EP3810726A1 - Method for producing a coking product - Google Patents
Method for producing a coking productInfo
- Publication number
- EP3810726A1 EP3810726A1 EP18762837.5A EP18762837A EP3810726A1 EP 3810726 A1 EP3810726 A1 EP 3810726A1 EP 18762837 A EP18762837 A EP 18762837A EP 3810726 A1 EP3810726 A1 EP 3810726A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carrier material
- carbon carrier
- container
- coking
- carbon
- 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.)
- Granted
Links
- 238000004939 coking Methods 0.000 title claims abstract description 195
- 238000004519 manufacturing process Methods 0.000 title abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 250
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 230
- 239000012876 carrier material Substances 0.000 claims abstract description 174
- 238000010438 heat treatment Methods 0.000 claims abstract description 134
- 238000011049 filling Methods 0.000 claims abstract description 37
- 230000009969 flowable effect Effects 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract 3
- 239000000047 product Substances 0.000 claims description 123
- 238000000034 method Methods 0.000 claims description 79
- 230000008569 process Effects 0.000 claims description 48
- 239000000571 coke Substances 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 23
- 229910002804 graphite Inorganic materials 0.000 claims description 23
- 230000005484 gravity Effects 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 11
- 239000003245 coal Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000010426 asphalt Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000011269 tar Substances 0.000 claims description 4
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003830 anthracite Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001639 boron compounds Chemical class 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 25
- 239000013067 intermediate product Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000001007 puffing effect Effects 0.000 description 4
- 239000012791 sliding layer Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011331 needle coke Substances 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052580 B4C Inorganic materials 0.000 description 2
- 229910000976 Electrical steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011271 tar pitch Substances 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
- C10B47/02—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge
- C10B47/06—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge in retorts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
- C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
Definitions
- the invention relates to a method for producing a coking product.
- Coking products of the type produced and procured according to the invention are used, for example, as anodes in the production of aluminum or as electrodes in the melting or metallurgical treatment of steels in electric arc furnaces and in reduction furnaces.
- carbon is used in solid form, typically as coke, for the production of coking products of the type in question here.
- the coke is produced in the manner known per se, as a rule from residues which arise from the refining of petroleum or other petrochemical processes. Coking carbon carriers, such as residues resulting from the distillation of petroleum or comparable carbon carriers, become one
- coal tar pitch is used as a starting product for coking.
- green coke is a calcining process to remove the volatile hydrocarbons that are still present, especially in petroleum coke.
- the expensive needle coke can be partially or completely replaced by a cheaper type of coke or one of the other carbon carriers (e.g. anthracite coal).
- the coke is ground into a pourable amount of grains, from which eight grain fractions are typically separated by sieving.
- coke of different grain fractions is mixed into a coke grain mixture with a grain size distribution which is considered to be optimal with regard to the properties of the graphite element to be set.
- mixtures are created which consist of a third of dust and two thirds of grain in order to ensure a sufficient density. It is assumed that the coke dust fills the gaps between the coke grains.
- Additives, such as iron oxide can be added to the respective mixture. Iron oxide minimizes the irreversible thermal expansion of the coke (“puffing"), which occurs in the subsequent heat treatments when sulfur still present in the coke is driven out of the carbon lattice.
- Grain mixture is mixed with a binder, such as tar pitch, Stearic acid or mixtures of these binders, mixed to a plastically deformable, pasty, homogeneously mixed mass, the binder content of which is typically 20-24% by weight.
- a binder such as tar pitch, Stearic acid or mixtures of these binders
- the carbon binder mass obtained which is also referred to in technical jargon as “green mass”, is now shaped into a “green body” by pressing, extruding, shaking or stamping. During this molding process, the
- the green compacts are then slowly heated to a temperature of typically 800 to 950 ° C. in the absence of oxygen. During this firing process, part of the binder decomposes into gas, which must escape from the green body. This gas development causes a slowly progressing heating, because otherwise the gas pressure developing in the green compact could lead to crack formation and the associated instability of the carbon or graphite element to be produced.
- impregnating agent which has a lower viscosity than the binder originally used, typically tar pitch, is pressed into the intermediate product in order to fill pores present there.
- the intermediate product is then fired again.
- part of the previously pressed-in impregnating agent evaporates, with the result that, even after an impregnating step, the intermediate product inevitably has open pores which are not filled with carbon.
- the impregnation process must be repeated if necessary until the intermediate product has the density required for its further processing.
- the intermediate product is subjected to a graphitization process for further processing to a graphite element of the highest quality.
