CN1238315C - Method of eliminating polyethylene from ethylene tripolymerizing reaction liquid - Google Patents
Method of eliminating polyethylene from ethylene tripolymerizing reaction liquid Download PDFInfo
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- CN1238315C CN1238315C CN 200310101420 CN200310101420A CN1238315C CN 1238315 C CN1238315 C CN 1238315C CN 200310101420 CN200310101420 CN 200310101420 CN 200310101420 A CN200310101420 A CN 200310101420A CN 1238315 C CN1238315 C CN 1238315C
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 71
- -1 polyethylene Polymers 0.000 title claims abstract description 71
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000005977 Ethylene Substances 0.000 title claims description 41
- 239000012295 chemical reaction liquid Substances 0.000 title abstract 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000007791 liquid phase Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000012071 phase Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 53
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000001816 cooling Methods 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 23
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 3
- 238000001704 evaporation Methods 0.000 abstract 3
- 239000007789 gas Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000007701 flash-distillation Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a method for removing polyethylene in a 1-hexene reaction liquid prepared by ethene trimerization, which comprises the following steps: firstly, the temperature of a reaction liquid from an ethene trimerization reactor is reduced by adiabatic flash evaporation to cause the reaction liquid to be divided into a gas phase and a liquid phase; secondly, the liquid phase material treated by adiabatic flash evaporation is partially condensed to obtain a condensate liquid; thirdly, the condensate liquid is mixed with the liquid phase treated by adiabatic flash evaporation to further reduce the temperature of the reaction liquid and separate polyethylene from the reaction liquid; finally, the polyethylene in the reaction liquid is filtered out by a filter. On one hand, the method guarantees the operation of apparatus in a long period, and on the other hand, the method can replace the conventional heat trace process to reduce energy consumption and cost.
Description
Technical field
The present invention relates to a kind ofly from ethylene trimerization prepares the mixture of reaction products liquid of 1-hexene, remove the poly method of by product.
Background technology
Ethylene trimerization prepares the 1-hexene, and its reaction is in solution, carries out under the effect of multicomponent catalyst, because the effect of catalyzer, its side reaction meeting produces certain polyethylene by product.At US 5523507, the synthetic method that has all related to the 1-hexene among US 5811618 and the US 5968866, its reaction is in varsol, under the effect of multicomponent catalyst, finish, in above-mentioned document, also having illustrated has poly existence in the product, but does not clearly provide the poly method that removes.Find that if do not take certain measure, polyethylene will be separated out in the production of reality and test from the ethylene trimerization reaction solution, stifled hanging is equipped with inwall and process pipeline, makes that device can't long-time running.
In order to address this problem, industrial method of taking to accompany heat usually, promptly on the pipeline of streams warp and equipment, add the boosting facility, material is remained under the higher temperature, separate out, but this mode at first is to have increased facility investment to prevent material, also to consume lot of energy in addition, improve the operation cost of device, like this, just reduced the economic benefit of device.
If can just deviate from polyethylene in the outlet of ethylene trimerization reactor, it can be brought in the following operation, so just can not stop up later pipeline, do not need to add simultaneously expensive high tracing system yet.For the polyethylene that is dissolved in the hydrocarbon solution, its solvability and temperature have direct relation; When being higher than a certain temperature, polyethylene is dissolved in the solvent, and when temperature was lower than a certain value, polyethylene can be separated out from solvent, around this principle, can make the polyethylene in the solution separate out and by suitable means it be removed by cooling.But adopt the conventional type of cooling (as interchanger) directly to cool off reaction solution, because the surface temperature of interchanger is low, polyethylene will be separated out and stick on the inwall on the inwall of interchanger, causes the extension of equipment stifled.So at present industrial method that still adopts companion's heat.
Summary of the invention
The invention provides a kind of poly method in the ethylene trimerization reaction solution that removes, can avoid the problems referred to above, effectively remove the polyethylene in the reaction solution, simultaneously the recovery part reaction raw materials.
