CN115007323A - Method for inhibiting flotation of pyrite in minerals - Google Patents
Method for inhibiting flotation of pyrite in minerals Download PDFInfo
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- CN115007323A CN115007323A CN202210684195.0A CN202210684195A CN115007323A CN 115007323 A CN115007323 A CN 115007323A CN 202210684195 A CN202210684195 A CN 202210684195A CN 115007323 A CN115007323 A CN 115007323A
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- China
- Prior art keywords
- flotation
- pyrite
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- mol
- chalcopyrite
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- Granted
Links
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 113
- 239000011028 pyrite Substances 0.000 title claims abstract description 113
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000005188 flotation Methods 0.000 title claims abstract description 94
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 45
- 239000011707 mineral Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 20
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052951 chalcopyrite Inorganic materials 0.000 claims abstract description 64
- 239000003112 inhibitor Substances 0.000 claims abstract description 64
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 239000008396 flotation agent Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000012190 activator Substances 0.000 claims abstract 2
- 238000011084 recovery Methods 0.000 claims description 35
- 239000003153 chemical reaction reagent Substances 0.000 claims description 29
- 239000004088 foaming agent Substances 0.000 claims description 18
- 125000001424 substituent group Chemical group 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- -1 carboxyethyl Chemical group 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229960000411 camphor oil Drugs 0.000 claims description 2
- 239000010624 camphor oil Substances 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 230000000994 depressogenic effect Effects 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000010642 eucalyptus oil Substances 0.000 claims description 2
- 229940044949 eucalyptus oil Drugs 0.000 claims description 2
- 229910052949 galena Inorganic materials 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052961 molybdenite Inorganic materials 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000012141 concentrate Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 16
- 230000005764 inhibitory process Effects 0.000 description 15
- 229910052569 sulfide mineral Inorganic materials 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 9
- 239000006260 foam Substances 0.000 description 9
- 238000007790 scraping Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000009837 dry grinding Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229940124639 Selective inhibitor Drugs 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- ROCOTSMCSXTPPU-UHFFFAOYSA-N copper sulfanylideneiron Chemical compound [S].[Fe].[Cu] ROCOTSMCSXTPPU-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HPNSFSBZBAHARI-UHFFFAOYSA-N micophenolic acid Natural products OC1=C(CC=C(C)CCC(O)=O)C(OC)=C(C)C2=C1C(=O)OC2 HPNSFSBZBAHARI-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- HPNSFSBZBAHARI-RUDMXATFSA-N mycophenolic acid Chemical compound OC1=C(C\C=C(/C)CCC(O)=O)C(OC)=C(C)C2=C1C(=O)OC2 HPNSFSBZBAHARI-RUDMXATFSA-N 0.000 description 1
- 229960000951 mycophenolic acid Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000002351 wastewater Substances 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
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- 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
- B03D2201/04—Frothers
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of mineral flotation, and particularly discloses a method for inhibiting pyrite flotation in minerals, which comprises the step of adding an inhibitor shown in formula 1 into the minerals containing pyrite
The flotation agent of (2) is used for flotation to inhibit pyrite flotation. The method disclosed by the invention can effectively inhibit the flotation of the pyrite and can be beneficial to realizing the separation of the pyrite and the target ore due to the use of the inhibitor shown in the formula 1. For example, highly selective flotation separation of pyrites and floatable target ores such as chalcopyrite can be achieved without the use of any collectors, dispersants and activators。
Description
Technical Field
The invention belongs to the field of mineral flotation, and particularly relates to a selective inhibition method of pyrite.
Background
Copper is one of the most important metals in the world and is widely used in many industries such as manufacturing, construction and defense due to its good ductility, thermal and electrical conductivity. The world copper metal mainly comes from sulphide ores, and pyrite is the most common chalcopyrite gangue mineral, which seriously influences the high-efficiency utilization of chalcopyrite resources. Pyrite has certain natural floatability, and the conventional collecting agent has poor selectivity on the pyrite and the chalcopyrite, so that the pyrite can float out together with the chalcopyrite concentrate, and the grade and the recovery rate of the chalcopyrite concentrate are influenced. And in the subsequent smelting process, the remaining pyrite can release harmful gases of sulfur dioxide, thus causing pollution to the environment.
