EP3810299A1 - Recyclage d'eau dans un dérivé minier - Google Patents
Recyclage d'eau dans un dérivé minierInfo
- Publication number
- EP3810299A1 EP3810299A1 EP19740607.7A EP19740607A EP3810299A1 EP 3810299 A1 EP3810299 A1 EP 3810299A1 EP 19740607 A EP19740607 A EP 19740607A EP 3810299 A1 EP3810299 A1 EP 3810299A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- less
- water
- ntu
- particles
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- 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
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- 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 preparing an aqueous suspension (S) of mineral particles of a metallic ore, a metal ore residue or a metal to be valorised comprising a particular polymer (P) and water recycling from an aqueous metal ore residue, an aqueous suspension of metal ore or an aqueous suspension of a metal to be upgraded.
- the invention also relates to a method for controlling, improving or reducing the turbidity of supernatant water from an aqueous suspension (S).
- the invention also provides an aqueous suspension (S).
- 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 treatment or transport medium for dry matter.
- These mining processes can be implemented for various mining derivatives that may be a metal ore, a metal to be upgraded, a metal derivative to be upgraded or a metal ore residue.
- 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.
- 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.
- an essential step consists in adding at least one polymer (P) to particles of a mining derivative.
- This step is therefore generally implemented within a mining process comprising different stages of treatment of the metallic ore and different stages of treatment of the metal ore residue and the metal to be upgraded or the metal derivative to be upgraded.
- 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 ore. 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 valorized 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 a mining derivative, in particular such methods used during the treatment, transport or storage of such a derivative.
- Suspensions of mining derivative may have a particle size of relatively dry or not very homogeneous dry matter particles.
- EP 636578 discloses the fluidification of aqueous slurried red mud slurries during the manufacture of bauxite by the Bayer process, using a flocculation agent and a dispersing agent (D).
- GB 1414964 relates to a deflocculating method of a particulate material, which comprises adding to a slurry of the particulate material a copolymer or a water-soluble derivative of a vinyl copolymer.
- WO 2007-082797 discloses a method of concentrating an aqueous suspension of solid particles combining the use of a flocculating polymer and the implementation of radiation or radical agents, oxidizing agents or enzymes.
- WO 2017-097799 discloses a method of treating an aqueous effluent from oil sands mining comprising the addition of a sulfonated dispersant and the addition of a flocculating agent.
- 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.
- the compatibility with the various constituents of the aqueous mineral suspensions prepared from a 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 residue of metallic ore, in particular 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.
- the recycling water is separated water, including separate supernatant water.
- the recycle water can come from a mining process step that implements a thickener of a material to be concentrated or a storage pond, for example a storage tank of an aqueous residue of ore metal or metal ore residue sludge storage.
- the method according to the invention makes it possible to provide a solution to all or part of the problems of the methods for preparing an aqueous mineral suspension from mining derivatives of the state of the art.
- the invention provides a method for preparing an aqueous suspension (S) of mineral particles selected from particles of at least one metal ore, particles of at least one metal ore residue, particles of at least one metal to be valorized or at least one metal derivative to be valorized, and their combinations, comprising the addition in a mixture (ME) chosen from:
- ME1 comprising water and particles of at least one metal ore
- ME2 a mixture comprising water and particles of at least one metal ore residue
- ME3 a mixture (ME3) comprising water and particles of at least one metal to be efficientlyzed or of at least one metal derivative to be efficientlyzed
- a mixture comprising at least two mixtures chosen from (ME1), (ME2) and (ME3);
- the method according to the invention allows the preparation of an aqueous suspension (S) of mineral particles from different mining derivatives.
- the mining derivative is selected from a metal ore, a metal ore residue, a metal to be upgraded and a metal derivative to be upgraded.
- the mixture (ME) according to the invention is chosen from mixtures (ME1), (ME2), (ME3) and (ME4).
- the mixture (ME1) is prepared by mixing water and particles of at least one metal ore.
