EP3408355A1 - Coke innovant comprenant des additifs - Google Patents

Coke innovant comprenant des additifs

Info

Publication number
EP3408355A1
EP3408355A1 EP17705034.1A EP17705034A EP3408355A1 EP 3408355 A1 EP3408355 A1 EP 3408355A1 EP 17705034 A EP17705034 A EP 17705034A EP 3408355 A1 EP3408355 A1 EP 3408355A1
Authority
EP
European Patent Office
Prior art keywords
coke
additives
diameter
graphite
μιτι
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.)
Pending
Application number
EP17705034.1A
Other languages
German (de)
English (en)
Inventor
Oswin ÖTTINGER
Heribert Walter
Martin Christ
Johann Daimer
Wilhelm Frohs
Frank Hiltmann
Rainer Schmitt
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.)
Tokai Cobex GmbH
Original Assignee
Sgl Cfl Ce GmbH
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 Sgl Cfl Ce GmbH filed Critical Sgl Cfl Ce GmbH
Publication of EP3408355A1 publication Critical patent/EP3408355A1/fr
Pending legal-status Critical Current

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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/205Preparation
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/52Shaped 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
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    • C04B35/528Shaped 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
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    • C04B35/532Shaped 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
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08Cell construction, e.g. bottoms, walls, cathodes
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B7/00Heating by electric discharge
    • H05B7/02Details
    • H05B7/06Electrodes
    • H05B7/08Electrodes non-consumable
    • H05B7/085Electrodes non-consumable mainly consisting of carbon
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    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232Titanium oxides or titanates, e.g. rutile or anatase
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    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
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    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
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    • C04B2235/3804Borides
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    • C04B2235/42Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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Definitions

