CN115213016A - Flotation recovery method for sulfide ore in cyanidation tailings - Google Patents

Flotation recovery method for sulfide ore in cyanidation tailings Download PDF

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CN115213016A
CN115213016A CN202110418858.XA CN202110418858A CN115213016A CN 115213016 A CN115213016 A CN 115213016A CN 202110418858 A CN202110418858 A CN 202110418858A CN 115213016 A CN115213016 A CN 115213016A
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flotation
ore
organic polyamine
cyanidation tailings
sulfide
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曹亦俊
曹世明
李景超
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Zhengzhou University
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Zhengzhou University
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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
    • B03D1/018—Mixtures of inorganic and organic compounds
    • 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
    • B03D1/14—Flotation machines
    • 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
    • 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
    • B03D2201/02—Collectors
    • 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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  • Engineering & Computer Science (AREA)
  • Biotechnology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a flotation recovery method of sulfide ore in cyanidation tailings, belongs to the technical field of cyanidation tailings treatment, and solves the problem that the sulfide ore in the cyanidation tailings is difficult to recycle in the prior art. The flotation recovery method takes hydrophobic organic polyamine as polydentate ligand to react with Fe in aqueous solution 2+ Or Cu + Stirring to react to obtain hydrophobic organic polyamine-metal ion complex; and (3) treating the cyanided tailings by using the hydrophobic organic polyamine-metal ion complex, and then performing flotation to obtain the sulfide ore. The method effectively realizes cyanidation tailAnd (4) recycling sulfide ores in the slag.

Description

Flotation recovery method for sulfide ore in cyanidation tailings
Technical Field
The invention belongs to the technical field of cyanidation tailing treatment, and particularly relates to a flotation recovery method of sulfide ore in cyanidation tailing.
Background
Among the many methods and processes for gold dressing and metallurgy, cyanidation leaching extraction is the main method for gold dressing and metallurgy in the world. However, the drawback of the cyanidation method is also obvious, a large amount of cyanidation tailings are generated in the gold extraction process of the cyanidation method, the mineral composition of the cyanidation tailings is complex, and the cyanidation tailings contain a certain amount of valuable elements such As Fe, S, cu, pb, zn, sb, as, si and the like, highly toxic CN & residual pollution agents besides low-grade Au and Ag, and are high-pollution metallurgical waste residues with high comprehensive utilization value.
The current cyanide tailings treatment mode in China is simple stacking or landfill, a large amount of valuable elements are wasted, and the economic loss caused by stacking, pollution and treatment reaches billions yuan every year. The piling up of the cyanidation tailings inevitably causes serious influence on the environment, such as large land occupation, waste of mineral resources and residue of highly toxic CN - Causing pollution to river soil and influencing ecological environment.
The cyanidation tailings subjected to the multi-element recovery treatment also contain a large amount of sulfide ores (generally containing 19 to 30 percent of sulfur), but because of the spontaneous aggregation effect of fine-grained minerals and a large amount of CN (carbon nitride) after the treatment of a plurality of working procedures - The existence of the inhibitor has an inhibiting effect on the floatability of the sulphide ores, and brings great difficulty for enriching and separating the sulphide ores in the cyanidation tailings. At present, certain enterprises in China simply add sulfuric acid into ore pulp for treatment, toxic HCN gas can be generated by the method, environmental pollution can be caused, and the harm to the body of workers is large in the treatment process; at present, xanthate is often used as a collector for flotation, but the flotation effect is extremely poor due to the inhibition effect of cyanide on sulfide ore; therefore, the recovery rate of the sulfide ore is low, the treatment cost of enterprises is high, a large amount of resources are wasted, and the efficient recovery of the sulfide ore in the cyanidation tailings is not facilitated. Therefore, how to efficiently separate the sulfide ores in the cyanidation tailings becomes an urgent problem to be solved.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a flotation recovery method for sulfide ore in cyanidation tailings, so as to solve the problem that the sulfide ore in the cyanidation tailings is difficult to recycle.
The invention is mainly realized by the following technical scheme:
the invention provides a flotation recovery method of sulfide ore in cyanidation tailingsThe flotation recovery method prepares hydrophobic organic polyamine-metal ion complexes by using hydrophobic organic polyamines as polydentate ligands, wherein the metal ions comprise: fe 2+ Or Cu + (ii) a And (3) treating the cyanidation tailings by using the hydrophobic organic polyamine-metal ion complex, and then performing flotation to obtain the sulfide ore.
