WO2020041991A1 - 一种羟肟酸-金属氢氧化物配合物及其制备和应用 - Google Patents

一种羟肟酸-金属氢氧化物配合物及其制备和应用 Download PDF

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WO2020041991A1
WO2020041991A1 PCT/CN2018/102839 CN2018102839W WO2020041991A1 WO 2020041991 A1 WO2020041991 A1 WO 2020041991A1 CN 2018102839 W CN2018102839 W CN 2018102839W WO 2020041991 A1 WO2020041991 A1 WO 2020041991A1
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Prior art keywords
hydroxamic acid
metal hydroxide
hydroxide complex
complex according
metal
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English (en)
French (fr)
Inventor
胡岳华
孙伟
韩海生
卫召
王建军
王若林
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Central South University
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Central South University
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Priority to PCT/CN2018/102839 priority Critical patent/WO2020041991A1/zh
Priority to US17/270,961 priority patent/US12180236B2/en
Priority to CA3110915A priority patent/CA3110915C/en
Publication of WO2020041991A1 publication Critical patent/WO2020041991A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • 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
    • B03D1/008—Organic compounds containing oxygen
    • 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
    • B03D1/001—Flotation agents
    • B03D1/018—Mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/22—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/0475—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2224—Compounds having one or more tin-oxygen linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/24—Lead compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to an organometallic hydroxide complex, in particular to a hydroxamic acid-metal hydroxide complex and a method for preparing and separating and purifying the same, and also relates to a hydroxamic acid-metal hydroxide complex as
  • flotation collectors such as tungsten ore, tin ore, titanium ore or rare earth ore belongs to the field of ore dressing technology.
  • Mineral resources are the basic material materials of the national economy. The degree of guarantee is related to the long-term stable development of the national economy and national security.
  • the efficient development and utilization of mineral resources has been included in the outline of national long-term scientific and technological development plans.
  • oxide ore as the main mineral of metals such as tungsten, tin, iron, manganese, lead, zinc, copper and titanium, plays an important role in the development and utilization of mineral resources.
  • oxidized ore has a more complicated symbiotic relationship, which is difficult to sort and has low utilization rate; as resource poverty becomes more detailed, the difficulty of sorting further increases, and the selectivity in the process of mineral sorting Higher requirements are put forward.
  • Tungsten ore, cassiterite, and rutile are typical representatives of oxidized ore resources. They face a series of common scientific problems in the efficient and comprehensive utilization of resources, such as the characteristics of "poor, fine, and miscellaneous" resources and the selectivity of collectors in the flotation process. Key issues such as inadequacy.
  • Luanchuan's associated ultra-low-grade tungsten resource reserves amount to 620,000 tons. Due to the lack of effective technical means, a large amount of tungsten resources have been lost in tailings. ; Calcium persimmon garden, Xingluokeng, and other typical skarn-type high-calcium black and white tungsten associated resource reserves are up to 1.3 million tons. As the grade decreases and the calcium-containing gangue increases, the comprehensive utilization of such resources becomes more difficult. The recovery rate once dropped to about 63%.
  • Scheelite, calcite, and fluorite are all soluble salt minerals with relatively high solubility and the phenomenon of mutual conversion between calcium-containing minerals, which complicates the flotation behavior of each mineral and separates the calcium-containing minerals even more. difficult.
  • the use of this resource is essentially a problem of the separation of scheelite (a useful mineral containing calcium) from a mineral containing gangue, which is a worldwide problem.
  • the selectivity of flotation agents is the key to the efficient development of such resources.
  • China is one of the richest tin ore resources in the world, accounting for 28.85% of the world's proven reserves.
  • China's tin resources are characterized by complex associated components, and more than 80% are associated resources.
  • Hunan Shizhuyuan tungsten-tin-molybdenum-bismuth polymetallic ore Take Hunan Shizhuyuan tungsten-tin-molybdenum-bismuth polymetallic ore as an example.
  • the proven tin reserves are up to 460,000 tons.
  • the grade of the associated tin of the original ore is only 0.1 ⁇ 0.12%, and 60% of the associated tin is a colloidal tin mineral. It was once concluded by related experts that tin minerals could not be recovered at all. At present, due to the fine grain size of the ore, the complicated associated relationship, the relatively low grade, the poor floatability, and the difficulty of comprehensive utilization, the comprehensive recovery of tin resources is still blank. The amount of tin metal discharged to the tailings pond each year reaches 1,500 tons. The comprehensive recovery of low-grade associated tin resources is facing huge challenges.
  • collectors of oxidized ores such as tungsten ore, cassiterite and rutile are mainly anion collectors such as fatty acids and chelating collectors.
  • anion collectors such as fatty acids and chelating collectors.
  • Such collectors contain N, O
  • the organic acid functional groups such as P and P interact with the active sites on the surface of the mineral to achieve the capture of the target mineral.
  • useful minerals in oxidized ore systems have similar surface chemistry to gangue minerals, and these traditional anion collectors are difficult to improve qualitatively in terms of novelty selection. For example: scheelite, fluorite, calcite, etc. are calcium-containing minerals.
  • the preparation method is to add a soluble metal salt to a solution containing the ligand and react to obtain a metal ion.
  • Complex collectors; metal ion complex collectors have strong selective collection capabilities for tungsten-containing minerals, rare earths and cassiterite, and can achieve tungsten-containing minerals and cassiterite without calcium-containing mineral inhibitors
  • the selective separation of rare earths and calcium gangue minerals fundamentally solves the problem of difficult separation of calcium minerals.
  • the complex formed by the metal ion and the organic ligand in the solution system is not a single component. In fact, a mixture of multiple components in a mineral flotation process really plays a role in the surface charge Therefore, the content of the effective portion of the metal ion complex obtained by this method is low, resulting in low utilization rate, high cost, and relatively poor application effect.
  • the first object of the present invention is to provide a method for treating tungsten ore, cassiterite, and ilmenite Hydroxamic acid-metal hydroxide complex collectors with strong selectivity and strong collection ability such as ore, rutile and rare earth, compared to existing similar hydroxamic acid metal complexes, it acts on tungsten ore , Cassiterite, ilmenite, rutile, and rare earth minerals have a high content of active ingredients (the active ingredient here refers to the part that has the ability to collect metal minerals), the harvesting effect is more significant, and the cost is low.
  • the second object of the present invention is to provide a method for preparing the hydroxamic acid-metal hydroxide complex with simple process, mild reaction conditions and low cost.
  • a third object of the present invention is to provide an application of the hydroxamic acid-metal hydroxide complex.
  • the hydroxamic acid-metal hydroxide complex is used for tungsten ore, cassiterite, ilmenite, Flotation separation of rutile and rare earth from gangue minerals such as calcite, fluorite, apatite and aluminosilicate minerals, fundamentally solves the problem of difficult and low efficiency of flotation separation of complex low-grade oxide ore, and The use cost is greatly reduced.
  • the present invention provides a hydroxamic acid-metal hydroxide complex, which is formed by coordinating hydroxamic acid with a divalent or higher divalent metal ion under alkaline conditions;
  • the hydroxamic acid has the structure of Formula 1:
  • R is a hydrophobic organic group.
  • the hydrophobic organic group in the hydroxamic acid means that its hydrophilic-lipophilic balance value is small, and generally, the hydrophilic-lipophilic balance value is less than 9, preferably less than 6.
  • R is preferably an aliphatic hydrocarbon group or an aryl group.
  • the aliphatic hydrocarbon group may be a saturated alkyl chain, the alkyl chain may be a straight chain, or it may contain a branched chain, or a naphthenic chain.
  • the aliphatic hydrocarbon group may be an unsaturated alkyl chain, such as containing at least one carbon-carbon double bond or containing At least one carbon-carbon triple bond. Or the aliphatic hydrocarbon may contain some common substituent groups, such as halogen, etc.
  • the substituent group is preferably not a hydrophilic group. If a hydrophilic group is selected, it is necessary to make the entire aliphatic hydrocarbon group hydrophilic and lipophilic. The equilibrium value is at a lower value, for example, the hydrophilic-lipophilic balance is less than 6.
  • R is an aliphatic hydrocarbon group
  • a C 4 to C 12 alkane group and a C 4 to C 12 unsaturated aliphatic hydrocarbon group are preferred.
  • Aryl is preferably phenyl or substituted phenyl.
  • the substituted phenyl group contains at least one substituent on the benzene ring. Common examples include short-chain alkyl groups, halogens, and alkoxy groups.
  • the substituents are preferably not hydrophilic groups.
  • the hydrophilic-lipophilic balance value of the substituted phenyl group should be smaller, for example, the hydrophilic-lipophilic balance value is less than 6.
  • R is most preferably phenyl.
  • the divalent or higher divalent metal ions include at least one of Pb 2+ , Ca 2+ , Mn 2+ , Cu 2+ , Fe 3+ , and Al 3+ .
  • the hydroxamic acid-lead complex produced by divalent lead ions is relatively Ca 2+ , Mn 2+ , Cu 2 Hydroxamic acid-metal hydroxide complexes generated by other metal ions such as + , Fe 3+ , Al 3+, etc., perform flotation capture of tungsten ore, cassiterite, ilmenite, rutile, and rare earth, etc.
  • Pb 2+ is greater than Ca 2+
  • Ca 2+ is greater than Mn 2+
  • Fe 3+ is greater than Al 3+
  • Mn 2+ , Fe 3+ and Al 3+ are greater than Cu 2+ .
  • the metal ion is most preferably Pb 2+ .
  • the coordination molar ratio of the divalent or higher divalent metal ion to the hydroxamic acid is (1 to 4): (1 to 5).
