WO2013146699A1 - 重合反応器、および吸水性樹脂の製造方法 - Google Patents
重合反応器、および吸水性樹脂の製造方法 Download PDFInfo
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- WO2013146699A1 WO2013146699A1 PCT/JP2013/058618 JP2013058618W WO2013146699A1 WO 2013146699 A1 WO2013146699 A1 WO 2013146699A1 JP 2013058618 W JP2013058618 W JP 2013058618W WO 2013146699 A1 WO2013146699 A1 WO 2013146699A1
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- container body
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- support layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
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- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
- B01J2219/0236—Metal based
Definitions
- the present invention relates to a polymerization reactor for performing a polymerization reaction, and in particular, a polymerization reactor configured to perform heat exchange through a wall of a container body by passing a cooling medium, and the polymerization reactor.
- the present invention relates to a method for producing a water absorbent resin.
- a polymerization reactor used at the time of producing a polymer such as a water-absorbing resin is generally provided so as to cover a container main body 91 for containing a reaction liquid and the outer surface of the container main body 91.
- a jacket provided with a jacket (jacket portion 92) is employed.
- a cooling medium (refrigerant or heating medium) is allowed to flow through the jacket portion 92 as necessary, and the contents (for example, reaction liquid or reaction mixture) are cooled or heated by heat exchange through the wall surface of the container body 91. And the contents of the container main body 91 are controlled to reach a predetermined temperature.
- the container main body 91 since predetermined
- the vessel main body 91 is provided with a stirring blade 93, and the operation of the stirring blade 93 makes the contents uniform and uniform.
- a polymerization reactor equipped with a container main body and a mantle is described, for example, in Patent Document 1 below.
- the following three factors are given as representative factors that affect the heat transfer efficiency (heat transfer amount Q) between the cooling medium and the contents through the wall of the container body. It is done.
- the first factor is the heat transfer resistance between the cooling medium and the wall of the container body (for example, the flow rate of the cooling medium medium in the jacket), and the second factor is the heat transfer resistance between the wall of the container body and the contents.
- the third factor is the metal resistance by the wall of the container body itself.
- the first factor is an increase in the flow rate of the cooling medium in the jacket portion
- the second factor is the homogenization or temperature equalization of the contents by the stirring blades.
- the third factor metal resistance
- the third factor has the greatest effect on the overall heat transfer coefficient. Therefore, in order to shorten the heat transfer time, it is considered most effective to reduce the thickness of the wall of the container body.
- Patent Document 1 discloses a configuration in which a passage of the cooling medium is formed inside the container body.
- a belt-like support is provided on the inner surface of the container body in an upright state at a predetermined interval by welding, and the interval between adjacent supports is arranged. Is attached to the tip of the support by welding.
- the sealed space defined by the wall of the container body, the support, and the tension plate serves as a passage for the cooling medium.
- the structure in which the partition wall of the cooling medium passage provided inside the container main body is thin and this partition wall is provided by welding has poor reliability in long-term use in consideration of damage due to aging of the partition wall. .
- the water-soluble ethylenically unsaturated monomer is an acidic substance, usually sodium hydroxide. Used after neutralization.
- an organic solvent is used as a reaction solvent.
- acid, alkali or organic solvent is used in the polymerization reaction, and therefore, the material of the polymerization reactor (container body) should be a corrosion-resistant metal such as stainless steel. Is considered.
- the container body 91 is made of stainless steel in the structure shown in FIG. 4, heating or cooling of the reaction liquid (contents) is provided outside the container body.
- the cooling medium is allowed to flow through the jacket 92, the heat transfer efficiency through the wall of the container body is reduced, and the heat transfer time is longer than that of carbon steel even with the same thickness. .
- the present invention has been conceived under such circumstances, and provides a polymerization reactor suitable for shortening the heat transfer time in the polymerization process while maintaining reliability in long-term use.
- the challenge is to do.
- Another object of the present invention is to provide a method suitable for efficiently producing a water absorbent resin using such a polymerization reactor.
