CN112662874A - Method for separating and extracting rhenium and co-producing ferromolybdenum alloy from rhenium and molybdenum mixed solution - Google Patents
Method for separating and extracting rhenium and co-producing ferromolybdenum alloy from rhenium and molybdenum mixed solution Download PDFInfo
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Abstract
The invention discloses a method for separating and extracting rhenium and coproducing a ferromolybdenum alloy from a rhenium and molybdenum mixed solution, which comprises the steps of adding a molybdate precipitator into the rhenium and molybdenum mixed solution, precipitating molybdate radicals under a weak acid condition, and carrying out solid-liquid separation to obtain molybdenum-rich slag and a rhenium-containing solution; adding a rhenium acid radical precipitator and a flocculating agent into the rhenium-containing solution to flocculate and precipitate rhenium acid radicals, and performing solid-liquid separation to obtain rhenium-rich slag; the method has the advantages of good selective separation effect on molybdenum and rhenium, simple process flow, wide application range and low cost, and is particularly suitable for separating and recycling rhenium and molybdenum in a solution with low molybdenum content and high rhenium content.
Description
Technical Field
The invention relates to a method for separating molybdenum and rhenium, in particular to a method for separating and extracting rhenium and co-producing a ferromolybdenum alloy from a rhenium and molybdenum mixed solution, and belongs to the technical field of metallurgy.
Background
Molybdenum and rhenium are respectively rare refractory metals and rare dispersion metals and are strategic metals which are extremely important and scarce, but the molybdenum and rhenium are extremely poor in resources, and the abundance of the molybdenum in nature is 1 multiplied by 10-4(%), the abundance of rhenium was only 1 × 10-7(％)。
Molybdenum is a rare metal, is a non-renewable important strategic resource, and is an important basic material for developing high and new technologies, realizing national modernization and building modern national defense. According to the statistical data of USGS, the total molybdenum production amount in 2019 is 290 ten thousand tons, and the main molybdenum ore mining areas in the world are China, America, Chilean, Peru and other areas. The consumption fields of molybdenum mainly comprise building engineering, machinery manufacturing, automobiles, shipbuilding, aircrafts, petroleum pipelines and drilling platforms, and production of chemical products such as catalysts, pigments, lubricants and the like, and in most of the application fields, molybdenum has no direct substitute, so that the consumption of molybdenum is highly related to the global production of crude steel. About 75% of molybdenum products are applied to the steel industry in the form of molybdenum furnace burden such as molybdenum oxide or ferromolybdenum and the like, and about 25% of the molybdenum products are applied to the industries such as molybdenum chemical industry, molybdenum metal products and the like.
Rhenium is a strategic material, and is primarily used for high-temperature rhenium alloys for aerospace, petroleum reforming catalysts, electronic products and the like. According to survey statistics of USGS, the total production of rhenium globally in 2019 totals 49 tons. The largest application of rhenium is to manufacture turbine blades of aeroengines, and the nickel-based rhenium superalloy can improve the creep strength of the alloy and the working temperature of the blades, which cannot be replaced by other metals; and secondly as a reforming catalyst for oil refining. The high temperature alloy is the largest consumption field of rhenium, and accounts for about 65% of the total consumption amount of rhenium, and the catalyst accounts for 22% of the total consumption amount of rhenium. The consumption of rhenium in China is stabilized at about 10t, the comprehensive utilization level of rhenium-containing molybdenum ore in China is low, the yield of rhenium is low, partial requirements need to be met by importing from abroad, and the external dependence degree is high.
Rhenium has a strong affinity for sulfur, due to Mo4+And Re4+The radii of the molybdenum are similar, so rhenium is often like replacing molybdenum to be enriched in molybdenite. Molybdenite is a sulfide of molybdenum, is a mineral with the highest rhenium content, has a total storage capacity of about 1689.3 ten thousand tons, and is the most main mineral for extracting rhenium and molybdenum. In industry, molybdenite is often treated by oxidizing roasting, in which molybdenum is mainly in the form of MoO3Is introduced into the molybdenum calcine, rhenium is oxidized to Re2O7And the molybdenum and the rhenium are enriched due to the characteristic of high water solubility in the flue gas, so that the primary separation of the molybdenum and the rhenium is realized. But also a small amount of MoO3And Re2O7The volatile smoke gas passes through a smoke dust collecting system and finally enters leacheate. The method for separating and recovering molybdenum and rhenium from smoke dust leaching solution and leacheate mainly comprises a chemical precipitation method, an ion exchange method, a solvent extraction method, an adsorption method and the like.
