hydrometallurgical process and method to recover metals

专利摘要:
HYDROMETALLURGICAL PROCESS AND METHOD FOR RECOVERING METALS, where a mineral processing facility is provided that includes a cogeneration unit to provide electrical energy and residual heat for the installation and an electrochemical acid generation unit to generate, from a salt, a mineral acid for use when recovering valuable metals.
公开号:BR112012017939A2
申请号:R112012017939-0
申请日:2011-01-21
公开日:2020-09-24
发明作者:John Burba
申请人:Molycorp Minerals, L.L.C.；
IPC主号:

专利说明:

| . 1/53 | i "HYDRO-METALLURGICAL PROCESS AND | METHOD FOR RECOVERING METALS" Cross Reference to Related Order This order claims the benefits of North American Provisional Order Serial No. 61 / 297,536, filed on January 22, 2010; 61 / 427,745, filed on December 28, 2010 and 61 / 432,075, filed on January 12, 2011, all with the same title, each of which is incorporated herein by reference in its entirety.
Field The present invention generally relates to mineral processing units and facilities, and specifically hydrometallurgical units and facilities for recovering metals. | 15 History | A common method of recovering valuable metals from ores and concentrates is by leaching with an acid | mineral.
For example, rare earth metals are generally recovered from bastnaesite by leaching the host stone with hydrochloric acid.
Uranium can be recovered from the uranium-containing host stone by leaching with phosphoric acid.
Copper, beryllium, nickel, iron, lead, molybdenum, aluminum and manganese can be recovered from the stone: host by leaching with nitric acid.
Copper, beryllium, nickel, iron, lead, molybdenum, aluminum, germanium, uranium, gold, silver, cobalt and manganese can be recovered from the host stone by leaching with sulfuric acid or hydrochloric acid.
While leaching is effective for dissolving valuable metals, numerous obstacles are encountered.
The | :
. 2/53 hydrometallurgical processes require water.
Water may only be available in limited quantities.
The water available is often saline.
In addition, any process water generated must be suitable for disposal.
Typically, process water is disposed of using evaporation ponds, which can be expensive to build and harmful to the environment.
Evaporation lakes have environmental coverage areas | specifically long term.
Furthermore, the process of ”. leaching requires electricity.
Electricity can be difficult and expensive to obtain, specifically when the warehouse is in a remote location.
This generally requires the mine operator to build, at high operating and capital costs, adequate power generation facilities.
Summary These and other needs can be addressed by the various aspects, achievements, and configurations disclosed here.
In one configuration, a process is revealed to recover a valuable metal from a material containing valuable metal using a mineral acid produced by an electrochemical acid generation process, such as a chlor-alkali cell or electrodialysis system. of bipolar membrane.
In one embodiment, the process includes the steps: (a) contacting a material containing valuable metal with a leach solution to form a pregnant leach solution comprising a dissolved valuable metal; (b) recovering the valuable dissolved metal to form a valuable metal product and a by-product salt solution, characterized by the fact that, typically, at least most of the by-product salt solution
. 3/53 is derived from a reaction of an acid with a base in .one or both of the contact and recovery steps; (c) converting, by more than one bipolar membrane and chlor-alkali electrodialysis cell, the by-product salt solution into acid and base; and (d) recycle at least most of the acid and base for the IS contact and / or recovery steps. i Commonly, at least most of the by-product salt solution is converted to acid and base, and at least most of the acid and base is recycled.
In one application, acid is a component of the leaching solution, the valuable metal is a rare earth, the acid component is hydrochloric acid, the salt in the by-product salt solution is one or more of sodium chloride and sodium chloride "potassium, the base is one or more of sodium hydroxide and potassium hydroxide, and the valuable metal product is a rare earth oxide.
In another application, acid is a component of the leach solution, the electrodialysis cell of:. bipolar membrane is employed, the valuable metal is one or more of copper, beryllium, nickel, iron, lead, molybdenum and manganese, the acid component is nitric acid, the salt in the by-product salt solution is one or more nitrate sodium and potassium nitrate, and the base is one or more sodium and potassium hydroxide.
In another application, acid is a component of the leaching solution, the bipolar membrane electrodialysis cell is used, the valuable metal is uranium, the acid component is phosphoric acid, the salt in the by-product salt solution is one or more than sodium phosphate and potassium phosphate, and the base is one or more sodium and potassium hydroxide.
In yet another application, the acid is an À
. 4/53 component of the leach solution, the bipolar membrane electrodialysis cell is used, the valuable metal is one or more of | a platinum group metal, copper, beryllium, nickel, iron, lead, 'molybdenum, aluminum, germanium, uranium, gold, silver, cobalt, zinc, tin, titanium, like and manganese, the salt in the by-product salt solution is one or more of sodium sulfate and potassium sulfate, the acid component is (hydro) sulfuric acid, and the base is one or more of sodium and potassium hydroxide.
In yet another application, acid is a component of the leaching solution, the valuable metal is one or more of yttrium, scandium, lanthanide, a platinum group metal, copper, chromium, beryllium, nickel, iron, lead, motibdenum , aluminum, germanium, uranium, gold, silver, cobalt, zinc, tin, titanium and manganese, the salt in the by-product salt solution is one or more. . 15 sodium chloride and potassium chloride, the acid component is hydrochloric acid, and the base is one or more sodium and potassium hydroxide.
The process configuration (s) may include the purification of the by-product salt solution upstream of the electrochemical acid generation unit.
In one example, at least the majority of a selected polyvalent impurity is removed from the by-product salt solution to form a purified salt solution.
The polyvalent impurity selected is commonly a cation that is removed from the by-product salt solution by precipitation induced by a change in pH of contact of the base with the by-product salt solution.
In another example, the impurity '' to be removed is an organic one, which can originate in the feed material and / or result from the use of organic reagents in the process.
. 5/53 The process configuration (s) may also include the concentration of the purified salt solution by a salt concentrator to form a concentrated and purified salt solution followed by the introduction of the concentrated and purified solution and, optionally, a mineral acid, in an anolyte recirculation tank. The salt solution is removed from the tank and supplied to the electrochemical acid generation unit. : To produce hydrochloric acid efficiently, an approximate stoichiometric balance is typically maintained between chlorine and hydrogen gas produced in the conversion step. The process is particularly applicable to '. a metal recovery operation in which an acid and base are reacted to produce a salt by-product solution. The salt by-product solution is electrochemically regenerated to the acid and base components, which are then reused in the process.
In another configuration, a cogeneration unit is used to supply heat and waste electrical energy to the appropriate process steps in a metal wicking process.
Achievements, aspects and configurations can provide numerous advantages depending on the specific configuration. First, the process can be used to economically dispose of residual brine solutions from terrestrial aquifers and / or generated by industrial processes. The electrochemical acid generating unit converts the residual salt (eg sodium chloride) water, such as from evaporation ponds and terrestrial aquifers, to a mineral acid (eg hydrochloric acid) and other valuable products , such as sodium hydroxide and hypochlorite
A A ii DEDE Ea hi hi hi hi DA A]: 6/53 | sodium.
Mineral acid and other valuable products can be used in the industrial process (eg, process for recovering valuable hydrometallurgical metal) and / or sold.
The recycling of | material can greatly reduce acidic and caustic reagent requirements.
The cogeneration unit can supply energy and heat to | acid generation unit.
This combination can create a | positive environmental impact.
In one example, 936,000 lb / year of water and 104,000,000 lb of salt are recycled back to a 'mineral processing plant.
This methodology can avoid the need for residual water lakes that represent long-term environmental coverage areas while reducing operating costs.
For example, reagent costs and transport requirements can be reduced significantly.
Because the water is internally recycled, the need for fresh water can be radically reduced. . These and other advantages will be apparent from this revelation.
As used herein, "at least one", "one or more" and "and / or" are unlimited expressions that are both | conjunctive and disjunctive in operation.
For example, each of the i expressions "at least one of A, B and C". "at least one of A, B or C", "one or more of A, B and C", "one or more of A, Bou C" and "A, B and / or C" means A alone, B alone , C alone, A and B together, A and C together, B and C together, or A, B and C together. 'The term "one" or "an" entity refers to one or more of such an entity.
As such, the terms "a" (or "one"), "one or more" and "at least one" can be used interchangeably here.
The terms "comprising", "including" and "having" can be used interchangeably.
: 7/53 "Absorption" is the incorporation of a “substance in one state into another from a different state (eg, liquids being absorbed by a solid or gases being absorbed by a liquid). Absorption is a physical or chemical phenomenon or a process in which atoms, molecules or ions enter some form. volume phase - gas, liquid or solid material.
This is a different process from adsorption, since the molecules being subjected to absorption are obtained by volume, not by surface (as in the case for adsorption). "Adsorption" is the adhesion of atoms, ions, biomolecules or molecules of gas, liquid, or solids dissolved on a surface.
This process creates a film of the adsorbate (the molecules or atoms being accumulated) on the surface of the adsorbent.
It differs from absorption, in which a fluid permeates or is dissolved by a liquid or solid.
Similar to surface tension, adsorption is generally a consequence of surface energy.
The exact nature of the link depends on the details of the | species involved, but the adsorption process is generally classified as physisorption (characteristic of weak van der Waals forces) or chemisorption (characteristic of covalent bonding). It can also occur due to electrostatic attraction.
A "plant" refers to any facility or set of facilities that process a material containing metal, typically by recovering or substantially isolating a metal or metal-containing mineral from a feed material.
In general, the plant includes an open or closed comminution circuit, which includes autogenous, semi-autogenous or non-autogenous crushers or grinding mills.
A "mineral acid" is an inorganic acid, such as
. 8/53 like, sulfuric acid, nitric acid or hydrochloric acid.
A "rare earth" refers to any class | i large of chemical elements, including scandium (atomic number 21), yttrium (39), and the 15 elements from 57 (lanthanum) to 71 (lutetium) (known as lanthanides). A "salt" is an ionic compound that results from the neutralization reaction of an acid and a base.
The salts are composed of cations (positively charged ions) and anions (negative ions) so that the product is electrically neutral (without a net charge). These component ions can be inorganic, such as chloride (CI), as well as, organic, such as acetate (CH; yCOO ') and monoatomic ions, such as fluoride (F), as well as polyatomic ions, such as such as sulfate (SO). The. : salts that hydrolyze to produce hydroxide ions when dissolved in water are the basic salts and salts that hydrolyze to produce ions in water are acid salts.
Neutral salts are those that are neither acid salts nor basic salts.
A "sorbent" is a material that absorbs another: substance: that is, the material has the capacity or tendency to obtain it by sorption. "Sipping" means obtaining a liquid or a gas by sorption. "Sorption" refers to adsorption and absorption, while desorption is the inverse of adsorption.
The foregoing is a simplified summary to provide an understanding of some of the aspects, achievements and configurations disclosed herein.
This summary is not a comprehensive or in-depth overview of aspects, achievements or configurations.
It is not intended to identify the elements
: 9/53 |
It is either key or critical, nor does it outline the scope of aspects, achievements or configurations, but to present the selected concepts in a simplified way as an introduction to the more detailed description presented below. As will be appreciated, other aspects, achievements and configurations are possible using, alone or in combination, one or more of the “characteristics set out above or described in detail below. Brief Description of the Drawings The accompanying drawings are incorporated and h: form a part of the specification to illustrate an example of the aspects, achievements or configurations disclosed here. The drawings, together with the description, explain the principles of the aspects, achievements or configurations. The drawings simply illustrate preferred and alternative examples of how aspects, achievements or configurations can be made and used and should not be construed as limiting aspects, achievements or configurations to only the illustrated example (s) and described (s). The additional features and benefits will become apparent from the following more detailed description of the various aspects, achievements or configurations, as illustrated by the drawings mentioned below. Í Figure 1 is a block diagram illustrating a unit according to a configuration; Figure 2 is a block diagram illustrating a unit according to a configuration; Figure 3 is a block diagram illustrating a purification process according to a configuration; Figure 4 shows the concentration of each
