CN111036412A - Application of high-efficiency inhibitor HPMA in positive flotation and magnesium removal of phosphate ore - Google Patents
Application of high-efficiency inhibitor HPMA in positive flotation and magnesium removal of phosphate ore Download PDFInfo
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- CN111036412A CN111036412A CN201911182805.1A CN201911182805A CN111036412A CN 111036412 A CN111036412 A CN 111036412A CN 201911182805 A CN201911182805 A CN 201911182805A CN 111036412 A CN111036412 A CN 111036412A
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- flotation
- hpma
- phosphate
- magnesium
- inhibitor
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- 238000005188 flotation Methods 0.000 title claims abstract description 156
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 90
- 239000010452 phosphate Substances 0.000 title claims abstract description 90
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 90
- 239000003112 inhibitor Substances 0.000 title claims abstract description 77
- 239000011777 magnesium Substances 0.000 title claims abstract description 56
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 56
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 44
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 title claims 20
- 239000002367 phosphate rock Substances 0.000 claims abstract description 57
- 239000010459 dolomite Substances 0.000 claims abstract description 47
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 47
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims abstract description 41
- 239000012141 concentrate Substances 0.000 claims abstract description 36
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004137 magnesium phosphate Substances 0.000 claims abstract description 33
- 229960002261 magnesium phosphate Drugs 0.000 claims abstract description 33
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims abstract description 33
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 27
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005642 Oleic acid Substances 0.000 claims abstract description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- 239000006260 foam Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000007790 scraping Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims 2
- 230000003389 potentiating effect Effects 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910001748 carbonate mineral Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229940124639 Selective inhibitor Drugs 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
-
- 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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
-
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
- B03D2203/06—Phosphate ores
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- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
An application of HPMA (high efficiency inhibitor) in positive flotation and magnesium removal of phosphate ore belongs to the field of the ore dressing and purification process of phosphate ore. The application is a technological process for removing gangue mineral dolomite by using the high-efficiency inhibitor HPMA in the phosphorite direct flotation. Dissolving the high-efficiency inhibitor HPMA in water to prepare an inhibitor HPMA solution with the mass concentration of 2-4 g/L for use in preparation of the phosphorite flotation ore pulp. Under a sodium oleate or oleic acid flotation system, according to the addition of a high-efficiency inhibitor HPMA (hydrolyzed polymaleic anhydride), the floatability difference of phosphorite (apatite) and gangue mineral (dolomite) in phosphorite is increased, the magnesium-containing mineral (dolomite) in the phosphorite is removed, magnesium impurities are reduced, the quality of low-magnesium phosphate concentrate products is improved, and particularly, a new high-efficiency flotation inhibitor is provided for the flotation separation of high-magnesium low-grade phosphorite.
Description
Technical Field
The invention relates to the technical field of ore dressing and purification processes of phosphate ore, in particular to application of a high-efficiency inhibitor HPMA in positive flotation and magnesium removal of phosphate ore.
Background
In the process of separating and purifying the phosphate ore, the key for improving the quality of the phosphate ore product is to reduce the MgO content of phosphate concentrate. The MgO impurity in the phosphate ore is mainly derived from magnesium-containing carbonate mineral dolomite. Apatite is a typical useful mineral containing phosphorus of phosphorus ore, but because apatite and gangue dolomite belong to salt minerals containing calcium, the similar physical and chemical properties thereof cause difficulty in flotation separation of apatite and dolomite. In addition, the phosphate ore has the characteristics of poor quality, fineness and impurities, the monomer dissociation of useful phosphorus minerals can be realized only by fine grinding, and the fine dolomite is easy to enter flotation foam in the flotation process to reduce the grade of phosphorus concentrate and increase the difficulty of the subsequent production of phosphorus chemical products. The efficient inhibitor is added in the positive flotation process of the phosphate ore, so that the dolomite flotation can be effectively inhibited, the separation efficiency of the flotation and the magnesium removal of the phosphate ore is improved, and the quality of the phosphate concentrate is improved, therefore, the efficient dolomite selective inhibitor is found to be of great significance for the efficient separation of the phosphate mineral and the dolomite in the phosphate ore.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the application of the high-efficiency inhibitor HPMA in the positive flotation and the demagging of the phosphate ore, which is to increase the difference of the floatability of the phosphorite mineral (apatite) and the gangue mineral (dolomite) in the phosphate ore according to the addition of the high-efficiency inhibitor HPMA (hydrolyzed polymaleic anhydride) in a sodium oleate or oleic acid flotation system, remove the magnesium-containing mineral (dolomite) in the phosphate ore, reduce magnesium impurities, improve the product quality of low-magnesium phosphate concentrate, and particularly provide a new high-efficiency flotation inhibitor for the flotation and the separation of high-magnesium low-grade phosphate ore.
