This application is a National Phase Entry under 35 USC § 371 of PCT Patent Application Serial No. PCT/FI2015/050779 filed Nov. 10, 2015, which claims priority to Finnish Patent Application No. 20145980, filed Nov. 10, 2014, the disclosure of each of these applications is expressly incorporated herein by reference in their entirety.
The present invention relates to treatment of ore concentrate for leaching, and more particularly to a process of treating complex sulfide concentrate comprising Ni, Cu, Co, Fe and/or PGM.
CA2098521 discloses a method for producing a high-grade nickel matte and a highly oxidized slag in a flash smelting furnace, and for reducing the slag from the flash smelting furnace and for sulfidizing the resulting matte in an electric furnace. The matte produced in the flash smelting furnace and in the electric furnace are both directly conducted to further hydrometallurgical treatment. The method consists of drying, flash smelting, slag cleaning, and sulfurizing in one or two electric furnace(s) and gas cleaning for all the process step. This method requires much energy for drying, much technical oxygen for smelting and much energy for producing technical oxygen and oil or other fuel for smelting. This method requires also coke or other reductant for slag cleaning. The use of organic fuel and reductants in this process produces significant amounts of CO2 emissions. This process produces two different types of matte: matte from smelting and matte from reduction. This means, that also two different leaching processes are required. Use of fuels increases the amount of gas flow and the big gas flow requires big boiler and gas line. Further, the smelting step requires high temperatures and furnace walls much cooling water.
An object of the present invention is thus to provide a process so as to alleviate the above disadvantages. The objects of the invention are achieved by a process which is characterized by what is stated in the independent claims. The preferred embodiments of the invention are disclosed in the dependent claims.
The invention is based on the realization that it is possible to produce a single type of matte and a more economical step up when a process of the present invention is employed.
It is an advantage of the process of the present invention that it is possible to feed concentrate into the process without drying. If a small part of the concentrate fed directly to the smelting step only a small dryer is needed. Resultantly no steam and/or fuel and nitrogen or only small amount of steam and nitrogen is needed for drying.
Further with the process of the present invention that no flash smelting furnace is needed although a concentrate comprising significant amounts of MgO and other oxide material is employed. Thus no technical oxygen is needed for oxygen enrichment and no water heating in cooling staves is required. Additionally, no concentrate burner is needed as concentrate dries and reacts quickly up to target level.
In the following the invention will be described in greater detail by means of preferred embodiments with reference to the attached [accompanying] drawings, in which
The present invention provides a process of treating complex sulfide concentrate, comprising the steps of
(a) roasting a wet or slurried complex sulfide concentrate in a furnace at a temperature of at least 720° C. to obtain a calcine; and
(b) smelting the calcine obtained in step (a) under inert or oxygen free atmosphere in a smelting furnace to obtain a matte.
The process typically further comprises the step of (c) granulating the matte obtained in step (b) to obtain a granulated matte.
The process of the present invention is particularly suitable for complex sulfide concentrate comprising Ni, Cu, Co, Fe and/or PGM (platinum group metal(s)). The process of the present invention allows treatment of small deposits as well as complex sulfide ores and/or concentrates which comprise sulfides of several, at least two, metals. For example such complex sulfide concentrate can be obtained from complex sulfide ore comprising 2 to 20 wt % Ni, 0 to 15 wt % Cu, and 10 to 55 wt % Fe of the total weight of the concentrate. The concentrate typically also comprises smaller amounts other metals. Thus the term “complex sulfide concentrate” as used herein preferably refers to concentrates obtained from complex sulfide ores comprising sulfides of two or more, preferably three or more, metals.
In accordance with the process of the present invention all of the complex sulfide concentrate can be fed into the roasting step (a). Alternatively a first part of the complex sulfide concentrate is introduced into roasting step (a) and a remaining second part is introduced into smelting step (b) after drying. Typically in such case the first part is 80 to 90% of the total amount of the treated complex sulfide concentrate.
Roasting may be carried out in a drum furnace or in a fluidizing bed furnace. The fluidizing bed roasting can be accomplished either in a bubbling bed or a circulating bed. Circulating bed is possible in case where mainly iron has to be oxidized.
The desired outcome of roasting step (a) is dependent on the local oxygen pressure and temperature.
The temperature of the roasting step (a) should be at least 720° C. as sulfates are not wanted in the product and for example iron, copper and nickel form sulfates at temperatures below 700° C. The highest possible roasting temperature is depended on the composition of the concentrate as sintering of calcine or bed caused by ensuing melting is not desired. Advantageously the roasting temperature in step (a) is from 720 to 870° C., more preferably from 750 to 850, most preferably from 780 to 820° C. In temperatures above 870° C. the complex sulfide concentrates tend to produce molten phases.
Oxygen can be introduced into the roasting step (a) for example as oxygen enriched air, or any oxygen containing gas, preferably as oxygen enriched air. The required amount of oxygen in the roasting step (a) depends on the quality of the complex sulfide concentrate and the desired sulfide concentration of obtained calcine. Roasting is preferably carried out using such roasting conditions (oxygen pressure and temperature) that sulfates are not forming. The oxygen partial pressure is dependent of the wanted matte quality and is typically below 1000 Pa.