- the polymerization reactor provided by the first aspect of the present invention is provided so as to cover the outer surface of the container body and the container body, and a passage for allowing a cooling medium to flow between the outer surface of the container body.
- the container body has a metal support layer having an inner surface located inside the container body and an outer surface located outside the container body, and joined to the inner surface of the metal support layer And a clad metal plate having an inner skin layer made of a corrosion-resistant metal having a thickness smaller than that of the metal support layer.
- the inner skin layer has a thickness of 1/10 to 1/2 of the thickness of the metal support layer.
- the clad metal plate further includes an outer skin layer made of a corrosion-resistant metal bonded to the outer surface of the metal support layer, and the outer skin layer has a thickness smaller than that of the metal support layer.
- the metal support layer is made of carbon steel, and the outer skin layer and the inner skin layer are made of stainless steel.
- the thickness of the inner skin layer is larger than the thickness of the outer skin layer.
- the metal support layer has a thickness of 5 to 15 mm.
- an inert gas supply means for supplying an inert gas to the passage is further provided.
- the inside of the jacket portion is partitioned by a spiral partition plate, and the passage extends spirally along the partition plate.
- the container body has an upper end opening that is closed by a lid.
- the lid is joined to an additional metal support layer having an inner surface located inside the container body and an outer surface located outside the container body, and an inner surface of the additional metal support layer, It is constructed using an additional clad metal plate having an additional inner skin layer made of a corrosion resistant metal that is thinner than the additional metal support layer.
- the additional clad metal plate further has an additional outer skin layer made of a corrosion-resistant metal bonded to an outer surface of the additional metal support layer, and the additional outer skin layer is the additional metal layer.
- the thickness is smaller than the support layer.
- the method for producing a water-absorbent resin provided by the second aspect of the present invention is a method for producing a water-absorbent resin comprising reverse-phase suspension polymerization of a water-soluble ethylenically unsaturated monomer in a petroleum hydrocarbon dispersion medium. Then, the polymerization reaction is performed in the container body in the polymerization reactor according to the first aspect of the present invention.
- FIG. 1 It is a longitudinal section showing a schematic structure of a polymerization reactor concerning an embodiment of the present invention. It is a principal part enlarged view of FIG. It is a table
- the polymerization reactor X of this embodiment includes a container body 1, a jacket portion 2, and a lid 3.
- the container body 1 has a cylindrical side wall portion 11 and a bottom wall portion 12 integrally welded to the lower end of the side wall portion 11.
- the side wall part 11 is comprised with the three-layer clad steel plate. More specifically, as shown in FIG. 2, the three-layer clad steel plate constituting the side wall portion 11 is made of, for example, stainless steel skin layers 11b and 11c on both surfaces of a support layer 11a made of a carbon steel plate. Is pressure-bonded by hot rolling.
- a cylindrical side wall 11 is formed by bending the three-layer clad steel plate into a cylindrical shape and welding and joining both end edges that face each other along the axial direction of the cylinder.
- the upper end portion of the side wall portion 11 is open, and an annular flange 111 is integrally formed on the outer periphery of the upper end portion.
- the dimension of the side wall 11 is that the diameter is about 200 to 400 cm and the height (length in the axial direction) is about 200 to 600 cm.
- the thickness of the support layer 11a in the side wall 11 is, for example, about 5 to 15 mm
- the thickness of the inner skin layer 11b is, for example, about 1 to 4 mm
- the thickness of the outer skin layer 11c is, for example, about 1 to 3 mm.
- the thickness of the inner skin layer 11b is larger than the thickness of the outer skin layer 11c.
- the thickness of the inner skin layer 11b is preferably in the range of 1/10 to 1/2 of the thickness of the support layer 11a, more preferably in the range of 1/5 to 1/2 of the thickness of the support layer 11a.
- the bottom wall portion 12 is configured by using the same three-layer clad steel plate as the three-layer clad steel plate constituting the side wall portion 11, and is formed in a downward convex surface shape (for example, a hemispherical shape).
