CN1510151A

CN1510151A - Cobalt slag containing treating method

Info

Publication number: CN1510151A
Application number: CNA021587442A
Authority: CN
Inventors: 彤邓; 邓彤; 凌云汉
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2002-12-26
Filing date: 2002-12-26
Publication date: 2004-07-07

Abstract

A process for treating the cobalt contained slag includes such steps as mixing said slag with water to become slurry, adding concentrated sulfuric acid, stirring, ageing for transforming the valuable components (Co, Cu, Ni, Zn and Fe) to their solutions, and separating them by the well known technology. Its residual dregs (SiO2) can be used as building material.

Description

The treatment process of cobalt slag containing

Technical field

The invention belongs to chemical industry and field of metallurgy, relate to the treatment process of slag, especially the treatment process of cobalt slag containing.

Background technology

Slag is the main solid emission in metallurgical and the chemical engineering industry, and it causes the problem of three aspects at least: (1) land occupation.According to estimates, China only copper nickel smeltery will produce nearly 3,000,000 tons of slags every year, also has the old slag of accumulation of storing up more than 1,500 ten thousand tons.Need take a large amount of soils for its slag field of storing up.(2) contaminate environment.Contain heavy metal and other poisonous elements in the slag, be subjected to the erosion of various weather condition in the process of storing up, dissolving enters environment gradually, constantly polluted-water and soil.(3) waste resource.Often contain various metallic elements in the slag, especially the metallurgical slag enormous amount is the principal mode of Metal smelting loss.Some are worth higher strategy metal such as cobalt etc., and sizable part can enter the slag phase when pyrometallurgical smelting, for example enters flash slag or converter slag.As not handling recovery, then finally all lose with waste.Therefore, the processing of slag and utilization, existing tangible economic implications has important Significance for Environment again.

Present industrial employing or exploitation in the treatment process of cobalt slag containing mainly contain two classes (Norbert L.Piret, JOM, Vol.54, No 10,1998, p.42): a class is with various pyrometallurgy methods, comprises direct Returning smelting or carries out the melting of slag separately with various metallurgical furnaces in the presence of vulcanizing agent and reductive agent in addition, make metal in the dreg be converted into elementary state or its sulfide, form sulfonium and separate with slag.These class methods one are to have the sulfur dioxide pollution problem, and near element of those character and iron phase such as cobalt etc. enter in the slag and the rate of recovery is not high easily once more, the sulfonium that obtains are leached when extracting metal also need add reductive agent more simultaneously.Second class is with the slag sulfurization roasting, uses the source as sulphur such as pyrite, various vitriol and even sulfuric acid usually, wherein heavy metal is converted into vitriol leaches with hot water or weak acid then.There is the sulfur dioxide pollution problem equally in these class methods, but also need the investment of equipment such as stoving oven.Flotation process also can be used for handling metallurgical slag, but it only is suitable for being recovered in element such as copper and the zinc etc. that are the sulfide existence in the slag, and can not reclaim element such as the elements such as cobalt and nickel that enter wustite or ferrosilicate easily.In addition, also once tested with the direct normal pressure of dilute sulphuric acid leach (Anand S.et al., Trans.IIM, 33,1980, p.77), but the extraction time that needs is long, metal recovery rate is not high, and owing to there is silica gel to generate, leaches ore pulp and be difficult to filtration.In autoclave, press leaching (Anand S.et al. with dilute sulphuric acid oxygen, Hydrometallurgy, 10,1982, p.305) though leaching yield is made moderate progress, the service requirements corresponding apparatus of autoclave is invested, and operation easier is also high, in addition, handle with autoclave that to contain the low slag of cobalt grade also uneconomical.

Summary of the invention

The objective of the invention is to: low and form silica gel and be difficult to problem such as filtrations in order to overcome the sulfur dioxide pollution, the metal recovery rate that exist in the above-mentioned slag treatment process, provide a kind of can fully reclaim valuable components such as cobalt, copper, zinc and iron in the slag effectively, economy and environment amenable slag treatment process.

The treatment process of slag provided by the invention, this method comprises: slag and water are mixed make slurry, join the vitriol oil in the slurry then and be mixed to evenly, resulting sulfuric acid-water-slag mixture is placed and is carried out slaking.

Adopt method of the present invention to handle slag, slag is worn into powder usually earlier, and granularity is preferably less than 0.15mm, makes slag be convenient to handle and be beneficial to slag and fully contact with reactant.

In the methods of the invention, at first slag and water are mixed and make slurry, wherein the mass ratio of iron level is (0.2-10) in water and the slag: 1; With the vitriol oil, preferably adopt the vitriol oil of undiluted mistake then, join in the above-mentioned slurry of making and uniform mixing, the vitriolic consumption is whenever to contain one ton of iron in the slag to add sulfuric acid 0.5-5 ton.

Mix acid phase at this, vigorous reaction takes place rapidly in the mixture of sulfuric acid-water and slag, makes especially iron mineral and silicate decomposition of essential mineral in the slag, and components such as the cobalt in the mineral lattice, nickel, zinc change into water soluble sulfate.Emitting a large amount of heat simultaneously provides the temperature of reaction needed and evaporates redundant moisture, and makes the silicon-dioxide partial dehydration.

