AU2016360842A1 - Method and apparatus for preheating and smelting manganese ore sinter - Google Patents
Method and apparatus for preheating and smelting manganese ore sinter Download PDFInfo
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- AU2016360842A1 AU2016360842A1 AU2016360842A AU2016360842A AU2016360842A1 AU 2016360842 A1 AU2016360842 A1 AU 2016360842A1 AU 2016360842 A AU2016360842 A AU 2016360842A AU 2016360842 A AU2016360842 A AU 2016360842A AU 2016360842 A1 AU2016360842 A1 AU 2016360842A1
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- Prior art keywords
- carbonaceous gas
- carbon dioxide
- containing carbonaceous
- arc furnace
- electric arc
- Prior art date
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- 239000011572 manganese Substances 0.000 title claims abstract description 52
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000003723 Smelting Methods 0.000 title claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000007789 gas Substances 0.000 claims abstract description 95
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 72
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 238000010891 electric arc Methods 0.000 claims abstract description 47
- 238000002203 pretreatment Methods 0.000 claims abstract description 45
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000007599 discharging Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229910000914 Mn alloy Inorganic materials 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000571 coke Substances 0.000 claims description 16
- 229910021532 Calcite Inorganic materials 0.000 claims description 11
- 239000003610 charcoal Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000005201 scrubbing Methods 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003830 anthracite Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 229910000514 dolomite Inorganic materials 0.000 claims description 4
- 239000010459 dolomite Substances 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003570 air Substances 0.000 description 5
- 239000000306 component Substances 0.000 description 5
- 239000003039 volatile agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000010744 Boudouard reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000012080 ambient air Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
- C22B47/00—Obtaining manganese
- C22B47/0018—Treating ocean floor nodules
- C22B47/0027—Preliminary treatment
-
- 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
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/08—Apparatus
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
- C22B47/00—Obtaining manganese
- C22B47/0018—Treating ocean floor nodules
- C22B47/0036—Treating ocean floor nodules by dry processes, e.g. smelting
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
- C22B9/103—Methods of introduction of solid or liquid refining or fluxing agents
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
- C22B9/106—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents the refining being obtained by intimately mixing the molten metal with a molten salt or slag
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
- C22B9/226—Remelting metals with heating by wave energy or particle radiation by electric discharge, e.g. plasma
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/10—Details, accessories, or equipment peculiar to hearth-type furnaces
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ocean & Marine Engineering (AREA)
- Oceanography (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Engineering & Computer Science (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Described is a method and an apparatus for preheating and smelting manganese ore sinter. The method comprises feeding feed mixture (1) containing manganese ore sinter (2), reducing agent (3), and fluxing agent (4) into an submerged electric arc furnace (5), smelting feed mixture (1) to form a layer containing liquid manganese alloy and a layer containing slag, withdrawing liquid manganese and, discharging carbon monoxide containing carbonaceous gas (6), combusting carbon monoxide containing carbonaceous gas (6) in presence of oxygen such as air in a burner (7) to form carbon dioxide containing carbonaceous gas (9), and heating said feed mixture (1) in a pre-treatment silo (8) prior feeding said feed mixture (1) into the submerged electric arc furnace (5) with said carbon dioxide containing carbonaceous gas (9).
Description
invention
The invention relates to a method for preheating and smelting manganese ore sinter as defined in the preamble of independent claim 1.
The invention also relates to an apparatus for preheating and smelting manganese ore sinter as defined in the preamble of independent claim 14.
Objective of the invention
The object of the invention is to provide a method and an arrangement for energy efficient smelting manganese ore sinter.
Short description of the invention
The method for preheating and smelting manganese ore sinter is characterized by the definitions of independent claim 1.
Preferred embodiments of the method are defined in the dependent claims 2 to 13.
The apparatus for preheating smelting manganese ore sinter is correspondingly characterized by the definitions of independent claim 14.
Preferred embodiments of the apparatus are defined in the dependent claims 15 to 26.
The invention is based on preheating the feed mixture containing at least manganese ore sinter and reducing agent in order to eliminate the moisture from the feed mixture and to preheat the feed mixture to as high a temperature as possible without burning or loosing carbon in the reduction agent required for reduction purposes in the feed mixture.
In preheating of manganese containing, the carbon consuming reactions, especially the Boudouard reaction (C(s) + CO2(g) θ 2CO (g)), is an limiting factor. Water gas reaction occurs also, H2O + C ft H2 + CO. Thus the preheating temperature in the pre-treatment silo can locally be maximum 600 to 700 °C, depending on the reactivity of the carbon in the reducing agent of the feed mixture. The average temperature of the hot charge to the electric furnace is typically below 600°C.