Further, the flotation recovery method comprises the following steps:
step 1: hydrophobic organic polyamine is used as polydentate ligand to react with Fe in aqueous solution 2+ Or Cu + Stirring for reaction, wherein the reaction product is a solution containing hydrophobic organic polyamine-metal ion complex;
step 2: preparing cyaniding tailings into ore pulp with the mass concentration of 20-45%, and adjusting the pH of the ore pulp to 7-9;
and 3, step 3: adding the reaction product obtained in the step (1) into the ore pulp obtained in the step (2), and stirring for reaction to obtain mixed ore pulp;
and 4, step 4: and introducing the mixed ore pulp into flotation equipment for flotation to obtain floated sulfide ore.
Further, the main components of the cyanidation tailings comprise: sulfide minerals and gangue minerals.
Further, the hydrophobic organic polyamine has the following characteristics:
containing more than two-NH groups in the molecular structure 2 and/or-NH-structure;
the molecular structure also contains a hydrophobic structure, and the hydrophobic structure comprises an aromatic group or a C4-C20 alkyl group.
Further, the hydrophobic organic polyamine is alkyl polyamine ether or tetradecyl diamine.
Further, in the step 1, hydrophobic organic polyamine and Fe 2+ Or Cu + In a molar ratio of 1 to 3.
Further, in the step 3, the addition amount of the reaction product is 80-200g/t Mine 。
Further, in the step 3, the stirring reaction time is 3-15min.
Further, the flotation recovery method adopts a flotation recovery system of sulfide ore in cyanidation tailings, and the flotation recovery system of sulfide ore in cyanidation tailings comprises an accurate chemical feeder, a reagent pre-mixing reaction stirring barrel, an ore pulp stirring barrel and flotation equipment; a peristaltic pump is arranged between the medicament pre-mixing reaction stirring barrel and the ore pulp stirring barrel; and a slurry pump is arranged between the ore pulp stirring barrel and the flotation equipment.
Further, the precise dosers comprise a first precise doser and a second precise doser; the first precise doser is used for adding metal ions into the reagent premixing reaction stirring barrel, and the second precise doser is used for adding organic polyamine into the reagent premixing reaction stirring barrel.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) According to the flotation recovery method of the sulphide ore in the cyanidation tailings, metal ions and hydrophobic organic polyamine are mixed and reacted to generate a hydrophobic organic polyamine-metal ion complex, one end of ammonia/amino-metal ions in the hydrophobic organic polyamine-metal ion complex and a cyanide component on the surface of sulphide minerals are subjected to a complex reaction, and an organic polyamine-metal ion-metal cyanide complex is generated on the surface of the minerals, so that the organic polyamine-metal ion-metal cyanide complex is selectively adsorbed on the surface of the sulphide ores, and the inhibition effect of cyanide on sulphide ore flotation is eliminated; and one end of the hydrophobic group faces to the solution, so that the surface of the mineral is hydrophobic, and the flotation separation of sulfide minerals and gangue minerals is realized in the flotation process. The sulfide ore obtained by the method has high sulfur grade and recovery rate.
2) The hydrophobic organic polyamine-metal ion complex can also react with residual free cyanide in ore pulp to generate precipitate, so that the interference of the residual cyanide on the flotation of sulfide ore is eliminated, and the harm to the environment is also solved.
3) The flotation recovery system is provided with a medicament pre-mixing reaction stirring barrel and Fe 2+ Or Cu + Firstly, introducing the ionic and hydrophobic organic polyamine into a medicament premixing reaction stirring barrel, carrying out full mixing reaction under proper conditions, introducing the reaction product into ore pulp, and stirringMixing the pulp in a barrel; the interference of the complex environment in the ore pulp on the reaction between the reagents is avoided, and the action efficiency of the flotation reagents is increased.
4) The existing method for recovering sulfide ore from cyanidation tailings usually needs to add sulfuric acid into ore pulp, and the process can generate highly toxic cyanide gas (HCN); in the flotation method, metal ions and organic polyamine are reacted in a reagent pre-mixing reaction stirring barrel to generate a flotation reagent organic polyamine-metal ion complex capable of being selectively adsorbed on the surface of sulfide ore, so that no dangerous product is generated; in addition, the agent can also precipitate residual cyanide in the original cyanidation tailings, thereby eliminating the original potential safety hazard of the cyanidation tailings and having higher environmental friendliness.
5) The reagent pre-mixing reaction stirring barrel, the ore pulp stirring barrel and the flotation equipment of the flotation recovery system are arranged in a modularized manner, so that the reagent pre-mixing reaction stirring barrel, the ore pulp stirring barrel and the flotation equipment can be combined and adjusted conveniently according to the production practice of different mines; and a reasonable flotation process is designed, so that the high-efficiency recovery of the sulfide ore is realized. The system has the characteristics of less equipment, short flow, low operation cost, small maintenance difficulty and less investment.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a schematic view of the overall construction of the flotation recovery system of the present invention;
FIG. 2 is a schematic view of the overall construction of the flotation plant of the present invention;
FIG. 3 is one of the structural formulas of the hydrophobic organic polyamine of the present invention;
FIG. 4 is a second structural formula of the hydrophobic organic polyamine of the present invention;
FIG. 5 is a third structural formula of the hydrophobic organic polyamine of the present invention.
