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EP2836299A1 - 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 - Google Patents

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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Publication number
EP2836299A1
EP2836299A1 EP13737669.5A EP13737669A EP2836299A1 EP 2836299 A1 EP2836299 A1 EP 2836299A1 EP 13737669 A EP13737669 A EP 13737669A EP 2836299 A1 EP2836299 A1 EP 2836299A1
Authority
EP
European Patent Office
Prior art keywords
coal
coke
devolatilisation
csr
cri
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.)
Withdrawn
Application number
EP13737669.5A
Other languages
German (de)
English (en)
Inventor
Jayant Moreshwar SATHAYE
Murugesa Sivasubramonia PILLAI
Krishnachetty Bommannan NAGASHANMUGAM
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.)
JSW Steel Ltd
Original Assignee
JSW Steel Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JSW Steel Ltd filed Critical JSW Steel Ltd
Publication of EP2836299A1 publication Critical patent/EP2836299A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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 PROCESS FOR THE MANUFACTURE OF COKE FROM COAL WITH IMPROVED CRI AND CSR VALUES BY EARLY CATALYTIC DEVOLATILISATION.
  • the present invention relates to a process for producing coke with improved CRI and CSR and with reduced porosity.
  • the invention is also directed to catalytic early devolatilisation of coals, which is an advancement in the manufacture of coke with improved CRI and CSR even involving coal blends containing non-coking coals.
  • the advancement provides for a variety of devolatilisation catalysts including divalent and multivalent metal oxides (metals capable of exhibiting multiple oxidation states) which can be reduced at temperatures within the fluidity range of coking coals favouring a cost effective process for producing coke from coal blends containing even non coking coals and reduced quantity of costly and scarce hard coking coals.
  • the process of catalytic early devolatilisation of coal/coal blend is adopted to provide on one hand superior quality coke with decrease in CRI to an extent of 1.0-3.5% and an increase in CSR to an extent of 1.0-3.5 % (depending on the nature of coals used in the blend) at less cost and on the other hand reduce the carbonization completion time by 3% and thus improving the coke oven productivity by about 3%, making the process useful for industrial application.
  • GB746,697 discloses that addition of specific metal oxides, including copper and manganese oxides to coal prior to coking leads to reduction of ammonia formation during the coking process, by superficial wetting of the oven charge by contact mass consisting of metal oxides such as oxides of iron, aluminium, zinc, magnesium, manganese, copper and nickel. Wetting is done by a suspension of metal oxide. The contact mass is applied to destroy or prevent the formation of ammonia during the coking of coal in coke or like ovens. Moreover, experiments under this prior work suggest that destroying or preventing ammonia generation during coking, metal oxides and in particular ferric oxides performs in a superior manner than other metal salts.
  • GB 28941- A.D. 1913 discloses a process for the production of a metallurgical coke without materially increasing the contents of slag to render harmless all sulphur compounds of the coal by replacing in the coking process part of the usual lime addition by a compound of phosphorous which favourably aids in the manufacture of pig iron.
  • the addition is so calculated that the lime contained therein just suffices to bind the sulphur.
  • Phosphorous compound for addition include phosphorite, phosphate chalk, apatite, vivianite and the like.
  • a further addition apart from phosphorous compound to mixture of coal to be coked is made of manganese ore such as manganese di-oxide for the purpose of oxidizing the sulphur compounds by the oxygen and causing them to be carried away with the gases.
  • the process increases the rigidity of the coke by increasing, the phosphide of iron and avoiding formation of sulphides of iron detrimental to properties of coke.
  • GB963,435 disclosed a process for the carbonization of poorly-coking coals to obtain metallurgical coke of high quality comprising drying ground coals or mixtures of ground coals at a temperature greater than 100°C but less than the pyrolysis temperature of the coal, adding a hydrocarbon binder in a liquid or viscous state to the coals before or after drying the coals.
  • This prior art disclosed an improved method for obtaining metallurgical coke form poorly-coking coals by adding a hydrocarbon binder to increase the charge density of coal cake.
