OA19880A - Method for controlling the sedimentation of a mining derivative. - Google Patents

Method for controlling the sedimentation of a mining derivative. Download PDF

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Publication number
OA19880A
OA19880A OA1202000420 OA19880A OA 19880 A OA19880 A OA 19880A OA 1202000420 OA1202000420 OA 1202000420 OA 19880 A OA19880 A OA 19880A
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weight
métal
less
suspension
chosen
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OA1202000420
Inventor
Mehdi Bouzid
Benoît Magny
Jacques Mongoin
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Coatex
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Publication of OA19880A publication Critical patent/OA19880A/en

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Abstract

The invention relates to a method for controlling the sedimentation of an aqueous mineral suspension of a mining derivative by means of the gravimetric concentration of the aqueous suspension in the presence of a flocculating agent and a polymer (P) which has a GPC-measured molecular mass Mw of between 2000 and 20000 g/mol and is prepared using at least one free radical polymerisation reaction of at least one anionic monomer (M). The invention also relates to the resulting suspension, which has a Brookfield viscosity of less than 1 800 mPa.s or a yield point of less than 80 Pa.

Description

METHOD FOR CONTROLLING THE SEDIMENTATION OF A MINING
DERIVATIVE
DESCRIPTION
The invention relates to a method for controlling the settling of an aqueous minerai suspension of a mining dérivative by gravimétrie concentration of the aqueous suspension in the presence of a flocculating agent and of a polymer (P) with a molecular mass Mw, measured by GPC, ranging from 2,000 to 20,000 g/mol, prepared by at least one radical polymérisation reaction of at least one anionic monomer (M).
The invention also relates to thé suspension produced whose Brookfield viscosity is less than 1,800 mPa.s or whose flow threshold is less than 80 Pa.
The method according to the invention is used in a mining process involving at least one minerai deposit. These mining methods generally make it possible to obtain at least one useable métal from a métal ore. The métal ore also comprises a residue of this métal ore.
The mining methods are usually implemented using water as a medium for processing or conveying the solids content. Therefore, the mining dérivative is usually an aqueous mining dérivative. .
According to the invention, the fraction of the useable métal ore is a métal or several metals or a dérivative of a métal or a dérivative of several metals.
According to the invention, the aqueous métal ore residue thus results from at least one step in which the useable métal or a dérivative of the useable métal is separated from a métal ore, in particular a métal ore produced by mining extraction.
When using the method according to the invention, an essential step consists of adding at least one polymer (P) to an aqueous mining dérivative. This step therefore relates to the 25 processing of a mining dérivative. It can also relate to the processing of the useable métal ore. This step is therefore generally used in a mining method comprising various steps for processing the-metal oreymetal or a dérivative of a useable métal orrfor processing the métal ore residue.
Typically, mining methods comprise several steps for processing the métal ore, several steps for processing the useable métal or for processing the dérivative of the useable métal, as well as several steps for processing the métal ore residue.
' A mining method typically comprises one or more of the following steps: ‘
- crushing the métal ore, ,
- grinding the métal ore, in particular dry grinding or wet grinding, usually in water,
- separating, in particular by flotation, the useable métal or a dérivative of the useable métal and the métal ore residue, particularly the aqueous residue,
- purifying or enriching the useable métal or a dérivative of the useable métal, in particular by flotation,
- concentrating the métal ore residue or the useable métal or a dérivative of the useable métal, for example by filtration, by settling, by gravity, by using a thickener, by flocculation,
- partially separating the aqueous métal ore residue and part of the water,
- conveying the métal ore, the aqueous métal ore residue or the useable métal or a dérivative of the useable métal, .....
- storing the métal ore, the aqueous métal ore residue or the useable métal or a dérivative of the useable métal.
As the case may be, it is important to hâve effective methods that improve settling or that do not resuit in a decrease in the settling speed.
There are known methods for preparing an aqueous minerai suspension from an aqueous mining dérivative, particularly the methods used to process, convey or store such a dérivative.
Document EP 2686275 describes a method for controlling the rheology of an aqueous dispersion that comprises the addition of a natural polymer then the addition of a synthetic polymer to the aqueous system.
Document EP 1976613 relates to the concentration of an aqueous suspension of solid particles by adding an organic 'flocculant polymer and an agent chosen in the group comprising radical agents, oxidising agents, enzymes and radiation.
An article by Aixing Fan et al. (A study of dual polymer flocculation; Colloids and Surfaces A: Physicochemical and Engineering Aspects, 162,2000, 141-148) describes the improvement in the flocculation of alumina particles with two different polymers.
Document EP 2771289 also relates to the concentration of an aqueous suspension of solid particles by introducing an organic flocculant polymer and adding a system of agents comprising an oxidising agent and a control agent.
Document WO 2014-019993 describes a method for concentrating an aqueous suspension of solid particles by adding an organic flocculant polymer and an active agent chosen among radical agents, oxidising agents and reducing agents.
To facilitate their handling, the known suspensions typically hâve a lower solids content.
In fact, adding water may help to lower the viscosity or the flow threshold of these suspensions.
However, adding water leads to problems with water consumption, energy consumption or even problems with organising and storing the aqueous métal ore residues. Typically, settling is disrupted when water is added to an aqueous suspension of a mining dérivative. It is therefore important to hâve methods for controlling the settling of an aqueous minerai suspension from an aqueous mining dérivative with a high dry solids content.
It is also important to hâve such methods that make it possible to préparé stable suspensions, in particular at high dry solids contents. Likewise, it is important to hâve such methods which make it possible to préparé suspensions that are stable and in which the particles of dry solids content hâve a particle size distribution that is relatively coarse or is not very uniform.
Compatibility with the various constituents of the aqueous minerai suspensions prepared from an aqueous mining dérivative is also an important property to look for, in particular compatibility with a flocculating agent that can be used to process the aqueous mining dérivative, in particular compatibility with a polyacrylamide or a polyacrylamide dérivative.
Likewise, it is important to be able to control the viscosity of aqueous minerai suspensions prepared from a mining dérivative, in particular to make it easier to pump, stir or convey them.