The sulfur content of the calcine is advantageously controlled. With the process of the present invention is possible to obtain calcine having sulfur content below 10% w/w. Depending of the sulfur content of the calcine, the quality of the produced matte is adjusted during roasting and/or smelting.
If quality of the matte is adjusted in the roasting step (a) oxygen coefficient is kept such that sulfur content of calcine will be such that smelted calcine with flux will produce in the smelting step (b) desired matte for leaching. For controlling, but not for completely removing, the sulfur content of the calcine it is possible to increase the temperature of the upper part of the furnace and the cyclone employed for treating the off gas obtained from the roasting step (b) by using secondary air for oxidation the sulfur of the dust. The sulfur content of the calcine will thus be controlled, but it will not be completely removed. This offers possibility to minimize retention time. The complete removal of sulfur would need longer retention time. In accordance with the present invention the sulfur content of the calcine may preferably be up to 10% w/w depending on the process type.
If quality of the matte is adjusted during smelting then dried complex sulfide concentrate is fed into the smelting step (b). The dried complex sulfide concentrate can be fed into the smelting furnace thorough a hollow electrode or using injection.
The off gas resulting from the roasting step (a) is typically led into heat recovery boiler which removes heat and produces steam. Steam can be then used from drying, leaching and other processes. Calcine dusts are typically removed from the off gas in boiler, cyclone(s) and/or electric precipitator(s). Cleaned off gas can be led to an acid plant.
When circulating bed roasting cyclone is utilized it is located before the waste heat boiler. Recovered calcine from the cyclone and the boiler can be directly introduced to smelting step (b) as due to optimized oxygen coefficient the calcine dust does not contain sulfates.
Calcine obtained from step (a) can be directly led into a smelting furnace in smelting step (b) as hot from the roasting furnace. When calcine is lead to smelting step (b) as hot, melting is quick and effective. It is typically led through a lined pipe, where it may be heated or kept as hot using off-gas of the smelting furnace, to a rotating feeding ring and onward to the smelting furnace, or using feeding pipe, where it may be heated or kept as hot using off-gas of the smelting furnace, to the smelting furnace.
Smelting in step (b) can be carried out as batches or continuously. Dry complex sulfide concentrate is mixed with the calcine obtained from step (a) and feed to the smelting furnace or calcine is fed like it was described earlier and the dried complex sulfide concentrate is injected or fed through hollow electrodes.
Smelting is preferably carried out with an electric furnace as the smelting furnace. The electric furnace may be resistance heated with Soder-berg electrodes or a DC furnace.
The gas atmosphere in smelting step (b) is inert, i.e. oxygen free. The gas flow is typically very low and therefore the amount of dust in minimized.
The temperature of the smelting step (b) is typically from 1250 to 1500° C., preferably from 1300 to 1450° C. Optimal temperature offers possibility to optimize energy requirement and recovery of valuable metals to matte.
The off gas resulting from smelting step (b) is preferably used for heating of calcine before cooling by either direct or indirect cooling and cleaned by scrubbing or with a bag filter.
Matte produced in the smelting furnace during the smelting step (b) is preferably granulated thereafter, because fine granule is possible to leach without milling.
Dusts of granulation gas can be removed by a cyclone. From the cyclone the gases can be led to a multi venture scrubber for removing sulfur dioxide and other impurities using e.g. a sodium hydroxide solution.
With the process of the present invention matte is separated from the slag very clearly. Further, the slag obtained by the process of the present invention contains no or very little copper sulfide, which could disturb the slag inertity.
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It will be obvious to a person skilled in the art that, as the technology advances, the inventive concept can be implemented in various ways. The invention and its embodiments are not limited to the examples described herein but may vary within the scope of the claims.
Complex sulfide concentrate: Cu 9%, Ni 2.3%, Co 0.1% and PGM 10 g/t, FeS 46% and gangue 54% was treated in laboratory scale using method of the present invention to produce the following slag and matte:
Perceptibly noticeable is that matte separated from the slag very clearly in these laboratory experiments. The sulfur content of the slag was very low. This means, that slag does not contain copper sulfide, which could disturb the slag inertity. This matte was mainly copper sulfide, nickel sulfide and nickel-iron sulfide. Matte contained a little amount of metallic copper, but no metallic iron.
Number | Date | Country | Kind |
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20145980 | Nov 2014 | FI | national |
Filing Document | Filing Date | Country | Kind |
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PCT/FI2015/050779 | 11/10/2015 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2016/075368 | 5/19/2016 | WO | A |
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4069041 | Gorling et al. | Jan 1978 | A |
4344792 | O'Neill | Aug 1982 | A |
5182014 | Goodman | Jan 1993 | A |
5332414 | Makinen | Jul 1994 | A |
20140026713 | Bezuidenhout et al. | Jan 2014 | A1 |
Number | Date | Country |
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2098521 | Dec 1993 | CA |
1730684 | Feb 2006 | CN |
102181662 | Sep 2011 | CN |
103572056 | Feb 2014 | CN |
0 052 595 | May 1982 | EP |
WO-9006898 | Jun 1990 | WO |
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Number | Date | Country | |
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20180298467 A1 | Oct 2018 | US |