CN104718027B

CN104718027B - The method for improving selectivity and the rate of recovery in the flotation of the nickel sulfide ores containing magnetic iron ore by using the synergy of various inhibitors

Info

Publication number: CN104718027B
Application number: CN201380030461.7A
Authority: CN
Inventors: J·董; M·徐
Original assignee: Vale SA
Current assignee: Vale SA
Priority date: 2012-04-12
Filing date: 2013-04-12
Publication date: 2017-07-18
Anticipated expiration: 2033-04-12
Also published as: AU2013247335A1; KR102062935B1; AU2013247335B2; EP2864052A1; KR20150067088A; CN104718027A; CA2873696C; RU2014145344A; RU2633465C2; CA2873696A1; WO2013152412A1

Abstract

The suppression of the iron sulfide in the flotation of nonferrous metal sulfide is improved using the synergy of various inhibitors without damaging the rate of recovery of valuable sulfide mineral while reducing or eliminating the method using environment-conscious chemicals such as polyamines.This method has significant economy and environmental benefit.The various inhibitors include at least one organic polymer, at least one sulfur-containing compound and/or at least one organic compounds containing nitrogen.

Description

By using the synergy of various inhibitors in the nickel sulfide ore containing magnetic iron ore The method that selectivity and the rate of recovery are improved in the flotation of stone

This application claims entitled " the A Method for Improving submitted April 12 for 2012 Selectivity and Recovery in the Flotation of Nickel Sulphide Ores that The Contain Pyrrhotite by Exploiting the Synergy of Multiple Depressants " U.S. is special Profit application No.61/623,459 priority, and be herein incorporated by it herein with it by quoting.

Invention field

The method that present disclosure is directed to use with the next selective froth flotation sulfide mineral of combination of inhibitor reagent.

Background of invention

Since twentieth century early stage, sulfide mineral flotation has been put into practice.Its industrial significance is recognized well, Because can more economic melting and refining the concentrate from flotation, to provide crude metal.Froth flotation is by using surface Method of the hydrophobic difference from the useless valuable mineral of rock material Selective Separation.Usually, method for floating is included in underflow The ore pulverized is ground in material to monomer separation granularity, then it is adjusted with different reagents in suitably dilution slurries (conditioning).These reagents include trapping agent, inhibitor, foaming agent, modifying agent etc..Trapping agent passes through physical/chemical Absorption makes the surface of required mineral be hydrophobic, and this contributes to bubbles attached, and the bubble make it that mineral grain floats to slurry Material surface simultaneously forms stable foam, collects the foam of the stabilization for further processing.Inhibitor has and trapping agent phase Anti- effect, by adsorb hydrophilic component or by remove for trapping agent absorption avtive spot, make unwanted The surface of mineral grain becomes hydrophilic, so that particle is retained in mine tailing part.Foaming agent contributes to the stable conjunction in slurry The bubble of suitable size, to capture and transfer particle is to flotation area.Modifying agent is generally used for pH controls.Used froth flotation Various schemes it is generally considerably complicated, maximized so as to the grade and the rate of recovery of the valuable mineral that make presence, and make to have The rock of little commercial value and sulfide mineral give up maximization.

In the processing of the sulfide ore for reclaiming non-ferric rich ore metal, the mineral of handled common value include Respectively for the pentlandite and capillose for W metal, Cu, Pb and Zn, chalcopyrite and vitreous copper and bornite, galena, And zincblende.However, these valuable mineral natively with iron sulfide, i.e., without commercial value and be considered as sulfide Magnetic iron ore, pyrite and the marcasite of gangue are combined.Concentrate can be significantly improved by selectively giving up iron sulfide in flotation SO in economic worth and also reduction smelting device₂Discharge, wherein iron sulfide significantly assist in the discharge of these gases.However, magnetic Giving up for pyrite is challenging.It is directed not only to the abundance of magnetic iron ore in ore, and further relates to magnetic iron ore Crystal structure (i.e. monocline, six sides or troilite).In addition, magnetic iron ore closely with other mineral, mainly and pentlandite With reference to.By magnetic iron ore selective depression without damaging the Cu and Ni rate of recovery for being processed in industrial mineral in floatation process It is a key for generation commercial value in factory.

United States Patent (USP) No.5,074,993 method for describing flotation sulfide, wherein by consumption>50g/mt mill Magnetic iron ore is suppressed using water-soluble polyamines in garrulous mineral mixture.Water-soluble polyamines are preferably diethylenetriamines (DETA), and it is further selected from including following lists：Including trien, tetren, penten, 2- [(2- aminoethyls) amino] ethanol, three-(2- aminoethyls) amine, N- lethylenediamines and 1,2-diaminourea 2- methylpropanes.

