CN113477405B - Beneficiation activator for sphalerite and willemite and method for reducing zinc by flotation of iron ore concentrate - Google Patents
Beneficiation activator for sphalerite and willemite and method for reducing zinc by flotation of iron ore concentrate Download PDFInfo
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- CN113477405B CN113477405B CN202110564898.5A CN202110564898A CN113477405B CN 113477405 B CN113477405 B CN 113477405B CN 202110564898 A CN202110564898 A CN 202110564898A CN 113477405 B CN113477405 B CN 113477405B
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- flotation
- ore concentrate
- iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 179
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000011701 zinc Substances 0.000 title claims abstract description 85
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 85
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 82
- 239000012141 concentrate Substances 0.000 title claims abstract description 61
- 229910052950 sphalerite Inorganic materials 0.000 title claims abstract description 52
- 239000012190 activator Substances 0.000 title claims abstract description 40
- 238000005188 flotation Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052844 willemite Inorganic materials 0.000 title description 8
- 229940024606 amino acid Drugs 0.000 claims abstract description 29
- 235000001014 amino acid Nutrition 0.000 claims abstract description 29
- 150000001413 amino acids Chemical group 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 27
- 230000003213 activating effect Effects 0.000 claims abstract description 18
- 238000007885 magnetic separation Methods 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 14
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 12
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims abstract description 10
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims abstract description 5
- 229960003707 glutamic acid hydrochloride Drugs 0.000 claims abstract description 5
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims abstract description 4
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 4
- DWHMPBALQYTJFJ-DKWTVANSSA-N (2s)-2-aminobutanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CC(O)=O DWHMPBALQYTJFJ-DKWTVANSSA-N 0.000 claims abstract description 3
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims abstract description 3
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004473 Threonine Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 12
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 229940116411 terpineol Drugs 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 4
- -1 methyl isobutyl Chemical group 0.000 claims description 4
- 239000012991 xanthate Substances 0.000 claims description 4
- KOVPITHBHSZRLT-UHFFFAOYSA-N 2-methylpropoxymethanedithioic acid Chemical compound CC(C)COC(S)=S KOVPITHBHSZRLT-UHFFFAOYSA-N 0.000 claims description 2
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical compound CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 claims description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 2
- IDTYIZVHFFKWAD-UHFFFAOYSA-N hexoxymethanedithioic acid Chemical compound CCCCCCOC(S)=S IDTYIZVHFFKWAD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 4
- 230000004913 activation Effects 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000011946 reduction process Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 12
- 229960005261 aspartic acid Drugs 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 9
- 229910000365 copper sulfate Inorganic materials 0.000 description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 8
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 8
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 235000013922 glutamic acid Nutrition 0.000 description 8
- 239000004220 glutamic acid Substances 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 150000002306 glutamic acid derivatives Chemical class 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910001608 iron mineral Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QWENMOXLTHDKDL-UHFFFAOYSA-M pentoxymethanedithioate Chemical compound CCCCCOC([S-])=S QWENMOXLTHDKDL-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940049906 glutamate Drugs 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000024121 nodulation Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052952 pyrrhotite Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a zinc blende and iron blende beneficiation activator and a method for reducing zinc in iron ore concentrate flotation, wherein the activator is amino acid or a mixture containing amino acid; the amino acid is one or more of aspartic acid, aspartic acid hydrochloride, glutamic acid hydrochloride, threonine and serine. The method for reducing zinc in the iron ore concentrate by flotation by using the activating agent is to add the activating agent into the ore pulp of the iron ore concentrate subjected to low-intensity magnetic separation, add a collecting agent and a foaming agent, perform primary roughing and primary concentration, float zinc blende and iron blende, and obtain the iron ore concentrate with the zinc content lower than 0.02 percent and the iron loss less than 5 percent. The method solves the problems of poor activation selectivity of the conventional activating agent for sphalerite and wurtzite, difficult deep removal of zinc impurities in the iron ore concentrate and large iron loss in the zinc reduction process, is simple, easy to operate and good in zinc reduction effect, can reduce the zinc to be below 0.02 percent, and meets the content requirement of high-purity iron ore concentrate on the zinc impurities.