- the bottom wall portion 12 is welded to the lower end of the side wall portion 11 along the circumferential direction of the side wall portion 11.
- the bottom wall portion 12 includes a support layer and a skin layer bonded to each of both surfaces of the support layer.
- the thickness of the inner skin layer in the bottom wall portion 12 is larger than the thickness of the outer skin layer.
- the inner skin layer 11b is a corrosion-resistant metal layer
- the outer skin layer 11c is an additional corrosion-resistant metal layer. .
- a stirring blade 13 for stirring the inside of the container body 1 is provided on the bottom wall portion 12 of the container body 1.
- the stirring blade 13 passes through the center of the bottom wall portion 12.
- the bottom wall 12 is provided with a discharge port 121 for discharging the contents of the container body 1 to the outside.
- the internal volume of the container body 1 having the above configuration is, for example, about 10 to 60 m 3 .
- the jacket part 2 covers the outer surface of the container body 1.
- the jacket portion 2 covers a range from the upper portion of the side wall portion 11 to the bottom wall portion 12 so as to form a passage through which the cooling medium flows, between the outer surface of the container body 1.
- the jacket part 2 is made of stainless steel, for example, and is joined to the container body 1 by welding.
- An inlet 21 for introducing a cooling medium into the jacket 2 is provided at the lower part of the jacket 2, and an outlet 22 for leading the cooling medium in the jacket 2 to the outside at the upper part of the jacket 2. Is provided.
- a partition plate 23 is provided on the inner side of the jacket portion 2 for allowing the cooling medium to flow spirally on the outer periphery of the container body 1.
- the partition plate 23 is in the form of a spiral band, and is welded to the inner surface of the jacket portion 2 in an upright state, for example.
- a spiral passage is formed by a space surrounded by the outer surface of the container body 1, the inner surface of the jacket portion 2, and the spiral partition plate 23.
- the introduction port 21 is connected to a cooling medium tank (not shown), and a cooling medium adjusted to a desired temperature is introduced into the jacket portion 2 through the introduction port 21.
- the outlet 22 is connected to a temperature control device (not shown).
- the cooling medium that has passed through the jacket portion 2 is introduced into a temperature adjusting device (not shown) through the outlet port 22, adjusted to a desired temperature, and then supplied to the cooling medium tank.
- the cooling medium supplied from the cooling medium tank passes through the jacket portion 2 and the temperature adjusting device in this order, and is circulated.
- the cooling medium passed through the jacket portion 2 is, for example, a liquid such as water or ethylene glycol (antifreeze).
- a branch pipe 24 is connected to the end of the outlet 22.
- nitrogen (N 2 ) which is a kind of inert gas
- An on-off valve (not shown) is provided on the downstream side of the branch pipe 24, and the on-off valve is closed when the supply of the cooling medium into the jacket portion 2 is stopped.
- the lid 3 covers the upper end opening of the container body 1 and is made of, for example, a three-layer clad steel plate similar to the side wall 11.
- the lid 3 is formed in an upward convex shape (for example, a hemispherical shape).
- a supply port 31 for supplying a reaction liquid or the like is provided at the top of the lid 3.
- An annular flange 32 is integrally formed on the outer periphery of the lower end portion of the lid 3, and the container body 1 and the lid 3 are connected to bolt holes (not shown) formed in the flanges 111 and 32. They are fixed in a sealed state by bolts (not shown) to be inserted.
- an appropriate sealing material is interposed between the flange 111 of the container main body 1 and the flange 32 of the lid 3, and the sealed state in the container main body 1 is maintained.
- the polymerization reactor X can be used as a container for performing various polymerization reactions, in this embodiment, the polymerization reactor X is used for producing a water-absorbing resin by the reverse phase suspension polymerization method. The case will be described.
- a water-soluble ethylenically unsaturated monomer is used in a petroleum hydrocarbon dispersion medium (organic solvent) using a radical polymerization initiator in the presence of a dispersant, Reverse phase suspension polymerization is performed.
