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WO1994029016A1 - Reacteur mecanique tubulaire - Google Patents

Reacteur mecanique tubulaire Download PDF

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Publication number
WO1994029016A1
WO1994029016A1 PCT/CA1993/000246 CA9300246W WO9429016A1 WO 1994029016 A1 WO1994029016 A1 WO 1994029016A1 CA 9300246 W CA9300246 W CA 9300246W WO 9429016 A1 WO9429016 A1 WO 9429016A1
Authority
WO
WIPO (PCT)
Prior art keywords
vapour
fluorine
fluid
carrier
housing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CA1993/000246
Other languages
English (en)
Inventor
Gregorio Tarancon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde Canada Inc
Original Assignee
Liquid Carbonic Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Liquid Carbonic Inc filed Critical Liquid Carbonic Inc
Priority to AU43040/93A priority Critical patent/AU4304093A/en
Priority to PCT/CA1993/000246 priority patent/WO1994029016A1/fr
Publication of WO1994029016A1 publication Critical patent/WO1994029016A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • 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
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
    • 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
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
    • 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
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/187—Details relating to the spatial orientation of the reactor inclined at an angle to the horizontal or to the vertical plane

Definitions

  • This invention relates to the direct fluorination of polymeric resins and, more particularly, relates to a tubular mechanical reactor apparatus for the direct fluorination of polymeric resins in particulate form which are capable of being fluorinated by contact with elemental fluorine and a carrier fluid.
  • FIELD OF THE INVENTION The fluorination of polymers to enhance lubricity, nonflam ability and chemical inertness, such as resistance to oxidation, and to reduce permeability by organic solvents, particularly non polar solvents, by the replacement of hydrogen by fluorine by the use of fluorine itself or by the use of a metal fluoride is well known.
  • Fluorination of polymeric resins is usually carried out with carriers in the gas phase or in the liquid phase.
  • the temperature of operation is generally lower than room temperature and the fluorine concentration is lower than 2 mole per cent.
  • the temperature of operation is above the room temperature and the fluorine concentration generally is higher than 2 mole per cent.
  • Gaseous carrier fluids essentially are ideal gases with low heat capacity per unit of volume, low polarizability or ability to induce dipole moment, and low critical temperature as well as a cryogenic boiling point.
  • fluorine reacts with solid particles of polymeric resin, such as polyolefin resins including polyethylene
  • hydrogen in the polymer molecule combines with fluorine atoms to form hydrogen fluoride.
  • the reaction is exothermic and, in order to prevent deterioration of the resin during fluorination due to local overheating, generated heat must be dissipated.
  • the carrier fluids used in the prior art are gases that have a low-solubility capacity for the byproduct hydrogen fluoride which is produced because of their polarizability, low critical temperature, low density, and low heat capacity, which reduces their ability for heat transfer in both directions.
  • U.S. Patent No. 4,536,266 issued August 20, 1985 teaches a process for the fluorination of surface layers of articles by exposure of the surface layer to a fluorine- yielding liquid solvent or solvent mixture in a controllable reaction by controlled introduction of fluorine gas in order to overcome problems considered inherent with the use of gaseous carrier fluids.
  • the apparatus of the present invention for fluorinating particulate polymeric materials comprises a tubular reactor having a mechanical fluidizer mounted for rotation within a housing, said fluidizer having a plurality of openings for allowing a fluid to pass therethrough, said housing having a feed end and a discharge end, means for rotating said fluidizer, means for feeding said polymeric material in particulate form to the housing at the feed end thereof for passage through the reactor, means for discharging said polymeric material from the discharge end thereof, means for feeding a mixture of fluorine and carrier fluid to said reactor at one end of the housing for passage through the openings in the fluidizer to react with the fluidized polymeric material, and means in communication with the housing for passing the fluorine and carrier fluid mixture through the reactor.