- the mixture (ME2) is prepared by mixing water and particles of at least one metal ore residue.
- the mixture (ME3) is prepared by mixing water and particles of at least one metal for recovery or by mixing water and particles of at least one metal derivative to be valorized. .
- the mixture (ME4) is prepared by mixing at least two mixtures selected from (ME1), (ME2) and (ME3).
- the mixture (ME4) can also be prepared by mixing water and particles of at least one metal ore or by mixing water and particles of at least one metal ore residue or by mixing water and particles of at least one metal to be upgraded or by mixing water and particles of at least one metal derivative to be upgraded.
- the preferred mixture (ME) is the mixture (ME2).
- 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. More preferably, the metal ore is not an aluminum ore. More preferably according to the invention, 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 comes from at least one metal ore 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. More preferably, it comes from a metal ore selected from a uranium ore, molybdenum, manganese, iron, cobalt, nickel, copper, silver, gold. Most preferably, it comes from a copper ore. Also preferably according to the invention, the metal ore residue comes from at least one metal ore comprising a metal oxide, a metal sulfide 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 metal to be upgraded is chosen from among lithium, 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, preferably from uranium, molybdenum, manganese, iron, cobalt, nickel, copper, silver, gold. More preferably, it is copper.
- the metal derivative to be upgraded comprises at least one metal chosen from among lithium, 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.
- it comprises at least one metal selected from uranium, molybdenum, manganese, iron, cobalt, nickel, copper, silver, gold. More preferably, it comprises copper.
- the method according to the invention uses recycling water.
- the recycling water used according to the invention comprises polymer (P).
- the recycling water used according to the invention comprises a fraction of the polymer (P) introduced into the mixture (ME). More preferably, this polymer fraction (P) ranges from 5 to 30%, preferably from 15 to 25%, in particular 20%, by weight (dry for dry) of the amount of polymer (P) introduced into the polymer. mixture (ME).
- the recycle water has a turbidity of less than 1000 NTU, preferably less than 800 NTU, more preferably less than 600 NTU or even less than 400 NTU, less than 300 NTU, or even less than 300 NTU. 200 NTU.
- the turbidity of the recycle water is greater than 0 NTU or greater than 10 NTU or greater than 20 NTU.
- the turbidity of the recycling water thus ranges from 0 NTU to 1000 NTU, 800 NTU, 600 NTU, 400 NTU, 300 NTU, 200 NTU.
- the turbidity of the recycling water can thus also range from 10 NTU to 1000 NTU, 800 NTU, 600 NTU, 400 NTU, 300 NTU, 200 NTU or even 20 NTU. 1,000 NTU, 800 NTU, 600 NTU, 400 NTU, 300 NTU, 200 NTU.
- the use of the polymer (P) according to the invention makes it possible to improve the turbidity of the recycling water in comparison with a water not comprising this polymer (P).
- the recycle water has a turbidity reduced by at least 30 to 50% or reduced by at least 30 to 60%, with respect to the turbidity of a suspension which does not comprise any polymer.
- the recycle water has a reduced turbidity of at least 30 to 75% or reduced by 30 to 80% or 30 to 90%, compared to the turbidity of a slurry. comprising no polymer.
- the recycle water according to the invention is separated water, especially supernatant water separated during a mining process step.
- the recycle water preferably the supernatant water
- the recycling water preferably the supernatant water
- the recycling water comes from the preliminary separation during at least one concentration step of the aqueous suspension. (S). More preferably for the method according to the invention, the recycling water comes from the prior separation during at least one concentration stage chosen from:
- Gravimetric concentration preferably gravimetric concentration in at least one aqueous suspension storage tank (S) or gravimetric concentration by means of at least one device chosen from a conventional thickener, a high-density thickener, a high-performance thickener;
- Densimetric concentration preferably densimetric concentration by means of at least one device selected from a conventional thickener, a high density thickener, a high efficiency thickener;
- Concentration by filtration preferably concentration by filtration using at least one device selected from a filter, a filter press, a rotary filter.
