HYDROXIMIC ACID-METAL HYDROXIDE COORDINATION COMPLEX AND PREPARATION AND APPLICATION THEREOF

Abstract

A hydroximic acid-metal hydroxide coordination complex and preparation and application thereof are disclosed. The hydroximic acid-metal hydroxide coordination complex is formed by a coordination of hydroximic acid with divalent or higher valent metal ions under an alkaline condition. The hydroximic acid-metal hydroxide coordination complex has a strong selectivity and a strong collection ability for metal oxide minerals such as tungsten-containing minerals, ilmenite, rutile, cassiterite, and rare earth. The preparation method is simple and low in costs, and is beneficial to industrialized production.

Claims

1. A hydroximic acid-metal hydroxide coordination complex, formed by a coordination of hydroximic acid with divalent or higher valent metal ions under an alkaline condition, wherein the hydroximic acid has a structure of formula 1, wherein the formula 1 is expressed as: ##STR00003## wherein R is a hydrophobic organic group.

2. The hydroximic acid-metal hydroxide coordination complex according to claim 1, wherein R is an aliphatic hydrocarbon radical or an aryl.

3. The hydroximic acid-metal hydroxide coordination complex according to claim 2, wherein R is a C.sub.4-C.sub.12 alkyl, a C.sub.4-C.sub.12 unsaturated aliphatic hydrocarbon radical, phenyl, or substituted phenyl.

4. The hydroximic acid-metal hydroxide coordination complex according to claim 3, wherein R is the phenyl.

5. The hydroximic acid-metal hydroxide coordination complex according to claim 1, wherein the divalent or higher valent metal ions comprise at least one of Pb.sup.2+, Ca.sup.2+, Mn.sup.2+, Cu.sup.2+, Fe.sup.3+, and Al.sup.3+.

6. The hydroximic acid-metal hydroxide coordination complex according to claim 5, wherein the divalent metal ions are Pb.sup.2+.

7. The hydroximic acid-metal hydroxide coordination complex according to claim 1, wherein a coordination mole ratio of the divalent or higher valent metal ions to the hydroximic acid is (1-4):(1-5).

8. The hydroximic acid-metal hydroxide coordination complex according to claim 7, wherein the coordination mole ratio of the divalent or higher valent metal ions to the hydroximic acid is (1-2):(1-3).

9. The hydroximic acid-metal hydroxide coordination complex according to claim 1, wherein a pH value of the alkaline condition is 8-11.

10. The hydroximic acid-metal hydroxide coordination complex according to claim 9, wherein the pH value of the alkaline condition is 8.5-9.5.

11. A preparation method of a hydroximic acid-metal hydroxide coordination complex, comprising: performing a coordination reaction between hydroximic acid and divalent or higher valent metal ions in an alkaline solution system to obtain the hydroximic acid-metal hydroxide coordination complex; wherein the hydroximic acid has a structure of formula 1, and the formula 1 is expressed as: ##STR00004## wherein R is a hydrophobic organic group.

12. The preparation method according to claim 11, wherein R is an aliphatic hydrocarbon radical or an aryl.

13. The preparation method according to claim 12, wherein R is a C.sub.4-C.sub.12 alkyl, a C.sub.4-C.sub.12 unsaturated aliphatic hydrocarbon radical, phenyl, or substituted phenyl.

14. The preparation method according to claim 13, wherein R is the phenyl.

15. The preparation method according to claim 11, wherein the divalent or higher valent metal ions comprise at least one of Pb.sup.2+, Ca.sup.2+, Mn.sup.2+, Cu.sup.2+, Fe.sup.2+, and Al.sup.3+.

16. The preparation method according to claim 15, wherein the divalent metal ions are Pb.sup.2+.

17. The preparation method according to claim 11, wherein a coordination mole ratio of the divalent or higher valent metal ions to the hydroximic acid is (1-4):(1-5).

18. The preparation method according to claim 17, wherein the coordination mole ratio of the divalent or higher valent metal ions to the hydroximic acid is (1-2):(1-3).