: 10/53 divalent cation of magnesium, calcium, strontium and barium in the feed solution and after each of the precipitation stages M1, M2, M3 and ion exchange stages IX1 and IX2; 'Figure 5 shows the concentration of each trivalent lanthanum, cerium, praseodymium, neodymium, samarium and iron cation in the feed solution and after each of the precipitation stages M1, M2, M3 and ion exchange stages IX1 and IX2; ,. Fig. 6 shows the challenge curve for Amberlite 748i (about 4 grams) challenged with a solution containing about 83 mg lanthanum / L (as lanthanum chloride) | at a flow rate of about 2.5 mL / minute at about 21 degrees Celsius, with the x-axis being the total volume of the lanthanum solution defying Amberlite 748i and the y-axis being the lanthanum concentration in mg / L of effluent from the challenged column; Fig. 7 shows the concentration of lanthanum “contained within each fraction collected from an Amberlite 748i resin loaded with lanthanum; Fig. 8 shows the concentration of lanthanum contained with each fraction collected from a resin of: 20 - Amberlite IPC 747 loaded with lanthanum; Fig. 9 shows the variation of current, voltage, temperature and salinity during a process of dividing salt to 12 L of a solution of 75 g of NaCl / liter; and Fig. 10 shows, as a function of time, the current, voltage and temperature of a salt-dividing process for a salt feed containing 95 g of NaCl / L and the resulting decrease in the NaCl concentration for the feed. of salt and the respective increase in the concentrations of acid and base in the acid and base tanks of the dividing cell of e
'11/53 “salt.
Detailed Description A first configuration is an industrial unit (100) for processing a feed material (104). THE . : 5 industrial unit (100) will first be discussed with reference to Figure 1. The industrial unit (100) includes a plant (108), a process unit (112), an electrochemical acid generation unit (116) and a factory cogeneration (120). The industrial unit (100) processes a feed material containing valuable metal (104). The feed material containing valuable metal (104) may comprise an extracted, concentrated ore, Tefuges, metallurgical residue or mixtures thereof.
Commonly, the feed material containing valuable metal (104) comprises an acid-soluble metal.
With reference to the Periodic Table of the Elements, the valuable metal is typically a transition metal, i 'another metal, actinide metal or rare earth metal (e.g., lanthanide). The metal can qualify as a light or heavy metal.
Specific examples of valuable metals include metals from the antimony group, uranium, lanthanides, copper, beryllium, nickel, iron, lead, molybdenum, aluminum, germanium, uranium, titanium, chromium, gold, silver, cobalt, tin, zinc, cadmium , manganese and platinum.
The metal in the material containing valuable metal (104) is typically in the form of a fiery mineral (whether abyssal, plutonic, hypabissal, extrusive or effusive), metamorphic (whether igneous or sedimentary) or sedimentary (be it clastic or chemical precipitated sediments) , such as, sulfide, oxide, phosphate, H i carbonate, halide, sulfate, silicate, telluride, oxisal, sulfosal and mixtures thereof.
Examples of rare earth minerals include sus rr AIIIO O
. 12/53 bastnasite (a carbonate / fluoride mineral) and monazite.
Others: minerals containing rare earth include Esquinite, Allanite, Apatite, | britolite, broquita, cerita, fluorcerita, fluorita, gadolinita, parisita, stillwellita, sinquisita, titanita, xenotima, zirconia e zirconolita.
Exemplary uranium minerals include uraninite (UO> z), pechblende (a mixed oxide, usually U; zOg), branerite (a complex uranium oxide, rare earths, iron and titanium), cofinite (uranium silicate), carnotite , autunita, daviditaa gummita, torbernita and uranofânio.
Exemplary copper minerals include cuprite, | 10 chalcolate, covelita, bornita, malachite, azurite, chrysocolla and | chalcopyrite.
Exemplary nickel minerals include millerite and | enamelled.
Exemplary cobalt minerals include arsenide Co (As), known as enamel or flux cobalt; cobalt. : sulfarsenide (CoAsSS), known as cobaltite or cobalt reflex; and hydrated arsenate (CO (As (X1)., 8H2O), known as erythrite or cobalt luster.
Exemplary molybdenum minerals include molybdenite (MoS,) and vulfenite (PDMoO,). As will be appreciated and noted above, valuable metals are included in a wide variety of other minerals known to those skilled in the art.
As will be further appreciated, the feed material containing valuable metal (104) may include a mixture of minerals of different metals and / or a mixture of minerals containing valuable metal, minerals containing non-valuable metal, and / or minerals containing no metal.
Feed material containing metal | valuable (104) is introduced into the plant (108) to produce a crushed material (122) and waste material (124). Depending on the feed material containing valuable metal (104), the plant (108) can have any of a number of different configurations. —-
”13/53 In one configuration, the plant (108) includes a wet (using water (128)) and / or dry comminution circuit to reduce an average or median size of the feed material containing valuable input metal (104) , one or more conditioning containers to condition the fragmented feed material for subsequent processing, and a direct or reverse flotation circuit to isolate in a concentrate or fraction of scrap, respectively, the metal-containing mineral (s). The flotation circuit can operate at a high temperature (relative to the ambient temperature and / or temperature of the fragmented feed material). The plant (108) may have, or include, other concentration devices or mechanisms, such as separation mechanisms of specific gravity or gravity (eg, settling circuits, cyclones, hydraulic classifiers, mechanical classifiers, settlement tanks and the like), size separation mechanisms (eg, fixed and vibrating screens, filters, aerators, drums and the like), magnetic separation mechanisms and color separation mechanisms. The plant (108) can include other components, including dryers, slurry containers, mixing or conditioning containers, pumps, thickeners, conveyor belts, e.g. helical feeders, agitators and the like. The water (128) is used to form slurry of the feed material for further processing.
The process unit (112) converts the ground material (122) into a product containing metal (136) and a by-product or waste product (132). Depending on the ground material (122), the process unit (112), like the mill (108), can have any of a number of different configurations.
. 14/53 In one configuration, the process unit (112) includes an oxidative or non-oxidative leach circuit, which can be an atmospheric or super-thermostatic stack, “barrel and / or tank leach, conducted at an ambient or elevated temperature, wherein a leachate is applied to the ground material (122) to leach and / or dissolve chemically and / or biologically, at least most of one or more of the valuable metals from the ground material (122), leaving the by-product and / or waste (132) The by-product material (132) can comprise a sterile material containing valuable metal.
The leachate can, or alternatively, also be used to overcome the inhibitory effect of sulfides, carbonates, oxides, phosphates, silicate halides and the like contained with some materials containing valuable metal (104). | The composition of the leachate depends on the | composition of material containing valuable metal (104). Typical leachers are mineral acids, such as sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid, hydrochloric acid, À: hydroiodic acid, hydrofluoric acid and mixtures thereof.
The leachate can include other inorganic and organic acids.
Once dissolved, the valuable metal is isolated from impurities, such as iron, by an appropriate recovery technique, such as precipitation, ion exchange (cationic and / or anionic) (eg, by a resin or solvent ),: sorption (eg, carbon in leaching and resin in leaching), solvent extraction, electrochemistry (eg, electron extraction), calcination, roasting, casting, amalgamation, cementation, “gravimetry, other types of refining and their combinations.
The process unit (112) may include other components, including dryers, slurry containers,
. 15/53 mixture, conditioning containers, pumps, thickeners, conveyor belts, filters, helical feeders, agitators and the like.
As will be appreciated, mineral acids and salts can also be used as a removing agent to remove a valuable metal from an ion exchange medium (eg, resins or solvent) or a sorbent and / or as a electrolyte in electron extraction.
In a process unit configuration (112), caustic soda (NaOH) is used to extract | | 10 solvent to supply sodium ions to the ion exchange resin.
Rare earth metal ions replace sodium ions in the ion exchange resin.
The rare earth metal ions are extracted from the resin by hydrochloric acid for subsequent recovery by techniques known to those skilled in the extractive metallurgy technique. . : The industrial unit (100) still includes the electrochemical acid generation unit (1168). Commonly, the electrochemical acid generating unit (116) produces from a salt (118) at least the majority of one or more of the leachate, removal agent and / or electrolyte used by the process unit (112). The electrochemical acid generation unit (116) electrolyzes an alkali metal salt containing halogen to produce an elemental form of halogen and an alkali metal hydroxide.
The electrochemical acid generation unit (116) can have different configurations and commonly includes one of a chlor-alkali electrolysis process, an electrolytic salt-splitting process or a bipolar membrane electrodialysis process, or one:. combination of these.
As will be appreciated, the process of
:. 16/53 -: | chlor-alkali can be configured as a  'membrane electrolysis cell, diaphragm electrolysis cell or mercury electrolysis cell (eg Castner-Kellner process). Due to the environmental problems associated with mercury, the preferred type of cell is the membrane cell.
i In the membrane cell, the chlor-alkali process electrolyzes, in the anode compartment, a salt containing saturated or substantially saturated halogen (commonly 'containing alkali metal) (eg, a chlorine containing salt) to produce an elemental form of halogen (eg, chlorine gas) and a salt cation hydroxide (eg, alkali metal). Commonly, hydroxide comprises caustic soda (eg sodium hydroxide). F | An anode and cathode are electrically interconnected and an electrical potential is applied to the anode and cathode by the cogeneration unit (120) and electrical current flows between the anode and cathode. No | anode, chloride ions are oxidized to chlorine:. 2CI - Ch + 2e (1) At the cathode, the hydrogen in the water is reduced to hydrogen gas, releasing hydroxide ions into the solution: 2H20 + 26º - H; + 20H (2) The chlor-alkali process includes an ion permeable membrane separating the anodic and cathodic compartments. To maintain the load balance between the anodic and cathodic compartments, the cations (eg, Na * or K ”) f. 25 pass from the anodic compartment through the ion permeable membrane to the cathodic compartment, where they react with hydroxide ions to produce, for example, caustic soda (NaOH). At least most halogen anions (such as chloride anions) and other anions (such as hydroxide ions)
-. 17/53 are not passed through the membrane and kept inside the anode compartment.
Assuming that the brine is NaCl, the general reaction for the brine electrolysis is as follows:: 2NaCl + 2H50 - Cl; + Ho; + 2NaOH (3) In the case of potassium chloride as the salt | (118), salt electrolysis produces chlorine gas in the compartment | anodic and potassium hydroxide in the cathodic compartment.
The membrane prevents the reaction between chlorine and hydroxide ions.
If the reaction were to occur, chlorine would be disproportionate to form the chloride and hypochlorite ions: Í Cl + 20H "- CI + CIO! + 2H0 (4) Above about 60ºC, chlorate can be formed: 3Cl; + SOH '- 5CI + CIO; + 3HO (5) | If the chlorine gas produced at the anode and the sodium hydroxide produced at the cathode were combined, sodium hypochlorite (NaCIO) (see equation 6 below) and / or chloride « sodium (NaClO;) would be produced.
In the diaphragm cell, the anode and cathode compartments are separated by an ion-permeable diaphragm.
The brine is introduced into the anode compartment and gone! to the cathode compartment.
Like the membrane cell, halogen ions are oxidized at the anode to produce elemental halogens, and, at the cathode, water is divided, by | example, in caustic soda and hydrogen.
The diaphragm prevents the reaction of caustic soda with halogen.
A caustic: diluted brine leaves the cell.
The caustic soda is typically concentrated to about 50%, and the salt is removed.
This can be accomplished using an evaporative process (discussed below).
'18/53: commonly contains molecular oxygen that can be removed by liquefaction and evaporation.
The ion exchange membrane can be “any cation or anion permeable membrane or bipolar membrane, commonly a substantially stable ion membrane in the presence of hydroxide anions.
Most commonly, the ion membrane is permeable to alkaline ions and substantially impermeable to hydroxide and / or halide anions.
The ion permeable membrane can comprise a fluoropolymer having one or more sulfonic acid groups hanging, a fluoropolymer compound having one or more sulfonic acid groups, and a fluoropolymer having one or more groups of carboxylic acid, phosphoric acid groups and / or groups of sulfonamide and fluorinated membranes.