- the carbon contained in the intermediate product is converted to graphite by heating to approx. 2800 ° C, which is characterized by an increasingly three-dimensional
- a pasty carbon carrier material which consists of a mixture of granular coke and liquid tar distillate serving as a binder, is filled into a tubular housing of an electrode, which has one end in the furnace space of a reduction furnace ( Arc furnace) Melting / reduction of, for example, phosphorus, tantalum or
- Ferromanganese is made from ores.
- the housing of the electrode is made of an electrically conductive carbon steel. A current is applied to the housing of the electrode, which is applied to the one filled in the housing
- Carbon carrier material is transferred.
- an arc ignites in the furnace chamber, causing the temperatures in the region of the end of the electrode reaching into the furnace chamber to rise to more than 2000 ° C.
- the electrode contained in the housing
- Carbon carrier material a temperature gradient through which the pasty
- Carbon carrier material in the upper region of the electrode is kept molten at about 200 ° C.
- the temperature of the carbon carrier rises continuously in the direction of the end of the electrode assigned to the furnace space.
- the disintegrate in the temperature range from 400 ° C to 600 ° C
- Carbon material containing hydrocarbon compounds should be able to escape in the direction of the upper end of the electrode protruding into the furnace space. At the same time, it should come from
- Carbon derived from hydrocarbons fill the spaces between the coke grains. With increasing approach to the tip of the electrode protruding into the furnace chamber, this process continues until the carbon carrier material becomes a solid, compact body in the
- Oven space protruding tip of the electrode has arisen.
- the electrode is consumed and has to be pushed from above in order to maintain the arc in the furnace chamber.
- Söderberg process is used in a furnace to melt one
- Steel alloy also arranged an electrode with a cylindrical container, which is guided with its upper open end through the wall of the furnace.
- the container is made of a conductive stainless steel.
- the container is charged with a non-baked, lumpy electrode mass via its open upper end.
- the electrode mass is liquefied by the supply of heat, which takes place via heated air which is conducted in a central region around the container of the electrode, until it is in the region of a plate-shaped element which is positioned adjacent to the lower outlet opening of the container
- the electrode mass is also burned “in situ” there.
- the solid electrode strand thus burned from the electrode mass is continuously fed from the lower outlet opening of the container into the
- Furnace chamber promoted and serves as an electrode for the supply of electrical energy, via which the arc and thus the melting process in the furnace is kept going.
- the problem of ensuring a certain density of the graphite element produced in this way is also not addressed here, nor is the setting of certain mechanical or other properties which are important for the use of coking products with which the invention is concerned.
- the method according to the invention for producing a coking product accordingly comprises the following working steps: a) provision of a container which delimits an interior and one
- the carbon carrier material comprising a liquefiable, coking carbon component and optionally solid, in particular coking carbon components and also optionally additives which are used to adjust the properties of the
- Coking temperature the carbon carrier material heated to the respective coking temperature in each case for as long as
- Coking temperature is maintained until the carbon support material is kept at the coking temperature by coking to the
- Coking product is solidified and
- step c) wherein gas which escapes from the carbon support material during the heating and holding (step c)) is discharged from the container;
- Starting material is used, which is converted into a moldable mass by mixing with a binder in order to form a green body, which is then subjected to a coking treatment, the process according to the invention starts from a flowable starting product, namely one
- Carbon carrier material the essential component of which is a liquid or liquefiable carbon carrier, the carbon carrier material also being able to contain solid carbon components and other solid or liquid constituents (additives) without, however, losing its liquid character.
- additives used here are iron oxide or titanium oxide to reduce the puffing effect, a boron source, such as pure boron or boron carbide, to improve the crystal structure and thereby reduce the coefficient of thermal expansion, or carbon or graphite fibers to improve the mechanical properties and also contribute to reducing the coefficient of thermal expansion.
- a carbon-rich, coking product that is already liquid at room temperature or by heating and thus is used as the carbon carrier material accompanying melting is brought into the flowable state, but in any case is liquid during the coking access.
- the carbon carrier materials used according to the invention are typically obtained in the processing of petroleum from the heavy fraction, as residues in the distillation of petroleum, from coal tar derivatives, from liquid phase pyrolysis (other flowable organic components).
- Carbon carrier material in particular from at least one component from the following group: "Residues from the distillation of petroleum and
- coal-based products such as tars and their derivatives, pitch, flowable bitumen, resins or products from the processing of biomass such as cellulose, sugar and starch ".
- At least one component from the following group can be present as the solid carbon component in the carbon carrier material used according to the invention: “Granular coke, coal, bitumen in solid form, lignites, anthracite coal, graphite, materials from the recycling of
- Carbon fibers whereby these materials are only mentioned as examples and of course other carbon-containing residues, which are in solid form and can be coked, can be used for the purposes of the invention.