Moreover, it is important to hâve methods that make it possible to control the flow threshold of the aqueous métal ore residue. It is particularly important to confer on an aqueous métal ore residue a minimum flow threshold that makes it possible to eliminate or reduce the risk of the solid portion of the residue settling in case there is no shearing or if there is slight shearing.
Reducing the consumption of water when processing aqueous mining dérivatives should also be sought. Water recovery or recycling during the various steps in the mining methods is also to be preferred.
Both the amount of water that is separated or recycled and the quality of the separated or recycled water should be sought.
It is also important to be able to control the behaviour of the aqueous minerai suspensions prepared from an aqueous mining dérivative in order to avoid problems with the processing, storage or conveying equipment. Indeed, this equipment can be damaged, jammed or clogged if there is a drift in or lack of control of the viscosity, flow threshold or settling of an aqueous minerai suspension prepared from an aqueous mining dérivative.
There is therefore a need for improved methods for controlling the settling of an aqueous minerai suspension from an aqueous mining dérivative.
The method according to the invention provides a solution to ail or part of the problems with the methods used in the prior art to control the settling of an aqueous minerai suspension from an aqueous mining dérivative.
Thus, the invention provides a method for controlling the settling of an aqueous minerai suspension comprising at least one flocculating agent and with a dry solids content that is greater than 10% by weight of the suspension, chosen among:
- an aqueous métal ore residue,
- an aqueous suspension of métal ore and
- an aqueous suspension of useable métal or of a useable métal dérivative and derived from métal ore, comprising the gravimétrie concentration of the aqueous suspension in the presence of at least one polymer (P) with a molecular mass Mw, measured by GPC, ranging from 2,000 to 20,000 g/mol and prepared by at least one radical polymérisation reaction, at a température greater than 50°C, of at least one anionic monomer (M) comprising at least one polymerisable olefînic unsaturation and at least one carboxylic acid group or one of its salts, in the presence of at least one radical-generating compound chosen among hydrogen peroxide, benzoyl peroxide, acetyl peroxide, laurel peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulphate, an alkaline métal persulphate, preferably sodium persulphate or potassium persulphate, an azo compound such as 2,2’-azobis(2-(4,5-dihydroimidazolyl)propane, 2,2’-azobis(2-methylpropionamidine) dihydrochloride, diazo-valeronitrile, 4,4'-azobis-(4-cyanovaleric) acid, AZDN or 2,2’-azobisisobutyronitrile and their respective combinations or associations with an ion chosen among Fe11, Fe111, Cu1, Cu11 and mixtures thereof.
The method according to the invention makes it possible to control the settling of an aqueous minerai suspension with a dry solids content greater than 10% by weight of the suspension, the rheology of the suspension prepared for a dry solids content is greater than
10% by weight or greater than 15% by weight of the suspension.
Preferably, the suspension prepared according to the method according to the invention has a dry solids content of less than 20% by weight or less than 30% by weight or less than 35% by weight or even less than 40% by weight or less than 50% by weight. Also preferably, the suspension prepared according to the method according to the invention has a dry solids content ranging from 10 to 50% by weight or from 10 to 40% by weight or from 10 to 35% by weight or from 10 to 30% by weight or from 10 to 20% by weight or ranging from 15 to 50% by weight or from 15 to 40% by weight or from 15 to 35% by weight or from 15 to 30% by weight or from 15 to 20% by weight or even ranging from 20 to 50 % by weight or from 20 to 40% by weight or from 20 to 35 % by weight or from 20 to 30% by weight.
The method according to the invention comprises the gravimétrie concentration of the aqueous suspension. Preferably, this gravimétrie concentration of the aqueous suspension comprises the séparation of a supematant phase and a settling bed.
According to the invention, these two phases which constitute these two fractions of the aqueous suspension vary mainly by their différence in dry solids content.
Such a différence leads to different properties for the supematant phase and for the settling bed.
Preferably according to the invention, the gravimétrie concentration ofthe aqueous suspension comprises the séparation of a supematant phase with a dry solids content of less than 5% by weight. Preferably according to the invention, the gravimétrie concentration of the aqueous suspension comprises the séparation of a settling bed with a dry solids content greater than 40% by weight.
More preferably according to the invention, the gravimétrie concentration of the aqueous suspension comprises the séparation of a supematant phase with a dry solids content of less than 5% by weight and of a settling bed with a dry solids content greater than 40% by weight.
According to the invention, the supematant phase and the settling bed hâve different rheological properties. In particular according to the invention, the settling bed has particular rheological properties.
Thus, in addition to settling, the method according to the invention makes it possible to control other essential properties of the aqueous suspension prepared. This method therefore makes it possible to control both the Brookfîeld viscosity and the flow threshold of the prepared suspension, in particular of the settling bed.
Preferably according to the invention, the gravimétrie concentration of the aqueous suspension comprises the séparation of a supematant phase and of a settling bed that has:
- a Brookfield viscosity, measured at 100 rpm and at 25°C, of less than 1,800 mPa.s or
- a flow threshold measured at a température of 25°C using a rheometer with imposed shearing, equipped with a bladed spindle, for a particular torsional loading, of less than 80 Pa or
- a Brookfield viscosity, measured at 100 rpm and at 25°C, of less than 1,800 mPa.s and a flow threshold, measured at a température of 25 °C using a rheometer with imposed shearing, equipped with a bladed spindle, for a particular torsional loading, of less than 80 Pa.
According to the invention, the flow threshold, which characterises the flow résistance, is measured on a sample of an aqueous minerai suspension, particularly of an aqueous métal ore residue. The flow threshold is the shearing that must be applied to a suspension to cause it to flow. If the shearing is insufïïcient, the suspension deforms elastically whereas if the shearing is sufficient, the suspension can flow like a liquid.
According to the invention, the flow threshold expressed in Pascals (Pa) is measured at a température of 25°C using a Brookfield DV3T rheometer with imposed shearing, equipped with a suitable spindle with blades. Without destroying the underlying structure, the bladed spindle is immersed into the material up to the first immersion mark. After a five-minute wait time, the measure is taken without pre-shearing at a speed of 0.5 rpm. This relatively low speed is preferred so as to minimise the inertia effect of the bladed spindle. The variation in torsional loading measured by the instrument in order to maintain a spin speed of 0.5 rpm is tracked over time. The value of the flow limit or flow threshold of the aqueous residue is indicated by the instrument when this variation is zéro.