The invention relates to an application of a high-efficiency inhibitor HPMA in direct flotation and magnesium removal of phosphate ore, in particular to a process for applying the high-efficiency inhibitor HPMA to direct flotation and removal of gangue mineral dolomite in the phosphate ore.
Further, the application of the high-efficiency inhibitor HPMA in the direct flotation and magnesium removal of phosphate ores is to use the high-efficiency inhibitor HPMA in the preparation of the phosphate ore flotation pulp.
Further, the application of the high-efficiency inhibitor HPMA in the positive flotation and magnesium removal of phosphate ore is to dissolve the high-efficiency inhibitor HPMA in water to prepare an inhibitor HPMA solution with the mass concentration of 2-4 g/L for use.
The high-efficiency inhibitor HPMA is used for the process of removing gangue mineral dolomite by phosphorite direct flotation, and specifically comprises the following steps:
step 1: ore grinding
Crushing and grinding high-magnesium low-grade phosphate ore to obtain phosphate ore powder; wherein, in the phosphate rock powder, the mass of the phosphate rock powder with the granularity less than or equal to 74 mu m accounts for 75-80% of the total mass of the phosphate rock powder;
step 2: size mixing
Placing the phosphate rock powder into flotation equipment, adding deionized water and a high-efficiency inhibitor HPMA aqueous solution, and uniformly stirring and mixing to obtain phosphate rock flotation pulp; wherein, according to the mass ratio, deionized water: phosphate rock powder (3-7): 1; the mass concentration of the HPMA aqueous solution of the high-efficiency inhibitor is 2-4 g/L; the mass concentration of the high-efficiency inhibitor HPMA in the phosphate ore flotation pulp is 40-70 mg/L.
And step 3: direct flotation demagging
Adding NaOH solution into the phosphorite flotation pulp at room temperature, adjusting the pH value of the phosphorite flotation pulp to 8.5-11.5, and uniformly stirring to obtain the phosphorite flotation pulp with the pH value of 8.5-11.5;
adding a collecting agent sodium oleate solution or a collecting agent oleic acid solution into phosphate ore flotation pulp with the pH value of 8.5-11.5, uniformly stirring, carrying out direct flotation rough separation and magnesium removal in flotation equipment, adopting a flotation froth scraping mode, wherein the froth scraping time is 4-5 min, obtaining flotation foam, and obtaining tailings as residual products in the flotation equipment; wherein the molar concentration of the collecting agent in the phosphorite flotation pulp is 0.3-0.4 mmol/L, preferably 0.35 mmol/L;
and 4, step 4: flotation froth aftertreatment
And drying the flotation foam to obtain the low-magnesium phosphate concentrate.
In the step 1, the high-magnesium low-grade phosphate ore comprises the following main components in percentage by mass: p2O524-32%, MgO 1.5-7.5%, CaO 40-55%, F not more than 3.5%, SiO2Less than or equal to 1.8 percent, and the balance of inevitable impurities.
In the step 2, the flotation equipment is preferably a hanging-groove type flotation machine, and the rotating speed can be adjusted at 1500-2600 r/min.
In the step 2, the stirring speed of the stirring and the uniform mixing is 1800-2100 r/min, and the stirring time is 2-3 min.
In the step 3, the temperature for direct flotation, roughing and magnesium removal is preferably 21-25 ℃.
In the step 3, the NaOH solution added for adjusting the pH value is preferably added with a NaOH aqueous solution with the mass percentage concentration of 0.4-1.2%.
In the step 3, the mixture is uniformly stirred, the stirring speed is 1800-2100 r/min, and the stirring time is 2-3 min.
In the step 3, the pH value is preferably 10.5.
In the step 3, the magnesium is removed by the direct flotation roughing, and in the process of the direct flotation roughing magnesium removal, the rotating speed is set to be 1800-2100 r/min, preferably 1900 r/min.
