AU722599B2 - Process for recycling a fine-particulate solid discharged from a reactor vessel by means of a carrier gas - Google Patents

Process for recycling a fine-particulate solid discharged from a reactor vessel by means of a carrier gas Download PDF

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Publication number
AU722599B2
AU722599B2 AU51208/98A AU5120898A AU722599B2 AU 722599 B2 AU722599 B2 AU 722599B2 AU 51208/98 A AU51208/98 A AU 51208/98A AU 5120898 A AU5120898 A AU 5120898A AU 722599 B2 AU722599 B2 AU 722599B2
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AU
Australia
Prior art keywords
solids
reactor vessel
separator
injector
gas
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.)
Ceased
Application number
AU51208/98A
Other versions
AU5120898A (en
Inventor
Hado Heckmann
Rainer Walter Kastner
Herbert Lassnig
Herbert Mayr
Johannes Schenk
Josef Stockinger
Kurt Wieder
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
Original Assignee
Voest Alpine Industrienlagenbau GmbH
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Filing date
Publication date
Application filed by Voest Alpine Industrienlagenbau GmbH filed Critical Voest Alpine Industrienlagenbau GmbH
Publication of AU5120898A publication Critical patent/AU5120898A/en
Application granted granted Critical
Publication of AU722599B2 publication Critical patent/AU722599B2/en
Anticipated expiration legal-status Critical
Ceased 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
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/0006Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/0006Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
    • C21B13/0013Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state introduction of iron oxide into a bath of molten iron containing a carbon reductant
    • C21B13/002Reduction of iron ores by passing through a heated column of carbon
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B5/00Making pig-iron in the blast furnace
    • C21B5/02Making special pig-iron, e.g. by applying additives, e.g. oxides of other metals
    • C21B5/023Injection of the additives into the melting part
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2100/00Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/40Gas purification of exhaust gases to be recirculated or used in other metallurgical processes
    • C21B2100/44Removing particles, e.g. by scrubbing, dedusting
    • 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
    • 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
    • Y02P10/20Recycling

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Cyclones (AREA)
  • Crucibles And Fluidized-Bed Furnaces (AREA)
  • Air Transport Of Granular Materials (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Manufacture Of Iron (AREA)