- Coking products produced according to the invention can be used as
- coking products produced according to the invention can be used as an intermediate product for the production of high-quality graphite elements, as are required, for example, as electrodes in the melting or in the metallurgical treatment of steels in an electrical steel plant.
- the procedure according to the invention ensures that the smallest possible amount of gas bubbles is included in the coking product obtained.
- the dimensions of the container determining the shape of the coking product according to the invention can be selected so that, taking into account any machining allowance that may be required, they correspond to the final dimension adapted for the respective application.
- the container provided according to the invention can be made in a manner known per se from a sufficiently temperature-resistant steel sheet.
- the container can be covered at least in sections with a sliding layer on its inner surfaces surrounding the interior of the container.
- a separately prefabricated liner, tightly fitting against the inner surface of the container can be introduced into the interior of the container or a coating consisting of a suitable material can be applied directly to the relevant inner surface.
- a light metal material, in particular an aluminum material, but also a thin steel sheet can be used as the material for the sliding surface.
- step b) of the method according to the invention the flowable carbon carrier material is introduced into the container via the filler opening
- the filling opening can be formed by a filling tube or the like that by a cover, a wall or a lid of the container in the bounded by it
- the carbon component itself or the entire carbon carrier material may be expedient to preheat the carbon component itself or the entire carbon carrier material before filling it into the interior of the container.
- the preheating is preferably carried out in such a way that the meltable carbon component which may be present and which is to be attributed to the liquid component is already liquefied when it reaches the container.
- the heating in the container can also take place in such a way that the carbon carrier material is first optimally liquid and then the coking process begins.
- the filling can take place in such a way that the total amount of carbon carrier material to be coked is first filled into the container (work step b)) and the heating only after filling to the coking temperature and holding at the coking temperature is carried out (step c)), that is, the heating of the
- Carbon carrier material (step b)) is completed.
- Carbon carrier material is still filled into the interior (work step b)) -
- the second variant enables the production of particularly dense, high-quality coking products with minimal porosity.
- the coking temperatures set according to the invention during the coking process (step c)) are typically 450-900 ° C., with coking temperatures of at least 600 ° C. within a practical coking period even for large volumes
- the coking temperature in the range of 450 - 900 ° C, it is ensured that sufficient flowable carbon carrier material is always available in the process to automatically fill the pores created in the coking by the degassing processes in the partial volume of carbon carrier material .
- the penetrating flowable carbon carrier material which fills the openings and cavities left behind by the gas inevitably formed during coking according to the invention ensures an optimally high density of the coking product obtained.
- the electrical conductivity of the products produced according to the invention can be influenced directly by adjusting the coking temperature.
- the electrical conductivity increases with increasing coking temperature.
- electrical conductivities can therefore already be achieved on the coking product produced according to the invention, which allow a direct graphitization or another direct use of these products after the coking process according to the invention.
- products produced according to the invention can be used directly as anodes or cathodes, in particular as anodes, in the production of aluminum.
- Coking temperatures of at least 800 ° C result.
- a suitable setting of the coking temperature of usually at least 800 ° C.
- a longitudinal graphitability of the coking product can already be achieved in the course of the process according to the invention.
- Coking temperature no longer improves the conductivity, so that the range of coking temperature can in practice be limited to at most this upper limit.
- the invention sees a suitable temperature and quantity regime, especially when going through the temperature range of 450 - 600 ° C, to a) ensure that a sufficient amount of liquid
- Carbon carrier material is present in order to ensure automatic replenishment of the pores formed, b) at the same time keeping the amount of liquid carbon carrier material as low as possible in order to promote outgassing and removal of the gas bubbles which form, c) allowing the coking process to proceed quickly and d ) a spontaneous coking and associated "freezing" of
- the coking time over which the carbon carrier material is kept at the respective coking temperature is directly dependent on the volume heated in each case.
- the coking time is to be dimensioned such that the carbon carrier material held at the coking temperature is completely coked in the technical sense after the coking time has ended.
- the coking time depends on the volume to be coked and, in the case of successive filling, on the progress of the filling process. Typical coking times for larger-volume coking products, such as electrodes, are in practice from 6 h to 96 h.
- Coking products with a smaller volume or small cross-sections can also last less than an hour.
- Carbon support material can support the inside of the container existing atmosphere can be extracted. This creates a vacuum in the interior of the container above the carbon carrier material filled into it, which can reach as far as a vacuum.
- Absolute pressure is in the range of 1 to 50 hPa.
