CN1176109C - Fluidized bed polymerization reactor - Google Patents
Fluidized bed polymerization reactor Download PDFInfo
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- CN1176109C CN1176109C CNB021544816A CN02154481A CN1176109C CN 1176109 C CN1176109 C CN 1176109C CN B021544816 A CNB021544816 A CN B021544816A CN 02154481 A CN02154481 A CN 02154481A CN 1176109 C CN1176109 C CN 1176109C
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- Prior art keywords
- annular
- reactor
- fluidized
- hollow
- polymerization reactor
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 17
- 238000009826 distribution Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 37
- 239000007789 gas Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 9
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention discloses a fluidized bed polymerization reactor. The present invention comprises an expanding section of the upper end of the reactor, a straight-cylinder reaction part of the reactor, a gas distributing plate and a gas mixing chamber; one or a plurality of gas flow guiding devices are arranged on the gas mixing chamber; each flow guiding device comprises an annular plate; a hollow, inverse and annular conical table is arranged in the inner ring of the annular plate; a central striker is arranged in the center of the annular plate and is fixed by the ribbed plate of the hollow, inverse and annular conical table. The present invention has the advantages that 1) after recycle streams enter the mixing chamber, liquid-phase material and powder are uniformly distributed in gas phase; the direct impact active force of the gas flows of a center hole to the distributing plate is reduced; as a result, carried block-shaped polymers are difficult to enter a distributing hole; 2)when the liquid-phase content of the recycle steams is within a range of 3 wt% to 35 wt%, the reactor can safely run; the space-time yield of the reactor can be further increased to 250% of an original design value; the continuously running period of the reactor can be improved by more than 1 time of an original period; the adjusting time of the reactor is shortened to 1/3 of an original value.
Description
Technical field
The present invention relates to fluidized-bed, especially a kind of fluidized-bed polymerization reactor that relates to.
Background technology
When carrying out the polyreaction of heat release with fluidized-bed reactor, to limit to some extent speed of reaction, so that make liberated heat be able to do in time from fluidized-bed, to migrate out, prevent the generation of fault in the fluidized-bed.A kind of method that improves the reaction heat transfer rate is that the gas that is free state with required circulation Returning reactor is compressed and cools off, and makes it to take place the condensation of part.The monomer air-flow that the liquid that is produced is recycled is carried secretly and is turned back in the reactor thereupon.This is called as the polyreaction methodology of " condensation mode ", people's such as Jenkins United States Patent (USP) 4,543,399 and 4,588,790 disclose this methodology, and this patent documentation points out that this " condensation mode " methodology can reduce the temperature of circulating current, and, under the combination of these two kinds of effects, make the space-time yield of this method apparently higher than " non-condensing pattern " because evaporation of liquid will absorb heat.The condensing liquid quantity that people such as DeChellis declare to enter fluidized-bed can substantially exceed the limit of " condensation mode " patent defined, and this is called as the polyreaction methodology of " supercool coagulates pattern ", and its space-time yield is apparently higher than " condensation mode ".
Three kinds of above-mentioned operator schemes require to use different reactor inlet devices, reactor shutdowns will be changed inlet device when the conversion of needs operator scheme.In order to address this problem and further improve the production efficiency of fluidized-bed reactor, a kind of novel reactor inlet device one director is disclosed in the Chinese patent application 85106978.This director is installed in the below of distributing plate of fluidized-bed reactor, and two gas channels that make gas enter mixing section can be provided, promptly along first gas channel that mixes locular wall and second gas channel that directly makes progress.Preferable director is a kind of annular director, and there is a through hole centre, and a upward air stream passage in central authorities is provided, and it also provides one around around the director and along the peripheral gas channel that mixes locular wall in addition.It is said, in the operation engineering of the director of this structure, by director with mix air-flow that peripheral annular second gas channel between the locular wall enters and make and mix locular wall and washed away, thereby prevent the gathering in mixing section of liquid and solid.The air-flow of mediad overdraught and periphery mixes, thereby has guaranteed in the air-flow that any liquid and/or solid matter reach more uniform distribution.
Yet the operating practice for many years of this annular director that this Unipol fluidized-bed polymerization reactor of introducing from union carbide corporation is generally adopted by us finds that this director when condensing state is operated, has following deficiency:
1) gas distribution inequality.Annular director central fluidizing gas amount is excessive, excessive velocities, recycle stream and the powder of carrying secretly thereof, liquid directly impact on the basal surface of grid distributor, when carrying bulk polymer secretly as recycle stream, less than φ 16mm sole piece shaped polymer under the effect of high-velocity stream, enter in the distribution hole, result in blockage.And in radially interior about 500mm bottom annular zone, grid distributor neighboring, logistics speed reduces, and often deposited powder causes the grid distributor zone to stop up.