Chemical precipitation method: the method is a method for separating metal ions from other impurities by utilizing the difference of the solubility of each compound in a solution. Molybdenum-rhenium separation and enrichment processes often achieve molybdenum-rhenium separation by the difference in the solubility of molybdate and rhenate. The separation and enrichment of molybdenum and rhenium has been achieved by stepwise precipitation of molybdenum and rhenium using the characteristic that calcium molybdate has a lower solubility than calcium rhenate and potassium rhenate has the lowest solubility of all rhenates, but this method is only suitable for the treatment of highly concentrated solutions and is highly influenced by impurity ions. In addition, because methyl violet has better selectivity to rhenium, in industry, rhenium is often precipitated by using methyl violet under an alkaline condition and is dissolved by ammonia water, so that the enrichment of rhenium and the regeneration of the methyl violet are realized. The chemical precipitation method is a traditional rhenium extraction method, has simple process and easy operation, but has lower rhenium recovery rate and needs further improvement.
Ion exchange method: the anion exchange resin is utilized to selectively adsorb anions in the solution to achieve the purpose of separating the anions from other metals, then the anion solution with stronger bonding property with the resin is adopted to carry out desorption,so as to realize the separation and enrichment of molybdenum and rhenium. The commonly used anion exchange resins mainly include strongly basic anion exchange resins, weakly basic anion exchange resins and the like. The strong-alkaline anion exchange resin has good adsorbability and strong dissociation property on rhenium, can normally work under neutral and alkaline conditions, has good effect on treating high-concentration molybdenum-containing solution, and is a resin commonly used for separating molybdenum and rhenium in industrial production. Although strong base anion exchange resin can achieve good molybdenum-rhenium separation effect, high concentration of NH is needed for desorption4SCN、HNO3、HClO4And the resin after desorption is difficult to regenerate, and the recycling property is poor. The weak-base anion exchange resin has good adsorption capacity on rhenium, can achieve good desorption effect only under the condition of low ammonia water concentration, but is limited by pH and can only be used under the condition of strong acidity or neutrality. The ion exchange method can well realize the separation of molybdenum and rhenium, the process is simple, the environment is not polluted, the resin can be repeatedly used after regeneration treatment, but the adsorption capacity of the resin is limited and needs to be further improved.
Solvent extraction method: the method utilizes the process of transferring components between two mutually insoluble liquid phases, and the theoretical basis is that the solubility or partition coefficient of substances in the two phases is different. The solvent extraction method is a method commonly used in industry for separating molybdenum and rhenium, and commonly used extracting agents comprise amine extracting agents, neutral extracting agents, ketone extracting agents, ether extracting agents and the like. The extraction method is a main method for industrially separating and extracting rhenium at present, has the advantages of mature process, high efficiency, low energy consumption and the like, is widely applied, but most of the used extraction agents are volatile organic matters, and some extraction agents have toxicity, so that the environment is polluted, and the search for the nontoxic or low-toxic extraction agents is urgently needed.
An adsorption method: the method is a method for realizing the enrichment of metal ions by utilizing the adsorption effects of physical adsorption, chemical adsorption, exchange adsorption and the like between a solid adsorbent with a high specific surface area structure or special functional groups and an adsorbate, and common adsorbents comprise active carbon, mesoporous material adsorbents, nano particles, polymeric high polymer material adsorbents, biomass adsorbents and the like. The activated carbon is the most widely used adsorbent with better adsorption effect, and has higher adsorption rate to molybdenum and rhenium, but has poor separation effect and is not suitable for the separation of molybdenum and rhenium. The biomass adsorbent can well realize molybdenum-rhenium separation through chemical modification, and the biomass adsorbent is wide in raw material source, renewable and wide in application prospect. The mesoporous material has extremely high specific surface area, and can have different special functional groups through different surface modifications, so that the molybdenum and rhenium in the solution are selectively adsorbed, and the separation and enrichment of the molybdenum and rhenium are realized. But the mesoporous material has less application in the field of molybdenum-rhenium separation due to complex synthesis steps and poor stability of functional modification. The adsorption method has the advantages of high efficiency, simplicity, good selectivity, high separation degree and the like, and particularly has unique utilization value for low-concentration solution; however, the development of the adsorbent is limited because the adsorbent is expensive and cannot be regenerated.
