CN114686704A - Combined smelting process of molybdenum ore and tungsten ore - Google Patents

Combined smelting process of molybdenum ore and tungsten ore Download PDF

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CN114686704A
CN114686704A CN202011630584.2A CN202011630584A CN114686704A CN 114686704 A CN114686704 A CN 114686704A CN 202011630584 A CN202011630584 A CN 202011630584A CN 114686704 A CN114686704 A CN 114686704A
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molybdenum
ore
tungsten
leaching
raffinate
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CN114686704B (en
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李永立
赵中伟
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Zhengzhou University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/36—Obtaining tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention relates to a combined smelting process of molybdenum ore and tungsten ore, belongs to the technical field of non-ferrous metal smelting, and solves the problems of difficult treatment of smelting wastewater and high smelting cost in the process of smelting tungsten and molybdenum ore separately in the prior art. The combined smelting process of molybdenum ore and tungsten ore jointly smelts molybdenum concentrate and scheelite; carrying out oxygen pressure cooking leaching on the molybdenum concentrate by using a molybdenum ore leaching aid, filtering to obtain molybdenum ore filtrate, and extracting the molybdenum ore filtrate to obtain molybdenum ore raffinate; and (3) adopting the molybdenum ore raffinate as a tungsten ore leaching agent to carry out atmospheric leaching on the scheelite. Realizes the clean smelting of the tungsten and molybdenum ores and the comprehensive utilization of resources.

Description

Combined smelting process of molybdenum ore and tungsten ore
Technical Field
The invention relates to the technical field of non-ferrous metal smelting, in particular to a combined smelting process of molybdenum ore and tungsten ore.
Background
More than 99% of molybdenum in nature exists in the form of molybdenite, which is the most main mineral raw material for extracting molybdenum. The molybdenite smelting process in the prior art mostly adopts an oxidizing roasting-ammonia leaching process, and a large amount of low-concentration sulfur dioxide flue gas is generated in the oxidizing roasting process, so that the sulfur element in the molybdenite cannot be effectively recycled, and the air is polluted greatly. Meanwhile, the temperature control difficulty in the roasting process is high, and the molybdenum is also sublimated and lost due to overhigh temperature in the roasting process; if the temperature in the roasting process is too low, the molybdenum is not completely oxidized, and the leaching difficulty is increased.
The main smelting raw material scheelite of tungsten, however, with the annual exploitation of tungsten resources, it presents the situation of reduced grade, complex components and associated with other metals, so that the beneficiation and smelting cost of tungsten resources is increased. The existing common method for treating tungsten ore is a high-pressure alkaline leaching method, the process can decompose the tungsten ore under the conditions of high alkali, high temperature and high pressure, but the content of tungsten in slag is high, and the low-grade complex tungsten ore is difficult to treat. Meanwhile, for scheelite with high barium content, the tungsten and the barium in the scheelite are very difficult to decompose because of the existence of the very stable barium tungstate, and the higher the barium content is, the greater the influence on the decomposition is, the more difficult the traditional high-pressure alkaline leaching method is to effectively decompose the scheelite, and the leaching rate of the tungsten is low.
Chinese patent document CN104372169A discloses a method for extracting tungsten from high barium tungsten ore, which is to mix the high barium tungsten ore with a certain amount of SiO2With Na2CO3Mixing, roasting at high temperature, and using Na as roasting slag2CO3The solution leaches tungsten, and the leaching rate of tungsten is improved. The method can effectively extract tungsten from the high barium tungsten ore, but in the roasting link, the temperature needs to reach 800-.
At present, the acid method synergistic treatment process developed for scheelite not only can efficiently treat low-grade scheelite, but also can realize tungsten ore leaching under normal pressure, has no sodium salt wastewater discharge, is environment-friendly, has very wide application prospect, and only consumes sulfuric acid. If the molybdenum pressing and boiling waste acid and the scheelite acid method smelting technology can be organically combined in a proper mode, the problems of molybdenum smelting waste acid output and tungsten smelting acid consumption can be effectively solved. However, due to the problems of the difference of smelting technical routes and the like, the combined smelting of tungsten ore and molybdenum ore cannot be realized.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a combined smelting process for molybdenum ore and tungsten ore, so as to solve the problem that the reagents used in the smelting cannot be comprehensively and effectively utilized when the molybdenum ore and the tungsten ore are respectively smelted independently.
