CN110721813B - Hydroximic acid-alkylamine multi-ligand metal complex collecting agent and preparation method and application thereof - Google Patents
Hydroximic acid-alkylamine multi-ligand metal complex collecting agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN110721813B CN110721813B CN201911098405.2A CN201911098405A CN110721813B CN 110721813 B CN110721813 B CN 110721813B CN 201911098405 A CN201911098405 A CN 201911098405A CN 110721813 B CN110721813 B CN 110721813B
- Authority
- CN
- China
- Prior art keywords
- hydroximic acid
- alkylamine
- ligand
- metal complex
- collecting agent
- 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.)
- Active
Links
Images
Classifications
-
- 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
- B03D1/01—Organic compounds containing nitrogen
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydroximic acid-alkylamine multi-ligand metal complex collecting agent, and a preparation method and application thereof. The hydroximic acid-amine multi-ligand metal complex collecting agent is obtained by carrying out coordination reaction on hydroximic acid-alkylamine multi-ligand complex micelle prepared from hydroximic acid salt and alkylamine and metal ions. The hydroximic acid-alkylamine multi-ligand metal complex collecting agent has extremely strong selective collecting capability on rare earth ore, can realize selective flotation separation of rare earth minerals such as monazite, bastnaesite, xenotime and the like and gangue minerals under the condition of no or only a small amount of gangue mineral inhibitor, and fundamentally solves the technical problem of difficult flotation separation of rare earth and gangue minerals.
Description
Technical Field
The invention relates to a flotation collector, in particular to a hydroximic acid-alkylamine multi-ligand metal complex collector for flotation separation of rare earth substances, a preparation method thereof, and a method for realizing efficient flotation separation of rare earth and gangue minerals by using the hydroximic acid-alkylamine multi-ligand metal complex, belonging to the technical field of mineral flotation.
Background
Rare earth is a general name of seventeen metal elements including lanthanide elements, scandium and yttrium in a chemical periodic table. At present, more than 250 rare earth minerals are found in the world, wherein the most industrially valuable rare earth minerals are about 50-60, and the most valuable rare earth minerals are less than 10. The most important rare earth minerals comprise bastnaesite, monazite, xenotime, ion adsorption type rare earth ore and the like. Rare earth minerals in endogenous rare earth ore deposits are commonly associated with non-sulfidic minerals such as quartz, feldspar, calcite, fluorite, barite, apatite, silicate minerals, and the like. The rare earth minerals in the endogenous rare earth deposit are generally in compact symbiosis with associated minerals, the embedding granularity is small, the property is crisp, and the mineral separation difficulty is high due to easy over-crushing and argillization during mineral grinding. The rare earth ore is generally selected by a flotation method, and fluorite, barite, calcite and other gangue minerals have better floatability, so that a collecting agent with high selectivity and collecting capacity is used in the rare earth mineral flotation. The novel efficient rare earth flotation collector is developed, the efficient selective flotation recovery of target minerals is realized, and the method has great significance for processing and utilizing mineral resources.
Disclosure of Invention
Aiming at the problems of difficult separation of rare earth and gangue mineral, low recovery rate and the like in the flotation of rare earth in the prior art by adopting the traditional single chelating collector or fatty acid collector, the first aim of the invention is to provide a hydroximic acid-alkylamine multi-ligand metal complex collector which has extremely strong selective collecting capability on rare earth such as monazite, bastnaesite, xenotime and the like and can realize the efficient separation of the rare earth, silicate and calcium-containing gangue mineral.
The invention also aims to provide a method for preparing the hydroximic acid-alkylamine 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 hydroximic acid-alkylamine multi-ligand metal complex collecting agent, the hydroximic acid-alkylamine multi-ligand metal complex collecting agent is used as a rare earth flotation collecting agent for flotation separation of rare earth and gangue minerals, the grade and recovery rate of flotation concentrate of the rare earth can be greatly improved, and the hydroximic acid-alkylamine 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 a rare earth flotation separation process.
In order to accomplish the above technical objects, the present invention provides a hydroximic acid-alkylamine 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 or aryl group;
R2、R3、R4independently selected from alkyl or hydrogen, and R2、R3And R4Not both can be H.
