CN111068926B - Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof - Google Patents
Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof Download PDFInfo
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- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
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- B03D1/001—Flotation agents
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- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
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- B03D1/02—Froth-flotation processes
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- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
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Abstract
The invention discloses a hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent, and a preparation method and application thereof. The hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is obtained by carrying out coordination reaction on hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle prepared from hydroximic acid salt and alkyl sulfate and metal ions. The hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent has extremely strong selective collecting capability on tungsten-containing minerals, can realize high-efficiency flotation separation of the tungsten-containing minerals and the calcium-containing gangue minerals under the condition of no or only containing a small amount of calcium-containing mineral inhibitors, and fundamentally solves the technical problem of difficult flotation separation of the tungsten-containing minerals and the calcium-containing gangue minerals.
Description
Technical Field
The invention relates to a flotation collector, in particular to a hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collector for flotation separation of tungsten-containing minerals, a preparation method of the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collector, and a method for realizing efficient flotation separation of tungsten-containing minerals and calcium-containing gangue minerals by using the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex, and belongs to the technical field of mineral flotation.
Background
The tungsten-containing minerals are important mineral resources, common tungsten-containing minerals mainly comprise scheelite, wolframite and the like, and the recovery and utilization of the tungsten-containing minerals are generally realized by adopting a flotation method. Tungsten-containing minerals often coexist with gangue minerals such as silicate and carbonate, and the flotation efficiency in the flotation process is low. In the case of scheelite, the scheelite ore types can be classified into scheelite-quartz (or silicate mineral), scheelite-calcite, and fluorite (barite) types. Generally, scheelite-quartz type ores are easier to select; the scheelite-fluorite, calcite (barite) type ores are difficult to sort because scheelite is difficult to separate from calcium-containing gangue minerals due to their similar floatability. The flotation separation of scheelite and calcium-containing minerals such as fluorite, calcite and the like is one of the ore dressing problems in the world. In the prior art, the common collector for tungsten-containing minerals is fatty acid and derivatives thereof, and the action mechanism of the collector and calcium-containing minerals is represented by the combination of functional groups and calcium particles on the surfaces of minerals, so that the collector lacks selectivity on the calcium-containing gangue minerals, and the recovery rate and the coarse concentrate grade of scheelite in the flotation process are low. The dense slurry high temperature method, namely the Peterov method, is commonly applied to the white tungsten flotation production practice to improve the rough concentrate grade. The method is invented by Suyi expert Bidelov in the end of 40 years of the 20 th century. Concentrating the rough concentrate to about 70%, adding water glass, heating to above 90 ℃, stirring for 30-60 minutes, and diluting and floating at normal temperature. However, the petarov method requires thermal flotation, which has high energy consumption, high cost, complicated operation and poor labor conditions, so that the new process for realizing the normal-temperature flotation of the white tungsten is an objective requirement and an inevitable requirement for the development of the times. The flotation reagent is used as a key factor in the flotation process and plays a vital role in flotation indexes. Therefore, the novel efficient flotation collector is developed, the efficient selective flotation recovery of the target minerals is realized, and the method has great significance for processing and utilizing mineral resources.
Disclosure of Invention
The invention aims to solve the problems that the separation of tungsten-containing minerals and calcium-containing gangue minerals is difficult, the using amount of a water glass inhibitor is large, the separation of rough concentration and fine concentration operation is difficult, the recovery rate is low and the like due to the adoption of a traditional fatty acid collecting agent in the flotation of the tungsten-containing minerals in the prior art.
The invention also aims to provide a method for preparing the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent, which has the advantages of simple process, mild reaction conditions and low cost.
The third purpose of the invention is to provide an application of the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent, the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is used for flotation separation of tungsten-containing minerals and calcium-containing gangue minerals, the grade and recovery rate of flotation concentrate of the tungsten-containing minerals can be greatly improved in the absence or in the presence of a small amount of calcium-containing mineral inhibitor, and the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent has the characteristics of small using amount, low cost, strong collecting capability, good selectivity and the like, and can be widely applied to flotation separation processes of the tungsten.