- the recycling water comes from the prior separation during at least one concentration stage chosen from:
- Gravimetric concentration preferably gravimetric concentration in at least one aqueous suspension storage tank (S) or gravimetric concentration by means of at least one device chosen from a conventional thickener, a high-density thickener, a high-performance thickener;
- Densimetric concentration preferably densimetric concentration by means of at least one device selected from a conventional thickener, a high-density thickener, a high-performance thickener.
- the recycling water comes from at least one thickener of the aqueous suspension (S) or comes from at least one storage tank of the aqueous suspension (S).
- the recycle water is a supernatant water from the prior separation producing a supernatant phase and a bed of sediment, more preferably in at least one stage of concentration of the aqueous suspension (S).
- the dry matter concentration of the suspension (S) can vary quite widely during the concentration steps implemented.
- the concentration of the suspension (S) is increased from 10 to 50% by weight or from 20 to 50% by weight or else from 10 to 40% by weight or else from 20 to 40% by weight.
- the concentration of the suspension (S) is increased from 10 to 60% by weight or from 20 to 60% by weight.
- the concentration of the suspension (S) is increased from 10 to 70% by weight or from 20 to 70% by weight.
- the decantation used may be a counter current decantation (CCD), in particular a countercurrent decantation of an aqueous suspension of metal to be upgraded or metal derivative to be valorised.
- CCD counter current decantation
- the recycle water is a supernatant water originating from the prior separation producing a supernatant phase and a sediment bed. More preferably according to the invention, the recycle water is a supernatant water from the prior separation producing a supernatant phase and a bed of sediment having:
- Brookfield viscosity measured at 100 rpm and at 25 ° C., of less than 1800 mPa.s;
- 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.
- 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.
- 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 torsional torque measured by the apparatus in order to maintain a rotation speed of 0.5 rev / min is followed as a function of time.
- the value of the flow limit or flow threshold of the aqueous residue is indicated by the apparatus when this variation becomes zero.
- the recycle water is supernatant water from the prior separation producing a supernatant phase and a bed of sediment having:
- a yield point less than 70 Pa or less than 60 Pa, preferably less than 50 Pa or less than 40 Pa, more preferably less than 30 Pa or less than 20 Pa; or
- a yield threshold greater than 10 Pa preferably greater than 12 Pa, more preferably 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 preferably lower; at 30 Pa or less than 20 Pa; or
- the recycle water is supernatant water from the prior separation producing a supernatant phase and a bed of sediment.
- the method according to the invention can implement one or more polymers (P).
- the suspension (S) 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 makes it possible to prepare an aqueous suspension (S) which notably comprises recycle water, a polymer (P) and a mixture (ME).
- the aqueous suspension (S) thus comprises particles of at least one mining derivative.
- the aqueous suspension (S) has a solids concentration of greater than 10% by weight or greater than 15% by weight or even greater than 20% by weight.
- the aqueous suspension (S) has a dry matter concentration of less than 50% by weight or less than 40% by weight or even less than 35% by weight.
- the aqueous suspension (S) has a dry matter concentration ranging from 10 to 50% by weight or from 15 to 50% by weight or from 15 to 40% by weight or from 15 to 35% by weight. % by weight, or from 20 to 50% by weight or from 20 to 40% by weight or from 20 to 35% by weight.
- the polymer (P) can be used in different amounts.
- the aqueous suspension (S) comprising the mixture (ME) and the recycle water comprises from 0.01 to 2% by weight of polymer (P) (dry on dry basis with respect to aqueous suspension (S)), more preferably from 0.01 to 1.8% or from 0.01 to 1.5%, more preferably 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%, even more preferably from 0.04 to 0.25% or from 0.04 to 0.15%.