- step b) The manner of filling the mold (step b)) and heating (step c)) can be selected in the method according to the invention depending on the requirements placed on the density distribution of the
- Coking product produced according to the invention If, for example, there is a requirement that a maximum density over a sufficient thickness should be present in the outer edge areas of the coking products, whereas a certain residual porosity is accepted in the central core area, it may be sufficient if a stationary container has the total volume filled in the container is arranged on flowable heating element detecting carbon carrier material.
- the coking process proceeds in the direction of the core region of the carbon carrier material starting from the edge region of the carbon carrier material adjoining the inner surface of the container, which is first and most intensely affected by the heat generated by the heating device.
- the gas bubbles formed during coking can escape through the core area of the carbon carrier material, which is still liquid over a long period of time.
- liquid carbon carrier material is forced out of the liquid core area into the pores left by the gas bubbles in the edge area that has already been coked, so that an optimally dense edge area of considerable thickness is obtained in the finished coking product.
- the diameter of the core area affected by the resulting porosity is in comparison to the thickness of the optimally dense surface layer of the one produced according to the invention Coking product so small that it is negligible in applications such as electrodes for reduction furnaces.
- a porosity which is minimized over the entire cross section of the coking product produced according to the invention and the associated optimized density can be achieved in that during step c) a relative movement takes place along the longitudinal axis of the mold between the respectively heated carbon carrier material and the heating zone generated by the heating device.
- This relative movement can take place continuously or step by step.
- the speed of this movement can also be varied depending on the progress of the carbonization of the carbon carrier material.
- the heating zone or the container remains in one position for a certain length of time until the heating zone or the container moves to the next position
- the duration of action of the heat on the volume of carbon carrier material detected by the heating zone can be controlled by adjusting the dwell time.
- Carbon carrier material is moved relative to the heating zone, it can be achieved that the coking process not only as in the above-explained variant of the method according to the invention from the outer edge to the central core area of each of the heat of the heating device
- Carbon carrier material progresses, but at the same time also in the direction of the relative movement. In this way, a uniform increase in the respective coked volume of the carbon carrier material can be achieved over the entire cross-section, and this can be used to ensure that a high density is also present in the core area of the coking product obtained according to the invention.
- the heat given off by the heating device in the heating zone in each case only covers a partial volume of the carbon carrier material filled into the interior that extends over a specific partial section of the height of the interior of the container, the carbon carrier material filled into the interior during the heating (step c)) stops, whereas the heating zone generated by the respective heating device is moved against the direction of gravity towards the upper end of the container, starting from the bottom arranged in the direction of gravity.
- Carbon carrier material urges openings and cavities left behind by the gas bubbles and fills them, so that an overall dense, largely pore-free coking product is automatically obtained.
- a relative movement between the heating zone and the carbon carrier material contained in the container can be brought about by moving the heating device generating the heating zone along the container.
- carbon support material heating device which is divided into several heating segments in the longitudinal direction of the container. These can then be activated and deactivated successively, so that a continuous or step-wise movement of the heating zone generated by the heating segments of the heating device along the container is achieved.
- the heat given off by the heating device in the heating zone likewise only captures a partial volume of the volume filled into the interior that extends over a specific section of the height of the interior of the container
- Carbon carrier material but here the heating device is arranged in a stationary manner, while the carbon carrier material filled in the container is moved relative to the heating zone generated by the heating device.
- the container can be filled with it
- Carbon carrier material are moved along the fixed heater.
- a particularly productive embodiment of this method variant based on a fixed heating device, which is also optimal
- the container is mounted in a fixed position, wherein a drain opening is provided in the bottom of the container, through which the coking product as from the respectively solidified
- Carbon carrier material formed strand is continuously removed from the container (work step e)).
- the container is designed in the manner of a casting mold. At the same time it is
- Heating device mounted on the container and the withdrawal speed with which the coked coke product is continuously removed as a strand from the container, selected so that the carbon carrier material filled in the flowable state on its way to the
- Discharge opening in the technical sense is completely coked and solidified accordingly.
- the volume of flowable carbon carrier material which is above the already coked part of the carbon carrier material in the container, can be set in such a way that, on the one hand, the path from which in the coking process (work step c)) located partial volume of escaping gas bubbles has to be covered, is short and on the other hand there is always sufficient liquid carbon carrier material available to fill the pores left by the gas bubbles in the already coked carbon carrier material.
- the coking product drawn off as a strand from the container can optionally be accelerated to allow rapid further processing. From the coke product strand obtained, coke products of the respective
- the speed of the relative movement depends on the diameter or cross section of the product to be produced.