The separation of chalcopyrite and pyrite is currently mainly achieved by inhibiting pyrite, the most common method of inhibition being to add a large amount of lime to increase the pulp pH to alkalinity. However, the use of a large amount of lime causes severe scaling of the pipes and adversely affects the subsequent wastewater treatment. Therefore, the development of a novel, efficient and selective inhibitor for pyrite is a research focus in the field, and can provide technical support and guarantee for the utilization of the copper-containing sulphide ore. On the other hand, the chalcopyrite has excellent natural floatability, and the recovery rate of more than 85 percent can be realized only by adding a foaming agent. If a novel pyrite selective inhibitor-based copper-iron separation method without a collector is developed, the medicament cost and the treatment difficulty of subsequent beneficiation wastewater are greatly reduced.
Disclosure of Invention
The invention aims to provide a method for inhibiting the flotation of pyrite in minerals, and aims to inhibit the flotation of pyrite in the minerals and improve the separation effect of target minerals and pyrite.
A second object of the present invention is to provide a flotation reagent capable of suppressing flotation of pyrite.
A method for inhibiting floatation of pyrite in minerals comprises subjecting minerals containing pyrite to floatation in a floatation agent containing inhibitor of formula 1 to inhibit floatation of pyrite therein;
said R 1 、R 2 Independently is K + ，H + ，NH 4 + Or Na + ；
Said R 3 、R 4 Independently of H, carboxyl, hydroxyl, C 1 -C 6 Alkyl of (C) 3 -C 6 Cycloalkyl, alkenyl, alkynyl or substituted alkyl of (a);
the substituted alkyl is at C 1 -C 6 The saturated carbon chain of (2) has an alkyl group with a substituent, wherein the substituent is at least one of a hydroxyl group, an amino group, a cyano group, an alkenyl group, an alkynyl group, a carboxylic acid group, an amide group, an ester group, a phenyl group and an ether group.
The research of the invention shows that the compound with the structure shown in the formula 1 can inhibit the floatation of pyrite with high selectivity, and is beneficial to realizing the separation selectivity of target ores and pyrite.
In the present invention, the target ore included in the ore is an ore having a recovery rate of 50% or more in a simple foamer system (also referred to as natural floatable ore in the present invention). The pure frother system refers to a flotation system only containing frother.
Preferably, the target ore is at least one of chalcopyrite, coal, molybdenite and galena; chalcopyrite is preferred.
In the invention, the inhibitor of the formula 1 has excellent inhibiting effect on pyrite and basically has no inhibiting effect on the floating of target ores, so that the high-selectivity separation of the target ores such as chalcopyrite and pyrite can be realized.
In the inhibitor of formula 1 of the present invention, the α - β bis-SO 3 - The structure of the method is the key for synergistically improving the inhibition effect of the pyrite and improving the separation selectivity of the target ore and the pyrite. The research also finds that R 3 、R 4 The substituent groups are further controlled, which is favorable for further improving the inhibiting performance of the pyrite and further improving the separation selectivity of the target ore and the pyrite.
In the present invention, the alkyl group is, for example, a straight chain alkyl group or a branched chain alkyl group. The cycloalkyl group is preferably a monocyclic cycloalkyl group having three to six carbon atoms, or a bridged ring or spiro cycloalkyl group having six or more carbon atoms. Substituents of substituted phenyl are, for example, C 1 ～C 3 Alkyl, alkoxy or halogen, etc. In the present invention, the substituted alkyl group is a group having a substituent on the carbon chain of the alkyl group, preferably a group having a substituent on the alkyl group of C1 to C3, the substituent may be a hydroxyl group, a carboxyl group, an amino group or the like, and the substituted alkyl group is, for example, a hydroxyethyl group, a carboxyethyl group or the like.
The research of the inventor also finds that the control of the types of the substituents and the total carbon number is helpful for further improving the intramolecular synergy of the compounds and further improving the separation selectivity of the pyrite and the target ore.