Preheating of the feed mixture saves electrical energy of the submerged electric arc furnace, improves the operation, improves production and safety of the smelting by preventing reaction between carbon and oxygen in the feed mixture and prevents thus uncontrolled increase of temperature and possible explosions.
List of figures
In the following the method and the apparatus for preheating and smelting manganese ore sinter will described in more detail by referring to the figures, of which
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Figure 1 shows a flow sheet of first embodiment, and
Figure 2 shows a flow sheet of second embodiment.
Detailed description of the invention
First the method for preheating of smelting manganese ore sinter and some preferred embodiments and variants of the method will be described in greater detail.
The method comprises a feeding step for feeding feed mixture 1 comprising at least manganese ore sinter 2, reducing agent 3 , and fluxing agent 4 into an submerged electric arc furnace 5.
The method comprises a smelting step for smelting said feed mixture 1 in the submerged electric arc furnace 5 to form a layer containing liquid manganese alloy (not shown in the drawings) and a layer containing slag (not shown in the drawings) above the layer containing liquid manganese alloy.
The method comprises a withdrawing step for withdrawing liquid manganese alloy and slag separately or simultaneously from the submerged electric arc furnace 5.
The method comprises a first discharging step for discharging carbon monoxide containing carbonaceous gas 6 from the submerged electric arc furnace 5.
The method comprises a combusting step for combusting carbon monoxide containing carbonaceous gas 6 discharged in the first discharging step from the submerged electric arc furnace 5 in presence of oxygen such as air in a burner 7 to form carbon dioxide containing carbonaceous gas 9.
The feeding step of the method comprises a heating step for heating said feed mixture 1 with said carbon dioxide containing carbonaceous gas 9 formed in the combusting step in a pretreatment silo 8 prior feeding feed mixture 1 into the submerged electric arc furnace 5.
The submerged electric arc furnace 5 that is used in the method is preferably an alternating current (AC) submerged electric arc furnace 5.
The burner 7 is preferably connected to the pre-treatment silo 8 and the pre-treatment silo 8 is preferably connected to the submerged electric arc furnace 5 so that gases such as oxygen from the ambient air is prevented from entering the burner 7, the pre-treatment silo 9 and the submerged electric arc furnace 5 so as to prevent uncontrolled reactions of said feed material 1.
The manganese ore sinter 9 may have a particle size between 6 and 75 mm.
The method may include heating the feed mixture 1 in the heating step to a temperature in the range between 400 and 700°C preferably to a temperature between 500 and 650°C.
The method includes preferably, but not necessarily, adjusting the temperature of said carbon dioxide containing carbonaceous gas 9 that is used in the heating step. The temperature of the said carbon dioxide containing carbonaceous gas 9 that is used in the heating step may be controlled to a temperature in the range between 600 and 900°C.
In the burner 7, the carbon monoxide containing carbonaceous gas 6 received from the
WO 2017/089651
PCT/FI2016/050821 submerged electric arc furnace 5 is preferably burned by an air ratio below 1, such as between 0.9 and 0.95. Oxygen (O2) content in the carbon dioxide containing carbonaceous gas 9 formed in the combusting step should be very low to minimize the oxidation of carbon in the feed mixture 1. The content of carbon monoxide (CO) and hydrogen (H2) in the carbon dioxide containing carbonaceous gas 9 formed in the combusting step should be very low for avoiding the explosions in the gas lines especially between the burner 7 and the pre-treatment silo 8 or in the pre-treatment silo 8.
The method may include burning carbon monoxide containing carbonaceous gas 6 discharged from the submerged electric arc furnace 5 by means of butane in the burning step
The method may include burning carbon monoxide containing carbonaceous gas 6 discharged from the submerged electric arc furnace 5 by means of CO gas or e.g. butane (C4H10) in the burning step so that the molar ratio of air to butane is in the range between 0.9 - 0.95.
The carbon dioxide containing carbonaceous gas 9 that is formed in the combusting step and that is used in the heating step, may containing in percentages of volume:
CO2: between 25 and 35 %,
N2: between 50 and 65 %,
H2O: between 3 and 8 % H2O
O2: less than 1 %
H2: less than 1 %, and
CO: less than 2 %.
The heating step comprises preferably heating said feed mixture 1 by feeding said carbon dioxide containing carbonaceous gas 9 formed in the combusting step into the pre-treatment silo
8. In such case, the heating step includes preferably feeding said carbon dioxide containing carbonaceous gas 9 formed in the combusting step into the pre-treatment silo 8 from below so that carbon dioxide containing carbonaceous gas 9 flows in the opposite direction, such as upwards, with respect the feed mixture in the pre-treatment silo 8.
The method may, as shown in figure 2, include a first scrubbing step of the carbon monoxide gas 6 discharged from the submerged electric arc furnace 5. This is prior burning the carbon monoxide gas 6 in the burner 7.
