CN108315556B - Method and system for removing molybdenum through vulcanization in tungsten smelting process - Google Patents

Method and system for removing molybdenum through vulcanization in tungsten smelting process Download PDF

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CN108315556B
CN108315556B CN201810298995.2A CN201810298995A CN108315556B CN 108315556 B CN108315556 B CN 108315556B CN 201810298995 A CN201810298995 A CN 201810298995A CN 108315556 B CN108315556 B CN 108315556B
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戴征文
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Jiangxi Tonggu Nonferrous Metallurgical Chemical Co ltd
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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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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    • C01B17/00—Sulfur; Compounds thereof
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B34/36—Obtaining tungsten
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Abstract

The invention is thatThe method comprises the steps of pretreatment of clean liquid by hydrogen sulfide tail gas generated in the acid regulating step, preparation of hydrogen sulfide gas, vulcanization, acid regulating and filtration, wherein the clean liquid pretreatment and the vulcanization step absorb hydrogen sulfide by using a pump spraying method, and the hydrogen sulfide gas preparation and the acid regulating step are both carried out by adopting concentrated sulfuric acid so as to obtain S in a vulcanized solution 2‑ The concentration determines the end point of vulcanization. Compared with the prior art, the invention adopts the hydrogen sulfide gas for vulcanization, new impurities are not introduced in the vulcanization process, and the product quality is good; the hydrogen sulfide can be recycled, so that the cost is saved; the contact area of the feed liquid and the hydrogen sulfide is large, the reaction is thorough, and the speed is high; the concentrated sulfuric acid is diluted and participates in the reaction at the same time, and the heat generated by dilution can promote the reaction; the whole molybdenum removal process is continuous, so that the consumption of hydrogen sulfide is reduced, and the environmental pollution is avoided; the molybdenum removal efficiency reaches more than 99.9%, and the tungsten yield is more than 99%.

Description

Method and system for removing molybdenum through vulcanization in tungsten smelting process
Technical Field
The invention belongs to the technical field of metallurgical technology, and particularly relates to a method and a system for removing molybdenum through vulcanization in a tungsten smelting process.
The term "clean liquid" refers to sodium tungstate solution after phosphorus, arsenic and silicon removal, wherein molybdenum impurities and sodium hydroxide are contained.
MoO during pretreatment and vulcanization 4 2- And H is 2 The reaction of S is as follows:
Figure DEST_PATH_IMAGE001
according to the reaction equation, theoretically S 2- The dosage is 1.333 times of Mo;
MoS during acidification 4 2- And H is 2 SO 4 The reaction of (2) is as follows:
Figure 965008DEST_PATH_IMAGE002
background
Because the chemical properties of tungsten and molybdenum are very similar and are difficult to separate under alkaline and acidic conditions, the separation of tungsten and molybdenum is the biggest problem in the technical field of tungsten smelting. The prior industrial molybdenum removal process from sodium tungstate solution is developed based on that molybdenum can preferentially generate thiomolybdate ions under certain conditions, and the chemical properties of the thiomolybdate ions are different from those of the tungstate ions, such as molybdenum trisulfide precipitation method, copper salt precipitation method, solvent extraction method and ion exchange method. Copper salt precipitation method althoughThe selectivity is strong, the molybdenum removal is thorough, but the copper reagent is expensive, the dosage is large, and the economic cost is too high; solvent extraction has not been used industrially until now; the existing ion exchange method has quite difficult desorption of the molybdenum-rich resin. Therefore, only molybdenum trisulfide precipitation is currently widely used in industry. The pH value of the vulcanized solution is 7-8, and the sulfur in the solution is mainly Na 2 MoS 4 And free S 2- In the form of (2) and controlling the pH of the acid end point to be 2.5-3, a large amount of hydrogen sulfide can be generated; in addition, when sodium tungstate solution with higher molybdenum content is treated, the content of tungsten co-precipitated along with molybdenum is high, and the tungsten yield is lower. The vulcanizing agent currently used is Na 2 S、NaHS、(NH 4 ) 2 S、H 2 S, however, the adding amount of the vulcanizing agent in the prior art is large, generally 4-8 times or more of the theoretical value, and the pollution is large and the carried harmful impurities are more; the vulcanizing effect is also poor, and the separated molybdenum-containing compound as a byproduct has low grade and is difficult to recycle.
According to the invention, the whole operation system is sealed, and the hydrogen sulfide tail gas generated in the acid regulating process is used for pretreatment at night for preliminary vulcanization, so that the use amount of hydrogen sulfide in the vulcanization process is reduced, resources are recycled, and the hydrogen sulfide tail gas can be discharged up to the standard.
Disclosure of Invention
In order to solve the problems of the prior molybdenum removal process in the sodium tungstate solution, the invention provides a method and a system for removing molybdenum by vulcanization in the tungsten smelting process.