Description
Technical Field
The invention belongs to the technical field of mineral processing, and particularly relates to a beneficiation activator for sphalerite and wurtzite and a method for reducing zinc by flotation of iron ore concentrate.
Background
At present, the furnace entering standard of iron ore concentrate in China is that the zinc content is lower than 0.1 percent, and certain large-scale steel companies require the zinc content to be lower than 0.02 percent when producing high-purity iron ore concentrate. The excessive zinc content in the iron ore concentrate not only directly affects the quality of steel, but also causes various problems of abnormal blast furnace gas flow distribution, upwarp of a tuyere, damage of refractory bricks, furnace wall bonding and nodulation, material collapse, high damping down rate and the like in the steelmaking process, and affects the normal production of a blast furnace. Therefore, the quality of high-end special steel is improved, the smooth operation of the iron-making blast furnace is ensured, and the zinc content in iron ore concentrate needs to be reduced as much as possible.
The zinc, a detrimental impurity in iron concentrates, is typically present in the form of sphalerite or willemite. Although the sphalerite is not magnetic and can be removed by magnetic separation, the sphalerite is difficult to remove to the extent that the zinc content is lower than 0.02 percent, and deep zinc removal by flotation is needed. The removal difficulty is greater when the zinc in the iron concentrate exists mainly in the form of wurtzite. The zinc blende containing more than 6% of iron is called iron zinc blende, and is converted by replacing zinc atoms in the crystal lattice of the zinc blende with iron atoms in the form of isomorphism. The magnetic strength of the sphalerite is influenced by the iron content, and generally, the higher the iron content is, the stronger the magnetism is, and the more easily the sphalerite enters a magnetic concentrate product during magnetic separation. The floatability of the sphalerite is inversely related to the iron content in the mineral, when the iron content in the mineral is increased, the lattice parameter of the mineral is increased, the hydration effect of the mineral is enhanced, and the natural floatability is reduced.
In actual production, sphalerite and wurtzite often show the characteristics of poor floatability, sensitivity to media and the like, and the floatability of the sphalerite and wurtzite is far smaller than that of other sulfides. Therefore, the floatation of the sphalerite and the sphalerite without activation is very difficult, and the activation is an important link in the floatation of the sphalerite and the sphalerite. The activators for activating sphalerite and willemite in industry at present are copper sulfate, ammonium chloride, lead nitrate and the combination activators thereof. Although these activators do activate sphalerite and willemite, there are the following drawbacks as deep dezincification activators for iron concentrates: (1) the activation effect is not outstanding, and the deep zinc reduction of the iron ore concentrate (such as reducing the zinc content to be below 0.02%) is difficult to realize; (2) the loss amount of iron is large, the activating performance of the medicament under the weak acidic or alkaline condition is good, and copper ions can activate iron minerals, so that part of the iron concentrates subjected to weak magnetic separation inevitably enter zinc concentrates, and a large amount of iron loss is caused. Patents CN1817468A and CN101816979A disclose a complex compound ([ Cu (NH) with copper and ammonia3)X]2+Wherein X is 1-8) is a flotation activator of the zincblende and a preparation method thereof; patent CN108940604A discloses a preparation method of a composite sphalerite activator, which is prepared by reacting copper sulfate, lead nitrate, sodium sulfide, oxidized paraffin soap and lauric acid at high temperature and high pressure. The disclosed sphalerite and wurtzite flotation activators, while enhancing the selective activation and inhibition properties of the agent, can be used at low pHAnd (7) activating under the condition of (11), but the method is still not suitable for the deep flotation zinc reduction of iron concentrate, a large amount of iron ore enters the zinc concentrate, and the iron loss is large.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a sphalerite and wurtzite activating agent which is simple in method, good in activating performance, capable of effectively reducing the zinc content and small in iron loss, and a method for reducing zinc by flotation of iron ore concentrate.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an activator for beneficiation of sphalerite and willemite, the activator being an amino acid or a mixture comprising an amino acid; the amino acid is one or more of aspartic acid, aspartic acid hydrochloride, glutamic acid hydrochloride, threonine and serine.
