EP1927666B1 - A smelting process of ferronickel with nickel oxide ore containing of crystal water in a blast furnace - Google Patents

A smelting process of ferronickel with nickel oxide ore containing of crystal water in a blast furnace Download PDF

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Publication number
EP1927666B1
EP1927666B1 EP05801995.1A EP05801995A EP1927666B1 EP 1927666 B1 EP1927666 B1 EP 1927666B1 EP 05801995 A EP05801995 A EP 05801995A EP 1927666 B1 EP1927666 B1 EP 1927666B1
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Prior art keywords
ore
limestone
blast
fluorite
nickel
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EP05801995.1A
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German (de)
French (fr)
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EP1927666A1 (en
EP1927666A4 (en
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Shenjie Liu
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/02—Making special pig-iron, e.g. by applying additives, e.g. oxides of other metals
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/02—General features in the manufacture of pig-iron by applying additives, e.g. fluxing agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/008—Composition or distribution of the charge
    • 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
    • C22B1/16—Sintering; Agglomerating
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • C22B1/2413—Binding; Briquetting ; Granulating enduration of pellets

Definitions

  • the present invention relates to a method of blast-furnace smelting, more particularly to a metallurgical method of ferronickel production by blast-furnace smelting nickel oxide ore with crystal water.
  • Blast-furnace smelting may also be used, however, because Cr 2 O 3 as concomitant commonly exists in laterite nickel ore, extremely high melting point of its own can lead to large viscosity of molten iron so that molten iron containing nickel and chrome can't flow out successfully and cause severe results such as frozen furnace and damaged furnace.
  • ferronickel nickel iron
  • Patent application JP 58-213837 A discloses a metallurgical method to obtain sintering of chrome in short-time, by blending fine chrome ore, coke breeze and return ore as principal starting materials with suitable amounts of secondary starting materials such as powdered limestone and silica sand, and possibly fluorite, to prepare a starting material to be sintered.
  • the present invention provides a metallurgical method of ferronickel by blast-furnace smelting nickel oxide ore containing crystal water in one-step way.
  • the invention provides a metallurgical method of ferronickel production according to claim 1.
  • the metallurgical method of ferronickel production by blast-furnace smelting nickel oxide ore with crystal water in the present invention further includes the following steps:
  • the preferable weight ratio of the additives to the sintered ore is: fluorite 0.3 ⁇ 10% dolomite 0.5 ⁇ 5% limestone/calcium lime 8 ⁇ 20%.
  • the content of CaO in limestone is greater than 50%, while that of CaO in calcium lime is greater than 80%; the content of Mg in the dolomite is higher than 10% and that of CaF 2 in fluorite is bigger than 80%.
  • furnace temperature can reach up to about 1700 °C in the conventional blast-furnace smelting technology
  • chrome contained in nickel oxide ore mainly exists in the form of Cr 2 O 3 whose melting point is about 2300° C, consequently, the reduction degree of chrome in nickel oxide ore is limited to cause bad fluidity of the obtained molten iron and easily to produce phenomenon of frozen furnace, and even result in accidents.
  • the metallurgical method of one-step blast-furnace smelting provided by the present invention is characterized by short technical process, high yield of continuous production, total extraction of nickel, chrome and iron in laterite nickel ore once for all, high ratio of resource utilization.
  • the slag obtained by smelting is an excellent raw material to produce concrete, except the exhaustion of a given mass of CO 2 gas, no other solid or liquid wastes are produced and there is no pollution.
  • the metallurgical technology of blast-furnace smelting provided by the present invention has some advantages, for example low cost.
  • Blast furnace in the technology provided by the present invention can consume 150-200 kilowatt-hours per ton iron, while the conventional ore smelting technology need consume 2000-4000 kilowatt-hours and coke of 0.5 ton per ton iron;
  • high yield namely the mean yield of blast furnace is bigger than that of ore-smelting furnace; such as little pollution, little dust, high recovery rate of the raw materials which are respectively 97 ⁇ 98% for iron, 99% for nickel and 40 ⁇ 50% for chrome.
  • Raw ores in examples are selected from nickel and chrome iron ores imported form Bulgaria.
  • the main components in used nickel and chrome iron ore and its content are: components Fe Ni Cr Ca Si Mg Al Series code 1 7.18 4.37 11.93 18.14 21.08 0.84 6.17 2 17.81 3.21 9.26 16.25 18.27 1.18 5.77 3 26.28 2.68 8.10 14.36 17.35 1.45 4.69 4 36.54 2.30 6.32 11.87 16.09 1.64 3.14 5 43.51 1.83 4.71 8.29 15.14 1.94 2.84 6 54.26 0.57 0.35 4.57 5.88 2.11 2.11
  • the main components in obtained sintered ore and its content are: components Fe Ni Cr Ca Si Series code 1 9.01 4.23 10.29 16.17 19.14 2 23.14 3.60 7.39 14.19 16.32 3 33.83 2.97 7.10 13.24 16.10 4 46.83 2.51 5.48 12.31 14.26 5 55.59 2.13 3.62 7.25 4.77 6 65.51 0.63 0.33 3.67 2.59
  • Metallurgical technology parameters of blast furnace items Crucible diameter Vent diameter fan Wind pressure Type code Capacity of blast furnace 36 m 3 2.1 m 75 mm 230 m/s 559.95 kPa (4200 mmHg) Capacity of blast furnace 90 m 3 2.9 m 100 mm 380 m/s 613.28 kPa (4600 mmHg)
  • the main components in the obtained nickel iron by smelting and its content are: components Fe Ni Cr S P Series code 1 48.26 15.10 33.11 0.060 0.061 2 52.31 10.59 23.10 0.059 0.060 3 64.58 8.32 22.38 0.058 0.059 4 75.51 5.98 13.36 0.059 0.062 5 85.29 3.24 7.09 0.057 0.057 6 93.46 0.92 0.63 0.061 0.058

