WO2016052634A1 - 溶液移送冷却装置 - Google Patents
溶液移送冷却装置 Download PDFInfo
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- WO2016052634A1 WO2016052634A1 PCT/JP2015/077767 JP2015077767W WO2016052634A1 WO 2016052634 A1 WO2016052634 A1 WO 2016052634A1 JP 2015077767 W JP2015077767 W JP 2015077767W WO 2016052634 A1 WO2016052634 A1 WO 2016052634A1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
- F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/10—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically
- F28D7/106—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically consisting of two coaxial conduits or modules of two coaxial conduits
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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
- B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
- B01J19/1875—Stationary reactors having moving elements inside resulting in a loop-type movement internally, i.e. the mixture circulating inside the vessel such that the upwards stream is separated physically from the downwards stream(s)
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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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F1/00—Tubular elements; Assemblies of tubular elements
- F28F1/003—Multiple wall conduits, e.g. for leak detection
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/082—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys
- F28F21/083—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys from stainless steel
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/085—Heat exchange elements made from metals or metal alloys from copper or copper alloys
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F9/00—Casings; Header boxes; Auxiliary supports for elements; Auxiliary members within casings
- F28F9/02—Header boxes; End plates
- F28F9/0236—Header boxes; End plates floating elements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
- F28G5/00—Cleaning by distortion
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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
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00085—Plates; Jackets; Cylinders
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/10—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/10—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically
- F28D7/103—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically consisting of more than two coaxial conduits or modules of more than two coaxial conduits
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
- F28D7/1607—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation with particular pattern of flow of the heat exchange media, e.g. change of flow direction
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F1/00—Tubular elements; Assemblies of tubular elements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/002—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using inserts or attachments
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2255/00—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes
- F28F2255/04—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes comprising shape memory alloys or bimetallic elements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
- F28G13/00—Appliances or processes not covered by groups F28G1/00 - F28G11/00; Combinations of appliances or processes covered by groups F28G1/00 - F28G11/00
Definitions
- the present invention relates to a solution transfer cooling device. More specifically, when producing polymer products such as polyethylene and polypropylene, for example, adhesion of a polymer to the inner wall of a polymer reactor by reacting a catalyst with ethylene in a solvent such as normal hexane to form polyethylene, The deposition of the polymer on the inner wall of the transfer means for cooling and transferring the mixed solution of the solvent and the polymerization product from the polymer reactor to the post-treatment apparatus such as pelletization, so-called polymer fouling occurs.
- the present invention relates to a solution transfer cooling device capable of easily and efficiently removing the polymer fouling and the like.
- a shell and tube heat exchanger is set as the transfer means for cooling and transferring from the inner wall of the polymer reactor and the polymer reactor to the post-treatment apparatus such as pelletization in order to remove the heat of reaction.
- polymer fouling is formed on the inner wall of the metal pipe separating the coolant and the polymer contained in the solvent.
- polymer fouling has a thermal conductivity lower by about two orders of magnitude compared to metal tubes, polymer fouling significantly reduces the removal of the heat of reaction removal or cooling. At the same time, the substantial reduction in pipe diameter increases the load on the transport pump, causing damage to the transport pump and an adverse effect on flow reduction.
- an antifouling agent containing a polyoxyethylene polymer having a number average molecular weight of 30,000 or less represented by a specific general formula is used as a solvent polymer in a polymerization apparatus or in a later step It has been proposed to add to in-solution components (see, for example, Patent Document 1).
- Another prior art polymer fouling prevention method that is, an olefin polymerization method as an olefin polymerization method which prevents clogging of a catalyst slurry supply system to a polymerization reactor and enables continuous operation, is supported on a solid
- an olefin polymerization method as an olefin polymerization method which prevents clogging of a catalyst slurry supply system to a polymerization reactor and enables continuous operation, is supported on a solid
- a heat transfer device 10 for heating or cooling a process stream the heat transfer device 10 being a tube formed of a steel alloy comprising X, Y and Z, wherein the tube is 40 micro inches Chromium-enriched oxidation comprising 10 to 40% by weight of chromium formed on at least one of an inner surface and an outer surface of a base layer of a steel alloy having an arithmetic average surface roughness of less than (1.1 ⁇ m)
- Heat transfer device 10 and the like including three layers of the above-mentioned chromium-enriched oxide layer containing a substance layer, a sulfide, an oxide, an acid sulfide or a mixture thereof It has a surface protective layer formed on the surface has been proposed (e.g., see Patent Document 3).