The method may, as shown in figure 2, include a second discharging step for discharging carbon dioxide containing carbonaceous gas 9 from the pre-treatment silo 8 and for feeding carbon dioxide containing carbonaceous gas 9 discharged from the pre-treatment silo 8 to the burner 7 and/or into the carbon dioxide containing carbonaceous gas 9 that is formed in the combusting step by means of the burner 7 to adjust the temperature of the carbon dioxide containing carbonaceous gas 9 that is formed in the combusting step. In such case, the method may include a second scrubbing step for scrubbing carbon dioxide containing carbonaceous gas 9 discharged in the second discharging step from the pre-treatment silo 8 in a second scrubber
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11.
The reducing agent 3 of the feed mixture 1 may contain carbonaceous material such as metallurgical coke, anthracite or charcoal.
The fluxing agent 4 of the feed mixture 1 may contain e.g. calcite, coarse burned lime, quartz, dolomite.
The chemical analysis of the manganese ore sinter 2 is depending on the chemical analysis of manganese ore. Manganese ores are calcium based, carbonate based and oxidized based which of chemical analyses greatly varies. A possible content of the manganese ore sinter 2 is:
Mn: 40 to 55 %,
Fe: 1 to 10 %,
SiO2:4 to 10 %
MgO:0.4 to 8 %
CaO: 1.0-15%
A2O3: 1-15 %
K2O: less than 1.5 %
BaO: less than 0.6 %
Next the apparatus for preheating and smelting manganese ore sinter and some preferred embodiments and variants of the method will be described in greater detail.
The apparatus comprises a submerged electric arc furnace 5 for smelting feed mixture 1 comprising at least manganese ore sinter 2, reducing agent 3, and fluxing agent 4. A layer containing liquid manganese alloy and a layer containing slag above the layer containing liquid manganese alloy are formed in the smelting in the submerged electric arc furnace 5.
The apparatus comprises first feeding means 12 configured to feed said feed mixture 1 into the submerged electric arc furnace 5.
The apparatus comprises withdrawing means 13 for withdrawing liquid manganese and slag separately or simultaneously from the submerged electric arc furnace 5.
The apparatus comprises first discharging means 14 for discharging carbon monoxide containing carbonaceous gas 6 from the submerged electric arc furnace 5.
The apparatus comprises a burner 7 for combusting carbon monoxide containing carbonaceous gas 6 received from the first discharging means 14 in presence of oxygen such as air to form carbon dioxide containing carbonaceous gas 9.
The first feeding means 12 of the apparatus comprises a pre-treatment silo 8 for heating said feed mixture 1 with said carbon dioxide containing carbonaceous gas 9 formed by means of the burner 7 prior feeding said feed mixture 1 into the submerged electric arc furnace 5.
The submerged electric arc furnace 5 in the apparatus is preferably an alternating current (AC) submerged electric arc furnace 5.
The burner 7 is preferably connected to the pre-treatment silo 8 and the pre-treatment silo
WO 2017/089651
PCT/FI2016/050821 is preferably connected to the submerged electric arc furnace 5 so that gases such as oxygen from the ambient air is prevented from entering the burner 7, the pre-treatment silo 9 and the submerged electric arc furnace 5 so as to prevent uncontrolled reactions of said feed material 1..
The manganese ore sinter 9 may have a particle size between 6 and 75 mm.
The pre-treatment silo 8 of the apparatus may be configured to heat the feed mixture 1 to a temperature in the range between 400 and 700°C, preferable to a temperature in the range between 500 and 650°C.
The apparatus comprises preferably, but not necessarily, gas temperature adjusting means (not shown in the figures) configured to adjust the temperature of said carbon dioxide containing carbonaceous gas 9 prior feeding said carbon dioxide containing carbonaceous gas 9 to the pretreatment silo 8. The temperature of the feed carbon dioxide containing carbonaceous gas 9 that is fed to the pre-treatment silo 8 may be controlled to the range between 600 and 900°C.
In the burner 7, the carbon monoxide containing carbonaceous gas 6 received from the submerged electric arc furnace 5 is preferably burned by an air ratio below 1, such as between 0.9 and 0.95. Oxygen (O2) content in the carbon dioxide containing carbonaceous gas 9 formed in the combusting step should be very low to minimize the oxidation of carbon in the feed mixture 1. The content of carbon monoxide (CO) and hydrogen (H2) in the carbon dioxide containing carbonaceous gas 9 formed in the combusting step should be very low for avoiding the explosions in the gas lines or in the pre-treatment silo 8.
The burner 7 may be a CO, a butane, and a LPG burner.