  • the coordination molar ratio is more preferably (1 to 2): (1 to 3).
  • metal ions and hydroxamic acid can form different hydroxamic acid-metal hydroxide complexes, and their structures and properties are very different.
  • the content of active ingredients can be generated.
  • the highest hydroxamic acid-metal hydroxide complex (the active ingredient here refers to the part that has the ability to collect metal minerals). If the ratio is too high or too low, it will affect the content of the active ingredient and its surface on the mineral. Influence the adsorption performance.
  • the pH in the alkaline condition is 8 to 11, and the more preferable pH is 8.5 to 9.5.
  • some hydroxides can participate in the coordination, and co-ordinate the metal ions with the hydroxamic acid to form a hydroxamic acid / hydroxy-metal hydroxide complex.
  • the pH is too low to effectively participate in the reaction. If it is too large, a large amount of hydroxide reacts with the ligand and forms a hydroxide precipitate, making it difficult to form a complex.
  • the invention also provides a method for preparing a hydroxamic acid-metal hydroxide complex.
  • the hydroxamic acid and a divalent or higher divalent metal ion are subjected to a coordination reaction in an alkaline solution system to obtain a hydroxamic acid.
  • the hydroxamic acid has the structure of Formula 1:
  • R is a hydrophobic organic group.
  • R is an aliphatic hydrocarbon group or an aryl group.
  • R is more preferably a C 4 to C 12 alkane group, a C 4 to C 12 unsaturated aliphatic hydrocarbon group, a phenyl group, or a substituted phenyl group.
  • R is most preferably phenyl.
  • the divalent or higher divalent metal ion metal ions include at least one of Pb 2+ , Ca 2+ , Mn 2+ , Cu 2+ , Fe 3+ , and Al 3+ .
  • the divalent metal ion is preferably Pb 2+ .
  • the coordination molar ratio of the divalent or higher divalent metal ion to the hydroxamic acid is (1 to 4): (1 to 5).
  • the coordination molar ratio is more preferably (1 to 2): (1 to 3).
  • the pH of the alkaline condition is 8 to 11, and the preferred pH is 8.5 to 9.5.
  • the alkaline solution can be adjusted with common alkalis such as sodium hydroxide and potassium hydroxide.
  • the temperature of the coordination reaction is 20 to 80 ° C, and the reaction time is 0.5 to 6 hours. A more preferable temperature is 55 to 65 ° C. A more preferred reaction time is 1 to 2 hours. More preferred reaction conditions for the coordination reaction are: the temperature is 55 ⁇ 65 ° C, and the reaction time is 1 ⁇ 2h.
  • the reaction temperature affects the reaction rate and the structure of the complex. If the temperature is too low, the reaction rate is slow and the conversion rate is low. If the reaction temperature is too high, a large number of non-hydroxide complexes will be formed.
  • the hydroxamic acid-metal hydroxide complex is separated and purified by a carrier adsorption-flotation flotation method.
  • the carrier adsorption-foam flotation method is as follows: the hydroxamic acid-metal hydroxide complex in the solution system is adsorbed by the carrier particles; after the adsorption is completed, the supported hydroxamic acid-metal hydrogen is recovered by foam flotation Oxide complex carrier particles, and the hydroxamic acid-metal hydroxide complex-supported carrier particles are washed by ultrasound to obtain a hydroxamic acid-metal hydroxide complex solution.
  • the carrier particles are added to the solution system, and the hydroxamic acid-metal hydroxide complex is adsorbed on the surface of the carrier particles by electrostatic effect to wrap the surface of the carrier particles, so that the surface of the carrier particles exhibits strong hydrophobicity.
  • the carrier particles of the acid-metal hydroxide complex enter the foam layer.
  • the hydroxamic acid-metal hydroxide complex with higher purity can be separated by the carrier adsorption-flotation method.
  • the carrier particles are quartz particles having a particle size range of 10 to 37 ⁇ m.
  • the particle size of quartz particles is in the range of 10 ⁇ 37 ⁇ m, which is conducive to the floating of particles in the subsequent flotation process.
  • the relative addition amount of quartz particles in the system is not less than 100g / L to ensure that the hydroxamic acid-metal hydroxide complex is fully separated and recovered.
  • the ultrasonic washing uses anhydrous ethanol as a detergent.
  • any solvent capable of dissolving and dispersing the benzhydroxamic acid-metal hydroxide complex can be used as a detergent, and cheap, safe and non-toxic ethanol is preferred as a detergent.
  • the metal ions are mainly provided by a water-soluble metal salt solution, such as nitrate, and the concentration of the metal ions is not particularly required.
  • the hydroxamic acid is mainly dissolved by an organic solvent, such as ethanol, and the concentration of the hydroxamic acid is not particularly required.
  • the invention also provides the application of a hydroxamic acid-metal hydroxide complex.
  • the hydroxamic acid-metal hydroxide complex is used as a flotation collector in at least one of tungsten, tin, titanium and rare earth. Flotation Separation of Species of Metal Oxide Minerals from Gangue Minerals.
  • the tungsten-containing metal mineral includes at least one of scheelite, wolframite and tungstate.
  • the tin-containing metal mineral includes cassiterite.
  • the titanium-containing mineral includes ilmenite and / or rutile.
  • the gangue mineral includes at least one of calcite, fluorite, apatite, quartz, and aluminosilicate minerals.
  • the slurry system is in an alkaline environment during the flotation separation process. It is preferably 8 to 11.
  • the method for preparing the hydroxamic acid-metal hydroxide complex of the present invention specifically includes the following steps:
  • the hydroxamic acid ethanol solution and metal salt solution separately, add sodium hydroxide to the hydroxamic acid solution to adjust the pH to 8.5 ⁇ 9.5, heat it to 55 ⁇ 65 ° C, and slowly add the metal salt solution to the hydroxamic acid solution.
  • the molar ratio of the metal salt and the hydroxamic acid is (1 ⁇ 2): (1 ⁇ 3), and the reaction time is 1 ⁇ 2 h;
  • the third step is the desorption of the hydroxamic acid-metal hydroxide complex:
  • the quartz product obtained in the second step is put into an ethanol solution, and is subjected to shaking washing by an ultrasonic scrubber, so that the hydroxamic acid-metal hydroxide complex adsorbed on the quartz surface is desorbed, and the hydroxamic acid-metal is obtained by immersion in the ethanol solution.
  • Hydroxide complex ethanol mixed liquid can be used as flotation collector.
  • Hydroxamic acid-metal hydroxide complex of the present invention for flotation enrichment of tungsten ore, cassiterite, ilmenite, rutile and rare earth (Tungsten ore flotation is taken as an example for specific explanation): After grinding, magnetic separation and desulfurization, add sodium carbonate to adjust the pH of the pulp, and then add hydroxamic acid-metal hydroxide complexes to stir the slurry, add pinitol oil for aerated flotation, and the foam product is tungsten coarse concentrate
  • the amount of collector added to the original ore is 200 ⁇ 500g / t; the flotation pH is 7 ⁇ 12, and the flotation temperature is 0 ⁇ 90 °C.
  • the benzhydroxamic acid-metal hydroxide complex of the present invention has strong selectivity and collection ability for scheelite, wolframite, ilmenite, rutile, rare earth and other minerals, mainly because these minerals are alkaline
  • the surface is negatively charged, and the hydroxamic acid-metal complex has a colloidal structure.
  • the surface is positively charged, and there is a classical adsorption between the two. Therefore, the hydroxamic acid-metal complex is easily adsorbed to these surface charges by electrostatic interaction.
  • the negatively charged mineral surface, and the hydroxamic acid-metal hydroxide complex has a hydroxyl structure, which easily interacts with active particles on the mineral surface, thereby enhancing its adsorption on the surface.
  • the adsorption model is shown in Figure 1.
  • the existing hydroxamic acid-metal hydroxide complex is a complex metal hydroxide complex system, which can contain scheelite, wolframite, ilmenite, rutile and rare earth. The content of effective components on the surface of other minerals is low.
  • a coordination reaction is performed under basic conditions, so that hydroxide and hydroxamic acid are used as co-ligands to coordinate with high-valent metal ions to generate hydroxime.
  • the acid-metal hydroxide complex has significantly improved the effective components of scheelite, wolframite, ilmenite, rutile, and rare earth minerals, and shows stronger selectivity and collection ability, making The cost of using the hydroxamic acid-metal hydroxide complex as a collector is greatly reduced.
  • the preparation method of the hydroxamic acid-metal hydroxide complex of the present invention is simple, mild conditions, and low cost, which is beneficial to industrial production.
  • the benzhydroxamic acid-metal hydroxide complex of the present invention has strong selectivity and collection ability for tungsten ore, cassiterite, rutile, ilmenite, rare earth and other metal oxide minerals, and can realize tungsten ore , Flotation and enrichment of metal oxide minerals such as cassiterite, ilmenite, rutile and rare earth; especially suitable for efficient enrichment of tungsten-containing minerals, making the tungsten-containing minerals enrichment ratio up to 50 times and the recovery rate is greater than 85% . It has created favorable conditions for subsequent normal temperature selection operations, completely replacing heating selection operations, and achieving an efficient connection between rough selection operations and selection operations.
  • the flotation process of the benzhydroxamic acid-metal hydroxide complex of the present invention as a collector has a short process flow, simple medicament, convenient operation, low labor intensity, low energy consumption, environmental protection and high efficiency, which not only greatly reduces This reduces the cost and significantly improves the utilization of metal resources such as tungsten.
  • the benzhydroxamic acid-metal hydroxide complex of the present invention has good selective collection effect, stable performance, small amount and low cost, and can be widely used in tungsten ore, cassiterite, ilmenite, rutile and In the floatation separation process such as rare earth, the quality of concentrate is effectively improved.
  • FIG. 1 A schematic diagram of an adsorption model of benzhydroxamic acid-lead hydroxide complex for flotation of scheelite.
  • FIG. 3 is an XRD spectrum of the benzhydroxamic acid-lead hydroxide complex prepared in Examples 3 to 5.
  • FIG. 3 is an XRD spectrum of the benzhydroxamic acid-lead hydroxide complex prepared in Examples 3 to 5.
  • FIG. 4 is a thermogravimetric analysis (TGA) spectrum of the benzhydroxamic acid-lead hydroxide complex prepared in Examples 5 to 6.
