阅读说明：本技术 一种含高硅高钾低度白钨矿短流程利用方法 (Short-process utilization method of scheelite with high silicon content, high potassium content and low content ) 是由 江亲义 曾斌 邓诗辉 胡俊杰 袁善禧 于 2021-07-27 设计创作，主要内容包括：本发明涉及稀有金属冶金领域,尤其涉及一种含高硅高钾低度白钨矿短流程利用方法,包含稀酸浸出、混酸浸出、氨水溶出、氢氧化钠浸出等步骤。该方法,首先将含高硅高钾的白钨矿用稀酸浸出K、Ca,得到富集WO-(3)的熟矿,再利用混酸浸出富集了WO-(3)的熟矿,将K、Ca、Si深度浸出,利用氨水浸出钨酸中的WO-(3)、MoO-(3),氨水浸出液进入钨冶炼主流程,氨水浸出渣经过氢氧化钠浸出,回收残留在氨水浸出渣中的WO-(3)和Mo,达到短流程高效利用含高硅、高钾低度白钨矿的目的。(The invention relates to the field of rare metal metallurgy, in particular to a short-process utilization method of high-silicon high-potassium low-concentration scheelite, which comprises the steps of dilute acid leaching, mixed acid leaching, ammonia water dissolution, sodium hydroxide leaching and the like. The method comprises leaching high-silicon high-potassium scheelite with dilute acid K, Ca to obtain enriched WO 3 The mature ore is leached by mixed acid to enrich WO 3 The K, Ca and Si are deeply leached out of the mature ore, and the WO in the tungstic acid is leached out by ammonia water 3 、MoO 3 The ammonia water leaching solution enters a tungsten smelting main flow, the ammonia water leaching residue is leached by sodium hydroxide, and WO remained in the ammonia water leaching residue is recovered 3 And Mo, so that the purpose of efficiently utilizing the scheelite with high silicon content, high potassium content and low concentration in a short process is achieved.)

1. A short-process utilization method of scheelite with high silicon content, high potassium content and low degree is characterized in that: comprises the following steps:

(1) leaching with dilute acid: firstly, dilute acid leaching is carried out on scheelite with high silicon content, high potassium content and low degree, the process is controlled in such a way that the concentration of dilute hydrochloric acid at the end of acid leaching reaction is 1.0-1.5mol/L, the liquid-solid ratio is 3:1-4:1, the temperature is room temperature, the leaching time is 60-80 min, the leaching stirring speed is 60-90 r/min, the leaching is completed, the filtration and hot water washing are carried out, the filtrate and the washing water are collected and treated, and the filter residue enters the next treatment link;

(2) mixed acid leaching: obtaining enriched WO through the step (1)₃Leaching the mature ore by using mixed acid, wherein the concentration of hydrochloric acid is controlled to be 9-12 mol/L, the dosage of hydrofluoric acid is 0.6-1.2 times of the theoretical dosage, the liquid-solid ratio is 3:1-4:1, the leaching temperature is 90-100 ℃, the leaching time is 60-90 min, the leaching stirring speed is 60-90 r/min, the leaching is finished, filtering is carried out, the filtrate enters a wastewater treatment system, the filter residue is high-purity tungstic acid, and the next treatment link is carried out;

(3) ammonia water dissolution: performing ammonia water dissolution treatment on the high-purity tungstic acid obtained in the step (2), controlling the dissolution time to be 60-90 min at room temperature, controlling the dissolution stirring speed to be 60-90 r/min, controlling the dissolution liquid solid ratio to be 2:1-4:1, controlling the concentration of free ammonia in the dissolution liquid to be 20-30 g/L and the K concentration to be less than or equal to 0.008g/L at the end point of dissolution reaction, determining that the dissolution liquid is qualified, feeding the dissolution liquid into a tungsten smelting molybdenum removing process, and feeding ammonia water dissolution slag into the next step;

(4) leaching with sodium hydroxide: the ammonia water dissolving slag obtained through the step (3) contains a small amount of WO₃And Mo, leaching with sodium hydroxide under the condition that the dosage of the sodium hydroxide is 1.5-2.5 times of the theoretical dosage, and the solid-to-solid ratio of a leaching solution is 1: 1-1:1.5, leaching pressure of 0.25-0.5 Mpa, leaching time of 90-120 min, leaching stirring speed of 60-90 r/min, filtering and washing, collecting leaching residue, and delivering the leaching solution to an ion exchange link.

