CN111187908A - Floating extraction-based tungsten-molybdenum selective separation method - Google Patents
Floating extraction-based tungsten-molybdenum selective separation method Download PDFInfo
- Publication number
- CN111187908A CN111187908A CN202010167041.5A CN202010167041A CN111187908A CN 111187908 A CN111187908 A CN 111187908A CN 202010167041 A CN202010167041 A CN 202010167041A CN 111187908 A CN111187908 A CN 111187908A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- molybdenum
- parts
- selective
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/28—Amines
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses a tungsten-molybdenum selective separation method based on floating extraction, which comprises the steps of sequentially adding a pH regulator I and a vulcanizing agent into a tungsten-molybdenum solution containing tungstate and molybdate radicals to convert molybdate radicals into thiomolybdate radicals, adding a selective floating extraction agent I and a bubble dispersing agent into the solution, introducing air into the solution to form microbubbles, promoting the bubbles to be hydrophobized and mineralized to form thiomolybdate radicals, a floating extraction agent and bubble micro-droplets, and then carrying out deep enrichment separation on thiomolybdate radicals through floating extraction; and sequentially adding a pH regulator, a selective floating extraction agent II and a bubble dispersing agent into the tungsten-rich flotation raffinate, introducing air, and finally enriching and separating the tungstate radical component through floating extraction. The method has good selective separation effect on tungsten and molybdenum, simple process flow and low operation cost, and is particularly suitable for deep separation of tungsten and molybdenum in different concentration ranges.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a tungsten-molybdenum selective separation method based on floating extraction.
Background
Due to the lanthanide contraction effect, many properties of tungsten and molybdenum are very similar, and tungsten and molybdenum separation is always a great technical problem in the industry. The tungsten-molybdenum separation is taken as an important process in tungsten extraction metallurgy, and the importance of the tungsten-molybdenum separation is increasingly highlighted along with the development of the tungsten industry. In recent years, wolframite with low molybdenum content is gradually depleted, and more wolframite enters a tungsten smelting system, so that the content of impurity molybdenum in the solution is gradually increased. At present, the traditional MoS is mainly used as an industrial tungsten-molybdenum separation method3Precipitation, ion exchange, solvent extraction, and the like.
MoS3A precipitation method: aiming at the separation of tungsten and molybdenum in the early stage, foreign classical MoS is mainly adopted3Removing molybdenum by precipitation. MoS3The precipitation method is based on the affinity difference of tungsten and molybdenum on sulfur by adding Na into alkalescent solution2S, etc. vulcanizing agent, such as molybdate acid radical (MoO)4 2-) Conversion to thiomolybdate (MoS)4 2-) Then adjusting the pH value of the solution to enable MoS4 2-Generating MoS3And removing the precipitate. The general Chong En et al (CN 101736171A) adopt a sulfide precipitation method to separate molybdenum from tungstate solution with high molybdenum concentration, firstly convert molybdate radical into sulfo-molybdate radical, and then selectively separate the sulfo-molybdate radical from tungstate, thereby realizing tungsten-molybdenum separation. Showthorn et al (CN 102140578A) used a sulfide precipitation method to separate tungsten and molybdenum from a molybdenum-tungsten mixed ammonium salt solution in tungsten hydrometallurgy by converting molybdate radicals into ammonium tetrathiomolybdate and then separating out the ammonium tetrathiomolybdate by appropriately reducing the temperature to realize tungsten and molybdenum separation.
Ion exchange method: based on the difference of the affinity of thiomolybdate ions and tungstate ions to the resin, the separation of tungsten and molybdenum is realized. In the patent (CN 105441679A), tungsten and molybdenum are efficiently separated by adopting an ion exchange method, firstly, (NH)4)2S molybdate radicalSulfurizing to obtain thiomolybdate, and then carrying out ion exchange by using weak-base anion exchange resin to adsorb the thiomolybdate so as to realize tungsten-molybdenum separation. Hoogosheng et al (CN 102162030A) of Zhongnan university adopts an ion exchange method to separate tungsten and molybdenum in a tungstate and molybdate mixed solution, tungstate radicals in the solution are polymerized into paratungstate ions by adjusting the pH value of the solution, and tungsten in the solution is preferentially adsorbed by strong-base anion exchange resin, so that tungsten and molybdenum separation is realized.
