CN105013615A - Technology for extracting scheelite from low-grade scheelite floatation tailing - Google Patents

Abstract

The invention discloses a technology for extracting scheelite from a low-grade scheelite floatation tailing, and belongs to the technical field of ore separating. The technology comprises the steps of raw ore selecting, alkali liquor circulating leaching, purifying and silica removing, de-magging and scheelite crystallization. In the alkali liquor circulating leaching operation, a scheelite tailing is placed into a sodium hydroxide solution for agitation leach, and leaching liquid can be recycled repeatedly; in the purifying and silica removing operation, hydrochloric acid is added, silicic acid sediments are filtered and removed, a magnesium chloride solution is added, and desiliconizing is further carried out; and in the scheelite crystal operation, calcium chloride and the hydrochloric acid are used as precipitating agents, the scheelite is separated by crystallization again, and a high-grade scheelite concentrate is obtained. Low-grade scheelite floatation tailing resources are reutilized, the high-grade scheelite concentrate is obtained, the technology is simple, the economic value is high, and the technology for extracting the scheelite from the low-grade scheelite floatation tailing is suitable for application and popularization.

Description

A kind of technique by extracting white tungsten in low grade white tungsten flotation tailing

Technical field

The present invention relates to a kind of ore-dressing technique extracting white tungsten from low grade white tungsten flotation tailing, belong to technical field of beneficiation.

Background technology

Tungsten is the metal that fusing point is the highest, has very high hardness simultaneously, so be widely used in Aero-Space, and electronics, the industry such as electrical equipment and chemical industry.According to statistics, the primary tungsten annual requirement in the world is 6.23 ten thousand tons in recent years.China is the abundantest country of world's tungsten ore resource, to the end of the year 2008, and tungsten ore (WO ₃) find out basic unit price 2,350,000 tons, wherein wolframite 460,000 tons, scheelite 1,710,000 tons, along with the consumption of the wolframite resource of easily choosing, scheelite has become the primary raw material of China's Tungsten smelting.But the scheelite resource of China to have rich ore few, lean ore is many, and altogether, associated minerals are many, the feature that simple ore kind is few.

In the reserves of China's tungsten ore, tungsten grade (WO ₃) be greater than 0.5% only account for 20%, and in the commercial reserves of scheelite, grade be greater than 0.5% only account for about 2%.Meanwhile, the tungsten ore of China mostly is the types such as Skarn-type tungsten deposit, hydrothermal filling many metal molds tungsten ore, postigneous stage height hydrotherm of middle temperature plough mineral deposit, and usual and copper, molybdenum, antimony, tin and gold, silver etc. are total to, association, and single mineral deposit is little.Because the grade of China's scheelite resource is low, complicated component, altogether, associated mineral is many, so ore-dressing technique is complicated, Comprehensive Recovery Technology is comparatively difficult.

The main method of scheelite ore dressing is floatation, according to the kind of gangue in mineral, can be divided into white tungsten-quartz (or silicate mineral), white tungsten-calcite, fluorite (barite) type.For white tungsten-quartz type ore, generally more easily select; White tungsten-calcite, the more difficult choosing of fluorite type, mainly because three kinds of mineral are all calcareous mineral, floatability is close, is difficult to suppress.To this kind of ore, generally adopt floatation process of heating, this technique is divided into normal temperature flotation and heating concentration two sections, roughly selects operation at normal temperature, uses sodium carbonate, NaOH, lime as inhibitor, eliminates the siliceous and calcareous gangue of part to greatest extent; In heating concentration operation, after rough concentrate is concentrated, add a large amount of waterglass, strong long-time stirring under 90 DEG C of high temperature, the suppression of strengthening gangue mineral, then dilutes normal temperature flotation.