The amino terminal and the carboxyl terminal of the amino acid can form five-membered or six-membered chelate rings with a plurality of metal ions and can be used as chelating agents of the metal ions. For other polydentate ligand amino acids, such as tyrosine, lysine, etc., since the distance of the remote hydroxyl group or amino group is too far, the coordination effect on metal ions is not so great, and the effect is not as good as that of the polydentate ligand amino acids.
Preferably, the mixture comprising the amino acid is an aqueous solution of the amino acid or an acid solution of the amino acid; the acid solution of the amino acid is prepared by mixing the amino acid and acid, and the acid is hydrochloric acid or sulfuric acid. Further, from the viewpoint of environmental protection, addition of sulfuric acid is preferable.
In the present invention, when the mixture containing the amino acid is an acid solution of the amino acid, the acid is added to the amino acid for two purposes: the solubility of aspartic acid, glutamic acid and the like can be improved; secondly, a lower pH value environment is created for the activation flotation of the sphalerite and the wurtzite.
As a general inventive concept, the present invention also provides a method for the flotation zinc reduction of iron ore concentrate, comprising the following steps:
(1) adding the activating agent into the low-intensity magnetic separation iron ore concentrate pulp, and uniformly stirring;
(2) adding a collecting agent into the ore pulp treated in the step (1), mixing and stirring, adding a foaming agent, uniformly stirring, starting aeration for flotation and rough separation, and separating most of dissociated sphalerite and willemite;
(3) adding a collecting agent into the ore pulp obtained after the treatment in the step (2), mixing and stirring, adding a foaming agent, uniformly stirring, starting aeration for flotation and fine selection, and separating continuous zinc blende and zinc blende to obtain fine iron powder.
The removal efficiency of sphalerite and ferrosphalerite in iron ore concentrate is closely related to factors such as ore grinding fineness, flotation feeding concentration, the type and the amount of an activating agent, the structure and the amount of a collecting agent, the type and the amount of a foaming agent, the pH value of ore pulp and the like. The present invention is preferable for each parameter in steps (1) to (3).
Preferably, in the step (1), the feeding concentration of the iron ore concentrate ore pulp subjected to the low-intensity magnetic separation is 30-60%, and the feeding granularity of-0.045 mm accounts for 40-100%; the addition amount of the amino acid is 1 kg/t-8 kg/t, and the pH value of the ore pulp is 3.0-6.0.
Further preferably, the feeding concentration of the low-intensity magnetic separation iron ore concentrate pulp is 30-50%, and the feeding granularity of-0.045 mm accounts for 65-90%; the addition amount of the amino acid is 3 kg/t-6 kg/t, and the pH value of the ore pulp is 4-5.5.
Preferably, in the step (2) and the step (3), the collector is at least one of butyl xanthate, isobutyl xanthate, amyl xanthate, isoamyl xanthate, hexyl xanthate, methyl isobutyl xanthate and isooctyl xanthate; the addition amount of the collecting agent is 50-400 g/t;
the foaming agent is at least one of terpineol, methyl isobutyl carbinol and BK 60; the addition amount of the foaming agent is 15-100 g/t.
Further preferably, in the step (2) and the step (3), the collecting agent is amyl xanthate, and the foaming agent is terpineol;
in the step (2), the addition amount of the amyl xanthate is 150-300 g/t, and the addition amount of the terpineol is 50-90 g/t;
in the step (3), the addition amount of the amyl xanthate is 60-150 g/t, and the addition amount of the terpineol is 20-40 g/t.
Preferably, in the step (2), the time for flotation and roughing is 5-10 min, and in the step (3), the time for flotation and concentration is 3-6 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention solves the difficult problem of activation of sphalerite and wurtzite. The amino acid and the hydrochloride activator thereof disclosed by the invention have the synergistic effect of coupling multiple activation functions: (ii) an excellent chelating action, namely, a hydrophilic substance Fe (OH) covering the surfaces of sphalerite and wurtzite3、Zn(OH)2、Ca(OH)2Isochelate to synthesize a soluble complex, and the fresh surface of the removed mineral is chemically cleaned and stripped, so that the absorption of a collecting agent is facilitated; ② directional oxidation ability, can improve oxidation potential of sphalerite and wurtzite, induce sphalerite and wurtzite surface oxidation to generate hydrophobic So or S2o, improving its floatability; and thirdly, the concentration of the surface positioning ions of the sphalerite and the wurtzite is improved, a hydration layer on the surface of the mineral is compressed or destroyed, and the action efficiency of the collecting agent is improved. By applying the activating agent and the iron ore concentrate flotation zinc reduction method, the zinc impurities in the iron ore concentrate can be deeply removed, and the zinc content can be reduced to be below 0.02%.
