WO2014137177A1 - 올레핀의 중합 방법 - Google Patents
올레핀의 중합 방법 Download PDFInfo
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- WO2014137177A1 WO2014137177A1 PCT/KR2014/001872 KR2014001872W WO2014137177A1 WO 2014137177 A1 WO2014137177 A1 WO 2014137177A1 KR 2014001872 W KR2014001872 W KR 2014001872W WO 2014137177 A1 WO2014137177 A1 WO 2014137177A1
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- Prior art keywords
- reactor
- height
- fluidized bed
- olefin
- polymerization
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 46
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 43
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 65
- 229920000098 polyolefin Polymers 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 239000004711 α-olefin Substances 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
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- 239000005977 Ethylene Substances 0.000 description 17
- 238000005243 fluidization Methods 0.000 description 10
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a polymerization method of olefins, and more particularly, to a polymerization method of olefins capable of polymerizing polyolefins with high productivity while suppressing reactor sheeting and caking.
- FIG. 1 is a schematic diagram of a conventional fluidized bed polymerization reactor in which olefin polymerization is performed.
- the inside of the fluidized bed polymerization reactor 10 is a reaction zone A in which olefins are polymerized and a free zone B located in the upper part of the reaction zone A, where solid polymer particles are mostly separated from the gas phase. ).
- the reaction zone (A) is limited to the vertical cylindrical portion (a) of the reactor (10), in order to maintain a fluidized bed of polyolefin polymerized in the reaction zone (A),
- the stream is fed continuously to the inlet 11 at the bottom of the reactor 10.
- the unreacted monomers of the reaction gas stream are discharged through an outlet 13 located at the top of the reactor 10, and after residual particles are removed and cooled from the discharged reaction gas, the inlet 11 under the reactor 10 is again opened. Is sent back to the bottom of the polymer layer.
- the polymer (product) polymerized in the reactor 10 is continuously removed from the fluidized bed.
- reference numeral 14 denotes a catalyst or prepolymer inlet
- reference numeral 12 denotes a gas dispersion plate.
- FIG. 2 is a schematic view of another type of fluidized bed polymerization reactor in which olefin polymerization is carried out.
- the polymerization reactor shown in FIG. 2 is an internal circulating fluidized bed reactor 10 for circulating solid particles (polyolefin) through a draft tube 20 provided inside the fluidized bed A.
- the inner circulating fluidized bed reactor 10 is divided into two polymerization zones by a draft tube 20, and the riser region in which the polyolefin polymer is moved upwards under high speed fluidization conditions is grown inside the draft tube 20.
- the outside of the draft tube 20 forms an annulus region in which the polyolefin polymer passing through the riser region is moved downward by gravity.
- a conventional fluidized bed polymerization reactor 10 used for the polymerization of olefins has a lower cylindrical portion (a) in which a reaction zone (A) is formed and an upper cone shape in which a free zone (B) is formed. Part (b).
- 3,984,387 discloses a method of suppressing formation of locally superheated polymer particles by injecting an inert gas such as nitrogen or helium together with a monomer gas into a polymerization reactor, but in this case, the partial pressure of the monomer in the reactor is disclosed.
- an inert gas such as nitrogen or helium
- the partial pressure of the monomer in the reactor is disclosed.
- the catalytic activity is reduced by reducing the.
- US Patent Nos. 4,650,841 and 4,551,509 disclose methods for preventing fouling by reducing catalytic activity by using an inactive agent
- US Pat. No. 5,733,988 as an antifouling agent as alcohol, ether, ammonia The use of sulfur-containing materials is disclosed, and US Pat. No.
- 5,804,678 discloses a method of preventing fouling by adding substances of water, alcohols and ketones.
- the above techniques have a disadvantage in that the catalytic activity is lowered, thereby preventing the aggregation of particles, and thus the reaction activity is lowered.
- U.S. Patent No. 5,473,028 discloses a method of preventing fouling without reducing catalytic activity, and a method of adding supported alumoxane or solid alumoxane to a reactor, but since alumoxane is expensive, it is economical for commercial applications. That comes with difficulty.
