CN107971140B - Dithio non-metal acid salt and oligomer flotation inhibitor thereof as well as preparation and use methods thereof - Google Patents

Dithio non-metal acid salt and oligomer flotation inhibitor thereof as well as preparation and use methods thereof Download PDF

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CN107971140B
CN107971140B CN201711205819.1A CN201711205819A CN107971140B CN 107971140 B CN107971140 B CN 107971140B CN 201711205819 A CN201711205819 A CN 201711205819A CN 107971140 B CN107971140 B CN 107971140B
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oligomer
dithio
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CN107971140A (en
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向平
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Hunan Huaqi Resource Environment Technology Development Co ltd
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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
    • B03D1/0046—Organic compounds containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—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
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/014—Organic compounds containing phosphorus
    • 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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Abstract

A flotation inhibitor for dithio-nonmetallic acid salt and oligomer thereof is composed of the dithio-nonmetallic acid salt and oligomer thereof, and can inhibit the floatation of zinc sulfide ore from iron sulfide ore under the natural pH condition. The dithio-nonmetallic acid salt and the oligomer thereof comprise two molecular structural formulas, wherein the two molecular structural formulas have the structural characteristics of the dithio-nonmetallic acid salt and the oligomer, and the dithio-nonmetallic acid salt is a nonmetallic oxysalt. The inhibitor can be used for inhibiting the zinc sulfide mineral to be floated by the light inhibition method without adding lime in the floatation process, and the pH value of the ore pulp in the operation of floating the zinc sulfide mineral is obviously different from that in the operation of floating the zinc sulfide mineral by adopting lime as the inhibitor of the iron sulfide mineral, and is higher than 12 and is in the neutral range of 6-9.

Description

Dithio non-metal acid salt and oligomer flotation inhibitor thereof as well as preparation and use methods thereof
Technical field:
the invention relates to an inhibitor for a flotation clean production method and a preparation and use method thereof, in particular to an inhibitor for inhibiting pyrite from floating zinc sulfide ore under a natural pH condition and a preparation and use method thereof, which are the inhibitor for inhibiting pyrite from floating zinc sulfide ore under the natural pH condition and the preparation and use method thereof, and belong to the field of mineral processing flotation medicaments.
The background technology is as follows:
there are two common methods for floatation separation of zinc sulfide mineral and iron sulfide mineral at home and abroad, one is a preferential floatation flow carried out according to the operation sequence of firstly floatation of zinc sulfide mineral and then floatation of iron sulfide mineral, in the operation of firstly floatation of zinc sulfide mineral, lime is added firstly to adjust the pH value of ore pulp to be more than 12 so as to inhibit the iron sulfide mineral; in the subsequent operation of flotation of iron sulphide minerals, it is necessary to adjust the pH of the slurry to neutral or even acidic conditions with sulfuric or hydrochloric acid on the floating zinc tailings to activate the inhibited iron sulphide minerals. The other is according to the mixed flotation and separation flow that firstly, zinc sulfide and iron sulfide are floated together, and then the mixed concentrate obtained by the together flotation is separated, in the mixed flotation operation, the flotation is carried out under the condition of not adding lime or adding a small amount of lime; in the following separation flotation operation on bulk concentrates, it is necessary to add a large amount of lime (pH is adjusted to above 12) to the bulk concentrate slurry to suppress the iron sulphide minerals.
According to the two zinc sulfide minerals and the iron sulfide mineral flotation separation methods, lime is used as an inhibitor to inhibit the zinc blende in the iron pyrite flotation. For example, a sequential flotation process of selecting zinc sulfide and then selecting iron sulfide by using lead zinc ore in yellow sand plateau is adopted, the lime consumption is up to 10-13 kg/ton of raw ore, and a process of 'mixed flotation and re-separation' is adopted for lead zinc ore in the Bay of Kangjia at a water gap, and the lime consumption is 5-6 kg/ton of raw ore.
