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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
  • C04B35/515—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
  • C04B35/522—Graphite
• • H—ELECTRICITY
  • H04—ELECTRIC COMMUNICATION TECHNIQUE
  • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
  • H04N21/00—Selective content distribution, e.g. interactive television or video on demand [VOD]
  • H04N21/80—Generation or processing of content or additional data by content creator independently of the distribution process; Content per se
  • H04N21/83—Generation or processing of protective or descriptive data associated with content; Content structuring
  • H04N21/835—Generation of protective data, e.g. certificates
  • H04N21/8358—Generation of protective data, e.g. certificates involving watermark
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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
  • C04B35/515—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
  • C04B35/528—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 obtained from carbonaceous particles with or without other non-organic components
  • C04B35/532—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 obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
• • H—ELECTRICITY
  • H04—ELECTRIC COMMUNICATION TECHNIQUE
  • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
  • H04N19/00—Methods or arrangements for coding, decoding, compressing or decompressing digital video signals
  • H04N19/46—Embedding additional information in the video signal during the compression process
  • H04N19/467—Embedding additional information in the video signal during the compression process characterised by the embedded information being invisible, e.g. watermarking
• • H—ELECTRICITY
  • H04—ELECTRIC COMMUNICATION TECHNIQUE
  • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
  • H04N21/00—Selective content distribution, e.g. interactive television or video on demand [VOD]
  • H04N21/20—Servers specifically adapted for the distribution of content, e.g. VOD servers; Operations thereof
  • H04N21/23—Processing of content or additional data; Elementary server operations; Server middleware
  • H04N21/234—Processing of video elementary streams, e.g. splicing of video streams or manipulating encoded video stream scene graphs
  • H04N21/2347—Processing of video elementary streams, e.g. splicing of video streams or manipulating encoded video stream scene graphs involving video stream encryption
• • H—ELECTRICITY
  • H04—ELECTRIC COMMUNICATION TECHNIQUE
  • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
  • H04N21/00—Selective content distribution, e.g. interactive television or video on demand [VOD]
  • H04N21/20—Servers specifically adapted for the distribution of content, e.g. VOD servers; Operations thereof
  • H04N21/25—Management operations performed by the server for facilitating the content distribution or administrating data related to end-users or client devices, e.g. end-user or client device authentication, learning user preferences for recommending movies
  • H04N21/266—Channel or content management, e.g. generation and management of keys and entitlement messages in a conditional access system, merging a VOD unicast channel into a multicast channel
  • H04N21/26613—Channel or content management, e.g. generation and management of keys and entitlement messages in a conditional access system, merging a VOD unicast channel into a multicast channel for generating or managing keys in general
• • H—ELECTRICITY
  • H04—ELECTRIC COMMUNICATION TECHNIQUE
  • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
  • H04N21/00—Selective content distribution, e.g. interactive television or video on demand [VOD]
  • H04N21/40—Client devices specifically adapted for the reception of or interaction with content, e.g. set-top-box [STB]; Operations thereof
  • H04N21/45—Management operations performed by the client for facilitating the reception of or the interaction with the content or administrating data related to the end-user or to the client device itself, e.g. learning user preferences for recommending movies, resolving scheduling conflicts
  • H04N21/462—Content or additional data management, e.g. creating a master electronic program guide from data received from the Internet and a Head-end, controlling the complexity of a video stream by scaling the resolution or bit-rate based on the client capabilities
  • H04N21/4622—Retrieving content or additional data from different sources, e.g. from a broadcast channel and the Internet
• • C—CHEMISTRY; METALLURGY
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
  • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
  • C04B2235/422—Carbon
  • C04B2235/425—Graphite
• • C—CHEMISTRY; METALLURGY
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
• • C—CHEMISTRY; METALLURGY
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
• • C—CHEMISTRY; METALLURGY
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
• • C—CHEMISTRY; METALLURGY
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
• • C—CHEMISTRY; METALLURGY
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5463—Particle size distributions
  • C04B2235/5472—Bimodal, multi-modal or multi-fraction
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C04B2235/6562—Heating rate

Definitions

• the Invention concerns a method for producing graphite bodies from a granular solid carbon containing material and at least one liquid binder able to be coked at elevated temperatures and additives, comprising at least the steps mixing, forming, baking and graphitisation, wherein an additive to reduce the irreversible volume expansion at temperatures above 1400 °C is used, a graphite body produced by said method and an installation for executing the method.
