CN104086350B - Ethylene oligomerization produces the method for alpha alkene - Google Patents
Ethylene oligomerization produces the method for alpha alkene Download PDFInfo
- Publication number
- CN104086350B CN104086350B CN201310110252.5A CN201310110252A CN104086350B CN 104086350 B CN104086350 B CN 104086350B CN 201310110252 A CN201310110252 A CN 201310110252A CN 104086350 B CN104086350 B CN 104086350B
- Authority
- CN
- China
- Prior art keywords
- external container
- reaction
- passed
- vinyl monomer
- reaction dissolvent
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the method that ethylene oligomerization produces alpha alkene, the method provides the reaction unit that external container is connected with annular-pipe reactor, wherein said external container is provided with gas distributor, reaction dissolvent is passed through external container, described reaction dissolvent is made to contact with the part or all of of gas distributor, so that vinyl monomer is in gas distributor is passed through solvent, promote that the mass transfer between vinyl monomer and reaction dissolvent is to increase vinyl monomer meltage in external container, contacting with catalyst in the reactor can quickly cause ethylene oligomerization to react, it is easily achieved the high activity of catalyst.Compared with prior art have the Stress control of reactor easily, avoid the stifled extension of reactor, and catalyst activity advantages of higher.
Description
Technical field
The present invention relates to olefin(e) oligomerization field, be specifically related to a kind of ethylene oligomerization and produce alpha alkene
The method of hydrocarbon.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry, can by oligomerisation reaction
To be changed into by cheap small-numerator olefin, there is high value-added product, such as 1-hexene and 1-
Octene.Wherein, 1-hexene is the important comonomer producing LLDPE and HDPE, is also
The raw material of some fine chemicals.The LLDPE resin of 1-hervene copolymer and the copolymerization of 1-butylene
Thing is compared, its hot strength, impact strength, and tear resistance and property durable in use are the most excellent
Different, it is particularly suitable for packaging film and the agricultural mulch films such as greenhouse, canopy room.
EP0608447A1 reports a kind of chromium-based catalysts composition, as ethylene oligomerization and
/ or the catalyst of copolymerization, wherein using a kind of compound containing chromium is the component of carbon monoxide-olefin polymeric
One of；The two of the component using azole compounds to be chromium-based catalysts composition；Have employed one
Using lewis acid and/or metal alkyl compound for catalyst as the group of this carbon monoxide-olefin polymeric
/ tri-；Also indicating that, halogen source of also can choosing any one kind of them in catalyst system is as this catalysis simultaneously
The four of the component of agent composition, this halogen source both can be inorganic halides, it is possible to for numerous types
Organohalogen compounds, this catalyst is higher to the selectivity of 1-hexene, but its catalysis activity the highest.
USP5910619 reports employing 1,2,3,4,5,6-hexachlorocyclohexanes as modifier,
Composition four-way catalyst composition, though the activity of this catalyst increases；Chinese patent is " a kind of
The catalyst of preparing 1-hexene from ethene by oligomerization and application thereof " (CN1294109A) employ novel urging
Agent, catalyst activity is significantly improved.But still requirement can not be met, it is desirable to into one
Step improves the performance of catalyst, to improve the activity of catalyst.
Above ethylene oligomerization method all lays particular emphasis on the research to catalyst, CN1203034C pair
Ethylene oligomerization method is studied, but similar to other patents, and reaction is substantially commonly
Autoclave is carried out.The present invention uses annular-pipe reactor to carry out ethylene oligomerization reaction, by
In this course of reaction, solvent and ethene etc. are all the modes of continuous feed, are complete in reactor
The course of reaction that liquid phase is full of, and this course of reaction is strong exothermal reaction, due to liquid can not
Compressibility so that the Stress control in course of reaction is more difficult, makes to the stable operation of commercial plant
Become impact；And with reactor connecting place, newly-increased external container easily occurs that polymer blocks up showing of extension
As, it is unfavorable for the continuous and steady operation of commercial plant.Therefore, it is necessary to find one to have
Effect control method, it is achieved safely, steadily produce.