Although the production history of the two flotation separation methods for zinc sulfide minerals and iron sulfide minerals is long, the process is mature and reliable, and a stable separation effect can be obtained, the accompanying disadvantages are numerous, besides the problems that lime milk is difficult to prepare and a pipeline added with the lime milk is easy to scale and block, serious environmental pollution exists, and the main appearance is that:
(1) The tail water pH exceeds the standard. The pH value of the water removed from the zinc sulfide concentrate, the iron sulfide concentrate and the tailings obtained by using a lime process is often more than 12, the pH value is seriously beyond the industrial wastewater discharge standard of pH6-9, and acid is added into the tail water for neutralization at a wastewater treatment station; the improper control of the acid addition often occurs, the pH value of the aqueous solution is adjusted to be less than 6, and the pH value is adjusted to be neutral by adding alkali reversely. Therefore, how to adjust the pH value of the wastewater to the standard range of 6-9 becomes a problem for frequent headache of on-site operators and management staff.
(2) The content of heavy metal ions and COD in the tail water exceeds the standard. The pH value of the water removed by the zinc sulfide concentrate, the iron sulfide concentrate and the tailings obtained by using the lime process is often more than 12, so that the contents of lead, zinc, cadmium, sulfur and other heavy metal pollution factors and COD in the tail water are often out of standard.
In the traditional mine industry, the last decades adopt extensive development modes, and most of the development modes adopt 'end treatment' measures for treating pollution after pollution is generated, but the industry all over the world now increasingly pays attention to clean production, and the environment protection work is advocated to be changed from single end treatment in the past to clean production technology controlled by pollution sources. As lime is used in the flotation separation process of zinc sulfide minerals and iron sulfide minerals, the problem of excessive pollution of heavy metal ions caused by high pH value of tail water is generated, acid addition is adopted for adjusting the tail water in the past, and heavy metal trapping agents are added to remove heavy metal ions and other terminal treatment measures, so that the root causes of the problems are rarely thought, and a great amount of lime is needed to be added while the zinc sulfide mineral trapping agents are added in the production process, so that the flotation separation of the zinc sulfide minerals and the iron sulfide minerals can be realized. Because the production method for carrying out flotation separation on zinc sulfide minerals and iron sulfide minerals by adding lime has long history, mature and reliable process, stable separation effect can be obtained, and the source of lime is wide and the price is low, in the past times of less importance on environmental protection, few people think about replacing lime with other inhibitors. On the other hand, the production method for carrying out flotation separation on zinc sulfide minerals and iron sulfide minerals by adding lime has long history, mature and reliable process, stable separation effect, wide lime source and low price, so in the past times of less importance on environmental protection, few people think about whether pollution source control can be realized without adding lime, and the flotation pollution is increasingly serious, and the improvement is necessary.
Patent documents which do not find the same technology as the present invention through patent search report that the patent with certain relation to the present invention mainly has the following:
1. the invention relates to a patent number CN201210173054.9, and discloses a pyrite inhibitor for low alkalinity, which consists of 40-50 parts by weight of sodium thiosulfate, 40-50 parts by weight of citric acid and 5-15 parts by weight of polyacrylamide, wherein the polyacrylamide is low molecular weight polyacrylamide containing hydroxyl groups, and the molecular weight of the polyacrylamide is 400-600. The inhibitor is prepared by the following method: weighing sodium thiosulfate, citric acid and polyacrylamide, uniformly mixing to prepare an aqueous solution with the weight percentage concentration of 1-5%, and stirring.
2. The patent No. CN201010275649.6, named as a preparation method and application of a copper-zinc sulfide mineral flotation separation inhibitor, discloses a preparation method of a lead-zinc sulfide mineral flotation separation inhibitor, which comprises the steps of adding 200-300 ml of sulfuric acid solution with the volume percentage content of 40-50% into a three-mouth flask with the volume percentage content of 500ml at room temperature, adding 120-150 g of pyrite cinder with the iron content of 40-50% by weight, stirring for 4-6 h at 60 r/min, filtering while the solution is hot to obtain an acid leaching solution, taking 200ml of the acid leaching solution into a three-mouth flask with the volume percentage content of 500ml, adding 50-60 g of iron powder as a reducing agent, heating and refluxing for 1-2 h at 75-85 ℃, filtering while the solution is hot, transferring filtrate into an evaporation vessel, evaporating and concentrating to crystallize at the constant temperature of 75-80 ℃, filtering while the solution is hot, and drying to obtain white powder, namely the zinc sulfide mineral inhibitor.