- 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'-azobisisobutyronitrile, and combinations or combinations thereof with an ion selected from Fe 11 , Fe ffl , Cu 1 , Cu 11 and their mixtures
- 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 can be carried out in the presence of at least one compound comprising phosphorus at the IP oxidation state, 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 the IP oxidation state 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 be carried out in the presence of at least one compound comprising a bisulfite ion, preferably a compound chosen from ammonium bisulfite, an alkali metal bisulfite, in particular sodium bisulfite, potassium bisulfite. calcium bisulfite, magnesium bisulfite and combinations thereof.
- a bisulfite ion preferably a compound chosen from ammonium bisulfite, an alkali metal bisulfite, in particular 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 5 -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. It can also be used in 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 provided with a steric exclusion column 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 NaElCO 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 ZnO, MgO, NaOH, KOH, NH 4 OH, Ca (OH) 2 , Mg (OH) 2 , monoisopropylamine, triethanolamine, triisopropylamine, 2-amino-2-methyl-1-propanol (AMP ), triethylamine, diethylamine, monoethylamine.
- the neutralization is carried out using ZnO, MgO, NaOH, 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 thereof 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 function, 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 chosen from acrylic acid, methacrylic acid, and mixtures thereof, for example hydroxyethylacrylate, hydroxypropylacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, alkyl acrylate, in particular Ci-Cio-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 2 -CH 2 -CH 2 ,
- L 2 independently represents a group chosen from (CH 2 -CH 0) x , (CH 2 CH (CH 3 ) 0) 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 10 and 150.
- 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 10 and 150.
- the polymer (P) used according to the invention is a non-sulfonated polymer.
- a separation step can also be implemented. According to the invention, 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 belonging in particular to the group are then used. consisting of methanol, ethanol, n-propanol, isopropanol, butanols, acetone, tetrahydrofuran, thus producing a two-phase separation.
- 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.
- the liquid phase obtained after treatment can be subjected to distillation to remove the solvent (s) used for the treatment.
- the preparation method according to the invention makes it possible to prepare a suspension (S) comprising at least one polymer (P) which has particularly advantageous properties, especially particularly advantageous rheological properties.
- the invention also provides an aqueous mineral suspension (S) of mineral particles selected from particles of at least one metal ore, particles of at least one metal ore residue, particles of at least one metal to recovering or at least one metal derivative to be valorized, and combinations thereof, comprising the addition in a mixture (ME) chosen from:
- a mixture comprising water and particles of at least one metal ore
- ME2 a mixture (ME2) comprising water and particles of at least one metal ore residue
- a mixture (ME3) comprising water and particles of at least one metal to be valorized or of at least one metal derivative to be valorized, a mixture (ME4) comprising at least two mixtures chosen from (ME1), (ME2) and (ME3);
- the recycle water is a supernatant water coming from the preliminary separation producing a supernatant phase and a bed of sediment, preferably during at least one stage concentration of the aqueous suspension (S).
- the recycle water is a supernatant water from the prior separation producing a supernatant phase and a bed of sediment having:
- a Brookfield viscosity measured at 100 rpm and at 25 ° C., of less than 1800 mPa.s; or
- the recycle water is a supernatant water from the prior separation producing a supernatant phase and a bed of sediment having:
- a flow threshold greater than 10 Pa preferably greater than 12 Pa, more preferably 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 preferably lower; at 30 Pa or less than 20 Pa; or
- the recycle water is a supernatant water from the prior separation producing a supernatant phase and a bed of sediment.
- the invention also provides a method for controlling, improving or reducing the turbidity of the supernatant water from the supernatant phase and sediment bed separation, of an aqueous suspension (S) of mineral particles selected from particles of at least one metal ore, particles of at least one metal ore residue, particles of at least one metal to be upgraded or at least one metal derivative to be upgraded, and their combinations, comprising adding to a mixture (ME) selected from: a mixture (ME1) comprising water and particles of at least one metal ore,
- ME2 a mixture (ME2) comprising water and particles of at least one metal ore residue
- ME3 a mixture (ME3) comprising water and particles of at least one metal to be efficientlyzed or of at least one metal derivative to be efficientlyzed
- a mixture comprising at least two mixtures chosen from (ME1), (ME2) and (ME3);
- this method implements a separation step producing a supernatant phase and a sediment bed from the aqueous suspension (S) which is carried out during at least one concentration step of the aqueous suspension (S). .
