KR20150097128A - Agitator of polyketon high pressure reactor - Google Patents

Abstract

The present invention relates to a polyketone polymerization reactor. The purpose of the present invention is to provide a polyketone polymerization reactor which: can generated strong circulation flow by forming an impeller, arranged in an agitator in the polymerization reactor, to have a large unit area and to be able to agitate at a low speed; can effectively prevent a fouling phenomenon wherein a solvent such as power or fouling is aggregated, stuck, and attached on an inner wall of the polymerization reactor and a shaft of an agitator during a polymerization reaction; consequently increases a polymerization reaction rate; and can prevent powder, generated by the solvent when the polymerization reaction is performed, from being scattered. According to a technological composition of the present invention, the polyketone polymerization reactor includes: a reactor which performs the polymerization reaction; a motor arranged on an upper portion of the reactor; a gear box which is operated by the motor; the agitator comprising a shaft, rotatably connected to the gear box, and the impeller arranged on the shaft; a baffle arranged in the reactor. A subsidiary impeller is formed to be extended from the impeller arranged on the shaft of the agitator to have a large cross-sectional area.

Description

[0001] The present invention relates to a polyketone polymerization reactor,

The present invention relates to a polymerization reactor, and more particularly, to a polymerization reactor that suppresses the fouling phenomenon in which a solvent is entangled or adhered to a wall surface of a polymerization reactor and a shaft of an agitator, To a polymerization reactor.

In general, polymerization is a process of producing a molecule having a large molecular weight by continuously bonding molecules having a small molecular weight.

As described above, Korean Patent No. 837,422 discloses a polymer production apparatus for preventing polymerization products from entangling on the inner wall of a reaction chamber and a stirrer, as disclosed in Korean Patent Publication No. 1998-059857 A scraping disk is installed in the reaction vessel to increase the surface area of the reaction liquid to maximize the stirring effect of the stirring liquid of the lower liquid to increase the reaction rate and to remove the generated bubbles.

As shown in FIGS. 1 and 2, the polymerization reactor for carrying out the polymerization reaction comprises a reactor 110 for injecting a solvent and a stirrer 130 in the reactor 110, (130) comprises a shaft (131) formed of a rod-shaped body and a plurality of impellers (133) spaced apart from the shaft (131) at regular intervals in the vertical direction.

The shaft 131 is rotatably connected to a gear box 105 and a motor 103 provided at an upper portion of the stirrer 130.

At this time, in the reactor 110, at least one baffle 111 having a substantially "b" shape corresponding to the side and bottom shapes of the reactor 110 is provided in the circumferential direction, Are installed at a predetermined interval on the inner surface of the reactor 110.

In the polyketone polymerization reactor 1 having the structure as described above, the gear box 105 is operated by driving the motor 103 provided at the upper portion of the reactor 110, and the operation of the gear box 105 A plurality of impellers 133 spaced apart from each other by a predetermined distance in a direction perpendicular to the shaft 131 by the rotation of the shaft 131 are rotated by the rotation of the shaft 131 so that the solvent injected into the reactor 110, And the catalyst are stirred to proceed the polyketone polymerization reaction.

On the other hand, when the polyketone polymerization reaction proceeds in the polymerization reactor, a powder is formed in the solvent.

However, in the polymerization reactor, the volume increases as the powder is formed in the solvent during the polymerization reaction, and the fouling phenomenon occurs at the reaction interface and the upper part of the shaft where the stirring ability is weak, and at the same time, the fouling grows .

That is, in the polymerization reactor, the volume and viscosity of the polymerization solution are increased during the polymerization reaction in which a polymer powder is formed in a polymerization solvent such as a polyketone polymerization, and the flow rate of the solution is reduced on the reaction interface and the shaft and baffle of the stirrer, A fouling phenomenon occurs, which is adhered, adhered and attached.

There has been a problem in that a process problem is caused by the growth of the fouling.

As a result, due to the fouling formed in the reaction interface and the shaft of the agitator in the polymerization reactor, a loop gas system that circulates the monomer gas in the polymerization reactor, And the load of the loop gas compressor is increased and when the fouling lumps fall into the polymerization liquid, the lump is broken to form the transfer valve There is a problem that a phenomenon of blocking the polymerization solution transfer pump (pump) and the piping occurs.

