CA1071402A - Process for the treatment of coke-oven gas - Google Patents

Process for the treatment of coke-oven gas

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Publication number
CA1071402A
CA1071402A CA285,485A CA285485A CA1071402A CA 1071402 A CA1071402 A CA 1071402A CA 285485 A CA285485 A CA 285485A CA 1071402 A CA1071402 A CA 1071402A
Authority
CA
Canada
Prior art keywords
gas
coke
coal
cracked
oven
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.)
Expired
Application number
CA285,485A
Other languages
French (fr)
Inventor
Joachim F. Meckel
Claus Flockenhaus
Dietrich Wagener
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.)
Didier Engineering GmbH
Original Assignee
Didier Engineering 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
Application filed by Didier Engineering GmbH filed Critical Didier Engineering GmbH
Application granted granted Critical
Publication of CA1071402A publication Critical patent/CA1071402A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/0073Selection or treatment of the reducing gases
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/10Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen

Abstract

ABSTRACT OF THE DISCLOSURE
A process for the Treatment of coke-oven gas, in Which hot coke-oven gas coming from a block of coke-ovens is directly, without cooling or purification, subjected to partial oxidation by means of oxygen, oxygen enriched air or other gas mixtures containing oxygen and cracked and thus converted to a cracked gas rich in carbon monoxide and hydrogen, this novel process providing an economical coke-oven gas treatment by utilization of the coke-oven gas heat energy.

Description

: ;

The invention relates to a process for the treatment of coke-oven gas.
Hot coke-oven gases from a block of coke-ovens are convention-ally cooled in a succeeding condensing stage. The gaseous as well as the liquid constituents are further treated in a by-product plant. In this plant particularly tar, ammonia, sulphur, benzene and naphthalene are removed.
About half of the purified coke-oven gas is reused for undergrate firing of the block of coke-ovens. In addition blast furnace gas is used for undergrate firing of the block of coke-ovens. The latter presupposes, that the coking plant is integrated with a steel making plant in the vicinity of the coking plant. Because the proceeds that can be realized from the sale of the products produced in the by-product plant is getting less and less, and because the economy of production of by-products became doubtful, the production of by-products has of late been carried out often only for the purpose of gas purification. Some of the by-products have even been destroyed ~for example, burning of almmonia).
; It would be a great advantage to use the sensible heat of the ' coke-oven gas, which has a temperature of about 700 to 750C when leaving the i block of coke-ovens for other processes using heat. This would at the same time be a lesser load on the environment by heat which no longer has to be dissipated.
From the journal "Brennstoff-Chemie", Volume 41 (Nr. 10), 1960 .,il pages 294 to 297 a process is known for producing town gas from natural gas containing about 90% methane by partial oxidation with oxygen în a free (an open) flame.
DT-OS 22 32 650 discloses a process for producing a reducing gas.
~ In this process a waste gas from the top of a reduction furnace, for example a ( blast furnace or a shaft furnace is heated with a gas containing methane, for example coke-oven gas or natural gas is heated. As an example a mixture of methane or a hydrocarbon gas containing methane, for example cooled and , . .,. . ;i .;
; : - , ., . :
::. . :