Said carbon dioxide containing carbonaceous gas 9, that is produced by the burner 7 contains preferably, but not necessarily, in percentages of volume
CO2: between 25 and 35 %,
N2: between 50 and 65 %,
H2O: between 5 and 15 % H2O
02: less than 1 %
H2: less than 1 %, and
CO: less than 2 %
The arrangement, preferably the burner 7, is preferably configured to feed said carbon dioxide containing carbonaceous gas 9 into the pre-treatment silo 8 from below so that said carbon dioxide containing carbonaceous gas 9 flows upwards in the pre-treatment silo 8 through the feed mixture.
The apparatus may, as shown in figure 2, comprise a first scrubber 10 configured to scrub carbon monoxide containing carbonaceous gas 6 discharged from the electric arc furnace 5 prior combusting carbon monoxide to the burner 7.
The apparatus may, as shown in figure 2, comprise second discharging means 15 configured to discharge carbon dioxide containing carbonaceous gas 9 from the pre-treatment silo 8 and third feeding means (not marked with a reference numeral) configured to feed carbon
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PCT/FI2016/050821 dioxide containing carbonaceous gas 9 discharged from the second discharging means 15 to the burner 7 and/or to into carbon dioxide containing carbonaceous gas 9 formed by the burner 7 to adjust the temperature of the carbon dioxide containing carbonaceous gas 9 formed by the burner
7.
The second discharging means 15 of the apparatus may, as shown in figure 2, comprise a second scrubber 11 configured to scrub carbon dioxide containing carbonaceous gas 9 discharged from the pre-treatment silo 8. Cold and scrubbed gases removed from the carbon dioxide containing carbonaceous gas 9 in the second scrubber 11 may be used in the optional temperature adjustment means for adjusting the temperature of the carbon dioxide containing carbonaceous gas 9 that is fed to the pre-treatment silo 8.
The first feeding means 12 of the apparatus may be configured to feed reducing agent 3 containing carbonaceous material such as metallurgical coke, anthracite and/or charcoal.
The first feeding means 12 of the apparatus may be configured to feed fluxing agent 4 containing at least one of calcite, coarse burned lime, dolomite and quartz.
The first feeding means 12 of the apparatus may be configured to feed manganese ore sinter 2 containing in percentages of mass:
Mn: 40 to 55 %.
Fe: 1 to 10 %,
SiO2: 4 to 10 %
MgO: 0.4 to 8 %
CaO: 1 to 15 %
A2O3: 1 to 15 %
K2O: less than 1.5 %, and
BaO: less than 0.6 %
The first feeding means 12 may, as shown in figure 2, comprise a silo arrangement 16 comprising a first silo 17 for manganese ore sinter 2, a second silo 18 for reducing agent 3, and a third silo 19 for fluxing agent 4.
Example 1
Metallurgical coke having the composition defined in table 1 and calcite manganese ore sinter having the composition defined in column “Original sinter” in table 2 was mixed in ratio 80 percentages by weight (wt.%) calcite ore and 20 wt.% and heated in a vessel to four different temperatures: 500°C, 600°C, 700°C and 800°C. The calcite manganese ore sinter was prior the mixing crushed and sieved into a particle size of 2.38 to 6.73 mm and the metallurgical coke was prior the mixing crushed and sieved into a particle size of 0.595 to 4.76 mm
The heating was performed by induction heating and gas containing carbon dioxide and nitrogen in ratio 30% carbon dioxide and 70% was blown into the vessel to simulate actual heating conditions.
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The composition of the calcite manganese ore sinter was measured in each case: 500°C,
600°C, 700°C and 800°C. As can be seen from columns “500°C”,” 600°C”, “700°C” and “800°C” table 3, the change in the composition of the calcite manganese ore sinter was only marginal, which means for example that hardly any reduction of the oxides occurred.
