US3716352A - Sintered desulfurizer for off-furnace use - Google Patents

Sintered desulfurizer for off-furnace use Download PDF

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Publication number
US3716352A
US3716352A US00082717A US3716352DA US3716352A US 3716352 A US3716352 A US 3716352A US 00082717 A US00082717 A US 00082717A US 3716352D A US3716352D A US 3716352DA US 3716352 A US3716352 A US 3716352A
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parts
weight
sodium
fluoride
calcium
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US00082717A
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H Ooi
H Nakato
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JFE Steel Corp
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Kawasaki Steel Corp
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Priority claimed from JP8466369A external-priority patent/JPS49652B1/ja
Priority claimed from JP8322470A external-priority patent/JPS4918690B1/ja
Priority claimed from JP8322370A external-priority patent/JPS4916006B1/ja
Application filed by Kawasaki Steel Corp filed Critical Kawasaki Steel Corp
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    • 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

  • a desulfurization composition for off-furnace use consisting of crushed particles of sintered material comprising 100 parts by weight of calcium oxide and 3 to 50 parts by weight, in total, of at least one compound selected from the group consisting of up to 30 parts by weight of'calcium fluoride, sodium fluoride, magnesi um fluoride, barium fluoride, and sodium silicofluoride, and up to 40 parts by weight, in terms of sodium carbonate, of sodium carbonate, sodium hydroxide, and sodium oxide.
  • the ladle After adding the desulfurizer, the ladle is preferably vibrated, shaken, or stirred for thoroughly mixing the desulfurizer with the molten pig iron.
  • Conventional desulfurizers for such purposes consist of calcium carbide (caC because calcium carbide has a high desulfurizing ability. For instance, by using 4 to 6 Kg of calcium carbide per one ton of molten pig iron, 0.05 percent of sulfur-content can be reduced to 0.01 percent, or 80 percent of desulfurization can be achieved by such addition of calcium carbide.
  • Calcium carbide has another advantage in that it is available in solid phase and never melts by itself in the ladle while being stirred. Accordingly, such solid phase desulfurizer does not cause any chemical reaction either with the refractory bricks on the ladle wall, or with the blast-furnace slag. With the desulfurizer consisting of calcium carbide, sulfur once isolated from the molten pig iron seldom redissolves in the molten iron. Furthermore, the slag formed by the desulfurization by calcium carbide is easy to remove from the ladle.
  • calcium carbide has a serious drawback in that it is rather expensive, and that it quickly reacts with water and generates acetylene gas which is very easily inflammable. Accordingly, extra care is necessary in handling calcium carbide.
  • sulfur-capturing ability of the solid desulfurizer is extremely small, and reasonable sulfur-capturing ability can be obtained only after the calcium oxide is melted.
  • a large amount solvent e.g., silica SiO alumina Al O calcium fluoride CaF has to be added. The use of large amount of such solvents tends to cool the molten pig iron.
  • the molten desulfurizer consisting of calcium oxide corrodes refractory bricks of the ladle. Accordingly, such combination of quick lime and flux material is not suitable for off-furnace use, because it causes temperature reduction of the molten pig iron.
  • the desulfurizing ability of such mixture in the case of pig iron containing 0.05 percent of sulfur is 50 percent when the mixture is added at a rate of 10 Kg of the mixture per ton of the pig iron, 60 to 65 percent when 20 Kg/ton, and 70 to 75 percent when Kg/ton.
  • about six times in weight of such mixture has to be addedin comparison with calcium carbide.
  • quick lime itself is fairly inexpensive, if a large amount of it is used, e.g., 20 Kg/ton, the total cost of desulfurizer consisting of such mixture becomes almost comparable with that of calcium carbide.
  • the use of a large amount of desulfurizer results in an increase of slag, which means more man-hours for slag removal after the desulfurization.
  • the overall efficiency of the desulfurizing process with such mixture is fairly poor.
  • Japanese Patent Publication No. 29,867/1968 discloses a desulfurizer consisting of a composite slag made by melting a mixture of quick'lime, calcium fluoride (CaF soda ash (Na CO caustic soda (NaOH), and/or calcium carbide (CaC
  • the desulfurizer of this Japanese Patent is suitable for final desulfurization of molten steel, which is refined in a special furnace, but it is not suitable for off-furnace pretreatment of starting molten pig iron for steel-making,
  • an object of the present invention is to obviate the aforesaid difficulties of conventional quick lime base desulfurizer, which consists of a mere mixture of quick lime and flux material or amolten slag of quick lime with suitable additives, by providing an improved quick lime base desulfurizer.
