TWI558460B - A method for improving selectivity and recovery in the flotation of nickel sulphide ores that contain pyrrhotite by exploiting the synergy of multiple depressants - Google Patents

Description

Method for promoting selectivity and recovery of flotation of nickel-bearing ore containing pyrrhotite by using synergistic effects of complex inhibitors

U.S. Patent Application Serial No. 61/623,459, filed on Apr. 12, 2012, entitled <RTIgt;"""""" The priority of the method of Sexuality and Recovery, and it is incorporated herein by reference in its entirety.

This invention relates to a process for the selective foam flotation of sulfide minerals using a combination of inhibitor agents.

Sulfide mineral flotation was implemented in the early 20th century. The industrial importance of flotation is recognized because concentrates from flotation can be smelted and refined to provide raw metal. Froth flotation is a method by which valuable minerals are selectively separated by utilizing the difference in hydrophobicity of the surface of the waste gangue material. In general, the flotation process involves grinding the crushed ore in a high density mortar to a liberation size, which is then adjusted with different reagents in a suitable dilute slurry. Reagents include collectors, inhibitors, foaming agents, conditioning agents, and the like. The collector makes the surface of the desired mineral hydrophobic by physical/chemical adsorption, which promotes the adhesion of the bubbles, which cause the mineral particles to float to the mortar table. The surface forms a stable foam that is captured for further processing. The inhibitor has the opposite effect of the collector by adsorbing the hydrophilic component or by removing the active site for adsorption of the collector, thereby allowing the particles to remain in the tailings portion The surface of the mineral particles is required to become hydrophilic. The blowing agent helps to stabilize the bubbles of the appropriate size in the mortar to capture and transfer the particles to the foam area. Conditioners are commonly used for pH control. The different options for froth flotation are often quite complex to maximize the level and recovery of valuable minerals present and to maximize the abandonment of rock and sulfide minerals with minimal commercial value.

Common minerals that have been treated in the treatment of sulphide ore for the recovery of non-ferrous, mining-value metals include pentlandite and needle nickel, chalcopyrite and chalcopyrite and porphyrite, galena and sphalerite It is relative to the metals Ni, Cu, Pb and Zn, respectively. However, such valuable minerals are naturally combined with iron sulphide (i.e., pyrrhotite, pyrite, and pyrite, which are not of commercial value and are considered to be sulfide gangues). The selective disposal of iron ore in the flotation can significantly increase the economic value of the concentrate and also reduce the SO ₂ emissions at the smelting furnace (an important contributor to such gaseous emissions in the smelting furnace). However, pyrrhotite disposal is challenging. It is not only about the abundance of pyrrhotite in the ore, but also about the crystal structure of pyrrhotite (ie, monoclinic, hexagonal or sulphur iron). In addition, pyrrhotite is tightly bound to other minerals, mainly with pentlandite. The selective inhibition of pyrrhotite does not impair the recovery of Cu and Ni during flotation, which is the key to creating commercial value in industrial mineral processing plants.

U.S. Patent No. 5,074,993 describes a process for the flotation of sulfides wherein the pyrrhotite is inhibited by the use of a water-soluble polyamine in an amount of >50 g/mt finely ground mineral mixture. The water-soluble polyamine is preferably diethylenetriamine (DETA), and may also be selected from the group consisting of triethylenetetramine, tetraethyleneamine, pentaethyleneamine, 2-[(aminoethyl) A list of amino]ethanol, cis-(2-aminoethyl)amine, N-methylethylenediamine, and 1,2-diamino-2-methylpropane.

U.S. Patent No. 5,411,148 describes a method for the improved separation of mono- or poly-metal sulfide minerals from iron sulfide. The process comprises a conditioning stage with at least one water-soluble sulfur-containing inorganic compound prior to flotation as a prerequisite step, followed by further adjustment by a nitrogen-containing organic chelating agent as described in U.S. Patent No. 5,074,993. The water-soluble sulfur-containing inorganic compound is preferably sodium sulfite (Na ₂ SO ₃ ), and the amount of the treated dry solid in the range of 50 to 600 g/mt is selected from the group consisting of sulfide, disulfonate, and tetrasulfonate. And a group of sulfur dioxide. The nitrogen-containing organic chelating agent is preferably a polyethylene polyamine such as diethylenetriamine (DETA), which is used in a sufficient dosage for a particular flotation feed. Pyrrhotite is inhibited by the combined effect of sulfur-containing compounds and nitrogen-containing organic compounds added in a specific order.