Reference numerals:
1-an accurate doser, 2-a medicament pre-mixing reaction stirring barrel, 3-a peristaltic pump, 4-a pulp stirring barrel, 5-a slurry pump, 6-a flotation device, 7-an overflow port, 8-a underflow port, 9-a feed port and 10-a bubble generator.
Detailed Description
A process for the flotation recovery of sulphide ores from cyanidation tailings is described in further detail below with reference to specific examples, which are provided for purposes of comparison and explanation only and to which the present invention is not limited.
The invention provides a flotation recovery method of sulfide ore in cyanidation tailings, which takes hydrophobic organic polyamine as a polydentate ligand to prepare a hydrophobic organic polyamine-metal ion complex, wherein the metal ions comprise: fe 2+ Or Cu + (ii) a And (3) treating the cyanided tailings by using a hydrophobic organic polyamine-metal ion complex, and then performing flotation to obtain the sulfide ore.
Specifically, the flotation recovery method of the sulphide ore in the cyanidation tailings comprises the following steps:
step 1: hydrophobic organic polyamine is used as polydentate ligand to react with Fe in aqueous solution 2+ Or Cu + Stirring for reaction, wherein the reaction product is a solution containing hydrophobic organic polyamine-metal ion complex;
and 2, step: preparing cyaniding tailings into ore pulp with the mass concentration of 20% -45%, and adjusting the pH of the ore pulp to 7-9;
and 3, step 3: adding the reaction product obtained in the step 1 into the ore pulp obtained in the step 2, wherein the addition amount of the reaction product obtained in the step 1 is 80-200g/t Mine (ii) a Stirring and reacting to obtain mixed ore pulp;
and 4, step 4: and introducing the mixed ore pulp into flotation equipment, and introducing air for flotation to obtain floated sulfide ore.
Specifically, the cyanidation tailings mainly comprise the following components: pyrite, chalcopyrite, galena, sphalerite and other sulfide minerals and quartz, aluminosilicate and other gangue minerals. Wherein the sulfur grade is 10-35%.
Specifically, in the step 1, the hydrophobic organic polyamine has the following characteristics:
1. the molecular structure containing more than two-NH groups 2 and/or-NH-structure;
2. the molecular structure also contains a hydrophobic structure, and the hydrophobic structure comprises C4-C20 alkyl or aromatic groups.
Specifically, the hydrophobic organic polyamine can be alkyl polyamine ether, the alkyl can be a hydrocarbon chain containing four to twenty carbon atoms, and the molecule contains one to four ammonia/amino groups; specifically, the alkyl polyamine ether may be dodecyl diamine ether or hexadecyl triamine ether. Exemplary, e.g. N 1 - (2- (decyloxy) ethyl) -1, 2-ethanediamine, N 1 - (2-aminoethyl) -N 2 - (3-tridecyloxy) propyl) -1, 2-ethylenediamine, and the like.
Specifically, in the step 1, the hydrophobic organic polyamine may be N-tetradecyl-1, 3-propyldiamine or the like.
Specifically, in step 1, the hydrophobic organic polyamine may be:
CH 3 -(CH 2 ) 9 -O-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH 2
or
CH 3 -(CH 2 ) 12 -O-(CH 2 ) 3 -NH-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH 2
Or
CH 3 -(CH 2 ) 13 -NH-(CH 2 ) 3 -NH 2
Specifically, in the step 1, the hydrophobic organic polyamine and Fe 2+ Or Cu + Too large molar ratio of (A) can cause incomplete coordination reaction and low complex yield; too low a molar ratio can result in excess metal ions interfering with subsequent flotation. Thus, control of the hydrophobicity of the organic polyamine with Fe 2+ Or Cu + In a molar ratio of 1 to 3.
Specifically, the aboveIn step 1, fe 2+ Can be FeCl 2 ，Cu + The source of (b) may be CuCl.
Specifically, in the step 1, the mass fraction of the hydrophobic organic polyamine in water is 1-20%.
Specifically, in the step 1, too short stirring reaction time may result in insufficient reaction, and too long stirring reaction time may result in increased energy consumption. Therefore, the stirring reaction time is controlled to be 2-15min; exemplary, such as 3min, 5min, 7min, 10min, 12min, 15min.
Specifically, in the step 2, too high mass concentration of the ore pulp can cause that the flotation reagent is difficult to effectively disperse and react in the ore pulp, and the gangue entrainment phenomenon is serious in the subsequent flotation process; too low a slurry concentration can result in reduced system capacity and reduced flotation recovery. Therefore, the mass concentration of the ore pulp is controlled to be 20-45%; exemplary, such as 20%,25%,30%,35%,40%,45%.
