Reactor for a metallocene catalyst-based solution polymerization process for preparing polyolefin polymers

Abstract

Disclosed is a reactor for solution polymerization process using a metallocene catalyst for preparing polyolefin. The reactor includes: a reaction vessel for mixing a hydrocarbon-based solvent and an olefin monomer to produce polyolefin; a feed inlet installed at a lower portion of the reaction vessel to feed a feed including an unreacted monomer, a solvent, and a catalyst into the reaction vessel; a guide pipe having a cylinder shape being open at respective ends, installed along a central axis of the reaction vessel, and dividing an internal space of the reaction vessel into an up-flow region where a reaction mixture flows upward and a down-flow region where the reaction mixture flows downward; a swirling flow-inducing blade attached to the exterior surface of the guide pipe, causing the reaction mixture in the reaction vessel to rise along the exterior surface of the guide pipe while forming a swirling flow.

Claims

1. A reactor for a solution polymerization process using a metallocene catalyst for preparing polyolefin polymers, the reactor comprising: a reaction vessel configured to mix a hydrocarbon-based solvent and an olefin monomer, thereby preparing polyolefin polymers; a feed inlet installed at a lower portion of the reaction vessel and feeding a feed including an unreacted monomer, a solvent, and a catalyst into the reaction vessel; a guide pipe having a cylinder shape being open at respective ends, installed in the reaction vessel along a central axis of the reaction vessel, and dividing an internal space of the reaction vessel into an up-flow region where a reaction mixture flows upward and a down-flow region where the reaction mixture flows downward; a swirling flow-inducing blade having a helical screw blade shape and attached to an exterior surface of the glide pipe, the swirling flow-inducing blade causing the reaction mixture in the reaction vessel to rise along the exterior surface of the guide pipe while forming a swirling flow, then to enter into the guide pipe at an upper end portion of the reaction vessel, and finally to flow down through the guide pipe; an outlet that is provided to the reaction vessel so that the reaction mixture is discharged outside the reaction vessel; and an external loop through which a predetermined fraction of the reaction mixture discharged from the reaction vessel is returned, in a predetermined recycle ratio, to the reaction vessel through the feed inlet, wherein the recycle ratio that is a ratio of an amount of the feed introduced into the reaction vessel and an amount of the reaction mixture returned to the reaction vessel through the external loop is in a range of from 1:0.1 to 1:3.

2. The reactor according to claim 1, further comprising: an internal circulation guide plate disposed under the guide pipe and functioning as a guide for causing internal circulation of the reaction mixture in the reaction vessel such that the feed, introduced into the reaction vessel through the feed inlet, and a flow of the reaction mixture, flowing downward through the guide pipe, are guided to be directed away from the guide pipe.

3. The reactor according to claim 1, further comprising: a cooler or heat exchanger configured to remove reaction heat generated through a reaction of the reaction mixture circulating through the external loop.

4. The reactor according to claim 1, wherein the recycle ratio is adjusted in accordance with a viscosity of the reaction mixture in the reaction vessel.

5. The reactor according to claim 1, wherein the reaction vessel comprises at least two reaction vessels connected in parallel, in series, or in a series-parallel mixed manner.

6. The reactor according to claim 1, further comprising: a comonomer preparation unit preparing a comonomer, necessarily used in the solution polymerization process, using ethylene or butane, and then supplying the comonomer to the reaction vessel.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic diagram illustrating an internal structure of a reactor for a metallocene catalyst-based solution polymerization process for preparing polyolefin polymers according to one embodiment of the present invention; and

(2) FIG. 2 is a block diagram illustrating an external loop of the reactor for metallocene catalyst-based solution polymerization process for preparing polyolefin polymers according to one embodiment of the present invention.

BEST MODE

(3) Hereinafter, reactors for a metallocene catalyst-based solution polymerization process for preparing polyolefin polymers according to preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings such that an ordinarily skilled person in the art can easily utilize the present invention.

(4) In the drawings, the sizes and dimensions of components may be exaggerated for clarity, and well-known elements may not be illustrated so that features of the present invention can be stood out. Therefore, the construction of the present invention is not limited to the drawings.

(5) In describing principles of preferred embodiments of the present invention, detailed descriptions of known functions and components incorporated herein will be omitted when it may make the subject matter of the present invention unclear.

(6) The embodiments described in the present specification and the configurations shown in the drawings are provided as merely the most preferred embodiments of the present invention, but are not provided as the entirety of technical ideas of the present invention. Therefore, it should be understood that equivalents and modifications are possible.