Korean Patent No. 837,422, Korean Patent Publication No. 1998-059857.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems as described above, and it is an object of the present invention to provide a method of producing a polymer blend, which is capable of forming a strong circulation flow by forming an impeller provided in a stirrer in a polymerization reactor with a large unit area, It is possible to effectively suppress the fouling phenomenon in which the solvent such as powder or fouling is entangled, adhered and adhered to the wall of the polymerization reactor and the shaft of the agitator, thereby improving the polymerization reaction rate And a polyketone polymerization reactor capable of preventing the development of powder (Powdwe) formed in a solvent during the course of the polymerization reaction.

The present invention also provides a loop gas system for circulating monomer gas by suppressing the growth of fouling by stirring the impeller having a large unit area at low speed to prevent the powder from flowing into the loop gas system, It is possible to minimize the increase of the scaling and the load of the loop gas compressor while preventing the fouling from falling into the polymerization liquid to form a lump, And a polyketone polymerization reactor capable of preventing the phenomenon of blocking the polymerization solution transfer pump (pump) and the piping.

According to an aspect of the present invention, A motor provided at an upper portion of the reactor; A gear box operated by a motor; An agitator composed of a shaft rotatably connected to the gear box and an impeller provided in the shaft; And a baffle provided inside the reactor; Wherein the auxiliary impeller is extended to an impeller provided on the shaft of the agitator to have a large cross-sectional area.

Here, the lower portion of the auxiliary impeller extending from the impeller is formed in a rounded shape corresponding to the lower side shape of the reactor, and is positioned close to the inner side of the lower side of the reactor.

On the other hand, the upper part of the baffle provided on the inner side of the reactor is made flush with the upper part of the stirrer impeller.

The lower portion of the baffle provided on the inner surface of the reactor is formed to have the same height as the auxiliary impeller extending from the impeller of the agitator.

As described above, the present invention having such a structure as described above can be applied to a wall surface of a polymerization reactor and to a shaft of an agitator by a fouling process in which a solvent such as powder or fouling is entangled, ) Can be effectively suppressed and continuous polymerization is facilitated. As a result, the polymerization reaction rate can be improved to shorten the reaction time and improve the productivity, and it is possible to prevent the development of the powder (Powdwe) It prevents the inflow of powder into the loop gas system that circulates the monomer gas, minimizes the increase of the piping scaling and the load of the loop gas compressor, It is possible to prevent the blocking of the transfer valve (valve) and the polymerization liquid transfer pump (pump) and the piping, and the continuous operation of the polymerization reactor can be performed, Can participate, it can achieve effects such that the application is available in the polyketone polymerized similar reactor and other polymerization reactor equipped with a stirrer form.

Brief Description of the Drawings Figure 1 is a schematic representation of a prior art polyketone polymerization reactor,
Figure 2 schematically shows the internal flow during stirring of a polyketone polymerization reactor according to the prior art,
3 is a schematic view of a polyketone polymerization reactor according to the present invention,
4 is a schematic view showing the internal flow during stirring of the polyketone polymerization reactor according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the scope of the present invention, but is merely an example, and various modifications can be made without departing from the technical spirit of the present invention.

FIG. 3 is a schematic view of a polyketone polymerization reactor according to the present invention, and FIG. 4 is a view schematically showing an internal flow during a polymerization of a polyketone polymerization reactor according to the present invention.

As shown in the figure, a polyketone polymerization reactor (1) according to the present invention comprises a reactor (10) for injecting a solvent, a monomer gas and a catalyst to perform a polymerization reaction, And an agitator (30) for performing agitation for polymerization reaction.

A motor (not shown) is provided at an upper portion of the polyketone polymerization reactor 1 and connected to a gear box (not shown) operated by driving the motor.

Meanwhile, the stirrer 30 includes a shaft 31 rotatably connected to a gear box and an impeller 33 provided on the shaft 31.

Here, the auxiliary impeller 35 is extended to the impeller 33 provided in the shaft 31 of the stirrer 30. [ That is, the auxiliary impeller 35 is extended under the impeller 33 provided at the lower part of the shaft 31 of the stirrer 30 to have a large sectional area.

As a result, the auxiliary impeller 35 is extended to the impeller 33 provided in the agitator 30 of the polyketone polymerization reactor 1 according to the present invention to form an impeller 33 having a large sectional area of the Max blend type .

Here, the impeller 33 has a shape capable of stirring at a low speed.

As described above, since the impeller 33 provided in the stirrer 30 has a large cross-sectional area by extending the auxiliary impeller 35, the polymerization reaction rate is improved and the reaction time is shortened to improve the productivity have.