The foregoing method is extremely effective in improving the Ni and Cu concentrate grades and recovery rates by selective pyrrhotite inhibition. However, the use of DETA may complicate the operation of wastewater treatment of Cu and Ni with respect to the entire (soluble and insoluble) discharged from the effluent. DETA is a strong chemical chelating agent that forms stable complexes with heavy metal ions such as Cu and Ni. Such complexes cannot be precipitated by increasing the pH to above 11 as is customary in wastewater treatment plants. Instead, a polyamine precipitant such as NALMET® 8702 (available from Nalco Company, Naperville, IL) is added to the wastewater to react with the DETA-metal complex and form a precipitate. However, these precipitates are extremely fine particles that do not settle in the clarifier, making it difficult to effectively remove Cu and Ni from the wastewater. In order to avoid the high levels of Cu and Ni in the wastewater when using DETA, efforts have been made to identify alternative iron sulfide inhibitors to reduce or eliminate the use of DETA.

A current patent from LignoTech (U.S. Patent No. 8,221,709) describes the use of hardwood lignosulfonates to separate gangue materials from metal sulfide ore. The patent details three hardwood lignosulfonates obtained from eucalyptus, maple and birch with different sulfur or sulfonate content and molecular weight, and compares them in fine grinding mortar containing copper sulfide, zinc sulfide or lead sulfide. The performance of the flotation of the finely ground ore mortar with iron sulfide at a dose of about 250-500 g/mt. The lignosulfonate can be added before or after other reagents and pH adjusters. However, only the lignosulfonate was added in the industrial process, and the selectivity between the Cu/Ni sulfide and the pyrrhotite was not improved.

In this sense, current state-of-the-art technologies lack the selectivity and recovery for a) improving the flotation of Cu/Ni sulfide minerals combined with iron sulfide, and b) reducing or eliminating the use of problematic polyamine chemicals. (such as DETA) to minimize the negative impact on the environment.

In view of the above problems and unmet needs, the present invention discloses a synergistic effect of a plurality of inhibitors to improve the inhibition of iron sulfide without compromising the recovery of valuable sulfide minerals in the flotation of non-ferrous metal sulfides, At the same time reduce or eliminate the use of environmentally problematic chemicals such as polyamines. This method has important economic and environmental benefits. An example of flotation of a Cu/Ni sulfide ore having pyrrhotite is included in the form of a fresh fine mortar during the flotation process, or in the form of a pretreated and fine powder process intermediate. .

Elements of the method include the use of multiple inhibitors, the use of individual inhibitors of individual chemicals, and synergistic effects to improve selectivity and recovery and reduce the amount of polyamine used by at least 50%, or eliminate the amount whenever possible. The three chemicals used include: 1) polyamines such as DETA; 2) water-soluble sulfur-containing inorganic compounds such as sodium sulfite; and 3) hardwood lignosulfonate products, preferably having a molecular weight of 6 kDa, 5% sulfonate And 2% sugar calcium sulfonate, and specifically from LignoTech's D-912 product. The chemicals used alone or a) do not produce sufficient pyrrhotite inhibition, or b) reduce Cu/Ni recovery, or c) cause environmental problems in wastewater treatment plants due to potentially higher levels of Caused by heavy metals.

The three chemicals may be added separately at the same time, or sequentially added in no preferred order, or pre-mixed into a single solution having a preferred ratio. Similarly, the two components can be pre-mixed into a single solution having a preferred ratio and added separately to the third component in different amounts. Inhibitors can be added before or after other flotation reagents.

The invention of the invention promotes the selection of non-ferrous mining value metals combined with iron sulfide Improvement in sexual recovery.

The aspect of the invention promotes synergy between the inhibitor and the collector such that the dose of polyamine (i.e., DETA) is reduced by at least 50% relative to the user typically in combination with DETA/Na ₂ SO ₃ without damaging the float Selectivity and recovery rate during the selection period.

The aspect of the invention helps to avoid emissions of heavy metals and DETA from wastewater treatment plants exceeding legal limits, which may occur due to the formation of DETA-metal complexes.

Additional advantages and novel features of this aspect of the invention will be set forth in part in the description which follows. Become obvious.

Referring to the following figures (but not limited to), various exemplary aspects of the system and method will be described in detail, wherein: Figure 1 is a graph illustrating the inhibition of ineffective pyrrhotite using only D-912 in coarse flotation. Figure 2 is a graph showing the effective pyrrhotite inhibition effect of D-912 and Na ₂ SO ₃ in coarse flotation; Figures 3A and 3B illustrate the use of D-912 and Na ₂ SO ₃ for intermediate flow Graphs of lower recovery; Figures 4A and 4B are graphs showing the synergistic effect of D-912, Na ₂ SO ₃ , DETA and PAX on the inhibition of pyrrhotite in the intermediate stream - the effect of dosage and order of addition; Figure 5 is a graph illustrating the synergistic effect of D-912, Na ₂ SO ₃ , DETA and PAX on the inhibition of pyrrhotite in the intermediate flow - the optimum dose according to the factor design test; Figures 6A and 6B illustrate the use of D -912, Na ₂ SO ₃ and DETA for the synergistic effect of the intermediate flow pyrrhotite inhibition - according to the synergistic study of optimization and repeated testing; Figure 7 illustrates the use of D-912, Na ₂ SO ₃ And the graph of the inhibition of pyrrhotite of DETA - the effect of the order/method of adding reagents; Figures 8A and 8B are illustrated Stream using D-912, a graph of Na ₂ SO ₃ and the synergistic inhibition of DETA pyrrhotite; and 9A and 9B illustrate system using D-912, Na ₂ SO ₃ and pyrrhotite inhibition of DETA The histogram of the action - reducing the concentration of residual DETA, Cu, and Ni in the concentrate and tailings water, respectively.