The reactor discharging that ethylene trimerization prepares the 1-hexene is an ethylene trimerization outlet reaction solution, its composition comprises unreacted ethene, the 1-hexene, solvent and byproduct of reaction and remainder catalyst that trimerization reaction uses, its weight percentage scope is respectively usually: ethylene content is 1-15%, 1-hexene content is 15～40%, solvent is 40～80%, the content of byproduct of reaction and remainder catalyst is 1～20%, wherein by product comprises that carbon is generally the alkene and the polyethylene of carbon 8-carbon 100 more than 8, wherein poly weight percentage scope account for usually total material 0.01% to 1% between, its molecular weight ranges is usually 5,000 to 5, between 000,000; The temperature range of reaction solution is being between 50 ℃ to 140 ℃ usually, the pressure range of reaction solution usually at 4.0Mpa between the 6.0Mpa (pressure among the application is absolute pressure).Technical scheme of the present invention is: the outlet at the reactor of ethylene trimerization is provided with a flasher, by adiabatic flash the temperature of reaction solution is reduced and makes it to be divided into the vapour-liquid two-phase, will separate out in reaction solution by some polyethylene like this; With the vapour phase of adiabatic flash in lower temperature lower section condensation, liquid-phase mixing behind the phlegma of gained and the described reaction solution adiabatic flash, further reduced the temperature of reaction solution, most like this polyethylene will be separated out from reaction solution, with strainer polyethylene is filtered from reaction solution, the polyethylene in the reaction solution just has been removed so again.
The amplitude that flash vaporization point reduces is relevant with the state of the pressure of flash distillation and reactor outlet material.The pressure of flash distillation is low more, and the amplitude that temperature reduces is big more; Ethylene content is high more in the reactor outlet material of ethylene trimerization, and the amplitude that temperature reduces under the same flash conditions is big more.The pressure of flasher preferably is controlled at 0.5Mpa between the 4.0Mpa, and the residence time preferably was controlled between 10 to 60 minutes.The amplitude that flash vaporization point reduces generally between 5 ℃ to 40 ℃,
According to an aspect of the present invention, technical process of the present invention comprises that reaction solution outlet line (1), flasher (2), flash distillation gas phase outlet line (3), water cooler (4), cooler gas recovery line (5), water cooler liquid phase discharging pipeline (6), flasher liquid phase outlet line (7), mixing tank (8), mixer outlet pipeline (9), strainer (10), strainer discharging pipeline (11), polyethylene discharging pipeline (12) form (seeing accompanying drawing 1).Its specific embodiment is: reaction solution enters flasher (2) through pipeline (1) and carries out adiabatic flash, pass through adiabatic flash, temperature of charge reduces makes it to be divided into the vapour-liquid two-phase, vapour phase comprises ethene, 1-hexene and solvent, the weight percentage scope of therein ethylene is usually between 40% to 75%, between 20% to 50%, the content range of solvent is usually between 1% to 50% usually for the content range of 1-hexene.Flashed vapour enters water cooler (4) by pipeline (3) mutually and carries out partial condensation.Water cooler can adopt water-cooled, air cooling or other the type of cooling.Usually be controlled between-10 ℃ to 40 ℃ according to different material characteristic cooling temperatures.The component of the noncondensable gas of water cooler mainly is an ethene, weight percentage is generally between 90% to 99%, generally between 1% to 10%, it uses through the nonessential reactor cycles of returning of pipeline (5) for the mixture that also comprises 1-hexene and solvent in addition, its weight percentage.The component of the liquid phase of water cooler mainly is the mixture of 1-hexene and solvent, the weight percentage scope is usually between 90% to 99%, also comprise a spot of ethene in addition, its weight percentage scope is usually between 1% to 10%, through pipeline (6) and flasher liquid product after pipeline (7) enters mixing tank (8) and mixes, temperature of charge further reduces, mix back material temperature scope usually between 50 ℃ to 120 ℃, this moment, most of polyethylene was separated out, entering strainer (10) through pipeline (9) filters, the polyethylene that filters out is discharged by pipeline (12), and the material that removes behind the polyethylene is discharged by pipeline (11).