  • the desulfurizer of the present invention retains all the advantages of solid desulfurizer, inclusive of a desulfurizing ability which is comparable with that of calcium carbide.
  • the desulfurizer of the invention is featured in its low cost, so that it is particularly suitable for the production of a large quantity of low-sulfur steel.
  • the desulfurizer for off-furnace use consists of crushed particles of sintered material comprising parts by weight of calcium oxide and 3 to 50 parts by weight, in total, of at least one compound selected from the group consisting of up to 30 parts by weight of calcium fluoride, sodium fluoride, magnesium fluoride, barium fluoride, and
  • sodium silicofluoride and up to 40 parts by weight, in terms of sodium carbonate, of sodium carbonate, sodium hydroxide, and sodium oxide.
  • sodium carbonate refers to the number of sodium atoms in each of such compounds. For instance, 40 parts by weight of sodium carbonate is equivalent to 30 parts by weight of sodium hydroxide, as given by the following formula.
  • Specimens of desulfurizer of the invention were prepared by adding 3 to 30 parts by weight of calcium fluoride having a particle size smaller than 0.3 mm, in 100 parts by weight of a main ingredient consisting of calcium oxide of a particle size smaller than 0.3 mm, sintering the mixture thus prepared at I,200,C to 1,600C, and crushing the sintered products to a particle size of 3 mm or less.
  • Tests were made on the desulfurizing speed by using the aforesaid specimens which consisted of different amounts of calcium fluoride added in calcium oxide and sintered at I,300C. Each of the specimens for the tests was in the form of a sintered cylinder of 25 mm diameter and 30 mm height.
  • the specimen cylinders of the desulfurizer were immersed in a molten pig iron at l,350C, which contained about 0.07 percent of sulfur. Each specimen cylinder was rotated in the molten pig iron at 200 RPM.
  • FIG. 1 shows the variation of sulfur content in the molten pig iron as time elapses.
  • the addition of calcium oxide alone does not cause any material reduction in sulfur-content of the pig iron, while the desulfurizing effects increase with the addition of calcium fluoride in the calcium oxide and the desulfurizing ability of the specimens of the invention containing more than I parts by weight of calcium fluoride is superior to that of conventional calcium carbide.
  • the desulfurizing speed of the desulfurizer of the invention increases with the content of calcium fluoride of up to about parts by weight, but when the additional quantity of calcium fluoride further increases, e.g., to 35 parts by weight, the desulfurizing speed 7 decreases,. as shown in the figure.
  • the desulfurizing speed of the desulfurizer of the invention saturates at a certain addition quantity of the aforesaid compound in calcium oxide, for instance at about 30 parts by weight of calcium fluoride per 100 parts of calcium oxide.
  • magnesium fluoride, and barium fluoride also had a similar desulfurizing ability to that of FIG. 1.
  • the suitable addition quantity of such compounds to calcium oxide was found to be 3 to 30 parts per I00 parts by weight of calcium oxide.
  • the calcium oxide to be used in actual desulfurization at plant can be replaced with calcium carbonate (CaCO or calcium hydroxide (Ca(OH) which are less expensive than calcium oxide.
  • the sintering temperatures of I,200C to 1,600C also apply to calcium carbonate and calcium hydroxide base desulfurizers, which are crushed into a particle size of 4 mm of less.
  • a suitable binder such as sodium dihydrogen phosphate, calcium chloride, starch, and clay.
  • the pellets of the desulfurizer is improved, so that during the sintering process, the shape of the desulfurizer pellets can be kept intact, and its workability is improved.
  • calcium oxide alone is not effective in desulfurization, and what is effective in desulfurization seem to be dispersed mixture of calcium compound and the added compound, e.g., calcium fluoride, which mixture has a structure consisting of molecules of the ingredient compounds well dispersed therein by the sintering process. Such fact was confirmed by microscopic tests of the desulfurizer after the desulfurizing process.
  • the particle size of the ingredients in the desulfurizer is too large, the sintering time increases. More particularly, if the particle size of the ingredients exceeds 0.3 mm, it is difficult to produce desulfurizer having a sufflcient desulfurizing ability by sintering at I ,200C, for several hours.