Solvent extraction method: the selective separation of metal ions is achieved according to the difference in the partition coefficient of the metal ions between the aqueous and organic phases. The method mainly comprises the following two steps: firstly, separating by utilizing the difference of properties of thiomolybdate radicals and tungstate radicals; secondly, separating by utilizing the difference of the properties of molybdenum cations and tungsten anions; zhang Gui Qing et al (CN 108342573A) of Zhongnan university adopts a solvent extraction method to extract and separate tungsten and molybdenum from a molybdenum-containing ammonium tungstate solution, firstly carries out vulcanization treatment on the tungsten and molybdenum solution, and uses a bicarbonate containing methyl trialkyl ammonium and a carbonate composite extractant to extract and separate sulfo-molybdate acid radicals, thereby realizing tungsten and molybdenum separation. Nippon Song, etc. (CN 103320612A), the institute of Process engineering, Chinese academy of sciences, extracted tungsten and molybdenum containing tungsten molybdate solution by a complex amine-hydroximic extractant, can effectively remove tungsten impurity from sodium molybdate solution.
The tungsten-molybdenum separation method is particularly suitable for a high-concentration tungsten-molybdenum separation system, when the concentration of tungsten and molybdenum in a solution is low, the separation process has the defects of poor selectivity, high operation cost, complex flow and the like, and the deep separation is difficult to realize. Therefore, the research on the selective deep separation technology of tungsten and molybdenum has great significance for the green, healthy and sustainable development of the tungsten and molybdenum industry in China.
Disclosure of Invention
Aiming at the problems that the selective deep separation is difficult to realize by the existing tungsten-molybdenum separation technology, the invention aims to provide a tungsten-molybdenum selective separation method based on floating extraction.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a tungsten-molybdenum selective separation method based on floating extraction comprises the following steps: adding a pH regulator I and a vulcanizing agent into a tungsten-molybdenum solution containing tungstate and molybdate to convert molybdate into thiomolybdate, sequentially adding a selective flotation extractant I and a bubble dispersant into the solution, introducing air into the solution for flotation, wherein a foam phase is a molybdenum-rich component, sequentially adding a pH regulator II, a selective flotation extractant II and a bubble dispersant into the flotation raffinate, introducing air into the flotation raffinate for flotation, wherein a foam phase is a tungsten-rich component, and performing filter pressing, drying and calcining on the tungsten-rich and molybdenum-rich components to obtain tungsten and molybdenum products respectively.
The key point of the method is to regulate the selectivity of tungsten and molybdenum ions, change the existence form of molybdate ions by adjusting the pH value of the solution and adding a vulcanizing agent, and enlarge the selectivity difference of the tungsten and molybdenum ions. For example, tungsten molybdenum ions have a significant difference in their affinity for sulfur; the affinity of the thiomolybdate and the quaternary ammonium salt stripping agent is far greater than that of tungstate. On the basis, a floating extraction agent with high selectivity on thiomolybdate is selected, and based on a floating extraction method, mass transfer separation of the thiomolybdate, the floating extraction agent and the bubble micro-droplet is enhanced through heterogeneous reaction and dynamic diffusion, so that selective and efficient separation of tungsten and molybdenum is finally realized.
In a preferred scheme, the vulcanizing agent consists of the following components in parts by mass: 30-60 parts of alkyl sodium xanthate, 20-40 parts of sodium thiosulfate, 10-20 parts of copper sulfide and 10-20 parts of sodium sulfide; the addition amount of the vulcanizing agent is 100 mg/L-20 g/L.
In a preferred scheme, the selective floating extraction agent I comprises the following components in parts by mass: 30-60 parts of quaternary ammonium salt, 20-40 parts of P20440 parts and 20-40 parts of tributyl phosphate; the quaternary ammonium salt is at least one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide; the addition amount of the first selective floating extraction agent is 100 mg/L-10 g/L. The selective stripping agent has high selectivity on molybdate, and can realize enrichment and separation of molybdate in the leaching solution.
In a preferred scheme, the selective floating extraction agent II comprises the following components in parts by mass: primary amine N192330-60 parts, trialkyl phosphorus oxide 20-40 parts, and hexadecyl trimethyl ammonium bromide 20-40 parts; the addition amount of the selective extraction agent II is 100 mg/L-10 g/L. The selective stripping agent has high selectivity to the double tungstate radicals, and can realize enrichment and separation of the tungstate radicals in the leaching solution.
In a preferred scheme, the bubble dispersing agent is at least one of tripolyphosphate, sodium hexametaphosphate and humic acid; the addition amount of the bubble dispersing agent is 50-200 mg/L. The preferred bubble dispersing agent can effectively disperse bubbles and promote the bubbles to hydrophobically mineralize micro-droplets.