  • TGA thermogravimetric analysis
  • FIG. 5 A flow chart of a tungsten desulfurization tailings separation process using benzohydroxamic acid-lead hydroxide complex as a collector in Example 13.
  • FIG. 6 shows the effect of pulp pH on the buoyancy of scheelite when the benzhydroxamic acid-lead hydroxide complex prepared in Example 1 is used as a collector.
  • the medicaments and ore raw materials used are all raw materials directly available in the market without special instructions.
  • the experimental conditions are the same as in Example 1, except that the ratio of lead nitrate to hydroxamic acid is different: 0.5 mol / L lead nitrate solution 80mL and 0.1 100 mL of mol / L benzhydroxamic acid ethanol solution.
  • the experimental conditions are the same as in Example 1, except that the ratio of lead nitrate to hydroxamic acid is different: 0.5 mol / L lead nitrate solution 40mL and 0.1 100 mL of mol / L benzhydroxamic acid ethanol solution.
  • the experimental conditions are the same as in Example 1, except that the ratio of lead nitrate to hydroxamic acid is different: 0.5 20 mL of a mol / L lead nitrate solution and 100 mL of a 0.1 mol / L benzhydroxamic acid ethanol solution.
  • the experimental conditions are the same as in Example 1, except that the ratio of lead nitrate to hydroxamic acid is different: 0.5 10 mL of mol / L lead nitrate solution and 100 mL of 0.1 mol / L benzhydroxamic acid ethanol solution;
  • the experimental conditions are the same as in Example 1, except that the ratio of lead nitrate to hydroxamic acid is different: 0.5 mol / L lead nitrate solution 5mL and 0.1 100 mL of mol / L benzhydroxamic acid ethanol solution;
  • the experimental conditions are the same as in Example 1, except that the ratio of lead nitrate to hydroxamic acid is different: 0.5 mol / L lead nitrate solution 4mL and 0.1 100 mL of mol / L benzhydroxamic acid ethanol solution;
  • the experimental conditions were the same as in Example 7, except that only metal salt solutions containing different metal ions were used: the lead nitrate solution was replaced with a solution containing Ca 2+ , Mn 2+ , Cu 2+ , Fe 3+ or Al 3+ .
  • Example 6 The experimental conditions were the same as in Example 6, and only salicylic hydroxamic acid was used in place of benzyl hydroxamic acid.
  • Example 5 The experimental conditions were the same as in Example 5, except that only acetohydroxamic acid was used in place of benzhydroxamic acid.
  • the infrared spectra of the benzhydroxamic acid-lead hydroxide complex (Pb-BHA) and benzhydroxamic acid (BHA) prepared in Examples 2 to 5 are shown in FIG. 2.
  • the absorption peaks of BHA are 3295 cm -1 and 3060.17 cm -1 , which may be the stretching vibration absorption peaks of OH and NH.
  • the broad band of about 2747.24 cm -1 is the intramolecular OOH stretch band of BHA.
  • Fig. 3 shows the XRD patterns of Pb-BHA at different Pb / BHA ratios. No characteristic peaks of BHA and Pb (NO 3 ) 2 were observed, and some strong peaks appeared at 5.4578 °, 11.0964 °, 12.2432 °, indicating that new Pb-BHA species were generated. The peak intensities of the Pb-BHA complex relative to the Pb / BHA ratio are different from each other, and it was found that more than one stable complex was produced in the reaction between BHA and Pb 2+ .
  • the Pb-BHA thermogravimetric analysis (TGA) spectra prepared in Examples 5 and 6 are shown in Figure 4:
  • the molecular structure of the Pb-BHA complex is PbBHA 2 ⁇ 2Pb (OH) 2 or Pb 3 (OH) 4 BHA 2 .
  • Figure 4 is a thermogravimetric analysis of Pb-BHA during the temperature rise from 30 ° C to 600 ° C, which shows that the Pb-BHA precipitates have gone through three stages. In the first stage (30 ⁇ 300 °C), the weight of Pb-BHA is reduced due to the evaporation of water (such as free water and crystal water) and the decomposition of the absorbed BHA molecules.
  • the first stage Pb (BHA) 2 gxPb (OH) 2 gmBHAgnH 2 O + O 2 — Pb (BHA) 2 gxPb (OH) 2 + CO 2 + NO + H 2 O;
  • the second stage Pb (BHA) 2 gxPb (OH) 2 + H 2 O + O 2 — Pb (OH) 2 + CO 2 + NO 2 ;
  • the third stage Pb (OH) 2 — PbO + H 2 O.
  • the structure of Pb-BHA can be inferred to be 2Pb (OH) 2 • Pb (BHA) 2 • mBHA • nH 2 O, and the most stable structure may be 2 Pb (OH) 2 • Pb (BHA ) 2 .
  • BHA molecules can be adsorbed on this structure by hydrogen bonding.
  • the desulfurized tailings were added with a pH adjuster to adjust the pH of the pulp to 9.6, and then the benzyl hydroxyl prepared in Example 1 was added.
  • the hydroxamic acid-lead hydroxide complex is stirred and mixed, and the pinol oil foaming agent is added for aerated flotation.
  • the foam product is tungsten concentrate; the amount of benzhydroxamic acid-lead hydroxide complex relative to the original ore.
  • the pH of the slurry was adjusted to 9.6 by adding a pH adjuster to the desulfurization tailings, and then the benzhydroxamic acid-metal hydroxide complex prepared in Example 1 The product is stirred and adjusted, and the pinolol oil foaming agent is added for aerated flotation.
  • the foam product is tungsten concentrate; the amount of collector added to the original ore is 300g / t, the foaming agent is 5g / t, and the pH adjusting agent is Sodium carbonate, flotation temperature is 25 °C, water glass and aluminum sulfate are added as inhibitors in the selection operation, and one concentrate and two concentrates are used to obtain a concentrate WO 3 grade 16.43% scheelite concentrate with a recovery rate of 92.64% (flotation process The process is shown in Figure 5).
  • Example 6 The operation steps were the same as those in Example 13, and the flotation effect of scheelite on the scheelite at different pH conditions was examined using the hydroxamic acid-lead hydroxide complex prepared in Example 7.
  • the flotation effect is shown in Figure 6, which shows that under basic conditions, benzhydroxamic acid-metal hydroxide has a better flotation effect on scheelite, especially when the pH is between 8-10.
  • Example 7 The operation steps were the same as those in Example 13.
  • the hydroxamic acid-lead hydroxide complexes in Examples 2 to 5 were respectively used to investigate the flotation effect of these complex collectors on scheelite under different pH conditions.
  • the flotation effect is shown in Figure 7. It can be seen from the figure that the hydroxamic acid-lead hydroxide complex has a flotation effect on scheelite in the pH range of 3-12, and under alkaline conditions, such as in the range of 7-10, Flotation effect is better.
  • Control experiment group The operation steps are the same as those in Example 13.
  • the hydroxamic acid-lead hydroxide complexes in Examples 2 to 5 were respectively used to investigate the effects of these complex collectors on fluorite ore at different pH conditions. Flotation effect. The flotation effect is shown in Figure 13.
  • Example 8 The operation steps are the same as those in Example 13, and various benzhydroxamic acid-metal hydroxide complexes in Example 8 are used. And the flotation effect on scheelite under different pH conditions was investigated. The flotation effect is shown in Figure 8. It can be seen from FIG.
  • hydroxamic acid-lead complex generated by divalent lead ions is formed against the hydroxamic acid of other metal ions such as Ca 2+ , Mn 2+ , Cu 2+ , Fe 3+ , Al 3+ - Metal hydroxide complexes show better selectivity and strong collection ability for flotation collection of scheelite, such as Pb 2+ is greater than Ca 2+ , Ca 2+ is greater than Mn 2+ , Fe 3+ , Al 3+ , Mn 2+ , Fe 3+ and Al 3+ are larger than Cu 2+ .
  • the metal ion is most preferably Pb 2+ .
  • Example 13 The operation steps are the same as those in Example 13, and various hydroxamic acid-lead hydroxide complexes in Examples 9 to 11 are used. And the flotation effect on scheelite under different pH conditions was investigated. The flotation effect is shown in Figures 9 ⁇ 11. It can be seen from the figure that under the same conditions, the hydroxamate-lead hydroxide complex prepared by benzyl hydroxamic acid, salicylic hydroxamic acid, and octyl hydroxamic acid is used as a collector, and the flotation of scheelite The effect is higher than that of acetohydroxamic acid-lead hydroxide complex.
  • the pH of the slurry was adjusted to 8.5 by adding a pH adjuster to the desulfurization tailings, and then the benzhydroxamic acid-metal hydroxide complex prepared in Example 1 Stir and adjust the slurry, add secondary octanol foaming agent for aerated flotation, the foam product is tin concentrate; the amount of collector added to the original ore is 400g / t, the foaming agent is 10g / t, and the pH adjusting agent is Sodium carbonate, flotation temperature is 25 °C, 50g / t carboxymethylcellulose is added as the inhibitor in the selection operation, and the tin concentrate with a grade of SnO 2 of 40.5% is obtained through one coarse and three concentrates. The recovery rate is 83.89%.
  • This process is used to treat fine-grained ilmenite in Panzhihua, Sichuan, and the pH of the slurry is adjusted by adding a pH adjuster to the desulfurization tailings. 5.6, then add the benzyl hydroxamic acid-metal hydroxide complex prepared in Example 1 and stir the slurry, add secondary octanol foaming agent for aerated flotation, the foam product is ilmenite concentrate; collector
  • the relative amount of raw ore is 600g / t
  • the foaming agent is 10g / t
  • the pH adjuster is sulfuric acid
  • the flotation temperature is 25 ° C.
  • 100g / t of acidified water glass is added as the inhibitor in the selection operation.
  • the ilmenite concentrate with a grade of 49.80% was obtained and the recovery rate was 67.93%.
  • This process is used to treat a heavy rare earth ore in Baotou.
  • the raw ore is adjusted to a pH of 8.0 by a pH adjuster, and then the benzyl hydroxamic acid-metal hydroxide complex prepared in Example 1 is added to stir and slurry.
  • the foam product is heavy rare earth concentrate; the amount of metal ion complex collector added to the original ore is 300g / t, the foaming agent is 10g / t, the pH adjuster is sodium carbonate, the flotation temperature At 25 °C, 150g / t of water glass was added as the inhibitor in the selection operation, and the crude rare earth concentrate with a grade of 52.24% was obtained after one rough and four refinements, with a recovery rate of 53.68%.
  • This process is used to treat a low-grade rutile mine in Hubei. After the raw ore is crushed and ground, a pH adjuster is added to adjust the pH of the pulp 5.0, and then the benzyl hydroxamic acid-metal hydroxide complex prepared in Example 1 is added to stir and adjust the pulp.
  • the foam product is rutile concentrate; the amount of collector added to the original ore is 400g / t, the foaming agent is 10g / t, the pH adjusting agent is sulfuric acid, and the flotation
  • the temperature was 25 °C, 100 g / t acidified water glass was added as the inhibitor in the selection operation, and 63.70% of rutile concentrate was obtained after one crude and three fines, with a recovery rate of 81.09%.

