WO2001042338A2 - Dispositif d'isolation thermique - Google Patents

Dispositif d'isolation thermique Download PDF

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Publication number
WO2001042338A2
WO2001042338A2 PCT/US2000/033018 US0033018W WO0142338A2 WO 2001042338 A2 WO2001042338 A2 WO 2001042338A2 US 0033018 W US0033018 W US 0033018W WO 0142338 A2 WO0142338 A2 WO 0142338A2
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WO
WIPO (PCT)
Prior art keywords
sheet
shell
thermal insulating
insulating device
graphite
Prior art date
Application number
PCT/US2000/033018
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English (en)
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WO2001042338A3 (fr
Inventor
David Paul Blain
Robert Angelo Mercuri
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Graftech 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
Priority claimed from US09/459,209 external-priority patent/US6387462B1/en
Priority claimed from US09/684,952 external-priority patent/US6413601B1/en
Application filed by Graftech Inc. filed Critical Graftech Inc.
Priority to CA002393697A priority Critical patent/CA2393697A1/fr
Priority to AU19476/01A priority patent/AU1947601A/en
Publication of WO2001042338A2 publication Critical patent/WO2001042338A2/fr
Publication of WO2001042338A3 publication Critical patent/WO2001042338A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/536—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite based on expanded graphite or complexed graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
    • C04B35/63476—Phenol-formaldehyde condensation polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/008—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of an organic adhesive, e.g. phenol resin or pitch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2313/00—Elements other than metals
    • B32B2313/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/08—Non-oxidic interlayers
    • C04B2237/086—Carbon interlayers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C04B2237/363—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/38—Fiber or whisker reinforced
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/60—Forming at the joining interface or in the joining layer specific reaction phases or zones, e.g. diffusion of reactive species from the interlayer to the substrate or from a substrate to the joining interface, carbide forming at the joining interface
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/704—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/708—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the interlayers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/76—Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc
    • C04B2237/765—Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc at least one member being a tube
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/84—Joining of a first substrate with a second substrate at least partially inside the first substrate, where the bonding area is at the inside of the first substrate, e.g. one tube inside another tube
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • F27D1/0009—Comprising ceramic fibre elements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0033—Linings or walls comprising heat shields, e.g. heat shieldsd
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D2001/0059—Construction elements of a furnace
    • F27D2001/0069—Means to prevent heat conduction
    • F27D2001/0073—Surrounding protection around the furnace, e.g. covers, circulation of gas