The method for separating molybdenum and rhenium has poor selectivity, high cost and complex flow for the molybdenum-rhenium acid radical, and has very important significance for the green sustainable development of the molybdenum industry in China by researching the selective high-efficiency separation technology for the molybdenum-rhenium acid radical.
Disclosure of Invention
Aiming at the problems of poor selectivity, high cost and complex flow of molybdenum-rhenium acid radical separation in the prior art, the invention aims to provide a method for efficiently and selectively separating molybdenum and rhenium in a solution system and obtaining a ferromolybdenum alloy by a fractional precipitation method.
In order to achieve the technical purpose, the invention provides a method for separating and extracting rhenium and co-producing a ferromolybdenum alloy from a rhenium and molybdenum mixed solution, which comprises the following steps:
1) adding a molybdate precipitator into the rhenium and molybdenum mixed solution, precipitating molybdate under a weak acidic condition, and carrying out solid-liquid separation to obtain molybdenum-rich slag and a rhenium-containing solution; the molybdate precipitator comprises trivalent ferric salt and organic carboxylic acid compounds and/or organic carboxylic acid compounds;
2) adding a rhenium acid radical precipitator and a flocculating agent into the rhenium-containing solution to flocculate and precipitate rhenium acid radicals, and performing solid-liquid separation to obtain rhenium-rich slag; the rhenate precipitating agent comprises basic fuchsin and a long chain alkyl quaternary ammonium salt;
3) and calcining the molybdenum-rich slag at high temperature and reducing and roasting to obtain the ferromolybdenum alloy.
The key point of the technical scheme of the invention is that a composite precipitator consisting of Fe (III) and organic carboxyl compounds is utilized, the composite precipitator has different binding capacities on molybdate radicals and rhenate radicals, particularly under the weak acid condition, Fe (III) can selectively react with molybdate radicals to be converted into precipitates, and meanwhile, organic carboxylic acid compounds are utilized to inhibit the reaction of rhenate radicals and Fe (III), so that the rhenate radicals are left in solution as much as possible, and the separation of the molybdate radicals and the rhenate radicals can be realized through simple solid-liquid separation; then rhenate precipitating agent consisting of basic fuchsin and long-chain alkyl quaternary ammonium salt is added to realize high-efficiency precipitation of rhenate, so that selective step-by-step separation of molybdate and rhenate can be realized through a two-step precipitation method.
The molybdenum-rich slag obtained by the method contains a large amount of iron and molybdenum, and the molybdenum-rich slag is directly reduced by an aluminothermic reduction method, so that the ferro-molybdenum alloy can be directly obtained.
As a preferred scheme, the molybdate precipitate comprises the following components in parts by mass: 60-100 parts of ferric chloride; 20-30 parts of humic acid; 5-10 parts of sodium humate; 5-10 parts of sodium oleate. Fe (III) in the preferred molybdate precipitator has high selectivity to molybdate, can react with molybdate to generate precipitate particles, and humic acid, sodium humate, sodium oleate and the like are rich in carboxylate radical organic anions and can well inhibit the reaction of rhenate radical and Fe (III).
Preferably, the addition concentration of the molybdate precipitate in the rhenium and molybdenum mixed solution is 300 mg/L-30 g/L.
Preferably, the pH under the weak acidic condition is 4 to 6. The precipitation reaction between Fe (III) and molybdate is favoured in the preferred pH range.
As a preferred embodiment, the rhenate precipitating agent comprises the following components in parts by mass: 50-70 parts of basic fuchsin; 30-50 parts of hexadecyl trimethyl ammonium bromide. The preferable rhenate precipitator has a good combination effect on rhenate, can realize rhenate reaction to generate fine precipitate particles, and can easily recover rhenium-rich slag from a liquid phase system under the flocculation effect.
Preferably, the concentration of the rhenate precipitator added in the rhenium-containing solution is 300 mg/L-600 mg/L.
As a preferred embodiment, the flocculant comprises at least one of sodium oleate, sodium dodecyl benzene sulfonate, disodium ethylene diamine tetraacetate, and polyacrylamide. The flocculating agents are common flocculating agents in the market, and the flocculating agents are added to enable fine precipitate particles generated by the rhenate and rhenate precipitating agents to be further aggregated into larger rhenium-rich particles, so that the subsequent solid-liquid separation is facilitated.