- the speed increases increasing diameter or cross-sectional size due to the proportion of carbon carrier material used to coke the respective heating zone.
- the speed of the relative movement lies between the heating zone and that contained in the container
- Carbon carrier material typically in the range of 0.025-1.5 m / h, in particular 0.05-0.5 m / h.
- the degassing (step d)) of the gas escaping from the carbon support material in the coking process (step c)) can be supported in that the carbon support material contained in the container is at least temporarily set in motion.
- a vibration device or the like which excites the carbon carrier material contained in the container as a whole or in regions to vibrations, which ideally lie in the range from 0.5 Hz to 50 kHz.
- the heating device used can be designed in such a way that it brings about a specific temperature profile within the carbon carrier material contained in the container and captured by the heat of the heating device.
- the method according to the invention provides coking products which already have a geometry close to the final dimensions during coking. This eliminates the conventional steps in the manufacture of electrodes
- Coking product of high strength and density are characterized by the fact that they have an average density of at least 1.4 g / cm 3 , densities of at least 1.5 g / cm 3 being regularly achieved.
- Coking process is a monolithic structure close to the final dimensions, this is characterized by a high mechanical strength.
- the spatial expression of the physicochemical coke properties can be controlled through the targeted application of heat.
- Figures 1a - 1d a first device for producing a
- Coking product at four operating times spaced at equal intervals, each in a section along the longitudinal axis of the device;
- Fig. 3 shows a third device for producing a
- Fig. 4a shows a fourth device for producing a
- Fig. 4b a generated in the device shown in Fig. 4a
- Coking product in a longitudinal section Coking product in a longitudinal section.
- the device 1 for producing a coking product VK shown in FIGS. 1a-1d comprises a container 2, which is vertically aligned with its longitudinal axis L and is shaped like a cylinder tube and is made of a heat-resistant material, such as a steel customary for this purpose.
- the container 2 delimits an interior space 3 which widens in a funnel shape in an upper section 4 in the direction of the upper edge of the container 2.
- the slim, cylindrical shape of the interior 3 is selected such that the coking product VK produced in the device 1 has an equally slim cylindrical shape at the end of the coking process carried out in the device 1, which is optimally approximated to the shape that the coking product VK or should have a graphite product produced from it.
- the dimensions of the coking product VK can be used
- the shape and dimensions of the cylindrical shape shown by the interior 3 of the container 2 correspond to the shape that graphite electrodes must have in order to be able to be used in arc furnaces in steelworks.
- the shape of the interior allows 3 other shapes of
- Coking products such as coking
- Blocks formed of carbon support materials or the like can be imaged. Their shape can then, for example, be optimally adapted to the conditions in plants for producing aluminum, if necessary also including the required machining allowance.
- the inner surfaces of the container 2 bordering the interior 3 can be covered at least in sections as a separating layer with a thin sliding layer 5, for example made of an aluminum material, in the form of a prefabricated liner inserted into the interior 3 or by a suitable coating method in a manner known per se is applied directly to the relevant sections of the inner surfaces.
- a thin sliding layer 5 for example made of an aluminum material, in the form of a prefabricated liner inserted into the interior 3 or by a suitable coating method in a manner known per se is applied directly to the relevant sections of the inner surfaces.
- the opening at the top of the container 2 is closed by a removable cover 6.
- a filling tube 7 for filling the interior 3 of the
- Container 2 performed with a flowable carbon carrier material K.
- a suction pipe 8 is passed through the lid 6, which is connected to an evacuation device, not shown here, via which in the
- Interior 3 a suppressor for suction of gases present in the interior 3 can be generated.
- the device 1 further comprises an electrically operated, controllable heating device 10, which is placed with its heating coils 11 in a ring shape and with play around the outer surface 12 of the container 2.
- Heating device 10 corresponds to a small fraction of the height H3 of
- the height H3 can be up to 15 m, whereas the height H10 is typically only 1 m.
- the heating device 10 is carried by an actuating device 13, which is set up in a manner known per se to move the heating device 10 in the vertical direction V along the container 2.
- the adjusting device 13 can have a linear guide 14 aligned axially parallel to the longitudinal axis L, along which the heating device 10 can be moved by means of a linear drive 15 of the adjusting device 13.
- the device 1 also comprises a device 16 which is provided to apply vibrations in the range from 0.5 Hz to 50 kHz to the liquid carbon carrier material K filled in the interior 3 of the container 2.
- the vibrating device 16 can also be carried by the actuating device 13 and moved along the container 2 during the coking process with the heating device 10.