19. The preparation method according to claim 11, wherein a pH value of the alkaline solution system is 8-11.

20. The preparation method according to claim 19, wherein the pH value of the alkaline solution system is 8.5-9.5.

21. The preparation method according to claim 11, wherein a temperature of the coordination reaction is 20-80° C., and a reaction time is 0.5-6 hours.

22. The preparation method according to claim 21, wherein the temperature of the coordination reaction is 55-65° C., and the reaction time is 1-2 hours.

23. The preparation method according to claim 11, wherein after the coordination reaction is completed, the hydroximic acid-metal hydroxide coordination complex is separated and purified by a carrier adsorption-foam floatation method.

24. The preparation method according to claim 23, wherein the carrier adsorption-foam floatation method comprises the steps of; adsorbing the hydroximic acid-metal hydroxide coordination complex in a solution system by carrier particles; after the step of adsorbing is completed, recovering the carrier particles loading the hydroximic acid-metal hydroxide coordination complex through a foam floatation; and obtaining a hydroximic acid-metal coordination complex solution by an ultrasonic washing of the carrier particles loading the hydroximic acid-metal hydroxide coordination complex.

25. The preparation method according to claim 24, wherein the carrier particles are quartz particles with a particle size of 10-37 μm.

26. The preparation method according to claim 24, wherein absolute ethyl alcohol is used as a washing agent for the ultrasonic washing.

27. A method of using the hydroximic acid-metal hydroxide coordination complex according to claim 1, comprising: applying the hydroximic acid-metal hydroxide coordination complex as a floatation collector to a floatation separation process of metal oxide minerals containing at least one of tungsten, tin, titanium, and rare earth from gangue minerals.

28. The method according to claim 27, wherein tungsten-containing metal oxide minerals comprise at least one of scheelite, wolframite, and tungstite; tin-containing metal oxide minerals comprise cassiterite; and titanium-containing metal oxide minerals comprise ilmenite and/or rutile.

29. The method according to claim 27, wherein the gangue minerals comprise at least one of calcite, fluorite, phosphorite, quartz, and aluminosilicate minerals.

30. The method according to claim 27, wherein a pulp system in the floatation separation process is an alkaline environment.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0053] FIG. 1 is a schematic diagram of an adsorption model of floatation collection of scheelite by a benzohydroximic acid-lead hydroxide coordination complex.

[0054] FIG. 2 is an infrared spectrogram of a benzohydroximic acid-lead hydroxide coordination complex prepared according to Embodiments 2-5 and benzohydroximic acid.

[0055] FIG. 3 is an XRD spectrogram of a benzohydroximic acid-lead hydroxide coordination complex prepared according to Embodiments 3-5.

[0056] FIG. 4 is a thermogravimetric analysis (TGA) spectrogram of a benzohydroximic acid-lead hydroxide coordination complex prepared according to Embodiments 5-6.

[0057] FIG. 5 is a flow diagram of a desulfurization tailing tungsten separation process of using a benzohydroximic acid-lead hydroxide coordination complex according to Embodiment 13 as a collector.

[0058] FIG. 6 is influence of a pH value of ore pulp on floatability of scheelite when a benzohydroximic acid-lead hydroxide coordination complex prepared according to Embodiment 1 is used as a collector.

[0059] FIG. 7 is influence of a pH value of ore pulp on floatability of scheelite when a benzohydroximic acid-lead hydroxide coordination complex prepared according to Embodiments 2-5 is used as a collector.

[0060] FIG. 8 is influence of a pH value of ore pulp on floatability of scheelite when a benzohydroximic acid-metal hydroxide coordination complex prepared according to Embodiment 8 is used as a collector.

[0061] FIG. 9 is influence of a pH value of ore pulp on floatability of scheelite when a salicyl hydroximic acid-lead hydroxide coordination complex is used as a collector.

[0062] FIG. 10 is influence of a pH value of ore pulp on floatability of scheelite when an octyl hydroximic acid-lead hydroxide coordination complex is used as a collector.

[0063] FIG. 11 is influence of a pH value of ore pulp on floatability of scheelite when an acetohydroximic acid-lead hydroxide coordination complex is used as a collector.

