EP3801811A2 - Verfahren zur kontrolle der sedimentation eines abbauderivates - Google Patents

Verfahren zur kontrolle der sedimentation eines abbauderivates

Info

Publication number
EP3801811A2
EP3801811A2 EP19737157.8A EP19737157A EP3801811A2 EP 3801811 A2 EP3801811 A2 EP 3801811A2 EP 19737157 A EP19737157 A EP 19737157A EP 3801811 A2 EP3801811 A2 EP 3801811A2
Authority
EP
European Patent Office
Prior art keywords
weight
less
suspension
metal
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19737157.8A
Other languages
English (en)
French (fr)
Inventor
Mehdi Bouzid
Benoît MAGNY
Jacques Mongoin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coatex SAS
Original Assignee
Coatex SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Coatex SAS filed Critical Coatex SAS
Publication of EP3801811A2 publication Critical patent/EP3801811A2/de
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D3/00—Differential sedimentation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D3/00—Differential sedimentation
    • B03D3/06—Flocculation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/09—Viscosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a method for controlling the sedimentation of an aqueous mineral suspension of a mining derivative by gravimetric concentration of the aqueous suspension in the presence of a flocculation agent and a polymer (P) of molecular weight Mw measured by GPC ranging from 2,000 to 20,000 g / mol prepared by at least one radical polymerization reaction of at least one anionic monomer (M).
  • the invention also relates to the suspension produced whose Brookfield viscosity is less than 1800 mPa.s or the flow threshold is less than 80 Pa.
  • the method according to the invention is implemented during a mining process for mining at least one mining deposit.
  • These mining processes generally make it possible to obtain at least one metal to be valorized from a metallic ore.
  • the metallic ore also includes a residue of this metallic ore.
  • Mining processes are usually carried out using water as a carrier for the treatment or transport of solids.
  • the mining derivative is therefore usually an aqueous mining derivative.
  • the fraction of the metal ore to be upgraded is a metal or several metals or a derivative of a metal or a derivative of several metals.
  • the aqueous metal ore residue thus results from at least one step of separating the metal to be upgraded or a derivative of the metal to be valorized from a metal ore, in particular from a metal ore produced by mineral extraction.
  • an essential step consists in adding at least one polymer (P) in an aqueous mining derivative.
  • P polymer
  • This step therefore concerns the treatment of a mining derivative. It can also concern the treatment of the metallic ore which is to be valorized.
  • This step is therefore generally implemented in a mining process comprising different stages of treatment of the metal ore, metal or metal derivative for recovery or treatment of the metal ore residue.
  • the mining processes comprise several stages of treatment of the metallic ore, several stages of treatment of the metal to be valorized or treatment of the metal derivative to be valorized as well as several stages of treatment of the metal ore residue.
  • a mining process comprises one or more of the following steps:
  • concentration of the residue of metal ore or of the metal to be valorised or of a derivative of the metal to be valorised for example by filtration, by sedimentation, by gravity, by use of a thickener, by flocculation,
  • Methods are known for preparing an aqueous mineral suspension from an aqueous mining derivative, in particular such methods used during the treatment, transport or storage of such a derivative.
  • EP 2686275 discloses a method for controlling the rheology of an aqueous dispersion which comprises adding a natural polymer and then adding a synthetic polymer to the aqueous system.
  • EP 1976613 relates to the concentration of an aqueous suspension of solid particles by adding a flocculant organic polymer and an agent selected from the group consisting of radical agents, oxidizing agents, enzymes and radiation.
  • EP 2771289 also relates to the concentration of an aqueous suspension of solid particles by introduction of a flocculant organic polymer and the addition of an agent system comprising an oxidizing agent and a control agent.
  • WO 2014-019993 describes a method for concentrating an aqueous suspension of solid particles by adding a flocculant organic polymer and an active agent chosen from radical agents, oxidizing agents and reducing agents.
  • the known suspensions In order to make them manipulable, the known suspensions generally have a reduced concentration of solids. In fact, the addition of water can make it possible to lower the viscosity or the yield point of these suspensions.
  • Compatibility with the various constituents of the aqueous mineral suspensions prepared from an aqueous mining derivative is also an important property to be investigated, in particular the compatibility with a flocculating agent that can be used to treat the aqueous mining derivative, especially the compatibility with a polyacrylamide or with a polyacrylamide derivative.