An exemplary membrane 15. Is Nafion '"produced by DuPont, which passes substantially cations, but substantially repels neutrals and anions.
The diaphragm can be any suitable ion-permeable material.
Typically, the diaphragm is an 'ion permeable membrane made of asbestos.
It can be appreciated that while the chlor-alkali process was discussed in terms of alkali cations, having a +1 charge, the process may include different cations than alkali cations.
The other cations can have a charge of +2, +3 or. +4, The ionic membrane can be configured to be permeable to other cations and / or to pass cations having a selected ionic and / or hydrodynamic radius. 'Numerous products can be formed.
Using sodium chloride as an exemplary brine solution:
. 19/53 Cl7 + 2NaãaOH - 2NaClO discolorant) (6) Cla + H2 - 2HCl, (7) HClÊ + HO> HClag) (8) Equation 7 is catalyzed by an alkaline earth metal, typically calcium.
These equations apply to | KCI as the salt, if K is replaced by Na.
These equations also apply to halogens other than chlorine, as long as appropriate changes are made to differences in oxidation states.
In another embodiment, the ionic membrane may comprise a bipolar membrane electrodialysis membrane process.
Commonly, the bipolar membrane electrodialysis process is conducted in a bipolar membrane electrodialysis cell having a (diluted) feed compartment, such as the cathode compartment, and a compartment! concentrate (brine), such as the anode compartment, | separated by one or more anion exchange membranes and one or more cation exchange membranes placed between the anodic and cathodic compartments.
In most bipolar membrane electrodialysis processes, multiple cells: bipolar membrane electrodialysis are arranged in a configuration called a bipolar membrane electrodialysis cell, with alternating anion and cation exchange membranes forming the multiple bipolar membrane electrodialysis cells .
Bipolar membrane electrodialysis processes are unique compared to distillation techniques and other membrane-based processes (such as reverse osmosis) so that dissolved species are moved away from the feed stream instead of the other way around.
. 20/53 A membrane electrodialysis process It is bipolar, or "water division", converts aqueous salt solutions into acids and bases, typically without chemical addition, avoiding by-product or residue streams and expensive downstream purification steps.
Under the force of an electric field, a bipolar membrane can dissociate water into hydrogen (H *, in fact "hydronium" H3; O *) and hydroxyl (OH) ions. The membrane is formed by layers of anion and cation exchange and a thin interface in which | the water diffuses from the external aqueous salt solutions.
The transport, from the bipolar membrane, of the ions of H 'and OH obtained from the water division reaction is possible if the | bipolar membrane is electrically oriented correctly. P . With the anion exchange side in front of the anode and the cation exchange side in front of the cathode, the hydroxyl anions are transported through the anion exchange layer and the hydrogen cations through the cation exchange layer.
The ions generated from hydroxyl and hydrogen are used in an electrodialysis cell | to combine with cations and anions in salt to produce acids | and bases. | 20 Bipolar membrane electrodialysis can use many different cell configurations.
For example, a three-compartment cell is formed by locating the bipolar membrane in a conventional electrodialysis cell.
The bipolar membrane is flanked anywhere by the Ê: 25 anion and cation exchange membranes to form three compartments, that is, acid between the bipolar and anion exchange membranes, the base between the bipolar and cation exchange membranes, and salt between the cation and anion exchange membranes.
As with electrodialysis cells, many cells can be installed in one cell and
"21/53 a collector system supplies all the corresponding compartments in parallel, creating three circuits through the stack: acid, base and salt.
Other configurations include two cells | compartments with bipolar and cation exchange membranes (only) or with bipolar and anion exchange membranes. . As will be appreciated, the electrochemical acid generation unit (116) may include a bipolar membrane electrodialysis process conducted before and / or after the chlor-alkali process.
The membrane electrodialysis process. bipolar still purifies the aqueous currents produced by the respective anodic and cathodic compartments.
Commonly at least most of a mineral acid (142) and hydroxide (190) used in the process unit, such as, for a leachate, or extraction agent. Regeneration, or electrolyte, is produced by the electrochemical acid generation unit (116) from a suitable salt (118). For example, hydrochloric acid is produced from an “alkali metal chloride by burning chlorine gas from the anode compartment and hydrogen gas from the cathode compartment, typically in the presence of a suitable catalyst (see equation 7 above) . Hydro-sulfuric or sulfuric acid is produced using: 'salt-splitting or bipolar membrane electrodialysis techniques, from an alkali metal sulfate.
In other examples, nitric acid is produced from an alkali metal nitrate, phosphoric acid is produced from an alkali metal phosphate, hydrobromic acid from alkali metal bromides, 'hydroiodic acid from iodides alkali metal and hydrofluoric acid from alkali metal fluorides. : The electrochemical acid generation unit
'22/53 (116) can also produce products (140) for sale and water (198) for recycling.
Examples of such products include hydrogen gas, halogen gas (such as chlorine gas, bromine gas, iodine gas and the like), caustic soda, decolorizer (such as hypochlorite) and the like.
In one configuration, the solution containing: salt (150) is produced by the process unit (112). The solution | containing salt (150) can, for example, be produced by one or more of the leaching, solvent extraction and electron extraction processes. In a process unit configuration, caustic soda is used in the extraction of solvent to supply ions. sodium to the ion exchange resin.
Valuable metal ions replace sodium ions in the ion exchange resin.
Valuable metal ions are extracted from the resin by hydrochloric acid for “subsequent recovery” by techniques known to those skilled in the extractive metallurgy technique.
In the electrochemical acid generation unit, the solution containing salt (150) is subjected to. . chemical treatment, in a primary purification system, using | 20 caustic soda (or cell liquor from the cathode compartment of the electrochemical acid generating unit (116)), sodium carbonate and / or other additives that eliminate at least the majority of any polyvalent metal ion impurities, such as calcium, magnesium and iron.
Such polyvalent cations can have a detrimental impact on the performance and operational life of the ion exchange membrane and / or electrodialysis cell of the bipolar membrane.
One or both of a thickener and filter commonly remove all-purpose impurities.
The solution containing treated salt is then
'23/53 passed through a secondary purification system to remove most of any remaining polyvalent cations.
Caustic soda can be used to adjust pH 1 above ss | about pH 7 before introduction into the secondary system | 5 purification.
Any conventional secondary brine purification treatment system associated with membrane operations can be used, such as a chelate ion exchange resin.
Brine phosphate treatment can also be used.
Phosphates can form a gel coating on the membrane in a way that best maintains the membrane's efficiency.
The solution containing purified salt is then processed by a salt concentrator, such as an evaporator, energy efficient vapor recompressor or combination thereof.
The proper design of these units with the proper use of stoves and elutriation legs was determined to be f. energy efficient and the required concentrations of slurry easy to control without the need to centrifuge and separate the solid salt from the slurry.
The slurry is then introduced into an anolyte recirculation tank, in which a mineral acid, such as hydrochloric acid (produced from chlorine and hydrogen gases), can be introduced.
From the anolyte recirculation tank, the slurry is introduced into the anode compartment.
This process is not required in the case where the chlorine / alkali cell uses a diaphragm, rather than a membrane.
With reference now to the cogeneration unit (120), the cogeneration unit (120) uses any suitable fuel source (160) to generate energy (170) and heat | residual (180) (e.g., steam). The energy (170) is used in unit operations at one or more of the plant (108), process unit
. 24/53: | (112) and electrochemical acid generation unit (116). As will be appreciated, "cogen" or cogeneration uses a heat engine or a power station to simultaneously generate both electricity and useful heat. Although any cogeneration unit can be used, common cogen units include gas turbine cogeneration units using the residual heat in the flue gas of the gas turbines, gas engine cogeneration units using an alternating gas engine, units “combined cycle energy adapted for cogeneration, steam turbine cogeneration units using the heating system as the steam condenser for the steam turbine, and molten carbon fuel cells having a heat escape which is:. suitable for heating. Smaller cogen units typically use an alternating or Stirling engine. Heat is removed from the exhaust and radiator.
The fuel source (160) can be any suitable source of combustion fuel, including compressed or liquefied natural gas, coal, methane, petroleum, liquefied petroleum gas, diesel fuel, kerosene, coal, propane, other fossil fuels, radioactive materials (eg, uranium) and alternative fuel sources such as biodiesel, bioalcohol! (methanol, ethanol and butanol), hydrogen, HONG, liquid nitrogen, compressed air, non-fossil methane, non-fossil natural gas, vegetable oil and biomass sources. | Residual heat (180) can be directly supplied to one or more of the unit operations, such as flotation, leaching and the like, through a heat exchange loop, which circulates the residual heat (180) from the unit cogeneration (120) through a heat exchange loop in contact
= 25/53 thermal with the material in the operation of the unit to be heated.
Alternatively, an intermediate heat exchange medium can collect the residual heat (180), by means of a first heat exchange loop, from the residual heat (180) and supply the thermal energy: to the material to be heated by means of of a second heat exchange loop.
The operation of the industrial unit (100) will be | now discussed in relation to several illustrative achievements. | With reference to Figure 1, the material of; : 10 feed containing valuable metal (104) is introduced into the plant (108) to produce a ground material (122). In a process configuration, the feed material (104) comprises one or more minerals containing rare earth, which are compressed and crushed.
The crushed material is subjected to direct flotation, at elevated temperature (which can vary from about 30 to about 70ºC) and using suitable foaming agents, collectors, activators and / or depressants known to those with ordinary skill in the technique, to produce a concentrate (or ground material (122)) comprising at least most rare earth minerals and scrap.
Refuse is commonly suitable for disposal and substantially without rare earths. | The cogeneration unit (120) supplies energy for comminution and flotation cell agitators and residual heat (180), typically in the form of steam, to the material ground in fluid paste before the flotation operation. | | The ground material (122), or concentrate fraction is supplied to the process unit (112) for | additional processing. | : In a common process configuration |
'26/53 for recovery of valuable metal, the ground material (122) is leached from a barrel or assembled by a mineral acid, “commonly by an aqueous hydrochloric acid solution, to dissolve the valuable metal and form a leaching solution pregnant comprising most of the valuable metal in the concentrate fraction.
The pregnant leach solution is subjected to extraction: solvent or ion exchange to remove at least most of the dissolved valuable metal from the solution and form a charged resin containing the removed valuable metal and a sterile leach solution for recycling for operation leaching.
The charged resin comes in contact with an extraction solution to dissolve at least most of the removed valuable metal, forming a sterile resin for recycling in the solvent extraction step and a loaded extraction solution containing at least most of the valuable metal.
The valuable dissolved metals are separated from the charged extraction solution, such as, by precipitation, additional solvent extraction or extraction of | phase transfer (such as with a nitrogen-containing phase transfer agent) to form a sterile extraction solution for recycling in the solvent extraction step and a separate material containing valuable metal. The cogeneration unit (120) supplies energy (170) to pumps and other process equipment in the process unit (112) and residual heat (180), as needed, for proper unit operations.
In a "configuration, the leachate solution and / or extraction solution includes hydrochloric acid, and the above unit operations in the process unit (112) produce a by-product salt solution, which, in some applications, is a solution of acidic brine.:
oc 27/53 As noted, this solution can be recycled to the primary and secondary treatment circuits for purification prior to introduction to the electrochemical acid generation unit ': to generate more acid (142) and other products (140). The primary and secondary treatment circuits treat the by-product salt solution, as noted above, to remove at least | most polyvalent cations before introducing the solution | by-product salt treated or purified to the electrochemical acid generation unit.
