EP0485309B1 - Produit pour désulfuration des fontes ou aciers liquides à base de magnésium enrobé - Google Patents

Produit pour désulfuration des fontes ou aciers liquides à base de magnésium enrobé Download PDF

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Publication number
EP0485309B1
EP0485309B1 EP91420388A EP91420388A EP0485309B1 EP 0485309 B1 EP0485309 B1 EP 0485309B1 EP 91420388 A EP91420388 A EP 91420388A EP 91420388 A EP91420388 A EP 91420388A EP 0485309 B1 EP0485309 B1 EP 0485309B1
Authority
EP
European Patent Office
Prior art keywords
product
refractory
powder
organic
magnesium
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 - Lifetime
Application number
EP91420388A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0485309A1 (fr
Inventor
Paul Henri Galvin
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.)
Ferroglobe France SAS
Original Assignee
Pechiney Electrometallurgie SAS
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 Pechiney Electrometallurgie SAS filed Critical Pechiney Electrometallurgie SAS
Priority to AT91420388T priority Critical patent/ATE95249T1/de
Publication of EP0485309A1 publication Critical patent/EP0485309A1/fr
Application granted granted Critical
Publication of EP0485309B1 publication Critical patent/EP0485309B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C21C7/0645—Agents used for dephosphorising or desulfurising

Definitions

  • the invention relates to a product for desulfurization of cast irons or liquid steels, based on coated magnesium particles.
  • magnesium powder is well known for the desulfurization of cast iron and steel.
  • magnesium presents difficulties of use which we try to overcome by coating the particles of magnesium, the diameter of which is generally less than 2 mm, a layer of fine powder mineral product consisting of grains whose diameter is generally less than 150 microns.
  • the adhesion can be carried out using organic binders which has certain advantages.
  • the organic products more particularly cited in this patent are: . starch, dextrin, molasses, which are sugars, carboxymethylcellulose, phenolic resins, urea resins, melamine resins, furan resins, epoxy resins, polyester resins, pitch and tar.
  • application EP 292 205 describes a similar coating where the magnesium is first covered with a first layer of a hydrophobic product and then with a second layer of a particulate refractory product.
  • hydrophobic products which are also organic products, are selected from aliphatic or aromatic liquid oils with a low viscosity at 25 ° C., or solid at room temperature but liquid at low temperatures (for example waxes or paraffin).
  • the refractory mineral product used is generally constituted by metal oxides, mixtures or complexes of oxides (for example: MgO, Al2O3, SiO2, TiO2, vermicullite, ...), by fluorides, by carbon. .
  • the magnesium particles can also be coated only with a varnish or a layer of carbon, by prior coating of said particles with the aid of polymerizable oils which are then heat treated and decomposed more. or less completely to finally obtain said varnish or said carbon layer;
  • the oils used can be animal fats, petroleum oils with high boiling point, fatty acids, etc.
  • Desulfurizing products based on coated magnesium, obtained using refractory products and organic binders, however, have drawbacks. First of all, they are not completely impermeable to humidity, which gives off hydrogen in the event of contact with water (liquid or vapor); this release of hydrogen obviously presents a risk which must be avoided. In addition, a slight rise in temperature can cause softening of the organic matter and thus cause deterioration of the refractory coating of the magnesium grains; this results in a risk of sticking and agglomeration of the grains between them, causing difficulties and irregularities in processing during the introduction of the desulfurizing agent into the liquid metal. These harmful temperature rises generally occur during the storage of products in exposed places, for example near ovens, sunshine ...
  • the invention is a product for desulfurization of cast irons or liquid steels based on magnesium grains coated with an organic product which is solid at room temperature and a refractory powder, characterized in that the organic product is based on saturated aliphatic acids or their esters.
  • Solid acids or esters are usually used at low temperature, preferably below 60 ° C or better of 80 ° C, the melting point not generally exceeding 110 ° C, with a clear melting, without going through a softening phase.
  • esters usually used are the glycerine triesters or their mixtures, in particular the saturated triesters obtained by hydrogenation of castor oil, which essentially leads to glycerol trihydroxystearate.
  • Hydrogenated sunflower oil, glycerol stristearate and sometimes stearic acid can also be used.
  • the solid coating products of the invention make it possible on the one hand to make a coating of Mg which is stable at high temperature, without it being necessary to carry out chemical transformations of starting materials in order to obtain it.
  • an Mg powder can withstand severe temperature storage conditions (proximity of ovens, sun, etc.) without its flowability being deteriorated.
  • the esters of the invention generally constitute most or preferably all of the organic product used for coating the magnesium.
  • said organic product may contain other organic products than the esters of the invention, in particular unprocessed residues of the products used to obtain said esters.
  • They are particularly suitable for coating magnesium on which they adhere remarkably thanks to their non-zero but low acidity which makes it possible to react very superficially with the Mg particles.
  • hydrogenated castor oil has an acid number of 4 (which represents the weight of KOH in mg to neutralize 1 g of product) and melts at 86 ° C.
  • any infusible metal oxides or other powdered refractories known from the prior art can be used, but also desulfurizing agents such as C2Ca, CO3Ca, CaO ... or other minerals such as carbons ... or their mixtures.
  • the refractory product is sensitive to humidity, such as for example C2Ca
  • the magnesium particles are usually less than 2 mm in size, preferably between approximately 300 and 800 ⁇ m and the refractory product powder has a grain size between approximately 0 and 80 ⁇ m.
  • ester according to the invention 0.5 to 1.5 parts by weight of ester according to the invention are used (for example hydrogenated castor oil) per 5 parts by weight of refractory protection product, most often about 1 part of ester for 5 parts of protective slag.
  • the proportion of coating product relative to the desulphurizing agent can range from 2% to 25% (weight).
  • the coated magnesium desulfurizing product according to the invention can be mixed with other desulfurizing agents, in particular with calcium carbide, or with other mixtures based on calcium carbide (for example mixture of the carbonate type of calcium + calcium carbide + carbon), with or without lime. It can also be mixed with inert products.
  • the magnesium particles and the ester according to the invention in the solid state are introduced simultaneously into a heated mixer so as to initially produce particles uniformly covered with ester; the refractory product powder is then introduced and particles coated with slag are then obtained which are removed from the mixer and then cooled.
  • the invention makes it possible to obtain desulfurizing products which are inert to water and humidity, giving no release of hydrogen and not even agglomerating, under severe conditions of storage or use. These products have improved safety in use.
  • coated magnesium was prepared according to Example 1 of EP 292 205; 25 g were immersed in water at pH 7 and 19 ° C, and a regular evolution of 50 cm3 of hydrogen was observed per hour.
  • a desulfurizing product was prepared containing 20% of product No. 1 and 80% of a pulverulent mixture of composition (% by weight):
  • Such a product according to the invention is particularly suitable for use in admixture with a powder also of calcium carbide. It has great storage security in hot environments, on the other hand, it is sensitive to water due to the presence of calcium carbide on the surface.
  • This product was injected in the same liquid iron as in Example 1 with the same proportion of 0.1%. The final sulfur content obtained is 0.005%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Products (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Paints Or Removers (AREA)
EP91420388A 1990-11-05 1991-10-30 Produit pour désulfuration des fontes ou aciers liquides à base de magnésium enrobé Expired - Lifetime EP0485309B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT91420388T ATE95249T1 (de) 1990-11-05 1991-10-30 Beschichtete magnesiumteilchen zur entschwefelung von gusseisen oder flussstahl.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9014092 1990-11-05
FR9014092A FR2668776B1 (fr) 1990-11-05 1990-11-05 Produit pour desulfuration des fontes ou aciers liquides a base de magnesium enrobe.