  • the resulting coke was found to exhibit improved M40 and M10 indices (cold strength properties).
  • WO2009/047682 A2 disclosed a method of making coke that included feeding an admixture of coking coal and non-coke fines susceptible to microwave volumetric heating and/or induction heating into a coke oven and heating the admixture in the substantial absence of air to drive off volatile compounds from the coal thereby producing coke.
  • the heating is at least partially by microwave irradiation and/or induction heating.
  • the coking coal may be soft coking coal or may be an admixture of hard coking coal and soft coking coal.
  • the admixture may also include non-coking coal.
  • the non-coke fines is selected from the group consisting of a ferro alloy, a ferro alloy ore, a chromium compound, a chromium ore, a nickel compound, a nickel ore, a manganese compound, a manganese ore, a titanium containing material and mixture of two or more of these.
  • 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 generally 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 set specification in terms of CRI and CSR are charged into the furnace.
  • Another object of the present invention is directed to explore the possibility of developing a process, whereby it could be possible to involve a coal blend even consisting of minimum of hard coking coal and maximum of semi-hard and non-coking coal, produces coke with required CRI and CSR suitable for blast furnace operation, at reduced cost per ton of coke.
  • Another object is directed to developing a process for coke production with improved quality whereby the furnace temperature in coke ovens could rise quickly favouring reduced carbonization time in the case of self heated non-recovery coke ovens and improved coke oven productivity.
  • a further object of the present invention is directed to use of selective devolatilisation catalysts mixed in micro proportion with coal blend for coke production in coke ovens, catalyzing early devolatilisation of coal blend, leading to reduced porosity in coke.
  • a still further object of the present invention is directed to use of devolatilisation catalysts, which could initiate volatilization of hydrocarbons and volatile matter in coal at lower temperatures.
  • the basic aspect of the present invention is thus directed to a process for the manufacture of coke from coal with improved CRI and CSR values comprising: subjecting the coal to heating in absence of air to its fluidity range temperatures (comprising initial softening stage , maximum fluidity stage and final resolidification stage) whereby, the coal initially softens and gradually becomes fluid and finally resolidifies to form hard mass of coke involving early devolatilisation of most volatiles during fluid stage (in presence of catalysts) before resolidification, such that the resultant coke possesses improved CRI and CSR properties.
  • a further aspect of the present invention is directed to said process wherein said step of early devolatilisation is carried out involving devolatilisation catalysts consisting of elements which are good oxygen carriers, which readily undergo redox reactions.
  • a still further aspect of the present invention is directed to said process wherein said devolatilization catalyst comprise of selective oxides of divalent and multivalent metals which can be reduced at temperatures within the fluidity range and noble metal oxides which can easily part with oxygen.
  • Yet another aspect of the present invention is directed to a process wherein said devolatilisation catalysts are metal oxides including copper oxide, manganese oxide, vanadium oxide, cobalt oxide, nickel oxide, silver oxide, chromium (III) oxide, chromium (VI) oxide and copper chromite. But, oxides of iron, sodium, potassium and calcium are detrimental to the final properties of coke and hence not to be used as devolatilisation catalysts.
  • a further aspect of the present invention is directed to said process wherein said devolatilization catalyst are finely divided and powdered to at least minus 200 mesh (75 microns) preferably minus 70 mesh (212 microns).
  • a still further aspect of the present invention is directed to said process wherein said devolatilisation catalyst preferably contains lower levels of iron oxide and alkali metal oxides for producing coke with improved CRI and CSR properties.
  • a further aspect of the present invention is directed to a process for the manufacture of coke wherein said catalyst is in finely divided form and uniformly distributed in coal cake.
  • a still further aspect of the present invention is directed to a process, wherein the fluidity range temperatures is in the range of 375-550°C and said catalyst promote early devolatilisation predominantly within said fluidity range temperatures such as to release most of the volatiles (devolatilisation) at this fluid range and before resolidification, whereby the resulting coke is less porous and exhibit improved CRI & CSR properties.
