EP1899095A2 - Vorrichtung und verfahren zum kontinuierlichen katalytischen entbindern mit verbesserten strömungsbedingungen - Google Patents

Vorrichtung und verfahren zum kontinuierlichen katalytischen entbindern mit verbesserten strömungsbedingungen

Info

Publication number
EP1899095A2
EP1899095A2 EP06763566A EP06763566A EP1899095A2 EP 1899095 A2 EP1899095 A2 EP 1899095A2 EP 06763566 A EP06763566 A EP 06763566A EP 06763566 A EP06763566 A EP 06763566A EP 1899095 A2 EP1899095 A2 EP 1899095A2
Authority
EP
European Patent Office
Prior art keywords
furnace
process gas
binder removal
gas
binder
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.)
Withdrawn
Application number
EP06763566A
Other languages
German (de)
English (en)
French (fr)
Inventor
Martin Blömacher
Johan Herman Hendrik Ter Maat
Hans Wohlfromm
Tsung-Chieh Cheng
Franz-Dieter Martischius
Arnd Thom
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1899095A2 publication Critical patent/EP1899095A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/003Apparatus, e.g. furnaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1017Multiple heating or additional steps
    • B22F3/1021Removal of binder or filler
    • B22F3/1025Removal of binder or filler not by heating only
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing 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
    • C04B35/638Removal thereof
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/02Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity of multiple-track type; of multiple-chamber type; Combinations of furnaces
    • F27B9/021Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity of multiple-track type; of multiple-chamber type; Combinations of furnaces having two or more parallel tracks
    • F27B9/022With two tracks moving in opposite directions
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/04Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity adapted for treating the charge in vacuum or special atmosphere
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/14Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment
    • F27B9/20Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/30Details, accessories or equipment specially adapted for furnaces of these types
    • F27B9/3005Details, accessories or equipment specially adapted for furnaces of these types arrangements for circulating gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the invention relates to a device for the catalytic debinding of produced by a powder injection molding process or PIM (Powder Injection Molding), metallic and / or ceramic moldings, in which a plastic is used as an aid for molding.
  • a plastic is used as an aid for molding.
  • This is usually a polyoxymethylene (POM), which is catalytically dissolved out after shaping in a debindering step, without the moldings themselves changing their shape.
  • a reaction partner e.g. Nitric acid in a carrier gas
  • suitable process conditions especially in terms of temperature
  • the debindering step precedes a sintering step and thus influences, in particular in a continuous process management, the throughput and the quality which are required for the shaped bodies according to their intended purpose after the sintering step.
  • the determined binder removal conditions are generally maintained much longer than would be necessary per se.
  • the operating costs increase considerably, which are due, among other things, to a high consumption of process gas, the process gas essentially containing reactants and carrier or protective gas.
  • Catalytic debinding takes place in kilns in which the green compacts are exposed to a suitable temperature over a period of time in a gaseous, acidic atmosphere.
  • the design and materials of the furnace must ensure that the temperature in the furnace volume is constant, and good heat transfer to the bodies to be debinded is achieved. In particular, cold spots in the interior of the furnace system are to be avoided in order to prevent the condensation of decomposition products.
  • internals or circulation elements are known from the prior art, which ensure uniform distribution and turbulence of the process gas in the reaction space, so that all green moldings are subject to the same reaction conditions.
  • a method for debinding of metallic moldings under vacuum is known.
  • the moldings are preheated in a furnace at a certain temperature.
  • a gas flow is generated from the furnace wall to the inside of the molds, while at the same time the prevailing pressure is gradually reduced, and the temperature remains constant or gradually increases.
  • the binder removal and sintering cycle times are affected.
  • deducting the gas from the environment of the moldings i. essentially from the middle of the furnace interior, a pressure difference between the furnace wall and the surroundings of the moldings and thus a radially inwardly directed flow is generated. This flow prevents the binder from condensing or precipitating on the thermal insulation and the furnace wall, which influence the vacuum.
  • a continuous catalytic debinder In a continuous catalytic debinder, the flow of the process gas in a suitable apparatus is of particular importance for the efficiency and quality of the debindering step. It is therefore an object of the present invention to provide a device for continuous catalytic debinding in which improved flow conditions prevail in a debinding furnace. Above all, a maximum utilization of the process gas, a minimum short-circuit current and thus a homogeneous process atmosphere in the binder removal furnace should be achieved, at the same time preventing condensation out. This would enable safe process management and a significantly higher throughput of the binder removal furnace.
  • a device for the continuous catalytic debinding of metallic and / or ceramic shaped bodies produced by powder injection molding methods comprising a debinding furnace, which the shaped bodies pass through in a transport direction, whereby they are cooled to a suitable process temperature.
  • the device according to the invention is then characterized in that one or more devices are present, which lead to a specifically directed transversely to the transport direction flow of the process gas in the device.
  • the apparatus for continuous catalytic debinding comprises a debindering oven, through which the moldings to be debindered, for example distributed on transport boxes, are transported in accordance with a suitable dwell time.
  • the transport boxes can be designed such that a uniform circulation of the moldings to be debinded is promoted.
  • a transport box has a gas-permeable bottom and gas-permeable side walls.
  • a vertical flow of the process gas and a desired Queranströmung be achieved.