In order to achieve the above technical objects, the present invention provides a hydroximic acid-alkylsulfate multi-ligand metal complex collector having a structure of formula 1:
wherein the content of the first and second substances,
m is a positive divalent metal ion;
R1is an alkyl group, a phenyl group or a hydroxyphenyl group;
R2is an alkyl group.
In a preferred embodiment, M is Pb2+、Cu2+、Ca2+Or Fe2+。
Preferred embodiment, R1When it is an alkyl group, it is selected from C1～C18An alkyl group of (a); the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group, or a cyclic alkyl group, specifically, methyl, propyl, isopropyl, octyl, dodecyl, cyclohexyl, or the like.
Preferred embodiment, R2When it is an alkyl group, it is selected from C2～C18An alkyl group of (a); the alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group or a cyclic alkyl group, such as ethyl, propyl, isopropyl, hexyl, octyl, dodecyl, and octadecylAlkyl, cyclohexyl, and the like.
The invention also provides a preparation method of the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent, which comprises the following steps:
1) reacting a hydroximic acid compound with an alkali metal hydroxide to obtain a hydroximic acid salt;
2) reacting alkyl sulfate with hydroximic acid salt to obtain hydroximic acid-alkyl sulfate multi-ligand compound;
3) adding the hydroximic acid-alkyl sulfuric acid multi-ligand compound into the alcohol-water mixed solution to obtain a hydroximic acid-alkyl sulfuric acid multi-ligand compound micelle;
4) carrying out coordination polymerization reaction on the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle and metal salt to obtain the product.
According to the preferable scheme, a hydroximic acid compound is dissolved in a solvent to obtain a hydroximic acid compound solution, then ethyl acetate and alkali metal hydroxide are added, and the mixture is stirred and reacts for 20-40 min at room temperature to obtain hydroximic acid salt; wherein the molar ratio of the hydroximic acid compound to the ethyl acetate is 5: 1-8: 1, and the addition amount of the alkali metal hydroxide is used for controlling the pH value of the solution to be 8.5-9.5. Preferably, the solvent is an alcoholic solvent, such as methanol. Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like.
In a preferred embodiment, the hydroxamic acid compound has the structure of formula 2,
wherein R is1Is alkyl, phenyl or hydroxyphenyl.
In the preferable scheme, the alkyl sulfate and the hydroximic acid salt react for 10-30 min in glycerol at the temperature of 80-100 ℃; wherein the molar ratio of the hydroximic acid salt to the alkyl sulfate is 1-1.5: 1, and the mass percentage concentration of the alkyl sulfate and the hydroximic acid salt in the glycerol is 30-45%.
In a preferred embodiment, the alkyl sulfate has the structure of formula 3:
wherein R is2Is alkyl radical, and X is alkali metal ion, such as sodium, potassium, etc.
In a preferable scheme, the alcohol-water mixed solution is composed of water and methanol according to a volume ratio of 6-8: 1.
In a preferable scheme, the mass percentage concentration of the hydroximic acid-alkyl sulfuric acid multi-ligand compound in the alcohol-water mixed solution is 30-50%.
According to the preferable scheme, hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle is stirred for 10-40 min at the temperature of 50-90 ℃, then metal salt solution is slowly dripped, the temperature is kept for reaction for 0.5-1.5 h, and then the mixture is aged for 24-36 h at normal temperature, so that the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is obtained.
In the preferable scheme, the mass percentage concentration of metal ions in the metal salt solution is 3-6%. The metal salt being readily ionizable to yield Pb2+、Cu2+、Ca2+Or Fe2+Such as nitrate, chloride, etc.
In a preferable scheme, the molar ratio of metal ions to hydroximic acid-alkyl sulfuric acid multi-ligand complex micelles in the metal salt solution is 1: 1-1: 3, wherein the hydroximic acid-alkyl sulfuric acid multi-ligand complex micelles are measured by the number of molecules.
In a preferable scheme, the dropping speed of the metal salt solution is not higher than 0.03 g/s.
The invention also provides an application of the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent, which is applied to flotation of tungsten-containing minerals.