• Graphitized carbon bodies in the following named graphite bodies, are commonly used in electrochemical and electro thermal processes due to their electrical and thermal conductivity and due to the ability to withstand extreme high temperatures.
• One of the main fields of application for carbon bodies are graphite electrodes for electric arc furnaces, used in steel plants to melt scrap or to refine molten steel as so called ladle furnaces.
• graphite bodies are used for furnace linings, for instance for the lower part of blast furnaces.
• the production process contains at least the steps of
• One of the problems in the production process of the state of the art is the forming of cracks at elevated temperatures between 1400 °C and 2000 °C during the graphitisation step.
• the reason for the formation of these cracks is well known and described as so called puffing caused from sulfur, which sulfur is present as an impurity in the raw materials.
• the sulfur is exciting a volume expansion in the mentioned temperature range causing an increase in porosity of the graphite bodies.
• To control the puffing and to reduce the risk of forming cracks a lot of different solutions are known. Most of these solutions result in the adding of metals or compounds of metals to the coke before or during the mixing step.
• the addition of these substances - named inhibitors - results in the advantage of controlling the puffing.
• GB 733,073 A it is described to use 1 to 5 % by mass of iron, chromium, copper or nickel as well as oxides thereof as puffing inhibitor. These substances are dosed to the coke, preferably at the grinding stage, to have an excellent distribution of the puffing controlling substance in the green carbon body.
• FR 1 491 497 A describes the addition of chromium, nickel or cobalt or a mixture of said metals as catalyst to the mixture of coke and binder. ln the US 3 563 705 B it is described to use in the mixture of coke and binder in addition to conventional puffing inhibitors, like iron or calcium oxide, also low quantities of titanium and zirconium compounds to reduce the puffing.
• US 3 338 993 B describes the use of fluorides of calcium, magnesium, strontium or barium or mixtures thereof for puffing reduction.
• JP 62059511 A describes the use of an iron compound like iron oxide or iron hydroxide having ⁇ 3 ⁇ average particle diameter to be blended with coal tar needle coke and one or more compounds selected from Ca-compounds, Mg-compounds, Ce-compounds or La- compounds as inhibitors. With these substances, the coke is blended before being mixed with pitch to produce graphite electrodes.
• substances with a single corn diameter of lower than 3 pm always form agglomerates which cannot be destroyed in a mixing process, so that the actual diameter of the iron compound in the mixture with pitch is much higher than 3 ⁇ .
• fine grained substances are brought into contact with liquids, the fine grains form agglomerates which are quite hard and cannot easily be destroyed by a mixer. Therefore, the actual diameter of the iron compound in the mixture is dictated by the diameter of the agglomerate but not the diameter of the single corn.
• the goal of the present invention is to ameliorate the effect of cost effective solid puffing control substances such as metals or metal compounds (preferably metal oxides) which are insoluble in binders like petrol pitch or coal tar pitch or phenolic resins. This amelioration will result in a reduction of the needed quantity of puffing control substance improving the quality of the graphite bodies produced following the method of the invention.
• Second goal of the present invention is to create a graphite body produced according to the method of the invention, which is characterized in the form of the puffing control substance being in the graphite body.
• a further, third goal of the present invention is to create an installation in which the proposed method can be used. It is not the intention of the invention to find new substances but to use the very well known ones in a better way.
