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CN107971140A - Two thio nonmetallic hydrochlorates and its oligomer depressing agent and preparation application method - Google Patents

Two thio nonmetallic hydrochlorates and its oligomer depressing agent and preparation application method Download PDF

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Publication number
CN107971140A
CN107971140A CN201711205819.1A CN201711205819A CN107971140A CN 107971140 A CN107971140 A CN 107971140A CN 201711205819 A CN201711205819 A CN 201711205819A CN 107971140 A CN107971140 A CN 107971140A
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thio
nonmetallic
oligomer
hydrochlorates
flotation
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CN107971140B (en
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向平
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Hunan Huaqi Resources Environment Science And Technology Development Co Ltd
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Hunan Huaqi Resources Environment Science And 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 kind of two thio nonmetallic hydrochlorates and its oligomer depressing agent, inhibitor are made of two thio nonmetallic hydrochlorates and its oligomer, and suppress pyrites flotation zinc sulfide ore under the conditions of natural pH.The two thio nonmetallic hydrochlorates and its oligomer include two kinds of molecular structural formula forms, and two kinds of molecular structural formulas all have two thio nonmetallic hydrochlorates and oligomer structure feature, wherein two thio nonmetallic hydrochlorates are all nonmetal oxyacid hydrochlorate.Inhibitor using the present invention, the light suppressing method that lime can not be added in floatation process suppresses iron sulfide mineral flotation zinc sulfide mineral, the slurry pH of the operation of its flotation zinc sulfide mineral, be up to the slurry pH of the operation of the known inhibitor flotation zinc sulfide mineral that iron sulfide mineral is done using lime it is more than 12 significantly different, in 69 neutral range.

Description

Two thio nonmetallic hydrochlorates and its oligomer depressing agent and preparation application method
Technical field：
The present invention relates to the inhibitor and its preparation application method of a kind of flotation clean preparation method, and in particular to a kind of Suppress the inhibitor of pyrites flotation zinc sulfide ore under the conditions of natural pH and its prepare application method, the inhibitor and its match somebody with somebody Application method processed is a kind of inhibitor for suppressing pyrites flotation zinc sulfide ore under the conditions of natural pH and its prepares user Method, belongs to mineral processing floating agent field.
Background technology：
The method of domestic and international common zinc sulfide mineral and iron sulfide mineral FLOTATION SEPARATION has two kinds, and one kind is according to first floating Select zinc sulfide mineral again flotation iron sulfide mineral the sequence of operation carry out selective flotation flowsheet, first flotation zinc sulfide mineral , it is necessary to which first adding lime adjusts slurry pH more than 12 to suppress iron sulfide mineral in operation；Vulcanize in ensuing flotation , it is necessary to adjust slurry pH to neutral even acid condition with sulfuric acid or hydrochloric acid to floating zinc tailing in the operation of iron mineral, with Activate depressed iron sulfide ore.Another kind is according to first by zinc sulphide and iron sulfide mineral together flotation, then to a floating Select obtained bulk concentrate to carry out separated bulk flotation separation process again, in bulk flotation operation, first be not added with lime or Add and carry out flotation under conditions of a small amount of lime；It is ensuing to bulk concentrate carry out separating flotation operation in, it is necessary to Large quantities of lime (pH value is transferred to more than 12) is added in bulk concentrate ore pulp to suppress iron sulfide mineral.
Both zinc sulfide minerals and iron sulfide mineral flotation separation method, inhibitor used are all to do to press down using lime Preparation, suppresses flotation of pyrite zincblende.As Huangshaping lead and zinc mine uses the order flotation for preferentially selecting zinc sulphide to select iron sulfide again Flow, lime consumption are up to 10-13 kgs/tonne of raw ore, and Shuikoushan Kang Jia gulfs Pb-Zn deposits use the stream of " bulk flotation separates again " Journey, 5-6 kgs/tonne of raw ore of lime consumption.
Although the production history of both zinc sulfide minerals and iron sulfide mineral flotation separation method is long, technical maturity can Lean on, can obtain stable separating effect, but with the shortcomings that it is also very much, prepared except milk of lime is difficult and the pipe of addition milk of lime Outside the easy fouling and clogging problem in road, also there are serious problem of environmental pollution, it is mainly manifested in：
(1) tail water pH is exceeded.Zinc sulfide concentrates, the pH of iron sulfide concentrate and tailings removing water obtained using lime technology Value is often more than 12, the serious industrial wastewater discharge standard for exceeding pH6-9, waste water processing station need into tail water acid adding into Row neutralizes；Often occur adding that acid amount control is improper, and pH value of water solution is transferred to less than 6 acidity, and need instead plus alkali is adjusted PH value is to neutrality.Therefore, pH value of waste water how is adjusted to the critical field of 6-9, is become and is allowed execute-in-place work and administrative staff to pass through Often the problem of headache.