In a preferred embodiment, the tungsten-containing mineral includes at least one of scheelite, wolframite, and wolframite.
Preferably, the gangue minerals are silicates, calcium-containing gangue minerals, such as fluorite, calcite, garnet, and the like.
In a preferable scheme, the addition amount of the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent relative to raw ore is 50-400 g/t.
According to the preferable scheme, when the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is used, water needs to be added into the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent to prepare a solution, and the mass percentage concentration of the agent is 2-10%.
In the preferable scheme, the pH value of ore pulp is 6-11 in the flotation process.
The hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is used for the flotation of tungsten ores in the following process: the method comprises the steps of crushing tungsten-containing ores and grinding the tungsten-containing ores by a wet method to obtain ore pulp; and sequentially carrying out iron removal and desulfurization on the obtained ore pulp, and then entering a tungsten sorting process. Roughing, namely using the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex as a collecting agent, using pinitol oil as a foaming agent, and under the condition that the pH value of ore pulp is 6.0-11.0, roughing to obtain rough concentrate and tailings, carrying out 1-4 times of concentration on the rough concentrate in a concentration operation to obtain final concentrate, carrying out scavenging on the rough concentrate in a scavenging operation, and carrying out 1-4 times of scavenging to obtain final tailings. The whole process is a closed-loop process for returning the middling sequence.
The preparation method of the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent comprises the following steps:
1) the preparation process of the hydroximic acid-alkyl sulfuric acid multi-ligand complex micelle comprises the following steps: weighing a hydroximic acid compound, putting the hydroximic acid compound into a flask, adding methanol as a solvent, adding ethyl acetate according to the ratio of the hydroximic acid compound to ethyl acetate of 5: 1-8: 1 after the hydroximic acid compound and the ethyl acetate are completely dissolved, then adding an alkali metal hydroxide to adjust the pH value to be 8.5-9.5, and stirring and reacting for 20-40 min at room temperature to obtain hydroximic acid salt; adding a hydroximic acid salt and an alkyl sulfate into a flask according to a molar mass ratio of 1-1.5: 1, adding glycerol to make the mass concentration of the glycerol 30-45%, then placing the mixture into a constant-temperature water bath kettle, stirring the mixture by using magnetons, heating the mixture to 80-100 ℃, reacting the mixture for 10-30 min, and performing rotary evaporation on the obtained liquid and recrystallization for three times to obtain a solid; adding the solid into a flask, preparing a mixed liquid of water and methanol according to the volume ratio of the water to the methanol of 6-8: 1, and adding the mixed liquid into the flask to ensure that the mass percentage concentration of the solid in the mixed solution of the water and the methanol is 30-50% to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand complex micelle.
2) The preparation process of the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent comprises the following steps: placing hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle in a flask, placing the flask in a constant-temperature water bath kettle, stirring by using a magneton, heating to 50-90 ℃, stirring for 10-40 min, dropwise adding a metal salt solution with the metal ion mass percentage concentration of 3-6% into the multi-ligand composite micelle, wherein the dropping speed of the metal salt solution is not higher than 0.03g/s, the molar ratio of the metal ions to the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle is 1: 1-1: 3, continuously preserving heat for 0.5-1.5 h after the dropping is finished, aging for 24-36 h at normal temperature, filtering, and drying for 24h in a vacuum drying oven at 40-50 ℃ to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is used as a collecting agent of a target mineral in a tungsten-containing mineral flotation process, has extremely strong selective collecting capacity on the tungsten-containing mineral, can realize efficient flotation separation of the tungsten-containing mineral, silicate and calcium-containing gangue mineral, and is greatly beneficial to improving the concentrate grade and the flotation operation recovery rate.
2. The hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent disclosed by the invention is low in using amount in the using process, is non-toxic and pollution-free, reduces the mineral separation cost, and is beneficial to environmental protection.
3. The hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is simple in preparation method, low in cost and beneficial to large-scale production and application.