United States Patent (USP) No.5,411,148 describes the improvement that list-or many metallicity sulfide minerals are separated from iron sulfide Method.The regulation section that this method is included in before the inorganic compound flotation with least one water-soluble sulfur-bearing is used as using such as The steps necessary before the further regulation of nitrogenous organic sequestering agent described in US5,074,993.The water-soluble sulfur-bearing is inorganization Compound is preferably sodium sulfite (Na₂SO₃), and sulfide, dithionate, tetrathionate and sulfur dioxide are further selected from, its Consumption changes to the drying solid that 600g/mt is processed from 50.Nitrogenous organic sequestering agent is preferably for specific flotation feed For the polyethylene polyamine that is used under enough dose, such as diethylenetriamines (DETA).Due to being added with particular order Sulfur-containing compound and organic compounds containing nitrogen combined effect, magnetic iron ore is suppressed.

Suppressed using selective magnetic iron ore, preceding method has very much in terms of increase Ni and Cu concentrate grade and the rate of recovery Effect.However, for total (the solvable and insoluble) Cu and Ni discharged in effluent, the behaviour of wastewater treatment can be made using DETA Complicate.DETA is extensive chemical chelating agent, and it forms stable complex compound with heavy metal ion such as Cu and Ni.Pass through rise PH is higher than 11 (this is generally carried out in wastewater treatment plant), it is impossible to go out these complex compound sediments.On the contrary, polyamines is sunk Shallow lake agent is for example8702 (available from Nalco Company, Naperville, IL) are added to waste water, with DETA- Metal complex reacts and forms precipitation.However, precipitation is very thin particle, it is not settled in clarifier, so that It must be difficult to effectively remove Cu and Ni from waste water.In order to avoid when using DETA in waste water high content Cu and Ni, make great efforts true Fixed alternative iron sulfide inhibitor, DETA is used to reduce or eliminate.

Newest patent (United States Patent (USP) No.8,221,709) from LignoTech, which describes, uses hardwood lignin sulfonic acid Salt is used for the method that rock material is separated from metallicity sulfide ore.The patent is specified to be obtained from eucalyptus, maple and birch Three kinds of hardwood lignosulfonates with different sulphur or sulfonate content and molecular weight, and in ore slurry (it ground Including copper sulfide, zinc sulphide or vulcanized lead and iron sulfide) flotation in~250-500g/mt dosage NaCN additions Under, compare their performance.Lignosulfonates can be added before or after other reagents and pH regulations.However, in work In the case of only adding ligninsulfonate in industry method, the selectivity between Cu/Ni sulfide and magnetic iron ore is not changed Enter.

In this meaning, prior art lacks following methods：A) in the Cu/Ni sulfide minerals combined with iron sulfide Flotation in improve selectivity and the rate of recovery, and b) reduce or eliminate using problematic polyamines chemicals (such as DETA), with Minimize the negative effect to environment.

Summary of the invention

In view of the above the problem of and unmet needs, the invention discloses the collaboration using various inhibitors The suppression for acting on improving the iron sulfide in the flotation of nonferrous metal sulfide is without damaging returning for valuable sulfide mineral Yield reduces or eliminates the method using environment-conscious chemicals such as polyamines simultaneously.This method have it is significant economical and Environmental benefit.It is included in during method for floating as the slurry of fresh ground or as preprocessed and fine ground technique The Cu/Ni sulfide ores of intermediate and the flotation example of magnetic iron ore.

The essence of this method is directed to use with various inhibitors, so that using the single inhibition of every kind of chemicals, and Produce synergy to improve selectivity and the rate of recovery and the use of polyamines is reduced at least 50%, or just eliminate as possible The use of polyamines.Used three kinds of chemicals include 1) polyamines, such as DETA；2) water-soluble sulfur-bearing inorganic compound, for example Sodium sulfite；With 3) hardwood lignin sulfonic acid product salt, the preferably lignin with 6kDa molecular weight, 5% sulfonate and 2% sugar Sulfoacid calcium, and especially from LignoTech D-912 products.These chemicals are used alone, and or a) no generation is filled The magnetic iron ore of foot suppresses, otherwise the Cu/Ni rate of recovery b) is reduced, or c) due to the heavy metal of potential high content, at waste water Cause environmental effluent problems in science and engineering factory.

Can addition or in order three kinds of chemicals of (without preferred sequence) addition respectively simultaneously, or by three kinds of chemicals with It is preferred that ratio be pre-blended into single solution.Similarly, two kinds of components can be pre-blended into single solution with preferred ratio, and The third component is added separately to the consumption of change.Inhibitor can be added before or after other flotation reagents.

The improvement for the non-ferric rich ore metal that each aspect of the present invention promotion selective recovery is combined with iron sulfide.

Each aspect of the present invention promotes the synergy between inhibitor and trapping agent, so that with using DETA/Na₂SO₃Group Close the polyamines dosage typically used to compare, it is allowed to which polyamines (i.e. DETA) dosage reduces at least 50%, without damaging floatation process In selectivity and the rate of recovery.

Each aspect of the present invention helps to avoid to cause because forming DETA- metal complexs in wastewater treatment plant The discharge of the heavy metal and DETA of existing pressure limitation.

Additional advantage and the novel feature part of the aspects of the invention will be listed in subsequent explanation, and for For those skilled in the art, when consulting the description below or when being learnt by putting into practice the present invention, a part will become It is more obvious.