The following embodiments are not intended to limit the scope, applicability or configuration of the invention in any way. More specifically, the following embodiments provide the understanding needed to construct the exemplary features of the invention. Using the teachings provided herein, one skilled in the art can identify suitable alternatives that can be used without inferring the scope of the invention.

The present invention describes a method for selectively flotation of sulfide minerals using synergistic effects of a plurality of inhibitors comprising at least one or more non-ferrous, exploitable metals and vulcanized with mainly consisting of pyrrhotite Iron combines to achieve an excellent level and recovery of non-ferrous metals. By utilizing the synergistic effect obtained by the use of complex inhibitors, the dose of one of the key chemicals (i.e., DETA) can be significantly reduced, thereby mitigating potential negative effects on the environment. The method includes:

i) treatment of sulfide ore in fresh alkaline mortar in the presence of a collector, a foaming agent, a pH adjuster and a carrier gas and a plurality of inhibitors throughout the mortar (fresh fine mortar or pretreated and finely powdered) Process intermediate) comprising at least one or more non-ferrous, exploitable metal sulfide minerals (Cu/Ni) having iron sulfide (maghemite).

The mortar to be treated contains up to about 80% iron sulfide. Non-ferrous mining value metal sulfides may be nickel pyrite and needle nickel, chalcopyrite and chalcopyrite and porphyrite, galena and sphalerite, which are relative to Ni, Cu, Pb and A valuable mineral of Zn. The iron sulfide may be pyrrhotite, pyrite and pyrite.

The ruthenium trapping agent may be selected from the group consisting of xanthate, dithiophosphate, and thioamine. At least one of a formate, a dithiocarbamate, a dithiophosphinate, a xanthate formate, a xanthic ester, or a mixture thereof. Potassium pentyl xanthate was used as an example. In order to have a good recovery of the exploitable metal, the dose of the collector is adjusted according to the dose of the inhibitor.

The foaming agent tested is a polyethylene glycol ether (F160-13, Flottec), but may also be selected from at least one of a natural oil, an alkoxy paraffin, a fatty alcohol, a polyethylene glycol ether, and a polypropylene glycol. . The foaming agent is not a major factor of the invention.

The pH adjuster tested is a lime having a pH of 9.5, but may also be soda ash or sodium hydroxide. The pH can vary from 8 to 12.

载体 The carrier gas system air used. It can also be nitrogen, nitrogen-enriched air or oxygen-enriched air or carbon dioxide (enriched air).

The ̇ adjustment step must be after the addition of the collector or inhibitor.

The helium flotation machine can be a standard Denver flotation machine with a 2.2 L pool and a motor speed of 1200 rpm, or a 1.1 L pool and a 900 rpm motor speed.

Ii) a complex inhibitor comprising at least one organic polymer (calcium lignosulfonate from hardwood), at least one sulfur-containing compound and at least one nitrogen-containing organic compound (polyamine), the latter being present in the mixture in a lower amount than it is alone or The amount required for use in combination with a sulfur-containing compound.

The "organic polymer" is at least one water-soluble organic negatively charged polymer selected from the group consisting of lignosulfonate, dextrin, guar gum, tapioca, starch or cellulose. Preferred are calcium lignosulfonates from hardwood having a molecular weight of 6 kDa, 5% sulfonate and 2% sugar. Such products are "D-912" from LignoTech, as identified by the LignoTech patent.

The "sulfur-containing compound" is at least one selected from the group consisting of sulfide, sulfite, bisulfite, meta-heavy sulfate, disulfide, tetrasulfonate, and sulfur dioxide. A water-soluble inorganic sulfur-containing compound. Preferred is sodium sulfite (Na ₂ SO ₃ ).

The "nitrogen-containing organic compound" is at least one nitrogen-containing organic compound having a configuration selected from the group consisting of one or more polyethylene-polyamines having an OCNCCCNCNC and an NCCN structure, the polyethylene-polyamine Including diethylenetriamine, triethylenetetramine, tetraethyleneamine, pentaethyleneamine, hydroxyethyl-DETA, diethanolamine and aminoethylethanolamine. Preferred is diethylenetriamine (DETA).