Drawings
FIG. 1 is an infrared spectrum of hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collector (taking benzohydroxamic acid and sodium dodecyl sulfate as examples to coordinate with lead ions); 580.71cm in the figure-1And 620.34cm-1Under O-Pb stretching vibration of 689.64cm-1780.46cm for C-H bending vibration-1Is subjected to S-O telescopic vibration of 905.99-1023.83 cm-1Under the action of N-O stretching vibration, 1041.55cm-1Is in S ═ O stretching vibration, 1153.49cm-1Is subjected to C-N telescopic vibration of 1219.13cm-1Is symmetrically stretched when S is equal to OVibration at 1342.38cm-1The vibration is O-H bending vibration of 1440.81-1599.59 cm-12924.21cm for bending vibration of benzene ring skeleton-1Is in O-H symmetrical telescopic vibration of 3221.81cm-1The vibration is O-H asymmetric stretching vibration or N-H stretching vibration.
FIG. 2 is an X-ray photoelectron spectrum of hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collector (exemplified by the coordination of benzohydroxamic acid and sodium dodecyl sulfate with lead ions).
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the invention as claimed.
Example 1
Weighing 0.001mol of benzohydroxamic acid, putting the benzohydroxamic acid into a 500mL flask, adding 300mL of methanol as a solvent, adding 0.0002mol of ethyl acetate after complete dissolution, then adding sodium hydroxide to adjust the pH value to 9.0, and stirring and reacting for 30min at room temperature to obtain hydroxamate; adding a hydroximic acid salt and sodium dodecyl sulfate into a flask according to a molar mass ratio of 1:1, adding glycerol to enable the mass concentration of the glycerol to be 35%, then placing the mixture into a constant-temperature water bath kettle, stirring the mixture by using magnetons, heating the mixture to 90 ℃, reacting the mixture for 20min, and performing rotary evaporation on the obtained liquid and recrystallization for three times to obtain a solid; adding the solid into a flask, preparing a mixed liquid of water and methanol according to the volume ratio of the water to the methanol of 6:1, and adding the mixed liquid into the flask to ensure that the mass percent concentration of the solid in the mixed solution of the water and the methanol is 40 percent to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand complex micelle. Placing the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using a magneton, heating to 70 ℃, stirring for 20min, dropwise adding a lead nitrate solution with the metal ion mass percentage concentration of 3% into the multi-ligand composite micelle at the speed of 0.01g/s, keeping the temperature for 1.0h after dropwise adding, aging for 24h at normal temperature, filtering, and drying for 24h in a vacuum drying oven at 50 ℃ to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent.
Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is used for treating tungsten ore in Hunan persimmon orchard3The grade is 0.36%, the main tungsten minerals are scheelite, wolframite and a small amount of tungsten, and the gangue minerals are fluorite, calcite, garnet and the like. Soda serves as a pH regulator, the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent provided by the embodiment serves as a collecting agent, the terpineol oil serves as a foaming agent, and the obtained slurry is fully mixed and then enters a flotation machine to be subjected to primary coarse sweeping, tertiary fine sweeping and secondary fine sweeping. The adding amount of the medicament relative to the raw ore is roughly selected to be 550g/t of soda ash, 320g/t of collecting agent and 30g/t of pine oil; 80g/t of water glass and 40g/t of aluminum sulfate are used as the first extract, 40g/t of water glass and 20g/t of aluminum sulfate are used as the second extract, and no medicament is added to the third extract; the first scavenging is 40g/t of the collecting agent, and the second scavenging is 10g/t of the collecting agent. Experimental obtaining of WO3Concentrate of grade 66.54%, WO3The operating recovery was 83.37% (as in table 1).