Brief description

It will refer to but be not limited to following accompanying drawings, the various illustrative aspects of system and method are described in detail, wherein：

Fig. 1 is to be set forth in the curve map suppressed in coarse classifier flotation only with the low magnetic iron ore of D912 efficiency；

Fig. 2 is to be set forth in coarse classifier flotation to use D-912 and Na₂SO₃Effective magnetic iron ore suppress curve map；

Fig. 3 A and 3B are to illustrate to use D-912 and Na for intermediate stream₂SO₃The relatively low rate of recovery curve map；

Fig. 4 A and 4B are to illustrate to use D-912, Na for intermediate stream₂SO₃, DETA and PAX magnetic iron ore suppress Synergy curve map-dosage and the influence of order of addition；

Fig. 5 is to illustrate to use D-912, Na for intermediate stream₂SO₃, DETA and PAX the association that suppresses of magnetic iron ore The curve map of the same-action-optimization dosage from factorial design experiment；

Fig. 6 A and 6B are to illustrate to use D-912, Na for intermediate stream₂SO₃And DETA magnetic iron ore suppression The curve map of synergy-carry out self-optimizing and repeat the synergy research of experiment；

Fig. 7 is to illustrate to use D-912, Na₂SO₃And the order of curve map-addition reagent of DETA magnetic iron ore suppression/ The influence of method；

Fig. 8 A and 8B are to be set forth in middling stream (middling stream) to use D-912, Na₂SO₃And DETA magnetic The curve map for the synergy that pyrite suppresses；With

Fig. 9 A and 9B are illustrated using the new inhibitor mixture identified in embodiment 5 and 6 respectively to concentrate and tail The figure of the influence of the quality of mineral water.

Describe in detail

Following detailed description is in no way intended to limit the scope of the present invention, applicability or construction.More specifically, the description below is carried Necessary for the example feature for implementing the present invention understands.When using teaching provided herein, people in the art Member will recognize the workable suitable alternative in the case of no extrapolation scope of the invention.

The present invention describe contained using the synergy of various inhibitors come selective floation it is at least one or more of non- Iron rich ore metal and the sulfide mineral that is combined with iron sulfide are to obtain good degree and the recovery of non-ferric rich ore metal values The method of rate, the iron sulfide is mainly made up of magnetic iron ore.By using the synergy obtained using various inhibitors, close The dosage of one of chemicals of key (i.e. DETA) can be substantially reduced, so as to mitigate the potential negative effect to environment.This method bag Include：

I) in trapping agent, foaming agent, pH modifying agent and the vector gas being distributed among slurry in aqueous alkaline slurry And handle sulfide ore in the presence of various inhibitors, the sulfide ore for fresh ground slurry or it is preprocessed and The process intermediates of fine ground, it contains at least one or more of non-ferric rich ore bacterial attachment (Cu/Ni) and iron sulphur Compound (magnetic iron ore).

Pending slurry contains iron sulfide at most~80%.Non-ferric rich ore metal sulfide can be pentlandite And capillose, chalcopyrite and vitreous copper and bornite, galena, and zincblende are (for they are respectively for Ni, Cu, Pb and Zn It is valuable mineral).Iron sulfide can be magnetic iron ore, pyrite and marcasite.

Trapping agent may be selected from xanthates and/or ester, dithiophosphates and/or ester, thiocarbamate and/or Ester, dithiocar-bamate and/or ester, phosphonodithious acid salt and/or ester, xanthogen formate salt and/or ester, xanthan ester or its At least one in mixture.An example is used as using amylic potassium xanthate.For the good recovery of rich ore metal, The dosage of trapping agent is adjusted according to the dosage of inhibitor.

The foaming agent tested is polyglycol ether (F160-13, Flottec), it is also possible to selected from natural oil, alcoxyl At least one in base alkane, fatty alcohol, polyglycol ether, polypropylene glycol.Foaming agent be not in the present invention it is main because Element.

The pH modifying agent tested is pH 9.5 lime, it is also possible to being soda ash or NaOH.PH scopes can To be 8-12.

Used vector gas are air.It may also is that nitrogen, the air rich in nitrogen or rich oxygen containing air or two Carbonoxide (rich carbonated air).

, it is necessary to regulating step after addition trapping agent or inhibitor.

Flotation unit can be with 2.2L grooves and 1200rpm electromotor velocities or electronic with 1.1L grooves and 900rpm The standard Denver flotation units of machine speed.

Ii) various inhibitors contain at least one organic polymer (calcium lignosulfonate from hardwood), at least one Sulfur-containing compound and at least one organic compounds containing nitrogen (polyamines) if, be used alone the latter or with a kind of sulfur-bearing chemical combination Thing is used in combination and compared, and the latter is present in mixture with less consumption.

" organic polymer " is at least one electronegative watersoluble organic polymer, and it is selected from by sulfomethylated lignin The group of one or more compositions in hydrochlorate, dextrin, guar gum, cassava, starch or cellulose.It is preferred that one kind be to have The calcium lignosulfonate from hardwood of 6kDa molecular weight and 5% sulfonate and 2% sugar.A kind of such product is to come from LignoTech " D-912 ", this is determined by LignoTech patents.