Table 1. Chemical analysis of metallurgical coke
| Coke wt. % | Ash, wt. % | ||
| c | Leco 1) | 84 | |
| Cfix 6> | kem.2) | 85 | |
| s | Leco 1) | 0.78 | |
| Volatiles | kem. | 1.2 | |
| ash | kem. | 12.7 | |
| Fe | ICP 3) | 0.61 4> | 4.8 |
| SiCL | kem. | 7.144> | 56.2 |
| CaO | ICP 3) | 0.23 4> | 1.8 |
| MgO | ICP3) | 0.24 4> | 1.9 |
| AI2O3 | ICP 3) | 3.07 4> | 24.2 |
1) Leco on C, S -analyzer 2> by wet chemically 3> ICP (plasma emission spectrometer) 4) wt. % of the coke 5> ash amount in coke is 12.7 wt. % 6) Cfix - value: 100 % - (volatiles + ash + sulphur)
Table 2. Chemical analysis of the preheated sinters of calcite ore as function of preheating temperature 1) Metallic amount
| Component Original sinter | 500°C | 600°C | 700°C | 800°C | |
| Mn | 43.7 | 43.9 | 44.5 | 44.5 | 4.42 |
| C | 0.07 | 0.05 | 0.05 | 0.04 | 0.04 |
| Fe | 5.2 | 5.2 | 5.1 | 5,2 | 5.0 |
| SiO2 | 8.2 | 8.0 | 7.5 | 7.6 | 7.8 |
| MgO | 4.5 | 4.7 | 4.8 | 4.7 | 4.5 |
| CaO | 15.2 | 15.2 | 14.7 | 14.6 | 15.0 |
| AI2O3 | 0.71 | 0.72 | 0.68 | 0.71 | 0.68 |
| K2O | 0.02 | 0.01 | 0.02 | 0.02 | 0.01 |
| BaO | 0.24 | 0.24 | 0.24 | 0.23 | 0.24 |
| TiO2 | 0.04 | 0.04 | 0.04 | 0.03 | 0.03 |
| P2O5 | <0.03 | <0.03 | <0.03 | <0.03 | <0.03 |
| CoO | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Cr2O3 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| CuO | <0.01 | <0.01 | <0.01 | <0.01 | <0.01 |
| NiO | <0.01 | <0.01 | <0.01 | <0.01 | <0.01 |
| ZnO | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Fe 1> | 0.44 | 0.39 | 0.36 | 0.39 | 0.37 |
WO 2017/089651
PCT/FI2016/050821
Example 2
Metallurgical coke having the composition defined in table 1 and oxidized manganese ore sinter having the composition defined in column “Original sinter” in table 3 was mixed in ratio 80 wt.% calcite ore and 20 wt.% charcoal and heated in a vessel to four different temperatures: 500°C, 600°C, 700°C and 800°C. The oxidized manganese ore sinter was prior the mixing crushed and sieved into a particle size of 2.38 to 6.73 mm and the metallurgical coke was prior the mixing crushed and sieved into a particle size of 0.595 to 4.76 mm.
The heating was performed by induction heating and gas containing carbon dioxide and nitrogen in ratio 30% carbon dioxide and 70% was blown into the vessel to simulate actual heating conditions.
The composition of the oxidized manganese ore sinter was measured in each case: 500°C, 600°C, 700°C and 800°C. As can be seen from columns “500°C”,” 600°C”, “700°C” and “800°C” table 3, the change in the composition of the oxidized manganese ore sinter was only marginal, which means for example that hardly any reduction of the oxides occurred.
Table 3. Chemical analysis of the preheated sinters of oxidized ore as function of preheating temperature
| Compo nent Original sinter | 500°C | 600°C | 700°C | 800°C | |
| Mn | 59.0 | 60.8 | 58.9 | 59.8 | 59.7 |
| C | 0.03 | 0.03 | 0.03 | 0.15 | 0.04 |
| Fe | 2.7 | 2.6 | 3.1 | 2.7 | 3.0 |
| SiO2 | 3.4 | 3.4 | 3.3 | 3.4 | 3.1 |
| MgO | 0.28 | 0.24 | 0.41 | 0.26 | 0.39 |
| CaO | 0.62 | 0.66 | 0.53 | 0.58 | 0.66 |
| AI2O3 | 6.0 | 5.9 | 5.8 | 5.9 | 5.7 |
| K2O | 0.87 | 0.97 | 0.83 | 0.90 | 0.84 |
| BaO | 0.28 | 0.28 | 0.29 | 0.27 | 0.30 |
| TiO2 | 0.17 | 0.17 | 0.16 | 0.17 | 0.16 |
| P2O5 | 0.18 | 0.21 | 0.20 | 0.20 | 0.16 |
| CoO | 0.17 | 0.18 | 0.18 | 0.18 | 0.17 |
| Cr2O3 | 0.32 | 0.22 | 1.0 | 0.28 | 0.86 |
| CuO | 0.06 | 0.06 | 0.06 | 0.06 | 0.06 |
| NiO | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 |
| ZnO | 0.06 | 0.06 | 0.06 | 0.06 | 0.06 |
| Fe 1) | 0.57 | 0.53 | 0.37 | 0.35 | 0.42 |
1) 2)metallic amount
WO 2017/089651
PCT/FI2016/050821
Example 3
In an apparatus according to figure 2, manganese sinter as defined in table 4 was fed at a feed rate of 131 kg/h, and reducing agent as defined in row “charcoal” in table 5 was fed at a feed rate of 24 kg/h into the pre-treatment silo 8. Carbonaceous gas containing 57 vol-% N2, 30 vol.%, CO2 and 11 vol.% H2O and having a temperature of 850°C was fed at a feed rate of 970 m3/h into the pre-treatment silo 8.