Publications (2)

Publication Number Publication Date
EP0485309A1 EP0485309A1 (fr) 1992-05-13
EP0485309B1 true EP0485309B1 (fr) 1993-09-29

Family

ID=9402139

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91420388A Expired - Lifetime EP0485309B1 (fr) 1990-11-05 1991-10-30 Produit pour désulfuration des fontes ou aciers liquides à base de magnésium enrobé

Country Status (13)

Country Link
US (1) US5198016A (fi)
EP (1) EP0485309B1 (fi)
AT (1) ATE95249T1 (fi)
CS (1) CS334791A3 (fi)
DE (1) DE69100441T2 (fi)
ES (1) ES2046031T3 (fi)
FI (1) FI96518C (fi)
FR (1) FR2668776B1 (fi)
HU (1) HUT61344A (fi)
NO (1) NO177391C (fi)
PL (1) PL292273A1 (fi)
PT (1) PT99419B (fi)
SK (1) SK280853B6 (fi)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE142705T1 (de) * 1991-04-02 1996-09-15 Pechiney Electrometallurgie Entschwefelungsmittel für roheisen, aus calciumkarbid und organisches bindemittel
CN1087035C (zh) * 1999-11-02 2002-07-03 北京科技大学 用镁基脱硫剂进行的浅熔池铁水喷吹预处理方法
CN101778890B (zh) * 2007-08-09 2012-04-11 巴斯夫欧洲公司 用于可发性苯乙烯聚合物颗粒的涂料制剂
CN102108428B (zh) * 2011-01-17 2013-04-03 中国恩菲工程技术有限公司 粗镍铁的精炼工艺
CN102061358B (zh) * 2011-01-17 2012-12-26 中国恩菲工程技术有限公司 高硫粗镍铁的脱硫精炼工艺
CN103773914A (zh) * 2012-10-23 2014-05-07 刘秀凤 铸铁用复合脱硫材料的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2536362A (en) * 1949-12-19 1951-01-02 Du Pont Treatment of molten metals
US3410681A (en) * 1965-09-28 1968-11-12 Fur Tech Entwicklung Und Verwe Composition for the treatment of steel
JPS5261110A (en) * 1975-11-14 1977-05-20 Aikoh Co Desulfurization of iron melt
US4533572A (en) * 1984-03-20 1985-08-06 Amax Inc. Process for producing varnish-bonded carbon-coated metal granules
GB8712168D0 (en) * 1987-05-22 1987-06-24 Foseco Int Metallurgical treatment agents
GB8802951D0 (en) * 1988-02-09 1988-03-09 Foseco Int Metallurgical treatment agents

Also Published As

Publication number Publication date
PT99419A (pt) 1992-09-30
FR2668776A1 (fr) 1992-05-07
FI96518C (fi) 1996-07-10
FI915188A (fi) 1992-05-06
NO177391C (no) 1995-09-06
DE69100441T2 (de) 1994-01-20
HUT61344A (en) 1992-12-28
FR2668776B1 (fr) 1994-05-13
CS334791A3 (en) 1992-05-13
NO914257D0 (no) 1991-10-30
US5198016A (en) 1993-03-30
FI96518B (fi) 1996-03-29
DE69100441D1 (de) 1993-11-04
PT99419B (pt) 1999-04-30
EP0485309A1 (fr) 1992-05-13
ATE95249T1 (de) 1993-10-15
HU913471D0 (en) 1992-01-28
ES2046031T3 (es) 1994-01-16
FI915188A0 (fi) 1991-11-04
NO177391B (no) 1995-05-29
SK280853B6 (sk) 2000-08-14
PL292273A1 (en) 1992-06-01
NO914257L (no) 1992-05-06

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