TABLE 1 Hunan persimmon orchard tungsten ore flotation test results
| Product(s) | Yield/%) | WO3Grade/% | WO3Percent recovery% |
| Concentrate ore | 0.45 | 66.54 | 83.37 |
| Tailings | 99.55 | 0.06 | 16.63 |
| Raw ore | 100.00 | 0.36 | 100.00 |
Example 2
Weighing 0.002mol of propyl hydroximic acid, putting the propyl hydroximic acid into a 500mL flask, adding 300mL of methanol as a solvent, adding 0.0004mol of ethyl acetate after complete dissolution, then adding sodium hydroxide to adjust the pH value to 8.5, and stirring and reacting for 40min at room temperature to obtain hydroximic acid salt; adding a hydroximic acid salt and sodium n-octadecyl sulfate into a flask according to the molar mass ratio of 1:1, adding glycerol to ensure that the mass concentration of the glycerol is 40%, then placing the flask into a constant-temperature water bath kettle, stirring by using a magneton, heating to 100 ℃, reacting for 15min, and performing rotary evaporation on the obtained liquid and then recrystallizing for three times to obtain a solid; adding the solid into a flask, preparing a mixed liquid of water and methanol according to the volume ratio of the water to the methanol of 8:1, and adding the mixed liquid into the flask to ensure that the mass percent concentration of the solid in the mixed solution of the water and the methanol is 35 percent to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand complex micelle. Placing the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using a magnet, heating to 80 ℃, stirring for 15min, then dropwise adding a copper sulfate solution with the metal ion mass percentage concentration of 3% into the multi-ligand composite micelle at the speed of 0.01g/s, wherein the molar ratio of copper ions to the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle is 1:2, continuously preserving the temperature for 1.5h after dropwise adding, aging for 36h at normal temperature, finally filtering and drying for 24h in a vacuum drying oven at 50 ℃ to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent.
Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is used for treating Fujian wolframite, and used raw material WO3The grade is 0.52%, and the main gangue minerals are quartz, fluorite, garnet and the like. Sodium carbonate is used as a pH regulator, andthe hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent provided by the embodiment is used as a collecting agent, and the terpineol oil is used as a foaming agent, and after full size mixing, the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent enters a flotation machine to perform primary cleaning, secondary cleaning and fine cleaning. The adding amount of the medicament relative to the raw ore is roughly 460g/t of soda ash, 300g/t of collecting agent and 20g/t of pine oil; the first essence is 50g/t of carboxymethyl cellulose serving as an inhibitor, and the second essence is 20g/t of carboxymethyl cellulose; the first scavenging is 40g/t of the collecting agent, and the second scavenging is 10g/t of the collecting agent. Experimental obtaining of WO3Concentrate of grade 43.56%, WO3The operating recovery was 84.87% (as in table 2).
TABLE 2 Fujian wolframite flotation test results
| Product(s) | Yield/%) | WO3Grade/% | WO3Percent recovery% |
| Concentrate ore | 1.02 | 43.56 | 84.87 |
| Tailings | 98.98 | 0.08 | 15.13 |
| Raw ore | 100.00 | 0.52 | 100.00 |
Example 3
Weighing 0.001mol of salicylhydroxamic acid, putting the salicylhydroxamic acid into a 500mL flask, adding 300mL of methanol as a solvent, adding 0.0002mol of ethyl acetate after complete dissolution, then adding sodium hydroxide to adjust the pH value to 9.0, and stirring and reacting for 25min at room temperature to obtain a hydroxamate; adding a hydroximic acid salt and sodium tetradecyl sulfate into a flask according to a molar mass ratio of 1:1, adding glycerol to make the mass concentration of the glycerol 42%, then placing the mixture into a constant-temperature water bath kettle, stirring the mixture by using a magneton, heating the mixture to 85 ℃, reacting the mixture for 15min, and performing rotary evaporation on the obtained liquid and recrystallization for three times to obtain a solid; adding the solid into a flask, preparing a mixed liquid of water and methanol according to the volume ratio of the water to the methanol of 7:1, and adding the mixed liquid into the flask to ensure that the mass percent concentration of the solid in the mixed solution of the water and the methanol is 35 percent to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand complex micelle. Placing the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using a magnet, heating to 90 ℃, stirring for 15min, then dropwise adding a ferrous chloride solution with the metal ion mass percentage concentration of 4% into the multi-ligand composite micelle at the speed of 0.01g/s, wherein the molar ratio of ferrous ions to the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle is 1:1, continuously preserving heat for 1.0h after dropwise adding, aging for 48h at normal temperature, finally filtering and drying for 24h in a vacuum drying oven at 50 ℃ to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent.
Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is used for treating tungsten ore in Jiangxi3The grade is 0.22%, the main tungsten minerals are scheelite, wolframite and a small amount of tungsten, and the gangue minerals are quartz, calcite, garnet and the like. Soda serves as a pH regulator, the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent provided by the embodiment serves as a collecting agent, the terpineol oil serves as a foaming agent, and the obtained slurry is fully mixed and then enters a flotation machine to be subjected to primary and secondary fine sweeping. The adding amount of the medicament relative to the raw ore is roughly 450g/t of soda ash, 290g/t of collecting agent and 25g/t of pine oil; extract of Chinese medicinal materialsThe first is water glass 60g/t, aluminum sulfate 30g/t, the second is water glass 20g/t, aluminum sulfate 10 g/t; the first scavenging is 30g/t of the collecting agent, and the second scavenging is 10g/t of the collecting agent. Experimental obtaining of WO3Concentrate of grade 47.45%, WO3The operating recovery was 82.28% (as in table 3).
TABLE 3 flotation test results of certain tungsten ore in Jiangxi
Example 4
Weighing 0.002mol of octyl hydroximic acid, putting the octyl hydroximic acid into a 500mL flask, adding 300mL of methanol as a solvent, adding 0.0004mol of ethyl acetate after complete dissolution, then adding sodium hydroxide to adjust the pH value to 8.5, and stirring and reacting for 30min at room temperature to obtain hydroximic acid salt; adding a hydroximic acid salt and sodium n-octadecyl sulfate into a flask according to the molar mass ratio of 1.5:1, adding glycerol to ensure that the mass concentration of the glycerol is 38%, then placing the mixture into a constant-temperature water bath kettle, stirring the mixture by using a magneton, heating the mixture to 80 ℃, reacting the mixture for 25min, and performing rotary evaporation on the obtained liquid and recrystallization for three times to obtain a solid; adding the solid into a flask, preparing a mixed liquid of water and methanol according to the volume ratio of the water to the methanol of 8:1, and adding the mixed liquid into the flask to ensure that the mass percent concentration of the solid in the mixed solution of the water and the methanol is 45 percent to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand complex micelle. Placing the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using a magneton, heating to 80 ℃, stirring for 20min, dropwise adding a lead nitrate solution with the metal ion mass percentage concentration of 3% into the multi-ligand composite micelle at the speed of 0.01g/s, keeping the temperature for 1.5h after dropwise adding, aging for 36h at normal temperature, filtering, and drying for 24h in a vacuum drying oven at 50 ℃ to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent.
Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is used for treating certain tungsten ore in Henan province, and used raw material WO3The grade is 0.10%, the main tungsten mineral is scheelite, and the gangue mineral is calcite, fluorite, garnet and the like. Soda serves as a pH regulator, the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent provided by the embodiment serves as a collecting agent, the terpineol oil serves as a foaming agent, and the obtained slurry is fully mixed and then enters a flotation machine to be subjected to primary coarse sweeping, tertiary fine sweeping and secondary fine sweeping. The adding amount of the medicament relative to the raw ore is 290g/t of soda ash, 250g/t of collecting agent and 20g/t of pine oil; the first refined is 60g/t of water glass, 30g/t of aluminum sulfate, the second refined is 20g/t of water glass, 10g/t of aluminum sulfate, and the third refined is not added with a medicament; the first scavenging is 20g/t of collecting agent, and the second scavenging is 5g/t of collecting agent. Experimental obtaining of WO3Concentrate of grade 51.21%, WO3The operating recovery was 80.41% (as in table 4).
TABLE 4 flotation test results for certain tungsten ore in Henan
| Product(s) | Yield/%) | WO3Grade/% | WO3Percent recovery% |
| Concentrate ore | 0.16 | 51.21 | 80.41 |
| Tailings | 99.84 | 0.02 | 19.59 |
| Raw ore | 100.00 | 0.10 | 100.00 |
Claims (10)
1. A hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent is characterized in that: has the structure of formula 1:
wherein the content of the first and second substances,
m is a positive divalent metal ion;
R1is an alkyl group, a phenyl group or a hydroxyphenyl group;
R2is an alkyl group.