As a preferable scheme, the addition concentration of the flocculating agent in the rhenium-containing solution is 150-250 mg/L.
As a preferable scheme, the concentration of the molybdate in the rhenium and molybdenum mixed solution is 100 mg/L-10 g/L, and the concentration of the rhenium acid radical is 10 mg/L-100 mg/L.
As a preferable scheme, after the molybdenum-rich slag is calcined at the high temperature of 750-850 ℃, the molybdenum-rich slag is mixed with a reducing agent and is subjected to reduction roasting at the temperature of 1900-2100 ℃; the dosage of the reducing agent is 0.8-1.0 time of the total mass of the ferromolybdenum. Organic matters are fully volatilized in the high-temperature calcination process, and the molybdenum-rich slag is fully converted into ferric molybdate and ferric oxide. The reduction roasting time is preferably 1 to 3 hours.
As a preferred scheme, the reducing agent comprises the following components in parts by mass: 20 parts of fluorite; 50-70 parts of aluminum powder; 10-30 parts of molybdenum calcine. In the reducing agent, fluorite reacts with redundant iron, the viscosity and the melting point of the slag are reduced, and the aluminum powder mainly plays a role in reducing the oxides of iron and molybdenum into simple substances; the function of the molybdenum calcine in the reducing agent is to provide a molybdenum raw material to make up for the deficiency of the molybdenum raw material in the reaction process.
The pH condition is adjusted by using inorganic acid and alkali which are conventional in the field, such as sulfuric acid, hydrochloric acid, sodium hydroxide and the like in the process of precipitating the molybdate radical.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the technical scheme of the invention realizes the separation of the molybdate radical and the rhenate radical by a distributed precipitation method, has the advantages of good separation effect of the rhenium and the molybdenum, high recovery rate, low cost, short flow and the like, and has obvious advantages compared with the traditional technology for separating molybdenum and rhenium by an ion exchange method and a solvent extraction method.
The technical scheme of the invention utilizes the different binding capacities of molybdate and rhenate on Fe (III) to design a method for separating the molybdate and the rhenate, and the pH is regulated to a weakly acidic environment, so that the Fe (III) and molybdate selectively react and are converted into precipitates, and meanwhile, organic carboxylate anions are utilized to inhibit the reaction of the rhenate and iron (III), so that the rhenate stays in the solution as much as possible, and the separation of the molybdate and the rhenate is realized; and then adding a rhenate precipitator to realize high-efficiency precipitation of rhenate, thereby realizing selective step-by-step separation of molybdenum and rhenate.
The molybdenum-rich slag obtained by separation in the technical scheme of the invention contains a large amount of iron and molybdenum, and the ferromolybdenum alloy can be obtained by direct reduction by adopting an aluminothermic reduction method, so that the effective utilization of molybdenum element in the solution is realized.
The technical scheme of the invention adopts the special precipitator and the flocculating agent with high selectivity aiming at the rhenate, the precipitating agent can react with the metal anion group to generate fine precipitate particles, and then the flocculating agent is added to increase the aggregation of the precipitate particles, so that rhenate can be aggregated into the precipitate particles with high selectivity, and the valuable components can be recovered subsequently.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention as claimed.