(2) tail water heavy metal ion and COD contents are exceeded.Because of the zinc sulfide concentrates, the iron sulfide that are obtained using lime technology The pH value of concentrate and tailings removing water often more than 12, cause the heavy metal pollution factors such as lead in tail water, zinc, cadmium, sulphur and COD contents are often exceeded.
All it is in the past few decades the development pattern for taking extensive style in traditional mine industry, takes pollution mostly and produce " end treatment " measure of pollution administration again afterwards, but present all trades and professions all growing interest clean manufacturings all over the world, advocate ring Border protection work should change from past single end treatment to the process for cleanly preparing of pollution source control.Just as vulcanizing Lime is used during zinc mineral and iron sulfide mineral FLOTATION SEPARATION, tail water heavy metal ion caused by pH value height is generated and surpasses Pollution problem is marked, the past is all to use to adjust tail water using acid adding, and adds heavy metal chelating agent heavy-metal ion removal etc. End treatment measure, few people expect the root that problems above produces, and are all because adding vulcanization in process of production While zinc mineral collecting agent, it is necessary to add substantial amounts of lime, could realize the flotation point of zinc sulfide mineral and iron sulfide mineral From.Because adding, lime carries out zinc sulfide mineral and the production method of iron sulfide mineral FLOTATION SEPARATION is with a long history, technical maturity Reliably, stable separating effect can be obtained, and lime derives from a wealth of sources, it is cheap, therefore, less paid attention to environment in the past Can the epoch of protection, also few people's thinking replace lime with other inhibitor.On the other hand addition lime carries out sulphur The production method of change zinc mineral and iron sulfide mineral FLOTATION SEPARATION is with a long history, and technical maturity is reliable, can obtain stable point Effect is selected, and lime derives from a wealth of sources, it is cheap, therefore, less paid attention to the epoch of environmental protection in the past, also few people Can thinking be accomplished to be not added with lime to realize pollution source control, to thereby result in the pollution getting worse of flotation, necessary right This is improved.
By patent retrieval and do not find there be the patent literature constructed with the present invention, have certain relation with the present invention Patent mainly have it is following：
1st, Patent No. CN201210173054.9, entitled " a kind of Iron pyrite inhibitor being used under the conditions of low alkalinity " Patent of invention, which disclose it is a kind of be used for low alkalinity under the conditions of Iron pyrite inhibitor, by sodium thiosulfate, lemon Acid, polyacrylamide composition, parts by weight composition are:40-50 parts of sodium thiosulfate, 40-50 parts of citric acid, polyacrylamide 5-15 Part, polyacrylamide is the low molecular weight polyacrylamide of hydroxyl, its molecular weight is 400-600.The inhibitor, by following sides It is prepared by method：Sodium thiosulfate, citric acid, polyacrylamide are weighed, is uniformly configured to concentration expressed in percentage by weight 1%-5%'s after mixing Aqueous solution, stirring.
2nd, Patent No. CN201010275649.6, a kind of entitled " system of copper-zinc sulfide ore flotation separation inhibitor The patent of invention of Preparation Method and its application ", which disclose a kind of preparation side of lead-zinc sulfide ore thing FLOTATION SEPARATION inhibitor Method, at room temperature, the sulfuric acid that 40~50% volumn concentrations of 200~300ml are added in the three-necked flask of 500ml are molten Liquid, adds 120~150g of pyrite cinder that iron content is wt%40~50%, reacts 4~6h with 60 revs/min of stirrings, takes out while hot Filter, obtains pickle liquor, takes pickle liquor described in 200ml in the three-necked flask of 500ml, adds 50~60g iron powders as reduction Agent, while hot filters unreacted iron powder after 1~2h of heating reflux reaction at 75~85 DEG C, then filtrate is transferred to evaporating dish In, crystallization is concentrated into 75~80 DEG C of evaporation at constant temperature, filters while hot and dry obtained white powder is the zinc sulfide mineral Inhibitor.
3rd, Patent No. CN200710192426.1, a kind of entitled " be used for troilite in complicated sulfuration mine efficient group Close inhibitor and its application process " patent of invention, which disclose and a kind of be used for the efficient of troilite in complicated sulfuration mine Composite restrainer, the inhibitor are made of calper calcium peroxide, sodium humate, employ the combination of calper calcium peroxide and sodium humate Mode, since calper calcium peroxide has very strong oxidability, by coordinating the complexing of sodium humate and calcium ion, can select Property suppress complicated iron sulfide mineral, especially there is preferable rejection to mineral such as magnetic iron ore, pyrite and mispickel, be A kind of highly selective inhibitor.