- Reverse phase suspension polymerization is performed.
- the multistage polymerization reaction by the reverse phase suspension polymerization method is preferable in that the obtained water-absorbent resin has a large particle size, good wettability with water and productivity can be improved, and the amount of dispersant used is reduced.
- a petroleum hydrocarbon dispersion medium and a dispersant are introduced into the container body 1. Then, while stirring the inside of the container body 1 with the stirring blade 13, the heating medium is passed through the jacket portion 2 to heat the inside of the container body 1 to a predetermined temperature (for example, about 90 ° C.) (first). Heating step), a dispersant is dissolved in a petroleum hydrocarbon dispersion medium. Next, a coolant is passed through the jacket portion 2 to cool the inside of the container body 1 until a predetermined temperature (for example, about 50 ° C.) is reached (first cooling step).
- a predetermined temperature for example, about 50 ° C.
- the monomer solution is preferably prepared by adding a radical polymerization initiator to an aqueous solution of a water-soluble ethylenically unsaturated monomer.
- a radical polymerization initiator to an aqueous solution of a water-soluble ethylenically unsaturated monomer.
- the acid group may be neutralized with an alkaline neutralizing agent.
- the monomer solution adjusted to a predetermined temperature for example, about 10 ° C.
- a predetermined temperature for example, about 30 ° C.
- stable suspension is achieved.
- the heating medium is passed through the jacket portion 2 to heat the inside of the container body 1 to a predetermined temperature (for example, about 55 ° C.) (second).
- Heating step First stage polymerization is started. At this time, the temperature of the contents rises due to the heat of polymerization.
- a refrigerant for example, the same heat medium passed at the start of the previous polymerization
- a refrigerant for example, the same heat medium passed at the start of the previous polymerization
- the polymerization is performed for a predetermined time while maintaining a predetermined high temperature state (for example, about 80 ° C.).
- a coolant is passed through the jacket portion 2 to cool the contents of the container body 1 to a predetermined temperature (for example, about 5 to 30 ° C.) (second cooling step). A mixture is obtained.
- the second-stage monomer solution is added into the container body 1, and the second-stage reversed-phase suspension polymerization is performed.
- the second-stage monomer solution is preferably prepared by adding a radical polymerization initiator to an aqueous solution of a water-soluble ethylenically unsaturated monomer.
- a radical polymerization initiator to an aqueous solution of a water-soluble ethylenically unsaturated monomer.
- the acid group may be neutralized with an alkaline neutralizing agent.
- the second stage monomer solution adjusted to the same temperature as the reaction mixture in the container body 1 is added.
- the heating medium is passed through the jacket portion 2 to heat the inside of the container body 1 to a predetermined temperature (for example, about 55 ° C.) (third). Heating step)
- the second stage polymerization is started.
- the temperature of the contents rises due to the heat of polymerization.
- a refrigerant (same as the heating medium passed at the start of the previous polymerization) is allowed to flow through the jacket portion 2 so that the contents are predetermined.
- a refrigerant is passed through the jacket portion 2 to cool the contents of the container body 1 to a predetermined temperature (for example, about 5 to 30 ° C.) (third cooling step). A mixture is obtained.
- the third stage monomer solution is preferably prepared by adding a radical polymerization initiator to an aqueous solution of a water-soluble ethylenically unsaturated monomer.
- a radical polymerization initiator to an aqueous solution of a water-soluble ethylenically unsaturated monomer.
- the acid group may be neutralized with an alkaline neutralizing agent.
- the above third stage monomer solution adjusted to the same temperature as the reaction mixture in the container body 1 is added.
- the heating medium is passed through the jacket portion 2 to heat the inside of the container body 1 to a predetermined temperature (for example, about 55 ° C.) (fourth).
- a predetermined temperature for example, about 55 ° C.
- the third stage polymerization is started.
- the temperature of the contents rises due to the heat of polymerization.
- a refrigerant (same as the heating medium passed at the start of the previous polymerization) is allowed to flow through the jacket portion 2 so that the contents are predetermined.