  • control of the viscosity of aqueous mineral suspensions prepared from a mining derivative is important, in particular for their pumping, to facilitate their agitation or for their transport.
  • aqueous mineral suspensions prepared from an aqueous mining derivative it is important to be able to control the behavior of aqueous mineral suspensions prepared from an aqueous mining derivative in order to avoid problems within processing, storage or transport facilities. Indeed, these facilities can be damaged, blocked or clogged in the event of drift or lack of control of the viscosity, the flow threshold or sedimentation of an aqueous mineral suspension prepared from an aqueous mining derivative.
  • the method according to the invention makes it possible to provide a solution to all or part of the problems of the methods for controlling the sedimentation of an aqueous mineral suspension from an aqueous mining derivative of the state of the art.
  • the invention provides a method for controlling the sedimentation of an aqueous mineral suspension comprising at least one flocculation agent and whose solids content is greater than 10% by weight of the suspension, chosen from:
  • the method according to the invention makes it possible to control the sedimentation of an aqueous mineral suspension whose solids concentration is greater than 10% by weight of the suspension, the rheology of the suspension prepared for a solids concentration is greater than 10 % by weight or greater than 15% by weight of the suspension.
  • the suspension prepared according to the method according to the invention has a solids concentration of less than 20% by weight or less than 30% by weight or even less than 35% by weight or even less than 40% by weight. or 50% by weight.
  • the suspension prepared according to the method according to the invention has a dry matter concentration 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. % by weight or 10 to 20% by weight or alternatively 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 % by weight, or alternatively 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 gravimetric concentration of the aqueous suspension.
  • this gravimetric concentration of the aqueous suspension comprises the separation of a supernatant phase and a sediment bed.
  • these two phases constituting these two fractions of the aqueous suspension differ essentially by their difference in concentration of dry matter.
  • the gravimetric concentration of the aqueous suspension comprises the separation of a supernatant phase whose solids content is less than 5% by weight. In a preferred manner according to the invention, the gravimetric concentration of the aqueous suspension comprises the separation of a bed of sediment with a dry matter concentration greater than 40% by weight.
  • the gravimetric concentration of the aqueous suspension comprises the separation of a supernatant phase having a dry matter concentration of less than 5% by weight and a sediment bed whose concentration of material dry is greater than 40% by weight.
  • the supernatant phase and the sediment bed have different rheological properties.
  • the sediment bed has particular rheological properties.
  • the method according to the invention makes it possible to control other essential properties of the aqueous suspension prepared.
  • This method thus makes it possible to control both the Brookfield viscosity and the flow threshold of the prepared suspension, in particular the sediment bed.
  • the concentration by gravimetry of the aqueous suspension comprises the separation of a supernatant phase and a bed of sediment which has:
  • Brookfield viscosity measured at 100 rpm and at 25 ° C., of less than 1800 mPa.s or
  • Brookfield viscosity measured at 100 rpm and at 25 ° C., of less than 1800 mPa.s and a flow threshold measured at a temperature of 25 ° C. by means of an imposed stress rheometer equipped with a finned mobile, for a particular torque, less than 80 Pa.
  • the flow threshold which characterizes the flow resistance, is measured on a sample of an aqueous mineral suspension, in particular an aqueous metal ore residue.
  • the flow threshold is the stress that must be applied to a suspension in order to cause its flow. If the stress is insufficient, the suspension elastically deforms while if the stress is sufficient, the suspension can flow in the manner of a liquid.
  • the flow threshold expressed in Pascal (Pa) is measured at a temperature of 25 ° C. by means of an imposed constraint Brookfield DV3T rheometer equipped with a suitable finned wheel. Without destroying the underlying structure, the finned mobile is immersed in the material to the first immersion mark. After a waiting time of 5 min, the measurement is carried out without pre-shearing at the speed of 0.5 rpm. This relatively low speed is preferred in order to minimize the inertial effects of the finned mobile.
  • the variation of the torsion torque measured by the apparatus to maintain a rotational speed of 0.5 rpm is monitored as a function of time. The value of the limit
  • the flow rate or threshold of flow of the aqueous residue is indicated by the apparatus when this variation becomes zero.
  • the flow threshold is measured at a temperature of 25 ° C by means of an imposed stress rheometer equipped with a finned wheel for a particular torsion torque.