Although these above-mentioned patents are directed to the depressing agent of iron sulfide or zinc sulphide, and some is also related to and adopted The method that flotation is carried out with non-lime, but by the reading to these patents, it is known that these patents are wanted with the present invention Solve the problems, such as it is more complicated than flotation processing scheme proposed by the invention in not related and disclosed technical solution, Material used is also more, it is difficult to prepares and produces, therefore still needs further to be improved.
The content of the invention
The goal of the invention of the present invention is for present in present zinc sulfide mineral and iron sulfide mineral flotation separation method The problem of, propose a kind of inhibitor for suppressing pyrites flotation zinc sulfide ore under the conditions of natural ph, this kind of inhibitor energy Suppress pyrites flotation zinc sulfide ore under the conditions of natural ph, and using after such inhibitor, in the whole process of flotation In no longer need plus lime, achieve the purpose that cleaning manufacturing technique method.
Another goal of the invention of the present invention is to propose that a kind of above-mentioned inhibitor is suppressing vulcanization under the conditions of natural pH Preparation application method during floatation of iron ore zinc sulfide ore.
In order to reach this purpose, the present invention provides a kind of two thio nonmetallic hydrochlorates and its oligomer flotation to suppress Agent, inhibitor are made of two thio nonmetallic hydrochlorates and its oligomer, and suppress pyrites flotation sulphur under the conditions of natural pH Change zinc ore.
Further, the two thio nonmetallic hydrochlorates and its oligomer include two kinds of molecular structural formula forms, two kinds Molecular structural formula all has two thio nonmetallic hydrochlorates and oligomer structure feature, wherein two thio nonmetallic hydrochlorates are all non-gold Belong to oxysalt.
Further, the two thio nonmetallic hydrochlorates and its oligomer molecules structural formula
Wherein, X is S atom, C atoms or Si atoms, Y1、Y2For H atom, Na atoms, K atoms or NH4Group, but Y1、Y2 In at least one be not H atom；N=1,2,3 or 4.
Further, the two thio nonmetallic hydrochlorates and its oligomer molecules structural formula：
Wherein, X is P atoms, As atoms, Sb atoms or Bi atoms, Y1、Y2、Y3For H atom, Na atoms, K atoms or NH4Group, but Y1、Y2、Y3In at least one be not H atom；N=1,2,3 or 4.
Further, the two thio nonmetallic hydrochlorates and its oligomer-diminishing agent are mixture, by two thio non-gold Belong to hydrochlorate and its oligomer and the nonmetallic hydrochlorate of monothio and its oligomer, three thio non-metallic acid salt and its oligomer, four sulphur For nonmetallic hydrochlorate and its one or more of mixtures of oligomer, two thio nonmetallic hydrochlorates and its oligomer and monothio Nonmetallic hydrochlorate and its oligomer, three thio non-metallic acid salt and its oligomer and/or the nonmetallic hydrochlorate of tetrathio and its oligomeric Thing is mixed according to any weight ratio, obtains serial compound drug, with for different Containing Sulfur zinc and iron sulfide mineral Ore properties feature, respectively reaches optimal zinc sulphide and iron sulfide mineral FLOTATION SEPARATION effect.
A kind of preparation application method of above-mentioned two thio nonmetallic hydrochlorate and its oligomer-diminishing agent, it is thio nonmetallic by two Hydrochlorate and its oligomer wear into powdery, according to Containing Sulfur zinc and the component of the ore of iron sulfide mineral, add water to be configured to aqueous solution Inhibitor, roughing in flotation, scan and inhibitor be separately added into cleaning technological flowasheet, suppresses pyrites flotation zinc sulfide ore.
Further, the component according to Containing Sulfur zinc and the ore of iron sulfide mineral is according to different Containing Sulfurs The different characteristics of the ore properties of zinc and iron sulfide mineral, adjusts the percent by volume of two thio nonmetallic hydrochlorates and its oligomer Concentration, for different Containing Sulfur zinc and iron sulfide mineral ore properties feature, to respectively reach optimal zinc sulphide and vulcanization Floatation of iron mineral separating effect.
Further, the scope of the concentration of volume percent of the two thio nonmetallic hydrochlorates and its oligomer is volume The 40-60% of percentage.
Further, the use environment of the two thio nonmetallic hydrochlorates and its oligomer-diminishing agent is pH value in 6-9 Neutral range, carry out iron sulfide mineral flotation.