In the step 3, the foam scraping is performed once every 10 s.
In the step 3, the collector sodium oleate solution is preferably a sodium oleate solution with a molar concentration of 6-12 mmol/L, and the collector oleic acid solution is an oleic acid solution with a molar concentration of 6-12 mmol/L, wherein the preparation method of the collector sodium oleate solution comprises the following steps: adding solid powder of collecting agent sodium oleate into deionized water, heating to 50-60 ℃, and stirring until the solid powder of collecting agent sodium oleate is completely dissolved to obtain the collecting agent sodium oleate aqueous solution.
By adopting the method, the prepared low-magnesium phosphate concentrate contains P and Mg components, and the mass percent of each component is P2O5≥37.42％，MgO≤1.65％。
In the low-magnesium phosphate concentrate, the recovery rate of apatite is 70-90%, and the removal rate of gangue dolomite in the low-magnesium phosphate concentrate is 80-90%.
The invention relates to an application of a high-efficiency inhibitor HPMA in positive flotation and magnesium removal of phosphate ore, which mainly has the action mechanism that: the high-efficiency inhibitor HPMA has strong affinity to magnesium, can generate chemical action with magnesium ions on the surface of dolomite, and is strongly adsorbed on the surface of the dolomite, so that the adsorption of a collecting agent (sodium oleate or oleic acid) on the dolomite is hindered, the surface hydrophilicity of the dolomite is increased, and the floating of the dolomite is inhibited. In addition, because magnesium ions do not exist on the surface of main phosphorite containing phosphorite, the adsorption of the high-efficiency inhibitor HPMA on the surface of the phosphorite containing phosphorite is weak, the adsorption of a collecting agent (sodium oleate or oleic acid) on the surface is hardly influenced, and the phosphorite acted by the collecting agent (sodium oleate or oleic acid) has high surface hydrophobicity, so that the phosphorite has good flotation performance. Therefore, the addition of the high-efficiency inhibitor HPMA increases the flotation performance difference of dolomite and apatite, so as to realize positive flotation and demagging of phosphate ore, and the action mechanism is proved by contact angle and adsorption quantity measurement.
The invention provides an application of a high-efficiency inhibitor HPMA in positive flotation and magnesium removal of phosphate ore, compared with the prior art, the invention has the beneficial effects that:
1. the invention develops the application of the novel high-efficiency inhibitor HPMA, and the novel high-efficiency inhibitor HPMA selectively inhibits the magnesium-containing carbonate mineral dolomite, thereby realizing the direct flotation and magnesium removal of phosphate ore, improving the removal rate of magnesium impurities, simplifying the process flow of the direct flotation and magnesium removal of phosphate ore, and having stable flotation process and simpler operation.
2. The high-efficiency inhibitor HPMA is an environment-friendly agent without nitrogen, phosphorus and sulfur and toxicity, and compared with the traditional inhibitor for flotation and magnesium removal of phosphate ore, the high-efficiency inhibitor HPMA reduces the harm of agent residue to the environment. In addition, the inhibitor has the advantages of small dosage, low cost, easy commercial availability and convenient industrial production and application.
3. The high-efficiency inhibitor HPMA is a magnesium-philic chelating agent, is easy to act on magnesium locus of magnesium-containing carbonate minerals, is applied to an inhibitor of gangue dolomite in the positive flotation process of phosphate ores, increases the floating difference between phosphate ores and dolomite, and provides a novel flotation inhibitor for flotation and demagging of low-grade phosphate ores.
Drawings
FIG. 1 is a schematic diagram of a process flow of applying HPMA, an efficient inhibitor, in embodiment 3 of the present invention, to magnesium removal by direct flotation of phosphate ore.
Figure 2 is an XRD pattern of dolomite used in an example of the invention.
FIG. 3 is an XRD pattern of apatite used in examples of the present invention.
Fig. 4 is a graph showing the results of measuring the adsorption amount of HPMA, which is a highly effective inhibitor, and the mineral contact angle in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
The following limited examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
In the following examples, the test methods, unless otherwise specified, are conventional methods; the reagents and materials are commercially available, unless otherwise specified.