The invention provides a combined smelting process of molybdenum ore and tungsten ore, which combines molybdenum concentrate and scheelite;
the molybdenum concentrate is subjected to oxygen pressure cooking leaching by a molybdenum ore leaching aid, molybdenum ore filtrate is obtained through filtering, and molybdenum ore filtrate is extracted to obtain molybdenum ore raffinate;
and (3) adopting the molybdenum ore raffinate as a tungsten ore leaching agent to carry out atmospheric leaching on the scheelite.
Further, the scheelite smelting is leached by a tungsten ore leaching agent, the tungsten ore filtrate is obtained by filtration after leaching, and the tungsten ore filtrate is extracted to obtain tungsten ore raffinate;
the molybdenum ore leaching aid is obtained by removing impurities from tungsten ore raffinate through an impurity removing agent and regenerating through a regenerating agent. Further, the molybdenum ore leaching aid is phosphoric acid.
Further, the molybdenum concentrate comprises the following main components in percentage by mass: 40 to 50 percent of molybdenum and 2 to 5 percent of bismuth.
Further, the main component of the scheelite is 40% of tungsten trioxide.
Further, the oxygen pressure of the oxygen pressure digestion leaching is 0.8MPa to 1.5 MPa.
Furthermore, in the oxygen pressure cooking leaching of the molybdenum concentrate, the dosage of the leaching aid is 0.5 to 1.5 times of the mass of the molybdenum concentrate.
Further, the oxygen autoclaving time is 2 to 5 hours.
Further, the temperature of the oxygen autoclaving is 180 ℃ to 210 ℃.
Further, the molybdenum concentrate is leached by oxygen pressure cooking, and the leaching rate of molybdenum is more than 99%.
Further, the molybdenum ore raffinate includes phosphoric acid and sulfuric acid.
Further, the liquid-solid ratio of the tungsten ore leaching agent leaching is 8mL/g to 12 mL/g.
Further, the time for leaching the tungsten ore leaching agent is 5 to 7 hours.
Further, the scheelite leaching agent is used for leaching, and the leaching rate of tungsten is more than 98%.
Further, molybdenum ore filtrate is extracted to obtain molybdenum ore extract, and the molybdenum ore extract is subjected to back extraction, evaporation and crystallization by a molybdenum ore back-extraction agent to obtain a molybdenum product.
Further, the extracting agent for extracting the molybdenum ore filtrate is a neutral phosphine cation extracting agent, and the neutral phosphine cation extracting agent is one or a combination of P204 and P507.
Further, the concentration of the extracting agent is 10-50% by mass percent.
Further, the extraction phase ratio of molybdenum extraction is 4:1 to 2: 1.
Furthermore, the extraction mode of extracting molybdenum is countercurrent extraction.
Further, the extraction stage number of the molybdenum is 4 to 7.
Further, the molybdenum ore stripping agent is hydrogen peroxide.
Further, the mass fraction of the hydrogen peroxide is 10-20%.
Further, the extraction phase ratio of stripping molybdenum is 7:1 to 5: 1.
Furthermore, the extraction mode of the back extraction of the molybdenum is countercurrent extraction.
Furthermore, the extraction stage number of the stripping molybdenum is 2 to 4.
Further, tungsten ore filtrate is extracted to obtain tungsten ore extract, and the tungsten ore extract is subjected to stripping, evaporation and crystallization by a tungsten ore stripping agent to obtain a tungsten product.
Further, an extracting agent for extracting the tungsten ore filtrate is TBP.
Further, the tungsten ore stripping agent is an ammonia solution.
Further, the concentration of the ammonia water solution is 3mol/L to 8 mol/L.
Further, the impurity removing agent is one or more of calcium oxide, calcium hydroxide, calcium phosphate and calcium carbonate.
