CN1240860C - Pyrogenic enrichment method of valuable metals in ocean cobalt-rich crusts - Google Patents

Pyrogenic enrichment method of valuable metals in ocean cobalt-rich crusts Download PDF

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Publication number
CN1240860C
CN1240860C CNB2004100466667A CN200410046666A CN1240860C CN 1240860 C CN1240860 C CN 1240860C CN B2004100466667 A CNB2004100466667 A CN B2004100466667A CN 200410046666 A CN200410046666 A CN 200410046666A CN 1240860 C CN1240860 C CN 1240860C
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cobalt
rich
manganese
crust
ore
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CN1598007A (en
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沈裕军
陈文如
钟祥
郭锋
郭伟强
王东
黄元琼
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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Abstract

A pyrogenic enrichment method of valuable metals in ocean cobalt-rich crusts relates to the field of metallurgical chemistry of ocean polymetallic minerals containing Mn, Co, Ni, Cu, P and the like. The method mainly comprises the following steps: adding SiO-containing material into cobalt-rich crust2High silicon manganese ore more than 11% to make the binary alkalinity R2(% CaO/% SiO) of the ore fed into the furnace2) Less than 0.3, adding reducing agent and adhesive, after agglomeration, adopting traditional manganese-rich slag smelting process system to make reductionThe raw materials are smelted to obtain the high-quality manganese-rich slag with low phosphorus and low iron and the smelting alloy enriched with valuable metals such as Co, Ni, Cu and the like. The obtained manganese-rich slag contains more than 34 percent of Mn and less than 0.04 percent of P. The Co, Ni and Cu contents and the direct yield in the alloy are equal to those before adding. The method is also suitable for the pyrogenic enrichment and separation of Mn, Co, Ni, Cu and P-containing minerals such as ocean polymetallic nodules and the like in other ocean mineral resources.