In this flow process, mixing tank or line mixer that the form of mixing tank can adopt band to stir, the mixing tank residence time that band stirs, preferably between 5 to 15 minutes, the form of line mixer can be the threeway of T type tubular type, the threeway of Y-piece formula, or Venturi-type mixing tank.According to the characteristic of material, preferably use line mixer, preferred Venturi-type mixing tank in line mixer.
According to another aspect of the present invention, the present invention also can adopt the method for directly finishing mixing step in flasher, as shown in Figure 2.Technical process comprises reaction solution outlet line (1), flasher (2), flash distillation gas phase outlet line (3), water cooler (4), cooler gas recovery line (5), water cooler liquid phase discharging pipeline (6), flasher liquid phase outlet line (7), strainer (10), strainer discharging pipeline (11), polyethylene discharging pipeline (12) composition (seeing accompanying drawing 2).Its specific embodiment is: reaction solution enters flasher (2) through pipeline (1) and carries out adiabatic flash, pass through adiabatic flash, temperature of charge reduces makes it to be divided into the vapour-liquid two-phase, vapour phase comprises ethene, 1-hexene and solvent, between 50% to 95%, the content range of 1-hexene is usually 10% to 50% usually for the weight percentage scope of therein ethylene; Between, between 1% to 30%, flasher (2) has whipping appts to the content range of solvent usually.Flashed vapour enters water cooler (4) by pipeline (3) mutually and carries out partial condensation.Water cooler can adopt water-cooled, air cooling or other the type of cooling.Preferably be controlled between-10 ℃ to 40 ℃ according to different material characteristic cooling temperatures.The component of the noncondensable gas of water cooler mainly is an ethene, the weight percentage scope is usually between 90% to 99%, the mixture that also comprises 1-hexene and solvent in addition, its weight percentage use through the reactor cycles of returning that pipeline (5) is nonessential between 1% to 10%.The component of the liquid phase of water cooler mainly is the mixture of 1-hexene and solvent, the weight percentage scope is usually between 90% to 99%, also comprise a spot of ethene in addition, its weight percentage scope is usually between 1% to 10%, get back to flasher (2) through pipeline (6), with the flasher liquid-phase mixing, mix the back temperature range usually between 40 ℃ to 120 ℃, this moment, most of polyethylene was separated out, the flasher liquid phase enters strainer (10) through pipeline (7) and filters, the polyethylene that filters out is discharged by pipeline (12), and the material that removes behind the polyethylene is discharged by pipeline (11).
Flow process 1 shown in the accompanying drawing 1 is different on range of application with the flow process 2 shown in the accompanying drawing 2; When poly molecular-weight average less than 200,000 o'clock, by adiabatic flash the sub-fraction polyethylene is separated out, and most of polyethylene need just can be separated out, and preferably uses flow process 1 by further cooling; When poly molecular weight more than or equal to 200,000, just can separate out most of polyethylene by adiabatic flash, preferably use flow process 2.
Characteristics of the present invention are based on the polyethylene principle that low temperature is separated out in solution, at first reduce the temperature of reaction solution by adiabatic flash, separate out a part of polyethylene, secondly do not contain poly material by cryogenic condensation, it is the gaseous phase materials of flash distillation, and by cryogenic condensation liquid and flash distillation liquid phase are mixed into step reduction reacting liquid temperature, like this, make polyethylene to separate out in the reaction solution, and via strainer elimination polyethylene, realize poly removing, thereby avoided adopting directly cooling to cause polyethylene to separate out and cause stifled situation of hanging at equipment and pipeline inwall.Guarantee the long-term operation of device on the one hand, also can replace conventional companion's thermal process on the other hand, realized reducing energy consumption, the effect that reduces cost.
Ethylene trimerization legal system of the present invention is equipped with the reaction solution of 1 hexene, and its solvent can be alkane, naphthenic hydrocarbon, aromatic hydrocarbon or alkene, and as heptane, hexanaphthene, toluene, 1-hexene etc., full scale plant often uses at present heptane and hexanaphthene.