  • the apparatus of the invention comprises a tubular screw reactor having a rotatable screw with a continuous helichoid flight or sectional flights within a cylindrical housing, said housing having a feed end and a discharge end, means for rotating said screw, said screw flight or flights having a plurality of perforations for allowing a fluid to pass therethrough, means for feeding said polymeric material in particulate form to the housing at the feed end thereof, means for receiving said polymeric material from the discharge end thereof, means for feeding a mixture of fluorine and carrier fluid to said reactor at one end of the housing for passing through the perforations in the screw flight or flights for reaction with the fluidized polymeric material, and means in communication with the housing for drawing the fluorine and dense carrier fluid mixture through the screw reactor.
  • the apparatus of the invention for fluorinating particulate polymeric materials capable of being fluorinated comprises a vapour-tight tubular reactor having a rotatable mechanical fluidizer mounted for rotation within a housing, said rotatable mechanical fluidizer having a plurality of openings for allowing a vapour fluid to pass therethrough, said housing having a feed end and a discharge end, means for rotating said rotatable mechanical fluidizer, means for feeding a polymeric material in particulate form to the housing at the feed end thereof for passage through the vapour-tight tubular reactor, a closed mixing tank, a source of fluorine and a source of carrier vapour fluid, said closed mixing tank containing a mixture of fluorine and carrier vapour fluid preparatory to feeding a mixture of fluorine and carrier vapour fluid to the vapour-tight tubular reactor, said carrier vapour fluid selected from the group consisting of helium, nitrogen, argon, and a dense carrier fluid having a critical temperature higher than ambient temperature, a boiling point lower
  • the mechanical fluidizer may comprise a screw flight or flights, a ribbon conveyor, radial blades of uniform or variable length, or a cylindrical wire brush journalled for rotation within a housing.
  • the mechanical fluidizer is rotated at a speed sufficient to agitate or fluidize the particulate polymeric material.
  • the carrier fluid is selected from the group consisting of helium, nitrogen, argon and a dense carrier fluid having a critical temperature higher than ambient temperature minus 60 celcius degrees, and a molecular weight greater than the molecular weight of elemental fluorine.
  • the dense carrier fluids of the present invention are neither gases nor liquids but function, under the conditions of the process of the invention, as vapours, which are dense compared to ideal gases but sufficiently remote from the dew point not to be classified as liquids.
  • the dense carrier vapour fluid has a molecular weight in the range of from about 40 to 200, preferably about 44 to 188, which is greater than the molecular weight of fluorine, to provide a carrier fluid having a density greater than the density of fluorine. It is important in the selection of the dense carrier vapour fluid to consider the degree of reactivity of the dense carrier fluid with fluorine as a function of the fluorine partial pressure and the operating temperature range during the time the dense carrier fluid is in contact with the fluorine gas. The selection of dense carrier vapour fluid thus is based on its reactiveness with fluorine at the operating temperature and fluorine concentration while being compatible with the fluorine.
  • the dense carrier fluids have advantages compared with liquids and ideal gases. Liquids are difficult to totally remove from the reactor and represent hazardous environmental problem. The dense fluids approach the heat capacity of the liquids but can be extracted from the reactor in the same way as ideal gases which have a low heat capacity that permits easy elevation of the temperature in the reactor.
  • Liquid fluids have the critical temperature higher than the room temperature and the boiling point higher than the room temperature minus 60 celcius degrees.
  • Gas fluids (ideal gases) have the critical temperature lower than the room temperature minus 60 celcius degrees and the boiling point lower than the room temperature minus 60 celcius degrees, as shown in Table 1. TABLE 1
  • Vapor carrier fluids having a molecular weight of 40 to 200 have a range of density of 1.8 to 9 g/1 and a range of heat capacity of 9 cal/mole °C to 45 cal/mole "C.
  • Dense carrier fluids which meet the above criteria and are suited for the process of the invention are typified by perfluoropropane, chloropentafluoroethane, sulphurtetrafluoride, sulphur hexafluoride, tetrafluoroethylene, hexafluorothane, carbon dioxide, chlorotrifluoromethane, bromotrifluoromethane, and trifluoromethane.
  • Carbon dioxide (C0 2 ) for example, is a vapor at
  • 300°K is triatomic with different kinds of elements, and is a polarizable molecule, as opposed to the carrier fluids used in the prior art, which are diatomic or monotomic and have only one element.
