REACTOR
20200024371 ยท 2020-01-23
Inventors
- Tomoya Kotake (Tokyo, JP)
- Noriyuki Yoshio (Tokyo, JP)
- Shuhei Nishiyama (Tokyo, JP)
- Misato Matsuoka (Tokyo, JP)
Cpc classification
B01J19/18
PERFORMING OPERATIONS; TRANSPORTING
B01J19/1806
PERFORMING OPERATIONS; TRANSPORTING
C08F2/01
CHEMISTRY; METALLURGY
B01J2219/00085
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00765
PERFORMING OPERATIONS; TRANSPORTING
B01F27/86
PERFORMING OPERATIONS; TRANSPORTING
B01F35/93
PERFORMING OPERATIONS; TRANSPORTING
B01J19/0013
PERFORMING OPERATIONS; TRANSPORTING
B01F27/81
PERFORMING OPERATIONS; TRANSPORTING
International classification
C08F2/01
CHEMISTRY; METALLURGY
B01J19/18
PERFORMING OPERATIONS; TRANSPORTING
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A polymerization device that includes: a reaction vessel that houses a polymerization solution and in which a polymerization reaction is performed; a stirring blade that stirs the polymerization solution housed in the reaction vessel; a plurality of heat transfer pipes that transfer heat to the polymerization solution in order to start the polymerization reaction and cause the polymerization reaction to proceed, and that remove, from the polymerization solution, heat generated by the polymerization reaction; and a baffle arranged between a vessel wall of the reaction vessel and the heat transfer pipes.
Claims
1. A reactor comprising: a reaction vessel that houses a polymerization solution and in which a polymerization reaction is performed; a stirring blade configured to stir the polymerization solution housed in the reaction vessel; a plurality of heat transfer pipes configured to transfer heat to the polymerization solution in order to start the polymerization reaction and cause the polymerization reaction to proceed, and to remove, from the polymerization solution, heat generated by the polymerization reaction; and a baffle arranged between a vessel wall of the reaction vessel and the heat transfer pipes; wherein the plurality of heat transfer pipes are arranged in a circumferential shape around the stirring blade, include heat transfer pipes whose lower ends are arranged in a position higher than a bottom face of the reaction vessel, and restrict an amount of the polymerization solution circulated from an inner side to a vessel wall side of the reaction vessel, at a depth at which the heat transfer pipes are arranged, and the baffle changes a flow direction of the polymerization solution that has flowed between the vessel wall of the reaction vessel and the heat transfer pipes arranged in the circumferential shape, and generates a flow of the polymerization solution to an inward direction of the reaction vessel.
2. The reactor according to claim 1, wherein a plurality of the baffles are arranged so as to protrude from the vessel wall of the reaction vessel in the inward direction of the reaction vessel, and change the flow direction of the polymerization solution that rises while revolving along the vessel wall of the reaction vessel.
3. The reactor according to claim 1, wherein the baffle is arranged at a position such that a length of a section immersed in the polymerization solution is from 10% to 50% of a liquid level.
4. The reactor according to claim 1, wherein the baffle is arranged in a position at which an upper end thereof is higher than a position of a liquid surface and a lower end thereof is at a position lower than a position of the liquid surface.
5. The reactor according to claim 1, wherein upper ends of the plurality of heat transfer pipes are positioned more to a bottom face side than a position of the liquid surface.
6. The reactor according to claim 1, wherein a distance between lower ends of the plurality of heat transfer pipes and the bottom face of the reaction vessel is longer than a distance between the plurality of heat transfer pipes and the vessel wall of the reaction vessel.
7. The reactor according to claim 1, wherein the plurality of heat transfer pipes have a hairpin coil shape in which ends of two pipes that are arranged in a vertical direction are coupled together.
8. The reactor according to claim 7, wherein the plurality of heat transfer pipes having the hairpin coil shape are arranged in positions in which distances and angles from a center axis of the reaction vessel to each of the two pipes are different.
