CN105085132A - Method and device for optimizing ethylene oligomerization technology - Google Patents
Method and device for optimizing ethylene oligomerization technology Download PDFInfo
- Publication number
- CN105085132A CN105085132A CN201410192687.3A CN201410192687A CN105085132A CN 105085132 A CN105085132 A CN 105085132A CN 201410192687 A CN201410192687 A CN 201410192687A CN 105085132 A CN105085132 A CN 105085132A
- Authority
- CN
- China
- Prior art keywords
- reaction
- ethylene
- low
- ethylene oligomerization
- temperature
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method and device for optimizing an ethylene oligomerization technology. The method comprises the following steps of: performing light-component removal on a reaction liquid obtained after finishing ethylene oligomerization so as to extract a material flow which contains unreacted ethylene, butylene products generated during ethylene oligomerization, and a small amount of C6 olefin products, C7olefin products and C8 olefin products, and is rich in vinyl monomers; performing cooling separation on the material flow which is rich in vinyl monomers so as to remove the C6 olefin products, the C7olefin products and the C8 olefin products, and obtaining a gas material flow; and enabling the gas material flow and fresh ethylene to enter into a reactor together so as to perform a polymerization reaction. Through the adoption of the method, the investment in equipment of a separation unit is effectively reduced, and the energy consumption during separation is greatly reduced; besides, the butylene led in the reaction can perform a dimerization reaction, so that the C8 olefin products with a high additional value are obtained; the method does not influence the activity of a catalyst, and the purity of the C6 olefin products, the C7olefin products and the C8 olefin products, so that the method conforms to the production process of green chemical industry.
Description
Technical field
The present invention relates to a kind of method and device of Optimization of Ethylene oligomerization process, be specifically related to a kind of method being rich in ethylene streams and recycling in ethylene oligomerization technique, significantly can reduce the running cost of ethylene oligomerization device, increase economic efficiency.
Background technology
Obtained by olefin oligomerization acquisition high alpha-olefin and studied widely, wherein become by ethylene trimerization 1-hexene to become with ethylene tetramerization 1-octene aspect to have comparatively special meaning.By the LLDPE resin of 1-hexene, 1-octene copolymer compared with the multipolymer of 1-butylene, its tensile strength, resistance to impact shock, tear strength and performance durable in use are all obviously excellent, are specially adapted to packing film and the plastic film for agricultural use etc. such as greenhouse, canopy room.At alpha-olefin as in comonomer, 1-hexene and 1-octene progressively substitute 1-butylene and produce high performance PE product.
In the olefin polymerization process such as ethylene oligomerization, can carry out smoothly for making reaction and obtain having the catalyzer of greater activity, in reaction process, ethene is normally excessive, also be, in ethylene oligomerization process, the per pass conversion of vinyl monomer is less than 100%, so reactor generally adopts the mode of cyclical operation, namely unreacted vinyl monomer is delivered in reactor after recycle compressor supercharging again, reacts further.Usually, in olefin oligomerization, the ratio of cyclic ethylene amount/ethylene feed amount is generally between 1:10 ~ 5:10, and when producing load and being on the low side, the amount of cyclic ethylene even can be more.After a catalytic cycle, usually also a small amount of Ethylene oligomerisation products can be contained by the ethylene gas logistics discharged in reaction solution, as butylene, hexene etc., because hexene differs comparatively large with the physical property of ethene, adopt low-grade low-temperature receiver itself and vinyl monomer effectively can be separated; And the boiling point of butylene and ethene is all below 0 DEG C, butylene and vinyl monomer be separated completely, need higher-grade low-temperature receiver to be achieved, therefore, this just needs to increase low-temperature freezing facilities, finally obtains the vinyl monomer of higher degree, recycle, its separating difficulty enlarges markedly.The condensing pressure generally adopted at present is 1.6MPa ~ 2.3MPa, cooling medium generally adopts circulated refrigerated water or refrigeration agent, under above-mentioned condensing pressure and temperature condition, the rate of recovery of butylene is less than 85%, cause thus in cyclic ethylene and still remain a part of butylene, add very large cost to the operation of device, bring very large puzzlement also to the raising of device economic benefit.
Published technology all lays particular emphasis on the improvement of reactive system and catalyst system, is intended to obtain highly active catalyst system, extends the aspects such as the cycle of operation of full scale plant, utilizes system then to have very large deficiency to ethylene recovery.
