KR102015961B1 - Rare earth removal of hydrated and hydroxyl species - Google Patents

Abstract

The present invention generally relates to a process for removing target materials in the form of hydroxides, carbonates, hydrates, or oxyhydroxides from an aqueous, liquid medium and rare earth-containing additives.

Description

RARE EARTH REMOVAL OF HYDRATED AND HYDROXYL SPECIES}

Cross Reference of Related Applications

This application is part of an ongoing application 13 / 356,581 entitled "Rare Earth Removal of Hydrated and Hydroxylated Species" of the invention filed on January 30, 2012, claiming the benefit of the following US temporary application numbers:

Name of the invention filed on 3/4/2011 "Water treatment process and water treatment system using rare earth metal" 61 / 474,902;

Named invention filed on Dec. 3, 2011 "Methods and Apparatus for Oxidation and Oxidation and Removal of Oxy Anions Using Soluble and Insoluble Rare Earth" 61 / 475,155;

Entitled “Methods for Removing Targets from Fluid Streams Using Rare Earth and / or Rare Earth-Containing Additives”, filed Sep. 27, 2011; 61 / 539,780;

Entitled “Water Treatment Process and Water Treatment System Using Rare Earth Metals”, filed Oct. 31, 2011 61 / 553,809;

The invention filed Oct. 13, 2011 "Process of using rare earths to remove oxyhydrating species from an aqueous stream" 61 / 546,803;

The invention filed March 22, 2012 "Rare Earth Removal of Hydrated and Hydrolyzed Species" 61 / 614,427;

61 / 476,667 filed April 18, 2011 and 61 / 553,809 filed October 31, 2011, "Water Treatment Processes and Water Treatment Systems Using Rare Earth Metals";

Entitled “Water Treatment Process and Water Treatment System Using Rare Earth Metals”, filed Nov. 11, 2011 61 / 558,887;

Entitled “Water Treatment Processes and Water Treatment Systems Using Rare Earth Metals”, filed Nov. 28, 2011 61 / 564,132;

The invention filed March 22, 2012 "Rare Earth Removal of Phosphorus-Containing Material" 61 / 614,418;

The invention filed March 21, 2012 "Rare Earth Removal of Phosphorus-Containing Material" 61 / 613,883;

The invention filed March 21, 2012 “Removal of Non-Metal Containing Oxy Anions in Water Using Rare Earth” 61 / 613,857;

Entitled “Removal of Rare Earth Contaminants in Swimming Pools, Corn Baths, and Spas” filed Sept. 23, 2011 61 / 538,634;

Each of which is incorporated herein by reference in its entirety.

The present invention, which is hereby incorporated by reference in its entirety and filed on Sep. 23, 2011, filed "Water treatment process and water treatment system for descaling and reducing the tendency to scale." US patent application Ser. No. 13 / 244,092 Cross-referenced to

Mutual cerium dioxide and the simultaneous method of making and using the same; and US Pat. Appl. No. 13 / 244,117, incorporated herein by reference in its entirety and filed on file No. 6062-89-4 and filed Sep. 23, 2011; Reference is made.

Incorporated herein by reference in its entirety and cross-referenced to US patent application Ser. No. 13 / 410,081 entitled Agent File Nos.

Incorporated herein by reference in its entirety and cross-referenced to US patent application Ser. No. 13 / 356,574 with agent file no.

Regarding the invention "removing non-metal-containing oxyanions in water with rare earths" using the agent file No. 6062-89-2, filed March 28, 2012, incorporated herein by reference in its entirety, US Patent Application No. 13/433097 Cross-referenced.

Incorporated herein by reference in its entirety and cross-referenced to US patent application Ser. No. 13/432895 entitled Agent File No. 6062-89-5 and entitled “Rare Earth Removal of Phosphorus-Containing Material” filed March 28, 2012.

The present invention relates generally to rare earth removal of hydrated and hydroxide species, and more particularly to rare earth removal of metal and metalloid-containing hydrate and / or hydroxide species.

With the shortage of freshwater resources, water quality problems are rapidly becoming a global problem. In addition to the high levels of pollution and brine penetration into freshwater body layers due to industrialization and urbanization, disinfectants commonly used in drinking water, in particular free chlorine (HOCl / OCl ^- form) and monochloramine (NH ₂ Cl), are metals and metalloids. To form a soluble product. Monochloramines, for example, react with lead to form soluble Pb (II) products, resulting in elevated Pb levels in drinking water.

Various techniques have been used to remove contaminants from municipal, industrial and water baths. Examples of such techniques include adsorption of high surface area materials such as alumina and activated carbon, ion exchange using anion exchange resins, coprecipitation and electrodialysis. However, most contaminant removal techniques are not smooth due to the difficulty of removing contaminants, and more particularly, the difficulty of removing metal and metalloid contaminant species.

These and other needs are addressed with various embodiments and configurations of the present invention. The present invention utilizes rare earth-containing compositions to remove various contaminants, including metal and metalloid targets.

In one embodiment, the composition has the formula:

Where 0 ≦ X ≦ 8 and MS are one of the following:

M (H ₂ O) ₆ ⁿ , M (H ₂ O) ₅ OH ^(n-1) , M (OH) ^(n-1) , M (H ₂ O) ₄ (OH) ₂ ^(n-2) , M (OH) ₂ ^(n-2) , M (H ₂ O) ₃ (OH) ₃ ^(n-3) , M (OH) ₃ ^(n-3) , M (H ₂ O) ₂ (OH) ₄ ^(n-4) , M (OH) ₄ ^(n-4) , M (H ₂ O) (OH) ₅ ^(n-5) , M (OH) ₅ ^(n-5) , M (OH) ₆ ^{( n-6)} , M (H ₂ O) ₅ O ^(n-2) , M (H ₂ O) ₄ (O) ₂ ^(n-4) , M (H ₂ O) ₃ (O) ₃ ^{(n- 6)} , M (H ₂ O) ₂ (O) ₄ ^(n-8) , M (H ₂ O) (O) ₅ ^(n-10) , M (H ₂ O) ₅ CO ₃ ^(n-2) , MCO ₃ ^(n-2) , M (H ₂ O) ₄ (CO ₃ ) ₂ ^(n-4) , M (CO ₃ ) ₂ ^(n-4) , M (H ₂ O) ₃ (CO ₃ ) ₃ ^(n-6) , M (CO ₃ ) ₃ ^(n-6) , M (H ₂ O) ₂ (CO ₃ ) ₄ ^(n-8) , M (CO ₃ ) ₄ ^(n-8) , M (H ₂ O) (CO ₃ ) ₅ ^(n-10) , M (CO ₃ ) ₅ ^(n-10) , M (CO ₃ ) ₆ ^(n-12) , M (H ₂ O) ₄ ⁿ , M (H ₂ O) ₃ OH ^(n-1) , M (H ₂ O) ₂ (OH) ₂ ^(n-2) , M (H ₂ O) (OH) ₃ ^(n-3) , M (H ₂ O) ₃ O ^(n-2) , M (H ₂ O) ₂ (O) ₂ ^(n-4) , and M (H ₂ O) (O) ₃ ^(n-6) . “M” is a metal or It is a metalloid and has an atomic number selected from the group consisting of 5, 13, 22-33, 40-52, 56, 72-84, and 88-94. The symbol "n" represents real ≤ 8 and represents the charge or oxidation state of "M".

In one aspect, the composition is in a liquid medium or medium, the medium or medium having a pH and Eh sufficient for MS to be preferred as the main species of M.

In one aspect, M is one or more boron, vanadium, chromium, cadmium, antimony, lead, and bismuth.

In one embodiment, the method removes the target material in the medium by contacting the rare earth-containing additive with a metal or metalloid target material. Targets are the main species in the form of hydroxides, carbonates, hydrates, or oxyhdroxyl.

In one embodiment, a method of removing metal or metalloid hydroxides, carbonates, and / or hydrates in a medium is provided by contacting the rare earth-containing additive with one or more metal or metalloid hydroxides, carbonates, and hydrates.

The rare earth-containing additive may be water soluble or water insoluble.