Iii) the addition of a plurality of inhibitors with a certain adjustment time has the following options, which allow:

̇ these inhibitors are added separately at the same time; or

The inhibitors are added sequentially without any preferred order, with or without adjustment between each other; or

The inhibitors may be premixed into a single solution having a determined preferred ratio; or

̇ Two of the components may be pre-mixed into a single solution having a determined preferred ratio, with the third component being separately added to the third component in varying amounts as needed.

The hydrazine can be adjusted with some adjustment, and the inhibitor is added before or after the collector.

Iv) The dose of the inhibitor used to synergize and reduce the amount of polyamine used depends on the type, grade and mineral composition of the ore and should therefore be determined experimentally. For tested ore samples, the D-912 dose is in the range of 50 to 150 g/t, Na ₂ SO ₃ 100 g/t, and DETA is 0 to 50 g/t. The quoted doses are referred back to the finely ground ore, even for intermediate flows. The DETA dose is kept as low as possible without compromising overall selectivity and recovery to avoid higher levels of heavy metals in the wastewater.

v) Due to the competition between the collector and the inhibitor, the collector dose is adjusted accordingly for optimal metallurgy.

In a preferred embodiment, the present invention is directed to a method of selectively flotation of at least one or more sulfide minerals using a synergistic effect of a plurality of inhibitors, the sulfide minerals having at least one or more non-ferrous mineralized values Metal and combined with iron sulfide in sulfide ore, The method includes:

i) in an aqueous alkaline mortar, in a collector, a foaming agent, a pH adjuster, a carrier gas throughout the mortar, and comprising at least one organic polymer, at least one sulfur-containing compound and/or at least one nitrogen-containing organic compound Treating sulfide ore (fresh fine mortar or pretreated and finely divided process intermediate) in the presence of a plurality of selected inhibitors, comprising at least one such valuable sulfide mineral in combination with at least one iron sulfide mineral; and

Ii) Perform froth flotation to inhibit iron sulfide while allowing the flotation of valuable non-ferrous sulfides.

In another preferred embodiment, the present invention is directed to a method of selectively flotation of at least Ni/Cu/Co sulfide minerals using a synergistic effect of a plurality of inhibitors, the sulfide minerals comprising at least Ni, Cu, Co , Pt, Pd, Au, and Ag have a mining value metal and are combined with a sulfide mineral comprising at least pyrrhotite in the sulfide ore, the method comprising:

i) in an aqueous alkaline mortar, in a collector, a foaming agent, a pH adjuster, a carrier gas throughout the mortar, and a product comprising calcium lignosulfonate (preferably a product such as D-912), sodium sulfite (Na) Treatment of Ni/Cu/Co sulfide ore (fresh fine mortar or pretreated and fine powdered process intermediate) in the presence of ₂ SO ₃ ) and/or DETA complex inhibitors, containing at least pyrierite At least pentlandite and chalcopyrite minerals; and

Ii) Perform froth flotation to suppress pyrrhotite while allowing the flotation of valuable pentlandite and chalcopyrite.

Alternatively, the method of adding the three inhibitors may comprise 1) separately, but all at the same time; and 2) with individual adjustments in sequence.

Additionally, an inhibitor solution can be added before or after the collector.

The doses of inhibitors found to act synergistically and reduce the amount of polyamines depend on the type, grade and mineral composition of the ore and should therefore be determined experimentally. For tested ore samples, the D-912 dose is in the range of 50 to 150 g/t, Na ₂ SO ₃ 100 g/t, and DETA is 0 to 50 g/t. The quoted doses are referred back to the finely ground ore, even for intermediate flows.

Synergic pyrrhotite inhibition obtained using a complex inhibitor (ie, by combining DETA, Na ₂ SO ₃ and D-912) is achieved by maximizing pyrrhotite inhibition (by each inhibitor) Obtained at the minimum dose). More specifically, DETA, Na ₂ SO ₃ and D-912 have their own unique functions in the inhibition of iron sulfide. The pyrrhotite flotation has three suggested mechanisms, 1) copper activation to promote the adsorption of the collector (xanthate); 2) formation of poly-sulfur to produce some hydrophobicity on the surface of the pyrrhotite to which the bubbles are attached a portion; and 3) forming diaphoric acid for the hydrophobic portion. DETA may remove or mask the Cu ²⁺ activation site on the iron sulfide to inhibit trapping agent adsorption on the surface. Na ₂ SO ₃ may prevent iron sulfide flotation by removing the adsorptive collector or poly-sulfur formed on the surface of the iron sulfide. D-912 is a negatively charged hydrophilic polymer which may be adsorbed on the surface of iron sulfide via an active site such as Fe(OH) ²⁺ , Ca ²⁺ or Cu ²⁺ to render its surface hydrophilic. Suppress iron sulfide.