3. The invention relates to a high-efficiency combined inhibitor for pyrite in complex sulphide ores and an application method thereof, and discloses the high-efficiency combined inhibitor for pyrite in complex sulphide ores, wherein the inhibitor consists of calcium peroxide and sodium humate, adopts a combination mode of the calcium peroxide and the sodium humate, can selectively inhibit complex sulphide ores by matching with complexation of the sodium humate and calcium ions due to strong oxidizing ability of the calcium peroxide, and particularly has better inhibition performance on minerals such as pyrrhotite, pyrite, arsenopyrite and the like, and is a high-selectivity inhibitor.
Although these patents relate to flotation inhibitors of iron sulfide or zinc sulfide and some also to methods of flotation using non-lime, it is known from the reading of these patents that these patents are not relevant to the problem to be solved by the present invention, and the disclosed solutions are more complex than the flotation treatment solutions proposed by the present invention, and the materials used are more difficult to formulate and produce, and thus still need to be further improved.
Disclosure of Invention
Aiming at the problems of the existing flotation separation method for zinc sulfide minerals and iron sulfide minerals, the invention provides an inhibitor for inhibiting the floatation of the zinc sulfide minerals from iron sulfide ores under the condition of natural pH value, which can inhibit the floatation of the zinc sulfide minerals from the iron sulfide ores under the condition of natural pH value, and lime is not needed to be added in the whole flotation process after the inhibitor is used, so that the aim of a clean production process method is fulfilled.
Another object of the present invention is to provide a method for preparing and using the inhibitor for inhibiting the floatation of zinc sulfide ore from iron sulfide ore under the condition of natural pH.
In order to achieve the aim, the invention provides a dithio-nonmetallic acid salt and an oligomer flotation inhibitor thereof, wherein the inhibitor consists of the dithio-nonmetallic acid salt and the oligomer thereof, and can inhibit the floatation of zinc sulfide ore by iron sulfide ore under the condition of natural pH.
Further, the dithio-nonmetallic acid salt and the oligomer thereof comprise two molecular structural formulas, wherein the two molecular structural formulas have the structural characteristics of the dithio-nonmetallic acid salt and the oligomer, and the dithio-nonmetallic acid salt is a nonmetallic oxysalt.
Further, the dithio-nonmetallic acid salt and the molecular structural formula of the oligomer thereof
Figure GDA0001585473770000031
Wherein X is an S atom, a C atom or a Si atom, Y 1 、Y 2 Is H atom, na atom, K atom, or NH 4 A group, but Y 1 、Y 2 At least one of which is not an H atom; n=1, 2, 3 or 4.
Further, the dithio-nonmetallic acid salt and the oligomer thereof have the molecular structural formula:
Figure GDA0001585473770000041
wherein X is a P atom, an As atom, an Sb atom or a Bi atom, Y 1 、Y 2 、Y 3 Is H atom, na atom, K atom, or NH 4 A group, but Y 1 、Y 2 、Y 3 Middle toOne less than an H atom; n=1, 2, 3 or 4.
Further, the dithio nonmetallic acid salt and the oligomer inhibitor thereof are mixture, and the dithio nonmetallic acid salt and the oligomer thereof are mixed with one or more of the monothio nonmetallic acid salt and the oligomer thereof, the trithio nonmetallic acid salt and the oligomer thereof, the tetrathio nonmetallic acid salt and the oligomer thereof according to any weight ratio to obtain a series of compound medicament, so as to respectively achieve the best flotation separation effect of zinc sulfide and iron sulfide mineral aiming at the characteristics of different zinc sulfide and iron sulfide mineral properties.
The preparation and use method of the dithio non-metal acid salt and the oligomer inhibitor thereof comprises the steps of grinding the dithio non-metal acid salt and the oligomer thereof into powder, adding water according to the components of ores containing zinc sulfide and iron sulfide minerals to prepare an aqueous solution inhibitor, and respectively adding the inhibitor in roughing, scavenging and selecting processes of flotation to inhibit the zinc sulfide ores from being floated by the iron sulfide ores.
