WO2003062479A1 - Procede de fabrication d'elements metalliques de purete elevee tel que le chrome - Google Patents
Procede de fabrication d'elements metalliques de purete elevee tel que le chrome Download PDFInfo
- Publication number
- WO2003062479A1 WO2003062479A1 PCT/FR2003/000164 FR0300164W WO03062479A1 WO 2003062479 A1 WO2003062479 A1 WO 2003062479A1 FR 0300164 W FR0300164 W FR 0300164W WO 03062479 A1 WO03062479 A1 WO 03062479A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- alloy
- elements
- inclusions
- reducing agent
- Prior art date
Links
Classifications
-
- 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
- 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
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- 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
- 1 / invention relates to a process for manufacturing metals or metallic alloys of high purity, in particular metallic chromium.
- This process makes it possible, for example, to obtain without difficulty a product containing at most 300 to 400 ppm of total oxygen in the form of 200 to 300 ppm of alumina approximately containing 100 to 150 ppm of oxygen and approximately 500 ppm at most. unreduced chromium oxide containing approximately 150 ppm oxygen. It is therefore a chromium of high purity which makes it possible to develop superalloys which can be used in particular in the manufacture of the noble parts of aeronautical turbo-engines. This process has given and still gives all satisfaction.
- An object of the invention is therefore to provide metals and metal alloys of improved purity.
- a method of manufacturing elements made of metal or a metal alloy comprising the steps consisting in:
- a metal or a metal alloy having non-metallic inclusions essentially comprising oxides of the base metal; agglomerate the metal or alloy with a reducing agent to form elements; treat the elements under vacuum so that the reducing agent reacts to the inclusions; and
- the Applicant has in fact surprisingly found that the elimination of the surface layer increases the overall purity of the elements. This result appears paradoxical since the superficial elimination cannot have an effect on the composition of the core of the elements. However, it can be explained by the fact that the concentration of impurities is higher at the periphery of the element than at its center. Surface removal would therefore remove a higher proportion of impurities. It thus appears that this elimination step, in particular by tribofinishing, proves to be technically very advantageous. In addition, it improves the appearance of the product.
- the method according to the invention may also have at least any of the following characteristics:
- the elimination comprises an abrasion
- the process comprises a tribofinishing
- the elimination is carried out by means of a vibrating enclosure
- the layer eliminated has a thickness of between 0.01 and 0.5 mm
- the metal is chosen from chromium, titanium, vanadium, molybdenum, manganese, niobium, tungsten, and nickel
- the alloy comprises at least one of the preceding metals and / or boron
- the alloy is a ferroalloy
- the stage of preparation implements an aluminothermic reaction between at least one metal oxide and divided aluminum
- the reaction is unbalanced by a defect in aluminum compared to the quantity of aluminum necessary for a complete reaction to ensure that the metal or the alloy contains reducible non-metallic inclusions constituted mainly by inclusions of the metal oxide basic,
- the elements are steamed, in particular at a temperature between 200 and 230 ° C,
- the reducing treatment is carried out in a vacuum oven
- Chromium oxide (Cr 2 0 3 ), potassium dichromate (K 2 Cr 2 0) and divided aluminum are introduced into an aluminothermic crucible, lined with a refractory material.
- Chromium oxide is advantageously a commercial product having a particle size between 0 and 15 ⁇ m, while divided aluminum and potassium dichromate consist of grains less than 1 mm.
- Chromium oxide and potassium dichromate are present in the stoichiometric proportions of the aluminothermic reaction, while aluminum is present with a defect compared to the stoichiometric proportion of the conventional aluminothermic reaction.
- This defect in aluminum can represent from 0.5 to 8% by weight, preferably from 2 to 5% by weight, of the stoichiometric amount.
- the metallic chromium coming from stage a) is ground in an impact mill advantageously constituted by a high-energy hammer type grinder (mobile hammers versus fixed hammers) until a fine powder is obtained which passes entirely through a 500 ⁇ m sieve and does not pass through a 77 ⁇ m sieve.
- the grinding is a purifying grinding which produces ventilation, that is to say a certain flow of purge air.
- the air flow can be adjusted voluntarily to accentuate, if desired, the purifying effect.
- this purifying effect can be supplemented by elimination by sieving or any other selective separation of the finest particles from the ground product in which almost all of the non-metallic inclusions released by grinding are found concentrated.
- the purified chromium powder thus obtained is then intimately mixed with a reducing agent and a binder.
- a reducing agent and a binder are advantageously constituted by a mixture of bakelite and an organic binder such as furfuraldehyde.
- the purpose of this is to facilitate cold agglomeration, the bakelite dissolved in the binder forming cold glue, as well as the subsequent polymerization of hot bakelite.
- the reducer for its part, is advantageously constituted by carbon black which complements the carbon of the bakelite.
- the reducing / binder mixture can consist of 0.1% bakelite, 0.3% of furfuraldehyde and from 0.05 to 0.2% of carbon black, these percentages being related to the weight of the ground product.