Definitions

  • the present invention relates to a thermal insulating device. More particularly, the present invention relates to a thermal insulating device useful for a high temperature reactor, such as a reactor that utilizes highly reactive chemical gases, such as inorganic halides, especially chlorine and fluorine, in a non-oxidizing atmosphere.
  • the inventive thermal insulating device includes a shell comprising resin bonded spiral wound continuous flexible graphite sheet.
  • Graphites are made up of layer planes of hexagonal arrays or networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another.
  • the substantially flat, parallel equidistant sheets or layers of carbon atoms usually referred to as basal planes, are linked or bonded together and groups thereof are arranged in crystallites.
  • Highly ordered graphites consist of crystallites of considerable size: the crystallites being highly aligned or oriented with respect to each other and having well ordered carbon layers. In other words, highly ordered graphites have a high degree of preferred crystallite orientation.
  • Graphites possess amsotropic structures and thus exhibit or possess many properties that are highly o ⁇ ented, ⁇ e directional Graphites may be characte ⁇ zed as laminated structures of carbon, that is. structures consisting of superposed layers or laminae of carbon atoms joined together by weak van der Waals forces In conside ⁇ ng the graphite structure, two axes or directions are usually noted, i e the "c" axis or direction and the "a" axes or directions
  • the A" axis or direction may be considered as the direction perpendicular to the carbon layers
  • the "a” axes or directions may be considered as the directions parallel to the carbon layers or the directions perpendicular to the "c” direction
  • Natural graphites possess a high degree of orientation and hence anisotropy with respect to thermal and elect ⁇ cal conductivity and other properties
  • the bonding forces holding the parallel layers of carbon atoms together are only weak v an der Waals forces
  • Graphites can be treated so that the spacing betw een the superposed carbon layers or laminae can be appreciably opened up so as to provide a marked expansion in the direction perpendicular to the layers, that is. in the "c" direction and thus form an expanded or mtumesced graphite structure in which the laminar character is substantially retained
  • Graphite flake which has been greatly expanded and more particularly expanded so as to have a final thickness or "c" direction dimension which is up to about 80 or more times the original "c" direction dimension can be formed without the use of a binder into cohesive or integrated sheets, e g webs, papers, st ⁇ ps, tapes, or the like
  • the formation of graphite particles which have been expanded to have a final thickness or "c" dimension which is up to about 80 or more times the original "c” direction dimension into integrated sheets without the use of any binding mate ⁇ al is believed to be possible due to the excellent mechanical interlocking, or cohesion which is achieved between the voluminously expanded graphite particles
  • the sheet mate ⁇ al has also been found to possess a high degree of thermal anisotropy Sheet mate ⁇ al can be produced which has excellent flexibility, good strength and is highly resistant to chemical attack and has a high degree of o ⁇ entation
  • the process of producing flexible, binderless graphite sheet mate ⁇ al comprises compressing or compacting under a predetermined load and in the absence of a binder, expanded graphite particles which have a "c" direction dimension which is up to about 80 or more times that of the original particles so as to form a substantially flat, flexible, integrated graphite sheet
  • the expanded graphite particles which generally are worm-like or vermiform in appearance, will maintain the compression set
  • the density and thickness of the sheet material can be va ⁇ ed by controlling the degree of compression
  • the density of the sheet material can be within the range of from about 0 08 g/cm to about 2 0 g/cm
  • the flexible graphite sheet mate ⁇ al exhibits an appreciable degree of anisotropy, with the degree of anisotropy increasing upon roll pressing of the sheet mate ⁇ al to increased density In roll pressed amsotropic sheet mate ⁇ al, the thickness, i e the direction perpendicular to the sheet surface comp
  • the present invention comp ⁇ ses a shell, preferably a self-supporting, cyhnd ⁇ cally shaped shell, having two ends (denoted for the sake of convenience as “top” and “bottom") useful, for instance, for surrounding a high temperature radiant heat source, such as a reactor m which highly chemically active gases are contained
  • the shell can be used as a heat shield to reflect radiant heat energy back to the reactor and to minimize loss of thermal energy due to conduction
  • the aforementioned shell comp ⁇ ses multiple layers formed from a continuous spiral wound sheet of amsotropic flexible graphite, bonded with a cured resin
  • the resin is coated on both sides of a thin sheet of heat decomposable carbon based mate ⁇ al that du ⁇ ng the fab ⁇ cation process is co-extensive with the spiral wound sheet of flexible graphite and is cured in situ
  • the thin sheet of heat decomposable carbon based mate ⁇ al provides a path for the escape of gases which develop m the course of in situ cu ⁇ ng of the
  • the annular chamber can be closed, at one or both of its ends, by one or more flexible sheets of graphite that are advantageously resin-bonded to one or both of the first and second shells
