US2509189A - Process for the removal of sulfur from ferrous metals - Google Patents
Process for the removal of sulfur from ferrous metals Download PDFInfo
- Publication number
- US2509189A US2509189A US48310A US4831048A US2509189A US 2509189 A US2509189 A US 2509189A US 48310 A US48310 A US 48310A US 4831048 A US4831048 A US 4831048A US 2509189 A US2509189 A US 2509189A
- Authority
- US
- United States
- Prior art keywords
- sulphide
- molten
- slag
- aluminum
- sulphur
- 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
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 29
- 239000002184 metal Substances 0.000 title claims description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 8
- -1 ferrous metals Chemical class 0.000 title description 4
- 229910052717 sulfur Inorganic materials 0.000 title description 2
- 239000011593 sulfur Substances 0.000 title description 2
- 239000002893 slag Substances 0.000 claims description 28
- 239000005864 Sulphur Substances 0.000 claims description 22
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 21
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 claims description 12
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 150000004763 sulfides Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910000805 Pig iron Inorganic materials 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000897 Babbitt (metal) Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- FQDSYGKTHDFFCM-UHFFFAOYSA-N beryllium sulfide Chemical compound S=[Be] FQDSYGKTHDFFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- 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
Definitions
- My invention relates tothe desulphurization of ferrous metals.
- reagent slags composed of, or containing: sodium sulphide, potassium sulphide, or aluminum sulphide, are efiicient desulphurizers of molten ferrous metals. This discovery meets a need within ferrous refining metallurgy; for, more efiicientlow-melting point e lphuri a ents are in demand within said metallurgy.
- Fuming may be minimized by employing low extraction temperatures, and by employing the non-volatile-solute effect, wherein the boiling point of the sulphide is elevated by dissolving therein a solute that is non-volatile.
- a sulphide must be essentially immiscible in the molten metal that is to be desulphurized; must be a solvent for the sulphides which are to be extracted from said molten metal; and must be the sulphide of a metal whose affinity for sulphur exceeds the afiinity for sulphur exhibited by the molten metal that is to be treated.
- said slag was capable of lowering the sulphur content of said metal to 0.052%--the same weight of slag being employed in both tests, of course.
- I made with this molten iron containing 0.177% sulphur I treated the aluminum-treated metal with a reagent slag consisting of 40% sodium sulphide, 40% potassium sulphide and 20% aluminum sulphide, with the result that the sulphur content of said molten iron was lowered to 0.012%.
- My extraction process may be carried out in any refining vessel wherein two interacting metallurgical liquids may be entertained.
- the teapot ladle of the iron foundry may be used, for example. Such a ladle should be covered and should possess the means for maintaining a protective atmosphere over said sulphide slag.
- the method of removing sulphur from molten ferrous metal which comprises: contacting said molten ferrous metal with a molten sulphide slag consisting essentially of a sulphide selected from the group consisting of sodium sulphide, potassium sulphide, aluminum sulphide and mixtures thereof; maintaining said molten sulphide slag in contact with said molten ferrous metal until said slag has lowered the sulphur content of said metal; and separating said molten ferrous metal from said molten sulphide slag.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Patented May 23, 1950 PKGCESS FQR THE REMOVAL OF SULFUR FROM FERROUS METALS James Fernando J ordan'. Huntington Park,,Calif.
No'Drawing. Application'september 8, 1948,
Serial No. 48,310- r Claims. (01., li -55.)
My invention relates tothe desulphurization of ferrous metals.
This application is a continuation-impart. of my copendi-ng application." Serial No. 25,783, filed on May 7, 19 18, now abandoned'.
I have discovered that reagent slags composed of, or containing: sodium sulphide, potassium sulphide, or aluminum sulphide, are efiicient desulphurizers of molten ferrous metals. This discovery meets a need within ferrous refining metallurgy; for, more efiicientlow-melting point e lphuri a ents are in demand within said metallurgy.
Thus, in tests that. Imade with. a molten pig iron containing 1.09% manganese and 0.045%v sulphur, I found thatit was possible to lower said sulphur to 0.007% with molten sodium sulphide; to 0.010 with a slag composed of 75% potassium sulphide and 25%. aluminum. sulphide; and; to. 0.005% with a slag composed of aluminum sulphide.