- Patent No. 5399478 gazette JP, 2010-006988, A JP, 2013-011437, A Japanese Patent Application Laid-Open No. 10-204668 JP 05-093001 A JP, 2012-232512, A
- Non-Patent Document 1 As shown in Non-Patent Document 1, polymer fouling is physically passed at high speed, formation of a protective layer on the contact surface, retention prevention, chemically adding an antistatic agent It is thought that it is possible to eliminate it by etc.
- none of the polymer fouling measures in the above patent are incomplete, and the decrease in cooling efficiency due to the occurrence of polymer fouling or the narrowing of the flow path due to polymer fouling, that is, the decrease in flow rate , Remains a major obstacle in the industry.
- Patent Document 6 it is extremely difficult to mount the flexible and wound inner tube on the entire length of each cylindrical tube of the transfer device which bundles cylindrical cylinders, for example, about 10 meters. Yes, it is estimated that industrial implementation is practically impossible.
- the polymer transfer cooling device has an outer diameter of 25.4 mm, a wall thickness of 1.2 mm, and a length of 170 cm in diameter in a circular cross section.
- About 1,500 of the 10-meter SUS304 cylindrical tubes are fixed at an equal pitch to form a cylindrical tube bundle.
- the whole of the cylindrical tube bundle is mounted in the pressure-resistant shell, and the refrigerant flows into the space between the cylindrical tube bundles by press-fitting the refrigerant from the lower inlet in the shell.
- the refrigerant flows around each cylindrical tube to cool the mixed solution of the solvent and the polymer in each cylindrical tube.
- the polymer which is in a supersaturated state by being cooled is separated from the solvent and separated and partially adheres to the tube wall to form fouling.
- the liquid-solid mixed liquid flows in the cylindrical pipe having a narrow flow path, the flow rate of the constant pressure pump decreases, and steady operation can not be performed.
- This polymer transfer cooling system is a pressure vessel, and the regulations require regular inspections.
- the polymer solution transfer cooling device described above is usually operated continuously for 24 hours. In that case, after about six months to one year, the polymer fouling deposited and deposited on the inner wall of the cylindrical tube increases exponentially, and the flow of the polymer product solution becomes significantly impeded. As a result, the discharge amount of the constant pressure pump decreases, and steady operation conditions can not be secured, and the operation of the cooling device must be stopped to remove the polymer fouling.
- the removal operation of the polymer furring of the polymer transfer device is carried out by high pressure water washing in most cases in the industry.
- high-pressure water washing high-pressure water pressurized by a reciprocating pump is jetted from a nozzle, and polymer furling deposited by jet impact energy is peeled from a pipe wall, crushed, discharged, and removed.
- high pressure of 7 MPa or more and 30 MPa for example, high pressure of 7 MPa or more and 30 MPa, ultra high pressure of 30 MPa or more and 100 MPa, and ultra high pressure of 100 MPa or more and 250 MPa or more are also performed.
- high-pressure water cleaning is carried out by a worker who has received a specific test, and a supervisor is placed You have to make a good foothold. It may take two weeks or more from the setting of the scaffold to the end of the inspection to clean one polymer transfer cooling device.
- polymer production since polymer production must be stopped while high-pressure water cleaning is being performed, it causes non-operational loss, which is a serious obstacle to industrial activity.
- the present invention has been made in view of the above-described problems of the solution transfer cooling device in a polymer production line or the like not solved by any of the prior art, and it is intended to deposit solids in the solution transfer cooling device.