Further, the regenerant is sulfuric acid.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) according to the invention, phosphoric acid is used as an auxiliary leaching agent for oxygen pressure digestion leaching to convert sulfur elements in molybdenum concentrate into sulfuric acid, digestion and leaching of molybdenum concentrate ores are completed, mixed acid of sulfuric acid and phosphoric acid is continuously and fully utilized after molybdenum is extracted by a molybdenum ore extracting agent and is used for leaching tungsten ore, compared with the prior art, a large amount of leaching agent is not needed to be used for leaching molybdenum concentrate, impurity elements in minerals are effectively utilized, and target element molybdenum is directly used for leaching scheelite after being extracted, so that reagents used in the process are greatly saved, and waste is changed into wealth;
(2) according to the invention, after the scheelite is leached by using the sulfuric acid-phosphoric acid mixed acid, the scheelite is subjected to simple impurity removal and regeneration, the phosphoric acid is recovered and reused in the oxygen pressure cooking leaching of the molybdenum concentrate, so that the recycling of the leaching aid in the oxygen pressure cooking leaching of the molybdenum concentrate is realized, the reagents used in the process are greatly saved, and clean smelting is realized;
(3) the method provided by the invention has the advantages that the sulfur of the impurity elements in the molybdenum concentrate is oxidized into sulfuric acid, the molybdenum concentrate is leached and digested, the sulfuric acid is used for the leaching process of scheelite, the impurity-removed phosphoric acid obtained after the scheelite is leached is recycled and returned to be used for the oxygen pressure cooking leaching of the molybdenum concentrate, the elements in the molybdenum concentrate are fully utilized for the scheelite smelting, the phosphoric acid obtained after the tungsten ore smelting is fully utilized for the molybdenum concentrate smelting, and the tungsten ore and the molybdenum ore combined smelting is realized.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a flow chart of a tungsten ore and molybdenum ore combined smelting process.
Detailed Description
The invention provides a combined smelting process of molybdenum ore and tungsten ore, which has a process flow chart shown in figure 1 and is used for combined smelting of molybdenum concentrate and scheelite;
carrying out oxygen pressure cooking leaching on the molybdenum concentrate by using a molybdenum ore leaching aid, filtering to obtain molybdenum ore filtrate, and extracting the molybdenum ore filtrate to obtain molybdenum ore raffinate; and (3) adopting the molybdenum ore raffinate as a tungsten ore leaching agent to carry out atmospheric leaching on the scheelite.
Specifically, the molybdenum concentrate comprises the following main components in percentage by mass: 40 to 50 percent of molybdenum and 2 to 5 percent of bismuth; the main component of the scheelite is 40 percent of tungsten trioxide.
Specifically, the molybdenum ore leaching aid is phosphoric acid.
Specifically, the molybdenum ore raffinate includes phosphoric acid and sulfuric acid.
The invention adopts a treatment method combining oxygen pressure boiling and leaching, phosphoric acid and/or calcium phosphate is used as an auxiliary leaching agent to play a role in auxiliary leaching and ore digestion in a system, under the condition of oxygen, the oxygen oxidizes molybdenum disulfide in molybdenum concentrate, the sulfur in the molybdenum concentrate is oxidized into IV-valent sulfur and further oxidized into VI-valent sulfuric acid, and under the action of the sulfuric acid generated by oxidizing the sulfur in the molybdenum concentrate, molybdenum in the molybdenum concentrate is converted into soluble molybdenum acyl cations so as to be completely dissolved in a liquid phase to form a solution.
Through experimental research, the molybdenum concentrate cannot be digested by singly using the leaching aid phosphoric acid and/or calcium phosphate; oxygen is introduced to carry out oxygen autoclaving in water environment alone, and the ores cannot be oxidized and digested. Therefore, under the oxygen condition, the digestion and leaching of the molybdenum concentrate ore are realized by using phosphoric acid and/or calcium phosphate as leaching aids to carry out oxygen autoclaving, and the leaching of molybdenum is realized. Bismuth is not leached out and is completely enriched in the residual leaching slag, and the bismuth can be recycled or directly sold.