9. The reactor according to claim 1, wherein the polymerization solution contains one of a raw material of polyarylene sulfide and polyarylene sulfide produced from the raw material.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0012]
[0013]
[0014]
[0015]
[0016]
DESCRIPTION OF EMBODIMENTS
[0017]
[0018] The reactor 100 includes a reaction vessel 110, a stirring blade 120, a plurality of heat transfer pipes 130, and baffles 140.
[0019] The reaction vessel 110 houses a polymerization solution, and causes a polymerization reaction therein. The reaction vessel 110 is a container, for example, in which a substantially hemispherical lower lid is attached to one end of a cylindrical long trunk portion, and a substantially hemispherical upper lid is attached to the other end of the long trunk portion such that the upper lid is able to open and close. The reaction vessel 110 can be a known reaction vessel used for a polymerization reaction that has one or more supply ports 112 for supplying a polymerization solution or a material thereof into the interior of the reaction vessel 110, and a jacket 114 for adjusting a temperature of the interior of the reaction vessel 110. Note that a pump (not illustrated) may be arranged upstream of the supply port 112, and may limit a supply amount of raw material into the interior of the reaction vessel 110. Furthermore, the shape of the lower lid and the upper lid need not necessarily be substantially hemispherical, and may be an oval hemispherical shape or the like.
[0020] Note that the above described polymerization solution is a liquid or a solid-liquid system (slurry or the like) whose composition changes due to the above described polymerization reaction, and is a liquid or solid-liquid system that contains a raw material of a reaction product or the reaction product. In other words, the above described polymerization solution is a liquid that, before a start of the reaction and in initial stages of the reaction, contains a monomer that is the raw material of a polymer generated by the above described polymerization reaction, components added as necessary, such as a molecular weight modifier, a branching/cross-linking agent, and a phase separation agent, and a solvent, such as an organic solvent. Furthermore, the above described polymerization solution may be a liquid or a solid-liquid system (slurry or the like) that contains a prepolymer, which is an intermediate product generated in the liquid during the progress of the reaction, a polymer, which is a reaction product, and particles formed by granulation of the above described polymer, and the like (hereinafter, when the reaction product is simply referred to, this includes all of the prepolymer, the polymer, and the particles).
[0021] The stirring blade 120 stirs the polymerization solution housed inside the reaction vessel 110. The stirring blade 120 can be a known stirring blade, such as a paddle blade, a Maxblend (Maxblend is a trade name of Sumitomo Heavy Industries Process Equipment Co., Ltd.). Note that, when granulating the polymer inside the reaction vessel 110, for example, it is preferable to increase a circulating amount of the flow caused by stirring the polymerization solution using the stirring blade 120, and to prevent adhesion of the polymer, which is the product, and the granulated particles to the stirring blade 120, the vessel wall of the reaction vessel 110, and the like. From the point of view of reaching the above described high circulating amount using low power, the stirring blade 120 is preferably the Maxblend that has a large discharge flow rate.
[0022] The plurality of heat transfer pipes 130 heat the polymerization solution housed in the interior of the reaction vessel 110, thus causing the polymerization reaction to start and progress, while also removing the heat of polymerization, from the polymerization solution, generated by the polymerization reaction.