According to the invention, the flow threshold is measured at a température of 25 °C using a rheometer with imposed shearing, equipped with a bladed spindle, for a particular torsional loading.
Preferably according to the invention, the settling bed has a flow threshold of less than
Pa or less than 60 Pa, more preferentially less than 50 Pa or less than 40 Pa, much more preferentially less than 30 Pa or less than 20 Pa.
Also preferably according to the invention, the settling bed has a flow threshold greater than 10 Pa, preferably greater than 12 Pa, much more preferably greater than 15 Pa.
Also preferably according to the invention, the settling bed has a flow threshold greater than 10 Pa, more preferentially greater than 12 Pa, much more preferentially greater than
Pa and less than 70 Pa or less than 60 Pa, more preferentially less than 50 Pa or less than 40 Pa, much more preferentially less than 30 Pa or less than 20 Pa.
According to the invention, the Brookfield viscosity is measured at 100 rpm and at 25 °C, for example using a Brookfield DV3T rheometer. According to the invention, the Brookfield viscosity of the prepared suspension is generally less than 1,800 mPa.s.
Preferably, the method according to the invention makes it possible to préparé a suspension with a viscosity of less than 1,500 mPa.s or less than 1,200 mPa.s. More preferably, the viscosity is less than 1,000 mPa.s or less than 900 mPa.s. Much more preferentially, the viscosity is less than 800 mPa.s or less than 700 mPa.s or even less than 500 mPa.s.
According to the invention, the amount of polymer (P) used may vary quite widely. Preferably according to the invention, the prepared suspension comprises from 0.01 to 2% by weight or from 0.01 to 1.8% or from 0.01 to 1.5% of polymer (P) (dry/dry relative to the ore residue). More preferentially, the prepared suspension comprises from 0.01 to 1.2% or from 0.01 to 1% or from 0.02 to 0.8% or from 0.03 to 0.5% or from 0.04 to 0.25% or from 0.04 to 0.15% by weight of polymer (P) (dry/dry relative to the ore residue).
The method according to the invention may use one or more polymers (P). Preferably, the suspension prepared thus comprises one, two or three different polymers (P). The method according to the invention may also comprise the further addition of at least one compound chosen among a lignosulphonate dérivative, a silicate, an unmodified polysaccharide and a modified polysaccharide.
The method according to the invention comprises the addition of at least one polymer (P) to an aqueous minerai ore residue. Preferably, the métal ore is not an aluminium ore. Also preferably according to the invention, the métal ore is chosen among lithium, strontium, lanthanide, actinide, uranium, rare earth, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganèse, iron, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, tin and lead ores. More preferably according to the invention, the métal ore is chosen among uranium, molybdenum, manganèse, iron, cobalt, nickel, copper, silver and gold ores. Much more preferably, it is a copper ore. It can also be a dérivative of several useable metals comprising copper, zinc and cobalt.
According to the invention, the métal ore comprises at least one useable métal or at least one useable métal dérivative obtained by separating ail or part of the residue from the métal ore. Preferably according to the invention, the métal ore comprises a métal oxide, a métal sulphide or a métal carbonate.
According to the invention, the métal ore residue may comprise a certain residual amount of métal. Particularly, the métal ore residue may comprise a residual amount of métal of less than 2,000 g per tonne (dry/dry) relative to the amount of métal ore residue. This amount of métal in the métal ore residue can typically range from 10 to 2,000 g per tonne (dry/dry) or from 10 to 1,000 g per tonne (dry/dry), relative to the amount of métal ore residue.
When using the method according to the invention, the polymer (P) can be added during one or several steps in the mining process comprising the gravimétrie concentration of the aqueous suspension.
Preferably according to the invention, the gravimétrie concentration of the suspension is carried out using at least one device chosen among a conventional thickener, a highdensity thickener, a high yield thickener.
Also preferably according to the invention, the polymer (P) is added before the gravimétrie concentration of the suspension or during the gravimétrie concentration of the suspension.
More preferably according to the invention, the polymer (P) is added at the same time as the addition of the flocculating agent, thus carried out simultaneously with the addition of the flocculating agent. Also more preferably according to the invention, the polymer (P) is added during the gravimétrie concentration of the suspension and simultaneously with the addition of the flocculating agent.
Also more preferably according to the invention, the polymer (P) is added in the same spot as the addition of the flocculating agent, thus carried out in parallel to the addition of the flocculating agent. Also more preferably according to the invention, the polymer (P) is added during the gravimétrie concentration of the suspension and in parallel to the addition of the flocculating agent.
The method according to the invention uses at least one particular polymer (P). It is prepared by a polymérisation reaction in the presence of at least one radical-generating compound chosen among hydrogen peroxide, benzoyl peroxide, acetyl peroxide, laurel peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulphate, an alkaline métal persulphate, preferably sodium persulphate or potassium persulphate, an azo compound such as 2,2’-azobis(2-(4,5-dihydroimidazolyl)propane, 2,2’-azobis(2-methylpropionamidine) dihydrochloride, diazo-valeronitrile, 4,4'-azobis-(4-cyanovaleric) acid, AZDN or 2,2’-azobisisobutyronitrile, and their respective combinations or associations with an ion chosen among Fe11, Fe111, Cu1, Cu11 and mixtures thereof. Preferably, this polymérisation reaction does not use benzoyl peroxide. In addition to this radical-generating compound, the polymérisation reaction can also be carried out in the presence of at least one compound comprising phosphorus in the oxidation I State, preferably a compound chosen among hypophosphorous acid (H3PO2) and a dérivative of hypophosphorous acid (H3PO2), preferably a compound comprising at least one hypophosphite ion (H2PO2·), more preferentially a compound chosen among sodium hypophosphite (H2PO2Na), potassium hypophosphite (H2PO2K), calcium hypophosphite ([H2PO2]2Ca) and mixtures thereof.
Likewise, the polymérisation reaction can be carried out in the presence of at least one compound comprising phosphorus in the oxidation III state, preferably a compound chosen among phosphorous acid and a dérivative of phosphorous acid, more preferentially a compound comprising at least one phosphite ion, in particular a compound chosen among sodium phosphite, calcium phosphite, potassium phosphite, ammonium phosphite, and combinations thereof.
