CN103966432A - Method for leaching nickel and molybdenum from amorphous nickel-molybdenum sulfide mineral by oxidative conversion - Google Patents
Method for leaching nickel and molybdenum from amorphous nickel-molybdenum sulfide mineral by oxidative conversion Download PDFInfo
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Abstract
The invention belongs to the field of metallurgical chemical industry, and particularly relates to a method for leaching nickel and molybdenum from an amorphous nickel-molybdenum sulfide mineral by oxidative conversion. According to the technical scheme, the method comprises the following steps: mixing the amorphous nickel-molybdenum sulfide mineral which is finely ground with water to prepare pulp; adding the pulp into a pressure kettle, introducing industrial oxygen, and performing temperature rising reaction under the pressure of 0.8-2.0 MPa and at the temperature of 110-200 DEG C; converting the nickel and the molybdenum into sulfates, dissolving the sulfates into a solution, and filtering the pulp to obtain a leachate containing nickel sulfate and molybdenum sulfate acyl. The characteristics of large specific surface area and high activity of the amorphous nickel-molybdenum sulfide mineral are fully utilized; under the condition that acid is not added, colloidal sulfide is directly converted into sulfuric acid and sulfate in an oxidative manner, so that the nickel and the molybdenum can be leached, the process flow is short, conventional roasting is not needed, harmful smoke pollution is avoided, the process is clean, the consumption of reagents is low, and the leaching rate of metal is high.
Description
Technical field
The invention belongs to field of metallurgy and chemical engineering, be specifically related to a kind of method of amorphousness nickelous sulfide molybdenum ore oxidation conversion leaching nickel molybdenum.
Background technology
Amorphousness nickelous sulfide molybdenum ore is a kind of multi-metal complex mineral wealth, base metal is composed and is stored in amorphousness sulfidal compound, disseminated grain size is superfine, and most carbonaceous are amorphous and are filled between quartz, sericite and kaolin particle or in crack, adopt technique of preparing to be difficult to valuable mineral separation and concentration.The technology of existing processing amorphousness nickelous sulfide molybdenum ore is mainly to use for reference molybdenum glance pyrogenic attack technique to process.Main technological method has: oxidizing roasting, calcification baking, vitriol oil slaking roasting etc.The primary process of these techniques is all the compound that is converted into the soluble salt of nickel molybdenum after the nickel molybdenum oxidation sweetening at high temperature making in amorphousness nickelous sulfide molybdenum ore or is soluble in acid (alkali), the calcining of output adopts water logging, alkali to soak mostly or the method for acidleach obtains leach liquor, obtains respectively nickel molybdenum product after purification separation.But high-temperature calcination process, the sulphur in mineral is oxidized to sulfurous gas and enters in flue gas, and the sulfur dioxide concentration in flue gas is low, be difficult to cost-effective relieving haperacidity, cause the smoke gas treatment difficulty containing sulfurous gas, sulphur can not get effective utilization, and technical process is long, metal recovery rate is lower.