In particular, in step 2 above, the pH is controlled to be between 7 and 9 (e.g. 7, 7.5, 8, 8.5, 9) in order to provide a suitable solution environment for the interaction between the flotation reagent and the mineral surface.
Specifically, in the step 3, too long stirring time can cause desorption of part of the organic polyamine-metal ion complex adsorbed on the surface of the sulfide ore, and mechanical stirring energy consumption can be increased; and the stirring time is too short, which can affect the full adsorption of the organic polyamine-metal ions on the mineral surface. Thus, the stirring reaction time is controlled to be 3 to 15min, illustratively, 3min, 5min, 7min, 10min, 12min, 15min.
Specifically, the principle of the flotation recovery method of sulfide ore in cyanidation tailings is as follows:
in step 1, the organic polyamine contains-NH 2 or-NH-contains an unshared pair of electrons on the N atom, so that the organic polyamine can give out a lone pair of electrons in a chemical reaction; metal ions such as Fe 2+ Or Cu + Can accept lone pair electrons; thus, organic polyamines as polydentate ligands with Fe as central atom 2+ Or Cu + Can generate inverseShould form organic polyamine-metal ion complexes, such as [ Fe (C) 14 H 32 N 2 O)] + 、[Cu(C 20 H 45 N 3 O) 2 ] + 、[Cu(C 17 H 38 N 2 ) 2 ] + And so on.
In the step 3, the organic polyamine-metal ion complex is added into the ore pulp of the cyanidation tailings, and can react with the hydrophilic cyanogen component on the surface of the sulfide mineral (in cyanidation gold extraction operation, the cyanides change the surface property of the sulfide mineral and generate cyanogen-containing components on the surface of the sulfide mineral), so that the organic polyamine-metal ion-cyanogen complex is generated on the surface of the mineral. Wherein one end of ammonia/amino-metal ions in the organic polyamine-metal ion complex reacts with a cyanogen component on the surface of the sulphide ore, so that the complex is adsorbed on the surface of the sulphide ore, and one end of a hydrophobic group faces to the solution, so that the surface of the mineral is hydrophobic.
Specifically, in untreated cyanidation tailings, the surface of all mineral particles (including sulfide minerals and gangue minerals) appears hydrophilic. In the above step 3, the sulfide ore surface is hydrophilic with a cyanogen component (e.g., [ Fe (CN) ]) 6 ] 4- 、Fe 4 [Fe(CN) 6 ] 3 And the like) and the hydrophobic organic polyamine-metal ion complex generated in the step 1 are subjected to a complex reaction, so that the complex is adsorbed on the surface of the sulphide ore, and the surface of the sulphide ore is hydrophobic; therefore, during the flotation process in the step 4, the hydrophobic sulfide ore can be adhered to the air bubbles and rise into the foam layer along with the air bubbles, and the hydrophilic gangue minerals are left in the ore pulp, so that the flotation separation of the sulfide ore and the gangue minerals is realized. On the other hand, a small amount of free cyanide remains in the flotation pulp of the cyanidation tailings, and although the concentration of the free cyanide is extremely low (mg/L grade), the flotation of sulfide ores can be remarkably inhibited; the hydrophobic organic polyamine-metal ion complex can also react with residual free cyanide in the ore pulp to generate solid precipitate, so that the inhibiting effect of the cyanide on the sulphide ore is eliminated, the flotability of the sulphide ore is improved, and the recovery rate of the sulphide ore is improved.
On the other hand, the invention also provides a flotation recovery system of sulphide ore in cyanidation tailings, which comprises an accurate doser 1, a medicament pre-mixing reaction stirring barrel 2, an ore pulp stirring barrel 4 and flotation equipment 6; a peristaltic pump 3 is arranged between the reagent premixing reaction stirring barrel 2 and the ore pulp stirring barrel 4; a slurry pump 5 is arranged between the ore pulp stirring barrel 4 and the flotation equipment 6; the precise doser 1 comprises a first precise doser and a second precise doser; the first precise doser is used for adding metal ions into the medicament premixing reaction stirring barrel 2, the second precise doser is used for adding organic polyamine into the medicament premixing reaction stirring barrel 2, and the metal ions and the organic polyamine can react in the medicament premixing reaction stirring barrel 2 to generate an organic polyamine-metal ion complex.
In particular, the flotation device 6 comprises a flotation column and/or a flotation machine. As shown in fig. 3 below, illustrated as a flotation column: the top of the flotation equipment 6 is provided with an overflow port 7 and a feed port 9, the bottom of the flotation equipment is provided with a underflow port 8, and the lower part of the flotation equipment 6 is provided with a bubble generator 10.
