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US20030106395A1 - Agglomerates containing iron and at least one further element of groups 5 or 6 of the periodic system - Google Patents

Agglomerates containing iron and at least one further element of groups 5 or 6 of the periodic system Download PDF

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Publication number
US20030106395A1
US20030106395A1 US10/210,531 US21053102A US2003106395A1 US 20030106395 A1 US20030106395 A1 US 20030106395A1 US 21053102 A US21053102 A US 21053102A US 2003106395 A1 US2003106395 A1 US 2003106395A1
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United States
Prior art keywords
agglomerates
sintered agglomerates
molybdenum
further element
oxide
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.)
Abandoned
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US10/210,531
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English (en)
Inventor
Jurgen Leitner
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.)
Treibacher Industrie AG
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Treibacher Industrie AG
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Filing date
Publication date
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Assigned to TREIBACHER INDUSTRIE AG reassignment TREIBACHER INDUSTRIE AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEITNER, JURGEN
Publication of US20030106395A1 publication Critical patent/US20030106395A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52—Manufacture of steel in electric furnaces
    • C21C5/5264—Manufacture of alloyed steels including ferro-alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • C21C2007/0062—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires with introduction of alloying or treating agents under a compacted form different from a wire, e.g. briquette, pellet
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to agglomerates containing iron and at least one further element of groups 5 or 6 of the periodic system, their use, and a method for producing them.
  • further element one may in particular consider molybdenum and tungsten.
  • Molybdenum is used f.i. as an alloying element for producing high-strength structural steels containing molybdenum, alloyed cast iron types as well as molybdenum-containing, rust-resisting, acid-resisting and heat-resisting steels and nickel base alloys.
  • Ferromolybdenum is an iron/molybdenum alloy usually having 60-80% by weight of molybdenum and produced by way of a metallothermal process.
  • the metallothermal production according to the thermite burning process is complex, given that the metals iron and molybdenum have to be melted on and together.
  • the use of expensive reducing agents such as aluminium or ferrosilicon is required.
  • the process may be automated only to a limited extent. This results in a higher market price of the ferromolybdenum as compared to the molybdenum trioxide (MoO 3 ).
  • a disadvantage of ferromolybdenum produced according to the thermite process is the relatively high lump density (fi. about 8.8 g/cm 3 in standard FeMo70), resulting in that when alloying f.i. steel melts (density about 7.5 g/cm 3 ), the material sinks to the bottom of the melting vessel where it forms depositions difficult to dissolve which only come off in the subsequent melts. Dissolving such ferromolybdenum lumps in the liquid steel bath is additionally made more difficult by the high melting point of the material, which in the case of a usual commercial FeMo70 quality is about 1950° C. The temperatures in the steel bath are significantly below this level so that now the dissolution of the FeMo parts can only be effected by way of diffusion processes which, accordingly, require long periods of time.
  • agglomerates are produced from an iron/molybdenum blend by briquetting, wherein the iron/molybdenum blend is obtained by reducing a fine-grained molybdenum-trioxide/iron-oxide blend with hydrogen-containing gas. Briquetting is carried out by adding a binding agent such as water glass in order to improve the grain binding. Agglomerates having a lump density higher than 3.5 g/cm 3 are formed therein.
  • U.S. Pat. No. 5,954,857 describes the production of briquets consisting of molybdenum oxide with NaOH as binding agent.
  • the molybdenum oxide is reduced to the metallic molybdenum by the liquid iron, wherein iron oxide is formed.
  • Disadvantages of this process are the danger of losing molybdenum oxide by absorption in the slag which is on the surface of the liquid steel, and the losses of iron occurring in the reduction of the molybdenum oxide.
  • a disadvantage thereof is the formation of silicon oxide as a reaction product which has to be set in the slag, which in the steel-making processes used today is only possible when taking additional measures.
  • the invention has as its object to provide agglomerates containing iron and at least one further element of groups 5 or 6 of the periodic system and having an improved dissolubility in metal melts, in order to keep the costs of treating the melt low.
  • the agglomerates should not sink to the bottom of a metal melt and should have, furthermore, a sufficient resistance in view of storage and transport.
  • the quality of the metal melt should not be prejudiced by tramp elements being in the agglomerate and acting as binding agents, fi., and a loss of molybdenum and iron should be avoided.
  • this object is achieved insofar as the agglomerates have a porosity in the range of 20 to 65% by volume, particularly of 30 to 45% by volume.
  • the agglomerates according to the invention have a porosity and, by that, a lump density which on the one hand allows the penetration of a slag cover on a metal melt and allows the agglomerates to penetrate into the metal melt.
  • the inventive porosity of the agglomerates results in that capillary action fills the pores of the agglomerates with metal melt and in that the thereby occurring enlargement of the boundary surface between the metal melt and the agglomerate rapidly dissolves the regions filled with metal melt.
  • dissolving means the melting of the agglomerates and the homogeneous distribution of the components of the agglomerates in the metal melt.
  • the liquid steel penetrates into the pores of the agglomerates.
  • the thereby produced large boundary surface between the agglomerate and the melt leads to a rapid warming and diffusion of iron in this boundary layer, which eventually causes the dissolution of the agglomerates.
  • the gas included in the pores of the agglomerates expands because of the rapid warming and enters into the metal melt.
  • the thereby generated turbulent flow on the surface of the agglomerates causes the rapid reduction of the existing concentration gradients on alloying agents between the boundary surface and the melt, which leads to an increase in the diffusion rate that depends, according to Fick's law, on the concentration gradients.
  • a high dissolution rate means the saving of time and costs in the production of alloyed metal melts.