[0064] FIG. 12 is influence of a pH value of ore pulp on floatability of fluorite ore when a benzohydroximic acid-lead hydroxide coordination complex prepared according to Embodiments 2-5 is used as a collector.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0065] Embodiments below further illustrate contents of the present invention, and are not intended to limit the scope of the present invention claimed to be protected in claims.

[0066] In the embodiments below, used agents and ore raw materials, unless otherwise specified, are all common raw materials directly obtained on the market in the art.

Embodiment 1

[0067] 100 mL of 0.1 mol/L benzohydroximic acid (BHA) ethyl alcohol solution and 8 mL of 0.5 mol/L lead nitrate solution were respectively prepared. Sodium hydroxide was added into the benzohydroximic acid solution to regulate a pH value to 9. The solution was heated to 60° C. The lead nitrate solution was slowly added into the benzohydroximic acid solution. A reaction time was 1.5 h. An obtained benzohydroximic acid-lead coordination complex solution was transferred into a floatation cell with a volume of 100 mL. 30 g of quartz powder with a particle size of 10-37 μm was added. Pulp conditioning and stirring were performed for 15 min. Then, inflation floatation was performed. Floatation foam was collected, and filtration was performed. Quartz products in the floatation foam were transferred into the ethyl alcohol solution. Oscillation washing was performed by an ultrasonic washing device so that the benzohydroximic acid-lead hydroxide coordination complex adsorbed on the quartz surface was desorbed. A benzohydroximic acid-lead hydroxide coordination complex-ethyl alcohol mixed solution was obtained, and might be used as a floatation collector. According to this embodiment, the benzohydroximic acid-lead hydroxide coordination complex was prepared under a condition of C.sub.Pb/C.sub.BHA=1:2.5.

Embodiment 2

[0068] Experiment conditions were identical to those in Embodiment 1. Only proportions of lead nitrate and hydroximic acid were different: 80 mL of 0.5 mol/L lead nitrate solution and 100 mL of 0.1 mol/L benzohydroximic acid ethyl alcohol solution.

[0069] According to this embodiment, the benzohydroximic acid-lead hydroxide coordination complex was prepared under a condition of C.sub.Pb/C.sub.BHA=4:1.

Embodiment 3

[0070] Experiment conditions were identical to those in Embodiment 1. Only proportions of lead nitrate and hydroximic acid were different: 40 mL of 0.5 mol/L lead nitrate solution and 100 mL of 0.1 mol/L benzohydroximic acid ethyl alcohol solution.

[0071] According to this embodiment, the benzohydroximic acid-lead hydroxide coordination complex was prepared under a condition of C.sub.Pb/C.sub.BHA=2:1.

Embodiment 4

[0072] Experiment conditions were identical to those in Embodiment 1. Only proportions of lead nitrate and hydroximic acid were different: 20 mL of 0.5 mol/L lead nitrate solution and 100 mL of 0.1 mol/L benzohydroximic acid ethyl alcohol solution.

[0073] According to this embodiment, the benzohydroximic acid-lead hydroxide coordination complex was prepared under a condition of C.sub.Pb/C.sub.BHA=1:1.

Embodiment 5

[0074] Experiment conditions were identical to those in Embodiment 1. Only proportions of lead nitrate and hydroximic acid were different: 10 mL of 0.5 mol/L lead nitrate solution and 100 mL of 0.1 mol/L benzohydroximic acid ethyl alcohol solution.

[0075] According to this embodiment, the benzohydroximic acid-lead hydroxide coordination complex was prepared under a condition of C.sub.Pb/C.sub.BHA=1:2.

Embodiment 6

[0076] Experiment conditions were identical to those in Embodiment 1. Only proportions of lead nitrate and hydroximic acid were different: 5 mL of 0.5 mol/L lead nitrate solution and 100 mL of 0.1 mol/L benzohydroximic acid ethyl alcohol solution.

[0077] According to this embodiment, the benzohydroximic acid-lead hydroxide coordination complex was prepared under a condition of C.sub.Pb/C.sub.BHA=1:4.