In the following examples, in order to clarify the properties of the present invention, the phosphate ore was artificially mixed phosphate ore, in which the sizes of apatite and dolomite are less than or equal to 74 μm and the mass ratio of apatite to dolomite is 7:3, and the purities of dolomite and apatite are 98.39% and 97.36%, respectively, and the XRD patterns thereof are shown in FIG. 2 and FIG. 3.
In some of the following examples, the high-magnesium low-grade phosphate ore was obtained from hong Kong and subjected to elemental analysis according to X-ray fluorescence spectroscopy, the main component of which is, in mass percent, P2O528.89% of CaO, 53.65% of CaO, 3.04% of C, 3.12% of F, Al2O33.78% of Fe2O32.46% of SiO20.57%, MgO 4.26%, K2O is 0.23%.
In the following examples, the inhibitor HPMA is commercially pure, the collector sodium oleate or oleic acid is chemically pure, and the pH adjuster sodium hydroxide is analytically pure.
In the following examples, the reagents used in the tests were, unless otherwise specified, prepared as aqueous solutions of corresponding concentrations using deionized water.
In the following examples, the preparation method of the collector sodium oleate solution used was: adding solid powder of collecting agent sodium oleate into deionized water, heating to 50-60 ℃, and stirring until the solid powder of collecting agent sodium oleate is completely dissolved to obtain the collecting agent sodium oleate aqueous solution.
Example 1
The application of HPMA as a high-efficiency inhibitor in the direct flotation and magnesium removal of phosphate ore comprises the following steps:
step 1: size mixing
Placing the artificial mixed phosphate ore sample into a flotation device, namely a hanging-groove type flotation machine, adding deionized water and a high-efficiency inhibitor HPMA solution with the mass concentration of 2g/L, and stirring for 3min at the impeller rotating speed of 1800r/min until the mixture is uniformly mixed to obtain phosphate ore flotation pulp; wherein the mass ratio of the deionized water to the phosphate ore is 6:1, and the mass concentration of the high-efficiency inhibitor HPMA in the phosphate ore flotation pulp is 40 mg/L;
step 2: direct flotation demagging
Adding NaOH aqueous solution with the mass percentage concentration of 1.2% into the phosphorite flotation pulp at the room temperature (21-25 ℃), adjusting the pH value of the phosphorite flotation pulp to 11.5, and stirring for 2min to obtain the phosphorite flotation pulp with the pH value of 11.5;
adding a collecting agent sodium oleate solution with the molar concentration of 6mmol/L into phosphate ore flotation pulp with the pH value of 11.5, stirring for 3min, and performing direct flotation and rough separation to remove magnesium, namely flotation and foam scraping, wherein the foam scraping time is 4 min; wherein the molar concentration of the sodium oleate dosage in the phosphorite flotation ore pulp is 0.3 mmol/L; after finishing the flotation, respectively drying, weighing and testing the grade of a flotation foam product, namely the low-magnesium phosphate concentrate, and a product in a cell, namely tailings, and calculating product indexes; wherein, the flotation foam product after drying and weighing is the low-magnesium phosphate concentrate product.
In the embodiment, the low-magnesium phosphate concentrate contains the following components in percentage by mass: p2O537.95 percent of MgO, 1.65 percent of MgO; the recovery rate of apatite in the low-magnesium phosphate concentrate is 88.89%, and the removal rate of dolomite in the low-magnesium phosphate concentrate is 84.74%.
In this example, the adsorption amounts of the high efficiency inhibitor HPMA on the apatite and dolomite surfaces and the influence of the addition of the high efficiency inhibitor HPMA in the sodium oleate system on the contact angles of the apatite and dolomite surfaces were respectively detected.
