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    • 专利摘要:
    Process for the depression of iron sulphides and other disposable elements in the concentration of ore by flotation and electrochemical reactor. The proposed invention represents a method based on the action of electrodes on the mineral, being able to replace, complement or minimize the consumption of chemical reagents, as well as improve its effect. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2653736A1
    申请号:ES201730450
    申请日:2017-03-28
    公开日:2018-02-08
    发明作者:Eva María LAÍN RODRÍGUEZ
    申请人:Inforock S L；Inforock SL；
    IPC主号:
    专利说明:

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    PROCESS FOR THE DEPRESSION OF IRON SULFURES AND OTHER DISPOSABLE ELEMENTS IN THE CONCENTRATION OF MINERAL BY FLOAT AND REACTOR
    ELECTROCHEMICAL
    DESCRIPTION
    OBJECT OF THE INVENTION
    The present invention relates to a process for the depression of iron sulphides and other disposable elements, mainly pyrite, although not exclusively, in the concentration of ore by flotation. It also refers to an electrochemical reactor.
    Said process, as well as the reactor, substitute, minimize, optimize or complement the use of depressants and other chemical reagents during the depression of iron sulphides and other disposable elements such as arsenic, antimony, bismuth, mercury and lead. This invention is particularly relevant for the flotation of sulphide minerals of all types.
    The field of the invention is mainly applied in nickel, copper, zinc and lead ores.
    BACKGROUND OF THE INVENTION
    Flotation is used to concentrate or separate mineral species by selective adhesion of mineral particles of each species to air bubbles. These bubbles float to the surface of the liquid, forming foams that are collected as the product of said process. The adhesion of the particles to the bubbles occurs mainly as a function of the hydrophobicity of the mineral surface. Those more hydrophobic particles tend to adhere to the bubbles, so they float, while the more hydrophilic ones tend to be surrounded by liquid, so they depress. To modulate the hydrophobicity and consequent flotation of the different mineral species, chemical reagents are typically added, such as collectors, depressants, activators, inhibitors, foaming agents or modifiers [11].
    In the flotation of sulphides, for example nickel, copper, zinc and lead ores, a main objective to concentrate the mineral (s) of interest is the selective depression of pyrite (sulfur ore and iron), since rarely It is profitable to trade iron. In addition, pyrite and other sulfides may be associated with or contain elements that are not of interest or harmful, which may be commercially penalized, such as arsenic, antimony, bismuth, mercury and lead. Therefore, by eliminating / reducing said elements of the concentrate, the penalties for said elements can be reduced. Normally, the depression of pyrite and other sulfides to be discarded is achieved by modifying the pH as well as by the addition of chemical depressants, typically
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    cyanide or sodium metabisulfite [10].
    Several ways of depressing pyrite have been devised. The main methods are as follows:
    - Increase the pH of the solution, for example by adding lime [1].
    - Addition of cyanide salts, such as potassium cyanide, sodium cyanide and potassium ferricyanide [2].
    - Addition of compounds based on sulfur and oxygen, such as sulfite, bisulfite, metabisulfite and sulfur dioxide [3], [4], [5], [6], [7]
    - Addition of iron salts, such as ferric sulfate or ferrous sulfate [2]
    - Addition of hypochlorite salts, such as sodium hypochlorite and calcium hypochlorite [8]
    - The use of organic reagents, such as starch, pyrogallic acid and tannic acid [8]
    Although they are used industrially in flotation mineral concentration plants, conventional methods for depression of pyrite and other sulphides by adding chemical depressants have several drawbacks. First, they involve relatively high consumable costs, as well as process water treatment to clean and adapt it for reuse in flotation circuits. On the other hand, the use of certain depressants such as cyanide is increasingly restricted, given its toxicity and the associated environmental risk [9].
    The process object of the present invention supposes a great advantage over the conventional methods, since it makes possible the saving of chemical reagents, which currently represent a significant cost. Specifically, the proposed process and reactor involve an electrochemical method for the depression of pyrite and other sulfides to be discarded, which does not necessarily employ chemical depressants.
    The choice of electric potential allows the use of any potential value, unlike chemical reagents, which are limited to discrete potential values. In addition, it allows varying the pH and electrochemical potential independently, not only at the macro level but also at the local level. Consequently, this process allows a greater specificity in the action of depression, increasing the resolution in the differential flotation between the minerals of interest and the unwanted sulphides. Thus, it allows optimizing the law-recovery relationship of the metals of interest, offering greater benefits from the same plant head. In sum, not only the treatment of the minerals introduced into the plant is optimized, but the improvement in the quality of the concentrate can lead to the reclassification of certain minerals, previously considered sterile for not passing the quality cut, resulting in the treatment in mineral plant that would otherwise be discarded. On the one hand, this could mean significant savings, by moving less mineral
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    to generate the same product; On the other hand, this could simplify the logistics of the mine, by not having to avoid or fly and discard certain areas currently considered sterile. Also, "blending" between better and worse concentrates could be prevented or minimized to obtain certain levels of quality.