[0023] In order to efficiently perform the heating and heat removal, the plurality of heat transfer pipes 130 are arranged in a circumferential shape around the periphery of the stirring blade 120, at equal intervals. In order to perform sufficient heat removal and to prevent the runaway reaction when a high concentration polymerization solution is used, each of the plurality of heat transfer pipes 130 of the present embodiment preferably has the hairpin coil shape in which two of the pipes arranged in the vertical direction are coupled at end portions thereof. Heat transfer pipes having the hairpin coil shape can increase the heating surface area while minimizing a reduction in the practical volume (in
[0024] The plurality of heat transfer pipes 130 are arranged at the equal intervals such that a distance between the adjacent heat transfer pipes is from 3% to 97% of a diameter of the reaction vessel 110. From the point of view of improving the heating surface area, the distance between the adjacent heat transfer pipes is preferably from 3% to 85% of the diameter of the reaction vessel 110, more preferably from 5% to 65%, and even more preferably from 10% to 50%. More specifically, for the reaction vessel 110 having a diameter of 3200 mm, when 18 hairpin coils are used, the distance between the adjacent heat transfer pipes is preferably 20% or less of the distance to the center of the reaction vessel. Note that the diameter of the reaction vessel 110 is the diameter of a circle configuring a cross-section obtained by horizontally cutting the reaction vessel 110. When the diameter of the circle configuring the above described cross-section of the reaction vessel 110 changes in the depth direction, a value of the diameter at the depth at which the above described diameter is the largest value (in the present embodiment, the diameter of the circle configuring the cross-section obtained by horizontally cutting the reaction vessel 110 at the long trunk portion) of the diameter of the reaction vessel 110. Furthermore, the above described distance between the adjacent heat transfer pipes is a shortest distance between surfaces of the heat transfer pipes, of the two heat transfer pipes arranged to be adjacent.
[0025] As illustrated in
[0026] Furthermore, as illustrated in
[0027] Note that, in the present embodiment, the position of the liquid surface refers to the position of the liquid surface of the polymerization solution when the polymerization solution is supplied to the interior of the reaction vessel 110 and the polymerization reaction is progressing, and the liquid level refers to the height from the bottom-most portion of the reaction vessel 110 to the liquid surface of the polymerization solution when the polymerization reaction is progressing. When the amount of liquid changes and the position of the liquid surface changes during the polymerization reaction, of the heights of the changing liquid surface, a maximum position is the position of the liquid surface, and the height from the bottom-most portion of the reaction vessel 110 to the liquid surface at that time is the liquid level. The position of the liquid surface is normally clearly displayed on the reaction vessel 110 in order to indicate the amount of the polymerization solution to be supplied.
[0028] Meanwhile, as illustrated in
[0029] When the stirring blade 120 rotates, a strong discharge flow occurs from the lower end of the stirring blade 120 to the side of the vessel wall. This strong discharge flow reaches the vessel wall of the reaction vessel 110 while passing through the above described gap between the lower ends of the plurality of heat transfer pipes 130 and the bottom face of the reaction vessel 110. After that, the discharge flow converges with a weak discharge flow circulating between the plurality of heat transfer pipes 130, and rises while revolving along the vessel wall of the reaction vessel 110 through a gap between the plurality of heat transfer pipes 130 and the vessel wall of the reaction vessel 110, thus creating the flow of the polymerization solution. Note that, the above described strong discharge flow occurs particularly notably when the stirring blade 120 is the large stirring blade, such as the Maxblend.
[0030] The flow of the polymerization solution that is rising prevents stagnation of the polymerization solution in the bottom face portion and on the vessel wall side of the reaction vessel 110, and allows the polymerization solution to be more easily mixed.
[0031] From the point of view of allowing the above described flow of the polymerization solution that rises to occur more easily and more strongly, and causing the stagnation of the above described polymerization solution to less easily occur, the plurality of heat transfer pipes 130 are preferably arranged in positions such that a distance L1 between the lower ends of the plurality of heat transfer pipes 130 and the bottom face of the reaction vessel 110 is longer than a distance L2 between the plurality of heat transfer pipes 130 and the vessel wall of the reaction vessel 110. Note that the distance L1 between the lower ends of the plurality of heat transfer pipes 130 and the bottom face of the reaction vessel 110 in a mode in which the plurality of heat transfer pipes 130 have the hairpin coil shape, as in the present embodiment, is a distance between a position on the bottom-most portion side of a coupling portion at the lower end of the heat transfer pipes having the above described hairpin coil shape and the bottom face of the reaction vessel 110. Note also that the distance L2 between the above described plurality of heat transfer pipes 130 and the vessel wall of the reaction vessel 110 in the mode in which the plurality of heat transfer pipes 130 have the hairpin coil shape, as in the present embodiment, is a distance between the surface of the pipe that is arranged on the outer side of the two pipes having the hairpin coil shape and the vessel wall of the reaction vessel 110.