Summary of the invention
The present invention is directed to unreacted ethylene recycle in existing production technique to utilize in process and have that separating energy consumption is large, the high deficiency of separation costs, a kind of method and device of Optimization of Ethylene oligomerization process are provided, there is simple to operate, that separation costs is low, running cost is low advantage.
Particularly, the amount of ethylene oligomerization device cyclic ethylene in stably manufactured process is larger, cyclic ethylene still contains a small amount of butene component after low-grade low-temperature receiver is purified, in order to obtain the higher cyclic ethylene of purity, need to adopt higher-grade low-temperature receiver to carry out further purifying to cyclic ethylene, this adds very large investment to the operation of complete assembly.
For solving the problems of the technologies described above, reduce the running cost of device, the present inventor proposes a kind of method of Optimization of Ethylene oligomerization process after testing and verification, is made up of following steps:
First the reaction solution obtained after terminating ethylene oligomerization reaction carries out de-light, isolates the logistics being rich in vinyl monomer containing the butene product generated in unreacted ethene, reaction process and a small amount of C6 ~ C8 olefin product; By the described logistics refrigerated separation removing C6 ~ C8 olefin product being wherein rich in vinyl monomer, obtain gas stream; Described gas stream is made to proceed polyreaction again.
In a particular embodiment of the present invention, described ethylene oligomerization reacts for ethylene trimerization prepares 1-hexene, or ethylene tetramerization prepares the reaction of octene.
In one particular embodiment of the present invention, described ethylene oligomerization reaction is carried out in ethylene oligomerization reactor.
In one particular embodiment of the present invention, described de-light process can be carried out in lightness-removing column.1-hexene is prepared for ethylene trimerization, after terminating ethylene oligomerization reaction, the reaction solution that obtains mainly comprises unreacted ethene, a small amount of butylene, 1-hexene, solvent and comprises more than C8 and is generally the alkene of C8-C100 and molecular weight is generally 1,00 to 5, the poly heavy component by product of 000,000 and remainder catalyst.In general, wherein ethylene content is 1 ~ 15% weight, 1-ahexene content is 15 ~ 40% weight, solvent is 40 ~ 80% weight, heavy component by product and remainder catalyst content are 1 ~ 20% weight, the temperature of lightness-removing column is generally 50 ~ 200 DEG C, and pressure is generally 0.2-2.0MPa (in this patent, pressure is all absolute pressure); Through the separation of lightness-removing column, the butene product generated in unreacted ethene, reaction process and a small amount of hexene product, as the logistics being rich in vinyl monomer, are discharged by tower top discharging pipeline, are entered next step refrigerated separation step.Material at the bottom of lightness-removing column tower enters weight-removing column, and the heavy component of more than C8 and remainder catalyst are discharged by discharging pipeline at the bottom of weight-removing column tower, and the mixture of 1-hexene and solvent is by weight-removing column overhead extraction.Described lightness-removing column, weight-removing column can adopt equipment as known in the art, and its stage number is preferably between 20 to 60, and column internals can adopt such as sieve plate, float valve, filler and other forms of column plate.If ethylene tetramerization prepares octene, the reaction solution obtained mainly comprises unreacted ethene, a small amount of butylene, a small amount of hexene, octene, solvent, more than C10 heavy component by product and remainder catalyst, and other treating processes is identical.
In one particular embodiment of the present invention, the reaction solution obtained after terminating ethylene oligomerization reaction first carries out adiabatic flash, then carries out de-light.Described adiabatic flash process of hot potassium can be carried out in flasher, concrete scheme is: arrange a flasher in the outlet of ethylene oligomerization reactor, by adiabatic flash, the temperature of reaction solution is reduced to make it to be divided into vehicle repair major, in reaction solution, most vinyl monomer is split in gas phase, because this reducing the burden of equipment in ensuing de-light process.The amplitude that flash vaporization point reduces is relevant with the state of reactor outlet material with the pressure of flash distillation.The pressure of flash distillation is lower, and the amplitude that temperature reduces is larger; In the material of ethylene oligomerization reactor outlet, ethylene content is higher, and the amplitude that under same flash conditions, temperature reduces is larger.The temperature of flasher is preferably 50 ~ 300 DEG C, is more preferably 80-200 DEG C, and pressure preferably controls between 0.5 ~ 3.0MPa.