Carry out polyethylene by separation method of the present invention and remove, can not stop continuous operation 2～3 months and plugging and wall sticking phenomenon do not take place.
Description of drawings
Fig. 1 removes poly process flow sheet to Fig. 2 for dividing from the ethylene trimerization reaction product according to the present invention.
Embodiment
The following examples only are in order to illustrate the present invention better, but do not limit its scope.
Embodiment 1
Technical process such as accompanying drawing 1, the ethylene trimerization legal system is equipped with the 1-hexene, raw material is an ethene, and solvent is a heptane, and the temperature of reaction afterreaction liquid is 130 ℃, pressure is 5.1Mpa, 700 kilograms/hour of flows, reaction solution weight consists of: ethylene content 13.7%, solvent, product and remainder catalyst content 86%, polymerized ethylene content 0.3%, polyethylene molecular-weight average are 100,000.Reaction solution enters flasher (2) and carries out adiabatic flash, and the volume of flasher is 1 cubic metre, and 20 minutes residence time, flashing pressure is controlled at 3.5Mpa, and temperature of charge is reduced to 125 ℃ after the flash distillation.Flashed vapour phase composite weight percentage is respectively ethene 66%, 1-hexene 20%, heptane 14%, enter water cooler (4) by pipeline (3) and carry out the part cooling, the cooling temperature of water cooler is controlled at 40 ℃, after the cooling, non-condensable gas is formed weight percentage and is respectively ethene 93%, 1-hexene 6.5%, heptane 0.5%, noncondensable gas uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler is formed weight percentage and is respectively ethene 9%, 1-hexene 50%, heptane 41%, through pipeline (6) with the flasher liquid product after pipeline (7) enters mixing tank (8) and mixes, temperature of charge further is reduced to 115 ℃, enter strainer (10) through pipeline (9) and filter, the polyethylene that filters out is discharged by pipeline (12), and the material that removes behind the polyethylene is discharged by pipeline (11).
Effect: polyethylene extrusion rate: 70%
2 months parking maintenances of operation are not found wall sticking phenomenon continuously.
Technical process such as accompanying drawing 1, the ethylene trimerization legal system is equipped with the 1-hexene, raw material is an ethene, and solvent is a hexanaphthene, and the temperature of reaction afterreaction liquid is 130 ℃, pressure is 5.1Mpa, 700 kilograms/hour of flows, reaction solution weight consists of: ethylene content 13.7%, solvent, product and remainder catalyst content 86%, polymerized ethylene content 0.3%, polyethylene molecular-weight average are 100,000.Reaction solution enters flasher (2) and carries out adiabatic flash, and the volume of flasher is 1 cubic metre, and 20 minutes residence time, flashing pressure is controlled at 1.5Mpa, and temperature of charge is reduced to 115 ℃ after the flash distillation.Flashed vapour phase composite weight percentage is respectively ethene 55%, 1-hexene 22%, hexanaphthene 23%, enter water cooler (4) by pipeline (3) and carry out the part cooling, the cooling temperature of water cooler is controlled at 40 ℃, after the cooling, non-condensable gas is formed weight percentage and is respectively ethene 93%, 1-hexene 3%, hexanaphthene 4%, noncondensable gas uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler is formed weight percentage and is respectively ethene 9%, 1-hexene 45%, hexanaphthene 46%, through pipeline (6) with the flasher liquid product after pipeline (7) enters mixing tank (8) and mixes, temperature of charge further is reduced to 98 ℃, enter strainer (10) through pipeline (9) and filter, the polyethylene that filters out is discharged by pipeline (12), and the material that removes behind the polyethylene is discharged by pipeline (11).
Effect: polyethylene extrusion rate: 85%
2 months parking maintenances of operation are not found wall sticking phenomenon continuously.