- a high temperature for example, about 80 ° C.
- polymerization is carried out for a predetermined time.
- a third-stage reaction mixture is obtained.
- a water absorbing resin is obtained by isolate
- the container main body 1 (side wall portion 11 and bottom wall portion 12) is bonded to the carbon steel support layer 11a and both surfaces of the support layer 11a, and is thinner than the support layer 11a. It is comprised using the three-layer clad steel plate which has the skin layers 11b and 11c made from a stainless steel.
- the carbon steel constituting the support layer 11a is superior in strength to the stainless steel constituting the skin layers 11b and 11c and has excellent heat transfer performance, so that it is relatively thick as described above.
- the support layer 11a made of carbon steel the entire thickness of the wall (three-layer clad steel plate) of the container body 1 can be made relatively thin while ensuring a predetermined strength.
- a cooling medium (refrigerant or heating medium) is placed in the jacket portion 2 provided on the outside of the container body 1 to heat or cool the contents.
- a cooling medium refrigerant or heating medium
- the inner skin layer 11b of the container body 1 is made of stainless steel, even when it comes into contact with an acid, an alkali, and an organic solvent during the polymerization reaction of the water-absorbent resin, it is not easily corroded.
- the skin layer 11b is pressure-bonded to the support layer 11a, and the support layer 11a and the skin layer 11b are configured as a clad steel plate whose surface is uniformly pressure-bonded. Thereby, the situation that the skin layer 11b peels from the support layer 11a can be prevented, and the corrosion resistance of the inner surface of the container body 1 can be reliably maintained.
- the thickness of the skin layer 11b is set to 1/10 to 1/2 of the thickness of the support layer 11a, and an appropriate thickness is secured. This is preferable from the viewpoint of appropriately maintaining the corrosion resistance while avoiding the strength reduction of the container body 1.
- the jacket part 2 is provided so as to cover the outer surface of the container body 1, and a cooling medium is passed between the container body 1 and the jacket part 2. Therefore, the polymerization reactor X of the present embodiment can easily check the status of the jacket portion 2 as compared with, for example, a case where a cooling medium passage is provided inside the container body, and can be used for a long time. Excellent in reliability.
- the container main body 1 (side wall portion 11 and bottom wall portion 12) has a skin layer 11c (12c) made of stainless steel on the outside. Thereby, it can prevent that the container main body 1 corrodes by the cooling medium which flows through the channel
- a skin layer 11c (12c) made of stainless steel on the outside.
- the container body 1 can be composed of a two-layer clad steel plate having a support layer 11a and an inner skin layer 11b.
- the cooling and heating operations are repeatedly performed, and the ratio of the heat transfer time in the entire polymerization time (polymerization process time) is relatively large. Therefore, the rate of shortening the polymerization process time by shortening the heat transfer time is also relatively large, which contributes to the improvement of production efficiency.
- the container body is made of a three-layer clad steel plate in which stainless steel skin layers 11b, 11c (corrosion resistant metal layer) are pressure-bonded to both surfaces of a carbon steel support layer 11a (metal support layer).
- stainless steel skin layers 11b, 11c corrosion resistant metal layer
- metal support layer is preferably a material excellent in strength and thermal conductivity, and other materials such as an aluminum alloy may be used.
- the corrosion-resistant metal layer may be any material that has better corrosion resistance than the metal support layer, and other materials such as titanium, chromium, or alloys thereof may be used. Further, the thicknesses of the metal support layer and the corrosion-resistant metal layer can be variously changed according to the materials constituting them or the internal volume of the container body.
- Example ⁇ Using the polymerization reactor X having the schematic configuration shown in FIGS. 1 and 2, the time for each step when the water-absorbent resin was produced by the above-described reversed-phase suspension polymerization method was measured.
- a water-soluble ethylenically unsaturated monomer is suspended in a reverse phase suspension in a petroleum hydrocarbon dispersion medium using a radical polymerization initiator in the presence of a dispersant.
- a three-stage polymerization reaction was performed by a polymerization method.