  • a still further aspect of the present invention is directed to a process for the manufacture of coke comprising the steps of: providing coal blend and crushing to desired size; adding the said devolatilization catalyst to the thus blended coal before sizing of the blend by crushing ; subjecting the coal blend with said devolatilization catalyst to carbonization such as to favour said devolatilisation at the maximum fluidity of coal blend and favour producing coke with reduced porosity.
  • said devolatilization catalyst is mixed in two stages to ensure homogeneous mixing whereby in the first stage, the catalyst and coal/coal blend is premixed in a ratio preferably 1 : 10-12 and thereafter the pre-mixed material is blended with the main coal in the ratio of 12-15 part of catalyst to million parts of coal particles.
  • Yet another aspect of the present invention is directed to said process for the manufacture of coke, which comprises the addition of catalysts as follows: Initially the catalysts are powdered to minus 70 mesh (212 microns). The finer the size of the catalysts, better is their performance. The total quantity of catalyst added per oven remains same irrespective of the nature of catalyst used.
  • Stage I About 555 grams of finely divided catalyst is mixed manually with 6445 grams of any coal / coal blend / inert coal / non-coking coal, so that, the total quantity becomes 7 kg.
  • Stage II This 7 kg of material containing the catalyst is mixed with 50 tons of coal blend. This can be done in two ways. a) Initially 7 kg of material is mixed with 50 tons of coal blend in three layers in stamping station.
  • Coal cake is prepared by compacting about 50 tons of coal blend.
  • the coal blend is stored in overhead bunkers (coal tower). In stamping station, coal blend is discharged three times
  • the addition is mechanized whereby, the blended material is added by means of feeder such that, the same ratio of catalyst gets mixed with coal blend, which is then stored in coal towers for the subsequent preparation of coal cake.
  • a still further aspect of the present invention is directed to a process for the manufacture of coke providing for improved CRI by 1.0-3.5% and CSR by 1.0-3.5% at less cost and reduce the carbonization completion time by about 3% and thereby improving the coke oven productivity by about 3%.
  • a further aspect of the present invention is directed to said use of devolatilization catalyst comprise finely divided powdered to atleast minus 200 mesh (75 microns) preferably minus 70 mesh (212 microns) preferably selected from metal oxides including copper oxide, manganese oxide, vanadium oxide, cobalt oxide, nickel oxide, silver oxide, chromium (III) oxide, chromium (VI) oxide and copper chromite having high purity containing preferably lower levels of iron oxides and alkali metal oxides, for early devolatilization of coal/coal blend enabling producing coke with improved CRI and CSR values.
  • metal oxides including copper oxide, manganese oxide, vanadium oxide, cobalt oxide, nickel oxide, silver oxide, chromium (III) oxide, chromium (VI) oxide and copper chromite having high purity containing preferably lower levels of iron oxides and alkali metal oxides, for early devolatilization of coal/coal blend enabling producing coke with improved CRI and CSR
  • Figure 1 is the flow chart showing the steps involved in the production of coke by carbonization of various coal blends 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 is the schematic diagram showing the apparatus used for the determination of devolatilisation of coals.
  • Figure 4 is the graphical representation to illustrate the phenomenon of early devolatilisation vis-a-vis the fluidity temperature range of any coal blend sample.
  • Figure 5 graphically illustrates the phenomenon of early devolatilisation of Goonyella coal in presence of catalyst as compared to conventional process of heating of Goonyella coal in absence of catalyst.
  • Figure 6 graphically illustrates the phenomenon of early devolatilisation of Hail creek coal in presence of catalyst as compared to conventional process of heating of hail creek coal in absence of catalyst.
  • Figure 7 is the graphical presentation showing devolatilisation curve of Illawara coal (i) without catalyst & (ii) with silver oxide as devolatilisation catalyst.
  • Figure 8 is the graphical presentation showing quantum of devolatilisation curve for Illawara coal- without catalyst & (ii) with silver oxide as devolatilisation catalyst.