The polymérisation reaction can also be carried out in the presence of at least one compound comprising a bisulphite ion, preferably a compound chosen among ammonium bisulphite, an alkaline métal bisulphite, in particular sodium bisulphite, potassium bisulphite, calcium bisulphite, magnésium bisulphite, and combinations thereof.
The polymérisation reaction can also be carried out in the presence of from 0.05 to 5% by weight, relative to the total amount of monomers, of at least one compound chosen among a xanthate dérivative, a mercaptan compound and a compound of formula (I):
xooc s s coox (I) wherein:
ο X independently represents H, Na or K and o R independently represents a Ci-Cs-alkyl group, preferably a methyl group, particularly a compound of formula (I) which is disodic diisopropionate trithiocarbonate (DPTTC).
According to the invention, the polymérisation reaction is carried out at a température greater than 50°C. Preferably, the polymérisation reaction is carried out at a température ranging from 50 to 98°C or from 50 to 95°C or from 50 to 85°C.
A higher température, in particular above 100°C, may be used by adjusting the pressure of the reaction medium to prevent évaporation.
Preferably, the polymérisation reaction is carried out in water.
It can also be carried out in a solvent, alone or mixed with water, in particular an alcoholic solvent, particularly isopropyl alcohol. More preferably, it is carried out in water. Advantageously, the polymer (P) used according to the invention has a molecular mass Mw, measured by GPC, ranging from 2,200 to 10,000 g/mol. Preferably, the polymer (P) used according to the invention has a molecular mass Mw ranging from 2,400 to 9,500 g/mol or from 2,400 to 8,000 g/mol, more preferentially from 2,400 to 6,500 g/mol. The polymer (P) used according to the invention is therefore not a flocculating agent.
According to the invention, the molecular mass Mw is determined by Gel Perméation Chromatography (GPC). This technique uses a Waters liquid chromatography apparatus equipped with a detector. This detector is a Waters refractive index detector. This liquid chromatography apparatus is equipped with a size exclusion column in order to separate the various molecular weights of the copolymers studied. The liquid elution phase is an aqueous phase adjusted to pH 9.00 using IN sodium hydroxide containing 0.05 M of NaHCOj, 0.1 M ofNaNO3, 0.02 M of triethanolamine and 0.03% of NaN3.
According to a first step, the copolymer solution is diluted to 0.9% by dry weight in the dissolution solvent of the GPC, which corresponds to the liquid elution phase of the GPC to which is added 0.04% of dimethyl formamide which acts as a flow marker or internai standard. Then, it is filtered using a 0.2 pm filter. Then, 100 pL are injected into the chromatography instrument (eluent: an aqueous phase adjusted to pH 9.00 by IN sodium hydroxide containing 0.05 M ofNaHCO3, 0.1 M ofNaNO3, 0.02 M of triethanolamine and 0.03% of NaN3).
The liquid chromatography instrument has an isocratic pump (Waters 515) the flow rate of which is set to 0.8 mL/min. The chromatography instrument also comprises an oven which itself comprises the following System of columns in sériés: a Waters Ultrahydrogel Guard precolumn 6 cm long and 40 mm in inner diameter and a Waters Ultrahydrogel linear column 30 cm long and 7.8 mm in inner diameter. The détection System is comprised of a
Waters 410 RI refractive index detector. The oven is heated to 60°C and the reffactometer is heated to 45°C.
The chromatography instrument is calibrated using powdered sodium polyacrylate standards of different molecular masses certified by the supplier: Polymer Standards Service or American Polymers Standards Corporation (molecular mass ranging from 900 to 2.25 x 106 g/mol and polymolecularity index ranging from 1.4 to 1.8).
The polymer (P) used according to the invention can be completely or partially neutralised, in particular at the end of the polymérisation reaction.
According to the invention, the neutralisation of the polymer is carried out by neutralising or salifying ail or part of the carboxylic acid groups présent in the polymer.
Preferably, this neutralisation is carried out using a base, for example using a dérivative of an alkaline métal or a dérivative of an alkaline-earth métal.
The preferred bases are chosen among CaO, ZnO, MgO, NaOH, KOH, NH4OH, Ca(OH)2, Mg(OH)2, monoisopropylamine, triethanolamine, triisopropylamine, 2-amino-2-methyl-l-propanol (AMP), triethylamine, diethylamine, monoethylamine. Particularly preferably, neutralisation is carried out using MgO, NaOH, KOH, Ca(OH)2, Mg(OH)2, alone or in combination.
According to the invention, the polymérisation reaction uses at least one anionic monomer (M) comprising at least one polymerisable olefinic unsaturation and at least one carboxylic acid group or one of its salts. Preferably, the anionic monomer (M) comprising at least one polymerisable olefinic unsaturation comprises one or two carboxylic acid groups, particularly a single carboxylic acid group. More preferably, it is chosen among acrylic acid, methacrylic acid, an acrylic acid sait, a methacrylic acid sait and mixtures thereof, much more preferentially acrylic acid.
Preferably, the polymérisation reaction uses 100% by weight of anionic monomer (M) or from 70% to 99.5% by weight of anionic monomer (M) and from 0.5% to 30% by weight of at least one other monomer.