With the continuous proceeding of oxygen pressure boiling, molybdenum sulfide in the ore is continuously oxidized and combined with phosphate radical under the combined action of oxygen and leaching aid, and is converted into phosphomolybdic heteropoly acid and sulfuric acid, and the acidity is gradually increased. Under strong acid environment, the reaction balance of the mutual conversion of the phosphomolybdic heteropoly acid and the molybdenum acyl cation continuously moves to the direction of generating the molybdenum acyl cation, and the molybdenum in the ore is dissolved and converted into the state of the molybdenum acyl cation with good solubility. Phosphoric acid or calcium phosphate assists molybdenum to be converted into phosphomolybdic acid in the ore digestion and leaching process, and is released in the process of converting phosphomolybdic acid into molybdyl cation, so that the phosphoric acid or calcium phosphate plays a role in assisting leaching in the ore digestion and leaching process.
It should be noted that sulfur in the molybdenum concentrate is firstly oxidized into sulfur with IV valence in the leaching oxygen autoclaving process, the sulfur with IV valence is further oxidized into sulfuric acid with VI valence, the sulfuric acid and the leaching assistant phosphoric acid act together to complete the digestion and leaching of the ore, and meanwhile, the phosphoric acid is combined with molybdenum to form phosphomolybdic heteropoly acid which is further converted into molybdyl cation under the strong acid condition provided by the sulfuric acid. The molybdenum acyl cation and the proton in the cation extracting agent are subjected to cation exchange and enter an organic phase, and sulfuric acid and phosphoric acid are remained in raffinate. The extraction of the raffinate of the molybdenum ore containing acid is very important, and the resource is wasted after the raffinate is neutralized by alkali and then discharged. Through research, the invention fully utilizes the sulfuric acid obtained by strengthening in the molybdenum concentrate, and raffinate containing the sulfuric acid and the phosphoric acid can be directly used for leaching the scheelite without being treated. The sulfur in the molybdenum concentrate is leached out of the molybdenum ore firstly through oxidation and pressure boiling, and then the scheelite is leached out, so that the sulfur element in the molybdenum concentrate is fully utilized.
Specifically, the oxygen pressure is 0.8MPa to 1.5 MPa.
Oxygen is a key factor playing an oxidation role in the oxygen autoclaving process, and as the oxygen autoclaving leaching process is a gas-solid-liquid heterogeneous reaction, common gas participates in the reaction and mainly depends on the gas-solid and gas-liquid interface heterogeneous reaction, the reaction rate of the gas-participated interface reaction is slow, and the efficiency of the oxygen autoclaving leaching is seriously influenced. The oxygen provides enough pressure to be better dissolved in the liquid, and gas-solid-liquid heterogeneous reaction is generated at a liquid-solid heterogeneous reaction interface, so that the efficiency of oxygen autoclaving leaching is greatly improved.
Specifically, in the molybdenum concentrate and leaching assistant system, the amount of the leaching assistant is 0.5 to 1.5 times of the mass of the molybdenum concentrate.
Specifically, the autoclaving time is 2 to 5 hours.
Specifically, the leaching oxygen autoclaving temperature is 180 ℃ to 210 ℃.
The longer the oxygen autoclaving time, the more complete the reaction, but at the same time, too long autoclaving results in higher energy consumption, so that autoclaving times of from 2 to 5 hours are chosen.
The higher the leaching oxygen autoclaving temperature, the faster the autoclaving rate, but at the same time, the higher the energy consumption, so that the leaching oxygen autoclaving temperature is determined to be 180 ℃ to 210 ℃ according to the efficiency-cost ratio, taking into account the production efficiency and energy consumption of autoclaving in a comprehensive manner.
Specifically, the leaching rate of molybdenum is more than 99%.
Specifically, the liquid-solid ratio of the tungsten ore leaching agent is 8mL/g to 12 mL/g.
Specifically, the leaching time of the tungsten ore leaching agent is 5 to 7 hours.
Specifically, the scheelite leaching agent is used for leaching, and the leaching rate of tungsten is more than 98%.
The main component of the scheelite is tungsten trioxide, a large amount of acid is required to be consumed in the leaching process of the scheelite in the prior art, the acid consumed in the scheelite leaching process is derived from the oxygen pressure boiling process of the molybdenum concentrate, the sulfur in the molybdenum concentrate is oxidized into sulfuric acid through oxygen oxidation, and the sulfuric acid is used for leaching the scheelite after the molybdenum ore is leached, so that the combined smelting of the molybdenum ore and the tungsten ore is realized.