- U. S. Patent No. 4,003, 712 discloses a vertical fluidized bed reactor having a cylindrical bottom followed by a short truncated cross section and an additional cylindrical bottom having a larger cross section than the cylindrical bottom.
- the polymerization reaction is carried out at the bottom, but the polymer particles are separated from the gas stream at the top in the stable zone.
- International Publication No. 96/04322 European Patent Publication No. 0301 872, European Patent Publication No. 0 475 603, European Patent Publication No. 0 728 771, etc., solve the problem of product coagulation based on the geometry of the reactor.
- U. S. Patent No. 5,428, 118 also discloses a method of feeding a stream of air along the walls of the free zone in a tangential direction to suppress sheeting and caking of the product or to remove caked particles, in which case
- the structure of the reactor becomes complicated.
- a common feature of the above mentioned methods is that the fluidized bed A is always located in the cylindrical part a of the reactor.
- Another object of the present invention is to provide a polymerization method of olefins capable of polymerizing polyolefins with high productivity while suppressing reactor sheeting and caking.
- the present invention comprises the steps of supplying a circulating gas containing at least one alpha-olefin and an inert gas to the reactor; In the reaction zone inside the reactor, polymerizing the alpha-olefin into a polyolefin; And evacuating the resulting polyolefin polymer from the reactor, wherein the reactor is located at the lower cylindrical portion (a) and the upper cylindrical portion (a), the upper conical portion of which is open upward (b), the inclination angle (s) of the upper conical portion (b) with respect to the vertical line is 4 to 7 degrees, the reaction zone (A) and the reaction inside the reactor is a fluidized bed region in which olefins are polymerized It is divided into a free zone (B) located above the zone (A) and in which the solid polyolefin particles are separated from the gas phase, and the height of the fluidized bed is at least the height of the lower cylindrical portion (a), and 80 of the height of the upper conical portion (
- the polyolefin can be polymerized with high productivity while suppressing the sheeting and caking phenomena in the reactor which are often generated in the fluidized bed polymerization reaction.
- FIG. 1 is a schematic diagram of a conventional fluidized bed polymerization reactor in which olefin polymerization is performed.
- Figure 2 is a schematic diagram of another conventional fluidized bed polymerization reactor in which olefin polymerization is performed.
- FIG 3 is a view showing an example of a fluidized bed polymerization reactor to which the polymerization method of olefins according to the present invention can be applied.
- FIG. 4 is a view showing another example of a fluidized bed polymerization reactor to which the polymerization method of olefins according to the present invention can be applied.
- the same reference numerals are assigned to components having the same or similar functions.
- the step of supplying a circulating gas containing at least one alpha ( ⁇ ) -olefin and an inert gas to the reactor in the reaction zone inside the reactor, the alpha-olefin is polymerized into polyolefin And evacuating the resulting polyolefin polymer from the reactor.
- the reactor 10 to which the polymerization method of the present invention may be applied includes (i) a lower cylindrical portion (a) and (ii) the lower cylindrical portion (a) located below the reactor 10. It is located at the top of the upper portion, and consists of an upper conical portion (b) of the open shape.
- reaction zone (A) which is a fluidized bed zone in which olefins are polymerized
- free zone (B) which is located above the reaction zone (A), from which solid polyolefin particles are separated from the gas phase.
- an inlet 11 through which a circulating gas (reactor gas) containing alpha-olefin and an inert gas is continuously supplied is formed in the lower portion of the reactor 10, and the upper portion of the reactor 10 is provided.
- the gas distribution plate 12 for dispersing the circulating gas may be further provided inside the reactor 10. The polymer (product) polymerized in the reactor 10 is continuously removed from the fluidized bed A through a polyolefin outlet (not shown).
- the fluidized bed A in which the polymerization reaction is carried out is formed to extend to the upper conical part b. That is, the uppermost end of the fluidized bed A is formed in the upper conical portion b.
- the position at the top of the fluidized bed A i.e., the height of the fluidized bed A, should be at least equal to the height of the lower cylindrical part (a) and not more than 80% of the height of the upper conical part (b).
- the upper conical part (b) is in the range of 30% of the height.