The advantage of the invention is that：
1st, inhibitor using the present invention, the light suppressing method that lime can not be added in floatation process suppress iron sulfide Mineral floating zinc sulfide mineral, the slurry pH of the operation of its flotation zinc sulfide mineral, iron sulfide is done with known using lime The slurry pH of the operation of the inhibitor flotation zinc sulfide mineral of mineral be up to it is more than 12 significantly different, in the neutral range of 6-9.
2nd, inhibitor using the present invention, can not add the light activation method flotation of sulfuric acid or hydrochloric acid in floatation process Iron sulfide mineral, the iron sulfide after the slurry pH of the operation of its flotation iron sulfide mineral, with known flotation zinc sulfide mineral The slurry pH of mineral floating operation is low significantly different to less than 6, in the neutral range of 6-9.
3rd, inhibitor using the present invention, the light suppressing method that lime can not be added in floatation process suppress iron sulfide Mineral floating zinc sulfide mineral, the slurry pH of the operation of its flotation zinc sulfide mineral cause flotation sulphur in the neutral range of 6-9 Change the pH value of the removing water of the zinc sulfide concentrates slurry of the operation acquisition of zinc mineral, pyrites suppression is done using lime with known The pH value of the removing water for the zinc sulfide concentrates slurry that the operation of preparation flotation zinc sulfide mineral obtains be up to it is more than 12 significantly different, In the neutral range of 6-9.
4th, inhibitor using the present invention, can not add the light activation method flotation of sulfuric acid or hydrochloric acid in floatation process Iron sulfide mineral, the slurry pH of the operation of its flotation iron sulfide mineral cause flotation iron sulfide mineral in the neutral range of 6-9 Operation obtain vulcanization iron ore concentrate slurry and Tailings Slurry removing water pH value, with it is known first plus lime suppress iron sulfide After mineral floating zinc sulfide mineral, then the vulcanization iron ore concentrate slurry and Tailings Slurry of the flotation operation acquisition of acid adding cure activation iron mineral Removing water pH value it is low significantly different to less than 6, in the neutral range of 6-9.
5th, inhibitor using the present invention, the vulcanization iron ore concentrate slurry that can be obtained in floatation process are flotation froth ore deposit Slurry, pulp density are up to more than 40%, mix and float in the case where not adding the neutrallty condition of slurry pH 6-9 of lime with known elder generation Zinc sulphide and iron sulfide mineral, then the bulk concentrate to zinc sulphide and iron sulfide mineral are selected, it is high in the ore pulp pH value of addition lime Up to more than 12 it is high-alkali under the conditions of carry out suppression iron sulfide mineral, the vulcanization that the floatation separation process of flotation zinc sulfide mineral obtains Iron ore concentrate slurry is ore pulp in groove, and pulp density as low as less than 25% has significant difference.
The benefit that the present invention is brought shows the following aspects：
First, whole process eliminates lime, beneficiation reagent cost can be saved；
It second, whole process eliminates lime, can be not provided with washing the post with lime, save and select factory's post recruitment, reduce Mineral processing production cost of human resources；
Third, whole process does not add lime, difficult easy fouling and clogging of pipeline prepared and add milk of lime of milk of lime etc. is overcome The problem of influencing production target；
Fourth, the flotation operation in iron sulfide mineral need not add sulfuric acid or hydrochloric acid, solve because sulfuric acid and hydrochloric acid are Easy drugs processed, use and examine the problem of all very troublesome in some places；
Fifth, concentrate and tailings removing water pH value in the neutral range of the 6-9 of qualified discharge standard, concentrate and tail Heavy metal ion content and COD contents in ore deposit removing water will be lower than the technique of tradition plus lime, or even concentrate and tailings takes off Heavy metal ion content and COD contents in water removal are without any processing just already below discharge standard.
Embodiment
The embodiment of the present invention is further described with reference to example, but cited embodiment is not Limitation of the present invention.
Embodiment one
This example is medicament formulation example：Using the sodium ditionite Na of two thio nonmetallic hydrochlorates and its oligomer2S3O As inhibitor raw material, wherein two thio nonmetallic hydrochlorates are all nonmetal oxyacid hydrochlorate.
The two thio nonmetallic hydrochlorates and its oligomer have following molecular structural formula：
The proportioning of above-mentioned raw materials is：When preparing inhibitor, first according to Containing Sulfur zinc and the component of the ore of iron sulfide mineral Determine required sodium ditionite deal, add water to be deployed into the aqueous solution that concentration of volume percent is 40-60%, form suppression Preparation aqueous solution, roughing in the ore of iron sulfide mineral, scan and be separately added into selected flotation flowsheet by two thio sulfurous The inhibitor aqueous solution that sour sodium is prepared, and inhibitor is added when suppressing pyrites flotation zinc sulfide ore under the conditions of natural pH, The roughing of flotation, scan the pH with cleaning technological flowasheet in 8-9.