Embodiment 7

[0078] Experiment conditions were identical to those in Embodiment 1. Only proportions of lead nitrate and hydroximic acid were different: 4 mL of 0.5 mol/L lead nitrate solution and 100 mL of 0.1 mol/L benzohydroximic acid ethyl alcohol solution.

[0079] According to this embodiment, the benzohydroximic acid-lead hydroxide coordination complex was prepared under a condition of C.sub.Pb/C.sub.BHA1=1:5.

Embodiment 8

[0080] Experiment conditions were identical to those in Embodiment 7. Only metal salt solution containing different metal ions was used: the lead nitrate solution was replaced by a solution containing Ca.sup.2+, Mn.sup.2+, Cu.sup.2+, Fe.sup.3+ or Al.sup.2+.

Embodiment 9

[0081] Experiment conditions were identical to those in Embodiment 6. Only the benzohydroximic acid was replaced by salicyl hydroximic acid.

Embodiment 10

[0082] Experiment conditions were identical to those in Embodiment 5. Only the benzohydroximic acid was replaced by octyl hydroximic acid.

Embodiment 11

[0083] Experiment conditions were identical to those in Embodiment 5. Only the benzohydroximic acid was replaced by acetohydroximic acid.

[0084] An infrared spectrogram of a benzohydroximic acid-lead hydroxide coordination complex (Pb-BHA) prepared according to Embodiments 2-5 and benzohydroximic acid (BHA) is shown in FIG. 2. Absorption peaks of the BHA were 3295 cm.sup.−1 and 3060.17 cm.sup.−1, and these might be telescopic vibration absorption peaks of O—H and N—H. A broadband about 2747.24 cm.sup.−1 was an intramolecular O—H—O extension band of the BHA. IR spectrum comparison of the Pb-BHA and the BHA showed that disappearance or decrease of the broadband (intramolecular O—H—O extension band) in a 2700 cm.sup.−1 position and broadband position movement were caused by loss of OH in CO—NHOH. Meanwhile, a feature peak of O—H in a 3295.33 position also disappeared, and some new peaks of 3200 cm.sup.−1 to 3600 cm.sup.1 were generated, it might be Fermi resonance of O—H induced by the Pb-BHA. C═O or C═N peaks in a 1665.50 cm.sup.−1 position were separated, movement was performed in the complex to a certain degree, and it showed that the ligand performed coordination through O or N. In a region of 550-630 cm.sup.−1, two (or more) strong absorption peaks of the Pb-BHA were v (Pb—O or Pb—N). A plurality of Pb—O or Pb—N bands existed. This was more obvious on a mixed ligand complex. Different Pb—O or Pb—N bond lengths were reflected. It could be predicted that most Pb-BHA coordination complexes would exist in a form of C═O and Pb—O to form stable five-membered rings, because the BHA mainly used a sealed (hydrogen bonded) Z structure in a water solution.

[0085] An XRD spectrogram of the Pb-BHA prepared according to Embodiments 3, 4, and 5 is shown in FIG. 3. FIG. 3 shows an XRD spectrogram of the Pb-BHA at different Pb/BHA rates. Feature peaks of the BHA and Pb(NO.sub.3).sub.2 were not observed. Additionally, some strong peaks occurred in positions of 5.4578°, 11.0964°, and 12.24320. It showed that new Pb-BHA types were generated. The peak intensities of the Pb-BHA complex are different from each other relative to the Pb/BHA rates. It was discovered that more than one stable complex was formed in a reaction between the BHA and Pb.sup.2+.

[0086] A thermogravimetric analysis (TGA) spectrogram of the Pb-BHA prepared according to Embodiments 5 and 6 is shown in FIG. 4. A molecular structure of the Pb-BHA coordination complex is PbBHA.sub.2.2Pb(OH).sub.2 or Pb.sub.3(OH).sub.4BHA.sub.2. FIG. 4 is thermogravimetric analysis of the Pb-BHA in a temperature rise process of 30° C. to 600° C. It showed that Pb-BHA precipitates went through three stages. In the first stage (30-300° C.), the weight of the Pb-BHA was reduced through evaporation of water (such as free water and crystal water) and decomposition of absorbed BHA molecules. In the second stage (300-450° C.), exothermic decomposition peaks were prominent, and Pb(BHA).sub.2.xPb(OH).sub.2 started to be decomposed into Pb(OH).sub.2. In the third stage (450-600° C.), the Pb(OH).sub.2 was decomposed into PbO. The reaction might be concluded as follows:

Pb(BHA).sub.2gxPb(OH).sub.2gmBHAgnH.sub.2O.sub.2+O.sub.2—Pb(BHA).sub.2gxPb(OH).sub.2+CO.sub.2+NO+H.sub.2O;  first stage:

Pb(BHA).sub.2gxPb(OH).sub.2+H.sub.2O+O.sub.2—Pb(OH).sub.2+CO.sub.2+NO.sub.2; and  second stage:

Pb(OH).sub.2—PbO+H.sub.2O.  third stage:

[0087] According to weight loss at each stage, a structure of the Pb-BHA might be predicated into 2Pb(OH).sub.2.Pb(BHA).sub.2.mBHA.nH.sub.2O. A most stable structure might be 2Pb(OH).sub.2.Pb(BHA).sub.2. BHA molecules might be adsorbed onto the structure through hydrogen bonds.

Embodiment 12

[0088] After Shizhuyuan wolframite and scheelite mixed ore in Hunan (containing a small amount of tungstite) was subjected to crushing, ore grinding, magnetic separation deferrization, and desulfurization, a pH regulator was added into desulfurization tailings to regulate the pH value of ore pulp to 9.6. Then, the benzohydroximic acid-lead hydroxide coordination complex prepared according to Embodiment 1 was added for stirring and pulp conditioning. A terpenic oil foaming agent was added for inflation floatation. A foam product was a tungsten concentrate. An addition amount of the benzohydroximic acid-lead hydroxide coordination complex relative to the raw ore was 400 g/t, and an addition amount of the foaming agent was 5 g/t. The pH regulator was sodium carbonate. The floatation temperature was 25° C. During concentration operation, water glass and aluminum sulfate were added to be used as inhibitors. A wolframite and scheelite mixed concentrate with the concentrate WO.sub.3 grade of 12.63% was obtained through one roughing and two concentrations. A recovery rate was 82.58% (as shown in Table 1).

TABLE-US-00001 TABLE 1 Whole-flow-process closed-circuit test result of new tungsten separation process of desulfurization tailings WO.sub.3 CaF.sub.2 CaCO.sub.3 WO.sub.3 CaF.sub.2 Sn CaCO.sub.3 Product Yield grade grade Sn grade grade recovery recovery recovery recovery name (%) (%) (%) (%) (%) rate (%) rate (%) rate (%) rate (%) Tungsten 2.56 12.63 12.66 1.08 14.58 82.58 1.53 31.05 4.67 concentrate Tailings 97.44 0.07 21.37 0.11 7.82 17.42 98.47 68.95 95.33 Feeding 100.0 0.39 21.15 0.14 7.99 100 100 100 100

Embodiment 13

[0089] After Chaishan single scheelite ore in Hunan was subjected to crushing, ore grinding, magnetic separation deferrization, and desulfurization, a pH regulator was added into desulfurization tailings to regulate the pH value of ore pulp to 9.6. Then, the benzohydroximic acid-metal hydroxide coordination complex prepared according to Embodiment 1 was added for stirring and pulp conditioning. A terpenic oil foaming agent was added for inflation floatation. A foam product was a tungsten concentrate. An addition amount of the collector relative to the raw ore was 300 g/t, and an addition amount of the foaming agent was 5 g/t. The pH regulator was sodium carbonate. The floatation temperature was 25° C. During concentration operation, water glass and aluminum sulfate were added to be used as inhibitors. A scheelite concentrate with the concentrate WO.sub.3 grade of 16.43% was obtained through one roughing and two concentrations. A recovery rate was 92.64% (the floatation process flow process was as shown in FIG. 5).