Preferably, the first pH adjuster is one of the following: (1) HNO3And NaNO3(ii) a (2) HCl and NaOH; (3) h3PO4And NaH2PO4（4）H3PO4And Na2HPO4Adding a pH regulator I to regulate the pH value of a solution system to 9; and the pH regulator II is phosphoric acid, and is added to regulate the pH of the solution system to 3.5.
In a preferred scheme, the drying refers to drying at 100-150 ℃ for 30-60 min, and the calcining refers to calcining at 600-700 ℃ for 2.5-3.5 h.
Preferably, the tungsten-molybdenum solution is derived from leachate or wastewater of waste vanadium/molybdenum/tungsten catalysts and metallurgical tungsten slag, and the concentration ranges of tungstate and molybdate in the solution are both 50 mg/L-5 g/L.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention realizes the selective separation of tungsten and molybdenum by a floating extraction method. By adjusting proper pH and adding a vulcanizing agent, molybdate is converted into thiomolybdate, the selectivity difference of tungstate and molybdate is enlarged, and thiomolybdate ions are efficiently separated by a selective floating extraction agent, so that the deep separation of tungsten and molybdenum is realized. The defects of low separation efficiency, long process and high operation cost of the traditional tungsten-molybdenum separation method are overcome by the floating extraction, and the deep separation of tungsten and molybdenum can be realized for the low-concentration tungsten-molybdenum ion solution. Thus, this technique has significant advantages over conventional separation methods.
The invention adopts the floating extraction process, and has the advantages that: can process tungsten-molybdenum ion solutions with different concentration ranges; when the concentration of tungsten and molybdenum ions in the solution is low, the selective deep separation of tungsten and molybdenum can be realized. In addition, the existing floating extraction technology is rarely reported in the field of tungsten-molybdenum separation.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be noted that these examples are only for better understanding of the present invention, and do not limit the scope of the present invention.
Example 1
A tungsten-molybdenum selective separation method based on floating extraction is shown in figure 1, and comprises the following processes:
(1) adding 1mol/L phosphoric acid and 1mol/L sodium dihydrogen phosphate or 1mol/L disodium hydrogen phosphate into 1L of solution with molybdate concentration of 5 g/L and tungstate concentration of 5 g/L, adjusting the pH value of the solution to 9.0, and adding a vulcanizing agent into the solution, wherein the vulcanizing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of copper sulfide and 10 parts by mass of sodium sulfide, wherein the concentration is 20 g/L, and the mixture is fully stirred until molybdic acid radicals are fully vulcanized to form thiomolybdate radicals;
(2) adding a selective floating extractant I into the solution, wherein the selective floating extractant I comprises the following components: 50 parts by mass of hexadecyl trimethyl ammonium bromide, 25 parts by mass of P20425 parts by mass of tributyl phosphate, the concentration of which is 10 g/L, then adding a sodium hexametaphosphate dispersant, the concentration of which is 200mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m in the whole flotation process, and selectively floating and enriching the hydrophobically mineralized bubbles, sulfo-molybdate radicals and micro-droplets of the flotation reagent for 5 min, wherein the foam phase is a molybdenum-rich component substance;
(3) adding 1mol/L phosphoric acid into the tungsten-rich flotation residual liquid to adjust the pH value of the solution to be 3.5, and adding a second selective floating extraction agent into the solution, wherein the second selective floating extraction agent comprises the following components: primary amine N192360 parts by mass, trialkyl phosphorus oxide 20 parts by mass, cetyl trimethyl ammonium bromide 20 parts by mass, the concentration is 10 g/L, sodium hexametaphosphate dispersant is added, the concentration is 100 mg/L, the mixture is uniformly stirred and air is introduced to obtain bubbles, tungstate ions and flotation extract agent micro-droplets, tungstate is enriched for 3 min through flotation, and the foam phase is a tungsten-rich component substance;
(4) and (3) carrying out filter pressing on the foam phase, drying at 120 ℃ for 60 min, and calcining at 650 ℃ for 3 h to obtain a tungsten oxide product and a molybdenum oxide product.
The mass of the tungsten oxide product is 4.905 g, the content of molybdenum impurity in the tungsten oxide product is 89 mg, and the purity of the tungsten oxide product is as high as 98.2%; the mass of the molybdenum oxide product is 4.911 g, the content of impurity tungsten in the molybdenum oxide product is 95 mg, the purity of the molybdenum oxide product is as high as 98.1%, and the tungsten-molybdenum separation effect is good.