In one particular embodiment of the present invention, described process of cooling can be carried out in low-grade low-temperature receiver.Low-grade low-temperature receiver can adopt water-cooled, air cooling or other the type of cooling.Control at 0-55 DEG C according to different material characteristic cooling temperatures, be preferably 0.5-40 DEG C (pressure can not require) herein.The logistics being rich in vinyl monomer is separated into gas-liquid two-phase after low-grade low-temperature receiver, 1-hexene is prepared for ethylene trimerization, component mainly ethene and the butylene of noncondensable gas, weight percent ranges is usually between 90 ~ 99%, also comprise the mixture of 1-hexene and solvent in addition, its weight percentage is between 1 ~ 10%; The mixture of liquid phase component mainly 1-hexene and solvent, weight percent ranges, usually between 90 ~ 99%, also comprises a small amount of ethene and butylene in addition, and its weight percent ranges is usually between 1 ~ 10%.Therefore hexene product is mainly arranged in liquid phase component, and liquid phase component is separated removing, containing more ethene and butylene in the gas stream obtained.If ethylene tetramerization prepares octene, difference is containing more ethene, a small amount of butylene and hexene in gaseous component, and the mixture of liquid phase component mainly octene and solvent, octene is still mainly arranged in liquid phase component.
In one particular embodiment of the present invention, by recycle compressor, cooling is separated the gas stream obtained afterwards and carries out supercharging, then pass in polymerization reactor together with fresh ethylene, initiated polymerization.In polymerization reactor, catalyst charge, ethylene feed are all continuous print processes, and solvent and unreacted ethylene recycle use.For ethylene trimerization, the ethene generation trimerization reaction passed in polymerization reactor generates 1-hexene, and the butene component in the gas stream after supercharging dimerization reaction can occur and generates C8 alkene.For ethylene tetramerization, there are four poly-reactions and generate octene in the ethene passed in polymerization reactor, the butene component in the gas stream after supercharging dimerization reaction can occur and generates C8 alkene.
In method of the present invention, the reaction conditions of described ethylene oligomerization is well known in the art, and preferred reaction pressure is 1-7MPa, is more preferably 2-6MPa, and preferable reaction temperature is 10-160 DEG C, is more preferably 60-145 DEG C.The preferred reaction time is 10-100 minute, is more preferably 20-60 minute.
In method of the present invention, the solvent for ethylene oligomerization is organic solvent, is preferably alkane, naphthenic hydrocarbon, aromatic hydrocarbon or alkene, is more preferably heptane, hexanaphthene, methylcyclohexane, toluene, dimethylbenzene or 1-hexene.
In method of the present invention, the catalyzer for ethylene oligomerization is well known in the art, and this catalyzer comprises heteroatom ligand, transistion metal compound and promotor three kinds of components.Described transition metal-type catalyzer is preferably the compound of chromium, iron, zirconium, molybdenum, titanium, tungsten or tantalum, and described promotor is preferably alkylaluminium cpd and/or aluminium alkoxide compound.The specific examples of operational this kind of catalyzer is specifically disclosed in Chinese patent 99120585.5, 01140236.9, 201010500316.9, 201010138127.1, 200910076736.6, 201210072684.7, 200610009027.2, 200910152284.5, 201110256330.3, 201110329270.3, 201210072998.7, 200710178826.7, 201010523105.7, 201010576892.1, 201010576860.1, 201110356143.2, 201110354464.9, 201110354443.7, 201110217919.2 in.The catalyzer recorded in Chinese patent 99120585.5, has advantage especially for the present invention.
In method of the present invention, the product obtained in polymerization reactor is entered after flasher carries out termination reaction, introduce tripping device again, the alpha alkene obtained through separation and purification can be used as the raw material of subsequent processing, the 1-hexene be obtained by reacting as ethylene trimerization can directly as the comonomer of linear low density polyethylene (LLDPE), and described reaction solvent can be recycled.Reaction solution, before entering separation system, carries out sampling analysis.