  • the cove ⁇ ng flexible sheets of graphite are themselves multi- layered, with the individual layers bonded together through resin, in the same manner as the shell is formed.
  • the resin is coated on both sides of a thin sheet of heat decomposable carbon based mate ⁇ al that du ⁇ ng the fab ⁇ cation process is co-extensive with the sheet of flexible graphite and is cured in situ
  • the thm sheet of heat decomposable carbon based mate ⁇ al provides a path for the escape of gases which develop in the course of ...
  • Figure 1 is a top plan view of a heat shield in accordance with the present invention, Figure 1(A) to 1(E) show enlarged portions of Figure 1.
  • Figure 2 is a side elevation view of the heat shield of Figure 1 ,
  • Figure 3 and Figure 4 show sheets of heat decomposable carbon-based material for use m the present invention
  • FIG. 5 shows, schematically, the forming of a heat shield in accordance with the present mv ention
  • Figure 6 shows a fragmentary cross-section of a heat shield of this invention p ⁇ or to cooling
  • Figure 7 shows a perspective view of a further embodiment of the present invention
  • Graphite is a crystalline form of carbon comprising atoms covalently bonded in flat layered planes with weaker bonds between the planes
  • particles of graphite such as natural graphite flake
  • the crystal structure of the graphite reacts to form a compound of graphite and the intercalant
  • the treated particles of graphite are hereafter referred to as "particles of intercalated graphite "particles of intercalated graphite"
  • the intercalant within the graphite decomposes and volatilizes, causing the particles of intercalated graphite to expand in dimension as much as about 80 or more times its o ⁇ ginal volume in an accordion-like fashion in the "c" direction, I e in the direction perpendicular to the crystalline planes of the graphite
  • the exfoliated graphite particles are vermiform in appearance, and are therefore
  • Graphite starting materials suitable for use in the present invention include highly graphitic carbonaceous mate ⁇ als capable of reversibly intercalating alkali metals These highly graphitic carbonaceous mate ⁇ als have a degree of graphitization above about 0 80 and most preferably about 1 0
  • Fxamples of highly graphitic carbonaceous anode materials include synthetic graphites and natural graphites from va ⁇ ous sources, as well as
  • the graphite starting mate ⁇ als used in the present invention may contain non-carbon components so long as the crystal structure of the starting mate ⁇ als maintains the required degree of graphitization Generally, any carbon-containing mate ⁇ al, the crystal structure of which possesses the required degree of graphitization. is suitable for use with the present inv ention Such graphite preferably has an ash content of less than six weight percent
  • a common method for manufactu ⁇ ng graphite sheet or foil is desc ⁇ bed by Shane et al in U S Pat No 3,404,061, the disclosure of which is incorporated herein by reference
  • graphite flakes are intercalated by dispersing the flakes in a solution containing an oxidizing agent such as a mixture of nit ⁇ c and sulfu ⁇ c acid
  • the intercalation solution contains oxidizing and other intercalating agents known in the art Examples include those containing oxidizing agents and oxidizing mixtures, such as solutions containing nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium dichromate, perchlo ⁇ c acid, and the like, or mixtures, such as for example, concentrated nit ⁇ c acid and chlorate, chromic acid and phospho ⁇ c acid, sulfu ⁇ c acid and nit ⁇ c acid, or mixtures of a strong organic acid, e g
  • the preferred intercalating agent is a solution of a mixture of sulfunc acid, or sulfu ⁇ c acid and phospho ⁇ c acid, and an oxidizing agent, i e nit ⁇ c acid, perchlo ⁇ c acid, chromic acid, potassium permanganate, hydrogen peroxide, lodic or pe ⁇ odic acids, or the like
  • the intercalation solutions may contain metal halides such as feme chlo ⁇ de, and feme chloride mixed with sulfu ⁇ c acid, or a halide, such as bromine as a solution of bromine and sulfu ⁇ c acid or bromine in an organic solvent
  • the quantity of intercalation solution retained on the flakes after draining may range from about 20 to 150 parts of solution by weight per 100 parts by weight of graphite flakes (pph) and more typically about 50 to 120 pph Alternatively, the quantity of the intercalation solution may be limited to between about 10 to 50 parts of solution per hundred parts of graphite by weight (pph) which permits the washing step to be eliminated as taught and desc ⁇ bed in U S Pat No 4,895,713, the disclosure of which is also incorporated herein by reference
  • the intercalated graphite flakes are exfoliated by exposing them to an energy source, such as a heat source like a flame, or energy provided by infrared, microwave or radiofrequency radiation In the case of a flame, the intercalated graphite flakes are advantageously exposed for only a few seconds, preferably at a temperature greater than about 700°C, more typically about 1000°C or higher