Embodiment two
This example is medicament formulation example：Using the dimerization bisthiosulfate ammonium of two thio nonmetallic hydrochlorates and its oligomer (NH4)4S6O4As inhibitor raw material, wherein two thio nonmetallic hydrochlorates are all nonmetal oxyacid hydrochlorate.
The two thio nonmetallic hydrochlorates and its oligomer have following molecular structural formula：
During inhibitor processed, first determine that required dimerization two is thio according to the component of Containing Sulfur zinc and the ore of iron sulfide mineral Ammonium sulfate deal, adds water to be deployed into the aqueous solution that concentration of volume percent is 40-60%, forms inhibitor aqueous solution, vulcanizing The roughing of the ore of iron mineral, scan and be separately added into selected flotation flowsheet by the inhibitor of dimerization bisthiosulfate ammonium preparation Aqueous solution, and inhibitor is added when suppressing pyrites flotation zinc sulfide ore under the conditions of natural pH, the roughing of flotation, scan and The pH of cleaning technological flowasheet is in 8-9.
Embodiment three
This example is medicament formulation example：Use two thio nonmetallic hydrochlorates and its oligomer and other materials for raw material, match somebody with somebody Two thio nonmetallic hydrochlorates and its oligomer-diminishing agent mixture are made, by two thio nonmetallic hydrochlorates and its oligomer and a sulphur For nonmetallic hydrochlorate and its oligomer, the three nonmetallic hydrochlorates of thio non-metallic acid salt and its oligomer, tetrathio and its oligomer One or more of mixtures, two thio nonmetallic hydrochlorates and its oligomer and the nonmetallic hydrochlorate of monothio and its oligomer, Three thio non-metallic acid salt and its oligomer and/or the nonmetallic hydrochlorate of tetrathio and its oligomer are blended according to any weight ratio Together, serial compound drug is obtained, for different Containing Sulfur zinc and iron sulfide mineral ore properties feature, to respectively reach most Good zinc sulphide and iron sulfide mineral FLOTATION SEPARATION effect.Inhibitor employs following four material as raw material:
(A) sodium sulfite Na2SO3
(B) bisthiosulfate sodium Na2S3O2
(C) phosphordithiic acid sodium Na3PS2O2
(D) sodium ditionite Na2S3O
The proportioning of above-mentioned raw materials is：According to A:B:C:D=0.2:0.3:0.2:When 0.3, prepare according to the method described above to obtain the final product Qualified inhibitor.
During preparation, nonmetallic hydrochlorate and its oligomer are worn into powdery, according to Containing Sulfur zinc and the ore of iron sulfide mineral Component, add water to be configured to aqueous solution inhibitor, roughing in flotation, scan and be separately added into inhibitor in cleaning technological flowasheet, presses down Pyrites flotation zinc sulfide ore processed.
The component according to Containing Sulfur zinc and the ore of iron sulfide mineral is according to different Containing Sulfur zinc and vulcanization The different characteristics of the ore properties of iron mineral, adjusts the concentration of volume percent of two thio nonmetallic hydrochlorates and its oligomer, with For different Containing Sulfur zinc and iron sulfide mineral ore properties feature, respectively reach optimal zinc sulphide and iron sulfide mineral floats Select separating effect.
The scope of the concentration of volume percent of the two thio nonmetallic hydrochlorates and its oligomer is percent by volume 40-60%.
The use environment of the two thio nonmetallic hydrochlorates and its oligomer-diminishing agent is neutral model of the pH value in 6-9 Enclose, carry out iron sulfide mineral flotation.
Example IV
This example is the ore of sort applications example, certain Containing Sulfur zinc and iron sulfide mineral, containing zinc 7.67%, sulfur-bearing 19.64%, Principle process according to diffeential floatation zinc sulfide mineral carried out 4 circulation select the closed circuit flow test of zinc, select zinc operation use One roughing, once purging selection, primary cleaning flowage structure, suppress iron sulfide mineral, dosage 350g/t using this example inhibitor. Lime consumption is zero.The average separation index obtained is shown in Table 2.
2 embodiment of table, 4 separation index
It will be apparent that it should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention, After reading the present invention, modification of the those skilled in the art to the various equivalent forms of the present invention each falls within right appended by the application will Seek limited range.
Suppress it can be seen from above-described embodiment that the present invention is a kind of two thio nonmetallic hydrochlorates and its oligomer flotation Agent, inhibitor are made of two thio nonmetallic hydrochlorates and its oligomer, and suppress pyrites flotation sulphur under the conditions of natural pH Change zinc ore.