    Another advantage is the rapidity in changing the electrical potential, which allows a fast (practically instantaneous) response by the flotation process control system, which is relatively slow (typically minutes or hours) in the current system, since It depends on the concentration and flow of chemical reagents, which can remain recirculated in the system for relatively long periods of time.
    Likewise, this process allows greater versatility in flotation circuits, since the process water is not chemically conditioned as at present, the flotation conditions can be varied more easily in a modular way, within the same circuit, line or plant of treatment.
    DESCRIPTION OF THE INVENTION
    The present invention concerns a process, according to claim 1, and an electrochemical reactor, according to claim 13, for the depression of iron sulphides and other disposable elements, mainly pyrite, although not exclusively, in the concentration of flotation ore, which replaces, minimizes, optimizes or complements the use of depressants and other chemical reagents. This invention is especially relevant for the flotation of sulphide minerals of all types.
    The process is based on the application of electrical potential by means of at least one electrode, to simulate the electrochemical effect that chemical depressants and other reagents have on mineral particles. Thus, by direct contact between the electrode and the mineral particles, it is possible to alter the surface of the mineral to be depressed, so that its hydrophilic character is increased, thus preventing its adhesion to the bubbles and resulting in its depression. It is an electrochemical alteration of the surface of the mineral particles, so that this translates into a better selectivity in the flotation separation. It is not, however, about electrostatically attracting the electrode (s) or repelling mineral particles (or mineral-bubble complexes) from the electrode.
    As mentioned, the process involves the application of potential, by means of a working electrode, in situ or ex situ, directly or indirectly, on the ore particles in the pulp. Said application requires either direct contact between the electrode and the mineral, which most likely occurs if the particles are in motion, for example by agitation, or the transfer of potential by means of
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    electrochemical mediators.
    It is a typically electrolytic process, although it can also be galvanic, in which the working electrode is polarized to certain potential values. These values are chosen to condition the surface of the species of pyrite or other sulfides to be discarded, in order to increase the hydrophilic character of said surface. Typically, it is intended to catalyze the selective formation of hydroxides on the surface of the pyrite. For this, the election potential is usually positive; The working electrode acts as an anode. In addition, said potential would typically be below the electrolysis potential of water, so that no bubbles are generated on the electrode surface and the pH does not change. It should be noted that the application of potential is a variable independent of pH, at least at the macro level (although it would be possible to modify the pH at the macro level, if it entails changes in the pH, this would typically occur at the local level) which allows a higher resolution in the differential flotation of the minerals in question. The alteration of the pH at the local level can be carried out by using the potential / s / s necessary to generate or consume protons / hydroxyl ions, eg. acidification of the medium as a result of water hydrolysis, when generating protons. Such pH alteration occurs in the local environment of the electrode, without affecting the pH of the general medium, when the influence of electrochemical reactions performed by the electrode is limited, in relation to those determining parameters, such as relatively high volumes and flows and / or relatively short residence times, which mask the pH changes generated by the electrode / s. If the pH is altered, it is most normal for it to occur locally. However, it would be possible to alter the pH at the macro / general level, since the electrochemical reactions performed by the electrode have an important influence on the pH of the medium, in relation to determining parameters, such as relatively low volumes and flows and / or residence times relatively long, which allow to extend the pH changes originally generated locally at the surface of the electrode / s at the macro level.
    The process is based on the use of an electrochemical cell within the ore pulp circuit, at any point of the same, either in the same flotation cells or in conditioning or passing tanks or previous pipes, downstream of, or interspersed in, the process, pre-existing or added.
    The electrochemical reactor can take any form, from a single reactor with two parallel flat electrodes, to devices of greater complexity, such as column, bed and / or multitubular reactors, and / or that constitute or take advantage of at least part of
    elements of the mineral treatment line, such as the same cells of
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    flotation, containers or passages of pulp and mills, including any structure or element within the plant or treatment line / circuit, the electrodes (at least partially) being submerged in liquid / pulp (at least while they are in operation). For example, baffles, pipes, passages, conditioning tanks, thickeners / cyclones, air or mineral dispersers, agitators, false floors, screens / filters, coatings or elements of the elements can be coated and / or used as electrode / s mills like balls and bars.
    The electrodes may be constituted of any conductive or semiconductor material, being able to be treated for example to modify affinity with the pulp and / or mineral species and / or liquid (s), for example, by (pre) treatment / s to increase the hydrophobicity or surface hydrophilicity, as well as
    modified / treated / impregnated / associated with / doped with catalysts or potential modifiers, activation energy or other energy or thermodynamic considerations. Also, the electrodes may be magnets or be magnetized, optionally to preferentially attract or repel certain mineral species. Typically, 316L stainless steel electrodes (iron, nickel, chromium, molybdenum and carbon alloy) would be used to prevent oxidation of the electrode given the medium and potential used.