Description

The pyrogenic process enriching method of valuable metal in a kind of oceanic cobalt-rich crust
Technical field: the pyrogenic process enriching method that the present invention relates to contain valuable metal in metallurgical treatment process, the especially oceanic cobalt-rich crust of oceanic multi-metal mineral such as Mn, Co, Ni, Cu, P.
Background technology: the characteristics of oceanic cobalt-rich crust chemical constitution are: contain Co0.4~0.6%, and Ni0.3~0.5%, but it is low to contain Mn, is 18~20%; Containing the P height, is 0.85~1.07%; Natural alkalinity height, dual alkalinity R2 are 0.4, and ternary basicity R3 is 0.5~0.6.Up to the present, adopted exhausted oceanic cobalt-rich crust pyrogenic process enriching method and had two kinds: 1. cobalt-bearing crust only allocate into carbonaceous reducing agent one natural alkalinity (R2=0.40) carry out melting (hair support the army Shen Yujun.The pyrogenic process enrichment of valuable metal research in the oceanic cobalt-rich crust.China's manganese industry, 2000,18 (3): 31-33); 2. cobalt-bearing crust is allocated silica and carbonaceous reducing agent one simultaneously into and dual alkalinity R2 is reduced to 0.29 is carried out melting (research that the applicant had carried out, still unexposed).These two kinds of melting method can reach manganese in slag and Cu, Co, Ni, the P enrichment in alloy to some extent, realize separating of Mn and Cu, Co, Ni, Fe, P.But method 1 is unfavorable for the reduction of P because of the basicity of slag height; In order to make the good phase-splitting of slag and molten alloy, the melting separation temperature must not be lower than 1450 ℃, has surpassed the theoretical allowable temperature (being lower than 1420 ℃) of rich manganese slag melting, makes the volatilization loss of manganese increase, and P is higher in the rich manganese slag.The rich manganese slag that obtains contains Mn32.37%, P0.1%, is underproof product.Method 2 is by adding silica, make the slag dual alkalinity be reduced to 0.29, slag, well phase-splitting of iron under 1360~1420 ℃ melting separation temperature, thereby reduced the volatilization loss of Mn, improved the condition that the P reduction enters alloy simultaneously, but the silica that adds has almost all entered slag, diluted the Mn in the slag, the rich manganese slag that obtains contains Mn31.2%, and P0.07% is substandard product equally.Therefore, these two kinds of melting method all fail to reach the purpose of the qualified rich manganese slag that the cobalt-bearing crust melting can directly utilize.
Summary of the invention: the present invention is intended to develop the novel method of a kind of cobalt-bearing crust pyrogenic process enrichment.Novel method does not change the legacy equipment and the traditional technology of rich manganese slag melting, and is simple, effectively in the enrichment, obtains to contain Mn, contain all qualified rich manganese slag of P not influencing the contained Co of cobalt-bearing crust, valuable metals such as Ni, Cu in molten alloy.Rich manganese slag contains Mn>34%, P<0.04.In the alloy Co, Ni, Cu content and direct yield with add before do not flush.And can make full use of the abundant high silicon poor manganese ore of the high phosphorus resource of poor manganese ore resource, especially reserves that to utilize at present.This novel method is equally applicable to pyrogenic process enrichment that other ocean Mineral resources such as oceanic multi-metal nodule etc. contain Mn, Co, Ni, Cu, P mineral and separates.
For achieving the above object, technical scheme of the present invention is: add mass ratio in the dried cobalt-bearing crust and be 1: 0.05~0.5 and contain SiO 2>11% high bannisterite, the dual alkalinity R2 of stove ore is reduced to below 0.3, allocate reductive agent and binding agent into, after agglomeration, adopt traditional rich manganese slag melting process system to carry out retailoring, the molten alloy of valuable metals such as Co, Ni, Cu that obtained the rich manganese slag of high-quality of low-phosphorous low iron and enrichment.
The first step of present method is a batching: the addition of high silicomanganese ore is 5~50% of a cobalt-bearing crust weight, makes the dual alkalinity CaO/SiO into the stove ore 2<0.3; The addition of reductive agent is 8%~12% of cobalt-bearing crust and a high silicomanganese ore total amount; The high bannisterite that is added can be that land manganese ore, ocean contain that manganese ore produces and other contain in manganese slag, waste residue or the stove dirt one or more; Reductive agent is coke powder or coal dust.
Second step of present method is agglomeration.If the manganese ore that is added is a lump ore, can be directly into the stove melting; If fine ore then can pass through the melting of agglomeration fed to boiler with cobalt-bearing crust; Agglomeration method can adopt sintering, pelletizing or briquetting.Wherein the program of pelletizing method is:
1. dried cobalt-bearing crust, high silicomanganese ore, coke powder or coal dust are finely ground to-60 orders;
2. the binding agent that adds above-mentioned ingredients by weight 0.5~15%; Binding agent can be a kind of in water glass, Sodium salts humic acids, spent pulping liquor, waste molasses or the xylogen calcium sulfonate.
3. the admixtion behind the above-mentioned adding additives was gone into the wheel roller mixed grind 5~20 minutes;
4. in the dish pelletizer of garden, add water and make ball, green-ball moisture content 29~33%, pelletizing granularity 8~16mm;
5. the drying of pelletizing, 105~150 ℃ of drying temperatures.
The 3rd step of present method is to adopt traditional rich manganese slag melting process system to carry out retailoring, and in fusion process, the Mn of furnace charge enters slag, and Co, Ni, Cu, Fe, P enter alloy, and alloy separates by the proportion difference under molten state with the Fu Meng slag.Retailoring can be carried out in electric furnace, blast furnace or other smelting furnaces.
Adopt pyrogenic process enriching method of the present invention, realized separating of manganese and valuable metals such as cobalt, nickel, copper, not only obtained the molten alloy of valuable metals such as enriched in cobalt, nickel, copper, also obtained containing Mn, contained all qualified rich manganese slag of P.The recovery rate of valuable metals height, and realized the optimum recovery of manganese having significantly reduced follow-up material treatment capacity simultaneously, reduce and smelt construction investment and industrial scale.And can make full use of the poor manganese ore resource of the abundant high silicon of high phosphorus of poor manganese ore resource, the especially reserves that can't utilize at present.
Specific embodiment:
The main chemical compositions of used oceanic cobalt-rich crust (%): Mn19.85, Fe15.22, Co0.56, Ni0.42, Cu0.10, P0.85, SiO 210.96, CaO4.82, MgO1.84; Manganese ore A chemical ingredients (%): Mn17.82, Fe11.07, P0.22, Cu0.007, Co0.023, Ni0.072, SiO 239.50, CaO0.29, MgO0.27; Manganese ore B chemical ingredients (%): Mn41.38, Fe1.44, P0.49, Cu0.013, Co0.029, Ni0.020, SiO 219.6, CaO0.64, MgO 0.12; Coke powder contains fixed carbon 83.50%.
With the dried cobalt-bearing crust of 18.50kg, the dried manganese ore A of 1.110kg, the dried manganese ore B of 2.95kg, the dried coke powder batching of 2.44kg, and all be milled to-60 orders; Admixtion is through artificial mixing three times, goes into then that wheel roller is at first dried to be mixed 10 minutes, evenly add water 22~26Kg by every 100Kg dry mix after, mixed grind is 15 minutes again; After admixtion draws off, make ball, pelletizing granularity 8~16mm, moisture 30~32% at  1000mm garden dish machine water spray; The group of giving birth to goes into loft drier and is dried to moisture 0~6% in 105~150 ℃; Pelletizing is gone into discontinuity melting in the 60KVA direct current electric arc furnace, feeding section voltage 38~40V, electric current 400~450A, 60~80 minutes time; Fusing section voltage 35~40V, electric current 600~700A, 15~20 minutes time; Molten segmentation voltage 32~35V, electric current 1000~1030A, 10~15 minutes time.The fused scum is poured ingot mould into, separates, cools off by the proportion difference.Get alloy 3.68kg, rich manganese slag 12.48kg; Rich manganese slag contains (%) Mn37.11, P0.037, Co0.0068, Ni0.0040, Cu0.0038, Fe0.51; Mn/Fe=72.76, P/Mn=0.001; Alloy contains (%) Mn10.71, Fe75.68, Co2.80, Ni2.14, Cu0.50, P3.49; It is 91.0% that Mn goes into the slag rate, and Co goes into alloy rate 98%, and Ni goes into alloy rate 99%, and Cu goes into alloy rate 96%.