This technique is the main technique that the white tungsten of China is produced, because the effect of the normal temperature section of roughly selecting inhibitor is poor, so the content of white tungsten is higher in this section of mine tailing; Simultaneously because scheelite is easy and calcareous gangue adhesion, fine-grained disseminated grain, waterglass consumption when suppressing of heating is very large, so the scheelite of adhesion very easily enters mine tailing.The white tungsten flotation tailing WO in current many mines ₃content reach more than 0.2%, even up to 0.4%, and these mine tailings are due to the strong inhibition of inhibitor waterglass, and floatability is very poor, and disseminated grain size is very thin, and ore dressing difficulty is very large, are difficult to realize the recycling to tungsten white in flotation tailing.

Summary of the invention

The present invention, for solving prior art defect, provides a kind of technique extracting white tungsten fine ore from low grade white tungsten mine tailing; For fine grain teeth cloth, low grade white tungsten flotation tailing containing a large amount of calcareous gangue mineral, there is provided and therefrom extract white tungsten fine ore, the ore-dressing technique of scheelite resource in synthetical recovery mine tailing, adopts the obtainable high-grade white tungsten fine ore of this technique, and the rate of recovery is higher simultaneously.

Ore-dressing technique by extracting white tungsten in low grade white tungsten mine tailing of the present invention, carry out as follows:

(1) leach first: in ore pulp, add NaOH, in the basic conditions, heating leaching scheelite;

(2) circulating leaching: by slurry filtration, after leached mud discharge, after leachate supplemental hydrogen sodium oxide molybdena, rejoin the process that white Tungsten tailing repeats (1), repetitive cycling like this leaches, and finally obtains containing the higher leachate of white tungsten concentration;

(3) leachate desiliconization: under the state of heating, more slowly add watery hydrochloric acid, sediment fraction silicic acid in the leachate that obtains of step (2), after filtration, then add the further desiliconization of magnesium chloride;

(4) white tungsten precipitation: use calcium chloride as the precipitating reagent of wolframic acid, is added in the leachate after the desiliconization removal of impurities that (3) obtain, stirs, separates out white tungsten fine ore.

Described in step of the present invention (1), the consumption of NaOH is 50-150kg/t in leaching process first, and the liquid-solid ratio of ore pulp is 2:1-5:1, and extraction time is 30 ~ 120min, and the temperature of leaching is 50-80 DEG C.

In the described circulating leaching process of step of the present invention (2), the amount of each supplemental hydrogen sodium oxide molybdena is 10-30kg/t.

In the described leachate desiliconization process of step of the present invention (3), the mass percent concentration of hydrochloric acid is 10-30%, and consumption is 10-20kg/t; The mass percent concentration of magnesium chloride is 10-20%, consumption 3-5kg/t, and mixing time is 10-30min, and temperature is 40-60 DEG C.

The mass percent concentration of step of the present invention (4) described calcium chloride solution is 5-20%, and consumption is 0.5-2.5kg/t, and mixing time is 5-30min, and temperature is 40-60 DEG C.

Principle of the present invention is:

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Beneficial effect of the present invention:

(1) the present invention is directed to white Tungsten tailing, the embedding cloth of white tungsten be thin, feature that harmful element is many, select alkaline Leaching, avoid the leaching of harmful element to greatest extent, reduce the requirement of technique to equipment simultaneously; Adopt the technique of circulating leaching, add WO in leachate ₃content, significantly reduce the cost of leaching.

(2) adopt hydrochloric acid and magnesium chloride as desiliconization precipitating reagent, can under highly alkaline conditions, removed with the form of silicic acid and magnesium silicate precipitation by the silicon in circulating leaching liquid, the extrusion rate of silicon is very high, can obtain high-grade white tungsten fine ore.

(3) use calcium chloride as the precipitating reagent of white tungsten, directly can be obtained by reacting white tungsten fine ore under alkalescence, reaction is simple, is easy to factory's practical operation.

Accompanying drawing explanation

Fig. 1 is that white tungsten leaches flow chart;

Fig. 2 is that white tungsten separates out extraction flow chart.