    Said electrodes may take any form, from flat plates (smooth, perforated or articulated), to the form of existing structures in the treatment line (s) (or coating thereof). In addition, the surface can be maximized or modulated by using electrodes with three-dimensional, perforated or rough surfaces. The electrodes may be assisted by systems, in situ or ex situ, for cleaning and / or maximization / modification of current efficiency, for example mechanical systems to keep the surface clean, prevent / correct / minimize / act on impurities or aggregates , such as brushes or vibration / ultrasonic systems for detachment of particles / adhered species, and / or systems to prevent / correct / mitigate / act on physicochemical problems, such as programs of variation of the potential / is against passivation layers formed on or from the electrode or chemical treatment systems. The reactor may be assisted by washing systems such as hoses / karcher / other hydraulic cleaning systems, which operate manually / semi-automatically / automatically, optionally in conjunction with systems to move said cleaning elements or reactor elements, such as hoists, or emptying / filling the tank that houses the reactor. The electrochemical reactor as well as the elements that house it may have safety systems to prevent, mitigate or act in the event of electric shock or short circuit,
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    as separators, gummed, insulating coatings, earthing, fuses and intelligent systems to ensure safety. Likewise, the reactor may have adequate mechanical supports for the correct fastening of its components.
    The process has two main modalities. In the first, the potential is conferred to the mineral directly by means of the electrode. This requires direct contact between the mineral and the electrode. In the second modality, the potential is conferred to the mineral through chemical / electrochemical mediators, typically dissolved in the medium, being added or already being present in the medium (for example thiosales), although they may also be conductive or semiconductor solids, of again being added or already present (for example mineral particles), or a combination thereof. Likewise, the process allows combining the two modalities, both simultaneously, sequentially, in series and / or in parallel, using the same reactor or different reactors.
    In case of requiring direct contact between the electrode and the mineral, the electrochemical reactor may be assisted by additional mechanisms to encourage / maximize / force said contact. Such mechanisms may be for example agitators and / or pumping and / or mixing and / or aeration and / or bubbling and / or vibration systems to promote / maximize contact, and / or press filters and / or other types of presses and / or filters to force said contact or physicochemical methods to modulate the affinity between the electrode and the mineral, for example modulation of the hydrophobicity or magnetization of the electrode, optionally to propitiate the affinity (or lack thereof) selectively with certain mineral species.
    Through the process object of the invention several objectives are achieved:
    - The first objective of the process is the depression of iron species, mainly pyrite, to increase the metal grade of interest in the concentrate. To this end, potentials are applied to the mineral, directly and / or indirectly, which cause the surface of the species to be depressed to become more hydrophilic, preferably selectively, preventing or minimizing said effect on the minerals of interest to float. This effect can be carried out both in the absence of reagents and / or pH modifiers, as well as in their presence, acting independently or in collaboration with said agents. For example, one way to selectively depress pyrite is to catalyze the formation of hydroxides on its surface, which makes it more hydrophilic. In addition, potentials can be applied to positivize or negativize certain mineral species; Depending on the load of the collector / s and / or reagent / s, it will lead to its flotation or depression. This greater selectivity between the fractions to float and depress results in an increase in the law of the metal of interest in the float concentrate. That is, by depressing more iron species, a higher percentage is achieved.
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    of the metal of interest in the floated fraction.
    The second objective of the process is the depression of species that contain or are associated with elements that are to be discarded, mainly criminalizing elements such as arsenic, antimony, bismuth and mercury, as well as elements discarded by economic or logistical considerations (for example differential flotation), such as zinc and lead. For this purpose, as for the depression of iron species, potentials are applied directly and / or indirectly to the ore, which cause the surface of the species to be depressed to become more hydrophilic, preferably of selectively, preventing or minimizing said effect on the minerals of interest to float. Again, this effect can be performed both in the absence of reagents and / or pH modifiers, and in the presence of them, acting independently or in collaboration with said agents.
    The third objective of said process is the purging of metals in solution or other substances that are desired to be cleaned, by deposition / precipitation, optionally selective (for example by choosing a separator and / or potential / s), preferably within a compartment in the relevant configurations, preferably by electrodeposition on / constituting the cathode. For example, purging copper in solution through its electrodeposition in the cathode allows minimizing the activation of sphalerite, while being able to recover copper in a useful way. Said cleaning is not restricted to the elimination of the solution of said substances, but also to their transformation to other forms that do not imply or minimize problems derived from them, and / or that reduce their management (for example, the oxidation of thiosales ).
    The fourth objective of the process is to promote the recovery of metals or substances of interest, by promoting buoyancy, for example by means of mineral positivity, optionally by allowing less alkaline pH ranges for the same metal grade of interest in the concentrate final, optionally in the presence of reagents such as negative collectors.
    The fifth objective is the saving / optimization of certain reagents, either eliminating their addition, minimizing it or maximizing its effectiveness, such as lime and / or certain collectors, depressants, modifiers or chemical reagents / additives. Said optimization may take place in all or any part of the process, for example by minimizing lime and / or depressants in roughing flotation but maintaining, however, the conventional levels of said reagents downstream of the trailer / in the washings. . An added advantage of this is the greater recovery of metals and / or substances of interest, for example by achieving a greater recovery at least in the roughing concentrate as a result of performing it at a less alkaline pH,
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    which, enabled by this process, would not harm the law of the metal of interest in the concentrate.