  • the invention relates to a novel coke comprising additives and its use.
  • Cokes such as petroleum cokes and coal tar pitch cokes can be used after the
  • Delayed coking process are produced, however, these are made of different raw materials.
  • Raffinie residuals Vauum Resid, Slurry Oil, Decant Oil, Thermal Tar, Ethylene Tar
  • green petroleum coke which is then in a Kalzi - N ists intimid at 1 100 ° C to 1500 ° C in calcined petroleum coke can be converted.
  • coal tar In the production of coal tar, the coal tar resulting from the production of metallurgical coke is distilled and the obtained coal tar pitch is fed to the delayed coker, whereby at temperatures of 450 ° C. to 550 ° C. green coal tar coke is obtained, which subsequently in a calcination step at 1100 ° C to 1500 ° C in calcined coal tar coke can be converted.
  • the life can be improved
  • Titanium diboride (TiB 2 ) is used, for example, in the aluminum industry as an additive in the manufacture of the cathode blocks to achieve better wetting with liquid aluminum.
  • TiB 2 Titanium diboride
  • US6258224 for example, the addition of TiB 2 is described in the upper layer of a layered cathode block.
  • CN101 158048 also discloses a carbon composite containing 20% to 60% TiB 2 described.
  • US6428885 describes a support body with a titanium diboride-containing protective coating.
  • TiB 2 is produced with high energy consumption at high temperatures. In the production of carbon products with improved wetting properties of the coarse-grained coke and fine-grained TiB 2 must be technically very complex homogeneously mixed. This is due to the different ones
  • the object of the invention is therefore to provide a coke which increases the lifetime of the carbon products produced from the coke.
  • the object is achieved by a coke comprising additives, characterized in that additives are accumulated at the flow limits or in the areas enclosed by the flow boundaries.
  • flow limits are understood as meaning the boundary lines between optically non-anisotropic regions formed during the solidification of the mesophase during coke formation.
  • the term "mesophase” defines a characteristic state of order between the liquid and solid phases of a system, and the transition from the liquid phase to the solid phase during pyrolysis involves conversion from a disordered isotropic phase to an ordered anisotropic phase.
  • the properties of the coke can be tailored by the accumulation of additives at the flow limits or in the areas enclosed by the flow boundaries, wherein, for example, the wettability and, by suitable choice of additives
  • Abrasion resistance can be influenced. This influence in turn requires a longer life, the carbon products produced from the coke.
  • the coke is selected from the group consisting of petroleum coke, coal tar coke or coke made from the residues of coal gasification, coal hydrogenation or the Fischer-Tropsch synthesis or from a petroleum pitch or coal tar pitch obtained from the mixture of petroleum and coal tar pitch residues. Mixture or any mixture of said cokes.
  • the additives accumulated at the flow limits or in the regions enclosed by the flow boundaries may be accumulated at the flow boundaries or embedded in the regions enclosed by the flow boundaries or accumulated both at the flow boundaries and in the regions enclosed by flow boundaries be embedded.
  • the additive particles at the yield points include all additive particles that touch the yield point.
  • the accumulation at the yield points or in the regions enclosed by the flow boundaries is understood to mean that at least 70% of the additive particles are arranged at the yield points or in the regions enclosed by the yield points. With less than 70% additive particles, coke properties are not affected.
  • additive particles% is meant the percentage of additive particles in a sample.
  • the accumulation of the additive particles is determined by light microscopy or
  • the additives are selected from the group consisting of acetylene coke, fluid coke, flexi-coke, shot cokes, carbon black, non-graphitizable carbons (chars), non-graphitic anthracite, silicon carbide, titanium carbide, titanium diboride or mixtures thereof.
  • Acetylene coke is a coke which is obtained as a by-product in the production of unsaturated hydrocarbons, in particular of acetylene, and subsequently, irrespective of the type of unsaturated hydrocarbon in the preparation of which it is obtained, is referred to as acetylene coke.
  • Acetylene coke has a fine-grained and onion-peel-like structure.
  • non-graphitic anthracite is meant according to this invention, an anthracite, which is obtained by a temperature treatment of below 2000 ° C.
  • Fluid coke in the context of this invention is understood to mean the coking product of high-boiling hydrocarbon fractions (heavy residues from mineral oil or coal processing produced by the fluid coker process.) Fluid coke has an isotropic structure
  • flexi-coke is understood to mean a coke which is produced by the fluidized bed process, such as, for example, the flexi-coking process developed by Exxon Mobile, a thermal cracking process using fluidized bed reactors are obtained coke particles with spherical to ellipsoidal shape, which is constructed onion-like.
  • shot coke is understood as meaning a coke which is produced by delayed coking (delayed coking).
  • the particles of this coke have a spherical morphology.
  • Carbon black is understood to mean an industrially produced finely divided carbon consisting of spherical primary particles.
  • Chars are non-graphitizable, solid products that are formed during the carbonization process of natural or synthetic organic material (Polymer Carbons by Gwyn Morgan Jenkins, Kiyoshi Kawamura, 1967, "Coals of lowest rank (lignite) are said to possess a Polymerie strueturetinct.
  • coals of low rank isotropic chars (polymer carbon) bituminous coals produce textured crystalline cokes, while anthracites, although not coking in the normal sense, eventually yield graphites at sufficiently high temperatures " ).
  • the additives can also be formed according to a further advantageous embodiment only by an "in-situ formation" in the graphitization of the carbon products produced from the coke.
  • the coke contains B2O3 or B C and ⁇ 2 as precursors.
  • the in-situ formation of titanium diboride in the graphitization of the carbon products produced from the coke has the advantage that the additives formed are homogeneously distributed. This has the advantage, for example, in the case of cathode blocks that the wettability is improved and thus the service life is also increased.
  • complicated mixing processes for producing a homogeneous coke-titanium diboride mixture can be dispensed with.
  • the "in situ formation" of titanium diboride has the advantage that can be dispensed with costly and expensive production of titanium diboride.
  • the additives have a diameter of 0.1 to 49 ⁇ m, more preferably from 1 to 3 ⁇ m.
  • the diameter falling within this range is determined by laser light diffraction (ISO 13320-2009).
  • the Mesophasen Guess is disturbed in the implementation of the Delayed Coker feed material to the extent that a coke is obtained, which has completely different properties, as a coke in which the Mesophasen Struktur is not disturbed ,
  • These properties include coke hardness, achievable material strength, thermal and electrical conductivity, thermal expansion, and isotropy of these properties.
  • Another property that can be affected is the wettability of the surface; For example, in a "drained cell", it is desired that the wettability be increased with molten aluminum, living in one Metal crucible wettability is to be lowered.