  • Figure 9 is the graphical presentation showing devolatilisation curve of Illawara coal - (i) without catalyst & (ii) with V 2 O s as catalyst.
  • Figure 10 is the graphical presentation showing quantum of devolatilisation curve for Illawara coal - (i) without catalyst & (ii) with V 2 O s as catalyst.
  • Figure 11 is the graphical presentation showing devolatilisation curve of Poitrel coal-(i) without catalyst & (ii) with Cr0 3 as catalyst.
  • Figure 12 is the graphical presentation showing quantum of devolatilisation curve for Poitrel coal- (i) without catalyst & (ii) with Cr0 3 as catalyst.
  • Figure 13 is the graphical presentation showing devolatilisation curve of Chippanga Mozambique coal- (i) without catalyst & (ii) with Co 2 0 3 as catalyst.
  • Figure 14 is the graphical presentation showing Quantum of devolatilisation curve for Chippanga Mozambique coal - (i) without catalyst & (ii) with Co 2 0 3 as catalyst.
  • Table 1 Table showing various properties of coals:
  • Coals used for the experiments included those mixed in definite proportions to obtain the desired coal blend.
  • Coal blend is designed to minimize the use of scarce resources, to minimize cost per ton of coke produced while producing coke of required quality.
  • CRI and CSR of coke is carried out as per ASTM D-5341-99 (Reapproved 2004), (Standarad test method for measuring Coke Reactivity Index (CRI) and Coke Strength after Reaction (CSR)).
  • CRI Coke Reactivity Index
  • CSR Coke Strength after Reaction
  • the metal oxides having shown favourable contributions towards effective devolatilization, further studies on the effect on CRI and CSR of coke prepared from a wide variety of coal blend and the purity level of such metal oxides involved as given below: Copper oxide (specification: preferably CuO- 90% minimum and preferably containing lower levels of iron and alkali metal oxides and Manganese dioxide (specification: preferably Mn0 2 - 90% minimum and preferably containing lower levels of iron and alkali metal oxides).
  • the metal oxides 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 metal oxide 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.
  • Test Type Coal Blend 4:1 (CuO: Mn0 2 )
  • the fluidity range lies between 375-550°C and devolatilisation predominantly starts after 450°C (and is maximum mainly at the temperature range of 550 -700°C). It was thus identified that the addition of metal oxides to coals promoted early devolatilisation at this fluid range (and before resolidification), whereby the resulting coke was less porous and exhibited improved CRI & CSR properties.
  • the metal oxides were thus identified by way of the present invention for the first time have been found to do exactly this, by promoting early devolatilisation of coals and improve CRI & CSR of the resultant coke.
  • Porosity in coke arises as a result of the path left by the escaping gases (volatiles) during resolidification.
  • the metal oxides being very good devolatalising agents are selected to drive out volatile matter from coal blend.
  • the addition of these metal oxides (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 metal oxides, the gases escape faster (than in their absence) much before the coke resolidifies and thus making the coke less porous.
  • a hard and less porous coke tends to exhibit better CRI & CSR property than the soft and porous coke.
  • the coke obtained from these tests are analysed for porosity. Porosity measurements revealed that, use of catalysts as additives during carbonization yield coke with improved porosity (by making coke more hard and less porous). In this way, the selected catalysts, serve to improve CRI and CSR of coke by reducing porosity.
  • the porosity of coke obtained with and without the addition of catalyst is presented in the following Table 8.
  • Procedure for Box test Box tests for carbonization of coal samples under the experiments are carried out as per procedure involving (applicants copending patent application no. 811/CHE/2012 dated 27.02.2012) a cost effective method for evaluating suitability of different coal blend samples for coke manufacture involving box test by filling coal blend of desired size fraction, duly moisturized and homogenized, in a cubic box of desired size made of mild steel / stainless steel preferably stainless steel, stamped to desired bulk density, carbonized and then carrying out CRI(Coke Reactivity Index) and CSR(Coke Strength after Reactivity) analysis of the coke sample obtained to thereby determine the suitability of the coal blend for coke for use in blast furnace. After carbonisation, the box is removed and the contents are analysed for CRI and CSR properties.