2) deposited powder is tied sheet easily.Upper surface at the bottom of the annular director (promptly recycle stream flows on the end direction dorsad), relatively large because of area, logistics makes that again from two side flow this surface is one " dead band ", often deposited powder.These powder reach when being enough to make its softening bonding in the inlet stream temperature, just form identical big sheet polymer with annular director top surface area.When at condensation operation, these flaps because of impact, soaked with liquid comes off and by after the logistics impact grinding, rush at grid distributor, result in blockage.
3) the condensing agent amount ranges is little.This annular director is only limited to the scope of condensing agent consumption at 3～10% (wt), is not suitable for the use of higher condensing agent consumption.
Chinese patent 99118186.7 (application number) improves this director, this director can provide three passages that make air-flow feed mixing section at least, promptly air-flow enter reactor bottom go into interruption-forming along the mixing section wall make progress mobile first gas channel, the annular plate centre hole of flowing through to conical plate bottom, upper edge to second gas passage of side flow and directly mobile the 3rd gas channel upwards of conical plate centre hole that continues upwards to flow through.This invention prevents that the circulation gas-liquid flow by mixing locular wall from falling after rise from the mixing section wall because of gravity and wall effect, has avoided liquid at reactor bottom with mix gathering of locular wall; Another part recycle stream is by the sidewall of conical plate in the centre hole of annular plate, forms with first air-flow and shears, impacts, and breaks away from that the liquid of carrying secretly or falling after rise is carried secretly again and atomizing again thereby make, and in the gaseous stream that suspends again; Another part logistics by the annular plate centre hole continues upwards to form that the 3rd air-flow continues and first, second air-flow produces shearings, impact and mixing in mixing section, further isolated liquid is atomized again and is carried secretly.
Through practice, such method still has following shortcoming: if from the liquid film and the liquid piece content height of transport pipe, be that liquid holdup is higher, then the centre hole at the 3rd air-flow may form " liquid volume ", liquid piece and liquid twist in and are further disperseed by the air-flow in the sidewall passage in the process of whereabouts and carry secretly, the drop that produces about this redispersion is bigger usually, and the form with drop group moves upward mostly, cause the rain phenomenon in the mixing section easily, also cause the orifice of grid distributor regional area to form geyser easily.
For this reason, the present invention transforms the structure of director, actual service condition proves that director of the present invention has overcome the above-mentioned shortcoming of prior art director fully, the liquid content of recycle stream at 3～35% (wt) but equal safe and stable operation in the scope, because the increase of condensation number, be to move heat to increase, the space-time yield of reactor can be brought up to 250% of original technical capacity.
Summary of the invention
The purpose of this invention is to provide a kind of fluidized-bed polymerization reactor.
It comprises expanding reach, the straight tube of reactor reactive moieties, gas distribution grid, the gas mixing chamber of reactor upper end, in said gas mixing chamber, be provided with one or more gas flow guiding devices, this director comprises an annular plate, be provided with the inversion annular frustum of a hollow at the annular plate inner ring, the annular plate center is provided with the center striker, and is fixed by the floor of the inversion of hollow annular frustum.
Director of the present invention has been compared the following advantage with the director of prior art:
1) after the ring logistics entered mixing section, liquid phase material and powder were evenly distributed in the gas phase, and the air-flow that reduces centre hole makes the bulk polymer of carrying secretly be difficult for entering in the distribution hole directly to the impact forces of grid distributor.
2) atomizing is more even, the design of center striker and floor, increase is to the shearing-crushing effect of upward air stream, make the brin of rising/when the liquid piece bumps against the center striker, part brin/liquid piece directly becomes small droplets and is taken away by air-flow, another part brin/liquid piece has formed liquid film as thin as a wafer on the striker wall, like this at the director central core region because the atomizing of striker has just been avoided the jet phenomenon of liquid, the jet phenomenon of liquid also can not appear in the orifice of grid distributor axle center near zone.
3) the centre pilot angle of cone angle, guide angle and the center striker of the annular frustum of inversion makes the brin/liquid piece of rising be subjected to shearing, ballistic effect, form good redispersion and atomizing effect, and can avoid the formation of air-flow vortex in the sidewall passage as far as possible.Guide angle makes more uniform distribution of drop simultaneously, and can dwindle and mix the flow downward size in zone of indoor gas.
4) change guide angle in the prior art more than difficult on this cone type director, the guide angle of our this technology can design according to concrete operational condition.