2. A hydroximic acid-alkylsulfate syndet collector as claimed in claim 1 wherein:
m is Pb2+、Cu2+、Ca2+Or Fe2+；
R1When it is an alkyl group, it is selected from C1～C18An alkyl group of (a);
R2when it is an alkyl group, it is selected from C2～C18An alkyl group of (1).
3. The method for preparing a hydroximic acid-alkylsulfuric acid multi-ligand metal complex collector according to claim 1 or 2, characterized in that: the method comprises the following steps:
1) reacting a hydroximic acid compound with an alkali metal hydroxide to obtain a hydroximic acid salt;
2) reacting alkyl sulfate with hydroximic acid salt to obtain hydroximic acid-alkyl sulfate multi-ligand compound;
3) adding the hydroximic acid-alkyl sulfuric acid multi-ligand compound into the alcohol-water mixed solution to obtain a hydroximic acid-alkyl sulfuric acid multi-ligand compound micelle;
4) carrying out coordination reaction on the hydroximic acid-alkyl sulfate multi-ligand composite micelle and a metal salt solution to obtain the complex.
4. The method of preparing a hydroximic acid-alkylsulfuric acid multi-ligand metal complex collector as claimed in claim 3, wherein: dissolving a hydroximic acid compound in a solvent to obtain a hydroximic acid compound solution, adding ethyl acetate and an alkali metal hydroxide, and stirring and reacting for 20-40 min at room temperature to obtain hydroximic acid salt; wherein the molar ratio of the hydroximic acid compound to the ethyl acetate is 5: 1-8: 1, and the addition amount of the alkali metal hydroxide is measured by controlling the pH value of the solution to be 8.5-9.5.
5. The method of preparing a hydroximic acid-alkylsulfuric acid multi-ligand metal complex collector as claimed in claim 3, wherein: reacting alkyl sulfate and hydroximic acid salt in glycerol at the temperature of 80-100 ℃ for 10-30 min; wherein the molar ratio of the hydroximic acid salt to the alkyl sulfate is 1-1.5: 1, and the mass percentage concentration of the alkyl sulfate and the hydroximic acid salt in the glycerol is 30-45%.
6. The method of preparing a hydroximic acid-alkylsulfuric acid multi-ligand metal complex collector as claimed in claim 3, wherein: the alcohol-water mixed solution consists of water and methanol according to the volume ratio of 6-8: 1;
the mass percentage concentration of the hydroximic acid-alkyl sulfuric acid multi-ligand compound in the alcohol-water mixed solution is 30-50%.
7. The method of preparing a hydroximic acid-alkylsulfuric acid multi-ligand metal complex collector as claimed in claim 3, wherein: stirring the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelle at the temperature of 50-90 ℃ for 10-40 min, slowly dropwise adding a metal salt solution, reacting for 0.5-1.5 h at a constant temperature, and aging at the normal temperature for 24-36 h to obtain the hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent.
8. The method of preparing a hydroximic acid-alkylsulfuric acid multi-ligand metal complex collector of claim 7, wherein:
the mass percentage concentration of metal ions in the metal salt solution is 3-6%;
the molar ratio of metal ions to hydroximic acid-alkyl sulfuric acid multi-ligand composite micelles in the metal salt solution is 1: 1-1: 3, wherein the hydroximic acid-alkyl sulfuric acid multi-ligand composite micelles are measured by the number of molecules;
the dropping rate of the metal salt solution is not higher than 0.03 g/s.
9. Use of a hydroximic acid-alkylsulfate syndet collector according to claim 1 or 2, characterized in that: the method is applied to flotation separation of tungsten-containing minerals and calcium-containing gangue minerals.
10. The use of a hydroximic acid-alkylsulfate syndet collector as claimed in claim 9 wherein: the tungsten-containing mineral comprises at least one of scheelite, wolframite and wolframite.
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