WO2013153555A1 - Catalyseur d'extraction de matières volatiles pour l'extraction de matières volatiles de charbons et procédé pour la fabrication de coke présentant des valeurs de cri et de csr améliorées utilisant un tel catalyseur - Google Patents

Catalyseur d'extraction de matières volatiles pour l'extraction de matières volatiles de charbons et procédé pour la fabrication de coke présentant des valeurs de cri et de csr améliorées utilisant un tel catalyseur Download PDF

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Publication number
WO2013153555A1
WO2013153555A1 PCT/IN2012/000408 IN2012000408W WO2013153555A1 WO 2013153555 A1 WO2013153555 A1 WO 2013153555A1 IN 2012000408 W IN2012000408 W IN 2012000408W WO 2013153555 A1 WO2013153555 A1 WO 2013153555A1
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WIPO (PCT)
Prior art keywords
coke
coal
catalyst
devolatalization
iron oxide
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Application number
PCT/IN2012/000408
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English (en)
Inventor
Jayant Moreshwar SATHAYE
Murugesa Sivasubramonia PILLAI
Krishnachetty Bommannan NAGASHANMUGAM
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Jsw Steel Limited
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Publication of WO2013153555A1 publication Critical patent/WO2013153555A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • 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
    • C10B45/00—Other details
    • C10B45/02—Devices for producing compact unified coal charges outside the oven
    • 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
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives

Definitions

  • TITLE A DEVOLATALIZATION CATALYST FOR DEVOLATALIZATION OF COALS AND A PROCESS FOR THE MANUFACTURE OF COKE WITH IMPROVED CRI AND CSR VALUES USING SUCH CATALYST.
  • the present invention relates to a devolatalisation catalyst and, in particular, to a devolatalization catalyst for use in producing coke with improved CRI(Coke Reactivity Index) and CSR(Coke Strength after Reactivity) and also related to a process for producing coke with improved CRI and CSR by faster carbonization of coal blend in presence of such devolatalisation catalyst. More particularly, the present invention is directed to providing a cost effective process for producing coke from blend of coal varieties including even inferior quality coal (non coking coal) and reduced quantity of costly and scarce hard coking coal.
  • the process of catalytic devolatalisation of coal blend is adopted to provide on one hand superior quality coke with improved CRI by 1.0-3.0% and CSR by 1,5-4% at less cost and on the other hand reduce the carbonization completion time by about 2hrs and thus improving the coke oven productivity by about 3%, making the process useful for industrial application.
  • the quality of coke, especially, CRI and CSR of coke are important parameters for the smooth operation of the blast furnace. It is experienced from past performance of blast furnace that coke having a maximum of 25% CRI and a minimum of 64% CSR are found to be suitable for blast furnace operation (though this might differ from furnace to furnace). Charging an inferior coke inside the blast furnace poses problems such as high dust generation, poor permeability, hanging, slips, high fuel rate, reduction in the quantity of coal injection, low productivity etc. To avoid this, the coke produced is tested for CRI & CSR before charging in the blast furnace. Only that coke, which meets the above specification in terms of CRI and CSR are charged into the furnace.
  • the present practice is to blend various types of coals viz. hard coking coal, semi-hard coking coal and non-coking coal in various proportions to minimize the use of scarce resource (hard coking coal), to minimize the cost of coke produced as there is a direct dependence of cost of coke to profitability of a steel industry and also to maintain the required coke quality.
  • the values of CRI and CSR depend directly on the quality of coals or coal blend used for bulk production of coke.
  • Another object is directed to providing for advancements in the art of devolatalisation of coals, which would enable faster and efficient devolatalisation of coal blend and a method for improving coke oven productivity.
  • a further object of the present invention is directed to development of devolatalization catalysts for use in coke ovens.
  • a further object of the present invention is directed to providing a method for producing coke with improved CRI and CSR using catalyst with coal blend, which would ensure reduced porosity of finished coke even after replacement of hard coking coal with inferior quality coal.
  • a still further object of the present invention is directed to providing a method for producing coke with improved CRI and CSR using catalysts with coal blend which would enable use of higher percentage of low cost inferior variety of coal (non-coking coal) and reduced proportion of costly and scarce hard coking coals in coal blend for bulk manufacturing of coke while still resulting in improved CRI and CSR values of coke fit for use in blast furnace application at reduced cost of production.
  • a still further object of the present invention is directed to developing coal devolatalization catalyst and also its process of application and industrial utility for benefitting efficient and cost-effective production of quality coke from coal blends even of non-coking variety.
  • a still further object of the present invention is directed to providing a method for producing coke with improved CRI and CSR involving catalyst with coal blend which could decrease carbonization time by catalysing faster devolatalisation, leading to increase in coke output and consequent improvement in productivity of coke ovens.
  • a devolatalization catalyst for devolatalization of coals enabling production of coke with improved CRI and CSR values comprising: atleast one of copper oxide (CuO) substantially free of any iron oxide with a maximum of 0.3% iron oxide and Manganese Dioxide (Mn02) substantially free of any iron oxide with a maximum of 0.3%.
  • CuO copper oxide
  • Mn02 Manganese Dioxide
  • Another aspect of the present invention is directed to said catalyst comprising a combination of said copper oxide (CuO) substantially free of any iron oxide with a maximum of 0.3% iron oxide and said Manganese Dioxide (Mn02) substantially free of any iron oxide with a maximum of 0.3%.
  • CuO copper oxide
  • Mn02 Manganese Dioxide
  • a still further aspect of the present invention is directed to said catalyst comprising a combination of said copper oxide (CuO) substantially free of any iron oxide with a maximum of 0.3% iron oxide and said Manganese Dioxide (Mn02) substantially free of any iron oxide with a maximum of 0.3% in the ratio of 4: 1 to 1 :4 preferably copper oxide (CuO) : Manganese Dioxide (Mn02) in the ratio of 4: 1.
  • CuO copper oxide
  • Mn02 Manganese Dioxide
  • Yet another aspect of the present invention is directed to a process for the manufacture of coke from coal with improved CRI and CSR values comprising: carrying out carbonization of coal blend involving a devolatalization catalyst comprising atleast one of copper oxide (CuO) substantially free of any iron oxide with a maximum of 0.3% iron oxide and Manganese Dioxide (Mn02) substantially free of any iron oxide with a maximum of 0.3%, said catalyst favouring devolatalization at the maximum fluidity of coal blend.
  • CuO copper oxide
  • Mn02 Manganese Dioxide
  • a further aspect of the present invention is directed to a process for the manufacture of coke wherein said coal blend includes higher percentages in the level of 10 to 25% of inferior coals including non-coking coals and yet achieve controlled maximum of 25% CRI and a minimum of 64% CSR.
  • a still further aspect of the present invention is directed to a process for the manufacture of coke wherein involvement of said devolatalization catalyst would favour apart from improving CRI and CSR of coke, improve productivity of coke ovens by decreasing carbonization time and increasing output.
  • a still further aspect of the present invention is directed to a process for the manufacture of coke comprises the steps of:
  • said process for the manufacture of coke as above comprises: subjecting the blended coal of desired sizes prior to adding said devolatalization catalysts to stamping such as to achieve a bulk density of about 1.0 to 1.16 preferably above 1.10 tons/m3
  • Yet another aspect of the present invention directed to said process for the manufacture of coke comprises: loading the blended coal of desired sizes in plurality onto the charging plate in layers; preparing coal cake by stamping of the thus loaded coal blend in layers such as to achieve the bulk density in the range of 1.0 to 1.16 preferably above 1.10 tons/m3; adding the said devolatalization catalysts on each said layer of the coal cake preferably by uniformly spreading the catalyst over the coal cake layers; charging the coal cake on the charging plates into oven for carbonization and production of coke.
  • a further aspect of the present invention is directed to said process for the manufacture of coke wherein said devolatalization catalyst used comprises a combination of said copper oxide (CuO) substantially free of any iron oxide with a maximum of 0.3% iron oxide and said Manganese Dioxide (Mn02) substantially free of any iron oxide with a maximum of 0.3%.
  • said devolatalization catalyst used comprises a combination of said copper oxide (CuO) substantially free of any iron oxide with a maximum of 0.3% iron oxide and said Manganese Dioxide (Mn02) substantially free of any iron oxide with a maximum of 0.3%.
  • a still further aspect of the present invention is directed to said process for the manufacture of coke wherein said devolatalization catalyst used comprises a combination of said copper oxide (CuO) substantially free of any iron oxide with a maximum of 0.3% iron oxide and said Manganese Dioxide (Mn02) substantially free of any iron oxide with a maximum of 0.3% in the ratio of 4:1 to 1:4 preferably copper oxide (CuO): Manganese Dioxide (Mn02) in the ratio of 4: 1.
  • coke is quenched and then screened and then sent to coke cutter for coke cutting. Further in said process for the manufacture of coke, after coke cutting, coke is screened by double deck screen according to sizes preferably three size fractions comprising Hard Coke in the range of 25-75 mm, nut coke in the range of 12-25mm and coke breeze ⁇ 12mm.
  • Figure 1 is the flow chart showing the steps involved in the production of coke by carbonization of various coal blend using catalysts according to the present invention.
  • Figure 2 shows the three dimensional schematic view of the coal cake preparation by stamping of coal blend in three layers with a layer of catalyst uniformly sprayed on each of the coal blend layers.
  • Figure 3 graphically illustrates the phenomenon of early devolatalisation of Goonyalla coal in presence of catalyst as compared to conventional process of heating of Goonyalla coal in absence of catalyst.
  • Figure 4 graphically illustrates the phenomenon of early devolatalisation of Hail creek coal in presence of catalyst as compared to conventional process of heating of hail creek coal in absence of catalyst.
  • catalysts A and B in the desired ratio are added by manually spreading it over the coal cake.
  • the catalysts A and B (4: 1 weight ratio) are added during stamping of coal in stamping station (step 4 of Annexure 1).
  • the blended coal is filled on the charging plate in 3 layers and the coal cake is prepared by stamping, such that, its bulk density (BD) is approximately 1.10 tons/m 3 .
  • the dimension of coal cake is 12.87 m x 3.32 m xl.02 m.
  • the catalysts are added to the regular coal blend (after stamping each layer), by spreading the catalysts over the coal cake, approximately at 500 mm, 800 mm and 970 mm height of coal cake.
  • the stamped coal cake is then charged into coke ovens for carbonization as per normal procedure.
  • FIG. 2 schematically illustrates a three dimensional view of coal cake prepared by stamping of coal blend in three layers in accordance with a preferred embodiment with a layer of catalysts on each layer of coal blend according to an embodiment of the present invention following the above stated process.
  • Stamping of coal blend is done mainly to improve BD (>1.10 tons/m 3 ).
  • BD is maintained mainly to improve the quality of coke obtained, to replace hard coking coal with non-coking coal/semi-hard coking coal and to improve productivity (by about 3%).
  • This optional step (stamping of coal) is normally bypassed in conventional coke oven batteries by top charging of coal.
  • Porosity of coke can be reduced with the presence of selective catalysts with coal blend during coke making process.
  • Porosity is reduced by devolatalisation at the maximum fluidity of coal.
  • Catalysts A & B promote this activity.
  • Such ineffective catalysts include oxides of iron and alkali metals such as Calcium, Barium, Sodium and Potassium.
  • Porosity in coke arises as a result of the path left by the escaping gases (volatiles) during resolidification.
  • the catalysts A and B being very good devolatalising agents are selected to drive out volatile matter from coal blend.
  • the addition of these catalysts to coal blend drives out faster the volatile components present in the coal cake, when the coal blend is highly fluid.
  • the volatile components are driven out, when the coal blend (coke) is pasty and during the period of its resolidification. But, in the presence of catalysts A and B, the gases escape faster (than in their absence) much before the coke resolidifies and thus making the coke less porous.
  • the coal cake is prepared as follows:
  • Coal cake is prepared by compacting about 50 tons of coal blend.
  • the coal blend is stored in overhead bunkers (coal tower).
  • stamping station coal blend is discharged three times (to make the coal cake in three layers) from the coal tower onto the charging plate, which is then stamped by "cam operated mechanical hammers".
  • the coal blend is subjected to three layers of stampings before it becomes a coal cake ready for charging into coke ovens.
  • the catalyst (4CuO: lMn0 2 ) is prepared by thoroughly mixing 444gms of CuO with lllgms of Mn0 2 (4: 1 ratio, weight basis). As the quantity of this combined catalyst is very less (555 gms), it is then added to 6.445 kgs of current coal blend (the coal blend to which the catalysts are to be added at stamping station to prepare the coal cake) so that the total weight is 7 kgs and is thoroughly mixed for homogenization. During the preparation of coal cake, the catalyst thus prepared is added on top of each layer (after it is stamped by hammers) by manually spreading over the surface of the coal cake.
  • catalyst is applied on top of all the three layers of coal cake (such that about 2.33 kg of catalyst is added in one layer) and the coal cake thus prepared is then charged inside the ovens for carbonization for 65-67 hrs.
  • the product coke is then discharged and quenched with water in quenching tower.
  • the coke then goes to coke cutter and crushed to different sizes as hard coke (25-65mm), nut coke (12-25mm) and coke breeze (minus 12mm) and dispatched to blast furnace and sinter plant (coke breeze).
  • the method of the invention helps reducing the porosity of coke by driving out volatile matter from coal cake in fluid state and thus improves the CRI and CSR.
  • the process according to the invention favour reducing the carbonization time by about 2hrs as compared to conventional coke making process without the use of any catalysts, thus improving the productivity of coke oven plant by faster devolatalisation and reduces the production cost per ton of coke.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