(2) The activating agent provided by the invention not only can obviously activate the sphalerite and the iron sphalerite, but also has outstanding capacity of activating pyrrhotite, and can synchronously remove sulfur while reducing zinc in iron ore concentrate.
(3) The activating agent has high activation selectivity, does not activate iron minerals, can adjust the pH value of ore pulp to a lower value while activating the sphalerite and the wurtzite, and solves the problems that the activating selectivity of copper sulfate and lead nitrate is not high, the yield of foam products is high, and the loss of iron is large when magnetic iron ore enters zinc concentrate.
(4) The method for reducing zinc by flotation of the iron ore concentrate has simple steps, only needs to increase flotation operation, has strong operability, and can float most of sphalerite and sphalerite by adding the sphalerite and the iron sphalerite activator for rough concentration and fine concentration for one time under the condition that the zinc content in ore is close to 0.1 percent, and the zinc content of the iron ore concentrate after fine concentration can be reduced to be below 0.02 percent, so that the obtained iron ore concentrate can meet the raw material requirement of various steel companies for producing high-purity special steel.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the zinc content of a certain zinc-containing iron ore and the iron ore concentrate subjected to low intensity magnetic separation is 0.048%, wherein the zinc content of sphalerite is 0.022%, the zinc content of sphalerite is 0.021%, the zinc content of zinc-iron spinel is 0.005%, and the zinc content exceeds the quality requirement of 0.02% of a user.
The zinc removing treatment is carried out by adopting the blende and iron blende beneficiation activator and the iron concentrate flotation zinc reduction method, and the zinc removing treatment specifically comprises the following steps:
(1) adding an L-aspartic acid solution according to an effective dosage of 6kg/t (namely the addition amount of the L-aspartic acid is 6kg/t) into the low-intensity magnetic separation iron concentrate with the feeding concentration of 34% and the feeding granularity of-0.045 mm accounting for 80%, stirring for 3min, and adjusting the pH value of ore pulp to 4.5; the L-aspartic acid solution is prepared by adding sulfuric acid (the mass fraction of the sulfuric acid is 30%) into L-aspartic acid, and the mass fraction of the L-aspartic acid in the solution is 10%.
(2) Adding a pentyl xanthate collecting agent into the ore pulp obtained by the treatment in the step (1), mixing and stirring for 2min, adding a terpineol foaming agent, mixing and stirring for 1min, aerating for roughing, wherein the roughing time is 5min, separating most dissociated sphalerite and sphalerite, and floating most zinc to enter a foam product.
(3) And (3) adding the amyl xanthate collecting agent into the ore pulp obtained by the treatment in the step (2) again, mixing and stirring for 2min, adding terpineol again, mixing and stirring for 1min, aerating for concentration for 3min, separating out the continuously-produced sphalerite and the sphalerite, further reducing the zinc content in the iron ore concentrate, and finally obtaining the iron concentrate powder and the foam product.
The results of the flotation comparative tests of the L-aspartic acid activator in this example with the copper sulfate activator using the above process are shown in Table 1.
TABLE 1 comparative test results for activators copper sulfate and L-aspartic acid
As can be seen from Table 1, by using the L-aspartic acid activator, the zinc content in the refined iron powder can be reduced to 0.016% through the above process, and the recovery rate of TFe in the obtained refined iron powder is 95.26%, while the traditional copper sulfate activator adopts the same process, the zinc content in the obtained refined iron powder is 0.030%, and the recovery rate of TFe is only 84.43%.
