CN103613614A - Alpha-hydroxy unsaturated alkylphosphonic acid compound as well as preparation method and application of alpha-hydroxy unsaturated alkylphosphonic acid compound - Google Patents
Alpha-hydroxy unsaturated alkylphosphonic acid compound as well as preparation method and application of alpha-hydroxy unsaturated alkylphosphonic acid compound Download PDFInfo
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Abstract
The invention discloses an alpha-hydroxy unsaturated alkylphosphonic acid compound as well as a preparation method and application of the alpha-hydroxy unsaturated alkylphosphonic acid compound. The alpha-hydroxy unsaturated alkylphosphonic acid compound has the structural formula I as shown in the specification. The preparation method comprises the steps: subjecting 2-ethyl-2-hexenal and hypophosphorous acid or hypophosphite to addition reaction in the existence of an acid catalyst to generate 1-hydroxyl-2-ethyl-2-hexenyl-1-phosphorous acid; subjecting 1-hydroxyl-2-ethyl-2-hexenyl-1-phosphorous acid and an oxidizing agent to reaction to generate 1-hydroxyl-2-ethyl-2-hexenyl-1-phosphonic acid. 30-600g/t of 1-hydroxyl-2-ethyl-2-hexenyl-1-phosphonic acid is used as a flotation collector for bauxite, ilmenite, rutile, scheelite, wolframite, rare earth ores, tin ores, fluorite ores or lithium ores, and the pH value of a flotation solution is controlled at 4-12, so that a target ore and a gangue mineral can be effectively separated.
Description
Technical field
The invention belongs to technique of preparing field, relate to a kind of new compound as mineral floating collecting agent and preparation method thereof, and this compound in bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or the flotation of lithium ore deposit as the application of collecting agent.
Background technology
The collecting agent of long carbochain, owing to having hydroxyl and the phosphonic acid functional groups of polarity, is a kind of good oxide mineral collector.Alkyl phosphonic acid is very weak for silicate minerals collecting ability, in flotation, adds suitable inhibitor, as starch, dextrin, Sodium salts humic acids or water glass etc., and just can be successfully that valuable mineral is separated with gangue mineral.In industrial floatation process, the most frequently used oxide mineral collector is oleic acid and modified product thereof at present.Patent CN101648157A and CN101757983A disclose a kind of use and comprise that oleic acid is black in interior mixed fatty acid flotation, the method for sheelite; Patent CN102302982A discloses a kind of beneficiation method that reclaims sheelite from leaf gneiss type ore; Oleic-acid collecting agent is subject to the welcome of mineral floating producer because of its low price, wide material sources, but in flotation, also has obvious shortcoming, and selectivity is not high, freezing tolerance is poor, the dispersed shortcoming such as bad; Phosphonic acid based collecting agent also has a large amount of patents to announce as a kind of Novel Titanium iron ore, rutile ore selective copper collector: collecting agent patent CN1047462A discloses a kind of 1-hydroxyl-1, the method for 1-bis phosphoric acid flotation zircon; CN106327A discloses a kind of α-nitroso-group phosphonic acid ester as the method for pyrite collecting agent; Patent CN102500462A discloses the method for phosphoric acid class and the composite flotation rutile of hydroximic acid; Patent CN101879479A has announced styryl phosphonic acid, oxidized paraffin wax soap, lipid acid, tal fibre wet goods medicament for the method for floating of eclogite rutile ore; Also the report to sulphide ores, oxidized ore and complicated ore flotation: patent US5411148 has announced the method for floating of diisobutyl dithiophosphinic acids sodium to sulphide ores and association rare precious metal about phosphoric acid class collecting agent to have a large amount of patents and document abroad; Patent US4561970 has announced the mineral floating method of diisobutyl dithiophosphinic acids sodium for complex system.In above-mentioned phosphonic acid based collecting agent production process, there is problems such as polluting large, technical process complexity, preparation difficulty.