[ technical field ] A method for producing a semiconductor device

The invention relates to the field of rare metal metallurgy, in particular to a short-process utilization method of high-silicon high-potassium low-concentration scheelite.

[ background of the invention ]

Scheelite is an important tungsten mineral resource (statistically, the scheelite reserves account for about 70 percent of tungsten mineral resources with useful value on the earth). With the consumption of high-quality scheelite, the utilization of scheelite which is difficult to smelt, complex in properties and low in grade is gradually paid attention. The scheelite with high silicon content, high potassium content and low degree is a complex scheelite, typically the scheelite produced by Xinjiang Hami, and containing WO₃18 to 25 percent of Ca, 5 to 10 percent of Si and 0.01 to 0.1 percent of K (associated in scheelite in the form of potassium feldspar mineral).

The advantages of the scheelite ore are obvious by adopting the process of roasting, sodium carbonate high-pressure decomposition, alkaline extraction, primary crude crystallization, molybdenum removal and secondary crystallization, and WO₃The decomposition rate is high, the feed liquid realizes large circulation, the output of waste water is reduced by 80 percent, but the problems of long flow, high energy consumption, complex process control and high requirement on the entry control of alkaline extraction feed liquid exist. The sulfur-phosphorus mixed acid leaching process is used for realizing the high-efficiency dissolution of scheelite, has low energy consumption and high efficiency, but the subsequent impurity removal process is controlled more finely, and the control difficulty of impurity elements of the product is high. The treatment process of the classic tungsten smelting process of hydrochloric acid decomposition, sodium hydroxide dissolution, ion exchange adsorption, molybdenum removal and crystallization has the advantages of stable process and convenient operation, but has the problems of long flow and large wastewater treatment capacity. The technological treatment of hydrochloric acid decomposition, ammonia dissolution, molybdenum removal, impurity removal and crystallization has short flow and high efficiency, but the ammonia dissolution slag is more, WO₃The loss is large, and the potassium content of the product is easy to exceed the standard (the potassium concentration in the ammonia solution is usually more than or equal to 0.01 g/L).

The invention develops research aiming at the problem of difficult utilization of the scheelite with high silicon, high potassium and low degree, provides a treatment method with simple operation, low cost and good impurity removal effect, and primarily leaches the scheelite with high silicon and high potassium by dilute hydrochloric acidLeaching Ca and K in low-degree scheelite by mixed acid to deeply dissolve Ca, K and Si, and dissolving out most of WO in the mixed acid leaching residue by ammonia water₃Dissolving out the waste water, dissolving the waste water into tungsten, dissolving the waste water into ammonia, dissolving the waste water into slag, leaching the waste water with sodium hydroxide, and further leaching WO in the waste water₃And finally, the purpose of efficiently utilizing the short flow is realized.

[ summary of the invention ]

The invention aims to overcome the defects of the prior art and provides a short-process utilization method of the scheelite with high silicon content, high potassium content and low degree, which can efficiently remove Ca, K and Si in the scheelite with high silicon content, high potassium content and low degree and realize low-cost, high-efficiency and short-process utilization.

The invention discloses a short-process utilization method of scheelite with high silicon content, high potassium content and low degree, which comprises the following steps:

(1) leaching with dilute acid: firstly, dilute acid leaching is carried out on the scheelite with high silicon content, high potassium content and low degree, the process is controlled in such a way that the concentration of dilute hydrochloric acid at the end of acid leaching reaction is 1.0-1.5mol/L, the liquid-solid ratio is 3:1-4:1, the temperature is room temperature, the leaching time is 60-80 min, the leaching stirring speed is 60-90 r/min, the leaching is completed, the filtration and hot water washing are carried out, the filtrate and the washing water are collected and treated, and the filter residue enters the next treatment link.

(2) Mixed acid leaching: obtaining enriched WO through the step (1)₃Leaching the mature ore by using mixed acid, controlling the concentration of hydrochloric acid to be 9-12 mol/L, controlling the dosage of hydrofluoric acid to be 0.6-1.2 times of the theoretical dosage, controlling the liquid-solid ratio to be 3:1-4:1, controlling the leaching temperature to be 90-100 ℃, controlling the leaching time to be 60-90 min, controlling the leaching stirring speed to be 60-90 r/min, completing leaching, filtering, enabling the filtrate to enter a wastewater treatment system, enabling the filter residue to be high-purity tungstic acid, and enabling the filter residue to enter the next treatment link.