Further, the two thio nonmetallic hydrochlorates and its oligomer include two kinds of molecular structural formula forms, two kinds Molecular structural formula all has two thio nonmetallic hydrochlorates and oligomer structure feature, wherein two thio nonmetallic hydrochlorates are all non-gold Belong to oxysalt.
Further, the two thio nonmetallic hydrochlorates and its oligomer molecules structural formula
Wherein, X is S atom, C atoms or Si atoms, Y1、Y2For H atom, Na atoms, K atoms or NH4Group, but Y1、 Y2In at least one be not H atom；N=1,2,3 or 4.
Further, the two thio nonmetallic hydrochlorates and its oligomer molecules structural formula：
Wherein, X is P atoms, As atoms, Sb atoms or Bi atoms, Y1、Y2、Y3For H atom, Na atoms, K atoms or NH4Group, but Y1、Y2、Y3In at least one be not H atom；N=1,2,3 or 4.
Further, the two thio nonmetallic hydrochlorates and its oligomer-diminishing agent are mixture, by two thio non-gold Belong to hydrochlorate and its oligomer and the nonmetallic hydrochlorate of monothio and its oligomer, three thio non-metallic acid salt and its oligomer, four sulphur For nonmetallic hydrochlorate and its one or more of mixtures of oligomer, two thio nonmetallic hydrochlorates and its oligomer and monothio Nonmetallic hydrochlorate and its oligomer, three thio non-metallic acid salt and its oligomer and/or the nonmetallic hydrochlorate of tetrathio and its oligomeric Thing is mixed according to any weight ratio, obtains serial compound drug, with for different Containing Sulfur zinc and iron sulfide mineral Ore properties feature, respectively reaches optimal zinc sulphide and iron sulfide mineral FLOTATION SEPARATION effect.
A kind of preparation application method of above-mentioned two thio nonmetallic hydrochlorate and its oligomer-diminishing agent, it is thio nonmetallic by two Hydrochlorate and its oligomer wear into powdery, according to Containing Sulfur zinc and the component of the ore of iron sulfide mineral, add water to be configured to aqueous solution Inhibitor, roughing in flotation, scan and inhibitor be separately added into cleaning technological flowasheet, suppresses pyrites flotation zinc sulfide ore.
Further, the component according to Containing Sulfur zinc and the ore of iron sulfide mineral is according to different Containing Sulfurs The different characteristics of the ore properties of zinc and iron sulfide mineral, adjusts the percent by volume of two thio nonmetallic hydrochlorates and its oligomer Concentration, for different Containing Sulfur zinc and iron sulfide mineral ore properties feature, to respectively reach optimal zinc sulphide and vulcanization Floatation of iron mineral separating effect.
Further, the scope of the concentration of volume percent of the two thio nonmetallic hydrochlorates and its oligomer is volume The 40-60% of percentage.
Further, the use environment of the two thio nonmetallic hydrochlorates and its oligomer-diminishing agent is pH value in 6-9 Neutral range, carry out iron sulfide mineral flotation.
The advantage of the invention is that：
1st, inhibitor using the present invention, the light suppressing method that lime can not be added in floatation process suppress iron sulfide Mineral floating zinc sulfide mineral, the slurry pH of the operation of its flotation zinc sulfide mineral, iron sulfide is done with known using lime The slurry pH of the operation of the inhibitor flotation zinc sulfide mineral of mineral be up to it is more than 12 significantly different, in the neutral range of 6-9.
2nd, inhibitor using the present invention, can not add the light activation method flotation of sulfuric acid or hydrochloric acid in floatation process Iron sulfide mineral, the iron sulfide after the slurry pH of the operation of its flotation iron sulfide mineral, with known flotation zinc sulfide mineral The slurry pH of mineral floating operation is low significantly different to less than 6, in the neutral range of 6-9.
3rd, inhibitor using the present invention, the light suppressing method that lime can not be added in floatation process suppress iron sulfide Mineral floating zinc sulfide mineral, the slurry pH of the operation of its flotation zinc sulfide mineral cause flotation sulphur in the neutral range of 6-9 Change the pH value of the removing water of the zinc sulfide concentrates slurry of the operation acquisition of zinc mineral, pyrites suppression is done using lime with known The pH value of the removing water for the zinc sulfide concentrates slurry that the operation of preparation flotation zinc sulfide mineral obtains be up to it is more than 12 significantly different, In the neutral range of 6-9.