" sulfur-containing compound " is at least one water-soluble inorganic sulfur-containing compound, and it is selected from by one or more sulphur Compound, sulphite, bisulfites, metabisulfite (meta-bisulphate), dithionate, tetrathionate, The group constituted with sulfur dioxide.It is preferred that one kind be sodium sulfite (Na₂SO₃)。

" organic compounds containing nitrogen " is at least one organic compounds containing nitrogen, its have be selected from by with The configuration of the group of one or more compositions in polyethylene-polyamines of OCNCCCNCNC and NCCN structures, including diethylidene Triamine, trien, tetren, penten, ethoxy-DETA, diethanol amine and aminoethyl ethanol Amine.It is preferred that one kind be diethylenetriamines (DETA).

Iii) addition various inhibitors have following selections, wherein allowing certain regulating time：

Them can be added simultaneously respectively；Or

Them can be added (without any preferred sequence) in order, and be with or without regulation among each other；Or

They can be pre-blended into single solution with predetermined preferred proportion；Or

Two kinds of components can be pre-blended into single solution with predetermined preferred proportion, and optionally with the consumption of change Individually add the third component.

Inhibitor can be added before or after trapping agent, and with certain regulation.

Iv) for the polyamines use of synergy and reduction, the dosage of inhibitor will depend on ore type, grade Constitute, and therefore should be determined by experiment with its mineralogy.For the ore sample tested, D-912 Dosage range be 50-150g/t, Na₂SO₃>=100g/t, and DETA are 0-50g/t.For intermediate stream, quote Dosage referring again to the ore ground.DETA dosage keeps as low as possible without damaging global selectivity and the rate of recovery, to keep away Exempt from high-caliber heavy metal in waste water.

V) therefore, regulation is trapped into agent dose for the metallurgy method of optimization, because between trapping agent and inhibitor In the presence of competition.

In preferred embodiments, the present invention relates to the use of various inhibitors synergy selective floation contain to Few one or more non-ferric rich ore metal and at least one or more of sulfide mine combined with the iron sulfide in sulfide ore The method of thing, this method includes：

I) in trapping agent, foaming agent, pH modifying agent and the carrier being distributed among the slurry in aqueous alkaline slurry Sulfide ore is handled in the presence of gas and various inhibitors, the sulfide ore is for the slurry of fresh ground or through pre- Processing and the process intermediates of fine ground, it contains combined with least one iron sulfide mineral at least one described valuable Sulfide mineral, select the various inhibitors to include at least one organic polymer, at least one sulfur-containing compound and/or extremely A kind of few organic compounds containing nitrogen；With

Ii froth flotation) is carried out so that iron sulfide to be suppressed, while allowing the valuable non-iron sulfide of flotation.

In another preferred embodiment, the present invention relates to contained using the synergy selective floation of various inhibitors There is at least Ni, Cu, Co, Pt, Pd, Au and Ag rich ore metal and (it is included in sulfide ore at least with iron sulfide mineral Magnetic iron ore) at least Ni/Cu/Co sulfide minerals that combine, this method includes：

I) in trapping agent, foaming agent, pH modifying agent, the carrier gas being distributed among the slurry in aqueous alkaline slurry Ni/Cu/Co sulfide ores are handled in the presence of body and various inhibitors, the Ni/Cu/Co sulfide ores are fresh ground Slurry or preprocessed and fine ground process intermediates, it contains at least mineral nickel yellow combined with least magnetic iron ore Iron ore and vitreous copper, and the various inhibitors include lignin sulfonic acid calcium product (preferred product, such as D-912), sulfurous acid Sodium (Na₂SO₃) and/or DETA；With

Ii froth flotation) is carried out so that magnetic iron ore to be suppressed, while allowing the valuable pentlandite of flotation and vitreous copper.

Or, the method for three kinds of inhibitor of addition may include：1) respectively but all simultaneously；With 2) in order and individually adjust Section.

In addition, inhibitor solution can be added before or after trapping agent.

For the polyamines use of synergy and reduction, it is found that the dosage of inhibitor depends on ore type, grade Constitute, and therefore should be determined by experiment with its mineralogy.For the ore sample tested, D-912's Dosage range is 50-150g/t, Na₂SO₃>=100g/t, and DETA are 0-50g/t.For intermediate stream, reference Dosage is referring again to the ore ground.