    This fifth objective is to improve the resolution in the separation of mineral species, by adding a more (potential) dimension to the differential flotation, which is possible because the pH and potential are independent variables since in this process we typically find ourselves below the potential for hydrolysis of water, and changing the pH, it can be guaranteed to occur exclusively at the local level, and not general / macro. This is not possible in conventional flotation, since the potential tends to be linearly dependent on the pH, so in order to negativize the potential the pH must necessarily be alkalized and vice versa, which tends to be negative at the recovery level (if alkalize the solution), or at the law level of the metal or substance of interest in the concentrate (s) (final) (if the solution is acidified). This leaves a window open for the improvement of the law and recovery as a whole, which is achieved through the use of this process.
    Finally, the ideal industrial configuration would be the implementation of the process both in a passage (for example a pipe or widening / compartment that houses the reactor in question, optionally by means of perforated or ring-shaped electrodes or of favorable configurations at the hydrodynamic level) or tank of conditioning prior to roughing flotation, as in a passage such as the one described above or conditioning tank prior to any stage of the washings and / or rush. The reactor may be configured as a combination and / or matrix of the morphological unit (s).
    The reactor may be installed parallel to the walls of the tank or compartment containing or through which the pulp passes, and / or constituting / taking advantage of at least part thereof, and / or arranged in any way, for example in such a way as to maximize the electrode surface by pulp volume, optionally using reactor mosaics, column reactor and / or bed reactor configurations (eg packaging, percolator, suspended phase and / or bubbling), configurations (multi) tubular, screening, and / or to promote / modulate hydrodynamics in the tanks or passages, optionally taking advantage of or acting as a baffle (s). The reactor may take any form, from a simple configuration of two flat electrodes in parallel, to devices of greater complexity such as a reactor that constitutes and / or takes advantage of at least part of the structures and / or elements of the line (s) ) of mineral treatment, such as the same flotation cells, tanks, containers or pulp passages, including any element of the plant or treatment line / circuit, such as pipes, conditioning tanks, elements such as air dispersers, agitators , false floors, deflectors, coatings and / or structures, and / or mill elements such as
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    balls, bars and / or structures.
    Mechanical / physical, electrical and / or chemical system parameters can be controlled by intelligent control systems, optionally remote, to monitor and adjust the reactor, optionally in relation to process data such as laboratory analysis / Courier data / parameters Physicochemical or mechanical. In addition, automated transport systems can be used for processes such as the distribution of ore to the electrode, recirculation of the pulp, liquid / medium and / or solids, and / or extraction / clean / spare / movement / modification / regeneration of electrodes or other reactor elements. In addition, the reactor design could allow the change of the separator (s), electrodes and / or other constituent elements without the need for disassembly.
    DESCRIPTION OF THE FIGURES
    To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, according to a preferred example of practical implementation thereof, a set of figures is attached as an integral part of said description. where, for illustrative and non-limiting purposes, the following has been represented:
    Figure 1 shows a first example of a reactor formed by a simple electrochemical cell
    Figure 2 shows a second example of a reactor also formed by a simple electrochemical cell.
    Figure 3 shows a third reactor example that is a variant of the first example.
    Figure 4 shows a fourth reactor example that is a combination of the second and third previous examples of the reactor.
    Figure 5 shows a fifth reactor example that is a variation of the third example.
    Figure 6 shows a sixth reactor example that is a combination of the second and fifth examples.
    Figure 7 shows an example of the arrangement of the reactors inside a tank (eg conditioning).
    Figure 8 shows an example of the arrangement of the reactors within a passage (eg column reactor).
    Figure 9 shows a block diagram of the sulfide depression process of
    iron.
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    PREFERRED EMBODIMENTS OF THE INVENTION
    The present invention relates to a process for the depression of iron sulphides and other disposable elements in the flotation of mineral particles in liquid, which would typically take place after the stages of extraction, crushing, grinding and liquid suspension of the mineral.
    Below is an example of such processing for copper ores, illustrated in Figure 9. First, mineral rich in copper sulphides would be extracted from the mine when blasting. Subsequently, said ore would be transported by dump trucks to the primary crusher, where the diameter of the ore particles would be reduced from approximately less than 1000 mm to less than 175 mm. The product of the primary crusher would be screened so that particles with a diameter greater than 65 mm would pass through the secondary crusher, obtaining particles smaller than 65 mm in diameter. Such particles would pass through the tertiary crusher, obtaining particles with a diameter smaller than 19 mm.
    The next step would be a grinding stage, either in a bar mill or in a ball mill, to produce particles smaller than 0.2 mm in diameter. The next step would be the agitation of the ore pulp in a conditioning tank prior to roughing flotation, which would be an ideal time for the application of electrical potential. In this way, the particles could be conditioned before the first flotation. The product of the roughing flotation is the roughing concentrate, which has as main objective to eliminate most of the bargain (mainly silicates), as well as part of the iron sulphides (in particular pyrite).