  • the inventive agglomerates contain as further element molybdenum in an amount of 45 to 85% by weight, preferably of 60 to 80% by weight.
  • the lump density of these agglomerates is preferably 4.2 to 6.3 g/cm 3 , particularly preferred 4.5 to 5.7 g/cm 3 .
  • the agglomerates contain as further element tungsten in an amount of 60 to 90% by weight, preferably of 70 to 85% by weight.
  • Their lump density is preferably 4.7 to 8.4 g/cm 3 , particularly preferred 5.8 to 7.4 g/cm 3 .
  • the present invention also relates to the use of the agglomerates for producing alloyed metal melts, especially molybdenum-alloyed and/or tungsten-alloyed metal melts.
  • the invention further relates to a process for producing the agglomerates, wherein iron oxide and oxides of at least one further element of groups 5 or 6 of the periodic system are reduced to the respective metals.
  • U.S. Pat. No. 3,865,573 relates to a process for producing molybdenum powder and/or ferromolybdenum, wherein molybdenum oxide and/or a blend of molybdenum oxide and iron oxide are reduced in a two-stage fluidized-bed process.
  • U.S. Pat. No. 4,045,216 describes a process for producing directly reduced molybdenum-oxide pellets, based on the two-stage reduction of molybdenum-oxide pellets in an hydrogen-containing atmosphere. As reduction aggregate, a shaft furnace is used which is traversed in counterflow by the product and the reducing gas. In this process, pellets having a very low density and abrasion resistance are produced.
  • the process according to the invention is characterized in that the reduced metals are compacted, especially briquetted, without adding any binding agents and in that the thereby formed compacted products are sintered.
  • Sintering is effected preferably at temperatures from 1000 to 1400° C., in air or preferably in an inert-gas atmosphere, for 15 to 60 minutes.
  • the iron contained in the agglomerates acts as sinter-active phase and as a binder for the particles contained in the agglomerates.
  • the agglomerates are prevented from becoming too dense during the sintering process, which would have a negative effect on their dissolution in metal melts.
  • Table 1 shows the porosities of FeMo agglomerates as a function of the sintering period and the resulting lump density. Here, the porosity was measured with an Hg porosimeter. By comparison, the density and porosity of a conventional FeMo agglomerate is indicated (Comparative Example). TABLE 1 Sintering period at 1170° C. Density [g/cm 3 ] Porosity Sample 1 15 4.15 42.4 Sample 2 25 4.3 39.7 Sample 3 45 5.48 23.1 Sample 4 60 6.0 — Comparative Example 8.0 0
  • FIG. 1 shows the pore size distribution of FeMo agglomerates produced with the process according to the invention.
  • the particle size of the agglomerates was in a range of 2 to 4 mm.
  • the measurements were taken by means of an Hg porosimeter at an Hg column pressure of 200 mm.
  • the curve numbered 1 represents the pore size distribution of the FeMo agglomerates referred to as sample 1 in the above table after sintering at 1170° C. The molybdenum content of these agglomerates was 74%.
  • the curve numbered 2 represents the pore size distribution of the FeMo agglomerates according to sample 2.
  • the curve numbered 3 represents the pore size distribution of the agglomerates according to sample 3. It can be seen from this that the mere choice of different sintering parameters (temperature and period of time) makes it possible to vary the number of the pores and the distribution of the pore size within a wide range.
  • FIG. 2 shows, in an exemplary manner, the dissolution rate of an inventive FeMo agglomerate as compared to standard FeMo (produced by way of a silicothermal process).
  • the curves were recorded when smelting a high-speed-steel quality (S-6-5-2, 1.3343) with a molybdenum content of 5%.
  • the composition of the steel produced in the experiment is indicated in table 2 below. TABLE 2 S-6-5-2, 1.3343 % by weight C 0.9 Cr 4.1 Mo 5 V 1.8 W 6.4 Fe rest
  • Electrodes graphite ⁇ 100 mm, automatic control
  • Furnace crucibles infeed with magnesite, with a casting nose effective volume about 100 1
  • the size of the experimental melt was 300 kg.
  • the melt was used in a three-phase electric-arc furnace as a set-up charge, that is, the steel composition was set to a pure-iron melt by adding ferro-alloys in a corresponding amount.
  • As a first step all of the alloying elements except Mo were added and set according to the target analysis.
  • the steel bath was covered with a calcium aluminate slag.
  • the molybdenum content was set by adding ferromolybdenum having a grain size of 5-50 mm and produced according to the thermite process. After having added the FeMo, samples were taken from the melt at short intervals. A second melt was produced in the same way except that here, the inventive agglomerates were used to set the molybdenum content. It could be seen that the inventive agglomerates (represented in FIG. 2 by the broken line) dissolved much faster than standard FeMo (represented in FIG. 2 by the unbroken line).
  • the significant advantage of the agglomerates according to the invention is that they dissolve faster in steel melts than standard FeMo, which results in the saving of time and, by that, costs for the user.
  • the inventive agglomerates dissolve much faster, yielding more molybdenum. From the curves relating to standard FeMo it can be seen that even after periods of treating the melt of about 10 min, less than 80% of the added molybdenum has dissolved in the melt. In practice, this means that such a melt has to be heated up once again in a pan furnace in order to obtain a commercial molybdenum yield, which, however, requires higher treatment costs.
  • Table 6 indicates the chemical composition of the produced steel. TABLE 6 Elements % by weight C 0.02 Si 0.5 Mn 1.5 P ⁇ 0.04 S ⁇ 0.0055 Cr 17 Ni 11 Mo 2.0 Al ⁇ 0.007 N 2 ⁇ 0.03
  • FIG. 4 shows a comparison of the dissolution rates of the ferromolybdenum produced according to the thermite process vs. those of the inventive agglomerates. It can be seen that also in Example 3, the inventive agglomerates dissolve faster in steel than the standard FeMo.
  • FIGS. 5 and 6 show further examples of the dissolution rates of inventive FeMo agglomerates as compared to standard FeMo.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)
US10/210,531 2000-02-04 2002-08-01 Agglomerates containing iron and at least one further element of groups 5 or 6 of the periodic system Abandoned US20030106395A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0017900A AT409271B (de) 2000-02-04 2000-02-04 Verfahren zur herstellung von agglomeraten, enthaltend eisen und mindestens ein weiteres element der gruppen 5 oder 6 des periodensystems
ATA179/2000 2000-02-04
PCT/AT2000/000197 WO2001057279A1 (de) 2000-02-04 2000-07-17 Poröse agglomerate, enthaltend eisen und mindestens ein weiteres element der gruppen 5 oder 6 des periodensystems zur verwendung als legierungsmittel