As one aspect of the technical scheme of the invention, the method for removing molybdenum through vulcanization in the tungsten smelting process comprises the following steps:
(1) Pretreatment of the clean liquid: adjusting the pH value of the purified liquid to 7.5-8.5, using a pump spraying method in a purified liquid storage tank to enable the purified liquid to absorb the hydrogen sulfide tail gas generated in the acid adjusting step to obtain pretreatment liquid, and pumping the pretreatment liquid into a sulfide liquid circulation tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator, and slowly adding concentrated sulfuric acid to react with the sodium sulfide solution to prepare hydrogen sulfide gas;
(3) Vulcanizing: introducing the hydrogen sulfide gas prepared in the step (2) into a sulfide liquid circulation tank pump for spraying and absorbing, vulcanizing at the normal pressure and 50-80 ℃, and when S in the solution 2- Judging as a vulcanization end point when the concentration is 0-2 g/L, and transferring into a vulcanizing liquid storage tank;
(4) Acid regulation: heating to 60-80 ℃, adding concentrated sulfuric acid into the vulcanized liquid under the condition of stirring to adjust the pH to 2.5-3, boiling to obtain acidified liquid and hydrogen sulfide tail gas, immediately transferring the acidified liquid out of the tank for filtering, and introducing the hydrogen sulfide tail gas into a clean liquid storage tank for absorbing the clean liquid;
(5) And (3) filtering: cooling the acidified solution to room temperature, and filtering and separating molybdenum sulfide precipitate to obtain high-purity sodium tungstate solution.
The hydrogen sulfide gas is adopted for vulcanization, new impurities are not introduced in the vulcanization process, and the product quality is good; the hydrogen sulfide can be recycled, so that the cost is saved; introducing excessive hydrogen sulfide gas, S at the end of vulcanization 2- The concentration is controlled in a lower range, and the molybdenum is removed while the low tungsten coprecipitation amount is ensured; the preparation and acidification processes of the hydrogen sulfide both use concentrated sulfuric acid, the sulfuric acid dilution and the reaction are carried out simultaneously, the concentrated sulfuric acid dilution step is omitted, and meanwhile, the reaction can be promoted by heat generated by the sulfuric acid dilution.
Further, the pH value of the purified liquid in the step (1) is 8.0-8.2, and the tungsten, molybdenum and H 2 The reaction difference of S is large, and the separation effect is good.
Further, in order to absorb the hydrogen sulfide tail gas as much as possible, the hydrogen sulfide consumption in the vulcanizing step and the tail gas emission can be reduced, and the time cost is considered, and the absorption time of the purified liquid in the step (1) is 1-3 hours, preferably 1-2 hours.
In the step (2), more than 90% of concentrated sulfuric acid and 160-180 g/L of sodium sulfide solution are used for preparing the hydrogen sulfide gas, and the hydrogen sulfide gas is high in generation speed and purity.
Further, in the step (3), the vulcanization temperature is 62-68 ℃ and the vulcanization time is 1-4 hours. When the temperature is lower, the vulcanization reaction speed is low, the time consumption is long, the vulcanization speed can be accelerated by increasing the temperature, but when the temperature is too high, the energy consumption is increased and the safety is reduced.
Further, the methodIn the step (3), the vulcanization temperature is 65 ℃, the vulcanization time is 2 h, and S in the vulcanized solution 2- The concentration is 0.5-1.5 g/L, the vulcanization efficiency is best, and the tungsten yield is high.
Further, in the step (4), the heating temperature is 65-75 ℃, and the concentrated sulfuric acid with the concentration of more than 90% is used for acidification, so that the conversion of thiomolybdate into precipitate can be accelerated by proper heating temperature and sulfuric acid concentration, and the tungsten-molybdenum separation is promoted.
As another aspect of the technical solution of the present invention, a system for removing molybdenum by sulfuration in a tungsten smelting process, comprising: a clean liquid storage tank having a clean liquid inlet, a hydrogen sulfide tail gas inlet, and a pretreatment liquid outlet; the hydrogen sulfide generator comprises a stirring device, a feeding device and a hydrogen sulfide gas outlet; the sulfuration liquid circulation tank comprises a pretreatment liquid inlet communicated with the pretreatment liquid outlet, a hydrogen sulfide gas inlet communicated with the hydrogen sulfide gas outlet and a sulfuration liquid outlet; the acidification reaction kettle comprises a stirring device, a vulcanizing liquid inlet communicated with the vulcanizing liquid outlet, a sulfuric acid feeding device, an acidifying liquid outlet and a hydrogen sulfide tail gas outlet communicated with a hydrogen sulfide tail gas inlet in the purified liquid storage tank; the filter device comprises an acidified liquid inlet, an acidified liquid filter residue outlet and an acidified liquid filter filtrate outlet, wherein the acidified liquid inlet is communicated with the acidified liquid outlet; the parts of the system are communicated through sealed pipelines, and pumps are arranged on the communicated pipelines of the system; the clean liquid storage tank and the vulcanizing liquid circulating tank are provided with spray pumps, are connected with the bottom and the top of the side face of the clean liquid storage tank or the vulcanizing liquid circulating tank through sealed pipelines, and are used for circularly spraying and absorbing the hydrogen sulfide for the liquid in the clean liquid storage tank or the vulcanizing liquid circulating tank.