L'invention porte sur un catalyseur d'extraction de matières volatiles pour l'extraction de matières volatiles de charbons, comprenant au moins l'un de l'oxyde de cuivre et de l'oxyde de manganèse, et sur un procédé pour la production de coke présentant un CRI et un CSR améliorés, par une carbonisation plus rapide de mélange de charbons en présence dudit catalyseur. Plus précisément, l'invention porte sur un procédé économiquement rentable permettant l'utilisation de charbon de qualité inférieure (charbon non cokéfiant) et d'une quantité réduite de coke métallurgique onéreux et rare, par pressage de mélange de charbons en couches multiples à une masse volumique apparente souhaitée avec une couche uniforme d'une association de deux produits chimiques différents mélangés en un rapport préféré utilisée comme catalyseur, sur chaque couche de mélange de charbons soumis à une carbonisation. L'extraction catalytique de matières volatiles du mélange de charbons entraîne les composants volatils vers l'extérieur plus tôt lorsque le mélange de charbons est hautement fluide, ce qui produit ainsi du coke métallurgique et moins poreux présentant un CRI amélioré (inférieur) de 1,0-3,0 % et un CSR amélioré (supérieur) de 1,5-4 % et réduit le temps pour arriver à une carbonisation complète, ce qui améliore la productivité d'environ 3 %.
PCT/IN2012/000408 2012-04-12 2012-06-11 Catalyseur d'extraction de matières volatiles pour l'extraction de matières volatiles de charbons et procédé pour la fabrication de coke présentant des valeurs de cri et de csr améliorées utilisant un tel catalyseur WO2013153555A1 (fr)