The use of either of the inhibitors alone does not provide effective pyrrhotite inhibition without compromising the recovery of the exploitable metal or the high content of heavy metals in the wastewater. Synergism is produced by using three different inhibitors simultaneously. One benefit is obtained from each of the three reagents, resulting in maximum inhibition of iron sulfide while minimizing the reduction in recovery of valuable minerals.

Instance

The following examples are intended to illustrate, but not to limit, the scope, applicability, or configuration of the claimed invention.

In the drawing, it should be noted that the short format has been used for the axis title for minerals. These symbols are included: Pn (nickel pyrite), Cp (chalcopyrite), and Po (magnetic pyrite).

Example 1 Use only the invalid pyrrhotite inhibition of D-912

Figure 1 is presented in containing about 1.5% Ni (3.7% nickel pyrite), 1.5% Cu (4.3% chalcopyrite) and 21% Fe (19.7% pyrrhotite) and 72.3% rock (other tannins) Nickel-copper ore Flotation (according to U.S. Patent No. 8,221,709 (LignoTech) using only hardwood lignosulfonate product D-912 as a procedure for pyrrhotite inhibitors), cumulative recovery of pentlandite and pyrrhotite The result of the rate. In this test, 1 kg of ore was ground in a rod mill to reach P80-106 μm with the addition of 5 g/t of collector (PAX-pentyl xanthate potassium) and 400 g/t of lime. The incremental rough selection test was carried out with a pH of 9.5 with lime as a conditioning agent. There was a 2 minute adjustment after the addition of the inhibitor and the collector, respectively, and 15 ppm of a blowing agent (F160-13) was present in the process water. A 2.2 L Denver flotation cell was used at 1200 rpm and 3 L/min air was applied in the flotation. Concentrates were collected after 0.5, 1, 2, 5, 8 and 12 minutes. The chemical additions added to the coarse selection tank are summarized in Table 1.

The test using only the collector (PAX) did not show pyrrhotite inhibition. The test using DETA/Na ₂ SO ₃ exhibited acceptable pyrrhotite inhibition and a recoverable metal recovery.

Compared to the combination of DETA and Na ₂ SO ₃ (also known as "baseline" chemicals), the use of hardwood lignosulfonate product D-912 as a pyrrhotite inhibitor at 25 to 50 g/t does not improve. Magnesite inhibition. Compared to DETA and Na ₂ SO ₃ combination of high dose D-912 nickel 250g / t of pyrite not significantly improved selectivity for inhibition pentlandite / pyrite magnetic.

Example 2 Effective pyrrhotite inhibition of D-912 and Na ₂ SO ₃ for a single ore feed

Figure 2 presents the cumulative recovery of nickel pyrite and pyrrhotite in the crude flotation of the same nickel-copper ore used in Example 1 (where Na ₂ SO _{3 is} accompanied by D-912 addition to the coarse tank). The result. The ore was ground in the same manner as in Example 1, including a 5 g/t collector (PAX) additive and a 400 g/t lime additive. When Na ₂ SO ₃ dose At 50 g/t, pyrrhotite inhibition was observed. The chemicals added to the crude flotation are summarized in Table 2.

The test using only the collector (PAX) did not show pyrrhotite inhibition. The test using DETA/Na ₂ SO ₃ exhibited acceptable pyrrhotite inhibition and a recoverable metal recovery.

The dose of 200 g/t Na ₂ SO ₃ alone has been shown to have some effect on pyrrhotite inhibition, but the results are not as good as those obtained using the baseline chemicals DETA and Na ₂ SO ₃ . In the tests using D-912 and Na ₂ SO ₃ , some indications of pyrrhotite inhibition were observed when the dose of Na ₂ SO ₃ was >100 g/t. When Na ₂ SO ₃ dose 200g/t and D-912 dose At 50 g/t, the pentlandite/magpyrite selectivity curve obtained using D-912/Na ₂ SO ₃ was similar to the baseline DETA/Na ₂ SO ₃ . The dose of D-912 of from 25g / t increased to 100g / t and the dose of Na ₂ SO ₃ of from 200g / t increased to 400g / t does not significantly change the shape of the selectivity curve of pentlandite / pyrrhotite (ie, the recovery of pentlandite decreases as the recovery of pyrrhotite decreases).

Regarding this feed, there is no need to add DETA, which is better for environmental problems.

Example 3 Lower recovery for D-912 and Na ₂ SO ₃ for intermediate streams

Figures 3A and 3B are respectively shown to contain about 7.6% Cu (21.9% chalcopyrite), 6.4% Ni (17.3% nickel pyrite) and 37% Fe (39.8% pyrrhotite) and 21% rock (where Na ₂ SO ₃ with D-912 added to the middle of the selected tank) fine flotation, accumulating nickel pyrite / pyrrhotite and chalcopyrite / pyrrhotite selectivity results. This study involved coarse flotation and fine flotation tests with inhibitors added during the selection phase. A total of 10 g/t of collector (PAX) was added to the coarse flotation and the coarse concentrate was captured for 6 min. The rough concentrate is treated in the selection stage with a pH of 9.5 with lime as a regulator. There was a 2 minute adjustment after the addition of the inhibitor and the collector, respectively, and 15 ppm of a blowing agent (F160-13) was present in the process water. A 1.1 L Denver flotation cell was used with a 900 rpm spindle and 1 L/min of air was applied at the fine flotation. The selected concentrates were captured after 1.5, 3, 5, and 16 minutes. The chemicals added to the fine flotation are summarized in Table 3.