  • the density of C0 2 within the temperature range of the fluorination process of polyethylene (300°K to 400°K) is very high in comparison to the density of N 2 in the same range.
  • C0 2 Because the critical temperature of C0 2 is 31°C, it can be stored at room temperature in regular tank containers.
  • the carrier fluids in the prior art required cryogenic tanks with very sensitive temperature release valves to protect the container from excessive pressure.
  • the partial pressure of fluorine during the process of the invention is in the range of about 12 to about 120 torr and the total pressure is in the range of about 12 to 12,000 torr, preferably about 25 to about 2500 torr.
  • the fluorine concentration in the carrier fluid is in the range of about 2 to about 15% by volume, preferably about 3 to about 12% by volume.
  • Figure 1 is a schematic illustration of a batch screw reactor of the present invention
  • Figure 2 is a schematic illustration of said screw reactor arranged in a continuous mode
  • Figure 3 is a schematic illustration of another embodiment of screw reactor arranged in a continuous mode
  • Figure 4 is a perspective view, partly cut away, of a further embodiment of tubular reactor
  • Figure 5 is a side elevation of a single flight standard pitch ribbon conveyor
  • Figure 6 is a side elevation of another embodiment of a of a single flight standard pitch ribbon conveyor
  • Figure 7 is a side elevation of a uniform blade mixer; and Figure 8 is a side elevation of a variable length blade mixer.
  • tubular screw reactor 60 shown inclined at an angle of about 45° to the horizontal has a screw 62 in the form of a helichoid continuous flight or sectional flights within tubular housing 64.
  • Screw 62 has a plurality of perforations of 50 to 250 microns diameter to permit the flow of gases and vapours through the flight(s) and along the tubular reactor.
  • the pitch of the screw normally is equal to the diameter of the flight and the screw conveyor operates at a rate of revolution (rpm) of from 1 to 100 rpm sufficient to fluidize or at least agitate the particles as they are conveyed through the reactor.
  • the reactor 60 and its components may be fabricated from iron, steel, stainless steel, aluminum, copper, brass and the like. Gaskets may be formed from fluorinated rubber or plastic.
  • the heat of reaction may affect the temperature in the reactor with temperature elevation normally causing an increase in the pressure in the closed vessels.
  • Solid particulate polymeric material is transferred from feed hopper 66 to the bottom of reactor 60 and particulate material is discharged from the top of reactor 60 into collector hopper 68.
  • a mixing tank 70 having a supply of fluorine and carrier fluid, is in communication with the bottom of feed hopper 66 through line 72 having control valve 74.
  • An exhaust line 76 from collector hopper 68 permits the exhaust of air and other gases from hopper 68 through two-way discharge valve 78 to evacuating pump 80 and through scrubber 82 to the atmosphere.
  • solid polymeric resins preferably in the form of a particulate such as powder, pellets or granules
  • the particulate feed is conveyed by screw reactor 60 driven by variable speed motor 61 to the top of collector hopper 68 by screw 62, the desired dwell time of the polymeric material within the reactor 60 and the degree of fluidizing being determined by the speed (i.e. rate of rotation) of variable speed screw 62.
  • valve 74 is opened to allow the ingress of fluorine and the carrier gas mixture co-current with the direction of flow of solid particulate rising within the reactor 60 for intimate contact with the particulate material as the fluids passed through apertures formed in the screw flight(s) .
  • the carrier fluid with by-product gases pass through scrubber 82 for removal of toxic fluids before discharge to the atmosphere.
  • the fluorination reaction is completed upon transfer of solid particulate to the collector hopper 68, valve 74 is closed, and evacuation pump 80 removes all toxic fluids within the system for treatment in scrubber 82.
  • Inlet 90 is then opened to permit the ingress of air into feed hopper 66, screw reactor 60 and collector hopper 68, and the fluorinated polymer is unloaded from collector hopper 68 through discharge port 92.
  • the mixture of fluorine and carrier gas is described with reference to co-current flow with the solid particulate, the gas flow may be counter-current to the particulate flow.
  • FIG. 2 illustrates another embodiment of screw reactor system of the invention in which screw reactor 110 is vertically inclined and interconnects at least a pair of feed hoppers 112, 114 and collector hoppers 124, 140 to permit a continuous mode of operation.
  • Solid polymeric particles are charged to feed hoppers 112, 114 through inlet port 117, 118, respectively.