- the mixture obtained is shaped into balls or pellets by means of a conventional compacting press, such as a ball press with tangential wheels or a tableting press. After agglomeration, the mixture is steamed at the appropriate temperature (200 to 230 ° C approximately) to remove the organic binder and polymerize the bakelite which forms binder and gives resistance to the balls or pellets.
- a conventional compacting press such as a ball press with tangential wheels or a tableting press.
- the oven temperature must be limited to the minimum necessary to avoid any oxidation of the product.
- the balls or pellets obtained in the previous step are then subjected to a reducing treatment to
- the bakelite decomposes at a certain temperature, leaving a carbon skeleton which is added to the carbon black introduced as a reducing agent in the mixture. Once it has reached the processing temperature, this carbon reacts on the oxygen of the Cr 2 0 3 remaining in the product but practically not on the oxygen of the alumina A1 2 0 3 .
- the vacuum is brought back to the treatment oven at
- Stage d During this subsequent stage, a surface layer of the balls is removed by light abrasion. This step is implemented in this case by tribofinition.
- a tribonifition machine consisting of a coated bowl, which is vibrated by means of unbalance motors. Under the effect of vibrations, the balls are eroded against each other.
- the tribofinishing takes about 10 minutes.
- the abraded layer has a thickness between 0.01 and 0.5 mm. This step not only helps to improve the aesthetics of the balls by polishing effect, but also it removes a large amount of impurities.
- the impurities removed are mainly 0 2 , N 2 .
- the Applicant has carried out experiments on 30 pairs of samples of chromium balls. It measured the general content of oxygen, nitrogen and carbon atoms in a sample from each pair that had not been tribofinished. It made the same measurements on the other sample of each pair after tribofinition of the latter. The results are summarized in the following table.
- Lines (1) and (2) give mean values on the samples respectively without and with tribofinishing.
- Line (3) gives the difference between lines (1) and (2).
- the average gain is 31 ppm on oxygen (or 8%), and 7 ppm on nitrogen (or 16%). On the other hand, it is lower on carbon.
- the tribofinishing stage therefore makes it possible to increase the purity of the balls.
- step a) can be carried out other than by aluminothermy, for example by silicothermal or else by reduction in an electric furnace, to obtain a metal or an alloy comprising oxidized non-metallic inclusions of the base metal.
- silicothermia there may be mentioned, by way of nonlimiting examples, the manufacture of ferrochrome or chromium metal by reduction with silicon metal or silicon chromium, as well as the manufacture of ferro-tungsten or ferro-molybdenum by reduction with high-grade ferro-silicon or silicon metal.
- the elimination step can be implemented by means other than tribofinishing, for example by polishing, emery-making, micro-blasting, or sandblasting.
- step a) can be carried out other than by aluminothermy, for example by silicothermal or else by reduction in an electric furnace, to obtain a metal or an alloy comprising oxidized non-metallic inclusions of the base metal.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03712263A EP1468123B1 (fr) | 2002-01-21 | 2003-01-20 | Procede de fabrication d'elements metalliques de purete elevee tel que le chrome |
DE60304996T DE60304996T2 (de) | 2002-01-21 | 2003-01-20 | Verfahren zur herstellung hochreiner metalle und legierungen insbes. chrom |
JP2003562345A JP2005526177A (ja) | 2002-01-21 | 2003-01-20 | クロムなどの高純度の金属要素の製造方法 |
US10/502,305 US7361205B2 (en) | 2002-01-21 | 2003-01-20 | Method for production of metallic elements of high purity such as chromes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0200678A FR2834999B1 (fr) | 2002-01-21 | 2002-01-21 | Procede de fabrication d'elements metalliques de purete elevee |
FR02/00678 | 2002-01-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003062479A1 true WO2003062479A1 (fr) | 2003-07-31 |
Family
ID=27589526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2003/000164 WO2003062479A1 (fr) | 2002-01-21 | 2003-01-20 | Procede de fabrication d'elements metalliques de purete elevee tel que le chrome |
Country Status (9)
Country | Link |
---|---|
US (1) | US7361205B2 (fr) |
EP (1) | EP1468123B1 (fr) |
JP (1) | JP2005526177A (fr) |
CN (1) | CN1639362A (fr) |