Description

    Technical field
  • The present invention relates to a method of blast-furnace smelting, more particularly to a metallurgical method of ferronickel production by blast-furnace smelting nickel oxide ore with crystal water.
    • Background of the invention
  • Global extensive uses of stainless steel and special steel lead to supply shortage and rapid rise in price of nickel metal, a main element used to smelt stainless steel and special steel. Conventional technology is mature that nickel metal is produced by mainly extracting from nickel sulfide ore, which covers 30% of the nickel resources on the earth. But at present, reserves are in shortage and resources are in crises after continuous exploitation for nearly one century. People have to pay more attention to the extraction of nickel metal from laterite nickel ore (nickel oxide ore) covering 70% of nickel resources on the earth. The main reason that laterite nickel ore hasn't been exploited on a large scale for a long time is that the technology extracting Ni from such mineral resources is characterized by high cost, technological complexity, low yield, severe pollution. At present, for high-grade laterite nickel ore (nickel content above 2.0%), ore-smelting furnace is generally used to smelt on the international, however, this method is provided with disadvantages such as high power consumption, severe environmental pollution and low yield of intermittent production. For low-grade laterite nickel ore, hydrometallurgy is commonly used, namely, a method of vitriol soaking, i.e. converting solid-state nickel oxide, chromic oxide, ferric oxide or the like in the laterite nickel ore to mixed solution of liquid-state nickel sulfate, chrome sulfate, iron sulfate (Fe2+) and the like, then separating nickel sulfate thereby, forming nickel metal only accounting for 1-2% of the gross by electrolysis with all the other components wasted. The process equipment is characterized by large one-off investment, complex process, long periodicity, severe environmental pollution. Blast-furnace smelting may also be used, however, because Cr2O3 as concomitant commonly exists in laterite nickel ore, extremely high melting point of its own can lead to large viscosity of molten iron so that molten iron containing nickel and chrome can't flow out successfully and cause severe results such as frozen furnace and damaged furnace. Many corporations and research organizations at home and abroad have studied the technology for a long time that ferronickel (nickel iron) can be obtained by blast-furnace smelting laterite nickel ore in one-step way, but hitherto no success is reported.
  • Patent RU 2,157,412 C1 discloses a metallurgical method of ferronickel production by blast-furnace including the preparation of ore, production of sinter and its charging into furnace together with coke, supply of heated air blast and discharge of heat products; in this method, prior to sintering, ore is mixed with hot nickel sinter and fluxed up to basicity CaO/SiO2=0.4-0.6, and Fe/Ni ratio is maintained within 6-12; fluorite is not used in the method of this document.
  • Patent application JP 58-213837 A discloses a metallurgical method to obtain sintering of chrome in short-time, by blending fine chrome ore, coke breeze and return ore as principal starting materials with suitable amounts of secondary starting materials such as powdered limestone and silica sand, and possibly fluorite, to prepare a starting material to be sintered.
  • Consequently, it is urgent problem to be solved in this business to find an industrial method that nickel iron is smelted directly from laterite nickel ore, which is characterized by high efficiency, low consumption, high yield, low cost and no pollution or little pollution.
    • Summary of the invention
  • To solve the above problem, the present invention provides a metallurgical method of ferronickel by blast-furnace smelting nickel oxide ore containing crystal water in one-step way.
  • The above inventive object is achieved by the following technical proposal.
  • The invention provides a metallurgical method of ferronickel production according to claim 1.
  • The metallurgical method of ferronickel production by blast-furnace smelting nickel oxide ore with crystal water in the present invention further includes the following steps:
    • Crushing and sieving the sintered blocks obtained by first sintering by means of a sieve with openings in the range between 25 and 53 µm (300-500 meshes), and then producing refined ore powder by magnetic sorting;
    • Mixing the feed of the refined ore powder with coke powder, calcium lime/limestone and sintering to obtain sintered ore blocks;
    • Mixing the sintered ore blocks obtained by second sintering with coke, lime/limestone, dolomite and fluorite, and then blast-furnace smelting to obtain ferronickel.
  • Wherein the preferable weight ratio of the additives to the sintered ore is:
    fluorite 0.3 ∼ 10%
    dolomite 0.5 ∼ 5%
    limestone/calcium lime 8 ∼ 20%.