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Abstract

本发明公开了一种羟肟酸-金属氢氧化物配合物及其制备和应用，羟肟酸-金属氢氧化物配合物由羟肟酸与二价或高于二价金属离子在碱性条件下配位生成，羟肟酸-金属氢氧化物配合物对于含钨矿物、钛铁矿、金红石、锡石及稀土等金属氧化矿物具有极强选择性和极强捕收能力，且其制备方法简单、成本低，有利于工业化生产。

Description

一种羟肟酸-金属氢氧化物配合物及其制备和应用 技术领域
本发明涉及一种有机金属氢氧化物配合物，具体涉及一种羟肟酸-金属氢氧化物配合物及其制备和分离纯化的方法，还涉及羟肟酸-金属氢氧化物配合物作为含钨矿、锡矿、钛矿或稀土矿等浮选捕收剂应用，属于选矿技术领域。
 背景技术
矿产资源是国家经济的基础物质材料，其保证程度关系到国民经济长期稳定发展和国家安全。矿产资源高效开发利用已列入国家中长期科学和技术发展规划纲要。其中，氧化矿作为钨、锡、铁、锰、铅、锌、铜和钛等金属的主要矿物在矿产资源的开发利用中占重要地位。相比于硫化矿而言，氧化矿具有更加复杂的共生关系，分选难度大、利用率低；随着资源贫细化加剧，分选难度进一步加大，对矿物分选过程中的选择性提出了更高的要求。钨矿、锡石和金红石是氧化矿资源的典型代表，在资源的高效综合利用方面面临一系列的共性科学问题，例如资源 “贫、细、杂”的特点和浮选过程中捕收剂选择性不足等关键问题。
我国钨资源较为丰富，但70%以上的资源属于难处理资源，其中仅栾川伴生超低品位钨资源储量就达62万吨，由于缺乏有效的技术手段，大量钨资源曾流失在尾矿中；柿竹园、行洛坑等典型的矽卡岩型高钙黑白钨伴生资源储量高达130万吨，随着品位降低、含钙脉石增加，这类资源综合利用更加困难，柿竹园钨回收率一度下降至63%左右。白钨矿、方解石和萤石均属于可溶性盐类矿物，溶解度比较大，含钙矿物之间存在相互转化的现象，这使各矿物的浮选行为变得很复杂，含钙矿物间的分离更加困难。该资源的利用问题本质是白钨矿（含钙有用矿物）与含钙脉石矿物的分离问题，属世界性难题，浮选药剂的选择性是此类资源高效开发的关键。
中国是世界上锡矿资源最为丰富的国家之一，占全球探明储量的28.85%。但是，我国锡资源的特点是共伴生组分复杂，80%以上为共伴生资源。随着锡石原矿品位的日益降低，难浮的磁黄铁矿及密度相近的脉石矿物等日益增加，微细粒锡石的处理难度加大，复杂多金属微细粒锡石的浮选分离成为选矿领域的难题。以湖南柿竹园钨锡钼铋多金属矿为例，锡探明储量高达46万吨，由于原矿伴生锡的品位只有0.1~0.12 %，且伴生锡的60%系胶态类锡矿物，曾一度被相关专家定论为根本不能回收的锡矿物。目前因矿石嵌布粒度细、共伴生关系复杂、品位相对较低，可浮性差，综合利用难度大，锡资源的综合回收目前还是空白，每年排往尾矿库的锡金属量达到1500吨，低品位伴生锡资源的综合回收面临巨大的挑战。
资源综合利用率低的本质原因在于：钨矿、锡石和金红石等氧化矿的捕收剂多以脂肪酸、螯合捕收剂等阴离子捕收剂为主，此类捕收剂通过含N、O、P等的有机酸官能团与矿物表面活性位点作用，实现对目的矿物的捕收。然而，氧化矿体系中有用矿物与脉石矿物具有类似的表面化学性质，这些传统阴离子捕收剂在选择新性方面很难再有质的提高。例如：白钨矿与萤石、方解石等均为含钙矿物，传统捕收剂通过钙质点与矿物表面同时发生作用，选择性差；锡石浮选体系中大量铜、铁、铅、钙等金属离子在矿物表面吸附，使锡石和脉石矿物表面性质趋同，传统阴离子捕收剂难以高效选择性吸附，导致资源利用率低、生产过程能耗和成本高、选矿过程环境问题突出；金红石与硅酸盐矿物（例如绿帘石、角闪石等）结构相近、表面性质相似，细粒级金红石资源未能得到有效的开发。因此，开发具有高度选择性捕收能力的新型氧化矿捕收剂成为选矿工作者重要的研究方向。
近年来，金属离子配位调控分子组装已成为化工、材料、生物、医学等领域的研究热点，大量结构新颖、多样化、具有各种功能的配位聚合物被设计、开发，解决了各领域中的一系列关键问题。通过金属离子与配体的配位组装形成具有特定捕收能力的配位捕收剂，或通过金属离子的配位调控形成具有特定结构的胶束，为新型浮选药剂的的开发提供了新的思路。如中国专利（CN105618272A）公开了一种由配位体与金属离子配位形成的金属离子配合物捕收剂，其制备方法是将含配位体的溶液中加入可溶性金属盐反应，得到金属离子配合物捕收剂；金属离子配合物捕收剂对于含钨矿物、稀土及锡石等具有较强的选择性捕收能力，能够在无含钙矿物抑制剂条件下实现含钨矿物、锡石、稀土等与含钙脉石矿物的选择性分离，从根本上解决了含钙矿物分离困难的问题。但是由金属离子与有机配体在溶液体系下形成的配合物并非单一组分，其实多种多种组分的混合物，在矿物浮选过程中真正起作用的是表面荷正电的某一组分，因此，通过该方法获得的金属离子配合物有效部分含量低，导致其利用率低，成本高，且应用效果相对较差。
 技术问题
针对现有的钨矿、锡石和金红石等氧化矿的浮选捕收的金属氢氧化物配合物存在的问题，本发明的第一个目的是在于提供一种对钨矿、锡石、钛铁矿、金红石和稀土等具有极强选择性和极强捕收能力的羟肟酸-金属氢氧化物配合物捕收剂，相对现有的类似的羟肟酸金属配合物，作用于钨矿、锡石、钛铁矿、金红石和稀土等矿物的有效成分含量高（这里的有效成分指的是对金属矿物具有捕收能力的部分），捕收效果更加显著，成本低。
本发明的第二个目的是在于提供一种流程简单、反应条件温和、成本低的制备所述羟肟酸-金属氢氧化物配合物的方法。
本发明的第三个目的在于提供一种所述羟肟酸-金属氢氧化物配合物的应用，将羟肟酸-金属氢氧化物配合物其用于钨矿、锡石、钛铁矿、金红石和稀土等与方解石、萤石、磷灰石和铝硅酸盐矿物等脉石矿物的浮选分离，从根本上解决了复杂低品位氧化矿浮选分离困难、效率低的问题，且使用成本大大降低。
 技术解决方案
为了实现上述技术目的，本发明提供了一种羟肟酸-金属氢氧化物配合物，由羟肟酸与二价或高于二价金属离子在碱性条件下配位生成；
所述羟肟酸具有式1结构：
Figure 664425dest_path_image001
式1
其中，R为憎水性有机基团。
    优选的方案，所述羟肟酸中憎水性有机基团指其亲水亲油平衡值较小，一般来说亲水亲油平衡值小于9，最好是小于6。R优选为脂肪烃基或芳基。脂肪烃基可以为饱和的烷基链，烷基链可以为直链，也可以含支链，或者环烷链，脂肪烃基可以为非饱和的烷基链，如含至少一个碳碳双键或者含至少一个碳碳三键。或者脂肪烃上可以含一些常见的取代基团，如卤素等，取代基团最好是不为亲水基团，如果选择亲水基团时，是要在整个脂肪烃基团的亲水亲油平衡值在较小值，如亲水亲油平衡值小于6。R为脂肪烃基时，优选为C 4~C 12的烷烃基、C 4~C 12的不饱和脂肪烃基。芳基优选为苯基或取代苯基。取代苯基为苯环上含有至少一个取代基，常见的如短链烷基、卤素、烷氧基等，取代基最好不为亲水基团。如果选择亲水基团时，是要在整个取代苯基基团的亲水亲油平衡值在较小值，如亲水亲油平衡值小于6。在所有的羟肟酸中苯甲羟肟酸具有最佳的效果。R最优选为苯基。
    优选的方案，所述二价或高于二价金属离子包括Pb 2+、Ca 2+、Mn 2+、Cu 2+、Fe 3+、Al 3+中至少一种。大量实验表明，在相同条件下采用不同金属离子制备的羟肟酸-金属氢氧化物配合物中，二价铅离子生成的羟肟酸-铅配合物相对Ca 2+、Mn 2+、Cu 2+、Fe 3+、Al 3+等其他金属离子生成的羟肟酸-金属氢氧化物配合物，对钨矿、锡石、钛铁矿、金红石和稀土等矿物的浮选捕收，表现出更好的选择性和强捕收能力，如Pb 2+大于Ca 2+，Ca 2+大于Mn 2+、Fe 3+、Al 3+，Mn 2+、Fe 3+及Al 3+大于Cu 2+。所述金属离子最优选为Pb 2+。
优选的方案，二价或高于二价金属离子与羟肟酸的配位摩尔比为（1~4）:（1~5）。配位摩尔比更优选为（1~2）:（1~3）。在不同的配比下，金属离子与羟肟酸可以生成不同的羟肟酸-金属氢氧化物配合物，其结构和性质存在很大的差异，而在配比范围内，可以生成有效成分含量最高的羟肟酸-金属氢氧化物配合物（这里的有效成分指的是对金属矿物具有捕收能力的部分），配比过高或过低均会对有效成分的含量及其在矿物表面的吸附性能产生影响。
优选的方案，所述碱性条件的pH为8~11，更优选的pH为8.5~9.5。在碱性条件下，部分氢氧根可以参与配位，与羟肟酸共同配位金属离子，生成羟肟酸/羟基-金属氢氧化物配合物，pH过低羟基难以有效参与反应，而pH过大，大量氢氧根与配体形成竞争反应并形成氢氧化物沉淀，难以生成配合物。
    本发明还提供了一种羟肟酸-金属氢氧化物配合物的制备方法，将羟肟酸和二价或高于二价金属离子在碱性溶液体系中进行配位反应，即得羟肟酸-金属氢氧化物配合物；