Example 2
A tungsten-molybdenum selective separation method based on floating extraction is shown in figure 1, and comprises the following processes:
(1) adding 1mol/L phosphoric acid and 1mol/L sodium dihydrogen phosphate or 1mol/L disodium hydrogen phosphate into 1L of solution with molybdate concentration of 5 g/L and tungstate concentration of 100 mg/L, adjusting the pH value of the solution to 9.0, and adding a vulcanizing agent into the solution, wherein the vulcanizing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of copper sulfide and 10 parts by mass of sodium sulfide, wherein the concentration is 20 g/L, and the mixture is fully stirred until molybdic acid radicals are fully vulcanized to form thiomolybdate radicals;
(2) adding a selective floating extractant I into the solution, wherein the selective floating extractant I comprises the following components: 50 parts by mass of hexadecyl trimethyl ammonium bromide, 25 parts by mass of P20425 parts by mass of tributyl phosphate, the concentration of which is 10 g/L, adding a sodium hexametaphosphate dispersant, the concentration of which is 200mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, and selectively floating and enriching the hydrophobically mineralized bubbles-sulfo molybdate radical-flotation medicament droplets for 5 min, wherein the foam phase is a molybdenum-rich component substance;
(3) adding 1mol/L phosphoric acid into the tungsten-rich flotation residual liquid to adjust the pH value of the solution to be 3.5, and adding a second selective floating extraction agent into the solution, wherein the second selective floating extraction agent comprises the following components: primary amine N192350, trialkyl phosphorus oxide 30 and hexadecyl trimethyl ammonium bromide 20, wherein the concentration is 200mg/L, a sodium hexametaphosphate dispersant is added, the concentration is 50 mg/L, the mixture is uniformly stirred and air is introduced to obtain bubbles, tungstate ions and a flotation extract agent micro-droplet, tungstate is enriched for 3 min through flotation, and a foam phase is a tungsten-rich component substance;
(4) and (3) carrying out filter pressing on the foam phase, drying at 120 ℃ for 60 min, and calcining at 650 ℃ for 3 h to obtain a tungsten oxide product and a molybdenum oxide product.
The mass of the tungsten oxide product is 91.1 mg, the content of molybdenum impurity in the tungsten oxide product is 43 mg, and the purity of the tungsten oxide product is 52.8%; the quality of the molybdenum oxide product is 4.957 g, the content of impurity tungsten in the molybdenum oxide product is 8.9 mg, the purity of the molybdenum oxide product is up to 99.8%, and the tungsten-molybdenum separation effect is good.
Example 3
A tungsten-molybdenum selective separation method based on floating extraction is shown in figure 1, and comprises the following processes:
(1) adding 1mol/L phosphoric acid and 1mol/L sodium dihydrogen phosphate or 1mol/L disodium hydrogen phosphate into 1L of solution with molybdate concentration of 100 mg/L and tungstate concentration of 5 g/L, adjusting the pH value of the solution to 9.0, and adding a vulcanizing agent into the solution, wherein the vulcanizing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of copper sulfide and 10 parts by mass of sodium sulfide, wherein the concentration is 500 mg/L, and the mixture is fully stirred until molybdic acid radicals are fully vulcanized to form thiomolybdate radicals;
(2) adding a selective floating extractant I into the solution, wherein the selective floating extractant I comprises the following components: 50 parts by mass of hexadecyl trimethyl ammonium bromide, 25 parts by mass of P20425 parts by mass of tributyl phosphate and 200mg/L of the solution, adding a sodium hexametaphosphate dispersant with the concentration of 100 mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, and selectively floating and enriching the hydrophobically mineralized bubbles-sulfo molybdate radical-flotation medicament droplets for 5 min, wherein the foam phase is a molybdenum-rich component;
(3) adding 1mol/L phosphoric acid into the tungsten-rich flotation residual liquid to adjust the pH value of the solution to be 3.5, and adding a second selective floating extraction agent into the solution, wherein the second selective floating extraction agent comprises the following components: primary amine N192360 parts by mass, trialkyl phosphorus oxide 20 parts by mass, cetyl trimethyl ammonium bromide 20 parts by mass, the concentration is 10 g/L, sodium hexametaphosphate dispersant is added, the concentration is 100 mg/L, the mixture is uniformly stirred and air is introduced to obtain bubbles, tungstate ions and flotation extract agent micro-droplets, tungstate is enriched for 3 min through flotation, and the foam phase is a tungsten-rich component substance;
(4) and (3) carrying out filter pressing on the foam phase, drying at 120 ℃ for 60 min, and calcining at 650 ℃ for 3 h to obtain a tungsten oxide product and a molybdenum oxide product.