[0032] The baffles 140 change a circulation direction of the polymerization solution occurring when the stirring blade 120 stirs the polymerization solution. In a cross-section when the reaction vessel 110 is cut in the horizontal direction, the baffles 140 are plate-shaped members that are arranged between a region in which the plurality of heat transfer pipes 130 are arranged in the circumferential shape and the vessel wall of the reaction vessel 110 and that extend from the vessel wall of the reaction vessel 110 in a direction toward the center of the reaction vessel 110 (an inward direction).
[0033] Of the above described flow of the polymerization solution that rises, in the vicinity of the boundary surface of the polymerization solution, a revolving flow mainly occurs, and the circulation of the polymerization solution between the outer side and the inner side is limited. In the present embodiment, the baffles 140 disturb the flow of the above described revolving flow, change a circulation direction thereof, and generate a flow drawing a flow from the outer side to the inner side of the reaction vessel 110. In this way, the baffles 140 generates the flow from the outer side to the inner side of the reaction vessel 110 in the vicinity of the boundary surface, thus boosting the generation of the circulating flow in the interior of the reaction vessel 110.
[0034]
[0035] Note that the simulation was performed under the following conditions.
[0036] Diameter of reaction vessel: 3200 mm
[0037] Stirring blade: Maxblend
[0038] Shape of heat transfer pipe: Hairpin coil shape
[0039] Number of heat transfer pipes: 16
[0040] Distance between adjacent heat transfer pipes: 6.875% of diameter of reaction vessel
[0041] Coil radius: 82.6 mm
[0042] Number of baffles: 4
[0043] Content liquid (virtual polymerization solution): Water
[0044]
[0045] As illustrated in
[0046] Furthermore, as clearly illustrated from a comparison of
[0047] The baffles 140 are arranged at equal intervals along the vessel wall of the reaction vessel 110. From the point of view of effectively improving the miscibility of the polymerization solution, from one to four of the baffles 140 are preferably arranged, and more preferably, from two to four of the baffles 140 are arranged in the reaction vessel 110.
[0048] Note that the baffles 140 are arranged such that the upper ends thereof are arranged at the position of the liquid surface, or are arranged at a position that is higher than the position of the liquid surface. Of these, the baffles 140 are preferably arranged such that the upper ends thereof are arranged at a position that is higher than the position of the liquid surface. When the upper ends of the baffles 140 are arranged at the position that is higher than the position of the liquid surface, the baffles 140 disturb the boundary surface of the polymerization solution, and cause the flow from the outer side to the inner side in the vicinity of the boundary surface of the polymerization solution to more easily occur. In the vicinity of the boundary surface of the polymerization solution, from the point of view of effectively causing the above described flow from the outer side to the inner side to occur, the position of the upper ends of the baffles 140 are preferably at a position that is higher than the position of the liquid surface, by an amount that is from 10% to 50% of the liquid level height above the position of the liquid surface.
[0049] An extending length of the baffles 140 from the vessel wall toward the inner direction is not particularly limited, and can be from 10% to 30% of a distance from the vessel wall to the center of the reaction vessel 110 (a radius of the reaction vessel 110), and is preferably from 14% to 24% of the distance. Note that, from the point of view of causing the flow from the outer side to the inner side in the vicinity of the boundary surface of the polymerization solution to occur more easily, the extending direction of the above described baffles 140 is preferably shorter than the distance between the vessel wall of the reaction vessel 110 and the heat transfer pipes 130.