    The product of the roughing flotation would be subjected to a tipping stage, where the diameter of the particles would be reduced from less than 0.2 mm to less than 0.05 mm. Subsequently, the mineral pulp is stirred in a conditioning tank, before the three washes are done and the rush is done. Again, said tank could be used for the application of electrical potential, in order to condition the mineral prior to the relieved ones. Likewise, conditioning tanks or intermediate passages could be introduced where electrical potential would be applied, for example between the first and the second waste, as well as between the second and the third waste. The product of the flotation process, after thickening and filtration stages, is the final concentrate, which would typically be composed of copper sulfides such as chalcopyrite and calcosine, containing at least 20% copper.
    The process described above incorporates at least one reactor for the application of the electric potential, said reactor being able to present different configurations. TO
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    Some of the possible reactor configurations are cited below. In all reactor configurations, the ore may or may not come into contact with the working electrode, although the first of the options is preferred. As mentioned, the contact option is that the particles come into contact with the working electrode, which can be done by agitation or movement of the pulp, thus ensuring contact for at least an instant. In the contactless or indirect configuration, some electrochemical mediator, present or added, is used to transfer the electrical potential from the electrode to the ore particles, in which case direct contact between the mineral and the electrode is not necessary. In any case, if an electrochemical mediator is used, it will also be possible to use a reactor with direct contact, although in that case it would not be necessary to guarantee the contact from the hydrodynamic point of view. Other options would be to use an ex situ reactor or coat the electrode of interest by means of a separator to avoid direct contact with the mineral. Typically, a relatively low potential difference, from 0 to 12 volts, is used between the anode and the cathode.
    The first reactor configuration is a simple electrochemical cell. Said cell, illustrated in Figure 1, consists of a counter electrode (1), a working electrode (2), an electrical input (3) and at least one connection between these three elements (4). In this example, the anodic and / or cathodic and / or medium and / or cell potentials can be controlled with a potentiometer and / or potentiostat, and / or with any input
    electrical / circuit / electrical component (battery, plug, rectifier, etc. that may be assisted by a potentiometer and / or potentiostat).
    The second reactor configuration is a simple electrochemical cell, where at least one of the electrodes, partially or totally, is isolated from the pulp medium and / or other electrode (s) and / or liquid by means of a separator / is. This arrangement, which avoids contact between the counter electrode and the mineral particles by means of a physical separator, is the most favorable process configuration. Said cell, illustrated in Figure 2, consists of a counter electrode (1), a working electrode (2), an electrical input (3) and a connection (s) between these three elements (4), where the anodic potentials and / or cathodic and / or of the medium and / or cell can be controlled with a potentiometer and / or potentiostat, and / or with any electrical input / circuit / electrical component (battery, plug, rectifier, etc. that can be assisted by a potentiometer and / or potentiostat). In addition, it consists of the separator (s) (5), which may be constituted by ion exchange membrane (s), for example anionic or cationic exchange membranes, both generic and specific ion / elements / compounds, fluid membrane (s) (s), organic phase (s), dialysis membrane (s), grid (s), perforated plate (s) or structure (s), ionic bridge (s),
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    filter (s), sponge (s), separator (s) (porous) for batteries or any type, or a combination of the above. Said separators may be at a distance from the electrode (s), eg. “finite-gap” configuration (or in direct contact with the electrode (s), eg. "zero-gap" configuration (or zero gap), or as a combination thereof.
    The third reactor configuration is a variant of the first configuration. Said cell, illustrated in Figure 3, consists of the same elements as the first configuration (a counter electrode (1), a working electrode (2), an electrical input (3) and a connection / s between these three elements (4 ), where the anodic and / or cathodic and / or the medium and / or cell potentials can be controlled with a potentiometer and / or potentiostat, and / or with any electrical input / circuit / electrical component (battery, plug, rectifier, etc. which may be assisted by a potentiometer and / or potentiostat)). In addition, it consists of a third electrode (5), optionally a reference electrode such as silver / silver chloride, connected to at least one of the electrodes through a connection (s) (7), and an element (6) to measure the potential difference between the working electrode and the third electrode and / or between the counter electrode and the third electrode. Said element (6) is preferably a voltmeter or multimeter, and can count / be connected to / collaborate with feedback / response / monitoring / adjustment systems related to the control system of the anodic and / or cathodic potentials and / or of the medium and / or cell and / or partial ion and / or the pulp and / or zeta or a combination thereof.
