EP2379682B1 - Verfahren zur herstellung von kohlepartikel enthaltenden presslingen - Google Patents

Verfahren zur herstellung von kohlepartikel enthaltenden presslingen Download PDF

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Publication number
EP2379682B1
EP2379682B1 EP09801979.7A EP09801979A EP2379682B1 EP 2379682 B1 EP2379682 B1 EP 2379682B1 EP 09801979 A EP09801979 A EP 09801979A EP 2379682 B1 EP2379682 B1 EP 2379682B1
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EP
European Patent Office
Prior art keywords
water
coal particles
weight
insoluble
binder system
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.)
Not-in-force
Application number
EP09801979.7A
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German (de)
English (en)
French (fr)
Other versions
EP2379682A1 (de
Inventor
Hado Heckmann
Johannes Leopold Schenk
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.)
Primetals Technologies Austria GmbH
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Primetals Technologies Austria 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
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Priority to PL09801979T priority Critical patent/PL2379682T3/pl
Publication of EP2379682A1 publication Critical patent/EP2379682A1/de
Application granted granted Critical
Publication of EP2379682B1 publication Critical patent/EP2379682B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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 pellets containing pellets, the pellets obtained thereby and the use of the pellets in processes for producing pig iron in a fixed bed or in processes for the preparation of carbon carriers for processes for producing pig iron in a fixed bed.
  • the hot strength of compacts - 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.
  • the development of undersized particles from compacts or coke particles prior to charging into a fixed bed or within a fixed bed is undesirable because this results in the permeability of the product Fixed bed is deteriorated. In the particular case of a process for the production of pig iron this concerns both the gas permeability and the drainage behavior of the fixed bed with respect to the molten pig iron and the slag. If the permeability of the fixed bed deteriorates, adverse effects on its productivity, its specific energy requirement and its product quality are to be expected.
  • molasses contains components that act catalytically with respect to a reaction of carbon with hot, CO 2 -containing gases, whereby, especially in the hot zones of a production of pig iron serving fixed bed at temperatures> 800-1000 ° C, depending on the pressure, the extent a conversion of solid carbon with CO 2 increases according to Boudouard reaction. As a result, the hot strength of molasses-treated compacts is relieved by pyrolysis-derived, semi-coke or coke particles.
  • bitumen as a binder does not pose such problems associated with molasses.
  • the production of pellets with bitumen is associated with very high binder costs.
  • the object of the present invention is to provide a process for the production of compacts, in which these disadvantages of the prior art are overcome, and compacts with sufficient green and hot strength even with the use of carbon particles, which must be pre-dried, using a known Lesser amount of a water-containing binder system can be produced.
  • 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 is needed on the coal particle surface for binding purposes, can no longer fulfill these binding purposes after penetration into the pores. 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 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 belongs to the group of substances consisting of waxes, organic coking or refinery products, as well as plastics or plastic waste. It may be also to deal with waste oil. These substances are usually available in large quantities at low cost.
  • the impregnation step takes place 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.
  • the carbonaceous substances When entering 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 resulting from the substances contain few 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 compacts, 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 is 5% by weight, preferably 3% by weight, more preferably 2% by weight, based on the weight of the compacts 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.
  • the binder system contains molasses as well as 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.
  • iron or iron oxide-containing particles are 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 ° C and ⁇ 350 ° C at 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.
  • concentration of the solutions, suspensions or emulsions and, correspondingly, a coating of the pore walls with dissolved, suspended or emulsified components 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.
  • the maximum temperature of the heat treatment is limited by the pyrolysis of the carbon particles and is at 350 ° C.
  • the lower limit for the temperature in this heat treatment is 150 ° C.
  • the processing into compacts after the impregnation step can be carried out by known methods, for example as in WO 02 / 50219A1 or in AT005765U1 described, or by any suitable for processing coal particles with a water-containing binder system to compacts suitable methods.
  • An inventive according to the invention after the impregnation step with a water-insoluble and / or water-repellent substance addition of water-containing binder systems in the production of compacts reduces the process costs compared to conventional methods such as according to WO02 / 50219A1 .
  • the avoidance of carbon uptake during the manufacture of briquettes with binder systems containing water reduces specific coal consumption in pig iron production processes using the briquettes or coke obtained therefrom, since less water from the binder system is present in the briquette and correspondingly less energy must be spent for its evaporation.
  • the reduction of the CO 2 reactivity of the coke or the coke is achieved in that the inner surface of the pores of the carbon particles in the compact can no longer be coated by the impregnation of 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.
  • a minor fraction of undersized coke is often added to the feed coal in the COREX® or FINEX® process for producing pig iron in a fixed bed of a melter gasifier in order to improve the permeability of the fixed bed.
  • a softening of the coke or coke particles is inhibited by hot CO 2 and thus counteracts a disintegration of the particles.
  • a significantly better gas permeability and a better drainage behavior of the fixed bed are made possible than in the prior art.
  • the improvement of the reactive properties of the semi-coke therefore makes it possible Reduction or even avoidance of coke addition to COREX® or FINEX® charcoal
  • the inventive method for the production of compacts 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 compacts of the starting materials.
  • the compacts may be, for example, briquettes or slugs from a compaction.
  • the compacts contain up to 97% by weight of carbon particles, and up to 12% by weight of binder system components, as well as carbon particles, water-insoluble and / or water-repellent substances, or solids having water repellency, in an amount based on the weight of the article to be processed whose lower limit is 0.5% by weight, preferably 1% by weight, and whose upper limit is 5% by weight, preferably 3% by weight, particularly preferably 2% by weight
  • the compact 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 coal 1 to be processed into compacts 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 inventive method according to FIG. 2 is different from the one 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 and the further processing of the resulting mixture accordingly FIG. 1 ,
  • FIG. 3 is a variant of the method FIG. 2 in which after the impregnation step 10, before mixing with the water-containing binder system 4, a heat treatment 12 is performed.