In a preferred embodiment, M is Pb2+、Cu2+、Ca2+Or Fe2+。
Preferred embodiment, R1When it is an alkyl group, it is selected from C1～C18The alkane group of (2) can be a straight-chain alkane group or a branched alkane group, or a cyclic alkyl group, such as methyl, propyl, isopropyl, octyl, dodecyl, cyclohexyl and 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, R2、R3、R4Is independently selected from C2～C18An alkyl radical of (A) or hydrogen, and R2、R3And R4Not both can be H. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group, and is most preferably a straight chain alkyl group, specifically, methyl, propyl, octyl, dodecyl and the like.
The invention also provides a preparation method of the hydroximic acid-alkylamine 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 alkylamine with hydroximic acid salt to obtain hydroximic acid-alkylamine multi-ligand compound;
3) adding the hydroximic acid-alkylamine multi-ligand compound into the alcohol-water mixed solution to obtain a hydroximic acid-alkylamine multi-ligand compound micelle;
4) carrying out coordination reaction on the hydroximic acid-alkylamine multi-ligand composite micelle and a metal salt solution 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. Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like. Preferably, the solvent is an alcoholic solvent, such as methanol.
In a preferred embodiment, the hydroxamic acid compound has the structure of formula 2,
wherein R is1Is alkyl, phenyl or hydroxyphenyl.
According to the preferable scheme, alkylamine and hydroximic acid salt react for 60-100 min in glycerol at the temperature of 80-100 ℃; wherein the molar ratio of the hydroximic acid salt to the alkylamine is 1: 1-3, and the mass percentage concentration of the alkylamine and the hydroximic acid salt in the glycerol is 30-40%.
In a preferred embodiment, the alkylamine has the structure of formula 3:
wherein R is2、R3、R4Independently selected from alkyl or hydrogen, and R2、R3And R4Not both can be H.
In a preferable scheme, the alcohol-water mixed solution is composed of water and methanol according to a volume ratio of 6-10: 1.
In a preferable scheme, the mass percentage concentration of the hydroximic acid-alkylamine multi-ligand compound in the alcohol-water mixed solution is 30-50%.
According to the preferable scheme, hydroximic acid-alkylamine multi-ligand composite micelle is stirred for 30-60 min at the temperature of 60-90 ℃, 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-alkylamine 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-alkylamine multi-ligand complex micelles in the metal salt solution is 1: 1-1: 3, wherein the hydroximic acid-alkylamine multi-ligand complex micelles are measured by the number of molecules; the dropping rate of the metal salt solution is not higher than 0.03 g/s.
The invention also provides application of the hydroximic acid-alkylamine multi-ligand metal complex collecting agent in flotation separation of rare earth and gangue minerals.
Preferably, the rare earth includes at least one of monazite, bastnaesite and xenotime.
Preferably, the gangue minerals are silicates, fluorites, calcites, garnets, etc.
In a preferable scheme, the addition amount of the hydroximic acid-alkylamine multi-ligand metal complex collecting agent is 80-400 g/t relative to raw ore.
In the preferable scheme, when the hydroximic acid-alkylamine multi-ligand metal complex collecting agent is used, water needs to be added into the hydroximic acid-alkylamine 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-alkylamine multi-ligand metal complex collecting agent is applied to the rare earth flotation process as follows: crushing rare earth ore, and grinding the ore 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 rare earth sorting process. Roughing, namely using the hydroximic acid-alkylamine multi-ligand metal complex as a collecting agent and pine oil as a foaming agent, 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 fine concentration on the rough concentrate to obtain final concentrate, carrying out scavenging on the rough concentrate to obtain scavenging tailings, 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 metal-based multi-ligand complex collecting agent of hydroximic acid and alkylamine comprises the following steps:
1) the preparation process of the hydroximic acid-alkylamine 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 5: 1-8: 1 of the hydroximic acid to ethyl acetate after the hydroximic acid and the ethyl acetate are completely dissolved, then adding sodium 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 alkylamine into a flask according to the molar mass ratio of 1: 1-3, adding glycerol to enable the mass concentration of the hydroximic acid salt and alkylamine to be 30-40%, then placing the mixture into a constant-temperature water bath kettle, stirring with magnetons, heating to 80-100 ℃, reacting for 60-100 min, carrying out rotary evaporation on the obtained liquid, and 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 6-10: 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-alkylamine multi-ligand complex micelle.