Specifically, a cationic extractant is used for extracting molybdenum from a molybdenum leaching solution to obtain a molybdenum raffinate and a molybdenum-loaded cationic extractant.
Specifically, the cation extracting agent is one or a combination of P204 and P507, and the molybdenum back-extracting agent is hydrogen peroxide.
Specifically, the concentration of the cationic extractant is 10 to 50 percent by mass percent.
Specifically, the extraction ratio of the extracted molybdenum is 4:1 to 2:1 compared with the O/A.
The extraction phase ratio is an important influence factor of extraction, when the extraction phase ratio is less than 2:1, the due organic extraction property is insufficient, and part of molybdenum cannot be transferred into the organic phase, so that from the viewpoint of molybdenum recovery rate, the molybdenum is transferred into the organic phase more completely and remains in the water phase less when the O/A ratio is larger. However, the cost of solvent and process is increased by adding too much organic phase, and it is studied that the extraction efficiency-cost ratio is seriously reduced when the O/A is more than 4:1, so the extraction ratio of molybdenum is selected to be 4:1 to 2: 1.
Specifically, the extraction mode for extracting molybdenum is countercurrent extraction.
Specifically, the extraction stage number of the molybdenum is 4 to 7.
Specifically, molybdenum ore filtrate is extracted to obtain molybdenum ore extract, and the molybdenum ore extract is subjected to back extraction, evaporation and crystallization by a molybdenum ore back extractant to obtain a molybdenum product.
Specifically, the mass fraction of the hydrogen peroxide is 10 to 20 percent.
Specifically, the extraction ratio of stripping molybdenum is 7:1 to 5:1 compared with O/A.
Specifically, the extraction mode of the back extraction of the molybdenum is countercurrent extraction.
Specifically, the extraction stage number of the stripping molybdenum is 2 to 4.
And (3) chemically extracting the leachate by using a cation extracting agent, carrying out cation exchange on hydrogen ions in the cation extracting agent and the leached molybdenum acyl cations, and transferring the molybdenum acyl cations to an organic phase.
In the back extraction process, a stripping agent hydrogen peroxide converts a small amount of molybdic acid radicals entering the water phase and converted into peroxymolybdate radical anions, promotes the chemical equilibrium to move towards the direction that the molybdic acid radicals are converted into the molybdate radical ions, and completely separates the peroxymolybdic acid radicals and the anions from the organic phase, thereby realizing the reverse chemical extraction of molybdenum from the molybdenum-loaded cation extractant and completely back extracting the molybdenum into the stripping agent water phase.
Specifically, the main component of the molybdenum concentrate is 45 to 55 mass percent of molybdenum.
Specifically, the recovery rate of molybdenum is more than 99%.
Specifically, tungsten ore filtrate is extracted to obtain tungsten ore extract, and the tungsten ore extract is subjected to back extraction, purification and crystallization to obtain a tungsten product.
Specifically, the extractant for extracting the tungsten ore filtrate is TBP, and the tungsten ore back-extractant is ammonia water.
Specifically, the tungsten ore stripping agent is an ammonia water solution.
Specifically, the concentration of the ammonia water solution is 3mol/L to 8 mol/L.
In one possible embodiment, the scheelite smelting is leached by a tungsten ore leaching agent, the tungsten ore leaching agent is filtered to obtain a tungsten ore filtrate, and the tungsten ore filtrate is extracted to obtain a tungsten ore raffinate; the molybdenum ore leaching aid is obtained by removing impurities from tungsten ore raffinate through an impurity removing agent and regenerating through a regenerating agent.
Specifically, the impurity removing agent is one or more of calcium oxide, calcium hydroxide, calcium phosphate and calcium carbonate.
Specifically, the regenerant is sulfuric acid.
