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US2512578A - Method of desulfurizing and decopperizing ferrous metal - Google Patents

Method of desulfurizing and decopperizing ferrous metal Download PDF

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US2512578A
US2512578A US95591A US9559149A US2512578A US 2512578 A US2512578 A US 2512578A US 95591 A US95591 A US 95591A US 9559149 A US9559149 A US 9559149A US 2512578 A US2512578 A US 2512578A
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sulphide
copper
sulphur
molten
slag
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US95591A
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Jordan James Fernando
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04Removing impurities by adding a treating agent
    • C21C7/064Dephosphorising; Desulfurising

Definitions

  • g l My invention relates to the desulphurization and decopperization of molten ferrous metals.
  • My reagent slag contains, as its principal desulphurizing and decopperizing agent, either sodium sulphide, or potassium sulphide, or aluminum sulphide.
  • sufiicient sulphur is present in the ferrous metal to convert the copper content of said metal to cuprous sulphide, my previously-disclosed desulphurizing slag will also decopperize said ferrous metal.
  • the sulphur requirements of copper may be estimated by multiplying the copper content of the metal by 0.28; that the sulphur requirements of the manganese may be estimated by multiplying the manganese content of the metal by 0.64.; and that the sulphur requirements of the aluminum may be estimated by multiplying the aluminum content of the metal by 1.9.
  • the copper and manganese factors are about 10% abovethe assumed equation requirements; the aluminum factor being satisfactory in the presence of the usually small aluminum content-of ferrous metal.
  • I treated a molten iron contaming 4.35% carbon, 3.34% silicon, 0.89% manganese, and 0.25% copper, with a 0.65% sulphur addition.
  • Contact with a molten sodium-aluminum sulphide lowered these values to 0.05% manganese, 0.03% copper, and 0.027% sulphur.
  • Deoxldized steel may be treated with sulphide slag to remove copper andsulphur therefrom.
  • sulphide slag containing aluminum sulphide. and 10% aluminum oxide lowered these valuesto 0.02% manganese, 0.05% copper, and 0.020% sulphur.
  • I made with this steel I added enough aluminum to the steel to yield a residual aluminum content of 0.05%, and then I treated the resulting metal with 0.43% sulphur.
  • Contact with the molten aluminum sulphide aluminum oxide reagent gave 0.02% manganese, 0.07% copper, and 0.011% sulphur.
  • the ferrous metal contains other elements which have a greater afiinity for sulphur than has copper, then sufiicient sulphur must be added to the metal to convert these other elements into their corresponding sulphides; for,
  • the efliciency of the extraction may-be greatly increased by employing a counter current extractor--this in keepingr with the well known increased efiiciency derived from employing the counter-current principle in extraction processes.
  • Counter-current extractors suitable-for use-'in extracting sulphur and copper from molten ferrous metals are disclosed'inmy' copending applications: Serial No. 783,391,.fi1eddn- O ctj 3-1,
  • the method of refining iron and steel containing: copper which comprises: melting the copper-bearing metal; adding suificient sulphur to the-molten metal to convert into their respective sulphides any metals present in said molten metal having a greater affinity for sulphur than the affinity of copper for sulphura-nd'to convert a substantial portionof theoopper present into cuprous sulphide; contacting; said molten metal witha: molten sulphide slag consisting essentially of a sulphide selected from the group consisting of sodium sulphide, potassium sulphide, aluminum sulphide, and mixtures thereof; and separating said slag from saidmetal after said molten sulphide slag has lowered the copper content of said molten metal and after said; molten sulphide slaghas extracted from said molten metal a substantial portion of the sulphur that was added to said moltenmetal.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Description