  • the sediment bed has a yield point less than 70 Pa or less than 60 Pa, more preferably less than 50 Pa or less than 40 Pa, much more preferably less than 30 Pa or less than 30 Pa. 20 Pa.
  • the sediment bed has a yield point greater than 10 Pa, preferably greater than 12 Pa, much more preferably greater than 15 Pa.
  • the sediment bed has a yield point greater than 10 Pa, more preferably greater than 12 Pa, much more preferably greater than 15 Pa and less than 70 Pa or less than 60 Pa, more preferably less than 50 Pa or less than 40 Pa, much more preferably less than 30 Pa or less than 20 Pa.
  • the Brookfield viscosity is measured at 100 rpm and at 25 ° C, for example by means of a Brookfield DV3T rheometer.
  • the Brookfield viscosity of the suspension prepared is generally less than 1800 mPa.s.
  • the method according to the invention makes it possible to prepare a suspension which has a viscosity of less than 1500 mPa.s or less than 1200 mPa.s. More preferably, the viscosity is less than 1000 mPa.s or less than 900 mPa.s. More preferably, the viscosity is less than 800 mPa.s or less than 700 mPa.s, or even less than 500 mPa.s.
  • the amount of polymer (P) used can vary quite widely.
  • the suspension prepared comprises from 0.01 to 2% by weight or from 0.01 to 1.8% or else from 0.01 to 1.5% of polymer (P) (dry on dry relative to the ore residue). More preferably, the suspension prepared 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 else from 0, 04 to 0.25% or 0.04 to 0.15% by weight of polymer (P) (dry on dry relative to the ore residue).
  • the method according to the invention can implement one or more polymers (P).
  • the suspension prepared then comprises one, two or three different polymers (P).
  • the method according to the invention may also comprise the addition addition of at least one compound selected from a lignosulfonate derivative, a silicate, an unmodified polysaccharide and a modified polysaccharide.
  • the method according to the invention comprises the addition to an aqueous residue of metal ore of at least one polymer (P).
  • the metal ore is not an aluminum ore.
  • the metal ore is selected from lithium ore, strontium, lanthanides, actinides, uranium, rare earths, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, cobalt , rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, tin, lead.
  • the metal ore is selected from uranium ore, molybdenum, manganese, iron, cobalt, nickel, copper, silver, gold. More preferably, it is a copper ore. It can also be a derivative of several metals to be valued including copper, zinc and cobalt.
  • the metallic ore comprises at least one metal or at least one metal derivative for recovery obtained by separating all or part of the residue from the metal ore.
  • the metallic ore comprises a metal oxide, a metal sulphide or a metal carbonate.
  • the metal ore residue may comprise some residual amount of metal.
  • the metal ore residue may comprise a residual amount of metal less than 2,000 g per tonne (dry / dry) based on the amount of metal ore residue.
  • This amount of metal within the metal ore residue can generally range from 10 to 2,000 g per tonne (dry / dry) or from 10 to 1,000 g per tonne (dry / dry), based on the amount of residue of metallic ore.
  • the polymer (P) may be added during one or more steps of the mining process comprising the gravimetric concentration of the aqueous suspension.
  • the gravimetric concentration of the suspension is carried out by means of at least one device chosen from a conventional thickener, a high-density thickener and a high-performance thickener.
  • the addition of the polymer (P) is carried out before the gravimetric concentration of the suspension or during the gravimetric concentration of the suspension.
  • the addition of the polymer (P) is carried out at the same time as the addition of the flocculating agent, thus carried out simultaneously with the addition flocculating agent. Also more preferably according to the invention, the addition of the polymer (P) is carried out during the gravimetric concentration of the suspension and simultaneously with the addition of the flocculating agent.
  • the addition of the polymer (P) is carried out at the same place as the addition of the flocculating agent, thus carried out parallel to the addition of the flocculating agent. Also more preferably according to the invention, the addition of the polymer (P) is carried out during the gravimetric concentration of the suspension and in parallel with the addition of the flocculating agent.