- Solution transfer cooling that can remove fouling deposits in a short time by a small number of on-site workers and without performing dangerous work such as high-pressure water washing with extremely simple work equipment compared to the prior art It aims at providing an apparatus.
- Another object of the present invention is to provide a solution transfer and cooling device that is less likely to cause unwanted tube deposits such as unwanted polymers in a solution such as a liquid-solid mixture produced.
- Another object of the present invention is to provide a solution transfer and cooling device which is an industrial waste discharge amount which is extremely small as compared with the industrial waste discharge amount generated by high-pressure water washing of the prior art.
- the present invention In a solution transfer and cooling device in which a plurality of rigid solution outer cylinders are arranged in parallel with each other inside a rigid refrigerant outer cylinder,
- the rigid solution cylinder has an outer diameter smaller than the inner diameter of the rigid solution cylinder at normal temperature and pressure, and is stretched by at least one of temperature increase and pressure increase of the solution to be transferred to the rigid solution cylinder.
- a thin-walled inner cylinder which is in contact with the inner surface of the housing and which is reduced due to cooling by the refrigerant or a pressure drop.
- a polymer production apparatus comprising: a polymerization reaction device; and a cooling channel (heat exchanger) connected to a polymerization product outlet of the polymerization reaction device,
- the cooling channel portion has a liquid-solid mixture transfer device in which a plurality of rigid outer cylinders are arranged in parallel with each other inside a rigid refrigerant outer cylinder,
- the rigid mixture outer cylinder has an outer diameter smaller than the inner diameter of the rigid mixture outer cylinder at normal temperature and pressure, and is extended by at least one of temperature increase and pressure increase of the solution to be transferred to the rigid mixture outer cylinder.
- a thin-walled inner cylinder which is in contact with the inner surface of the housing and which is reduced by cooling or pressure reduction of the solution by the refrigerant.
- the accumulation of solid content such as the polymer in the liquid transfer device can be removed by a small number of workers in a short time and safely by extremely simple working equipment as compared with the prior art. You can get the effect of being able to
- the solution transfer and cooling device of the present invention it is also possible to obtain the effect that there is no risk that undesired impurities such as existing polymers attached to the inner surface of the tube are mixed into the transferred cooling fluid such as newly generated polymer solution. it can.
- liquid transfer device of the present invention it is possible to obtain an effect that the discharge of industrial waste is extremely small as compared with the conventional high pressure water washing technology.
- the liquid transfer apparatus of the present invention can be suitably carried out by solution transfer in the process of physical operation such as chemical reaction such as polymerization reaction or crosslinking reaction in production of polymer, desolvation, mixing and the like.
- the present invention is also applicable to mixing of a polymer and other components in the manufacture of a composition containing a polymer such as a paint or an adhesive as a main component, and solution transfer in physical operation steps such as solvent removal.
- the present invention includes, for example, (meth) acrylic acid ester polymers such as methyl poly (meth) acrylate, ethyl poly (meth) acrylate and butyl poly (meth) acrylate, urethane polymers, and vinyl chloride-based polymers.
- the thin-walled inner cylinder is made of SUS300 series stainless steel, aluminum alloy, copper alloy or the like.
- the thin-walled inner cylinder is characterized in that the end portion thereof is crimped to the thin-walled inner cylinder support disc.
- the invention is also characterized in that the solution is a mixed solution of a solvent and a polymerization product.
- FIG. 2 is a cross-sectional view taken along line II-II of FIG. It is an enlarged view of the area
- the solution transfer and cooling device 1 has a heat exchange function and is a shell-and-tube type device used for a pressure vessel that carries out a low-pressure polyethylene polymerization method.
- shell-and-tube type heat exchangers three types of fixed tube sheet type, floating head type, and U-shaped pipe type are known.
- the solution transfer / cooling device 1 is a floating head type, and absorbs the expansion and contraction of the long heat exchange tube due to the high temperature and high pressure of the heat exchange fluid by the movement of the floating skull.
- the solution transfer / cooling device 1 forms a heat exchange fluid chamber 14 and a refrigerant chamber 16 by dividing the inside of a body or shell 10 by a tube sheet 12.