  • Table I shows the desulfurizing ability of simple mixtures of calcium oxide and calcium fluoride.
  • Table 2 shows the desulfurizing ability of the sintered desulfurizers of the invention.
  • Table 2 also indicates the desulfurizers of non-sintered quick lime base desulfurizers containing calcium fluoride and sodium fluoride.
  • the desulfurizing ability, or the rate of desulfurization, of Tables I and 2 were determined by adding the desulfurizers in about 60 tons of molten pig iron carried by a ladle, and stirring the contents of the ladle by a gate-type impeller.
  • the desulfurizers of Table 2 were prepared by mixing calcium oxide having a particle size of about 0.2 mm with calcium fluoride having a similar particle size, sintering the mixture at I,300C for 30 minutes, and then crushing the sintered products into a particle size of about 2 mm.
  • Table I Simple mixtures consisting of parts by weight of CaO and 20 parts by weight of CaF, Temper- Quantity ature Sulfur- Sulfur- Rate of desulof Treating content, content, of furizer molten time before after desulin pig pig (minute) treating treating furiza iron iron (96) ('11) tion g 8.3 I350 10 0.043 0.023 46.5 8.4 I320 I0 0.045 0.028 37.8
  • fluoride ingredient is contained i desulfurizer and has a very stricture of sulfur. It was confirmed that no substantial redissolution of sulfur was noticed by standing the molten pig ir The slag removal after desulfurizationby the desulfurizers of the present invention proved to because the slag floats on the surface of t solid state.
  • the addition quantity of the binder in each specimen is shown in percent by weight, based on the total weight of CaCOa, NaaCOz, and CaFz.
  • Tables 4-1 and 4-2 show the compositions of the specimens thus prepared, in which the content of calcium oxide is used as the base, regardless of whether it is in the form of calcium oxide or calcium carbonate.
  • Tables 4-l and 4- It is apparent from Tables 1 and 2 that the simp mixture of the ingredients do not have a high desu furizing ability, but the sintered desulfurizer of the invention has a very desulfurizing ability.
  • the desulfurizer of the invention retains the advantages of solid state desulfurizcrs. More particularly, flux which contains a fluoride usually tends to corrode the refractory brick of the ladle wall, but with the present invention, the
  • the desired desulfurizing effects cannot be achieved by using an economical amount of the desulfurizer.
  • the desulfurizing abilities, or the rates ofclesulfuriza- 5 It is an important feature of the resent invention i bl 4-1 d 4-2 were d i d b ddi that the sintermg temperature of the desulfurrzer can the desulfurizers into a ladle carrying 60,tons of molten be not ceably reduced by using calc1um oxide material pig iron, and stirring the contents of the ladle by a gat together w1th the aforesa1d sod1um compounds.
  • type impeller with a rotary member having two vertical the slntermg temperature of the desulfunzer of Examl 10 ple l in the range of 1,200C to 1,600C can be It is apparent from the Tables 4-1 and 4-2 that excelreduced to the range of 900C to l,100C of Example lent desulfurizing effects can be achieved by the desul- 2. As compared w1th the treatmg temperature of furizers of the invention.
  • the sintering temperature is 2,000C to 2,500C necessary for the manufacture of below 800C, most of the calcium carbonate does not conventional calcium carbide desulfurizers, the dissociate, and such residual calcium carbonate conaforesaid sintering temperature range of 900C to tains about 40 wt.% of carbon dioxide which does not 1,lC of this Example of the present invention is very participate in the desulfurization, so that it becomes low, so that the desulfurizers of the invention ensures necessary to increase the addition quantity of such considerable economy while retaining the high desuldesulfurizer in the molten pig iron.
  • Example 2 the 20 furizing ability and other advantages of solid phase' desulfurizers which were sintered at 900C provided desulfurizers, as described hereinbefore referring to similar high desulfurizing effects as those sintered at Example 1.
  • 011 7 201 111. 0 1,100 0.5 1,410 10. 0 0.01:1 0. 001 75 1 110 110,001,100, M 1, 100 0. 5 1, 350 0. 0 0. 015 0. 010 71 J00 10.