2) The preparation process of the hydroximic acid-alkylamine multi-ligand metal complex collecting agent comprises the following steps: placing hydroximic acid-alkylamine multi-ligand composite micelle in a flask, placing the flask in a constant-temperature water bath, stirring by using magnetons, heating to 60-90 ℃, stirring for 30-60 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 dropwise adding speed of a copper salt solution is not higher than 0.03g/s, the molar ratio of metal ions to the hydroximic acid-alkylamine multi-ligand composite micelle is 1: 1-1: 3, continuously preserving heat for 0.5-1.5 h after dropwise adding 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-alkylamine multi-ligand composite micelle.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the hydroximic acid-alkylamine multi-ligand metal complex collecting agent is used as a collecting agent of target minerals in the rare earth flotation process, has extremely strong selective collecting capacity on rare earth, can realize efficient flotation separation of rare earth substances, silicate and calcium-containing gangue minerals, and is greatly beneficial to improving the concentrate grade and the flotation operation recovery rate.
2. The hydroximic acid-alkylamine 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-alkylamine multi-ligand metal complex collecting agent disclosed by the invention 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-alkylamine multi-ligand metal complex collectors of the present invention (exemplified by the coordination of benzohydroxamic acid and didecylmethylamine with lead ions); 596.76cm in FIG. 1-1And 629.87cm-1Under O-Pb stretching vibration, 680.16 and 700.57cm-1894.97, 1020.88 and 1069.65cm for C-H bending vibration-1Under N-O stretching vibration, 1121.17 and 1151.03cm-1Is subjected to C-N telescopic vibration of 1345.58cm-1The vibration is O-H bending vibration of 1436.42-1599.15 cm-12851.96 and 2922.76cm for bending vibration of benzene ring skeleton-1At the position of the vibration is O-H symmetrical telescopic vibration, 3199.38 and 3414.27cm-1The vibration is O-H asymmetric stretching vibration or N-H stretching vibration.
FIG. 2 is an X-ray photoelectron spectrum of hydroximic acid-alkylamine multi-ligand metal complex collector of the present invention (exemplified by the coordination of benzohydroxamic acid and didecylmethylamine to 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 didecylmethylamine 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 a magneton, heating the mixture to 90 ℃, reacting the mixture for 60min, 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-alkylamine multi-ligand complex micelle. Placing the hydroximic acid-alkylamine 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 30min, 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-alkylamine multi-ligand complex collecting agent.
Treating certain rare earth ore by using hydroximic acid-alkylamine multi-ligand metal complex collecting agent, wherein the ReO grade of the used raw material is 0.34 percent, the main rare earth minerals comprise bastnaesite and monazite, and the gangue minerals comprise quartz, fluorite, calcite and the like. Soda is used as a pH regulator, the hydroximic acid-alkylamine 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 the obtained slurry is fully mixed and then enters a flotation machine for 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 260g/t of soda ash, 190g/t of collecting agent and 30g/t of pine oil; the first refined is 70g/t of water glass, 35g/t of aluminum sulfate, the second refined is 30g/t of water glass, 15g/t of aluminum sulfate, and the third refined is not added with a medicament; the first scavenging is 50g/t of the collecting agent, and the second scavenging is 10g/t of the collecting agent. The test obtained concentrate with ReO grade of 45.32%, and the ReO operation recovery rate of 67.87% (as shown in Table 1).
TABLE 1 Baotou rare earth ore flotation test results
| Product(s) | Yield/%) | ReO grade/% | ReO recovery/% |
| Concentrate ore | 0.51 | 45.32 | 67.87 |
| Tailings | 99.49 | 0.11 | 32.13 |
| Raw ore | 100.00 | 0.34 | 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 30min at room temperature to obtain hydroximic acid salt; adding hydroximic acid salt and dodecylamine into a flask according to the molar mass ratio of 1:2, adding glycerol to enable the mass concentration of the glycerol to be 36%, then placing the mixture into a constant-temperature water bath kettle, stirring by using magnetons, heating to 85 ℃, reacting for 75min, and performing rotary evaporation on the obtained liquid and recrystallization for three times to obtain a solid; adding the obtained 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 45 percent to obtain the hydroximic acid-alkylamine multi-ligand complex micelle. Placing the hydroximic acid-alkylamine 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 30min, 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 1.2h after dropwise adding, aging for 30h at normal temperature, filtering, and drying for 24h in a vacuum drying oven at 50 ℃ to obtain the hydroximic acid-alkylamine multi-ligand complex collecting agent.