For fear of the drawback of traditional sinter process, the technical process that scientific and technical personnel extract nickel molybdenum improves.The technique that the patent that application number is 201310018448.1 provides a kind of selective sulfate roasting-sulfuric acid leaching-baking tail gases to absorb relieving haperacidity, the selectivity that has realized nickel molybdenum leaches.The patent that application number is 201110252329.3 provides a kind of Technology of nickel molybdenum sulfide type mineral oxidizing roasting desulfurization-retailoring-refining desiliconization, prepares high purity nickel molybdenum alloy.In addition, for fundamentally solving the flue gas difficult treatment existing in traditional calcining process, the difficult problem that metal recovery rate is low, researchist proposes the technological line of the full hydrometallurgy of some nickel-molybdenum ores.It is that 1.5～3.5 be precipitated-supernatant liquors add the second basic oxide to regulate pH value to be the technique that 5～7 obtains nickel compound, precipitates alkaline leaching-extraction-back extraction and obtain molybdenum compound, to realize the recovery of nickel molybdenum that the patent that number of patent application is 201110042020.1 provides a kind of sodium chlorate or Potcrate Oxidation Leaching-add the first basic oxide to regulate pH value.The patent of number of patent application 201210016246.9 provides a kind of employing FeCl
3and NaClO
3carry out the technique of soak-leached mud of catalyzed oxidation alkaline leaching, realized the extraction of nickel molybdenum.85th～88 pages of " rare metal " the 31st volume special editions (in June, 2007 date of publication) improve nickel molybdenum extraction process, the technical process of ore reduction ball milling-clorox decomposition-ion-exchange-purification-crystallization-oven dry has been proposed, the ammonium molybdate product of output has reached GB MSA-1 standard, and whole process metal recovery rate is greater than 85%.Aforesaid method all can be realized the extraction of nickel molybdenum from different perspectives, respectively has superiority.But the common issue existing is not make full use of large, active high, the oxidizable mineralogical characteristic that is converted into sulfuric acid and vitriol of amorphousness nickelous sulfide molybdenum ore specific surface area.
Summary of the invention
Technical problem to be solved of the present invention is to provide a kind of method of amorphousness nickelous sulfide molybdenum ore oxidation conversion leaching nickel molybdenum, its technical process is simple, reagent consumption less, cost is low, process is clean, metal leaching rate is high, can in the aqueous solution, direct oxidation transform amorphousness nickelous sulfide molybdenum ore, generate sulfuric acid and vitriol, and realize nickel molybdenum and efficiently leach.
The technical scheme that realizes object employing of the present invention is: amorphousness nickelous sulfide molybdenum ore and water after fine grinding are sized mixing, add in autoclave pressure, pass into industrial oxygen temperature reaction, pressure is 0.8MPa～2.0MPa, temperature is 110 DEG C～200 DEG C, nickel and molybdenum are converted into vitriol and dissolve and enter solution, obtain the leach liquor of sulfur acid nickel and molybdenum trisulfate acyl by slurry filtration.
2. the method for amorphousness nickelous sulfide molybdenum ore oxidation conversion leaching nickel molybdenum according to claim 1, it is characterized in that: 1. the grinding particle size of amorphousness nickelous sulfide molybdenum ore accounts for more than 80% for being less than 0.1mm, ore particle and water are sized mixing by liquid-solid ratio 1.5:1～5:1 L/Kg; 2. the reaction times of material in autoclave pressure of sizing mixing should keep 180min～360min.
In described amorphousness nickelous sulfide molybdenum ore, nickel content accounts for 3.0%～11.7% of total mass, accounts for 2.0%～9.8% of total mass containing molybdenum amount, and sulphur content accounts for 5.0%～30.5% of total mass.
Concrete steps of the present invention and processing parameter are:
1. by the fragmentation of amorphousness nickelous sulfide molybdenum ore, be finely ground to and be less than 0.1mm part and account for the more than 80% of total mass, the breeze that fine grinding is obtained and water are sized mixing by liquid-solid ratio 1.5:1～5:1, employing acid proof pump pumps into ore pulp in autoclave pressure;
2. in still, pass into industrial oxygen, make still internal pressure remain on 0.8MPa～2.0MPa;
3. open heating system, ore pulp in still is heated up, control 110 DEG C～200 DEG C of temperature of reaction, reaction 180min～360min, and in control still, solution acidity is 5g/L～60g/L.；
4. discharge ore pulp, filter the leach liquor and the leached mud that obtain sulfur acid nickel and molybdenum trisulfate acyl.