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IN1465CH2012 2012-04-12
IN1465/CHE/2012 2012-04-12

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PCT/IN2013/000224 WO2013153557A1 (fr) 2012-04-12 2013-04-03 Procédé pour la fabrication de coke à partir de charbon présentant des valeurs de cri et de csr améliorées par extraction catalytique précoce de matières volatiles

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WO2016109704A1 (fr) * 2014-12-31 2016-07-07 Suncoke Technology And Development Llc Lits multi-modaux de matière à cokéfier
CN109988590B (zh) * 2017-12-29 2021-04-27 新疆八一钢铁股份有限公司 一种大型高炉使用低热态强度焦炭的冶炼方法
CN112036628B (zh) * 2020-08-25 2022-06-03 武汉钢铁有限公司 建立表征配煤成本变化模型的方法
CN115074147B (zh) * 2022-05-30 2023-12-15 鞍钢股份有限公司 一种改善顶装焦炉生产焦炭耐磨强度的方法

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GB746697A (en) * 1953-05-08 1956-03-21 Bergwerksgesellschaft Hibernia Process for destroying, or preventing the formation of ammonia during the coking of coal
GB963435A (en) * 1960-05-21 1964-07-08 Charbonnages De France Improved method for obtaining metallurgical coke from poorly-coking coals
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* Cited by examiner, † Cited by third party
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CN115433593A (zh) * 2022-08-10 2022-12-06 武汉钢铁有限公司 一种与入炉煤细度相匹配的焦炉加热方法
CN115433593B (zh) * 2022-08-10 2023-06-09 武汉钢铁有限公司 一种与入炉煤细度相匹配的焦炉加热方法

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