Related Parent Applications (1)

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PCT/AT2000/000197 Continuation WO2001057279A1 (de) 2000-02-04 2000-07-17 Poröse agglomerate, enthaltend eisen und mindestens ein weiteres element der gruppen 5 oder 6 des periodensystems zur verwendung als legierungsmittel

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US20030106395A1 true US20030106395A1 (en) 2003-06-12

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US10/210,531 Abandoned US20030106395A1 (en) 2000-02-04 2002-08-01 Agglomerates containing iron and at least one further element of groups 5 or 6 of the periodic system

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US (1) US20030106395A1 (de)
EP (1) EP1252342A1 (de)
JP (1) JP2003529678A (de)
KR (1) KR100475042B1 (de)
CN (1) CN1206374C (de)
AT (1) AT409271B (de)
AU (1) AU2000261384A1 (de)
CA (1) CA2397524A1 (de)
RU (1) RU2244025C2 (de)
TW (1) TW491906B (de)
WO (1) WO2001057279A1 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130037524A1 (en) * 2010-04-28 2013-02-14 Ihi Corporation Electrode applied to discharge surface treatment and production method thereof
EP2597165A1 (de) 2011-11-25 2013-05-29 AB Ferrolegeringar Eisen- und molybdänhaltige Pellets
WO2013076300A1 (en) * 2011-11-25 2013-05-30 Ab Ferrolegeringar Iron and molybdenum containing pellets
WO2014193299A1 (en) * 2013-05-27 2014-12-04 Ab Ferrolegeringar Iron and tungsten containing briquettes
WO2014193298A1 (en) * 2013-05-27 2014-12-04 Ab Ferrolegeringar Iron and molybdenum containing compacts
US9540707B2 (en) 2011-11-25 2017-01-10 Ab Ferrolegeringar Iron and molybdenum containing agglomerates
WO2020239536A1 (de) * 2019-05-28 2020-12-03 Thyssenkrupp Steel Europe Ag Verfahren zur herstellung von eisenpulver