Principle of the present invention is:
In leaching process, the gluey high reactivity sulfide of amorphousness in mineral contacts with oxygen, is sulfuric acid by highly active sulphur oxidation conversion in sulfidal compound, becomes effective leaching agent.By controlling solution acidity and extraction temperature, making the molybdenum oxidation conversion of most nickel and part is that corresponding vitriol enters solution, and iron is converted into hydrous iron oxide and stays in slag, and the molybdenum of part enters in slag with the form precipitation of molybdic acid or molybdate.Meanwhile, the iron cpd in this ore forms Fe in leaching process
3+/ Fe
2+ion pair, make the gas-solid reaction of original oxygen to directly oxidize sulfidal compound, be transformed into gas-liquid reaction and the liquid-solid reaction of ferric ion to sulfidal compound that dioxygen oxidation ferrous ion generates ferric ion, accelerate the transmission of oxygen and the oxidation conversion speed of sulfidal compound, realize nickel molybdenum and leach.
The invention has the beneficial effects as follows:
The present invention makes full use of amorphousness nickelous sulfide molybdenum ore and has large, the active high feature of specific surface area, outside not under the condition of acid adding, be directly sulfuric acid and vitriol by sulfidal compound oxidation conversion, realizing nickel molybdenum leaches, technical process is short, do not need traditional roasting, pollute without harmful smoke, process is clean, reagent consumption less, metal leaching rate is high.
Embodiment
Embodiment 1: the mass percent of amorphousness nickelous sulfide molybdenum ore main chemical compositions is Ni 11.5%, Mo 2.0%, S 30.5%, by corresponding mineral fragmentation, be finely ground to granularity and be less than 0.1mm and account for 80%.Get the sample ore after 5kg fine grinding, mix size mixing (liquid-solid ratio is 1.5:1) with 7.5L water, adopt acid proof pump that ore pulp is pumped in autoclave pressure.In still, pass into industrial oxygen, make still internal pressure remain on 0.8MPa; Open heating system, ore pulp in still is heated up, controlling temperature is 110 DEG C, reaction 360min, and it is 60g/L that reaction finishes solution acidity; Discharge ore pulp, filter, obtain leach liquor and the leached mud of sulfur acid nickel and molybdenum trisulfate acyl.Leached mud is dried, obtain dry slag 1.95kg, the chemical composition of corresponding slag is Ni 1.27%, Mo 0.98%, S 14.9%.
The technical indicator obtaining: nickel leaching yield is 92.8%, and molybdenum leaching rate is 68.2%.
Embodiment 2: the mass percent of amorphousness nickelous sulfide molybdenum ore main chemical compositions is Ni 6.2%, Mo 5.1%, S 21.8%, by corresponding mineral fragmentation, be finely ground to granularity and be less than 0.1mm and account for 80%.Get the sample ore after 3.5kg fine grinding, mix size mixing (liquid-solid ratio is 2:1) with 7.0L water, adopt acid proof pump that ore pulp is pumped in autoclave pressure.In still, pass into industrial oxygen, make still internal pressure remain on 1.2MPa; Open heating system, ore pulp in still is heated up, controlling temperature is 125 DEG C, reaction 300min, and it is 30g/L that reaction finishes solution acidity; Discharge ore pulp, filter, obtain leach liquor and the leached mud of sulfur acid nickel and molybdenum trisulfate acyl.Leached mud is dried, obtain dry slag 2.21kg, the mass percent of the chemical composition of corresponding slag is Ni 0.42%, Mo 1.75%, S 12.1%.
The technical indicator obtaining: nickel leaching yield is 95.7%, and molybdenum leaching rate is 78.3%.