Further, according to the components of the ore containing zinc sulfide and iron sulfide minerals, the volume percentage concentration of dithio-nonmetal acid salt and oligomer thereof is adjusted according to different characteristics of the ore properties of different zinc sulfide and iron sulfide minerals, so that the optimal flotation separation effect of zinc sulfide and iron sulfide minerals is respectively achieved according to the characteristics of the ore properties of different zinc sulfide and iron sulfide minerals.
Further, the dithio-nonmetallic acid salt and the oligomer thereof have a volume percentage concentration ranging from 40 to 60 percent by volume.
Further, the dithio non-metal acid salt and the oligomer inhibitor thereof are used in neutral environment with pH value of 6-9 for floatation of iron sulfide mineral.
The invention has the advantages that:
1. the inhibitor can be used for inhibiting the zinc sulfide mineral to be floated by the light inhibition method without adding lime in the floatation process, and the pH value of the ore pulp in the operation of floating the zinc sulfide mineral is obviously different from that in the operation of floating the zinc sulfide mineral by adopting lime as the inhibitor of the iron sulfide mineral, and is higher than 12 and is in the neutral range of 6-9.
2. The inhibitor can be used for floatation of iron sulfide minerals by a light activation method without adding sulfuric acid or hydrochloric acid in the floatation process, and the pH value of ore pulp of the operation for floatation of the iron sulfide minerals is obviously different from that of ore pulp of the floatation operation of the iron sulfide minerals after the floatation of the zinc sulfide minerals, which is obviously lower than 6, and is in the neutral range of 6-9.
3. The inhibitor can be used for inhibiting the zinc sulfide mineral by a light inhibition method without adding lime in a flotation process, wherein the pH value of ore pulp of operation for floating the zinc sulfide mineral is in a neutral range of 6-9, so that the pH value of water removal of zinc sulfide concentrate pulp obtained by operation for floating the zinc sulfide mineral is obviously different from the pH value of water removal of zinc sulfide concentrate pulp obtained by operation for floating the zinc sulfide mineral by using lime as a pyrite inhibitor, which is obviously higher than 12, and is in the neutral range of 6-9.
4. The inhibitor of the invention is adopted to float iron sulfide minerals in a light activation mode without adding sulfuric acid or hydrochloric acid in a floatation process, the pH value of ore pulp of operation of floating the iron sulfide minerals is in a neutral range of 6-9, the pH value of water removal of iron sulfide concentrate pulp and tailing pulp obtained by operation of floating the iron sulfide minerals is obviously different from the pH value of water removal of iron sulfide concentrate pulp and tailing pulp obtained by the well-known operation of adding lime to inhibit the iron sulfide minerals to float zinc sulfide minerals and then adding acid to activate the iron sulfide minerals, and the pH value of water removal of the iron sulfide concentrate pulp and the tailing pulp is obviously lower than 6 and is in a neutral range of 6-9.
5. The inhibitor of the invention is adopted, the obtained iron sulfide concentrate pulp in the flotation process is flotation foam pulp, the pulp concentration is up to more than 40%, the method is obviously different from the known method that zinc sulfide and iron sulfide minerals are mixed and floated under the neutral condition that the pH value of the pulp without lime is 6-9, then the mixed concentrate of the zinc sulfide and the iron sulfide minerals is subjected to the inhibition of the iron sulfide minerals under the high alkaline condition that the pH value of the pulp with lime is up to more than 12, the iron sulfide concentrate pulp obtained by the flotation separation process for floating the zinc sulfide minerals is pulp in a tank, and the pulp concentration is as low as below 25%.
The advantages of the invention are expressed in the following aspects:
firstly, lime is eliminated in the whole process, so that the cost of the beneficiation reagent can be saved;
secondly, lime is cancelled in the whole process, and a post for washing and matching lime is not required, so that labor for a factory selection post is saved, and labor resource cost for mineral separation production is reduced;
thirdly, lime is not added in the whole process, so that the problems that lime milk is difficult to prepare, a pipeline added with lime milk is easy to scale and block, and the like, and the production index is influenced are solved;
fourthly, sulfuric acid or hydrochloric acid is not needed to be added in the floatation operation of the iron sulfide minerals, so that the problem that the sulfuric acid and the hydrochloric acid are easy to prepare drugs and are very troublesome to use and examine in certain places is solved;
fifthly, the pH value of the water for removing the concentrate and the tailings is in the neutral range of 6-9 reaching the standard of emission, the heavy metal ion content and the COD content of the water for removing the concentrate and the tailings are lower than those of the water for removing the heavy metal ion content and the COD content of the water by the traditional lime adding process, and even the heavy metal ion content and the COD content of the water for removing the concentrate and the tailings are lower than the emission standard without any treatment.