Embodiment 3
Technical process such as accompanying drawing 1, the ethylene trimerization legal system is equipped with the 1-hexene, raw material is an ethene, and solvent is a heptane, and the temperature of reaction afterreaction liquid is 130 ℃, pressure is 5.1Mpa, 700 kilograms/hour of flows, reaction solution weight consists of: ethylene content 13.7%, solvent, product and remainder catalyst content 86%, polymerized ethylene content 0.3%, polyethylene molecular-weight average are 100,000.Reaction solution enters flasher (2) and carries out adiabatic flash, and the volume of flasher is 1 cubic metre, and 20 minutes residence time, flashing pressure is controlled at 1.5Mpa, and temperature of charge is reduced to 115 ℃ after the flash distillation.Flashed vapour phase composite weight percentage is respectively ethene 50%, 1-hexene 35%, heptane 15%, enter water cooler (4) by pipeline (3) and carry out the part cooling, the cooling temperature of water cooler is controlled at-5 ℃, after the cooling, non-condensable gas is formed weight percentage and is respectively ethene 99%, 1-hexene 1%, heptane 0%, noncondensable gas uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler is formed weight percentage and is respectively ethene 1%, 1-hexene 69%, heptane 30%, through pipeline (6) with the flasher liquid product after pipeline (7) enters mixing tank (8) and mixes, temperature of charge further is reduced to 67 ℃, enter strainer (10) through pipeline (9) and filter, the polyethylene that filters out is discharged by pipeline (12), and the material that removes behind the polyethylene is discharged by pipeline (11).
Effect: polyethylene extrusion rate: 97%
2 months parking maintenances of operation are not found wall sticking phenomenon continuously.
Embodiment 4
Technical process such as accompanying drawing 2, the ethylene trimerization legal system is equipped with the 1-hexene, raw material is an ethene, and solvent is a heptane, and the temperature of reaction afterreaction liquid is 130 ℃, pressure is 5.1Mpa, 700 kilograms/hour of flows, reaction solution weight consists of: ethylene content 14%, solvent, product and remainder catalyst content 85.8%, polymerized ethylene content 0.2%, polyethylene molecular-weight average are 500,000.Reaction solution enters flasher (2) and carries out adiabatic flash, and the volume of flasher is 2 cubic metres, and 40 minutes residence time, flashing pressure is controlled at 0.6Mpa.Flashed vapour phase composite weight percentage is respectively ethene 60%, 1-hexene 28%, heptane 12%, enter water cooler (4) by pipeline (3) and carry out the part cooling, the cooling temperature of water cooler is controlled at 40 ℃, after the cooling, non-condensable gas is formed weight percentage and is respectively ethene 95%, 1-hexene 4%, heptane 1%, noncondensable gas uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler is formed weight percentage and is respectively ethene 10%, 1-hexene 62%, heptane 28% is after pipeline (6) is got back to flasher (2) mixing, temperature of charge is reduced to 95 ℃, enter strainer (8) through pipeline (7) and filter, the polyethylene that filters out is discharged by pipeline (10), and the material that removes behind the polyethylene is discharged by pipeline (9).
Effect: polyethylene extrusion rate: 87%
2 months parking maintenances of operation are not found wall sticking phenomenon continuously.
Embodiment 5
Technical process such as accompanying drawing 2, the ethylene trimerization legal system is equipped with the 1-hexene, raw material is an ethene, and solvent is a heptane, and the temperature of reaction afterreaction liquid is 130 ℃, pressure is 5.1Mpa, 700 kilograms/hour of flows, reaction solution weight consists of: ethylene content 14%, solvent, product and remainder catalyst content 85.8%, polymerized ethylene content 0.2%, polyethylene molecular-weight average are 500,000.Reaction solution enters flasher (2) and carries out adiabatic flash, and the volume of flasher is 2 cubic metres, and 40 minutes residence time, flashing pressure is controlled at 0.6Mpa.Flashed vapour phase composite weight percentage is respectively ethene 65%, 1-hexene 27%, heptane 8%, enter water cooler (4) by pipeline (3) and carry out the part cooling, the cooling temperature of water cooler is controlled at 10 ℃, after the cooling, non-condensable gas is formed weight percentage and is respectively ethene 97%, 1-hexene 3%, heptane 0%, noncondensable gas uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler is formed weight percentage and is respectively ethene 3%, 1 hexene 81%, heptane 16% is after pipeline (6) is got back to flasher (2) mixing, temperature of charge is reduced to 88 ℃, enter strainer (8) through pipeline (7) and filter, the polyethylene that filters out is discharged by pipeline (10), and the material that removes behind the polyethylene is discharged by pipeline (9).