The invention provides a kind of novel flotation collector, relate to the preparation of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds and the application in bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or the flotation of lithium ore deposit thereof.The collecting agent of present patent application due to have carbon-carbon double bond and and branched structure, fusing point is less than-15 ℃, compares with collecting agents such as traditional lipid acid, oxidized paraffin wax soaps, its use range is more wide, operating environment is looser; The collecting agent that present method is produced has hydroxyl and phosphonate group bipolarity group, mineral surface metalloform-selective is adsorbed, make bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit sorting mineral effective, the rate of recovery and concentrate quality are high, sorting pH value wide ranges, do not need the advantages such as flotation of heating.This catenanes hydroxy unsaturated acid has suitable hydrophobicity carbochain (C
8) and double-hydrophilic configuration, in its molecule, there are a hydroxyl and a phosphonate group, be a kind of brand-new compound, having no it has bibliographical information.
Summary of the invention
The object of this invention is to provide a kind of new Alpha-hydroxy unsaturated alkyl phosphinic acid compounds and preparation method thereof, and provide this compound to be applied to the floatation process in bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit, in order to strengthen the method to the collecting ability of valuable mineral in ore, thereby it is separated with the efficient flotation separation of its gangue mineral to realize object mineral.
The object of the invention is to realize by following manner:
An Alpha-hydroxy unsaturated alkyl phosphinic acid compounds, structure is suc as formula shown in I:
The preparation method of described Alpha-hydroxy unsaturated alkyl phosphinic acid compounds, comprises the following steps:
Under the condition existing at acid catalyst, Hypophosporous Acid, 50 or hypophosphite and 2-ethyl-2-hexenoic aldehyde generation addition reaction, extracting and separating, distillation, can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, 2-ethyl-2-hexenoic aldehyde structure is suc as formula shown in II, and 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid structure is as shown in formula III;
(2) 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid and oxygenant generation oxidizing reaction, separatory, can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids;
The acid catalyst of addition reaction comprises one or both in hydrochloric acid, sulfuric acid, and its consumption is no more than 30% of 2-ethyl-2-hexenoic aldehyde quality.
The solvent of addition reaction and oxidizing reaction comprises one or more in methyl alcohol, ethanol, water, Isosorbide-5-Nitrae-dioxane, acetonitrile, acetone, tetrahydrofuran (THF); The temperature of reaction of addition reaction is 60～100 ℃, reaction times 1～6h; The temperature of oxidizing reaction is 0～50 ℃, reaction times 0.5～8h.
Hypophosporous Acid, 50 or hypophosphite used in addition reaction comprise: one or more in Hypophosporous Acid, 50, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, the mol ratio of Hypophosporous Acid, 50 or hypophosphite and 2-ethyl-2-hexenoic aldehyde is 1～3:1.
The solvent using in extraction process comprises one or more in ethyl acetate, ether, toluene, propyl carbinol, tetrahydrofuran (THF) or chloroform; Its consumption is 20%～60% of addition reaction product volume, and extraction temperature is 10～40 ℃, and extraction progression is 1～3.
The oxygenant of oxidizing reaction comprises one or several in clorox, dimethyl sulfoxide (DMSO), hydrogen peroxide, air, oxygen, and the mol ratio of oxygenant and 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid is 1～3:1.Take dimethyl sulfoxide (DMSO) during as oxygenant, and adding the iodine that is no more than dimethyl sulfoxide (DMSO) quality 20% is catalyzer; After oxidizing reaction completes, add KI solution washing and remove iodine, the mass concentration of the KI aqueous solution is that 5%～20%, KI consumption is 50%～70% of iodine quality.
In aforesaid method, after oxidizing reaction, also carry out cancellation reaction if desired in order to stop strong oxidizing reaction, the reagent using comprises one or several in sodium bisulfite, Sulfothiorine or Hypophosporous Acid, 50, and its consumption is no more than oxygenant consumption.
The application method of described Alpha-hydroxy unsaturated alkyl phosphinic acid compounds, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is directly added or adds sodium hydroxide solution to be made into salt, as bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit flotation collector.Collector dosage is 30～600g/t, and flotation pH is 4～12.