Advantageously, the polymérisation reaction can thus also use at least one other monomer chosen among:
- another anionic monomer, preferably a monomer chosen among acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride and mixtures thereof,
- 2-acrylamido-2-methylpropanesulphonic acid, a sait of 2-acrylamido-2methylpropanesulphonic acid, 2-(methacryloyloxy)ethanesulphonic acid, a sait of
2-(methacryloyloxy)ethanesulphonic acid, sodium methallyl sulphonate, styrene sulphonate and combinations or mixtures thereof,
- a non-ionic monomer comprising at least one polymerisable olefinic unsaturation, preferably at least one polymerisable ethylenic unsaturation and in particular a polymerisable vinyl group, more preferentially a non-ionic monomer chosen among styrene, vinyl caprolactam, the esters of an acid comprising at least one monocarboxylic acid group, in particular an ester of an acid chosen among acrylic acid, methacrylic acid and mixtures thereof, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl méthacrylate, hydroxypropyl méthacrylate, alkyl acrylate, in particular Ci-Cio-alkyl acrylate, preferentially Ci-C4-alkyl acrylate, more preferentially methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, alkyl méthacrylate, in particular Ci-Cio-alkyl méthacrylate, preferentially Ci-C4-alkyl méthacrylate, more preferentially methyl méthacrylate, ethyl méthacrylate, n-propyl méthacrylate, isopropyl méthacrylate, isobutyl méthacrylate, n-butyl méthacrylate, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, aryl méthacrylate, preferably phenyl méthacrylate, benzyl méthacrylate, phenoxyethyl méthacrylate and
- a monomer of formula (II):
R1
(Π) wherein:
- R1 and R2, identical or different, independently represent H or CH3,
- L1 independently represents a group chosen among C(O), CH2, CH2-CH2 and O-CH2-CH2-CH2-CH2,
- L2 independently represents a group chosen among (CH2-CH2O)X, (CH2CH(CH3)O)y, (CH(CH3)CH2O)Z and combinations thereof and
- x, y and z, identical or different, independently represent an integer or décimal comprised in a range from 0 to 150 and the sum of x+y+z is comprised in a range from 10 to 150.
Particularly preferably, the monomer of formula (II) is such that:
- R1 represents CH3,
- R2 represents H,
- L1 represents a C(O) group,
- L2 independently represents a combination of groups chosen among (CH2-CH2O)X, (CH2CH(CH3)O)y, (CH(CH3)CH2O)Z and
- x, y and z, identical or different, independently represent an integer or décimal comprised in a range from 0 to 150 and the sum of x+y+z is comprised in a range from 10 to 150.
Preferably, the polymer (P) used according to the invention is a non-sulphonated polymer.
When preparing the polymer (P) used according to the invention, a séparation step can also be carried out. According to the invention, the séparation can be carried out after the full or partial neutralisation of the polymer (P). It can also be carried out prior to neutralising the polymer (P).
The aqueous solution of the fully or partially neutralised polymer (P) can be processed using the static or dynamic split methods known as such. To do so, one or more polar solvents is used, in particular from the group comprised of methanol, éthanol, n-propanol, isopropanol, butanols, acetone and tetrahydrofuran, thus resulting in a two-phase séparation. During the séparation, the least dense phase comprises the largest fraction of the polar solvent and the fraction of polymers of low molecular weight, and the densest aqueous phase comprises the fraction of polymers with the highest molecular weight. The température at which the polymer fraction sélection is processed can influence the partition coefficient. It is typically comprised within a range of from 10 to 80°C, preferably from 20 to 60°C. During the séparation, it is important to control the ratio of the amounts of dilution water and polar solvents.
When using a dynamic séparation method, for example centrifugation, the ratios of the extracted fractions typically dépend on the centrifugation conditions.
The sélection of the fraction of the polymers can also be improved by re-processing the densest aqueous phase using a new amount of polar solvent, which can be different. It can also be a mixture of polar solvents. Lastly, the liquid phase obtained after processing can be distilled to eliminate the solvent(s) used in processing.
Particularly unexpectedly, the method according to the invention makes it possible to control the properties of the aqueous minerai suspension, in particular to control its settling, despite the presence of at least one flocculating agent in that suspension. The method according to the invention is effective in the presence of many types of flocculating agent. Preferably according to the invention, the flocculating agent is chosen among polyacrylamide, a polyacrylamide dérivative.
The method of controlling the settling according to the invention makes it possible to préparé a suspension of aqueous métal ore residue comprising at least one polymer (P) that has particularly advantageous properties, in particular rheological properties that are particularly advantageous.
Thus, the invention also provides an aqueous minerai suspension comprising at least one flocculating agent and with a dry solids content that is greater than 10% by weight of the suspension, chosen among:
- an aqueous métal ore residue,
- an aqueous suspension of métal ore and
- an aqueous suspension of useable métal or of a useable métal dérivative and derived from métal ore, comprising at least one polymer (P) with a molecular mass Mw, measured by GPC, ranging from 2,000 to 20,000 g/mol and prepared by at least one radical polymérisation reaction, at a température greater than 50°C, of at least one anionic monomer (M) comprising at least one polymerisable olefinic unsaturation and at least one carboxylic acid group or one of its salts, in the presence of at least one radical-generating compound chosen among hydrogen peroxide, benzoyl peroxide, acetyl peroxide, laurel peroxide, tertbutyl hydroperoxide, cumene hydroperoxide, ammonium persulphate, an alkaline métal persulphate, preferably sodium persulphate or potassium persulphate, an azo compound such as 2,2’-azobis(2-(4,5-dihydroimidazolyl)propane, 2,2’-azobis(2-methylpropionamidine) dihydrochloride, diazo-valeronitrile, 4,4'-azobis-(4-cyanovaleric) acid, AZDN or 2,2’-azobisisobutyronitrile, and their respective combinations or associations with an ion chosen among Fe11, Fe111, Cu1, Cu11 and mixtures thereof.
Preferably, the aqueous minerai suspension according to the invention is obtained by gravimétrie concentration of the aqueous suspension in the presence of at least one polymer (P) according to the invention.
Also preferably, the aqueous minerai suspension according to the invention is obtained when using the method according to the invention.
The particular, advantageous or preferred characteristics of the method according to the invention define suspensions according to the invention which are also particular, advantageous or preferred.
EXAMPLES
The following examples illustrate the various aspects of the invention.
A polymer used in the method according to the invention is prepared.
Polymer (Pl) is prepared by placing 212 g water and 0.08 g of iron sulphate heptahydrate into a one-litre glass reactor with mechanical stirring and oil bath heating.
303 g of acrylic acid at 100% by weight and 15 g of water are weighed into a 500 mL beaker fîtted with a dosing pump.
25.6 g of sodium hypophosphite monohydrate diluted with 30 g of water are weighed into a 100 mL test tube fîtted with a dosing pump.
21g of hydrogen peroxide at 130 V and 35 g of water are weighed into a 100 mL test tube fîtted with a dosing pump.
The reactor is heated to 95°C and the monomer, the hypophosphite solution and the hydrogen peroxide solution are added in parallel in 120 min while keeping the température of the reaction medium at 95°C.
Lastly, the pumps are rinsed with water.
The medium is heated again for 60 min at 95°C.