In the electrochemical acid generation unit (116), the by-product salt solution is converted, as noted above, into caustic soda, sodium hypochlorite, hydrogen gas and chlorine gas.
Hydrogen gas and chlorine gas are thermally reacted to produce hydrochloric acid (142) for recycling in the process unit (112). Due to a | portion of the hydrogen gas is lost and a substantial stoichiometric imbalance (see equations 1-6 above) exists between the hydrogen gas and chlorine gas, a portion of the chlorine gas can be used to manufacture bleach for sale.
Alternatively, chlorine gas can be sold for other applications, such as, | manufacture of chlorinated or chlorinated organic solvents.
In this way, an approximate stoichiometric balance between hydrogen and chlorine gas is maintained in the process.
The cogeneration unit (120) supplies energy (170) and residual heat (180) (typically in the form of steam) to the appropriate unit operations in the electrochemical acid generation unit (116). By-product water. (128) of the unit (116) is recycled in the cogeneration unit (120), plant (108) and process unit (112). : With reference to Figure 2, a second:
28/53. configuration will now be discussed.
The material containing metal | valuable (acid-soluble) (104) is milled at the plant (108). At the plant, the material (104) is fragmented, by wet and / or dry crushers and crushing mills in an open or closed circuit, to produce a fragmented material (not shown). The fragmented material is commonly concentrated, such as, by flotation or size or weight separation techniques, to produce a concentrate (200), which is commonly in the form of a slurry.
The concentrate (slurry) (200) is | inserted into the process unit (112). In the process unit | (112), the concentrate (200) is leached by barrel or pile (step 204), biologically and / or chemically, by a leach solution (not shown) comprising a mineral acid to dissolve | at least most of the valuable metal in the leaching solution for | form a pregnant leach solution (208). The pregnant leach solution (208) is optionally separated (step 212) for | producing a sterile valuable metal material (132), a sterile valuable metal salt solution (216) and a solution enriched with valuable metal (220). The valuable metal-enriched solution (220) includes at least most of the valuable metal dissolved in the pregnant leach solution.
In one configuration, the separation includes one. : thickener / wash circuit, such as a countercurrent settling circuit, to remove the sterile material from: valuable solid phase metal (132) from the liquid phase enriched with valuable metal (not shown). As will be appreciated, other liquid / solid separation techniques can be employed, such as filtration, screening, cyclones and other separation techniques.
= 29/53 | size or weight. | The metal-enriched liquid phase: valuable is then subjected to sorption (such as using an ion exchange or chelate resin) or membrane filtration to remove at least most of the valuable metal from the liquid phase and form a leach solution sterile valuable metal for recycling in the valuable metal dissolution step (204). The sorbent can be an ion exchange or chelate resin, a porous medium (eg, activated carbon, zeolites and other porous medium) and the like. | While membrane sorption and separation are discussed with reference to the removal of a selected or target valuable metal, it should be understood that membrane sorption and / or separation can also be used, in addition to or in place of target valuable metal sorption, in separation (212) to remove impurities such as other valuable or non-valuable metals, thereby purifying the pregnant leach solution containing target valuable metal. : Sorbed target valuable metal is extracted from the sorbent (not shown) by an extraction solution (such as an eluting agent) by a change (relative to the pregnant leach solution) in temperature and / or pH (which changes preference E: for the target valuable metal sorbent) to form a solution enriched with target extraction valuable metal (not shown) and extracted sorbent for further contact with the pregnant leach solution (208). The target enriched metal enriched solution is formed into a target valuable metal product (not shown) (operation 136) and a by-product salt solution (224). The formation of the valuable metal product can be, for example, by electrolysis or electron extraction, precipitation (which,
E Pa DA o o Doo io o EE3EERA o il o a a nd '30/53: for example, forms a target metal sulphide or oxide), sorption (such as using activated carbon), membrane filtration, cementation and amalgamation.
At the plant (108) and process unit (112), | there are countless processes to recover rare earth metals | as valuable metals. ss' A process configuration, which is | specifically applicable to bastnasite, selectively oxidizes rare earths.
Cerium is separated after the oxidation of cerium (Ill) to cerium (IV), simplifying the subsequent separation of less abundant lanthanides.
Oxidation occurs when the bastnasite is heated in the presence of molecular oxygen to a temperature typically of at least about 500 ° C and even more typically of at least about 600 ° C or when rare earth hydroxides are dried in the presence of molecular oxygen at a temperature , commonly in the range from about 120 to about 130ºC.
Cerium (IV) is separated from rare earths: trivalent by selective dissolution of rare earths trivalent with | diluted acid or by complete dissolution of the trivalent species with concentrated acid followed by selective precipitation of cerium hydroxide or extraction of cerium (IV) solvent, as noted below.
In aqueous solutions, the cerium (Ill) is oxidized to cerium (IV) by electrolysis or treatment with hydrogen peroxide or sodium hypochlorite.
The precipitation of hydrated cerium oxide then occurs when the pH is commonly adjusted to a "pH of at least about pH 3 and even more commonly ranging from about pH 3 to about pH 7. Another configuration of the process for recovering rare earth is established in the North-ss Patents |
IAEA AND A EA EA IR O O REA EARARREREESNEEE EA ARA AAa AA AA RO RARA RR DENNIS us !!!) UN sasassass0 '31/53 American 5,207,995 and 5,433,931, each of which is incorporated herein by this reference.
The process is specifically useful for recovering rare bastnasite lands.
In the process, an ore | 'of rare earth is ground to a size of P90 of mesh 100 (Tyler) (or a medium, medium or size P90 ranging from about | about 100 microns and even more commonly from about 5 to about 25 microns). The crushed ore is floated to form a rare earth concentrate (comprising most of the bastnasite in the rare earth ore with quartz, barite, calcite and stroncianite being separated into refuse). The .concentrate is typically at least about 25 wt.% And even more typically ranges from about 35 to about 75 wt.% Of rare earths.
The concentrate is subjected to a first acid leaching with dilute hydrochloric acid (pH about 1.0)! to remove some of the alkaline earth constituents from | concentrate and the roasted leachate ore.
Roasting is typically at around 400ºC at about 800ºC in the presence of oxygen | molecular to convert the fluorocarbonate mineral to a mixture of fluorides and oxides and oxidize the cerium to cerium (IV). The roasted ore is subjected to a second acid leach with a more concentrated hydrochloric acid solution (which commonly comprises from about 0.1 to about 0.5N to about 0.2N of hydrochloric acid) to remove the remaining alkaline earth constituents and separate cerium from other rare earth oxides.
The ore is then treated with a third acid leach with an even more concentrated hydrochloric acid solution (eg, usually at least about 25 wt.%, Most commonly from about 35 to about 75 wt.%, and even more commonly from about 40 to about 50 wt.% hydrochloric acid) for
. 32/53 | solubilize the cerium values for further processing.
The pregnant leach solution typically includes at least most of the rare earth content of the rare earth concentrate and even more typically includes from about 25 to about 95 wt.% Of rare (rare) earths. In another configuration of the process used for bastnasite, the rare earth concentrate is leached with “dilute hydrochloric acid or concentrated to dissolve, at least partially, the rare earths, which combine with the fluorine in the ore.
The mixed waste of rare earth / fluoride is decomposed using caustic soda at a temperature commonly varying to. : from about 100 to about 300ºC.
The resulting rare earth hydroxides are leached with diluted or concentrated hydrochloric acid.
In another version of the process, diluted or concentrated sulfuric acid, instead of hydrochloric acid, can be used to dissolve the residue at a temperature commonly ranging from about 200 to about 500ºC.
The dissolved rare earths are then recovered as water-soluble sulphates.
Polyvalent impurities, such as iron, are removed by pH neutralization.
In another configuration of the process, rare earth is present in the monazite and recovered by industrial digestion using caustic soda.
The phosphate content of the ore is recovered as sodium triphosphate and rare earth as | rare earth hydroxides.
The leachate commonly contains from: about 25 in about 75 wt.% Of the sodium or potassium hydroxide solution at a temperature ranging from about 125 in about 200ºC.
The resulting rare earth mixed and precipitated with thorium hydroxide is dissolved in hydrochloric acid and / or acid
. 33/53 nitric, processed to remove at least the majority of thorium and other rare non-earth elements, and processed to recover | individual rare earths.
In another configuration of the process, rare earth is present in loparite and recovered by a chlorination technique.
This technique is conducted using chlorine gas at a temperature commonly ranging from about 500 to about 1,000ºC in the presence of carbon.
The volatile chlorides are separated from the molten calcium, sodium and rare earth chloride), and the resulting precipitate dissolved in the water.
Rare earth | | dissolved are recovered by suitable techniques. | In another process configuration, the land | rare is present in loparite and recovered by a | sulfation.
This technique is conducted using an acid solution | 15 sulfuric (typically having from about 50 to about 95wt.% Sulfuric acid) at a temperature ranging from about 100 to about 250ºC in the presence of ammonium sulfate.
The product is leached with water, while the double sulfates from rare earths remain in the residue.
The titanium, tantalum and niobiotic sulfates are transferred to the solution.
The residue is converted to rare earth carbonates and then dissolved in, and isolated by suitable nitric acid techniques.
In the above process configurations, concentrated rare earths can be recovered by any number of different techniques.
In one configuration, concentrated rare earths are separated by ion exchange.
For example, pH-dependent rare earth complexes form with citric acid or aminopolycarboxylate eluting agents (eg, ethylenediaminetetraacetic acid (EDTA) and
'34/53 hydroxyethylenediaminetriacetic acid (HEEDTA). Phosphate-free resins are preferred to avoid poisoning rare earth | resin due to incomplete elution of the rare earth from the resin. Rare earths are recovered by elution using a concentrated solution of a monovalent salt, such as ammonium chloride or. | sodium chloride. If the complexing agent exhibiting significantly different affinities for the different lanthanides is added to the eluting agent, a separation occurs. In another | configuration, oil-soluble compounds separate rare earths by liquid-liquid extraction using acidic, basic and / or neutral extraction agents. Typical acidic, basic and neutral extraction agents include carboxylic acids, organophosphorous acids and their esters, tetraalkylammonium salts, alcohols, ethers and ketones. In another configuration, rare earth halides are reduced to metal by reaction of more electropositive metals, such as calcium, lithium, sodium, potassium and aluminum. In another configuration, electrolytic reduction is used to produce ': light lanthanide metals, including didymium (a mixture of Nd-Pr). In another configuration, fractional distillation is used to recover and separate rare earths. In another configuration, zone fusion is used to recover and separate rare earths. Due to the highly electropositive nature of rare earths, rare earth metals can be formed from aqueous solutions by molten salt electrolysis or metallothermic reduction.
25 ... The by-product salt solution (224) and salt solution (216) can each include a variety of polyvalent impurities, including one or more of: more than about 20 ppb of divalent calcium, more than about 20 ppb of | divalent magnesium, more than about 100 ppb of strontium
:. 35/53 divalent, more than about 500 ppb of divalent barium, more than about 100 ppb of trivalent aluminum, more than about J 1 ppm of trivalent iron, more than about 15 ppm of divalent mercury, more than about 10 g / L sulfate anion - divalent, more than about 10 ppm silica, more than about 400 ppb monovalent fluorine, more than about 100 ppm radioactive nuclides (e.g. radio, uranium and thorium) and their: offspring, and more than about 10 ppb of divalent nickel.
Some of the impurities can be present in relatively high concentrations up to their solubility limits. | The by-product salt solution (224) is combined with the salt solution (216), and the combined solution (228) optionally subjected to inorganic contaminant purification (step 232) to form a first i '15 purified solution (236) Although any contaminant removal techniques can be employed, removal of the inorganic contaminant can be by saturation, precipitation (such as with sodium or potassium hydroxide, oxide or carbonate), clarification, filtration (such as, membrane filtration), sorption (such as using a chelate ouresin ion exchange (eg, resins having aminomethylphosphonic, iminodiacetic or thiol type functional groups))) activated carbon, .zeolites, alumina, silica alumina and the like, electrolysis, dechlorination, cementation, and amalgamation.