  • the method according to the invention implements at least one particular polymer (P). It is prepared by a polymerization reaction in the presence of at least one radical-generating compound chosen from hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, a persulfate of alkali metal, preferably sodium persulfate or potassium persulfate, an azo compound, such as 2,2'-azobis (2- (4,5-dihydroimidazolyl) propane, 2,2'-azobis (2-methylpropionamidine) dihydrochloride) , diazo-valero-nitrile, 4,4'-azobis (4-cyanovaleric), AZDN or 2,2'-azo-bis-isobutyronitrile, and combinations or combinations thereof with an ion selected from Fe 11 , Fe m , Cu 1 , Cu 11 and mixtures thereof
  • the polymerization reaction can also be carried out in the presence of at least one compound comprising phosphorus at the oxidation state I, preferably a compound chosen from hypophosphorous acid (H 3 PO 2 ) and a derivative of hypophosphorous acid (H 3 PO 2 ), preferably a compound comprising at least one hypophosphite ion (H 2 PO 2 ), more preferably a compound chosen from sodium hypophosphite (H 2 PO 2 Na), potassium hypophosphite (H 2 PO 2 K), calcium hypophosphite ([H 2 PO 2 ] 2 Ca) and mixtures thereof.
  • a compound chosen from hypophosphorous acid (H 3 PO 2 ) and a derivative of hypophosphorous acid (H 3 PO 2 ) preferably a compound comprising at least one hypophosphite ion (H 2 PO 2 ), more preferably a compound chosen from sodium hypophosphite (H 2 PO 2 Na), potassium hypophosphite (H 2 PO 2 K), calcium hypophosphite (
  • the polymerization reaction may be carried out in the presence of at least one compound comprising phosphorus at oxidation level III, preferably a compound chosen from phosphorous acid and a phosphorous acid derivative, more preferably a compound comprising at least one phosphite ion, especially a compound selected from sodium phosphite, calcium phosphite, potassium phosphite, ammonium phosphite and combinations thereof.
  • at least one compound comprising phosphorus at oxidation level III preferably a compound chosen from phosphorous acid and a phosphorous acid derivative, more preferably a compound comprising at least one phosphite ion, especially a compound selected from sodium phosphite, calcium phosphite, potassium phosphite, ammonium phosphite and combinations thereof.
  • the polymerization reaction can also be carried out also in the presence of at least one compound comprising a bisulfite ion, preferably a chosen compound among ammonium bisulfite, an alkali metal bisulfite, especially sodium bisulfite, potassium bisulfite, calcium bisulfite, magnesium bisulfite and combinations thereof.
  • the polymerization reaction may 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 from a xanthate derivative, a mercaptan compound and a formula (I):
  • X is independently H, Na or K and
  • R is independently a C 1 -C 6 -alkyl group, preferably a methyl group, in particular a compound of formula (I) which is disodium trithiocarbonate diisopropionate (DPTTC).
  • DPTTC disodium trithiocarbonate diisopropionate
  • the polymerization reaction is carried out at a temperature above 50 ° C.
  • the polymerization reaction is carried out at a temperature ranging from 50 to 98 ° C or from 50 to 95 ° C or from 50 to 85 ° C.
  • a higher temperature especially greater than 100 ° C, can be implemented by adjusting the pressure of the reaction medium to prevent evaporation.
  • the polymerization reaction is carried out in water.
  • a solvent alone or in a mixture with water, in particular an alcoholic solvent, in particular isopropyl alcohol. More preferably, it is carried out in water.
  • the polymer (P) used according to the invention has a molecular weight Mw measured by GPC ranging from 2200 to 10 000 g / mol.
  • the polymer (P) used according to the invention has a molecular weight Mw ranging from 2,400 to 9,500 g / mol or from 2,400 to 8,000 g / mol, more preferably from 2,400 to 6,500 g / mol. g / mol.
  • the polymer (P) used according to the invention is therefore not a flocculation agent.
  • the molecular weight Mw is determined by Steric Exclusion Chromatography (CES) or in English "Gel Permeation Chromatography” (GPC).
  • CES Steric Exclusion Chromatography
  • GPC Gel Permeation Chromatography
  • This technique uses a Waters liquid chromatography apparatus equipped with a detector.
  • This detector is a Waters refractometric concentration detector.
  • This liquid chromatography apparatus is equipped with a column steric exclusion in order to separate the different molecular weights of the copolymers studied.
  • the liquid elution phase is an aqueous phase adjusted to pH 9.00 using 1 N sodium hydroxide containing 0.05 M NaHCO 3 , 0.1 M NaNO 3 , 0.02 M triethanolamine and 0.03% of NaN 3 .