Present invention also offers a kind of device realizing above-mentioned Optimization of Ethylene oligomerization process method, comprising:
Polymerization reactor, for carrying out ethylene oligomerization reaction;
Flasher, the opening for feed of described flasher exports with the reaction solution of polymerization reactor and is connected;
First low-grade low-temperature receiver, the described opening for feed of the first low-grade low-temperature receiver exports with the gaseous stream at flasher top and is connected, and the outlet of the gaseous stream of the first low-grade low-temperature receiver is connected with the opening for feed of polymerization reactor;
Lightness-removing column, the opening for feed of described lightness-removing column exports with the liquid stream of flasher base and is connected;
Second low-grade low-temperature receiver, the described opening for feed of the second low-grade low-temperature receiver exports with the gaseous stream at lightness-removing column top and is connected, and the outlet of the gaseous stream of the second low-grade low-temperature receiver is connected with the opening for feed of polymerization reactor, the liquid stream of the second low-grade low-temperature receiver is as the trim the top of column of lightness-removing column.
First, second low-grade low-temperature receiver described can adopt water-cooled, air cooling or other the type of cooling.Control at 0-55 DEG C according to different material characteristic cooling temperatures, be preferably 0.5-40 DEG C.
Beneficial effect of the present invention is:
The present invention mainly for the improvement of separating technology in ethylene oligomerization technique, as ethylene trimerization prepares the reaction that 1-hexene or ethylene tetramerization prepare octene.Compared with adopting the butylene in higher-grade low-temperature receiver partitioning cycle ethylene gas with prior art, the present invention only uses low-grade low-temperature receiver, ethene in circulation gas and butylene are together back in reactor, again initiated polymerization, this improves one's methods and effectively reduces the facility investment of separating unit, greatly reduce the energy consumption of sepn process, dimerization reaction can be there is and obtain the higher C8 olefin product of added value in the butene component simultaneously in introducing reactive system, on the activity of catalyzer and the purity of 1-hexene or octene product without any impact, meet the production process of green chemical industry.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram that method that the embodiment of the present invention prepares olefin polymer relates to.
Fig. 2 is the apparatus structure schematic diagram that method that comparative example of the present invention prepares olefin polymer relates to.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail, but the present invention is not limited to embodiment.
As shown in Figure 1, after ethylene oligomerization reaction terminates, reaction solution 6 from polymerization reactor outlet (not shown) enters flasher 1 and carries out adiabatic flash, the gaseous stream at flasher 1 top cools optionally through the first low-grade low-temperature receiver 4, and in the logistics 7 obtained, main component is ethene.Liquid stream 8 bottom flasher 1 comprises unreacted ethene, the butylene generated in reaction process, hexene, solvent, more than C8 component and waste catalyst component enter lightness-removing column 2, the logistics 9 being rich in vinyl monomer is isolated from lightness-removing column 2 top, logistics 9 is processed through the second low-grade low-temperature receiver 5, wherein contained C6 ~ C8 olefin product (i.e. hexene and octene) is back in lightness-removing column 2 as stream 10, gas stream 11 after de-C6 ~ C8 olefin product directly delivers to recycle compressor entrance (not shown), enter together with fresh ethylene in reactor after supercharging, again initiated polymerization.Main containing solvent, C6 ~ C8 olefin product and discarded catalyst component in stream 12 bottom lightness-removing column 2, obtain circulating solvent and C6 and/or C8 olefin product through further separation and purification.
Embodiment 1
For ethylene trimerization 1-hexene, material ethene flow required in reaction is 2 × 10
4kg/h, wherein cyclic ethylene amount 0.4 × 10
4kg/h (containing butene component 15%); Solvent heptane is 4.5 × 10
4kg/h, catalytic reaction system chromium-based catalysts 0.20kg/h (in chromium).By airtight polymerization reactor inert gas purge, with ethene displacement 2-3 time, and at 120 DEG C after dry 3 hours, temperature in maintenance reactor is 80 DEG C, pressure is 5.0MPa, open the inlet valve of required material successively, the solvent described in introducing, vinyl monomer and catalyzer, open the recycle pump in water cooler and polymerization reactor, original position causes ethylene trimerization reaction, keeps the residence time to be 40 minutes.After ethylene oligomerization reaction terminates, the reaction solution obtained is introduced in flasher and adds terminator, carry out sampling analysis.This reaction solution isolates the logistics being rich in ethene containing the butene product generated in reaction process and a small amount of hexene product through flasher and lightness-removing column; This logistics being rich in ethene, after circulating water is separated, is delivered to cyclic ethylene suction port of compressor, is sent in reactor, again participate in polyreaction after supercharging together with fresh ethylene.Wherein the pressure of flasher is 1.2MPa, and temperature is 130 DEG C; Lightness-removing column column bottom temperature is 180 DEG C, and pressure is 0.55MPa; Circulating water temperature is 10 DEG C.Under ethylene trimerization reaction conditions, the reaction that ethylene trimerization produces hexene occurs in reactor simultaneously, and butene dimerization generates the reaction of C8 alkene; Wherein cyclic ethylene amount is 50kg/h (be 12% containing butene component).
