Charge for depletion of nickel-cobalt converter slags

FIELD: nonferrous metallurgy.

SUBSTANCE: in order to reduce losses of cobalt and nickel with refuse slags and to increase recovery of valuable components into matte, charge containing sulfidizing agent, marble crumb (6-10%), and coke (15-25%) further contains 2 to 20% of aluminum-containing slag obtained in secondary aluminum processing.

EFFECT: reduced cobalt and nickel loss and lowered power and reagent consumption.

1 tbl, 2 ex

 

The invention relates to ferrous metallurgy, in particular to the technology of depletion Converter slag, and can be used in the implementation process in furnaces, with separation of matte and slag dump.

Methods impoverishment used for simultaneous recovery and sulfatirovnie oxides of non-ferrous metals and iron mixtures of pyrite and coke breeze, are used in many technological schemes. Generally, this pattern of depletion is always sequential, requires several pyrometallurgical operations and transportation melts. In General, the process is characterized by high energy consumption, low specific capacity and a low degree of depletion of the slag at one stage. To improve the economic performance of the process of impoverishment often go on the reduction of its stages, which can have a positive impact on the degree of depletion of the slag. Currently, a large number of blends and methods for depletion of toxins. To intensify the electric furnace depleted slag converting Nickel mattes, it is proposed to use as impoverishing agent mixture consisting of peristeras of sulfidization, carbon reductant and aluminium-containing material.

According to a known method [1] BOF slag containing 0-15% Cu, 0-15% Ni, 0-7% Is About, and SiO2, Fe2About3, Al2About3, CaO, MgO, mixed with one of the reducing agents - Al, CAC2, Fe - Si and subjected to melting. In the case of aluminothermic recovery enter 2-35% Al and up to 70% CaO (by weight of the mixture). After heating and melting the formed alloy based on iron, extracting heavy non-ferrous metals and waste silicate slag, which can be used for the production of refractories. The recovery is carried out in two stages. In the first stage, adding a small quantity of reducing agent is formed glandular Stein, which concentrates non-ferrous metals. This Stein is drained and returned to the head of the process, for example, reflective heat. After adding the next portion of the reducing agent is formed zhelezodelatelnye slag, depleted in non-ferrous metals. The disadvantage of this method is the formation of refractory alloys based on iron, the staging process and high energy costs. The method does not allow for the introduction of sulfidization.

By a known method [2] depletion is subjected to slag smelting of Nickel-copper concentrates containing, %: 0,2-1,0 Cu, 0.1 to 1.0 Ni, 0.1 to 0.3, 15-40 SiO2, 35-60 Fe2About3, 1-8 Al2About3, 2-20 Cao and 1-3 MgO. The slag is mixed with the carbonaceous reducing agent (1-10% by weight of slag) and aluminum (5-30%), add Cao and heated to melting. This forms a metal the economic melt iron-based in which is vested copper, Nickel and cobalt. Secondary slag consisting of silicates of calcium, aluminum and iron, becomes otvajnym. For the method has the same drawbacks as the previous one.

Method [3] is characterized by the fact that the slag melt in a stream of nitrogen under a pressure of 2.0-2.5 ATM is blown into the impoverishing mixture consisting of 10% of screenings aluminum shavings (class 5 mm), containing 52% aluminum, and 5% pyrite concentrate. The result is depletion in Stein goes 99% of Nickel, of 92.5% copper and 98.3% cobalt. Waste slag contains not more than 0,014% Nickel, of 0.085% copper and 0.007% of cobalt. This method is not used in industrial practice due to the complexity of the design of the unit, and also due to the abrasive and corrosive wear lances.

As a prototype taken charge [4], for the depletion of Converter slag, composed of Corsica (12-20%), marble chips (2-6%) and sulfidization - pyrites (35-75%). The use of such charge in the depletion of BOF slag in electric arc furnaces ensures matte with 4,36-20,0% Ni, 0.7 to 2.9 per cent and With a 5.0 29.4% of iron metal and slag from 0.14% Ni and 0,124%. The average recovery Stein: cobalt, or 48.2%, Nickel of 79.6%. To achieve high performance but the extraction of Nickel and cobalt in matte but this method requires a high consumption of reagents charge and electricity. Thus, power consumption can gain the AMB 555 kW· h/t, the consumption of Corsica to 7.5%, and pyrite up to 36.7% by weight of the Converter slag. In addition, the result is poor Stein. The method does not provide regulation of the degree of metallization of matte and recovery of oxides of iron, Nickel and cobalt to the extent necessary, and therefore the loss of the latter with the slag remain high, and the recovery Stein - low.

The task to be solved by the invention is the development charge for depletion of toxins, providing increased technical and economic indicators of the conversion process.