purified coke-oven gas which has subsequently been heated to a temperature below 1000C, and a gas containing C02~ H20 etc., for example the waste gas from a blast furnace or shaft furnace which is heated to above 1200C is fed :into a re:Eorming furnace and the gas is reformed to a reducing gas by heating to a temperature above 1200C in the reforming furnace. Thus a gas mixture containing a relative]y high fraction of inert gases, particularly nitrogen, is produced.
The purpose of the invention is to suggest a process of the type mentioned at the beginning, in which coke-oven gas is further treated in an economical way so that at the same time the sensible heat of the coke-oven gas is utilized and the purification of the coke-oven gas, which is a costly process, is largely discontinued.
According to the present invention the problem is solved, in that the hot coke-oven gas coming from the block of coke-ovens is directly, i.e. without cooling or purification, subjected to partial oxidation by means of oxygen, oxygen enriched air or other gas mixtures containing oxygen and cracked and thus converted to a cracked gas rich in carbon monoxide and hydrogen. ~ ;
In this process the sensible heat transported by the coke-oven gas is used for the chemical cracking itself ~partial oxidation). During oxidation most of the impurities in the coke-oven gas are cracked and rendered harmless so that the costly purification of the coke-oven gas, which was normal up till now, can be discontinued. At the same time gas for synthesis, gas for heating or reducing gas with a very high degree of reduction (reducing action) is formed. Production of by-products is dispensed with, and the high costs of investment and operation are saved.
A reducing gas with a higher degree of reduction is obtained, if coke-oven gas is used which is formed by coking of pre-heated coal.
The process can be more economical, if the cracked gas from the process is used to pre-heat the oxygen or the oxygen enriched air or other gas mixture containing oxygen.
~lso the heating gas required for coking and/or ~he heating gas required in a metallurgical plant can be pre-heated by means of the hot cracked gas.
S:ince the reducing action of the cracked gas is high, it can be used, particularly in a pit furnace, for direct reduction of iron ore, as is known from the journal "Stahl and Eisen" 82, Nr. 13 1962, pages 869 to 883.
In a specially conducted process the cracked gas is cooled by means of a coolant, the cooled cracked gas is compressed, the compressed cracked gas is finally purified, and the cracked gas thus purified is used, for example as gas for synthesis, gas for heating or reducing gas, in a pit furnace. The final stage of purification, which is still required in this case, is not costly.
Before its further use as gas for synthesis, gas for heating or reducing gas, the cold finally purified cracked gas may also be economically pre-heated by means of the hot cracked gas from the process.
It may also be advantageous to compress the hot coke-oven gas ` before the partial oxidation.
The process according to the invention is preferably used for a ; 20 block of coke-ovens which is integrated with a metallurgical plant. In this case the oxygen plant of the metallurgical plant, which exists anyway and is a ;
large investment, can be used in common and can be fully utili~ed.
Particularly in the latter case waste gas from the pit furnace, which is available anyway, may advantageously be used for heating of the block ;~
~` of coke-ovens, ~he pre-heating plant for coal or for other heating purposes.
Gasification and treatment of the gas is carried out particular-` ly in a pressure range from 0 - 30 bar, preferably 0 - 5 bar.
Cracking is preferably carried out at a reaction temperature from 950 to 1500C.
Purther characteristics, advantages and possibilities of appli-, `- ~LC37~

cation of the process according to the invention will be appreciated from the following description.
The invention may be put into practice in various ways and one spec:ific embodiment will be described by way of example with reference to the accompanying drawing which is a diagrammatic illustration of a plant for carrying out the process according to the invention for the special and particularly advantageous case of further treatment of hot coke-oven gas which is produced from pre-heated coal.
The coal which is to be used for coking, is dried in the coal pre~heating plant 0 and pre-heated to about 200C. The heat-carrying gas, from which heat is transferred to the coal, is produced in a combustion chamber by burning the coke-oven gas, blast furnace gas or other fuels. Since this preliminary stage evaporates and removes water from the coal as well as heating the coal to about 200C, the time for the succeeding process of coking can be shortened. Depending on the method chosen for pre-heating, the bulk r density of the coal in the oven increases to a greater or less extent and that :
improves the quality of the coke. Thus the range of coking coal which is suitable for coking is widened by means of this pre-heating. More uniform packing of the coke-oven with pre-heated coal as compared with damp coal, helps to produce more uniform heating of the packing. As compared with operation , ~ with damp coal, the coal is converted to coke more uniformly and this in turn again shortens the time required for coking. For production of reducing gas from coke-oven gas the combination of pre-heating with the block of coke-ovens ..
1 has a very significant effect on the quality of the reducing gas, as will be described in more detail below. The coke-oven gas ~a) which is produced in the block of coke-ovens 1, is fed directly, i.e. without cooling or purification, to a gasifica~ion plant 2, where the hot unpurified coke-oven gas is partially oxidized with oxygen, with oxygen enriched air or other gas mix~ures (1) containing oxygen. For a block of coke-ovens, integrated with a metallurgical plant, there are no difficulties in using the oxygen from the oxygen plant ~7~