4th, inhibitor using the present invention, can not add the light activation method flotation of sulfuric acid or hydrochloric acid in floatation process Iron sulfide mineral, the slurry pH of the operation of its flotation iron sulfide mineral cause flotation iron sulfide mineral in the neutral range of 6-9 Operation obtain vulcanization iron ore concentrate slurry and Tailings Slurry removing water pH value, with it is known first plus lime suppress iron sulfide After mineral floating zinc sulfide mineral, then the vulcanization iron ore concentrate slurry and Tailings Slurry of the flotation operation acquisition of acid adding cure activation iron mineral Removing water pH value it is low significantly different to less than 6, in the neutral range of 6-9.
5th, inhibitor using the present invention, the vulcanization iron ore concentrate slurry that can be obtained in floatation process are flotation froth ore deposit Slurry, pulp density are up to more than 40%, mix and float in the case where not adding the neutrallty condition of slurry pH 6-9 of lime with known elder generation Zinc sulphide and iron sulfide mineral, then the bulk concentrate to zinc sulphide and iron sulfide mineral are selected, it is high in the ore pulp pH value of addition lime Up to more than 12 it is high-alkali under the conditions of carry out suppression iron sulfide mineral, the vulcanization that the floatation separation process of flotation zinc sulfide mineral obtains Iron ore concentrate slurry is ore pulp in groove, and pulp density as low as less than 25% has significant difference.
For the different characteristics of the ore properties of different Containing Sulfur zinc and iron sulfide mineral, it is nonmetallic the above can be adjusted It is hydrochlorate and its nonmetallic hydrochlorate of oligomer, monothio and its oligomer, two thio nonmetallic hydrochlorates and its oligomer, three thio non- Metal acid-salt and its nonmetallic hydrochlorate of oligomer, tetrathio and its oligomer using species and the ratio of dosage component, obtain Serial compound drug, for different Containing Sulfur zinc and iron sulfide mineral ore properties feature, to respectively reach optimal vulcanization Zinc and iron sulfide mineral FLOTATION SEPARATION effect.
The benefit that the present invention is brought shows the following aspects：
First, whole process eliminates lime, beneficiation reagent cost can be saved；
It second, whole process eliminates lime, can be not provided with washing the post with lime, save and select factory's post recruitment, reduce Mineral processing production cost of human resources；
Third, whole process does not add lime, difficult easy fouling and clogging of pipeline prepared and add milk of lime of milk of lime etc. is overcome The problem of influencing production target；
Fourth, the flotation operation in iron sulfide mineral need not add sulfuric acid or hydrochloric acid, solve because sulfuric acid and hydrochloric acid are Easy drugs processed, use and examine the problem of all very troublesome in some places；
Fifth, concentrate and tailings removing water pH value in the neutral range of the 6-9 of qualified discharge standard, concentrate and tail Heavy metal ion content and COD contents in ore deposit removing water will be lower than the technique of tradition plus lime, or even concentrate and tailings takes off Heavy metal ion content and COD contents in water removal are without any processing just already below discharge standard.

Claims (9)

  1. A kind of 1. two thio nonmetallic hydrochlorates and its oligomer depressing agent, it is characterised in that：Inhibitor is by two thio non-gold Belong to hydrochlorate and its oligomer is formed, and suppress pyrites flotation zinc sulfide ore under the conditions of natural pH.
  2. 2. two thio nonmetallic hydrochlorate and its oligomer depressing agent as claimed in claim 1, it is characterised in that：Described Two thio nonmetallic hydrochlorates and its oligomer include two kinds of molecular structural formula forms, and two kinds of molecular structural formulas are all thio non-with two Metal acid-salt and oligomer structure feature, wherein two thio nonmetallic hydrochlorates are all nonmetal oxyacid hydrochlorate.
  3. 3. two thio nonmetallic hydrochlorate and its oligomer depressing agent as claimed in claim 2, it is characterised in that：Described Two thio nonmetallic hydrochlorates and its oligomer molecules structural formula
    Wherein, X is S atom, C atoms or Si atoms, Y1、Y2For H atom, Na atoms, K atoms or NH4Group, but Y1、Y2In extremely Rare one is not H atom；N=1,2,3 or 4.
  4. 4. two thio nonmetallic hydrochlorate and its oligomer depressing agent as claimed in claim 2, it is characterised in that：Described Two thio nonmetallic hydrochlorates and its oligomer molecules structural formula：
    Wherein, X is P atoms, As atoms, Sb atoms or Bi atoms, Y1、Y2、Y3For H atom, Na atoms, K atoms or NH4Group, But Y1、Y2、Y3In at least one be not H atom；N=1,2,3 or 4.