  • Wherein the content of CaO in limestone is greater than 50%, while that of CaO in calcium lime is greater than 80%; the content of Mg in the dolomite is higher than 10% and that of CaF2 in fluorite is bigger than 80%.
  • Compared with the prior art, furnace temperature can reach up to about 1700 °C in the conventional blast-furnace smelting technology, chrome contained in nickel oxide ore mainly exists in the form of Cr2O3 whose melting point is about 2300° C, consequently, the reduction degree of chrome in nickel oxide ore is limited to cause bad fluidity of the obtained molten iron and easily to produce phenomenon of frozen furnace, and even result in accidents. In metallurgical method of ferronickel production by smelting nickel and chrome iron ore provided by the present invention, the addition of fluorite can lower the influence of chrome on furnace temperature effectively and raise the fluidity of molten iron, meanwhile, because the addition quantity of fluorite in metallurgical method provided by the present invention is strictly calculated, the accidents, such as burnout of the crucible, caused by too high addition quantity of fluorite, can be effectively avoided. In the metallurgical method provided by the present invention, meanwhile, magnesium contained in dolomite may also be helpful to solve the problem on bad fluidity of molten iron caused by chrome in nickel and chrome ores. Limestone can not only provide alkalinity, but also can balance the above two additives. The metallurgical method of one-step blast-furnace smelting provided by the present invention is characterized by short technical process, high yield of continuous production, total extraction of nickel, chrome and iron in laterite nickel ore once for all, high ratio of resource utilization. The slag obtained by smelting is an excellent raw material to produce concrete, except the exhaustion of a given mass of CO2 gas, no other solid or liquid wastes are produced and there is no pollution.
  • By contrast, the metallurgical technology of blast-furnace smelting provided by the present invention has some advantages, for example low cost. Blast furnace in the technology provided by the present invention can consume 150-200 kilowatt-hours per ton iron, while the conventional ore smelting technology need consume 2000-4000 kilowatt-hours and coke of 0.5 ton per ton iron; For example economic resources, high yield, namely the mean yield of blast furnace is bigger than that of ore-smelting furnace; such as little pollution, little dust, high recovery rate of the raw materials which are respectively 97 ∼ 98% for iron, 99% for nickel and 40 ∼ 50% for chrome.
    • Specific embodiment:
  • The present invention can further be explained and described in combination with specific examples below.
  • Raw ores in examples are selected from nickel and chrome iron ores imported form Albania.
  • Crushing and sieving raw ores, mixing the feed of ore powder in grain diameter smaller than 2 mm thereof with coke powder, calcium lime/limestone and sintering to obtain sintered ore blocks;
  • Crushing and sieving the sintered blocks obtained by first sintering by means of a sieve with openings in the range between 25 and 53 µm (300-500 meshes) and then magnetic sorting to obtain refined ore powder.
  • Mixing the feed of the refined ore powder with coke powder, calcium lime/limestone and sintering to obtain sintered ore blocks.
  • Mixing sintered ore of the sintered ore blocks in particulate diameter of 10-50 mm with other raw materials and smelting to obtain ferronickel.
  • The main components in used nickel and chrome iron ore and its content (wt.%) are:
    components Fe Ni Cr Ca Si Mg Al
    Series code
    1 7.18 4.37 11.93 18.14 21.08 0.84 6.17
    2 17.81 3.21 9.26 16.25 18.27 1.18 5.77
    3 26.28 2.68 8.10 14.36 17.35 1.45 4.69
    4 36.54 2.30 6.32 11.87 16.09 1.64 3.14
    5 43.51 1.83 4.71 8.29 15.14 1.94 2.84
    6 54.26 0.57 0.35 4.57 5.88 2.11 2.11
  • The main components in obtained sintered ore and its content (wt.%) are:
    components Fe Ni Cr Ca Si
    Series code
    1 9.01 4.23 10.29 16.17 19.14
    2 23.14 3.60 7.39 14.19 16.32
    3 33.83 2.97 7.10 13.24 16.10
    4 46.83 2.51 5.48 12.31 14.26
    5 55.59 2.13 3.62 7.25 4.77
    6 65.51 0.63 0.33 3.67 2.59
  • Constitution of the furnace materials (Weight: Kg) is shown in following table.
    Components Sintered ore coke fluorite dolomite limestone/ calcium lime
    Series code
    1 1000 455 200 80 350
    2 1000 415 170 70 300
    3 1500 680 240 90 300
    4 1500 625 150 75 150
    5 2000 920 100 20 160
    6 2000 830 6 - 80
  • Metallurgical technology parameters of blast furnace:
    items Crucible diameter Vent diameter fan Wind pressure
    Type code
    Capacity of blast furnace 36 m3 2.1 m 75 mm 230 m/s 559.95 kPa (4200 mmHg)
    Capacity of blast furnace 90 m3 2.9 m 100 mm 380 m/s 613.28 kPa (4600 mmHg)
  • The main components in the obtained nickel iron by smelting and its content (wt.%) are:
    components Fe Ni Cr S P
    Series code
    1 48.26 15.10 33.11 0.060 0.061
    2 52.31 10.59 23.10 0.059 0.060
    3 64.58 8.32 22.38 0.058 0.059
    4 75.51 5.98 13.36 0.059 0.062
    5 85.29 3.24 7.09 0.057 0.057
    6 93.46 0.92 0.63 0.061 0.058