which exists anyway. The cracked gas Cb~, being formed by partial oxidation in the gasification plant 2, which may be further processed into gases for synthesis, heating gases or other gases, in the present case particularly into reducing gases, emerges from gasification plant 2 at about 950 to 1500C. The hot cracked gas ~b) is cooled in a heat exchanger 3. The heat released is used for pre-heating of oxygen carrier (1), required for gasification, to about 200C and for pre-h0ating the purified cracked gas, in the present case reducing gas (e), to about 800 to 900C. Special cooling is possible as indicated by the flow of coolant (m) - (n). The wnpurified cold cracked gas (reducing gas) ~c) is compressed in a succeeding compression stage 4 to about 5 bar. Compression can also take place before gasification, by dotted lines indicating a compressor between 1 and 2. The unpurified cold and compressed cracked gas (reducing gas) (d) is then fed through a final purification stage 5. The purified cracked gas (reducing gas) (e) is then pre-heated in heat-; exchanger 3, as indicated above, and fed to pit furance 6 in the form of pre-heated cracked gas (reducing gas) (f) and used for direct reduction. The waste -~
gas (h) which is formed in the process of direct reduction in the pit furnace may be partly used for wldergrate firing of the block of coke-ovens 1, partly as gas stream (k) as excess gas for other heating purposes in the metallurgical plant. The so-called waste gas (h) emerging from pit furnace 6 has a heat of -` combustion of about 2000 to 2500 kcal/m3.
The following comparison shows the special advantage, with respect to the increased degree of reduction of the cracked gas (reducing gas) produced, when coke-oven gas from pre-heated coal is used in the process according to the invention as compared with coke-oven gas ob~ained from damp coal.
The main point during production of reducing gas is to keep the fraction of oxidized components in the gas as low as possible or -- expressed in a different way -- to obtain the highest possible fraction of reducing components. A measure for the quality oE a reducing gas is its degree of .

l :;
oxidation .
C02(m n~ ~ H20(m n) x 100 COz(m n; -~ H20~m n) + H2~m n) ~ CO~m n) :in which the ratio of oxidized components in the gas to the sum of oxidized components and reduced components is expressed in %. Generally the process of direct reduction requires a value of about 5%. Another measure for the quality of a reducing gas is its degree of reduction CO~m n) + H2~m n) CO2~m n) -~ H2O(m n) which is the ratio of reducing components to oxidized components in the gas.
The following example shows a comparison of production of reducing gas on the basis of damp and pre-heated coal:

a) using damp b) using coal pre-heated coal 1. Characteristics of the coal used Volatile components ~% dry) 29.
Ash ~% dry) 9.8 Sulphur % 1.0 Water % 10.0 . m n = normal cubic metre : a) using damp b) using coal pre-heated coal
2. Characteristics and operating conditions for the block of :~:
coke-ovens and the pre-heating plant Width of chamber ~mm) ~50 Bulk density of coking coal 3 in oven ~dry) ~tons/m ) 0.76 0.83 Coking time ~hrs) 18 12.5 Heating flue temperature ~C) 1300 1300 Cont'd.

,~, ~0~Q~:
, a~ using dampb) using coal pre-heated coal Heat consumption of block of coke-ovens (kcal/kg damp coal) 550 360 ~leat consumption of pre-heating plant (kcal/kg damp coal) - 145 Total heat consumption (kcal/kg damp coal) 550 505
3. Characteristics of the crude coke-oven gas produced :
Temperature ~C) about 700 Pressure (bar abs) about Gas analysis ~% by volume, dry) C2 2.0 C0 5.7 H2 59.7
4 25.1 CnHm 3.1 6 6 1.1 H2S 0.7 N2 2.6 Tar ~kg/m3nJ dry gas) 0.13 Phenol (g/m3n, dry gas) 0.7 HCN ~g/m n, dry gas) 0.3 Wa~er content (% in wet gas) about 30 about 3.5 Yield of gas~ dry (m3n/ton coal, dry) 396 396 Yield of gas, wet (m3n/ton coal, dry) 565 410 Water content in gas (m3n/ton coal, dry) 169 14 The insignificant change in gas quality, referred to dry conditions, is neglec-ted in this comparison because it is unimportant for the product "reducing gas".