Detailed Description
The following description of the invention is further illustrated with reference to examples, which are not intended to limit the invention.
Example 1
The preparation example of the medicament comprises the following steps: sodium dithiosulfite Na using dithiononmetallic acid salts and oligomers thereof 2 S 3 O is used as an inhibitor raw material, wherein dithio nonmetallic acid salts are nonmetallic oxygen acid salts.
The dithio non-metal acid salt and the oligomer thereof have the following molecular structural formula:
Figure GDA0001585473770000061
the mixture ratio of the raw materials is as follows: when the inhibitor is prepared, firstly, the required sodium dithiosulfite amount is determined according to the components of ores containing zinc sulfide and iron sulfide minerals, water is added to prepare an aqueous solution with the volume percentage concentration of 40-60% to form an inhibitor aqueous solution, the inhibitor aqueous solution prepared by sodium dithiosulfite is respectively added in the roughing, scavenging and concentrating flotation processes of the ores of the iron sulfide minerals, and the inhibitor is added when the zinc sulfide ore is floated by the inhibiting iron sulfide ores under the natural pH condition, and the pH value of the roughing, scavenging and concentrating processes of the flotation is 8-9.
Example two
The preparation example of the medicament comprises the following steps: dimeric ammonium dithiosulfate (NH) using dithio-nonmetallic acid salts and oligomers thereof 4 ) 4 S 6 O 4 As a raw material of the inhibitor, dithio non-metal acid salts are non-metal oxysalts.
The dithio non-metal acid salt and the oligomer thereof have the following molecular structural formula:
Figure GDA0001585473770000062
when the inhibitor is prepared, firstly, the required amount of the dimeric ammonium dithiosulfate is determined according to the components of ores containing zinc sulfide and iron sulfide minerals, water is added to prepare an aqueous solution with the volume percentage concentration of 40-60%, the inhibitor aqueous solution is formed, the inhibitor aqueous solution prepared by the dimeric ammonium dithiosulfate is respectively added in the roughing, scavenging and concentrating flotation processes of the ores of the iron sulfide minerals, and the inhibitor is added when the zinc sulfide ore is subjected to the flotation of the iron sulfide ores under the natural pH condition, and the pH value of the roughing, scavenging and concentrating processes of the flotation is 8-9.
Example III
The preparation example of the medicament comprises the following steps: the dithio nonmetallic acid salt, the oligomer thereof and other materials are used as raw materials to prepare a dithio nonmetallic acid salt and oligomer inhibitor mixture, and the dithio nonmetallic acid salt, the oligomer thereof, one or a mixture of a monothio nonmetallic acid salt, the oligomer thereof, a trithio nonmetallic acid salt, a tetrathio nonmetallic acid salt, the oligomer thereof, the monothio nonmetallic acid salt, the oligomer thereof, the trithio nonmetallic acid salt, the oligomer thereof and/or the tetrathio nonmetallic acid salt and the oligomer thereof are mixed together according to any weight ratio to obtain a series of compound medicaments so as to respectively achieve the best flotation separation effect of zinc sulfide and iron sulfide minerals according to the characteristics of different zinc sulfide and iron sulfide minerals. The inhibitor adopts the following four substances as raw materials:
(A) Sodium sulfite Na 2 SO 3
Figure GDA0001585473770000071
(B) Sodium dithiosulfate Na 2 S 3 O 2
Figure GDA0001585473770000072
(C) Sodium dithiophosphate Na 3 PS 2 O 2
Figure GDA0001585473770000073
(D) Sodium dithiosulfite Na 2 S 3 O
Figure GDA0001585473770000074
Figure GDA0001585473770000082
The mixture ratio of the raw materials is as follows: and when the ratio of A to B to C to D=0.2 to 0.3 to 0.2 to 0.3, preparing the qualified compound inhibitor according to the method.