  • An advantageous embodiment of a device for continuous catalytic Entbindem based on the operation of a baffle in which, by the absence of means for transporting populated transport boxes, a narrow tunnel cross-section can be realized.
  • a significant improvement in the utilization of the process gas can be achieved.
  • a conveyor belt in accordance with the dwell time to be set, conveys the transport boxes equipped with the moldings to be debinded through the debinding furnace. It is known that a forward and return of the conveyor belt are separated by a perforated plate. According to the perforated plate is partially or over the entire length of the conveyor belt replaced by a closed sheet metal. Thus, a short-circuit current of the process gas directed downwards into the region of the conveyor belt return is minimized, which occurs predominantly in the region of the process gas inlet.
  • baffles which are provided according to the invention both in an upper region of the binder removal furnace and in the region of a conveyor belt conveyor reduce the short-circuit current of the unused process gas by reducing the free flow cross-section.
  • they define a flow path of the process gas directed largely vertically to the transport direction. So, and thus improve the flow around the moldings to be debonded.
  • Baffles which are provided in the lower region of the binder removal furnace, in which the conveyor belt runs, force a vertically upward flow of the process gas through the transport boxes and thus contribute to a homogeneous process atmosphere.
  • Guide plates which are provided in the upper region of the binder removal furnace, according to the invention can be arranged on the ceiling of the binder removal furnace.
  • an arrangement of the baffles on the uppermost layer of the equipped with moldings transport boxes, since so the height of the stored on the transport boxes, to be debinded molding charge can be varied.
  • a perforated separation can be provided between two transport boxes which follow one another in the transport direction, so that the residence time of the process gas per charge is further increased.
  • one or more circulation devices for example in the form of fans, which are distributed uniformly along the binder removal furnace, can be arranged in the device for continuous catalytic debindering.
  • Umisselz Hughesen invention which are arranged either only on one side wall of the binder removal oven or preferably alternately on two opposite side walls, there is a turbulence of the process gas and thereby a homogeneous mixing of the interior of the continuous device.
  • An advantageous embodiment provides one or more points of introduction of the process gas into the binder removal furnace.
  • a plurality of uniformly distributed introduction points are advantageous, since in this way additional mixing of the interior space is achieved.
  • a further preferred embodiment of the device for continuous catalytic debinding aims at a flow of the process gas largely transversely to the transport direction of the stored on transport boxes molding.
  • the process gas required for debindering is introduced into the interior of the binder removal furnace via one or preferably several laterally arranged introduction points.
  • These lateral discharge points may be evenly distributed over the entire length of the debindering softener or may be provided at only a portion of the same. be.
  • introduction points on one side of the binder removal furnace and preferably on two opposite sides with alternating introduction points are conceivable.
  • the introduction points may be formed as slots, as holes or as nozzles.
  • the process gas thus introduced laterally flows through the transport boxes and thus the moldings to be entbindern largely transverse to the transport direction.
  • Such a transverse inflow of the shaped bodies which is achieved by the lateral introduction points of the process gas, can be supplemented by circulating devices arranged on one or both sides.
  • a withdrawal of the process gas at the end of the furnace and a return of the same into the feed, which leads to the lateral introduction points process gas can be used.
  • a withdrawal of the process gas at the end of the furnace and a return of the same into the feed which leads to the lateral introduction points process gas can be used.
  • the continuous catalytic debinding apparatus includes means for heating the process gas prior to entering the furnace, thereby achieving improved utilization of the process gas.
  • the device according to the invention for continuous catalytic debindering can be used universally for all processes in which debindering and / or reacting substances take place on the surface of a base body, and in which a directed flow for optimized utilization of the process substances used is to be achieved.
  • a further solution to the problem is also a method for the catalytic debinding of produced by powder injection molding, metallic and / or ceramic moldings, wherein the moldings are transported through a debinding furnace according to a predetermined residence time, while at a process temperature in the range of 100 0th C are brought to 150 0 C and the introduced process gas containing a reactant in a carrier gas stream, is brought before introduction to an appropriate temperature.
  • the continuous catalytic debinder apparatus 10 comprises a continuous debinder oven 12, which is preferably made of a stainless steel.
  • the device for debinding 10 is intended to catalytically unbound ceramic and / or metallic shaped bodies produced in a powder injection molding process. This means that a matrix consisting of a polymeric plastic, which has made possible the production of the shaped bodies in their desired design, should be removed quantitatively therefrom, without the shape of the shaped bodies changing in the process.
  • the preferred material system is based on polyoxymethylene (POM) as matrix material.
  • the debindering in the continuous binder removal furnace 12 takes place in a reaction space 14.
  • a reaction space 14 preferably electrical heating elements ensure a homogeneous adjustment of the reaction temperature in the reaction chamber 14, which is preferably between 110 ° C to 140 ° C. Due to a complex composition of the binder system, a careful temperature adjustment is necessary.
  • a gaseous, acidic component e.g. here a highly concentrated nitric acid in a carrier gas stream e.g. Nitrogen used, which reacts with the matrix material in the sense of depolymerization such that arise as end products of the reaction monomeric components of the matrix material in a gaseous state.
  • Nitrogen used, which reacts with the matrix material in the sense of depolymerization such that arise as end products of the reaction monomeric components of the matrix material in a gaseous state.