Patented June 20, 1950 METHOD OF DESULFURIZING AND DECOPPERIZING FERROUS METAL James Fernando Jordan, Huntington Park, Calif.
N0 Drawing- Application May 26, 1949, Serial No. 95,591
4 Claims. (01475-53) g l My invention relates to the desulphurization and decopperization of molten ferrous metals.
This is a continuation-in-part of my copending application Serial No. 26,937, filed on May 13,
1948, and-my copending application Serial No.
49,217, filed on Sept. 14, 1948, both now abandoned;
The copper content of the steel being produced in the United States has been slowly gaining ground, as the result of the copper content of pig iron and the influx of copper-bearing metals into the steel-scrap portion of the typical steel-making charge. While a certain measure of copper is supposed to help the corrosion resistance of steel,
there are other effects of copper in steel which are bad. Thus, for example, copper harms the deep-drawing properties of steel. I
I have found a reagent slag that is capable of extracting copper and sulphur from molten iron or molten steel. My reagent slag contains, as its principal desulphurizing and decopperizing agent, either sodium sulphide, or potassium sulphide, or aluminum sulphide.
In my copending application, Serial No. 26,937,
I disclosed my reagent slag for desulphurizing molten iron, said slag containing either sodium sulphide, or potassium sulphide, or aluminum sulphide as its principal desulphurizing agent. I have found that when sufiicient sulphur is present in the ferrous metal to convert the copper content of said metal to cuprous sulphide, my previously-disclosed desulphurizing slag will also decopperize said ferrous metal.
While my discovery, indicates that copper has a greater afiinity for sulphur than iron has at those temperatures where ferrous metals are molten, other commonly-employed alloying constituents in said ferrous metals have a still greater afiinity for sulphur. Thus, for example, manganese and aluminum both have a greater afiinity for sulphur than copper has. As a consequence in the presence of such elements assaid manganese and/or aluminum, copper will not combine with the sulphur content of the ferrous metal until sufiicient sulphur is present to first satisfy the conversion requirements of said manganese and/or aluminum.
My practice in treating ferrous metal is to assume that the sulphur requirements of copper may be estimated by multiplying the copper content of the metal by 0.28; that the sulphur requirements of the manganese may be estimated by multiplying the manganese content of the metal by 0.64.; and that the sulphur requirements of the aluminum may be estimated by multiplying the aluminum content of the metal by 1.9. In general, the copper and manganese factors are about 10% abovethe assumed equation requirements; the aluminum factor being satisfactory in the presence of the usually small aluminum content-of ferrous metal.
for example, in a test that I made with an iron containing 3.34% carbon, 2.10% silicon, 0.10%manganese, and 0.30% copper, I added 0.155% sulphur. Contact with molten sodium sulphide at..2500 F. lowered these values to 0.009% manganese, 0.04% copper, and 0.019% sulphur. This sodium sulphide reagent contained 20% aluminum sulphide.
In another case, I treated a molten iron contaming 4.35% carbon, 3.34% silicon, 0.89% manganese, and 0.25% copper, with a 0.65% sulphur addition. Contact with a molten sodium-aluminum sulphide lowered these values to 0.05% manganese, 0.03% copper, and 0.027% sulphur.
Deoxldized steel may be treated with sulphide slag to remove copper andsulphur therefrom. In a test that I made with a steel containing 0.30% carbon, 0.41% silicon, 0.17% manganese, and 0.76% copper, I added 0.35% sulphur. Contact with molten sulphide slag containing aluminum sulphide. and 10% aluminum oxide lowered these valuesto 0.02% manganese, 0.05% copper, and 0.020% sulphur. In another test that I made with this steel, I added enough aluminum to the steel to yield a residual aluminum content of 0.05%, and then I treated the resulting metal with 0.43% sulphur. Contact with the molten aluminum sulphide aluminum oxide reagent gave 0.02% manganese, 0.07% copper, and 0.011% sulphur. I,
These molten sulphide slags must be protected fromv the air, for said sulphides show a marked tendency to oxidize to the corresponding sul phates. Furthermore, fume hoods are a required accessory in my process, although I have had good success in depressing the fuming of the molten sulphides by elevating their boiling points by means of the non-volatile-solute effect. Thus, I depressed the fuming of sodium sulphide by adding aluminum sulphide thereto, and I depressed the fuming of aluminum sulphide by adding aluminum oxide thereto.
