CN1310969C - Polymerizing method for olefine - Google Patents
Polymerizing method for olefine Download PDFInfo
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- CN1310969C CN1310969C CNB2004100747938A CN200410074793A CN1310969C CN 1310969 C CN1310969 C CN 1310969C CN B2004100747938 A CNB2004100747938 A CN B2004100747938A CN 200410074793 A CN200410074793 A CN 200410074793A CN 1310969 C CN1310969 C CN 1310969C
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000000379 polymerizing effect Effects 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 152
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 96
- 239000007789 gas Substances 0.000 claims abstract description 82
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 15
- 238000005243 fluidization Methods 0.000 abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 18
- 239000005977 Ethylene Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011800 void material Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000008246 gaseous mixture Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 230000002902 bimodal effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012827 research and development Methods 0.000 description 4
- 239000012809 cooling fluid Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Polymerisation Methods In General (AREA)
Abstract
The present invention provides a polymerizing method of olefine CH2=CHR. R in the formula is hydrogen or an alkyl group, a naphthenic group or an aryl group containing 1 to 12 carbon atoms. The method comprises: carrying CH2=CHR polymerization reaction in a series connected gas phase fluidization bed polymerization reaction region under the conditions of a catalyst and the polymerization reaction. The present invention is characterized in that the series connected gas phase fluidization bed polymerization reaction region at least comprises a low speed fluidizing reaction region and at least comprises a high speed fluidizing reaction region; a polymer or a mixture generated in the low speed fluidizing reaction region is continuously or intermittently conveyed to the connected high speed fluidizing reaction region; a fluidizing speed ratio of the high speed fluidizing reaction region to the low speed fluidizing reaction region is from 2 to 50.
Description
Technical field
The present invention relates to a kind of CH that is used to prepare
2The polymerization process of=CHR olefin polymer, wherein R is hydrogen or alkyl, cycloalkyl or the aryl that contains the 1-12 carbon atom, present method comprises at least two polymerization zones that fluidizing velocity is different, can prepare the olefin polymer with wide molecular weight distribution.
Technical background
As everyone knows, in placed in-line multiple reactor or multi-reaction-area, under different polymerizing conditions, carry out olefin polymer or the multipolymer that polyreaction can obtain having wide molecular weight distribution (MWD) by controlling each reactor or reaction zone.Can utilize diverse ways to control the molecular weight of each reactor or reaction zone, for example pass through type and concentration, the concentration of molecular weight regulator and the form of polyreaction etc. of suitably selective polymerization condition, the character that changes catalyzer or concentration, polymerization single polymerization monomer.
Known method normally in placed in-line two or more polymerization reactors, is introduced first reactor with catalyzer continuously, and through after the polyreaction, polymkeric substance enters second reactor, and formed polymkeric substance is discharged outside the reactor.In each reactor, control molecular weight by molecular weight regulator such as hydrogen.In such polymerization technique, the problem that generally runs into is because technical process is longer, and the transfer of polymkeric substance between different reactor is complicated, the residence time is longer, can cause the catalyst activity loss.
Have now found that, a kind ofly be used to prepare alkene CH
2The new gas phase polymerization process of the polymkeric substance of=CHR or multipolymer, by control to differential responses district in the same reactor (or in different reactors) fluidizing velocity, and according to the different suitable polymerizing conditions of fluidizing velocity selection, can realize producing the purpose that has than the polyolefin resin of wide molecular weight distribution, and the technical process of this polymerization process is short, and production cost is lower.
Summary of the invention
A kind of alkene CH
2The polymerization process of=CHR, R is hydrogen or alkyl, cycloalkyl or the aryl that contains the 1-12 carbon atom in the formula, this method is included under catalyzer existence and the polymeric reaction condition, comprises in the placed in-line gas fluidised bed polymerisation reaction zone one and carries out CH
2The polyreaction of=CHR, it is characterized in that, described placed in-line gas fluidised bed polymerisation reaction zone comprises a fluidized reaction zone and comprise a quick fluidized reaction zone at least at a slow speed at least, polymkeric substance that fluidized reaction zone generated or mixture are delivered to continuous quick fluidized reaction zone continuously or off and at a slow speed, and fast fluidized reaction zone is 2～50 with the ratio of the fluidizing velocity of fluidized reaction zone at a slow speed.