Table 4: Chemical analysis of the manganese sinter, wt.%
| Component | Analysis, wt. % |
| Mn | 50.2 |
| F© total | 6.6 |
| Fe 2+ | <0.05 |
| Fe metallic | <0.1 |
| SiO2 | 6.7 |
| CaO | 1.0 |
| MgO | 0.43 |
| A2O3 | 13.2 |
| K | 1.2 |
| Ba | 0.43 |
| C. total (volatiles) | 0.03 |
| H2O | 0.26 |
Table 5. Chemical analysis of reducing agents in examples 3 and 4, wt. %.
| Component | Charcoal | Coke |
| C total | 75 | |
| Cfix | 72 | 85.0 |
| Volatiles | 26 | 3.0 |
| ASH | 2.3 | 10.2 |
| S | 0.01 | 0.65 |
| Analysis of vola | tiles of charcoal | |
| h2 | 24.6 | |
| o2 | 0.1 | |
| n2 | 0.5 | |
| CO | 36.9 | |
| CO2 | 16.5 | |
| ch4 | 21.4 | |
| h2o | 8.0 |
Carbon components of charcoal starts to gasify at 450°C.
It was observed that a mixture of where charcoal is used as reducing agent 3 can be preheated to a temperature of 400°C without the carbon gasification. The charcoal starts to oxidize either through the Boudouard reaction or through the water-gas-reaction. In addition, the oxygen content and the water in the carbon dioxide containing carbonaceous gas 9 should be low
WO 2017/089651
PCT/FI2016/050821 to avoid oxidizing of the carbon.
Example 4
In an apparatus according to figure 2, manganese sinter as defined table 4 was fed at a feed rate of 131 kg/h, and reducing agent as defined in row “Coke” in table 5 was fed at a feed rate of 24 kg/h into the pre-treatment silo 8. Carbonaceous gas containing 57 vol-% N2, 30 vol%, CO2 and 11 vol.% H2O and having a temperature of 850°C was fed at a feed rate of 970 m3/h into the pre-treatment silo 8
Carbon of coke starts to gasify at 700°C.
It was observed that a mixture of where coke is used as reducing agent 3 can be preheated to a temperature of 650°C without the carbon in the coke starts to oxidize either through the Boudouard reaction or through the water-gas-reaction. In addition, the oxygen content and the water in the carbon dioxide containing carbonaceous gas 9 should be low to avoid oxidizing of the carbon.
It is apparent to a person skilled in the art that as technology advanced, the basic idea of the invention can be implemented in various ways. The invention and its embodiments are therefore not restricted to the above examples, but they may vary within the scope of the claims.
WO 2017/089651
PCT/FI2016/050821
Claims (26)
- Claims1. A method for preheating and smelting manganese ore sinter, characterized by a feeding step for feeding feed mixture (1) containing at least manganese ore sinter (2), reducing agent (3), and fluxing agent (4) into an submerged electric arc furnace (5), by a smelting step for smelting feed mixture (1) in the submerged electric arc furnace (5) to form a layer containing liquid manganese alloy and a layer containing slag above the layer containing liquid manganese alloy, by a withdrawing step for withdrawing liquid manganese and slag from the submerged electric arc furnace (5), by a first discharging step for discharging carbon monoxide containing carbonaceous gas (6) from the submerged electric arc furnace (5), by a combusting step for combusting carbon monoxide containing carbonaceous gas (6) discharged from the submerged electric arc furnace (5) in the first discharging step in presence of oxygen such as air in a burner (7) to form carbon dioxide containing carbonaceous gas (9), by a heating step for heating said feed mixture (1) in a pre-treatment silo (8) prior feeding said feed mixture (1) into the submerged electric arc furnace (5) with said carbon dioxide containing carbonaceous gas (9) formed in the combusting step, and by heating the feed mixture (1) in the heating step by feeding said carbon dioxide containing carbonaceous gas (9) into the pre-treatment silo (8).
- 2. The method according to claim 1, characterized by the submerged electric arc furnace (5) being an alternating current (AC) submerged electric arc furnace (5).
- 3. The method according to claim 1 or 2, characterized by the manganese ore sinter (2) having a particle size between 6 and 75 mm.
- 4. The method according to any of the claims 1 to 3, characterized by heating the feed mixture (1) in the pre-treatment silo (8) in the heating step to a temperature in the range between 400 and 700°C, preferably to a temperature in the range between 500 and 650°C.
- 5. The method according to any of the claims 1 to 4, characterized by adjusting the temperature of said carbon dioxide containing carbonaceous gas (9) that is used in the heating step to a temperature in the range between 580 and 900°C.