- the TDH means that the concentration of particles decreases toward the upper side in the fluidized bed A, and the height does not fall any more. If the height of the fluidized bed (A) is too high, the reactor gas due to the sheeting tends to occur because the circulating gas and the polyolefin particles are mixed at a gas linear velocity significantly lower than the gas linear velocity in the lower cylindrical portion (a). On the other hand, if the height of the fluidized bed (A) is too low, there is a risk that the sheeting and caking phenomenon occurs in the inclined portion of the upper conical portion (b) to contaminate the reactor (10).
- the gas flow rate in the polymerization zone i.e. reaction zone A
- the gas flow rate in the polymerization zone should be adjusted to smoothly remove the heat of reaction and prevent the formation of fine particles by interparticle friction.
- the operation should be performed above the minimum fluidization rate.
- the minimum fluidization rate can be calculated by the Ergen equation (1955) of Equation 1 below or by the Wen and Yu Equation (1966) of Equation 2.
- Equation 1 Is the minimum fluidization rate (m / s), Ar is the Archimedes constant, ⁇ is the viscosity of the gas (cP), d p is the particle diameter (m), and ⁇ p is the particle density (g / cc).
- Equation 2 Is the porosity at the minimum fluidization rate, Is the sphericity of the particles, ⁇ g is the gas density (g / cc), g is the gravitational acceleration, ⁇ , d p , , And ⁇ p are as defined in Equation 1 above.
- the terminal velocity in the gas phase is based on the Kuunii and Levenspiel (1969) relations according to the flow rate of the gas, and the Haider and Levenspiel (4) 1989).
- Equation 3 Is the end velocity of the particle, Re p represents the Reynolds number of the particle, the remaining symbols are as defined in equation (2).
- Equation 4 Represents the compensated particle diameter when the particle is not in the form of a sphere, Is a simplified terminal speed that can easily calculate the terminal speed when the particle is not a sphere, the remaining symbols are as defined in equation (2).
- the stable velocity is the flow rate of the circulating gas in the reaction zone (A) is higher than the minimum fluidization rate, and is less than twice the flow rate of the terminal speed. to be.
- the flow rate of the circulating gas in the reaction zone A is 0.1 m / sec to 1.5 m / sec, preferably 0.2 m / sec to 1.2 m / sec.
- the polymerization reaction proceeds in a state where the fluidization of the particle is less than the minimum fluidization rate, the temperature of the polymerized polymer increases above the melting point, the sheeting is generated, stable operation This may be difficult.
- the flow rate of the circulating gas is too fast, most of the polymer particles circulate through the circulation pipe and the heat exchanger instead of the reaction zone A, causing excessive static electricity, causing pipe caking, heat exchanger plugging, and the like. In addition, there is a risk of stabilization.
- the inclination angle s of the upper conical portion b with respect to the vertical line is increased. 4 to 7 degrees, preferably 5 to 6 degrees. If the inclination angle s is less than 4 degrees, since the height of the cylinder is small, relatively many polymers are located in the upper conical portion b, and the gas linear velocity along the height is lowered. When the linear velocity of the gas is lowered, heat transfer is insufficient in the upper portion of the fluidized bed A, and there is a fear that particle masses are generated by the hot spot.
- the inclination angle (s) exceeds 7 degrees, the height of the fluidized bed is limited to the cylindrical portion, or the linear velocity of the gas is sharply increased by this, the aggregation phenomenon such as sheeting, caking, etc. that are common in the fluidized bed reactor This may occur. Therefore, in order to prevent sheeting and caking, it is necessary to keep the inclination angle s of the upper conical portion b to be 4 to 7 degrees.
- the cross section of the lower cylindrical portion (a) and the upper conical portion (b) is preferably circular, but may have various cross-sectional shapes, such as oval and hexagon, as necessary.
- the height ratio of the total height (a + b): the lower cylindrical portion (a) of the reactor 10 is preferably 1: 0.2 to 0.85, more preferably 1: 0.5 to 0.7. to be.
- reactant aggregation such as sheeting and caking may occur. There is.
- FIG. 4 is a view showing another example of a fluidized bed polymerization reactor to which the polymerization method of olefins according to the present invention can be applied.