  • Liquid nitric acid which is preferably evaporated in a corresponding device directly in the reaction space 14 or in a device 20 upstream of the binder removal furnace 12, is introduced into the reaction space 14, for example, by means of a metering pump 18.
  • Typical volume flows of nitric acid are in the inventive device in the range of 0.2 l / h to 1.5 l / h.
  • Protective gas purging takes place via a flow rate control valve 22, preferably both at the inlet and at the outlet into the reaction space 14 of the debinder furnace 12.
  • Typical values of the nitrogen volume flow are at the entrance of the binder removal furnace between 0.5 m 3 / h and 3 m 3 / h and at the output between 6 m 3 / h to 20 m 3 / h.
  • the details of the volume flows of nitric acid, carrier gas and protective gas relate to a volume of the preferably cuboid reaction space 14 with values typically in a range from 0.3 m 3 to 0.6 m 3 .
  • the reaction products formed by the depolymerization reaction are converted in the torch 16 by burning into oxidic substances which can be safely released into the atmosphere.
  • the torch 16 is preferably arranged vertically standing on the top of the binder removal furnace 12.
  • the moldings to be entbined are introduced into the reaction chamber 14 of the binder removal furnace 12, which is preferably heated by electrical heating elements.
  • the shaped bodies can be distributed on transport boxes, which in turn are preferably permeable to the process gas at the bottom and at the side walls.
  • the transport boxes consist of perforated bottom and intermediate plates, which promote a flow around the charge of moldings stored thereon. Between individual in the transport direction successive transport boxes or batches according to the invention perforated sheets can be provided, which act as a kind of vertical separation. As a result, a vertically directed flow path of the process gas is achieved and thus improves the flow through the transport boxes.
  • the loaded transport boxes are transported through the reaction space 14 of the binder removal furnace 12, preferably by means of a conveyor belt 24.
  • a device based on the principle of a baffle can be used.
  • a separation of feed and return of the conveyor belt 24 is known by a perforated plate.
  • this perforated separating plate in particular at the inlet of the process gas, leads to a significant, downwardly directed short-circuit current, as a result of which the process gas flows counter to the outlet without being used.
  • the perforated separating plate in regions, in particular in the region of the gas inlet or preferably over the entire length of the reaction chamber 14, is replaced by a closed plate.
  • a downward short-circuit current decreases.
  • baffles In the upper region of the reaction space 14, flow paths of the process gas are defined by baffles. These baffles can be attached to the ceiling of the largely cuboid reaction chamber 14. As a result, the process gas is deflected, which increases its residence time, based on a stored on the transport boxes batch, and an unused short-circuit current is reduced.
  • baffles are arranged on top of the transport boxes, whereby the height of the stored thereon, to be debinded moldings can be varied.
  • baffles are provided in the lower part of the binder removal furnace 12, in which the conveyor belt is guided, which force an upward flow path of the process gas.
  • one or more circulation devices for example blowers or fans, are provided on a side wall of the binder removal furnace 12 and preferably alternately on two opposite side walls of the binder removal furnace 12.
  • one or more points of introduction of the process gas which are provided under fluidic aspects of the binder removal furnace, favor a desired turbulence of the process gas and / or an advantageous transverse flow of the moldings to be debinded.
  • injecting the process gas from above at high speed into the reaction space 14 of the binder removal furnace 12, preferably between successive transport boxes, can contribute to a turbulence of the process gas and thus to a homogenization of the process atmosphere.
  • the transverse flow can be achieved by a lateral introduction of the process gas into the binder removal furnace 12 according to the invention.
  • the introduction can take place in regions or preferably evenly distributed along the entire length of the binder removal furnace 12.
  • the introduction may be provided along one side of the debinder oven 12, preferably on two opposite sides of the debinder oven 12, the initiation being opposed to two opposite one another. Overlying sides of the binder removal furnace 12 preferably takes place alternately.
  • the introduction can be made via slots, holes or nozzles in the side walls of the binder removal furnace 12.
  • Particularly advantageous is a lateral introduction of the process gas at two opposite side walls of the binder removal furnace 12 with mutually arranged discharge points, which are supplemented at the respective opposite side wall of the binder removal furnace 12 by circulating means.
  • the thus achieved thorough mixing of the interior of the reaction chamber 14 and the transverse flow according to the invention lead to a homogeneous temperature and process gas distribution while accelerated removal of reaction products from the environment of the moldings to be entbindernden. This will create the conditions for a steady and accelerated process of exemption.
  • the internals and devices used result in a homogeneous mixing of the interior space and a flow path of the process gas which extends largely transversely to the transport direction.
  • This achieves a uniform distribution of the temperature and of the reactant as well as a removal of reaction products from the surroundings of the moldings, thereby creating a process atmosphere which leads to an efficient and to the same extent shortened debindering step while maintaining the same high quality of debindering.
  • the lateral introduction of the process gas according to the invention results in a maximized utilization of the process substances used.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Tunnel Furnaces (AREA)
  • Powder Metallurgy (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
EP06763566A 2005-06-13 2006-06-07 Vorrichtung und verfahren zum kontinuierlichen katalytischen entbindern mit verbesserten strömungsbedingungen Withdrawn EP1899095A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005027216A DE102005027216A1 (de) 2005-06-13 2005-06-13 Vorrichtung und Verfahren zum kontinuierlichen katalytischen Entbindern mit verbesserten Strömungsbedingungen
PCT/EP2006/062981 WO2006134054A2 (de) 2005-06-13 2006-06-07 Vorrichtung und verfahren zum kontinuierlichen katalytischen entbindern mit verbesserten strömungsbedingungen