Further, the device comprises a heater, a sulfuric acid dosage controller, a stirring device controller, a hydrogen sulfide gas flow controller and a solution pH value controller.
Further, the spray pump nozzle is positioned at no more than 1/8 of the top of the clean liquid storage tank and the vulcanizing liquid circulating tank.
Further, the spray nozzle of the spray pump comprises a spray direction adjusting device, the spray nozzle can be controlled to rotate, and the spray coverage area is wide.
Further, the spray nozzle of the spray pump comprises a nozzle cover, wherein a series of holes which are uniformly distributed are formed in the nozzle cover, so that the feed liquid is dispersed, and the contact area of the feed liquid and the hydrogen sulfide is increased.
Further, the stirring device is a mechanical stirring device, the rotating speed is high, the solution is uniformly dispersed, and the reaction rate is improved.
Further, in order to increase the filtering speed, the filtering device is a decompression filtering device.
Further, the material of the communication pipeline is PP, PE, PVC, FEP, PTFE material with stable property and corrosion resistance.
Further, the pumps arranged on the communication pipelines are acid-base resistant self-priming pumps, and the service life is long.
Further, the clean liquid storage tank and the vulcanized liquid circulation tank can be a packed tower, a sieve plate tower, a bubble cap tower, a turbulent ball tower or a dynamic wave tower, so that the contact area of the reaction liquid and the hydrogen sulfide is further increased, and the reaction is quicker and more thorough by being matched with a spray pump.
The beneficial effects of the invention are as follows:
1. the hydrogen sulfide gas is adopted for vulcanization, new impurities are not introduced in the vulcanization process, and the product quality is good; the hydrogen sulfide can be recycled, so that the cost is saved;
2. concentrated sulfuric acid is used in both the hydrogen sulfide preparation and acidification processes, the sulfuric acid dilution and the reaction are carried out simultaneously, the concentrated sulfuric acid dilution step is omitted, and meanwhile, the reaction can be promoted by heat generated by the sulfuric acid dilution;
3. introducing excessive hydrogen sulfide gas, S at the end of vulcanization 2- The concentration is controlled in a lower range, and the molybdenum is removed while the low tungsten coprecipitation amount is ensured;
4. the method adopts a pump spraying mode to carry out vulcanization, and adopts proper vulcanization conditions and acidification conditions, so that the molybdenum vulcanization efficiency is good, the molybdenum removal efficiency reaches more than 99.9%, and the tungsten yield is more than 99%;
5. the contact area of the feed liquid and the hydrogen sulfide is large, the reaction is thorough, and the speed is high;
6. the whole molybdenum removal process is continuously controllable, so that the dosage of hydrogen sulfide is reduced, and the environmental pollution is avoided.
Drawings
FIG. 1 is a flow chart of a method for sulfidizing molybdenum of the present invention;
FIG. 2 is a schematic illustration of a sulfidation molybdenum removal system of the present invention;
FIG. 3 is another sulfidation molybdenum removal system of the present invention;
FIG. 4 is a schematic view of a spray nozzle of a spray pump according to the present invention;
fig. 5 is a schematic view of a spray nozzle structure of another spray pump according to the present invention.
Detailed Description
The method and the system for removing molybdenum through vulcanization in the tungsten smelting process are further described below with reference to the accompanying drawings.