If, in addition to, or in place of, manganese and/or aluminum, the ferrous metal contains other elements which have a greater afiinity for sulphur than has copper, then sufiicient sulphur must be added to the metal to convert these other elements into their corresponding sulphides; for,
copper will not combine with sulphur in the pres-- sults with a slag composed of 60% potassium.
and 40% aluminum sulphide, and I have obtained good results with a slag composedi ofiT30,%L po-r tassium sulphide, 30% sodium sulphide,and 40% aluminum sulphide.
by my sulphide slag is apparently favored by 1947, now abandoned; Serial No. 69,467, filed on Jan. 6, 1949; and Serial No. 73,993, filed on Feb. 1, 1949-the latter two counter-current extractors being most suitable for use in an extraction process wherein intimate contact between the solvents and the absence of air are desirable, such as in the present case.
Having now described several forms of" my invention, I wish it to be understood that my invention is not to be limited to the specific form or arrangement of steps herein disclosed, except 1 insofar as such limitations are specified in the aphigher extraction temperatures.
In several tests that I made, the nickel content.
of the molten ferrous metal was observed to have partly passed into the sulphide slag with the cop: per; and in certain other tests made at very low extraction temperatures, the: molybdenum" eon tentof, the metalpassed, in part, into the sulphide slag with the copper. g 3
The factor which I use to figuretheproper concentration of sulphur in aferrous metal tob'e treated for, the removal of its copper content are my preferred embodiment; however'j l have ob} tained a certain measure f decopperizationwith lower sulphur.percentages -thus;. in a test that Imade with the" molten iron that'contained 323 3 75 carbon, 1' added'-0;099'% sulphur. Contactwith the molten sodium sulphide-aluminum sulphide slag gave the .following' results: ;009%"manganese, 0.22% copper, and" 0.012% sulphur.
The emimerated: tests employed one pound of slagf-or every pound of metal, treated-*whenithe sulphur content of the metaiwasbelow 0.25%; and said, tests employed every pound of metaljtreated when the metal contained more than 0.25% sulphur The efi'iciency of my process maybe; reatly increased by, recovering the copperamanganese bearing waste slag; This .may ing. saidwaste slag, while it'is molten, with aluminum, whereupon, said alummumwill displace the copper and, manganese thereinlyielding an alloy of copper and manganese, and alum nu sulphide. V
The efliciency of the extraction may-be greatly increased by employing a counter current extractor--this in keepingr with the well known increased efiiciency derived from employing the counter-current principle in extraction processes. Counter-current extractors suitable-for use-'in extracting sulphur and copper from molten ferrous metals are disclosed'inmy' copending applications: Serial No. 783,391,.fi1eddn- O ctj 3-1,
two pounds; of: slag for I be done by treat- 1 pended claims.
' I claim as my invention:
1. The method of refining iron and steel containing: copper, which comprises: melting the copper-bearing metal; adding suificient sulphur to the-molten metal to convert into their respective sulphides any metals present in said molten metal having a greater affinity for sulphur than the affinity of copper for sulphura-nd'to convert a substantial portionof theoopper present into cuprous sulphide; contacting; said molten metal witha: molten sulphide slag consisting essentially of a sulphide selected from the group consisting of sodium sulphide, potassium sulphide, aluminum sulphide, and mixtures thereof; and separating said slag from saidmetal after said molten sulphide slag has lowered the copper content of said molten metal and after said; molten sulphide slaghas extracted from said molten metal a substantial portion of the sulphur that was added to said moltenmetal.
2. The process according toclaim I in which said molten sulphide slag consists essentially of sodium sulphide.
3. The process according toclaim 1' in which said molten sulphide slag consists essentially of potassium sulphide.
4:. The process according toclaim 1 in which said molten sulphide slag consists essentially of aluminum sulphide.
JAMES FERNANDO JORDAN;
REFERENCES CITED' The following references are of record in th file of this patent:
UNITED STATES PATENTS Number Name Date 838,125 Maffett Dec. 11, 1906 1,425,701 Sem Aug; 15,1922 1,785,503 Spring Dec.. 16 1930 1,837,432 I-Ianak Dec. 22 .1931 1,982,959 Kuhlmann Dec. 4,, 1934 2,109,144 Betterton Feb, 22, 1938 2,301,360 Brennan Nov. 10, 1942