Description

Process for recycling a fine-particulate solid discharged from a reactor vessel by means of a carrier gas The invention relates to a process for recycling a fine-particulate solid, such as coal and iron particles, discharged from a reactor vessel, in particular a melter gasifier, by means of a carrier gas at a discharge point of a reactor vessel, at a recycling point of the reactor vessel, wherein the solid is separated in a solids separator, in particular a cyclone, and subsequently recycled into the reactor vessel by means of a carrier gas, maintaining a pressure difference between the solids separator and the recycling point, and at least partially gasified and/or burnt upon entry into the reactor vessel under the supply of oxygen, as well as an arrangement for carrying out the process.
A process of the aforementioned type is known from EP-A 0 493 752. In this process, hot dusts from a melter gasifier are separated in a hot cyclone and recycled into the melter gasifier via a bumrner. To overcome a pressure difference between the hot cyclone and the melter gasifier, recycling is accomplished via a sluice system with several bins provided between two sluices each.
The reducing gas withdrawn from the melter gasifier has a temperature of approx.
1050C and carries considerable amounts of powdered solids. The dust load is approx.
150 g/m S reducing gas. Immediately after exiting, the temperature of reducing gas is adjusted to approx. 850°C by adding cooling gas, mostly cospecific cooling gas. The solid, which mainly consists of a mixture of coal and iron particles, is continuously separated in the hot cyclone. As this solid is highly abrasive the known sluice system not only requires an expensive design but is also subjected to a high degree of wear. The solid is discontinuously conveyed to the injector, i.e. batchwise, so a continuous operating mode of the dust burner is not ensured and the effectiveness of the dust burner is impaired. The solid may settle on filling up a bin, and the dust flow may get blocked.
C E n ooc 2 oe *e A process for recycling a fine-particulate solid discharged from a reactor vessel by means of a carrier gas is known from EP-B-0 278 287. In this process, the solid accumulating in the solids separator is conveyed into a collecting tank and collected there. The collecting tank serves as compensation tank in this case, from which the solid is withdrawn by means of a hot reactor gas directly withdrawn from the reactor vessel and is directly recycled into the reactor vessel via an injector. In the collecting tank the solid may settle and the solids flow get blocked, in particular due to the hot carrier gas directly withdrawn from the reactor vessel, which may cause caking and partial melting of the solid. In the known process, the injector opens directly into the reactor vessel.
The object of the invention is to prevent these disadvantages and difficulties and to solve the technical problem of creating a process as well as an arrangement for carrying out the process, which allow recycling of the 20 solid without moving parts which would thus be subjected to a high degree of abrasion and alternating thermal stress wherein in particular recycling is to be performed continuously and in a controlled manner and the pressure difference between the outlet of the solids separator and 25 the reactor vessel is overcome without any problems.
Moreover, a troublefree continuous solids flow has to be ensured with a high degree of certainty.
According to the precent invention there is provided process for returning fine-particulate solids (such as coal and iron particles) discharged in a carrier gas stream from a discharge point of a reactor vessel (such as a melter gasifier) to a return point of the reactor vessel, wherein the solids are separated in a solids separator (such as a cyclone) and subsequently recycled into the reactor vessel by means of a carrier gas while a pressure differential is maintained between the solids ;r~j\L4
LO
(3 7 ~r \\me1bfi es\hrne\Piya nka\KeeI:e\s\ :eci\12 8 R. uc 02/06/ 3 separator and the recycling point, and wherein the solids are at least partially gasified and/or burnt with oxygen upon entry into the reactor vessel, characterized in that the separated solids are directly and continuously exhausted from the solids separator by means of a propellant gas under injector action, accelerated, and conveyed to the reactor vessel.
In a process of the aforementioned type, this problem is solved by directly and continuously exhausting the separated solid by means of a propellant gas under injector action, by accelerating it and by conveying it to the reactor vessel. According to the invention, a completely open line is thus provided between the solids separator and the reactor vessel in normal operating condition, without any retaining zones and storage baffles.
The propellant gas sucks the solid directly from the solids separator along with a small part of the carrier gas which the solids separator is dispersed with. This ensures that 20 the solid is constantly in motion and is not allowed to ":settle. The danger of sticking particles and, consequently, blocking of the dust flow is thus reliably prevented.
25 The flow velocity of the propellant gas should be preferably equal to or greater than sound velocity (in a supercritical pressure ratio) in order to ensure a high operational stability of solids recycling.
It is advantageous to use nitrogen and/or cooled and cleaned process gas as propellant gas.
According to a preferred embodiment, the cooled and cleaned process gas is formed by a reducing gas containing CO and H 2 0 ile~\h h-n\P riyank a\Keelsp e ci \S1208- 98. dc,c 02/06/ 3a An arrangement for carrying out the process described above including: a reactor vessel (such as a melter gasifier) a solids separator (such as a cyclone) a gas discharge duct leading from the reactor vessel to the solids separator an injector a solids discharge duct leading from the solids separator to the injector, and a solids recycling duct leading from the injector to the reactor vessel and opening into the reactor vessel via a dust burner, wherein the solids recycling duct, dust burner and injector are arranged so as to enable solids to be directly and S: continuously exhausted from the solids separator and conveyed to the reactor vessel.
20 The set-up of the arrangement according to the invention is simple and uncomplicated and allows a completely free solids flow during normal operation and, as the solids are directly and continuously exhausted, an improved efficiency of the solids separator, resulting in 25 greatly reduced dust losses. The simple set-up of the arrangement according to the invention ensures a very low maintenance expenditure and a high availability and o. performance of the arrangement.
To separate large particles, for example coarse coal and coke lumps, a coarse filter is advantageously connected downstream of the solids separator.