TABLE-US-00002 TABLE 2 Whole-flow-process closed-circuit test result of new tungsten separation process of desulfurization tailings Product name Yield % WO.sub.3 grade/% WO.sub.3 recovery rate/% Tungsten concentrate 1.51 16.43 92.64 Tailings 98.49 0.02 7.36 Feeding 100.00 0.27 100.00

Embodiment 14

[0090] Operation steps were identical to those in Embodiment 13. Floatation effects of the benzohydroximic acid-lead hydroxide coordination complex prepared according to Embodiment 7 on the scheelite under a condition of different pH values were investigated. The floatation effects are as shown in FIG. 6. It shows that under the alkaline condition, the floatation effect of benzohydroximic acid-metal hydroxide on the scheelite is better, and the effect is particularly prominent when the pH value is 8-10.

Embodiment 15

[0091] Operation steps were identical to those in Embodiment 13. Benzohydroximic acid-lead hydroxide coordination complexes in Embodiments 2-5 were respectively used. Floatation effects of these coordination complex collectors on the scheelite under a condition of different pH values were investigated. The floatation effects are as shown in FIG. 7. From the figure, it can be seen that the benzohydroximic acid-lead hydroxide coordination complexes with the pH value of 3-12 had floatation effects on the scheelite, and the floatation effects were better under the alkaline condition, such as a pH of 7-10.

[0092] Control experiment group: operation steps were identical to those in Embodiment 13. Benzohydroximic acid-lead hydroxide coordination complexes in Embodiments 2-5 were respectively used. Floatation effects of these coordination complex collectors on the fluorite ore under a condition of different pH values were investigated. The floatation effects are as shown in FIG. 13.

[0093] Through the control experiment group, it can be seen that the selectivity ability of the benzohydroximic acid-lead hydroxide coordination complexes on the scheelite under the alkaline condition is much higher than that of calcium-containing minerals such as fluorite. Efficient separation of the scheelite from the minerals such as fluorite can be realized.

Embodiment 16

[0094] Operation steps were identical to those in Embodiment 13. Various benzohydroximic acid-metal hydroxide coordination complexes in Embodiments 8 were respectively used. Floatation effects on the scheelite under a condition of different pH values were investigated. The floatation effects are as shown in FIG. 8. From FIG. 8, it can be seen that hydroximic acid-lead complexes formed by divalent lead ions showed better selectivity and strong collection ability on the floatation collection of the scheelite through being compared with hydroximic acid-metal hydroxide coordination complexes formed by other metal ions such as Ca.sup.2+, Mn.sup.2+, Cu.sup.2+, Fe.sup.3+, and Al.sup.3+.AsPb.sup.2+ is better than Ca.sup.2+, Ca.sup.2+ is better than Mn.sup.2+, Fe.sup.3+ and Al.sup.3+, and Mn.sup.2+, Fe.sup.3+ and Al.sup.3+ are better than Cu.sup.2+, the metal ions were most preferably Pb.sup.2+.

Embodiment 17

[0095] Operation steps were identical to those in Embodiment 13. Various hydroximic acid-lead hydroxide coordination complexes in Embodiments 9-11 were respectively used. Floatation effects on the scheelite under a condition of different pH values were investigated. The floatation effects are as shown in FIG. 9-11. From the figures, it can be seen that under the same conditions, the floatation effects on the scheelite when the hydroximic acid-lead hydroxide coordination complexes prepared from benzohydroximic acid, salicyl hydroximic acid, and octyl hydroximic acid were used as collectors were higher than those of acetohydroximic acid-lead hydroxide coordination complexes.

Embodiment 18

[0096] After Wenshan fine particle tin ore in Yunnan was subjected to crushing, ore grinding, magnetic separation deferrization, and desulfurization, a pH regulator was added into desulfurization tailings to regulate the pH value of ore pulp to 8.5. Then, the benzohydroximic acid-metal hydroxide coordination complex prepared according to Embodiment 1 was added for stirring and pulp conditioning. An octanol foaming agent was added for inflation floatation. A foam product was a tin concentrate. An addition amount of the collector relative to the raw ore was 400 g/t, and an addition amount of the foaming agent was 10 g/t. The pH regulator was sodium carbonate. The floatation temperature was 25° C. During concentration operation, 50 g/t of carboxymethylcellulose was added to be used as an inhibitor. A tin concentrate with the concentrate SnO.sub.2 grade of 40.15% was obtained through one roughing and three concentrations. A recovery rate was 83.89%.