The mass of the tungsten oxide product is 4.962 g, the content of molybdenum impurity in the tungsten oxide product is 9.1 mg, and the purity of the tungsten oxide product is as high as 99.8%; the molybdenum oxide product has the mass of 90.9 mg, the content of impurity tungsten in the molybdenum oxide product is 38 mg, the purity of the molybdenum oxide product is 58.2 percent, and the tungsten-molybdenum separation effect is good.
Example 4
A tungsten-molybdenum selective separation method based on floating extraction is shown in figure 1, and comprises the following processes:
(1) adding 1mol/L phosphoric acid and 1mol/L sodium dihydrogen phosphate or 1mol/L disodium hydrogen phosphate into 1L of solution with molybdate concentration of 50 mg/L and tungstate concentration of 50 mg/L, adjusting the pH value of the solution to 9.0, and adding a vulcanizing agent into the solution, wherein the vulcanizing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of copper sulfide and 10 parts by mass of sodium sulfide, wherein the concentration is 200mg/L, and the mixture is fully stirred until molybdic acid radicals are fully vulcanized to form thiomolybdate radicals;
(2) adding a selective floating extractant I into the solution, wherein the selective floating extractant I comprises the following components: 50 parts by mass of hexadecyl trimethyl ammonium bromide, 25 parts by mass of P20425 parts by mass of tributyl phosphate, the concentration of which is 100 mg/L, adding a sodium hexametaphosphate dispersant, the concentration of which is 100 mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, and selectively floating and enriching the hydrophobically mineralized bubbles-sulfo molybdate radical-flotation medicament droplets for 5 min, wherein the foam phase is a molybdenum-rich component substance;
(3) adding 1mol/L phosphoric acid into the tungsten-rich flotation residual liquid to adjust the pH value of the solution to be 3.5, and adding a second selective floating extraction agent into the solution, wherein the second selective floating extraction agent comprises the following components: primary amine N192350, trialkyl phosphorus oxide 20 and hexadecyl trimethyl ammonium bromide 30 in a concentration of 200mg/L, then adding a sodium hexametaphosphate dispersant in a concentration of 100 mg/L, uniformly stirring, and introducing air to obtain bubbles, tungstate ions and a flotation extract agent micro-droplet, wherein tungstate is enriched for 3 min by flotation, and a foam phase is a tungsten-rich component substance;
(4) and (3) carrying out filter pressing on the foam phase, drying at 120 ℃ for 60 min, and calcining at 650 ℃ for 3 h to obtain a tungsten oxide product and a molybdenum oxide product.
The quality of the tungsten oxide product is 46.5 mg, the content of molybdenum impurity in the tungsten oxide product is 3.2 mg, and the purity of the tungsten oxide product is as high as 93.1%; the quality of the molybdenum oxide product is 46.8 mg, the content of impurity tungsten in the molybdenum oxide product is 3.5 mg, the purity of the molybdenum oxide product is as high as 92.5 percent, and the tungsten-molybdenum separation effect is good.
Comparative example 1
The pH in this comparative example is not within the preferred range.
(1) Adding 1mol/L phosphoric acid and 1mol/L sodium dihydrogen phosphate or 1mol/L disodium hydrogen phosphate into 1L of solution with molybdate concentration of 5 g/L and tungstate concentration of 5 g/L, adjusting the pH value of the solution to be 11.0, and adding a vulcanizing agent into the solution, wherein the vulcanizing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of copper sulfide and 10 parts by mass of sodium sulfide, wherein the concentration is 20 g/L, and the mixture is fully stirred until molybdic acid radicals are fully vulcanized to form thiomolybdate radicals;
(2) adding a selective floating extractant I into the solution, wherein the selective floating extractant I comprises the following components: 50 parts by mass of hexadecyl trimethyl ammonium bromide, 25 parts by mass of P20425 parts by mass of tributyl phosphate, the concentration of which is 10 g/L, adding a sodium hexametaphosphate dispersant, the concentration of which is 200mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, and selectively floating and enriching the hydrophobically mineralized bubbles-sulfo molybdate radical-flotation medicament droplets for 5 min, wherein the foam phase is a molybdenum-rich component substance;
(3) adding 1mol/L phosphoric acid into the tungsten-rich flotation residual liquid to adjust the pH value of the solution to be 3.5, and adding a second selective floating extraction agent into the solution, wherein the second selective floating extraction agent comprises the following components: primary amine N192360 parts by mass, trialkyl phosphorus oxide 20 parts by mass, cetyl trimethyl ammonium bromide 20 parts by mass, the concentration is 10 g/L, sodium hexametaphosphate dispersant is added, the concentration is 100 mg/L, the mixture is uniformly stirred and air is introduced to obtain bubbles, tungstate ions and flotation extract agent micro-droplets, tungstate is enriched for 3 min through flotation, and the foam phase is a tungsten-rich component substance;
(4) and (3) carrying out filter pressing on the foam phase, drying at 120 ℃ for 60 min, and calcining at 650 ℃ for 3 h to obtain a tungsten oxide product and a molybdenum oxide product.