  • U 1, 3-10 (1.0 0.013 0.010 70 1,100 6. 5 l, 420 10.0 0. (H2 (l. 008 75 1,000 0. 5 1,1110 0. 0 0. 045 0. 011 70 1, 000 0. 5 1, 350 0. 0 0. 050 0. 010 00 1,000 6. 5 1,350 6.0 0. 055 0.000 841 Theinvention. 1,000 0. 5 1, 350 0. 0 0. 04's 0. 014 00 1,000 0. 5 1, 230 0. 0 0. 002 0. 023 03 1,100 6.5 1,1-160 6.0 0. 045 0.030 33 Reference.
  • Desulfurizers of the invention consisting of calcium carbonate and sodium silicofluoride were prepared by thoroughly mixing ingredients as shown in Table 5, each having a particle size of about 0.2 mm,- sintering the mixture at 1,300C for 30 minutes, and crushing the sintered product into particles of about 2 mm particle I size.
  • the sintered and crushed desulfurizer of the present invention has excellow sintering temperature is as low as that of simple mixture of the ingredients.
  • the desulfurizing ability of the products is not improved but the cost of the sintering furnace and the sintering operation increases in vain.
  • the excessively high sintering temperature is, of course, undesirable from heat economy.
  • the particle size of the crushed particles of the sintered material is preferably smaller than 4 mm, in order to achieve the desirable quick desulfurizing speed for ensuring high efficiency in the desulfurizing process.
  • the desulfurizer of the present invention is a kind of solid desulfurizer, and from the macroscopic viewpoint, the particles of the desulfurizer are not melted in the molten pig iron but the particles act to capture sulfur at the surface thereof from the molten pig iron. As the sulfur is captured, the active surface area of the individual desulfurizer particles becomes smaller to reduce desulfurizing ability, and the desulfurizing time increases. Accordingly, the particle size of the desulfurizer should preferably be smaller than 4 mm.
  • a granular desulfurizer composition for quickly desulfurizing pig iron in off-furnace treatment consisting of crushed particles of material sintered at a temlent desulfurizing ability. 5O perature of 8001 ,600C whereby the sulfur content TABLE 6 Contents of NlzSlFu in Sulfur content parts by Amount of Temper in pig iron Rate of weight per Sintorinr, desulfurizer nture (percent) desulfur- 100 parts temperin molten of pig Treating ization Specimen by weight ntnrv pig iron iron time Before After (pernnmber of (130 0.) (kg/ton) C.) (minute) treating treating cent) Remark 2 1, 300 6.
  • the preferable temperature range for the sintering the material of the present invention is 800C to 1,600C. if the sintering temperature is below 800C, the desired sintering effects cannot be obtained, and the desulfurizing ability of the products made by such a is substantially reduced, comprising .100 parts by weight of calcium oxide and 3 to parts by weight, in total, of at least one compound selected from the group consisting of up to 30 parts by weight of calcium fluoride, sodium fluoride, magnesium fluoride, barium desulfurized in an'off-furnace treatment.
  • the granular desulfurizer composition according to claim 1 consisting of crushed particles of sintered material comprising 100 parts'by weight of calcium oxide and 3 to 30 parts by weight of at least one compound selected from the group consisting of calcium fluoride, sodiumfluoride, magnesium fluoride, barium I fluoride and sodium silicofluoride.
  • the granular desulfurizer composition according to Claim 1 consisting of crushed particles of sintered material comprising 100 parts by weight of calcium oxide and 3 to 40 parts by weight, in terms of sodium carbonate, of at least one compound selected from the group consisting of sodium carbonate, sodium hydroxide, and sodium oxide.
  • the granular desulfurizer composition according to Claim 1 consisting of crushed particles of sintered material comprising 100 parts by weight of calcium oxide, and 3 to 50 parts by weight of at least two compounds, at least one of said two compounds being up to 40 parts by weight, in terms of sodium carbonate, of at least one compound selected from the group consisting selected from the group consisting of up to 30 parts by weight of calcium fluoride, sodium fluoride, magnesium fluoride, barium fluoride, and sodium silicofluoride.
  • a granular desulfurizer composition for quickly desulfurizing pig iron in off-furnace treatment according to claim 1, characterized in that said sintered "material comprises a binding amount of a binder selected from the group consisting of sodium dihydrogen clay.