- the fluidized bed polymerization reactor 10 shown in FIG. 4 is an internal circulating fluidized bed for forcibly circulating the polymerized polyolefin particles through a draft tube 20 installed inside the fluidized bed A, similarly to the fluidized bed polymerization reactor shown in FIG. 2. It is a polymerization reactor.
- a first circulating gas inlet 11 for supplying a circulating gas into the fluidized bed A is connected to a lower portion of the draft pipe 20, and polyolefin particles under the fluidized bed A are introduced into the draft pipe 20.
- a through hole 20a is formed below the draft pipe 20 to allow the inflow.
- the circulation gas and the polyolefin particles are discharged into the fluidized bed A from the top of the draft pipe 20.
- the circulation gas and the polyolefin particle discharge portion of the draft tube 20 is preferably located at the boundary between the lower cylindrical portion (a) and the upper conical portion (b). Therefore, as indicated by the arrow of FIG. 4, the circulating gas introduced from the first circulating gas inlet 11 and the polyolefin particles (polymer) introduced through the through hole 20a are formed inside the draft pipe 20. It moves upward in the upward direction, is discharged from the top of the draft pipe 20, and moved downward in the downward direction from the outside of the draft pipe 20, thereby circulating inside in the fluidized bed A.
- the fluidized bed polymerization reactor 10 is divided into two polymerization zones by the draft tube 20, and inside the draft tube 20, a riser in which the growing polyolefin polymer rises and moves under high speed fluidization conditions. ), And the outside of the draft tube 20 forms an annulus region in which the polyolefin polymer passing through the riser region moves downward by gravity.
- the polyolefin polymer that has passed through the annular region is introduced into the lower portion of the riser region and polymerized while circulating through the riser region and the annular region.
- a second circulating gas inlet 21 may be formed on the sidewall of the reactor 100 to inject a second circulating gas (reactor gas) into an annulus region inside the reactor 10. .
- the polymerization method of the olefin according to the present invention can be applied to various types of fluidized bed polymerization reactors, such as a reactor in which an annular dispersion plate is further formed, in addition to the fluidized bed polymerization reactor of the types shown in FIGS. 3 and 4.
- fluidized bed polymerization reactors such as a reactor in which an annular dispersion plate is further formed, in addition to the fluidized bed polymerization reactor of the types shown in FIGS. 3 and 4.
- Specific examples of such a polymerization reactor are disclosed in detail, for example, in Patent Registration Nos. 10-0999543, 10-0981612, and the like, which are incorporated herein by reference.
- the internal circulation of By inducing the internal circulation of, it causes a washing phenomenon of the upper conical portion (b), it is possible to further prevent the sheeting and caking of the polyolefin particles.
- the flow of the circulating gas is interrupted, the bubbles of the circulating gas are broken, and the size is reduced, thereby circulating.
- the reaction productivity is improved.
- the solid / gas ratio in the inlet portion of the draft tube 20 is higher than the general fluidized bed reactor, the gas content in the discharged polymer particles is less, so that the after-treatment device such as a dryer, degassing equipment (degassing equipment) It can reduce volume and reduce energy and equipment costs.
- the flow rate of the circulating gas supplied to the annular region and the riser region it is possible to adjust the circulation amount of the solid, it is possible to freely control the activity, the production amount and the like of the reactor (10).
- the polymer hold-up of the reactor 10 can be kept higher than that of a general fluidized bed reactor while suppressing the entrainment rate of the polymer, and the length (L) of the reactor 10 can be maintained. Since the influence of) / diameter (D) ratio is small, free reactor design is possible.
- a condensing agent into the reaction zone (A) when operating in the supercondensed mode (Supercondensed mode, US Patent No. 5,352,749) or condensed mode (Condensed mode, US Patent 4,543,399), the flow rate in the draft tube 20 This fast, supercondensing mode operation is possible by injecting a condensate, without special equipment.
- the process of the present invention can be applied to the polymerization of various polyolefins.