The hydroximic acid-alkylamine multi-ligand metal complex collecting agent is used for treating certain rare earth ore in the north of Hu, the ReO grade of the used raw material is 0.24 percent, the main rare earth mineral is bastnaesite, and the main gangue mineral is calcite, quartz, garnet and the like. The pH of the ore pulp is adjusted to 9.0 by taking soda as a pH adjusting agent, the hydroximic acid-alkylamine multi-ligand metal complex collecting agent provided by the embodiment is taken as a collecting agent, sec-octanol is taken as a foaming agent, and the ore pulp is fully adjusted and then enters a flotation machine for coarse, fine and double sweeping. Roughly selecting the adding amount of the medicament relative to the raw ore as a collecting agent of 280g/t and secondary octanol of 30 g/t; 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; the first scavenging is 30g/t of the collecting agent, and the second scavenging is 10g/t of the collecting agent. The test obtained concentrate with 38.32% ReO grade, and the ReO operation recovery rate was 66.35% (as shown in Table 2).
TABLE 2 flotation test results of certain rare earth ore in Hubei
| Product(s) | Yield/%) | ReO grade/% | ReO recovery/% |
| Concentrate ore | 0.41 | 38.32 | 66.35 |
| Tailings | 99.59 | 0.08 | 33.65 |
| Raw ore | 100.00 | 0.24 | 100.00 |
Example 3
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 octadecylamine into a flask according to the molar mass ratio of 1:2, adding glycerol to enable the mass concentration of the glycerol to be 40%, then placing the mixture into a constant-temperature water bath kettle, stirring by using magnetons, heating to 100 ℃, reacting for 65min, 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 35 percent to obtain the hydroximic acid-alkylamine multi-ligand complex micelle. Placing the hydroximic acid-alkylamine 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 45min, dropwise adding a copper sulfate 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 28h at normal temperature, filtering, and drying for 24h in a vacuum drying oven at 50 ℃ to obtain the hydroximic acid-alkylamine multi-ligand complex collecting agent.
The hydroximic acid-alkylamine multi-ligand metal complex collecting agent is used for treating certain Sichuan rare earth ore, the ReO grade of the used raw material is 0.17%, the main rare earth mineral is bastnaesite, and the main gangue mineral is quartz, feldspar, garnet and the like. The pH of the ore pulp is adjusted to 9.0 by taking sodium carbonate as a pH adjusting agent, the hydroximic acid-alkylamine multi-ligand metal complex collecting agent provided by the embodiment is taken as a collecting agent, the pinitol oil is taken as a foaming agent, and the ore pulp is fully mixed and then enters a flotation machine for primary coarse sweeping, tertiary fine sweeping and secondary fine sweeping. Roughly selecting 190g/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 50g/t, the second concentrate is acidified water glass 20g/t, and the third concentrate is acidified water glass 5 g/t; the first scavenging is 10g/t of collecting agent, and the second scavenging is 5g/t of collecting agent. The test obtained 31.38% ReO grade concentrate, ReO operation recovery 59.75% (as table 3).
TABLE 3 flotation test results of a rare earth ore from Sichuan
| Product(s) | Yield/%) | ReO grade/% | ReO recovery/% |
| Concentrate ore | 0.33 | 31.38 | 59.75 |
| Tailings | 99.67 | 0.07 | 40.25 |
| Raw ore | 100.00 | 0.17 | 100.00 |
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 hydroximic acid salt and dodecylamine into a flask according to the molar mass ratio of 1:2, adding glycerol to enable the mass concentration of the glycerol to be 36%, then placing the mixture into a constant-temperature water bath kettle, stirring by using magnetons, heating to 85 ℃, reacting for 75min, and performing rotary evaporation on the obtained liquid and recrystallization for three times to obtain a solid; adding the obtained 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 45 percent to obtain the hydroximic acid-alkylamine multi-ligand complex micelle. Placing the hydroximic acid-alkylamine 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 30min, 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 1.2h after dropwise adding, aging for 30h at normal temperature, filtering, and drying for 24h in a vacuum drying oven at 50 ℃ to obtain the hydroximic acid-alkylamine multi-ligand complex collecting agent.