In one aspect, the target material has an atomic number selected from the group consisting of 5, 13, 22-33, 40-52, 56, 72-84, and 88-94.

In one aspect, the contacting step includes the following sub-steps:

(a) introducing an oxidizing agent into the medium to oxidize the target-containing species to the principal species in the form of one or more other metal or metalloid hydroxides, carbonates, oxyhydroxides, and hydrates; And

(b) then contacting the rare earth-containing additive with the metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate in the medium to remove the metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate.

In one aspect, the contacting step includes the following sub-steps:

(a) introducing a reducing agent into the medium to reduce the target-containing species having the metal or metalloid to a major species in the form of other metals or metalloid hydroxides, carbonates, oxyhydroxides, and / or hydrates; And

(b) then contacting the rare earth-containing additive with the metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate in the medium to remove the metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate.

In one aspect, the contacting step includes the following sub-steps:

(a) introducing a base and / or equivalent base into the medium for converting a target-containing species having a metal or metalloid into a major species in the form of another metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate. Making; And

(b) then contacting the rare earth-containing additive with the metal or metalloid hydroxide, carbonate, and / or hydrate in the medium to remove the metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate.

In one aspect, the contacting step includes the following sub-steps:

Introducing an acid and / or an equivalent acid into the medium to convert the target-containing species having the metal or metalloid into a major species in the form of another metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate; And

Then contacting the rare earth-containing additive with the metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate in the medium to remove metal or metalloid hydroxide, carbonate, oxyhydroxide, and / or hydrate.

The present invention provides several advantages. For example, rare earth-containing compositions can effectively remove multiple targets, whether in soluble or insoluble species form. By way of example, the composition can remove various forms of lead and lead species, including colloids, hydrates, carbonates, hydroxides, and oxyhydroxides. The pH and / or Eh are adjusted to produce the selected target major species, which are effectively removed by the rare earth composition as compared to the rare earth removal of other target species. Thus, a high level of selected target removal is achieved.

The accompanying drawings are incorporated in and constitute a part of this specification, and are described in detail above and below.
The embodiments of the present invention together with the description serve to explain the principles of the present invention.
1 illustrates a water treatment system and method according to an embodiment;
2A-E show a preceding pullbay diagram for a boron major species under certain conditions;
3A-E show a preceding full bay diagram for an aluminum main species at certain conditions;
4A-D show preceding full bay diagrams for thallium major species under certain conditions;
Figures 5A-E show a preceding full bay diagram for vanadium main species under certain conditions;
6A-E show a preceding full bay diagram for chromium major species under certain conditions;
7A-F show preceding full bay diagrams for manganese major species under certain conditions;
8A-F show preceding full bay diagrams for iron main species under certain conditions;
9A-E show a preceding full bay diagram for cobalt dominant species under certain conditions;
10A-E show a preceding pullbay diagram for nickel primary species under certain conditions;
11A-E show preceding pulley diagrams for copper main species at certain conditions;
12A-D show preceding pulley diagrams for zinc main species under certain conditions;
13A-B show a preceding pullbay diagram for gallium main species under certain conditions;
FIG. 14 shows a preceding full bay diagram for germanium major species under certain conditions; FIG.
Figures 15A-D show preceding full bay diagrams for arsenic major species under certain conditions;
Figures 16A-D show preceding pulley diagrams for zirconium major species under certain conditions;
17A-D show a preceding pullbay diagram for niobium dominant species under certain conditions;
18A-C show preceding Fulbay diagrams for the molybdenum main species under certain conditions;
19A-F show preceding full bay diagrams for technetium major species under certain conditions;
Figures 20A-D show preceding full bay diagrams for ruthenium major species under certain conditions;
21A-B show preceding Fulbay diagrams for rhodium major species under certain conditions;
Figures 22A-C show a preceding pullbay diagram for the palladium major species under certain conditions;
Figures 23A-E show preceding full bay diagrams for the major silver species under certain conditions;
Figures 24A-C show a preceding full bay diagram for cadmium main species under certain conditions;
25A-B show a preceding pullbay diagram for an indium major species at certain conditions;
Figures 26A-E show a preceding full bay diagram for tin main species under certain conditions;
27A-D show preceding full bay diagrams for antimony main species under certain conditions;
FIG. 28 shows a preceding full bay diagram for tellurium dominant species under certain conditions;
FIG. 29 shows a preceding Fulbay diagram for hafnium dominant species under certain conditions;
FIG. 30 shows a preceding pullbay diagram for the lead main species under certain conditions; FIG.
FIG. 31A-B shows a preceding full bay diagram for a major Tungsten species under certain conditions;
32A-B show preceding full bay diagrams for rhenium major species under certain conditions;
FIG. 33 shows a preceding Fulbay diagram for the main species of ossium under certain conditions;
FIG. 34 shows a preceding full bay diagram for the major species of uranium under certain conditions;
Figures 35A-B show a preceding full bay diagram for platinum main species under certain conditions;
36A-C show a preceding full bay diagram for a major species of gold under certain conditions;
37A-D show a preceding full bay diagram for a major mercury species under certain conditions;
38A-E depict a preceding full bay diagram for lead major species under certain conditions;
FIG. 39 shows a preceding pullbay diagram for the lead main species under certain conditions; FIG.
40A-C show preceding full bay diagrams for bismuth major species under certain conditions;
Figures 41A-B show a preceding pullbay diagram for polonium major species under certain conditions;
42A-B show preceding Fulbay diagrams for actinium major species under certain conditions;
43A-E show a preceding pullbay diagram for the thorium major species under certain conditions;
44A-B show preceding Fulbay diagrams for actinium major species under certain conditions;
45A-G show a preceding full bay diagram for the major uranium species under certain conditions;
46A-E show preceding Fulbay diagrams for the Neptunium major species under certain conditions;
47A-F show a preceding pullbay diagram for the main plutonium species under certain conditions;
48 shows loading performance (mg / g) (vertical axis) versus arsenic concentration (g / L) (horizontal axis);
49 depicts the final arsenic concentration (mg / L) (vertical axis) to cerium: arsenic molar ratio (horizontal axis);
50 depicts the final arsenic concentration (mg / L) (vertical axis) to cerium molar ratio (horizontal axis) to arsenic;
FIG. 51 is a series of XRD patterns for the precipitate formed when adding Ce (III) or Ce (IV) solution to sulfide-arsenite solution and sulfate-arsenate solution;
52 shows fixed arsenic (micromolar) (vertical axis) and added cerium (micromolar) (horizontal axis);
FIG. 53 is a series of XRD patterns showing structural differences between gasparite (CeAsO ₄ ) and CeAsO _4. (H ₂ O) X in the new trigonal phase;
54 is a structural diagram between trigonal CeAsO _4. (H ₂ O) X (experimental), trigonal CeAsO _4. (H ₂ O) X (simulation), and trigonal BiPO _4. (H ₂ O) 0.67 (simulation). A series of XRD patterns that differ;
55 illustrates arsenic performance (mg As / g CeO ₂ ) for various solution compositions;
FIG. 56 shows arsenic (V) concentrations (ppb) for treated bed volumes; FIG.
FIG. 57 shows mg As / g CeO ₂ (vertical axis) for test solution conditions (horizontal axis); FIG.
58A-D show preceding Pool Bay diagrams for bismuth major species under certain conditions;
59A-E show preceding pulley diagrams for aluminum main species under certain conditions;
Figures 60A-E show a preceding full bay diagram for cobalt major species under certain conditions;
61A-E depict a preceding full bay diagram for chromium major species under certain conditions;
62A-E show preceding full bay diagrams for manganese major species under certain conditions;
63A-E show a preceding pullbay diagram for a copper main species at certain conditions;
64A-E show a preceding pullbay diagram for a major zirconium species under certain conditions;
65A-E depict a preceding pulley diagram for zinc main species under certain conditions;
66A-E depict a preceding full bay diagram for barium dominant species under certain conditions;
67A-E depict a preceding full bay diagram for radium major species under certain conditions.

These and other advantages will be apparent from the present invention.