• a method to produce graphitized carbon bodies from carbon containing granular material, like petrol coke or coal tar pitch coke, and at least one liquid binder which can be coked at elevated temperatures comprising at least the steps of mixing, coking and graphitizing, wherein a puffing inhibitor from the class of metals or metal compounds, preferably metal oxides, is added to the components before they are formed to green bodies, wherein the puffing inhibitor is used in a grain size of lower than 2 pm, preferably lower than 1 pm, and that the puffing inhibitor is dispersed in the liquid binder before the binder is mixed with the granular carbon containing material.
• the method comprises the steps of
• a shear rate in the liquid binder of more than 1000 [1/sec], preferably of more than 10.000 [1/sec] is used and an energy input of more than 5 kWh per ton of dispersion within 10 minutes, preferably of more than 8 kWh per ton of dispersion within 10 minutes is done (in other words: if 50 kg of a mixture of liquid binder and puffing inhibitor is dispersed for 10 minutes, the power of the driving motor has to have minimal 1 ,5 kW or preferably minimal 2,4 kW to be able to bring an energy of 0,25 kWh, preferably of 0,4 kWh into the dispersion).
• the installation to carry out the method according to the above preferred embodiments comprises a weighing vessel for binder and a mixer, wherein said binder weighing vessel is coupled via pipes and valves with a dispersing machine and that said binder weighing vessel is coupled with a preheating furnace 1 or 29 for preheating the puffing inhibitor to the temperature of the liquid binder.
• the puffing inhibitors being in the binder with a dispersing machine preferably with a shear rate of more than 1.000 [1/sec], preferably of more than 0.000 [1/sec] and with an energy input of more than 5 kWh per ton of dispersion within 10 minutes, preferably of more than 8 kWh per ton of dispersion within 10 minutes and
• the binder weighing vessel is coupled via pipes and valves with a dispersing machine (27) with a rotor stator system and said binder weighing vessel is coupled with a preheating furnace (1) for preheating the puffing inhibitor to the temperature of the liquid binder.
• dispersing machine an ultrasonic device is used. It is also preferred that as dispersing machine a wet grinding mill is used.
• each mixer is connected to at least two of said binder weighing vessels, said dispersing machines 10, 27 or 35 and said preheating furnaces 1 or 29.
• the advantage of having two of said binder weighing vessels, two of said dispersing machines and two of said preheating furnaces is not to loose mixing time, if the mixing time is lower than the dispersing time including the loading and unloading time of the binder in the weighing vessel.
• both dispersing machines are of identical shape to have identical conditions during dispersing.
• said weighing vessel for binder is coupled with pipes and valves with a self- aspirating dispersing machine with rotor stator system 35 and said self-aspirating dispersing machine with rotor stator system is coupled with pipes and valves with a preheating furnace 29 for preheating the puffing inhibitor to a temperature of the liquid binder.
• Fig. 1 is named as 1 a preheating furnace for the puffing inhibitors 2, which furnace can be for example a rotating drum furnace or a pot furnace.
• a pot furnace can be emptied either by shifting the furnace or by opening a bottom valve.
• the preheating furnace gets weighed quantities of inhibitor necessary for one mixer charge of the mixer 24 to mix the green mass and the whole quantity of the inhibitor from the preheating furnace is dosed via a pipe 3 into a vessel 6, or the inhibitor in the preheating furnace is a big quantity from which the needed quantity for one mixer charge of the mixer 24 to mix the green mass is dosed into the vessel 6 using a balance 9 of this vessel.
• the first mentioned alternative gives the chance to be able to create directly a mixture of different metals or metal compounds as puffing inhibitors. If the second alternative is used and a mixture of different puffing inhibitors is desired, the mixture must be created in a separate step before the preheating furnace into which the mixture is dosed.
• the preheating furnace can be heated electrically 4 or with burning 5 fossil energy like for example oil or gas.
• the inhibitor in a grain size of lower than 2 pm, preferably of lower than 1 pm is preheated to have the same temperature as the liquid binder has.
• Liquid binders like petrol pitch or coal tar pitch are commonly used at temperatures above 150 °C, in particular between 170 and 220 °C.