Example 1:
a system for sulfidizing molybdenum in a tungsten smelting process, as shown in fig. 2, comprising: a clean liquid tank 1 having a clean liquid inlet 11, a hydrogen sulfide tail gas inlet 12, and a pretreatment liquid outlet 13; a hydrogen sulfide generator 2 including a stirring device 21, a feeding device 22, and a hydrogen sulfide gas outlet 23; a sulfidation liquid circulation tank 3 including a pretreatment liquid inlet 32 communicating with the pretreatment liquid outlet 31, a hydrogen sulfide gas inlet 33 communicating with the hydrogen sulfide gas outlet 23, and a sulfidation liquid outlet 34; the acidification reaction kettle 4 comprises a stirring device 41, a vulcanized liquid inlet 42 communicated with the vulcanized liquid outlet 34, a sulfuric acid feeding device 43, an acidified liquid outlet 44 and a hydrogen sulfide tail gas outlet 45 communicated with the hydrogen sulfide tail gas inlet 12 in the purified liquid storage tank; a filtering device 5 comprising an acidified liquid inlet 51, an acidified liquid filter residue outlet 52 and an acidified liquid filter filtrate outlet 53 which are communicated with the acidified liquid outlet 44; the parts of the system are communicated through sealed pipelines, and pumps 7 are arranged on the communicated pipelines of the system; the clean liquid storage tank 1 and the vulcanizing liquid circulating tank 3 are provided with a spray pump 6, and are connected with the bottom and the top of the side face of the clean liquid storage tank 1 or the vulcanizing liquid circulating tank 3 through sealed pipelines, and are used for circularly spraying and absorbing the hydrogen sulfide for the liquid in the clean liquid storage tank 1 or the vulcanizing liquid circulating tank 3.
Example 2:
on the basis of the embodiment 1, as shown in fig. 2, the stirring devices 21 and 41 are mechanical stirring devices, and the filtering device 5 is a decompression filtering device; the material of the communication pipeline is PP material with stable property and corrosion resistance; the pump 7 arranged on each communication pipeline is an acid and alkali resistant self-sucking pump, the purified liquid storage tank 1 and the vulcanized liquid circulating tank 3 are filled towers, the contact area of the reaction liquid and the hydrogen sulfide is further increased, and the reaction is quicker and more thorough due to the mutual cooperation of the reaction liquid and the spraying pump 6.
Example 3:
as shown in fig. 3, a system for removing molybdenum by sulfuration in the tungsten smelting process, further, in the system shown in fig. 2, the hydrogen sulfide generator 2 further comprises a sulfuric acid dosage controller 24, a stirring device controller 25 and a hydrogen sulfide gas flow controller 26, the sulfuration liquid circulation tank 3 further comprises a heater 34, and the acidification reaction kettle 4 further comprises a heater 46, a sulfuric acid dosage controller 47, a stirring device controller 48 and a solution pH controller 49; the stirring devices 21 and 41 are mechanical stirring devices, and the filtering device 5 is a decompression filtering device; the material of the communication pipeline is PE material with stable property and corrosion resistance; the pump 7 arranged on each communication pipeline is an acid and alkali resistant self-sucking pump, and the purified liquid storage tank 1 and the vulcanized liquid circulating tank 3 are sieve plate towers.
Example 4:
as shown in fig. 3, the system for removing molybdenum by sulfuration in the tungsten smelting process further comprises a sulfuric acid dosage controller 24, a stirring device controller 25, a hydrogen sulfide gas flow controller 26, a sulfuration liquid circulation tank 3 further comprises a heater 34, an acidification reaction kettle 4 further comprises a heater 46, a sulfuric acid dosage controller 47, a stirring device controller 48 and a solution pH controller 49; the nozzle of the spray pump 6 is positioned at 1/8 of the top of the clean liquid storage tank 1 and the vulcanizing liquid circulating tank 3; the stirring devices 21 and 41 are mechanical stirring devices, and the filtering device 5 is a decompression filtering device; the material of the communication pipeline is a PVC material with stable property and corrosion resistance; the pump 7 arranged on each communication pipeline is an acid and alkali resistant self-sucking pump, and the purified liquid storage tank 1 and the vulcanized liquid circulating tank 3 are bubble-cap towers.
Example 5:
as shown in fig. 3, the system for removing molybdenum by sulfuration in the tungsten smelting process further comprises a sulfuric acid dosage controller 24, a stirring device controller 25, a hydrogen sulfide gas flow controller 26, a sulfuration liquid circulation tank 3 further comprises a heater 34, an acidification reaction kettle 4 further comprises a heater 46, a sulfuric acid dosage controller 47, a stirring device controller 48 and a solution pH controller 49; the nozzle of the spray pump 6 is positioned at 1/8 of the top of the clean liquid storage tank 1 and the vulcanizing liquid circulating tank 3; as shown in fig. 4, the spray pump 6 includes a spray direction adjusting device 61, which can control the rotation of the nozzle to increase the spray area; the stirring devices 21 and 41 are mechanical stirring devices, and the filtering device 5 is a decompression filtering device; the material of the communication pipeline is FEP material with stable property and corrosion resistance; the pump 7 arranged on each communication pipeline is an acid and alkali resistant self-sucking pump, and the clean liquid storage tank 1 and the vulcanized liquid circulating tank 3 are turbulent ball towers.