A strong circulation flow is formed by rotation of the impeller 33 having a large cross-sectional area to suppress the occurrence of fouling in the reactor 10, thereby preventing the wall surface of the reactor 10 and the shaft 31) is minimized and fouling of the powder formed in the solvent during the polymerization reaction can be prevented.

In addition, since the impeller 33 has a shape capable of stirring at a low speed relative to a conventional stirring speed, the power load of the impeller 33 can be reduced to reduce the power ratio of the polyketone polymerization reactor 1 according to the present invention.

In an embodiment of the present invention, the auxiliary impeller 35 is extended below the impeller 33 to have a large cross-sectional area, but it is also preferable that the impeller 33 has a large cross-sectional area.

The lower portion of the auxiliary impeller 35 extending to the lower portion of the impeller 33 is formed in a shape corresponding to the lower side of the reactor 10, . That is, the lower portion of the auxiliary impeller 35 extended to the lower portion of the impeller 33 is formed in a round shape corresponding to the shape of the lower side in the reactor 10 formed as a semicircular shape, And are spaced apart from each other by a predetermined distance.

Baffles 11 provided in the reactor 10 are installed outside the impeller 33 of the stirrer 30 and are spaced a predetermined distance from the inner surface of the stirrer 30.

At this time, the height of the baffle 11 in the reactor 10 is equal to the height of the impeller 33 of the stirrer 30. The height of the baffle 11 is equal to the height of the impeller 33 so that the height of the reaction interface in the reactor 10 is equal to the height of the impeller 33.

The lower part of the baffle 11 has a height equal to the height of the auxiliary impeller 35 extended to the impeller 33 of the agitator 30. [ That is, the lower portion of the baffle 11 has the same height as the upper portion of the auxiliary impeller 35 extended from the impeller 33.

The upper height of the baffle 11 is formed to be equal to the height of the upper portion of the impeller 33 of the stirrer 30 and the lower portion of the baffle 11 is extended to the impeller 33, The flow rate of the solvent at the reaction interface during the polymerization reaction in the reactor 10 can be improved and the formation of fouling can be suppressed.

Hereinafter, a polymerization reaction process through the polyketone polymerization reactor according to the present invention will be described.

First, a solvent, a monomer gas and a catalyst are injected into the reactor 10 of the polyketone polymerization reactor (1) according to the present invention.

Here, when a mixed solvent of acetic acid and water is used as a solvent, when the concentration of water is less than 10% by volume, the effect of the catalyst is less affected, but when the concentration is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. In the present invention, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 30 to 10% by volume of water as the liquid medium.

Examples of the ethylenically unsaturated compound include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, vinylcyclohexane and the like; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclodecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. These ethylenically unsaturated compounds are used singly or as a mixture of plural kinds. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

(A) a ligand having an element of Group 9, 10 or 11 of the Periodic Table (IUPAC Inorganic Chemical Nomenclature, 1989), (b) an element of Group 15, and (c) Is an anion of an acid of 4 or less.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates And specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, sulfonates and the like. Specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, Palladium acetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium, and palladium sulfate.

Examples of the Group 11 transition metal compound include copper or silver complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, , Silver trifluoroacetic acid, silver acetyl acetate, trifluoromethanesulfonic acid, and the like.

On the other hand, examples of ligands (b) having a Group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, (Diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Bis [di (2-methylpropyl) phosphine] propane, 1,3-bis [di Bis (diphenylphosphino) cyclohexane, 1, 2-bis (diphenylphosphino) phosphino] Benzene, 1,2-bis [[(di (2-methoxyphenyl) phosphino] methyl] benzene, (Diphenylphosphino) ferrocene, 2-hydroxy-1, 3-bis (diphenylphosphino) [Di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [ Di (2-methoxyphenyl) phosphino] propane, and the like.

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically.

Here, the ligand (b) having an intrinsic viscosity of the polyketone and an atomic group 15 preferred for emphasis on the improvement of the catalytic activity is 1,3-bis [di (2-methoxyphenyl) 3-bis (diphenylphosphino) propane, and most preferably 1,3-bis [di (2-methoxyphenyl) phosphino] propane.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) used varies depending on the kind of the ethylenically unsaturated compound to be selected and other polymerization conditions, and therefore the range But it is usually from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per liter of the reaction zone. The capacity of the reaction zone refers to the liquid capacity of the reactor 10.

Examples of the anion (c) of the acid having a pKa of 4 or less include an anion of an organic acid having a pKa of 4 or less such as trifluoroacetic acid, trifluoromethanesulfonic acid, or p-toluenesulfonic acid; Anions of inorganic acids having a pKa of 4 or less such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate.