In a configuration, | at least most polyvalent inorganic impurities | dissolved substances, such as calcium, magnesium, iron and other impurities, are removed by precipitation as oxides, carbonates and / or hydroxides. | This is typically done using precipitants having a cation | monovalent, such as sodium carbonate and sodium hydroxide.
As | precipitated impurities are removed or separated from the
: 36/53. liquid through a thickening, screening, filtration, cyclone circuit | It is similar.
In one configuration, at least most of the dissolved polyvalent inorganic impurities are removed by an ion exchange or chelate resin.
When the valuable metal is rare earth, the resin must be substantially free of phosphate groups to avoid "poisoning" the resin's rare earth by incomplete elution of the rare earth.
In one configuration, sulfate and other polyvalent anions are removed by refrigeration and crystallization, evaporative crystallization and / or salting of the contaminant.
The first purified solution (236) is optionally subjected to removal of the organic contaminant (step 240) to form a second purified solution (244). Although any contaminant removal techniques can be employed to remove at least most organics from the first purified solution (236), removal of the organic contaminant is commonly accomplished by one or more vacuum distillation, pervaporation, vapor extraction, sorption (such as, using an ion exchange or chelate resin) and membrane filtration.
The second purified solution (244) is optionally subjected to residual ion removal (step 248) to remove at least most of the remaining polyvalent ions. and forming a third purified solution (252). Step (248) is, in | effect, a polishing operation.
While any techniques (including those discussed above with reference to step (232)) can be employed to remove the remaining polyvalent ions, a common polishing mechanism is the sorption (such as using an ion exchange or chelate resin) of the impurities polyvalent inorganic remnants.
The third solution
: 37/53 | Purified water (252) must have a satisfactory level of impurities for the specific type of electrochemical acid generation employed. In one configuration, the third purified solution (252) has a salt in its saturation (under process temperature and operating pressure), which is normally between about 23 in about 28 wt.% Of salt dissolved in water.
Fig. 3 shows a specific configuration for purifying the combined solution (228) which is specifically applicable to rare earth metal recovery processes.
In a first-stage precipitation of impurities (304), a base, such as lye, is added to the combined solution (228), which typically has a typical pH of no more than about pH 8, to increase the pH to a Typical pH of at least about pH 9. Determined from the polyvalent cationic impurities, that is, trivalent rare earths, divalent alkaline earth metals, divalent strontium, divalent barium, divalent nickel and trivalent aluminum, form the carbonate precipitates. Trivalent iron typically does not precipitate in the first stage precipitation. D In a second stage rush | of the impurities (308), a stronger base, such as sodium hydroxide, comes in contact with the combined solution (228) to further increase the pH to a typical pH of at least about pH 10 and even more typically at least about pH 11. More of the multipurpose cationic impurities, that is, trivalent rare earths, divalent alkaline earth metals, divalent strontium, divalent barium, trivalent iron, divalent nickel and trivalent aluminum, “precipitated as hydroxides. After the first and second stages, typically at least the majority, even more typically at
38/53 minus about 75%, and even more typically at least about 90% of the polyvalent cations and anions are in the form of precipitates. After the second stage precipitation (308), the combined salt solution (228) comes into contact with a 'coagulant and flocculant and subjected to liquid / solid separation in step (312) by an appropriate technique. The right techniques | include size and / or weight separation techniques, such as filtration, cyclone, gravity settling, decanting, thickening and combinations thereof, to commonly remove the majority, even more commonly at least about 75%, and even more commonly at least 95% of the precipitates of the 'solution (228). After liquid / solid separation, the combined solution (228) can be adjusted by pH followed by contact, in step (316), of the pH-adjusted solution with one. sorbent to remove at least most of the organic matter. The sorbent commonly used is activated carbon. Organic matter commonly includes the extraction of dissolved solvent or ion exchange resin, surfactants, flotation reagents (eg, collectors and foaming agents), coagulants and flocculants. In one application, the pH of the combined solution (228) is lowered by adding mineral acid to a pH that is usually no higher than about pH 8.
25. The solution (228) is then subjected in step (324) to the removal of ion exchange from at least the majority of any remaining trivalent and higher valence cations. The commonly used resin has a functional group of type f: iminodiacetic.
39/53 The solution (228) is then passed through a mixed bed of anion and cation exchange resins to. . remove at least most of any remaining divalent cations and polyvalent anions, such as sulfates (SO, ”) and nitrates: (NC; 3”) The commonly used cation exchange resin has a | functional group of aminomethylphosphonic.
Sulfate and nitrate ions | are strongly attracted to most strong base anion exchange resins.
Exemplary anion exchange resins include polystyrene resins (eg Amberlite IRA-400, 402, 404, 900 and 996 "by Aldrich, Duolite A-101 D'TY, lonac ASB-1 or 27" and lonac SR- 77M, and Lewatit OC-19507Y), polyacrylic resins (eg Amberlite IRA-458 and 9587 “), pyridine resins (eg Reillex HPQTY, B-1 'and DP-1TY), and styrene-divinylbenzene copolymers which have been sulfonated to form strongly acidic i '15 cation exchangers or laminated to form the strongly basic or weakly basic anion exchangers.
The ordering of the resins of the iminodiacetic type group or functional aminomethylphosphonic group in the treatment series allows the removal of at least the majority of | any remaining trivalent or higher valence cations (step 320) by the iminodiacetic type functional group prior to the removal of divalent cations by the aminomethylphosphonic functional group.
As noted, trivalent cations and higher valence cations, specifically trivalent rare earths, can poison the functional aminomethylphosphonic group by incomplete elution of. : such cations.
Because a substantial portion, and in some cases at least the majority, of the fluorine in the combined solution (228) has not been removed by the previous purification steps and
'40/53 is due to fluoride being able to damage the platinum electrodes in the 3rd generation electrochemical acid system, typically at least the majority and even more typically at least about 85% of the fluorine is removed in step (322) by a technique proper.
One technique is to remove fluoride by passing the solution (228) through an aluminum oxide polishing column.
Another technique is that of | remove fluoride by passing the solution (228) through a column | containing rare earth.
The column contains particulates containing soil | rare that they can be supported or not supported.
The particulates mainly contain, on the basis of weight and molar, rare earth compounds.
A preferred rare earth particulate is composed, in weight and molar bases, mainly of the cerium (II!) (IV) compounds, or mixture thereof.
Stated differently, the rare earth component of particulates containing rare earth is mainly cerium. | The solution (228) is finally passed through a polishing column to remove at least the majority of any remaining cations and form the third 'purified' solution (252). A common polishing column comprises zeolites.
In another configuration, the various separations are carried out using the applied membrane filters! i to the solution (228) before or after the first and second stage precipitation (304) and (308). For example, after removing the precipitated impurities (312), the solution (228) is first passed | through the microfiltration and / or ultra-filtration membrane to remove in a first concentrate at least most of the suspended and colloidal solids and organic contaminants and form a first permeate comprising at least most of the
'41/53 inorganic ions, and the first permeate is passed through an ultra-filtration, nanofiltration and / or reverse osmosis membrane to remove in a second retained at least most of the polyvalent ions in the solution (228) and pass through a second “permeated at least most of the monovalent ions in the solution (228). The second permeate is then optionally polished to remove at least the majority of any remaining polyvalent ions and / or undesirable monovalent ions:: specifically fluorine.
Regardless of the specific techniques: purification employed, the third purified solution (252) | typically has no more than about 20 ppb of divalent calcium and magnesium, no more than about 100 ppb of strontium: divalent, no more than about 500 ppb of divalent barium, no more than about 100 ppb of trivalent aluminum, no more than about 1 ppm trivalent iron, no more than about 15 ppm divalent mercury, no more than about 10 g / L divalent sulfate anion, no more than about 10 ppm of silica (in the presence of divalent calcium and trivalent aluminum), not more than about 400 ppb of monovalent iodine (in the presence of divalent barium), and not more than about 10 ppb of divalent nickel.
In some applications, each impurity in the third purified solution (252) is present in a concentration of no more than about 1 ppm.
The above purification steps are typically performed to maintain at least most, even more typically at least about 75%, and even more typically at least about 95% of the cation and salt anion (e.g., sodium ion) and chlorine ion) in the solution.
The various stages
'42/53 | therefore, they are selectively carried out to remove “polyvalent and organic contaminants while avoiding the removal of salt components.
Stated differently, the cation and anion exchange resins and sorbents mentioned above, under the conditions of the solution (228), in general have affinity ': limited or nonexistent for sodium or chlorine ions (when salt is the sodium chloride). ; If necessary, the third purified solution (252) can be subjected to the concentration of salt (step 256) to adjust the salinity of the solution (252) to a level suitable for: generation of electrochemical acid.
The salt concentrator can include multiple effect evaporators, energy efficient vapor recompressors, recompressors and combinations thereof.
If necessary, the pH of the third purified solution (252) is carried out using an acid or base produced by the electrochemical acid generation operation (280). The third purified solution (252) is introduced in the electrochemical acid generation operation (280) to convert the salt into a desired mixture of the aforementioned end products.
In the configuration of Figure 2, the final products are an aqueous solution of mineral acid (260) and an aqueous solution of sodium hydroxide (264). The aqueous mineral acid solution (260) is directed to the dissolution of valuable metal (204). The aqueous base solution (264) is directed to product forming and separation operations (212) and (136), as needed.
The additional (fresh) salt solution (268), such as surface water, municipal water, industrial water, condensed steam, sea water, brine or saline water synthetically. : produced, is added, as needed, to replace the
'| 43/53 respective losses in the various unit operations.
The acid and base solutions can be f. concentrated, by optional concentrators (278) and (272), respectively, to produce the desired concentrations of acid or base.
Typically, the acid and base solutions will have concentrations of acid and base, respectively, not greater than about 90, even more typically not more than about 75, and even more typically not more than about 50 wt.% . Exemplary concentrators are evaporators and distillation columns.
In some applications, acid or base solutions may require dilution to produce adequate levels of concentration.
The base solution can be adjusted to pH in step (282) using a suitable pH adjuster, such as, | an acidic pH adjuster or basic pH as needed.
Typically, the basic pH adjuster is sodium or potassium hydroxide produced during the generation of electrochemical acid (116). Although not shown, additional hydrogen gas may be required to be supplied in order to | compensate for hydrogen losses during the process.
The water balance in the process can be: maintained by a multiple-effect evaporation step.
This occurs at the point in the process circuit where the salt is likely to precipitate due to excess saturation.
The precipitated salt can be recycled again for the operation of: generation of electrochemical acid (280). EXAMPLES i Example A Example A was a determination of a |
: 44/53 'multi-stage precipitation process and ion exchange to remove divalent and trivalent cations before a salt-splitting process.
Figs. 4 and 5, respectively, show decreases - in the earth cations divalent alkali | 5 (specifically, magnesium, calcium, strontium and barium) and trivalents (lanthanum, cerium, praseodymium, neodymium, samarium and iron) after each .one of the precipitation and ion exchange stages.
M1 is the first stage precipitation (Fig. 3) in which a salt solution (such as the by-product salt solution (224), the sterile valuable metal salt solution (216) or its combination (combined solution 228 ) as described above) | i having a pH of about pH 7 was contacted with a sodium carbonate solution having a pH of about pH 9.5 | to form a slurry of metal carbonate.
Dissolving sodium carbonate in the water with stirring formed the sodium carbonate solution.
The metal carbonate slurry had precipitates of metal carbonate dispersed in the salt water.