Further detailedization is as follows for above-mentioned preparation method:
(1) preparation of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid: add concentrated hydrochloric acid, solvent, Hypophosporous Acid, 50 or hypophosphite, 2-ethyl-2-hexenoic aldehyde, stirring reaction, after reaction finishes, be extracted with ethyl acetate, extraction progression is 3, and separatory, gets supernatant liquid, underpressure distillation, obtains 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid.
(2) preparation of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids: add oxygenant in 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, stir, after having reacted, add saturated NaHSO
3solution, till making starch-kalium iodide test paper test constant basket, standing separatory, gets supernatant liquid, can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids.
The present invention has the following advantages as the Alpha-hydroxy unsaturated alkyl phosphinic acid compounds tool of bauxite, ilmenite, rutile ore, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit flotation collector:
(1) in this Alpha-hydroxy unsaturated alkyl phosphonic acids molecule, contain a straight chain, and on straight chain, there is an ethyl and carbon-carbon double bond structure, be conducive to the hydrophobization of mineral surface, and make it be easy to stick to bubble, mineral are had to stronger collecting ability.
(2) in this Alpha-hydroxy unsaturated alkyl phosphonic acids molecule, contain a hydroxyl and a phosphonate group, there is double-hydrophilic group, be conducive to collecting agent and mineral generation adsorption, valuable mineral is had to stronger collecting ability.(3) this Alpha-hydroxy unsaturated alkyl phosphinic acid compounds has branched-chain alkene structure, and fusing point is less than 15 ℃, is conducive to dissolving and the dispersion of medicament in ore pulp, does not need the flotation of heating.
Accompanying drawing explanation:
Fig. 1 is the infrared spectrogram of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids;
Fig. 2 is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
31p nmr spectrum;
Fig. 3 is the process flow sheet of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids flotation fluorite;
Fig. 4 is the process flow sheet of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids flotation ilmenite;
Fig. 5 is the process flow sheet of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids Flotation of Cassiterite.
Embodiment
The present invention is further illustrated by the following example, but is not subject to the restriction of these embodiment.In embodiment, all umbers and percentage ratio all refer to quality except as otherwise herein provided.
The preparation of embodiment 1 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid
By 4.4 parts of 2-ethyl-2-hexenoic aldehydes, 40 parts of Isosorbide-5-Nitrae-dioxane, 7 parts of Hypophosporous Acid, 50,2 part of 20% dilute sulphuric acid fully mixes, 80 ℃ of stirring reaction 5h, with 1.4 parts of ethyl acetate extraction 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, extraction temperature is 30 ℃, extracts 3 times, separatory, get supernatant liquid underpressure distillation and remove ethyl acetate, distillation temperature is 50 ℃, and vacuum tightness is 0.098MPa, residuum is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, productive rate 75.2%.
The preparation of embodiment 2 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid
By 4.4 parts of 2-ethyl-2-hexenoic aldehydes, 40 parts of Isosorbide-5-Nitrae-dioxane, 7 parts of Hypophosporous Acid, 50,1 part of 37% concentrated hydrochloric acid fully mixes, 80 ℃ of stirring reaction 5h, with 1.4 parts of ethyl acetate extraction 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, extraction temperature is 30 ℃, extracts 3 times, separatory, get supernatant liquid underpressure distillation and remove ethyl acetate, distillation temperature is 50 ℃, and vacuum tightness is 0.098MPa, residuum is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, productive rate 83.5%.
The preparation of embodiment 3 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid
By 4.4 parts of 2-ethyl-2-hexenoic aldehydes, 40 parts of ethanol, 7 parts of Hypophosporous Acid, 50,1 part of hydrochloric acid fully mixes, and 80 ℃ of stirring reaction 5h, with 1.4 parts of ethyl acetate extraction 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, extraction temperature is 30 ℃, extract 3 times, separatory, gets supernatant liquid underpressure distillation and removes ethyl acetate, distillation temperature is 55 ℃, vacuum tightness is 0.098MPa, and residuum is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, productive rate 70.6%.