The mixture of the above-mentioned sulfuric acid-water that obtains-slag is remained on 0.5h to 8h between about 50 ℃ to 250 ℃, make the mineral decomposition in the slag more abundant,, silicon-dioxide is further dewatered, the solid-liquid separation after helping leaching to improve the leaching yield of metal.

Adopt the inventive method to handle the last resulting material of slag, further water or dilute acid soln leach wherein copper, cobalt, zinc, iron etc., the liquid-solid ratio, the temperature and time that leach can in very large range change with the composition and the different of character of processed slag, liquid-solid ratio generally can be at 1-10, extraction temperature is at 20-100 ℃, and extraction time is from 10min to 5h.Leaching the resulting leach liquor in back can make it to separate with insoluble leached mud with any known solid-liquid separating method, alternative solid-liquid separating method comprises sedimentation, dense and filtration, wherein the leached mud based on silicon compound can be used as material of construction, but also safety dumping; Copper in the leach liquor, cobalt, nickel, zinc, iron etc. can reclaim with any known technology.

The inventive method is particularly useful for the processing of cobalt slag containing, because carry out in the maturing process in the adding vitriol oil and placement in slurry, sulfuric acid-water-slag mixture reacts, metals such as cobalt wherein, nickel, copper, zinc, iron are converted into water-soluble form, can and separate with unreacted residue by aqueous solution leaching.

The treatment process of slag provided by the invention is for fully reclaiming effective, the economic and environment amenable cobalt slag containing treatment process of the valuable components such as cobalt, copper, nickel, zinc and iron in the slag, in simple machine and under the simple operations condition valuable component in the slag is converted into form soluble in water with inexpensive and well-off chemical, water leaches and reclaims with various known technology again.Whole process is not used the high equipment of cost, does not produce to hinder filtering colloidal state silicon, and the slag that soaks of generation mainly is made up of silicon-dioxide, can be used as material of construction.

Embodiment

The following examples just are used for specifically describing the present invention, and the present invention is not limited to these embodiment.

Embodiment 1

A kind of cobalt metallurgical slag that contains, its chemical constitution (weight percent) is as table 1.

Table 1

Elements C o Cu Fe Zn SiO ₂Al ₂O ₃MgO S CaO

Content % 0.44 2.33 51.04 4.03 24.86 1.53 0.62 0.54 0.10

Slag is milled to all by 200 mesh standard sieves, gets 20g levigated slag and place the 150mL beaker, add 25mL water, fully mix, add commercially available 93% sulfuric acid of 15mL then while stirring rapidly.Vigorous reaction takes place in this moment immediately, and follows a large amount of heat releases, and temperature moment is increased to boils.This sulfuric acid-water-slag mixture is maintained the temperature at 6h more than 75 ℃, add water to liquid-solid ratio then and leach at 5: 1.85 ℃ of extraction temperatures, extraction time 3h.Slurries filtration after the leaching, filtrate and filter residue are analyzed its chemical constitution respectively, and analytical results calculating leaching yield is as follows in view of the above: Co 93.62%, and Cu 87.23%, and Zn 85.66%, and Fe 76.28%.

Embodiment 2

A kind of nickel converter slag, its chemical constitution such as table 2.

Table 2 (weight percent)

Elements C o Ni Fe Cu SiO ₂Al ₂O ₃MgO S CaO

Content % 0.89 2.05 46.33 0.40 31.02 0.90 2.21 0.28 0.37

Slag is milled to-200 order 〉=60%, gets 1000g levigated slag and place the 10000mL beaker, add 1000mL water, fully mix, add commercially available 95% sulfuric acid of 600mL then while stirring.This sulfuric acid-water-slag mixture is maintained the temperature at 2h more than 150 ℃, add water to liquid-solid ratio then and leach at 4: 1.85 ℃ of extraction temperatures, extraction time 1h.Leaching yield is respectively: Co 94.43%, and Ni 89.36%, and Cu 82.56%, and Fe 77.68%.

Claims

1. the treatment process of a slag is characterized in that: this method comprises slag and water mixed makes slurry, joins the vitriol oil in the slurry then and is mixed to evenly, and resulting sulfuric acid-water-slag mixture is placed and carried out slaking.

2. treatment process as claimed in claim 1 is characterized in that: the consumption of described water and slag is that the mass ratio of iron level is (0.2-10) in water and the slag: 1.

3. treatment process as claimed in claim 1 is characterized in that: the consumption of the described vitriol oil is that the mass ratio of iron level is (0.5-5) in sulfuric acid and the slag: 1.

4. treatment process as claimed in claim 1 is characterized in that: it is between 50 ℃ to 250 ℃ that described sulfuric acid-water-slag mixture is placed the temperature of carrying out slaking.

5. treatment process as claimed in claim 1 is characterized in that: it is 0.5h to 8h that described sulfuric acid-water-slag mixture is placed the time of carrying out slaking.

6. treatment process as claimed in claim 1 is characterized in that: described slag is the slag that contains cobalt.

7. as claim 1 or 6 described treatment processs, it is characterized in that: described slag is the slag that granularity is not more than 0.15mm.