Typically precipitated metal carbonates are lanthanum carbonate, cerium carbonate, praseodymium carbonate, neodymium carbonate, samarium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, calcium carbonate, lead carbonate, uranium carbonate and E carbonate: aluminum.
M is the second stage precipitation (Fig. i 3) in which the metal carbonate slurry came into contact with a sodium hydroxide solution having about 8 wt% NaOH to further increase the pH to a pH from about PH 11 to about pH2 and to further precipitate as hydroxides any of the metals identified above (such as lanthanum, cerium,
'45/53 praseodymium, neodymium, samarium, magnesium, strontium, barium, calcium,' lead, uranium and aluminum) remaining in the solution.
M3 is the third stage precipitation (Fig. 3) in which a coagulant, such as alum (AI (SO, z) 3), came into contact with metal carbonates and hydroxides (hereinafter referred to as metal solids). The contact of the coagulant with the metal solids flocculated and / or increased the particle size of the metal solids, thus increasing the efficiency of separating the | i metal solids from the liquid phase of the solution.
The liquid phase contained NaCl, organics and decreased amounts of the divalent and trivalent cations compared to the salt solution (Figs. 46 5) Coagulation and flocculation in a high salt solution is difficult.
However, it is substantially preferred to remove divalent and trivalent ions and / or solids before conducting a chlor-alkali process.
Hydrochloric acid (about 18 wt% HCI) was added to the aqueous stream to adjust the pH to about pH7. The pH-adjusted aqueous stream was filtered and passed through an activated carbon filter before entering. . 20 in contact with the aqueous stream with a first IX1 ion exchange resin IX1 (Fig. 3). The first ion exchange resin was an iminodiacetic function resin sold under the trade name Amberlite IRC-748i from Rohm & Haas to form a first phon exchange solution having a reduced content of divalent and trivalent cations compared to the aqueous stream adjusted pH (Figs. 4 € 5). The first ion exchanged solution came in contact with a second 1X2 ion exchange resin (Fig. 3) to form a second ion exchanged solution having a content
'46/53 reduced in divalent and trivalent ion compared to the first ion exchanged solution (Figs. 4 and 5). The second ion exchange resin is an aminomethylphosphonic function resin sold under the trade name Amberlite IRC-747 by Rohm & Haas.
Example B i Example B was a determination of the carrying capacity of the trivalent cation in a chelate ion exchange resin IX1 in Fig. 3). The evaluated chelate ion exchange resin was an iminodiacetic resin sold under the trade name Amberlite IRC-748i from Rohnm & Haas.
The cation | trivalent was lanthanum.
A lanthanum feed solution having a pH of about pH 4, about 50 g / L of NaC! and 83 mg / L 'of lanthanum (as LaCl3) was prepared by dissolving about 400 mg of lanthanum oxide (La2O3) in hydrochloric acid (about 3.7 ml of 2NdeHCIl)) After dissolving the lanthanum oxide, about 200 grams of NaCl was added, the pH was adjusted with 1 N NaOH. to a pH of about pH 4 and deionized water was added to form a final volume of about 4 liters.
One column was packed with Amberlite IRC-748i resin.
The lanthanum feed solution as passed through the packed column at a rate of about 2.05 mL / min at about 21 degrees Celsius (see Figs. 6). The maximum trivalent cation capacity of the iminodiacetic resin was determined to be about 117 mg of lanthanum or about 29 mg of lanthanum per gram of the resin.
The resin was loaded with about 108 mg of lanthanum.
The total load was calculated when determining the area under the penetration curve (Fig. 6). Example C:: Example C was a determination of
À | 47/53 ability to remove the trivalent cation loaded on the resin at IX1 in Example B.
The tested resin was an iminodiacetic function resin sold under the trade name Amberlite IRC-748i by Rohm & Haas.
The trivalent cation was lanthanum.
About 108 'milligrams of lanthanum was loaded onto a resin column containing about 4 grams of Amberlite 748i.
The lanthanum loaded column was regenerated with a hydrochloric acid solution having a normality of about 2.6N, the flow rate of the hydrochloric acid solution was about 2.7 ml / min.
Fractions were collected in about every 5 minutes.
The first 5 fractions contained detectable amounts of lanthanum (see Fig. 7). The first 5 fractions contained a total of 104 mg of lanthanum, which was within the experimental error of 108 mg of lanthanum loaded in the column.
The second fraction had the highest lanthanum concentration of about 7.5 g / L.
Fractions beyond the fifth fraction did not contain any detectable amounts of lanthanum.
It was | It is assumed from this example that an iminodiacetic function resin charged with a trivalent cation, such as lanthanum, can be regenerated with hydrochloric acid.
Example D Example D was a determination of the ability to remove a trivalent cation loaded on a IX2 resin from the brine finishing process (Fig. 3). The tested resin was an aminomethylphosphonic resin sold under the trade name Amberlite IRC-747 by Rohm & Í: Haas.
The trivalent cation was lanthanum.
About 88mg of lanthanum was loaded onto a resin column containing about 4 grams: Amberlite IRC-747. The loaded column was regenerated with a hydrochloric acid solution having a normality of about 2.6
7 48/53 i N. The flow rate of the 2.6 N HCI solution was about 1.9! ml / min. 20 volume fractions were collected from the column.
Fractions were collected about every 5 minutes. Lanthanum was detected in each of the twenty volume fractions. While | about 88 mg of lanthanum appeared to be loaded onto the column, about 117 mg of lanthanum appeared to be discharged from the column (Fig. 8). It was believed that this discrepancy was due to an analytical error. More specifically, it was believed that the column was loaded with a feed solution containing 60 mg of lanthanum / L and not about 42 mg of lanthanum / L. About .
125 mg of lanthanum would have to be loaded onto the column from the 60 mg lanthanum / L solution, which would best match 117 ma of lanthanum discharged from the column.
| Example E: Example E was a determination of the ideal operating conditions for dividing salt before operating the salt divider in a fixed, continuous state. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) was used to verify the purity of the brine feed. The brine feed had no more than about 0.5 ppm of divalents and iron. The salinity of the feed tank was measured with a conductivity probe and found to be about 7.8 mmhos. The conductivity probe was calibrated against 3 calibration standards in 5, 50 and 100 g / L of salt, which had conductivities of 0.82, 6.84 and 13.21 mmhos, respectively. Current and voltage levels were read from the salt divider DC power supply. The brine feed solution was circulated through a bipolar membrane electrodialysis stack, which is an anion exchange membrane, |
: 49/53 cation exchange membrane and bipolar membrane, sealing rings, flow distribution, electrodes, etc., at about 0.8 gallons per minute.
This circulation rate spun each of the "salt, acid, base and electrode water wash tanks, respectively, taking about 12 liters of the solution, plus about every 4 minutes.
The acid and base salt divider tanks contained deionized water.
The electrode wash tank:. it contained the 2N NaOH solution and the brine feed solution contained about 75 g of NaCl / liter and had a pH of about pH2 2. After a consistent flow rate is established; through the membrane stack and a substantially bubble-free solution was obtained, the DC power supply was activated.
The DC power supply was adjusted to pass about 16 amps of current through the brine solution, while the voltage was left to vary.
The conductivity, current, voltage, temperature of the feed solution and acid and base normalities were determined as a function of the time until the NaCl content of the brine feed was substantially depleted by about zero (Fig. 9). The i '20 content of NaClda brine feed was depleted in about 3.5 hours.
The acid and base compartments, respectively, had termination normalities of about 0.8 N HCl and about 0.8 N NaOH.
Example F Example F was a determination of the conversion rate for a salt feed containing about 95 - grams of NaCl per liter.
The brine feed was checked for purity using ICP-AES.
The brine feed had no more than about 0.5 ppm of divalents and iron.
The salinity of the
: 50/53 feeding tank was measured with a conductivity probe and found to be about 7.8 mmbhos.
The conductivity probe was calibrated against 3 calibration standards in 5, 50 and 100 g / L of salt, which had conductivities of 0.82, 6.84 and 13.21 mmbhos, ': 5 - respectively.
Current and voltage levels were read from the salt divider's DC power supply.
The brine feed solution was circulated through a bipolar membrane electrodialysis stack at about 0.8 gallons per minute.
This circulation rate spun each of the salt, acid, base and electrode water wash tanks, respectively, having about 12 liters of solution in about every 4 minutes.
The acid and base salt divider tanks, respectively, contained about 0.5 N HCl and about 0.5 N NaOH.
The electrode wash tank contained a 2N NaOH solution and the brine feed tank contained about 95 g of NaCl / liter and had a pH of about pH2. | | The DC power supply was activated after a consistent flow rate was established across the membrane stack and the | solution was substantially free of bubbles.
The DC power supply was adjusted to pass about 16 amps of current through the brine solution and the voltage was allowed to vary.
After about 30 minutes of operation, the applied voltage and current stabilized at around 19 volts and 16 amps, respectively (Fig. 10). The conductivity, current, voltage, temperature of the feed solution and normalities of acid and base were measured as a function of time (Fig. 10). O | NaCl content of the brine feed decreases during the. electrolysis, from about 95 g / l to about 17 g / l in about a 5 hour electrolysis period.
In addition, in the period | | SA E
51/53 5 hour electrolysis, about 934 grams of NaCl was converted f. in hydrochloric acid and sodium hydroxide.
The average conversion rate was about 22 grams per square meter (of the electrode's surface area) per minute.
The acid and base compartments, respectively, had termination normalities of about 2 N HCl and about 2 N NaOH.
About 800 grams of water 1 were electrolyzed in the process.
A quantitative analysis of the amount of NaCl in the feed solution consumed per hour. By electrolysis produced the following quadratic equation: Cilg / L] -2.34tº - 1.76t + 95.81, where t is hours The DC power supply , on average, applied about 16 amps at about a 19 volt potential.
The theoretical equivalents of NaOH and HCl produced were | determined to be about 4.2 equivalents per hour, with a current efficiency of about 76%. The energy used to convert NaCl to hydrochloric and sodium hydroxide was about 1.6 kW hours per kg of NaCl produced. | Numerous variations and modifications can be used.
It would be possible to provide some resources without providing others. : The various aspects, realizations and configurations, include the components, methods, processes, systems and / or mechanisms substantially as illustrated and described here, including various realizations, configurations, F. 25 aspects, sub-combinations, and their subsets.
Those skilled in the art will understand how to perform and use aspects, | achievements or configurations disclosed herein after understanding the present disclosure.
The various aspects, achievements and configurations include providing devices and processes in the
. 52/53 absence of items not illustrated and / or described here or in various embodiments, configurations or aspects of the present, including in the absence of such items as they have been used in previous devices or processes, eg, to improve performance, achieve sunset & / or reduce the cost of implementation. . The preceding discussion was presented for purposes of illustration and description.
The precedent is not intended to limit aspects, achievements or configurations to the form or forms disclosed herein.
In the Detailed Description above, for example, several features of the aspects, achievements or "" configurations are grouped together into one or more achievements, configurations or aspects for the purpose of simplifying disclosure.
The features of the aspects, achievements or configurations can be combined into alternative aspects, achievements or configurations other than those discussed above.
This method of disclosure | it should not be interpreted as reflecting an intention that the aspects, achievements or configurations require more resources than 'expressly mentioned in each claim.
Instead, as the following claims reflect, the inventive aspects remain in less than all the features of a single embodiment, configuration or aspect revealed above.
This p. Accordingly, the following claims are now incorporated into this Detailed Description, with each independent claim as a separate aspect, realization or configuration.
Furthermore, although the description included the description of one or more aspects, achievements or configurations and certain variations and modifications, other variations, combinations and modifications are within the scope of the aspects, achievements or configurations, eg, as they may
It is 53/53 to be within the skill and knowledge of those in the technique, after understanding the present revelation.
It is intended to obtain the rights .which include the achievements, configurations or alternative aspects to the extent permitted, including the structures, functions, variations or alternative, interchangeable and / or equivalent steps for those | claimed, if such alternative, interchangeable and / or equivalent structures, functions, variations or D steps are disclosed here | or not, and without publicly intending to dedicate any patentable object. |