Summary of the invention
For problems of the prior art, the invention provides a kind of olefin(e) oligomerization and produce
The method of alpha alkene, uses the mode that an external container is connected, and profit with annular-pipe reactor
Realize steadily controlling the pressure of reactor with this external container, predissolve part vinyl monomer, for
The timely supplementing solvent of annular-pipe reactor, external container and reactor connecting place is avoided to be prone to produce stifled
The problem hung, it is ensured that device stable operation, improves catalyst activity and the selection of alpha alkene
Property, reduce production cost, improve the economic benefit of commercial plant.
The invention provides a kind of method that ethylene oligomerization produces alpha alkene, comprising:
A) reaction unit that external container is connected with annular-pipe reactor is provided, wherein said external
Container is provided with gas distributor, reaction dissolvent is passed through described external container, makes described reaction
Solvent partly or entirely contacts with gas distributor, so that vinyl monomer is distributed through gas
Device is passed through in solvent, promotes that the mass transfer between vinyl monomer and reaction dissolvent is to increase vinyl monomer
Meltage in external container；
B) by catalytic component predissolve in reaction dissolvent, then anti-by containing catalyst
Solvent is answered directly to be continually introduced in described annular-pipe reactor；
C) part for intensified vinyl monomer be passed through equipped with reaction dissolvent continuously is external
After container carries out predissolve then the reaction dissolvent dissolved with vinyl monomer is continuous from external container
It is passed through in annular-pipe reactor；The intensified vinyl monomer of another part is passed directly into equipped with reaction molten
In the annular-pipe reactor of agent；And
D) in a loop reactor, to carry out continuous print under the effect of catalyst neat for vinyl monomer
Poly-reaction, the alpha alkene that reaction obtains is dissolved in going out through annular-pipe reactor in reaction dissolvent
Mouth flows out.
In the present invention, reaction dissolvent is passed through from external container top, and a part of vinyl monomer is through gas
In the external container of body distributor Decentralized Pull in, it is passed through the disturbance effect caused continuously by gas,
Increase the contact area of gas and solvent so that fully pass between vinyl monomer and reaction dissolvent
Matter, accelerates vinyl monomer dissolution velocity in a solvent, thus improves vinyl monomer in solvent
Concentration, quickly causes the carrying out of ethylene oligomerization reaction so that catalyst has higher activity.
Another aspect of the present invention, external container is the most also for supplementing reaction institute in annular-pipe reactor
The solvent needed, if inactive state at external container is connected pipeline with reactor, then is prone to
Existing polymer blocks up the problem of extension, by being constantly reactor supplementing solvent, it is ensured that external container
The unimpeded phenomenon not occurring polymer to block up extension of the pipeline that is connected with reactor, it is simple to external container realizes
Pressure controlled effect, thus be beneficial to realize commercial plant stable operation.After another part supercharging
Vinyl monomer through be directly entered in annular-pipe reactor for replenish in course of reaction consume
Vinyl monomer.
The vinyl monomer being passed through in external container in the present invention accounts for the weight of vinyl monomer total feed
The 1～95% of amount, preferably 5～60%, more preferably 10～50%.
The reaction dissolvent being passed through in external container in the present invention accounts for the weight of reaction dissolvent total amount
1-99%, preferably 20-95%, more preferably 50-90%.
In method of the present invention, described reaction dissolvent is organic solvent, preferably alkane,
Cycloalkane, alkene or aromatic hydrocarbon.
Described catalyst be selected from transition metal-type catalyst, more preferably chromium system, iron system, zirconium system,
Molybdenum system, tungsten system, titanium system, nickel system or smooth series catalysts.
In the method for the present invention, described external container can be with any position phase of annular-pipe reactor
Even, the most described external container is connected with middle part or the top of annular-pipe reactor.The side of the present invention
In method, owing to there being the effect of external container, can effectively control the pressure of reactor, therefore,
Reactant liquor can enter separator by any position of reactor.
In the method for the present invention, the product that described reaction obtains is passed through in flash vessel termination reaction,
It is re-introduced into separator and carries out isolated and purified.
The annular-pipe reactor used in the present invention can be single loop reactors or many ring canal reactions
Device.
The external container used in the present invention is stainless steel high-pressure-resistant vessel.Described external container
Shape can be the arbitrary shapes such as cylindrical, spherical, square, elliposoidal.