    The fourth reactor configuration is a combination of the second and third configurations. Said cell, illustrated in Figure 4, consists of the same elements as the third configuration (a counter electrode (1), a working electrode (2), an electrical input (3) and a connection / s between these three elements (4 ), where the anodic and / or cathodic and / or the medium and / or cell potentials can be controlled with a potentiometer and / or potentiostat, and / or with any electrical input / circuit / electrical component (battery, plug, rectifier, etc. which may be assisted by a potentiometer and / or potentiostat), and a third electrode (5), optionally a reference electrode such as silver / silver chloride, connected to at least one of the electrodes by means of a connection / s (7), and of an element (6) for measuring the potential difference between the working electrode and the third electrode and / or between the counter electrode and the third electrode. Said element (6) is preferably a voltmeter or multimeter, and can count / be connected to / collaborate with if feedback / response / monitoring / adjustment stemas related to the control system of the anodic and / or cathodic potential and / or of the medium and / or cell and / or partial ionic and / or pulp and / or zeta or a combination thereof. In addition, like the second configuration, it consists of the separator / s (8), which can again be
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    constituted by ion exchange membrane (s), for example anionic or cationic exchange membranes, both generic and specific ion / elements / compounds, dialysis membrane (s), fluid membrane (s), phase (s) organic (s), grid (s), perforated plate (s) or structure, ionic bridge (s), sponge filter (s), separator (s) (porous) for batteries or any type, or a combination of the above. Said separators may be at a distance from the electrode (s), eg. “finite-gap” configuration, in direct contact with the electrode (s), ex. "zero-gap" configuration, or as a combination thereof.
    The fifth reactor configuration is a variation of the third configuration. Said cell, illustrated in Figure 5, consists of the same elements as the third configuration. However, the configuration of these elements is different. As in the third configuration, the reactor consists of a counter electrode (1), a working electrode (2), an electrical input (3) and a connection (s) between these three elements (4), where the anodic and / or cathodic and / or of the medium and / or of cell and / or partial ionic and / or of the pulp and / or zeta or a combination thereof, and / or with any electrical input / circuit / electrical component (battery, plug, rectifier, etc. which may be assisted by a potentiometer and / or potentiostat). In this case, the third electrode, typically reference (5), is connected to the electrical input (3) directly or remotely, optionally via a connection (s) (7). The electrical input may consist of or be connected / coupled to a potentiostat / potentiometer / rheostat or any monitoring / control / adjustment system, optionally to modify the cell potential based on and / or to control / adjust the anodic potentials and / or cathodic and / or of the medium and / or of cell and / or partial ionic and / or of the pulp and / or zeta or a combination thereof.
    The sixth reactor configuration is a combination of the second and fifth configurations. Said cell, illustrated in Figure 6, consists of the same elements as the fifth configuration (a counter electrode (1), a working electrode (2), an electrical input (3), a connection / s between these three elements (4 ), where the anodic and / or cathodic and / or the medium and / or cell potentials can be controlled with a potentiometer and / or potentiostat, and / or with any electrical input / circuit / electrical component (battery, plug, rectifier, etc. which can be assisted by a potentiometer and / or potentiostat), and a third electrode (5), optionally a reference electrode such as silver / silver chloride, connected to the electrical input (3) directly or remotely, optionally by a connection (s) (7) The electrical input may consist of or be connected / coupled to a potentiostat / potentiometer / rheostat or any monitoring / control / adjustment system, optionally to modify the cell potential depending on and / or to contro lar / adjust the anodic and / or cathodic and / or medium and / or cell potentials
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    and / or partial ionic and / or pulp and / or zeta or a combination thereof). In addition, like the second configuration, it consists of the separator / s (8), which can again be constituted by ion exchange membrane (s), for example anionic or cationic exchange membranes, both generic and ion / element / specific compounds, dialysis membrane (s), fluid membrane (s), organic phase (s), grid (s), perforated plate (s) or structure (s), ionic bridge (s) (s), sponge filter (s), separator (s) (porous) for batteries or of any kind, or a combination of the above. Said separators may be at a distance from the electrode (s), eg. “finite-gap” configuration, in direct contact with the electrode (s), ex. "zero-gap" configuration, or as a combination thereof.
    The reactor of any of the configurations uses at least one anode and at least one cathode, and is electro-assisted when applying and / or controlling an electric power source, to control and / or measure and / or modulate one or more of ( i) cell potential (s), (ii) partial anodic (s) and / or relative (s) and / or semi-cell potential (s), (iii) cathodic potential (s) partial and / or relative (s) and / or semi-cell, (iv) potential (s) of the medium, (v) partial potential (s) of species in solution, (vii) potential (s) of the pulp and (viii) potential (s) zeta or surface of the mineral particles.
    A simple example of use, as illustrated in Figure 7, is the introduction of several electrochemical reactors in a tank (1) with stirrer (5). The reactors (2,3,4 and 6) could be arranged next to the tank wall so that the potential is applied to the ore particles (directly or indirectly) in a conditioning stage, for example prior to or intercalated in the roughing flotation or other floating, for example selective, relaxed, rush, depleted, etc. Any possible cell shape and configuration could be used, as well as any arrangement of the different reactors, not necessarily placing them parallel to the tank walls.
    For example, the process in the conditioning tank prior to roughing flotation could be used. In this tank, it would be normal for between 800 and 1,200 tons of ore to enter an hour, at 20-40% weight / volume in water. If it is a copper ore, the input ore would typically contain 0.4 and 2% copper, between 2 and 30% sulfur, between 1 and 20% iron, between 0.1 and 5% zinc as well as bargain (typically silicates) and other elements in smaller quantities.