As described above, the solvent, the monomer gas and the catalyst are injected into the reactor 10 of the polyketone polymerization reactor 1, and then the motor is driven to rotate the stirrer 30 connected to the motor by the gear box.

The stirrer 30 is rotated to rotate the impeller 33 provided on the shaft 31 of the stirrer 30 to proceed the polymerization reaction. That is, the auxiliary impeller 35 is extended and the polyketone is polymerized while the impeller 33 having a large cross-sectional area is rotated and the polymerization of the solvent, the monomer gas and the catalyst injected into the reactor 10 proceeds.

 Here, the impeller 33 provided in the stirrer 30 of the polyketone polymerization reactor 1 according to the present invention is formed in a large area and is agitated at a low speed. As the polymerization reaction progresses, The reaction interface and the stirrer 30, in which fouling is grown, can be easily performed even when the volume and the viscosity are increased and the flow velocity of the upper part of the baffle 11 is prevented from being reduced. It is possible to prevent the fouling from being formed on the shaft 31 of the rotor.

Further, the impeller 33 having a large cross-sectional area is rotated at a low speed to shorten the reaction time to improve the productivity. By the strong circulation flow of the impeller 33, the upper portion of the reactor 10, It is possible to prevent and effectively reduce the adhesion of powder and fouling generated in the shaft 31 of the shaft 30.

In the loop gas system (not shown) for circulating the monomer gas in the polyketone polymerization reactor 1 by suppressing the fouling formed on the reaction interface and the shaft 31 of the agitator 30, It is possible to prevent the inflow of powder to reduce an increase in piping scaling and load of a loop gas compressor.

In addition, it is possible to prevent the lump of the powder and the lumps of the fouling from falling into the polymerization liquid to prevent the formation of the lump, thereby preventing the transfer valve and the polymerization liquid transfer pump Can be prevented in advance.

Although the stirrer 30 provided in the reactor 10 of the polyketone polymerization reactor 1 is described as an example in the embodiment of the present invention, it is possible to use all kinds of reactors having the form of the reactor 10 and the stirrer 30 But is not limited thereto.

Example 1

The solvent, the monomer gas and the catalyst were injected into the polyketone polymerization reactor.

Then, as shown in FIG. 4, the motor is driven to rotate the stirrer connected to the gear box to rotate the impeller, which is provided on the shaft of the stirrer, in which the auxiliary impeller is extended at a low speed to stir the solvent in the reactor .

Comparative Example 1

The solvent, the monomer gas and the catalyst were injected into the polyketone polymerization reactor.

Thereafter, as shown in FIG. 2, the motor was driven to rotate the stirrer connected to the gear box to rotate a plurality of impellers provided on the shaft of the stirrer to stir the solvent in the reactor.

Compare Example 1 Comparative Example 1 Continuous operation day 120 days 30 days Reaction time 200 minutes / Batch 276 minutes / Batch Stirrer speed (rpm) 70 to 90 rpm 248rpm Power load (Kw) 6.5kw 10Kw

As shown in the above Table 1, when the polyketone according to Example 1 undergoes a fouling phenomenon during the polymerization, the continuous operation time is shorter than the conventional polymerization reactor in which the continuous operation time is 30 days, It can be operated, and the power load can be remarkably reduced due to the low-speed stirring, thereby contributing to the reduction of the power ratio.

While the invention has been shown and described with respect to the specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. Anyone will know easily.

1: polyketone polymerization reactor, 10: reactor,
11: baffle, 30: stirrer,
31: shaft, 33: impeller,
35: Secondary impeller.

Claims (4)

A reactor for carrying out a polymerization reaction; A motor provided at an upper portion of the reactor; A gear box operated by the motor; A shaft rotatably connected to the gear box, and an impeller provided on the shaft; A baffle provided inside the reactor; Wherein the polyketone polymerization reactor comprises:
Wherein an auxiliary impeller is extended to an impeller provided on a shaft of the stirrer to have a large cross-sectional area.
The method according to claim 1,
Wherein a lower portion of the auxiliary impeller extending from the impeller is formed in a rounded shape corresponding to a shape of a lower side of the reactor and is positioned close to an inner side of a lower side of the reactor.
The method according to claim 1,
Wherein an upper portion of a baffle provided on an inner surface of the reactor has the same height as an upper portion of the stirrer impeller.
The method of claim 3,
Wherein a lower portion of a baffle provided on an inner surface of the reactor has a height equal to a height of an auxiliary impeller extending from an impeller of the stirrer.

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