Publications (1)

Publication Number Publication Date
EP1899095A2 true EP1899095A2 (de) 2008-03-19

Family

ID=37199178

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06763566A Withdrawn EP1899095A2 (de) 2005-06-13 2006-06-07 Vorrichtung und verfahren zum kontinuierlichen katalytischen entbindern mit verbesserten strömungsbedingungen

Country Status (11)

Country Link
US (1) US8235710B2 (enExample)
EP (1) EP1899095A2 (enExample)
JP (1) JP2009501842A (enExample)
KR (1) KR20080032092A (enExample)
CN (1) CN101198427B (enExample)
BR (1) BRPI0612135A2 (enExample)
DE (1) DE102005027216A1 (enExample)
EA (1) EA200702657A1 (enExample)
MX (1) MX2007015634A (enExample)
TW (1) TW200719991A (enExample)
WO (1) WO2006134054A2 (enExample)

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DE102005027216A1 (de) 2006-12-21
JP2009501842A (ja) 2009-01-22
TW200719991A (en) 2007-06-01
CN101198427B (zh) 2010-06-16
WO2006134054A3 (de) 2007-03-08
KR20080032092A (ko) 2008-04-14
US20080199822A1 (en) 2008-08-21
BRPI0612135A2 (pt) 2011-01-04
CN101198427A (zh) 2008-06-11
EA200702657A1 (ru) 2008-06-30
MX2007015634A (es) 2008-02-15
WO2006134054A2 (de) 2006-12-21

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