- the heat exchange fluid chamber 14 for containing the heat exchange fluid R is formed by closing the end of the shell 10 with a shell cover 20.
- the heat exchange fluid inlet 22 is disposed on the lower side of the shell 10 at a portion of the heat exchange fluid chamber 14, and the heat exchange fluid outlet 24 is formed on the upper side.
- the heat exchange fluid chamber 14 is divided by the dividing plate 40 into a lower heat exchange fluid chamber high temperature portion 14 a and a lower heat exchange fluid chamber low temperature portion 14 b.
- the heat exchange fluid R a mixture of normahexane and a polymer is exemplified.
- the end of the shell 10 of the refrigerant chamber 16 accommodating a refrigerant W such as cooling water is closed by a refrigerant chamber lid 30, and for example, about 2000 heat exchange tubes 32 are arranged in parallel with one another.
- An floating skull 34 is disposed on the opposite side of the tube sheet 12 in the refrigerant chamber 16.
- a baffle plate 36 for stirring the refrigerant W is disposed in the refrigerant chamber 16.
- the heat exchange tube 32 of the solution transfer / cooling device 1 distributes the mixed solution containing the product in the solvent inside the rigid iron refrigerant outer cylinder 100 for circulating the refrigerant.
- the rigid mixture outer cylinder 102 made of SUS304 is arranged in parallel to each other.
- the refrigerant circulating portion of the rigid refrigerant outer cylinder 102 has a length of 10 meters, and as shown in FIG. 3, the outer diameter is 25.4 mm, the wall thickness is 2.0 mm, and the inner diameter is 21.4 mm. is there.
- the rigid solution outer cylinder 102 is fixed by welding 106 to the rigid solution outer cylinder support plate 104 fixed inside in the vicinity of both ends of the rigid solution outer cylinder 102, as shown in FIG. There is.
- a thin-walled inner cylinder 110 is disposed inside each of the rigid mixture outer cylinders 102.
- the thin-walled inner cylinder 110 has an inner diameter of 21.30 mm and a thickness of 0.04 mm. Both ends of the thin-walled inner cylinder 110 are crimped and secured onto the end of the rigid mixture outer cylinder 102, as shown in FIG.
- the thin-walled inner cylinder 110 is stretched at the temperature and pressure of the solution to be transferred, for example, the mixture of reaction product and solvent, contacts the inner surface of the rigid solution outer cylinder 102 without breakage, Removal of the thin-walled inner cylinder 110 back to its original diameter, and when the thin-walled inner cylinder 110 is stretched at the temperature and pressure of the transferred solution, ie, the liquid-solid mixture, It will be described by calculation that the thin-walled inner cylinder 110 backed up by the above is supported by the rigid solution cylinder 102 by the periphery.
- the allowable tensile stress of SUS 304 is 194 megapascals at 40 ° C., 180 megapascals at 75 ° C., and 171 megapascals at 100 ° C.
- the temperature of the heat exchange fluid chamber high temperature part 14a is 70 ° C. and 1.20 megapascal
- the temperature of the heat exchange fluid chamber low temperature part 14 b is 57 ° C. and 1.14 megapascal, which are often found in industry. In consideration of certain things, the following values are calculated.
- the thickness of the rigid solution sleeve 102 is 2.0 millimeters.
- the inner diameter of the rigid solution sleeve 102 is 21.40 mm.
- the thin inner cylinder 110 has an outer diameter of 21.37 mm.
- the thickness of the thin-walled inner cylinder 110 is 0.04 mm.
- the internal pressure of the thin-walled inner cylinder 110 is 1.20 megapascals.
- the Young's modulus of SUS304 which is a material of the rigid solution outer cylinder 102 and the thin-walled inner cylinder 110, is 200 gigapascals.
- the clearance or spacing between the inner surface of the rigid solution cylinder 102 and the outer surface of the thin walled cylinder 110 is 0.015 mm, half of 0.03 mm.
