CN110721815B - Hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent and preparation method and application thereof - Google Patents

Hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent and preparation method and application thereof Download PDF

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CN110721815B
CN110721815B CN201911098212.7A CN201911098212A CN110721815B CN 110721815 B CN110721815 B CN 110721815B CN 201911098212 A CN201911098212 A CN 201911098212A CN 110721815 B CN110721815 B CN 110721815B
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hydroximic acid
ligand
acid
sulfonic acid
hydroximic
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CN110721815A (en
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韩海生
卫召
孙伟
胡岳华
王若林
孙文娟
付君浩
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores

Abstract

The invention discloses a hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent, and a preparation method and application thereof. The hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent is obtained by carrying out coordination reaction on hydroximic acid-sulfonic acid multi-ligand complex micelle prepared from hydroximic acid salt and sulfonate and metal ions. The hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent has extremely strong selective collecting capability on titaniferous minerals such as ilmenite, rutile, anatase and the like, can realize selective flotation separation of the titaniferous minerals and gangue minerals, and fundamentally solves the technical problem of difficult flotation separation of the titaniferous minerals and the gangue minerals.

Description

Hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent and preparation method and application thereof
Technical Field
The invention relates to a flotation collector, in particular to a hydroximic acid-sulfonic acid multi-ligand metal complex collector for flotation separation of titanium-containing minerals, a preparation method of the hydroximic acid-sulfonic acid multi-ligand metal complex collector, and a method for realizing efficient flotation separation of titanium-containing minerals and gangue minerals by using the hydroximic acid-sulfonic acid multi-ligand metal complex collector, and belongs to the technical field of mineral flotation.
Background
The Chinese titanium resource reserves are listed as the first global reserves and account for more than 30 percent of the total reserves in the world. The titanium resource types in China are relatively complete, and primary ores and secondary ores are both provided, wherein primary vanadium-titanium ferro-ferrihydrite is taken as a main material. The primary ilmenite accounts for 97% of the total resource reserves of the ilmenite in China, and the placer accounts for only 3%. 86% of the reserves of rutile resources in China are refractory primary ores, and the remaining 14% are placer ores. The domestic titanium selection method mainly comprises methods such as gravity separation, magnetic separation, electric separation, flotation, combined flow and the like, wherein the flotation is a common titanium selection method. Fatty acid collectors, such as tall oil, hydroximic acid, oxidized paraffin soaps, organic phosphoric acid, arsonic acid and the like, are common flotation collectors for ferro-iron ore. However, with the continuous development of the mining and mineral separation fields, the high-grade easy-separation ores are gradually reduced, so that the low-grade hard-separation ores need to be reasonably developed and utilized. In recent years, the mixed use of various ilmenite flotation reagents and the synthesis of new reagents have become one of the main research contents of the ilmenite flotation. The mixed reagent has better collecting capability for titanium-containing minerals with different ore properties, but the using effect is not as stable as that of a single reagent. The synthesis of the new medicament can finely design a proper collecting agent aiming at the crystal structure and the interface property of the titanium-containing mineral, and becomes a way for fundamentally realizing the high-efficiency flotation and recovery of the refractory titanium-containing mineral. 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
Aiming at the problems that the traditional fatty acid collecting agent and the like are adopted for the flotation of the titanium-containing minerals in the prior art, the separation of the titanium-containing minerals and the gangue minerals is difficult, the using amount of an inhibitor is large, the recovery rate is low and the like, the first purpose of the invention is to provide the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent which has extremely strong selective collecting capability on the titanium-containing minerals such as ilmenite, rutile, anatase and the like and can realize the high-efficiency separation of the titanium-containing minerals and the gangue minerals such as silicate, carbonate and the like.
The invention also aims to provide a method for preparing the hydroximic acid-sulfonic 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-sulfonic acid multi-ligand metal complex collecting agent, the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent is used for flotation separation of titanium-containing minerals and gangue minerals, the grade and recovery rate of flotation concentrate of the titanium-containing minerals can be greatly improved under the condition that no or a small amount of inhibitor exists, and the hydroximic acid-sulfonic 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 titanium-containing minerals such as ilmenite, rutile, anatase and the like.