Effect: polyethylene extrusion rate: 93%
2 months parking maintenances of operation are not found wall sticking phenomenon continuously.
Embodiment 6
Technical process such as accompanying drawing 2, the ethylene trimerization legal system is equipped with the 1-hexene, raw material is an ethene, and solvent is a hexanaphthene, and the temperature of reaction afterreaction liquid is 130 ℃, pressure is 5.1Mpa, 700 kilograms/hour of flows, reaction solution weight consists of: ethylene content 14%, solvent, product and remainder catalyst content 85.8%, polymerized ethylene content 0.2%, polyethylene molecular-weight average are 500,000.Reaction solution enters flasher (2) and carries out adiabatic flash, and the volume of flasher is 2 cubic metres, and 40 minutes residence time, flashing pressure is controlled at 1.0Mpa.Flashed vapour phase composite weight percentage is respectively ethene 62%, 1-hexene 18%, hexanaphthene 20%, enter water cooler (4) by pipeline (3) and carry out the part cooling, the cooling temperature of water cooler is controlled at 40 ℃, after the cooling, non-condensable gas is formed weight percentage and is respectively ethene 92%, 1-hexene 3%, hexanaphthene 5%, noncondensable gas uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler is formed weight percentage and is respectively ethene 8%, 1-is alkene 45%, and hexanaphthene 47% is after pipeline (6) is got back to flasher (2) mixing, temperature of charge is reduced to 97 ℃, enter strainer (8) through pipeline (7) and filter, the polyethylene that filters out is discharged by pipeline (10), and the material that removes behind the polyethylene is discharged by pipeline (9).
Effect: polyethylene extrusion rate: 85%
2 months parking maintenances of operation are not found wall sticking phenomenon continuously.
Technical process such as accompanying drawing 2, the ethylene trimerization legal system is equipped with the 1-hexene, raw material is an ethene, and solvent is a heptane, and the temperature of reaction afterreaction liquid is 130 ℃, pressure is 5.1Mpa, 700 kilograms/hour of flows, reaction solution weight consists of: ethylene content 14%, solvent, product and remainder catalyst content 85.8%, polymerized ethylene content 0.2%, polyethylene molecular-weight average are 500,000.Reaction solution enters flasher (2) and carries out adiabatic flash, and the volume of flasher is 2 cubic metres, and 40 minutes residence time, flashing pressure is controlled at 0.5Mpa.Flashed vapour phase composite weight percentage is respectively ethene 84%, 1-hexene 14%, heptane 2%, enter water cooler (4) by pipeline (3) and carry out the part cooling, the cooling temperature of water cooler is controlled at-5 ℃, after the cooling, non-condensable gas is formed weight percentage and is respectively ethene 99%, 1-hexene 1%, heptane 0%, noncondensable gas uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler is formed weight percentage and is respectively ethene 1%, 1-hexene 86%, heptane 13% is after pipeline (6) is got back to flasher (2) mixing, temperature of charge is reduced to 40 ℃, enter strainer (8) through pipeline (7) and filter, the polyethylene that filters out is discharged by pipeline (10), and the material that removes behind the polyethylene is discharged by pipeline (9).
Effect: polyethylene extrusion rate: 99%
2 months parking maintenances of operation are not found wall sticking phenomenon continuously.
Claims (10)
1. one kind removes ethylene trimerization and prepares poly method in the 1-hexene reaction solution, may further comprise the steps: at first temperature from the reaction solution of ethylene trimerization reactor is reduced and make it to be divided into the vapour-liquid two-phase by adiabatic flash, described vapor-phase material with adiabatic flash carries out partial condensation again, the phlegma of gained and described adiabatic flash liquid-phase mixing, the temperature that further reduces reaction solution is separated out polyethylene from reaction solution, with strainer polyethylene is filtered from reaction solution again.