所述羟肟酸具有式1结构：
Figure 519249dest_path_image001
式1
其中，R为憎水性有机基团。
    优选的方案，R为脂肪烃基或芳基。R较优选为C 4~C 12的烷烃基、C 4~C 12的不饱和脂肪烃基、苯基、取代苯基。R最优选为苯基。
    优选的方案，所述二价或高于二价金属离子金属离子包括Pb 2+、Ca 2+、Mn 2+、Cu 2+、Fe 3+、Al 3+中至少一种。所述二价金属离子优选为Pb 2+。
    优选的方案，二价或高于二价金属离子与羟肟酸的配位摩尔比为（1~4）:（1~5）。配位摩尔比更优选为（1~2）:（1~3）。
优选的方案，所述碱性条件的pH为8~11，优选的pH为8.5~9.5。碱性溶液可以采用氢氧化钠、氢氧化钾等常见的碱调节。
优选的方案，所述配位反应的温度为20~80℃，反应时间为0.5~6h。更优选的温度为55~65℃。更优选的反应时间为1~2h。更优选的配位反应反应条件为：温度为55~65℃，反应时间为l~2h。反应温度影响了反应的速率和生成配合物的结构，温度过低反应速率较慢且转化率较低，反应温度过高会导致大量非氢氧根配合物的生成。
    优选的方案，所述配位反应完成后，通过载体吸附-泡沫浮选方法分离纯化羟肟酸-金属氢氧化物配合物。
优选的方案，所述载体吸附-泡沫浮选方法为：通过载体颗粒吸附溶液体系中的羟肟酸-金属氢氧化物配合物，吸附完成后，通过泡沫浮选回收负载羟肟酸-金属氢氧化物配合物的载体颗粒，所述负载羟肟酸-金属氢氧化物配合物的载体颗粒通过超声洗涤，得到羟肟酸-金属氢氧化物配合物溶液。载体颗粒加入至溶液体系中，羟肟酸-金属氢氧化物配合物通过静电作用吸附在载体颗粒物表面将其包裹，使得载体颗粒表面表现出强疏水性，通过充气浮选，表面吸附了羟肟酸-金属氢氧化物配合物的载体颗粒物进入泡沫层。通过载体吸附-泡沫浮选方法可以分离得到纯度较高的羟肟酸-金属氢氧化物配合物。
较优选的方案，所述载体颗粒为粒度范围在10~37 μm范围内的石英颗粒。石英颗粒的粒度范围在10~37 μm范围内，有利于后续浮选过程中颗粒物上浮。石英颗粒的相对加入量在体系中不低于100g/L，以保证羟肟酸-金属氢氧化物配合物充分分离回收。
较优选的方案，所述超声洗涤采用无水乙醇作为洗涤剂。理论上能够溶解分散苯甲羟肟酸-金属氢氧化物配合物的溶剂都可以作为洗涤剂，优选廉价、安全无毒的乙醇作为洗涤剂。
优选的方案，金属离子主要由水溶性金属盐溶液提供，如硝酸盐等，金属离子的浓度没有特殊要求。
优选的方案，羟肟酸主要采用有机溶剂溶解，如乙醇等，羟肟酸的浓度没有特殊要求。
    本发明还提供了一种羟肟酸-金属氢氧化物配合物的应用，将羟肟酸-金属氢氧化物配合物作为浮选捕收剂应用于含钨、锡、钛和稀土中至少一种的金属氧化矿物与脉石矿物的浮选分离。
    优选的方案，所述含钨金属矿物包括白钨矿、黑钨矿和钨华中至少一种。
优选的方案，所述含锡金属矿物包括锡石。
优选的方案，所述含钛矿物包括钛铁矿和/或金红石。
优选的方案，所述脉石矿物包括方解石、萤石、磷灰石、石英和铝硅酸盐矿物中至少一种。
优选的方案，所述浮选分离过程中浆料体系为碱性环境。优选为8~11。
本发明的羟肟酸-金属氢氧化物配合物的制备方法具体包括以下步骤：
第一步，羟肟酸-金属氢氧化物配合物的合成：
分别配置羟肟酸乙醇溶液和金属盐水溶液，向羟肟酸溶液中加入氢氧化钠调节pH为8.5~9.5，将其加热至55~65℃，向羟肟酸溶液中缓慢加入金属盐溶液进行反应，金属盐和羟肟酸的摩尔比为（1~2）:（1~3），反应时间1~2 h；
第二步，石英载体浮选分离：
将第一步所得的羟肟酸-金属氢氧化物配合物溶液转入浮选槽，加入10~37 μm 石英粉，调浆搅拌10~30min，然后充气浮选，收集浮选泡沫并过滤；
第三步，羟肟酸-金属氢氧化物配合物的脱附：
将第二步所得石英产品进入乙醇溶液，并通过超声波洗涤器进行震荡洗涤，使得吸附在石英表面的羟肟酸-金属氢氧化物配合物脱附，浸入乙醇溶液，即得羟肟酸-金属氢氧化物配合物乙醇混合液，可作为浮选捕收剂。
本发明的羟肟酸-金属氢氧化物配合物对钨矿、锡石、钛铁矿、金红石及稀土的浮选富集（以钨矿浮选为例进行具体说明）：钨矿经破碎、磨矿、磁选脱铁、脱硫后，加入碳酸钠调节矿浆pH，然后加入羟肟酸-金属氢氧化物配合物搅拌调浆，加入松醇油进行充气浮选，泡沫产品即为钨粗精矿；捕收剂相对原矿的加入量为200~500g/t；浮选pH为7~12，浮选温度为0~90℃。
本发明的苯甲羟肟酸-金属氢氧化物配合物对白钨矿、黑钨矿、钛铁矿、金红石和稀土等矿物的选择性和捕收能力强，主要原因是这些矿物在碱性条件下表面荷负电，而羟肟酸-金属配合物具有胶体结构，其表面荷正电，两者之间存在经典吸附，因此羟肟酸-金属配合物极易通过静电作用吸附到这些表面荷负电的矿物表面，同时羟肟酸-金属氢氧化物配合物具有羟基结构，其容易与矿物表面的活性质点发生作用，从而强化其在表面的吸附。以苯甲羟肟酸-铅配合物捕收白钨矿为例，其吸附模型如图1所述。
 有益效果
1、现有的羟肟酸-金属氢氧化物配合物是一个成分复杂的金属氢氧化物配合物体系，其包含的可以作用于白钨矿、黑钨矿、钛铁矿、金红石和稀土等矿物表面的有效成分含量较低，而在本发明技术方案中，在碱性条件下进行配位反应，使氢氧根和羟肟酸作为共配体与高价金属离子进行配位生成羟肟酸-金属氢氧化物配合物，对白钨矿、黑钨矿、钛铁矿、金红石和稀土等矿物具有捕收能力的有效成分明显提高，表现出更强的选择性和捕收能力，使得羟肟酸-金属氢氧化物配合物作为捕收剂的使用成本大大降低。
2、本发明的羟肟酸-金属氢氧化物配合物制备流程简单、温和条件、成本低，有利于工业化生产。
3、本发明的苯甲羟肟酸-金属氢氧化物配合物对钨矿、锡石、金红石、钛铁矿及稀土等金属氧化矿物具有极强的选择性和捕收能力，可以实现钨矿、锡石、钛铁矿、金红石及稀土等金属氧化矿物的高效浮选富集；特别适用于含钨矿物的高效富集，使含钨矿物富集比高达50倍以上，回收率大于85%。为后续的常温精选作业创造了有利条件，彻底取代加温精选作业，实现了粗选作业与精选作业的高效衔接。
4、本发明的苯甲羟肟酸-金属氢氧化物配合物作为捕收剂进行浮选的过程流程短、药剂简单、操作方便、劳动强度低、能耗低、环保高效，不仅极大地降低了成本而且显著提高了钨等金属资源的利用率。
5、本发明的苯甲羟肟酸-金属氢氧化物配合物选择性捕收效果好、性能稳定、用量小、成本低，可广泛应用于钨矿、锡石、钛铁矿、金红石和稀土等浮选分离工艺中，有效提高精矿质量。
 附图说明
【图1】为苯甲羟肟酸-铅氢氧化物配合物浮选捕收白钨矿的吸附模型示意图。
【图2】为实施例2~5制得的苯甲羟肟酸-铅氢氧化物配合物及苯甲羟肟酸的红外光谱图。
【图3】为实施例3~5制备的苯甲羟肟酸-铅氢氧化物配合物的XRD谱图。
【图4】为实施例5~6制备的苯甲羟肟酸-铅氢氧化物配合物的热重分析（TGA）谱图。
【图5】为实施例13中采用苯甲羟肟酸-铅氢氧化物配合物作为捕收剂的脱硫尾矿选钨工艺流程图。
【图6】为实施例1制备的苯甲羟肟酸-铅氢氧化物配合物作为捕收剂时，矿浆pH对白钨矿可浮性的影响。
【图7】为实施例2~5制备的苯甲羟肟酸-铅氢氧化物配合物作为捕收剂时，矿浆pH对白钨矿可浮性的影响。
【图8】为实施例8各种苯甲羟肟酸-金属氢氧化物配合物作捕收剂时，矿浆pH对白钨矿可浮性的影响。
【图9】为水杨羟肟酸-铅氢氧化物配合物作为捕收剂时，矿浆pH对白钨矿可浮性的影响。
【图10】为辛基羟肟酸-铅氢氧化物配合物作为捕收剂时，矿浆pH对白钨矿可浮性的影响。
【图11】为乙酰氧肟酸-铅氢氧化物配合物作为捕收剂时，矿浆pH对白钨矿可浮性的影响。
【图12】为实施例2~5制备的苯甲羟肟酸-铅氢氧化物配合物作捕收剂时，矿浆pH对萤石矿可浮性的影响。
 本发明的最佳实施方式
在此处键入本发明的最佳实施方式描述段落。
 本发明的实施方式
以下实施例是对本发明的内容进一步说明，而不是限制本发明权利要求保护的范围。
以下实施例中，使用的药剂和矿石原料未经特殊说明，均为本领域常见市面上直接获得的原料。
实施例1
分别配置0.1 mol/L苯甲羟肟酸（BHA）乙醇溶液100 mL和0.5 mol/L硝酸铅溶液8 mL，向苯甲羟肟酸溶液中加入氢氧化钠调节pH为9，将其加热至60℃，向苯甲羟肟酸溶液中缓慢加入硝酸铅溶液，反应时间1.5h；将所得的苯甲羟肟酸铅配合物溶液转入体积为100 mL浮选槽，加入粒径范围为10~37 μm 石英粉30 g，调浆搅拌15min，然后充气浮选，收集浮选泡沫并过滤；将浮选泡沫中石英产品转入乙醇溶液，并通过超声波洗涤器进行震荡洗涤，使得吸附在石英表面的苯甲羟肟酸-铅氢氧化物配合物脱附，即得苯甲羟肟酸-铅氢氧化物配合物-乙醇混合液，可作为浮选捕收剂。该实施例是C Pb/C BHA=1:2.5条件下制备的苯甲羟肟酸-铅氢氧化物配合物。
 