In order to achieve the above technical objects, the present invention provides a hydroximic acid-sulfonic acid multi-ligand metal complex collector having a structure of formula 1:
Figure BDA0002269018080000021
wherein the content of the first and second substances,
m is a positive divalent metal ion;
R1is an alkyl or aryl group;
R2is alkyl or aryl.
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. R1When the aryl is selected from phenyl or phenyl containing hydroxyl substituent, the hydroxyl substituent position can be ortho-position, meta-position or para-position.
Preferred embodiment, R2When it is an alkyl group, it is selected from C2～C12An alkyl group of (1). The alkyl group may be a straight-chain alkyl group or a branched alkyl group or a cyclic alkyl group, specifically, ethyl, propyl, isopropyl, hexyl, octyl, dodecyl, octadecyl, cyclohexyl, and the like. R2When it is aryl, it is selected from phenyl or C2～C12Phenyl substituted by an alkanyl radical, which may be a straight-chain alkanyl radicalOr a branched alkyl group or a cyclic alkyl group, such as ethyl, propyl, isopropyl, hexyl, octyl, dodecyl, cyclohexyl, etc., and the substituted position is any substituted position on the benzene ring.
The invention also provides a preparation method of the hydroximic acid-sulfonic 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 sulfonate with hydroximic acid salt to obtain hydroximic acid-sulfonic acid multi-ligand compound;
3) adding the hydroximic acid-sulfonic acid multi-ligand compound into the alcohol-water mixed solution to obtain a hydroximic acid-sulfonic acid multi-ligand compound micelle;
4) and carrying out coordination reaction on the hydroximic acid-sulfonic acid multi-ligand composite micelle and a metal salt solution to obtain the complex.
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 6: 1-9: 1, and the addition amount of the alkali metal hydroxide is used for controlling the pH value of the solution to be 8.0-9.5. 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,
Figure BDA0002269018080000031
wherein R is1Is alkyl or aryl.
In the preferable scheme, sulfonate and hydroximic acid salt react for 20-30 min in glycerol at the temperature of 80-100 ℃; wherein the molar ratio of the hydroximic acid salt to the sulfonate is 1-1.5: 1, and the mass percentage concentration of the sulfonate and the hydroximic acid salt in the glycerol is 30-40%.
In a preferred embodiment, the alkyl sulfate has the structure of formula 3:
Figure BDA0002269018080000032
wherein R is2Is alkyl or aryl, 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-sulfonic acid multi-ligand compound in the alcohol-water mixed solution is 30-50%.
According to the preferable scheme, hydroximic acid-sulfonic acid multi-ligand composite micelle is stirred for 20-40 min at the temperature of 40-90 ℃, 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-sulfonic 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-sulfonate multi-ligand complex micelles in the metal salt solution is 1: 1-1: 3, wherein the hydroximic acid-sulfonate 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 application of the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent in flotation separation of titanium-containing minerals and gangue minerals.
In a preferred embodiment, the titaniferous ore includes at least one of ilmenite, rutile, and anatase.
Preferably, the gangue minerals are silicates, calcium-containing gangue minerals, such as quartz, fluorite, calcite, garnet, mica, and the like.
In a preferable scheme, the addition amount of the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent relative to raw ore is 60-400 g/t.
According to the preferable scheme, when the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent is used, water needs to be added into the hydroximic acid-sulfonic 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 4-7 in the flotation process.
The hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent is applied to the flotation separation of titanium-containing minerals, and comprises the following steps: crushing titanium-containing ores and grinding the ores by a wet method to obtain ore pulp; and sequentially performing iron removal and desulfurization on the obtained ore pulp, and then performing titanium separation. 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 4.0-7.0, 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-sulfonic acid multi-ligand metal complex collecting agent comprises the following steps:
1) the preparation process of the hydroximic acid-sulfonic acid multi-ligand complex micelle comprises the following steps: weighing hydroximic acid, putting the hydroximic acid into a flask, adding methanol as a solvent, adding ethyl acetate according to the ratio of 6: 1-9: 1 of the hydroximic acid to ethyl acetate after the hydroximic acid and the ethyl acetate are completely dissolved, then adding alkali metal hydroxide to adjust the pH value to be 8.0-9.5, and stirring and reacting for 20-40 min at room temperature to obtain hydroximic acid salt; adding a hydroximic acid salt and a sulfonate into a flask according to a molar mass ratio of 1-1.5: 1, adding glycerol to enable the mass concentration of the hydroximic acid salt and the sulfonate to be 30-40%, then placing the mixture into a constant-temperature water bath kettle, stirring the mixture by using magnetons, heating the mixture to 80-100 ℃, then reacting the mixture for 20-30 min, and carrying out 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-sulfonic acid multi-ligand complex micelle.