AT (1) | ATE325205T1 (fr) |
DE (1) | DE60304996T2 (fr) |
FR (1) | FR2834999B1 (fr) |
RU (1) | RU2306349C2 (fr) |
WO (1) | WO2003062479A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109554542A (zh) * | 2017-06-30 | 2019-04-02 | 马鞍山华盛冶金科技发展有限公司 | 一种钨钼矿球团的制备方法及火法冶炼低品位钨钼矿的方法 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101249127B1 (ko) | 2009-12-15 | 2013-03-29 | 주식회사 포스코 | 크롬분광 성형체, 그 제조방법 및 이를 이용한 스테인리스강 제조방법 |
RU2495945C1 (ru) * | 2012-07-04 | 2013-10-20 | Открытое акционерное общество "Ключевский завод ферросплавов" (ОАО "КЗФ") | Шихта и способ алюминотермического получения хрома металлического с ее использованием |
JP2015174046A (ja) * | 2014-03-17 | 2015-10-05 | Jfeマテリアル株式会社 | 粉末冶金用クロムの製造方法 |
CN103952574B (zh) * | 2014-04-30 | 2015-08-19 | 中国科学院过程工程研究所 | 一种利用金属镁还原无水氯化铬生产高纯金属铬的方法 |
US9771634B2 (en) | 2014-11-05 | 2017-09-26 | Companhia Brasileira De Metalurgia E Mineração | Processes for producing low nitrogen essentially nitride-free chromium and chromium plus niobium-containing nickel-based alloys and the resulting chromium and nickel-based alloys |
US10041146B2 (en) * | 2014-11-05 | 2018-08-07 | Companhia Brasileira de Metalurgia e Mineraçäo | Processes for producing low nitrogen metallic chromium and chromium-containing alloys and the resulting products |
CN107904410B (zh) * | 2017-11-03 | 2019-10-08 | 中信锦州金属股份有限公司 | 一种复合脱气剂制备高温合金和靶材专用高纯金属铬的生产方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4940232A (fr) * | 1972-08-26 | 1974-04-15 | ||
EP0102892A1 (fr) * | 1982-08-20 | 1984-03-14 | C. Delachaux | Procédé de fabrication de métaux ou d'alliages de pureté élevée |
WO2001013969A1 (fr) * | 1999-08-23 | 2001-03-01 | Shinhan Machinery Co., Ltd. | Dispositif et procede servant a fabriquer une moelle artificielle poreuse en titane-nickel au moyen d'une technique de synthese par rotation a chaud |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4005956A (en) * | 1973-04-11 | 1977-02-01 | Inoue-Japax Research Incorporated | Powder activation and integrated powder metallurgy system |
US5039476A (en) * | 1989-07-28 | 1991-08-13 | Ube Industries, Ltd. | Method for production of powder metallurgy alloy |
FR2692506B1 (fr) * | 1992-06-22 | 1997-02-14 | Renault | Materiau de friction destine a etre utilise dans un systeme tribologique lubrifie |
FR2787472B1 (fr) * | 1998-12-16 | 2001-03-09 | Onera (Off Nat Aerospatiale) | Procede pour produire une poudre d'alliage metallique de type mcraly et revetements obtenus avec cette poudre |
MXPA01009477A (es) * | 1999-03-19 | 2002-06-04 | Cabot Corp | Elaboracion de polvo de niobio y de otros metales mediante molienda. |
-
2002
- 2002-01-21 FR FR0200678A patent/FR2834999B1/fr not_active Expired - Lifetime
-
2003
- 2003-01-20 EP EP03712263A patent/EP1468123B1/fr not_active Expired - Lifetime
- 2003-01-20 WO PCT/FR2003/000164 patent/WO2003062479A1/fr active IP Right Grant
- 2003-01-20 RU RU2004125591/02A patent/RU2306349C2/ru active
- 2003-01-20 AT AT03712263T patent/ATE325205T1/de active
- 2003-01-20 DE DE60304996T patent/DE60304996T2/de not_active Expired - Lifetime
- 2003-01-20 US US10/502,305 patent/US7361205B2/en not_active Expired - Lifetime
- 2003-01-20 JP JP2003562345A patent/JP2005526177A/ja active Pending
- 2003-01-20 CN CNA038051125A patent/CN1639362A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4940232A (fr) * | 1972-08-26 | 1974-04-15 | ||
EP0102892A1 (fr) * | 1982-08-20 | 1984-03-14 | C. Delachaux | Procédé de fabrication de métaux ou d'alliages de pureté élevée |
WO2001013969A1 (fr) * | 1999-08-23 | 2001-03-01 | Shinhan Machinery Co., Ltd. | Dispositif et procede servant a fabriquer une moelle artificielle poreuse en titane-nickel au moyen d'une technique de synthese par rotation a chaud |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 197443, Derwent World Patents Index; Class M11, AN 1974-74939V, XP002215605 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109554542A (zh) * | 2017-06-30 | 2019-04-02 | 马鞍山华盛冶金科技发展有限公司 | 一种钨钼矿球团的制备方法及火法冶炼低品位钨钼矿的方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1468123A1 (fr) | 2004-10-20 |
US20050061109A1 (en) | 2005-03-24 |
FR2834999A1 (fr) | 2003-07-25 |
FR2834999B1 (fr) | 2004-06-18 |
DE60304996T2 (de) | 2006-12-21 |
JP2005526177A (ja) | 2005-09-02 |
ATE325205T1 (de) | 2006-06-15 |
RU2004125591A (ru) | 2005-06-10 |
RU2306349C2 (ru) | 2007-09-20 |
US7361205B2 (en) | 2008-04-22 |
EP1468123B1 (fr) | 2006-05-03 |
DE60304996D1 (de) | 2006-06-08 |
CN1639362A (zh) | 2005-07-13 |
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