  • the copolymer solution is diluted to 0.9% dry in the solubilization solvent of the CES, which corresponds to the liquid phase of elution of the CES, to which 0.04% of dimethylformamide which is added is added. the role of flow marker or internal standard. Then, it is filtered at 0.2 ⁇ m. 100 ⁇ l are then injected into the chromatography apparatus (eluent: an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05 M NaHCO 3 , 0.1 M NaNO 3 , 0.02 M of trietanolamine and 0.03% NaN 3 ).
  • the liquid chromatography apparatus contains an isocratic pump (Waters 515) with a flow rate of 0.8 mL / min.
  • the chromatography apparatus also comprises an oven which itself comprises in series the following column system: a precolumn of the Guard Column Ultrahydrogel Waters type, 6 cm long and 40 mm inside diameter, and a linear column of the Ultrahydrogel Waters type. 30 cm long and 7.8 mm inside diameter.
  • the detection system consists of a type RI Waters 410 refractometric detector. The oven is heated to a temperature of 60 ° C and the refractometer is heated to a temperature of 45 ° C.
  • the chromatography apparatus is calibrated by means of standards of powdered sodium polyacrylate of various molecular weights certified by the supplier: Polymer Standards Service or American Polymers Standards Corporation (molecular weight ranging from 900 to 2.25 ⁇ 10 6 g / mol and polymolecularity index ranging from 1.4 to 1.8).
  • the polymer (P) used according to the invention may be totally or partially neutralized, in particular at the end of the polymerization reaction.
  • the neutralization of the polymer is carried out by neutralizing or salifying all or part of the carboxylic acid functions present within the polymer.
  • the neutralization is carried out by means of a base, for example by means of an alkali metal derivative or an alkaline earth metal derivative.
  • the preferred bases are chosen from CaO, ZnO, MgO, NaOH, KOH, NH 4 OH, Ca (OH) 2 , Mg (OH) 2 , monoisopropyl amine, triethanolamine, triisopropylamine, 2-amino-2-methyl-1-propanol. (AMP), triethylamine, diethylamine, monoethylamine.
  • the neutralization is carried out using MgO, NaOH, KOH, Ca (OH) 2 , Mg (OH) 2 , alone or in combination.
  • the polymerization reaction uses at least one anionic monomer (M) which comprises at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or a salt thereof.
  • the anionic monomer (M) comprising at least one polymerizable olefinic unsaturation comprises one or two carboxylic acid functions, in particular a single carboxylic acid function. More preferentially, it is chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and their mixtures, more preferably acrylic acid.
  • the polymerization 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. at least one other monomer.
  • the polymerization reaction can therefore also employ at least one other monomer chosen from:
  • anionic monomer preferably a monomer selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride and mixtures thereof,
  • 2-acrylamido-2-methylpropanesulphonic acid 2-acrylamido-2-methylpropanesulphonic acid salt, 2- (methacryloyloxy) ethanesulfonic acid, 2- (methacryloyloxy) ethanesulfonic acid salt, sodium methallyl sulfonate styrene sulphonate and combinations or mixtures thereof
  • nonionic monomer comprising at least one polymerizable olefinic unsaturation, preferably at least one polymerizable ethylenic unsaturation and in particular a polymerizable vinyl functional group, more preferably a nonionic monomer chosen from styrene, vinylcaprolactam, esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid selected from acrylic acid, methacrylic acid, and mixtures thereof, for example hydroxyethylacrylate, hydroxypropylacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, alkyl acrylate, in particular C 1 -C 10 alkyl acrylate, preferentially Ci-C 4 -alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate
  • R 1 and R 2 which are identical or different, independently represent H or CH 3 ,
  • L 1 independently represents a group chosen from C (O), CH 2 , CH 2 -CH 2 and O-CH 2 -CH -CH 2 -CH 2 ,
  • L 2 independently represents a group chosen from (CH 2 -CH 2 O) x , (CH 2 CH (CH 3 ) O) y , (CH (CH 3 ) CH 2 0) z and their combinations and
  • x, y and z identical or different, independently represent an integer or decimal number between 0 and 150 and the sum x + y + z is between
  • the monomer of formula (P) is such that:
  • R 1 represents CH 3 ,
  • L 1 represents a group C (O)
  • L 2 independently represents a combination of groups chosen from (CH 2 -CH 2 O) x , (CH 2 CH (CH 3 ) O) y , (CH (CH 3 ) CH 2 0) z and
  • x, y and z identical or different, independently represent an integer or decimal number between 0 and 150 and the sum x + y + z is between
  • the polymer (P) used according to the invention is a non-sulfonated polymer.