Claims (6)

1. the pyrogenic process enriching method of valuable metal in the oceanic cobalt-rich crust is characterized in that: adding quality in the dried cobalt-bearing crust is the SiO of dried cobalt-bearing crust 0.05~0.5 2>11% high bannisterite, the dual alkalinity R2 of stove ore is reduced to below 0.3, allocate a kind of binding agent agglomeration in 0.5~15% water glass, Sodium salts humic acids, spent pulping liquor, waste molasses or the xylogen calcium sulfonate of 8%~12% coke powder of cobalt-bearing crust and high silicomanganese ore total amount or coal dust and above-mentioned batching gross weight into, after the agglomeration, adopt traditional rich manganese slag melting process system to carry out retailoring, the molten alloy of Co, Ni, Cu valuable metal that obtained the rich manganese slag of high-quality of low-phosphorous low iron and enrichment.
2, the pyrogenic process enriching method of valuable metal in the oceanic cobalt-rich crust according to claim 1 is characterized in that: the high bannisterite that is added is that land manganese ore, ocean contain that manganese ore produces and other contain in manganese slag, waste residue or the stove dirt one or more.
3, the pyrogenic process enriching method of valuable metal in the oceanic cobalt-rich crust according to claim 1 is characterized in that: pelletizing, sintering or briquetting are adopted in agglomeration.
4, the pyrogenic process enriching method of valuable metal in the oceanic cobalt-rich crust according to claim 1, it is characterized in that: retailoring is carried out in electric furnace, blast furnace smelting stove.
5, according to the pyrogenic process enriching method of valuable metal in claim 1 or the 4 described oceanic cobalt-rich crusts, it is characterized in that: the pelletizing agglomeration is:
1. dried cobalt-bearing crust, high silicomanganese ore, coke powder are finely ground to-60 orders;
2. the binding agent that adds above-mentioned ingredients by weight 0.5~15%;
3. the above-mentioned admixtion that has added binding agent was gone into the wheel roller mixed grind 5~20 minutes;
4. in the dish pelletizer of garden, add water and make ball, green-ball moisture content 29~33%, pelletizing granularity 8~16mm;
5. pelletizing drying, 105~150 ℃ of drying temperatures.
6, the pyrogenic process enriching method of valuable metal in the oceanic cobalt-rich crust according to claim 1 is characterized in that: the pyrogenic process enrichment that this method is equally applicable to other ocean Mineral resources mineral that contain Mn, Co, Ni, Cu, P with separate.
CNB2004100466667A 2004-08-18 2004-08-18 Pyrogenic enrichment method of valuable metals in ocean cobalt-rich crusts Expired - Lifetime CN1240860C (en)

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Publication number Priority date Publication date Assignee Title
CN101701297B (en) * 2009-11-19 2011-07-20 长沙矿冶研究院 Ore blending and smelting method for ocean cobalt-rich crusts
CN102534202A (en) * 2012-01-31 2012-07-04 安徽朗斯特复合材料科技有限公司 Method for producing bulk manganese ore furnace charge
CN103555968B (en) * 2013-10-23 2015-11-25 北京矿冶研究总院 Novel smelting process of cobalt-manganese multi-metal ore
CN109439895A (en) * 2018-11-23 2019-03-08 江苏科技大学 A kind of restoring method of polymetallic nodules
CN114350949A (en) * 2022-01-10 2022-04-15 江西理工大学 Method for treating manganese nodule by oxygen-enriched side-blown smelting technology
CN114990348A (en) * 2022-05-30 2022-09-02 金川镍钴研究设计院有限责任公司 Method for producing blister copper from copper-nickel slag

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