The technical result of using the invention is to reduce losses of cobalt and Nickel from waste slag, increasing the recovery of valuable components in Stein and reduction of specific consumption of electricity and chemicals.

This result is achieved in that famous charge for depletion of Nickel-cobalt containing BOF slag, including toxic, marble chips and sulfidization, according to the invention, further comprises aluminium-containing slag from the refining secondary aluminum in the following ratio of ingredients, % by weight:

marble chips6-10
toxic15-25
luminestra the th slag 2-20
sulfidizationrest

The essence of the invention lies in the fact that the proposed composition of the charge, including aluminium-containing slag (30-40% Altotal, 8-25% Almeth, 8-10% Fetotal, 4-8% Femeth, 10-20% Sitotal, 5-8% Simeth, 2-8% MgO and 0.8% Cao) allows you to create in the furnace conditions to improve process performance and complexity of the use of raw materials. In this case, aluminum metal will perform the role of an active reducing agent, both by direct reduction of metal oxides and the formation of Al2S3being active sulfidization and a reducing agent, and oxides of aluminum and silicon contained in the aluminum slag, will contribute to a better separation of the products of melting. In addition, when used as a reducing agent containing aluminum slag addresses the important problem of their utilization. The mixture with the addition of aluminium-containing slag reduces the duration of the direct reduction furnace slag coke and gases, which increases the productivity of the furnace. When small (less than 2.0%) aluminium-containing additives slag these positive effects do not occur due to lack of aluminum on the reduction of iron slag. The addition of slag in excess of the specified limit (20,0%) leads to excessive metallize the AI matte, allocation of ferronickel wall accretions on the hearth of the furnace and the temperature increase process. In addition, the delivery of large quantities of oxides of aluminium and silicon makes waste slag refractory, increases its viscosity and, consequently, degrades the separation of the products of melting. Sulfidization, which is used peristeraki material (pyrite), provides sulfatirovnie non-ferrous metals and the formation of low-melting matte. Marble chips allows to obtain a low-melting sulfide melt system CaO-FeS, which is also an active impoverish agent. When the amount thereof less than 6.0% increases the melting point of the slag and losses of non-ferrous metals. The introduction of a large number of marble chips (more than 10.0%) requires an increase in power consumption and has a little effect on further reducing the loss of metals from the slag. The specified number of Corsica in the blend provides the necessary restorative atmosphere in the electric furnace. When the amount thereof is less than 15% fail to achieve the desired metallization matte, and the introduction of more 25,0% - reduces the productivity of the furnace and does not affect the loss of metals. It should be noted that at high flow of Corsica formed refractory "skin" on the surface of the melt and requires the oxidation of carbon in the air.

Benchmarking declare what about the solutions to the prototype and analogues showed the charge differs from the known charge to depletion of Nickel slag the use of aluminium-containing slag from the smelting of secondary aluminum and ratio of ingredients. The optimum composition of the mixture provides getting dumped on cobalt and Nickel slag. Thus, the comparison of the proposed solutions with other technical solutions in this field of technology allows us to conclude that it complies with inventive step.

Examples of usage charge according to the tests.

Test method conducted in laboratory and industrial conditions.

To avoid strong foaming of the melt by adding aluminium-containing slag was subjected to preliminary drying, together with the rest of the mixture.

Example 1. BOF slag (0,79% Ni, 0,52%, 0,50% Femeth, 53-55% Fetotal, 1,1% S, 21-25% SiO2, 0.8% of CaO, 0.9% Of MgO and 0.3% Cr2About3) were loaded into a crucible, which was placed in an oven preheated to 1250-1300°C. After melting the slag was downloaded & tricks agents - aluminium-containing slag (34.6% of Altotal, 9,7% Almeththat 8.5% Fetotal, 14.6% of SiO2and 2.5% MgO, 0.8% Of CaO), pyrite (50,4% S, 44.0% of Fe, 0.2% of Cu), toxic (78,0%, 0,4% S and 20.0% ash content) and crumbs (51,9% CaO, 3.3% Of Al2O3, a 1.8% Fe2O3at 0.9% MgO). Impoverishing the agents are pre-mixed and dried to authorities who were not more than 4%. Once content is downloaded, the melt was kept for 10-20 minutes, the crucible was taken out from the furnace, cooled, melting products (slag and matte) determined the content of Ni, Co, Fe, S, SiO2. When using the burden of the proposed structure were obtained slag from Nickel 0,09-0,10% and cobalt - 0,07-0,11% and matte containing approximately 6.8 to 8.3% of Nickel, of 1.15 to 1.31% cobalt (table).

During the smelting of the charge outside of the proposed structure is not achieved low content of Nickel and cobalt in atalina the slag.