Preferably, in formula 1, R 3 And R 4 The total carbon number in (a) is less than or equal to 7. It was found that at this preferred total carbon number, the inhibition of pyrite and the selectivity of separation from the target ore can be further improved. In addition, it has been found that the compound of formula 1 having a linear substituent contributes to further improvement of the separation selectivity of chalcopyrite and pyrite at the same carbon number as compared to the aromatic ring substituent.
Preferably, R is 3 、R 4 Is alone H, C 1 -C 4 Alkyl of (C) 1 -C 4 At least one of hydroxyalkyl, carboxyethyl and phenyl. Even more preferably, R is 3 Or R 4 Is H or a small carbon chainSubstituents equal to or less than 3 are, for example, methyl, hydroxyethyl or carboxyethyl.
In the present invention, a foaming agent is allowed to be contained in the flotation agent.
The frother may be a frothing component known in the art of flotation, preferably at least one of terpineol, mycophenolic acid, bipyridine, methyl isobutyl carbinol, eucalyptus oil, camphor oil, higher alcohols and synthetic frothers.
In the present invention, the amount of the foaming agent can be adjusted according to the flotation requirement, so as to obtain stable foam, for example, the amount of the foaming agent in the ore pulp for flotation is 1 × 10 -6 mol/L～1×10 -3 mol/L。
In the invention, the flotation reagent can contain or not contain the collector, and the flotation reagent system in the invention preferably does not contain the collector in consideration of the inhibition effect of pyrite and the treatment cost. According to the invention, due to the good inhibition effect of the formula 1 on the pyrite, the flotation of the pyrite can be effectively inhibited, and the high-selectivity separation of the pyrite and the target ore can be realized without a collecting agent.
In the flotation system according to the present invention, it is preferable that at least one of the dispersing agent and the activating agent is not contained.
Preferably, the flotation agent consists of the depressant of formula 1 and a frother. In the invention, the combination of the inhibitor of the formula 1 and the foaming agent can realize the inhibition of the pyrite, and realize the high-selectivity separation of the pyrite and the target ore such as the chalcopyrite.
In the invention, the pH value of the ore pulp in the flotation process is 2-12. In the invention, considering the restraint of pyrite, the sorting selectivity of target ore and the requirement of industrial application, the pH value of the ore pulp in the flotation process is preferably 4-10, and further preferably 6-10.
Preferably, the inhibitor of formula 1 is used in an amount of greater than or equal to 5X 10 during flotation -5 mol/L; preferably 5X 10 -5 mol/L～1×10 -3 mol/L; more preferably 2X 10 -4 mol/L～5×10 -4 mol/L; most preferably 2 to 3X 10 - 4 mol/L. The research finds that under the preferable range, the good inhibition effect of the pyrite can be ensured, and the inhibition of the target ore can be reduced, so that the separation selectivity of the target ore and the pyrite can be improved.
The invention also provides a preferable selective separation method of the chalcopyrite and the pyrite, which comprises the step of carrying out flotation on mixed ores containing the chalcopyrite and the pyrite in a flotation agent containing an inhibitor and a foaming agent which are shown in the formula 1 to obtain chalcopyrite concentrate and pyrite tailings. The flotation reagent consists of the inhibitor shown in the formula 1 and a foaming agent. The pH value of ore pulp in the flotation process is 2-12, preferably 4-10, and further preferably 6-10. The inhibitor of formula 1 is used in the pulp of the flotation process in an amount of 5 x 10 or more -5 mol/L; preferably 5X 10 -5 mol/L～1×10 -3 mol/L; more preferably 2X 10 -4 mol/L～5×10 - 4 mol/L; in view of the cost of the drug, it is most preferably 2.5X 10 -4 mol/L。
Chalcopyrite (CuFeS) 2 ) And pyrite are often associated, and selective separation of the two is one of the worldwide problems. Aiming at the problem of selective separation of the chalcopyrite and the pyrite, the invention innovatively adopts the compound with the structure of the formula 1 as a flotation inhibitor of the chalcopyrite, which can specifically identify and bond active iron metal sites on the surface of the chalcopyrite, can inhibit the chalcopyrite with high selectivity, and basically has no inhibition effect on the chalcopyrite, so that the effective separation of the chalcopyrite and the pyrite can be realized under the assistance of other medicaments on the premise of no collecting agent, dispersing agent, activating agent and the like, and the separation selectivity of the chalcopyrite and the chalcopyrite can be further improved under the preferable pH value and medicament dosage; research shows that the difference between the recovery rates of the chalcopyrite and the pyrite is as high as 80%.