: `:
a~ using damp b) using coal pre-heated coal 4. Characteristics of the oxygen a _ ication Temperature after pre-heating (C)about 200 about 200 Pressure ~bar) (production) about 5 about 5 _n ysis ~% by volume) 2 99.5 N2/Ar 0.5 Quantity of oxygen ~m3n/ton coal, dry) 91 100
5. Characteristics of the reducing gas after gasification Temperature (C) 950 - 1100 1000 - 1150 Pressure (bar) about 0.9 Gas analysis (~0 by volume, wet) C2 3.20 0.40 C0 20.50 27.90 H2 58.80 60.70 CH4 2.50 2.60 N2 1.30 1.50 H20 13.70 1.90 : :
H2S/COS (g/m n in dry gas) about 5 about 5.2 `
Degree of oxidation C2 + H20 (m n) - = 17.8% 2.5%
C2 + H20 + H2 + C0 (m3n) Degree of reduction C0 + H2 _(m n) C2 + H20 (m3n) 4.6 39.8 Quantity of reducing gas dry (m3n/ton coal, dry) 810 775 Quantity of reducing gas wet (m n/ton coal dry) 939 790 a) using damp b) using coal pre-heated coal
6. Condensation of the reducing gas To obtain a technically acceptable degree of oxidation or reduction for the reducing gas which is produced from coke-oven gas, using damp coal, it is necessary to cool the gas to about 15C in order to remove the water in the gas by condensation. Using pre-heated coal, this stage of the production may be mitted.
Temperature ~C) 15 Pressure (bar) about 0.9 about 0.9 Gas analysis (% by volume, wet) C2 3.6 0.40 C0 23.3 27.90 H2 67.0 60.70 CH4 2.8 2.60 N2 1.5 1.50 H2O 1.8 l.9C
H2S/COS (g/m3n in dry gas)about 5 about 5.2 Degree of oxidation 5.6% 2.5%
Degree of reduction 16.7 35.8 Quantity of reducing gas dry (m3n/ton coal dry) 810 Quantity of reducing gas wet (m3n/ton coal) 825 This example for non-pressuri~ed conditions and for various reasons most likely gasification shows the obvious effect on the ~uality of the reducing gas of including an upstream stage of pre-heating.

Thus the process according to the invention, using coke-oven gas produced from pre-heated coal has significant advantages over a process using coke-oven gas produced fIom damp coal: The throughput of gas is smaller _ g _ Z

by the amount of water removed by pre-heating; giving a simultaneous improve-ment in the quality of the reducing gas, the gas throughput of the gasification plant in all stages including the cooling is reduced by the water content of the coal; therefore the relevant parts of the plant may be designed to a small~r scale so that the amount of invested capital is lowered; the fraction of oxidizing components become less by the absolute amount of water in the reducing gas; in relation to that the degree of oxidation becomes lower, or the degree of reduction becomes higher; the lower water content in the hot coke-oven gas has a corresponding effect during cracking in that it reduces (equilibrium reaction) the fraction of oxidizing components; the lower water content in the hot coke-oven gas has the effect of changing the gasification equilibrium during cracking towards reducing components.
For each isobar there is a minimum for the degree of oxidation or a maximum for the degree of reduction. The optima are in the range from 0.1 to 7% by volume methane in the dry reducing gas and thus determine the optimum temperature of reaction for each pressure range. The most economic pressure range for cracking is from 1 to 5 bar. In this range the lowest optimum degree of oxidation is obtained for the lowest consumption of oxygen.

.