Detailed description of the invention

Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.

In the embodiment of the present invention with the mine tailing of low-grade scheelite flotation or gravity treatment for handling object, wherein WO ₃content be 0.15-0.4%, the productive rate 31.57%, WO of granularity-0.019mm grade in mine tailing ₃be 51.26% at the distributive law of this grade; The productive rate of granularity 0.074mm-0.019mm is 41.4%, WO ₃be 29.72% at the distributive law of this grade.In visible mine tailing, the embedding cloth of white tungsten is superfine, and simultaneously as flotation tailing, the strong effect of flotation operation inhibitor, reduces the floatability of white tungsten, makes the white tungsten in mine tailing be difficult to reclaim.

Embodiment 1

The present embodiment with the flotation tailing of the white tungsten in somewhere, Yunnan for handling object, wherein WO ₃content be the content of 0.16%, Fe be 10%, SiO ₂content be 43.54%, Al ₂o ₃content be 5.43%.

(1) be that the ratio of 4:1 adds water and prepares ore pulp in the flotation tailing of white tungsten in liquid-solid ratio, in ore pulp, add NaOH by 50kg/t consumption, it is 75 DEG C that leaching temperature controls, and extraction time is 30min; After leachate filters, after leached mud discharge, leachate is recycled and reused for the leaching of white Tungsten tailing, use the liquid-solid ratio (liquid-solid ratio of leachate and white Tungsten tailing) identical with for the first time leaching test, extraction temperature and time, add the NaOH of 12kg/t, leachate is recycled and reused for the leaching of white Tungsten tailing at every turn; This leachate can reuse 4 times, and overall leaching rate can reach 72.01%.

(2) leachate desiliconization: circulating leaching liquid is heated to 60 DEG C, then slowly add the hydrochloric acid that mass percent concentration is 10%, consumption is 10 kg/t, makes silica gel Precipitation; Filter, supernatant adds the magnesium chloride solution that mass percent concentration is 10%, and consumption is 3kg/t, after 50 DEG C of stirring 10min, filters and obtains supernatant;

(3) white tungsten precipitation: add the calcium chloride solution 0.5kg/t that mass percent concentration is 10% in the supernatant obtained of step (2), stir 5min at 45 DEG C, artificial schellite Precipitation, filter and obtain artificial schellite product, grade 70.15%, the rate of recovery reaches 63.41%.

Embodiment 2

The present embodiment with the white tungsten flotation tailing in somewhere, Jiangxi for handling object, wherein WO ₃content be the content of 0.17%, Fe be 10.32%, SiO ₂content be 43.54%, Al ₂o ₃content be 5.42%.

(1) be that the ratio of 5:1 adds water and prepares ore pulp in the flotation tailing of white tungsten in solid-to-liquid ratio, in ore pulp, add NaOH by 100kg/t consumption, it is 80 DEG C that leaching temperature controls, and extraction time is 90min; After leachate filters, leachate is recycled and reused for the leaching of fresh white Tungsten tailing, at the liquid-solid ratio (liquid-solid ratio of leachate and white Tungsten tailing) identical with first time leaching test, extraction temperature and under the time, add the NaOH of 15kg/t, leachate is recycled and reused for the leaching of white Tungsten tailing at every turn; This leachate reuses 5 times, and overall leaching rate can reach 83.2%.

(2) leachate desiliconization: circulating leaching liquid is heated to 50 DEG C, then slowly add the hydrochloric acid that mass percent concentration is 20%, consumption is 15kg/t, makes silica gel Precipitation; Filter, supernatant adds the magnesium chloride solution that mass percent concentration is 15%, and consumption is 4kg/t, after stirring 20min, filters and obtains supernatant at 50 DEG C;

(3) white tungsten precipitation: add the calcium chloride solution 2kg/t that mass percent concentration is 10% in the supernatant obtained of step (2), stir 20min at 51 DEG C, artificial schellite Precipitation, filter and obtain artificial schellite product, grade 70.15%, the rate of recovery reaches 73.41%.