- polymers obtainable by the process of the present invention include (1) high density polyethylene (HDPE having a relative density greater than 0.940) consisting of ethylene homopolymer or a copolymer of ⁇ -olefins having 3 to 14 carbon atoms and ethylene, ( 2) low density (LLDPE having a relative density of less than 0.940), ultra low density and extremely low density (VLDPE and ULDPE having a relative density of 0.920 to 0.880) consisting of a copolymer of at least one C3-C14 alpha-olefin and ethylene Linear polyethylene, (3) an elastomeric copolymer of ethylene and propylene having a content of about 30 to 70% by weight of units derived from ethylene, or a small amount of an elastomeric terpolymer of diene and propylene and ethylene, (4) propylene and ethylene and / Or crystalline
- Alpha-olefins and inert gas used in the present invention is a raw material for the conventional olefin polymerization
- R is hydrogen or a hydrocarbon radical of 1 to 12 carbon atoms
- the inert gas may be selected from the group consisting of nitrogen and aliphatic hydrocarbons having 2 to 6 carbon atoms.
- the polymerization method of the olefin which concerns on this invention can use a normal metallocene catalyst as a catalyst component.
- a separate olefin polymerization reactor (bulk or gas phase, fluidized bed or fixed bed reactor) is further installed to perform polymerization of olefins in a continuous multistage process.
- a multi-step method may be used that performs two or more steps with the method of the present invention.
- a fluidized bed reactor as shown in FIG. 4 was used, using a di (n-butyl) cyclopentadienyl zirconium dichloride (di (n-Butyl) CpZrCl 2 ) dry metallocene supported catalyst supported on silica.
- the fluidized bed consists of polymer granules and reactants (ethylene and 1-hexene (comonomer)), hydrogen (molecular weight regulator) and ethane (inert gas) were introduced over the reactor bed into the recycle gas line.
- an antistatic agent Armostat 400 was added.
- the fluidized bed was held at a constant height by recovering a portion of the bed at the same rate as the rate of production of the individual particulate products, and the product was semi-continuously or continuously recovered into a fixed volume chamber through a series of valves. At the same time, the reactor was evacuated. As a result of the polymerization reaction, the catalyst productivity was 8,000 kg / kg-catalyst, run for 14 days or more continuously, and there was no shutdown due to polymer mass or fouling.
- the gas phase polymerization conditions and reaction results are shown in Table 1 overall.
- the polyolefin was polymerized in the same manner as in Example 1 except that the polymerization reaction conditions were changed as shown in Table 1.
- the catalyst productivity was 9,000 kg / kg-catalyst, operated for over 14 days continuously, and there was no shutdown due to polymer mass or fouling.
- the polyolefin was polymerized in the same manner as in Example 1 except that the polymerization reaction conditions were changed as shown in Table 1.
- the catalyst productivity was 9,000 kg / kg-catalyst, operated for 5 days in a row, and the operation was stopped by the generation of polymer mass by sheeting.