In polymerization process of the present invention, by at least two have different fluidizing velocities, in the interconnective fluidized bed reaction zone, carry out alkene CH
2The gas phase polymerization of=CHR.Usually at a slow speed fluidized reaction zone (first reaction zone) preceding, fast fluidized reaction zone (second reaction zone) after.Catalyzer is introduced at the front end of first reaction zone, under fluidized state at a slow speed, generated polymer particle all or major part flow through this reaction zone, enter second reaction zone after the outflow, flow through under action of gravity and fast fluidized regime, the polymkeric substance that is generated discharges continuously or off and on.Fast fluidized reaction zone is 2～50 with the ratio of the fluidizing velocity of fluidized reaction zone at a slow speed, preferred 3～20.Usually, fluidization regions gas empty tower gas velocity scope is 0.01～0.3m/s at a slow speed.
In polymerization process of the present invention, fluidized reaction zone (first reaction zone) both can be positioned at the inside of quick fluidized reaction zone (second reaction zone) at a slow speed, also can be positioned at the outside of quick fluidized reaction zone (second reaction zone).
In fluidized reaction zone at a slow speed, by means of gas distributor, introduce gaseous mixture continuously from the below of polymkeric substance bed, this gaseous mixture generally comprises polymerization single polymerization monomer, molecular weight regulator (hydrogen) and optional rare gas element.In first reaction zone, comprise mixture of polymers and all or most ofly draw from the top of polymerization zone (or polymkeric substance bed), introduce second polymerization zone by gravity or gas flow.At least 75% introduces fluidized reaction zone at a slow speed in the catalyzer total amount, the adding optimum seeking site of various catalyst components is in arbitrary place introducing of fluidized reaction zone at a slow speed, more preferably introduce, also the catalyzer of small part can be added at arbitrary place of quick fluidized reaction zone (second reaction zone) at the front end (bottom) of slug flow reaction zone (first reaction zone).
Effusive polymkeric substance and gaseous mixture flow in second reaction zone fully with form continuously or off and on from first reaction zone.Can introduce the mixed gas that contains fresh polymerization single polymerization monomer in arbitrary position of second reaction zone, also can introduce the catalyzer of small part.The gaseous mixture of not participating in reaction at second polymerization zone reactor top expanding reach with separated by entrained solid, the gas outflow reactor carries out outer circulation.The gaseous mixture of outflow reactor cools off through an interchanger, turns back to reactor after the cooling again.Usually with gaseous mixture at the interchanger internal cooling to the temperature that is lower than dew point, wherein phlegma returns fluidized reaction zone and/or fluidized reaction zone at a slow speed fast, non-condensable gas all turns back to bottom the quick fluidized reaction zone.The polymkeric substance that second reaction zone is generated discharges continuously or off and on.
In polymerization process of the present invention, the operating pressure of gas fluidised bed polymerisation reaction zone is 0.5～10MPa, preferred 1.5～6MPa, and wherein fluidized reaction zone pressure should be a little more than quick fluidized reaction zone at a slow speed, and pressure equilibrium is controlled voluntarily by the resistance to flow of material.
Because in different polymerization stage, catalyzer shows different polymerization kinetics characteristics.Higher in the initial reaction stage activity of such catalysts, can obtain more polymkeric substance in the short period of time.Therefore, in polymerization process of the present invention, because the residence time in first reaction zone (slug flow reaction zone) can be shorter, and it is also less at the initial reaction stage polymer particle, so first reaction zone is programmable less, polymerization single polymerization monomer contacts polymerization reaction take place with catalyzer in this reaction zone, and the outer portion of reaction heat removes the volatilization of heat or phlegma and removes, the reactor that whole conversion zone can a similar plug flow.It is within the scope of 0.01～0.3m/s that the gas empty tower gas velocity of this fluidized reaction zone can be controlled in, preferred 0.05～0.2.Comprise and enter further polymerization in second reaction zone after mixture of polymers all or most ofly is drawn from the top of first polymerization zone (or polymkeric substance bed), because speed of reaction descends, the reaction kinetics behavior is tending towards relaxing, reactor is programmable bigger, the gas empty tower gas velocity of this fluidized reaction zone is 2～50 times of slow fluidization regions, preferred 3～20 times, generally be controlled at 0.1～1.0m/s, and only just can withdraw from most of heat by recycle gas.