Example 1
Adding 60 parts by mass of ferric chloride hexahydrate, 30 parts by mass of humic acid, 5 parts by mass of sodium humate and 5 parts by mass of sodium oleate into 100mL of mixed solution containing 100mg/L of molybdate radical and 100mg/L of rhenate radical, controlling the pH value of the solution to be 5.0, uniformly stirring to obtain molybdenum precipitate particles, filtering, and drying a filter cake to obtain a molybdenum-rich component substance. Adding 70 parts by mass of fuchsin and 30 parts by mass of hexadecyl trimethyl ammonium bromide into the filtrate, controlling the pH value of the solution to be 8.0, adding a flocculating agent into the solution, wherein the flocculating agent comprises 50 parts by mass of sodium oleate, 20 parts by mass of sodium dodecyl benzene sulfonate, 20 parts by mass of ethylene diamine tetraacetic acid and 10 parts by mass of polyacrylamide, and the concentration of the flocculating agent is 200mg/L, uniformly stirring to obtain rhenium precipitate particles, centrifuging, and drying the product to obtain the rhenium-rich component substance. And fully roasting the obtained molybdenum-rich slag at the high temperature of 800 ℃ to obtain molybdic acid high iron and iron oxide, adding a reducing agent consisting of 70 parts by mass of aluminum powder, 20 parts by mass of fluorite and 10 parts by mass of molybdenum calcine, wherein the using amount of the reducing agent is 0.9 time of the total mass of the ferromolybdenum in the roasted slag, and roasting at the high temperature of 1900 ℃ to obtain a ferromolybdenum product. The rhenium content in the molybdenum-rich product is 4.52%, the recovery rate of molybdenum is up to 100%, the molybdenum content in the rhenium-rich product is 0.998%, the recovery rate of rhenium is up to 97.3%, the molybdenum-rhenium separation effect is good, and the molybdenum content in the ferromolybdenum product can be up to 52.2%.
Example 2
Adding 60 parts by mass of ferric chloride hexahydrate, 30 parts by mass of humic acid, 5 parts by mass of sodium humate and 5 parts by mass of sodium oleate into 100mL of mixed solution containing 100mg/L of molybdate radical and 100mg/L of rhenate radical, controlling the pH value of the solution to be 5.0, uniformly stirring to obtain molybdenum precipitate particles, filtering, and drying a filter cake to obtain a molybdenum-rich component substance. Adding 70 parts by mass of fuchsin and 30 parts by mass of hexadecyl trimethyl ammonium bromide into the filtrate, controlling the pH value of the solution to be 8.0, adding a flocculating agent into the solution, wherein the flocculating agent comprises 50 parts by mass of sodium oleate, 20 parts by mass of sodium dodecyl benzene sulfonate, 20 parts by mass of ethylene diamine tetraacetic acid and 10 parts by mass of polyacrylamide, and the concentration of the flocculating agent is 200mg/L, uniformly stirring to obtain rhenium precipitate particles, centrifuging, and drying the product to obtain the rhenium-rich component substance. And fully roasting the obtained molybdenum-rich slag at the high temperature of 800 ℃ to obtain molybdic acid high iron and iron oxide, adding a reducing agent consisting of 70 parts by mass of aluminum powder, 20 parts by mass of fluorite and 10 parts by mass of molybdenum calcine, wherein the using amount of the reducing agent is 0.9 time of the total mass of the ferromolybdenum in the roasted slag, and roasting at the high temperature of 1900 ℃ to obtain a ferromolybdenum product. The rhenium content in the molybdenum-rich product is 4.52%, the recovery rate of molybdenum is up to 100%, the molybdenum content in the rhenium-rich product is 0.998%, the recovery rate of rhenium is up to 83.5%, the molybdenum-rhenium separation effect is good, and the molybdenum content in the ferromolybdenum product can be up to 52.2%.
Example 3
60 parts by mass of ferric chloride hexahydrate, 30 parts by mass of humic acid, 5 parts by mass of sodium humate and 5 parts by mass of sodium oleate are added into 100mL of mixed solution containing 1g/L of molybdate radical and 100mg/L of rhenate radical, the concentration is 3g/L, the pH value of the solution is controlled to be 5.0, molybdenum precipitate particles are obtained by uniformly stirring, and the molybdenum-rich component substance is obtained by filtering and drying a filter cake. Adding 70 parts by mass of fuchsin and 30 parts by mass of hexadecyl trimethyl ammonium bromide into the filtrate, controlling the pH value of the solution to be 8.0, adding a flocculating agent into the solution, wherein the flocculating agent comprises 50 parts by mass of sodium oleate, 20 parts by mass of sodium dodecyl benzene sulfonate, 20 parts by mass of ethylene diamine tetraacetic acid and 10 parts by mass of polyacrylamide, and the concentration of the flocculating agent is 200mg/L, uniformly stirring to obtain rhenium precipitate particles, centrifuging, and drying the product to obtain the rhenium-rich component substance. And fully roasting the obtained molybdenum-rich slag at the high temperature of 800 ℃ to obtain molybdic acid high iron and iron oxide, adding a reducing agent consisting of 70 parts by mass of aluminum powder, 20 parts by mass of fluorite and 10 parts by mass of molybdenum calcine, wherein the using amount of the reducing agent is 0.9 time of the total mass of the ferromolybdenum in the roasted slag, and roasting at the high temperature of 1900 ℃ to obtain a ferromolybdenum product. The rhenium content in the molybdenum-rich product is 12.25%, the recovery rate of molybdenum is up to 100%, the molybdenum content in the rhenium-rich product is 0.998%, the recovery rate of rhenium is up to 97.3%, the molybdenum-rhenium separation effect is good, and the molybdenum content in the ferromolybdenum product can reach 57.4%.