According to this embodiment, catalyst activity is 380Kg oligomerization product/(gCrh), and wherein ahexene content is 91%, 1-hexene product purity is 99.3%, and octene content is 4.5%, needs low-grade low-temperature receiver 1.8 × 10
5kWh/h.
Embodiment 2
Embodiment 2 and the difference of embodiment 1 are that the amount of cyclic ethylene is 80kg/h (be 10% containing butene component), keep temperature of reactor 80 DEG C, pressure is 5.0MPa.
According to this embodiment, catalyst activity is 390Kg oligomerization product/(gCrh), and wherein ahexene content is 90.9%, and octene content is the positive structure rate of product of 4.8%, 1-hexene is 99.4%, and this technological process needs low-grade low-temperature receiver 2.82 × 10
5kWh/h.
Embodiment 3
Embodiment 3 difference from Example 1 to be cyclic ethylene amount be 20Kg/h (be 20% containing butene component), keeps temperature of reactor 120 DEG C, pressure is 3.0MPa.
According to this embodiment, catalyst activity is 366Kg oligomerization product/(gCrh), and wherein ahexene content is 90%, and octene content is the positive structure rate of product of 5.6%, 1-hexene is 99.2%, and this technological process needs low-grade low-temperature receiver 1.56 × 10
5kWh/h.
Comparative example
As shown in Figure 2, the difference of comparative example and embodiment is mainly: by flasher 1' top portion from the logistics 7 ' being rich in ethene obtained, and together send into C4 knockout tower 12 from the gas stream 11 ' after the isolated de-C6 ~ C8 olefin product in lightness-removing column 2 ' top, butene stream 16 is isolated from the bottom of C4 knockout tower 12, the overhead of C4 knockout tower 12 is separated the stream 14 obtained containing ethene and C4 product through higher-grade low-temperature receiver 13, stream 14 is delivered to recycle compressor entrance (not shown), enter together with fresh ethylene in reactor after supercharging, again initiated polymerization.
According to operational condition and the step of embodiment 1, keep reactive system, flasher and post-processing operation condition constant, difference is from flasher and the isolated unreacted vinyl monomer of lightness-removing column, dimerisation products butylene and a small amount of olefin product, first after low-grade low-temperature receiver separating-purifying, again through the further separating-purifying of higher-grade low-temperature receiver, butene content in cyclic ethylene is made to be 0.8%, ethene after twice purification is delivered to recycle compressor entrance, enter reactor after supercharging, cause ethylene oligomerization reaction.
According to this comparative example, catalyst activity is 385Kg oligomerization product/(gCrh), and wherein ahexene content is 92.6%, octene content is 1.3%, the positive structure rate of product of 1-hexene is 99.2%, and this flow process increases C4 knockout tower, low-grade low-temperature receiver 1.82 × 10 except needs
5kWh/h, also needs higher-grade low-temperature receiver 1.32 × 10
5kWh/h; Namely after have employed higher-grade low-temperature receiver purification cyclic ethylene, catalyst activity and product index are all more or less the same, and low-grade low-temperature receiver quantity variance is little, but the consumption of higher-grade low-temperature receiver increases by 100%.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (10)
1. the method for an Optimization of Ethylene oligomerization process, be made up of following steps: the reaction solution obtained after terminating ethylene oligomerization reaction carries out de-light, isolates the logistics being rich in vinyl monomer containing the butene product generated in unreacted ethene, reaction process and a small amount of C6 ~ C8 olefin product; By the described logistics refrigerated separation removing C6 ~ C8 olefin product being wherein rich in vinyl monomer, obtain gas stream; Described gas stream is made to proceed polyreaction again.