In the invention, the inhibitor shown in the formula 1 can be used for inhibiting pyrite flotation based on the existing flotation equipment and means, and the target ore concentrate is obtained.
The invention also provides a flotation reagent for selectively separating the chalcopyrite-pyrite, which consists of a foaming agent and the inhibitor shown in the formula 1. The research of the invention finds that the inhibitor shown in the formula 1 can realize the effective separation of the pyrite and the chalcopyrite under the condition of only compounding a foaming agent and without adding reagents such as a collecting agent and the like.
The invention also provides an application method of the flotation reagent, which is used for flotation of minerals containing chalcopyrite and pyrite, and collecting chalcopyrite concentrate and pyrite tailings, wherein the pH of ore pulp in a flotation stage is 2-12, preferably 4-10, and further preferably 6-10; the inhibitor of formula 1 is used in an amount of greater than or equal to 5X 10 -5 mol/L; preferably 5X 10 -5 mol/L～1×10 -3 mol/L; more preferably 2X 10 -4 mol/L～5×10 -4 mol/L。
Advantageous effects
1. The invention discovers that the compound shown in the formula 1 can unexpectedly specifically inhibit pyrite, is beneficial to improving the flotation separation of the pyrite and other target ores, and can realize the selective separation of the pyrite and floatable target ores such as the chalcopyrite without a collecting agent;
2. with a compound of formula 1, further complexed with R 3 And R 4 The combined control of the method is beneficial to further improving the inhibition selectivity of the pyrite, further improving the separation selectivity of the target ore and the pyrite, and improving the grade and the recovery rate of the target ore product.
3. The pH value in the flotation process and the dosage of the inhibitor in the formula 1 are further controlled, so that the separation effect of the target ore, namely the pyrite, can be further improved; moreover, under the condition, a collecting agent, a dispersing agent and an activating agent are innovatively not used, the flotation agent is only an inhibitor and a foaming agent, the using amount of the flotation agent is small, and the flotation condition is mild and easy to realize. The method not only reduces the cost of flotation, but also reduces the difficulty of subsequent beneficiation wastewater treatment, and saves manpower and material resources to the maximum extent.
4. Under a wide pulp pH (pH is 2-12), the efficient separation of the copper-iron sulfide minerals can be realized by using the pyrite selective inhibitor or the collector-free flotation separation method of the target mineral chalcopyrite-pyrite.
Drawings
FIG. 1 is a flotation scheme used in the examples;
FIG. 2 is a graph of recovery data for example 1;
FIG. 3 is a graph of recovery data for example 2;
FIG. 4 is a chart of recovery and ranking data for example 3;
Detailed Description
The effects of the present invention are illustrated by taking a single mineral of pyrite and chalcopyrite and a mixed sulfide mineral of chalcopyrite-pyrite (iron-copper mixed sulfide mineral) as an example. The following cases, except where specifically stated, the composition of the minerals employed are shown in table 1:
TABLE 1 original grade and origin of minerals
Example 1
In order to verify the separation effect of the inhibitor in the embodiment on chalcopyrite and chalcopyrite single minerals, high-purity chalcopyrite and chalcopyrite pure minerals (the grades are shown in table 1) in Hunan and Hunbei are adopted, the flow shown in the figure 1 is adopted, different sulfurized minerals are inhibited by the inhibitor in the embodiment, only a foaming agent is added for a flotation separation process, the parameters of the flotation process in each group of cases are the same, the type of the foaming agent is terpineol, and the concentration of the foaming agent is 1 × 10 -6 mol/L, differing only in the type of the floated sulphide mineral, thus comparing the flotation and sorting effect of the depressants of this case.