During the preparation, the nonmetallic acid salt and the oligomer thereof are ground into powder, water is added according to the components of the ore containing zinc sulfide and iron sulfide minerals to prepare an aqueous solution inhibitor, and the inhibitor is respectively added in the roughing, scavenging and concentrating processes of flotation to inhibit the floatation of the zinc sulfide ore by the iron sulfide ore.
According to the components of the ore containing zinc sulfide and iron sulfide minerals, the volume percentage concentration of dithio-nonmetal acid salt and oligomers thereof is adjusted according to different characteristics of the ore properties of the different zinc sulfide and iron sulfide minerals, so as to respectively achieve the optimal flotation separation effect of the zinc sulfide and the iron sulfide minerals according to the characteristics of the different zinc sulfide and iron sulfide minerals.
The volume percentage concentration of the dithio non-metal acid salt and the oligomer thereof ranges from 40 to 60 percent by volume.
The dithio non-metal acid salt and the oligomer inhibitor thereof are used in neutral environment with pH value of 6-9 for floatation of iron sulfide.
Example IV
The method is a sorting application example, wherein a zinc separation closed-circuit flow test of 4 cycles is carried out according to a principle flow of preferentially floating zinc sulfide minerals, wherein zinc separation operation adopts a flow structure of one roughing, one scavenging and one concentration, and the inhibitor is adopted to inhibit the iron sulfide minerals, and the dosage is 350g/t. The lime consumption is zero. The average sorting index obtained is shown in table 2.
Table 2 example 4 sorting index
Figure GDA0001585473770000081
It will be apparent that these embodiments are merely illustrative of the present invention and not intended to limit the scope of the invention, and that modifications to the invention in its various equivalent forms will fall within the scope of the invention as defined in the claims appended hereto, as interpreted by those skilled in the art to which the invention pertains.
From the above examples, it can be seen that the present invention is a dithio-nonmetallic acid salt and its oligomer flotation inhibitor, which consists of a dithio-nonmetallic acid salt and its oligomer, and inhibits the floatation of zinc sulfide ore from iron sulfide ore under natural pH conditions.
Further, the dithio-nonmetallic acid salt and the oligomer thereof comprise two molecular structural formulas, wherein the two molecular structural formulas have the structural characteristics of the dithio-nonmetallic acid salt and the oligomer, and the dithio-nonmetallic acid salt is a nonmetallic oxysalt.
Further, the dithio-nonmetallic acid salt and the molecular structural formula of the oligomer thereof
Figure GDA0001585473770000091
Wherein X is an S atom, a C atom or a Si atom, Y 1 、Y 2 Is H atom, na atom, K atom, or NH 4 A group, but Y 1 、Y 2 At least one of which is not an H atom; n=1, 2, 3 or 4.
Further, the dithio-nonmetallic acid salt and the oligomer thereof have the molecular structural formula:
Figure GDA0001585473770000092
wherein X is a P atom, an As atom, an Sb atom or a Bi atom, Y 1 、Y 2 、Y 3 Is H atom, na atom, K atom, or NH 4 A group, but Y 1 、Y 2 、Y 3 At least one of which is not an H atom; n=1, 2, 3 or 4.
Further, the dithio nonmetallic acid salt and the oligomer inhibitor thereof are mixture, and the dithio nonmetallic acid salt and the oligomer thereof are mixed with one or more of the monothio nonmetallic acid salt and the oligomer thereof, the trithio nonmetallic acid salt and the oligomer thereof, the tetrathio nonmetallic acid salt and the oligomer thereof according to any weight ratio to obtain a series of compound medicament, so as to respectively achieve the best flotation separation effect of zinc sulfide and iron sulfide mineral aiming at the characteristics of different zinc sulfide and iron sulfide mineral properties.
The preparation and use method of the dithio non-metal acid salt and the oligomer inhibitor thereof comprises the steps of grinding the dithio non-metal acid salt and the oligomer thereof into powder, adding water according to the components of ores containing zinc sulfide and iron sulfide minerals to prepare an aqueous solution inhibitor, and respectively adding the inhibitor in roughing, scavenging and selecting processes of flotation to inhibit the zinc sulfide ores from being floated by the iron sulfide ores.