5) liquid content in the ring logistics material all can safe and stable operation in 3%～35% (wt) scope, the space-time yield of reactor can further improve 250% of original design value, the continuous cycle of operation of reactor can be brought up to more than 2 times of original cycle, and the reactor adjustment time shortens to original 1/3.
Description of drawings
Fig. 1 is the fluidized-bed cross-section elevation that prior art is used;
Fig. 2 is the fluidized-bed reactor bottom inlet device that uses of the present invention and the enlarged view of director.
Embodiment
Fluidized-bed polymerization reactor, it comprises expanding reach 1, the straight tube of reactor reactive moieties 2, gas distribution grid 3, the gas mixing chamber 4 of reactor upper end, be provided with one or more gas flow guiding devices 5 in the gas mixing chamber, this director comprises an annular plate 6, be provided with the inversion annular frustum 7 of a hollow at the annular plate inner ring, the annular plate center is provided with center striker 9, and fixing by the floor 8 of the inversion of hollow annular frustum 7.
The section of the inversion of hollow annular frustum 7, floor 8 is that a drift angle is 2 (90-α) ° a isosceles triangle, α=30 °～60 ° wherein, and α=45 ° are good.
The diameter D of center striker 9
x=5～20mm, wherein D
x=15mm is good, and the internal diameter of the inversion annular frustum 7 of hollow compares D with the inlet caliber
i/ D
e=0.5～0.8, D wherein
i/ D
e=0.6 is good, and the internal diameter of annular plate 6 compares D with the inlet caliber
c/ D
e=0.8～1.2, D wherein
c/ D
e=1.0 is good, and the external diameter of annular plate 6 compares D with the inlet caliber
0/ D
e=1.4～2.2, D wherein
0/ D
e=1.8 is good.
The guide angle of the inversion of hollow annular frustum 7 is γ=10 °～40 °, and wherein γ=15 ° are good.
The centre pilot angle β of center striker 9=0 °～30 °, wherein β=5 ° are good.
As depicted in figs. 1 and 2, annular plate is fixed on the top of reactor bottom inlet by means of spacer, the inversion annular frustum of hollow is fixed on the annular plate by means of spacer, and the center striker is fixed on the concentric centre hole of inversion annular frustum of annular plate and hollow by means of floor.The recycle stream that enters from inlet device, under the guiding of annular plate periphery, form along mixing locular wall by smallest cross-sectional mobile first air-flow that makes progress, it will upwards impact from the liquid that the mixing section wall falls after rise because of gravity and wall effect, prevent that liquid is at reactor bottom with mix gathering of locular wall; Another part recycle stream forms second air-flow by the centre hole of the inversion annular frustum of hollow, be subjected to promptly continuing upwards after effect is torn to the liquid piece in center striker and floor and floor and conical plate junction, and and first air-flow in mixing section, produces shearings, the impact and the mixing, isolated liquid is atomized again and carried secretly, make any liquid and/or solid matter in the whole reactor space under the grid distributor realize more perfect mixing, and do not stay any dead angle, thereby uniform distribution fully when making air communication cross grid distributor to enter fluidized-bed.
The used catalyzer of the present invention comprises: coordination anion catalyzer, cationic catalyst, free radical catalyst.And comprise filter component or metallocenes and bimodal product catalyst.
Embodiment
The Unipol fluidized-bed olefin polymerization reactors that employing is introduced from connection carbon, director of the present invention is as illustrated in fig. 1 and 2 installed in its bottom.Under condensation mode, operate, produce new LDPE (film grade).
1. new LDPE (film grade) product service data
Reaction raw materials: ethene, 1-butylene, hydrogen
Recycle flow: 1.5*10
6Kg/hr
Content liquid in the recycle stream: 9%～26%wt
Space-time yield: 134.8kgPE/m
3* hr
2. move 12 months situation continuously:
The recycle stream stability of flow, the ripple disable phenomenon proves the director atomizing evenly.
Grid distributor pressure reduction zero growth phenomenon remains at 2700～2970kg/m
3Between, show that grid distributor does not have latch up phenomenon.
The temperature of four temperature detecting point on the grid distributor is very even, and the temperature difference between any 2 shows that grid distributor does not have stopping state, resin bed fluidized state all right less than 0.05 degree.
Instantaneous 37% (wt) that reach of total amount of liquid in the recycle stream, reactor is stable.
3. move the inspection situation after 18 months continuously.
No heat seal powder and knot sheet on the annular plate, very cleaning reaches the metalluster level.
Grid distributor lower surface neighboring radially in the 500mm annular region to whole grid distributor lower surface do not have powder deposition, hang hang, situation such as adhesion, very clean.