\\melb_files\home$\Priyanka\Keelp\slpeci\51208-98.doc 02/06/ c* 0VT^ 0 3b In order not to directly impede the solids separation in case of disturbances in the dust recycling line, a solids tank is connected downstream of the solids separator according to a preferred embodiment, which is provided with a fluidization element on transition into the solids discharge duct. This solids tank is not working during normal operation, i.e. the solid is freely dispersed in this tank by free fall.
In order to be able to discharge large particles originating e.g. from a refractory lining of the solids discharge duct without impeding the solids flow, the injector is expediently comprised of a solids collecting tank designed as bag tank, which is provided with a drain opening that can be closed with a shut-off element, with the solids collecting tank expediently provided with a fluidization element in the area of the bottom.
*9 *o 4[, Y 4- \\melb f iles\h(me$\ Priyanka\Ke~pp\sp c \512 08-98-d -oc 02/06/ In the following, the invention is explained in greater detail by the embodiments shown in the drawing, Fig. 1 showing a general layout of a state-of-the-art solids recycling system, and Fig. 2 schematically representing solids recycling according to the invention.
According to the state of the art illustrated in Fig. 1, the off-gas generated by coal gasification and subsequently used as reducing gas is discharged from a reactor vessel designed as melter gasifier 1, serving for sponge iron melting and simultaneous generation of a reducing gas from carbon-containing material, via gas discharge duct 2 opening into melter gasifier 1 in an upper region of the latter. As fine-grained to powdered solid is entrained by the off-gas, the latter, serving as carrier gas for this solid, is supplied to solids separator 4, which is advantageously designed as hot cyclone.
Immediately after the reducing gas has left melter gasifier 1, cospecific cooling gas is fed to the reducing gas via cooling gas duct 5 so that the reducing gas has a favorable temperature for the subsequent reduction of iron ore and an excessive temperature load on hot cyclone 4 is prevented.
The solids separated in hot cyclone 4 subside and are collected in cyclone bin 6 integrated with the hot cyclone. The solid is further conveyed batchwise via a bin system connected downstream. For this purpose, slide valves 10 are arranged between bins 6, 7 and 8 in solids discharge pipe 9 connecting bins 6, 7 and 8.
Finally, the solid is dosed to injector 12 as uniformly as possible by means of dosing element 11, for example a dosing valve or, according to another embodiment, a rotary valve (not represented here). Injector 12, which is operated e.g. with N 2 as propellant gas which is supplied via pipe 13 conveys the solid into melter gasifier 1 via solids recycling duct 14 opening into dust burner 15. Oxygen is supplied to dust burner 15 via oxygen supply duct 16.
As the C-share of the dust is burned/gasified, the remaining inert shares of the solid (Fe, coal ash, CaO, SiO 2 etc.) agglomerate. The agglomeration of the solid particles prevents the latter from being discharged by the gas exiting the reactor vessel. They subside 'Iktowards the bottom of the reactor vessel and are e.g. melted or withdrawn as slag.
~UJY
nrCHLNT *DD This type of solids recycling involves a high maintenance expenditure. Particular problems in solids recycling are posed by the system of bins 6 to 10, i.e. batchwise dust conveyance, and by the dosing of the solid. Another disadvantage of the solids recycling system illustrated in Fig. 1 is that the individual solids bins 6 to 10 have to be valved off against the gas system of the process taking place in reactor vessel 1 time and again. As the system pressure, i.e. the pressure in melter gasifier 1 proper, and also in the following reduction vessel not represented, into which the reducing gas generated in the melter gasifier is fed, is subject to variations, large pressure differences occur time and again, which, in combination with gas flows, leads to heavy wear of slide valves 10. In order to keep these pressure differences in bounds, pressure compensation pipes not represented in greater detail are required in the known arrangement between solids bins 6, 7 and 8, on the one hand, and between the gas system of melter gasifier 1 and the reduction vessel, on the other hand.
Fig. 2 shows the dust, recycling system according to the invention. The solid separated in hot cyclone 4 is conveyed into vessel 18 integrated at cyclone outlet 17. In this vessel 18, which is provided with a refractory lining, a sloping grate 19 is installed, which serves to separate large particles such as coal or coke lumps, which are withdrawn from vessel 18 via tapping hole 20 in case of need. From hot cyclone 4, the solid which vessel 18 which has no function during normal operation is dispersed with by free fall is sucked by injector 12 via solids discharge pipe 9 designed as downpipe. Downpipe 9 is cylindrical or expediently tapered, expanding downwards in order to avoid clogging. Expediently, it is also provided with a refractory lining. From injector 12, solids recycling duct 14 leads to dust burner Injector 12 is preferably operated at a supercritical pressure ratio, i.e. the velocity of the propellant gas fed via the injector via pipe 13 is equal to or greater than sound velocity.
E.g. nitrogen or cooling gas, such as cooled reducing gas, can be used as propellant gas. Underneath propellant nozzle 22 proper, injector housing 21 changes into collecting tank 23, in which coarse-grained particles, such as flakes or pieces of the lining, which may lead to clogging, are caught. To be able to discharge coarse-grained particles, bottom 24 of collecting tank 23 is provided with an outlet with shut-off element 25 or a pressure sluice (not represented here).
v:T -I2 G~~o..,EtnCOv;gGO To facilitate the withdrawal of particles, fluidization elements 26, such as an annular nozzle, purging elements made of refractory material, elements of sintered material, nozzles in the form of self-closing valves, etc., may be provided in tank bottom 24. The fluidization gas may simultaneously act as secondary gas for injector 12. Fluidization is adjusted in a way that fine particles can be exhausted by the injector and blown off and only coarse particles accumulate.
In the arrangement according to the invention, shut-off elements 27 at the entry of downpipe 9 and upstream of dust burner 15 are only provided for repair and maintenance purposes. In case of any problems occurring during operation, vessel 18 connected downstream of hot cyclone 4 can thus also serve as buffer tank, with shut-off element 27 being closed. In order to prevent the solids from settling in this case of emergency, fluidization elements 26 are also provided at tank outlet 28, i.e. at the transition to downpipe 9.
The invention is not limited to the described embodiment but can be modified in various respects. It is not only applicable to melter gasifiers but particularly to reactor vessels 1 of any type where solids are discharged by means of an off-gas.
Li
J
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Claims (13)