  • oven tests were conducted with Cr0 3 catalyst (as it is cheaper than other catalysts) and the results are presented in Table 18. Initially, the trials were conducted in selected ovens. Based on the results of oven test, it was decided to implement catalyst addition in all ovens and hence the addition of catalyst was mechanized, whereby, the required quantity of catalyst was added through belt and premixed with coal blend before it reaches the stamping station. At stamping station, the coal cake is prepared as per normal procedure and carbonized.
  • Table 17 reveals that, the addition of catalysts to coal blends improves both CRI & CSR properties of coke. It was also observed that, the coke produced exhibited a better micum indices (cold strength properties) with an increase in M40 value of 0.6-1.6 % and decrease in M10 value of 0.4-0.8 %, the related data are given in following Table 17.
  • the advancement also identifies possible varieties of metal oxide based catalysts for providing a process for producing coke by early and faster devolatilisation of coal/coal blend involving selective devolatilisation catalysts comprising oxides of divalent and multivalent metals such as chromium (VI) oxide, chromium (III) oxide, oxides of vanadium, cobalt, nickel and also copper chromite, which can be reduced at lower temperatures (and noble oxides (eg. silver oxide), which can easily part with oxygen) for use in producing coke with reduced porosity and improved CRI(Coke Reactivity Index) and CSR(Coke Strength after Reaction).
  • oxides of divalent and multivalent metals such as chromium (VI) oxide, chromium (III) oxide, oxides of vanadium, cobalt, nickel and also copper chromite, which can be reduced at lower temperatures (and noble oxides (eg. silver oxide), which can easily part with oxygen) for use in producing coke with reduced porosity and improved CRI(
  • the present invention is thus directed to providing a cost effective process for producing coke from blend of coal varieties including even non-coking coal and reduced quantity of costly and scarce hard coking coal.
  • the catalytic devolatilisation of coal blend according to the present invention improve coke quality by decreasing CRI to an extent of 1.0-3.5% and increasing CSR to an extent of 1.0-3.5% and corresponding improvement in micum indices (cold strength properties) with'an increase in M40 value of 0.6-1.6 % and decrease in M10 value of 0.4- 0.8 % achieved at less cost. Furthermore, the process reduces the carbonization time by 3% by the catalytic action of these catalysts in coke making.

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  • 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 procédé pour la production de coke présentant un indice de réactivité de coke (CRI) et une résistance du coke après réaction (CSR) améliorés et une porosité minimale par extraction plus rapide de matières volatiles à l'état fluide de mélanges de charbons. L'avancée identifie et permet de mettre en oeuvre une voie possible pour réaliser une telle extraction plus rapide de matières volatiles par l'utilisation d'un grand nombre de catalyseurs d'extraction de matières volatiles comprenant des oxydes de métaux divalents et multivalents qui peuvent être réduits à de plus basses températures, ce qui favorise un procédé économiquement rentable pour la production de coke à partir de charbons/mélange de charbons comprenant même du charbon non cokéfiant et une quantité réduite de charbon cokéfiant métallurgique onéreux et rare. De façon importante, le procédé d'extraction catalytique de matières volatiles de charbons/mélange de charbons permet d'obtenir d'un côté du coke de qualité supérieure présentant une diminution de CRI à un niveau de 1,0-3,5 % et une augmentation de CSR à un niveau de 1,0-3,5 % à moindre coût et d'un autre côté de réduire le temps pour arriver à une carbonisation complète de 3 %, ce qui améliore la productivité du four à coke d'environ 3 % et rend le procédé utile pour une application industrielle.
EP13737669.5A 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 Withdrawn EP2836299A1 (fr)

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IN1465CH2012 2012-04-12
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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EP2836299A1 true EP2836299A1 (fr) 2015-02-18

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ZA201408231B (en) 2016-08-31
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WO2013153557A4 (fr) 2013-12-05

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