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the further treatment of coke-oven gas to form carbon-monoxide and hydrogen-enriched cracked gas by means of partial oxidation in the presence of oxygen, oxygen-enriched air and further oxygen-containing gas mixtures, characterized in that hot coke oven gas, having been obtained by the coking of pre-heated coal, is directly cracked without cooling and purification.
2. A process according to claim 1, characterized in that the cracked gas is used in a pit furnace for the direct reduction of iron ore.
3. A process according to claim 1, characterized in that the blast furnace gas of the pit furnace is used for heating the coke oven battery from below, for pre-heating in the coke-preheating system, or for other heating purposes.
4. A process according to any one of claims 1 - 3, characterized in that the hot coke-oven gas is compressed prior to partial oxidation, or the cracked gas is compressed.
CA285,485A 1976-08-26 1977-08-25 Process for the treatment of coke-oven gas Expired CA1071402A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19762638348 DE2638348A1 (en) 1976-08-26 1976-08-26 PROCESS FOR PROCESSING COOKING GAS

Publications (1)

Publication Number Publication Date
CA1071402A true CA1071402A (en) 1980-02-12

Family

ID=5986379

Family Applications (1)

Application Number Title Priority Date Filing Date
CA285,485A Expired CA1071402A (en) 1976-08-26 1977-08-25 Process for the treatment of coke-oven gas

Country Status (12)

Country Link
JP (1) JPS5328603A (en)
AU (1) AU513439B2 (en)
BR (1) BR7705614A (en)
CA (1) CA1071402A (en)
DE (1) DE2638348A1 (en)
ES (1) ES461815A1 (en)
FR (1) FR2362789A1 (en)
GB (1) GB1566970A (en)
IT (1) IT1079339B (en)
PL (1) PL112456B1 (en)
SE (1) SE7709414L (en)
ZA (1) ZA774813B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU81427A1 (en) * 1979-06-26 1979-09-12 Arbed PROCESS AND PLANT FOR THE CONTINUOUS REDUCTION OF IRON ORE
DE3115391A1 (en) * 1981-04-16 1982-12-30 Bergwerksverband Gmbh, 4300 Essen "METHOD AND DEVICE FOR THE PRODUCTION OF HYDROGEN AND CARBON OXIDE GASES FROM RAW CARBON DISTILLATION GASES
DE3217422A1 (en) * 1982-05-08 1983-11-10 Fritz Werner Industrie-Ausrüstungen GmbH, 6222 Geisenheim Process and equipment for processing comminuted coal by gasification by means of a multi-chamber reactor
DE3510904A1 (en) * 1984-04-07 1985-10-17 Bergwerksverband Gmbh, 4300 Essen METHOD FOR OPERATING A BLAST FURNACE
SE457264B (en) * 1985-09-25 1988-12-12 Skf Steel Eng Ab SAVE TO CLEAN COOK Oven
SE457355B (en) * 1985-09-25 1988-12-19 Skf Steel Eng Ab MAKE SURE TO PREPARE A CLEAN, CARBON OXIDE AND GAS GAS INCLUDING GAS
DE3669534D1 (en) * 1986-05-07 1990-04-19 Voest Alpine Ind Anlagen INTEGRATED CABINET.
AT385051B (en) * 1986-08-07 1988-02-10 Voest Alpine Ag MILL PLANT AND METHOD FOR PRODUCING STEEL
DE4210003A1 (en) * 1992-03-27 1993-09-30 Ruhrkohle Ag Combined process for the production of metallurgical coke and sponge iron
CN101023023B (en) * 2004-08-03 2012-12-26 海尔萨可变资产股份有限公司 Method and apparatus for producing clean reducing gases from coke oven gas
JP6327888B2 (en) * 2013-03-07 2018-05-23 新日鐵住金株式会社 Hydrogen gas production apparatus and hydrogen gas production method from coal dry distillation gas
CN113501494A (en) * 2021-07-07 2021-10-15 山西晋南钢铁集团有限公司 Self-reforming system and method for coke oven gas for blast furnace iron making

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5067804A (en) * 1973-10-16 1975-06-06

Also Published As

Publication number Publication date
BR7705614A (en) 1978-07-11
ZA774813B (en) 1978-06-28
FR2362789B1 (en) 1980-05-16
GB1566970A (en) 1980-05-08
DE2638348A1 (en) 1978-07-13
IT1079339B (en) 1985-05-08
FR2362789A1 (en) 1978-03-24
PL200435A1 (en) 1978-04-24
PL112456B1 (en) 1980-10-31
AU2805577A (en) 1979-02-22
ES461815A1 (en) 1978-05-16
JPS5328603A (en) 1978-03-17
AU513439B2 (en) 1980-12-04
SE7709414L (en) 1978-02-27

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