实施例2
实验条件与实施例1相同，仅仅是硝酸铅与羟肟酸的比例不同：0.5 mol/L硝酸铅溶液80mL与0.1 mol/L苯甲羟肟酸乙醇溶液100 mL。
该实施例是C Pb/C BHA=4:1条件下制备的苯甲羟肟酸-铅氢氧化物配合物。
 
实施例3
实验条件与实施例1相同，仅仅是硝酸铅与羟肟酸的比例不同：0.5 mol/L硝酸铅溶液40mL与0.1 mol/L苯甲羟肟酸乙醇溶液100 mL。
该实施例是C Pb/C BHA=2:1条件下制备的苯甲羟肟酸-铅氢氧化物配合物。
 
实施例4
实验条件与实施例1相同，仅仅是硝酸铅与羟肟酸的比例不同：0.5 mol/L硝酸铅溶液20 mL与0.1 mol/L苯甲羟肟酸乙醇溶液100 mL。
该实施例是C Pb/C BHA=1:1条件下制备的苯甲羟肟酸-铅氢氧化物配合物。
 
实施例5
实验条件与实施例1相同，仅仅是硝酸铅与羟肟酸的比例不同：0.5 mol/L硝酸铅溶液10 mL与0.1 mol/L苯甲羟肟酸乙醇溶液100 mL；
该实施例是C Pb/C BHA=1:2条件下制备的苯甲羟肟酸-铅氢氧化物配合物。
 
实施例6
实验条件与实施例1相同，仅仅是硝酸铅与羟肟酸的比例不同：0.5 mol/L硝酸铅溶液5mL与0.1 mol/L苯甲羟肟酸乙醇溶液100 mL；
该实施例是C Pb/C BHA=1:4条件下制备的苯甲羟肟酸-铅氢氧化物配合物。
 
实施例7
实验条件与实施例1相同，仅仅是硝酸铅与羟肟酸的比例不同：0.5 mol/L硝酸铅溶液4mL与0.1 mol/L苯甲羟肟酸乙醇溶液100 mL；
该实施例是C Pb/C BHA=1:5条件下制备的苯甲羟肟酸-铅氢氧化物配合物。
 
实施例8
    实验条件与实施例7相同，仅仅采用含不同金属离子的金属盐溶液：以含Ca 2+、Mn 2+、Cu 2+、Fe 3+或Al 3+的溶液替换硝酸铅溶液。
 