Arbitrary type catalyst of using in the olefinic polyreaction all can be used for polymerization process of the present invention.For example, disclosed a large amount of in the prior art is that the catalyzer of matrix all can use having under carrier or the DNAcarrier free form with titanium, chromium, vanadium or zirconium.The specific examples of operational this class catalyzer is disclosed in Chinese patent CN85100997A, CN1258680A, CN1258683A, CN1258684A, CN1091748A, CN1330086A, CN1268520A, CN1491618A, CN1463991A.Described catalyzer can directly use, and also can add through after the prepolymerization.
In described fluidized reaction zone at a slow speed of polymerization process of the present invention and quick fluidized reaction zone, it is favourable keeping one or more rare gas elementes, and it is 5～80% of gas stagnation pressures that the amount of maintenance preferably makes the dividing potential drop sum of various rare gas elementes.Described rare gas element can be nitrogen or the paraffinic hydrocarbons that contains 2～6 carbon atoms, preferably propane.
For obtaining the molecular weight distribution broad or having the polymkeric substance of bimodal distribution, can in two reaction zones, control gas with various and form, as at the different molecular weight regulator of two reaction zone inner control and the concentration ratio of polymerization single polymerization monomer, to widen the molecular weight distribution of resulting polymers.In preparation during impact copolymer, can be in the different monomeric concentration of polymerization zone inner control different copolymer, can obtain like this multipolymer (rubber phase) matrix mutually in the extraordinary impact copolymer of dispersion.
In polymerization process of the present invention, polymerization temperature is 0～150 ℃, with 40～100 ℃ for well.
Embodiment
Two specific embodiments of the present invention by the reference accompanying drawing further specify the present invention, and accompanying drawing only is to explain rather than limit the present invention.
Fig. 1 fluidized-bed at a slow speed is positioned at the polymerizing reactor of fast fluidized bed inside
As shown in Figure 1, in a multi-region fluidized-bed reactor, comprise two reaction zones at least, first reaction zone (1) and second reaction zone (2), described first reaction zone is a drum shape fluidized-bed reactor that diameter is less, can there be expanding reach on its top or have expanding reach, the bottom is straight bucket section, is gas feed distributor (12) in the bottom of straight bucket section; Described second reaction zone is a drum shape fluidized-bed reactor that diameter is bigger, and an expanding reach (3) is arranged at its top, in straight bucket section polymer discharge system (14) is housed, and gas circulation sparger (13) is equipped with in the second reaction zone bottom;
Described first reaction zone is positioned at the inside of second reaction zone, and first reaction zone directly is opened in the second reaction zone expanding reach.
First reaction zone is equipped with gas feed device (10), and it is positioned at certain position of gas distributing device (12) bottom.Catalyzer joins catalyzer by feeding unit (9) certain position of the straight bucket section in distribution device (12) top.
Wherein the expanding reach of first reaction zone (1) upper end is a back taper type or vertical cylinder type, and the upper end of expanding reach is to open wide fully.
The top of second reaction zone (2) is provided with a gaseous mixture circulation line (4), the system (6) that it connects compressor (7), cooling system (8) and is used to introduce monomeric system (5) and introduces molecular weight regulator.
Fig. 2 fluidized-bed at a slow speed is positioned at the polymerizing reactor of fast fluidized bed outside
As shown in Figure 2, it comprises first reactor (1) and second reactor (2), and described first reactor is a drum shape fluidized-bed reactor that diameter is less, and its top is expanding reach, the bottom is straight bucket section, is gas feed distributor (12) in the bottom of straight bucket section; Described second reactor is a drum shape fluidized-bed reactor that diameter is bigger, its top is an expanding reach (3), the bottom is straight bucket section, at certain position of straight bucket section one polymer discharge system (14) is housed, and at second reactor lower part gas circulation sparger (13) is housed;
Described first reactor is positioned at the outside of second reactor, and the expanding reach of first reactor links to each other by a pipeline with the expanding reach of second reactor.
Identical with Fig. 1, first reactor is equipped with gas feed device (10), and it is positioned at certain position of gas distributing device (12) bottom.Connect a catalyst charge device (9) in described gas distributing device (12) a part, top by pipeline (11).
