifically: first time condensation process, condensation temperature control are being higher than 0 DEG C, and condensed liquid condensate is back to intermediate storage
Tank, uncondensable gas carry out second of condensation process, and condensation temperature control is at 0 DEG C hereinafter, by after obtained condensation again
Liquid condensate separation and recovery, other incondensable gases are entered into exhaust system；
Preferably, the step (3) and step (4) specifically:
(3) reaction mass being prepared in n-th grade of the n grade tandem reactor of step (2) is sent by pressure difference intermediate
Storage tank, carries out first time condensation process, and condensation temperature control is being greater than 0 DEG C to less than is being equal between 40 DEG C, condensing for the first time
Liquid condensate afterwards is back to intermediate storage tank, and incondensable gas carries out second of condensation process, and condensation temperature is controlled at 0 DEG C
Hereinafter, other incondensable gases are entered exhaust system by second of condensed liquid condensate butylene separation and recovery；
(4) reaction mass after condensation process twice in the intermediate storage tank of step (3) is pumped into centrifuge separation through conveying
System carries out Solid-Liquid Separation, wherein solid powder is transferred to drying device, is granulated after dry, and liquid phase enters knockout tower progress
Fractionation.
5. method according to any of claims 1-4, which is characterized in that in formula 1, R1-R6And R8It is identical or different,
It is independently from each other H, C1-C4Alkyl, C1-C4Alkoxy, substituted or unsubstituted phenyl；The substituent group is C1-C4
Alkyl, halogen, the C containing halogen1-C4Alkyl；The number of the substituent group is 1-3；R7And R9Selected from H；R10-R11It is selected from
Methyl；R ' and R " is identical or different, is independently from each other methyl, ethyl or n-propyl.
6. method according to any one of claims 1-5, which is characterized in that compound shown in formula 1 be selected from as following formula 1a,
Shown in formula 1b and formula 1c:
7. method according to claim 1 to 6, which is characterized in that ethylene contents are greater than in the gaseous mixture
20vol.%, it is preferable that ethylene contents are within the scope of 50-99.5vol.% in the gaseous mixture；Contain resistance in the gaseous mixture
Hinder the impurity of polymerization, such as CO, the content of acetylene, alcohol, mercaptan etc. meets the Active pharmaceutical of catalyst at ppm to ppb grades.
Preferably, the gross pressure of the gaseous mixture containing ethylene is within the scope of 0.1-10MPa.
Preferably, the gaseous mixture is the gaseous mixture that the ethylene contents that oil refinery dry gas is enriched with are 60vol.% or more.
Preferably, the conversion ratio of ethylene is greater than 90% in the gaseous mixture.
8. method according to any one of claims 1-7, which is characterized in that the temperature of the polymerization reaction is 60-100
℃。
Preferably, the residence time of the reaction mass every stage reactor in n grades of tandem reactors be 20 minutes -200 points
Clock.
9. method according to claim 1 to 8, which is characterized in that the co-catalyst is selected from methyl alumina
Alkane.
Preferably, the molar ratio of the co-catalyst and iron series major catalyst shown in formula 1 is 2000:1-50:1.
Preferably, the organic solvent is in alkanes organic solvent, olefines organic solvent or aromatic hydrocarbons organic solvent
At least one, such as selected from least one of n-hexane, hexamethylene, petroleum ether, toluene, dimethylbenzene or hexene -1.
Preferably, the organic solvent is also selected from the liquid ethylene oligomerisation olefin that above-mentioned polymerization reaction is prepared
Object.
10. method according to claim 1 to 9, which is characterized in that the ethylene oligomer being prepared melts
Point is between 40-125 DEG C.
Preferably, the carbon number distribution for the ethylene oligomer being prepared is concentrated mainly on C4-C300Between, wherein C4-C24Shared matter
Amount ratio is between 50-70wt%.
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Citations (5)
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|---|---|---|---|---|
| CN101671405A (en) * | 2008-09-08 | 2010-03-17 | 住友化学株式会社 | Apparatus and method for producing polyolefin |
| US20100249480A1 (en) * | 2009-03-31 | 2010-09-30 | Nicholas Christopher P | Process for Oligomerizing Dilute Ethylene |
| CN101906009A (en) * | 2010-07-29 | 2010-12-08 | 浙江大学 | Method for preparing linear alpha-olefin |
| CN105566038A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Ethene oligomerization continuous reaction method |
| CN105732849A (en) * | 2014-12-09 | 2016-07-06 | 中国石油化工股份有限公司 | Olefin polymerization device and method |
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2018
- 2018-01-08 CN CN201810016256.XA patent/CN110013876B/en active Active
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| CN101671405A (en) * | 2008-09-08 | 2010-03-17 | 住友化学株式会社 | Apparatus and method for producing polyolefin |
| US20100249480A1 (en) * | 2009-03-31 | 2010-09-30 | Nicholas Christopher P | Process for Oligomerizing Dilute Ethylene |
| CN101906009A (en) * | 2010-07-29 | 2010-12-08 | 浙江大学 | Method for preparing linear alpha-olefin |
| CN105566038A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Ethene oligomerization continuous reaction method |
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