The hole of 2077 φ 16mm does not have obstruction on the grid distributor.
Reactor size: diameter 5.2m; Direct tube section height 14.3m
Director size: inlet caliber D
e=900mm, gas transmission caliber D
t=900mm, distribuor of fluidized bed diameter D
b=5200mm, mixing section diameter D
m=5200mm, conical plate central aperture D
i=600mm, annular plate central aperture D
c=900mm, the thick h of director
1=9.5mm, axle center member (striker) diameter D
x=20mm, the thick h of floor
a=7mm, the external profile diameter D of director big disk
0=1650mm, the high Hm=0.8*5200=4160mm of mixing section.
The result shows and uses director of the present invention not observe the operational issue of production run and to the disadvantageous effect of product.Liquid content all can safe and stable operation in 3%～35% (wt) scope in the air-flow.This shows that under so high liquid content liquid still can well be carried secretly and atomize and can be at reactor bottom not sharply and produce liquid flooding, do not find when reactor shutdowns is checked to stop up, all clean at mixing section wall and director surface owing to buildup of resin causes grid distributor.
Claims (9)
1. fluidized-bed polymerization reactor, it comprises expanding reach (1), the straight tube of reactor reactive moieties (2), gas distribution grid (3), the gas mixing chamber (4) of reactor upper end, it is characterized in that in said gas mixing chamber (4), being provided with one or more gas flow guiding devices (5), this director comprises an annular plate (6), be provided with the inversion annular frustum (7) of a hollow at the annular plate inner ring, the annular plate center is provided with center striker (9), and fixing by the floor (8) of the inversion of hollow annular frustum (7).
2. a kind of fluidized-bed polymerization reactor according to claim 1 is characterized in that the inversion annular frustum (7) of said hollow, the section of floor (8) are that a drift angle is 2 (90-α) ° a isosceles triangle, wherein α=30 °～60 °.
3. a kind of fluidized-bed polymerization reactor according to claim 2 is characterized in that the inversion annular frustum (7) of said hollow, the section of floor (8) are that a drift angle is 90 ° a isosceles triangle.
4. a kind of fluidized-bed polymerization reactor according to claim 1 is characterized in that the diameter D of said center striker (9)
x=5～20mm, the internal diameter of the inversion annular frustum (7) of hollow compares D with the inlet caliber
i/ D
e=0.5～0.8, the internal diameter of annular plate (6) compares D with the inlet caliber
c/ D
e=0.8～1.2, the external diameter of annular plate (6) compares D with the inlet caliber
0/ D
e=1.4～2.2.
5. a kind of fluidized-bed polymerization reactor according to claim 4 is characterized in that the diameter D of said center striker (9)
x=15mm, the internal diameter of the inversion annular frustum (7) of hollow compares D with the inlet caliber
i/ D
e=0.6, the internal diameter of annular plate (6) compares D with the inlet caliber
c/ D
e=1.0, the external diameter of annular plate (6) compares D with the inlet caliber
0/ D
e=1.8.
6. a kind of fluidized-bed polymerization reactor according to claim 1 is characterized in that the inversion annular frustum (7) of hollow is γ with the guide angle that the line of floor (8) is become with the axis, wherein γ=10 °～40 °.
7. a kind of fluidized-bed polymerization reactor according to claim 6 is characterized in that the inversion annular frustum (7) of hollow is γ with the guide angle that the line of floor (8) is become with the axis, wherein γ=15 °.
8. a kind of fluidized-bed polymerization reactor according to claim 1 is characterized in that center striker (9) is β with the centre pilot angle that the line of floor (8) is become with the axis, wherein β=0 °～30 °.
9. a kind of fluidized-bed polymerization reactor according to claim 8 is characterized in that center striker (9) is β with the centre pilot angle that the line of floor (8) is become with the axis, wherein β=5 °.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021544816A CN1176109C (en) | 2002-12-17 | 2002-12-17 | Fluidized bed polymerization reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021544816A CN1176109C (en) | 2002-12-17 | 2002-12-17 | Fluidized bed polymerization reactor |
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| Publication Number | Publication Date |
|---|---|
| CN1445246A CN1445246A (en) | 2003-10-01 |
| CN1176109C true CN1176109C (en) | 2004-11-17 |
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|---|---|---|---|
| CNB021544816A Expired - Fee Related CN1176109C (en) | 2002-12-17 | 2002-12-17 | Fluidized bed polymerization reactor |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482372B (en) * | 2009-07-23 | 2013-09-04 | 尤尼威蒂恩技术有限公司 | Polymerization reaction system |
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