The top of second reactor (2) is provided with a gaseous mixture circulation line (4), the system (6) that it connects compressor (7), cooling system (8) and is used to introduce monomeric system (5) and introduces molecular weight regulator.
In Fig. 1 and Fig. 2, preferably, the inclination angle of the described first reaction zone expanding reach is 0～60 °, and the inclination angle of the second reaction zone expanding reach is 5～25 °.
The straight bucket section of described first reaction zone is 1/10～1/2 with the diameter ratio of the straight bucket section of second reaction zone.
The straight bucket section of described first reaction zone and second reaction zone is 1/3～1/1 with the diameter ratio of expanding reach.
The straight bucket section of described first reaction zone length-to-diameter ratio is 1/20～1/5.
The straight bucket section of described second reaction zone length-to-diameter ratio is 1/10～1/2.
The preparation of embodiment 1 bimodal polyethylene
Adopt poly-unit shown in Figure 3 and polymerization technique flow process shown in Figure 4.
Polymerizing reactor as shown in Figure 3.Fluidized-bed (first reaction zone at a slow speed, little fluidized-bed) is positioned at fast fluidized bed (second reaction zone, big fluidized-bed) inside, little fluidized-bed diameter is 100mm, straight bucket section highly is 1300mm, and little fluidized-bed directly is opened on big fluidized-bed upper extension section, and opening part has an inclination angle that extends out, angle is 11 °, and the expanding reach height is 100mm.Big fluidized-bed diameter is 350mm, straight bucket section highly is 1000mm, big fluidized-bed expanding reach inclination angle also is 11 °, the expanding reach height is 900mm, and what be attached thereto on expanding reach top is a settling section, and the settling section diameter is 700mm, settling section height 100mm, on settling section top is one 1/2 elipse heads, end socket center drilling, the unreacted monomer cooling heat exchanger that circulates thus.
The polymerization technique flow process as shown in Figure 4.Catalyzer is by adding above the little fluidized-bed lower gas sparger, catalyzer adopts Sinopec Beijing Research Institute of Chemical Industry's research and development, the BCG catalyzer that Aoda Shihua New Technology Development Centre, Beijing produces, present embodiment catalyst system therefor lot number is BCG-04-01.Catalyzer adds with dry powder form.Fresh reaction monomers joins the gas mixing chamber of little fluidized-bed sparger bottom, and according to the additional proportion of product different adjustment polymerization single polymerization monomer and molecular weight regulator and comonomer, each concentration of component is by online gas chromatographic measurement, and the reaction gas composition sees Table 1.Reaction gas enters conversion zone (little fluidized-bed) by gas distributor, contacts polymerization reaction take place at conversion zone with catalyzer.Little fluidized-bed is fluidisation at a slow speed, and gas void tower gas speed control is built in 0.09m/s, and polymerization temperature is controlled at about 80 ℃, polymerization pressure 2.35MPa, and polyreaction is more violent, and polymerization reaction heat is mainly removed by evaporating.Be used to remove the conversion zone (straight bucket section) that hot liquid directly sprays into little fluidized-bed, be uniformly dispersed in order to make polymkeric substance-reaction gas-cooling fluid, can add a stirring at conversion zone, stirring rake adopts scrapes wall design, and rotating speed is 15 rev/mins.Unreacted monomer, cooling fluid Volatile Gas enter big fluidized-bed and participate in circulation, and the motion class of polymkeric substance in little fluidized-bed is similar to the series connection of a piston flow reactor or several continuous stir reactors, enters big fluidized-bed through reacting the post polymerization thing after a while.
Polymkeric substance, unreacted monomer and fresh monomer from little fluidized-bed are mixed the continuation reaction in big fluidized-bed (second reaction zone), in order to obtain the polyethylene of bimodal or wide distribution, control gas composition difference in two reaction zones, the material ratio of in the present embodiment little fluidized-bed (first reaction zone) is that hydrogen/ethylene/butylene mol ratio equals 0.86/100/32.3, and big fluidized-bed (second reaction zone) material ratio hydrogen/ethylene/butylene mol ratio equals 19.1/100/26.6.Big fluidized-bed (second reaction zone) is a fast fluidization, and gas empty tower gas velocity scope is 0.61m/s, and polymerization reaction heat is mainly removed by circulation gas.In order to keep bed temperature, there is a large amount of gas to participate in circulation and removes heat, polymerization temperature is controlled at 85 ℃, reaction pressure is more lower slightly than little fluidized-bed, be 2.34MPa, unreacted monomer and flow out big fluidized-bed by the cooling fluid Volatile Gas that little fluidized-bed comes and enter cooling heat exchanger, the part that is condensed into liquid is returned little fluidized-bed with pump and is removed heat, and uncooled portion gas turns back to big fluidized bed circulation by recirculation blower and removes heat.