  • the extent of wettability can be tailored.
  • the coefficient of thermal expansion (CTE) is increased 10 times by the addition of the additives, depending on the amount and size of the additives.
  • the CTE is a parameter for thermal expansion and describes the behavior of a substance with respect to changes in its dimensions in the event of temperature changes.
  • the CTE is measured according to DIN 51909 (2009-05).
  • a coke obtained by mesophase-forming disorder has a higher hardness of up to 2 to 3 times a coke produced without additive.
  • HGI Hardgrove Index
  • the proportion of additives in the coke is 0.5 to 8 wt .-%, preferably 1 to 4 wt .-%.
  • an additive content of more than 8% by weight there is no further increase in the hardness of the coke.
  • At less than 0.5% by weight, the additives have no influence on the disruption of mesophase formation.
  • the content of coke particles is 96% by weight.
  • the additives have a diameter of 0.05 mm to 5 mm, preferably 1 to 3 mm.
  • the diameters in this range are determined by sieve analysis (DIN I 66165-2016, method F). With these diameters of the additives, an embedding is achieved in the areas enclosed by the flow limits. With a smaller diameter than 0.05 mm, as described above, the mesophase formation is disturbed and an accumulation of the additives occurs at the yield points. With a diameter greater than 5 mm, no embedding takes place in the areas enclosed by the flow boundaries, since the diameter of the additives is greater than the diameter of the areas enclosed by the flow boundaries. These blends are used in the production of polygranular carbon and graphite material.
  • the embedding of the additives in the areas enclosed by the flow limits causes an increase of the CTE by 2 to 3 times depending on the type, size and amount of the additives. Likewise, the hardness of the resulting coke is increased by 2 to 3 times.
  • the additives can be used to produce a custom coke. This results in a higher hardness and a higher CTE, whereby the products produced from the coke have a longer life.
  • the proportion of additives is 1 to 40% by weight, preferably 5 to 20% by weight. With a proportion of additives of greater than 20% by weight, no further increase in hardness can be achieved by embedding the additives in the regions enclosed by the flow limits. With less than 1% by weight of additives, the incorporated additives have no influence on the properties of the coke.
  • the coke is coke and additives, and the proportion of the additives is 20% by weight, then the coke content is 80% by weight.
  • the additives are present as a mixture of additives with a diameter of 0.1 ⁇ m to 49 ⁇ m and a diameter of 0.05 mm to 5 mm.
  • the coke By using a mixture of additive of different diameters, the coke can be more flexibly tailored in terms of coke hardness, achievable material strength, thermal and electrical conductivity, thermal expansion, and isotropy of these properties than when using one-diameter additives become. As a result, the carbon products produced therefrom have a longer service life.
  • Additives with a diameter of 0.05 mm to 5 mm are embedded in the areas enclosed by the flow limits. Whereas, by additives of the mixture having a diameter smaller than 0.05 mm, as described above, the mesophase formation is disturbed and accumulation of the additives at the yield points occurs.
  • the proportion of the mixture of additives having a diameter of from 0.1 ⁇ m to 49 ⁇ m is from 0.5 to 8% by weight, preferably 2% by weight and with a diameter of from 0.05 mm to 5 mm, from 5 to 20 Wt .-%, preferably 10 wt .-%.
  • the proportion of additives having a diameter of from 0.1 ⁇ m to 49 ⁇ m is greater than 8% by weight, and with a diameter of from 0.05 mm to 5 mm greater than 20% by weight, then the coke properties occur, such as strength , thermal and electrical conductivity and the thermal expansion in the background and the additive properties begin to dominate.
  • the coke properties occur, such as strength , thermal and electrical conductivity and the thermal expansion in the background and the additive properties begin to dominate.
  • a further subject matter of the present invention is the use of a previously described coke for blast furnace blocks, graphite electrodes for steelmaking, graphite bodies for connecting graphite electrodes, cathode blocks for aluminum production, nuclear applications, apparatus construction for process technologies in the field of highly corrosive media, shell and tube heat exchangers, special graphite for example for silicon production, solar wafer production, electrodes for spark erosion and heating elements, mechanical seals, graphite bearings, graphite pump impellers or graphite crucible, preferably for blast furnace blocks, for graphite electrodes for steel production or for cathode blocks for aluminum production.
  • new cathode blocks can be made according to the Drained Cell concept, which results in energy savings in aluminum production.
  • Figure 1 is a schematic representation of a section of a coke with
  • Figure 2 is a schematic representation of a section of a coke with
  • Figure 3 is a schematic representation of a section of a coke with
  • Figure 1 shows a schematic representation of a section of a coke with an accumulation of additives (1) at the flow limits (2).
  • the additives (1) have a diameter which is selected from the range 0.1 m to 49 ⁇ .
  • FIG. 2 shows a schematic representation of a section of a coke with an accumulation of additives (3) in the areas (4) enclosed by the flow boundaries.
  • the additives (3) have a diameter selected from the range 0.05 mm to 5 mm.
  • Figure 3 shows a schematic representation of a section of a coke with accumulation of additives (1) at the flow limits (2) and in the areas enclosed by the flow limits areas (4).
  • the additives (1) have a diameter which is selected from the range 0.1 ⁇ m to 49 ⁇ m.
  • the additives (3) have a diameter selected from the range 0.05 mm to 5 mm.
  • the additives may be accumulated at the flow limits or in the areas enclosed by the flow boundaries.
  • the wetting behavior of cathode blocks over aluminum melts can be improved.
  • the wetting behavior can be tailored.
  • a gas-calcined anthracite was ground on an impact mill to a diameter of about 3 ⁇ m and from this, by means of sieving, a grain fraction of 1 -3 ⁇ m was produced. provides. This was dispersed at 10% by weight in an ethylene tar. This dispersion was placed in a delayed coker at a temperature of 490 ° C. The coking pressure was 6.6 bar with a coking time of 10 hours. The green petroleum coke was calcined at 1300 ° C. The result is an isotropic petroleum coke with a CTE of 4.5 10 "6 K" 1 and an ash content of 0.09%, the boron content was 0.2 ppm. This coke is suitable for high-purity isographites and reactor graphite in nuclear power plants.
  • the additives having 70% additive particles are accumulated at the flow limits.
  • a petrol-based vacuum residue is fed to 460 ° C a Delayed Coker.
  • the coking pressure was 5.0 bar and a coking time of 8 hours.
  • 10% of the coker feed was added as a dispersion of vacuum residue and 10% by weight acetylene coke with a diameter of 0.4 to 0.8 mm at the top of the coke drum.
  • acetylene coke results.
  • the coke CTE was 3.5 10 "6 K -1.
  • the mechanical abrasion resistance was increased by 6% over a comparable coke without Acetylenkokseinlagerept.
  • the additives in this embodiment are accumulated by the space enclosed by the yield stress areas 70 additive% in the ,