In order to provide the maximum supply of bubbles and water flow, the height H of the bubble generator 10 from the underflow port 8 1 Too large results in too small rising path of bubbles from the bubble generator 10, reduced probability of collision between the bubbles and particles in the ore pulp, and reduced flotation effect; h 1 When the size of the ore pulp is too small, the ore pulp with high concentration at the bottom can block rising water flow and bubbles, so that the separation effect is reduced; thus, the height H of the bubble generator 10 from the underflow port 8 is controlled 1 Is 1/4 to 1/3 of the total height H of the flotation device 6, preferably H 1 Is 1/3H.
Specifically, the organic polyamine-metal ion complex can be added into an ore pulp stirring barrel 4 through a peristaltic pump 3, and the ore pulp stirring barrel 4 is filled with cyaniding tailing ore pulp which is formed by mixing cyaniding tailing and supplemented clear water and has the mass concentration of 20% -45% (such as 25%,30%,35%,40% and 45%); other flotation reagents such as organic polyamine-metal ion complexes, pH regulators and the like are fully mixed with mineral particles in the ore pulp stirring barrel 4 for reaction and size mixing, and in the process, the organic polyamine-metal ion complexes are selectively adsorbed on the surface of sulphide ores in cyanidation tailings.
Specifically, cyanide tailing pulp subjected to size mixing in the pulp stirring barrel 4 is fed into the flotation equipment 6 through the pulp pump 5, and in the flotation process of the flotation equipment 6, hydrophobic sulphide ore particles are adhered to bubbles and rise to enter a foam layer, and then overflow from the overflow port 7; the hydrophilic gangue particles cannot float upwards and are discharged as tailings from the underflow port 8 at the bottom of the flotation device 6.
On the other hand, the invention also provides a flotation recovery method for sulphide ore in cyanidation tailings by adopting the flotation recovery system, which comprises the following steps:
step S1: respectively adopting a first precise doser and a second precise doser to mix Fe 2+ Or Cu + Adding ionic and hydrophobic organic polyamine into a medicament containing water, mixing in advance, reacting in a stirring barrel 2, and stirring to react to obtain a reaction product which is a solution containing hydrophobic organic polyamine-metal ion complexes;
step S2: preparing cyaniding tailings into ore pulp with the mass concentration of 20% -45% in an ore pulp stirring barrel 4, and adjusting the pH of the ore pulp to 7-9;
and step S3: adding the reaction product obtained in the step S1 into the ore pulp obtained in the step S2 by adopting a peristaltic pump 3, wherein the addition amount of the reaction product obtained in the step S1 is 80-200g/t Mine (ii) a Stirring and reacting to obtain mixed ore pulp;
and step S4: and introducing the mixed ore pulp into flotation equipment 6 for aeration flotation to obtain floated sulfide ore.
Specifically, in step S4, the step of aeration flotation includes:
step S401, introducing the ore pulp in the ore pulp stirring barrel 4 into a flotation device 6 through a slurry pump 5, introducing air into the ore pulp in the flotation device in a self-suction or air-compressor inflation mode of the flotation device, and generating a large amount of bubbles through a bubble generator 10 or mechanical stirring;
after the step S402 and ventilation, the sulfide mineral particles are adhered to the air bubbles due to the hydrophobic surface and rise into the foam layer along with the air bubbles, and the gangue mineral particles cannot be adhered to the air bubbles and are left in the ore pulp due to the hydrophobic surface. Wherein, the separated sulfide minerals are discharged from an overflow port 7, and gangue minerals are discharged as tailings through a bottom flow port 8.
Specifically, in the step S402, the concentration of the ore pulp is 20-45%, and the flotation time is 10-25min.
Specifically, in the step S402, multiple flotation devices may be used in combination according to different flotation processes, for example, the roughed concentrate enters the second flotation device for fine cleaning, and the roughed tailings enters the third flotation device for scavenging. In order to achieve the best economic and technical indexes, the optimal flotation process flow is generally determined in advance through mineral separation tests aiming at different cyanidation tailings, such as a first-stage roughing flow, a first-stage roughing and first-stage scavenging open-circuit flow, a first-stage roughing and first-stage concentrating and first-stage scavenging closed-circuit flow and the like.
Compared with the prior art, the flotation recovery system provided by the invention is provided with the medicament pre-mixing reaction stirring barrel and Fe 2+ Or Cu + Firstly, introducing the ions and the hydrophobic organic polyamine into a medicament premixing reaction stirring barrel, carrying out full mixing reaction under proper conditions, and introducing the reaction product into an ore pulp stirring barrel for size mixing; the interference of complex environment in the ore pulp to the reaction between the reagents is avoided, and the action efficiency of the flotation reagents is increased.