The hydroximic acid-alkylamine multi-ligand metal complex collecting agent is used for treating certain rare earth ore in Yunnan, the ReO grade of the used raw material is 0.18 percent, the main rare earth minerals are bastnaesite and monazite, and the main gangue minerals are quartz, feldspar, garnet and the like. The pH value of the ore pulp is adjusted to be 8.0 by taking sodium carbonate as a pH adjusting agent, the hydroximic acid-alkylamine multi-ligand metal complex collecting agent provided by the embodiment is taken as a collecting agent, the pinitol oil is taken as a foaming agent, and after full size mixing, the ore pulp enters a flotation machine to be subjected to primary coarse cleaning, secondary fine cleaning and secondary cleaning. Roughly selecting 250g/t of collecting agent and 30g/t of sec-octanol according to the adding amount of the medicament relative to the raw ore; the first essence is acidified water glass 60g/t, the second essence is acidified water glass 20g/t, and the third essence does not add medicine; the first scavenging is 15g/t of the collecting agent, and the second scavenging is 5g/t of the collecting agent. The test obtained concentrate with 39.56% ReO grade, and the ReO operation recovery rate was 56.31% (see Table 4).
TABLE 4 flotation test results of some rare earth ore in Yunnan
| Product(s) | Yield/%) | ReO grade/% | ReO recovery/% |
| Concentrate ore | 0.26 | 39.56 | 56.31 |
| Tailings | 99.74 | 0.08 | 43.69 |
| Raw ore | 100.00 | 0.18 | 100.00 |
Claims (10)
1. A hydroximic acid-alkylamine multi-ligand metal complex collector 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 or aryl group;
R2、R3、R4independently selected from alkyl or hydrogen, and R2、R3And R4Not both can be H.
2. A hydroximic acid-alkylamine multi-ligand 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;
R2、R3、R4is independently selected from C2～C18An alkyl radical of (A) or hydrogen, and R2、R3And R4Not both can be H.
3. The method of preparing a hydroximic acid-alkylamine 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 alkylamine with hydroximic acid salt to obtain hydroximic acid-alkylamine multi-ligand compound;
3) adding the hydroximic acid-alkylamine multi-ligand compound into the alcohol-water mixed solution to obtain a hydroximic acid-alkylamine multi-ligand compound micelle;
4) carrying out coordination reaction on the hydroximic acid-alkylamine multi-ligand composite micelle and a metal salt solution to obtain the product.
4. The method of preparing a hydroximic acid-alkylamine 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 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-alkylamine multi-ligand metal complex collector according to claim 3, wherein: the alkylamine and the hydroximic acid salt react for 60-100 min in glycerol at the temperature of 80-100 ℃; wherein the molar ratio of the hydroximic acid salt to the alkylamine is 1: 1-3, and the mass percentage concentration of the alkylamine and the hydroximic acid salt in the glycerol is 30-40%.
6. The method of preparing a hydroximic acid-alkylamine 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 6-10: 1;
the mass percentage concentration of the hydroximic acid-alkylamine multi-ligand compound in the alcohol-water mixed solution is 30-50%.
7. The method of preparing a hydroximic acid-alkylamine multi-ligand metal complex collector according to claim 3, wherein: stirring the hydroximic acid-alkylamine multi-ligand composite micelle at the temperature of 60-90 ℃ for 30-60 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-alkylamine multi-ligand metal complex collecting agent.
8. The method of preparing a hydroximic acid-alkylamine 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-alkylamine multi-ligand composite micelles in the metal salt solution is 1: 1-1: 3, wherein the hydroximic acid-alkylamine 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-alkylamine multi-ligand metal complex collector according to claim 1 or 2, wherein: the method is applied to flotation separation of rare earth and gangue minerals.