权利要求:
Claims (17)
[1]
1. Process, characterized by the fact that it comprises: (a) contacting a material containing precious metal with an acid leaching solution having an acidic component in order to form an abundant leaching solution comprising a dissolved precious metal; (b) recovering the dissolved precious metal to form a precious metal product and a by-product saline, the by-product saline is derived from reaction of a base with the acid component; (c) electrochemically converting the by-product saline solution into the acid component and the base; (d) recycling the acidic component from step (c) to step (a); and (e) recycling the base of step (c) to at least one of steps (a) and (b).
[2]
2. Process, according to claim 1, characterized by the fact that, in each recycling step, the acid component and the base are one of concentrate, adjusted pH, or both, in which the conversion step Electrochemistry is performed by at least one chlor-alkali and bipolar membrane electrodialysis cell, in which at least the largest part of the by-product saline solution is converted into the acid component and the base, in which at least most of the acid component and the base are recycled, in which the precious metal is one or more of yttrium, scandium, lanthanide, a metal in the platinum group, copper, chromium, beryllium, nickel, iron, lead, molybdenum, aluminum, germanium, uranium, gold, silver, cobalt, zinc, tin, titanium and manganese, where the acid component is hydrochloric acid, where the by-product saline comprises one or both of sodium chloride and potassium chloride, where the base is one or both of sodium hydroxide and potassium hydroxide, where the product Precious metal is an oxide, in which the conversion step produces hydrogen gas and chlorine gas, and in which the electrochemical conversion step further comprises: the reaction of chlorine gas with hydrogen gas to produce the acid hydrochloric.
[3]
3. Process according to claim 1, characterized by the fact that the electrochemical conversion step is performed by a bipolar membrane electrodialysis cell, in which the precious metal is one or more of copper, beryllium, nickel, iron, lead, molybdenum and manganese, where the acid component is nitric acid, where the by-product saline comprises one or both of sodium nitrate and potassium nitrate, and where the base is one or both of hydroxide sodium and potassium hydroxide.
[4]
4, Process, according to claim 1, characterized by the fact that the electrochemical conversion step is carried out by a bipolar membrane electrodialysis cell, in which the precious metal is uranium, in which the acid component is the acid phosphoric, in which the by-product saline solution comprises one or both of sodium phosphate and potassium phosphate, and where the base is one or both of sodium and potassium hydroxide.
[5]
5. Process according to claim 1, characterized by the fact that the electrochemical conversion step is carried out by a bipolar membrane electrodialysis cell, in which the precious metal is one or more of a group of platinum metal , copper, beryllium, nickel, iron, lead, molybdenum, aluminum, germanium, uranium, gold, silver, cobalt, zinc, tin, titanium, chromium, manganese, and in which the by-product saline comprises one or both of sodium sulfate and potassium sulfate, where the acid component is sulfuric acid, and where the base is one or both of sodium hydroxide and potassium hydroxide.
[6]
6. Process, according to claim 1, characterized by the fact that the conversion step comprises: removing, by precipitation induced by a change in pH resulting from the contact of the base with the by-product saline solution, at least - in most of a multipurpose cationic impurity selected from the by-product solution to form a first purified solution; contacting the first purified solution with an ion exchange resin to remove additional polyvalent cationic impurities to form a second purified solution; processing the second purified solution through a salt concentrator to form a concentrated form of the second purified solution; introduce the concentrated form of the second purified solution and a mineral acid in an anolyte recirculation tank; and introducing the concentrated form of the second purified solution into at least one of the alkaline chlorides and bipolar membrane electrodialysis cell to form the acid and base component.
[7]
7. Process, according to claim 1, characterized by the fact that the by-product saline solution comprises an organic contaminant and in which the conversion step further comprises: removing at least most of the organic contaminant to form a solution purified saline, in which the purified saline solution is introduced into at least one of the alkali chlorides and a bipolar membrane electrodialysis cell to form the acid component and the base and which further comprises: receiving electrical energy from a cogeneration, electric energy being received by one or more of the stages of contact, recovery, conversion and recycling; receiving residual heat from the cogeneration plant, the residual heat being received by one or more of the contact, recovery, conversion and recycling steps.
[8]
8. Process according to claim 1, characterized by the fact that the electrochemical conversion step is performed by a chlor-alkali electrodialysis cell, which further comprises: maintaining an approximate stoichiometric balance between chlorine gas and hydrogen produced in the conversion step.
[9]
9. Process according to claim 1, characterized by the fact that the dissolved precious metal is a plurality of rare earths and the recovery step consists of: selectively oxidizing one of the rare earths to precipitate the oxidized rare earth while leaving the rare earths not oxidized in solution; separating the oxidized rare earth precipitate from the solution containing the unoxidized rare earths, in which the solution containing the unoxidized rare earths comprises cerium (Ill) and the oxidized rare earth comprises cerium (IV); recycle the acid and / or base to at least one of the contact and recovery steps.
[10]
10. Process according to claim 2, characterized by the fact that the precious metal is one or more of yttrium, scandium, a lanthanide, in which the acid is hydrochloric acid, in which the metal product needs oso is a rare earth oxide, in which the conversion step produces hydrogen gas and chlorine gas, and where the conversion step further comprises: reaction of chlorine gas with hydrogen gas to produce hydrochloric acid , and maintaining a substantial stoichiometric balance between chlorine gas and hydrogen gas produced in the conversion step.
[11]
11. Installation, characterized by the fact that it comprises: (a) a plant for at least one of (i) fragmenting a feed material comprising a mineral containing precious metal and (i) forming, from the mineral containing precious metal , a concentrate containing the mineral containing precious metal; (b) a process unit for recovering the precious metal from the mineral containing precious metal, in which at least one of the plant and process unit generates a by-product saline solution from a mineral acid and base; and (c) an electrochemical acid generation unit for generating mineral acid and base from the by-product saline solution and supplying mineral acid to at least one of the plant and process unit.
[12]
12. Installation, according to claim 11, characterized by the fact that the electrochemical acid generating unit comprises at least one of chlor-alkali and a bipolar membrane electrodialysis cell,
where the precious metal is one or more of yttrium, scandium, lanthanide, platinum group metal, copper, chromium, beryllium, nickel, iron, lead, molybdenum, aluminum, germanium, uranium, gold, silver, cobalt, zinc, tin, titanium and manganese, where the mineral acid is hydrochloric acid, where the salt in the by-product saline is one or both of sodium chloride and potassium chloride, where the base is one or both of hydroxide sodium and potassium hydroxide, and in which the electrochemical acid generating unit produces hydrogen gas and chlorine gas, and chlorine gas reacts with hydrogen gas to produce hydrochloric acid.
[13]
13. Installation according to claim 11, characterized by the fact that the electrochemical acid generating unit comprises at least one of chlor-alkali and a bipolar membrane electrodialysis cell, in which at least one of the chlor-alkali and cell bipolar membrane electrodialysis cell is the bipolar membrane electrodialysis cell, in which the precious metal is one or more of copper, beryllium, nickel, iron, lead, molybdenum and manganese, in which mineral acid is the acid nitric, where the salt in the by-product saline is one or both of sodium nitrate and potassium nitrate, and where the base is one or both of sodium hydroxide and potassium hydroxide.
[14]
14. Installation according to claim 11, characterized by the fact that the electrochemical acid generating unit comprises at least one of chlor-alkali and a bipolar membrane electrodialysis cell, in which at least one of a chlor-alkali and bipolar membrane electrodialysis cell is the bipolar membrane electrodialysis cell, where the precious metal is uranium, where the mineral acid is phosphoric acid, where the salt in the by-product saline is one or both of sodium phosphate and potassium phosphate, and where the base is one or both of sodium hydroxide and potassium hydroxide.
[15]
15. Installation according to claim 11, characterized by the fact that the electrochemical acid generating unit comprises at least one of a chlor-alkali and a bi-polar membrane electrodialysis cell, in which the at least one of chloro-alkali alkali and bipolar membrane electrodialysis cell is the bipolar membrane electrodialysis cell, in which the precious metal is one or more of a metal in the platinum group, copper, beryllium, nickel, iron, lead, molybdenum, aluminum, germanium, uranium, gold, silver, cobalt, zinc, tin, titanium, chromium, manganese, and where the salt of the by-product saline is one or both of sodium sulfate and potassium sulfate, where mineral acid is the sulfuric acid, and where the base is one or both of sodium hydroxide and potassium hydroxide.
[16]
16. Installation according to claim 11, characterized by the fact that the electrochemical acid generating unit comprises at least one of a chlor-alkali and bi-polar membrane electrodialysis cell, in which the electrochemical acid generation plant: removes at least most of a selected polyvalent cationic impurity from the by-product saline to form a first purified solution, in which the selected polyvalent cationic impurity is removed by precipitation induced by a change in pH resulting from contact of the base with the by-product saline solution, in which the electrochemical acid generation plant: contacts the first solution purified with an ion exchange resin to remove additional polyvalent cationic impurities to form a second purified solution; processes the second purified solution through a salt concentrator to form a concentrated form of the second purified solution; and introduces the concentrated form of the second purified solution and the mineral acid in an anolyte recirculation tank, and intrudes the form of concentrates into at least one of the chlor-alkali and bipolar membrane electrodialysis cells to form the mineral acid and the base.
[17]
17. Installation according to claim 11, characterized by - a form that further comprises: a cogeneration unit to supply waste electrical and thermal energy to one or both of the plant and process unit, where the electrochemical acid generation unit comprises at least one chlor-alkali and bipolar membrane electrodialysis cell, in which the by-product saline comprises an organic contaminant, in which the electrochemical acid generating unit eliminates at least the largest organic contaminant part to form a purified saline solution , and in which the purified saline solution is introduced in at least one of chlor-alkali and bipolar membrane electrodialysis cell to form the mineral acid and the base.
Í: 1/10 h the Ds. 'E rm pre] mentions es er eremions dera [aeee e)> Ns | | | | | | o o Fx. - ba elo E. E | 'Es. 2 | o 3 take off | Ds o 2 NC S&S o Ro | E N À Y uo = A ENS o 085 À un woo Prcossesomemenn dos or ms es res: a <o Ss WWE Not only the 7 ZÉ 1 à à G fan É Z | E 8 eg a |
PNG AND TA N | THIS id [NA RX i 2 ih NA Ts | Pei quam Enf. s Ss +: RPE Is it DR A | ! | Êo | IN O |! | E = eg lis] 28 Wu o Ad. To. i> Z Prá "az Te AO o | | Ss qe / 1 = - =: 1 38 VV! o JAZZ A, | TIA and E -
A N Ne s XY | z 8 | 1 SNI | | E | o 1 o i | Or) No PT j Ts Tv Ts 1 * | dO Nx e Ss 7 1 2 “oe za o N> j 82h a | E <o 2228 8 no 3 Zz SÉSÔ | one E 52 to 5 EDF A | ga | 1 FE Õ | 78 |