1. A process for returning fine-particulate solids discharged in a carrier gas stream from a discharge point of a reactor vessel to a return point of the reactor vessel, wherein the solids are separated in a solids separator and subsequently recycled into the reactor vessel by means of a carrier gas while a pressure differential is maintained between the solids separator and the recycling point, and wherein the solids are at least partially gasified and/or burnt with oxygen upon entry into the reactor vessel, characterized in that the separated solids are directly and continuously exhausted from the solids separator by means of a propellant gas under injector action, accelerated, and conveyed to the reactor vessel. 1 A process according to claim 1 wherein the fine- particulate solids comprise coal and iron particles. 20 3. A process according to claim 1 or claim 2 wherein :the reactor vessel is a melter gasifier.
4. A process according to any one of claims 1 to 3 wherein the solids separator is a cyclone. A process according to any one of claims 1 to 4, characterized in that the velocity of the propellant gas flow is equal to or greater than sound velocity upon coming into contact with the solids.
6. A process according to any one of claims 1 to characterized in that the solids are filtered after separation.
7. A process according to any one of claims 1 to 6, characterized in that the solids are fluidized after -j V\exiting the solid separator. e-4 A \\melb files\horme$\Priyanka\Keep\peci\51208-98. doc 02/06/ 8
8. A process according to any one or several of claims 1 to 7, characterized in that nitrogen and/or cooled and cleaned process gas is used as the propellant gas.
9. A process according to claim 8 characterized in that the cooled and cleaned process gas is formed by a reducing gas containing CO and H 2 An arrangement for carrying out the process according to any one of claims 1 to 9 including: a reactor vessel a solids separator a gas discharge duct leading from the reactor vessel to the solids separator an injector a solids discharge duct leading from the solids separator to the injector, and S- a solids recycling duct leading from the injector 20 to the reactor vessel and opening into the reactor vessel S. via a dust burner, wherein the solids recycling duct, dust burner and injector are arranged so as to enable solids to be directly and continuously exhausted from the solids separator and conveyed to the reactor vessel.
11. An arrangement according to claim characterized in that a coarse filter is connected downstream of the solids separator.
12. An arrangement according to claim 10 or 11 characterized in that a solids tank is connected downstream of the solids separator, said solids tank being provided with a fluidization element at the junction with the solids discharge duct. C \\melbtfiles\home$\Priyanka\Keep\speci\512 08-98 .doc 02/06/ 0^' 9
13. An arrangement according to any one of claims to 12 characterized in that the injector is comprised of a solids collecting tank designed as bag tank, which is provided with a drain hole that can be closed with a shut- off element.
14. An arrangement according to claim 13 characterized in that the solids collecting tank is provided with a fluidization element in a lower region thereof. An arrangement according to any one of claims 13 to 14 characterized in that the cross-sectional area of the solids discharge duct steadily increases from the solids tank towards the injector.
16. An arrangement according to any one of claims to 15 wherein the reactor vessel is a melter gasifier. 20 17. An arrangement according to any one of claims Sto 16 wherein the solids separator is a cyclone.
18. A process substantially as herein described with reference to the accompanying drawings.
19. An arrangement substantially as herein described with reference to the accompanying drawings. Dated this 2 n d day of June 2000 VOEST-ALPINE INDUSTRIEANLAGENBAU GMBH By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia \\melb_files\home\Priyanka\Keep\speci\ 51208-98.doc 02/06/
AU51208/98A 1996-10-30 1997-10-24 Process for recycling a fine-particulate solid discharged from a reactor vessel by means of a carrier gas Ceased AU722599B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT1899/96 1996-10-30
AT0189996A AT404255B (en) 1996-10-30 1996-10-30 METHOD AND DEVICE FOR RETURNING A FINE-PARTIC SOLID DISCHARGED FROM A REACTOR VESSEL WITH A CARRIER GAS
PCT/EP1997/005874 WO1998018969A1 (en) 1996-10-30 1997-10-24 Process for returning finely dispersed solids discharged with a carrier gas from a reactor vessel