By, using making the magnetic iron ore that every kind of inhibitor is obtained suppress to maximize, obtaining many when using under minimum dose (by by DETA, Na during kind of inhibitor₂SO₃With D-912 combine) obtain collaboration magnetic iron ore suppress.More specifically, in sulphur Change DETA, Na during iron suppresses₂SO₃There is themselves unique function with D-912.What PYRRHOTITE BY FLOTATION was proposed with three kinds Mechanism：1) Cu is activated, to promote trapping agent (xanthates and/or ester) to adsorb；2) formed many-sulphur (poly-sulfur), with Some hydrophobicity sites are produced on Surface of Pyrrhotite for bubble to adhere to；With 3) form two xanthan for hydrophobicity site Acid.DETA can remove or cover the Cu on iron sulfide²⁺Site is activated, is adsorbed with the trapping agent suppressed on a surface.Pass through Remove the trapping agent or many sulphur of formation in iron sulfide Adsorption on Surface, Na₂SO₃Iron sulfide flotation can be prevented.D-912 is that band is negative The hydrophilic polymer of electricity, it can pass through avtive spot (such as Fe (OH)²⁺, Ca²⁺Or Cu²⁺) be adsorbed onto on vulcanization iron surface, make Its surface is hydrophilic, so that iron sulfide be suppressed.

In the case of the single inhibitor using any one, do not damaging rich ore metal recovery rate or causing high in waste water In the case of the heavy metal of level, there is no effective magnetic iron ore and suppress.By using three kinds of different inhibitor simultaneously, Generate synergy.Advantage can be obtained by each in three kinds of reagents, so as to cause to make iron sulfide suppress maximization, simultaneously Minimize the reduction of the rate of recovery of valuable mineral.

Embodiment

Following embodiments are intended to illustrate, and are in no way intended to limit the scope, applicability or construction of claimed invention.

In the accompanying drawings, it shall be noted that used shorthand in the axle title of mineral.Including symbol：Pn (nickel yellow iron Ore deposit), Cp (chalcopyrite) and Po (magnetic iron ore).

Embodiment 1

Suppress only with the low magnetic iron ore of D-912 efficiency

Fig. 1 presents wooden using only hardwood in the process in United States Patent (USP) No.8,221,709 (LignoTech) The nickel-copper ore that plain sulfonate product D-912 is handled as magnetic iron ore inhibitor (contains about 1.5%Ni (3.7% nickel yellow iron Ore deposit), 1.5%Cu (4.3% chalcopyrite) and 21%Fe (19.7% magnetic iron ore) and 72.3% rock (other silicate)) it is thick Select the result of the accumulation rate of recovery of pentlandite and magnetic iron ore in machine flotation.In this experiment, in addition 5g/t trapping agents In the case of (PAX-amylic potassium xanthate) and 400g/t lime, 1kg ores are milled in rod mill and reach the μ of P80~106 m.Using lime as modifying agent, in 9.5 times progress of pH, incrementally coarse classifier is tested.In addition inhibitor and trapping agent respectively Afterwards, there is the regulation of 2 minutes, and 15ppm foaming agents (F160-13) are in process water.Using with 1200rpm rotary shafts 2.2L Denver flotation cells, and apply in flotation the air of 3L/ minutes.Essence is collected 0.5, after 1,2,5,8 and 12 minutes Ore deposit.Chemicals addition of the addition in coarse classifier is summarized in table 1.

Do not show that magnetic iron ore suppresses only with the experiment of trapping agent (PAX).Using DETA/Na₂SO₃Experiment represent Acceptable magnetic iron ore suppresses and rich ore metal recovery rate.

With using DETA and Na₂SO₃Combination (i.e. " benchmark " chemicals) compare, using hard under 25-50g/t dosage Wooden lignin sulfonic acid product salt D-912 does not improve magnetic iron ore as magnetic iron ore inhibitor and suppressed.With DETA and Na₂SO₃'s Combination is compared, and pentlandite is suppressed significantly under 250g/t high D-912 dosage, and without the yellow iron of improvement pentlandite/magnetic The selectivity of ore deposit.

Embodiment 2

D-912 and Na is used for a kind of ore₂SO₃Effective magnetic iron ore suppress

Fig. 2 presents pentlandite and magnetic in the coarse classifier flotation of nickel-copper ore identical with used in embodiment 1 The result of the accumulation rate of recovery of pyrite, wherein by Na₂SO₃It is added to D-912 in coarse classifier.With side same as Example 1 Formula grinds ore, including addition 5g/t trapping agents (PAX) and addition 400g/t lime.Work as Na₂SO₃During dosage >=200g/t, observation Suppress to magnetic iron ore.The chemicals addition in coarse classifier flotation is summarized in table 2.

Demonstrate using 200g/t Na₂SO₃Dosage suppress that there are some effects to magnetic iron ore in itself, but result is not so good as Use benchmark chemicals DETA and Na₂SO₃Those obtained are so good.Using D-912 and Na₂SO₃Experiment in, work as Na₂SO₃ Dosage>During 100g/t, it was observed that some signs that magnetic iron ore suppresses.Work as Na₂SO₃Dosage >=200g/t and D-912 dosage >= During 50g/t, using D912/Na₂SO₃Obtain and benchmark DETA/Na₂SO₃Similar pentlandite/magnetic iron ore selectivity curve. D-912 dosage is increased into 100g/t and by Na from 25₂SO₃Dosage increase to 400g/t from 200 and do not significantly change nickel yellow Iron ore/magnetic iron ore selectivity curve shape (i.e. the pentlandite rate of recovery with the decline of the magnetic iron ore rate of recovery under Drop).