Observed when D-912 dose 50g / t, and SO ₃ when accompanied by 200g / t of Na _2, and even more preferably improved selectivity ratio of DETA / Na ₂ SO ₃ baseline. However, the recovery rate of chalcopyrite is reduced by approximately 15%. If the dose of D-912 is further reduced ( An increase in the dose of 25 g/t) or PAX will impair selectivity. This is not acceptable for industrial production.

Example 4 Synergistic effect of D-912, DETA, Na ₂ SO ₃ and PAX on the inhibition of intermediate flow pyrrhotite

4A and 4B show the results of accumulating pentlandite/pyroxite and chalcopyrite/pyroxite selectivity, respectively, according to the same intermediate flow precision flotation as used in Example 3. In this example, DETA accompanied by Na ₂ SO ₃ and D-912 was added to the selection slot, but DETA and Na ₂ SO ₃ as part of the "base" as compared with the use of adjustment, dose reduction. This study involved coarse flotation and fine flotation tests as described in Example 3. The chemicals added to the fine flotation are summarized in Table 4.

In the test of the dose fixing of various chemicals (T18309, T18310, T18311), the order of adding chemicals changed. No significant differences were seen in the results.

In the test of changes in the dosage of inhibitors and collectors, or the selectivity of pentlandite and chalcopyrite is excellent but the recovery rate is much lower than the target (T18309, T18310, T18311), or pentlandite and Chalcopyrite recovery is acceptable but selectivity is significantly reduced (T18358, T18360).

When the balance between the collector and the inhibitor is reached (T18359), the selectivity and recovery are close to the "baseline" results. When D-912, DETA and Na ₂ SO ₃ and the collector (PAX) are in the proper dosage, good selectivity and recovery are obtained.

Example 5 Use factor design tests to find the optimal dose of D-912, DETA, and Na ₂ SO ₃ and PAX for the synergistic effect of the intermediate flow pyrrhotite inhibition

5 presents D-912, and the interaction between the DETA trapping agent (the PAX) while maintaining the results of the study of Na ₂ SO ₃ factorial design of fixed doses of ^23. The results according to Example 4 indicate that the combination of the three chemicals acts as an inhibitor to produce a synergistic effect that allows for a reduction in DETA dosage while maintaining good selectivity and a recoverable metal recovery. At the same time, it has been found that the dose of the collector plays an extremely important role. To further confirm synergy and determine the optimal range of various chemical doses, a 3-factor-2 order ( ²³ ) factor design study was performed on doses of PAX, DETA, and D-912, with chemicals added to the selection stage. The feed lines are the same as those described in Example 3. The coarse-fine flotation procedure is the same as described in Example 3. In all of these tests, Na ₂ SO ₃ was added at a fixed dose of 200 g/t. The dosages and test conditions of DETA, D-912 and PAX are detailed in Table 5.

In the test design, the criteria for selecting the dose include: a) the DETA dose should be lower than the amount used in the DETA/Na ₂ SO ₃ combination (ie typically 50 g/t); b) because the aforementioned results show the D-912 dose < 50g/t does not work, and the upper limit is unknown, so the dosage is extended to a higher content; and c) because the result of Example 5 shows that the recovery of pentlandite and chalcopyrite is sufficient at a PAX dose of 10 to 15 g/t Therefore, it is not necessary to reach a dose much higher than usual (i.e., 5 g/t).

In the higher dose group of D-912 (FD2, FD3, FD5 and FD7), higher concentrate grade and very low nickel pyrite recovery (20~50%) were obtained, indicating D-150g/t The 912 content is too high. In another group (FD8 and FD9) where the dose of PAX is higher and the dose of D-912 is lower (FD8 and FD9), the selectivity of pentlandite/pyrrolite is reduced, resulting in a concentrate level lower than the target. The use of a dose at the midpoint of the range (FD1) produces a result between these limits. It can be seen that 10g/t PAX, 50g/t D-912 and 15g/t DETA (FD6) give good pentlandite/magopite selectivity, and the result is close to the DETA/Na ₂ SO ₃ baseline. The recovery rate of these doses of chalcopyrite is also excellent (about 90%).