2. method according to claim 1, is characterized in that: described ethylene oligomerization reaction is ethylene trimerization or ethylene tetramerization reaction.
3. method according to claim 1 and 2, is characterized in that: described de-light process is carried out in lightness-removing column, and preferably de-light temperature is 50 ~ 200 DEG C, and pressure is 0.2 ~ 2.0MPa.
4. the method according to any one of claims 1 to 3, it is characterized in that: the reaction solution obtained after terminating ethylene oligomerization reaction first carries out adiabatic flash, then carry out de-light, the temperature of preferred adiabatic flash is 50 ~ 300 DEG C, be more preferably 80 ~ 200 DEG C, pressure is 0.5 ~ 3.0MPa.
5. the method according to any one of Claims 1 to 4, is characterized in that: the temperature of described process of cooling is 0-55 DEG C, is preferably 0.5-40 DEG C, and preferred described cooling adopts recirculated water to carry out.
6. the method according to any one of Claims 1 to 5, is characterized in that: by recycle compressor, cooling is separated the gas stream obtained afterwards and carries out supercharging, then pass in polymerization reactor together with fresh ethylene, initiated polymerization.
7. the method according to any one of claim 1 ~ 6, is characterized in that: the reaction pressure of described ethylene oligomerization is 1-7MPa, and temperature of reaction is 10-160 DEG C, and the reaction times is 10-100 minute; Preferred reaction pressure is 2-6MPa, and temperature of reaction is 60-145 DEG C, and the reaction times is 20-60 minute.
8. the method according to any one of claim 1 ~ 7, it is characterized in that: the solvent for ethylene oligomerization is organic solvent, be preferably alkane, naphthenic hydrocarbon, aromatic hydrocarbon or alkene, be more preferably heptane, hexanaphthene, methylcyclohexane, toluene, dimethylbenzene or 1-hexene.
9. the method according to any one of claim 1 ~ 8, it is characterized in that: the catalyzer for ethylene oligomerization comprises heteroatom ligand, transistion metal compound and promotor three kinds of components, described transition metal-type catalyzer is preferably the compound of chromium, iron, zirconium, molybdenum, titanium, tungsten or tantalum, and described promotor is preferably alkylaluminium cpd and/or aluminium alkoxide compound.
10. realize a device for method according to any one of claim 1 ~ 9, comprising:
Polymerization reactor, for carrying out ethylene oligomerization reaction;
Flasher, the opening for feed of described flasher exports with the reaction solution of polymerization reactor and is connected;
First low-grade low-temperature receiver, the described opening for feed of the first low-grade low-temperature receiver exports with the gaseous stream at flasher top and is connected, and the outlet of the gaseous stream of the first low-grade low-temperature receiver is connected with the opening for feed of polymerization reactor;
Lightness-removing column, the opening for feed of described lightness-removing column exports with the liquid stream of flasher base and is connected;
Second low-grade low-temperature receiver, the described opening for feed of the second low-grade low-temperature receiver exports with the gaseous stream at lightness-removing column top and is connected, and the outlet of the gaseous stream of the second low-grade low-temperature receiver is connected with the opening for feed of polymerization reactor, the liquid stream of the second low-grade low-temperature receiver is as the trim the top of column of lightness-removing column.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410192687.3A CN105085132A (en) | 2014-05-08 | 2014-05-08 | Method and device for optimizing ethylene oligomerization technology |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410192687.3A CN105085132A (en) | 2014-05-08 | 2014-05-08 | Method and device for optimizing ethylene oligomerization technology |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105085132A true CN105085132A (en) | 2015-11-25 |
Family
ID=54566570
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410192687.3A Pending CN105085132A (en) | 2014-05-08 | 2014-05-08 | Method and device for optimizing ethylene oligomerization technology |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105085132A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110627604A (en) * | 2019-10-31 | 2019-12-31 | 胜帮科技股份有限公司 | Production system and production method for synthesizing 1-octene and 1-hexene through ethylene oligomerization |
CN110639459A (en) * | 2019-10-10 | 2020-01-03 | 万华化学集团股份有限公司 | Device and method for preparing 1-octene by ethylene selective oligomerization |