After the extraction of the tungsten ore leaching solution is finished, a large amount of sulfuric acid is consumed, impurity removing agents are added to remove impurities generated in the tungsten ore leaching process, meanwhile, part of phosphoric acid is converted into monocalcium phosphate, and therefore, the regenerant sulfuric acid is added to regenerate the tungsten ore leaching solution. After impurity removal and regeneration, phosphoric acid of raffinate obtained after extraction of the tungsten ore leaching solution is completely recovered and is circularly used as a leaching agent in the oxygen pressure cooking leaching process of molybdenum ore, so that cyclic utilization of the phosphoric acid is realized.
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
Example one
One specific embodiment of the invention discloses a combined smelting process of molybdenum ore and tungsten ore, as shown in figure 1.
The main components of the molybdenum concentrate raw material comprise, by mass, 45.1% of molybdenum and 2.59% of bismuth.
Calcium phosphate is used as an auxiliary leaching agent, the dosage of the auxiliary leaching agent is 0.5 time of the mass of the molybdenum concentrate, the oxygen partial pressure is 0.8Mpa, and the oxygen pressure leaching is carried out in an autoclave for 5 hours under the condition that the temperature is 210 ℃.
After the oxygen pressure cooking leaching is finished, cooling to room temperature and filtering to obtain leaching residues containing 16.1% of bismuth and leaching solution containing molybdenum.
Wherein the leaching rate of the molybdenum is as high as 99 percent.
For the leaching solution containing molybdenum, firstly, 50% of cationic extractant P204 is used for extracting molybdenum to obtain P204 loaded with molybdenum, the extraction ratio is O/A (4: 1), and the extraction stage number is five counter-current stages.
Performing back extraction on the molybdenum-loaded P204 by using 15% hydrogen peroxide to obtain a back extraction solution of molybdenum and a raffinate of molybdenum; the stripping phase ratio is 7:1, and the stripping stage number is three stages of counter current.
The total recovery rate of molybdenum in the extraction and back extraction process reaches 99 percent.
And evaporating and crystallizing the stripping solution of molybdenum to obtain molybdic acid, and calcining to obtain the molybdenum trioxide product.
Adding the molybdenum raffinate into scheelite with a liquid-solid ratio (ml/g) of 10:1, heating to 95 ℃, and leaching the scheelite for 5 hours, wherein the leaching rate of tungsten reaches 98%;
and after the tungsten ore leaching is finished, cooling to room temperature and filtering to obtain the tungsten-containing leaching solution.
For the leachate containing tungsten, firstly extracting tungsten by using 50% of TBP to obtain TBP loaded with tungsten, wherein the extraction ratio is O/A (4: 1), and the extraction stage number is five counter-current stages.
And then carrying out back extraction on the TBP loaded with the tungsten by using 5mol/L ammonia water solution to obtain a back extraction solution of the tungsten and a raffinate of the tungsten.
And evaporating and crystallizing the strip liquor of the tungsten to obtain the ammonium paratungstate.
Neutralizing the raffinate of tungsten with calcium oxide to pH 4.5, filtering to obtain solution containing calcium dihydrogen phosphate, adjusting pH to 1 with dilute sulfuric acid to obtain purified solution, and using as leaching aid for pressure cooking molybdenite for recycling to realize internal circulation of leaching agent.
Example two
One embodiment of the invention discloses a combined smelting process of molybdenum ore and tungsten ore, which is shown in figure 1.
The main components of the raw materials of the molybdenum concentrate comprise, by mass, 45.9% of molybdenum and 2.89% of bismuth.
Phosphoric acid is used as an auxiliary leaching agent, the dosage of the auxiliary leaching agent is 0.8 time of the mass of the molybdenum concentrate, the oxygen partial pressure is 1.5Mpa, and the temperature is 180 ℃, and the oxygen pressure leaching is carried out in an autoclave for 2 hours.
After the oxygen pressure cooking leaching is finished, cooling to room temperature and filtering to obtain leaching residue containing 16.5% of bismuth and leaching liquid containing molybdenum.
Wherein the leaching rate of the molybdenum is as high as 99 percent.
For the leaching solution containing molybdenum, firstly, extracting molybdenum by using 40% of cationic extractant P507 to obtain P507 loaded with molybdenum, wherein the extraction ratio is O/A (equal to 5: 1), and the extraction stage number is five counter-current stages.