- the inner volume of the container body 1 was set to 60 m 3, and a paddle blade was used as the stirring blade 13.
- the side wall part 11 and the bottom wall part 12 of the container main body 1 were configured using a three-layer clad steel plate having a thickness of 18 mm.
- the support layer 11a is a carbon steel plate for medium / normal temperature pressure vessels (JIS: SGV480; JIS: Japanese Industrial Standard) with a thickness of 13 mm
- the inner skin layer 11b is stainless steel (JIS: SUS304) with a thickness of 3 mm.
- the outer skin layer 11c was made of stainless steel (JIS: SUS304) having a thickness of 2 mm.
- a heating medium (temperature 95 ° C., flow rate 1.5 m 3 / min, the same applies hereinafter) is passed through the jacket portion 2, so The product was heated to 90 ° C. (first heating step) to dissolve the dispersant. It took 88 minutes to heat the contents in the container body 1 to 90 ° C. after passing the heating medium through the jacket portion 2.
- a refrigerant (temperature 1 ° C., flow rate 1.5 m 3 / min, the same applies hereinafter) was passed through the jacket portion 2 to cool the contents in the container body 1 to 50 ° C. (first cooling step). It took 22 minutes to cool the contents in the container body 1 to 50 ° C. after passing the cold water medium through the jacket portion 2.
- the total amount of the first-stage monomer aqueous solution adjusted to 10 ° C. was added to the container body 1, the contents of the container body 1 were set to 30 ° C., and the system was sufficiently replaced with nitrogen.
- the heating medium is passed through the jacket part 2 and the contents in the container body 1 are heated to 55 ° C. (second heating step), Polymerization was started. After passing the heating medium through the jacket part 2, it took 26 minutes to raise the contents in the container body 1 to 55 ° C. After the polymerization is started, the content of the container body 1 is heated by the polymerization heat, and after the content reaches 80 ° C., polymerization is performed at 80 ° C. for 30 minutes, and then a refrigerant is passed through the jacket portion 2. The contents of the container body 1 were cooled to 13 ° C. (second cooling step) to obtain a first-stage reaction mixture. It took 107 minutes to cool the contents of the container body 1 to 13 ° C. after passing the coolant through the jacket portion 2.
- the heating medium is passed through the jacket portion 2 and the contents in the container body 1 are heated to 55 ° C. (third heating step), Polymerization was started. It took 48 minutes to pass the heating medium through the jacket part 2 and to raise the contents in the container body 1 to 55 ° C.
- the content of the container body 1 is heated by the polymerization heat, and after the content reaches 80 ° C., polymerization is performed at 80 ° C. for 30 minutes, and then a refrigerant is passed through the jacket portion 2.
- the contents of the container main body 1 were cooled to 13 ° C. (third cooling step) to obtain a second-stage reaction mixture. It took 132 minutes to cool the contents of the container body 1 to 13 ° C. after passing the coolant through the jacket portion 2.
- the hot water medium is passed through the jacket portion 2 and the contents in the container body 1 are heated to 55 ° C. (fourth heating step).
- the polymerization was started. After passing the hot water medium through the jacket portion 2, it took 54 minutes to raise the contents in the container body 1 to 55 ° C.
- the content of the container body 1 was heated by the polymerization heat, and polymerization was performed at 80 ° C. for 30 minutes from the time when the content reached 80 ° C. to obtain a third-stage reaction mixture. From the third-stage reaction mixture, n-heptane and water were separated by azeotropic distillation of n-heptane and water.
- the n-heptane was returned to the container body 1 and 16441 kg of water was extracted out of the system.
- the n-heptane was evaporated and dried to obtain 11315 kg of a water absorbent resin.
- the time required for each step in this example is shown in FIG.
- a water-absorbing resin was produced under the same conditions as in the above examples except that the material of the container body was made of stainless steel.
- the polymerization reactor used in this comparative example had the same internal volume of the container body as 60 m 3, and the stirring blade used the same paddle blade as in the above example.