As used herein, the term "a" or "an" refers to one or more of an individual. As such, the terms "a" (or "an"), "one or more" and "at least one" are used interchangeably herein. In addition, "constituting", "comprising" and "having" are used interchangeably.

"Absorbent" means that one substance penetrates into the internal structure of another substance and is distinct from adsorption.

"Adsorption" refers to the attachment of atoms, ions, molecules, polyatomic ions, or other materials to the surface of another material called an adsorbent. Typically, the attraction attraction can be in the form of bonds and / or forces such as covalent bonds, metal bonds, coordination bonds, ionic bonds, hydrogen bonds, electrostatic forces (eg, van der Waals forces and / or London forces). have.

"At least one", "one or more", and "and / or" are extensible expressions, which can be both combined and separated in function. For example, "at least one A, B, and C", "at least one A, B, or C", "at least one A, B, and C", "at least one A, B, or C", And the expressions of “A, B, and / or C” each represent A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B, and C It means to be together. The term “water” means any aqueous stream. The water may be derived from any aqueous stream derived from any natural and / or industrial source. Non-limiting examples of such aqueous streams and / or water include drinking water, constant water, bath water, process water, waste water, pool water, spa water, cooling water, boiler water, process water, municipal water, sewage, agricultural water, groundwater, Power generation water, restoration water, co-mingled water and combinations thereof.

The terms “agglomerate” and “agglomerate” refer to a composition in which one or more substances are formed in aggregates.

"Binder" means one or more materials that bind together materials that aggregate. The binders are typically solid, semi-solid, or liquid. Non-limiting examples of binders include polymeric materials, tars, pitches, asphalt, waxes. Cement water, solutions, dispersants, powders, silicates, gels, oils, alcohols, clays, starches, silicates, acids, molasses, lime, lignosulfonate oils, hydrocarbons, glycerin, stearates or combinations thereof. The binder may or may not chemically react with the aggregated material. Examples of chemical reactions include, but are not limited to, hydration / dehydration, metal ion reactions, precipitation / gelation reactions, and surface charge alterations.

"Carbonate" generally refers to a chemical compound containing a carbonate radical or ion (CO ₃ ^-2). Most familiar carbonates are salts formed by reaction with inorganic bases (eg metal hydroxides) and carbonic acid (H 2 CO 3). Ordinary carbonates have the same amount of acid and salt

Formed by group reaction; Bicarbonates, also called acid carbonates or hydrogen carbonates, are formed when acids are present in excess. Examples of carbonates are sodium carbonate (Na ₂ CO ₃ ), bicarbonate

Sodium (NaHCO ₃ ), and potassium carbonate (K ₂ CO ₃ ).

The term "purify" or "purify" means the removal of suspended and possibly colloidal solids by gravity settling techniques.

The term "agglomeration" refers to destabilizing the colloid by neutralizing the force of maintaining colloidal material suspension. Cationic flocculants provide electrical positive charge to reduce the negative charge (zeta potential) of the colloid. Colloids thus form larger particles (known as flocs).

The term “composition” generally refers to one or more chemical units consisting of one or more atoms such as molecules, polyatomic ions, chemical compounds, coordination complexes, coordination compounds, and the like. As will be appreciated, the compositions may be joined together by various kinds of bonds and / or forces such as covalent bonds, metal bonds, coordination bonds, ionic bonds, hydrogen bonds, electrostatic forces (eg, van der Waals forces and London forces), and the like. Can be combined.

“Chemical species” or “species” are atoms, elements, molecules, molecular fragments, ions, compounds, and other chemical structures.

"Chemical modification" refers to the process by which at least part of a substance is modified in chemical composition by a chemical reaction. "Chemical Modification" is different from "Physical Modification". Physical modification refers to the process by which chemical properties are not chemically modified but physical properties such as size or shape are modified.

The term “containing in water” generally means a substance suspended and / or dissolved in water. Water is typically a solvent for soluble and water soluble materials. In addition, water is typically not a solvent for insoluble matter water-insoluble matter. Suspended material is substantially insoluble in water and dissolved material is substantially soluble in water. Suspended matter has a particle size.

"De-toxify" or "detoxification" refers to non-toxic or non-toxic targets, such as chemical and / or biological targets, for example to living organisms such as the human body and / or other animals. It includes making it harmful. By converting the target to a non-toxic or non-hazardous form or species, the target can be made non-toxic.

The term "digest" or "digestion" means the use of microorganisms, in particular bacteria, to disinfect a target. This is usually established by forced mixing of contaminated water with bacterial and molecular oxygen.

The term "disinfect" or "disinfection" refers to the use of disinfectants to sterilize or inhibit the growth of microorganisms such as bacteria, fungi, protozoa, and viruses. Common fungicides include oxidizing agents, reducing agents, alcohols, aldehydes, halogens, phenols, quaternary ammonium compounds, silver, copper, ultraviolet light and other materials.

The term “entanglement” refers to the process of using a tangle agent, which is typically a polymer, which forms crosslinks between flocs and forms particles into larger aggregates or agglomerates. Crosslinking occurs when a portion of the polymer chain is adsorbed to different particles to assist in particle coagulation.

The term "fluid" means liquid, gas or both.

“Halogen” is a Group 17 IUPAC Style (formerly VII, VIIA) nonmetallic element of the periodic table and includes fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and asstatin (At). The anthropogenic element 117, temporarily the system name Ununseptun, may also be halogen.

A "halide compound" is a compound in which some of the compounds have at least one halogen atom and some of the compounds have elements or radicals that have a weak electronegativity (or strong electropositivity) than halogen. The halide compound is typically a fluoride, chloride, bromide, iodide, or astide compound. Many salts are halides with halide anions. Halide anions are halogen atoms with negative charges. Halide anions are fluoride (F ⁻ ), chloride (Cl ⁻ ), bromide (Br ⁻ ), iodide (I ⁻ ) and astide (At ⁻ ).

"Hydroxy" generally refers to a chemical group having an oxygen atom which is covalently bonded to a hydrogen atom. When present in chemical species, hydroxyl groups impart some reactivity and interaction properties of water (degree of ionization, hydrogen bonding, etc.). One or more hydroxyl group containing chemical species is typically referred to as “hydroxyl species”. The neutral form of the hydroxyl group is a hydroxyl radical. The anionic form of the hydroxyl group (OH ⁻ ) is called “hydroxide” or “hydroxide anion”.

The term “hydrating species” generally refers to any compound or collection of other species that is chemically bound to water, regardless of the species having a solid or fluid component or compound or charge. For some hydrates, such as laundry, Na ₂ CO ₃ · 10H ₂ O, moisture is loosely bound and easily lost by heating; In other cases, such as sulfuric acid, SO ₃ · H ₂ O, or H ₂ SO ₄ , water is strongly bound as a constituent.

The term “inorganic substance” generally refers to chemical compounds or other species that are not organic.

The term “insoluble” means a substance that is going to be solid in water and / or remains solid. Insoluble matter can be maintained in a device such as a column or can be easily recovered from the batch reaction using physical means such as filtration. Insoluble materials should be able to be exposed to long term exposure to water for weeks and months with little weight loss. Typically, little weight loss means that there is a weight loss within about 5% of the insoluble material after long term exposure to water.

"Ion" generally means a charged atom or group of atoms. The charge of the ions is negative or positive.

"Organic carbon" or "organic material" refers to heterogeneous compounds such as carbon dioxide, carbide, carbon disulfide, etc .; three kinds of compounds such as metal cyanide, metal carbonyl, phosgene, carbonyl sulfide, etc .; and metal carbonates such as alkali and alkaline earth metal carbonates. Any compound of carbon except for is shown.

The term "oxidant" generally refers to one or both of a chemical substance and a physical process that assists in the movement and / or removal of one or more electrons from the substance. The material from which one or more electrons are removed is oxidized. From a physical process standpoint, the physical process is to assist in the removal and / or removal of one or more electrons from the oxidized material. For example, the substance to be oxidized may be oxidized by the electromagnetic energy when the interaction with the electromagnetic energy and the substance to oxidize is sufficient to substantially remove one or more electrons from the substance. On the other hand, if the interaction of electromagnetic energy and the oxidized material is sufficient to remove one or more electrons, but is sufficient to excite the electrons to a higher energy state, the electrons in the excited state may be one or more chemicals, thermal energy, or It can be easily removed by the etc.