The flotation reagent of the invention: the inhibitor is:
(formula A; see Table 2 for amounts), the blowing agent is terpineol (concentration 1X 10) -6 mol/L)。
The process shown in FIG. 1 is adopted, and the specific operations are as follows: dry-grinding pure mineral ore (particle size of 3-0.5 mm) for 15min (particle size of 0.0740-0.0374mm after grinding, dry-grinding with horizontal ball mill, and grinding concentration of 35-40%), and weighing ground single mineral sample (chalcopyrite or chalcopyrite) for each groupPyrite) 2g is poured into a 40mL flotation tank, 35mL deionized water is added, then the flotation reagent is added, a proper amount of deionized water is supplemented, stirring is carried out for 3min, and terpineol (the concentration in ore pulp is controlled to be 1 x 10) -6 mol/L), stirring for 3min, beginning to scrape bubbles, scraping the bubbles for 3min, scraping the concentrate to a concentrate basin along with foams, leaving tailings in a flotation tank, filtering and drying the concentrate and the tailings, then respectively weighing, calculating the recovery rate, carrying out three parallel groups of experiments in each group, taking an average value and calculating errors (variances), wherein the errors are represented as error bars in the graph.
Figure 2 and table 2 show the recovery of chalcopyrite and pyrite pure minerals for example 1 at different agent dosages. (in the case, the depressor is used as the depressor, the terpineol is used as the foaming agent, other flotation reagents are not added, and the pH value of ore pulp is 7).
Table 2 flotation results of example 1
As can be seen from the results of fig. 2 and table 2, the flotation reagent of the present example has strong selective inhibition ability on pyrite and hardly inhibits chalcopyrite within the dosage range of the tested reagent, which means that the flotation inhibitor of the present example can realize efficient separation of chalcopyrite and pyrite without adding a collecting agent. As the inhibitor concentration increases from 0 to 2.5X 10 -4 mol/L, the inhibitor of the invention gradually enhances the inhibiting effect on the pyrite, obviously reduces the recovery rate of the pyrite to below 10 percent, and has no obvious influence on the recovery rate of the pyrite. When the amount of inhibitor is more than 2.5X 10 -4 After mol/L, the inhibiting effect on the pyrite tends to be stable, the recovery rate of the pyrite is slightly reduced, and the dosage of the inhibitor in the case is 5 multiplied by 10 -4 At mol/L, the recovery rate of the pyrite is reduced to 5 percent, and the recovery rate of the pyrite is still kept above 80 percent, namely 82 percent. In view of the prerequisites for recovering chalcopyrite as much as possible and for keeping the cost of the agent as low as possible, the amount of the agent to be used is preferably 2.5X 10 -4 mol/L, the separation effect of the chalcopyrite and the pyrite is excellent, the recovery rate of the chalcopyrite reaches 87 percent, and the pyrite is separatedThe recovery of (A) was only 7%, the difference being 80%. This shows that the inhibitor of the invention has further enhanced inhibiting ability on pyrite with the increase of the dosage of the medicament, and has very weak inhibiting effect on the pyrite, 2.5 multiplied by 10 -4 mol/L is selected as the preferred dose for subsequent experiments and testing.
Example 2
In this case, the performance of the inhibitor at different pH was studied, specifically:
the flotation reagent of the invention: the inhibitor is:
(formula A; dosage is 2.5X 10 -4 mol/L) and the foaming agent is terpineol (the concentration is 1 multiplied by 10) -6 mol/L)。
The pure ore of the yellow iron ore in Hunan province or the yellow copper ore in Hubei province is adopted (the grade is shown in the table 1). By adopting the flow shown in the figure 1, the flotation process parameters are the same, and the difference is only that different types of sulfide mineral single minerals and different pulp pH values are adopted, so that the flotation separation effect of the inhibitor on lead-iron sulfide minerals under different pH values is compared.
The process shown in FIG. 1 is adopted, and the specific operations are as follows: dry-grinding pure mineral ore (with particle size of 3-0.5 mm) for 15min (with particle size of 0.0740-0.0374mm after grinding), and dry-grinding with horizontal ball mill to obtain medium filling rate of 30-40%. Weighing 2g of ground single mineral sample in each group, pouring the single mineral sample into a 40mL flotation tank, adding 35mL deionized water, and adding a flotation reagent, wherein the use amounts of the collecting agents in the ore pulp are 2.5 multiplied by 10 -4 Adding deionized water at mol/L, stirring for 3min, adding pH regulator (sulfuric acid or sodium hydroxide) to adjust the flotation system to specific pH, stirring for 3min, adding terpineol (concentration of 1 × 10) -6 mol/L) and stirring for 3min, starting foam scraping, wherein foam scraping is carried out for 3min, the concentrate is scraped to a concentrate basin along with foam, tailings are remained in a flotation tank, the concentrate and the tailings are respectively weighed after being filtered and dried, and the recovery rate is calculated.
