Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
  • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
  • C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
  • C10L5/16—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders with bituminous binders, e.g. tar, pitch
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
  • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
  • C10L5/105—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with a mixture of organic and inorganic binders
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
  • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
  • C10L5/22—Methods of applying the binder to the other compounding ingredients; Apparatus therefor
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/34—Other details of the shaped fuels, e.g. briquettes
  • C10L5/36—Shape
  • C10L5/363—Pellets or granulates

Definitions

• the invention relates to a process for the production of carbon particle-containing pressings, the compacts obtained thereby and the use of the compacts in processes for producing pig iron in a fixed bed or in processes for the production of carbon carriers for processes for producing pig iron in a fixed bed.
• the hot strength of pressings - especially when used in thermal processes - is a criterion for their suitability for use.
• the term hot strength refers to a) the strength of the semi-coke or coke particles remaining after pyrolysis of the pellets in a high temperature zone, and b) a strength of these semi-coke or coke particles after chemical attack by a hot, CO 2 -containing gas.
• a minimum level of hot strength allows the size of these particles, which is present after the conversion of the compacts by pyrolysis in semicoke or coke particles, to be largely retained.
• coals which show an extraordinarily high water absorption capacity in particular characterized by a high inherent moisture content.
• the moisture content of the compacts should not be too high, ie at a maximum of 7% by weight. This is because this moisture is energetically stressful when using the pellets for pig iron production or for the production of carbon carriers for processes for pig iron production, since the moisture content of the pellets significantly increases the specific consumption of carbon carriers. Therefore, coals whose moisture is higher are to be dried before processing into pressings.
• the expulsion of water from cavities during drying produces additional pore volume.
• the unwetted pore volume can absorb a corresponding amount of water or aqueous media.
• the additional pore volume can again absorb water or aqueous medium.
• certain coals also tend to generate additional pore volume due to grain damage, especially during intense drying.
• a coal with a high water absorption capacity is dried to an acceptable moisture content before the application of the process described in WO 02/50219 A1 is carried out, a large additional pore volume is generated. Therefore, a dried carbon particle sucks a significant portion of the molasses needed to form a bond on the particle surface, which is to be understood as an aqueous solution, into its pores. Therefore, for such coals is common used molasses additives of ⁇ 10% by weight, based on the weight of the coal to be processed, not to achieve sufficient strength for the compacts.
• molasses contains components that act catalytically with respect to a reaction of carbon with hot, CO " 2 -containing gases, which in particular in the hot zones of a production of pig iron serving fixed bed at temperatures> 800-1000 0 C, depending on the pressure, the Extent of reaction of solid carbon with CO 2 increases according to the Boudouard reaction, as a result of which the hot strength of molasses-treated pressings is diminished by pyrolysis-resultant semi-coke or coke particles.
• bitumen as a binder proposed in WO9901583A1 does not pose such problems associated with molasses.
• the production of pressings with bitumen involves very high binder costs.
• This object is achieved by a method for producing a compact containing carbon particles, in which the carbon particles are mixed with a water-containing binder system and the resulting mixture is further processed by pressing into pressings, characterized in that prior to mixing with the water-containing binder system Carbon particles are subjected to an impregnation step in which they are impregnated with a substance.
• the substance either penetrates into the pores of the carbon particles and accordingly prevents the penetration of components of the aqueous binder system by filling in the pore space. Or the substance settles in the exit points of the pores on the carbon particle surface, also called pore necks, and prevents by this clogging of the pore necks penetration of components of the aqueous binder system in the pores. In this way it is prevented that aqueous binder system, which on the
• Carbon particle surface is required for binding purposes, these binding purposes after penetration into the pores can no longer meet. Accordingly, as compared with a method in which aqueous binder system can penetrate the pores, the amount of aqueous binder system required is reduced.
• the aqueous binder system may contain one or more other components besides water.
• the impregnation step can consist of steaming the carbon particles with the substance, spraying the carbon particles with the substance, mixing the substance into a moving bed of carbon particles, or mixing the substance into a fluidized bed of the carbon particles.
• the substance with which the carbon particles are impregnated in the impregnation step is water.
• the water input into the pig iron production process can be limited to an acceptable level.