The term "oxyanions" and / or "oxo-anion" is usually a general formula A _x O _y ^{z -} a

It means an anionic chemical compound with a negative charge (where A is a non-oxygen chemical element, “O” is an oxygen element and x, y and z are real). In embodiments having an oxyanion as the chemical contaminant, “A” represents a metal, metalloid, and / or non-metallic element. Examples of metal based oxyanions include chromate, tungstate, molybdate, aluminate, zirconate and the like. Examples of metalloid based oxyanions include arsenates, arsenites, antimonates, germanium salts, silicates and the like. Examples of non-metal based oxyanions include phosphates, selenates, sulfates, and the like. Preferably, the oxyanions are atomic number 7, 13-17, 22-26, 31-35, 40-42, 44, 45, 49-53, 72-75, 77, 78, 82, 83 85, 88, And 92 elemental oxyanions. These elements are nitrogen, aluminum, elemental, phosphorus, sulfur, chlorine, titanium, vanadium, chromium, manganese, barium, arsenic, selenium, bromine, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, indium, tin Iodine, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, iridium, platinum, lead, bismuth astatin, radium, and uranium.

The terms “oxy species” and / or “oxo species” generally refer to cationic, anionic, or neutral chemical compounds having the general formula A _x O _y (where A is a chemical element other than oxygen and O is oxygen Element and x and y are real) In embodiments having oxyanions as chemical contaminants, “A” represents a metal, metalloid, and / or non-metallic element Oxy anion or oxo anion represents an oxy species or It is a type of oxo species.

The term "polish" refers to any process, such as filtration, for removing small (usually fine) particulate matter or very low concentrations of soluble targets in water.

The terms "pore volume" and "pore size" are each pore volume and pore size determined by any suitable measuring means. Preferably, the pore size and pore volume are determined by any suitable Barrett-Joyner-Haleda method for determining pore size and volume. It can also be understood that the pore size and pore diameter used herein can be used interchangeably.

“Sedimentation” generally means removing the soluble target in the form of an insoluble target-containing rare earth composition. The target-containing rare earth composition includes a target-containing cerium (IV) composition, a target-containing rare earth-containing additive composition, a target-containing rare earth composition comprising cerium (IV) and other rare earths, or a combination thereof. Typically, the target-containing rare earth composition comprises an insoluble target-containing rare earth composition. For example, “precipitation” includes processes for adsorption and absorption of a target material by, for example, one or more cerium (IV) compositions, rare earth-containing additives, or rare earths other than cerium (IV). The target-material containing composition comprises +3 rare earths, such as cerium (III), lanthanum (III) or other lanthanides in the +3 oxidation state.

“Primary species” generally means that cations exist as the main species under certain conditions. Although commonly applied to cations, the term “major species” can be negatively charged or non-charged.

"Radial" generally refers to an atomic group that is bonded together in an atom or some specific spatial structure and generally participates in chemical reactions in a single unit. A radical is more generally an atom, molecule or ion (which may be an atom group) having one or more hole electrons. The radical may be net positive or negative charge or neutral.

"Rare earth" refers to one or more of yttrium, scandium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. As will be appreciated, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and ruthetium are known as lantanoids.

The terms “rare earth”, “rare earth-containing composition”, “rare earth-containing additive” and “rare earth-containing particles” refer to both single and plural forms. By way of example, the term “rare earth” refers to a single rare earth and / or rare earth combination and / or mixture and the term “rare earth-containing composition” refers to a single composition comprising a single rare earth and / or different rare earth-containing containing one or more rare earths. A single composition containing a mixture of compositions and / or one or more rare earths. The terms “rare earth-containing additive” and “rare earth-containing particle” refer to an additive or particle comprising a single composition comprising a single rare earth and / or a mixture of different rare earth-containing compositions containing one or more rare earths and / or one or more rare earth containing single compositions Means. The term “processed rare earth composition” means any composition containing rare earths that is not a non-compositionally modified rare earth-containing mineral. That is, the "processed rare earth-containing composition" as used herein excludes naturally occurring ground rare earth-containing minerals. However, as used herein, “processed rare earth-containing compositions” include rare earth-containing minerals whose composition and chemical structure have been altered chemically for the rare earth-containing portion of the mineral. More specifically, naturally derived pulverized bassite is not considered a processed rare earth-containing composition and / or a processed rare earth-containing additive. However, rare earth-containing compositions prepared by chemical modifications to synthetically prepared bastite or naturally derived bastite are considered processed rare earth-containing compositions and / or processed rare earth-containing additives. Processed rare earths and / or rare earth-containing compositions and / or additives, in one embodiment, are synthetically prepared and not naturally derived minerals. Exemplary naturally occurring rare earth-containing minerals include bathnase stones (fluorinated carbonate minerals) and monazite stones. Other naturally occurring rare earth-containing minerals include echinite, alanite, apatite, britorite, broachite, celite, fluorcerite, fluorite, gadolinite, parishite, stilwellite, cinchite, titanite and geno Thyme, pitch blend (mixed oxide, usually U ₃ O ₈ ), branite (uranium, rare earth, iron and titanium

Composite oxides), coffeeite (urinium silicate), carnotite, phosphate uranium ore, davidite, guite, tobernitite, and uranopayne. In one composition, the rare earth-containing composition is substantially a radioactive species such as 1,2,4-15, or Group 17 elements, uranium, sulfur, selenium, tellurium, and polonium on one or more periodic tables.

The term “reducing agent”, “reducing agent” or “reducing agent” generally refers to an element or compound that provides one or more electrons to the other species or substance to be reduced. In the reduction process, the reducing agent is oxidized and other species that accept one or more electrons are reduced.

The terms "removing", "removing" or "removing" include the absorption, precipitation, conversion, detoxification, deactivation, and / or combinations of targets contained in water and / or water treatment systems.

The term “soluble” refers to a substance that is readily soluble in a fluid, such as water or another solvent. For the purposes of the present invention, it is understood that dissolution of the soluble compound necessarily takes place in minutes rather than days. In order for a substance to be considered soluble, the substance / composition must have significant solubility in the fluid such that at least about 5 g / L of the substance is dissolved in about 1 liter of fluid and stable in the fluid.

The term "absorption" refers to adsorption, absorption or both adsorption and absorption.

The term "suspension" is a heterogeneous mixture of solids and is typically in the form of particulates in the liquid phase. In suspension, the solid particulates are dispersed in discontinuous phase form in a continuous liquid phase. The term "colloid" refers to a suspension comprising solid particulates that typically do not settle out of the continuous liquid phase by gravity. "Colloid" refers to a system that typically has fine particles of about 10 to 10,000 ohmsstrong size dispersed in a continuous medium. Hereinafter, the terms "suspension", "colloid" or "slurry" will be used interchangeably to refer to one or more substances dispersed and / or suspended in a continuous liquid phase.

The term "surface area" denotes the surface area of a material and / or material as determined by any suitable surface area measurement method. Preferably, the surface area is determined by any suitable Brunauer-Emmett-Teller (BET) analysis technique for determining the surface area of the material and / or material.

The term “water treatment system” refers to containing, conveying, manipulating, physically delivering, chemically treating, mechanically treating, purifying, generating and / or forming an aqueous composition, and treating, mixing and / or co-mixing an aqueous composition with one or more other waters. And any system in which any combination thereof is implemented.

“Water treatment system element” means one or more unit operations and / or portions of equipment (such as sewage tanks, reactors, septic tanks, treatment tanks or units, mixing tanks or elements, washing circuits, settling tanks, separation tanks, or Units, sedimentation tanks or tanks, reservoirs, pumps, aeration tanks, cooling towers, heat exchangers, valves, boilers, filtration devices, solid and / or gas phase liquid separators, nozzles, tenders, etc.), unit operations and / or equipment interconnections. By conduits (eg pipes, hoses, channels, water pipes, ditches, etc.) and water carried by the conduits. The water treatment system elements and conduits are in fluid communication.