Comparative example 1
The selective precipitation agent in this comparative example is not in the preferred range.
60 parts by mass of ferric chloride hexahydrate, 30 parts by mass of humic acid, 5 parts by mass of sodium humate and 5 parts by mass of sodium oleate are added into 100mL of mixed solution containing 1g/L of molybdate radical and 100mg/L of rhenate radical, the concentration is 3g/L, the pH value of the solution is controlled to be 5.0, molybdenum precipitate particles are obtained by uniformly stirring, and the molybdenum-rich component substance is obtained by filtering and drying a filter cake. Adding methyl green into the filtrate, controlling the pH value of the solution to be 8.0, adding a flocculating agent into the solution, wherein the flocculating agent comprises 50 parts by mass of sodium oleate, 20 parts by mass of sodium dodecyl benzene sulfonate, 20 parts by mass of disodium ethylene diamine tetraacetate, 10 parts by mass of polyacrylamide and 200mg/L in concentration, uniformly stirring to obtain rhenium precipitate particles, centrifuging, and drying the product to obtain the rhenium-rich component substance. And roasting the obtained molybdenum-rich slag at the high temperature of 800 ℃ to obtain high iron molybdate and iron oxide, adding a reducing agent consisting of 70 parts by mass of aluminum powder, 20 parts by mass of fluorite and 10 parts by mass of molybdenum calcine, wherein the using amount of the reducing agent is 0.9 time of the total mass of the ferromolybdenum in the roasted slag, and fully roasting at the high temperature of 1900 ℃ to obtain a ferromolybdenum product. The rhenium content in the molybdenum-rich product is 12.25%, the recovery rate of molybdenum is up to 100%, the molybdenum content in the rhenium-rich product is 0.998%, the recovery rate of rhenium is 30%, and the molybdenum-rhenium separation effect is poor.
Comparative example 2
The pH in this comparative example is in the preferred range.
60 parts by mass of ferric chloride hexahydrate, 30 parts by mass of humic acid, 5 parts by mass of sodium humate and 5 parts by mass of sodium oleate are added into 100mL of mixed solution containing 1g/L of molybdate radical and 100mg/L of rhenate radical, the concentration is 3g/L, the pH value of the solution is controlled to be 9.0, molybdenum precipitate particles are obtained by uniformly stirring, and the molybdenum-rich component substance is obtained by filtering and drying a filter cake. Adding 70 parts by mass of fuchsin and 30 parts by mass of hexadecyl trimethyl ammonium bromide into the filtrate, controlling the pH value of the solution to be 8.0, adding a flocculating agent into the solution, wherein the flocculating agent comprises 50 parts by mass of sodium oleate, 20 parts by mass of sodium dodecyl benzene sulfonate, 20 parts by mass of ethylene diamine tetraacetic acid and 10 parts by mass of polyacrylamide, and the concentration of the flocculating agent is 200mg/L, uniformly stirring to obtain rhenium precipitate particles, centrifuging, and drying the product to obtain the rhenium-rich component substance. And fully roasting the obtained molybdenum-rich slag at the high temperature of 800 ℃ to obtain molybdic acid high iron and iron oxide, adding a reducing agent consisting of 70 parts by mass of aluminum powder, 20 parts by mass of fluorite and 10 parts by mass of molybdenum calcine, wherein the using amount of the reducing agent is 0.9 time of the total mass of the ferromolybdenum in the roasted slag, and roasting at the high temperature of 1900 ℃ to obtain a ferromolybdenum product. The rhenium content in the molybdenum-rich product is 12.25 percent, the recovery rate of molybdenum is 27.4 percent, the molybdenum-rhenium separation effect is poor, and the molybdenum content in the ferromolybdenum product is 26.7 percent.