  • a separation step can also be implemented.
  • the separation can be carried out after the total or partial neutralization of the polymer (P). It can also be implemented before neutralization of the polymer (P).
  • the aqueous solution of the polymer (P), totally or partially neutralized can be treated according to static or dynamic fractionation methods known per se.
  • One or more polar solvents are thus used, in particular belonging to the group consisting of methanol, ethanol, n-propanol, isopropanol, butanols, acetone and tetrahydrofuran, thus producing a separation in two phases.
  • the least dense phase comprises the major fraction of the polar solvent and the fraction of low molecular weight polymers
  • the densest aqueous phase contains the fraction of polymers of higher molecular weight.
  • the temperature at which the selection process of the polymer fraction is carried out can influence the partition coefficient. It is generally between 10 and 80 ° C, preferably between 20 and 60 ° C. When separating, it is important to control the ratio of the amounts of dilution water and polar solvents.
  • the ratios of the extracted fractions generally depend on the centrifugation conditions.
  • Selection of the polymer fraction can also be improved by treating again the denser aqueous phase with a new amount of polar solvent, which may be different. It can also be a mixture of polar solvents. Finally, the liquid phase obtained after treatment can be subjected to distillation to remove the solvent (s) used for the treatment.
  • polar solvent which may be different. It can also be a mixture of polar solvents.
  • the method according to the invention makes it possible to control the properties of the aqueous mineral suspension, in particular to control its sedimentation, despite the presence of at least one flocculation agent in this suspension.
  • the method according to the invention is effective in the presence of many types of flocculating agent.
  • the flocculation agent is chosen from a polyacrylamide, a polyacrylamide derivative.
  • the sedimentation control method according to the invention makes it possible to prepare a suspension of aqueous metal ore residue comprising at least one polymer (P) which has particularly advantageous properties, especially particularly advantageous rheological properties.
  • the invention also provides an aqueous mineral suspension comprising at least one flocculation agent and whose solids content is greater than 10% by weight of the suspension, chosen from:
  • the aqueous inorganic suspension according to the invention is obtained by gravimetric concentration of the aqueous suspension in the presence of at least one polymer (P) according to the invention.
  • the aqueous mineral suspension according to the invention is obtained during the implementation of the method according to the invention.
  • a polymer is prepared during the method according to the invention.
  • the polymer (PI) is prepared by introducing into a one-liter glass reactor equipped with mechanical stirring and oil-bath heating 212 g of water and 0.08 g of sodium sulfate. iron heptahydrate.
  • 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 maintaining the temperature of the reaction medium at 95 ° C.
  • the medium is again heated for 60 min at 95 ° C.
  • the solution is then neutralized with sodium hydroxide 50% by weight in water to pH 8 and then diluted to a solids content of 42% by weight.
  • the polymer (P1) of molecular weight Mw measured by GPC of 4500 g / mol is obtained.
  • the raw material used for this series of tests is an aqueous metal ore residue from a Chilean copper mine in the north of the country. It is a waste resulting from the separation of the rock extracted from the ore mine including the metal to be valorized.
  • This aqueous residue of copper ore is in the form of a suspension in water.
  • Various prior measures have been carried out on the aqueous residue in the absence of polymer according to the invention:
  • a test is then carried out to evaluate the effectiveness of the polymer on the sedimentation of an aqueous residue suspension of copper ore during the concentration of this residue by sedimentation.
  • This sedimentation is carried out on a suspension having a solids content of 30% by weight.
  • This suspension having a solid content of 30% by weight is prepared by diluting the aqueous residue suspension having a solids content of 63.5% by weight.
  • a sample of 30% by weight aqueous copper ore slurry is transferred to a 500 ml beaker and then mechanically stirred with a Raynerie mixer. Stirring is performed at 500 rpm.
  • a polymer (P1) according to the invention is added at a dose of 0.05% by dry weight / sec relative to the dry residue and is left stirring for 15 min.
  • the suspension thus dispersed is then incorporated into a graduated 2-liter test tube equipped with mechanical stirring at 0.8 rpm.