The detection results are shown in FIG. 4, and it can be seen from FIG. 4 that the adsorption amount of HPMA, a high efficiency inhibitor, is higher in dolomite than in apatite, indicating that HPMA, a high efficiency inhibitor, strongly adsorbs to the surface of dolomite, but weakly adsorbs to the surface of apatite. When only collecting agent sodium oleate is added, the contact angles of apatite and dolomite are similar and have larger contact angles, which shows that the two kinds of sodium oleate can be adsorbed on the surfaces of two kinds of minerals, and the surfaces have better hydrophobicity. However, when the high-efficiency inhibitor HPMA and the collecting agent sodium oleate are added, the apatite and the dolomite show larger hydrophobicity difference, which means that the sodium oleate has obvious difference in adsorption on the surfaces of the apatite and the dolomite. It can be found that the contact angle of the apatite is not obviously changed and still has a larger contact angle, which indicates that the adsorption of the sodium oleate on the surface of the apatite is hardly influenced by adding the HPMA high-efficiency inhibitor, but the contact angle of the dolomite is obviously reduced, which proves that the adsorption of the sodium oleate on the surface of the dolomite is inhibited by adding the HPMA high-efficiency inhibitor, so that the hydrophobicity of the surface of the dolomite is reduced. Therefore, the adsorption difference of the HPMA (high efficiency inhibitor) on the surfaces of the apatite and the dolomite influences the adsorption behavior of the sodium oleate on the two minerals, so that the surface hydrophobicity difference is caused, the floatability difference of the two minerals is increased, and the effect of positive flotation and magnesium removal of the phosphate ore is realized.
Example 2
The application of HPMA as a high-efficiency inhibitor in the direct flotation and magnesium removal of phosphate ore comprises the following steps:
step 1: size mixing
Placing the artificial mixed phosphate ore sample into a flotation device, namely a hanging-groove type flotation machine, adding deionized water and a high-efficiency inhibitor HPMA solution with the mass concentration of 3g/L, and stirring for 3min at the impeller rotating speed of 2100r/min until the mixture is uniformly mixed to obtain phosphate ore flotation pulp; wherein the mass ratio of the deionized water to the phosphate ore is 6:1, and the mass concentration of the high-efficiency inhibitor HPMA in the phosphate ore flotation pulp is 60 mg/L;
step 2: direct flotation demagging
Adding NaOH aqueous solution with the mass percentage concentration of 0.4% into the phosphorite flotation pulp at the room temperature (21-25 ℃), adjusting the pH value of the phosphorite flotation pulp to 8.5, and stirring for 2min to obtain the phosphorite flotation pulp with the pH value of 8.5;
adding a collecting agent sodium oleate solution with the molar concentration of 9mmol/L into phosphate ore flotation pulp with the pH value of 8.5, stirring for 3min, and performing direct flotation and rough separation to remove magnesium, namely flotation and foam scraping, wherein the foam scraping time is 5 min; wherein the molar concentration of the sodium oleate dosage in the phosphorite flotation ore pulp is 0.35 mmol/L; after finishing the flotation, respectively drying, weighing and testing the grade of a flotation foam product, namely the low-magnesium phosphate concentrate, and a product in a cell, namely tailings, and calculating product indexes; wherein, the flotation foam product after drying and weighing is the low-magnesium phosphate concentrate product.
In this embodiment, the low-magnesium phosphate concentrate contains P and Mg in the following mass percentages: p2O538.15 percent of MgO, 1.12 percent of MgO; the recovery rate of apatite in the low-magnesium phosphate concentrate is 87.40%, and the removal rate of dolomite in the low-magnesium phosphate concentrate is 86.26%.
Example 3
The application of HPMA as high efficiency inhibitor in direct flotation and magnesium removal of phosphate ore includes the following steps:
step 1: ore grinding
Crushing and grinding high-magnesium low-grade phosphate ore to obtain phosphate ore powder; wherein, in the phosphate rock powder, the mass of the phosphate rock powder with the granularity less than or equal to 74 μm accounts for 75 percent of the total mass of the phosphate rock powder;
step 2: size mixing
Placing the phosphate rock powder into a flotation device, namely a single-groove flotation machine, adding deionized water and a high-efficiency inhibitor HPMA solution with the mass concentration of 4g/L, and stirring for 3min at the impeller rotating speed of 1900r/min until the mixture is uniformly mixed to obtain phosphate rock flotation pulp; wherein the mass ratio of the deionized water to the phosphate ore is 4:1, and the mass concentration of the high-efficiency inhibitor HPMA in the phosphate ore flotation pulp is 70 mg/L;
and step 3: direct flotation demagging
Adding NaOH aqueous solution with the mass percentage concentration of 0.9% into the phosphorite flotation pulp at the room temperature (21-25 ℃), adjusting the pH value of the phosphorite flotation pulp to 10.5, and stirring for 2min to obtain the phosphorite flotation pulp with the pH value of 10.5;
adding a collecting agent sodium oleate solution with the molar concentration of 12mmol/L into phosphate ore flotation pulp with the pH value of 10.5, stirring for 3min, and performing direct flotation and rough separation to remove magnesium, namely flotation and foam scraping, wherein the foam scraping time is 4.5 min; wherein the molar concentration of the sodium oleate dosage in the phosphorite flotation ore pulp is 0.4 mmol/L; after finishing the flotation, respectively drying, weighing and testing the grade of a flotation foam product, namely the low-magnesium phosphate concentrate, and a product in a cell, namely tailings, and calculating product indexes; wherein, the flotation foam product after drying and weighing is the low-magnesium phosphate concentrate product.