10. The use of a hydroximic acid-alkylamine multi-ligand metal complex collector according to claim 9, wherein: the rare earth comprises at least one of monazite, bastnaesite and xenotime.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911098405.2A CN110721813B (en) | 2019-11-12 | 2019-11-12 | Hydroximic acid-alkylamine multi-ligand metal complex collecting agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911098405.2A CN110721813B (en) | 2019-11-12 | 2019-11-12 | Hydroximic acid-alkylamine multi-ligand metal complex collecting agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110721813A CN110721813A (en) | 2020-01-24 |
| CN110721813B true CN110721813B (en) | 2021-07-27 |
Family
ID=69223904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911098405.2A Active CN110721813B (en) | 2019-11-12 | 2019-11-12 | Hydroximic acid-alkylamine multi-ligand metal complex collecting agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110721813B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533305A (en) * | 2001-07-27 | 2004-09-29 | Hydroxamate composition and method for froth fcoatation | |
| CN102302983A (en) * | 2011-05-31 | 2012-01-04 | 武汉工程大学 | Quaternary ammonium salt hydroximic acid phosphorus ore floatation collecting agent and preparation method thereof |
| CN104447409A (en) * | 2014-11-12 | 2015-03-25 | 中蓝连海设计研究院 | Synthesis method of hydroxyoximate |
| CN106423573A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of ester-based hydroximic acid collecting agent to mineral flotation |
| CN108672093A (en) * | 2018-04-18 | 2018-10-19 | 广东省资源综合利用研究所 | A kind of collecting agent and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10618058B2 (en) * | 2015-07-31 | 2020-04-14 | Colorado School Of Mines | Beneficiation of rare earth elements bearing ancylite |
-
2019
- 2019-11-12 CN CN201911098405.2A patent/CN110721813B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533305A (en) * | 2001-07-27 | 2004-09-29 | Hydroxamate composition and method for froth fcoatation | |
| CN102302983A (en) * | 2011-05-31 | 2012-01-04 | 武汉工程大学 | Quaternary ammonium salt hydroximic acid phosphorus ore floatation collecting agent and preparation method thereof |
| CN104447409A (en) * | 2014-11-12 | 2015-03-25 | 中蓝连海设计研究院 | Synthesis method of hydroxyoximate |
| CN106423573A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of ester-based hydroximic acid collecting agent to mineral flotation |
| CN108672093A (en) * | 2018-04-18 | 2018-10-19 | 广东省资源综合利用研究所 | A kind of collecting agent and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110721813A (en) | 2020-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108906331B (en) | Hydrocarbon amide-bishydroxyhydroxamic acid compound and application thereof in mineral flotation | |
| CN105413855B (en) | A kind of method of tungsten rough concentrate cleaning and Purification | |
| CN105618272B (en) | A kind of metal ion match collecting agent and its preparation method and application | |
| CN105642448A (en) | Method for efficiently separating wolframite concentrate and scheelite concentrate from tungsten ore | |
| CN108187917B (en) | Aromatic phosphonic acid and salt collector thereof and application thereof | |
| CN110721815B (en) | Hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent and preparation method and application thereof | |
| CN111068926B (en) | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof | |
| CN110548600B (en) | Copper-molybdenum bulk concentrate flotation separation reagent system and application thereof | |
| CN110721813B (en) | Hydroximic acid-alkylamine multi-ligand metal complex collecting agent and preparation method and application thereof | |
| CN113333178A (en) | Gold ore flotation collector and preparation method thereof | |
| CN110052332B (en) | Copper-based coordination polymer, preparation method thereof and application of copper-based coordination polymer as gangue mineral inhibitor in copper-nickel sulfide flotation | |
| CN110227609B (en) | Nano metal-organic carboxylic acid complex colloidal collector, preparation thereof and application of collector as metal mineral flotation collector | |
| CN110976099A (en) | Flotation method for lithium ore and collector composition | |
| CN110721816B (en) | Hydroximic acid-organic phosphoric acid multi-ligand metal complex collecting agent and preparation method and application thereof | |
| CN113600346B (en) | Secondary copper sulfide ore inhibitor and preparation and application thereof | |
| CN115090425B (en) | Collecting agent for spodumene floatation and preparation method thereof | |
| CN105127008A (en) | Method for preparing stibnite inhibitor | |
| CN117943210B (en) | Flotation separation inhibitor for chalcopyrite and pyrite, preparation method and application | |
| WO2015051585A1 (en) | Wet-method in atmospheric oxidation method for cerium in rare earth hydroxide | |
| CN109954588A (en) | A kind of sesquichloride inhibitor and preparation method thereof and purposes | |
| CN114832948B (en) | Flotation inhibitor and application thereof | |
| JPS5858143B2 (en) | Zinc flotation method | |
| CN114632629B (en) | Copper sulfide inhibitor and preparation method thereof | |
| RU2782753C2 (en) | Complex compound of hydroxamic acid and metal hydroxide, its preparation and use | |
| CN115155823B (en) | Method for normal-temperature floatation enrichment of high-calcium tungsten ore |
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 |