Cylindrically shaped, spherical, elliposoidal, the disc of described gas distributor, square,
Coiled pipe shape, it is also possible to according to the shape that can meet gas dispersion effect arbitrarily that needs,
Gas distributor percent opening can be any to meet ethene and solvent and uniformly divide in external container
The percentage of cloth, can be 0.02%-99.8%, preferably 0.1%-98%, preferably 1%-95%.
The alpha alkene obtained from separate section can be as the raw material of subsequent processing, as through second
The hexene that alkene trimerization reaction obtains can be directly as the comonomer of LLDPE, and described reaction is molten
Agent can recycle.Before entering piece-rate system, carry out sampling analysis.
The invention have the benefit that
The present invention be primarily directed to annular-pipe reactor homogeneous/heterogeneous method produces in alpha olefin process
The improvement of reaction process unit, this technique uses the side that external container is connected with annular-pipe reactor
Formula, if annular-pipe reactor is imported and exported, material is uneven or pressure oscillation, external container meeting and
Time supplement or disappearance or the material that exceeds the quata and pressure in buffering reactor.This improved method ensures
The pressure stability of annular-pipe reactor, it is simple to being smoothed out of follow-up ethylene oligomerization reaction.
Use above-mentioned process, be not only able to steadily control the pressure of reactor, dissolve part
Ethene is easy to ethylene oligomerization reaction and is quickly carried out giving full play to the effect of catalyst, improves catalyst
Activity, and be prevented from the stifled extension of annular-pipe reactor, simple and practical.
Accompanying drawing explanation
Fig. 1 is the newly-increased external container according to the present invention and ethylene oligomerization prepares alpha alkene
Process diagram.
Description of symbols: 1-the first solvent feeding mouth, 2-the first ethene feeding mouth, 3-the second solvent
Feeding mouth, 4-connection pipeline, 5-the second ethene feeding mouth, 6-catalyst feeding mouth, 7-endless tube are anti-
Answer reaction dissolvent liquid level, 11-in device, 8-product discharge mouth, the external container of 9-, the external container of 10-
Gas distributor
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail, but the scope of the present invention does not limit
In following example.
Embodiment 1
As it is shown in figure 1, process according to the invention flow process is as follows, with ethylene trimer 1-hexene
As a example by, material ethene flow in reaction (200kg/h, polymer grade, commercially available), reaction
Solvent be heptane (flow is 380kg/h, commercially available) and chromium-based catalysts (in terms of chromium,
Concentration is 1mol/L Cr, commercially available).By airtight reaction system inert gas purge
After, after being dried 3 hours at 120 DEG C after replacing 2-3 time with ethene, it is passed through outside ethene holding
The pressure putting container is 5.5MPa, and the ethene flow wherein entering external container is that 80kg/h(accounts for
The 40% of ethene total feed), entering the reaction dissolvent flow in external container is 320kg/h
(accounting for the 84% of total solvent consumption), the most external container uses cylindrical receptacle, external appearance
In device 9 gas distributor 11 be shaped as spherical, the percent opening of gas distributor is 1%.Instead
Answer solvent to introduce external container from the first solvent feeding mouth 1, and make described gas distributor with
Described reaction dissolvent contact, vinyl monomer in the first ethene feeding mouth 2 introduces external container 9,
Disperse through gas distributor 11 so that the reaction dissolvent in external container 9 is in advance dissolved with the denseest
The vinyl monomer of degree.
Hereafter, in external container 9, reaction dissolvent dissolved with vinyl monomer is introduced by connecting pipeline 4
In annular-pipe reactor, other remaining solvents and vinyl monomer are respectively by the second solvent feeding mouth 3
Being incorporated in annular-pipe reactor 7 with the second ethene feeding mouth 5, catalyst is then from catalyst pan feeding
Mouth 6 is introduced in annular-pipe reactor 7, and reacted material is entered follow-up by product discharge mouth 8
Separator in.