The pH gradient set for the experiment was: 2,4,6,7,8, 10, 12.
Figure 3 shows the recovery of chalcopyrite or pyrite pure minerals at different pH values for example 2. (this case Zhi)The concentration of the preparation is 2.5 × 10 -4 mol/L, pH regulator sodium hydroxide solution and sulfuric acid solution).
Table 3 flotation results of example 2
It can be seen from example 3 that the inhibitor of the present invention has excellent effect of inhibiting pyrite at pH 2-12, and the recovery rate of pyrite after the inhibitor of the present invention has been inhibited is less than or equal to 10% in this pH range, while the recovery rate of pyrite of the inhibitor of the present invention has no significant effect of inhibiting pyrite, and the recovery rate of pyrite is greater than 80% at pH 2-10 and 75% at pH 12. The difference of the flotation recovery rates of the chalcopyrite and the pyrite is always 74-88% between pH values of 2-12, and the inhibitor and the separation method are proved to have excellent effects and can realize the high-efficiency and high-selectivity separation of the copper-iron sulfide minerals.
The flotation reagent can effectively separate chalcopyrite-pyrite mixed sulphide minerals in a wide acid-base range (the pH value is between 2 and 12). In consideration of the problem of subsequent beneficiation wastewater treatment, in order to meet the concept of green mines, neutral pulp condition (pH 7) is selected as the preferable pulp pH, under the condition, even if collecting agents are not added, the flotation agent can recover 87% of chalcopyrite, and simultaneously recover 7% of the pyrite, and the difference between the two is as high as 80%.
Example 3
To verify the separation effect of the flotation reagent in the case of iron-copper mixed sulfide minerals, pyrite or chalcopyrite pure minerals (grades as shown in table 1) in the south and north of a lake are adopted according to the proportion of 1: 1 proportion to obtain the iron-copper mixed sulfide mineral, and adopting the flow shown in figure 1.
The flotation reagent of the invention: the inhibitor is:
(formula A; see Table 2 for amounts), the blowing agent is terpineol (concentration 1X 10) -6 mol/L), and the pH value of the flotation pulp is 4/7/10.
The specific operation is as follows: dry grinding mixed ores (1: 1 of pyrite and chalcopyrite, 3-0.5 mm in particle size) for 15min (0.0740-0.0374 mm in particle size after grinding, dry grinding by adopting a horizontal ball mill, and 30-40% in medium filling rate), weighing 2g of mixed ore samples which are ground and uniformly mixed according to a proportion in each group, pouring the 2g of mixed ore samples into a 40mL flotation tank, adding 35mL of deionized water, adding the inhibitor of the invention, supplementing a proper amount of deionized water, wherein the concentration of the inhibitor is 2.5 multiplied by 10 -4 mol/L, pH of the ore pulp is 4/7/10; stirring for 3min, adding terpineol (concentration of 1 × 10) -6 mol/L), stirring for 3min, starting to scrape bubbles, scraping the bubbles for 3min, scraping the concentrate to a concentrate basin along with foams, leaving tailings in a flotation tank, filtering and drying the concentrate and the tailings, then weighing the concentrate and the tailings respectively, detecting the grade of the concentrate and calculating the recovery rate.