Example 2:
the zinc content of certain zinc-containing iron ore and the iron ore concentrate subjected to low-intensity magnetic separation is 0.063%, wherein the zinc content of sphalerite is 0.031%, the zinc content of sphalerite is 0.024%, the zinc content of zinc-iron spinel is 0.008%, and the zinc content exceeds the quality requirement of 0.02% of a user.
The zinc removing treatment is carried out by adopting the blende and iron blende beneficiation activator and the iron concentrate flotation zinc reduction method, and the zinc removing treatment specifically comprises the following steps:
(1) adding a glutamic acid hydrochloride solution according to an effective dosage of 4kg/t (namely the addition amount of glutamic acid hydrochloride is 4kg/t) into low-intensity magnetic separation iron ore concentrate with the feeding concentration of 40% and the feeding granularity of-0.045 mm accounting for 70%, stirring for 3min, and adjusting the pH value of ore pulp to 5.1; the glutamate salt solution is prepared by directly adding water to glutamate salt, and the mass fraction of the glutamate salt in the solution is 15%.
(2) Adding a pentyl xanthate collecting agent into the ore pulp, wherein the addition amount is 200g/t, mixing and stirring for 2min, adding terpineol as a foaming agent, the addition amount is 80g/t, mixing and stirring for 1min, aerating for roughing, wherein the roughing time is 5min, separating most dissociated sphalerite and willemite, and floating most zinc to enter a foam product.
(3) And (3) adding the amyl xanthate collecting agent into the ore pulp obtained in the step (2) again, mixing and stirring for 2min, adding terpineol again, mixing and stirring for 1min, inflating for concentration, wherein the adding amount is 27g/t, separating the continuously generated sphalerite and the wurtzite, further reducing the zinc content in the iron ore concentrate, and finally obtaining fine iron powder and foam products.
Glutamate salt activator and copper tetraammine sulfate ([ Cu (NH) ] using the above process in this example3)4]·SO4) The results of the flotation comparative tests of the activators are shown in table 2.
TABLE 2 comparative test results for activating agents copper tetraammine sulfate and glutamate hydrochloride
As can be seen from table 2, with glutamate salt activator, the recovery rate of the TFe in the obtained refined iron powder is 96.47% and the recovery rate of the TFe in the obtained refined iron powder is 96.47% through the above process, while with the same process, the recovery rate of the TFe in the obtained refined iron powder is 90.85% and the zinc content in the obtained refined iron powder is 0.030%.
Example 3:
the zinc content of certain zinc-containing iron ore, the zinc content of the low-intensity magnetic separation iron ore concentrate is 0.075 percent, wherein the zinc content of the sphalerite is 0.038 percent, the zinc content of the sphalerite is 0.031 percent, the zinc content of the zinc oxide is 0.006 percent, and the zinc content exceeds the quality requirement of 0.02 percent of users.
The zinc removing treatment is carried out by adopting the blende and iron blende beneficiation activator and the iron concentrate flotation zinc reduction method, and the specific method is the same as the embodiment 2, and is different in that: in the step (1), a glutamic acid solution is added into the iron ore concentrate subjected to low-intensity magnetic separation, wherein the glutamic acid solution is prepared by adding sulfuric acid (the mass fraction of the sulfuric acid is 30%) into glutamic acid, and the mass fraction of the glutamic acid in the solution is 10%.
The results of the comparative flotation tests using the glutamic acid activator in this example and the copper sulfate + ammonium chloride combination activator used in the above process are shown in table 3.
TABLE 3 comparative test results for activators copper sulfate + ammonium chloride and glutamic acid
As can be seen from table 3, by using the glutamic acid activator, the recovery rate of the TFe in the iron concentrate powder is 96.95% and the recovery rate of the TFe in the iron concentrate powder is 0.033% through the above process, while the recovery rate of the TFe is only 90.05% through the same process using the conventional copper sulfate and ammonium chloride combined activator.
Example 4:
the zinc content of certain zinc-containing iron ore in the iron ore concentrate subjected to low-intensity magnetic separation is 0.086%, the zinc content of sphalerite is 0.045%, the zinc content of the zincblende is 0.032%, the zinc content of zinc oxide is 0.009%, and the zinc content exceeds the quality requirement of a user by 0.02%.