(3) Ammonia water dissolution: and (3) performing ammonia water dissolution treatment on the high-purity tungstic acid obtained in the step (2), wherein the temperature is room temperature, the dissolution time is controlled to be 60-90 min, the dissolution stirring speed is 60-90 r/min, the dissolution liquid solid ratio is 2:1-4:1, the concentration of free ammonia in the dissolution liquid is controlled to be 20-30 g/L at the end point of the dissolution reaction, the concentration of K is less than or equal to 0.008g/L, the dissolution liquid is qualified, the dissolution liquid enters a tungsten smelting molybdenum removal process, and the ammonia water dissolution slag enters the next step.

(4) Leaching with sodium hydroxide: the ammonia water dissolving slag obtained through the step (3) contains a small amount of WO₃And Mo, leaching with sodium hydroxide under the condition that the dosage of the sodium hydroxide is 1.5-2.5 times of the theoretical dosage, and the solid-to-solid ratio of a leaching solution is 1: 1-1:1.5, leaching pressure of 0.25-0.5 Mpa, leaching time of 90-120 min, leaching stirring speed of 60-90 r/min, filtering and washing, collecting leaching residue, and delivering the leaching solution to an ion exchange link.

Compared with the prior art, the invention has the following advantages:

primarily leaching Ca and K in the scheelite with high silicon, high potassium and low degree by dilute acid leaching, deeply leaching Ca, K and Si by mixed acid leaching to obtain high-purity tungstic acid, and dissolving WO in the high-purity tungstic acid by ammonia water₃Dissolving out ammonium tungstate feed liquid, entering a tungsten smelting main flow, finally leaching by using sodium hydroxide to dissolve WO remained in the ammonia water slag₃The leaching is a method for utilizing the scheelite with high silicon content, high potassium content and low degree with high efficiency, low cost and short process.

[ description of the drawings ]

The following detailed description of embodiments of the invention is provided in conjunction with the appended drawings, in which:

FIG. 1 is a process flow diagram of the present invention;

[ detailed description ] embodiments

The first embodiment is as follows: the high-silicon high-potassium low-grade scheelite in the embodiment is from a certain tungsten concentrating mill, and is subjected to sampling and drying, sample preparation, detection and detection, wherein the detection result is as follows: WO₃ 22.40％,Ca 12.51％，Si 7.30％、K 0.001％。

(1) Leaching with dilute acid: firstly, weighing 400g of high-silicon high-potassium low-concentration scheelite, carrying out dilute acid leaching, wherein the process control is that the concentration of dilute hydrochloric acid at the end of acid leaching reaction is 1.5mol/L, the liquid-solid ratio is 4:1, the temperature is room temperature, the leaching time is 60min, the leaching stirring speed is 90r/min, the leaching is completed, filtering is carried out, filtrate and washing water are collected and treated, and filter residue enters the next treatment link.

(2) Mixed acid leaching: obtaining enriched WO through the step (1)₃Leaching the mature ore by using mixed acid, controlling the concentration of hydrochloric acid to be 10mol/L, the dosage of hydrofluoric acid to be 0.6 times of the theoretical dosage, the liquid-solid ratio to be 3:1, the leaching temperature to be 95 ℃, the leaching time to be 60min, the leaching stirring speed to be 90r/min, completing the leaching, filtering, enabling the filtrate to enter a wastewater treatment system, and enabling filter residues to be high-purity tungstic acid (sampling, drying and measuring WO)₃88.23% content) and enters the next processing link.

(3) Ammonia water dissolution: and (3) performing ammonia water dissolution treatment on the high-purity tungstic acid obtained in the step (2), controlling the dissolution time to be 90min, the dissolution stirring speed to be 90r/min, the dissolution liquid-solid ratio to be 4:1, controlling the concentration of free ammonia in the dissolution liquid to be 25g/L and the concentration of K to be 0.0041g/L at the end point of the dissolution reaction, enabling the dissolution liquid to be qualified, enabling the dissolution liquid to enter a tungsten smelting molybdenum removal process, and enabling ammonia water dissolution slag to enter the next step.