  • exfoliated graphite particles, or worms are then compressed and subsequently roll pressed into a densely compressed flexible graphite sheet of desired density and thickness and substantially increased anisotropy with respect to thermal conductivity and other physical properties Suitable exfoliation methods and methods for compressing the exfoliated graphite particles into thm foils are disclosed in the aforementioned U S Pat No 3,404,061 to Shane et al It is conventional to compress the exfoliated worms m stages with the product of the first or early stages of compression referred to in the art as "flexible graphite mat " The flexible graphite mat is then further compressed by roll pressing into a standard density sheet or foil of preselected thickness A flexible graphite mat may be thus compressed by roll pressing into a thin sheet or foil of between about 0 05 to 1 75 mm in thickness with a density approaching theoretical density, although a density of about 1 1 g/cm is acceptable for most applications
  • Roll pressed flexible graphite sheet is known to be a relatively good thermal bamer in the direction ("c" axis) perpendicular to the parallel planar surfaces of the sheet.
  • a high temperature reactor is indicated schematically at 10. representing, for example, a reactor which involves the use of inorganic halides in a non- oxidizing atmosphere and which operates at temperatures of about 1000°C and higher
  • a heat shielding self-supporting shell is shown at 20 As shown in Figure 1.
  • the self- supporting shell 20 comp ⁇ ses an amsotropic, continuous spiral wound sheet 25 of graphite
  • the spiral of flexible graphite sheet 25 is suitably from about 1 to 100 mm thick and the density of the sheet 25 is suitably from 0 8 to 1 45 g/cm 1
  • the transfer of thermal energy through the thickness "t" of the amsotropic flexible graphite sheet 25 (the "c " axis direction) is less than in the plane "1" of the flexible graphite sheet 25 (the “a” axes directions)
  • heat source reactor 10 about 1000 °C and higher
  • the reactor 10 is reflected back to the reactor 10 from the inner surface 30 of shell 20, which is formed of amsotropic flexible graphite sheet
  • Some of the radiant heat energy from reactor 10 is not reflected back and causes the temperature at locations on the inner surface 30 of shell 20 to ⁇ se Heat at these locations is rapidly transferred and spread by conduction throughout the amsotropic flexible graphite sheet 25 in all directions ("1") of the
  • a thm layer of cured resm advantageously an in situ cured phenolic resm, indicated at 33 m Figure 1, co-extensive with the spiral wound sheet of flexible graphite, is used to bond the spiral wound sheets Dispersed within this in situ cured resin are typically small particles 35 of carbon, shown in Figure 1 (B) resulting from the chairing of a heat decomposable resm supporting substrate du ⁇ ng curing of the resm
  • a thin sheet of heat decomposable carbon based material or substrate such as kraft paper as shown at 50 in Figure 3, or preferably carbon fiber tissue as shown at 50 ' in Figure 4, is spiral wound with the anisotropic flexible graphite sheet 25 on mandrel 27 as shown in Figure 5.
  • the thin, heat decomposable carbon based sheet 50, 50', co-extensive with flexible graphite sheet 25, is impregnated with and coated on both sides with liquid resin 60 as shown in Figure 6.
  • the resin is coated on each side of sheet 50, 50' to a thickness that can vary between about 5 mm and about 75mm.
  • the spiral wound article, before curing of the resin, is shown in Figure 6. Curing of the resin 60 is accomplished by heating the spiral wound article 20 at 125° C for 16 minutes and 300° C for 16 hours.
  • the carbon base heat decomposable sheet 50, 50' is gradually reduced to particles of carbon char (35 in Figures 1(B), 1(E)) while the gases which evolve from the curing of the resin 60, and the charring of carbon-based sheet 50, escape from the spiral wound article 20 through a temporary channel created by the decomposing of sheet 20 and thus do not cause any delamination of the flexible graphite sheet in the spiral wound article 20.
  • the decomposition of the heat decomposable sheet into small, isolated particles of carbon enables the complete, co-extensive resin bonding of the spiral wound flexible graphite sheet as shown in Figure 1 (E).
  • the resulting shell is rigid, strong and resistant to corrosion, such as from highly reactive chemical gases, and the cured resin bonding does not significantly diminish the thermal properties of the spiral wound shell.
  • a second spiral wound shell 250 identical to the shell 25, except for having a larger cross section, surrounds shell 25, forming an annular chamber 70 therebetween which is at least partially (and preferably wholly) filled with an insulating material, such as individual particles 75 of uncompressed expanded graphite.
  • an insulating material such as individual particles 75 of uncompressed expanded graphite.
  • the resulting article relatively uniformly reflects radiant thermal energy back to reactor 10 and maintains an even temperature profile despite surges in heat radiation from reactor 10 while being highly resistant to attack by corrosive gases due to being formed completely from solid carbon components
  • the top and bottom of annular chamber can be sealed by sheets of flexible graphite 82 and 84 that can be in the form of the same mate ⁇ al as shells 25 and 250, being prepared in planar form in flat molds, and resin bonded, as indicated at 88
  • a suitable resin for use such as a phenolic resm like PHYOPHEN 43703 Phenolic Resm in methanol solvent available from Occidental Chemical Corporation, North Tonawanda, New York
  • the resin is suitably cured by heating at 125°C for 16 minutes and 300°C for 16 hours
  • Kraft paper can be used as the heat decomposable, carbon based substrate 50
  • the substrate 50 can be a PAN carbon fiber tissue or pitch fiber tissue available from Technical Fibre Products Limited. Cumbria, England