The terms "water" and "water treatment system" are used interchangeably. That is, the term "water" may be used to denote "water treatment system" and the term "water treatment system" may be used to denote the term "water".

The foregoing is a simplified summary provided to assist in understanding some aspects disclosed. This summary is not an extensive and exhaustive overview of the invention and the various embodiments. It is not intended to clarify the essential and critical elements of the disclosed subject matter or to delineate the scope of the disclosed subject matter, but rather as a guide to the more detailed description presented below, for the purpose of presenting the concepts selected in the disclosed subject matter in a simplified form. It is to be understood that other embodiments of the invention may be applied alone or in combination with one or more of the features described above or below. The metal or metalloid has an atomic number selected from the group consisting of 5, 13, 22-33, 40-52, 72-84, and 89-94.

survey

As shown in FIG. 1, the present invention relates to a water, water treatment system, or detoxification and / or water treatment system of an aqueous medium or other aqueous medium by a rare earth-containing composition, additive, or particles, or from an aqueous medium or other aqueous medium. To a target material or species containing a target material such as contaminants or contaminants. Preferably, the rare earth-containing composition, additives, or particles are processed rare earth-containing compositions, additives or particles. In some embodiments, the target or target-containing species are removed and / or detoxified by forming a target-containing rare earth-containing composition comprising the target, target-containing species, or derivatives thereof. The target material is one or more inorganic oxy species (not oxyanions), hydroxide ions or hydroxide radicals that are hydroxide radicals, hydrated species, or combinations thereof. Rare earth-containing compositions may be soluble or insoluble and are usually cerium, cerium-containing compounds, lanthanum, lanthanum-containing compounds, or mixtures thereof. More generally the rare earth-containing compositions are cerium (IV) oxide, cerium (III) oxide, cerium (IV) salt, cerium (III) salt, lanthanum (III) oxide, lanthanum (III) salt, or mixtures thereof. . The target-containing rare earth composition includes one or more targets and / or species thereof or portions of the targets and / or species thereof.

Rare earth-containing additives

The rare earth-containing compositions, additives, and / or particles may comprise rare earth-containing compositions, additives, and / or particles, partially water-soluble rare earth-containing compositions, additives, and / or water-soluble, water-insoluble, water-soluble and / or water-insoluble combinations. Or particles, and / or partially water-insoluble rare earth-containing compositions, additives and / or particles.

Typically, the rare earth-containing compositions, additives, and / or particles comprise cerium-containing compounds and / or cerium in the form of dissociation ions, lanthanum-containing compounds and / or lanthanum in the dissociation ion form, or mixtures thereof. More generally rare earth-containing compositions, additives, and particles include cerium (IV) oxide, cerium (III) oxide, cerium (IV) salt, cerium (III) salt, lanthanum (III) oxide, lanthanum (III) salt, Or mixtures and / or combinations thereof.

The rare earth-containing compositions, additives, and / or particles contain one or more rare earths and may be in any suitable form, such as a free-flowing powder, liquid composition, or other form. Exemplary rare earth-containing compositions, additives, and particles include cerium (III) oxides, cerium (IV) oxides, cerium (IV) salts such as cerium chloride, cerium bromide, cerium iodide, cerium sulfate , Cerium nitrate, cerium chlorate, and cerium oxalate), cerium (III) salts (such as cerium chloride, cerium bromide, cerium iodide, cerium sulfate, cerium nitrate, Cerium chlorate and cerium oxalate), lanthanum (III) oxide, lanthanum (III) salts (such as lanthanum chloride, lanthanum bromide, lanthanum iodide, lanthanum chlorate, lanthanum sulfate, lanthanum oxalate, and lanthanum nitrate), and these It contains a mixture of.

The rare earth and / or rare earth-containing compositions in the rare earth-containing additive may be rare earths in the form of elements, ions or compounds. The rare earth and / or rare earth-containing compositions may be contained in a fluid, such as water, or in the form of nanoparticles, particles larger than nanoparticles, aggregates, or aggregates or combinations and / or mixtures thereof. Rare earth and / or rare earth-containing compositions may or may not be supported. Rare earth and / or rare earth-containing compositions may include one or more rare earths. Rare earths may be of the same or different valences and / or oxidation states and / or numbers. The rare earth may be a mixture of different rare earths, such as two or more yttrium, scandium, cerium, lanthanum, praseodymium, and neodymium.

The rare earth and / or rare earth-containing composition, in one aspect, is a processed rare earth-containing composition or is substantially free or free of naturally occurring and / or generated minerals. In one composition, the rare earth and / or rare earth-containing compositions are substantially free of one or more elements of groups 1, 2, 4-15, or 17 of the periodic table, and are substantially radioactive species such as uranium, sulfur, selenium, tellurium. No rulium, and no polonium.

In some compositions, the rare earth-containing composition comprises one or more rare earths. Although not limited to the example, the rare earth-containing composition includes a first rare earth and a second rare earth. The first and second rare earths may have the same or different atomic numbers. In some compositions, the first rare earth comprises cerium (III) and the second rare earth comprises rare earth other than cerium (III). Rare earths other than cerium (III) can be one or more trivalent rare earths other than trivalent cerium, cerium (IV), or any other rare earth. For example, the mixture of rare earth-containing compositions may comprise a first rare earth in +3 oxidation state and a second rare earth in +4 oxidation state. In some embodiments, the first and second rare earths are the same and comprise cerium. More specifically, the first rare earth is composed of cerium (III) and the second rare earth is composed of cerium (IV). Preferably, cerium is mainly in the form of a water soluble cerium (III) salt, and the remaining cerium is present as cerium oxide, a substantially water insoluble cerium composition.

In one composition, cerium is mainly in the form of cerium (IV) oxide and the remaining cerium is present as the dissociated cerium (III) salt. In rare earth-containing compositions having a mixture of +3 and +4 oxidation states, at least some rare earths typically have a +4 oxidation state, more generally at least most rare earths have a +4 oxidation state, more generally at least About 75 wt% of rare earths have a +4 oxidation state, even more generally at least about 90 wt% of rare earths have a +4 oxidation state, and even more generally at least about 98 ppm, more generally at least about 10 ppm, and even more generally at least about 100 ppm of cerium (III) salt. In some embodiments, the rare earth-containing composition has at least about 0.0001 wt% cerium (III) salt, preferably at least about 0.001 wt% cerium (III) salt, more preferably at least about 0.01 wt when calculated as cerium oxide. % Cerium (III) salts. Further, in some embodiments, the rare earth composition-containing typically has at least about 20,000 ppm cerium (IV), more generally at least about 100,000 ppm cerium (IV) and even more generally at least about 250,000 ppm cerium (IV).

In some compositions, the molar ratio of cerium (IV) to cerium (III) is about 1 to about 1 × 10 ⁻⁶ , more generally about 1 to about 1 × 10 ⁻⁵ , even more generally about 1 to about 1 × 10 ⁻⁴ , even more Generally about 1 to about 1 × 10 ⁻³ , even more generally about 1 to about 1 × 10 ⁻² , even more generally about 1 to about 1 × 10 ⁻¹ , or even more generally about 1 to about 1. In addition, in some compositions the molar ratio of cerium (III) to cerium (IV) is about 1 to about 1 × 10 ⁻⁶ , more generally about 1 to about 1 × 10 ⁻⁵ , and more generally about 1 to about 1 × 10 ⁻⁴ , Even more generally about 1 to about 1 × 10 ⁻³ , even more generally about 1 to about 1 × 10 ⁻² , even more generally about 1 to about 1 × 10 ⁻¹ , or even more generally about 1 to about 1. These molar ratios also apply to any combination of Ce (III) in soluble and insoluble form and Ce (IV) in soluble and insoluble form.