  • a fixed dose of an acrylamide flocculating agent is incorporated in a dose equivalent to 12 g / T dry / sec of residue.
  • a threshold of flow (Pa) of the suspension having undergone a very low shear rate (approximately 1 to 10 s 1 ) (UN-YS) is carried out. It corresponds to the flow threshold of the aqueous residue suspension of copper ore at the bottom of a thickener.
  • a flow threshold (Pa) of the high shear suspension (about 100 to 1000 s 1 ) (FS-YS) is also performed.
  • the sedimentation rate is also measured using the graduation of the specimen and a stopwatch. The measurement is made by observing the separation of the supernatant water phase and sediment. It is done in cm per minute then converted to meter per hour (m / h).
  • the decanter is cylindrical in shape with a transparent wall. Its volume is 30 L, it is stirred by means of a low power motor feeding a stirring of 1 rpm.
  • the suspension of aqueous copper ore residue implemented has a solids content of 69%. dry weight
  • a fixed dose of an acrylamide flocculating agent is incorporated in a dose equivalent to 12 g / T dry / sec of residue.
  • the preparation of the suspension is similar to the previous preparation, the solids content is 30% by dry weight / sec.
  • the dose of polymer remains the same. It is 0.05% by dry weight / sec.
  • the polymer (P1) is introduced into the top of the thickener in parallel with the feed well.
  • the feedwell is the zone through which the feed of aqueous residue of ore is made and the introduction of flocculant.
  • the material used for the concentration of the aqueous residue in the presence of a polymer according to the invention is a plexiglass pilot thickener provided with a low intensity stirrer producing a stirring of 1 rpm.
  • a flow threshold measurement (Pa) of the medium shear suspension (about 10 to 100 s 1 ) (MS-YS) is performed. It corresponds to the flow threshold at the bottom of a thickener at the level of the transport pump to the aqueous residue storage units of copper ore.
  • a flow threshold measurement (Pa) of the suspension having undergone a very high shear rate (approximately 1000 to 10,000 s 1 ) (HFS-YS) is also carried out. It corresponds to the flow threshold in the pipe located after the transport pump at the outlet of a thickener and which leads to the aqueous tailings storage units of copper ore.
  • the results are shown in Table 2.
  • the sedimentation rate is also measured using the graduation of the specimen and a stopwatch. The measurement is made by observing the separation of the supernatant water phase and sediment. It is done in cm per minute then converted to meter per hour (m / h). It is between 7 and 8 m / h.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
EP19737157.8A 2018-06-08 2019-06-05 Verfahren zur kontrolle der sedimentation eines abbauderivates Pending EP3801811A2 (de)

Applications Claiming Priority (2)

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FR1854991A FR3082124B1 (fr) 2018-06-08 2018-06-08 Controle de la sedimentation d'un derive minier
PCT/FR2019/000092 WO2019234315A2 (fr) 2018-06-08 2019-06-05 Contrôle de la sédimentation d'un dérivé minier

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CA (1) CA3102186A1 (de)
CL (1) CL2020003159A1 (de)
CO (1) CO2020014705A2 (de)
FR (1) FR3082124B1 (de)
MA (1) MA52769A (de)
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CN112195340A (zh) * 2020-09-28 2021-01-08 穆索诺伊矿业简易股份有限公司 一种降低铜浸出液固体悬浮物的方法
CN113072150B (zh) * 2021-04-22 2022-06-17 重庆理工大学 一种基于硫酸酸解钒钛磁铁矿两步法制备铁钛钒三元无机高分子絮凝剂的方法

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AU2019282374A1 (en) 2020-12-03
CL2020003159A1 (es) 2021-04-23
WO2019234315A2 (fr) 2019-12-12
CN112272583B (zh) 2022-10-11
MX2020012448A (es) 2021-01-29
CA3102186A1 (fr) 2019-12-12
WO2019234315A3 (fr) 2020-01-30
CO2020014705A2 (es) 2020-12-10
MA52769A (fr) 2021-04-14
AU2019282374B2 (en) 2024-07-25
US20210170309A1 (en) 2021-06-10
CN112272583A (zh) 2021-01-26
FR3082124A1 (fr) 2019-12-13
BR112020023480A2 (pt) 2021-03-30
ZA202007711B (en) 2022-03-30
FR3082124B1 (fr) 2021-05-28

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