- 6. The method according to any of the claims 1 to 5, characterized said carbon dioxide containing carbonaceous gas (9) that is used in the heating step containing in percentages ofWO 2017/089651PCT/FI2016/050821 volume:CO2: between 25 and 35 %, N2: between 50 and 65 %, H2O: between 3 and 8 % O2: less than 1 %H2: less than 1 %, and CO: less than 2 %.
- 7. The method according to any of claims 1 to 6, characterized by feeding said carbon dioxide containing carbonaceous gas (9) into the pre-treatment silo (8) in the heating step from below so that said carbon dioxide containing carbonaceous gas (9) flows upwards in the pre-treatment silo (8) through the feed mixture (1) in the pre-treatment silo (8).
- 8. The method according to any of the claims 1 to 7, characterized by scrubbing carbon monoxide containing carbonaceous gas (6) discharged in the first discharging step from the submerged electric arc furnace (5) in a first scrubber (10) prior feeding carbon monoxide containing carbonaceous gas (6) discharged in the first discharging step to the burner (7).
- 9. The method according to any of the claims 1 to 8, characterized by a second discharging step for discharging carbon dioxide containing carbonaceous gas (9) from the pre-treatment silo (8), and by feeding carbon dioxide containing carbonaceous gas (9) discharged in the second discharging step to the burner (7) and/or into carbon dioxide containing carbonaceous gas (9) that is used in the heating step to adjust the temperature of the carbon dioxide containing carbonaceous gas (9) formed in the combusting step.
- 10. The method according to any of the claims 1 to 9, characterized by scrubbing carbon dioxide containing carbonaceous gas (9) discharged in the second discharging step in a second scrubber (11) prior feeding carbon dioxide containing carbonaceous gas (9) discharged in the second discharging step to the burner (7).
- 11. The method according to any of the claims 1 to 10, characterized by the reducing agent (3) containing carbonaceous material such as coke, anthracite, and/or charcoal.WO 2017/089651PCT/FI2016/050821
- 12. The method according to any of the claims 1 to 11, characterized by the fluxing agent (4) containing at least one of calcite, coarse burned lime, dolomite and quartz.
- 13. The method according to any of the claims 1 to 12, characterized by the manganese ore sinter (2) containing in percentages of mass:Mn: 40 to 55 %,Fe: 1 to 10 %,SiO2: 4 to 10 %MgO: 0.4 to 8 %CaO: 1 to 15 %A2O3: 1 to 15 %K2O: less than 1.5 %, and BaO: less than 0.6 %
- 14. An apparatus for preheating and smelting manganese ore sinter, characterized by an submerged electric arc furnace (5) for smelting feed mixture (1) containing at least manganese ore sinter (2), reducing agent (3), and fluxing agent (4) to in the submerged electric arc furnace (5) form a layer containing liquid manganese alloy and a layer containing slag above the layer containing liquid manganese alloy, by first feeding means (12) configured to feed the feed mixture (1) into the submerged electric arc furnace (5), by withdrawing means (13) for withdrawing liquid manganese alloy and slag from the submerged electric arc furnace (5), by first discharging means (14) for discharging carbon monoxide containing carbonaceous gas (6) from the submerged electric arc furnace (5), by a burner (7) for combusting carbon monoxide containing carbonaceous gas (6) received from the first discharging means (14) in presence of oxygen such as air to form carbon dioxide containing carbonaceous gas (9), by the first feeding means (12) comprising a pre-treatment silo (8) for heating said feed mixture (1) with said carbon dioxide containing carbonaceous gas (9) prior feeding feed mixture (1) into the submerged arc furnace, and by the burner (7) being configured to feed said carbon dioxide containing carbonaceous gas (9) into the pre-treatment silo (8).
- 15. The apparatus according to claim 14, characterized by the submerged electric arc furnace (5) being an alternating current (AC) submerged electric arc furnace (5).WO 2017/089651PCT/FI2016/050821
- 16. The apparatus according to claim 14 or 15, characterized by the manganese ore sinter (2) having particle size between 6 and 75 mm.
- 17. The apparatus according to any of the claims 14 to 16, characterized by the pre-treatment silo (8) being configured to heat the feed mixture (1) to a temperature in the range between 400 and 700°C, preferably to a temperature between 500 and 650°C.
- 18. The apparatus according to any of the claims 14 to 17, characterized by gas temperature adjusting means configured to adjust the temperature of said carbon dioxide containing carbonaceous gas (9) to a temperature in the range between 580 and 900°C.
- 19. The apparatus according to any of the claims 14 to 18, characterized by said carbon dioxide containing carbonaceous gas (9) that is fed to the pre-treatment silo (8) containing in percentages of volume:CO2: between 25 and 35 %,N2: between 50 and 65 %,H2O: between 3 and 8 %O2: less than 1 %H2: less than 1 %, andCO: less than 2 %
- 20. The apparatus according to any of the claims 14 to 19, characterized by the pre-treatment silo (8) being configured to feed said carbon dioxide containing carbonaceous gas (9) into the pre-treatment silo (8) from below so that said carbon dioxide containing carbonaceous gas (9) flows upwards in the pre-treatment silo (8) .