- the supernatant phase is then recyclable water.
- This water is recyclable in at least one aqueous metal ore residue or in at least one aqueous suspension of metal ore or in at least one aqueous suspension of a metal to be upgraded or a metal derivative to be upgraded.
- the particular, advantageous or preferred characteristics of the method for preparing the suspension (S) according to the invention define suspensions (S) according to the invention which are also particular, advantageous or preferred.
- the characteristics Specific, advantageous or preferred methods for the preparation of the suspension (S) according to the invention define methods for controlling, improving or reducing the turbidity of the supernatant water coming from the separation producing a supernatant phase and a sediment bed, an aqueous suspension (S) according to the invention which are also particular, advantageous or preferred.
- Polymers used during the method according to the invention are prepared.
- the polymer (PI) is prepared by introducing into a 1-liter glass reactor fitted with mechanical stirring and oil bath heating 156 g of water and 0.013 g of iron sulfate heptahydrate. .
- the reactor is heated to 80 ° C.
- the reaction medium is maintained at 80 ° C.
- the medium is then treated under heat for 30 minutes with a solution of 0.3 g of persulfate in 4 g of water and then with 4.5 g of 130 V hydrogen peroxide.
- the medium is again heated for 60 min at 80 ° 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 (PI) of molecular weight Mw measured by GPC of 2500 g / mol is obtained.
- the polymer (P2) 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 (P2) 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 from the ore comprising 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 the polymer according to the invention:
- a 30% aqueous copper residue slurry sample 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.
- the turbidity (in NTU or Nephelometric Turbidity Unit) of the supernatant water of the suspensions is measured using a portable turbidimeter (Hatch 2100Q). These measurements correspond to the turbidity of the supernatant water of the suspension of the aqueous residue at the upper level of a thickener, during the concentration phase of such a residue by sedimentation.
- 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.
- 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 aqueous copper ore slurry used has a solids content of 69% dry weight / sec.
- a fixed dose of an acrylamide flocculating agent is incorporated in a dose equivalent to 12 g / T dry / sec of residue.
- the turbidity (in NTU or Nephelometric Turbidity Unit) of the supernatant water of the suspensions is measured using a portable turbidimeter (Hatch 2100Q). These measurements correspond to the turbidity of the supernatant water (overflow) of the suspension of the aqueous residue at the upper level of a thickener, during the concentration phase of such a residue by sedimentation. About 3 hours are needed to sufficiently concentrate the sediment bed and obtain a relatively clear separation of the sediment and supernatant water. The results are shown in Table 2.
- the polymer (P1) according to the invention systematically improves the turbidity of supernatant water, whether it is surface water or water. overflow.
- This Supernatant water can then be easily recycled, especially in a mining process step. Indeed, this water therefore contains less fine particles, it is clearer. Less water loaded with fine particles can therefore be recycled more quickly; it requires fewer clarification steps.