Claims (10)
1. A method for separating and extracting rhenium and coproducing a ferromolybdenum alloy from a rhenium and molybdenum mixed solution is characterized by comprising the following steps: the method comprises the following steps:
1) adding a molybdate precipitator into the rhenium and molybdenum mixed solution, precipitating molybdate under a weak acidic condition, and carrying out solid-liquid separation to obtain molybdenum-rich slag and a rhenium-containing solution; the molybdate precipitator comprises trivalent ferric salt and organic carboxylic acid compounds and/or organic carboxylic acid compounds;
2) adding a rhenium acid radical precipitator and a flocculating agent into the rhenium-containing solution to flocculate and precipitate rhenium acid radicals, and performing solid-liquid separation to obtain rhenium-rich slag; the rhenate precipitating agent comprises basic fuchsin and a long chain alkyl quaternary ammonium salt;
3) and calcining the molybdenum-rich slag at high temperature and reducing and roasting to obtain the ferromolybdenum alloy.
2. The method for separating and extracting rhenium and coproducing the ferromolybdenum alloy from the rhenium and molybdenum mixed solution as claimed in claim 1, wherein the method comprises the following steps: the molybdate precipitator comprises the following components in parts by mass: 60-100 parts of ferric chloride; 20-30 parts of humic acid; 5-10 parts of sodium humate; 5-10 parts of sodium oleate.
3. The method for separating and extracting rhenium and coproducing the molybdenum-iron alloy from the rhenium-molybdenum mixed solution as claimed in claim 1 or 2, wherein the method comprises the following steps: the addition concentration of the molybdate radical precipitant in the rhenium and molybdenum mixed solution is 300 mg/L-30 g/L.
4. The method for separating and extracting rhenium and coproducing the ferromolybdenum alloy from the rhenium and molybdenum mixed solution as claimed in claim 1, wherein the method comprises the following steps: the pH value under the weak acidic condition is 4-6.
5. The method for separating and extracting rhenium and coproducing the ferromolybdenum alloy from the rhenium and molybdenum mixed solution as claimed in claim 1, wherein the method comprises the following steps: the rhenate precipitating agent comprises the following components in parts by mass: 50-70 parts of basic fuchsin; 30-50 parts of hexadecyl trimethyl ammonium bromide.
6. The method for separating and extracting rhenium and coproducing the molybdenum-iron alloy from the rhenium-molybdenum mixed solution as claimed in claim 1 or 5, wherein the method comprises the following steps: the addition concentration of the rhenate precipitator in the rhenium-containing solution is 300 mg/L-600 mg/L.
7. The method for separating and extracting rhenium and coproducing the ferromolybdenum alloy from the rhenium and molybdenum mixed solution as claimed in claim 1, wherein the method comprises the following steps:
the flocculating agent comprises at least one of sodium oleate, sodium dodecyl benzene sulfonate, ethylene diamine tetraacetic acid and polyacrylamide;
the addition concentration of the flocculating agent in the rhenium-containing solution is 150-250 mg/L.
8. The method for separating and extracting rhenium and co-producing the ferromolybdenum alloy from the rhenium and molybdenum mixed solution according to the claims 1, 2, 4, 5 or 7, is characterized in that: the concentration of the molybdate radical in the rhenium and molybdenum mixed solution is 100 mg/L-10 g/L, and the concentration of the rhenium radical is 10 mg/L-100 mg/L.
9. The method for separating and extracting rhenium and coproducing the ferromolybdenum alloy from the rhenium and molybdenum mixed solution as claimed in claim 1, wherein the method comprises the following steps: and calcining the molybdenum-rich slag at a high temperature of 750-850 ℃, mixing the molybdenum-rich slag with a reducing agent, and performing reduction roasting at a temperature of 1900-2100 ℃, wherein the using amount of the reducing agent is 0.8-1.0 time of the total mass of ferromolybdenum in the molybdenum-rich slag.
10. The method for separating and extracting rhenium and coproducing the ferromolybdenum alloy from the rhenium and molybdenum mixed solution, as recited in claim 9, is characterized in that: the reducing agent comprises the following components in parts by mass: 20 parts of fluorite; 50-70 parts of aluminum powder; 10-30 parts of molybdenum calcine.
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| CN113174499A (en) * | 2021-04-23 | 2021-07-27 | 北京科技大学 | Enrichment and recovery method of trace rhenium in extremely-low-concentration dilute solution |
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