Example 6:
as shown in fig. 3, the system for removing molybdenum by sulfuration in the tungsten smelting process further comprises a sulfuric acid dosage controller 24, a stirring device controller 25, a hydrogen sulfide gas flow controller 26, a sulfuration liquid circulation tank 3 further comprises a heater 34, an acidification reaction kettle 4 further comprises a heater 46, a sulfuric acid dosage controller 47, a stirring device controller 48 and a solution pH controller 49; the nozzle of the spray pump 6 is positioned at 1/8 of the top of the clean liquid storage tank 1 and the vulcanizing liquid circulating tank 3; as shown in fig. 5, the spray pump 6 includes a spray direction adjusting device 61, which can control the rotation of the nozzle to increase the spray area; the spray nozzle of the spray pump 6 comprises a nozzle cover 62, wherein the nozzle cover 62 is provided with a series of uniformly distributed holes 63 for dispersing feed liquid and increasing the contact area with the hydrogen sulfide; the stirring devices 21 and 41 are mechanical stirring devices, and the filtering device 5 is a decompression filtering device; the material of the communication pipeline is PTFE material with stable property and corrosion resistance; the pump 7 arranged on each communication pipeline is an acid and alkali resistant self-sucking pump, and the purified liquid storage tank 1 and the vulcanized liquid circulating tank 3 are dynamic wave towers.
Example 7:
the method for removing molybdenum by using the system of the invention in the tungsten smelting process, as shown in figure 1, comprises the following steps:
(1) Pretreatment of the clean liquid: regulating pH of the purified solution to 7.5, and regulating WO in the purified solution 3 Content 100 g/L, mo content 0.5 g/L, 4 m per batch 3 Spraying the purified liquid in the purified liquid storage tank 1 by using a spray pump 6 to absorb the hydrogen sulfide tail gas generated in the acid regulating step to obtain pretreatment liquid, and pumping the pretreatment liquid into a vulcanized liquid circulation tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator 2, slowly adding concentrated sulfuric acid under intense stirring to react with the sodium sulfide solution to prepare hydrogen sulfide gas, and controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows;
(3) Vulcanizing: introducing the hydrogen sulfide gas prepared in the step (2) into a sulfide liquid circulation tank 3 for pump spray absorption, vulcanizing at normal pressure and 50 ℃ and adjusting H 2 S is determined to be a vulcanization end point when the using amount is the theoretical amount, and the vulcanization end point is transferred into a vulcanizing liquid storage tank 4;
(4) Acid regulation: heating to 60deg.C, adding concentrated sulfuric acid into the sulfidation liquid under stirring, regulating pH to 2.5, boiling, the acidizing fluid and the hydrogen sulfide tail gas are obtained, the acidizing fluid is immediately turned out and filtered, and the hydrogen sulfide tail gas is introduced into the clean liquid storage tank 1 for absorption of the clean liquid;
(5) And (3) filtering: the acidified solution is cooled to room temperature, molybdenum sulfide precipitate is filtered and separated, the molybdenum sulfide precipitate is recovered from a filter residue outlet 52, and a high-purity sodium tungstate solution is obtained from a filtrate outlet 53.
Effect of removing molybdenum by vulcanization: the molybdenum removal rate is 99.9 percent, and the tungsten recovery rate is 99.2 percent.
Example 8:
the method for removing molybdenum by using the system of the invention in the tungsten smelting process, as shown in figure 1, comprises the following steps:
(1) Pretreatment of the clean liquid: regulating pH of the purified solution to 8.0, and regulating WO in the purified solution 3 Content 105 g/L, mo content 1.5 g/L, 4 m per batch 3 Spraying the hydrogen sulfide tail gas 1 h generated in the step of absorbing and regulating acid of the purified liquid in the purified liquid storage tank 1 by using a spray pump 6 to obtain a pretreatmentLiquid is treated and pumped into a vulcanizing liquid circulating tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator 2, slowly adding 90% concentrated sulfuric acid under intense stirring to react with the sodium sulfide solution to prepare hydrogen sulfide gas, and controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows;
(3) Vulcanizing: introducing the hydrogen sulfide gas prepared in the step (2) into a sulfide liquid circulation tank 3 for pump spray absorption, vulcanizing 4H at normal pressure and 60 ℃ and adjusting H 2 S is used in an excessive amount to S 2- When the concentration is 2 g/L, judging that the vulcanization is finished, and transferring the vulcanized product into a vulcanizing liquid storage tank 4;
(4) Acid regulation: heating to 80 ℃, under the condition of stirring, controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows, adding 90% of concentrated sulfuric acid into the vulcanized liquid, adjusting the pH to 3, boiling to obtain acidified liquid and hydrogen sulfide tail gas, immediately transferring the acidified liquid out of the tank for filtering, and introducing the hydrogen sulfide tail gas into a clean liquid storage tank 1 for absorbing the clean liquid;
(5) And (3) filtering: the acidified solution is cooled to room temperature, molybdenum sulfide precipitate is filtered and separated, the molybdenum sulfide precipitate is recovered from a filter residue outlet 52, and a high-purity sodium tungstate solution is obtained from a filtrate outlet 53.