In the embodiment, the low-magnesium phosphate concentrate comprises the following main components in percentage by mass: p2O537.76 percent of MgO, 0.60 percent of MgO; the recovery rate of apatite in the low-magnesium phosphate concentrate is 74.13%, and the removal rate of dolomite in the low-magnesium phosphate concentrate is 89.87%.
Example 4
The application of HPMA as a high-efficiency inhibitor in the direct flotation and magnesium removal of phosphate ore comprises the following steps:
step 1: ore grinding
Crushing and grinding high-magnesium low-grade phosphate ore to obtain phosphate ore powder; wherein, in the phosphate rock powder, the mass of the phosphate rock powder with the granularity less than or equal to 74 mu m accounts for 80 percent of the total mass of the phosphate rock powder;
step 2: size mixing
Placing the phosphate rock powder into a flotation device, namely a single-groove flotation machine, adding deionized water and a high-efficiency inhibitor HPMA solution with the mass concentration of 3g/L, and stirring for 3min at the impeller rotating speed of 2000r/min until the mixture is uniformly mixed to obtain phosphate rock flotation pulp; wherein the mass ratio of the deionized water to the phosphate ore is 4:1, and the mass concentration of the high-efficiency inhibitor HPMA in the phosphate ore flotation pulp is 50 mg/L;
and step 3: direct flotation demagging
Adding 0.7 mass percent NaOH dilute solution into the phosphate ore flotation pulp at room temperature (21-25 ℃), adjusting the pH of the phosphate ore flotation pulp to 9.5, and stirring for 2min to obtain the phosphate ore flotation pulp with the pH value of 9.5;
adding a collecting agent sodium oleate solution with the molar concentration of 6mmol/L into phosphate ore flotation pulp with the pH value of 9.5, stirring for 3min, and performing direct flotation and rough separation to remove magnesium, namely flotation and foam scraping, wherein the foam scraping time is 4.5 min; wherein the molar concentration of the sodium oleate dosage in the phosphorite flotation ore pulp is 0.3 mmol/L; after finishing the flotation, respectively drying, weighing and testing the grade of a flotation foam product, namely the low-magnesium phosphate concentrate, and a product in a cell, namely tailings, and calculating product indexes; wherein, the flotation foam product after drying and weighing is the low-magnesium phosphate concentrate product.
In the embodiment, the low-magnesium phosphate concentrate comprises the following main components in percentage by mass: p2O537.44 percent of MgO and 0.74 percent of MgO; the recovery rate of apatite in the low-magnesium phosphate concentrate is 72.13%, and the removal rate of dolomite in the low-magnesium phosphate concentrate is 87.87%.
Example 5
The application of HPMA as an efficient inhibitor in direct flotation and demagging of phosphate ore is similar to that in example 4, except that a collecting agent oleic acid solution is adopted to replace a collecting agent sodium oleate solution, so that the main component of the low-magnesium phosphate concentrate is obtainedThe material comprises the following components in percentage by mass: p2O537.42% and 0.70% MgO; the recovery rate of apatite in the low-magnesium phosphate concentrate is 70.03%, and the removal rate of dolomite in the low-magnesium phosphate concentrate is 88.87%.
Claims (10)
1. The application of the high-efficiency inhibitor HPMA in the direct flotation and magnesium removal of phosphate ore is characterized in that the high-efficiency inhibitor HPMA is used in the process of removing gangue mineral dolomite in the direct flotation of the phosphate ore.
2. The use of the HPMA of claim 1 in the direct flotation and demagging of phosphate ore, wherein the use of the HPMA is for the preparation of slurry for the flotation of phosphate ore.