The material ratio of little fluidized-bed (first reaction zone): hydrogen/ethylene/butylene mol ratio is 0.86/100/32.3, and gas void tower gas speed control is built in 0.09m/s, and polymerization temperature is controlled at 80 ℃, polymerization pressure 2.35MPa.
The material ratio of big fluidized-bed (second reaction zone): hydrogen/ethylene/butylene mol ratio is 19.1/100/26.6, and gas void tower gas speed control is built in 0.61m/s, and polymerization temperature is controlled at 85 ℃, polymerization pressure 2.34MPa.
By being controlled at the residence time ratio of two reaction zones, the polymkeric substance that obtains in little fluidized-bed (first reaction zone) accounts for 10% of overall yield, the polymkeric substance that obtains in big fluidized-bed (second reaction zone) accounts for 90% of overall yield, and the gained molecular weight of polyethylene is distributed as Mw/Mn=11.06.
Table 1
| Little fluidized-bed | Big fluidized-bed | |
| Reactor: | ||
| Fluidized-bed diameter (mm) | 100 | 350 |
| Fluidisation section height (mm) | 1300 | 1000 |
| Expanding reach height (mm) | 100 | 900 |
| The expanding reach inclination angle (°) | 11 | 11 |
| Settling section height (mm) | - | 100 |
| Settling section diameter (mm) | - | 700 |
| Greatly/rill bed position relation | The rill berth is in big fluidized-bed inside | |
| Inner member | Stirring is arranged | - |
| Polymeric reaction condition: | ||
| Temperature of reactor (℃) | 80 | 85 |
| Reactor pressure (MPa) | 2.35 | 2.34 |
| Mixing speed (rpm) | 15 | - |
| Reactor empty tower gas velocity (m/s) | 0.09 | 0.61 |
| Amount of liquid in the air-flow (wt%) | 29.5 | 6.5 |
| Fluidisation loose density (kg/m 3) | 355.5 | 307.5 |
| Productive rate (kg/hr) | 0.5 | 4.5 |
| Gas composition in the reactor: | ||
| Ethene (mol%) | 46.5 | 32.0 |
| Butene-1 (mol%) | 15.0 | 8.5 |
| Hydrogen (mol%) | 0.4 | 6.1 |
| Nitrogen (mol%) | 19.4 | 43.2 |
| Propane (mol%) | 18.5 | 10.0 |
| Ethane (mol%) | 0.2 | 0.2 |
| Methane (mol%) | - | - |
| The polymerisate feature: | ||
| Melting index (g/10min) | 1.90 | |
| Resin density (kg/m 3) | 918.0 | |
| Median size (mm) | 1.05 | |
| Tap density (kg/m 3) | 411.7 | |
The preparation of embodiment 2 impact polypropylenes
With embodiment 1, adopt poly-unit shown in Figure 3 and polymerization technique flow process shown in Figure 4.
Catalyzer adopts Sinopec Beijing Research Institute of Chemical Industry's research and development, the N type catalyzer that Aoda Shihua New Technology Development Centre, Beijing produces, present embodiment catalyst system therefor lot number is N-C-01-13, and the Catalyst Production method is seen patent CN85100997A.Catalyzer at first is made into a certain proportion of paste with white oil, and wherein catalyst content is 30wt%,, and is carried secretly by the certain amount of fluid propylene and to enter reactor catalyzer paste injecting catalyst opening for feed with screw metering pump.Other are with embodiment 1, and reaction conditions and polymer features see Table 2.
The material ratio of little fluidized-bed (first reaction zone): hydrogen/ethylene/propene mol ratio is 0.61/0.12/100, and gas void tower gas speed control is built in 0.08m/s, and polymerization temperature is controlled at 66 ℃, polymerization pressure 2.31MPa.