The slags from these tests indicated that the sulphur moved into said slags as manganese sulphide. It is therefore believed that the reaction mechanism consists of the extraction process wherein MnS(in the metal) MnS(in the slag) (1) That the presence of manganese within the molten pig iron is not required for efiicient desulphurization with these sulphide reagents was shown in tests that I made with another molten pig iron that contained 4.25% carbon, 1.25% silicon, 0.08% manganese and 0.097% sulphur. Sodium sulphide lowered the sulphur in this pig iron to 0.010 and the manganese to 0.06%, while aluminum sulphide lowered the sulphur to 0.010% and the manganese to 0.05%. Here, it may be assumed that the reaction mechanism is the extraction process where FeS(in the metal) FeS(in the slag) (2) These molten sulphides react with the oxygen in the air to form the corresponding sulphates. I protect the molten sulphides from such oxidation by sometimes covering the molten slag with powdered charcoal, and sometimes covering said molten slag with methane. The molten sulphides tend to fume, particularly the potassium sulphide. Fuming may be minimized by employing low extraction temperatures, and by employing the non-volatile-solute effect, wherein the boiling point of the sulphide is elevated by dissolving therein a solute that is non-volatile. When employing sodium or potassium sulphide, I use 2. 7 either aluminum or cale'= m sulphide to elevate the boiling point or the melt. other compounds". such as the corresponding oxides, may beemployed as the non-volatile solute.
Steel may be desulphurized with these sulphide reagents. Thus, in tests that I made with a,
molten steel containing 0.30% carbon, 0ig5 %.sili. con, 0.89% manganese and 0.039%. sulphur. I lowered the sulphur to 0.011% with a slaggopmposed of 90% aluminum sulphide and 10% aluminum oxide, and I lowered the sulphur to 0.012%. with a slag composed of aluminum sulphide, 10% aluminum oxide, 15% sodium sulphide and 15% potassium sulphide.
While I prefer sodium sulphide, or potassium sulphide, or aluminum sulphide, or combiner-I tions of these three sulphides, the use ofother similar sulphides is of-course permissible. Thus, as. previousl mentioned. I have employed cale i m phide in these reagent slaessandi I. have on occasion used beryllium sulphide as a substitute for aluminum sulphide. To be employed in my reagent slag, a sulphide must be essentially immiscible in the molten metal that is to be desulphurized; must be a solvent for the sulphides which are to be extracted from said molten metal; and must be the sulphide of a metal whose affinity for sulphur exceeds the afiinity for sulphur exhibited by the molten metal that is to be treated.
I have furthermore found that the addition of aluminum to the molten metal will greatly improve the efiectiveness of my reagent slags. Thus, in a test that I made with a molten iron containing 0.177% sulphur, I added a slight excess of aluminum to said molten iron before treating said iron with a molten sulphide slag consisting of aluminum sulphide and 10% aluminum oxide, said excess being figured on the basis of 3MnS+2Al Al-2S3+3Mn (3) This aluminum-treated metal showed 0.008% sulphur after said treatment with said slag. Without said aluminum addition to said metal, said slag was capable of lowering the sulphur content of said metal to 0.052%--the same weight of slag being employed in both tests, of course. In another test that I made with this molten iron containing 0.177% sulphur, I treated the aluminum-treated metal with a reagent slag consisting of 40% sodium sulphide, 40% potassium sulphide and 20% aluminum sulphide, with the result that the sulphur content of said molten iron was lowered to 0.012%.
Other tests that I have made have shown that the aluminum addition need not necessarily be in excess of the requirements predicted by Reaction 3; that is, I have obtained, for example, a marked improvement in my process when the aluminum addition was only 50% of the requirements predicted by Reaction 3. I have also noted that the addition of such elements as beryllium and zirconium to the molten metal improves the efficiency of my reagents, apparently in the same manner as the aluminum addition. It seems likely that the function of the aluminum addition relates to the conversion of the sulphur content of the molten metal into sulphur compounds whose solubility products are low.
My extraction process may be carried out in any refining vessel wherein two interacting metallurgical liquids may be entertained. The teapot ladle of the iron foundry may be used, for example. Such a ladle should be covered and should possess the means for maintaining a protective atmosphere over said sulphide slag.
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 insofar as such limitations are specific in the appended claims.
I claim as my invention:
1. The method of removing sulphur from molten ferrous metal, which comprises: contacting said molten ferrous metal with a molten sulphide slag consisting essentially of a sulphide selected from the group consisting of sodium sulphide, potassium sulphide, aluminum sulphide and mixtures thereof; maintaining said molten sulphide slag in contact with said molten ferrous metal until said slag has lowered the sulphur content of said metal; and separating said molten ferrous metal from said molten sulphide slag.