Example 6 Optimization and repeated testing of synergistic effects of D-912, DETA and Na ₂ SO ₃ for intermediate flow pyrrhotite inhibition

Figure 6 presents the results of the optimization test and the baseline test, which were performed to demonstrate the reproducible synergy shown in Example 5 when D-912, DETA, and Na ₂ SO ₃ were used together and to make the chemical The dose is optimized. The coarse-fine flotation procedure is the same as described in Example 3. The intermediate flows are the same as those described in Example 3. The dosages of the chemicals added to the selected tank are detailed in Table 6. Starting with a good result (FD6: with 15g/t DETA, 50g/t D-912 and 10g/t PAX), when D-912 (T18558) or DETA (T18560) or Na ₂ SO ₃ (T18612) is excluded At the time, the pentlandite/pyrromeite selectivity is not as good as when all chemicals are used together.

The other repeat and optimization results are all within the same range of pentindrite/magpyrite selectivity, indicating stable performance. It can be seen that a) increasing the D-912 dose to 75 g/t reduces the recovery of pentlandite and chalcopyrite by a few percentage points; b) changing the DETA dose from 15 g/t to 25 g/t and then to 35 g/t. It will affect recovery and selectivity, so that a lower DETA dose (15 g/t) is preferred; and c) a slight decrease in PAX dose (ie, from 10 to 7.5 g/t) has no significant effect on the results.

Example 7 The effect of the order and method of adding D-912, DETA and Na ₂ SO ₃

Figure 7 presents the results of an evaluation of the order and method of adding chemicals. The intermediate flows are the same as those described in Example 3. The coarse-fine flotation procedure is the same as described in Example 3, with the following conditions: 1) Adding three chemicals (D-912, DETA, and Na ₂ SO ₃ ) while conditioning; 2) Adding Na ₂ SO ₃ in sequence , DETA and D-912, each additive is accompanied by adjustment time; 3) premixing DETA and D-912 into a solution and adding this solution as a single reagent with adjustment to Na ₂ SO ₃ to the slurry; and 4 Premixing DETA, D-912, and Na ₂ SO ₃ into a solution with adjustment to add this solution to the slurry as a single reagent.

The conditions for the added chemicals and the addition method to the selected tank are summarized in Table 7.

It is not important that the results obtained differ due to the different methods of adding chemicals, as all results show good selectivity. The addition of three separate chemicals has the benefit of being able to individually adjust each dose. The use of premixed solutions provides a simpler solution for the configuration of chemical storage tanks and conveyor lines, which are good when conditions are fully established.

Example 8 Synergistic effect of D-912, DETA and Na ₂ SO ₃ on pyrrhotite inhibition in another intermediate stream

Figures 8A and 8B present the results showing the effect of the addition of D-912, Na ₂ SO ₃ and DETA on the inhibition of pyrrhotite in the intermediate stream. Two-stage coarse-fine grinding using an intermediate feed containing 1.0% Cu (2.7% chalcopyrite), 2.0% Ni (4.3% nickel pyrite), 44.6% Fe (65.7% pyrrhotite), and 27.3% rock Flotation test. The addition of chemicals to the coarse selection tank and the selection stage are summarized in Table 8.

Figure 8A presents the results obtained by adding only the inhibitor to the roughing stage. Compared to the case with only PAX (T20013), the addition of D-912 resulted in a significant reduction in the recovery of pyrrhotite. The combined effect of D-912 and Na ₂ SO ₃ (T20027) on pyrrhotite inhibition is not as good as when D-912, Na ₂ SO ₃ and DETA are used together (T20030). The results from tests with three chemicals were closer to the DETA/Na ₂ SO ₃ baseline (T20016), but the DETA addition was much lower (about 40% of DETA).

Figure 8B presents the results obtained by adding an inhibitor to both the roughing and selection stages. When using a combination of three chemicals (D-912, DETA, and Na ₂ SO ₃ ), it is most critical to add a sufficient amount of D-912 to the roughing stage. If this dose is not high enough during the roughing stage (i.e., D-912 is <75 g/t), very little pyrrhotite inhibition will result. The dose of D-912 is higher during the roughing stage, and the addition of more D-912 to the selection stage can further improve the pentlandite/pyrroxene selectivity. In summary, adequate dosing of D-912, DETA, Na ₂ SO ₃ and PAX is necessary to achieve good ferrite/magopite selectivity in the intermediate pyrolysis of higher pyrrhotite.

Example 9 Reducing the residual amount of DETA, Cu and Ni in the process water by using D-912, DETA and Na ₂ SO ₃ combination

Figures 9A and 9B illustrate the effect of using the new inhibitor mixture identified in Examples 5 and 6, respectively, on the quality of concentrate and tailings water. The coarse-fine flotation test was carried out on the same nickel-copper ore as used in Example 1 using the procedure described in Example 3. Use "baseline" condition, accompanied by 50g / t DETA, 200g / t Na 2 SO 3 to the first test. Using the new criteria, accompanied by 50g / t D-912,15g / t DETA and 200g / t Na ₂ SO ₃ to the second test. The conditions are set in advance to produce a similar flotation metallurgy. After flotation, concentrates and tailings water from each test were captured and analyzed for residual DETA, Cu and Ni. The results of the analysis are summarized in Table 9. A reduction in the residual content of DETA, Cu and Ni obtained with a new mixture of D-912, DETA and Na ₂ SO ₃ can be clearly seen.