Fig. 4 and table 4 show the recovery of chalcopyrite and pyrite and the grades of Cu and Fe (in pyrite) in the mixed ore mineral of example 3. (in the present case, the concentration of the inhibitor is 2.5X 10 -4 mol/L, pH 4/7/10)
Table 4 flotation results of example 3
As can be seen from the results of FIG. 4 and Table 4, when the concentration of the inhibitor was 2.5X 10 -4 At mol/L, the flotation reagent has better separation effect on chalcopyrite and pyrite mixed minerals under the conditions of pH 7 and 10 than under the condition of pH 4. Under the conditions of pH 7 and pH 10, the inhibitor and the flotation reagent have far stronger inhibiting capability on pyrite (the recovery rate is lower than 25 percent and the grade is lower than 9 wt.%) of iron-copper mixed sulfide minerals than the inhibiting effect on chalcopyrite (the recovery rate is higher than 93 percent and the grade is higher than 19 wt.%). According to the flotation result, the flotation reagent of the invention obviously improves the flotation separation effect of the chalcopyrite and the pyrite,the recovery rate and grade of useful mineral chalcopyrite are also obviously improved, and the recovery rate and grade are respectively as high as 95.8% and 23 wt% at the pH value of 7.
Example 4
In order to verify the influence of the regulating substituent in the inhibitor structure on the separation effect of the iron-copper mixed sulfide minerals, the compounds of the formula 1 with different structures are selected as the inhibitors, and the pyrite or the chalcopyrite pure minerals (the grade is shown in table 1) in the south of the lake and the north of the lake are still adopted according to the proportion of 1: 1 proportion to obtain the iron-copper mixed sulfide mineral, and adopting the flow shown in figure 1.
Flotation reagent: the following inhibitors (all concentrations in the pulp are 2.5X 10) -4 mol/L) and frother (concentration in pulp is 1X 10) -6 mol/L)；
Experimental group 1: inhibitor a:
experimental group 2: inhibitor b:
experimental group 3: and (3) inhibitor c:
experimental group 4: inhibitor d:
experimental group 5: inhibitor e:
experimental group 6: inhibitor f:
experimental group 7: the inhibitor g is chitosan
The inhibitor concentration in each group was 2.5X 10 -4 mol/L terpineol as foaming agent (concentration)Is 1 × 10 -6 mol/L), and the pH value of flotation pulp is 7.
The specific operation is as follows: dry grinding pure mineral ore (particle size of 3mm-0.5mm) for 15min (particle size of 0.0740-0.0374mm after grinding, dry grinding by adopting a horizontal ball mill, and medium filling rate of 30-40%), weighing 2g of mixed ore samples which are ground and uniformly mixed according to a proportion in each group, pouring the 2g of mixed ore samples into a 40mL flotation tank, adding 35mL of deionized water, adding the flotation reagent, supplementing a proper amount of deionized water, and adding the concentration of the inhibitor which is 2.5 multiplied by 10 -4 mol/L, pH of ore pulp is 7; stirring for 3min, adding terpineol (concentration of 1 × 10) -6 mol/L), stirring for 3min, starting foam scraping, performing foam scraping for 3min, scraping the concentrate to a concentrate basin along with foam, leaving tailings in a flotation tank, filtering and drying the concentrate and the tailings, then weighing the concentrate and the tailings respectively, detecting the grade of the concentrate and calculating the recovery rate.
The specific mixing proportion of the iron-copper sulfide mixed minerals in the series of examples is as follows:
this case of iron-copper sulfurized mixed minerals: 1, the weight ratio of the chalcopyrite to the pyrite is 1: 1, stirring for 5min at room temperature to fully mix the minerals for use, wherein the grades of the components of the iron-copper sulfide mixed mineral in the case are shown in table 1.
Table 5 shows the recovery of the chalcopyrite and pyrite flotation and the grades of Cu and Fe (in pyrite) in the mixed copper iron sulphide minerals of example 4. (in this case, each inhibitor concentration was 2.5X 10 4 mol/L, pH 7)
Table 5 flotation results of example 4
As can be seen from Table 5, when the collector concentration was 2.5X 10 -4 When the mol/L and the pH value are 7, the inhibitor and the compound shown in the formula 1 contained in the flotation reagent have the structures within the limit conditions (the inhibitors a-d) of the invention, and the inhibitor and the flotation reagent have good indexes in the separation of copper-iron sulfide minerals. When the compound structure is out of the range of the present invention (inhibitor e: R) 3 And R 4 Total carbon number of 9(>7) Wherein R is 4 Is a length containing aromatic ringsChain substituent), the product index of the chalcopyrite concentrate obtained by separating the iron sulfide minerals is obviously reduced.