- the thin-walled inner cylinder 110 is in close contact with the rigid solution outer cylinder 102 and backed up by the rigid solution outer cylinder 102. It recovers after and returns to the original size.
- the thin-walled inner cylinder 110 is inserted into the rigid mixture outer cylinder 102.
- the inserted thin inner cylinder 110 may be used as it is, but preferably, both ends of the thin inner cylinder 110 are fixed to both ends of the rigid mixture outer cylinder 102 by caulking or the like.
- the pressure of the polymerization product causes the thin-walled inner cylinder 110 to expand, and the entire outer peripheral surface of the thin-walled inner cylinder 110 is the inner periphery of the rigid mixture outer cylinder 102 Touch the face.
- the entire outer peripheral surface of the thin-walled inner cylinder 110 is supported by the inner peripheral surface of the rigid mixture outer cylinder 102.
- the entire outer peripheral surface of the thin-walled inner cylinder 110 is in contact with the inner peripheral surface of the rigid mixture outer cylinder 102, whereby the polymerization product transferred inside the thin-walled inner cylinder 110 is the rigid mixture outer cylinder 102 and the rigid refrigerant outer cylinder 100. Can be efficiently cooled by the refrigerant flowing between them.
- the inflow of the polymerization product to the liquid-solid mixture transfer device 1 is stopped.
- the thin-walled inner cylinder 110 returns to normal pressure, and the thin-walled inner cylinder 110 contracts and returns to its original diameter.
- a space is created between the inner peripheral surface of the rigid mixture outer cylinder 102 and the outer peripheral surface of the thin inner cylinder 110, and the thin inner cylinder 110 can be easily taken out from the rigid mixture outer cylinder 102.
- the thin-walled inner cylinder 110 taken out removes polymer fouling at a place where it is easy to work, such as a factory.
- the thin-walled inner cylinder 110 from which the polymer fouling has been removed is put into the rigid mixture outer cylinder 102 by the method described above.