Performing back extraction on the molybdenum-loaded P507 by using 10% hydrogen peroxide to obtain a molybdenum back extraction solution and a molybdenum raffinate; the stripping phase ratio is 5:1, and the stripping stage number is three stages of counter current.
The total recovery rate of molybdenum in the extraction and back extraction process reaches 99 percent.
And evaporating and crystallizing the stripping solution of molybdenum to obtain molybdic acid, and calcining to obtain the molybdenum trioxide product.
Adding the raffinate of molybdenum into scheelite with a liquid-solid ratio (ml/g) of 10:1, leaching the scheelite for 5 hours, heating to 95 ℃, wherein the leaching rate of tungsten reaches 98.3%;
and after the tungsten ore leaching is finished, cooling to room temperature and filtering to obtain the tungsten-containing leaching solution.
For the leachate containing tungsten, firstly extracting tungsten by using 50% of TBP to obtain TBP loaded with tungsten, wherein the extraction ratio is O/A (4: 1), and the extraction stage number is five counter-current stages.
And then carrying out back extraction on the TBP loaded with the tungsten by using 5mol/L ammonia water solution to obtain a back extraction solution of the tungsten and a raffinate of the tungsten.
And evaporating and crystallizing the stripping solution of tungsten to obtain the ammonium paratungstate.
Neutralizing the raffinate of tungsten with calcium oxide to pH 4.5, filtering to obtain solution containing calcium dihydrogen phosphate, adjusting pH to 1 with dilute sulfuric acid to obtain purified solution, and using as leaching aid for pressure cooking molybdenite for recycling to realize internal circulation of leaching agent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (10)

1. The combined smelting process of the molybdenum ore and the tungsten ore is characterized in that the molybdenum ore is molybdenum concentrate, and the tungsten ore is scheelite;
the molybdenum concentrate is subjected to oxygen pressure boiling leaching by a molybdenum ore leaching aid, and molybdenum ore filtrate is obtained through filtering;
extracting the molybdenum ore filtrate to obtain molybdenum ore extract and molybdenum ore raffinate;
and (3) taking the molybdenum ore raffinate as a tungsten ore leaching agent to carry out atmospheric leaching on the scheelite.
2. The combined molybdenum and tungsten smelting process according to claim 1,
leaching the scheelite with molybdenum ore raffinate, filtering to obtain tungsten ore filtrate, and extracting the tungsten ore filtrate to obtain tungsten ore raffinate;
and the tungsten ore raffinate is circularly used as a molybdenum ore leaching aid after impurity removal and regeneration.
3. The combined molybdenum and tungsten smelting process according to claim 1, wherein the molybdenum ore leaching aid is phosphoric acid.
4. The integrated molybdenum and tungsten smelting process according to claim 1, wherein the molybdenum raffinate comprises phosphoric acid and sulfuric acid.
5. The combined smelting process of molybdenum ore and tungsten ore according to claim 1, wherein an impurity removing agent is used for removing impurities from tungsten ore raffinate, and the impurity removing agent is one or more of calcium oxide, calcium hydroxide, calcium phosphate and calcium carbonate.
6. The combined molybdenum and tungsten smelting process according to claim 1, wherein the regeneration of the tungsten raffinate is carried out using a regenerant, which is sulfuric acid.
7. The combined smelting process of molybdenum ore and tungsten ore according to claim 1, wherein the molybdenum ore extract is subjected to stripping by a molybdenum ore stripping agent and evaporative crystallization to obtain a molybdenum product.
8. The combined smelting process of molybdenum ore and tungsten ore according to claim 7, wherein the extracting agent for molybdenum ore filtrate extraction is a neutral phosphine cation extracting agent, and the molybdenum ore back-extracting agent is hydrogen peroxide.
9. The combined smelting process of molybdenum ore and tungsten ore according to claim 2, wherein the tungsten ore filtrate is extracted to further obtain a tungsten ore extract, and the tungsten ore extract is subjected to stripping by a tungsten ore stripping agent, purification and crystallization to obtain a tungsten product.
10. The combined smelting process of molybdenum ore and tungsten ore according to claim 9, wherein the extracting agent for tungsten ore filtrate extraction is TBP, and the tungsten ore stripping agent is ammonia water.
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