• the vessel 6 is a balanced 8 and insulated 7 and heatable 8 vessel having a bottom valve 11 and a powermotor driven dissolving disc 10 which is known from the paint industry to create extremely high shear rate in the liquid.
• the liquid binder is dosed via a pipe 13 having a dosing valve 2 in such a quantity into the balanced vessel 6, that with the whole quantity of inhibitor for one mixer charge to mix the green mass, the content of solid material in the mixture in the vessel 6 is of more than 50 % by mass, in particular of more than 70 % by mass. If the solid content would be less, the dissolving disc 10 would not create enough shear rate in the mixture to destroy agglomerates and the energy input would not be sufficient.
• a dissolver disc a wet grinding mill coupled with pipes with the weighing vessel 6 (for example a Perl mill) or an ultrasonic device can be used, both are not expressed in the drawing.
• Named as 15 is a vessel which is balanced 16, insulated 17 and heatable 18 and having a bottom valve 19 and a motor driven agitator 20.
• the binder is dosed with a pipe 22 having a dosing valve 21 in a quantity for one mixer charge of the mixer 24 to mix the green mass lowered of the weight of the binder quantity dosed into the vessel 6 for the same mixer charge of the mixer 24.
• the bottom valve 11 of the vessel 6 is opened and the desagglomerated dispersion being in the vessel 6 flows in a pipe 14 from vessel 6 into vessel 15 while vessel 15 is agitated with the agitator 20 to homogenize the mixture completely.
• the homogenized mixture of binder and inhibitor is fed to the mixer 24 with a pipe 23 by opening the bottom valve 19 of the vessel 15 in which mixer 24 solid carbon containing granular material is fed and mixed with the liquid binder to green mass for forming green carbon bodies.
• the vessel 6 including its installations, including the dispersing machine 10, and including the preheating furnace 1 can be installed twice if the mixing time of the mixer 24 is so fast, that one installed installation for dispersing the solid inhibitor in the liquid binder would create a loss of capacity in the mixer 24.
• Fig.2 an installation is shown wherein 1 designates a preheating furnace which can be for example a rotating drum furnace or a pot furnace.
• a pot furnace can be emptied either by shifting the furnace or by opening a bottom valve.
• the dosing of the inhibitor either the preheating furnace gets weighed quantities of inhibitor necessary for one mixer charge of the mixer 24 to mix the green mass and the whole quantity of the inhibitor from the preheating furnace is dosed via a pipe 3 into a vessel 15 or the inhibitor in the preheating furnace is a big quantity from which the needed quantity for one mixer charge of the mixer 24 to mix the green mass is dosed into the vessel 15 using the balance 16 of this vessel 15.
• the first mentioned alternative gives the chance to create directly a mixture of different puffing inhibitors.
• the mixture must be created in a separate step before the preheating furnace into which the mixture is dosed.
• the type of heating energy for the preheating furnace there is no limitation, it can be heated electrically or with burning fossil energy like for example oil or gas.
• the inhibitor in a grain size of lower than 2 ⁇ , preferably of lower than 1 ⁇ is preheated to have the same temperature as the liquid binder has.
• Liquid binders as petrol pitch or coal tar pitch are commonly used at temperatures above 150 °C, in particular between 170 and 220 °C.
• Named as 15 is a vessel which is insulated 17 and heatable 18 and has a balance 16 to know the weight of its content and two bottom valves 25 and 26 and a motor driven agitator 20.
• the vessel 15 With a pipe 23 the vessel 15 is connected with an inlet of a motor driven rotor/stator dispersing machine 27, the outlet of the motor driven rotor /stator dispersing machine 27 is connected with the vessel 15 via a pipe 28 to form a loop in which the binder is pumped continuously while the high shear rate in the dispersing machine disperses the puffing inhibitors to single corns in the mixture with binder, which mixture is at the same time homogenized in the vessel 15 with the agitator 20.
• the homogenized mixture of binder and inhibitor is feed to the mixer 24 with the pipe 23 by opening the bottom valve 25 of the vessel 15.
• solid carbon containing granular material is feed and mixed with the homogenized mixture of binder and inhibitor to green mass for forming green carbon bodies.