Claims (1)

1. THE METHOD OF REFINING IRON AND STEEL CONTAINING COPPER, WHICH COMPRISES: MELTING THE COPPER-BEARING METAL; ADDING SUFFICIENT SULPHUR TO THE MOLTEN METAL TO CONVERT INTO THEIR RESPECTIVE SULPHIDES ANY METALS PRESENT IN SAID MOLTEN METAL HAVING A GREATER AFFINITY FOR SULPHUR THAN THE AFFINITY OF COPPER FOR SULPHUR AND TO CONVERT A SUBSTANTIAL PORTION OF THE COPPER PRESENT INTO CUPROUS SULPHIDE; CONTACTING SAID MOLTEN METAL WITH A MOLTEN SULPHIDE SLAGE CONSISTING ESSENTIALLY OF A SULPHIDE SELECTED FROM THE GROUP CONSISTING OF SODIUM SULPHIDE, POTASSIUM SULPHIDE, ALUMINUM SULPHIDE, AND MIXTURES THEREOF; AND SEPARATING SAID SLAG FROM SAID METAL AFTER SAID MOLTEN SULPHIDE SLAG HAS LOWERED THE COPPER CONTENT OF SAID MOLTEN METAL AND AFTER SAID MOLTEN SULPHIDE SLAG HAS EXTRACTED FROM SAID MOLTEN METAL A SUBSTANTIAL PORTION OF THE SULPHUR THAT WAS ADDED TO SAID MOLTEN METAL.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424574A (en) * 1965-10-22 1969-01-28 Meherwan C Irani Ferrous metal refining
US4033761A (en) * 1976-05-10 1977-07-05 Asarco Incorporated Process for the separation of copper sulfide from metallic lead entrained in a dross
US4925488A (en) * 1987-07-30 1990-05-15 Milton Blander Removal of copper from ferrous scrap
EP2248916A4 (en) * 2008-03-05 2011-01-05 Jfe Steel Corp PROCESS FOR REMOVING COPPER CONTAINED IN STEEL WASTE

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US838125A (en) * 1905-12-23 1906-12-11 Int Nickel Co Separation of nickel from copper.
US1425701A (en) * 1919-04-04 1922-08-15 Norske Elektrokemisk Ind As Process of freeing metals from copper
US1785503A (en) * 1928-06-16 1930-12-16 Crane Co Apparatus for desulphurizing cast iron
US1837432A (en) * 1931-01-19 1931-12-22 Hanak Albert Purification of metals and alloys
US1982959A (en) * 1932-06-04 1934-12-04 Electro Metallurg Co Method of refining alloys
US2109144A (en) * 1933-08-17 1938-02-22 American Smelting Refining Process of treating metal
US2301360A (en) * 1940-08-03 1942-11-10 Electro Metallurg Co Purification of high silicon iron alloys

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US838125A (en) * 1905-12-23 1906-12-11 Int Nickel Co Separation of nickel from copper.
US1425701A (en) * 1919-04-04 1922-08-15 Norske Elektrokemisk Ind As Process of freeing metals from copper
US1785503A (en) * 1928-06-16 1930-12-16 Crane Co Apparatus for desulphurizing cast iron
US1837432A (en) * 1931-01-19 1931-12-22 Hanak Albert Purification of metals and alloys
US1982959A (en) * 1932-06-04 1934-12-04 Electro Metallurg Co Method of refining alloys
US2109144A (en) * 1933-08-17 1938-02-22 American Smelting Refining Process of treating metal
US2301360A (en) * 1940-08-03 1942-11-10 Electro Metallurg Co Purification of high silicon iron alloys

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424574A (en) * 1965-10-22 1969-01-28 Meherwan C Irani Ferrous metal refining
US4033761A (en) * 1976-05-10 1977-07-05 Asarco Incorporated Process for the separation of copper sulfide from metallic lead entrained in a dross
US4925488A (en) * 1987-07-30 1990-05-15 Milton Blander Removal of copper from ferrous scrap
EP2248916A4 (en) * 2008-03-05 2011-01-05 Jfe Steel Corp PROCESS FOR REMOVING COPPER CONTAINED IN STEEL WASTE
US20110000340A1 (en) * 2008-03-05 2011-01-06 Jfe Steel Corporation Method for removing copper in steel scraps
TWI409338B (en) * 2008-03-05 2013-09-21 Jfe Steel Corp Removal of copper from steel scrap
CN101960023B (en) * 2008-03-05 2014-06-18 杰富意钢铁株式会社 Method for removing copper from steel shavings

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