The solution is then neutralised using 50% by weight of sodium hydroxide in water until it reaches pH 8 and then diluted to a solids content of 42% by weight. Polymer (Pl) is obtained, with a molecular mass Mw, measured by GPC, of 4,500 g/mol.
The raw material used for this sériés of tests is an aqueous métal ore residue from a Chilean copper mine located in the north of the country. This is waste resulting from the séparation of the ore containing the useable métal from the rock extracted from the mine. This aqueous copper ore residue is in the form of a water-based suspension.
Various measures were taken beforehand on the aqueous residue in the absence of the polymer according to the invention:
- particle size distribution using a Mastersizer 2000 laser granulometer (Malvem):
D(80) of243.1 pm and
- solids content using a Mettler-Toledo dry balance: 63.5%.
A test is then performed to assess the effectiveness of the polymer on the settling of a suspension of aqueous copper ore residue when concentrating this residue by settling. This settling test is carried out using a suspension with a solids content of 30% by weight. This suspension with a solids content of 30% by weight is prepared by diluting the aqueous suspension of residue with a solids content of 63.5% by weight.
A sample of suspension of aqueous copper ore residue at 30% by weight is transferred into a 500 mL beaker and then mechanically stirred with a Raynerie mixer. Stirring is carried out at 500 rpm.
Then, a polymer (Pl) according to the invention is added at a dose of 0.05% by weight dry/dry relative to the dry residue and the mixture is left under stirring for 15 min.
The dispersed suspension is then incorporated into a 2-litre graduated test tube with a mechanical stirrer at 0.8 rpm.
A fixed dose of an acrylamide flocculating agent is incorporated at a dose équivalent to 12 g/T dry/dry of residue.
A test is carried out using the polymer (Pl) and a comparative test is carried out without any polymer in the suspension.
After preparing a sample of the suspension, settling takes place gradually over time due to the phenomenon of flocculation of the solid particles comprised in the aqueous copper ore residue. These particles agglomerate to form heavier particle clusters. These clusters then settle faster. The aqueous supernatant phase is on the surface and the settled phase is at the bottom of the test tube.
At 25°C and using a Brookfîeld DV3T viscometer with a suitable bladed module, the flow thresholds are measured on samples ofthe aqueous suspension of copper ore residue at 30% by weight of solids content.
The flow threshold (Pa) of the suspension is measured after it has been subjected to a very low shear rate (approximately 1 to 10 s’1) (UN-YS). This corresponds to the flow threshold of the aqueous suspension of copper ore residue at the bottom of a thickener. The flow threshold (Pa) of the suspension is also measured after it has been subjected to a very high shear rate (approximately 100 to 1,000 s'1) (FS-YS).
This corresponds to the flow threshold of the aqueous suspension of copper ore residue at the outlet of a thickener.
The settling speed is also measured using the scale on the test tube and a stopwatch. This measure is performed by observing the séparation of the supematant water phase and settling phase. It is measured in cm/minute and then converted to meter/hour (m/h).
The results are shown in Table 1.
Suspension UN-YS FS-YS Settling speed % Solids content
Without additive 400 41 7.6 64.6
With polymer (PI) 218 15 7.1 63.7
Table 1
Moreover, a test is carried out using semi-industrial equipment. The settler is cylindrical with a clear wall.
It has a capacity of 30 L and is stirred by means of a low-power motor supplying a stirring speed of 1 rpm. The suspension of aqueous copper ore residue used has a solids content of 69% by weight dry/dry.
A fixed dose of an acrylamide flocculating agent is incorporated at a dose équivalent to 12 g/T dry/dry of residue.
The suspension is prepared in a similar manner to the previous préparation, at a solids content of 30% by weight dry/dry. The polymer dose remains the same. It is 0.05% by weight dry/dry. The polymer (PI) is introduced into the top of the thickener parallel to the feed shaft. The feed shaft is the area through which the aqueous ore residue is fed and the flocculant introduced.
The instrument used for the concentration of aqueous residue in the presence of a polymer according to the invention is a Plexiglass pilot thickener with a low-intensity stirrer that generates a stirring speed of 1 rpm. The flow threshold (Pa) of the suspension is measured after it has been subjected to a mean shear rate (approximately 10 to 100 s'1) (MS-YS). This corresponds to the flow threshold at the conveying pump that sends the aqueous copper ore residue to the storage units.
The flow threshold (Pa) of the suspension is also measured after it has been subjected to a very high shear rate (approximately 1,000 to 10,000 s'1) (HFS-YS). This corresponds to the flow threshold in the pipe located after the conveying pump at the outlet of a thickener and that conveys the aqueous copper ore residue to the storage units. The results are shown in Table 2.
The settling speed is also measured using the scale on the test tube and a stopwatch. This measure is performed by observing the séparation of the supematant water phase and settling phase. It is measured in cm/minute and then converted to meter/hour (m/h). It is comprised between 7 and 8 m/h.
Suspension MS-YS HFS-YS % Solids content
Without additive 175 50 69
With polymer (PI) 60 20 69
Table 2
It can be seen that with the use of a polymer according to the invention, increasing the solids content of the aqueous suspension of copper ore residue at a thickener output does not resuit in a viscosity drift in the suspension.
This more consistent suspension can still be stirred using conventional equipment and is easier to handle, thus helping to prevent the risk of clogging the stirrers.
In addition, its improved solids content makes it possible to reduce water consumption relative to the amount of copper ore residue processed.
These tests also show that the presence of the polymer (PI) according to the invention significantly improves the flow threshold values of the aqueous suspensions of copper ore residue without disrupting the settling speed inside the concentration device.
Controlling the rheology at the outlet of a thickener makes it easier to discharge and convey this aqueous suspension to storage pools.