(4) Leaching with sodium hydroxide: and (4) leaching the obtained ammonia water dissolution slag with sodium hydroxide by the step (3), wherein the leaching condition is that the using amount of the sodium hydroxide is 2.5 times of the theoretical using amount, the solid-to-solid ratio of a leaching solution is 1:1.5, the leaching pressure is 0.25Mpa, the leaching time is 120min, the leaching stirring speed is 90r/min, the leaching is completed, filtering and washing are carried out, the leaching slag is collected and dried, the weighing is 13.40g, and the WO is measured₃Content of 0.86%, WO₃The leaching rate is 99.87%, and the leaching solution is sent to an ion exchange link.

Example two:

the high-silicon high-potassium low-grade scheelite in the embodiment is from a certain tungsten concentrating mill, and is subjected to sampling and drying, sample preparation, detection and detection, wherein the detection result is as follows: WO₃ 22.40％,Ca 12.51％，Si 7.30％、K 0.001％。

(1) Leaching with dilute acid: firstly, weighing 400g of high-silicon high-potassium low-concentration scheelite, carrying out dilute acid leaching, wherein the process control is that the concentration of dilute hydrochloric acid at the end of acid leaching reaction is 1.5mol/L, the liquid-solid ratio is 4:1, the temperature is room temperature, the leaching time is 60min, the leaching stirring speed is 90r/min, the leaching is completed, filtering is carried out, filtrate and washing water are collected and treated, and filter residue enters the next treatment link.

(2) Mixed acid leaching: obtaining enriched WO through the step (1)₃The ripe ore is leached by mixed acid and the process is controlledThe concentration of hydrochloric acid is 10mol/L, the dosage of hydrofluoric acid is 1.2 times of the theoretical dosage, the liquid-solid ratio is 3:1, the leaching temperature is 95 ℃, the leaching time is 60min, the leaching stirring speed is 90r/min, the leaching is finished, the filtration is carried out, the filtrate enters a wastewater treatment system, the filter residue is high-purity tungstic acid (sampling, drying and measuring WO)₃94.52%) and enters the next processing step.

(3) Ammonia water dissolution: and (3) performing ammonia water dissolution treatment on the high-purity tungstic acid obtained in the step (2), controlling the dissolution time to be 90min, the dissolution stirring speed to be 90r/min, the dissolution liquid-solid ratio to be 4:1, controlling the concentration of free ammonia in the dissolution liquid to be 43.35g/L and the concentration of K to be 0.0032g/L at the end point of the dissolution reaction, enabling the dissolution liquid to be qualified, enabling the dissolution liquid to enter a tungsten smelting molybdenum removal process, and enabling ammonia water dissolution slag to enter the next step.

(4) Leaching with sodium hydroxide: and (4) leaching the obtained ammonia water dissolution slag with sodium hydroxide by the step (3), wherein the leaching condition is that the using amount of the sodium hydroxide is 2.5 times of the theoretical using amount, the solid-to-solid ratio of a leaching solution is 1:1.5, the leaching pressure is 0.3Mpa, the leaching time is 120min, the leaching stirring speed is 90r/min, the leaching is completed, filtering and washing are carried out, the leaching slag is collected and dried, the weighing is 10.33g, and WO (measured)₃Content of 0.78%, WO₃The leaching rate is 99.91%, and the leaching solution is sent to an ion exchange link.

Example three:

the high-silicon high-potassium low-grade scheelite in the embodiment is from a certain tungsten concentrating mill, and is subjected to sampling and drying, sample preparation, detection and detection, wherein the detection result is as follows: WO₃ 24.30％,Ca 10.20％，Si 5.80％、K 0.002％。

(1) Leaching with dilute acid: firstly, weighing 400g of high-silicon high-potassium low-concentration scheelite, carrying out dilute acid leaching, wherein the process control is that the concentration of dilute hydrochloric acid at the end of acid leaching reaction is 1.5mol/L, the liquid-solid ratio is 4:1, the temperature is room temperature, the leaching time is 60min, the leaching stirring speed is 90r/min, the leaching is completed, filtering is carried out, filtrate and washing water are collected and treated, and filter residue enters the next treatment link.

(2) Mixed acid leaching: obtaining enriched WO through the step (1)₃The mature ore is leached by mixed acid, the concentration of hydrochloric acid is controlled to be 10mol/L, and the dosage of hydrofluoric acid is controlled0.8 time of theoretical dosage, 3:1 of liquid-solid ratio, 95 ℃ of leaching temperature, 60min of leaching time, 90r/min of leaching stirring speed, completion of leaching, filtration, entry of filtrate into a wastewater treatment system, and high-purity tungstic acid as filter residue (sampling, drying and measuring WO)₃91.36% content) and enters the next processing link.