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Abstract

L'invention concerne du coke contenant des additifs, caractérisé en ce que des additifs sont accumulés dans les seuils d'écoulement ou dans les zones comprises dans les seuils d'écoulement. Pour obtenir une répartition homogène, les additifs sont amenés de manière dosée en continu dans l'unité de cokéfaction différée durant le temps de remplissage. Le dosage peut s'effectuer par injection sous forme de poussières à l'aide d'un gaz inerte (azote) mais aussi de manière répartie dans une suspension constituée des composants de réaction et dans un flux partiel de l'arrivée de l'unité de cokéfaction (résidu sous vide, pytar, huile de décantation ou distillats de goudron de houille). Selon un mode de réalisation avantageux, les additifs présentent un diamètre allant de 0,05 mm à 5 mm, de préférence de 1 à 3 mm. De préférence, les additifs sont choisis parmi le groupe constitué du coke d'acétylène, du coke fluide, du flexicoke, du coke en grenaille, du noir de carbone, des carbones non graphitables (produits de carbonisation), de l'anthracite non graphiteux, du carbure de silicium, du carbure de titane, du borure de titane ou de leurs mélanges. Le coefficient de dilatation thermique (CTE) est multiplié par 10 par addition des additifs selon leur quantité et leur grosseur.
EP17705034.1A 2016-01-29 2017-01-30 Coke innovant comprenant des additifs Pending EP3408355A1 (fr)

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DE102016201429.3A DE102016201429A1 (de) 2016-01-29 2016-01-29 Neuartiger Koks mit Additiven
PCT/EP2017/051882 WO2017129808A1 (fr) 2016-01-29 2017-01-30 Coke innovant comprenant des additifs

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES3038615T3 (en) * 2018-07-19 2025-10-14 Basf Se Blend composition comprising petroleum coke and pyrolytic carbon for electrodes
EP3966299A4 (fr) * 2019-05-09 2023-05-24 Arq Ip Limited Procédés d'utilisation de charbon purifié pour valoriser des composants de procédé de raffinerie dans la fabrication de coke de pétrole
AU2021338771A1 (en) * 2020-09-11 2023-04-27 Arq Ip Limited Methods for the production of increased anisotropic coke
CN113088311B (zh) * 2021-03-29 2024-04-19 临沂锦盛坤工贸有限公司 一种电解铝行业废阴极炭块的重利用方法及成焦剂
CN116444274B (zh) * 2023-03-21 2024-04-16 湖南大学 一种超细结构各向同性石墨材料的制备方法
CN121511212A (zh) * 2023-06-15 2026-02-10 埃克森美孚技术与工程公司 含有石墨化催化剂的沥青基复合粉末及其生产和使用方法
CN119912962B (zh) * 2023-10-31 2025-11-18 中国石油化工股份有限公司 一种高端预焙阳极专用石油焦及其制备方法与应用
WO2026035772A1 (fr) * 2024-08-06 2026-02-12 ExxonMobil Technology and Engineering Company Fluides hydrocarbonés modifiés pour produire des cokes et des brais améliorés