For this raw material, it is not necessary to add DETA, this is preferred for environmental concern.

Embodiment 3

D-912 and Na is used for intermediate stream₂S0₃The relatively low rate of recovery

Fig. 3 A and 3B are presented containing 7.6%Cu (21.9% chalcopyrite), 6.4%Ni (17.3% nickel yellow iron respectively Ore deposit), the pentlandite/magnetic accumulated in the refiner flotation of the intermediate stream of 37%Fe (39.8% magnetic iron ore) and 21% rock The result of pyrite and chalcopyrite/magnetic iron ore selectivity, wherein by Na₂SO₃It is added to D-912 in refiner.This research It is related to coarse classifier and refiner float test, and inhibitor is added in refiner section.10g/t trapping agents (PAX) will be amounted to It is added in coarse classifier flotation, and collects coarse classifier concentrate and continues 6 minutes.In refiner section, lime is used under pH 9.5 It is used as modifier treatment coarse classifier concentrate.Regulation after addition inhibitor respectively and trapping agent in the presence of 2 minutes, and 15ppm Foaming agent (F160-13) is in process water.Using the 1.1L Denver flotation cells with 900rpm rotary shafts and in refiner The air of application 1L/ minutes in flotation.1.5, after 3,5 and 16 minutes, refiner concentrate is collected.Summarized in table 3 Chemicals addition in refiner flotation.

As D-912 dosage >=50g/t and with 200g/t Na₂S0₃When, it was observed that selectivity is improved and even good In DETA/Na₂S0₃Benchmark.However, the rate of recovery of chalcopyrite declines~15%.If D-912 dosage further decline (≤ 25g/t) or PAX dosage increase, then will infringement selectivity.This is unacceptable for industrial production.

Embodiment 4

D-912, DETA, Na are used for intermediate stream₂S0₃The synergy suppressed with PAX magnetic iron ore

Fig. 4 A and 4B present the tired of the refiner flotation from intermediate stream identical with used in embodiment 3 respectively The result of long-pending pentlandite/magnetic iron ore and chalcopyrite/magnetic iron ore selectivity.In this embodiment, by DETA with Na₂S0₃Be added to D-912 in refiner, but with as DETA and Na₂S0₃It is used as a part of phase of " benchmark " condition together Than dosage is reduced.This research is related to the coarse classifier described in embodiment 3 and refiner float test.Summarized in table 4 Chemicals addition in refiner flotation.

In the experiment (T18309, T18310, T18311) of dosage for fixing every kind of chemicals wherein, change addition chemistry The order of product.The marked difference of result is not seen.

In the experiment of dosage of inhibitor and trapping agent is wherein changed, otherwise selectivity is very good, but pentlandite and The rate of recovery of chalcopyrite is far below target (T18309, T18310, T18311), otherwise the rate of recovery of pentlandite and chalcopyrite is It is acceptable, but be selectively remarkably decreased (T18358, T18360).

Only when reaching balance (T18359) between trapping agent and inhibitor, selectivity and the rate of recovery are close to " benchmark " As a result.In D-912, DETA and Na₂S0₃Under the suitable dose of trapping agent (PAX), good selectivity and the rate of recovery is obtained.

Embodiment 5

It is used for D-912, DETA and the Na for finding the synergy suppressed for magnetic iron ore for intermediate stream₂S0₃ With the factorial design experiment of PAX optimization dosage

Fig. 5, which is presented, is keeping Na₂S0₃Dosage fix while between D-912, DETA and trapping agent (PAX) mutually The 2 of effect³The result of factorial design experiment.Result from embodiment 4 shows that the combination of three kinds of chemicals is produced as inhibitor Synergy is given birth to, this allows DETA dose degradations, while the good selectivity of maintenance and rich ore metal recovery rate.It is same with this When, it is found that the dosage of trapping agent plays very important effect.In order to further confirm to act synergistically and determine every kind of chemicals Dosage optimization range, in the case where chemicals to be added to refiner section, carry out to PAX, DETA and D-912 dosage - two grades (2 of three factor³) factor design research.Raw material is identical with described in embodiment 3.Coarse classifier-refiner flotation circuit It is identical with described in embodiment 3.In all these experiments, Na is added under 200g/t fixed dosage₂S0₃.In table 5 Define DETA, D-912 and PAX dosage and experimental condition.

In the experimental design, the standard of selective dose includes：A) DETA dosage should be less than in DETA/Na₂S0₃Combination Used in level (i.e. usual 50g/t)；B) because result above is shown<50g/t D-912 dosage does not work, and And the upper limit is unknown, therefore extend the dosage to higher level；And c) because the result of embodiment 5 is shown in 10-15g/t's The rate of recovery of pentlandite and chalcopyrite is sufficient under PAX dosage, thus need not be reached more much higher than normal (i.e. 5g/t) Dosage.