  • a method of making granular desulfurizer composition for quickly desulfurizing pig iron in off-furnace treatment comprising steps of thoroughly mixing parts by weight of particles of calcium oxide, said calcium oxide particles being not greater than 0.3 mm in diameter, and 3 to 50 parts by weight, in total, of particles of at least one compound selected from the group consisting of up to 30 parts by weight of calcium fluoride, sodium fluoride, magnesium fluoride, barium fluoride and sodium silicofluoride, and up to 40 parts by weight, in terms of sodium carbonate, of at least one compound selected from the group consisting of sodium carbonate, sodium hydroxide and sodium oxide,
  • said compound particles being not greater than 0.3 mm in diameter; sintering the mixture thus prepared at 800C to 1,600C, whereby the sulfur content is substantially reduced and so as to bind said calcium oxide particles with said compound; and crushing the material thus sintered into a particle size of 4 mm or smaller; whereby the pig iron is substantially desulfurized in an off-furnace treatment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
US00082717A 1969-10-24 1970-10-21 Sintered desulfurizer for off-furnace use Expired - Lifetime US3716352A (en)

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JP8466369A JPS49652B1 (enrdf_load_stackoverflow) 1969-10-24 1969-10-24
JP8322470A JPS4918690B1 (enrdf_load_stackoverflow) 1970-09-24 1970-09-24
JP8322370A JPS4916006B1 (enrdf_load_stackoverflow) 1970-09-24 1970-09-24

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816099A (en) * 1971-03-01 1974-06-11 Ici Australia Ltd Process for producing metallic iron concentrates and titanium oxide concentrates from titaniferous ores
US3932170A (en) * 1974-08-19 1976-01-13 The United States Of America As Represented By The Secretary Of The Interior Use of scavenger in recovery of metal values
US3955966A (en) * 1974-03-06 1976-05-11 August Thyssen-Hutte Ag Method for dispensing a fluidizable solid from a pressure vessel
US4008104A (en) * 1974-05-09 1977-02-15 Nippon Steel Corporation Method for dephosphorization and denitrification of an alloy containing easily oxidizable components
US4097269A (en) * 1975-01-14 1978-06-27 Inteco Internationale Technische Beratung Gesellschaft M.B.H. Process of desulfurizing liquid melts
US4159906A (en) * 1972-10-27 1979-07-03 Suddeutsche Kalkstickstoff-Werke Aktiengesellschaft Method and composition for the desulfurization of molten metals
US4315773A (en) * 1979-11-27 1982-02-16 Skw Trostberg Aktiengesellschaft Desulfurization mixture and process for desulfurizing pig iron
US4358312A (en) * 1979-12-29 1982-11-09 Hoechst Aktiengesellschaft Desulfurizing agent and process for its manufacture
USRE31676E (en) 1982-09-29 1984-09-18 Thyssen Aktiengesellschaft vorm August Thyssen-Hutte AG Method and apparatus for dispensing a fluidizable solid from a pressure vessel
EP0355526A3 (en) * 1988-08-23 1991-06-05 Giovanni Crespi Desulphurising flux composition for basic steel-slags and relevant method
US20110023657A1 (en) * 2007-09-14 2011-02-03 Tetsuharu Ibaraki Process for producing reduced iron pellets, and process for producing pig iron
US20150082944A1 (en) * 2011-09-21 2015-03-26 Pheinkalk GmbH Granules Containing Agglomerated Bulk Material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572737A (en) * 1984-06-27 1986-02-25 The Boc Group, Inc. Agents for the removal of impurities from a molten metal and a process for producing same
CN107760884A (zh) * 2017-11-14 2018-03-06 临沂鑫海新型材料有限公司 Rkef法冶炼镍铁中回转窑窑内预还原脱硫装置

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US1769986A (en) * 1927-04-26 1930-07-08 Corson Michael George Process of refining (degasifying and deoxidizing) of copper
US1921180A (en) * 1929-03-19 1933-08-08 Mathieson Alkali Works Inc Process for the purification of copper
US2117348A (en) * 1937-07-30 1938-05-17 Pittsburgh Plate Glass Co Method of and composition for purifying metals
US2462871A (en) * 1946-05-18 1949-03-01 Union Carbide & Carbon Corp Treating agent