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294610A (en) * 1978-04-14 1981-10-13 Great Lakes Carbon Corporation Foundry coke
US4376029A (en) * 1980-09-11 1983-03-08 Great Lakes Carbon Corporation Titanium diboride-graphite composits
JP2004124014A (ja) * 2002-10-07 2004-04-22 Mitsubishi Chemicals Corp 仮焼コークス及びその製造方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US726284A (en) 1901-11-05 1903-04-28 John W Hamilton Baling-press.
NL7503286A (nl) * 1974-07-02 1976-01-06 Continental Oil Co Werkwijze voor de bereiding van petroleumcokes met terugvoer van fijnkool.
US4082650A (en) * 1975-11-28 1978-04-04 Continental Oil Company Manufacture of petroleum coke with fines recycling
US4366048A (en) * 1981-07-09 1982-12-28 Exxon Research And Engineering Co. Fluid coking with the addition of solids
JPH0269308A (ja) 1988-09-02 1990-03-08 Nippon Steel Corp 生ピッチコークス及び等方性高密度炭素材料の製造方法
US5174891A (en) 1991-10-29 1992-12-29 Conoco Inc. Method for producing isotropic coke
US5900189A (en) * 1994-04-07 1999-05-04 Nippon Steel Chemical Co., Ltd. Needle coke for graphite electrodes and process for producing same
DE19714432C2 (de) 1997-04-08 2000-07-13 Aventis Res & Tech Gmbh & Co Trägerkörper mit einer Schutzbeschichtung und Verwendung des beschichteten Trägerkörpers
US6024863A (en) * 1998-08-17 2000-02-15 Mobil Oil Corporation Metal passivation for anode grade petroleum coke
CA2354007C (fr) 1998-12-16 2004-04-27 Alcan International Limited Structures de cathodes a plusieurs couches
US7658838B2 (en) * 2003-05-16 2010-02-09 Exxonmobil Research And Engineering Company Delayed coking process for producing free-flowing coke using polymeric additives
CN102925182B (zh) 2003-05-16 2014-04-23 埃克森美孚研究工程公司 生产自由流动球状焦的延迟焦化方法
JP2004131739A (ja) * 2003-12-15 2004-04-30 Jfe Steel Kk コークスの製造方法
US7276284B2 (en) * 2003-12-18 2007-10-02 Sgl-Carbon Ag Carbon fiber reinforced coke from the delayed coker
US20050254545A1 (en) * 2004-05-12 2005-11-17 Sgl Carbon Ag Graphite electrode for electrothermic reduction furnaces, electrode column, and method of producing graphite electrodes
CN101158048A (zh) 2007-08-03 2008-04-09 中国铝业股份有限公司 一种铝电解槽用石墨化可湿润阴极炭块及其生产方法
DE102010029538A1 (de) 2010-05-31 2011-12-01 Sgl Carbon Se Kohlenstoffkörper, Verfahren zur Herstellung eines Kohlenstoffkörpers und seine Verwendung
DE102013217882A1 (de) * 2013-09-06 2015-03-12 Sgl Carbon Se Elektrodensubstrat aus Kohlenstofffasern
RU2560442C2 (ru) * 2013-11-18 2015-08-20 Государственное унитарное предприятие "Институт нефтехимпереработки Республики Башкортостан" (ГУП "ИНХП РБ") Способ получения коксующей добавки замедленным коксованием
CN104610993A (zh) * 2015-02-09 2015-05-13 马新攀 一种改焦炭性能的炼焦添加剂和炼焦方法
CN105199765A (zh) * 2015-09-14 2015-12-30 镇江华立煤质制样设备有限公司 一种炼焦添加剂

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294610A (en) * 1978-04-14 1981-10-13 Great Lakes Carbon Corporation Foundry coke
US4376029A (en) * 1980-09-11 1983-03-08 Great Lakes Carbon Corporation Titanium diboride-graphite composits
JP2004124014A (ja) * 2002-10-07 2004-04-22 Mitsubishi Chemicals Corp 仮焼コークス及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2017129808A1 *

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JP2019504914A (ja) 2019-02-21
US11434428B2 (en) 2022-09-06
CA3012407A1 (fr) 2017-08-03
CN109072087B (zh) 2022-07-12
CN109072087A (zh) 2018-12-21
CA3012407C (fr) 2020-11-03
RU2018130987A3 (fr) 2020-03-02
WO2017129808A1 (fr) 2017-08-03
RU2716791C2 (ru) 2020-03-16
UA124625C2 (uk) 2021-10-20
RU2018130987A (ru) 2020-03-02
DE102016201429A1 (de) 2017-08-03
US20190031961A1 (en) 2019-01-31

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