- Providing the spare thin-walled inner cylinder 110 and replacing the thin-walled inner cylinder 110 with the polymer fouling formed thereon with the spare thin-walled inner cylinder 110 makes it possible to safely remove the polymer fouling at high height and It is carried out in a short time, and is extremely effective for enhancing the production efficiency of the polymer.
- the present invention does not have a large temperature change like piping for taking out mineral oil from the ground, and can be implemented even when only the pressure changes, and the clogging can be eliminated efficiently.
- Solution transfer cooling device 100 Rigid refrigerant outer cylinder 102 Rigid solution outer cylinder 104 Rigid solution outer cylinder support plate 106 Welding 110 Thin walled inner cylinder
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Abstract
Description
さらに詳しくは、ポリエチレン、ポリプロピレン等の重合体製品を製造する際、例えばノルマルヘキサン等の溶媒の中で触媒とエチレンとを反応させてポリエチレンをつくる重合体反応器の内壁への重合体の付着や、重合体反応器からペレット化等の後処理装置に溶剤と重合生成物混合溶液を冷却しながら移送するための移送手段の内壁への重合体の析出付着、いわゆる重合体ファウリングが発生する。本発明は、この重合体ファウリング等を容易且つ効率的に除去することができる溶液移送冷却装置に関する。
一方、反応熱を除去するために、重合体反応器の内壁及び重合体反応器からペレット化等の後処理装置に冷却しながら移送するための移送手段に、シェルアンドチューブ熱交換器を設定する場合がある。この場合、冷却剤と溶媒中に含まれる重合体とを離隔する金属管内壁に重合体ファウリングが形成される。この重合体ファウリングは、熱伝導率が金属管に比し約二桁低いことから、重合体ファウリングが、前記反応熱の除去の除去すなわち冷却を著しく低下させる。同時に、実質的管径が細くなることにより、輸送ポンプの負荷が増加し、輸送ポンプの損傷や流量低減の弊害が発生する。
(1)反応器内及び移送管内の流速を上げること
(2)反応器内及び移送管内表面の凹凸をできるだけ小さくすること
(3)重合体ファウリングの起点が触媒及び重合体粒子の静電付着であるという説に基づく静電除去剤を添加すること
(4)エチレンフィードノズルの構造を改良すること
(5)フランジのギャップ等にポリマーが対流しないような構造を改良すること
が提案されている(例えば、非特許文献1参照)。
しかし、現実的には、前記特許の重合体ファウリング対策のいずれも不完全で、重合体ファウリングの発生による冷却効率の低下や、重合体ファウリングによる流路の狭隘化すなわち流量の減少が、産業界の大きな障害となったままである。
この円柱管束は、全体を耐圧シェル内に取付け、シェル内下部入口から冷媒を圧入することによって、冷媒が円柱管束の間に流入する。冷媒は、各円筒管の周囲を流れて各円筒管内の溶媒と重合物の混合溶液を冷却する。
前述した重合体溶液移送冷却装置は、通常24時間連続運転される。その場合、約6ヶ月~1年経過後には、円柱管内壁に析出堆積した重合体ファウリングが累乗的に増加し、重合体生成物溶液の流動を著しく妨げるようになる。その結果、定圧ポンプの吐出量が低下し、定常な運転条件が確保できなくなり、冷却装置の作動を停止して重合体ファウリングの除去をしなければならない。
高圧水洗浄は、往復動ポンプにより加圧した高圧水をノズルから噴射させ、噴射衝撃エネルギーにより堆積した重合体ファーリングを管壁から剥離し、粉砕し、排出・除去する。
一つの重合体移送冷却装置の洗浄には、足場設置等から検査終了までに二週間以上を要する場合がある。その上、高圧水洗浄を行っている間は、重合体製造を停止しなければならないのであるから、不稼働損を生じ、産業活動上きわめて影響の大きな障害である。
本発明は、従来技術のいずれによっても解決されていない重合体製造ライン等における溶液移送冷却装置の上述した問題点に鑑みてなされたものであって、溶液移送冷却装置内の固形分の堆積を、従来技術に比較して極めて簡易な作業設備によって、少数の現場作業者によって短時間に、しかも高圧水洗浄等の危険作業を行うことなく、ファウリング堆積物を除去することができる溶液移送冷却装置を提供することを目的とする。