实施例9
实验条件与实施例6相同，仅仅采用水杨羟肟酸替换苯甲羟肟酸。
 
实施例10
实验条件与实施例5相同，仅仅采用辛基羟肟酸替换苯甲羟肟酸。
 
实施例11
实验条件与实施例5相同，仅仅采用乙酰氧肟酸替换苯甲羟肟酸。
 
实施例2~5制备的苯甲羟肟酸-铅氢氧化物配合物（Pb-BHA）及苯甲羟肟酸（BHA）的红外光谱图如图2所示。 BHA的吸收峰为3295 cm -1和3060.17 cm -1，这可能是O-H和N-H的伸缩振动吸收峰。约2747.24cm -1的宽带是BHA的分子内O-H-O伸展带。Pb-BHA与BHA的IR光谱比较显示，在约2700cm -1处宽带（分子内O-H-O伸展带）的消失或减少和宽带位置移动，这是由于CO-NHOH中OH的损失引起，同时O-H在3295.33处的特征峰也消失，并且产生了从3200 cm -1到3600 cm -1的一些新峰，其可能是由Pb–BHA诱导的O-H的费米共振。分离出1665.50cm -1处的C=O或C=N峰，并在复合物中移动到一定程度，表明配体通过该氧或氮配位。在550~630cm -1区域中，Pb–BHA的两个（或更多个）强吸收峰为v（Pb-O或Pb-N）。存在多个Pb-O或Pb-N带，这对于混合配体络合物更明显，反映了不同的Pb-O或Pb-N键长。可以推测，大多数Pb-BHA配合物将以C=O和Pb-O的形式存在，形成稳定的五元环，因为BHA主要在水溶液中采用封闭的（氢键合的）Z构型。
实施例3、4和5制备的Pb-BHA 的XRD谱图如图3所示：图3显示了不同Pb/BHA比率下Pb-BHA的XRD图谱。未观察到BHA和Pb（NO 3） 2的特征峰，并且在5.4578°，11.0964°，12.2432°处出现一些强峰，表明产生了新的Pb-BHA种类。Pb-BHA复合物的峰强度相对于Pb/BHA比率彼此不同，发现在BHA和Pb 2+之间的反应中产生了多于一种稳定的络合物。
实施例5和实施例6制备的Pb-BHA热重分析（TGA）谱图如图4所示： Pb-BHA配合物的分子结构为PbBHA 2·2Pb(OH) 2 或Pb 3(OH) 4BHA 2。图4是在30℃至600℃升温过程中Pb-BHA的热重分析，表明Pb-BHA析出物经历了三个阶段。在第一阶段（30~300℃），Pb-BHA由于水（例如游离水和结晶水）的蒸发和吸收的BHA分子的分解而减轻的重量。在第二阶段（300~450℃），放热分解峰突出，Pb(BHA) 2·xPb(OH) 2开始分解为Pb(OH) 2。在第三阶段（450~600℃），Pb(OH) 2分解为PbO。反应可归纳如下：
第一阶段:Pb(BHA) 2gxPb(OH) 2gmBHAgnH 2O + O 2 — Pb(BHA) 2gxPb(OH) 2 + CO 2 + NO + H 2O；
第二阶段：Pb(BHA) 2gxPb(OH) 2 + H 2O + O 2 — Pb(OH) 2 + CO 2 + NO 2；
第三阶段：Pb(OH) 2 — PbO + H 2O。
根据每个阶段的重量损失，Pb-BHA的结构可推测为2Pb(OH) 2•Pb(BHA) 2•mBHA•nH 2O，最稳定的结构可能是2 Pb(OH) 2•Pb(BHA) 2。BHA分子可以通过氢键吸附在该结构上。
 
实施例12
湖南柿竹园黑白钨混合矿（含有少量钨华）经破碎、磨矿、磁选脱铁、脱硫后，脱硫尾矿加入pH调整剂调节矿浆pH 9.6，然后加入实施例1制备的苯甲羟肟酸-铅氢氧化物配合物搅拌调浆，加入松醇油起泡剂进行充气浮选，泡沫产品即为钨精矿；苯甲羟肟酸-铅氢氧化物配合物相对原矿的加入量为400g/t，起泡剂为5g/t，pH调整剂为碳酸钠，浮选温度为25 ℃，精选作业加入水玻璃和硫酸铝作为抑制剂，经一粗两精获得精矿WO 3品位12.63%的黑白钨混合精矿，回收率82.58%（如表1）。
表1 脱硫尾矿选钨新工艺全流程闭路试验结果
产品名称 产率（%） WO 3品位（%） CaF 2品位（%） Sn品位（%） CaCO 3品位（%） WO 3回收率（%） CaF 2回收率（%） Sn回收率（%） CaCO 3回收率（%）
钨精矿 2.56 12.63 12.66 1.08 14.58 82.58 1.53 31.05 4.67
尾矿 97.44 0.07 21.37 0.11 7.82 17.42 98.47 68.95 95.33
给矿 100.0 0.39 21.15 0.14 7.99 100 100 100 100
 
实施例13
湖南柴山单一白钨矿经破碎、磨矿、磁选脱铁、脱硫后，脱硫尾矿加入pH调整剂调节矿浆pH 9.6，然后加入实施例1制备的苯甲羟肟酸-金属氢氧化物配合物搅拌调浆，加入松醇油起泡剂进行充气浮选，泡沫产品即为钨精矿；捕收剂相对原矿的加入量为300g/t，起泡剂为5g/t，pH调整剂为碳酸钠，浮选温度为25 ℃，精选作业加入水玻璃和硫酸铝作为抑制剂，经一粗两精获得精矿WO 3品位16.43%的白钨精矿，回收率92.64%（浮选工艺流程如图5）。
表2 脱硫尾矿选钨新工艺全流程闭路试验结果
产品名称 产率/% WO 3品位/% WO 3回收率/%
钨精矿 1.51 16.43 92.64
尾矿 98.49 0.02 7.36
给矿 100.00 0.27 100.00
 
实施例14
操作步骤与实施例13相同，考察采用实施例7制备的甲羟肟酸-铅氢氧化物配合物在不同pH 条件下对白钨矿的浮选效果。浮选效果如图6所示，说明在碱性条件下，苯甲羟肟酸-金属氢氧化物对白钨矿的浮选效果较好，特别是pH在8~10之间效果特别突出。
 
实施例15
操作步骤与实施例13相同，分别采用实施例2~5中的甲羟肟酸-铅氢氧化物配合物，考察这些配合物捕收剂在不同pH 条件下对白钨矿的浮选效果。浮选效果如图7所示。从图中可以看出在pH为3~12的范围内甲羟肟酸-铅氢氧化物配合物对白钨矿均具有浮选效果，而在碱性条件下，如7~10的范围内，浮选效果较好。
对照实验组：操作步骤与实施例13相同，分别采用实施例2~5中的甲羟肟酸-铅氢氧化物配合物，考察这些配合物捕收剂在不同pH 条件下对萤石矿的浮选效果。浮选效果如13所示。
通过对照实验组可以看出，在碱性条件下甲羟肟酸-铅氢氧化物配合物对白钨矿的选择性能力远远高于萤石等含钙矿物。可以实现白钨矿与萤石等矿物的高效分离。
 
实施例16
操作步骤与实施例13相同，分别采用实施例8中的各种苯甲羟肟酸-金属氢氧化物配合物。且考察在不同pH 条件下的对白钨矿的浮选效果。浮选效果如图8所示。从图8中可以看出二价铅离子生成的羟肟酸-铅配合物相对Ca 2+、Mn 2+、Cu 2+、Fe 3+、Al 3+等其他金属离子生成的羟肟酸-金属氢氧化物配合物，对白钨矿的浮选捕收，表现出更好的选择性和强捕收能力，如Pb 2+大于Ca 2+，Ca 2+大于Mn 2+、Fe 3+、Al 3+，Mn 2+、Fe 3+及Al 3+大于Cu 2+。所述金属离子最优选为Pb 2+。
 
实施例17
操作步骤与实施例13相同，分别采用实施例9~11中的各种羟肟酸-铅氢氧化物配合物。且考察在不同pH 条件下的对白钨矿的浮选效果。浮选效果如图9~图11所示。从图中可以看出，在相同条件下，苯甲羟肟酸、水杨羟肟酸、辛基羟肟酸制备的羟肟酸-铅氢氧化物配合物作为捕收剂时，对白钨矿浮选效果要高于乙酰氧肟酸-铅氢氧化物配合物。
 
实施例18
云南文山细粒锡矿石经破碎、磨矿、磁选脱铁、脱硫后，脱硫尾矿加入pH调整剂调节矿浆pH 8.5，然后加入实施例1制备的苯甲羟肟酸-金属氢氧化物配合物搅拌调浆，加入仲辛醇起泡剂进行充气浮选，泡沫产品即为锡精矿；捕收剂相对原矿的加入量为400g/t，起泡剂为10g/t，pH调整剂为碳酸钠，浮选温度为25 ℃，精选作业加入羧甲基纤维素50g/t作为抑制剂，经一粗三精获得精矿SnO 2品位40.15%的锡精矿，回收率83.89 %。
表3 脱硫尾矿锡石浮选新工艺全流程闭路试验结果
产品 产率/% SnO 2/% SnO 2回收率/%
锡精矿 0.90 40.15 83.89
尾矿 99.10 0.07 16.11
给矿 100.00 0.43 100.00
 
实施例19
利用本工艺方法处理四川攀枝花细粒级钛铁矿，脱硫尾矿加入pH调整剂调节矿浆pH 5.6，然后加入实施例1制备的苯甲羟肟酸-金属氢氧化物配合物搅拌调浆，加入仲辛醇起泡剂进行充气浮选，泡沫产品即为钛铁矿精矿；捕收剂相对原矿的加入量为600g/t，起泡剂为10g/t，pH调整剂为硫酸，浮选温度为25 ℃，精选作业加入酸化水玻璃100g/t作为抑制剂，经一粗三精获得品位49.80%的钛铁矿精矿，回收率67.93 %。
表4脱硫尾矿钛铁矿浮选新工艺全流程闭路试验结果
产品 产率/% TiO 2品位/% TiO 2回收率/%
钛铁矿精矿 28.15 49.80 67.93
尾矿 71.85 9.21 32.07
给矿 100.00 20.64 100.00
 