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Laminated Bodies (AREA)
  • Thermal Insulation (AREA)

Abstract

On décrit un dispositif d'isolation thermique et un procédé de fabrication de ce dernier. Le dispositif d'isolation thermique selon la présente invention est constitué d'une enveloppe de forme cylindrique formée de multiples couches d'une feuille de graphite souple anisotrope continue enroulée en spirale, les couches de feuille de graphite étant séparées et soudées par une résine durcie.
PCT/US2000/033018 1999-12-10 2000-12-06 Dispositif d'isolation thermique WO2001042338A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002393697A CA2393697A1 (fr) 1999-12-10 2000-12-06 Dispositif d'isolation thermique
AU19476/01A AU1947601A (en) 1999-12-10 2000-12-06 Thermal insulating device

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/459,209 US6387462B1 (en) 1999-12-10 1999-12-10 Thermal insulating device for high temperature reactors and furnaces which utilize highly active chemical gases
US09/459,209 1999-12-10
US09/684,952 2000-10-10
US09/684,952 US6413601B1 (en) 1998-10-23 2000-10-10 Thermal insulating device

Publications (2)

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WO2001042338A2 true WO2001042338A2 (fr) 2001-06-14
WO2001042338A3 WO2001042338A3 (fr) 2002-01-24

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011128544A1 (fr) * 2010-04-14 2011-10-20 Total Sa Conduite pour le transport d'un fluide comprenant un hydrocarbure, et procede de fabrication d'une telle conduite
WO2013113445A1 (fr) * 2012-02-03 2013-08-08 Sgl Carbon Se Bouclier thermique à structure de fibres externe enroulée
US8701713B2 (en) 2010-04-14 2014-04-22 Total Sa Heating device for a device for transporting a fluid containing a hydrocarbon
US9020333B2 (en) 2010-04-14 2015-04-28 Total Sa Line for transporting a fluid containing a hydrocarbon, and method for producing such a line
CN111599742A (zh) * 2020-06-04 2020-08-28 西南大学 一种基于石墨的临时键合和解键方法
US20210086474A1 (en) * 2018-05-03 2021-03-25 Skc Co., Ltd. Multilayer graphite sheet with excellent electromagnetic shielding capability and thermal conductivity and manufacturing method therefor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3009600A (en) * 1960-01-25 1961-11-21 Union Carbide Corp Thermal insulation
US4279952A (en) * 1977-12-14 1981-07-21 Kureha Kagaku Kogyo Kabushiki Kaisha Multilayer insulating material and process for production thereof
US4888242A (en) * 1986-05-27 1989-12-19 Toyo Tanson Co., Ltd. Graphite sheet material
US5126112A (en) * 1989-07-18 1992-06-30 Hemlock Semiconductor Corporation Graphite and carbon felt insulating system for chlorosilane and hydrogen reactor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3009600A (en) * 1960-01-25 1961-11-21 Union Carbide Corp Thermal insulation
US4279952A (en) * 1977-12-14 1981-07-21 Kureha Kagaku Kogyo Kabushiki Kaisha Multilayer insulating material and process for production thereof
US4888242A (en) * 1986-05-27 1989-12-19 Toyo Tanson Co., Ltd. Graphite sheet material
US5126112A (en) * 1989-07-18 1992-06-30 Hemlock Semiconductor Corporation Graphite and carbon felt insulating system for chlorosilane and hydrogen reactor

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA022144B1 (ru) * 2010-04-14 2015-11-30 Тоталь Са Трубопровод для транспортировки жидкости, содержащей углеводород, и способ производства такого трубопровода
FR2958991A1 (fr) * 2010-04-14 2011-10-21 Total Sa Conduite pour le transport d'un fluide comprenant un hydrocarbure, et procede de fabrication d'une telle conduite.
US8701713B2 (en) 2010-04-14 2014-04-22 Total Sa Heating device for a device for transporting a fluid containing a hydrocarbon
US9020333B2 (en) 2010-04-14 2015-04-28 Total Sa Line for transporting a fluid containing a hydrocarbon, and method for producing such a line
US9046207B2 (en) 2010-04-14 2015-06-02 Total Sa Line for transporting a fluid containing a hydrocarbon, and method for producing such a line
WO2011128544A1 (fr) * 2010-04-14 2011-10-20 Total Sa Conduite pour le transport d'un fluide comprenant un hydrocarbure, et procede de fabrication d'une telle conduite
AP3804A (en) * 2010-04-14 2016-08-31 Total Sa Line for transporting a fluid containing a hydrocarbon, and method for producing such a line
WO2013113445A1 (fr) * 2012-02-03 2013-08-08 Sgl Carbon Se Bouclier thermique à structure de fibres externe enroulée
US11333290B2 (en) 2012-02-03 2022-05-17 Sgl Carbon Se Heat shield with outer fiber winding and high-temperature furnace and gas converter having a heat shield
US20210086474A1 (en) * 2018-05-03 2021-03-25 Skc Co., Ltd. Multilayer graphite sheet with excellent electromagnetic shielding capability and thermal conductivity and manufacturing method therefor
US11745463B2 (en) * 2018-05-03 2023-09-05 Skc Co., Ltd. Multilayer graphite sheet with excellent electromagnetic shielding capability and thermal conductivity and manufacturing method therefor
CN111599742A (zh) * 2020-06-04 2020-08-28 西南大学 一种基于石墨的临时键合和解键方法
CN111599742B (zh) * 2020-06-04 2023-06-16 西南大学 一种基于石墨的临时键合和解键方法

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CA2393697A1 (fr) 2001-06-14
AU1947601A (en) 2001-06-18
WO2001042338A3 (fr) 2002-01-24

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