US2527829A (en) * 1948-11-12 1950-10-31 Electro Refractories & Alloys Foundry additives
US2540173A (en) * 1948-01-30 1951-02-06 Olivo Mario Cupola briquette
US3309196A (en) * 1964-10-28 1967-03-14 Wyandotte Chemicals Corp Fluxing agent
US3537842A (en) * 1967-03-17 1970-11-03 Foseco Int Treatment of molten metal
US3567432A (en) * 1966-08-16 1971-03-02 Foseco Int Metal casting
US3598573A (en) * 1968-04-29 1971-08-10 Sueddeutsche Kalkstickstoff Desulfurization agent and process
US3615354A (en) * 1968-04-30 1971-10-26 Allegheny Ludlum Steel Method of removing contaminants from steel melts
US3619171A (en) * 1967-12-05 1971-11-09 Tno Method and a mixture for the preparation of an iron melt with a low sulphur content

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1769986A (en) * 1927-04-26 1930-07-08 Corson Michael George Process of refining (degasifying and deoxidizing) of copper
US1921180A (en) * 1929-03-19 1933-08-08 Mathieson Alkali Works Inc Process for the purification of copper
US2117348A (en) * 1937-07-30 1938-05-17 Pittsburgh Plate Glass Co Method of and composition for purifying metals
US2462871A (en) * 1946-05-18 1949-03-01 Union Carbide & Carbon Corp Treating agent
US2540173A (en) * 1948-01-30 1951-02-06 Olivo Mario Cupola briquette
US2527829A (en) * 1948-11-12 1950-10-31 Electro Refractories & Alloys Foundry additives
US3309196A (en) * 1964-10-28 1967-03-14 Wyandotte Chemicals Corp Fluxing agent
US3567432A (en) * 1966-08-16 1971-03-02 Foseco Int Metal casting
US3537842A (en) * 1967-03-17 1970-11-03 Foseco Int Treatment of molten metal
US3619171A (en) * 1967-12-05 1971-11-09 Tno Method and a mixture for the preparation of an iron melt with a low sulphur content
US3598573A (en) * 1968-04-29 1971-08-10 Sueddeutsche Kalkstickstoff Desulfurization agent and process
US3615354A (en) * 1968-04-30 1971-10-26 Allegheny Ludlum Steel Method of removing contaminants from steel melts

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816099A (en) * 1971-03-01 1974-06-11 Ici Australia Ltd Process for producing metallic iron concentrates and titanium oxide concentrates from titaniferous ores
US4159906A (en) * 1972-10-27 1979-07-03 Suddeutsche Kalkstickstoff-Werke Aktiengesellschaft Method and composition for the desulfurization of molten metals
US3955966A (en) * 1974-03-06 1976-05-11 August Thyssen-Hutte Ag Method for dispensing a fluidizable solid from a pressure vessel
US4008104A (en) * 1974-05-09 1977-02-15 Nippon Steel Corporation Method for dephosphorization and denitrification of an alloy containing easily oxidizable components
US3932170A (en) * 1974-08-19 1976-01-13 The United States Of America As Represented By The Secretary Of The Interior Use of scavenger in recovery of metal values
US4097269A (en) * 1975-01-14 1978-06-27 Inteco Internationale Technische Beratung Gesellschaft M.B.H. Process of desulfurizing liquid melts
US4315773A (en) * 1979-11-27 1982-02-16 Skw Trostberg Aktiengesellschaft Desulfurization mixture and process for desulfurizing pig iron
US4358312A (en) * 1979-12-29 1982-11-09 Hoechst Aktiengesellschaft Desulfurizing agent and process for its manufacture
USRE31676E (en) 1982-09-29 1984-09-18 Thyssen Aktiengesellschaft vorm August Thyssen-Hutte AG Method and apparatus for dispensing a fluidizable solid from a pressure vessel
EP0355526A3 (en) * 1988-08-23 1991-06-05 Giovanni Crespi Desulphurising flux composition for basic steel-slags and relevant method
US20110023657A1 (en) * 2007-09-14 2011-02-03 Tetsuharu Ibaraki Process for producing reduced iron pellets, and process for producing pig iron
US9034074B2 (en) * 2007-09-14 2015-05-19 Nippon Steel & Sumitomo Metal Corporation Process for producing reduced iron pellets, and process for producing pig iron
US20150082944A1 (en) * 2011-09-21 2015-03-26 Pheinkalk GmbH Granules Containing Agglomerated Bulk Material
US10781500B2 (en) 2011-09-21 2020-09-22 Rheinkalk Gmbh Granules containing agglomerated bulk material

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