2. method according to claim 1, when described polyethylene number-average molecular weight less than 200,000 o'clock, its technological process is: reaction solution enters flasher (2) through pipeline (1) to carry out adiabatic flash and temperature of charge is reduced make it to be divided into the vapour-liquid two-phase, flashed vapour enters water cooler (4) by pipeline (3) mutually and carries out partial condensation, the noncondensable gas of water cooler uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler through pipeline (6) and flasher liquid product after pipeline (7) enters mixing tank (8) and mixes, reacting liquid temperature further reduces, and separate out polyethylene, entering strainer (10) filters, the polyethylene that filters out is discharged by pipeline (12), and the material that removes behind the polyethylene is discharged by pipeline (11).
3. method according to claim 1, when poly number-average molecular weight more than or equal to 200,000 o'clock, its technological process is: reaction solution enters flasher (2) through pipeline (1) and carries out adiabatic flash, flasher (2) has agitator, by adiabatic flash temperature of charge is reduced and make it to be divided into the vapour-liquid two-phase, flashed vapour enters water cooler (4) by pipeline (3) mutually and carries out partial condensation, the noncondensable gas of water cooler uses through the nonessential reactor cycles of returning of pipeline (5), the liquid phase of water cooler is after pipeline (6) is got back to flasher and liquid product is mixed, reacting liquid temperature further reduces, entering strainer (10) through pipeline (7) filters, the polyethylene that filters out is discharged by pipeline (12), and the material that removes behind the polyethylene is discharged by pipeline (11).
4. method according to claim 2, mixing tank or line mixer that described mixing tank (8) stirs for band.
5. method according to claim 4, described line mixer are the threeway of T type tubular type, the threeway of Y-piece formula, or Venturi-type mixing tank.
6. method according to claim 5, described line mixer are the Venturi-type mixing tank.
7. according to each described method of claim 1-6, between the 4.0Mpa, the residence time was controlled between 10 to 60 minutes the pressure-controlling of flasher (2) at 0.5Mpa.
8. according to each described method of claim 2-6, water cooler (4) adopts the type of cooling of water-cooled or air cooling, and cooling temperature is controlled between-10 ℃ to 40 ℃.
9. according to each described method of claim 1-6, the reaction solution solvent that the ethylene trimerization legal system is equipped with the 1-hexene is alkane, naphthenic hydrocarbon, aromatic hydrocarbon or alkene.
10. method according to claim 9, wherein reaction solvent is heptane, hexanaphthene, toluene or 1-hexene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310101420 CN1238315C (en) | 2003-10-17 | 2003-10-17 | Method of eliminating polyethylene from ethylene tripolymerizing reaction liquid |
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| CN 200310101420 CN1238315C (en) | 2003-10-17 | 2003-10-17 | Method of eliminating polyethylene from ethylene tripolymerizing reaction liquid |
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| CN1609084A CN1609084A (en) | 2005-04-27 |
| CN1238315C true CN1238315C (en) | 2006-01-25 |
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| CN 200310101420 Expired - Lifetime CN1238315C (en) | 2003-10-17 | 2003-10-17 | Method of eliminating polyethylene from ethylene tripolymerizing reaction liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105085132A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Method and device for optimizing ethylene oligomerization technology |
| CN107151195A (en) * | 2016-03-02 | 2017-09-12 | 中国石油化工股份有限公司 | The method that catalyst and polyethylene are removed in ethylene oligomerization production alpha-olefin technique |
| CN110114132A (en) * | 2016-12-30 | 2019-08-09 | 沙特基础工业全球技术有限公司 | For the temprature control method in the bubbling column reactor of selective 1- hexene production |
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Effective date of registration: 20170209 Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Address before: 102500 Yanshan Phoenix Road, Fangshan District, No., No. 15 Patentee before: BEIJING YANSHAN BRANCH ACADEMY |
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