The material ratio of big fluidized-bed (second reaction zone): hydrogen/ethylene/propene mol ratio is 6.2/14.4/100, and gas void tower gas speed control is built in 0.59m/s, and polymerization temperature is controlled at 70 ℃, polymerization pressure 2.30MPa.
By being controlled at the residence time ratio of two reaction zones, the polymkeric substance that obtains in little fluidized-bed (first reaction zone) accounts for 19% of overall yield, the polymkeric substance that obtains in big fluidized-bed (second reaction zone) accounts for 81% of overall yield, and ethylene content is 9.1wt% in the resulting polymers.
Table 2
| Little fluidized-bed | Big fluidized-bed | |
| Reactor: | ||
| Fluidized-bed diameter (mm) | 100 | 350 |
| Fluidisation section height (mm) | 1300 | 1000 |
| Expanding reach height (mm) | 100 | 900 |
| The expanding reach inclination angle (°) | 11 | 11 |
| Settling section height (mm) | - | 100 |
| Settling section diameter (mm) | - | 700 |
| Greatly/rill bed position relation | The rill berth is in big fluidized-bed inside | |
| Inner member | Stirring is arranged | - |
| Polymeric reaction condition: | ||
| Temperature of reactor (℃) | 66 | 70 |
| Reactor pressure (MPa) | 2.31 | 2.30 |
| Mixing speed (rpm) | 15 | - |
| Reactor empty tower gas velocity (m/s) | 0.08 | 0.59 |
| Amount of liquid in the air-flow (wt%) | 85 | 15 |
| Fluidisation loose density (kg/m 3) | 375 | 310 |
| Productive rate (kg/hr) | 2.0 | 8.5 |
| Gas composition in the reactor: | ||
| Ethene (mol%) | 0.1 | 10.3 |
| Propylene (mol%) | 86.6 | 71.4 |
| Propane (mol%) | 10.0 | 10.7 |
| Hydrogen (mol%) | 0.53 | 4.4 |
| Nitrogen (mol%) | 2.77 | 3.2 |
| The polymerisate feature: | ||
| Melting index (g/10min) | 1.65 | |
| Ethylene content (wt%) | 9.1 | |
| Median size (mm) | 0.816 | |
| Tap density (kg/m 3) | 430.5 | |
The preparation of embodiment 3 bimodal polyethylenes
Adopt poly-unit shown in Figure 5 and polymerization technique flow process shown in Figure 6, other polymerizing conditions and resulting polymers the results are shown in Table 3.
Catalyzer adopts Sinopec Beijing Research Institute of Chemical Industry's research and development, the BCG catalyzer that Aoda Shihua New Technology Development Centre, Beijing produces, and present embodiment catalyst system therefor lot number is BCG-04-01.Catalyzer adds with dry powder form.Other are with embodiment 1, and reaction conditions and polymer features see Table 3.
The material ratio of little fluidized-bed (first reaction zone): hydrogen/ethylene/butylene mol ratio is 0.89/100/30.9, and gas void tower gas speed control is built in 0.10m/s, and polymerization temperature is controlled at 80 ℃, polymerization pressure 2.35MPa.
The material ratio of big fluidized-bed (second reaction zone): hydrogen/ethylene/butylene mol ratio is 19/100/29.4, and gas void tower gas speed control is built in 0.65m/s, and polymerization temperature is controlled at 85 ℃, polymerization pressure 2.34MPa.
By being controlled at the residence time ratio of two reaction zones, the polymkeric substance that obtains in little fluidized-bed (first reaction zone) accounts for 17% of overall yield, the polymkeric substance that obtains in big fluidized-bed (second reaction zone) accounts for 83% of overall yield, and the gained molecular weight of polyethylene is distributed as Mw/Mn=15.4.