Example 2. The experiments were performed on an industrial scale in the electric furnace with a capacity of 2500 kW with baking area 25 meters In the electric furnace filled BOF slag on the melt filed impoverish agents is a mixture of aluminium-containing slag, pyrite, Corsica and marble chips (the composition of example 1). The original slag contained, per cent: of 0.68-1.11 Nickel, 0,17-0,25 cobalt, 21-25 silicon dioxide and 53-55 total iron. As depletion poured from the furnace (temperature 1300° (C) depleted slag and poured fresh portions of the Converter slag. After depletion of the slag contained 0,12-0,18% Nickel and 0.06 to 0.13% cobalt. In the examples, tests (table) were recycled from 72 to 1524 tons of slag. Energy consumption ranged from 314 to 339 kW·h/t of slag. Received Stein contained, per cent: from 6.4 to 10.2 Ni; 0,84-1,08 With; 62,0-62,2 Fetotal; 17,0-18,6 Femeth; 23,8-25,4 S. the Degree of extraction of the slag in Stein was 788-81,1% Nickel and 47,3-56,6% cobalt.

The economic effect from the use of this method of depletion is achieved at the expense of increasing the complexity of the use of raw materials and increasing the extraction of non-ferrous metals in Stein.

Table
The results of experiments on the depletion of BOF slag
NameLaboratory experiments (1300°)Industrial tests
1 (outside the formula)23456 (outside the formula)7 (prot otyp)8910
The content in the original slag, %

- Nickel
0,790,790,790,790,790,790,850,651,070,72
- cobalt0,520,520,520,520,520,520,190,150,240,21
-SiO221,022,323,024,224,923,422,622,623,35 24,3
- Fetotal53,055,054,554,354,153,854,554,154,154,0
- S1,11,11,11,11,11,13,13,02,303,1
The amount of the charge for depletion in % to the Converter slag16,319,717,718,0to 33.820,519,817,817,920,5
The content in the charge, %
- aluminium-containing slag1,58,215,05,019,621,10,03,63,45,3
- sulfidization63,564,454,372,749,855,373,066,763,063,5
- toxic28,018,4 22,215,324,517,621,019,723,822,4
- marble chips7,09,08,576,16,06,010,09,88,8
The content in the slag after depletion %
- Nickel0,260,100,100,110,090,160,180,120,160,15
- cobalt0,210,110,080,090,070,120,100,060,100,10
-SiO223,024,223,223,123,224,324,523,523,224,7
- Fetotal53,153,653,955,852,854,154,153,74,6 53,1
- S3,6a 3.9the 3.8a 3.94,14,34,14,24,64,4
The content in the matte, %
- Nickel3,26,88,610,68,35,96,810,28,86,4
- cobalt0,821,150,971,121,310,950,861,081,130,84
- Fetotal59,361,562,361,063,262,062,062,561,062,2
- Femeth16,918,318,517,818,917,618,217,818,6of 17.0
- S22,324,3to 25.324,724,925,0 23,824,324,625,4
Factor
distribution
[Ni]/(Ni)12,368,08696,392,236,8of 37.885,041,942,6
[Co]/(From)a 3.914.4V12,112,432,77,98,618,09,48,4
The degree of depletion
slag, %:
Nickel 67,1of 87.3of 87.386,188,679,778,881,180,479,2
the cobaltto 59.678,884,682,786,576,947,356,650,052,4
Power consumption, kW·h/t------383322314339

SOURCES of INFORMATION

1. Method of recovering metals and producing a secondary slag from base metal smelter slag: Pat. 5868872 USA, IPC 6 22 5/04/ David Krofchak, Werner Dresler; Fenicem Minerals Inc.- No. 815508; Appl. 12.3.97; Publ. 2.2.99.

2. Method of recovering metals and producing a secondary slag from base metal smelter slag: Pat. 5626646 USA, MCI 6 21 15/00/ Krofchak D.; Fenicem Minerals Inc.- No. 663724; Appl. 14.6.96; Publ. 6.5.97.

3. Reznik IA, Ermakov, H.E., Schneerson D.M. Nickel: in 3 volumes. V.3. M: Science and technology, 2003. - P.129-130.

4. Baitov A.A., naboychenko S., Pimenov LI, V.P. Zhukov, the Results of single-stage depletion Converter slag//non-ferrous metallurgy. 1997, No. 2-3. P.10-13).

The charge for depletion of Nickel - cobalt containing Converter slag containing sulfidization, marble chips, toxic, characterized in that it further comprises aluminium-containing grinding is from the recycling of aluminum, in the following ratio of ingredients, wt.%:

Marble chips6-10
Toxic15-25
Aluminium-containing slag2-20
SulfidizationRest



 

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