(7) An embodiment of the present invention relates to a reactor for a solution polymerization process using a metallocene catalyst for preparing polyolefin polymers. The reactor of the present invention can produce polymers having homogeneous physical properties by improving a medium's flowability in a reactor filled with a highly viscous polymer solution. In addition, the reactor has high heat removal performance, which is difficult to be obtained only with the use of a jacket of a reactor filled with a highly viscous medium, by using an external loop, thereby having an effect of improving polymer preparation productivity. In addition, the reactor minimizes a local temperature variation within reaction vessel by improving medium's flowability, thereby minimizing a variation in reaction rate depending on temperature and resulting in polymers having homogeneous physical properties.

(8) Hereinafter, with reference to FIGS. 1 and 2, the structure and operation of a reactor for a metallocene catalyst-based solution polymerization process for preparing polyolefin polymers, according to one embodiment of the present invention, are described in detail.

(9) First, FIG. 1 a schematic view illustrating the internal structure of the reactor for a metallocene catalyst-based solution polymerization process for preparing polyolefin polymers, according to one embodiment of the present invention.

(10) As illustrated in FIG. 1, with respect to the reactor for a metallocene catalyst-based solution polymerization process for preparing polyolefin according to one embodiment of the present invention, the reactor includes a reaction vessel 100, a guide pipe 110, an internal circulation guide plate 120, a feed inlet 130, and an outlet 140.

(11) Specifically, the reaction vessel 100 refers to a housing in which a hydrocarbon-based solvent and an olefin monomer are mixed and polymerized to produce polyolefin. A lower end portion of the reaction vessel 100 is provided with the feed inlet 130 through which a feed including a monomer as a base material, a solvent, and a catalyst is introduced into the reaction vessel 100.

(12) A small mixer may be installed in the feed inlet 130 to uniformly blend the catalyst with a promoter included in the feed.

(13) The guide pipe 110 guides the feed introduced into the reaction vessel 100 through the feed inlet 130 and a reaction mixture that is under reaction in the reaction vessel 100 such that the feed and the reaction mixture circulate in the reaction vessel 100. The guide plate 110 is installed to extend along a central axis of the reaction vessel 100.

(14) More specifically, the guide pipe 110 has a cylinder shape that is open at an upper end and a lower end. The guide pipe 110 installed in the reaction vessel 100 to extend along the central axis of the reaction vessel 100, thereby dividing an internal space of the reaction vessel 100 into an up-flow region where the reaction mixture flows upward and a down-flow region where the reaction mixture flows downward. In the reaction vessel, the outside of the guide pipe 110 serves as the up-flow region and the inside of the guide pipe 110 serves as the down-flow region.

(15) A swirling flow-inducing blade 111 in the form of a helical screw blade is attached to the exterior surface of the guide pipe 110. Due to the swirling flow-inducing blade 111, the reaction mixture rising along the exterior surface of the guide pipe 110 forms a swirling flow.

(16) Due to the structure of the guide pipe 110, the reaction mixture in the reaction vessel 100 first swirlingly flows upward along the exterior surface of the guide pipe 110, then enters into the upper end opening of the guide pipe 110 at an upper end portion of the reaction vessel 100, and finally flows down through the guide pipe 110. That is, since the reaction mixture flows in a swirling manner, flowability of the reaction mixture is improved and thus a reaction rate becomes uniform throughout the entire region of the reaction vessel. Furthermore, a location temperature variation in the reaction vessel 100 is also reduced due to the improved flowability.

(17) In addition, the reactor for a solution polymerization process for preparing polymers, according to the present invention, is provided with the internal circulation guide plate 120 between the feed inlet 130 and the guide pipe 110. The internal circulation guide plate 120 is provided to address problem that the feed introduced into the reaction vessel 100 through the feed inlet 130 hinders internal circulation in the reaction vessel 100 when the feed is directly introduced into the guide pipe 110.

(18) The internal circulation guide plate 120 prevents the feed, introduced into the reaction vessel 100 through the feed inlet 130, from moving toward the guide pipe 110 and (guides the flow of the feed along a path that is directed away from the guide pipe 110. Besides, the internal circulation guide plate 120 causes the reaction mixture, flowing down through the guide pipe 110, to move away from the guide pipe 110 so as to be well-circulated in the reaction vessel 100.

(19) As described above, the reactor for a metallocene catalyst-based solution polymerization process for preparing polyolefin polymers, according to the present invention, circulates the reaction mixture with the use of the guide pipe 110 such that the reaction mixture rises up to an upper end portion of the reaction vessel 100 while forming a swirling up-flow in a region outside the guide pipe 110 and then falls through the guide pipe 110. Therefore, the reactor according to the present invention improves flowability in the reaction vessel 100 without using an additional mixer. For this reason, it is possible to reduce investment cost for facilities or equipment such as an expensive motor for a mixer and also to reduce operation and maintenance cost.

(20) FIG. 2 is a block diagram illustrating an external loop of the reactor for a metallocene catalyst-based solution polymerization process for preparing polyolefin polymers, according to one embodiment of the present invention.