Publications (2)

Publication Number Publication Date
AU5120898A AU5120898A (en) 1998-05-22
AU722599B2 true AU722599B2 (en) 2000-08-10

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AU51208/98A Ceased AU722599B2 (en) 1996-10-30 1997-10-24 Process for recycling a fine-particulate solid discharged from a reactor vessel by means of a carrier gas

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EP (1) EP0953057B1 (en)
JP (1) JP4323570B2 (en)
KR (1) KR100466348B1 (en)
CN (1) CN1070924C (en)
AT (1) AT404255B (en)
AU (1) AU722599B2 (en)
BR (1) BR9712609A (en)
CA (1) CA2270225C (en)
CZ (1) CZ294682B6 (en)
DE (1) DE59704696D1 (en)
ID (1) ID22035A (en)
MY (1) MY118781A (en)
PL (1) PL184215B1 (en)
RU (1) RU2183677C2 (en)
SK (1) SK284449B6 (en)
TR (1) TR199900949T2 (en)
TW (1) TW446571B (en)
UA (1) UA47498C2 (en)
WO (1) WO1998018969A1 (en)
ZA (1) ZA979715B (en)

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Publication number Priority date Publication date Assignee Title
KR100840265B1 (en) * 2006-12-27 2008-06-20 주식회사 포스코 Apparatus for collecting fine powders and apparatus for manufacturing molten irons having the same
AT510586B1 (en) * 2011-05-12 2012-05-15 Siemens Vai Metals Tech Gmbh METHOD AND DEVICE FOR DISPERSING DUST PARTICLES FROM A DUST LINE
CN102745691B (en) * 2012-07-16 2014-07-09 新特能源股份有限公司 Method and device for recovering waste silicon powder from trichlorosilane synthetic furnace
KR101666047B1 (en) * 2015-01-15 2016-10-14 한국에너지기술연구원 Loop Seal for Fluidized Bed Process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1713435A (en) * 1926-04-06 1929-05-14 Vereinigte Stahlwerke Ag Method of working blast furnaces with the aid of furnace dust
DE1137056B (en) * 1956-04-19 1962-09-27 Louis Leon Newman Method and device for the extraction of iron
DE1407958A1 (en) * 1962-10-18 1972-04-13 Kloeckner Humboldt Deutz Ag Centrifugal dust separator, especially for devices for heat exchange between a gas and a fine-grained solid material
JPS59153721A (en) * 1983-02-21 1984-09-01 Kawasaki Steel Corp Blocking preventing structure of granular powder transport pipe
US4733619A (en) * 1986-12-01 1988-03-29 Ube Industries Powder feeder
AT401777B (en) * 1992-05-21 1996-11-25 Voest Alpine Ind Anlagen METHOD AND INSTALLATION FOR THE PRODUCTION OF LIQUID GUT IRON OR LIQUID STEEL PRE-PRODUCTS

Also Published As

Publication number Publication date
CN1235644A (en) 1999-11-17
CZ113599A3 (en) 2000-01-12
AT404255B (en) 1998-10-27
ID22035A (en) 1999-08-26
CZ294682B6 (en) 2005-02-16
CA2270225C (en) 2009-08-11
ATA189996A (en) 1998-02-15
TR199900949T2 (en) 1999-09-21
TW446571B (en) 2001-07-21
AU5120898A (en) 1998-05-22
EP0953057B1 (en) 2001-09-19
BR9712609A (en) 1999-10-26
KR100466348B1 (en) 2005-01-13
JP2001504548A (en) 2001-04-03
RU2183677C2 (en) 2002-06-20
JP4323570B2 (en) 2009-09-02
UA47498C2 (en) 2002-07-15
PL184215B1 (en) 2002-09-30
PL333248A1 (en) 1999-11-22
DE59704696D1 (en) 2001-10-25
WO1998018969A1 (en) 1998-05-07
MY118781A (en) 2005-01-31
SK284449B6 (en) 2005-04-01
CA2270225A1 (en) 1998-05-07
KR20000048982A (en) 2000-07-25
EP0953057A1 (en) 1999-11-03
ZA979715B (en) 1998-05-22
CN1070924C (en) 2001-09-12
SK36699A3 (en) 1999-11-08

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