    The mineral entering the tank would typically have a D80 between 100 and 250 pm. In this tank, they are stirred for a time of about 2 to 5 minutes, before driving to the roughing float. After the application of potential in said conditioning stage, for example between 1 and 12 V between the anode and the cathode, the copper grade of the concentrate could be increased by several points (eg from 20% to 24% of copper without
    5
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    and with the reactor, respectively), as well as increasing the recovery of copper at several points (eg from 86% to 88% without and with the reactor, respectively). A lower pH could also be used for roughing flotation, maintaining the same law (eg 20%) but increasing recovery (eg increase between 4 and 6%). Normally, this would not be possible without using the reactor, since lowering the pH would also lower the copper grade in the concentrate. On the one hand, the use of a lower roughing pH (eg pH 10 instead of pH 11.5) would allow a significant saving of lime (typically several tons of lime per day), while obtaining a higher benefit from the same plant or mineral head that is introduced into the plant and that will be treated (typically with 1% copper, which is concentrated up to 20%), since less copper would be discarded. On the other hand, if we used this process to increase the copper grade in the concentrate, it could reduce and even completely eliminate the use of depressants such as sodium metabisulfite (eg 400 g / tonne of ore for trenching).
    Another example of use, illustrated in Figure 8, is the introduction of pulp into a passage, for example a column reactor (1), which contains one or more electrochemical cells (2) that can take any form. The pulp would be introduced at least by one input (3) and would come out at least by one output (4). The electrodes could take any form, starting for example large specific surfaces.
    References:
    [1] I.N. Plaksin and G. A. Miasnrkova; “Some Data on Depression of Pyrite by Lime”; Academy of Sciience SSSR, No. 4 (1956)
    [2] K. Milena; “Depression of pyrite mineral with cyanide and ferrous / ferric salts”; Underground Mining Engineering 19 (2011) 149-155
    [3] S.R. Grain, N.W. Johnson, J. Ralston; “Control of the solution interaction of metabisulphite and ethyl xanthate in the flotation of the Hilton ore of Mount Isa Mines Limited, Australia”; Minerals Engineering, 10, No.1, 17-45 (1997a).
    [4] S.R. Grano, C.A. Prestidge, J. Ralston; “Solution interaction of ethyl xanthate and sulphite and its effect on galena flotation and xanthate adsorption”; International Journal of Mineral Processing, 52, 161-186 (1997b).
    [5] T.N. Khmeleva, D.A. Beattie, T.V. Georgiev, W.M. Skinner; “Surface study of the effect of sulphite ions on copper-activated pyrite pre-treated with xanthate”; Minerals Engineering, 16, 601-608 (2003)
    [6] T.N. Khmeleva, W.M. Skinner, D.A. Beattie; "Depression mechanisms of sodium bisulphite in the xanthate-collectorless flotation of copper activated sphalerite"; International Journal of Mineral Processing, 76, 43-53 (2005)
    [7] T.N. Khmeleva, J.K. Chapelet, W.M. Skinner, D.A. Beattie; “Depression mechanisms of
    sodium bisulphite in the xanthate-induced flotation of copper activated sphalerite ”; International Journal of Mineral Processing, 79, 61-75 (2006)
    [8] A. Guanghua, Y. Zhou, Y. Wang; "A Study on the Combined Depressant for the Cu-S Separation in Low Alkaline Medium and its Depressing Mechanism”; Procedia Engineering,
    5 Volume 102, Pages 338-345 (2015)
    [9] B. Ball, R.S. Rickhard, edited by M.C. Fuerstenau; "A. M. Gaudin Memorial Volume"; American Institute of Mining Metallurgical and Petroleum Engineers, New York, 458 (1976).
    [10] M. C. Fuerstenau, G. J. Jameson, R. Yoon; "Froth Flotation: A Century of Innovation"; SME (2007)
    10 [11] S. Ramachandra Rao; "Surface Chemistry of Froth Flotation: Volume 1:
    Fundamentals ”; Springer Science & Business Media, Jun 29 (2013)
    权利要求:
    Claims (14)
    [1]
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    1. A process for the depression of iron sulfides and other disposable elements in the flotation of mineral particles in liquid, which after the extraction, crushing, grinding and liquid suspension stages of the mineral, is characterized in that at least one sulfide is electrochemically depressed by applying at least one electrical potential.
    [2]
    2. Process, according to claim 1, characterized in that at least one iron sulphide or other disposable element is electrochemically depressed by the direct action of at least one electrode, there being at least in part a direct contact between the electrode and the mineral particles.
    [3]
    3. Process according to claim 1, characterized in that at least one iron sulphide or other disposable element is electrochemically depressed by the indirect action of at least one electrode, where the at least one electrode potential is transferred to the ore particles by means of at least one mediator, typically dissolved in the liquid.
    [4]
    4. Process according to claim 1, characterized in that the at least one potential is less than the electrical potential required to oxidize and / or reduce the water.
    [5]
    5. Process according to claim 1, characterized in that the at least one potential of at least one electrode is modulated without altering the pH of the liquid.
    [6]
    6. Process according to claim 5, characterized in that the pH is altered only at the localized level but not at the macro / general level.