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1854990A FR3082197B1 (fr) | 2018-06-08 | 2018-06-08 | Recyclage d'eau dans un derive minier |
PCT/FR2019/000091 WO2019234314A1 (fr) | 2018-06-08 | 2019-06-05 | Recyclage d'eau dans un dérivé minier |
Publications (1)
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EP3810299A1 true EP3810299A1 (fr) | 2021-04-28 |
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EP19740607.7A Pending EP3810299A1 (fr) | 2018-06-08 | 2019-06-05 | Recyclage d'eau dans un dérivé minier |
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US (1) | US20210155512A1 (fr) |
EP (1) | EP3810299A1 (fr) |
CN (1) | CN112236207B (fr) |
CL (1) | CL2020003157A1 (fr) |
FR (1) | FR3082197B1 (fr) |
PE (1) | PE20210078A1 (fr) |
WO (1) | WO2019234314A1 (fr) |
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CN109928475B (zh) * | 2019-04-16 | 2021-11-30 | 常州清流环保科技有限公司 | 一种复合净水剂及其制备方法和应用 |
CN113072151B (zh) * | 2021-04-23 | 2022-05-31 | 重庆理工大学 | 一种盐酸酸溶钒钛磁铁矿一步法制备铁-钛-钒三元高分子絮凝剂的方法 |
Family Cites Families (15)
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GB1414964A (en) * | 1971-10-19 | 1975-11-19 | English Clays Lovering Pochin | Copolymers and their use in the treatment of materials |
US4767540A (en) * | 1987-02-11 | 1988-08-30 | American Cyanamid Company | Polymers containing hydroxamic acid groups for reduction of suspended solids in bayer process streams |
FR2708587B1 (fr) | 1993-07-29 | 1995-09-01 | Snf Sa | Procédé pour fluidifier les suspensions aqueuses de boues rouges dans la fabrication de l'alumine par la technique Bayer . |
US5603411A (en) * | 1994-12-07 | 1997-02-18 | Engelhard Corporation | Method for separating mixture of finely divided minerals |
CN100518879C (zh) * | 1997-12-19 | 2009-07-29 | 索尼株式会社 | 废水处理物质、废水处理方法、污泥脱水剂和污泥处理方法 |
EP1068162B1 (fr) * | 1998-03-27 | 2003-07-23 | Cytec Technology Corp. | Procede d'elimination des impuretes des argiles kaoliniques |
US6217778B1 (en) * | 1999-09-08 | 2001-04-17 | Nalco Chemical Company | Anionic and nonionic dispersion polymers for clarification and dewatering |
US6398967B2 (en) * | 2000-04-20 | 2002-06-04 | Nalco Chemical Company | Method of clarifying water using low molecular weight cationic dispersion polymers |
GB0601000D0 (en) * | 2006-01-18 | 2006-03-01 | Ciba Sc Holding Ag | Concentration of suspensions |
AU2013298635B2 (en) * | 2012-07-31 | 2016-04-07 | Basf Se | Concentration of suspensions |
US9567655B2 (en) * | 2012-10-22 | 2017-02-14 | Georgia-Pacific Chemicals Llc | Processes for the separation of ores |
CN105637122B (zh) * | 2013-10-15 | 2019-05-28 | 索理思科技公司 | 用于湿法冶金应用中矿石浆料体系的石膏阻垢剂 |
EP2949405B1 (fr) * | 2014-05-30 | 2016-12-14 | S.P.C.M. Sa | Procédé pour traiter des suspensions de particules solides dans l'eau en utilisant des polymères en peigne |
US10301414B2 (en) * | 2014-12-08 | 2019-05-28 | Cytec Industries Inc. | Silicon containing polymer flocculants |
FR3044655B1 (fr) * | 2015-12-07 | 2021-06-11 | Snf Sas | Procede de traitement d'effluent aqueux |
-
2018
- 2018-06-08 FR FR1854990A patent/FR3082197B1/fr active Active
-
2019
- 2019-06-05 PE PE2020001947A patent/PE20210078A1/es unknown
- 2019-06-05 US US16/972,260 patent/US20210155512A1/en active Pending
- 2019-06-05 WO PCT/FR2019/000091 patent/WO2019234314A1/fr unknown
- 2019-06-05 CN CN201980037911.2A patent/CN112236207B/zh active Active
- 2019-06-05 EP EP19740607.7A patent/EP3810299A1/fr active Pending
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Also Published As
Publication number | Publication date |
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FR3082197A1 (fr) | 2019-12-13 |
CN112236207B (zh) | 2022-11-22 |
PE20210078A1 (es) | 2021-01-11 |
FR3082197B1 (fr) | 2021-04-23 |
US20210155512A1 (en) | 2021-05-27 |
CL2020003157A1 (es) | 2021-04-23 |
WO2019234314A1 (fr) | 2019-12-12 |
CN112236207A (zh) | 2021-01-15 |
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