The existing method for recovering sulphide ore from cyanide tailings usually needs to add sulfuric acid into ore pulp, and the process can generate highly toxic cyanide gas (HCN); in the flotation method, metal ions and organic polyamine are reacted in a reagent pre-mixing reaction stirring barrel to generate a flotation reagent organic polyamine-metal ion complex capable of being selectively adsorbed on the surface of sulfide ore, so that no dangerous product is generated; in addition, the agent can also precipitate residual cyanide in the original cyanidation tailings, thereby eliminating the original potential safety hazard of the cyanidation tailings and having higher environmental friendliness.
The reagent pre-mixing reaction stirring barrel, the ore pulp stirring barrel and the flotation equipment of the flotation system are arranged in a modularized way, so that the reagent pre-mixing reaction stirring barrel, the ore pulp stirring barrel and the flotation equipment can be combined and adjusted conveniently according to the actual production of different mines; and a reasonable flotation process is designed, so that the high-efficiency recovery of the sulfide ore is realized. The system has the characteristics of less equipment, short flow, low operation cost, small maintenance difficulty and less investment.
In the flotation recovery method, the hydrophobic organic polyamine-metal ion complex generated by the mixed reaction of metal ions and hydrophobic organic polyamine can generate a complex reaction with metal cyanide on the surface of the sulfide ore, and the organic polyamine-metal ion-metal cyanide complex is generated on the surface of the mineral, so that the organic polyamine-metal ion-metal cyanide complex is selectively adsorbed on the surface of the sulfide ore, and the inhibition effect of cyanide on the sulfide ore flotation is eliminated. In addition, the flotation reagent can also react with residual cyanide in ore pulp to generate precipitate, so that the interference of the residual cyanide on the flotation of sulfide ores is eliminated, and the harm to the environment is also solved.
Example 1
The embodiment provides a flotation recovery method of sulphide ore in cyanidation tailings, wherein the sulphur grade in the cyanidation tailings is 19.89%, and the main sulphide ore is pyrite, and in addition, a small amount of chalcopyrite is contained; gangue minerals are mainly quartz and silicate minerals. The method comprises the following steps:
(1) FeCl 2 Mixing with alkyl polyamine (N-tetradecyl-1, 3-propyl diamine) in a molar ratio of 1; the reaction product is a solution containing hydrophobic organic polyamine-metal ion complex;
(2) Adjusting the mass concentration of the cyanidation tailing pulp to be 30% and the pH value of the pulp to be 8.5;
(3) Adding the reaction product in the step (1) into cyanidation tailing pulp, wherein the adding amount of the reaction product is 120g/t Mine Stirring and reacting for 10min in a stirring barrel to obtain mixed ore pulp;
(4) And introducing the mixed ore pulp into a flotation column, and performing aeration flotation to obtain sulfur concentrate. Wherein the concentration of the flotation ore pulp is 30 percent, and the flotation time is 15min; the sulphide ore floats upwards with the bubbles and overflows while the gangue minerals remain in the slurry and are subsequently discharged through the underflow opening 8 at the bottom of the flotation column.
By the method, the sulfur concentrate with the sulfur grade of 38.44 percent and the recovery rate of 87.64 percent can be obtained through one-time rough concentration, and the sulfur grade of the tailings is reduced to 4.50 percent.
Specifically, the above steps can be performed in the flotation recovery system for the sulfide ore in the cyanidation tailings, and the detailed steps are not repeated herein.
Example 2
The embodiment provides a flotation recovery method of sulphide ore in cyanidation tailings, wherein the sulphur grade in the cyanidation tailings is 23.38%, the main metal mineral is pyrite, and the second metal mineral is chalcopyrite, and in addition, a small amount of galena and zinc blende are contained; the gangue mineral contains sericite, plagioclase, calcite, etc. in addition to quartz. The method comprises the following steps:
(1) Mixing CuCl and alkyl polyamine ether (N) 1 Mixing (2- (decyloxy) ethyl) -1, 2-ethylenediamine) in an aqueous solution according to a molar ratio of 1; the reaction product is a solution containing hydrophobic organic polyamine-metal ion complex;
(2) Adjusting the mass concentration of the cyanidation tailing pulp to 35% and the pH value of the pulp to 8.0;
(3) Adding the reaction product in the step (1) into cyanidation tailing pulp, wherein the addition amount is 100g/t Mine Stirring and reacting for 10min in a stirring barrel;
(4) And introducing the ore pulp into an inflatable flotation machine, and performing inflatable flotation to obtain sulfur concentrate. Wherein the concentration of the flotation ore pulp is 35 percent, and the flotation time is 20min; the sulphide ore floats upwards with the bubbles and the gangue minerals remain in the slurry and are then discharged through the underflow port 8 at the bottom of the flotation column.