    [7]
    7. Process according to claim 1, characterized in that the pH is altered at macro / general level.
    [8]
    8. Process, according to previous claims, characterized in that the cathode electrodeposites and / or precipitates and / or removes metals or other compounds from the solution, optionally selectively, by compartments and / or sequentially.
    [9]
    9. Process, according to previous claims, characterized in that other mineral species are floated or depressed differentially, optionally by the use of chemical reagents and / or by electrodes, simultaneously, in parallel, in series, sequentially and / or in treatment lines different, for example to obtain different copper and zinc concentrates.
    [10]
    10. Process, according to claim 1, characterized in that the mineral is subjected to an additional pretreatment or treatment, for example biotreatment, passivation or oxidation by aeration.
    [11]
    11. Process, according to previous claims, characterized in that the liquid is fresh water, mains water, recirculated process water, cleaned / treated process water and / or distilled or treated water in any way, which optionally contains or to which it is add active agents at electrochemical level and / or pH.
    12. Process according to claim 1, characterized in that it is (a) galvanic, or (b)
    electrolytic.
    [13]
    13. Electrochemical reactor for the treatment of ore pulp, in order to depress iron sulfides and other disposable elements in the flotation of mineral particles in liquid, characterized in that it comprises:
    10 - At least one counter electrode (1),
    - At least one working electrode (2),
    - At least one electrical source (3) and
    - At least one connection between these three elements (4).
    [14]
    14. Reactor according to claim 13, characterized in that one of the electrodes is at
    15 less partially coated or within a delimited compartment to insulate
    said electrode of the mineral pulp.
    [15]
    15. Reactor according to claim 14, characterized in that said electrode is delimited by an ion exchange membrane (s), for example anionic or cationic exchange membranes, a dialysis membrane (s), membrane (s) ) liquid (s), phase (s)
    20 organic (s), a grid (s), ionic bridge (s), filter (s), sponge (s), separator (s) (porous) for batteries or any type, or a combination of the above, arranged in any way, including “zero-gap” and “finite-gap” configurations.
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    同族专利:
    公开号 | 公开日
    US20190169709A1|2019-06-06|
    AU2017305613A1|2019-02-21|
    US11180825B2|2021-11-23|
    MX2019001428A|2019-07-04|
    AU2017305613B2|2022-01-27|
    ES2653736B1|2018-11-16|
    PE20190820A1|2019-06-17|
    CA3032274A1|2018-02-08|
    EP3278879A1|2018-02-07|
    CL2019000284A1|2019-06-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB914067A|1958-04-01|1962-12-28|Ilseder Huette|Method and apparatus for flotation of minerals and other materials|
    US1891776A|1930-06-14|1932-12-20|Louis J O'malley|Selective separation of ores|
    US2258507A|1940-08-27|1941-10-07|Hoag Edward Hammond|Flotation process|
    JPS5620068B2|1973-01-13|1981-05-11|
    JPS5077201A|1973-11-14|1975-06-24|
    US6210648B1|1996-10-23|2001-04-03|Newmont Mining Corporation|Method for processing refractory auriferous sulfide ores involving preparation of a sulfide concentrate|
    GB201414847D0|2014-08-20|2014-10-01|Lain Eva Maria|Leaching of sulphide minerals|CN110386700B|2018-04-23|2020-07-31|中南大学|Combined treatment method for waste battery discharge and sulfur-containing wastewater desulfurization|
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    EP16382382|2016-08-03|
    EP16382382.6A|EP3278879A1|2016-08-03|2016-08-03|Process for the depression of iron sulphides and other disposable elements in the concentration of mineral by flotation and electrochemical reactor|CA3032274A| CA3032274A1|2016-08-03|2017-08-02|Process for the depression of iron sulphides and other disposable elements in the concentration of mineral by flotation and electrochemical reactor|
    MX2019001428A| MX2019001428A|2016-08-03|2017-08-02|Method for depressing iron sulphides and other disposable elements during the flotation concentration of minerals, and electrochemical reactor.|
    PCT/ES2017/070563| WO2018024934A2|2016-08-03|2017-08-02|Method for depressing iron sulphides and other disposable elements during the flotation concentration of minerals, and electrochemical reactor|
    PE2019000270A| PE20190820A1|2016-08-03|2017-08-02|PROCESS FOR THE DEPRESSION OF IRON SULFIDES AND OTHER DISPOSABLE ELEMENTS IN THE CONCENTRATION OF MINERAL BY FLOTATION AND ELECTROCHEMICAL REACTOR|
    US16/323,029| US11180825B2|2016-08-03|2017-08-02|Process for the depression of iron sulphides and other disposable elements in the concentration of mineral by flotation and electrochemical reactor|
    AU2017305613A| AU2017305613B2|2016-08-03|2017-08-02|Method for depressing iron sulphides and other disposable elements during the flotation concentration of minerals, and electrochemical reactor|
    CL2019000284A| CL2019000284A1|2016-08-03|2019-02-01|Process for the depression of iron sulphides and other disposable elements in the concentration of flotation ore and electrochemical reactor|
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