2) The preparation process of the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent comprises the following steps: placing hydroximic acid-sulfonic acid multi-ligand composite micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using magnetons, heating to 40-90 ℃, stirring for 20-40 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-sulfonic 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 box at 40-50 ℃ to obtain the hydroximic acid-sulfonic 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-sulfonic acid multi-ligand metal complex collecting agent is used as a collecting agent of a target mineral in the flotation process of the titanium-containing mineral, has extremely strong selective collecting capability on titanium-containing minerals such as ilmenite, rutile, anatase and the like, can realize high-efficiency flotation separation of the titanium-containing mineral, silicate and gangue mineral, and is greatly beneficial to improving the concentrate grade and the flotation operation recovery rate.
2. The hydroximic acid-sulfonic 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-sulfonic 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-sulfonic acid multi-ligand metal complex collector of the present invention (exemplified by coordination of benzohydroxamic acid and sodium dodecyl sulfate with lead ions); 599.52cm in FIG. 1-1And 630.79cm-1Under O-Pb stretching vibration of 690.19cm-1780.46cm for C-H bending vibration-1S-O telescopic vibration at position 903.74, N-O telescopic vibration at position 1039.7cm-1Is in S ═ O stretching vibration, 1151.65cm-1Is subjected to C-N telescopic vibration of 1344.07cm-1There is an O-H bending vibration, 1439.25～1599.36cm-12921.66cm for bending vibration of benzene ring skeleton-1Is in O-H symmetrical telescopic vibration of 3184.29cm-1The vibration is O-H asymmetric stretching vibration or N-H stretching vibration.
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 9.5, and stirring and reacting for 25min at room temperature to obtain hydroxamate; adding hydroximic acid salt and sodium n-octadecyl sulfonate 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 magnetons, heating to 85 ℃, reacting for 25min, 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 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 sulfonic acid multi-ligand complex micelle. Placing the hydroximic acid-alkyl sulfonic acid multi-ligand complex micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using a magnet, heating to 90 ℃, stirring for 25min, then dropwise adding a copper sulfate solution with the metal ion mass percentage concentration of 4% into the multi-ligand complex micelle at the speed of 0.01g/s, wherein the molar ratio of copper ions to the hydroximic acid-alkyl sulfonate multi-ligand complex micelle is 1:1, continuously preserving the temperature 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-sulfonic acid multi-ligand metal complex collecting agent.
Treating Panzhihua ilmenite with hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent2The grade is 17.01%, and the main gangue minerals are calcite, quartz, garnet and the like. The pH of the pulp was adjusted to 5.5 with sulfuric acid as a pH adjuster and the hydroxyl group provided in this exampleThe hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent is used as a collecting agent, sec-octanol is used as a foaming agent, and the mixture enters a flotation machine to be subjected to primary, secondary and fine sweeping after being fully mixed. Roughly selecting 280g/t of collecting agent and 20g/t of octanol according to the adding amount of the agent relative to the raw ore; the first refined product is acidified water glass 60g/t, and the second refined product is acidified water glass 30 g/t; the first scavenging is 40g/t of the collecting agent, and the second scavenging is 10g/t of the collecting agent. Test to obtain TiO2Concentrate of grade 62.23%, TiO2The operating recovery was 72.27% (as in table 1).
TABLE 1 results of the Sichuan Panzhihua ilmenite flotation test
Product(s) Yield/%) TiO2Grade/% TiO2Percent recovery%
Concentrate ore 19.76 62.23 72.27
Tailings 80.24 5.88 27.73
Raw ore 100.00 17.01 100.00
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 8.0, and stirring and reacting for 30min at room temperature to obtain hydroximic acid salt; adding hydroximic acid salt and sodium dodecyl 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 flask into a constant-temperature water bath kettle, stirring by using magnetons, heating to 80 ℃, reacting for 30min, 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 45 percent to obtain the hydroximic acid-alkyl sulfonic acid multi-ligand complex micelle. Placing the hydroximic acid-alkyl sulfonic acid multi-ligand complex 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 complex 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-sulfonic acid multi-ligand metal complex collecting agent.
Hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent is used for treating certain low-grade rutile ore in Hubei2The grade is 1.97%, and the main gangue minerals are calcite, quartz, garnet and the like. Sulfuric acid is used as a pH regulator to regulate the pH value of ore pulp to be 5.0, the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent provided by the embodiment is used as a collecting agent, sec-octanol is used as a foaming agent, and the ore pulp is fully regulated and enters a flotation machine to be subjected to primary, secondary, tertiary and fine sweeping. Roughly selecting 300g/t of collecting agent and 25g/t of octanol according to the adding amount of the medicament relative to the raw ore; the first concentrate is acidified water glass 60g/t, the second concentrate is acidified water glass 30g/t, and the third concentrate is acidified water glass 10 g/t; scavengingThe first is 30g/t of collecting agent, and the second scavenging is 10g/t of collecting agent. Test to obtain TiO2Concentrate of 67.43% grade, TiO2The operating recovery was 83.63% (as in table 2).
TABLE 2 flotation test results for rutile from Hubei
Figure BDA0002269018080000071
Figure BDA0002269018080000081
Example 3
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 hydroximic acid salt and sodium dodecyl benzene sulfonate into a flask according to the 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 ℃, then reacting the mixture for 30min, 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 sulfonic acid multi-ligand complex micelle. Placing the hydroximic acid-alkyl sulfonic acid multi-ligand complex micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using a magneton, heating to 60 ℃, stirring for 20min, then dropwise adding a lead nitrate solution with the metal ion mass percentage concentration of 3% into the multi-ligand complex micelle at the speed of 0.01g/s, keeping the temperature for 1.0h after dropwise adding, aging for 24h at normal temperature, and finally filtering and drying for 24h in a vacuum drying oven at 50 ℃ to obtain the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent.
With hydroximic acid-sulfonic acid multi-ligand metalsTiO raw material for treating Henan rutile ore by complex collecting agent2The grade is 2.83%, and the main gangue minerals are quartz, mica and the like. Sulfuric acid is used as a pH regulator to regulate the pH value of ore pulp to be 5.5, the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent provided by the embodiment is used as a collecting agent, sec-octanol is used as a foaming agent, and the ore pulp is fully regulated and enters a flotation machine to be subjected to primary, secondary, tertiary and fine sweeping. Roughly selecting 250g/t of collecting agent and 20g/t of octanol according to the adding amount of the medicament relative to the raw ore; the first concentrate is acidified water glass 50g/t, the second concentrate is acidified water glass 30g/t, and the third concentrate is acidified water glass 10 g/t; the first scavenging is 20g/t of collecting agent, and the second scavenging is 5g/t of collecting agent. Test to obtain TiO2Concentrate of grade 64.21%, TiO2The operating recovery was 74.38% (as in table 3).
TABLE 3 flotation test results for Henan certain rutile
Product(s) Yield/%) TiO2Grade/% TiO2Percent recovery%
Concentrate ore 3.28 64.21 74.38
Tailings 96.72 0.75 25.62
Raw ore 100.00 2.83 100.00
Example 4
Weighing 0.002mol of salicylhydroxamic acid, putting the salicylhydroxamic 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 a hydroxamate; adding hydroximic acid salt and sodium dodecyl benzene sulfonate into a flask according to the molar mass ratio of 1:1, adding glycerol to enable the mass concentration of the glycerol to be 40%, then placing the flask into a constant-temperature water bath kettle, stirring by using magnetons, heating to 100 ℃, reacting for 30min, 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 sulfonic acid multi-ligand complex micelle. Placing the hydroximic acid-alkyl sulfonic acid multi-ligand complex micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using a magnet, heating to 80 ℃, stirring for 20min, then dropwise adding a ferrous chloride solution with the metal ion mass percentage concentration of 3% into the multi-ligand complex micelle at the speed of 0.01g/s, wherein the molar ratio of ferrous ions to the hydroximic acid-alkyl sulfonic acid multi-ligand complex micelle is 1:1, 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-sulfonic acid multi-ligand complex collecting agent.