  • Valve 120 at the base of screw reactor 110 in communication with fee hopper 112 and valve 122 at the top of said reactor in communication with collector hopper 124 are opened and air is removed from the pair of hoppers through evacuation pump 126 in communication with upper hopper 124 by line 128 and valve 130. Upon completion of air removal, valve 130 is closed and the rotation of screw 111 commenced.
  • Valve 132 in flow line 134 from mixing tank 136 allows the flow of fluorine and dense carrier fluid from mixing tank 136 into feed hopper 112 through line 137 for co-current flow of the fluorine and the dense carrier with the flow of the particulate solids.
  • the reaction of fluorine with the polymeric resin takes place during the transfer of the solid particulate from hopper 112 to hopper 124 within screw reactor 110.
  • the pair of hoppers 114 and 140 are ready to continue the process reaction through screw reactor 110 upon emptying of solid particulate from feed hopper 112, the operation being carried on in the same manner as described for hoppers 112, 124.
  • Fluorinated polymeric particles are removed from collector hopper 124 through outlet port 138 and feed hopper 112 is charged during the operation with hoppers 114, 140.
  • Figure 3 schematically illustrates another embodiment of screw reactor arranged in a continuous mode in which the vertical screw reactor 150 has the feed hoppers 152, 154 disposed at a height above the top of the reactor 150 and the collector hoppers 156, 158 disposed at a height below the base of reactor 150.
  • the mixture of fluorine and carrier gas is introduced to the base of reactor 150 from mixing tank 160 to flow upwardly counter- current to the descending flow of particulate polymer.
  • the operation of this embodiment of screw reactor is otherwise the same as the embodiment described with reference to Figure 2.
  • the tubular screw reactors can be arranged vertically, horizontally or oriented at any angle between 0 to 90° with the horizontal.
  • the reactors can be 1 inch to 150 inches in diameter with a length of 1 foot to 150 feet, the preferred diameter being 6 - 36 inches and the preferred length being 5 - 20 feet.
  • the feed and discharge hoppers can have a capacity of 1 to 5000 cubic feet, preferably 5- 500 cubic feet.
  • Figure 4 illustrates an embodiment of vertical screw reactor 170 in which three mechanical fluidizers 172 are arranged vertically within respective cylindrical reactor zones 174.
  • Upper feed zone 176 receives particulate polymer from one of two feed hoppers 178, 190 for a continuous supply to the three fluidizers.
  • collector hoppers 182, 184 receives fluoridated polymeric material in the manner described with reference to the embodiments shown in Figures 2 and 3.
  • a mixture of fluorine and carrier fluid is supplied at inlet 186 at the base of reactor 170 for a counter-current flow relative to the descending flow of particulate solid material.
  • Fluidizer 172 can be helical screws, as illustrated, or ribbon conveyors, radial blades, wire brushes or the like rotating at a speed sufficient to continuously agitate or fluidize the particulate solid material descending in an annulus formed about the periphery of the fluidizer.
  • Figures 5 and 6 show two embodiments of single flight standard pitch ribbon conveyors which can be substituted for helical screws.
  • Figures 7 and 8 show uniform length and variable length blade mixers which can be substituted for helical screws.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un appareil pour la fluoration directe de particules solides de résines polymères pouvant être fluorées, dans lequel les particules solides sont mises en contact avec la phase gazeuse d'un mélange fluor/fluide porteur dense, dans un réacteur tubulaire (60) équipé d'un dispositif mécanique interne comprenant un axe tournant (62) avec une vis à ailettes, multilames ou à brosse métallique qui fluidifie mécaniquement la phase solide. La conception du dispositif mécanique interne est fonction du diamètre et de la longueur du réacteur tubulaire (60), du temps de réaction et d'autres propriétés physiques des particules solides des résines polymères. Le dispositif mécanique interne empêche l'agglomération des particules solides et avantage le contact uniforme avec la phase gazeuse en provoquant la mobilité des particules solides. L'amélioration du contact de surface avec la phase gazeuse améliore la réaction entre la résine polymère solide et le fluor élémentaire, ainsi que la dissipation de chaleur dans le fluide porteur dense.
PCT/CA1993/000246 1993-06-09 1993-06-09 Reacteur mecanique tubulaire Ceased WO1994029016A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU43040/93A AU4304093A (en) 1993-06-09 1993-06-09 Tubular mechanical reactor
PCT/CA1993/000246 WO1994029016A1 (fr) 1993-06-09 1993-06-09 Reacteur mecanique tubulaire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CA1993/000246 WO1994029016A1 (fr) 1993-06-09 1993-06-09 Reacteur mecanique tubulaire