- 21. The apparatus according to any of the claims 14 to 20, characterized by the first discharging means (14) comprising a first scrubber (10) configured to scrub carbon monoxide containing carbonaceous gas (6) discharged from submerged electric arc furnace (5) prior combusting carbon monoxide containing carbonaceous gas (6) discharged from the submerged electric arc furnace (5) in the burner (7) in presence of oxygen such as air to form carbon dioxide containing carbonaceous gas (9).
- 22. The apparatus according to any of the claims 14 to 21, characterized by second discharging means (15) configured to discharge carbon dioxide containing carbonaceous gas (9) from the pre-treatment silo (8), and by third feeding means for feeding carbon dioxide containing carbonaceous gas (9) fromWO 2017/089651PCT/FI2016/050821 the second discharging means (15) to the burner (7) and/or to into carbon dioxide containing carbonaceous gas (9) formed by the burner (7).
- 23. The apparatus according to any of the claims 14 to 22, characterized5 by the second discharging means (15) comprising a second scrubber (11) configured to scrub carbon dioxide containing carbonaceous gas (9) discharged from the pre-treatment silo (8).
- 24. The apparatus according to any of the claims 14 to 23, characterized by the first feeding means (12) being configured to feed the feed mixture (1) containing 10 reducing agent (3) containing carbonaceous material such as coke, anthracite and/or charcoal.
- 25. The apparatus according to any of the claims 14 to 24, characterized by the first feeding means (12) being configured to feed the feed mixture (1) containing fluxing agent (4) containing at least one of calcite, coarse burned lime, dolomite and quartz
- 26. The apparatus according to any of the claims 14 to 25, characterized by the first feeding means (12) being configured to feed mixture (1) containing manganese ore sinter (2) containing in percentages of mass:Mn: 40 to 55 %,20 Fe: 1 to 10 %,SiO2: 4 to 10 %MgO: 0.4 to 8 %CaO: 1 to 15 %A2O3: 1 to 15 %25 K2O: less than 1.5 %, andBaO: less than 0.6 %Fig. 1SUBSTITUTE SHEET (RULE 26)WO 2017/089651PCT/FI2016/0508212/2Fig. 2SUBSTITUTE SHEET (RULE 26)
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| FI20155868 | 2015-11-24 | ||
| FI20155868A FI127451B (en) | 2015-11-24 | 2015-11-24 | Method and apparatus for preheating and smelting manganese ore sinter |
| PCT/FI2016/050821 WO2017089651A1 (en) | 2015-11-24 | 2016-11-23 | Method and apparatus for preheating and smelting manganese ore sinter |
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| CA3134962A1 (en) * | 2019-03-27 | 2020-10-01 | The Governing Council Of The University Of Toronto | Methods for recovering a target metal from iron or steel slag using at least one of a carbothermic reduction process and a pyro-hydrometallurgical process |
| NL2026572B1 (en) * | 2020-09-29 | 2022-05-30 | Petrus Greyling Frederik | Process and system for melting agglomerates |
| NL2029142B1 (en) * | 2021-09-07 | 2023-03-21 | Petrus Greyling Frederik | Process for smelting a metalliferous feedstock |
| CN113981210A (en) * | 2021-10-29 | 2022-01-28 | 吉铁铁合金有限责任公司 | Production process for producing manganese series ferroalloy by roasting manganese ore |
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| US4307872A (en) * | 1980-07-21 | 1981-12-29 | Lectromelt Corporation | Apparatus for reducing ore |
| US4529439A (en) * | 1984-09-17 | 1985-07-16 | James C. Barber And Associates, Inc. | Energy conservation during the smelting of ores |
| CN100415909C (en) * | 2006-08-17 | 2008-09-03 | 偏关县晋电化工有限责任公司 | Production method of silicomangan of sintering powder by rotary kiln and hot filling in ore-smelting electric furnace |
| CN100497683C (en) * | 2007-07-13 | 2009-06-10 | 太原理工大学 | Method for preparing low-carbon metal manganese iron by using manganese-poor powdered ore |
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| CN102041400B (en) * | 2011-01-12 | 2012-11-07 | 董亚飞 | Process and equipment for producing high-content manganese silicon alloy from low-grade ferromanganese ore |
| CN102230115B (en) * | 2011-06-21 | 2013-03-20 | 重庆大学 | Manganese-base vanadium-containing MnAlV alloy smelted by high-phosphorus manganese ores and smelting method thereof |
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