Treating certain ilmenite in Hebei river with hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent2The grade is 17.29%, and the main gangue minerals are garnet, quartz and the like. Sulfuric acid is used as a pH regulator to regulate the pH value of ore pulp to be 5.0, the hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent provided by the embodiment is used as a collecting agent, sec-octanol is used as a foaming agent, and after full size regulation, slurryAnd entering a flotation machine for coarse cleaning, fine cleaning and fine cleaning. Roughly selecting 220g/t collecting agent and 15g/t sec-octanol according to the adding amount of the medicament relative to the raw ore; the first concentrate is acidified water glass 60g/t, the second concentrate is acidified water glass 20g/t, and the third concentrate is acidified water glass 10 g/t; the first scavenging is 25g/t of collecting agent, and the second scavenging is 5g/t of collecting agent. Test to obtain TiO2Concentrate of grade 61.12%, TiO2The operating recovery was 81.20% (as in table 4).
TABLE 4 flotation test results of certain ilmenite in Hebei
Product(s) Yield/%) TiO2Grade/% TiO2Percent recovery%
Concentrate ore 22.97 61.12 81.20
Tailings 77.03 4.22 18.80
Raw ore 100.00 17.29 100.00

Claims (10)

1. A hydroximic acid-sulfonic acid multi-ligand metal complex collector is characterized in that: has the structure of formula 1:
Figure FDA0003075499820000011
wherein the content of the first and second substances,
m is a positive divalent metal ion;
R1is an alkyl or aryl group;
R2is alkyl or aryl.
2. A hydroximic acid-sulfonic acid multiligand metal complex collector according to 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); r1When the aryl is selected from phenyl or phenyl containing hydroxyl substituent;
R2when it is an alkyl group, it is selected from C2～C18Alkyl of R2When it is aryl, it is selected from phenyl or C2～C12Alkyl substituted phenyl.
3. The method of preparing a hydroximic acid-sulfonic acid multi-ligand metal complex collector according to claim 1 or 2, wherein: 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 sulfonate with hydroximic acid salt to obtain hydroximic acid-sulfonic acid multi-ligand compound;
3) adding the hydroximic acid-sulfonic acid multi-ligand compound into the alcohol-water mixed solution to obtain a hydroximic acid-sulfonic acid multi-ligand compound micelle;
4) and carrying out coordination reaction on the hydroximic acid-sulfonic acid multi-ligand composite micelle and a metal salt solution to obtain the complex.
4. A method of preparing a hydroximic acid-sulfonic acid multi-ligand metal complex collector according to 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 6: 1-9: 1, and the addition amount of the alkali metal hydroxide is measured by controlling the pH value of the solution to be 8.0-9.5.
5. A method of preparing a hydroximic acid-sulfonic acid multi-ligand metal complex collector according to claim 3, wherein: reacting sulfonate and hydroximic acid salt in glycerol at the temperature of 80-100 ℃ for 20-30 min; wherein the molar ratio of the hydroximic acid salt to the sulfonate is 1-1.5: 1, and the mass percentage concentration of the sulfonate and the hydroximic acid salt in the glycerol is 30-40%.
6. A method of preparing a hydroximic acid-sulfonic acid multi-ligand metal complex collector according to 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-sulfonic acid multi-ligand compound in the alcohol-water mixed solution is 30-50%.
7. A method of preparing a hydroximic acid-sulfonic acid multi-ligand metal complex collector according to claim 3, wherein: stirring the hydroximic acid-sulfonic acid multi-ligand composite micelle at the temperature of 40-90 ℃ for 20-40 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-sulfonic acid multi-ligand metal complex collecting agent.
8. The method of preparing a hydroximic acid-sulfonic acid multi-ligand metal complex collector according to 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-sulfonate multi-ligand composite micelles in the metal salt solution is 1: 1-1: 3, wherein the hydroximic acid-sulfonate 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-sulfonic acid syndet collector according to claim 1 or 2, characterized in that: the method is applied to flotation separation of titanium-containing minerals and gangue minerals.
10. The use of a hydroximic acid-sulfonic acid multi-ligand metal complex collector according to claim 9, wherein: the titaniferous ore includes at least one of ilmenite, rutile, and anatase.
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