3. The application of the high-efficiency inhibitor HPMA in the phosphate ore direct flotation demagging as claimed in claim 1, wherein the application of the high-efficiency inhibitor HPMA in the phosphate ore direct flotation demagging is to dissolve the high-efficiency inhibitor HPMA in water to prepare an inhibitor HPMA solution with the mass concentration of 2-4 g/L for use.
4. The application of the high efficiency inhibitor HPMA in the process of direct flotation and demagging of phosphate ore according to claim 1, wherein the high efficiency inhibitor HPMA is used in the process of direct flotation and gangue mineral dolomite removal of phosphate ore, and specifically comprises the following steps:
step 1: ore grinding
Crushing and grinding high-magnesium low-grade phosphate ore to obtain phosphate ore powder; wherein, in the phosphate rock powder, the mass of the phosphate rock powder with the granularity less than or equal to 74 mu m accounts for 75-80% of the total mass of the phosphate rock powder;
step 2: size mixing
Placing the phosphate rock powder into flotation equipment, adding deionized water and a high-efficiency inhibitor HPMA aqueous solution, and uniformly stirring and mixing to obtain phosphate rock flotation pulp; wherein, according to the mass ratio, deionized water: phosphate rock powder (3-7): 1; the mass concentration of the HPMA aqueous solution of the high-efficiency inhibitor is 2-4 g/L; the mass concentration of the high-efficiency inhibitor HPMA in the phosphate ore flotation pulp is 40-70 mg/L;
and step 3: direct flotation demagging
Adding NaOH solution into the phosphorite flotation pulp at room temperature, adjusting the pH value of the phosphorite flotation pulp to 8.5-11.5, and uniformly stirring to obtain the phosphorite flotation pulp with the pH value of 8.5-11.5;
adding a collecting agent sodium oleate solution or a collecting agent oleic acid solution into phosphate ore flotation pulp with the pH value of 8.5-11.5, uniformly stirring, carrying out direct flotation rough separation and magnesium removal in flotation equipment, adopting a flotation froth scraping mode, wherein the froth scraping time is 4-5 min, obtaining flotation foam, and obtaining tailings as residual products in the flotation equipment; wherein the molar concentration of the collecting agent in the phosphorite flotation pulp is 0.3-0.4 mmol/L;
and 4, step 4: flotation froth aftertreatment
And drying the flotation foam to obtain the low-magnesium phosphate concentrate.
5. The application of the HPMA (high efficiency inhibitor) in the direct flotation and magnesium removal of phosphate ore according to claim 4, wherein in the step 1, the high-magnesium low-grade phosphate ore contains the following main components in percentage by mass: p2O524-32%, MgO 1.5-7.5%, CaO 40-55%, F not more than 3.5%, SiO2Less than or equal to 1.8 percent, and the balance of inevitable impurities.
6. The application of the HPMA (high efficiency inhibitor) in the direct flotation and magnesium removal of phosphate ore according to claim 4, wherein in the step 3, NaOH aqueous solution with the mass percentage concentration of 0.4-1.2% is added into the NaOH solution with the pH value adjusted.
7. The use of HPMA, a highly potent depressant, according to claim 4, in the direct flotation of magnesium from phosphate ores, wherein in step 3, the flotation froth scraping is performed every 10 s.
8. The application of the HPMA (high efficiency inhibitor) in direct flotation and demagging of phosphate ore according to claim 4, wherein in the step 3, the sodium oleate solution is a sodium oleate solution with a molar concentration of 6-12 mmol/L, and the oleic acid solution is an oleic acid solution with a molar concentration of 6-12 mmol/L, wherein the preparation method of the sodium oleate solution is as follows: adding solid powder of collecting agent sodium oleate into deionized water, heating to 50-60 ℃, and stirring until the solid powder of collecting agent sodium oleate is completely dissolved to obtain the collecting agent sodium oleate aqueous solution.
9. The application of the HPMA (high efficiency inhibitor) in the direct flotation and magnesium removal of phosphate ore according to claim 1 or 4, wherein the P and Mg components contained in the prepared low-magnesium phosphate concentrate are P in percentage by mass2O5≥37.42％，MgO≤1.65％。
10. The application of the HPMA (high efficiency depressant) in the direct flotation and the magnesium removal of phosphate ore according to claim 1 or 4 is characterized in that the recovery rate of apatite in the low-magnesium phosphate concentrate is 70-90%, and the removal rate of gangue dolomite in the low-magnesium phosphate concentrate is 80-90%.
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