The mass of the tungsten oxide product is 3.41 g, the content of molybdenum impurity in the tungsten oxide product is 1.715 g, and the purity of the tungsten oxide product is only 49.7%; the quality of the molybdenum oxide product is 3.285 g, the content of impurity tungsten in the molybdenum oxide product is 1.59 g, the purity of the molybdenum oxide product is only 51.6%, and the separation effect of tungsten and molybdenum is poor.
Comparative example 2
In this comparative example, the first stripping agent ratio was not in the preferred range.
(1) Adding 1mol/L phosphoric acid and 1mol/L sodium dihydrogen phosphate or 1mol/L disodium hydrogen phosphate into 1L of solution with molybdate concentration of 50 mg/L and tungstate concentration of 50 mg/L, adjusting the pH value of the solution to 9.0, and adding a vulcanizing agent into the solution, wherein the vulcanizing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of copper sulfide and 10 parts by mass of sodium sulfide, wherein the concentration is 200mg/L, and the materials are fully stirred to enable molybdic acid radicals to be fully vulcanized to form thiomolybdate radicals;
(2) adding a selective floating extractant I into the solution, wherein the selective floating extractant I comprises the following components: 20 parts by mass of hexadecyl trimethyl ammonium bromide, 55 parts by mass of tributyl phosphate, 50 mg/L in concentration, adding a sodium hexametaphosphate dispersant with the concentration of 100 mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, and selectively floating and enriching the hydrophobically mineralized bubbles-sulfo-molybdate radicals-flotation medicament droplets for 5 min, wherein the foam phase is a molybdenum-rich component substance;
(3) adding 1mol/L phosphoric acid into the tungsten-rich flotation residual liquid to adjust the pH value of the solution to be 3.5, and adding a second selective floating extraction agent into the solution, wherein the second selective floating extraction agent comprises the following components: primary amine N192330, trialkyl phosphorus oxide 40 and hexadecyl trimethyl ammonium bromide 30, wherein the concentration is 200mg/L, then sodium hexametaphosphate dispersant is added, the concentration is 100 mg/L, the mixture is uniformly stirred and air is introduced to obtain bubbles, tungstate ions and flotation extract agent micro-droplets, tungstate is enriched for 3 min through flotation, and a foam phase is a tungsten-rich component substance;
(4) and (3) carrying out filter pressing on the foam phase, drying at 120 ℃ for 60 min, and calcining at 650 ℃ for 3 h to obtain a tungsten oxide product and a molybdenum oxide product.
The mass of the tungsten oxide product is 37.05 mg, the content of molybdenum impurity in the tungsten oxide product is 13.4 mg, and the purity of the tungsten oxide product is only 63.8%; the quality of the molybdenum oxide product is 36.6 mg, the content of impurity tungsten in the molybdenum oxide product is 12.95 mg, the purity of the molybdenum oxide product is only 64.6%, and the separation effect of tungsten and molybdenum is poor.
In conclusion, through comparative example analysis, the floating extraction technology can significantly improve the tungsten-molybdenum separation efficiency for tungsten-molybdenum ion solutions with different concentration ranges. And the technology has the advantages of less medicament consumption, simple operation and lower equipment requirement, and is suitable for industrial scale-up production.
Claims (8)
1. A tungsten-molybdenum selective separation method based on floating extraction is characterized by comprising the following steps: adding a pH regulator I and a vulcanizing agent into a tungsten-molybdenum solution containing tungstate and molybdate to convert molybdate into thiomolybdate, sequentially adding a selective flotation extractant I and a bubble dispersant into the solution, introducing ventilation for flotation to obtain a foam phase, namely a molybdenum-rich component, sequentially adding a pH regulator II, a selective flotation extractant II and a bubble dispersant into the flotation raffinate, introducing air for flotation to obtain a foam phase, namely a tungsten-rich component, and performing filter pressing, drying and calcining on the foam phase tungsten-rich and molybdenum-rich components to obtain tungsten and molybdenum products respectively.
2. The planktonic extraction-based tungsten-molybdenum selective separation method according to claim 1, characterized in that the vulcanizing agent consists of the following components in parts by mass: 30-60 parts of alkyl sodium xanthate, 20-40 parts of sodium thiosulfate, 10-20 parts of copper sulfide and 10-20 parts of sodium sulfide; the addition amount of the vulcanizing agent is 100 mg/L-20 g/L.