[0050] The reactor 100 can also be applied to any polymerization reaction that performs a reaction in a liquid phase. In particular, even when the number of the heat transfer pipes 130 is increased in order to increase the heat removal performance when the polymerization solution is caused to be a high concentration or the like, the reactor 100 can sufficiently mix the polymerization solution that has become highly viscous, and can also prevent the adhesion of the reaction product to the stirring blade 120, the vessel wall of the reaction vessel 110 and the like. Furthermore, even when granulating and collecting the reaction product, such as the polymer, inside the reaction vessel 110, for example, the reactor 100 can prevent the adhesion of the particulate form reaction product to the stirring blade 120, the vessel wall of the reaction vessel 110, and the like.
[0051] For example, when producing a polyarylene sulfide (PAS) or the like, raw materials (paradichlorobenzene (p-DCB) as a monomer and sodium sulfide (Na.sub.2S) when producing polyphenylene sulfide (PPS), for example), are heated in a polar solvent (such as N-methylpyrrolidone (NMP) or the like), and polymerization is performed in two stages. At this time, in the first stage, the prepolymer is produced such that a monomer conversion ratio is 90% or more, and in the second stage, a liquid-liquid phase separation state configured by a dense phase and a dilute phase of different polymer concentrations is caused to be expressed in the above described prepolymer having a high moisture content and a high temperature, the polymerization reaction is caused to progress in the above described dense phase, and the polymer is caused to have a high molecular weight. After that, the PAS is granulated by lowering a reaction temperature, and slurry is collected and sieved. As a result, the particulate form PAS can be obtained.
[0052] In the above described production of the PAS, when the monomer that is the raw material is caused to have a high concentration in order to increase the yield, in order to prevent a runaway reaction caused by the reaction heat that occurs in large quantities in the first stage, there is a demand to improve the heat removal performance of the reactor 100. In order to improve the heat removal performance, with respect to this, when the multiple heat transfer pipes having the hairpin coil shape and the reduced diameter are arranged in the circumferential shape in order to increase the heating surface area of the heat transfer pipes while maintaining the practical volume, the mixing of the polymerization solution is obstructed. This causes an insufficient polymerization to occur, and the polymer and causes the granulated particles that are the reaction products to more easily adhere to the stirring blade 120 and the vessel wall of the reaction vessel 110.
[0053] In contrast, in the reactor 100 according to the present embodiment, a deterioration in the mixing performance of the polymerization solution is prevented while increasing the number of heat transfer pipes, and therefore problems such as the above described insufficient polymerization and the adhesion of the polymer and the granulated particles that are the reaction products do not easily occur.
[0054] Note that the above described embodiment merely illustrates a specific example of embodying the present invention, and should not be interpreted to limit a technical range of the present invention. Specifically, the present invention can be embodied in various ways insofar as they do not depart from the gist and main features of the present invention.
[0055] For example, as illustrated in
[0056] Furthermore, in the above described embodiment, the reaction vessel has a configuration in which the upper lid is opened and closed so as to remove the polymerization solution after the reaction, but may have a configuration in which a valve or a removal port is provided in a bottom portion of the reaction vessel and the polymer and other reaction products are removed from the bottom portion.
[0057] Furthermore, the above described plurality of heat transfer pipes may be configured such that, while being installed in the reactor, the positions thereof can be moved in the horizontal direction, and the gap between the adjacent heat transfer pipes is variable. In this way, when cleaning inside the vessel or the like, the gap between the heat transfer pipes can be widened, and cleaning of the vessel wall of the reaction vessel can be easily performed.
INDUSTRIAL APPLICABILITY
[0058] Even when the reaction raw material is caused to be a high concentration in order to increase the yield, for example, the reactor of the present embodiment can increase the mixing performance and can prevent insufficient polymerization and adhesion of the polymer, which is the reaction product, and the granulated particles, while sufficiently removing the heat from the polymerization and preventing the runaway reaction. Thus, the present invention can enable production of the polymer with a higher yield, and is expected to contribute to the development of this field.
REFERENCE SIGNS LIST
[0059] 100 Reactor [0060] 110 Reaction vessel [0061] 112 Supply port [0062] 114 Jacket [0063] 120 Stirring blade [0064] 130 Heat transfer pipe [0065] 140 Baffle