- the vibration device 16 is seated here
- the heating device 10 is positioned during the filling process in an initial position at the lower end of the container near the bottom element 9.
- the heating device 10 is charged with, for example, electrical energy, so that the partial volume of the carbon carrier material K lying in the effective range of the heating zone generated by the heating device 10 gradually increases to a coking temperature of 450-900 ° C , in particular 650 - 850 ° C, is heated.
- a coking temperature of 450-900 ° C , in particular 650 - 850 ° C
- Carbon carrier material K gases are released in the form of
- Ascend carbon carrier material K The space freed up by the decomposition processes in the carbon carrier material K is
- Carbon carrier material K of the carbon carrier material column present in the interior 3 of the container 2 is replaced. This process continues until the partial volume heated in each case by the heating device 10 in the heating zone it produces has coked completely in the technical sense and has assumed a solid form. Since all that have been released by gas formation
- Carbon carrier material K have been filled, the density of the part of the carbon carrier material K so coked is at least 1.4 g / cm 3 .
- Device 16 can be induced in the carbon carrier material K.
- the removal of the gas bubbles G from the carbon carrier material K is promoted in that a vacuum is maintained via the suction pipe 8 in the interior 3 of the container 2, which can reach a vacuum. Since the coking by symmetrical heating from the sides of the
- Coking runs from the outside inwards. When the outer layer is coked, liquid is initially viscous, both in the core area and in the layer above it
- Carbon carrier material K is present, through which the gas bubbles G can escape and possible pores are closed. This enables a high density of the coking product obtained. When the core area is coked, carbon carrier material K can flow in from the layer above it. Here, too, the pores are closed.
- Carbon carrier material K is coked, the heating device 10, which is still held in the heating mode, and with it the likewise still active one
- the speed of the upward movement of the heating device 10 and the vibrating device 16 coupled to it is dimensioned such that the partial volume of the carbon carrier material K located in the effective range of the heating zone generated by the heating device 10 gradually heats up and then over a coking period on the respective one
- Coking temperature is kept for one in a technical sense complete coking and associated complete solidification is sufficient. In practice, conveyor speeds for this are
- Heating device 10 typically in the range of 0.025-1.5 m / h,
- the movement of the heating device 10 continues until the upper section of the carbon carrier material K adjacent to the mirror SK of the carbon carrier material K is also coked.
- Carbon carrier material K is due to the from
- the container 2 is opened and the one formed in its interior 3
- Interior 3 bounding inner surfaces of the container 2 existing liner or sliding layer 5 facilitates the removal of the coking product VK.
- Carbon carrier material K was available to fill the voids left by the gas bubbles G being formed, the area BP in question is separated. It can be reused by grinding it into fine particles, which are solid
- Carbon components can be added to the carbon carrier material K, which are used for the production of further coking products VK in the
- the coking product VK thus obtained is used to produce a
- Graphite electrode as is required in an electrical steel plant, is subjected to a customary graphitization process in order to give it a graphitic structure. Because of the device 1 in the above
- the structure of the device 101 shown in FIGS. 2a-2d for producing a coking product VK corresponds to that of the device 1 shown in FIGS. 1a-1d, with the difference that in the device 101 instead of the fixedly mounted filling pipe 7 provided in the device 1 a filling tube 107 which can be inserted and pulled out in the manner of a lance into the interior 3 of the container 2 of the device 101 is provided.
- the maximum insertion length of the filling pipe 107 is dimensioned such that the filling pipe 107, when fully inserted into the interior 3, ends just above the height H10 over which the heating zone generated by the heating device 10 extends in the starting position of the heating device 10 (FIG. 2a). This avoids the negative effects of splashes that can be triggered during the coking process.
- the interior 3 of the container 2 is filled with a partial volume of flowable carbon carrier material K in the device 101 via the filling pipe 107 until the mirror SK of the carbon carrier material K contained in the interior 3 ends above the height H10 over which the heating zone generated by the heating device 10 in its starting position extends (FIG. 2a).
- filling tube 107 With the onset of coking, filling tube 107, raised by a corresponding amount of height, becomes quasi-continuous
- Carbon carrier material K supplied and the heating device 10 with the vibrating device 16 coupled to it is moved along the container 2 by means of the actuating device 13 in the manner already described for the device 1.
- Height-adjustable filling pipe 107 and the heating device 10 are coordinated with one another in such a way that the vertical distance between the
- Heating device 10 and the free end of the filling tube 107 projecting into the carbon carrier material K remains constant.