Embodiment 3

The present embodiment with the white tungsten flotation tailing in somewhere, Yunnan for handling object, wherein WO ₃content be the content of 0.21%, Fe be 6.02%, SiO ₂content be 25.21%, Al ₂o ₃content be 38.33%.

(1) be that the ratio of 3:1 adds water and prepares ore pulp in the flotation tailing of white tungsten in solid-to-liquid ratio, in ore pulp, add NaOH by 150kg/t consumption, it is 60 DEG C that leaching temperature controls, and extraction time is 120min; After leachate filters, leachate is recycled and reused for the leaching of fresh white Tungsten tailing, at the liquid-solid ratio (liquid-solid ratio of leachate and white Tungsten tailing) identical with first time leaching test, extraction temperature and under the time, add the NaOH of 30kg/t at every turn, reuse 6 times, leaching rate reaches 87.59%.

(2) leachate desiliconization: circulating leaching liquid is heated to 40 DEG C, then slowly add the hydrochloric acid that mass percent concentration is 30%, consumption is 20 kg/t, makes silica gel Precipitation; Filter, supernatant adds the magnesium chloride solution that mass percent concentration is 20%, and consumption is 5kg/t, after 40 DEG C of stirring 30min, filters and obtains supernatant;

(3) white tungsten precipitation: add the calcium chloride solution 2.5kg/t that mass percent concentration is 10% in the supernatant obtained of step (2), 43 DEG C are stirred 5min, artificial schellite Precipitation, and filter and obtain artificial schellite product, grade 65%, the rate of recovery reaches 78.02%.

Claims (5)

1. by the ore-dressing technique extracting white tungsten in low grade white tungsten mine tailing, it is characterized in that, carry out as follows:

(1) leach first: in ore pulp, add NaOH, in the basic conditions, heating leaching scheelite;

(2) circulating leaching: by slurry filtration, after leached mud discharge, after leachate supplemental hydrogen sodium oxide molybdena, rejoin the process that white Tungsten tailing repeats (1), repetitive cycling like this leaches, and finally obtains containing the higher leachate of white tungsten concentration;

(3) leachate desiliconization: under the state of heating, slowly adds watery hydrochloric acid in the leachate obtained, sediment fraction silicic acid, after filtration, then add the further desiliconization of magnesium chloride in step (2);

(4) white tungsten precipitation: use calcium chloride as the precipitating reagent of wolframic acid, is added in the leachate after the desiliconization removal of impurities that (3) obtain, stirs, separates out white tungsten fine ore.

2. the ore-dressing technique by extracting white tungsten in low grade white tungsten mine tailing according to claim 1, it is characterized in that: described in step (1), the consumption of NaOH is 50-150kg/t in leaching process first, the liquid-solid ratio of ore pulp is 2:1-5:1, extraction time is 30 ~ 120min, and the temperature of leaching is 50-80 DEG C.

3. the ore-dressing technique by extracting white tungsten in low grade white tungsten mine tailing according to claim 1, is characterized in that: in the described circulating leaching process of step (2), the amount of each supplemental hydrogen sodium oxide molybdena is 10-30kg/t.

4. the ore-dressing technique by extracting white tungsten in low grade white tungsten mine tailing according to claim 1, it is characterized in that: in leachate desiliconization process, the mass percent concentration of hydrochloric acid is 10-30%, consumption is 10-20kg/t; The mass percent concentration of magnesium chloride is 10-20%, consumption 3-5kg/t, and mixing time is 10-30min, and temperature is 40-60 DEG C.

5. the ore-dressing technique by extracting white tungsten in low grade white tungsten mine tailing according to claim 1, is characterized in that: the mass percent concentration of calcium chloride solution is 5-20%, and consumption is 0.5-2.5kg/t, and mixing time is 5-30min, and temperature is 40-60 DEG C.