2. The method according to claim 1 in which sodium sulphide is the principal desulphurizing agent in said molten sulphide slag.
3. The method according to claim 1 in which potassium sulphide is the principal desulphurizing agent in said molten sulphide slag.
4. The method according to claim 1 in which aluminum sulphide is the principal desulphurizing agent in said molten sulphide slag.
5. The method according to claim 1 in which aluminum is added to the molten sulphur-bearing metal before said metal is contacted with said molten sulphide slag.
JAIVBES FERNANDO JORDAN.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,425,701 Sem Aug. 15, 1922 1,658,879 Browne Feb. 14, 1928 1,982,959 Kuhlmann Dec. 4, 1934 2,110,066 Heuer Mar. 1, 1938 2,301,360 Brennan Nov. 10, 1942 FOREIGN PATENTS Number Country Date 685,623 Germany Dec. 21, 1939 OTHER REFERENCES Chemical Abstracts, volume 8, pages 1729 and Economic Geology, volume 28, pages 773-777 (1933).
Metals and Alloys," volume 10, page MA 18 (January) and page MA 84 (February), (1939).
Claims (1)
1. THE METHOD OF REMOVING SULPHUR FROM MOLTEN FERROUS METAL, WHICH COMPRISES: CONTACTING SAID MOLTEN FERROUS METAL WITH A MOLTEN SULPHIDE SLAG CONSISTING ESSENTIALLY OF A SULPHIDE SELECTED FROM THE GROUP CONSISTING OF SODIUM SULPHIDE, POTASSIUM SULPHIDE, ALUMINUM SULPHIDE AND MIXTURES THEREOF; MAINTAINING SAID MOLTEN SULPHIDE SLAG IN CONTACT WITH SAID MOLTEN FERROUS METAL UNTIL SAID SLAG HAS LOWERED THE SULPHUR CONTENT OF SAID METAL; AND SEPARATING SAID MOLTEN FERROUS METAL FROM SAID MOLTEN SULPHIDE SLAG.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48310A US2509189A (en) | 1948-09-08 | 1948-09-08 | Process for the removal of sulfur from ferrous metals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48310A US2509189A (en) | 1948-09-08 | 1948-09-08 | Process for the removal of sulfur from ferrous metals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2509189A true US2509189A (en) | 1950-05-23 |
Family
ID=21953857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US48310A Expired - Lifetime US2509189A (en) | 1948-09-08 | 1948-09-08 | Process for the removal of sulfur from ferrous metals |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2509189A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2995439A (en) * | 1959-02-02 | 1961-08-08 | Union Carbide Corp | Preparation of high purity chromium and other metals |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1425701A (en) * | 1919-04-04 | 1922-08-15 | Norske Elektrokemisk Ind As | Process of freeing metals from copper |
| US1658879A (en) * | 1925-10-21 | 1928-02-14 | Vere B Browne | Manufacture of alloys |
| US1982959A (en) * | 1932-06-04 | 1934-12-04 | Electro Metallurg Co | Method of refining alloys |
| US2110066A (en) * | 1935-05-09 | 1938-03-01 | Heuer Russell Pearce | Iron and steel desulphurization |
| DE685623C (en) * | 1938-09-01 | 1939-12-21 | Kaiser Wilhelm Inst Fuer Eisen | Process for decoppering copper-containing pig iron and copper-containing iron scrap |
| US2301360A (en) * | 1940-08-03 | 1942-11-10 | Electro Metallurg Co | Purification of high silicon iron alloys |
-
1948
- 1948-09-08 US US48310A patent/US2509189A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1425701A (en) * | 1919-04-04 | 1922-08-15 | Norske Elektrokemisk Ind As | Process of freeing metals from copper |
| US1658879A (en) * | 1925-10-21 | 1928-02-14 | Vere B Browne | Manufacture of alloys |
| US1982959A (en) * | 1932-06-04 | 1934-12-04 | Electro Metallurg Co | Method of refining alloys |
| US2110066A (en) * | 1935-05-09 | 1938-03-01 | Heuer Russell Pearce | Iron and steel desulphurization |
| DE685623C (en) * | 1938-09-01 | 1939-12-21 | Kaiser Wilhelm Inst Fuer Eisen | Process for decoppering copper-containing pig iron and copper-containing iron scrap |
| US2301360A (en) * | 1940-08-03 | 1942-11-10 | Electro Metallurg Co | Purification of high silicon iron alloys |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2995439A (en) * | 1959-02-02 | 1961-08-08 | Union Carbide Corp | Preparation of high purity chromium and other metals |
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