Table 3
| Little fluidized-bed | Big fluidized-bed | |
| Reactor: | ||
| Fluidized-bed diameter (mm) | 100 | 350 |
| Fluidisation section height (mm) | 1300 | 1000 |
| Expanding reach height (mm) | 100 | 900 |
| The expanding reach inclination angle (°) | 11 | 11 |
| Settling section height (mm) | - | 100 |
| Settling section diameter (mm) | - | 700 |
| Greatly/rill bed position relation | The rill berth is in big fluidized-bed outside | |
| Inner member | Stirring is arranged | - |
| Polymeric reaction condition: | ||
| Temperature of reactor (℃) | 80 | 85 |
| Reactor pressure (MPa) | 2.35 | 2.34 |
| Mixing speed (rpm) | 15 | - |
| Reactor empty tower gas velocity (m/s) | 0.10 | 0.65 |
| Amount of liquid in the air-flow (wt%) | 28.4 | 6.3 |
| Fluidisation loose density (kg/m 3) | 350.0 | 304.5 |
| Productive rate (kg/hr) | 0.9 | 4.5 |
| Gas composition in the reactor: | ||
| Ethene (mol%) | 47.0 | 31.0 |
| Butene-1 (mol%) | 14.5 | 9.1 |
| Hydrogen (mol%) | 0.42 | 5.9 |
| Nitrogen (mol%) | 19.0 | 42.9 |
| Propane (mol%) | 18.9 | 10.9 |
| Ethane (mol%) | 0.2 | 0.2 |
| Methane (mol%) | - | - |
| The polymerisate feature: | ||
| Melting index (g/10min) | 2.10 | |
| Resin density (kg/m 3) | 917.5 | |
| Median size (mm) | 1.06 | |
| Tap density (kg/m 3) | 412.5 | |
The preparation of embodiment 4 impact polypropylenes
With embodiment 3, adopt poly-unit shown in Figure 5 and polymerization technique flow process shown in Figure 6, other polymerizing conditions and resulting polymers the results are shown in Table 4.
Catalyzer adopts Sinopec Beijing Research Institute of Chemical Industry's research and development, the DQ catalyzer that Aoda Shihua New Technology Development Centre, Beijing produces, present embodiment catalyst system therefor lot number is DQ-03-85, and the Catalyst Production method is seen patent CN1330086A.Catalyst preparation and method for implanting are with embodiment 2, and reaction conditions and polymer features see Table 4.
The material ratio of little fluidized-bed (first reaction zone): hydrogen/ethylene/propene mol ratio is 0.59/0.12/100, and gas void tower gas speed control is built in 0.09m/s, and polymerization temperature is controlled at 67 ℃, polymerization pressure 2.31MPa.
The material ratio of big fluidized-bed (second reaction zone): hydrogen/ethylene/propene mol ratio is 6.5/16.3/100, and gas void tower gas speed control is built in 0.62m/s, and polymerization temperature is controlled at 70 ℃, polymerization pressure 2.30MPa.
By being controlled at the residence time ratio of two reaction zones, the polymkeric substance that obtains in little fluidized-bed (first reaction zone) accounts for 26% of overall yield, the polymkeric substance that obtains in big fluidized-bed (second reaction zone) accounts for 74% of overall yield, and ethylene content is 10.5wt% in the resulting polymers.
Table 4
| Little fluidized-bed | Big fluidized-bed | |
| Reactor: | ||
| Fluidized-bed diameter (mm) | 100 | 350 |
| Fluidisation section height (mm) | 1300 | 1000 |
| Expanding reach height (mm) | 100 | 900 |
| The expanding reach inclination angle (°) | 11 | 11 |
| Settling section height (mm) | - | 100 |
| Settling section diameter (mm) | - | 700 |
| Greatly/rill bed position relation | The rill berth is in big fluidized-bed outside | |
| Inner member | Stirring is arranged | - |
| Polymeric reaction condition: | ||
| Temperature of reactor (℃) | 67 | 70 |
| Reactor pressure (MPa) | 2.31 | 2.30 |
| Mixing speed (rpm) | 15 | - |
| Reactor empty tower gas velocity (m/s) | 0.09 | 0.62 |
| Amount of liquid in the air-flow (wt%) | 84 | 16.5 |
| Fluidisation loose density (kg/m 3) | 374 | 309 |
| Productive rate (kg/hr) | 2.5 | 7.0 |
| Gas composition in the reactor: | ||
| Ethene (mol%) | 0.1 | 11.5 |
| Propylene (mol%) | 86.5 | 70.5 |
| Propane (mol%) | 9.5 | 10.5 |
| Hydrogen (mol%) | 0.51 | 4.6 |
| Nitrogen (mol%) | 3.39 | 2.9 |
| The polymerisate feature: | ||
| Melting index (g/10min) | 1.8 | |
| Ethylene content (wt%) | 10.5 | |
| Median size (mm) | 1.96 | |
| Tap density (kg/m 3) | 435.0 | |
Although invention has been described and explanation by specific embodiments of the present invention, but those of ordinary skills will understand is that, the present invention is applicable to the various changes that need not in this explanation, for example, use the active catalyzer of increase to increase productivity, or reduce temperature of cycling stream etc. by refrigeration plant, all fall within the scope of the present invention.Therefore, in order to determine scope of the present invention, must be with reference to appended claim.