- Example 1 Comparative Example 1 Angle of inclination (s) of the upper conical portion (b) 5 degrees 5 degrees 5 degrees Height of fluidized bed (A) 20% of the height of the upper conical section (b) 20% of the height of the upper conical section (b) In the lower cylindrical part (a) Circulating gas flow rate (m / s) 0.92 0.90 0.92 Reaction temperature (degrees) 78 75 76 Ethylene Concentration (mol%) 45 42 45 Output (ton / h) 14 15 15 15 Productivity (kg / kg-catalyst) 8,000 9,000 9,000 Driving days More than 14 days More than 14 days 5 days
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Abstract
Description
실시예 1 | 실시예 2 | 비교예 1 | |
상부 원뿔형 부분(b)의 경사 각도(s) | 5도 | 5도 | 5도 |
유동층(A)의 높이 | 상부 원뿔형 부분(b) 높이의 20% | 상부 원뿔형 부분(b) 높이의 20% | 하부 원통형 부분(a)에 위치 |
순환가스 유속(m/s) | 0.92 | 0.90 | 0.92 |
반응온도(도) | 78 | 75 | 76 |
에틸렌 농도(mol%) | 45 | 42 | 45 |
생산량(ton/h) | 14 | 15 | 15 |
생산성(kg/kg-촉매) | 8,000 | 9,000 | 9,000 |
운전일수(days) | 14일 이상 | 14일 이상 | 5일 |
실시예 3 | 비교예 2 | 비교예 3 | |
상부 원뿔형 부분(b)의 경사 각도(s) | 5.5 도 | 3.0 도 | 8.0 도 |
유동층(A)의 높이 | 상부 원뿔형 부분(b) 높이의 20% | 상부 원뿔형 부분(b) 높이의 20% | 상부 원뿔형 부분(b) 높이의 20% |
순환가스 유속(m/s) | 0.90 | 0.92 | 0.92 |
반응온도(도) | 78 | 75 | 75 |
에틸렌 농도(mol%) | 35 | 35 | 35 |
생산량(ton/h) | 18 | 15 | 15 |
생산성(kg/kg-촉매) | 5,000 | 6,000 | 5,500 |
운전일수(days) | 14일 이상 | 7일 | 8일 |
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BR112015021684-6A BR112015021684B1 (pt) | 2013-03-07 | 2014-03-07 | Método de polimerização de olefina |
US14/772,466 US9422381B2 (en) | 2013-03-07 | 2014-03-07 | Olefin polymerization method |
CN201480012633.2A CN105026436B (zh) | 2013-03-07 | 2014-03-07 | 烯烃聚合方法 |
EP14759507.8A EP2966094B1 (en) | 2013-03-07 | 2014-03-07 | Olefin polymerization method |
RU2015142512A RU2649007C2 (ru) | 2013-03-07 | 2014-03-07 | Способ полимеризации олефина |
SA515361012A SA515361012B1 (ar) | 2013-03-07 | 2015-09-07 | طريقة لبلمرة الأوليفين |
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US10059613B1 (en) * | 2012-07-23 | 2018-08-28 | Peter F. Santina | Removal of contaminants from water |
JP6804183B2 (ja) * | 2015-01-30 | 2020-12-23 | 三菱重工環境・化学エンジニアリング株式会社 | 流動床式汚泥焼却炉 |
US10370102B2 (en) * | 2016-05-09 | 2019-08-06 | Coban Technologies, Inc. | Systems, apparatuses and methods for unmanned aerial vehicle |
KR20180034062A (ko) * | 2016-09-27 | 2018-04-04 | 롯데케미칼 주식회사 | 비말동반 현상 방지를 위한 분리 장치 |
CN111148771B (zh) * | 2017-08-01 | 2023-07-18 | 埃克森美孚化学专利公司 | 聚烯烃固体回收的方法 |
WO2019027566A1 (en) * | 2017-08-01 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | METHODS OF RECOVERING POLYOLEFIN SOLIDS |
US11390698B2 (en) | 2017-08-01 | 2022-07-19 | Exxonmobil Chemical Patents Inc. | Methods of polyolefin solids recovery |
WO2019027565A1 (en) * | 2017-08-01 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | METHODS OF RECOVERING POLYOLEFIN SOLIDS |
CN111054280B (zh) * | 2018-10-17 | 2022-04-01 | 中国石油化工股份有限公司 | 多区硝基苯加氢制苯胺反应装置及反应方法 |
CN111111570B (zh) * | 2018-10-30 | 2022-07-12 | 中国石油化工股份有限公司 | 芳烃氨氧化流化床耦合反应装置及其反应方法 |
FI129793B (en) * | 2021-06-15 | 2022-08-31 | Neste Oyj | Process and apparatus for making polyalphaolefins |
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EP2966094B1 (en) | 2018-09-05 |
BR112015021684A2 (pt) | 2017-07-18 |
RU2015142512A (ru) | 2017-04-12 |
KR101462466B1 (ko) | 2014-11-17 |
EP2966094A4 (en) | 2016-11-02 |
CN105026436B (zh) | 2017-10-24 |
CN105026436A (zh) | 2015-11-04 |
KR20140110280A (ko) | 2014-09-17 |
US9422381B2 (en) | 2016-08-23 |
RU2649007C2 (ru) | 2018-03-29 |
EP2966094A1 (en) | 2016-01-13 |
BR112015021684B1 (pt) | 2020-05-26 |
SA515361012B1 (ar) | 2017-01-26 |
US20160002376A1 (en) | 2016-01-07 |
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