By the method, the sulfur concentrate with the sulfur grade of 36.28 percent and the recovery rate of 87.89 percent can be obtained through once roughing, and the sulfur grade of the tailings is reduced to 6.53 percent.
Specifically, the above steps can be performed in the flotation recovery system for the sulfide ore in the cyanidation tailings, and the detailed steps are not repeated herein.
Example 3
The embodiment provides a flotation recovery method of sulphide ore in cyanidation tailings, wherein the sulphur grade in the cyanidation tailings is 29.54%, and the main metal mineral is pyrite; the gangue minerals are quartz, feldspar, chlorite, kaolinite, etc. The method comprises the following steps:
(1) FeCl is added 2 And alkyl polyamine ethers (N) 1 - (2-aminoethyl) -N 2 - (3-tridecyloxy) propyl) -1, 2-ethylenediamine) with a molar ratio of 1Mixing the solution, and stirring for reaction for 10min; the reaction product is a solution containing hydrophobic organic polyamine-metal ion complexes;
(2) Adjusting the mass concentration of the cyanidation tailing pulp to be 40% and the pH value of the pulp to be 8.5;
(3) Adding the reaction product in the step (1) into cyanidation tailing pulp, wherein the adding amount is 125g/t Mine Stirring and reacting for 15min in a stirring barrel;
(4) And introducing the ore pulp into a flotation column, and performing aeration flotation to obtain sulfur concentrate. Wherein the concentration of the flotation ore pulp is 40 percent, and the flotation time is 15min; the sulphide ore floats upwards with the bubbles and overflows while the gangue minerals remain in the slurry and are subsequently discharged through the underflow opening 8 at the bottom of the flotation column.
By the method, the sulfur concentrate with the sulfur grade of 40.86 percent and the recovery rate of 91.45 percent can be obtained through one-time rough concentration, and the sulfur grade of the tailings is reduced to 7.45 percent.
Example 4
The embodiment provides a flotation recovery method of sulfide ore in cyanidation tailings, wherein the sulfur grade in the cyanidation tailings is 27.66%, wherein the main sulfide ore is pyrite, and the main gangue ore is quartz, plagioclase feldspar and the like. The method comprises the following steps:
(1) Mixing CuCl and alkyl polyamine ether (N) 1 Mixing (2- (decyloxy) ethyl) -1, 2-ethylenediamine) in an aqueous solution according to a molar ratio of 1; the reaction product is a solution containing hydrophobic organic polyamine-metal ion complexes;
(2) Adjusting the mass concentration of the cyanidation tailing pulp to be 40% and the pH value of the pulp to be 8.5;
(3) Adding the reaction product in the step (1) into cyanidation tailing pulp, wherein the addition amount is 150g/t Mine Stirring and reacting for 15min;
(4) And introducing the ore pulp into flotation equipment, and performing aeration flotation to obtain sulfur concentrate. Wherein, the flotation process comprises a closed circuit process of first-stage roughing, first-stage scavenging and first-stage refining, and the flotation equipment adopts a cyclone-static microbubble flotation column. The ore pulp is firstly introduced into a roughing flotation column with the diameter of 4.5m, the roughed concentrate enters the fine concentration, and the roughed tailings enter the scavenging; replenishing 70g/t of flotation agent in the scavenging section, adopting a flotation column with the diameter of 4m, scavenging tailings as final tailings, and returning scavenging concentrate to roughing; the fine separation section is not additionally provided with a flotation agent, a flotation column with the diameter of 4m is adopted, the fine separation tailings and scavenging concentrates return to the rough separation, and the fine separation concentrates are used as final concentrates.
Comparative example 1
The comparative example provides a method for recovering sulfide ores in cyanidation tailings, which comprises the following steps:
(1) Preparing cyaniding tailings into ore pulp with the mass concentration of 40%;
(2) Adding 25Kg/t of sulfuric acid into the ore pulp Mine After stirring and reacting for 20min, adding 500g/t of collecting agent butyl xanthate into the ore pulp, and stirring and reacting for 3min;
(3) And (3) introducing the ore pulp into a cyclone-static microbubble flotation column, wherein the flotation process is the same as that in example 4, the dosage of the scavenging section is 1/2 of that of the roughing section, and no dosage is added in the fine section.
Comparative example 2
The comparative example provides a method for recovering sulfide ores in cyanidation tailings, which comprises the following steps:
(1) Preparing cyaniding tailings into ore pulp with the mass concentration of 40%;
(2) Adding sulfuric acid into the ore pulp to adjust the pH value of the ore pulp to 5.5, stirring and reacting for 20min, then adding 350g/t of collecting agent butyl xanthate into the ore pulp, and stirring and reacting for 3min;
(3) And (3) introducing the ore pulp into a cyclone-static microbubble flotation column, wherein the flotation process is the same as that in example 4, the dosage of the scavenging section is 1/2 of that of the roughing section, and no dosage is added in the fine section.