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CA2787515A1|2011-07-28|

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KR20120139701A|2012-12-27|

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AU2011207307C1|2015-01-15|

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JP2013528696A|2013-07-11|

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EP2526213A1|2012-11-28|

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HK1247256A1|2018-09-21|

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EA024210B1|2016-08-31|

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WO2011091231A1|2011-07-28|

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EA201201035A1|2013-02-28|

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AP2012006439A0|2012-08-31|

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RU2763464C1|2021-07-29|2021-12-29|Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "Кольский научный центр Российской академии наук" |Method for processing monazite concentrate|

法律状态:
2018-10-23| B12F| Other appeals [chapter 12.6 patent gazette]|

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2020-09-29| B15I| Others concerning applications: loss of priority|Free format text: PERDA DAS PRIORIDADES US 61,297/536 , US 61/427,45 E US 61/432,075 REIVINDICADAS NO PCT/US2011/022018, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 167O E ART 2O DA RESOLUCAO INPI 179 DE 21/02/2017. ESTA PERDA SE DEU PELO FATO DE O DEPOSITANTE CONSTANTE DA PETICAO DE REQUERIMENTO DO PEDIDO PCT SER DISTINTO DAQUELES QUE DEPOSITARAM A PRIORIDADE REIVINDICADA E NAO APRESENTOU DOCUMENTO COMPROBATORIO DE CESSAO DENTRO DO PRAZO DE 60 DIAS A CONTAR DA DATA DA ENTRADA DA FASE NACIONAL, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 166O, E NO ART. 28 DA RESOLUCAO INPI-PR 77/2013. |

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2020-10-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2021-02-09| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: ARQUIVADO O PEDIDO DE PATENTE, NOS TERMOS DO ARTIGO 86, DA LPI, E ARTIGO 10 DA RESOLUCAO 113/2013, REFERENTE AO NAO RECOLHIMENTO DA 10A RETRIBUICAO ANUAL, PARA FINS DE RESTAURACAO CONFORME ARTIGO 87 DA LPI 9.279, SOB PENA DA MANUTENCAO DO ARQUIVAMENTO CASO NAO SEJA RESTAURADO DENTRO DO PRAZO LEGAL, CONFORME O DISPOSTO NO ARTIGO 12 DA RESOLUCAO 113/2013. |

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2021-07-20| B08K| Patent lapsed as no evidence of payment of the annual fee has been furnished to inpi [chapter 8.11 patent gazette]|Free format text: REFERENTE AO DESPACHO 8.6 PUBLICADO NA RPI 2614 DE 09/02/2021. |

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2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US29753610P| true| 2010-01-22|2010-01-22|

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US61,297/536|2010-01-22|

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US201061427745P| true| 2010-12-28|2010-12-28|

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US61/427,745|2010-12-28|

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US201161432075P| true| 2011-01-12|2011-01-12|

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US61/432,075|2011-01-12|

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PCT/US2011/022018|WO2011091231A1|2010-01-22|2011-01-21|Hydrometallurgical process and method for recovering metals|

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