- the height of the mirror SK of the carbon carrier material K is kept such that above the partial volume of the carbon carrier material K in the coking there is always a sufficient amount of flowable carbon carrier material K available to fill the cavities left by the gas bubbles G, the from the to the
- FIG. 3 shows a device 201 for producing a coking product VK, in which, in contrast to the devices 1 and 101, a heating device 210 provided on the device 201 is mounted in a stationary manner, that is to say it stands still during operation, whereas the one to be coked
- Carbon carrier material K moves along the heater 210 and in this way along the heater 210 to a solid
- Coking product VK is coked in the manner of a continuous
- Continuous casting process is continuously withdrawn from the device 201.
- the device 201 has a container 202 which delimits an interior space 3 which, like the interior spaces 3 of the devices 1, 101, widens in a funnel shape in an upper region and by a cover 206
- a suction pipe 208 and a filling pipe 207 arranged in the manner of the filling pipe 7 of the device 1 are passed through the cover 206 here, as in the case of the covers 6 of the devices 1, 101.
- the cylindrical region 217 of the interior 203 arranged under the funnel-shaped upper region is designed to be open at the bottom in the manner of a mold and is considerably shorter than in the devices 1, 101.
- the section of the container 202 surrounding the region 217 is seated in the ring-shaped heating device 210, which extends over a substantial part of the height of the area 217.
- the heating coil 211 are the
- Heating device 210 can be regulated in segments in order to achieve an optimal temperature profile in the effective range of that generated by heating device 10
- the lower outlet opening of the mold-like region 217 of the interior 203 is first covered with a Plug closed and filled a first partial volume of carbon carrier material K into the interior 203 of the container 202 via the fill tube 207.
- the carbon carrier material K located in the effective area of the heating zone generated by the heating device 210 is controlled step by step, heated to the coking temperature and held there until it is completely coked in the technical sense and has assumed a solid form.
- Carbon carrier material K as a strand is pulled continuously from the mold-like region 217 of the interior 203 of the container 202 by means of the stopper via its lower opening. At the same time, new, possibly preheated, carbon carrier material K is also continuously filled into the container 202 via the filling pipe 207.
- the lower opening region 218 of the region 217 can widen in a funnel shape in the direction of gravity SR in order to
- the pull-out forces are dimensioned such that the coking product is continuously withdrawn from the container 202 despite the underpressure A / akuums present in the container 202 above the carbon carrier material filled into it.
- Coking temperature is maintained which corresponds to the coking time required for its complete coking in the technical sense.
- the height of the level SK of the flowable carbon carrier material K is above that already as a result of the
- Coking hardened carbon carrier material K adjusted so that on the one hand the gas bubbles G that are in the coking Carbon carrier material K emerge, only have to travel a short way through the flowable carbon carrier material K until they are sucked out via the suction pipe 208 after exiting the carbon carrier material K, but on the other hand there is always a sufficient amount of liquid carbon carrier material K available to pass through into the solidifying carbon carrier material K pressing liquid
- Carbon carrier material K to fill the pores left by the gas bubbles G. Even with a device of the type shown in FIG. 3, optimally dense coking products with optimally homogeneous can thus be obtained
- the outgassing of the gas bubbles G can be supported by a vibration device 216, which, as in the case of the devices 1, 101, is above the vibration device 216, which, as in the case of the devices 1, 101, is above the vibration device 216, which, as in the case of the devices 1, 101, is above the vibration device 216.
- Heating device 210 is arranged, but here, according to the fixed arrangement of the heating device 210, is stationary. As already mentioned, a vacuum / vacuum can also be applied to the container 202, which functions in the manner of a mold, in the region above the carbon carrier material K filled into it, in order to outgass the gas
- Coking product VK passes through a cooling section 219 after it emerges from the container 202, in which it is accelerated to room temperature. The strand is then cut off in a cutting device 220
- two or more such mold-like container regions 217 each with a heating device 210 arranged thereon, can be connected to a central distributor (not shown here) which feeds the mold-like container regions 217 with carbon carrier material K. and a vibrator 216 also mounted thereon for maximum productivity.
- FIG. 4a shows a device 301 for producing a coking product VK, which comprises a pot-shaped container 302 made of a suitable steel material, which is closed by a lid 306.
- a suction pipe 308 is guided through the cover 306 and is used to evacuate the interior 303 surrounded by the container 302 to one not shown here
- Suction device is connected.
- the container 302 sits in one
- Heating device 310 the stationary, annular heating spiral 311 of which extends over the entire height of the container 302, so that the heating device 310 can generate a heating zone correspondingly extending over the entire height of the container 302.
- Carbon carrier material K filled in the interior 303 of the container 302. The container 302 is then closed by putting the lid 306 on and the carbon carrier material K contained in the container 302 is brought to a coking temperature of 450-900 ° C.