As can be seen from the test results, R 3 And R 4 The less the total carbon, the better the index of the chalcopyrite concentrate product obtained by separating the iron sulfide minerals, R 3 And R 4 The sorting effect is best for H. The combination of the above results shows that the inhibitor and the flotation reagent have very remarkable effect on the separation of the chalcopyrite and the pyrite, and the indexes of chalcopyrite concentrate products can be further improved by regulating and controlling substituent groups in the inhibitor compound.
From experimental group 6, it can be seen that when the disulfonic acid group is changed to the monosulfonic acid group, the inhibition effect is greatly reduced, the compound is converted from a pyrite inhibitor to a pyrite collector, the recovery rate of the pyrite suddenly rises to 78.8%, and the grade of the pyrite in the flotation concentrate is indirectly reduced to 18.6 wt.%. As can be seen from the experimental group 7, compared with the traditional macromolecular organic inhibitor chitosan of pyrite, the inhibitor of the invention has more excellent inhibition selectivity, can selectively inhibit pyrite in a copper-iron system, and has no obvious influence on the recovery rate of the pyrite. The traditional macromolecular inhibitor has poor inhibition selectivity, inhibits chalcopyrite while inhibiting pyrite, and causes the recovery rate and grade of the chalcopyrite in flotation concentrate to be reduced simultaneously.
Claims (10)
1. A method for inhibiting the flotation of pyrite in minerals, characterized by, carry on flotation in the mineral comprising pyrite in the flotation reagent comprising depressor of formula 1, inhibit the flotation of pyrite among them;
said R 1 、R 2 Independently is K + ，H + ，NH 4 + Or Na + ；
R is as described 3 、R 4 Independently of one another, H, carboxyl, hydroxyl, C 1 -C 6 Alkyl group of (A) or (B),C 3 -C 6 Cycloalkyl, alkenyl, alkynyl or substituted alkyl of (a);
the substituted alkyl is at C 1 -C 6 The saturated carbon chain of (2) has an alkyl group with a substituent, wherein the substituent is at least one of a hydroxyl group, an amino group, a cyano group, an alkenyl group, an alkynyl group, a carboxylic acid group, an amide group, an ester group, a phenyl group and an ether group.
2. The method of claim 1, wherein the minerals comprise a target mineral having a recovery of 50% or greater in a frother system;
preferably, the target ore is at least one of chalcopyrite, coal, molybdenite and galena; chalcopyrite is preferred.
3. The method of claim 1 or 2, wherein in formula 1, R is 3 、R 4 Is less than or equal to 7.
4. The method of claim 3, wherein R is 3 、R 4 Is alone H, C 1 -C 4 Alkyl of (C) 1 -C 4 At least one of hydroxyalkyl, carboxyethyl and phenyl.
5. The method of claim 1 or 2, wherein the flotation reagent comprises a frother;
preferably, the foaming agent is at least one of terpineol, methyl phenolic acid, heavy pyridine, methyl isobutyl carbinol, eucalyptus oil, camphor oil, higher alcohols and synthetic foaming agents.
6. The method of claim 5, wherein the frother is present in the slurry being floated at a level of 1 x 10 -6 mol/L～1×10 -3 mol/L。
7. The method of claim 5, wherein the flotation agent is free of collector;
preferably, the flotation reagent does not contain at least one of a dispersant and an activator;
preferably, the flotation agent consists of the depressant of formula 1 and a frother.
8. The method according to any of the claims 1 to 7, characterized in that the pulp pH of the flotation process is 2 to 12, preferably 4 to 10, more preferably 6 to 10.
9. The process of any of claims 1 to 8, wherein the inhibitor of formula 1 is used in an amount of 5 x 10 or more during the flotation process -5 mol/L; preferably 5X 10 -5 mol/L～1×10 -3 mol/L; more preferably 2X 10 -4 mol/L～5×10 -4 mol/L。
10. A flotation reagent for selective separation of chalcopyrite-pyrite, characterized by consisting of a frother and the inhibitor of formula 1 according to any one of claims 1 to 9.
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