Claims (16)

1. A method for controlling the settling of an aqueous minerai suspension comprising at least one flocculating agent and with a dry solids content that is greater than 10% by weight of the suspension, chosen among:
- an aqueous métal ore residue,
- an aqueous suspension of métal ore and
- an aqueous suspension of useable métal or of a useable métal dérivative and derived from métal ore, comprising the gravimétrie concentration of the aqueous suspension in the presence of at least one polymer (P) with a molecular mass Mw, measured by GPC, ranging from 2,000 to 20,000 g/mol and prepared by at least one radical polymérisation reaction, at a température greater than 50°C, of at least one anionic monomer (M) comprising at least one polymerisable olefinic unsaturation and at least one carboxylic acid group or one of its salts, in the presence of at least one radical-generating compound chosen among hydrogen peroxide, benzoyl peroxide, acetyl peroxide, laurel peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulphate, an alkaline métal persulphate, preferably sodium persulphate or potassium persulphate, an azo compound such as 2,2’-azobis(2-(4,5-dihydroimidazolyl)propane, 2,2’-azobis(2-methylpropionamidine) dihydrochloride, diazo-valeronitrile, 4,4'-azobis-(4-cyanovaleric) acid, AZDN or 2,2’-azobisisobutyronitrile and their respective combinations or associations with an ion chosen among Fe11, Fe111, Cu1, Cu11 and mixtures thereof.
2. The method according to claim 1, in which the suspension has a dry solids content:
- greater than 10% by weight or greater than 15% by weight or
- less than 20% by weight or less than 30% by weight or less than 35% by weight or less than 40% by weight or less than 50% by weight or
- ranging from 10 to 50% by weight or from 10 to 40% by weight or from 10 to 35% by weight or from 10 to 30% by weight or from 10 to 20% by weight or ranging from 15 to 50% by weight or from 15 to 40% by weight or from 15 to 35% by weight or from 15 to 30% by weight or from 15 to 20% by weight or even ranging from 20 to 50 % by weight or from 20 to 40% by weight or from 20 to 35 % by weight or from 20 to 30% by weight.
3. The method according to one of claims 1 or 2, in which the gravimétrie concentration of the aqueous suspension comprises the séparation of a supernatant phase and of a settling bed.
4. The method according to one of claims 1 to 3, in which the gravimétrie concentration of the aqueous suspension comprises the séparation of a supernatant phase and of a settling bed that has:
- a Brookfield viscosity, measured at 100 rpm and at 25°C, of less than 1,800 mPa.s or
- a flow threshold measured at a température of 25°C using a rheometer with imposed shearing, equipped with a bladed spindle, for a particular torsional loading, of less than 80 Pa or
- a Brookfield viscosity, measured at 100 rpm and at 25°C, of less than 1,800 mPa.s and a flow threshold, measured at a température of 25 °C using a rheometer with imposed shearing, equipped with a bladed spindle, for a particular torsional loading, of less than 80 Pa.
5. The method according to one of claims 1 to 4, in which the gravimétrie concentration of the aqueous suspension comprises the séparation of a supernatant phase and of a settling bed that has:
- a flow threshold of less than 70 Pa or less than 60 Pa, preferably less than 50 Pa or less than 40 Pa, more preferentially less than 30 Pa or less than 20 Pa or
- a flow threshold greater than 10 Pa, preferably greater than 12 Pa, more preferentially greater than 15 Pa or
- a flow threshold greater than 10 Pa, preferably greater than 12 Pa, more preferentially greater than 15 Pa and less than 70 Pa or less than 60 Pa, preferably less than 50 Pa or less than 40 Pa, more preferentially less than 30 Pa or less than 20 Pa or
- a viscosity of less than 1,500 mPa.s, preferably less than 1,200 mPa.s, more preferentially less than 1,000 mPa.s or less than 900 mPa.s, much more preferentially less than 800 mPa.s or less than 700 mPa.s, or even less than 500 mPa.s.
6. The method according to one of claims 1 to 5, in which the gravimétrie concentration of the aqueous suspension comprises the séparation of a supematant phase with a dry solids content of less than 5% by weight and of a settling bed with a dry solids content greater than 40% by weight.
7. The method according to one of claims 1 to 6, in which the suspension comprises from 0.01 to 2% by weight of polymer (P) (dry/dry relative to the ore residue), preferably from 0.01 to 1.8% or from 0.01 to 1.5%, more preferentially from 0.01 to 1.2% or from 0.01 to 1%, much more preferentially from 0.02 to 0.8% or from 0.03 to 0.5%, even more preferentially 0.04 to 0.25% or from 0.04 to 0.15%.
8. The method according to one of claims 1 to 7, comprising the addition of one, two or three different polymer(s) (P) or the further addition of at least one compound chosen among a lignosulphonate dérivative, a silicate, an unmodified polysaccharide and a modified polysaccharide.
9. The method according to one of claims 1 to 8, in which:
the métal ore is chosen among lithium, strontium, lanthanide, actinide, uranium, rare earth, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganèse, iron, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, tin and lead ores or • the métal ore comprises a métal oxide, a métal sulphide or a métal carbonate or • the métal ore residue comprises a residual amount of métal of less than 2,000 g per tonne (dry/dry) relative to the amount of métal ore residue; preferably an amount of métal ranging from 10 to 2,000 g per tonne (dry/dry) or from 10 to 1,000 g per tonne (dry/dry), relative to the amount of métal ore residue.
10. The method according to one of claims 1 to 9, in which:
• the gravimétrie concentration of the suspension is carried out using at least one device chosen among a conventional thickener, a high-density thickener, a high yield thickener, or in which:
• the polymer (P) is added:
- before the gravimétrie concentration of the suspension or
- during the gravimétrie concentration of the suspension or
- simultaneously with the addition of the flocculating agent or
- in parallel to the addition of the flocculating agent or
- during the gravimétrie concentration of the suspension and simultaneously with the addition of the flocculating agent or
- during the gravimétrie concentration of the suspension and in parallel to the addition of the flocculant agent.