剛性冷媒外筒の内部に、複数の剛性溶液外筒を互いに平行に配置した溶液移送冷却装置において、
前記剛性溶液外筒の内部に、常温常圧で前記剛性溶液外筒の内径より小さい外径を有し、移送される溶液の温度上昇及び圧力増加の少なくとも一方によって伸張して前記剛性溶液外筒の内面に接し、前記冷媒による冷却または圧力低下によって縮小する薄肉内筒を配置したことを特徴とする溶液移送冷却装置
である。
重合反応装置と、該重合反応装置の重合生成物出口部に連結された冷却流路部(熱交換器)を有する重合体製造装置であって、
前記冷却流路部は、剛性冷媒外筒の内部に、複数の剛性外筒を互いに平行に配置した液体固体混合物移送装置を有し、
前記剛性混合物外筒の内部に、常温常圧で前記剛性混合物外筒の内径より小さい外径を有し、移送される溶液の温度上昇及び圧力増加の少なくとも一方によって伸張して前記剛性混合物外筒の内面に接し、前記溶液の前記冷媒による冷却または圧力低下により縮小する薄肉内筒を配置したことを特徴とする重合体製造装置
である。
本発明は、例えば、ポリ(メタ)アクリル酸メチル、ポリ(メタ)アクリル酸エチル、ポリ(メタ)アクリル酸ブチル等の(メタ)アクリル酸エステル系重合体、ウレタン系重合体、塩化ビニル系重合体、塩化ビニリデン系重合体、SBR、酢酸ビニル系重合体等の重合体、或いはこれらを構成する単量体の共重合体の製造時の溶液移送に適用され、ウレタンエマルジョン、アクリルエマルジョン等のマルジョンにおける溶液移送にも好ましく適用できるものである。
前記本発明において、前記薄肉内筒が、SUS300系ステンレス鋼、アルミ合金、銅合金等によって製造されていることを特徴とする。
被熱交換流体Rを収容する被熱交換流体室14は、シェル10の端部をシェルカバー20によって塞いで形成されている。シェル10の被熱交換流体室14のある部分において、下側に被熱交換流体入口22が配置され、上側に被熱交換流体出口24が形成されている。被熱交換流体室14は、区切り板40によって、下側の被熱交換流体室高温部14aと下側の被熱交換流体室低温部14bとに分けられている。
被熱交換流体Rとして、ノルマヘキサンと重合体の混合体が例示される。
冷却水等の冷媒Wを収容する冷媒室16は、シェル10の端部を冷媒室蓋30によって塞がれ、内部に例えば約2000本の熱交換チューブ32が互いに平行に配置されている。冷媒室16内において、チューブシート12の反対側には、遊動頭蓋34が配置されている。冷媒室16には、冷媒Wを攪拌するための邪魔板36が配置されている。
剛性冷媒外筒102の冷媒流通部分の長さは10メートルであり、図3に示すように、外径が25.4ミリメートル、肉厚が2.0ミリメートルであり、内径が21.4ミリメートルである。
σi=pDl/2tl=PD/2t ・・・・・(1)
である。例えば、株式会社技術評論社平成24年5月25日発行「入門材料力学」(有光隆著)第70頁第8行の「円周方向に発生する引張り応力」に記載されているとおりである。
ここで、SUS304の許容引張り応力は、JISG4303によると、40℃において194メガパスカル、75℃において180メガパスカル、100℃において171メガパスカルである。
剛性溶液外筒102の肉厚は、2.0ミリメートルである。剛性溶液外筒102の内径は、21.40ミリメートルである。薄肉内筒110は、外径が21.37ミリメートルである。薄肉内筒110の肉厚は、0.04ミリメートルである。薄肉内筒110の内圧は、1.20メガパスカルである。剛性溶液外筒102及び薄肉内筒110の材料であるSUS304のヤング率は、200ギガパスカルである。
剛性溶液外筒102の内面と薄肉内筒110の外面のクリアランスすなわち間隔は、0.03ミリメートルの半分の0.015ミリメートルである。
フープ力 σi=PD/2t
=(1.2MPa×21.30mm)/(2×0.04mm)
=319.5(メガパスカル)
フックの法則により
歪みε=応力σi/ヤング率
=319.5MPa/200GPa
=0.0016(0.16%)
従って、薄肉内筒110の外径は、内圧によって
21.37mm×0.0016=0.034mm
増加することになる。この値は、内圧によって薄肉内筒110が剛性溶液外筒102に密着する可能性を示す。
剛性溶液外筒102に、内圧1.20メガパスカルが負荷されたと仮定する。
フープ力 σi=PD/2t
=(1.2MPa×23.40mm)/(2×2.0mm)
=7.02MPa
フックの法則により
歪みε=応力σi/ヤング率
=7.02 MPa/200GPa
=0.000
従って、剛性溶液外筒102に、内圧1.20メガパスカルが負荷されたとしても、剛性溶液外筒102はほとんど伸張せず、薄肉内筒110のバックアップが可能である。
「東京都立産業技術研究センター研究報告、第5号、2010年」(第78頁)等に記載された「0.2%耐力」は、ある圧力を負荷して除圧した時の残留歪みが0.2%以内であることを示す。同論文によると、SUS304の0.2%耐力は、314MPaである。すなわち、314MPaは、SUS304においては、降伏値以上の値である。ただし、本実施形態において、剛性溶液外筒102と薄肉内筒110のクリアランスが0.2%以内であれば、クリープ現象や金属疲労によって残留歪みが発生したとしても0.2%以内に留まる。仮に、剛性溶液外筒102と薄肉内筒110のクリアランスが0.1%以内であれば、薄肉内筒110は、剛性溶液外筒102に密着し、剛性溶液外筒102にバックアップされ、除圧後回復して原寸に戻る。