Effect of removing molybdenum by vulcanization: the molybdenum removal rate is 99.95 percent, and the tungsten recovery rate is 99.5 percent.
Example 9:
the method for removing molybdenum by using the system of the invention in the tungsten smelting process, as shown in figure 1, comprises the following steps:
(1) Pretreatment of the clean liquid: regulating pH of the purified solution to 8.5, and regulating WO in the purified solution 3 Content 112 g/L, mo content 3.0 g/L, 4 m per batch 3 Spraying the purified liquid in the purified liquid storage tank 1 by using a spray pump 6 to absorb the hydrogen sulfide tail gas 2 h generated in the acid regulating step to obtain pretreatment liquid, and pumping the pretreatment liquid into a vulcanized liquid circulation tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator 2, slowly adding 92% concentrated sulfuric acid under intense stirring to react with the sodium sulfide solution to prepare hydrogen sulfide gas, and controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows;
(3) Vulcanizing: handle step(2) The prepared hydrogen sulfide gas is introduced into a sulfide liquid circulation tank 3 for pump spray absorption, is vulcanized at 62 ℃ under normal pressure for 2H, and H is regulated 2 S is used in an excessive amount to S 2- When the concentration is 0.5 g/L, judging that the vulcanization is finished, and transferring the vulcanized product into a vulcanizing liquid storage tank 4;
(4) Acid regulation: heating to 72 ℃, under the condition of stirring, controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows, adding 96% of concentrated sulfuric acid into the vulcanized liquid to adjust the pH to 2.8, boiling to obtain acidified liquid and hydrogen sulfide tail gas, immediately transferring the acidified liquid out of the tank for filtering, and introducing the hydrogen sulfide tail gas into a clean liquid storage tank 1 for absorbing the clean liquid;
(5) And (3) filtering: the acidified solution is cooled to room temperature, molybdenum sulfide precipitate is filtered and separated, the molybdenum sulfide precipitate is recovered from a filter residue outlet 52, and a high-purity sodium tungstate solution is obtained from a filtrate outlet 53.
Effect of removing molybdenum by vulcanization: the molybdenum removal rate is 99.96 percent, and the tungsten recovery rate is 99.5 percent.
Example 10:
the method for removing molybdenum by using the system of the invention in the tungsten smelting process, as shown in figure 1, comprises the following steps:
(1) Pretreatment of the clean liquid: regulating pH of the purified solution to 8.2, and regulating WO in the purified solution 3 Content 118 g/L, mo content 1.2 g/L, 4 m per batch 3 Spraying the purified liquid in the purified liquid storage tank 1 by using a spray pump 6 to absorb the hydrogen sulfide tail gas 3 h generated in the acid regulating step to obtain pretreatment liquid, and pumping the pretreatment liquid into a vulcanized liquid circulation tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator 2, slowly adding 96% concentrated sulfuric acid under intense stirring to react with the sodium sulfide solution to prepare hydrogen sulfide gas, and controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows;
(3) Vulcanizing: introducing the hydrogen sulfide gas prepared in the step (2) into a sulfide liquid circulation tank 3 for pump spray absorption, vulcanizing 1H at the normal pressure and the temperature of 68 ℃ and adjusting H 2 S is used in an excessive amount to S 2- When the concentration is 1.5 g/L, judging that the vulcanization is finished, and transferring the vulcanized product into a vulcanizing liquid storage tank 4;
(4) Acid regulation: heating to 75 ℃, under the condition of stirring, controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows, adding 98% of concentrated sulfuric acid into the vulcanized liquid, adjusting the pH to 2.55, boiling to obtain acidified liquid and hydrogen sulfide tail gas, immediately transferring the acidified liquid out of the tank, filtering, and introducing the hydrogen sulfide tail gas into a clean liquid storage tank 1 for absorbing the clean liquid;
(5) And (3) filtering: the acidified solution is cooled to room temperature, molybdenum sulfide precipitate is filtered and separated, the molybdenum sulfide precipitate is recovered from a filter residue outlet 52, and a high-purity sodium tungstate solution is obtained from a filtrate outlet 53.
Effect of removing molybdenum by vulcanization: the molybdenum removal rate is 99.98 percent, and the tungsten recovery rate is 99.2 percent.