TABLE-US-00003 TABLE 3 Whole-flow-process closed-circuit test result of new cassiterite floatation process of desulfurization tailings Product Yield/% SnO.sub.2/% SnO.sub.2 recovery rate/% Tin concentrate 0.90 40.15 83.89 Tailings 99.10 0.07 16.11 Feeding 100.00 0.43 100.00

Embodiment 19

[0097] Panzhihua fine particle ilmenite in Sichuan was treated by this process method. A pH regulator was added into desulfurization tailings to regulate a pH value of ore pulp to 5.6. Then, the benzohydroximic acid-metal hydroxide coordination complex prepared according to Embodiment 1 was added for stirring and pulp conditioning. An octanol foaming agent was added for inflation floatation. A foam product was an ilmenite concentrate. An addition amount of the collector relative to the raw ore was 600 g/t, and an addition amount of the foaming agent was 10 g/t. The pH regulator was sulfuric acid. The floatation temperature was 25° C. During concentration operation, 100 g/t of acidified water glass was added to be used as an inhibitor. An ilmenite concentrate with the grade of 49.80% was obtained through one roughing and three concentrations. A recovery rate was 67.93%.

TABLE-US-00004 TABLE 4 Whole-flow-process closed-circuit test result of new ilmenite floatation process of desulfurization tailings Product Yieid/% TiO.sub.2 grade/% TiO.sub.2 recovery rate/% Ilmenite concentrate 28.15 49.80 67.93 Tailings 71.85 9.21 32.07 Feeding 100.00 20.64 100.00

Embodiment 20

[0098] Baotou heavy rare earth ore was treated by this process method. A pH value of raw ore was regulated by a pH regulator to 8.0. Then, the benzohydroximic acid-metal hydroxide coordination complex prepared according to Embodiment 1 was added for stirring and pulp conditioning. An octanol foaming agent was added for inflation floatation. A foam product was a heavy rare earth concentrate. An addition amount of a metal ion coordination complex collector relative to the raw ore was 300 g/t, and an addition amount of the foaming agent was 10 g/t. The pH regulator was sodium carbonate. The floatation temperature was 25° C. During concentration operation, 150 g/t of acidified water glass was added to be used as an inhibitor. A heavy rare earth concentrate with the coarse concentrate grade of 52.24% was obtained through one roughing and four concentrations. A recovery rate was 53.68%.

TABLE-US-00005 TABLE 5 Whole-flow-process closed-circuit test result of new heavy rare earth floatation process Product Yield/% Grade(REO)/% Yield/% Heavy rare earth 6.57 52.24 53.68 concentrate Tailings 93.43 3.17 46.32 Feeding 100.00 6.39 100.00

Embodiment 21

[0099] Hubei low-grade rutile ore was treated by this process method. Raw ore was subjected to crushing and ore grinding. Then, a pH regulator was added for regulating a pH value of ore pulp to 5.0. Then, the benzohydroximic acid-metal hydroxide coordination complex prepared according to Embodiment 1 was added for stirring and pulp conditioning. An octanol foaming agent was added for inflation floatation. A foam product was a rutile concentrate. An addition amount of a collector relative to the raw ore was 400 g/t, and an addition amount of the foaming agent was 10 g/t. The pH regulator was sulfuric acid. The floatation temperature was 25° C. During concentration operation, 100 g/t of acidified water glass was added to be used as an inhibitor. A rutile concentrate with the grade of 63.70% was obtained through one roughing and three concentrations. A recovery rate was 81.09%.

TABLE-US-00006 TABLE 6 Whole-flow-process closed-circuit test result of new rutile floatation process Product Yield/% TiO.sub.2 grade/% TiO.sub.2 recovery rate/% Rutile concentrate 2.94 63.70 81.09 Tailings 97.06 0.45 18.91 Feeding 100.00 2.31 100.00