11. The method according to one of claims 1 to 10, in which:
- the polymérisation reaction is carried out in the presence of at least one compound comprising phosphorus in the oxidation I state, preferably a compound chosen among hypophosphorous acid (H3PO2) and a dérivative of hypophosphorous acid (H3PO2), preferably a compound comprising at least one hypophosphite ion (H2PO2), more preferentially a compound chosen among sodium hypophosphite (H2PO2Na), potassium hypophosphite (H2PO2K), calcium hypophosphite ([H2PO2]2Ca) and mixtures thereof or
- the polymérisation reaction is also carried out in the presence of at least one compound comprising a bisulphite ion, preferably a compound chosen among ammonium bisulphite, an alkaline métal bisulphite, in particular sodium bisulphite, potassium bisulphite, calcium bisulphite, magnésium bisulphite and combinations thereof or
- the polymérisation reaction is carried out in the presence of at least one compound comprising phosphorus in the oxidation III State, preferably a compound chosen among phosphorous acid and a phosphorous acid dérivative, more preferentially a compound comprising at least one phosphite ion, in particular a compound chosen among sodium phosphite, calcium phosphite, potassium phosphite, ammonium phosphite and combinations thereof or
- the polymérisation reaction is also carried out in the presence of from 0.05 to 5% by weight, relative to the total amount of monomers, of at least one compound chosen among a xanthate dérivative, a mercaptan compound and a compound of formula (I):
R S F xooc'/^'s^~~s COOX © wherein:
ο X independently represents H, Na or K and o R independently represents a Ci-C5-alkyl group, preferably a methyl group, particularly a compound of formula (I) which is disodic diisopropionate trithiocarbonate (DPTTC) or
- the polymérisation reaction is carried out at a température ranging from 50 to 98°C, preferably from 50 to 95°C or from 50 to 85°C or
- the polymérisation reaction is carried out in water, in a solvent, alone or in a mixture with water, particularly an alcoholic solvent, in particular isopropyl alcohol, preferably in water or
- the polymer (P) has a molecular mass Mw, measured by GPC, ranging from 2,200 to 10,000 g/mol, preferably from 2,400 to 9,500 g/mol or from 2,400 to 8,000 g/mol, more preferentially from 2,400 to 6,500 g/mol or
- the polymer (P) is completely or partially neutralised, in particular at the end of the polymérisation reaction or
- the polymérisation reaction uses:
o 100% by weight of anionic monomer (M) or o from 70% to 99.5% by weight of anionic monomer (M) and from 0.5% to 30% by weight of at least one other monomer.
12. The method according to one of claims 1 to 10, in which the anionic monomer (M) comprising at least one polymerisable olefinic unsaturation comprises one or two carboxylic acid groups, preferably comprises a single carboxylic acid group, preferably is chosen among acrylic acid, methacrylic acid, an acrylic acid sait, a methacrylic acid sait and mixtures thereof, more preferentially acrylic acid.
13. The method according to one of claims 1 to 11, in which the polymérisation reaction also uses at least one other monomer chosen among:
- another anionic monomer, preferably a monomer chosen among acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride and mixtures thereof,
- 2-acrylamido-2-methylpropanesulphonic acid, a sait of 2-acrylamido-2methylpropanesulphonic acid, 2-(methacryloyloxy)ethanesulphonic acid, a sait of 2-(methacryloyloxy)ethanesulphonic acid, sodium methallyl sulphonate, styrene sulphonate and combinations or mixtures thereof,
- a non-ionic monomer comprising at least one polymerisable olefinic unsaturation, preferably at least one polymerisable ethylenic unsaturation and in particular a polymerisable vinyl group, more preferentially a non-ionic monomer chosen among styrene, vinyl caprolactam, the esters of an acid comprising at least one monocarboxylic acid group, in particular an ester of an acid chosen among acrylic acid, methacrylic acid and mixtures thereof, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl méthacrylate, hydroxypropyl méthacrylate, alkyl acrylate, in particular Ci-Cio-alkyl acrylate, preferentially Ci-C4-alkyl acrylate, more preferentially methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, alkyl méthacrylate, in particular Cj-Cio-alkyl méthacrylate, preferentially Ci-C4-alkyl méthacrylate, more preferentially methyl méthacrylate, ethyl méthacrylate, n-propyl méthacrylate, isopropyl méthacrylate, isobutyl méthacrylate, n-butyl méthacrylate, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, aryl méthacrylate, preferably phenyl méthacrylate, benzyl méthacrylate, phenoxyethyl méthacrylate and
- a monomer of formula (II):
R1
(Π) wherein:
- R1 and R2, identical or different, independently represent H or CH3,
- L1 independently represents a group chosen among C(O), CH2, CH2-CH2 and O-CH2-CH2-CH2-CH2,
- L2 independently represents a group chosen among (CH2-CH2O)X, (CH2CH(CH3)O)y, (CH(CH3)CH2O)z and combinations thereof and
- x, y and z, identical or different, independently represent an integer or décimal comprised in a range from 0 to 150 and the sum of x+y+z is comprised in a range from 10 to 150.
14. The method according to one of claims 1 to 13, in which the flocculating agent is chosen among polyacrylamide, a polyacrylamide dérivative.
15. An aqueous minerai suspension comprising at least one flocculating agent and with a dry solids content that is greater than 10% by weight of the suspension, chosen among:
- an aqueous métal ore residue,
- an aqueous suspension of métal ore and
- an aqueous suspension of useable métal or of a useable métal dérivative and derived from métal ore, comprising at least one polymer (P) with a molecular mass Mw, measured by GPC, ranging from 2,000 to 20,000 g/mol and prepared by at least one radical polymérisation reaction, at a température greater than 50°C, of at least one anionic monomer (M) comprising at least one polymerisable olefinic unsaturation and at least one carboxylic acid group or one of its salts, in the presence of at least one radical-generating compound chosen among hydrogen peroxide, benzoyl peroxide, acetyl peroxide, laurel peroxide, tertbutyl hydroperoxide, cumene hydroperoxide, ammonium persulphate, an alkaline métal persulphate, preferably sodium persulphate or potassium persulphate, an azo compound such as 2,2’-azobis(2-(4,5-dihydroimidazolyl)propane, 2,2’-azobis(2-methylpropionamidine) dihydrochloride, diazo-valeronitrile, 4,4'-azobis-(4-cyanovaleric) acid, AZDN or 2,2’-azobisisobutyronitrile, and their respective combinations or associations with an ion chosen among Fe11, Fein, Cu1, Cu11 and mixtures thereof.
16. The aqueous minerai suspension according to claim 15:
- obtained by gravimétrie concentration of the aqueous suspension in the presence of at least one polymer (P) or
- obtained according to the method according to one of claims 1 to 14.
OA1202000420 2018-06-08 2019-06-05 Method for controlling the sedimentation of a mining derivative. OA19880A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1854991 2018-06-08

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Publication Number Publication Date
OA19880A true OA19880A (en) 2021-06-23

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