In one composition, cerium is mainly in the form of dissociated cerium (III) salts and the remaining cerium is present as cerium (IV) oxide. In rare earth-containing compositions having a mixture of +3 and +4 oxidation states, at least some rare earths typically have a +3 oxidation state, more generally at least most rare earths have a +3 oxidation state, more generally at least About 75 wt% of rare earths have a +3 oxidation state, even more generally at least about 90 wt% of rare earths have a +3 oxidation state, and even more generally at least about 98 wt% of rare earths have a +3 oxidation state. Has Rare earth-containing compositions typically comprise at least about 1 ppm, more generally at least about 10 ppm, and even more generally at least about 100 ppm cerium (IV) oxide. In some embodiments, the rare earth-containing composition, as calculated from cerium oxide, has at least about 0.0001 wt% cerium (IV), preferably at least about 0.001 wt% cerium (IV) more preferably at least about 0.01 wt% cerium ( IV). Further, in some embodiments, the rare earth-containing composition typically has at least about 20,000 ppm cerium (III), more generally at least about 100,000 ppm cerium (III) and even more generally at least about 250,000 ppm cerium (III). .

In some compositions, the molar ratio of cerium (III) to cerium (IV) is about 1 to about 1 × 10 ⁻⁶ , more generally about 1 to about 1 × 10 ⁻⁵ , even more generally about 1 to about 1 × 10 ⁻⁴ , even more common About 1 to about 1 × 10 ⁻³ , even more generally about 1 to about 1 × 10 ⁻² , even more generally about 1 to about 1 × 10 ⁻¹ , and in some compositions the molar ratio of cerium (IV) to cerium (III) Is about 1 to about 1X10 ^-6 , more typically about 1 to about 1X10 ^-5 , even more generally about 1 to about 1X10 ^-4 , even more generally about 1 to about 1X10 ^-3 , even more generally about 1 to about 1 × 10 ⁻² , even more generally about 1 to about 1 × 10 ⁻¹ , or even more generally about 1 to about 1. These molar ratios also apply to any combination of Ce (III) in soluble and insoluble form and Ce (IV) in soluble and insoluble form.

It may be advantageous to have a mixture of +3 and +4 cerium in the form of dissociated cerium (III) salts and cerium (IV) compositions. Preferred, non-limiting exemplary cerium (IV) compositions are: cerium (IV) dioxide, cerium (IV) oxide, cerium (IV) oxyhydroxide, cerium (IV) hydroxide, and hydrous cerium (IV) oxide. For example, having dissociated cerium (III) is advantageous for absorption and / or precipitation chemistry of cerium (III) solutions, such as, but not limited to, formation of insoluble cerium oxyanion compositions. Having a cerium (IV) composition also favors the absorption and oxidation / reduction reactions of cerium (IV), such as strong interactions with cerium (IV) and compositions such as metal and / or metalloid target-containing species. . Cerium 2 (IV) is also commonly referred to as cerium (+4) and / or second cerium.

In one composition, the rare earth composition comprises a water soluble rare earth composition having a +3 oxidation state. Non-limiting examples of suitable water soluble rare earth compositions include rare earth chloride, rare earth bromide, rare earth iodide, rare earth astide, rare earth nitrate, rare earth sulfate, rare earth oxalate, rare earth perchlorate, rare earth carbonate, and mixtures thereof. In one composition, the rare earth-containing additive comprises a water soluble cerium (III) and lanthanum (III) composition. In some embodiments, the water soluble cerium composition comprises cerium (III) chloride, CeCl 3. Usually, cerium (III) is also called cerium (+3) and / or first cerium.

More preferably, the rare earth composition comprises a water soluble cerium +3 composition. Non-limiting examples of suitable water soluble cerium +3 compositions are cerium (III) chloride, cerium (III) nitrate, cerium (III) sulfate, cerium (III) oxalate, and mixtures thereof.

In some compositions, the water soluble cerium (III) composition includes, in addition to cerium, one or more other water soluble rare earths. Rare earths other than cerium include yttrium, scandium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Other rare earths may or may not be water soluble.

In some compositions, the water soluble cerium-containing additive contains water soluble cerium (III) and one or more other water soluble trivalent rare earths (eg, but not limited to, one or more lanthanum, neodymium, praseodymium, and samarium). The molar ratio of cerium (III) to other trivalent rare earths is usually at least about 1: 1, more generally at least about 10: 1, more generally at least about 15: 1, more generally at least about 20: 1, more Generally at least about 25: 1, more generally at least about 30: 1, more generally at least about 35: 1, more generally at least about 40: 1, more generally at least about 45: 1, more Generally at least about 50: 1.

In some compositions, the water soluble cerium-containing additive contains cerium (III) and one or more water soluble lanthanum, neodymium, praseodymium, and samarium. Water soluble rare earth-containing additives typically comprise at least about 0.01 wt.% Of one or more lanthanum, neodymium, praseodymium, and samarium. Water-soluble rare earth-containing additives are typically up to about 10 wt.% La on a dry basis, more generally up to about 9 wt.% La, even more generally up to about 8 wt.% La, even more generally up to about 7 wt. % La, even more generally at most about 6 wt.% La, even more generally at most about 5 wt.% La, even more generally at most about 4 wt.% La, even more generally at most about 3 wt.% La, even more generally at most about 2 wt.% La, even more generally at most about 1 wt.% La, even more generally at most about 0.5 wt.% La, and even more generally at most about 0.1 wt.% La Has Water-soluble rare earth-containing additives are usually on a dry basis up to about 8 wt.% Nd, more generally up to about 7 wt.% Nd, even more generally up to about 6 wt.% Nd, even more generally up to about 5 wt .% Nd, more generally at most about 4 wt.% Nd, even more generally at most about 3 wt.% Nd, even more generally at most about 2 wt.% Nd, even more generally at most about 1 wt.% Nd, even more generally at most about 0.5 wt.% Nd, and even more generally at most about 0.1 wt.% Nd. Water-soluble rare earth-containing additives are usually on a dry basis up to about 5 wt.% Pr, more generally up to about 4 wt.% Pr, even more generally up to about 3 wt.% Pr, even more generally up to about 2.5 wt % Pr, even more generally at most about 2.0 wt.% Pr, even more generally at most about 1.5 wt.% Pr, even more generally at most about 1.0 wt.% Pr, even more generally at most about 0.5 wt.% Pr, even more generally at most about 0.4 wt.% Pr, even more generally at most about 0.3 wt.% Pr, even more generally at most about 0.2 wt.% Pr, and still more generally at most about 0.1 wt.% Pr Has Water-soluble rare earth-containing additives are typically up to about 3 wt.% Sm on a dry basis, more generally up to about 2.5 wt.% Sm, even more generally up to about 2.0 wt.% Sm, even more generally up to about 1.5 wt. .% Sm, even more generally at most about 1.0 wt.% Sm, even more generally at most about 0.5 wt.% Sm, even more generally at most about 0.4 wt.% Sm, even more generally at most about 0.3 wt.% Sm, even more generally at most about 0.2 wt.% Sm, even more generally at most about 0.1 wt.% Sm, even more generally at most about 0.05 wt.% Sm, and still more generally at most about 0.01 wt.% Sm Has

In some compositions, the water soluble cerium-containing additive contains water soluble cerium (III) and one or more other water soluble trivalent rare earths (eg, one or more lanthanum, neodymium, praseodymium, and samarium). The molar ratio of cerium (III) to other trivalent rare earths is usually at least about 1: 1, more generally at least about 10: 1, more generally at least about 15: 1, more generally at least about 20: 1, more Generally at least about 25: 1, more generally at least about 30: 1, more generally at least about 35: 1, more generally 50: 1.

In one composition, the rare earth-containing additive is substantially a water soluble cerium (III) salt such as cerium (III) chloride, cerium (III) bromide, cerium (III) iodide, cerium (III) astide, cerium perhalogen Cargo, cerium (III) carbonate, cerium (III) nitrate, cerium (III) sulfate, cerium (III) oxalate and mixtures thereof. Rare earth in this composition is usually predominantly cerium (III), and more generally at least about 75 mole% of rare earth of rare earth-containing additive is cerium (III), i.e. at most about 25 mole% of rare earth of rare earth-containing additive It consists of rare earths other than cerium (III). Even more generally, rare earths in this composition are usually predominantly at least about 80 mol% cerium (III), even more generally at least about 85 mol% cerium (III), even more generally at least about 90 mol% cerium (III), And even more generally at least about 95 mol% cerium (III).