Claims (13)
1, alkene CH
2The polymerization process of=CHR, R is hydrogen or alkyl, cycloalkyl or the aryl that contains 1-12 carbon atom in the formula, this method is included under catalyzer existence and the polymeric reaction condition, comprises in the placed in-line gas fluidised bed polymerisation reaction zone one and carries out CH
2The polyreaction of=CHR, it is characterized in that, described placed in-line gas fluidised bed polymerisation reaction zone comprises a fluidized reaction zone and comprise a quick fluidized reaction zone at least at a slow speed at least, polymkeric substance that fluidized reaction zone generated or mixture are delivered to continuous quick fluidized reaction zone continuously or off and at a slow speed, and fast fluidized reaction zone is 2～50 with the ratio of the fluidizing velocity of fluidized reaction zone at a slow speed.
2, polymerization process according to claim 1, wherein fast fluidized reaction zone is 3～20 with the ratio of the fluidizing velocity of fluidized reaction zone at a slow speed.
3, polymerization process according to claim 1, wherein fluidized reaction zone gas empty tower gas velocity scope is 0.01～0.3m/s at a slow speed.
4, polymerization process according to claim 1, at least 75% introduces fluidized reaction zone at a slow speed in the catalyzer total amount.
5, polymerization process according to claim 1 is in fluidized reaction zone at a slow speed, by means of gas distributor, introduce polymerization single polymerization monomer from the below of polymkeric substance bed, polymkeric substance that is generated or mixture are drawn from the top of polymerization zone or polymkeric substance bed, enter quick fluidized reaction zone.
6, polymerization process according to claim 1, in fluidized reaction zone at a slow speed, partially polymerized at least reaction heat is removed by polymerization single polymerization monomer that is frozen state or the volatilization of other inert substances.
7, polymerization process according to claim 1, unreacted monomer and other inert liq volatile matters flow into quick fluidized reaction zone continuously or off and on polymkeric substance in fluidized reaction zone at a slow speed.
8, polymerization process according to claim 1 in quick fluidized reaction zone, is introduced fresh polymerization single polymerization monomer in arbitrary position, unreacted gas the top of reaction zone and solids constituent from and flow out, the polymkeric substance that is generated discharges continuously or off and on.
9, polymerization process according to claim 1, wherein be cooled to below the temperature of dew point from quick fluidized reaction zone effluent air mixture, wherein phlegma returns fluidized reaction zone and/or fluidized reaction zone at a slow speed fast, and non-condensable gas all turns back to quick fluidized reaction zone bottom.
10, polymerization process according to claim 1, wherein the operating pressure of gas fluidised bed polymerisation reaction zone is 0.5～10MPa.
11, polymerization process according to claim 1, wherein there is at least a rare gas element in the gas fluidised bed polymerisation reaction zone, and its dividing potential drop sum is 5～80% of a gas stagnation pressure.
12. polymerization process according to claim 11, wherein said rare gas element are nitrogen or the paraffinic hydrocarbons that contains 2～6 carbon atoms.
13, polymerization process according to claim 1, wherein said catalyzer comprises the reaction product of an aluminum alkyls and a titanium-containing catalyst component.
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| CN102050892B (en) * | 2009-10-27 | 2013-03-27 | 中国石油化工股份有限公司 | Method for controlling production of broad-distribution polyolefin |
| CN102477111B (en) * | 2010-11-30 | 2013-08-14 | 中国石油化工股份有限公司 | Method for hydrogenating polymer |
| CN105617947B (en) * | 2014-10-27 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of fixed bed-fluidized bed reactor and its application |
| CN108264599A (en) * | 2018-03-20 | 2018-07-10 | 南京金陵塑胶化工有限公司 | Batch process slurry process prepares the production system and technique of ultra-high molecular weight polyethylene |
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