- the container body of this comparative example was configured using stainless steel (JIS: SUS304) having a thickness of 18 mm, and was set to have the same strength as the container body 1 of the above example.
- the supply mode of the refrigerant and the heat medium was also the same as in the above example.
- the first heating process it took 113 minutes to raise the contents in the container body to 90 ° C.
- the first cooling step it took 28 minutes to cool the contents in the container body to 50 ° C.
- the second heating step it took 33 minutes to raise the contents in the container body to 55 ° C.
- the second cooling step it took 135 minutes to lower the contents in the container body to 13 ° C.
- the third heating step it took 61 minutes to raise the contents in the container body to 55 ° C.
- the third cooling step it took 165 minutes to lower the contents in the basic body to 13 ° C.
- the fourth heating step it took 69 minutes to raise the contents in the container body to 55 ° C.
- the time required for each process in this comparative example is shown in FIG.
- the heat transfer time is 21% compared to the comparative example in which the container body is configured by using stainless steel.
- an Example has a shortening effect of 18% compared with a comparative example, and when manufacturing the said water absorbing resin by batch processing, the improvement of production efficiency is anticipated.
Abstract
Description
図1、図2に示す概略構成を有する重合反応器Xを使用して、上述した逆相懸濁重合法による吸水性樹脂の製造を行う場合の各工程の時間を測定した。本実施例における吸水性樹脂の製造においては、水溶性エチレン性不飽和単量体を、石油系炭化水素分散媒中で、分散剤の存在下にラジカル重合開始剤を用いて、逆相懸濁重合法により3段の重合反応を行った。
上記実施例とは異なる重合反応器を使用して、上述した逆相懸濁重合法による吸水性樹脂の製造を行う場合の重合工程時間を測定した。
1 容器本体
2 ジャケット部
3 蓋体
11 側壁部
12 底壁部
11a,12a 支持層(金属支持層)
11b,12b 表皮層(耐腐食性金属層)
11c,12c 表皮層(追加の耐腐食性金属層)
111 フランジ
121 排出口
13 攪拌翼
21 導入口
22 導出口
23 仕切板
31 供給口
32 フランジ
Claims (12)
- 重合反応を行うための重合反応器であって、
容器本体と、当該容器本体の外面を覆うように設けられ、上記容器本体の外面との間に冷熱媒体を通流させるための通路を形成するジャケット部と、を備え、
上記容器本体は、上記容器本体の内側に位置する内面と上記容器本体の外側に位置する外面とを有する金属支持層と、当該金属支持層の内面に接合され、上記金属支持層よりも厚みの小さい耐腐食性金属からなる内側表皮層と、を有するクラッド金属板を用いて構成されている、重合反応器。 - 上記内側表皮層の厚みは、上記金属支持層の厚みの1/10~1/2である、請求項1に記載の重合反応器。
- 上記クラッド金属板は、上記金属支持層の外面に接合された耐腐食性金属からなる外側表皮層をさらに有し、上記外側表皮層は上記金属支持層よりも厚みが小さい、請求項1または2に記載の重合反応器。
- 上記金属支持層は炭素鋼からなり、上記外側表皮層および上記内側表皮層はステンレス鋼からなる、請求項3に記載の重合反応器。
- 上記内側表皮層の厚みは、上記外側表皮層の厚みより大きい、請求項3または4に記載の重合反応器。
- 上記金属支持層の厚みは5~15mmである、請求項1ないし5のいずれかに記載の重合反応器。
- 不活性ガスを上記通路に供給するための不活性ガス供給手段をさらに備える、請求項1ないし6のいずれかに記載の重合反応器。
- 上記ジャケット部は螺旋状の仕切板により内部が仕切られており、上記通路は上記仕切板に沿って螺旋状に延びる、請求項1ないし7のいずれかに記載の重合反応器。
- 上記容器本体は、蓋体によって閉鎖された上端開口を有している、請求項1ないし8のいずれかに記載の重合反応器。