3. The method for selectively separating tungsten and molybdenum based on planktonic extraction as claimed in claim 1, wherein the selective stripping agent I comprises the following components in parts by mass: 30-60 parts of quaternary ammonium salt, 20-40 parts of P20440 parts and 20-40 parts of tributyl phosphate; the quaternary ammonium salt is at least one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide; the addition amount of the first selective floating extraction agent is 100 mg/L-10 g/L.
4. The method for selectively separating tungsten and molybdenum based on planktonic extraction according to claim 1, wherein the selective stripping agent II comprises the following components in parts by mass: primary amine N192330-60 parts, trialkyl phosphorus oxide 20-40 parts, and hexadecyl trimethyl ammonium bromide 20-40 parts; the addition amount of the selective extraction agent II is 100 mg/L-10 g/L.
5. The method for selectively separating tungsten and molybdenum based on planktonic extraction according to claim 1, wherein the bubble dispersing agent is at least one of tripolyphosphate, sodium hexametaphosphate and humic acid; the addition amount of the bubble dispersing agent is 50-200 mg/L.
6. The method for selectively separating tungsten and molybdenum based on planktonic extraction as claimed in claim 1, wherein the first pH regulator is one of the following: (1) HNO3And NaNO3(ii) a (2) HCl and NaOH; (3) h3PO4And NaH2PO4（4）H3PO4And Na2HPO4Adding a pH regulator I to regulate the pH value of a solution system to 9; and the pH regulator II is phosphoric acid, and is added to regulate the pH of the solution system to 3.5.
7. The method for selectively separating tungsten and molybdenum based on planktonic extraction as claimed in claim 1, wherein the drying is drying at 100-150 ℃ for 30-60 min, and the calcining is calcining at 600-700 ℃ for 2.5-3.5 h.
8. The method for selectively separating tungsten and molybdenum based on planktonic extraction as claimed in claim 1, wherein the concentration range of tungstate and molybdate in the tungsten and molybdenum solution is 50 mg/L-5 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010167041.5A CN111187908B (en) | 2020-03-11 | 2020-03-11 | Floating extraction-based tungsten-molybdenum selective separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010167041.5A CN111187908B (en) | 2020-03-11 | 2020-03-11 | Floating extraction-based tungsten-molybdenum selective separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111187908A true CN111187908A (en) | 2020-05-22 |
| CN111187908B CN111187908B (en) | 2022-01-28 |
Family
ID=70704103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010167041.5A Active CN111187908B (en) | 2020-03-11 | 2020-03-11 | Floating extraction-based tungsten-molybdenum selective separation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111187908B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112538570A (en) * | 2020-12-03 | 2021-03-23 | 郑州大学 | Method for separating rare and noble metals based on floating extraction system |
| CN112662874A (en) * | 2020-12-03 | 2021-04-16 | 郑州大学 | Method for separating and extracting rhenium and co-producing ferromolybdenum alloy from rhenium and molybdenum mixed solution |
| CN113926324A (en) * | 2021-09-03 | 2022-01-14 | 郑州大学 | Method for preparing microbubbles by using carbon dioxide liquid-gas phase change and application of microbubbles |
| CN116462228A (en) * | 2023-05-05 | 2023-07-21 | 四川顺应动力电池材料有限公司 | Method for producing high-purity molybdenum trioxide by crude sodium molybdate solution in short process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288413A (en) * | 1979-05-14 | 1981-09-08 | Gte Products Corporation | Separating molybdenum values from an aqueous solution containing tungsten by solvent extraction |
| RU2368427C1 (en) * | 2008-04-15 | 2009-09-27 | Институт проблем комплексного освоения недр РАН (ИПКОН РАН) | Flotation method of noble metals |
| CN105200246A (en) * | 2015-10-22 | 2015-12-30 | 中南大学 | Method for separating tungsten and molybdenum |
| CN110835681A (en) * | 2019-10-17 | 2020-02-25 | 中南大学 | Method for separating molybdenum from tungstate solution by vulcanization |
-
2020
- 2020-03-11 CN CN202010167041.5A patent/CN111187908B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288413A (en) * | 1979-05-14 | 1981-09-08 | Gte Products Corporation | Separating molybdenum values from an aqueous solution containing tungsten by solvent extraction |
| RU2368427C1 (en) * | 2008-04-15 | 2009-09-27 | Институт проблем комплексного освоения недр РАН (ИПКОН РАН) | Flotation method of noble metals |