• the substance with which the carbon particles are impregnated in the impregnation step is a water-insoluble and / or water-repellent substance. If the pores are filled with such a substance in the impregnation step and the pore walls are coated with such substances, the tendency of the pores to absorb components of the aqueous binder system decreases. If the exit points of the pores on the carbon particle surface are closed by such substances, components of the aqueous binder system can no longer penetrate into the pores. As a result, previously sucked into pores and thus ineffective for the binding of the compacts components can make a contribution to the binding of the compacts.
• the water-insoluble and / or water-repellent substance preferably belongs to the group of substances consisting of waxes, organic coking or refinery products, as well as plastics or waste plastics. It may be also to deal with waste oil. These substances are usually available in large quantities at low cost.
• the impregnation step is advantageously carried out at a temperature at which the water-insoluble and / or water-repellent substance is liquid, in particular viscous.
• liquids are considered whose viscosity is at least 1 Pas, and a maximum of 100 Pas, for example, 10 Pas.
• the substance spreads on the surface of the carbon particles and penetrates into the exit points of the pores but hardly into the interior of the pores.
• the consumption of the water-insoluble and / or water-repellent substance in the impregnation step is kept low.
• the water-insoluble and / or water-repellent substance solidifies on cooling in the exit points of the pores on the coal particle surface.
• Impregnation be impregnated, an aqueous solution of a substance or a mixture of substances.
• a substance or a mixture of substances for example, it is molasses, which is an aqueous solution of a mixture of carbohydrates and other natural products.
• dissolved substances of all kinds which improve the hot strength and green strength of the compacts, for example starch or lignin bases from waste liquors of pulp production.
• the substance with which the carbon particles are impregnated in the impregnation step is an aqueous suspension of
• Solid colloids wherein the solid has water-repellent properties.
• examples include suspensions of colloidal talc, graphite or waxes in water. If the solids settle in the pores or in the pore necks, the entry of water-containing binder systems is difficult due to the high surface tension of the water-repellent solids.
• the substance with which the carbon particles are impregnated in the impregnation step an emulsion containing on the one hand water and on the other hand carbonaceous substances such as bitumens, raw tars obtained from hard coal, pitches, waxes, oils.
• the carbonaceous substances Upon penetration of such emulsions into the pores, the carbonaceous substances are deposited in thin layers on the pore surface. During pyrolysis, carbon films are formed from these thin layers. These reduce the reactivity of the compact to hot CO 2 -containing gases compared to an embodiment in which no thin layers of the substances are deposited in the pores. This is because the carbon layers formed from the substances contain little or no catalytically active substances with respect to reaction with hot CO 2 -containing gases. In contrast, contain the carbon particles or the material to be processed into compressions, catalytically active compounds, such as iron or alkalis. Accordingly, the reactivity of a compact whose surface and pores are covered with a carbon layer resulting from the substances is lower than that of a compact without such a carbon layer.
• the lower limit of the amount of substance added in the impregnation step, called impregnating agent, is 0.5% by weight, preferably 1% by weight, the upper limit being 5% by weight, preferably 3% by weight, particularly preferably 2% by weight, based on the weight of the pressings to be processed good, so the Carbon particles. Addition of more than 5% by weight of impregnating agent does not make economic sense. If less than 0.5% by weight of impregnating agent is added, impregnation is no longer effective.
• Binder system molasses and quicklime or hydrated lime. It can also consist of these components.
• the binder system contains molasses in combination with strong inorganic acids, such as phosphoric acid, sulfuric acid, nitric acid.
• the binder system contains an emulsion of bitumen in water. It can also consist of such an emulsion.
• the binder system contains products from waste liquors of pulp production, starches, cellulose, beet pulp, waste paper pulp, groundwood, or long-chain polyelectrolytes such as carboxymethylcellulose.
• quicklime or hydrated lime binder systems have the disadvantage that quicklime CaO and hydrated lime Ca (OH) 2 increase the reactivity of the pellets to hot C ⁇ 2 -containing gases due to catalytic activity, the embodiments without lime or hydrated lime have the advantage of compacts compared with to provide lower reactivity.
• iron or iron oxide-containing particles are also processed in a mixture with the carbon particles.
• the compacts are subjected to a heat treatment after the pressing.
• the heat treatment is carried out at a temperature higher than the pressure.
• the heat treatment causes a drying and / or hardening of the compacts.
• the heat treatment can be carried out at temperatures of preferably ⁇ 250 0 C and ⁇ 350 0 C, in which irreversible chemical processes can convert binder components.
• water-soluble binder components can be converted to water-insoluble compounds.
• the compounds formed in such conversions can contribute to the strength of the compacts.
• molasses-containing binder system for example, a conversion of molasses by caramelization.
• the carbon particles are subjected to a heat treatment after the impregnation step prior to mixing with the water-containing binder system.
• the heat treatment causes a drying.