Further, according to the components of the ore containing zinc sulfide and iron sulfide minerals, the volume percentage concentration of dithio-nonmetal acid salt and oligomer thereof is adjusted according to different characteristics of the ore properties of different zinc sulfide and iron sulfide minerals, so that the optimal flotation separation effect of zinc sulfide and iron sulfide minerals is respectively achieved according to the characteristics of the ore properties of different zinc sulfide and iron sulfide minerals.
Further, the dithio-nonmetallic acid salt and the oligomer thereof have a volume percentage concentration ranging from 40 to 60 percent by volume.
Further, the dithio non-metal acid salt and the oligomer inhibitor thereof are used in neutral environment with pH value of 6-9 for floatation of iron sulfide mineral.
The invention has the advantages that:
1. the inhibitor can be used for inhibiting the zinc sulfide mineral to be floated by the light inhibition method without adding lime in the floatation process, and the pH value of the ore pulp in the operation of floating the zinc sulfide mineral is obviously different from that in the operation of floating the zinc sulfide mineral by adopting lime as the inhibitor of the iron sulfide mineral, and is higher than 12 and is in the neutral range of 6-9.
2. The inhibitor can be used for floatation of iron sulfide minerals by a light activation method without adding sulfuric acid or hydrochloric acid in the floatation process, and the pH value of ore pulp of the operation for floatation of the iron sulfide minerals is obviously different from that of ore pulp of the floatation operation of the iron sulfide minerals after the floatation of the zinc sulfide minerals, which is obviously lower than 6, and is in the neutral range of 6-9.
3. The inhibitor can be used for inhibiting the zinc sulfide mineral by a light inhibition method without adding lime in a flotation process, wherein the pH value of ore pulp of operation for floating the zinc sulfide mineral is in a neutral range of 6-9, so that the pH value of water removal of zinc sulfide concentrate pulp obtained by operation for floating the zinc sulfide mineral is obviously different from the pH value of water removal of zinc sulfide concentrate pulp obtained by operation for floating the zinc sulfide mineral by using lime as a pyrite inhibitor, which is obviously higher than 12, and is in the neutral range of 6-9.
4. The inhibitor of the invention is adopted to float iron sulfide minerals in a light activation mode without adding sulfuric acid or hydrochloric acid in a floatation process, the pH value of ore pulp of operation of floating the iron sulfide minerals is in a neutral range of 6-9, the pH value of water removal of iron sulfide concentrate pulp and tailing pulp obtained by operation of floating the iron sulfide minerals is obviously different from the pH value of water removal of iron sulfide concentrate pulp and tailing pulp obtained by the well-known operation of adding lime to inhibit the iron sulfide minerals to float zinc sulfide minerals and then adding acid to activate the iron sulfide minerals, and the pH value of water removal of the iron sulfide concentrate pulp and the tailing pulp is obviously lower than 6 and is in a neutral range of 6-9.
5. The inhibitor of the invention is adopted, the obtained iron sulfide concentrate pulp in the flotation process is flotation foam pulp, the pulp concentration is up to more than 40%, the method is obviously different from the known method that zinc sulfide and iron sulfide minerals are mixed and floated under the neutral condition that the pH value of the pulp without lime is 6-9, then the mixed concentrate of the zinc sulfide and the iron sulfide minerals is subjected to the inhibition of the iron sulfide minerals under the high alkaline condition that the pH value of the pulp with lime is up to more than 12, the iron sulfide concentrate pulp obtained by the flotation separation process for floating the zinc sulfide minerals is pulp in a tank, and the pulp concentration is as low as below 25%.
Aiming at the different characteristics of the ore properties of different zinc sulfide and iron sulfide-containing minerals, the adopted types and the proportion of the medicament components of the nonmetallic acid salts and the oligomers thereof, the monothiononmetallic acid salts and the oligomers thereof, the dithiononmetallic acid salts and the oligomers thereof, the trithiononmetallic acid salts and the oligomers thereof, the tetrathiononmetallic acid salts and the oligomers thereof can be adjusted to obtain a series of compound medicaments so as to respectively achieve the optimal flotation separation effect of the zinc sulfide and the iron sulfide minerals aiming at the characteristics of the different zinc sulfide and iron sulfide-containing minerals.