The zinc removing treatment is carried out by adopting the blende and iron blende beneficiation activator and the iron concentrate flotation zinc reduction method, and the specific method is the same as the embodiment 1, and is different in that: in the step (1), a serine solution is added into the iron ore concentrate subjected to low-intensity magnetic separation, the serine solution is prepared by directly adding water into serine, and the mass fraction of the serine in the solution is 5%.
The results of the flotation comparative tests of the serine activator in this example with the lead nitrate activator using the process described above are shown in table 4.
TABLE 4 comparative test results for activators lead nitrate and serine
As can be seen from table 4, by using the serine activator, the zinc content in the refined iron powder can be reduced to 0.019% and the recovery rate of TFe in the obtained refined iron powder is 96.03% through the above process, while the zinc content in the obtained refined iron powder is 0.025% and the recovery rate of TFe is only 88.03% through the same process using the conventional lead nitrate activator.
Claims (7)
1. The beneficiation activator for sphalerite and wurtzite is characterized in that the activator is amino acid and salts thereof or a mixture containing the amino acid and the salts thereof; the amino acid and its salts are one or more of aspartic acid, aspartic acid hydrochloride, glutamic acid hydrochloride, threonine and serine;
the mixture is an aqueous solution of amino acid and salts thereof or an acid solution of the amino acid; the acid solution of the amino acid is prepared by mixing the amino acid and acid, and the acid is hydrochloric acid or sulfuric acid.
2. The method for reducing zinc in the iron ore concentrate by flotation is characterized by comprising the following steps of:
(1) adding the activating agent as described in claim 1 into the iron ore concentrate pulp subjected to low intensity magnetic separation, and uniformly stirring;
(2) adding a collecting agent into the ore pulp treated in the step (1), mixing and stirring, adding a foaming agent, uniformly stirring, starting aeration for flotation and rough separation, and separating most of dissociated sphalerite and wurtzite;
(3) adding a collecting agent into the ore pulp obtained after the treatment in the step (2), mixing and stirring, adding a foaming agent, uniformly stirring, starting aeration for flotation and fine selection, and separating continuous zinc blende and zinc blende to obtain fine iron powder.
3. The method for reducing zinc by iron ore concentrate flotation according to claim 2, characterized in that in the step (1), the feeding concentration of the ore pulp of the iron ore concentrate subjected to low-intensity magnetic separation is 30-60%, and the feeding granularity is-0.045 mm, which accounts for 40-100%; the addition amount of the amino acid is 1 kg/t-8 kg/t, and the pH value of the ore pulp is 3.0-6.0.
4. The method for reducing zinc in the flotation of iron ore concentrate according to claim 3, wherein the feeding concentration of the ore concentrate pulp subjected to low intensity magnetic separation is 30-50%, and the feeding granularity is-0.045 mm and accounts for 65-90%; the addition amount of the amino acid is 3 kg/t-6 kg/t, and the pH value of the ore pulp is 4-5.5.
5. The method for reducing zinc by flotation of iron ore concentrate according to claim 2, wherein in the step (2) and the step (3), the collector is at least one of butyl xanthate, isobutyl xanthate, amyl xanthate, isoamyl xanthate, hexyl xanthate, methyl isobutyl xanthate and isooctyl xanthate; the addition amount of the collecting agent is 50-400 g/t;
the foaming agent is at least one of terpineol and methyl isobutyl carbinol; the addition amount of the foaming agent is 15-100 g/t.
6. The method for reducing zinc by flotation of iron ore concentrate according to claim 5, wherein in the step (2) and the step (3), the collecting agent is amyl xanthate, and the foaming agent is terpineol;
in the step (2), the addition amount of the amyl xanthate is 150-300 g/t, and the addition amount of the terpineol is 50-90 g/t;
in the step (3), the addition amount of the amyl xanthate is 60-150 g/t, and the addition amount of the terpineol is 20-40 g/t.
7. The method for reducing zinc by flotation of iron ore concentrate according to any one of claims 2 to 6, wherein in the step (2), the time for flotation roughing is 5 to 10min, and in the step (3), the time for flotation concentrating is 3 to 6 min.
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