Publications (1)

Publication Number Publication Date
WO1994029016A1 true WO1994029016A1 (fr) 1994-12-22

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Family Applications (1)

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PCT/CA1993/000246 Ceased WO1994029016A1 (fr) 1993-06-09 1993-06-09 Reacteur mecanique tubulaire

Country Status (2)

Country Link
AU (1) AU4304093A (fr)
WO (1) WO1994029016A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2534752A (en) * 1947-06-21 1950-12-19 Sinclair Refining Co Process for the catalytic conversion of hydrocarbons
FR2118157A1 (en) * 1970-12-18 1972-07-28 Sandoz Sa Fixed phase condensation - in continuous operation to give polyester from polyethylene terephthalate
WO1982000646A1 (fr) * 1980-08-14 1982-03-04 Co B F Goodrich Procede de chloruration de chlorure de polyvinyle avec du chlore liquide et composition de chlorure de polyvinyle chlore
AU590081B2 (en) * 1987-05-20 1989-10-26 Air Products And Chemicals Inc. Polymeric materials having controlled physical properties and process for obtaining these
US4994308A (en) * 1988-05-31 1991-02-19 Tarancon Corporation Direct fluorination of polymeric materials by using dioxifluorine fluid (mixture of CO2 and F2)
US5149744A (en) * 1990-06-28 1992-09-22 Liquid Carbonic Inc. Process for the direct fluorination of polymeric resins
US5260033A (en) * 1990-06-28 1993-11-09 Liquid Carbonic, Inc. Tubular mechanical reactor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2534752A (en) * 1947-06-21 1950-12-19 Sinclair Refining Co Process for the catalytic conversion of hydrocarbons
FR2118157A1 (en) * 1970-12-18 1972-07-28 Sandoz Sa Fixed phase condensation - in continuous operation to give polyester from polyethylene terephthalate
WO1982000646A1 (fr) * 1980-08-14 1982-03-04 Co B F Goodrich Procede de chloruration de chlorure de polyvinyle avec du chlore liquide et composition de chlorure de polyvinyle chlore
AU590081B2 (en) * 1987-05-20 1989-10-26 Air Products And Chemicals Inc. Polymeric materials having controlled physical properties and process for obtaining these
US4994308A (en) * 1988-05-31 1991-02-19 Tarancon Corporation Direct fluorination of polymeric materials by using dioxifluorine fluid (mixture of CO2 and F2)
US5149744A (en) * 1990-06-28 1992-09-22 Liquid Carbonic Inc. Process for the direct fluorination of polymeric resins
US5260033A (en) * 1990-06-28 1993-11-09 Liquid Carbonic, Inc. Tubular mechanical reactor

Also Published As

Publication number Publication date
AU4304093A (en) 1995-01-03

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