Rare earth compositions include water-insoluble compositions such as water-insoluble rare earth oxides, oxyhydroxides, and / or hydrous oxides. Insoluble rare earth compositions can be in the form of dispersion, suspension or slurry of rare earth particulates. The average particle size of rare earth particulates can be less than 1 micron to greater than microns or microns. The surface area of the insoluble rare earth composition is at least about 1 m ² / g. Typically, the insoluble rare earth has a surface area of at least about 70 m ² / g. In other compositions, the surface area of the insoluble rare earth composition is from about 25 m ² / g to about 500 m ² / g.

In some compositions, the rare earth composition may aggregate. Typically, rare earth compositions may be in the form of aggregates, including polymeric binders and rare earth-containing compositions.

In one composition, the rare earth-containing additive comprises a rare earth and / or rare earth-containing composition, and the composition comprises at least some water insoluble cerium (IV) and water soluble cerium (III) and / or lanthanum (III). Rare earth and / or rare earth-containing compositions typically comprise at least some water soluble cerium (III) in the form of a water soluble cerium (III) salt. Typically, the rare earth-containing additive is more than about 1 wt.% Water soluble cerium (III) composition, more generally greater than about 5 wt.% Water soluble cerium (III) composition, even more generally greater than about 10 wt.%. Water soluble cerium (III) composition, even more generally greater than about 20 wt.% Water soluble cerium (III) composition, even more generally greater than about 30 wt.% Water soluble cerium (III) composition, or even more generally about 40 greater than wt.% water soluble cerium (III) compositions.

According to some compositions, the rare earth-containing additive typically comprises more than about 50 wt.% Water soluble cerium (III) composition, and more typically the rare earth-containing additive is more than about 60 wt.% Water soluble cerium (III) composition. And, more typically, the rare earth-containing additive comprises more than about 65 wt.% Water soluble cerium (III) composition, and even more typically, the rare earth-containing additive is more than about 70 wt.% Water soluble cerium (III) composition. And, more typically, the rare earth-containing additive comprises more than about 75 wt.% Water soluble cerium (III) composition, and even more typically, the rare earth-containing additive is more than about 80 wt.% Water soluble cerium (III) composition. And, more typically, the rare earth-containing additive comprises more than about 85 wt.% Water soluble cerium (III) compositions, and even more typically, the rare earth-containing additive is more than about 90 wt.% A soluble cerium (III) composition, even more typically a rare earth-containing additive comprising more than about 95 wt.% Water soluble cerium (III) compositions, even more typically a rare earth-containing additive of more than about 98 wt.%. A water soluble cerium (III) composition, even more typically the rare earth-containing additive comprises more than about 99 wt.% Water soluble cerium (III) composition, or even more typically about 100 wt.% Water soluble cerium (III) Composition.

In some compositions, the rare earth-containing additive includes one or more nitrogen-containing materials. One or more nitrogen-containing materials are typically at least one ammonia, ammonium-containing composition, primary amine, secondary amine, tertiary amine, amide, cyclic amine, cyclic amide, polycyclic amine, polycyclic amide, and their Combinations. Nitrogen-containing materials are typically less than about 1 ppm, less than about 5 ppm, less than about 10 ppm, less than about 25 ppm, less than about 50 ppm, less than about 100 ppm, less than about 200 ppm, about 500 of the water-soluble rare earth-containing additive. less than about ppm, less than about 750 ppm or less than about 1000 ppm. Typically, rare earth-containing additives comprise water soluble cerium (III) and / or lanthanum (III) compositions. More generally, rare earth-containing additives include cerium (III) chloride. Rare earth-containing additives are typically soluble in liquids. The liquid in which the rare earth-containing additive is dissolved is preferably water.

In some compositions, the rare earth-containing additive is in the form of one or more of the following: an aqueous solution containing the rare earth and / or rare earth-containing composition in substantially dissociated, dissolved form; Free flowing granules, powders, particles, and / or particulates of rare earth and / or rare earth-containing compositions containing at least some water soluble cerium (III); Free-flow flocculating granules, powders, particles, and / or particulates of rare earth and / or rare earth-containing compositions that are substantially free of binder and contain at least some water soluble cerium (III); The binder and one or both are free flowing flocculating granules, powders, particles, and / or particulates, including rare earth and / or rare earth-containing compositions containing at least some water soluble cerium (III) in agglomerated and unaggregated form; Rare earth and / or rare earth-containing compositions containing at least some water soluble cerium (III) and supported on a support; And combinations thereof.

In rare earth-containing composition particle forms, in one composition, the particle size is from about 1 nanometer to about 1,000 nanometers. In other embodiments the particle size is less than about 1 nanometer. In another embodiment, the particle size is about 1 micrometer to about 1,000 micrometers.

For rare earth and / or rare earth-containing compositions supported on the support, suitable supports include porous and fluid permeable solids having the desired shape and physical dimensions. The support may be, for example, sintered ceramic, sintered metal, micro-porous carbon, glass fiber, cellulose fiber, alumina, gamma-alumina, activated alumina, acidified alumina, labile anion containing metal oxide, crystalline aluminum silicate such as zeolite, amorphous Silica-alumina, ion exchange resins, clays, ferric sulfate, porous ceramics, and others. Such supports may be in the form of meshes, such as screens, tubes, honeycomb structures, monoliths, and various types of blocks, including cylindrical and donut shaped. The support structure depends on the application. Suitable support structure forms include woven supports, nonwoven supports, porous membranes, filters, fabrics, fibers, or other fluid permeable structures. The rare earth-containing additive may be bonded or applied to a filter block or monolith for use as a filter, such as a crossflow type filter. Rare earth and / or rare earth-containing additives may be in the form of particles that are applied or bonded to the support. In some configurations, rare earth and / or rare earth-containing additives may ionically replace cations in the support. Typically, the rare earth-coated support is at least about 0.1%, more typically 1%, more typically at least about 5%, more typically at least about 10%, more typically at least about 15%, more typically At least about 20%, more typically at least about 25%, more typically at least about 30%, more typically at least about 35%, more typically at least about 40%, more typically at least about 45% %, And more typically at least about 50% by weight of rare earth and / or rare earth-containing compositions. Typically, the rare earth-coated support will have at most about 95 weight percent, more typically at most about 90 weight percent, more typically at most about 85 weight percent, more typically at most about 80 weight percent, more typically at most about 75 weight percent, More typically at most about 70% by weight, and even more typically at most about 65% by weight of rare earth and / or rare earth-containing compositions.

In some compositions, the rare earth-containing additive comprises a rare earth-containing composition supported, applied or bonded to a support, preferably the rare earth-containing composition is in particulate form. The rare earth-containing fine particles are supported or applied to the support, for example in the presence or absence of a binder. The binder can be any suitable binder, such as the binder disclosed herein.

Also in compositions comprising rare earth-containing additives having agglomerated and / or agglomerated rare earth-containing granules, powders, particles, and / or particulates in the presence or absence of a binder, are usually average, medium, or P ₉₀ The particle size is at least about 1 um, more generally at least about 5 um, more generally at least about 10 um, even more generally at least about 25 um. In some compositions, the average, median, or P ₉₀ particle size distribution of the rare earth-containing aggregates or agglomerates may range from about 100 to about 5,000 microns; Average, medium, or P ₉₀ particle size distributions range from about 200 to about 2,500 microns; The mean, medium, or P ₉₀ particle size distribution can range from about 250 to about 2,500 microns; Or the mean, medium, or P ₉₀ particle size distribution is about 300 to about 500 microns. In other compositions, the mean, median, or P ₉₀ particle size distribution of the aggregates and / or aggregates is at least about 100 nm, in particular at least about 250 nm, more specifically at least about 500 nm, even more specifically at least about 1 um and even more specifically at least about 0.5 nm, and the mean, median, or P ₉₀ particle size distribution of the aggregates and / or aggregates may be about 1 micron or more. Also, dog

Rare earth-containing particulates in the form of discrete and / or aggregated and / or aggregated masses, in some cases,

Surface area is at least about 5 m ² / g, and in other cases at least about 10

At least about 85 m ² / g, in still other cases at least about 100 m ² / g, another