CN113233951A (en) * | 2021-05-12 | 2021-08-10 | 天津科技大学 | Production device and production process for producing linear alpha-olefin by selective oligomerization of ethylene |
CN113597419A (en) * | 2019-03-13 | 2021-11-02 | Tpc集团有限责任公司 | Elastomeric manufacturing system for selectively producing different linear alpha-olefins |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN1609084A (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 eliminating polyethylene from ethylene tripolymerizing reaction liquid |
CN102381956A (en) * | 2011-09-06 | 2012-03-21 | 安徽皖维高新材料股份有限公司 | Method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope and method for separation |
WO2014008964A1 (en) * | 2012-07-10 | 2014-01-16 | Saudi Basic Industries Corporation (Sabic) | Method for oligomerization of ethylene |
-
2014
- 2014-05-08 CN CN201410192687.3A patent/CN105085132A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN1609084A (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 eliminating polyethylene from ethylene tripolymerizing reaction liquid |
CN102381956A (en) * | 2011-09-06 | 2012-03-21 | 安徽皖维高新材料股份有限公司 | Method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope and method for separation |
WO2014008964A1 (en) * | 2012-07-10 | 2014-01-16 | Saudi Basic Industries Corporation (Sabic) | Method for oligomerization of ethylene |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113597419A (en) * | 2019-03-13 | 2021-11-02 | Tpc集团有限责任公司 | Elastomeric manufacturing system for selectively producing different linear alpha-olefins |
CN110639459A (en) * | 2019-10-10 | 2020-01-03 | 万华化学集团股份有限公司 | Device and method for preparing 1-octene by ethylene selective oligomerization |
CN110627604A (en) * | 2019-10-31 | 2019-12-31 | 胜帮科技股份有限公司 | Production system and production method for synthesizing 1-octene and 1-hexene through ethylene oligomerization |
CN113233951A (en) * | 2021-05-12 | 2021-08-10 | 天津科技大学 | Production device and production process for producing linear alpha-olefin by selective oligomerization of ethylene |
CN113233951B (en) * | 2021-05-12 | 2022-11-18 | 天津科技大学 | Production device and production process for producing linear alpha-olefin by selective oligomerization of ethylene |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103387628B (en) | A kind of system and method for olefinic polymerization | |
CN102795956B (en) | Method for separating reaction products produced during preparation of propylene by dehydrogenating propane | |
CN104923029B (en) | The recovery method of vapor phase method polyolefin emission | |
CN105085132A (en) | Method and device for optimizing ethylene oligomerization technology | |
WO2009013217A4 (en) | Method for cooling in distillation and polymerisation process by absorption refrigeration | |
CN103998403A (en) | Hydrocarbon dehydrogenation with inert diluent | |
EP2336201A1 (en) | Polyolefin manufacturing process | |
CN110997731B (en) | Polymerization process comprising discharging polyolefin particles from a gas-phase polymerization reactor | |
CN102153682B (en) | Removal of catalyst and cocatalyst residues in a polyolefin manufacturing process | |
CN103936542B (en) | A kind of olefins by catalytic cracking system and method improving alkene total conversion rate | |
CN110627604A (en) | Production system and production method for synthesizing 1-octene and 1-hexene through ethylene oligomerization | |
CN104926963A (en) | Method for synthesizing poly alpha-olefin base oil through 1-butene oligomerization | |
EP1713839B1 (en) | Process for preparing polyolefins in suspension | |
WO2013137962A1 (en) | Processes and apparatus for continuous solution polymerization | |
CN109369318A (en) | A method of the raw material based on C5 alkene maximizes production propylene | |
TWI633086B (en) | Process and apparatus for separating c5 di-olefins from pyrolysis gasoline | |
CN212532823U (en) | Production device of ternary copolymerized polypropylene | |
US11834531B2 (en) | Suspension process for preparing ethylene copolymers in a reactor cascade | |
CN103772117A (en) | Method for preparing butadiene through multistage adiabatic oxidative dehydrogenation of butylene | |
KR101928766B1 (en) | Method of separating for recovering ethylene and process system | |
CN106588551A (en) | Separation method of 1-hexylene namely ethylene oligomerization product | |
CN108602904B (en) | Olefin polymerization process | |
EP2848635A1 (en) | Polymerization process | |
CN1587242A (en) | Improved method for producing styrene by ethyl benzene catalyzed dehydrogenation | |
CN108484806B (en) | Process for preparing bimodal polyethylene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151125 |