(21) As illustrated in FIG. 2, the reactor for a metallocene catalyst-based solution polymerization process for preparing polyolefin polyers, according to one embodiment of the present invention, has an effect of further improving flowability in the reaction vessel and consequently reducing a local temperature variation by using the external loop.

(22) More specifically, the reactor the present invention has the external loop through which a predetermined fraction of the reaction mixture discharged from the outlet 140 of the reaction vessel 100 is returned, in a predetermined recycle ratio, to the reaction vessel 100 through the feed inlet 130.

(23) The recycle ratio refers to a ratio of the amount of the feed introduced into the reaction vessel 100 and the amount of the reaction mixture returned to the reaction vessel 100 through the external loop. The external loop in the present invention is designed such that the recycle ratio is about 1:0.1 to 1:3. The recycle ratio may be preferably 1:0.1 to 1:2, and more preferably 1:0.1 to 1:1, and most preferably 1:0.3 to 1:0.8. When the recycle ratio is lower than 1:0.1, a mixing effect of the reaction mixture obtained by the external loop is insufficient. Conversely, when the recycle ratio is beyond 1:3, energy consumption for the circulation of the reaction mixture through the external loop is excessively large. Therefore, the reactor is preferably operated at a recycle ratio within the above-mentioned range.

(24) As described, the reactor of the present invention primarily improves the flowability of the reaction mixture through the internal circulation induced by the guide plate and further improves the flowability through the external loop by adjusting the recycle ratio. For reference, as to the recycle ratio, as a ratio of the reaction mixture returned to the reaction vessel through the external loop is increased, the velocity of a solution is increased and thus the flowability of a solution is accordingly improved.

(25) Specifically, since the recycle ratio is determined in accordance with the viscosity of the reaction mixture, it is possible to minimize a local temperature variation in the reactor by adjusting the flowability of the reaction mixture.

(26) Conventionally a method of lowering a polymer-to-solvent ratio is used to produce a highly viscous polymer. Therefore, productivity of polymer preparation was low. However, the reactor of the present invention adopts a method of minimizing a local temperature variation in the reaction vessel 100 by improving the flowability of the reaction mixture in the reaction vessel 1000. Therefore, the reactor of the present invention can produce polymers having homogeneous physical properties while maintaining high productivity.

(27) The external loop further includes a circulation pump 140 that pumps the reaction mixture, discharged through the outlet 140, to the feed inlet 130.

(28) In addition, the external loop may further include a cooler or a heat exchanger 300, such as a shell and tube and a single jacket tube, to remove reaction heat caused by a reaction of the reaction mixture. The external loop minimizes exhaust of non-reacted residual gas, thereby improving operation stability and productivity.

(29) On the other hand, the reactor the present invention may include two more reaction vessels 100 connected with each other in parallel, in series, or in a mixed (series-parallel) manner. In this case, it is possible to increase the productivity of polymer preparation and to control the physical properties and molecular weights of the produced polymers.

(30) Typically, when preparing a polymer through a solution process using a metallocene catalyst, a reaction mixture contains several tens of percentages by weight of a comonomer for reduction of the density. Examples of the comonomer include butane, hexane, octane, and others having a larger molecular weight than these.

(31) As described above, since a solution polymerization process using a metallocene catalyst requires a large amount of a comonomer and since the price of a comonomer fluctuates according to the supply of a comonomer and economic and fluctuations, it is difficult to secure production profitability.

(32) To solve this problem, the reactor of the present invention includes a comonomer preparation unit 400 that prepares a comonomer, for use in a solution polymerization process, using ethylene or butane. The comonomer preparation unit 400 is provided at a previous stage of the reaction vessel 100 and supplies the prepared comonomer to the reaction vessel 100. Since the reactor of the present invention prepares a comonomer on site by using ethylene or butane that is relatively inexpensive and more stable in price, and directly supplies the prepared comonomer to the reaction vessel 100, it is possible to secure stable production profitability.

(33) In addition, since this method enables supply of a comonomer to polymerization process without requiring transportation, storage facilities, and refining facilities associated with the usage of a comonomer, it is possible to produce a polymer mixture at relatively low cost without being worried about the demand-supply status of a comonomer.

(34) Although a preferred embodiment of the present invention has been described for illustrative purposes, those skilled in the art will appreciate that various modifications and equivalents thereof are possible, without departing from the scope and spirit of the invention. Accordingly, the technical protection scope of the present invention should be defined only by the accompanying claims.

DESCRIPTION OF THE REFERENCE NUMERALS IN THE DRAWINGS

(35) 100: Reaction vessel

(36) 110: Guide pipe

(37) 111: Swirling flow-inducing blade

(38) 120: Internal circulation guide plate

(39) 130: Feed inlet

(40) 140: Outlet

(41) 200: Circulation pump

(42) 300: Cooler or heat exchanger

(43) 400: Comonomer preparation unit