Comparative example 3
The comparative example provides a method for recovering sulfide ores in cyanidation tailings, which comprises the following steps:
(1) Preparing cyaniding tailings into ore pulp with the mass concentration of 40%;
(2) Adding 40Kg/t of sulfuric acid into the ore pulp, stirring and reacting for 20min, adding 300g/t of collecting agent butyl xanthate and 200g/t of butylamine black pigment into the ore pulp, and stirring and reacting for 3min;
(3) And (3) introducing the ore pulp into a cyclone-static microbubble flotation column, wherein the flotation process is the same as that in example 4, the dosage of the scavenging section is 1/2 of that of the roughing section, and no dosage is added in the fine section.
Table 1 below shows the test results of example 4 and comparative examples 1 to 3
TABLE 1 test results of example 4 and comparative examples 1 to 3
Figure BDA0003027024150000151
As shown in table 1 above, in comparative examples 1-3, the recovery of sulfide ore from cyanidation tailings was not efficient with conventional sulfide ore collectors (xanthate, xanthate + blackant) after the acid decyanation. In example 4, the sulfur grade and recovery of the concentrate were higher than in comparative examples 1-3.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (10)

1. A flotation recovery method for sulfide ore in cyanidation tailings is characterized in that hydrophobic organic polyamine-metal ion complexes are prepared by taking hydrophobic organic polyamine as a polydentate ligand, and the metal ions comprise: fe 2+ Or Cu + (ii) a And (3) treating the cyanided tailings by using the hydrophobic organic polyamine-metal ion complex, and then performing flotation to obtain the sulfide ore.
2. The method for flotation recovery of sulfide ores in cyanidation tailings according to claim 1, wherein the method for flotation recovery comprises:
step 1: hydrophobic organic polyamine is taken as polydentate ligand to react with Fe 2+ Or Cu + Stirring and reacting, wherein the reaction product is a solution containing hydrophobic organic polyamine-metal ion complex;
and 2, step: preparing cyaniding tailings into ore pulp with the mass concentration of 20-45%, and adjusting the pH of the ore pulp to 7-9;
and step 3: adding the reaction product obtained in the step (1) into the ore pulp obtained in the step (2), and stirring for reaction to obtain mixed ore pulp;
and 4, step 4: and introducing the mixed ore pulp into flotation equipment for flotation to obtain floated sulfide ore.
3. The method for flotation recovery of sulphide ores in cyanidation tailings according to claim 1, characterized in that the main components of the cyanidation tailings comprise: sulfide minerals and gangue minerals.
4. The process for the flotation recovery of sulfide ores from cyanidation tailings according to claim 1 wherein the hydrophobic organic polyamine has the following characteristics:
the molecular structure containing more than two-NH groups 2 and/or-NH-structure;
the molecular structure also contains a hydrophobic structure which comprises an aromatic group or a C4-C20 alkyl group.
5. The method for flotation recovery of sulfide ore in cyanidation tailings according to claim 4, characterized in that the hydrophobic organic polyamine is alkyl polyamine ether or tetradecyl diamine.
6. The method of claim 2, wherein in step 1, the hydrophobic organic polyamine and the Fe are selected from the group consisting of 2+ Or Cu + 1-3.
7. The method for flotation and recovery of sulfide ore in cyanidation tailings according to claim 2, characterized in that in the step 3, the addition amount of the reaction product is 80-200g/t Mine 。
8. The method for flotation recovery of sulfide ore in cyanidation tailings according to claim 2, characterized in that in the step 3, the stirring reaction time is 3 to 15min.
9. The flotation recovery method of sulphide ore in cyanidation tailings according to claim 2 to 8 is characterized by adopting a flotation recovery system of sulphide ore in cyanidation tailings, wherein the flotation recovery system of sulphide ore in cyanidation tailings comprises a precise chemical feeder (1), a chemical pre-mixing reaction stirring barrel (2), a pulp stirring barrel (4) and flotation equipment (6); a peristaltic pump (3) is arranged between the reagent pre-mixing reaction stirring barrel (2) and the ore pulp stirring barrel (4); and a slurry pump (5) is arranged between the ore pulp stirring barrel (4) and the flotation equipment (6).
10. The method for flotation recovery of sulphide ores in cyanidation tailings according to claim 9, characterized in that the precision dosers (1) comprise a first precision doser and a second precision doser; the first accurate doser is used for adding metal ions into the reagent premixing reaction stirring barrel (2), and the second accurate doser is used for adding organic polyamine into the reagent premixing reaction stirring barrel (2).
CN202110418858.XA 2021-04-19 2021-04-19 Flotation recovery method for sulfide ore in cyanidation tailings Pending CN115213016A (en)

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