- a coking temperature 450-900 ° C.
- the coking and solidification of the carbon carrier material K begins from the lateral inner surfaces of the interior 303.
- the core region KB of the carbon carrier material K remains highly fluid over a long period of time, so that gas bubbles G reaching there, like those resulting from the Coking partial volumes of the
- Carbon carrier material K emerging gas bubbles G move for a long time against gravity in the direction of the mirror SK of the carbon carrier material K contained in the container.
- the coking product VK places the highest demands on conductivity and stability, while the quality of the core area KB only plays a subordinate role.
- Such requirement profiles arise, for example, in plants for the production of aluminum, if there
- Coking products VK of the type produced according to the invention are to be used as anodes or cathodes, in particular as anodes.
- the flowable carbon carrier material K used in the devices 1, 101, 201, 301 for producing the respective coking product VK consists in each case of the distillation of petroleum products and the
- This carbon carrier material K is optionally with granular coke or graphite with a grain size of at most 10 mm and optionally one or more additives, such as iron oxide to reduce the puffing effect, a boron source, such as boron carbide, to reduce the coefficient of thermal expansion or to improve the generated Crystal structure, or carbon or graphite fibers, which improve the mechanical properties and also reduce the coefficient of thermal expansion, mixed.
- the carbon carrier material K used in each case is liquid at the process temperature in such a way that it flows under the action of gravity into the interior 3, 103, 203, 303 bounded by the container 2, 102, 202, 302.
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- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Coke Industry (AREA)
Abstract
Description
Claims
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PL18762837.5T PL3810726T3 (en) | 2018-08-31 | 2018-08-31 | Method for producing a coking product |
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PCT/EP2018/073509 WO2020043314A1 (en) | 2018-08-31 | 2018-08-31 | Method for producing a coking product |
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EP3810726A1 true EP3810726A1 (en) | 2021-04-28 |
EP3810726B1 EP3810726B1 (en) | 2022-03-16 |
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EP (1) | EP3810726B1 (en) |
ES (1) | ES2915668T3 (en) |
PL (1) | PL3810726T3 (en) |
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WO (1) | WO2020043314A1 (en) |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US1440724A (en) | 1919-09-08 | 1923-01-02 | Norske Elektrokemisk Ind As | Electrode for electric furnaces and process for manufacturing the same |
US1640735A (en) | 1923-05-16 | 1927-08-30 | Norske Elektrokemisk Ind As | Process of making channeled continuous electrodes |
US3365533A (en) | 1967-02-23 | 1968-01-23 | Monsanto Co | Continuous electrodes |
US4106996A (en) * | 1974-09-14 | 1978-08-15 | Werner Wenzel | Method of improving the mechanical resistance of coke |
CH646992A5 (en) * | 1980-02-26 | 1984-12-28 | Maurer A Ing Sa | Method for the continuous heat treatment of raw materials verkohlbarem. |
BR9900252A (en) | 1999-02-02 | 2000-08-29 | Companhia Brasileira Carbureto | Stainless steel container for forming self-baking electrodes for use in electric reduction blast furnaces |
US7604731B2 (en) | 2004-06-25 | 2009-10-20 | Indian Oil Corporation Limited | Process for the production of needle coke |
US20080256852A1 (en) * | 2007-04-20 | 2008-10-23 | Schobert Harold H | Integrated process and apparatus for producing coal-based jet fuel, diesel fuel, and distillate fuels |
RU2385343C1 (en) * | 2008-12-10 | 2010-03-27 | Закрытое Акционерное Общество Научно-Производственная Компания "Интергаз" | Method of processing carbon and/or carbon containing products and reactor for implementation of this method |
RU2544669C1 (en) * | 2014-02-03 | 2015-03-20 | Закрытое Акционерное Общество Научно-Производственная Компания "Интергаз" | Method for processing combustible carbon- and/or hydrocarbon-containing products, and reactor for implementing it |
-
2018
- 2018-08-31 RU RU2021108578A patent/RU2762192C1/en active
- 2018-08-31 EP EP18762837.5A patent/EP3810726B1/en active Active
- 2018-08-31 WO PCT/EP2018/073509 patent/WO2020043314A1/en active Search and Examination
- 2018-08-31 ES ES18762837T patent/ES2915668T3/en active Active
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PL3810726T3 (en) | 2022-08-01 |
ES2915668T3 (en) | 2022-06-24 |
EP3810726B1 (en) | 2022-03-16 |
RU2762192C1 (en) | 2021-12-16 |
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