It is known that different tailings solids each have a specific ability to stably adsorb DETA. The results are given in Table 9 was confirmed by the use of D-912, DETA and Na ₂ SO ₃ combination of, accompanied by reducing the dose of DETA, DETA residual amount of process water can be significantly reduced. The amount of DETA can be adsorbed on the tailings solid without any negative impact on the wastewater treatment plant.

Claims (22)

A synergistic effect of a plurality of inhibitors to improve the selectivity and recovery of valuable non-iron sulfide minerals combined with iron sulfide on non-ferrous metal sulfides during froth flotation, while reducing or eliminating the use environment A method of problematic chemicals, such as polyamines, comprising: i) in an aqueous alkaline mortar, in a collector, a foaming agent, a pH adjuster, and a carrier gas throughout the mortar and including at least one organic polymerization The treatment of sulfide ore (fresh fine mortar or pretreated and finely divided process intermediate) in the presence of at least one sulfur-containing compound and/or at least one selected nitrogen-containing organic compound, which contains at least one or a variety of non-ferrous metal sulfide minerals having iron sulfide; and ii) performing froth flotation to inhibit the iron sulfide while allowing flotation of such valuable non-ferrous sulfides. The method of claim 1, wherein the sulfide minerals are at least one of pentlandite and needle nickel, chalcopyrite and chalcopyrite and porphyrite, galena or sphalerite or a mixture thereof It is a fresh finely ground ore or a pretreated intermediate stream. The method of claim 1, wherein the at least one or more non-ferrous, exploitable metals are selected from the group consisting of nickel, copper, zinc, and lead, cobalt, platinum, palladium, gold, and silver fractions of sulfide minerals. The method of claim 1, wherein the iron sulfide is pyrrhotite, pyrite, and pyrite or a mixture thereof. The method of claim 1, wherein the aqueous alkaline mortar has a pH between about 8 and 12. The method of claims 1 and 5, wherein the aqueous alkaline mortar has a pH of 9.5. The method of claim 1, wherein the collector is xanthate, dithio At least one of a phosphate ester, a thiocarbamate, a dithiocarbamate, a dithiophosphinate, a xanthate formate, a xanthic ester, or a mixture thereof By. The method of claim 7, wherein the collector is xanthate. The method of claim 1, wherein the carrier gas system is selected from the group consisting of air, nitrogen, nitrogen-enriched air or oxygen-enriched air or carbon dioxide (enriched air) or a mixture thereof. The method of claim 9, wherein the carrier gas is air. The method of claim 1, wherein the nitrogen-containing organic compound is at least one of a nitrogen-containing organic compound having a configuration selected from the group consisting of one or more polyethylene-polyamines having an OCNCCCNCNC and an NCCN structure, or a mixture thereof Including diethylenetriamine, triethylenetetramine, tetraethyleneamine, pentaethyleneamine, hydroxyethyl-DETA, diethanolamine and aminoethylethanolamine. The method of claim 11, wherein the nitrogen-containing organic compound is DETA (diethylenetriamine). The method of claim 1, wherein the sulfur-containing compound is at least one selected from the group consisting of one or more sulfides, sulfites, bisulfites, meta-heavy sulfates, disulfonates, tetrasulfonates, sulfur dioxide or A water-soluble inorganic sulfur-containing compound composed of a mixture thereof. The method of claim 13, wherein the sulfur-containing compound is a sulfite. The method of claim 1, wherein the organic polymer is at least one selected from the group consisting of one or more hardwood lignosulfonates, dextrin, guar gum, tapioca, starch or cellulose. Things. The method of claim 15, wherein the organic polymer is derived from calcium lignosulfonate having a 6 kDa molecular weight and comprising about 5% sulfonate and about 2% sugar hardwood. The method of claim 1, wherein the optimal dose of each inhibitor is for each sulfide ore The experimental method is determined. The method of claim 1, wherein the nitrogen-containing organic compound is present in the mixture in an amount lower than that required when used alone or in combination with the sulfur-containing compound. The method of claim 1, wherein the plurality of inhibitors are separately added at the same time. The method of claim 1, wherein the plurality of inhibitors are sequentially added in a non-specific order. The method of claim 1, wherein the plurality of inhibitors are added in the form of a premixed single solution in which the components have a determined preferred ratio. The method of claim 1, wherein the plurality of inhibitors are added in the form of a premixed single solution in which the two components have a determined preferred ratio, and the third component is added separately in different amounts as needed.