Example 11:
the method for removing molybdenum by using the system of the invention in the tungsten smelting process, as shown in figure 1, comprises the following steps:
(1) Pretreatment of the clean liquid: regulating pH of the purified solution to 7.9, and regulating WO in the purified solution 3 Content 120 g/L, mo content 0.8 g/L, 4 m per batch 3 Spraying the purified liquid into a purified liquid storage tank 1 by using a spray pump 6 to absorb hydrogen sulfide tail gas 1.5 h generated in the acid regulating step to obtain pretreatment liquid, and pumping the pretreatment liquid into a vulcanized liquid circulation tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator 2, slowly adding 98% concentrated sulfuric acid under intense stirring to react with the sodium sulfide solution to prepare hydrogen sulfide gas, and controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows;
(3) Vulcanizing: introducing the hydrogen sulfide gas prepared in the step (2) into a sulfide liquid circulation tank 3 for pump spray absorption, vulcanizing 2H at the normal pressure and 65 ℃ and adjusting H 2 S is used in an excessive amount to S 2- When the concentration is 1.2 g/L, judging that the vulcanization is finished, and transferring the vulcanized product into a vulcanizing liquid storage tank 4;
(4) Acid regulation: heating to 68 ℃, under the condition of stirring, controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows, adding 96% of concentrated sulfuric acid into the vulcanized liquid to adjust the pH to 2.6, boiling to obtain acidified liquid and hydrogen sulfide tail gas, immediately transferring the acidified liquid out of the tank for filtering, and introducing the hydrogen sulfide tail gas into a clean liquid storage tank 1 for absorbing the clean liquid;
(5) And (3) filtering: the acidified solution is cooled to room temperature, molybdenum sulfide precipitate is filtered and separated, the molybdenum sulfide precipitate is recovered from a filter residue outlet 52, and a high-purity sodium tungstate solution is obtained from a filtrate outlet 53.
Effect of removing molybdenum by vulcanization: the molybdenum removal rate is 99.98 percent, and the tungsten recovery rate is 99.4 percent.
Example 12:
the method for removing molybdenum by using the system of the invention in the tungsten smelting process, as shown in figure 1, comprises the following steps:
(1) Pretreatment of the clean liquid: regulating pH of the purified solution to 8.1, and regulating WO in the purified solution 3 110. 110 g/L, mo.2. 2 g/L, 4. 4 m each batch 3 Spraying the purified liquid in the purified liquid storage tank 1 by using a spray pump 6 to absorb the hydrogen sulfide tail gas 2 h generated in the acid regulating step to obtain pretreatment liquid, and pumping the pretreatment liquid into a vulcanized liquid circulation tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator 2, slowly adding 98% concentrated sulfuric acid under intense stirring to react with the sodium sulfide solution to prepare hydrogen sulfide gas, and controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows;
(3) Vulcanizing: introducing the hydrogen sulfide gas prepared in the step (2) into a sulfide liquid circulation tank 3 for pump spray absorption, vulcanizing 2.5 and H at the normal pressure and 66 ℃ and adjusting H 2 S is used in an excessive amount to S 2- When the concentration is 0.8 g/L, judging that the vulcanization is finished, and transferring the vulcanized product into a vulcanizing liquid storage tank 4;
(4) Acid regulation: heating to 65 ℃, under the condition of stirring, controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows, adding 98% of concentrated sulfuric acid into the vulcanized liquid to adjust the pH to 2.6, boiling to obtain acidified liquid and hydrogen sulfide tail gas, immediately transferring the acidified liquid out of the tank for filtering, and introducing the hydrogen sulfide tail gas into a clean liquid storage tank 1 for absorbing the clean liquid;
(5) And (3) filtering: the acidified solution is cooled to room temperature, molybdenum sulfide precipitate is filtered and separated, the molybdenum sulfide precipitate is recovered from a filter residue outlet 52, and a high-purity sodium tungstate solution is obtained from a filtrate outlet 53.
Effect of removing molybdenum by vulcanization: the molybdenum removal rate is 99.96 percent, and the tungsten recovery rate is 99.8 percent.
Example 13:
the method for removing molybdenum by using the system of the invention in the tungsten smelting process, as shown in figure 1, comprises the following steps:
(1) Pretreatment of the clean liquid:regulating pH of the purified solution to 8.0, and regulating WO in the purified solution 3 Content 98 g/L, mo content 1.8 g/L, 4 m per batch 3 Spraying the purified liquid in the purified liquid storage tank 1 by using a spray pump 6 to absorb hydrogen sulfide tail gas 2.5 h generated in the acid regulating step to obtain pretreatment liquid, and pumping the pretreatment liquid into a vulcanized liquid circulation tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator 2, slowly adding 98% concentrated sulfuric acid under intense stirring to react with the sodium sulfide solution to prepare hydrogen sulfide gas, and controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows;
(3) Vulcanizing: introducing the hydrogen sulfide gas prepared in the step (2) into a sulfide liquid circulation tank 3 for pump spray absorption, vulcanizing 1.5 and H at the normal pressure and 67 ℃ and adjusting H 2 S is used in an excessive amount to S 2- When the concentration is 1.8 g/L, judging that the vulcanization is finished, and transferring the vulcanized product into a vulcanizing liquid storage tank 4;
(4) Acid regulation: heating to 78 ℃, under the condition of stirring, controlling the concentrated sulfuric acid to flow down slowly in a plurality of thin flows, adding 96% of concentrated sulfuric acid into the vulcanized liquid to adjust the pH to 2.6, boiling to obtain acidified liquid and hydrogen sulfide tail gas, immediately transferring the acidified liquid out of the tank for filtering, and introducing the hydrogen sulfide tail gas into a clean liquid storage tank 1 for absorbing the clean liquid;
(5) And (3) filtering: the acidified solution is cooled to room temperature, molybdenum sulfide precipitate is filtered and separated, the molybdenum sulfide precipitate is recovered from a filter residue outlet 52, and a high-purity sodium tungstate solution is obtained from a filtrate outlet 53.