予備の薄肉内筒110を準備して、重合体ファウリングが形成された薄肉内筒110を該予備の薄肉内筒110に置換することは、重合体ファウリングの高所除去作業を安全に且つ短時間に行うことであり、重合体の生産効率を高めるために極めて有効である。
100 剛性冷媒外筒
102 剛性溶液外筒
104 剛性溶液外筒支持板
106 溶接
110 薄肉内筒
Claims (11)
- 剛性冷媒外筒の内部に、複数の剛性溶液外筒を互いに平行に配置した溶液移送冷却装置において、
前記剛性溶液外筒の内部に、常温常圧で前記剛性溶液外筒の内径より小さい外径を有し、移送される溶液の温度上昇及び圧力増加の少なくとも一方によって膨張して前記剛性溶液外筒の内面に接し、前記溶液による冷却または圧力低下によって、前記剛性溶液外筒の内周面と薄肉内筒の間に空間ができるように縮径する前記薄肉内筒を配置したことを特徴とする溶液移送冷却装置。 - 前記薄肉内筒が、SUS300系ステンレス鋼によって製造されていることを特徴とする請求項1に記載の溶液移送冷却装置。
- 前記薄肉内筒が、アルミニュウム合金によって製造されていることを特徴とする請求項1に記載の溶液移送冷却装置。
- 前記薄肉内筒が、銅合金によって製造されていることを特徴とする請求項1に記載の溶液移送冷却装置。
- 前記溶液が、溶剤と重合生成物の混合溶液であることを特徴とする請求項1に記載の溶液移送冷却装置。
- 重合反応装置と、該重合反応装置の重合生成物出口部に連結された冷却流路部(熱交換器)を有する重合体製造装置であって、
前記冷却流路部は、剛性冷媒外筒の内部に、複数の剛性溶液外筒を互いに平行に配置し、前記剛性容液外筒の内部に、常温常圧で前記剛性溶液外筒の内径より小さい外径を有し、移送される溶液の温度上昇及び圧力増加の少なくとも一方によって膨張して前記剛性溶液外筒の内面に接し、前記溶液による冷却または圧力低下により、前記剛性溶液外筒の内周面と薄内筒の間に空間ができるように縮径する前記薄肉内筒を配置したことを特徴とする重合体製造装置。 - 前記薄肉内筒が、SUS300系ステンレス鋼によって製造されていることを特徴とする請求項6に記載の重合体製造装置。
- 前記薄肉内筒が、アルミニュウム合金によって製造されていることを特徴とする請求項6に記載の重合体製造装置。
- 前記薄肉内筒が、銅合金によって製造されていることを特徴とする請求項6に記載の重合体製造装置。
- 前記薄肉内筒が,その端部を前記剛性溶液外筒にかしめられていることを特徴とする請求項6に記載の重合体製造装置。
- 前記溶液が、溶剤と重合生成物の混合溶液であることを特徴とする請求項6に記載の重合体製造装置。
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2015
- 2015-09-30 WO PCT/JP2015/077767 patent/WO2016052634A1/ja active Application Filing
- 2015-09-30 KR KR1020167027580A patent/KR101851486B1/ko active IP Right Grant
- 2015-09-30 US US15/302,022 patent/US20170176109A1/en not_active Abandoned
- 2015-09-30 EP EP15847874.3A patent/EP3203177B1/en active Active
- 2015-09-30 CN CN201580017956.5A patent/CN106133472B/zh active Active
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Also Published As
Publication number | Publication date |
---|---|
EP3203177B1 (en) | 2019-10-23 |
KR20160130285A (ko) | 2016-11-10 |
US20170176109A1 (en) | 2017-06-22 |
KR101851486B1 (ko) | 2018-06-07 |
JP2016070611A (ja) | 2016-05-09 |
EP3203177A4 (en) | 2018-05-09 |
CN106133472A (zh) | 2016-11-16 |
EP3203177A1 (en) | 2017-08-09 |
JP5953619B2 (ja) | 2016-07-20 |
CN106133472B (zh) | 2018-01-16 |
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