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106399811B (zh) * 2016-10-10 2018-05-22 江铃汽车股份有限公司 钼铁扩散熔解方法及其应用
CZ308005B6 (cs) * 2017-12-19 2019-10-16 Martin Gajdzica Briketa či peleta pro vsázku do metalurgických agregátů
CN109778059B (zh) * 2019-01-21 2021-01-26 西安建筑科技大学 一种多孔钼铁合金及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865573A (en) * 1973-05-23 1975-02-11 Kennecott Copper Corp Molybdenum and ferromolybdenum production
US4039325A (en) * 1974-09-24 1977-08-02 Amax Inc. Vacuum smelting process for producing ferromolybdenum

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Publication number Priority date Publication date Assignee Title
DE2156795C3 (de) * 1970-11-20 1980-09-25 Ugine Kuhlmann Verfahren zur Herstellung von porösen Molybdänbriketts
US4113479A (en) * 1976-02-27 1978-09-12 Amax Inc. Vacuum smelting process for producing ferrotungsten
SU730823A1 (ru) * 1977-10-03 1980-04-30 Челябинский Ордена Ленина Электрометаллургический Комбинат Шлакообразующа смесь дл выплавки ферровольфрама
SU829709A1 (ru) * 1979-07-10 1981-05-15 Всесоюзный Научно-Исследовательскийи Проектный Институт Тугоплавких Металлови Твердых Сплавов Лигатура на основе молибдена
SU1542074A1 (ru) * 1987-03-12 1995-06-27 Чусовской металлургический завод Лигатура и шихта для ее получения
DE19622097A1 (de) * 1996-06-01 1997-12-04 Treibacher Ind Ag Eisenmolybdänlegierung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865573A (en) * 1973-05-23 1975-02-11 Kennecott Copper Corp Molybdenum and ferromolybdenum production
US4039325A (en) * 1974-09-24 1977-08-02 Amax Inc. Vacuum smelting process for producing ferromolybdenum

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130037524A1 (en) * 2010-04-28 2013-02-14 Ihi Corporation Electrode applied to discharge surface treatment and production method thereof
EP2597165A1 (de) 2011-11-25 2013-05-29 AB Ferrolegeringar Eisen- und molybdänhaltige Pellets
WO2013076300A1 (en) * 2011-11-25 2013-05-30 Ab Ferrolegeringar Iron and molybdenum containing pellets
CN104053799A (zh) * 2011-11-25 2014-09-17 法罗雷格林加股份公司 含有铁和钼的丸粒
US9540707B2 (en) 2011-11-25 2017-01-10 Ab Ferrolegeringar Iron and molybdenum containing agglomerates
WO2014193299A1 (en) * 2013-05-27 2014-12-04 Ab Ferrolegeringar Iron and tungsten containing briquettes
WO2014193298A1 (en) * 2013-05-27 2014-12-04 Ab Ferrolegeringar Iron and molybdenum containing compacts
EP3003605A4 (de) * 2013-05-27 2017-02-15 AB Ferrolegeringar Eisen- und molybdänhaltige pellets
WO2020239536A1 (de) * 2019-05-28 2020-12-03 Thyssenkrupp Steel Europe Ag Verfahren zur herstellung von eisenpulver

Also Published As

Publication number Publication date
KR100475042B1 (ko) 2005-03-10
KR20020080409A (ko) 2002-10-23
RU2244025C2 (ru) 2005-01-10
CA2397524A1 (en) 2001-08-09
AU2000261384A1 (en) 2001-08-14
AT409271B (de) 2002-07-25
ATA1792000A (de) 2001-11-15
CN1433483A (zh) 2003-07-30
JP2003529678A (ja) 2003-10-07
WO2001057279A1 (de) 2001-08-09
TW491906B (en) 2002-06-21
CN1206374C (zh) 2005-06-15
EP1252342A1 (de) 2002-10-30

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