Open above-mentioned material inlet valve successively, introduce reaction dissolvent, vinyl monomer and catalyst,
Temperature and pressure in retaining ring pipe reactor 7 is 120 DEG C, pressure is 5.2MPa, introduces institute
Reaction dissolvent, vinyl monomer and the catalyst stated, opens circulating pump and cooler, causes in situ
Ethylene oligomerization reacts, and keeping the time of staying is 40 minutes, and reacted material is through product discharge
Mouth 8 leads to flash vessel, and adds terminator, sampling analysis in flash vessel.
According to this embodiment, catalyst activity is 370Kg oligomerization product/(g Cr h), endless tube
Reactor 7 runs 100 days continuously does not occurs that pressure oscillation exception, annular-pipe reactor do not occur
Stifled wall sticking phenomenon of hanging, holding steady production.
Embodiment 2
Embodiment 2 is same as in Example 1, and difference is to enter the ethene in external container
Flow is that 20Kg/h(accounts for the 10% of ethene total feed, and solvent flux is that 190kg/h(accounts for always
The 50% of solvent load), in external container, gas distributor is shaped as disc, its percent opening
It is 85%.
According to this embodiment, catalyst activity is 365kg oligomerization product/(g Cr h), endless tube
Reactor runs 93 days continuously there is not improper fluctuation, keeps steady production.
Embodiment 3
Embodiment 3 is same as in Example 1, and difference is to enter the ethylene stream in external container
Amount accounts for the 50% of ethene total feed for 100Kg/h(), solvent flux is that 342kg/h(accounts for always
The 90% of solvent load), external container is elliposoidal, the gas distributor in external container
Cylindrically shaped, its percent opening is 35%.Reaction temperature in reactor remains 110 DEG C,
Reaction pressure is 5.1MPa.
According to this embodiment, the activity of catalyst is 360kg oligomerization product/(g Cr h), instead
Answer system continuous and steady operation 92 days, not occur polymer in annular-pipe reactor stifled hangs, pressure
The situations such as fluctuation is abnormal, keep steady production.
Embodiment 4
Embodiment 4 is same as in Example 3, difference be external container be shaped as spherical,
Gas distributor 11 is elliposoidal, and gas distributor percent opening is 30%.
According to this embodiment, the activity of catalyst is 350kg oligomerization product/(g Cr h), instead
Answer system continuous and steady operation 95 days, not occur polymer in annular-pipe reactor stifled hangs, pressure
The situations such as fluctuation is abnormal, keep steady production.
Embodiment 5
Implementing 5 same as in Example 1, difference is that in external container, gas distributor is side
Shape, gas distributor percent opening is 20%.
According to this embodiment, the activity of catalyst is 345kg oligomerization product/(g Cr h), instead
Answer system continuous and steady operation 98 days, not occur polymer in annular-pipe reactor stifled hangs, pressure
The situations such as fluctuation is abnormal, keep steady production.
Embodiment 6
Embodiment 6 is same as in Example 1, and difference is that in external container, gas distributor is
Coiled pipe shape, the percent opening of gas distributor is 10%.
According to this embodiment, catalyst activity is 380kg oligomerization product/(g Cr h), reaction
System continuous and steady operation 105 days, there is not the stifled extension of polymer, pressure wave in annular-pipe reactor
Move the situations such as abnormal, keep steady production.
Embodiment 7
Embodiment 7 is same as in Example 1, difference be external container be square, gas divides
Cloth device is coiled pipe shape, and gas distributor percent opening is 45%.
According to this embodiment, catalyst activity is 363kg oligomerization product/(g Cr h), reaction
System continuous and steady operation 95 days, there is not the stifled extension of polymer, pressure wave in annular-pipe reactor
Move the situations such as abnormal, keep steady production.
Embodiment 8
Embodiment 8 is same as in Example 1, difference be gas distributor be disc, its
Percent opening is 95%.
According to this embodiment, catalyst activity is 360kg oligomerization product/(g Cr h), reaction
System continuous and steady operation 101 days, there is not the stifled extension of polymer, pressure wave in annular-pipe reactor
Move the situations such as abnormal, keep steady production.
Claims (18)
1. the method that ethylene oligomerization produces alpha alkene, comprising:
A) reaction unit that external container is connected with annular-pipe reactor is provided, wherein said external container is provided with gas distributor,
Reaction dissolvent is passed through described external container, makes described reaction dissolvent contact with the part or all of of gas distributor, so that
Vinyl monomer in solvent, promotes that the mass transfer between vinyl monomer and reaction dissolvent is to increase ethene in gas distributor is passed through reaction
Monomer meltage in external container, the material that described external container lacks or exceeds the quata in supplementing or buffer reactor in time
And pressure, thus ensure the pressure stability of annular-pipe reactor；
B) by catalytic component predissolve in reaction dissolvent, then the reaction dissolvent containing catalyst is continually introduced into described endless tube
In reactor；
C) after a part for intensified vinyl monomer being passed through continuously equipped with carrying out predissolve in the external container of reaction dissolvent, then
Reaction dissolvent dissolved with vinyl monomer is passed through in annular-pipe reactor continuously from external container；The vinyl monomer that another part is intensified
It is passed directly into equipped with in the annular-pipe reactor of reaction dissolvent；And
D) in a loop reactor, vinyl monomer carries out continuous print oligomerisation reaction, the alpha that reaction obtains under the effect of catalyst
The outlet that alkene is dissolved in reaction dissolvent through annular-pipe reactor is flowed out.
Method the most according to claim 1, it is characterised in that described in be passed through in external container vinyl monomer account for ethene list
The 1～95% of the weight of body total feed.
Method the most according to claim 2, it is characterised in that described in be passed through in external container vinyl monomer account for ethene list
The 5～60% of the weight of body total feed.
Method the most according to claim 2, it is characterised in that described in be passed through in external container vinyl monomer account for ethene list
The 10～50% of the weight of body total feed.
Method the most according to claim 1, it is characterised in that described in the reaction dissolvent amount that is passed through in external container account for reaction
The 1～99% of the weight of total solvent amount.
Method the most according to claim 5, it is characterised in that described in the reaction dissolvent amount that is passed through in external container account for reaction
The 20～95% of the weight of total solvent amount.
Method the most according to claim 5, it is characterised in that described in the reaction dissolvent amount that is passed through in external container account for reaction
The 50～90% of the weight of total solvent amount.
Method the most according to claim 1, it is characterised in that described reaction dissolvent is organic solvent.
Method the most according to claim 8, it is characterised in that described organic solvent be alkane, cycloalkane, alkene or
Aromatic hydrocarbon.
Method the most according to claim 1, it is characterised in that described catalyst is selected from transition metal-type catalyst.
11. methods according to claim 10, it is characterised in that described transition metal-type catalyst be chromium system, iron system,
Zirconium system, molybdenum system, tungsten system, titanium system, nickel system or smooth series catalysts.
12. methods according to claim 1, it is characterised in that the middle part of described external container and annular-pipe reactor or on
Portion is connected.
13. according to the method according to any one of claim 1-12, it is characterised in that the product that described reaction obtains is passed through sudden strain of a muscle
Steaming device terminates reaction, is re-introduced into separator and carries out isolated and purified.
14. according to the method according to any one of claim 1-12, it is characterised in that described annular-pipe reactor is that monocycle pipe is anti-
Answer device or multiple loop reactors.
15. according to the method according to any one of claim 1-12, it is characterised in that described external container is that stainless steel holds
Device.
16. according to the method described in any one of claim 1-12, described gas distributor be cylindrical, spherical, elliposoidal,
Disc, the square or container of coiled pipe shape；And cavernous structure being also distributed on described gas distributor, percent opening is
0.02%-99.8%.
17. methods according to claim 16, it is characterised in that described percent opening is 0.1%-98%.
18. methods according to claim 16, it is characterised in that described percent opening is 1%-95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310110252.5A CN104086350B (en) | 2013-04-01 | 2013-04-01 | Ethylene oligomerization produces the method for alpha alkene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310110252.5A CN104086350B (en) | 2013-04-01 | 2013-04-01 | Ethylene oligomerization produces the method for alpha alkene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104086350A CN104086350A (en) | 2014-10-08 |
| CN104086350B true CN104086350B (en) | 2016-08-17 |
Family
ID=51634142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310110252.5A Active CN104086350B (en) | 2013-04-01 | 2013-04-01 | Ethylene oligomerization produces the method for alpha alkene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104086350B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10414699B2 (en) * | 2016-05-27 | 2019-09-17 | Chevron Phillips Chemical Company Lp | Process improvements in selective ethylene oligomerizations |
| KR102545533B1 (en) * | 2016-05-27 | 2023-06-21 | 에스케이이노베이션 주식회사 | Oligomerization Catalyst And Process For Preparing Ethylene Oligomer Using Thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1922219A (en) * | 2004-02-13 | 2007-02-28 | 托塔尔石油化学产品研究弗吕公司 | Process for improving the co-polymerization of ethylene and an olefin co-monomer in a polymerization loop reactor. |
| CN102050900A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Method for polymer degassing and propylene recycling in polymerization process of polypropylene liquid-phase loop reactor |
| CN102464545A (en) * | 2010-11-11 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing 1-octene by ethylene oligomerization |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0764625B2 (en) * | 1987-05-25 | 1995-07-12 | 新日本製鐵株式会社 | Superconducting material |
| JPH1087518A (en) * | 1996-09-18 | 1998-04-07 | Mitsubishi Chem Corp | Production of 1-hexene |
-
2013
- 2013-04-01 CN CN201310110252.5A patent/CN104086350B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1922219A (en) * | 2004-02-13 | 2007-02-28 | 托塔尔石油化学产品研究弗吕公司 | Process for improving the co-polymerization of ethylene and an olefin co-monomer in a polymerization loop reactor. |
| CN102050900A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Method for polymer degassing and propylene recycling in polymerization process of polypropylene liquid-phase loop reactor |
| CN102464545A (en) * | 2010-11-11 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing 1-octene by ethylene oligomerization |
Non-Patent Citations (1)
| Title |
|---|
| 微孔膜气体分布器气液传质比表面积的研究;刘有智等;《化工进展》;20090905;第28卷(第9期);第1536-1539页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104086350A (en) | 2014-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2646401B1 (en) | Heat management in ethylene oligomerization | |
| RU2467796C2 (en) | Ethylene oligomerisation catalyst, method of producing said catalyst and oligomerisation method using said catalyst | |
| US20180237360A1 (en) | Selective oligomerization reaction process of ethylene | |
| FI2908941T3 (en) | System and method for catalyst preparation | |
| JP2014500251A (en) | Process for producing 1-octene by oligomerization of ethylene | |
| CA2767615A1 (en) | Multi reactor ethylene oligomerization process with recycle | |
| CN107282126A (en) | A kind of catalyst for ethylene tetramerization composition and its application | |
| CN104086350B (en) | Ethylene oligomerization produces the method for alpha alkene | |
| CN114789067B (en) | Ethylene selective oligomerization catalyst composition and preparation method thereof | |
| JP2017519084A5 (en) | ||
| CN104086349B (en) | Ethylene oligomerization produces the method for alpha alkene | |
| CN103896704B (en) | Ethylene oligomerization produces the method for alpha alkene | |
| CN103100421B (en) | Catalyst composition for ethylene tetramerization | |
| CN106380368B (en) | Method for preparing 1, 5-cyclooctadiene by cyclizing butadiene | |
| US7723446B2 (en) | Polypropylene series reactor | |
| SG174405A1 (en) | Methods of preparing a polymerization catalyst | |
| CN105582933A (en) | Catalyst used for double-bond isomerization | |
| CN111229329B (en) | Silica gel supported monophosphine ligand, ethylene oligomerization catalyst composition comprising same and ethylene oligomerization method | |
| CN105566046B (en) | A kind of method of ethylene tetramerization | |
| CN107282112B (en) | Ethylene oligomerization catalyst composition and application thereof | |
| CN105566036B (en) | A kind of method of ethylene tetramerization | |
| CN105566045B (en) | A kind of method of ethylene tetramerization | |
| CN109422827A (en) | Main catalyst component for solution-process ethylene polymerization, preparation method thereof and catalyst system | |
| CN104549351A (en) | Isomerization catalyst | |
| CN114849780B (en) | Ligand combination for ethylene oligomerization catalyst, preparation method thereof and catalyst for ethylene oligomerization |
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 |