The preparation of embodiment 4 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
Under 10 part of 10% clorox stirred, be added drop-wise to 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid that 4.4 parts of embodiment 1 make, stirring reaction 6h under room temperature, adds saturated NaHSO
3solution, till the constant basket of starch-kalium iodide test paper, standing separatory, gets upper organic phase and is dried, and obtains 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, productive rate 89%.
The preparation of embodiment 5 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
Under 10 part of 30% hydrogen peroxide stirred, be added drop-wise to 4.4 parts of embodiment 1 and make 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, stirring reaction 6h under room temperature, adds saturated NaHSO
3solution, till the constant basket of starch-kalium iodide test paper, standing separatory, gets upper organic phase and is dried, and obtains 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, productive rate 92%.
The preparation of embodiment 6 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid that 4.4 parts of embodiment 1 are made, under agitation add 3.6 parts of dimethyl sulfoxide (DMSO) in batches, 0.5 part of iodine, 65 ℃ of stirring reaction 5h, by filtrate with 3 parts of 10%KI solution washings, standing separatory, get upper organic phase underpressure distillation and can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, productive rate 94%, its infrared spectrum is shown in Fig. 1,1445cm
-1, 1148cm
-1for P=O stretching vibration peak, 3468cm
-1for the stretching vibration peak of-OH, 2940cm
-1for CH
3or CH
2stretching vibration peak, 1637cm
-1for C=C stretching vibration peak;
31p nucleus magnetic resonance figure is shown in Fig. 2,1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
31pNMR (CD
3cOCD
3/ H
3pO
4) chemical displacement value is 32.8.
Embodiment 7, the application of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids on fluorite is roughly selected
Certain quartz-fluorite ore raw ore CaF
2grade 38.83%, grinding fineness-200 order accounts for 60%, is placed in flotation cell, at sodium carbonate amount 1400g/t, water glass consumption 400g/t, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids consumption 450g/t, under the condition that room temperature is 10 ℃, carry out flotation, flotation process figure is shown in Fig. 3.The flotation contrast and experiment of the 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids collecting agent in the present invention and conventional oleic collector is in Table 1.From table, at 10 ℃, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is higher 16.09 percentage points than traditional oleic acid for the flotation recovery rate of fluorite.
At 10 ℃, table 1, collecting agent is roughly selected fluorite contrast and experiment
| Collector dosage (g/t raw ore) | CaF 2Grade (%) | CaF 2The rate of recovery (%) |
| Oleic acid 450 | 85.93 | 70.41 |
| 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids 450 | 82.48 | 83.28 |
Ilmenite sample is taken from the floating titanium raw ore (coarse grain production line floats sulphur mine tailing) of Xuan Tai factory of Pan Gangtai industry company coarse fraction flotation production line, head grade TiO
222.48%, granularity accounts for 65% for-74 μ m, by per ton, to ore deposit, add 1800g sulfuric acid, 800g1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 200g2 oil to carry out ilmenite and roughly select flotation, scan by per ton and add 200g1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 50g2 oil to ore deposit, primary cleaning adds 350g sulfuric acid by per ton to ore deposit, recleaning adds 250g sulfuric acid by per ton to ore deposit, triple cleaning adds 200g sulfuric acid by per ton to ore deposit, four times selected adds 100g sulfuric acid by per ton to ore deposit, and flotation process figure is shown in accompanying drawing 4.After one roughing, once purging selection, four selected operations, obtain TiO
2grade 47.03%, the ilmenite concentrate of the rate of recovery 82.78%.The flotation contrast and experiment of the 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids collecting agent in the present invention and conventional vinylbenzene phosphoric acid is in Table 2.From table 2,1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is higher 7.69 percentage points than traditional vinylbenzene phosphoric acid for the flotation recovery rate of ilmenite.