In one group (FD2, FD3, FD5 and FD7) using high dose D-912, obtain with low-down nickel yellow iron The high concentrate grade of the ore deposit rate of recovery (20~50%), this shows that 150g/t D-912 levels are too high.Using high dose PAX and In low dosage D-912 another group (FD8 and FD9), pentlandite/magnetic iron ore selectively declines, so as to cause to be less than target Concentrate grade.The result between these limiting values is generated using the dosage (FD1) at the intermediate point of the scope.It can see Go out under 10g/t PAX, 50g/t D-912 and 15g/t DETA (FD6), obtain good pentlandite/magnetic iron ore choosing Selecting property, and result is close to DETA/Na₂0₃Those of benchmark.Under these dosage the chalcopyrite rate of recovery it is also very good (~ 90%).

Embodiment 6

D-912, DETA and Na are used for the synergy that the magnetic iron ore of intermediate stream suppresses₂S0₃Optimization and Repeat to test

Fig. 6 presents is used together D-912, DETA and Na to verify to work as₂S0₃When repeatable synergy (it is in reality Apply and be proven in example 5) and optimization chemicals dosage and the Optimum Experiment and the result of reference test that carry out.Coarse classifier-essence Select machine flotation circuit identical with described in embodiment 3.Intermediate stream is identical with described in embodiment 3.Defined in table 6 It is added to the dosage of the chemicals of refiner.By providing good result (FD6：Using 15g/t DETA, 50g/t D-912 and 10g/t PAX) condition be starting, when excluding D-912 (T18558) or DETA (T18560) or Na₂S0₃(T18612) when, nickel Pyrite/magnetic iron ore selectivity is less as so good when being used together all chemicals.

The result of other repetitions and optimization is all in the selective scope of identical pentlandite/magnetic iron ore, and this shows Stable performance.It can be seen that：A) pentlandite and the chalcopyrite rate of recovery a little hundred can be reduced by D-912 dosage being increased into 75g/t Branch；B) DETA dosage is changed to 25 from 15, then change does not influence the rate of recovery and selectivity to 35g/t, thus preferably Relatively low DETA dosage (15g/t)；And c) slightly reduction PAX dosage (i.e. from 10 to 7.5g/t) has no significant effect to result.

Embodiment 7

Add D-912, DETA and Na₂S0₃Order and method influence

Fig. 7 presents the result of the order and method of evaluating addition chemicals.Intermediate stream and the phase described in embodiment 3 Together.Coarse classifier-refiner flotation circuit is identical with embodiment 3, and uses following conditions：1) addition three simultaneously under regulation Plant chemicals (D-912, DETA and Na₂S0₃)；2) Na is added in order₂S0₃, DETA and D-912 and come for adding each time Say with a regulating time；3) DETA and D-912 are pre-blended into a kind of solution, and as single agents under regulation With Na₂S0₃It is added in slurries；With 4) by DETA, D-912 and Na₂S0₃A kind of solution is pre-blended into, and is made under regulation It is added to for single agents in slurries.

The chemicals addition in refiner and the condition of adding method are summarized in table 7.

The difference with insignificance of the result obtained using the various methods of addition chemicals, because all results are shown well Selectivity.The advantage for adding three kinds of chemicals respectively is individually to adjust each dosage.Being provided using aqueous premix is used for The fairly simple scheme of arranging chemical product holding vessel and transfer line, when condition is completely set up, this is good.

Embodiment 8

D-912, DETA and Na are used for another middling stream₂S0₃Magnetic iron ore suppress synergy

Fig. 8 A and 8B, which are presented, is shown in addition D-912, Na in middling stream₂S0₃With DETA to the suppression of magnetic iron ore The result of influence.Using containing 1.0%Cu (2.7% chalcopyrite), 2.0%Ni (4.3% pentlandite), 44.6%Fe The middling raw material of (65.7% magnetic iron ore) and 27.3% rock, carries out two sections of coarse classifier-refiner float tests.In table 8 In summarize coarse classifier and refiner section in chemicals addition.

Fig. 8 A are presented by the way that inhibitor only is added into the result obtained in coarse classifier section.With the situation only with PAX (T20013) compare, addition D-912 causes the significantly reduced magnetic iron ore rate of recovery.By D-912 and Na₂S0₃(T20027) combine The influence suppressed to magnetic iron ore is less as being used together D-912, Na₂S0₃(T20030) is so good during with DETA.From use The result of the experiment of these three chemicals is relatively close to DETA/Na₂S0₃Benchmark (T20016), but added with much lower DETA (~40%DETA).

Fig. 8 B present result by the way that inhibitor to be added to the two the interior acquisition of coarse classifier and refiner section.When using three Plant chemicals (D-912, DETA and Na₂S0₃) combination when, by enough D-912 be added to coarse classifier section in be most critical. If coarse classifier section in this dose be not it is sufficiently high (i.e.<75g/t D-912), then there is seldom magnetic iron ore suppression System.In the case of using high dose D-912 in coarse classifier section, more D-912 is added in refiner section and can further be changed Enter pentlandite/magnetic iron ore selectivity.In a word, it is necessary to the D- of enough dose in the flotation of high magnetic iron ore middling stream 912、DETA、Na₂S0₃It is selective to realize good pentlandite/magnetic iron ore with PAX.