  5. 5. the two thio nonmetallic hydrochlorates and its oligomer depressing agent as described in claim 3 or 4, it is characterised in that：Institute The two thio nonmetallic hydrochlorates and its oligomer-diminishing agent stated are mixture, by two thio nonmetallic hydrochlorates and its oligomer and one Thio nonmetallic hydrochlorate and its oligomer, three nonmetallic hydrochlorates of thio non-metallic acid salt and its oligomer, tetrathio and its oligomeric One or more of mixtures of thing, two thio nonmetallic hydrochlorates and its oligomer hydrochlorate nonmetallic with monothio and its oligomeric Thing, three thio non-metallic acid salt and its oligomer and/or the nonmetallic hydrochlorate of tetrathio and its oligomer are mixed according to any weight ratio It is combined, obtains serial compound drug, for different Containing Sulfur zinc and iron sulfide mineral ore properties feature, reaches respectively To optimal zinc sulphide and iron sulfide mineral FLOTATION SEPARATION effect.
  6. A kind of 6. preparation application method of above-mentioned two thio nonmetallic hydrochlorate and its oligomer-diminishing agent, it is characterised in that：By two Thio nonmetallic hydrochlorate and its oligomer wear into powdery, according to Containing Sulfur zinc and the component of the ore of iron sulfide mineral, add water to match somebody with somebody Aqueous solution inhibitor is made, roughing in flotation, scan and inhibitor is separately added into cleaning technological flowasheet, suppresses pyrites flotation Zinc sulfide ore.
  7. 7. the preparation application method of two thio nonmetallic hydrochlorate and its oligomer depressing agent as claimed in claim 6, its It is characterized in that：The component according to Containing Sulfur zinc and the ore of iron sulfide mineral is according to different Containing Sulfur zinc and vulcanization The different characteristics of the ore properties of iron mineral, adjusts the concentration of volume percent of two thio nonmetallic hydrochlorates and its oligomer, with For different Containing Sulfur zinc and iron sulfide mineral ore properties feature, respectively reach optimal zinc sulphide and iron sulfide mineral floats Select separating effect.
  8. 8. the preparation application method of two thio nonmetallic hydrochlorate and its oligomer depressing agent as claimed in claim 7, its It is characterized in that：The scope of the concentration of volume percent of the two thio nonmetallic hydrochlorates and its oligomer is percent by volume 40-60%.
  9. 9. the preparation application method of two thio nonmetallic hydrochlorate and its oligomer depressing agent as claimed in claim 8, its It is characterized in that：The use environment of the two thio nonmetallic hydrochlorates and its oligomer-diminishing agent is neutral model of the pH value in 6-9 Enclose, carry out iron sulfide mineral flotation.
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CN109365138A (en) * 2018-11-30 2019-02-22 河南城建学院 A new type of composite flotation agent for flotation of copper-nickel sulfide ore

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CN102698878A (en) * 2012-05-30 2012-10-03 西北矿冶研究院 Pyrite inhibitor used under low-alkalinity condition
CN103157560A (en) * 2013-03-29 2013-06-19 云南金鼎锌业有限公司 Flotation method of vulcanizing lead and zinc by weak acid full pulp
TW201438820A (en) * 2013-04-15 2014-10-16 Vale Sa A method for improving selectivity and recovery in the flotation of nickel sulphide ores that contain pyrrhotite by exploiting the synergy of multiple depressants
CN104718027A (en) * 2012-04-12 2015-06-17 瓦勒股份有限公司 A method for improving selectivity and recovery in the flotation of nickel sulphide ores that contain pyrhotite by exploiting the synergy of multiple depressants

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US20030231995A1 (en) * 2002-02-12 2003-12-18 Javier Jara Use of ozone to increase the flotation efficiency of sulfide minerals
CN104718027A (en) * 2012-04-12 2015-06-17 瓦勒股份有限公司 A method for improving selectivity and recovery in the flotation of nickel sulphide ores that contain pyrhotite by exploiting the synergy of multiple depressants
CN102698878A (en) * 2012-05-30 2012-10-03 西北矿冶研究院 Pyrite inhibitor used under low-alkalinity condition
CN103157560A (en) * 2013-03-29 2013-06-19 云南金鼎锌业有限公司 Flotation method of vulcanizing lead and zinc by weak acid full pulp
TW201438820A (en) * 2013-04-15 2014-10-16 Vale Sa A method for improving selectivity and recovery in the flotation of nickel sulphide ores that contain pyrrhotite by exploiting the synergy of multiple depressants

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109365138A (en) * 2018-11-30 2019-02-22 河南城建学院 A new type of composite flotation agent for flotation of copper-nickel sulfide ore

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