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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)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
EP09801979.7A 2009-01-16 2009-12-23 Verfahren zur herstellung von kohlepartikel enthaltenden presslingen Not-in-force EP2379682B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09801979T PL2379682T3 (pl) 2009-01-16 2009-12-23 Sposób wytwarzania kształtek prasowanych zawierających cząsteczki węgla

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA65/2009A AT507851B1 (de) 2009-01-16 2009-01-16 Verfahren zur herstellung von kohlepartikel enthaltenden presslingen
PCT/EP2009/067839 WO2010081620A1 (de) 2009-01-16 2009-12-23 Verfahren zur herstellung von kohlepartikel enthaltenden presslingen

Publications (2)

Publication Number Publication Date
EP2379682A1 EP2379682A1 (de) 2011-10-26
EP2379682B1 true EP2379682B1 (de) 2017-05-17

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EP09801979.7A Not-in-force EP2379682B1 (de) 2009-01-16 2009-12-23 Verfahren zur herstellung von kohlepartikel enthaltenden presslingen

Country Status (7)

Country Link
US (1) US20120000316A1 (pl)
EP (1) EP2379682B1 (pl)
KR (1) KR20110106932A (pl)
CN (1) CN102272271B (pl)
AT (1) AT507851B1 (pl)
PL (1) PL2379682T3 (pl)
WO (1) WO2010081620A1 (pl)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT510136B1 (de) * 2010-07-12 2016-11-15 Primetals Technologies Austria GmbH Verfahren zur herstellung von kohlepartikeln enthaltenden presslingen
AT510135B1 (de) * 2010-07-12 2016-11-15 Primetals Technologies Austria GmbH Verfahren zur herstellung von kohlepartikeln enthaltenden presslingen
CN104220604A (zh) 2012-04-10 2014-12-17 西门子Vai金属科技有限责任公司 用于进行煤砖制造的方法和装置
EP2662458A1 (de) 2012-05-08 2013-11-13 Siemens VAI Metals Technologies GmbH Verfahren und Vorrichtung zur Reduktion der BTX-Entwicklung bei der Pyrolyse von kohlenstoffhältigen Energieträgern.
WO2015099420A1 (ko) * 2013-12-26 2015-07-02 주식회사 포스코 성형탄, 그 제조 방법 및 그 제조 장치
KR101634069B1 (ko) * 2014-12-23 2016-06-28 주식회사 포스코 성형탄 및 그 제조 방법
US10549496B2 (en) * 2015-06-08 2020-02-04 Billion Sung Hoon ZORH Apparatus for manufacturing mineral fiber
US10526556B2 (en) * 2017-05-16 2020-01-07 Omnis Mineral Technologies, Llc Agglomeration of ultra-fine coal particles

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Also Published As

Publication number Publication date
US20120000316A1 (en) 2012-01-05
PL2379682T3 (pl) 2017-10-31
CN102272271A (zh) 2011-12-07
WO2010081620A1 (de) 2010-07-22
AT507851B1 (de) 2017-10-15
KR20110106932A (ko) 2011-09-29
EP2379682A1 (de) 2011-10-26
AT507851A1 (de) 2010-08-15
CN102272271B (zh) 2015-11-25

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