- 上記蓋体は、上記容器本体の内側に位置する内面と上記容器本体の外側に位置する外面とを有する追加の金属支持層と、当該追加の金属支持層の内面に接合され、上記追加の金属支持層よりも厚みの小さい耐腐食性金属からなる追加の内側表皮層と、を有する追加のクラッド金属板を用いて構成されている、請求項9に記載の重合反応器。
- 上記追加のクラッド金属板は、上記追加の金属支持層の外面に接合された耐腐食性金属からなる追加の外側表皮層をさらに有し、上記追加の外側表皮層は上記追加の金属支持層よりも厚みが小さい、請求項10に記載の重合反応器。
- 石油系炭化水素分散媒中で水溶性エチレン性不飽和単量体を逆相懸濁重合する吸水性樹脂の製造方法であって、
請求項1ないし11のいずれかに記載の重合反応器における上記容器本体内にて重合反応を行う、吸水性樹脂の製造方法。
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EP13768824.8A EP2832751B1 (en) | 2012-03-29 | 2013-03-25 | Polymerization reactor and method for manufacturing water-absorbing resin |
SG11201405562PA SG11201405562PA (en) | 2012-03-29 | 2013-03-25 | Polymerization reactor and method for manufacturing water-absorbing resin |
KR1020147025889A KR101991540B1 (ko) | 2012-03-29 | 2013-03-25 | 중합 반응기, 그리고 흡수성 수지의 제조 방법 |
US14/382,996 US20150080539A1 (en) | 2012-03-29 | 2013-03-25 | Polymerization reactor and method for producing water absorbent resin |
BR112014022148-0A BR112014022148B1 (pt) | 2012-03-29 | 2013-03-25 | Reator de polimerização |
RU2014135560A RU2614433C2 (ru) | 2012-03-29 | 2013-03-25 | Реактор полимеризации и способ получения водопоглощающей смолы |
CN201380016285.1A CN104203988B (zh) | 2012-03-29 | 2013-03-25 | 聚合反应器和吸水性树脂的制造方法 |
JP2014507871A JP6069299B2 (ja) | 2012-03-29 | 2013-03-25 | 重合反応器、および吸水性樹脂の製造方法 |
US15/630,564 US10207243B2 (en) | 2012-03-29 | 2017-06-22 | Polymerization reactor and method for producing water absorbent resin |
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JP2020518702A (ja) * | 2017-05-02 | 2020-06-25 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 疎水性溶媒中に分散されたモノマー水溶液の重合による超吸収剤粒子の不連続的な製造方法 |
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JP7130670B2 (ja) | 2017-05-02 | 2022-09-05 | ビーエーエスエフ ソシエタス・ヨーロピア | 疎水性溶媒中に分散されたモノマー水溶液の重合による超吸収剤粒子の不連続的な製造方法 |
KR20220054051A (ko) * | 2020-10-23 | 2022-05-02 | 주식회사 엘지화학 | 고흡수성 수지 제조용 중합 반응기 |
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EP2832751B1 (en) | 2021-02-24 |
US20150080539A1 (en) | 2015-03-19 |
CN104203988A (zh) | 2014-12-10 |
SA113340425B1 (ar) | 2015-10-22 |
RU2614433C2 (ru) | 2017-03-28 |
EP2832751A1 (en) | 2015-02-04 |
JPWO2013146699A1 (ja) | 2015-12-14 |
TW201406788A (zh) | 2014-02-16 |
BR112014022148B1 (pt) | 2021-04-27 |
US20170282146A1 (en) | 2017-10-05 |
US10207243B2 (en) | 2019-02-19 |
KR20140140034A (ko) | 2014-12-08 |
JP6069299B2 (ja) | 2017-02-01 |
EP2832751A4 (en) | 2015-11-11 |
KR101991540B1 (ko) | 2019-06-20 |
SG11201405562PA (en) | 2014-10-30 |
TWI568750B (zh) | 2017-02-01 |
CN104203988B (zh) | 2016-02-10 |
RU2014135560A (ru) | 2016-05-20 |
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