| CN105200246A (en) * | 2015-10-22 | 2015-12-30 | 中南大学 | Method for separating tungsten and molybdenum |
| CN110835681A (en) * | 2019-10-17 | 2020-02-25 | 中南大学 | Method for separating molybdenum from tungstate solution by vulcanization |
Non-Patent Citations (1)
| Title |
|---|
| 吉布洛夫 等: "泡沫浮选萃取—一种从水溶液中分离金属的新方法", 《国外金属矿选矿》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112538570A (en) * | 2020-12-03 | 2021-03-23 | 郑州大学 | Method for separating rare and noble metals based on floating extraction system |
| CN112662874A (en) * | 2020-12-03 | 2021-04-16 | 郑州大学 | Method for separating and extracting rhenium and co-producing ferromolybdenum alloy from rhenium and molybdenum mixed solution |
| CN112662874B (en) * | 2020-12-03 | 2022-07-26 | 郑州大学 | Method for separating and extracting rhenium and co-producing ferromolybdenum alloy from rhenium and molybdenum mixed solution |
| CN112538570B (en) * | 2020-12-03 | 2022-07-29 | 郑州大学 | Method for separating rare and noble metals based on floating extraction system |
| CN113926324A (en) * | 2021-09-03 | 2022-01-14 | 郑州大学 | Method for preparing microbubbles by using carbon dioxide liquid-gas phase change and application of microbubbles |
| CN113926324B (en) * | 2021-09-03 | 2023-08-22 | 郑州大学 | Method for preparing microbubbles by utilizing carbon dioxide liquid-gas phase transition and application of microbubbles |
| CN116462228A (en) * | 2023-05-05 | 2023-07-21 | 四川顺应动力电池材料有限公司 | Method for producing high-purity molybdenum trioxide by crude sodium molybdate solution in short process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111187908B (en) | 2022-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111187908B (en) | Floating extraction-based tungsten-molybdenum selective separation method | |
| CN103243218B (en) | A kind of from containing extracting the method for molybdenum and the application of extraction agent molybdenum high-concentration acidic wastewater leach liquor | |
| CN105200246A (en) | Method for separating tungsten and molybdenum | |
| CN101736153B (en) | Method for extracting ammonium molybdate from molybdenum concentrate by pressure ammonia leaching | |
| CN101914678B (en) | Method for producing industry molybdenum oxide from molybdenum concentrate | |
| CN103611633B (en) | Tungsten-bearing limonite processing method | |
| CN102660676A (en) | Method for separating rhenium and molybdenum in molybdenum-rhenium ore concentrate | |
| CN105692698B (en) | The depth separation method of molybdenum, vanadium in a kind of vanadium solution containing molybdenum | |
| CN105779760B (en) | A kind of clean metallurgical method of scheelite | |
| CN111206150B (en) | Dissolved state high-similarity rare and precious metal enrichment and separation method based on floating extraction | |
| CN111286608B (en) | Method for selectively separating tantalum and niobium step by step based on floating extraction | |
| CN104928502B (en) | A kind of allocate the method that high phosphorus scheelite extracts tungsten from wolframite or Scheelite-Wolframite Mixed Mine into | |
| CN101265522A (en) | Technique for extracting vanadium pentoxide by tunnel kiln calcification roasting | |
| CN113800569B (en) | Recovery method for preparing ammonium molybdate, tungsten, copper and sulfur by molybdenum removal slag | |
| CN112174209B (en) | Green molybdenum smelting ion exchange process | |
| CN113088700A (en) | Method for efficiently separating vanadium and chromium based on pH regulation | |
| CN104803417A (en) | Ammonium paratungstate and preparation method thereof | |
| CN104878223B (en) | A kind of method that tungsten is extracted from wolframite or Scheelite-Wolframite Mixed Mine | |
| CN207699643U (en) | A kind of system that molybdenum is recycled in the raffinate from catalysts containing molybdenum | |
| CN109628737A (en) | A method of it decomposing high seyrigite and extracts tungsten, molybdenum | |
| CN112662874B (en) | Method for separating and extracting rhenium and co-producing ferromolybdenum alloy from rhenium and molybdenum mixed solution | |
| CN111304466A (en) | Method for selectively separating vanadium and chromium from vanadium and chromium-containing solution | |
| CN109055747B (en) | Method for extracting and separating molybdenum and rhenium under acidic condition | |
| CN101956069A (en) | Method for reducing and leaching manganese from pyrolusite in sulfuric acid solution by using sludge | |
| CN106367589A (en) | Short-process low-consumption high-purity manganese sulfate solution preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |