CN103896704B - Ethylene oligomerization produces the method for alpha alkene - Google Patents
Ethylene oligomerization produces the method for alpha alkene Download PDFInfo
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- CN103896704B CN103896704B CN201310089293.0A CN201310089293A CN103896704B CN 103896704 B CN103896704 B CN 103896704B CN 201310089293 A CN201310089293 A CN 201310089293A CN 103896704 B CN103896704 B CN 103896704B
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Abstract
The present invention relates to the method that ethylene oligomerization produces alpha alkene, the method comprises: a) provide the reaction unit that external container is connected with annular-pipe reactor; B) by catalyst component predissolve in reaction solvent, then the solution of catalyzer is introduced in described annular-pipe reactor continuously; C) after a part for the vinyl monomer through supercharging is passed into continuously carrying out predissolve in the external container that reaction solvent is housed, then the reaction solvent being dissolved with vinyl monomer is passed in annular-pipe reactor continuously from external container; Another part directly passes into through the vinyl monomer of supercharging and is equipped with in the annular-pipe reactor of reaction solvent; D) in a loop reactor, vinyl monomer carries out continuous print oligomerisation reaction under the effect of catalyzer, and the alpha alkene be obtained by reacting is dissolved in reaction solvent and flows out through the outlet of annular-pipe reactor.Compared with prior art have the pressure-controlling of reactor easily, avoid the stifled extension of reactor and catalyst activity advantages of higher.
Description
Technical field
The present invention relates to olefin oligomerization field, be specifically related to a kind of method that ethylene oligomerization produces alpha alkene.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry, the small-numerator olefin of cheapness can be changed into have high value-added product, as 1-hexene and 1-octene by oligomerisation reaction.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 is compared with the multipolymer of 1-butylene, and its tensile strength, resistance to impact shock, tear strength and property durable in use are all obviously excellent, are particularly suitable for packing film and the agricultural mulch films such as greenhouse, canopy room.
Report a kind of chromium-based catalysts composition in EP0608447A1, as the catalyzer of ethylene oligomerization and/or copolymerization, wherein use a kind of containing one of the compound of chromium component that is catalyst composition; Use the component two that azole compounds is chromium-based catalysts composition; Have employed a kind of using Lewis acid and/or metal alkyl compound for catalyzer is as the component three of this catalyst composition; Also point out simultaneously, also can choose any one kind of them in catalyst system the component four of halogen source as this catalyst composition, this halogen source both can be inorganic halides, also can be many eurypalynous Organohalogen compounds, the selectivity of this catalyzer to 1-hexene is higher, but its catalytic activity is not high.
Report employing 1,2,3,4,5,6-HEXACHLOROBUTADIENE in USP5910619 as improving agent, composition four-way catalyst composition, though the activity of this catalyzer increases; Chinese patent " a kind of catalyzer of preparing 1-hexene from ethene by oligomerization and application thereof " (CN1294109A) employs new catalyst, and catalyst activity is significantly improved.But still can not meet the demands, people wish the performance improving catalyzer further, to improve the activity of catalyzer.
Above ethylene oligomerization method all lays particular emphasis on the research to catalyzer, and CN1203034C is studied ethylene oligomerization method, but similar to other patents, and reaction is carried out substantially in ordinary high pressure reactor.The present invention adopts annular-pipe reactor to carry out ethylene oligomerization reaction, due in this reaction process, solvent and ethene etc. are all the modes of continuously feeding, the reaction process be full of for full liquid phase in reactor, and this reaction process is strong exothermal reaction, due to the incompressibility of liquid, make the pressure-controlling in reaction process more difficult, cause impact to the steady running of full scale plant.Therefore, be necessary to find a kind of method that can effectively control, realize safety, steadily produce.
Summary of the invention
For problems of the prior art, the invention provides a kind of method that alpha alkene is produced in olefin oligomerization, adopt the mode that an external container is connected with annular-pipe reactor, realize continuously feeding and production, and utilize this external container to realize steadily controlling the pressure of reactor, predissolve part vinyl monomer, for the timely supplementing solvent of annular-pipe reactor, external container and reactor connecting place is avoided to be easy to produce stifled problem of hanging, guarantee device steady running, improve the selectivity of catalyst activity and alpha alkene, reduce production cost, improve the economic benefit of full scale plant.
The invention provides a kind of method that ethylene oligomerization produces alpha alkene, it comprises:
A) reaction unit providing external container to be connected with annular-pipe reactor;
B) by catalyst component predissolve in reaction solvent, then the solution of catalyzer is introduced in described annular-pipe reactor continuously;
C) after a part for the vinyl monomer through supercharging is passed into continuously carrying out predissolve in the external container that reaction solvent is housed, then the reaction solvent being dissolved with vinyl monomer is passed in annular-pipe reactor continuously from external container; Another part directly passes into through the vinyl monomer of supercharging and is equipped with in the annular-pipe reactor of reaction solvent;
D) in a loop reactor, vinyl monomer carries out continuous print oligomerisation reaction under the effect of catalyzer, and the alpha alkene be obtained by reacting is dissolved in reaction solvent and flows out through the outlet of annular-pipe reactor.
In the present invention, part vinyl monomer pass in the external container that solvent is housed make this partial solvent enter annular-pipe reactor before namely containing certain density vinyl monomer, be convenient to catalyzer in ethylene oligomerization reaction process play a role in time, oligomerisation reaction carries out fast.External container is also the solvent in annular-pipe reactor needed for postreaction simultaneously, if to be connected with reactor pipeline place stationary state at external container, then be easy to occur that polymkeric substance blocks up the problem of extension, by being constantly reactor supplementing solvent, ensure that is connected external container pipeline is unimpeded with reactor there is not the phenomenon that polymkeric substance blocks up extension, be convenient to external container and realize pressure controlled effect, thus be beneficial to and realize full scale plant steady running.Vinyl monomer after another part supercharging is through directly entering in annular-pipe reactor for replenishing the vinyl monomer consumed in reaction process.
The weight percentage that the vinyl monomer passed in the present invention in external container accounts for vinyl monomer total feed is 1 ~ 95%, is preferably 2 ~ 60%, is more preferably 5 ~ 40%.
The weight percent that the reaction solvent passed in the present invention in external container accounts for reaction solvent total amount is 1-99%, is preferably 20-95%, is more preferably 50-90%.
In method of the present invention, described reaction solvent is organic solvent, preferred alkane, naphthenic hydrocarbon, alkene or aromatic hydrocarbon.
Described catalyzer is selected from transition metal-type catalyzer, is more preferably chromium system, iron system, zirconium system, molybdenum system, tungsten system, titanium system, nickel system or smooth series catalysts.
In method of the present invention, described external container is preferably connected with the middle part of annular-pipe reactor or upper position.In method of the present invention, owing to there being the effect of external container, effectively can control the pressure of reactor, therefore, reaction solution enters tripping device preferably by the middle part of reactor or top.
In method of the present invention, the product be obtained by reacting passes into termination reaction in flasher, then introduces tripping device and carry out separation and purification.
The annular-pipe reactor used in the present invention can be single loop reactors or multiple loop reactors.
The external container used in the present invention is stainless steel high-pressure-resistant vessel.Lipophilicity filler can also be added in the inside of described external container.
The shape of described external container can be cylindrical, cube shaped, elliposoidal or spherical, can make arbitrary shape as required.
The alpha alkene obtained from separate part can be used as the raw material of subsequent processing, and the hexene as being obtained by reacting through ethylene trimerization can directly as the comonomer of LLDPE, and described reaction solvent can be recycled.Reaction solution, before entering separation system, carries out sampling analysis.
Beneficial effect of the present invention is:
The present invention mainly produces the improvement of reaction process unit in alpha olefin process for annular-pipe reactor homogeneous phase/heterogeneous method, the mode that this technique adopts external container to connect with annular-pipe reactor, if annular-pipe reactor imports and exports material imbalance or pressure surge, the material that external container can supplement in time or lack in buffering reaction device or exceed the quata and pressure.This improve one's methods ensure that annular-pipe reactor pressure-stabilisation, be easy to control, be convenient to follow-up ethylene oligomerization reaction carry out smoothly.
Adopt above-mentioned processing method, external container not only can be prevented to be connected with annular-pipe reactor the stifled extension of pipeline, and can dissolve part ethene be convenient to ethylene oligomerization reaction carry out fast giving full play to catalyzer effect, improve the activity of catalyzer, realize the pressure steadily controlling reactive system simultaneously, simple and practical.
Accompanying drawing explanation
Fig. 1 is the process diagram preparing alpha alkene according to external container of the present invention and ethylene oligomerization.
Description of symbols: 1-first solvent feeding mouth, 2-first ethene feeding mouth, 3-second solvent feeding mouth, 4-connecting tube, 5-second ethene feeding mouth, 6-catalyzer feeding mouth, 7-annular-pipe reactor, 8-product discharge mouth, the external container of 9-
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1
As shown in Figure 1, technical process according to the present invention is as follows, for ethylene trimerization 1-hexene, material ethene flow (200kg/h, polymerization-grade in reaction, commercially available), solvent (380kg/h, heptane, commercially available) and chromium-based catalysts (in chromium, concentration is 0.5mol/LCr, commercially available), external container 9(cylindrical) volume be 0.5 cubic metre.After airtight reactive system inert gas purge, with ethene displacement 2-3 time after at 120 DEG C drying 3 hours after, passing into ethene keeps the pressure of external container to be 5.3MPa, the ethene flow wherein entering external container is that 80kg/h(accounts for 40% of ethene total feed), the solvent flux entered in external container is that 320kg/h(accounts for 84% of total solvent consumption), external container adopts cylindrical container here.Solvent is introduced in external container from the first solvent feeding mouth 1, and vinyl monomer is introduced in external container 9 through the first ethene feeding mouth 2, makes the solvent in external container 9 be dissolved with certain density vinyl monomer in advance.
After this, the solvent being dissolved with vinyl monomer in external container 9 is introduced in annular-pipe reactor by connecting tube 4, other remaining solvents and vinyl monomer are incorporated in annular-pipe reactor 7 by the second solvent feeding mouth 3 and the second ethene feeding mouth 5 respectively, catalyzer is then introduced into annular-pipe reactor 7 from catalyzer feeding mouth 6, and reacted material is entered in follow-up tripping device by product discharge mouth 8.
Open above-mentioned material inlet valve successively, introduce solvent, vinyl monomer and catalyzer, temperature in retaining ring pipe reactor 7 is 120 DEG C, pressure is 5.1MPa, solvent described in introducing, vinyl monomer and catalyzer, open recycle pump and water cooler, and original position causes ethylene oligomerization reaction, the residence time is kept to be 40 minutes, reacted material leads to flasher through product discharge port 8, and adds terminator in flasher, sampling analysis.
According to this embodiment, catalyst activity is 280Kg oligomerization product/(gCrh), and annular-pipe reactor 7 runs continuously and within 90 days, do not occur that pressure surge is abnormal, annular-pipe reactor does not occur that polymkeric substance is stifled and hangs phenomenon, keeps stably manufactured.
Embodiment 2
Embodiment 2 is identical with embodiment 1, and difference is that described external container is cube shaped, and the ethene flow entered in external container is 20Kg/h(accounts for 10% of ethene total feed, and solvent flux is that 190kg/h(accounts for 50% of total solvent consumption).
According to this embodiment, catalyst activity is 274kg oligomerization product/(gCrh), and annular-pipe reactor runs 80 days continuously and do not occur improper fluctuation, keeps stably manufactured.
Embodiment 3
Embodiment 3 is identical with embodiment 1, and difference is described external container is elliposoidal, and the ethene flow entered in external container is 80Kg/h(accounts for 40% of ethene total feed), solvent flux is that 342kg/h(accounts for 90% of total solvent consumption).Temperature of reaction in reactor remains 110 DEG C, and reaction pressure is 5.5MPa.
According to this embodiment, the activity of catalyzer is 286kg oligomerization product/(gCrh), does not occur that polymkeric substance blocks up situations such as hanging, pressure surge is abnormal, keep stably manufactured in reactive system continuous and steady operation 100 days, annular-pipe reactor.
Embodiment 4
Embodiment 4 is identical with embodiment 1, and difference is external container shapes is spherical stainless steel container, and the ethene flow entering external container is 40Kg/h(accounts for 20% of ethene total feed), solvent flux is that 342kg/h(accounts for 90% of total solvent consumption).Temperature of reaction in reactor remains 110 DEG C, and reaction pressure is 5.5MPa.
According to this embodiment, the activity of catalyzer is 280kg oligomerization product/(gCrh), does not occur that polymkeric substance blocks up situations such as hanging, pressure surge is abnormal, keep stably manufactured in reactive system continuous and steady operation 95 days, annular-pipe reactor.
Embodiment 5
Embodiment 5 is identical with embodiment 1, and difference is that the ethene flow entered in external container is that 10Kg/h(accounts for 5% of ethene total feed, and solvent flux is that 190kg/h(accounts for 50% of total solvent consumption).
According to this embodiment, catalyst activity is 265kg oligomerization product/(gCrh), and annular-pipe reactor runs 95 days continuously and do not occur improper fluctuation, keeps stably manufactured.
Claims (16)
1. ethylene oligomerization produces a method for alpha alkene, and it comprises:
A) reaction unit providing external container to be connected with annular-pipe reactor;
B) by catalyst component predissolve in reaction solvent, then the solution of catalyzer is introduced in described annular-pipe reactor continuously;
C) after a part for the vinyl monomer through supercharging is passed into continuously carrying out predissolve in the external container that reaction solvent is housed, then the reaction solvent being dissolved with vinyl monomer is passed in annular-pipe reactor continuously from external container; Another part directly passes into through the vinyl monomer of supercharging and is equipped with in the annular-pipe reactor of reaction solvent;
D) in a loop reactor, vinyl monomer carries out continuous print oligomerisation reaction under the effect of catalyzer, and the alpha alkene be obtained by reacting is dissolved in reaction solvent and flows out through the outlet of annular-pipe reactor.
2. method according to claim 1, is characterized in that, described in the vinyl monomer passed in the external container weight percentage that accounts for vinyl monomer total feed be 1 ~ 95%.
3. method according to claim 2, is characterized in that, described in the vinyl monomer passed in the external container weight percentage that accounts for vinyl monomer total feed be 2 ~ 60%.
4. method according to claim 2, is characterized in that, described in the vinyl monomer passed in the external container weight percentage that accounts for vinyl monomer total feed be 5 ~ 40%.
5. method according to claim 1, is characterized in that, described in the reaction solvent amount passed in the external container weight percent that accounts for reaction total solvent amount be 1 ~ 99%.
6. method according to claim 5, is characterized in that, described in the reaction solvent amount passed in the external container weight percent that accounts for reaction total solvent amount be 20 ~ 95%.
7. method according to claim 5, is characterized in that, described in the reaction solvent amount passed in the external container weight percent that accounts for reaction total solvent amount be 50 ~ 90%.
8. method according to claim 1, is characterized in that, described reaction solvent is organic solvent.
9. method according to claim 8, is characterized in that, described reaction solvent is alkane, naphthenic hydrocarbon, alkene or aromatic hydrocarbon.
10. method according to claim 1, is characterized in that, described catalyzer is selected from transition metal-type catalyzer.
11. methods according to claim 10, is characterized in that, described catalyzer is chromium system, iron system, zirconium system, molybdenum system, tungsten system, titanium system, nickel system or smooth series catalysts.
12. methods according to claim 1, is characterized in that, middle part or the top of described external container and annular-pipe reactor are connected.
13. methods according to any one of claim 1-12, it is characterized in that, the product that described method obtains passes into termination reaction in flasher, then introduces tripping device and carry out separation and purification.
14. methods according to any one of claim 1-12, it is characterized in that, described annular-pipe reactor is single loop reactors or multiple loop reactors.
15. methods according to any one of claim 1-12, it is characterized in that, described external container is stainless steel high-pressure-resistant vessel.
16. methods according to any one of claim 1-12, it is characterized in that, the shape of described external container is cylindrical, cube shaped, elliposoidal or spherical.
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| US10414699B2 (en) * | 2016-05-27 | 2019-09-17 | Chevron Phillips Chemical Company Lp | Process improvements in selective ethylene oligomerizations |
| CN109020773B (en) * | 2017-06-12 | 2021-08-03 | 中国石油天然气股份有限公司 | Method for synthesizing alpha-olefin by ethylene oligomerization and pretreatment method of catalyst and solvent thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| EP2374823A1 (en) * | 2010-04-07 | 2011-10-12 | Borealis AG | Production of alpha-olefin copolymers in a loop reactor with variable comonomer feed |
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| JPH1087518A (en) * | 1996-09-18 | 1998-04-07 | Mitsubishi Chem Corp | Production of 1-hexene |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| EP2374823A1 (en) * | 2010-04-07 | 2011-10-12 | Borealis AG | Production of alpha-olefin copolymers in a loop reactor with variable comonomer feed |
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