The advantages of the invention are expressed in the following aspects:
firstly, lime is eliminated in the whole process, so that the cost of the beneficiation reagent can be saved;
secondly, lime is cancelled in the whole process, and a post for washing and matching lime is not required, so that labor for a factory selection post is saved, and labor resource cost for mineral separation production is reduced;
thirdly, lime is not added in the whole process, so that the problems that lime milk is difficult to prepare, a pipeline added with lime milk is easy to scale and block, and the like, and the production index is influenced are solved;
fourthly, sulfuric acid or hydrochloric acid is not needed to be added in the floatation operation of the iron sulfide minerals, so that the problem that the sulfuric acid and the hydrochloric acid are easy to prepare drugs and are very troublesome to use and examine in certain places is solved;
fifthly, the pH value of the water for removing the concentrate and the tailings is in the neutral range of 6-9 reaching the standard of emission, the heavy metal ion content and the COD content of the water for removing the concentrate and the tailings are lower than those of the water for removing the heavy metal ion content and the COD content of the water by the traditional lime adding process, and even the heavy metal ion content and the COD content of the water for removing the concentrate and the tailings are lower than the emission standard without any treatment.

Claims (2)

1. A dithio-nonmetallic acid salt and its oligomer flotation suppressant, characterized in that: the dithio non-metal acid salt and the oligomer inhibitor thereof are composed of the dithio non-metal acid salt and the oligomer thereof, and the flotation of the zinc sulfide ore by the iron sulfide ore is inhibited under the natural pH condition; the dithio non-metal acid salt and the oligomer thereof comprise two molecular structural formulas;
wherein, a dithio non-metal acid salt and an oligomer thereof have the molecular structural formula:
Figure QLYQS_1
wherein X is an S atom, a C atom or a Si atom, Y 1 、Y 2 Is H atom, na atom, K atom, or NH 4 A group, but Y 1 、Y 2 At least one of which is not an H atom; n=1, 2, 3 or 4;
the other dithio non-metal acid salt and its oligomer have the molecular structural formula:
Figure QLYQS_2
wherein X is a P atom, an As atom, an Sb atom or a Bi atom, Y 1 、Y 2 、Y 3 、Y 4 Is H atom, na atom, K atom, or NH 4 A group, but Y 1 、Y 2 At least one of which is not an H atom; n=1, 2, 3 or 4;
and both molecular structural formulas have the structural characteristics of dithio non-metal acid salts and oligomers, wherein the dithio non-metal acid salts are non-metal oxygen acid salts;
the dithio non-metal acid salt and the oligomer inhibitor thereof are mixture, and the mixture consisting of one or more of the monothio non-metal acid salt and the oligomer thereof, the trithio non-metal acid salt and the oligomer thereof, the tetrathio non-metal acid salt and the oligomer thereof and the dithio non-metal acid salt and the oligomer thereof is used for obtaining a series of compound medicament.
2. A method of formulating the dithio-nonmetallic acid salt and its oligomer suppressing agent as defined in claim 1, wherein: grinding dithio non-metal acid salt and oligomer inhibitor thereof into powder, adding water to prepare an aqueous solution inhibitor according to the components of ores containing zinc sulfide and iron sulfide minerals, and respectively adding the aqueous solution inhibitor in roughing, scavenging and concentrating processes of flotation to inhibit the flotation of the zinc sulfide ores by the iron sulfide ores; according to the components of the ore containing zinc sulfide and iron sulfide minerals, according to the different characteristics of the ore properties of the different zinc sulfide and iron sulfide minerals, the volume percentage concentration of dithio-nonmetal acid salt and oligomer inhibitor thereof is adjusted so as to respectively achieve the optimal flotation separation effect of the zinc sulfide and the iron sulfide minerals according to the characteristics of the different zinc sulfide and iron sulfide minerals; the volume percentage concentration of the dithio non-metal acid salt and the oligomer inhibitor is in the range of 40-60%.
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