Claims (6)

  1. A metallurgical method of ferronickel production by blast-furnace smelting nickel oxide ore with crystal water containing from 0.5% to 4% by weight of nickel, from 0.3% to 12% by weight of chromium, and from 7% to 55% by weight of iron, wherein the said method of blast- furnace smelting mainly comprising the following steps:
    Crushing and sieving raw ores, mixing the feed of ore powder in grain diameter smaller than 2 mm thereof with coke powder, calcium lime/limestone and sintering to obtain sintered ore blocks;
    Mixing sintered ore blocks, coke, limestone/calcium lime, dolomite and fluorite and blast-furnace smelting to obtain ferronickel; wherein the weight ratio of the following additives to sintered ore is:
    fluorite 0.3∼20%
    dolomite 0.5∼8%
    limestone/calcium lime 4∼35%.
  2. The metallurgical method according to Claim 1, wherein the blast furnace smelting further comprising the following steps:
    Crushing and sieving the sintered blocks obtained by first sintering by means of a sieve with openings in the range between 25 an 53 µm (in 300-500 meshes) and then producing refined ore powder by magnetic sorting; Mixing the feed of the refined ore powder with coke powder, calcium lime/limestone and sintering to obtain sintered ore blocks;
    Mixing the sintered ore blocks obtained by second sintering with coke, lime/limestone, dolomite and fluorite, and then blast-furnace smelting to obtain ferronickel.
  3. The metallurgical method according to Claim 1 or 2, wherein the preferable weight ratio of the said additives to the sintered ore is:
    fluorite 0.3∼10%
    dolomite 0.5∼5%
    limestone/calcium lime 8∼20%.
  4. The metallurgical method according to Claim 1 or 2, wherein the content of CaO in the limestone is greater than 50% ,while that of CaO in calcium lime is greater than 80%.
  5. The metallurgical method according to Claim 1 or 2, wherein the content of Mg in the dolomite is higher than 10%.
  6. The metallurgical method according to Claim 1 or 2, wherein the content of CaF2 in the fluorite is bigger than 80%.
EP05801995.1A 2005-09-16 2005-11-02 A smelting process of ferronickel with nickel oxide ore containing of crystal water in a blast furnace Not-in-force EP1927666B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB200510102985XA CN1300352C (en) 2005-09-16 2005-09-16 Nickel-iron smelting process from nickel oxide ore containing crystal water through blast furnace
PCT/CN2005/001828 WO2006045254A1 (en) 2005-09-16 2005-11-02 A smelting process of ferronickel with nickel oxide ore containing of crystal water in a blast furnace

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EP1927666A1 EP1927666A1 (en) 2008-06-04
EP1927666A4 EP1927666A4 (en) 2008-12-03
EP1927666B1 true EP1927666B1 (en) 2013-04-24

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EP (1) EP1927666B1 (en)
JP (1) JP4734415B2 (en)
KR (2) KR20070085068A (en)
CN (1) CN1300352C (en)
AU (1) AU2005299184B2 (en)
MY (1) MY147763A (en)
WO (1) WO2006045254A1 (en)

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KR101536745B1 (en) * 2012-12-28 2015-07-15 재단법인 포항산업과학연구원 Material for smelting magnesium
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CN111663034B (en) * 2020-06-28 2022-10-14 宝钢德盛不锈钢有限公司 Low-cost blast furnace molten iron production process
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CN1300352C (en) 2007-02-14
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MY147763A (en) 2013-01-31
AU2005299184B2 (en) 2009-06-04
EP1927666A1 (en) 2008-06-04
EP1927666A4 (en) 2008-12-03
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KR20070085068A (en) 2007-08-27
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