• the vessel 15 including its installations and the dispersing machine 27 and the preheating furnace 1 can be installed twice if the mixing time of the mixer 24 is so fast, that one installed installation for dispersing the solid inhibitor in the liquid binder would create a loss of capacity in the mixer 24.
• Fig.3 an installation is shown with a preheating pot furnace 29 having a balance 30 to get the weight of its content and having a bottom valve 31 to empty the furnace with a pipe 32.
• the puffing inhibitors 2 are dosed in the right quantity for one mixer charge to mix green mass.
• the heating of the puffing inhibitors is done using either electrical heating 33 or fossil energy burner 34.
• Liquid binder is dosed via a pipe 22 having a dosing valve 21 into a vessel 15 which is insulated 17 and heatable 18 and has a balance 16 to get the weight of its content.
• the quantity of binder dosed into the vessel 15 is the right quantity for one mixer charge of the mixer 24 to mix green mass.
• the liquid binder is pumped in a loop using a pipe 23 and a bottom valve 26 direction to a self-aspirating rotor/stator dispersing machine 35, the outlet of the self-aspirating rotor/stator dispersing machine 35 is connected with a pipe 36 with the vessel 15.
• the emptying valve 31 of the preheating furnace 29 is opened and the preheated inhibitor 2 having the temperature of the liquid binder is sucked from the preheating furnace with the self-aspirating dispersing machine into the liquid binder and dispersed while destroying agglomerates using high shear rate in the rotor/stator machine.
• an agitator 20 can be used, but it is not a must to have it because the pumping effect of the self- aspirating rotor stator dispersing machine is sufficient due to the fact, that no puffing inhibitor can swim on the surface of the binder
• the emptying valve 31 is closed and the liquid binder is pumped further on in the loop to homogenize the content of the vessel 15.
• the homogenized mixture of binder and inhibitor is fed to the mixer 24 with the pipe 23 by opening the bottom valve 25 of the vessel 15.
• solid carbon containing granular material is fed and mixed with the homogenized mixture of binder and inhibitor to green mass for forming green carbon bodies.
• the vessel 15 including its installations and the dispersing machine 35 and the preheating furnace 29 can be installed twice if the mixing time of the mixer 24 is so fast, that one installed installation for dispersing the solid inhibitor in the liquid binder would create a loss of capacity in the mixer 24.
• the present invention is now illustrated by the following example, to which it should not be limited.
• a part of the mass is transferred into a preheated (115 °C) metal shaping die of 5 cm diameter and 25 cm length, which is brought to a hydraulic press with which a stamp is pressed onto the mass with 10 tons on it.
• the pressure is hold till the temperature of the shaping die and the mass is lower than 50 °C.
• the green body is pressed out from the shaping die and baked in a laboratory furnace while being in a covered metal can having the green body in a packing media of petrol coke (grain size 1 mm).
• the temperature increase is 8 °C per hour till 800 °C are reached. Thereafter, heating is stopped and the furnace cools down over night.
• the carbon body is brought into an electrically heated argon flooded carbon tube furnace and heated up to 3000 °C for 5 hours to give a body according to the present invention.
• a sample is created by adding 14 g of a commonly used milled natural iron ore as inhibitor with a grain size of about 90 % between 10 to 40 pm to a preheated (150 °C) petrol coke mixture of 1 kg containing the same fraction as mentioned above. After adding of 200 g of hot binder pitch (180 °C) the same process was carried out as described above. Both samples have comparable values for density and specific electrical resistivity, the ash content of the first sample (following the inventive process) is 30 % lower as the ash content of the second sample.

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• 2013
  • 2013-03-21 AT ATA9466/2013A patent/AT515863B1/de not_active IP Right Cessation
  • 2013-03-21 DE DE112013006851.6T patent/DE112013006851B4/de not_active Expired - Fee Related
  • 2013-03-21 WO PCT/IB2013/000486 patent/WO2014147434A1/en active Application Filing

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