Embodiment 3: the mass percent of amorphousness nickelous sulfide molybdenum ore main chemical compositions is Ni 3.0%, Mo 9.8%, S 8.0%, by corresponding mineral fragmentation, be finely ground to granularity and be less than 0.1mm and account for 80%.Get the sample ore after 1.5kg fine grinding, mix size mixing (liquid-solid ratio is 5:1) with 7.5L water, adopt acid proof pump that ore pulp is pumped in autoclave pressure.In still, pass into industrial oxygen, make still internal pressure remain on 2.0MPa; Open heating system, ore pulp in still is heated up, controlling temperature is 200 DEG C, and it is 5g/L that reaction 180min reaction finishes solution acidity; Discharge ore pulp, filter, obtain leach liquor and the leached mud of sulfur acid nickel and molybdenum trisulfate acyl.Leached mud is dried, obtain dry slag 0.92kg, the mass percent of the chemical composition of corresponding slag is Ni 0.11%, Mo 2.77%, S 4.4%.
The technical indicator obtaining: nickel leaching yield is 97.8%, and molybdenum leaching rate is 82.7%.
Claims (3)
1. the method for an amorphousness nickelous sulfide molybdenum ore oxidation conversion leaching nickel molybdenum, it is characterized in that: amorphousness nickelous sulfide molybdenum ore and water after fine grinding are sized mixing, add in autoclave pressure, pass into industrial oxygen temperature reaction, pressure is 0.8MPa～2.0MPa, temperature is 110 DEG C～200 DEG C, nickel and molybdenum is converted into vitriol and dissolves and enter solution, obtains the leach liquor of sulfur acid nickel and molybdenum trisulfate acyl by slurry filtration.
2. the method for amorphousness nickelous sulfide molybdenum ore oxidation conversion leaching nickel molybdenum according to claim 1, it is characterized in that: 1. the grinding particle size of amorphousness nickelous sulfide molybdenum ore accounts for more than 80% for being less than 0.1mm, ore particle and water are sized mixing by liquid-solid ratio 1.5:1～5:1 L/Kg; 2. the reaction times of material in autoclave pressure of sizing mixing should keep 180min～360min, and controlling solution acidity in still is 5g/L～60g/L.
3. the method for amorphousness nickelous sulfide molybdenum ore oxidation conversion leaching nickel molybdenum according to claim 1, it is characterized in that: in amorphousness nickelous sulfide molybdenum ore, nickel content accounts for 3.0%～11.7% of total mass, account for 2.0%～9.8% of total mass containing molybdenum amount, sulphur content accounts for 5.0%～30.5% of total mass.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105925796A (en) * | 2016-04-29 | 2016-09-07 | 昆明理工大学 | Method for separating and recycling nickel-molybdenum iron from black rock series nickel-molybdenum iron sulfide ores |
| CN108950199A (en) * | 2018-07-13 | 2018-12-07 | 兰州金川新材料科技股份有限公司 | A method of it being used for the nickel and cobalt solution of synthesis of ternary presoma using the preparation of nickel sulfide cobalt ore |
| CN114477319A (en) * | 2022-03-03 | 2022-05-13 | 湖南中先智能科技有限公司 | Nickel sulfate preparation process and equipment |
| CN116287683A (en) * | 2022-12-31 | 2023-06-23 | 广西中伟新能源科技有限公司 | Leaching method of sulfide minerals |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105925796A (en) * | 2016-04-29 | 2016-09-07 | 昆明理工大学 | Method for separating and recycling nickel-molybdenum iron from black rock series nickel-molybdenum iron sulfide ores |
| CN108950199A (en) * | 2018-07-13 | 2018-12-07 | 兰州金川新材料科技股份有限公司 | A method of it being used for the nickel and cobalt solution of synthesis of ternary presoma using the preparation of nickel sulfide cobalt ore |
| CN114477319A (en) * | 2022-03-03 | 2022-05-13 | 湖南中先智能科技有限公司 | Nickel sulfate preparation process and equipment |
| CN114477319B (en) * | 2022-03-03 | 2024-06-11 | 湖南中先智能科技有限公司 | Nickel sulfate preparation process and equipment |
| CN116287683A (en) * | 2022-12-31 | 2023-06-23 | 广西中伟新能源科技有限公司 | Leaching method of sulfide minerals |
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Application publication date: 20140806 |