(3) Ammonia water dissolution: and (3) performing ammonia water dissolution treatment on the high-purity tungstic acid obtained in the step (2), controlling the dissolution time to be 90min, the dissolution stirring speed to be 90r/min, the dissolution liquid-solid ratio to be 4:1, controlling the concentration of free ammonia in the dissolution liquid to be 33.35g/L and the concentration of K to be 0.0046g/L at the end point of the dissolution reaction, enabling the dissolution liquid to be qualified, enabling the dissolution liquid to enter a tungsten smelting molybdenum removal process, and enabling ammonia water dissolution slag to enter the next step.

(4) Leaching with sodium hydroxide: and (4) leaching the obtained ammonia water dissolution slag with sodium hydroxide by the step (3), wherein the leaching condition is that the using amount of the sodium hydroxide is 2.5 times of the theoretical using amount, the solid-to-solid ratio of a leaching solution is 1:1.5, the leaching pressure is 0.3Mpa, the leaching time is 120min, the leaching stirring speed is 90r/min, the leaching is completed, filtering and washing are carried out, the leaching slag is collected and dried, the weighing is 9.60g, and the WO is measured₃Content 1.1%, WO₃The leaching rate is 99.89%, and the leaching solution is sent to an ion exchange link.

Example four:

the high-silicon high-potassium low-grade scheelite in the embodiment is from a certain tungsten concentrating plant in hami of Xinjiang, and is subjected to sampling, drying, sample preparation, detection and detection, wherein the detection result is as follows: WO₃ 24.30％,Ca 10.20％，Si 5.80％、K 0.002％。

(1) Leaching with dilute acid: firstly, weighing 400g of high-silicon high-potassium low-concentration scheelite, carrying out dilute acid leaching, wherein the process control is that the concentration of dilute hydrochloric acid at the end of acid leaching reaction is 1.3mol/L, the liquid-solid ratio is 4:1, the temperature is room temperature, the leaching time is 60min, the leaching stirring speed is 90r/min, the leaching is completed, filtering is carried out, filtrate and washing water are collected and treated, and filter residue enters the next treatment link.

(2) Mixed acid leaching: obtaining enriched WO through the step (1)₃Leaching the mature ore by using mixed acid, wherein the concentration of hydrochloric acid is controlled to be 10mol/L, the dosage of hydrofluoric acid is 1.2 times of the theoretical dosage, and the liquid-solid ratio is 3:1, leaching at 95 ℃, leaching time of 60min, leaching stirring speed of 90r/min, completing leaching, filtering, introducing filtrate into a wastewater treatment system, and taking high-purity tungstic acid as filter residue (sampling, drying and measuring WO)₃95.21% content) and enters the next processing link.

(3) Ammonia water dissolution: and (3) performing ammonia water dissolution treatment on the high-purity tungstic acid obtained in the step (2), controlling the dissolution time to be 90min, the dissolution stirring speed to be 90r/min, the dissolution liquid-solid ratio to be 4:1, controlling the concentration of free ammonia in the dissolution liquid to be 28.41g/L and the concentration of K to be 0.0033g/L at the end point of the dissolution reaction, enabling the dissolution liquid to be qualified, enabling the dissolution liquid to enter a tungsten smelting molybdenum removal process, and enabling ammonia water dissolution slag to enter the next step.

(4) Leaching with sodium hydroxide: and (4) leaching the obtained ammonia water dissolution slag with sodium hydroxide by the step (3), wherein the leaching condition is that the using amount of the sodium hydroxide is 2.5 times of the theoretical using amount, the solid-to-solid ratio of a leaching solution is 1:1.5, the leaching pressure is 0.4Mpa, the leaching time is 120min, the leaching stirring speed is 90r/min, the leaching is completed, filtering and washing are carried out, the leaching slag is collected, drying is carried out, the weighing is 8.70g, and the WO is measured₃Content of 0.93%, WO₃The leaching rate is 99.92%, and the leaching solution is sent to an ion exchange link.

The above description is only a preferred embodiment of the present invention, and it should be noted that a person skilled in the art can make various changes, modifications, substitutions and alterations to the embodiments without departing from the technical principles of the present invention, and such changes, modifications, substitutions and alterations should also be regarded as the protection scope of the present invention.