• the heat treatment additionally causes a concentration of the solutions, suspensions or emulsions and, correspondingly, a coating of the pore walls with dissolved, suspended or emulsified components. These may, in addition to the aqueous binder system added thereafter, contribute to increased hot strength and green strength of the compacts.
• the heat treatment can effect the conversion of the coating of the pore walls initially formed as a result of the heat treatment into water-insoluble compounds, or compounds which reduce the reactivity of the carbon particles with respect to hot CO 2 -containing gases.
• Maximum temperature of the heat treatment is limited by the pyrolysis of the coal particles and is at 350 ° C.
• the lower limit for the temperature during this heat treatment is 150 ° C.
• the amount added in the impregnation step is less than the amount of water-containing binder system added during the subsequent mixing. For example, when using bitumen in water - emulsion in the impregnation step and as a binder system takes place in the impregnation step Add 2-3% by weight while adding 7-10% by weight later as the binder system.
• Impregnation step and as a binder system is carried out in the impregnation step, an addition of 3 to 5% by weight, while added as a binder later 6 to 8% by weight.
• the limits of the specified ranges are included.
• a heat treatment is necessary to remove the carrier liquid water so far that the emulsified substances or the dissolved substances settle in the pores or the pore necks. As a result, the pores are occupied or the pore necks are blocked. Overall, therefore, less water-containing binder system is required for the production of the compacts as in a production without impregnation step.
• the processing into pressings after the impregnation step can be carried out by known methods, for example as described in WO 02 / 50219A1 or in AT005765U1, or by any method suitable for processing carbon particles containing a water-containing binder system into pressings.
• the reduction in the CO 2 reactivity of the coke or of the coke is achieved in that the inner surface of the pores of the carbon particles can no longer be coated by the impregnation with a binder which contains reactivity-promoting substances.
• the binder component molasses contains alkalis as reactivity-promoting substances. Is-containing substances by impregnation, such as bitumens or waxes avoided that molasses coats the inner surface of the pores, the CO 2 reactivity is thus over by a method reduced without the impregnation step recovered char or coke.
• the inventive method for producing pressings makes it possible to reduce the consumption of binder or to curb the harmful effects of reactant-promoting binder components even in the production of coke using pressings of the starting materials.
• the compacts may be, for example, briquettes or slugs from a compaction.
• the pellets contain up to 97% by weight of carbon particles, and up to 12% by weight of components of a binder system, as well as, based on the weight of the material to be pressed
• the pressing also contains iron or iron oxide-containing particles.
• Such particles can originate, for example, from dusts or sludges produced in the production of pig iron or steel.
• the method according to the invention is outlined below with reference to the block diagrams shown in FIGS. 1 to 3.
• FIG. 1 shows a conventional method for producing pressings without an impregnation step.
• FIG. 2 shows a method according to the invention for the production of pressings with impregnation step.
• FIG. 3 shows a method according to the invention for the production of pressings with a heat treatment upstream of the impregnation step.
• the coal 1 to be processed for pressing in this case briquettes, is subjected to drying 2 and then brought to a desired grain size by granulation 3.
• the carbon particles thus obtained are then followed by the addition of a water-containing binder system 4, in this case molasses, optionally with the addition of solid, finely divided binder components such as hydrated lime or quicklime, with mixing 5, wherein the mixing 5 may be one or more stages.
• the mixture thus obtained is subjected to kneading 6 and a mixture 7.
• the product obtained after curing 7 is the briquette.
• the method according to the invention according to FIG. 2 differs from the method illustrated in FIG. 1 in that prior to mixing 5 with the binder system 4 containing the water, the carbon particles are subjected to an impregnation step 10 in which they are impregnated with a substance 11, the impregnating agent , Only after this impregnation step 10 is the mixing with the water-containing binder system 4 carried out and the further processing of the resulting mixture according to FIG. 1
• FIG. 3 shows a variant of the method from FIG. 2, in which after the impregnation step 10, prior to mixing with the water-containing binder system 4, a heat treatment 12 is carried out.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Geology (AREA)
• Oil, Petroleum & Natural Gas (AREA)
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• Inorganic Chemistry (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

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Citations (9)

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• 2009
  • 2009-01-16 AT ATA65/2009A patent/AT507851B1/de not_active IP Right Cessation
  • 2009-12-23 EP EP09801979.7A patent/EP2379682B1/de not_active Not-in-force
  • 2009-12-23 WO PCT/EP2009/067839 patent/WO2010081620A1/de active Application Filing
  • 2009-12-23 KR KR1020117019062A patent/KR20110106932A/ko not_active Application Discontinuation
  • 2009-12-23 PL PL09801979T patent/PL2379682T3/pl unknown
  • 2009-12-23 US US13/144,984 patent/US20120000316A1/en not_active Abandoned
  • 2009-12-23 CN CN200980153989.7A patent/CN102272271B/zh not_active Expired - Fee Related

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