Table 2 collecting agent flotation ilmenite contrast and experiment
| Collecting agent | Ilmenite concentrate TiO 2Grade (%) | The rate of recovery (%) |
| Vinylbenzene phosphoric acid | 47.12 | 75.09 |
| 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids | 47.03 | 82.78 |
Embodiment 9 application of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids in tin ore flotation
Certain technics of cassiterite clay raw ore tin grade 1.38%, granularity accounts for 95% for-19 μ m, by per ton, to ore deposit, add 1000g sodium carbonate, 700g Xylo-Mucine, 1000g1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 24g2 oil to roughly select, scan by per ton and add 500g1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 12g2 oil to ore deposit, primary cleaning adds 200g Xylo-Mucine by per ton to ore deposit, recleaning adds 150g Xylo-Mucine by per ton to ore deposit, and flotation process figure is shown in accompanying drawing 5.After one roughing, once purging selection, twice selected operation, obtain tin grade 21.46%, the tin rough concentrate of the rate of recovery 91.22%.The flotation contrast and experiment of the 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids collecting agent in the present invention and conventional Using Salicyl Hydroximic Acid is in Table 3.From table, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is higher 3.64 percentage points than traditional Using Salicyl Hydroximic Acid for the flotation recovery rate of tin ore.
Table 3 collecting agent flotation tin ore contrast and experiment
| Collecting agent | Tin concentrate grade (%) | The tin rate of recovery (%) |
| Using Salicyl Hydroximic Acid | 20.91 | 87.58 |
| 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids | 21.46 | 91.22 |
Claims (9)
1. an Alpha-hydroxy unsaturated alkyl phosphinic acid compounds, is characterized in that, structure is suc as formula shown in I:
2. the preparation method of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds claimed in claim 1, is characterized in that, comprises the following steps:
(1) under the condition existing at acid catalyst, Hypophosporous Acid, 50 or hypophosphite and 2-ethyl-2-hexenoic aldehyde generation addition reaction, extracting and separating, distillation, can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, 2-ethyl-2-hexenoic aldehyde structure is suc as formula shown in II, and 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid structure is as shown in formula III;
(2) 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid and oxygenant generation oxidizing reaction, separatory, can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids;
3. the preparation method of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds according to claim 2, is characterized in that: the acid catalyst of addition reaction comprises one or both of hydrochloric acid, sulfuric acid, and its consumption is no more than 30% of 2-ethyl-2-hexenoic aldehyde quality.
4. the preparation method of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds according to claim 2, it is characterized in that, the solvent of addition reaction and oxidizing reaction comprises one or more in methyl alcohol, ethanol, water, Isosorbide-5-Nitrae-dioxane, acetonitrile, acetone, tetrahydrofuran (THF); The temperature of reaction of addition reaction is 60～100 ℃, reaction times 1～6h; The temperature of oxidizing reaction is 0～50 ℃, and the reaction times is 0.5～8h.
5. the preparation method of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds according to claim 2, it is characterized in that, Hypophosporous Acid, 50 or hypophosphite used in addition reaction comprise: one or more in Hypophosporous Acid, 50, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, the mol ratio of Hypophosporous Acid, 50 or hypophosphite and 2-ethyl-2-hexenoic aldehyde is 1～3:1.
6. the preparation method of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds according to claim 2, is characterized in that, the solvent using in extraction process comprises one or more in ethyl acetate, ether, toluene, propyl carbinol, tetrahydrofuran (THF) or chloroform; Its consumption is 20%～60% of addition reaction product volume, and extraction temperature is 10～40 ℃, and extraction progression is 1～3.
7. the preparation method of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds according to claim 2, it is characterized in that, the oxygenant of oxidizing reaction comprises one or several in clorox, dimethyl sulfoxide (DMSO), hydrogen peroxide, air, oxygen, and the mol ratio of oxygenant and 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid is 1～3:1.
8. the application method of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds claimed in claim 1, it is characterized in that, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is directly added or adds sodium hydroxide solution to be made into salt, as bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit flotation collector.
9. application method according to claim 8, is characterized in that, collector dosage is 30～600g/t, and flotation pH is 4～12.
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