实施例20
利用本工艺方法处理包头某重稀土矿，原矿通过pH调整剂调整pH为8.0，后加入实施例1制备的苯甲羟肟酸-金属氢氧化物配合物搅拌调浆，加入仲辛醇起泡剂进行充气浮选，泡沫产品即为重稀土精矿；金属离子配合物捕收剂相对原矿的加入量为300g/t，起泡剂为10g/t，pH调整剂为碳酸钠，浮选温度为25 ℃，精选作业加入水玻璃150g/t作为抑制剂，经一粗四精获得粗精矿品位52.24%的重稀土精矿，回收率53.68%。
表5重稀土选新工艺全流程闭路试验结果
产品 产率/% 品位（REO）/% 回收率/%
重稀土精矿 6.57 52.24 53.68
尾矿 93.43 3.17 46.32
给矿 100.00 6.39 100.00
实施例21
利用本工艺方法处理湖北某低品位金红石矿，原矿经破碎、磨矿后加入pH调整剂调节矿浆pH 5.0，然后加入实施例1制备的苯甲羟肟酸-金属氢氧化物配合物搅拌调浆，加入仲辛醇起泡剂进行充气浮选，泡沫产品即为金红石精矿；捕收剂相对原矿的加入量为400g/t，起泡剂为10g/t，pH调整剂为硫酸，浮选温度为25 ℃，精选作业加入酸化水玻璃100g/t作为抑制剂，经一粗三精获得品位63.70%的金红石精矿，回收率81.09 %。
表6金红石矿浮选新工艺全流程闭路试验结果
产品 产率/% TiO 2品位/% TiO 2回收率/%
金红石精矿 2.94 63.70 81.09
尾矿 97.06 0.45 18.91
给矿 100.00 2.31 100.00
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Claims (30)

  1. 一种羟肟酸-金属氢氧化物配合物，其特征在于：由羟肟酸与二价或高于二价金属离子在碱性条件下配位生成；
    所述羟肟酸具有式1结构：
    式1
    其中，R为憎水性有机基团。
  2. 根据权利要求1所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：R为脂肪烃基或芳基。
  3. 根据权利要求2所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：R为C 4~C 12的烷烃基、C 4~C 12的不饱和脂肪烃基、苯基或取代苯基。
  4. 根据权利要求3所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：R为苯基。
  5. 根据权利要求1所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：所述二价或高于二价金属离子包括Pb 2+、Ca 2+、Mn 2+、Cu 2+、Fe 3+、Al 3+中至少一种。
  6. 根据权利要求5所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：所述二价金属离子为Pb 2+。
  7. 根据权利要求1~6任一项所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：二价或高于二价金属离子与羟肟酸的配位摩尔比为（1~4）:（1~5）。
  8. 根据权利要求7所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：二价或高于二价金属离子与羟肟酸的配位摩尔比为（1~2）:（1~3）。
  9. 根据权利要求1~6任一项所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：所述碱性条件的pH为8~11。
  10. 根据权利要求9所述的一种羟肟酸-金属氢氧化物配合物，其特征在于：所述碱性条件的pH为8.5~9.5。
  11. 一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：将羟肟酸与二价或高于二价金属离子在碱性溶液体系中进行配位反应，即得羟肟酸-金属氢氧化物配合物；
    所述羟肟酸具有式1结构：
    式1
    其中，R为憎水性有机基团。
  12. 根据权利要求11所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：R为脂肪烃基或芳基。
  13. 根据权利要求12所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：R为C 4~C 12的烷烃基、C 4~C 12的不饱和脂肪烃基、苯基或取代苯基。
  14. 根据权利要求13所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：R为苯基。
  15. 根据权利要求11所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述二价或高于二价金属离子包括Pb 2+、Ca 2+、Mn 2+、Cu 2+、Fe 3+、Al 3+中至少一种。
  16. 根据权利要求15所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述二价金属离子为Pb 2+。
  17. 根据权利要求11~16任一项所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：二价或高于二价金属离子与羟肟酸的配位摩尔比为（1~4）:（1~5）。
  18. 根据权利要求17所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：二价或高于二价金属离子与羟肟酸的配位摩尔比为（1~2）:（1~3）。
  19. 根据权利要求11~16任一项所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述碱性条件的pH为8~11。
  20. 根据权利要求19所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述碱性条件的pH为8.5~9.5。
  21. 根据权利要求11~16任一项所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述配位反应的温度为20~80℃，反应时间为0.5~6h。
  22. 根据权利要求21所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述配位反应的温度为55~65℃，反应时间为l~2h。
  23. 根据权利要求11~16任一项所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述配位反应完成后，通过载体吸附-泡沫浮选方法分离纯化羟肟酸-金属氢氧化物配合物。
  24. 根据权利要求23所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述载体吸附-泡沫浮选方法为：通过载体颗粒吸附溶液体系中的羟肟酸-金属氢氧化物配合物，吸附完成后，通过泡沫浮选回收负载羟肟酸-金属氢氧化物配合物的载体颗粒，所述负载羟肟酸-金属氢氧化物配合物的载体颗粒通过超声洗涤，得到羟肟酸-金属配合物溶液。
  25. 根据权利要求24所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述载体颗粒为粒度范围在10~37 μm范围内的石英颗粒。
  26. 根据权利要求24所述的一种羟肟酸-金属氢氧化物配合物的制备方法，其特征在于：所述超声洗涤采用无水乙醇作为洗涤剂。
  27. 权利要求1~10任一项所述一种羟肟酸-金属氢氧化物配合物的应用，其特征在于：将羟肟酸-金属氢氧化物配合物作为浮选捕收剂应用于含钨、锡、钛和稀土中至少一种的金属氧化矿物与脉石矿物的浮选分离。
  28. 根据权利要求27所述的一种羟肟酸-金属氢氧化物配合物的应用，其特征在于：
    所述含钨金属矿物包括白钨矿、黑钨矿和钨华中至少一种；
    所述含锡金属矿物包括锡石；
    所述含钛矿物包括钛铁矿和/或金红石。
  29. 根据权利要求27所述的一种羟肟酸-金属氢氧化物配合物的应用，其特征在于：所述脉石矿物包括方解石、萤石、磷灰石、石英和铝硅酸盐矿物中至少一种。
  30. 根据权利要求27所述的一种羟肟酸-金属氢氧化物配合物的应用，其特征在于：所述浮选分离过程中浆料体系为碱性环境。
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* Cited by examiner, † Cited by third party
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103012677A (zh) * 2011-09-23 2013-04-03 中南大学 一种离子印迹羟肟酸螯合树脂的制备方法
CN105618272A (zh) * 2015-12-30 2016-06-01 中南大学 一种金属离子配合物捕收剂及其制备方法和应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103012677A (zh) * 2011-09-23 2013-04-03 中南大学 一种离子印迹羟肟酸螯合树脂的制备方法
CN105618272A (zh) * 2015-12-30 2016-06-01 中南大学 一种金属离子配合物捕收剂及其制备方法和应用

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GAO, YUESHENG ET AL.: "Research Progress of Influence of Metal Ions on Mineral Flotation Behavior and Underlying Mechanism", THE CHINESE JOURNAL OF NONFERROUS METALS, vol. 27, no. 4, 24 April 2017 (2017-04-24), pages 859 - 868 *
HU , YUEHUA ET AL.: "The Application of Metal-coordinated Complexes in the Flotation of Oxide Minerals and Fundamental Research of the Adsorption Mechanism", CONSERVATION AND RESEARCH OF MINERAL RESOURCES, 25 February 2018 (2018-02-25), pages 42 - 47 ; 53 *
ISKANDER, G.M. ET AL.: "Synthesis and Copolymerization of Methacryloyl Hydroxamic Acids", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 78, no. 4, 4 August 2000 (2000-08-04), pages 751 - 758, XP002321039, DOI: 10.1002/1097-4628(20001024)78:4<751::AID-APP80>3.0.CO;2-0 *
WANG, JIANJUN ET AL.: "The Synthesis and Photoacoustics of Rare Earth Complexes of Benohydroxamix Acid", JOURNAL OF NANJING UNIVERSITY ( NATURAL SCIENCES EDITION, vol. 24, no. 4, 31 October 1988 (1988-10-31), pages 737 - 742 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111715408A (zh) * 2020-06-30 2020-09-29 中南大学 一种用于浮选白钨矿中萤石的浮选药剂及其浮选方法
CN111715408B (zh) * 2020-06-30 2021-07-02 中南大学 一种用于浮选白钨矿中萤石的浮选药剂及其浮选方法
CN113941453A (zh) * 2021-09-30 2022-01-18 郑州大学 钛铁矿物的浮选方法及系统
CN113941453B (zh) * 2021-09-30 2024-01-30 郑州大学 钛铁矿物的浮选方法及系统
CN116532229A (zh) * 2023-04-13 2023-08-04 长沙矿冶研究院有限责任公司 一种铜钼混合精矿梯次分选的选矿方法

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