Embodiment 9

By using D-912, DETA and Na₂S0₃Combination reduction process water in DETA, Cu and Ni residual quantity

Fig. 9 A and 9B are elaborated using the new inhibitor mixture identified in embodiment 5 and 6 respectively to concentrate and tail The influence of the quality of mineral water.Using the process described in embodiment 3, on nickel-copper ore identical with used in embodiment 1 Carry out two coarse classifier-refiner float tests." benchmark " condition of use, using 50g/t DETA, 200g/t Na₂S0₃Carry out First experiment.Using new condition, using 50g/t D-912,15g/t DETA and 200g/t Na₂S0₃Second is carried out to test.Before Face shows this two groups of conditions, result in similar flotation metallurgy.After flotation, collect concentrate from each experiment and Tailing water, and analyze DETA, Cu and Ni of residual.Analysis result is summarized in table 9.It can be clearly seen that using D-912, DETA and Na₂S0₃New blend obtain DETA, Cu and Ni reduction residual level.

Known different gangue solids each have the certain capabilities for stably adsorbing DETA.The result provided in table 9 is tested Demonstrate,prove by using D-912, DETA and Na₂S0₃Combination with reduction DETA dosage, DETA in process water can be significantly reduced Residual quantity.The DETA of this amount can be adsorbed on gangue solids, and not have any negative effect to wastewater treatment plant.

Claims

1. improve the valuable non-ferric vulcanization combined in the foam flotation method on nonferrous metal sulfide with iron sulfide The selectivity of thing mineral and the method for the rate of recovery, this method include：

In trapping agent, foaming agent, pH modifying agent, vector gas being distributed among slurry and a variety of in aqueous alkaline slurry Sulfide ore is handled in the presence of inhibitor, the sulfide ore is the slurry or preprocessed and fine ground of fresh ground Process intermediates, it contains at least one or more of non-ferric rich ore bacterial attachment and iron sulfide, selects this variety of Inhibitor includes at least one organic polymer selected from hardwood lignosulfonates, at least one and is selected from water-soluble inorganic sulfur-bearing The sulfur-containing compound of compound and at least one organic compounds containing nitrogen, at least one organic compounds containing nitrogen have choosing Freely there is the configuration of the group of one or more polyethylene polyamines composition of OCNCCCNCNC and NCCN structures；With

Froth flotation is carried out so that iron sulfide to be suppressed, while allowing the valuable non-iron sulfide of flotation.

2. method according to claim 1, wherein the sulfide mineral is pentlandite and capillose, chalcopyrite and vitreous copper And at least one in bornite, galena, or zincblende, or its mixture, it is the ore or preprocessed of fresh ground Intermediate stream.

3. method according to claim 1, wherein at least one or more of non-ferric rich ore metal is selected from sulfide mineral Nickel, copper, zinc and lead, cobalt, platinum, palladium, gold and silver-colored part.

4. method according to claim 1, wherein the iron sulfide is magnetic iron ore, pyrite and marcasite or its mixing Thing.

5. method according to claim 1, wherein the pH of the aqueous alkaline slurry is 8 to 12.

6. according to the method for claim 1 or 5, wherein the pH of the aqueous alkaline slurry is 9.5.

7. method according to claim 1, wherein the trapping agent be xanthates and/or ester, dithiophosphates and/or Ester, thiocarbamate and/or ester, dithiocar-bamate and/or ester, phosphonodithious acid salt and/or ester, xanthan first At least one in hydrochlorate and/or ester, xanthan ester or its mixture.

8. method according to claim 7, wherein the trapping agent is xanthates and/or ester.

9. method according to claim 1, wherein the vector gas are to select free air, nitrogen, carbon dioxide or its mixture At least one of the group of composition.

10. method according to claim 9, wherein the vector gas are air.

11. method according to claim 1, wherein the organic compounds containing nitrogen is DETA (diethylenetriamines).

12. method according to claim 1, wherein the sulfur-containing compound is sulphite.

13. method according to claim 1, wherein the organic polymer is with 6kDa molecular weight and contains about 5% sulfonic acid The calcium lignosulfonate from hardwood of salt and about 2% sugar.

14. method according to claim 1, wherein for every kind of sulfide ore, being determined by experiment every kind of inhibitor Optimization dosage.

15. method according to claim 1, if wherein organic compounds containing nitrogen is with than being used alone it or and sulfur-containing compound The few consumption of required consumption is used in combination to be present in mixture.

16. method according to claim 1, wherein simultaneously various inhibitors can be added respectively.

17. method according to claim 1, wherein in the case of no particular order various inhibitors can be added in order.

18. method according to claim 1, wherein can be single molten with the premixing of each component of the preferred proportion with determination Liquid adds various inhibitors.

19. method according to claim 1, wherein can be single with the premixing of two kinds of components of the preferred proportion with determination Solution adds various inhibitors, and optionally individually adds the third component with the consumption of change.

20. method according to claim 9, wherein the air is the air rich in nitrogen, rich oxygen containing air, rich in two The air of carbonoxide or its mixture.