Effect of removing molybdenum by vulcanization: the molybdenum removal rate is 99.97 percent, and the tungsten recovery rate is 99.4 percent.

Claims (5)

1. The method for removing molybdenum by sulfuration in the tungsten smelting process is characterized by comprising the following steps of:
(1) Pretreatment of the clean liquid: regulating the pH value of the purified liquid to 7.5-8.5, using a pump spraying method in a purified liquid storage tank to enable the purified liquid to absorb the hydrogen sulfide tail gas generated in the acid regulating step, obtaining pretreatment liquid, and pumping the pretreatment liquid into a sulfide liquid circulation tank;
(2) Hydrogen sulfide gas is prepared: preparing sodium sulfide solution with a certain concentration, transferring into a hydrogen sulfide generator, and slowly adding concentrated sulfuric acid to react with the sodium sulfide solution to prepare hydrogen sulfide gas;
(3) Vulcanizing: introducing the hydrogen sulfide gas prepared in the step (2) into a sulfide liquid circulation tank pump for spraying and absorbing, and carrying out 50-50% under normal pressure
80. Vulcanizing at a temperature of C, when S is in solution 2- Judging the vulcanization end point when the concentration is 0-2 g/L, and transferring the vulcanization end point into a vulcanizing liquid storage tank;
(4) Acid regulation: heating to 60-80 ℃, adding concentrated sulfuric acid into the vulcanized liquid under the condition of stirring to adjust the pH to 2.5-3, boiling to obtain acidified liquid and hydrogen sulfide tail gas, immediately transferring the acidified liquid out of the tank for filtering, and introducing the hydrogen sulfide tail gas into a clean liquid storage tank for absorbing the clean liquid;
(5) And (3) filtering: and standing the acidified solution, cooling to room temperature, and filtering and separating molybdenum sulfide precipitate to obtain a high-purity sodium tungstate solution.
2. The method for removing molybdenum by vulcanization in a tungsten smelting process according to claim 1, wherein the pH of the solution after purification in the step (1) is 8.0-8.2; the absorption time of the purified liquid is 1-3 hours.
3. The method for removing molybdenum by sulfuration in the tungsten smelting process according to claim 2, wherein the hydrogen sulfide gas in the step (2) is prepared by using more than 90% of concentrated sulfuric acid and 160-180 g/L of sodium sulfide solution.
4. The method for removing molybdenum by vulcanization in a tungsten smelting process according to claim 3, wherein the vulcanization temperature in the step (3) is 62-68 ℃, the vulcanization time is 1-4 h, and S is contained in the solution after vulcanization 2- The concentration is 0.5-1.5 g/L.
5. The method for removing molybdenum by vulcanization in a tungsten smelting process according to any one of claims 1 to 4, wherein the heating temperature in the step (4) is 65-75 ℃, and more than 90% of concentrated sulfuric acid is used for acid regulation.
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RU2031167C1 (en) * 1992-08-21 1995-03-20 Институт неорганической химии СО РАН Method of treating tungsten-molybdenum concentrates
CN101736171A (en) * 2008-11-24 2010-06-16 洛阳钼都钨钼科技有限公司 Method for separating and recovering molybdenum from tungstate solution with high molybdenum concentration
JP5636142B2 (en) * 2009-03-02 2014-12-03 三菱マテリアル株式会社 Method for producing high purity ammonium paratungstate
CN101880780B (en) * 2010-06-04 2012-11-14 中南大学 Method for separating and extracting tungsten-molybdenum from mixed solution of tungstate-molybdate
CN102140578B (en) * 2011-03-07 2013-01-16 中南大学 Molybdenum-tungsten separating process for molybdenum-tungsten mixed ammonium salt solution in tungsten hydrometallurgy
JP6018958B2 (en) * 2013-03-15 2016-11-02 株式会社アライドマテリアル Method for producing sodium tungstate
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