In at least about 115 m ² / g and in still other cases at least about 125

m ² / g, in other cases at least about 150 m ² / g, in other cases

At least 300 m ² / g, and in other cases at least about 400 m ² / g. part

In configurations, rare earth-containing particulates in the form of individual and / or aggregates and / or aggregates

Chair usually has a surface area of about 50 to about 500 m ² / g, or more generally about 110 to about

About 250 m ² / g. Typically, rare earth-containing aggregates are greater than 10.01 wt.%, More generally

Rare earth-containing particulates of greater than about 85 wt.%, Even more generally greater than about 90 wt.%, Even more generally greater than about 92 wt.% And even more generally from about 95 to about 96.5 wt.%. And the balance is primarily a binder. In other words, the binder is less than about 15 weight percent of the aggregate, in some cases less than about 10 weight percent, in other cases less than about 8 weight percent, in other cases less than about 5 weight percent, and yet another In less than about 3.5% by weight. In some compositions, the rare earth-containing particulates are in powder form and have aggregated nano-crystalline regions. The binder includes one or more polymers selected from the group consisting of thermosetting polymers, thermoplastic polymers, elastomeric polymers, cellulose polymers and glass. Preferably, the binder comprises a fluorocarbon-containing polymer and / or an acrylic-polymer.

In one embodiment, the rare earth-containing composition is in the form of a colloid, suspension, or slurry of particulates. Particles usually have an average, medium and / or P ₉₀ particle size of less than about 1 nanometer, more generally an average, medium and / or P ₉₀ particle size of about 1 nanometer to about 1,000 nanometers, and more generally average The median and / or P ₉₀ particle size is from about 1 micron to about 1,000 microns, even more generally the average, medium and / or P ₉₀ particle size is at least about 1,000 microns. Preferably, the mean, medium and / or P ₉₀ particle size of the microparticles is from about 0.1 to about 1,000 nm, more preferably from about 0.1 to about 500 nm. More preferably, the mean, medium and / or P ₉₀ particle size of the cerium (IV) particles is about 0.2 to about 100 nm.

In some embodiments, the average and / or median surface area of the particulates is at least about 1 m ² / g, preferably the average and / or median surface area is at least about 70 m ² / g. In other embodiments, the particulates preferably have an average and / or median surface area of about 25 m ² / g to about 500 m ² / g and more preferably, an average and / or median surface area of about 100 to about 250 m. ² / g. In some embodiments, the particulate can be in the form of one or more granules, crystals, microcrystals, and particles.

In one aspect, the microparticles typically comprise cerium (IV) as the cerium (IV) oxide. Based on the total rare earth content of the cerium (IV) particulates, the cerium (IV) weight percentage (wt.%) Is typically at least about 50 wt.% Cerium (IV), more typically at least about 60 wt.% Cerium (IV) , Even more typically at least about 70 wt.% Cerium (IV), even more typically at least about 75 wt.% Cerium (IV), even more typically at least about 80 wt.% Cerium (IV), even more typically at least about 85 wt .% Cerium (IV), even more typically at least about 90 wt.% Cerium (IV), even more typically at least about 95 wt.% Cerium (IV), even more typically at least about 99 wt.% Cerium (IV). Preferably, the cerium (IV) fine particles are substantially free of rare earths other than cerium (IV). More preferably, based on the total rare earth content of the cerium (IV) particulates, the cerium (IV) weight percentage (wt.%) Is about 100 wt.% Cerium (IV) and at least one cerium (IV) oxide, cerium (IV) ) hydroxide, cerium (IV) oxy hydroxide, cerium (IV) singer oxide, cerium (IV) singer oxy hydroxide, CeO _2, and / or _{Ce (IV) (O) w} (OH) x (OH) y · zH 2 And O, wherein w, x, y and z are zero or positive real numbers.

Medium (or Medium) (104)

Medium (or medium) 104 may be any fluid stream. The fluid stream is from any source containing one or more targets. Typically, the medium (or medium) 104 is from any aqueous source containing one or more targets. Non-limiting examples of suitable media (or media) 104 include water bath, municipal water (eg, sewage, sewage, agricultural, or groundwater), industrial water (eg, cooling water, boiler water, or process water), waste water, well water. , Purified water, drinking water, natural derived water (such as lakes, ponds, reservoirs, rivers or streams), and / or other water and / or water treatment streams.

Non-limiting examples of water baths are swimming pool water, sea baths, therapeutic baths, diving sites, sauna water, spa water, and hot spring baths. Non-limiting examples of urban water are drinking water, irrigation water, well water, agricultural water, reflective pool waters, fountain objects, water walls, urban water and other urban water. Wastewater is not limited to, but is not limited to, municipal and / or agricultural sewage, purified water, water formed and / or generated during industrial and / or manufacturing processes, water formed and / or generated in medical facilities, mines, mining, recovery and / or Treated water (including oil), evaporation pound water, and general purpose treated water. Well waters include but are not limited to underground water wells for human consumption, agricultural use (including animal consumption, crop relations or livestock consumption), mineral water, mining and oil production related water. Non-limiting examples of naturally derived water include rain, storms, streams, rivers, lakes, groundwater, estuaries, lagoons, and the like.

Medium (or medium) 104 is typically obtained from one or more of these sources and processed, conveyed and / or manipulated by a water treatment system. The medium (or medium) is mainly water in the water treatment system.

Water treatment system components and configurations depend on the treatment process, water and water source. Although not limited to an example, municipal water and / or wastewater treatment systems typically have one or more of the following treatment units: sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, biodigestion, and polishing. The number and order of the processing units can be changed. In addition, some treatment units may occur more than once in a water treatment system. It will be appreciated that one or more processing units are in fluid communication.

Water treatment systems may or may not have sedimentation basins. Some water treatment systems may have one or more settling baths, such as a main settling bath and a final settling bath. Sedimentation baths typically reduce the turbidity of water by removing biological material (such as bacteria and / or algae), suspended and / or dispersed chemicals and / or particulates from the water. The purification process usually proceeds before and / or after the filtration treatment.

The water treatment system may or may not have a filtration process. Typically, the water treatment system has at least one filtration process. Non-limiting examples of common filtration processes include, but are not limited to, screen filtration, sprinkling filtration, particulate filtration, sand filtration, macro-filtration, micro-filtration, ultra-filtration, nano-filtration, reverse osmosis, carbon / active carbon filtration, two-layer Filtration, gravity filtration, and combinations thereof. Filtration is usually carried out before and / or after the disinfection process. For example, filtration to remove solid debris such as solid organics and gravel from water typically precedes the disinfection process. In some embodiments, the filtration process, such as activated carbon and / or sand filtration, follows the disinfection process. The post-sterilization filtration process removes at least some chemical disinfectants remaining in the treated water.

The water treatment system may or may not include a disinfection process. Disinfection processes include, but are not limited to, aqueous streams and / or water containing one or more fluorine, fluorinated, chlorine, chlorinated, bromine, brominated, iodine, iodide, ozone, ozonated, electromagnetic radiation, UV, gamma rays, electrolysis , chlorine dioxide, hypochlorite, heat, ultrasound, samyeomhwayi SOCCIA nulsan, soap / detergent, alcohol, chlorinated bromine (BrCl), copper ion (Cu ^{2 +),} silver, silver ions (Ag ^+), permanganate, phenol, and Treatment with a combination thereof. Preferably

The water treatment system has a single disinfection process, more preferably the water treatment system has two or more disinfection processes. Disinfection processes are typically provided to remove, sterilize and / or detoxify at least waterborne pathogens. Typically, pathogenic substances consist of biological contaminants, particularly biological contaminants, including targets. In some embodiments, the disinfection process converts the target species into a rare earth-containing composition, additives, and / or species that can be removed and / or detoxified into particles or particulates.

The water treatment system may or may not include a flocculation process. The water treatment system has one or more flocculation processes. Typically, the flocculation process involves adding flocculants to the water of the water treatment system. Typical tangles include aluminum sulfate, polyelectrolytes, polymers, lime and ferric chloride. The flocculant agglomerates the suspended and / or dispersed particulates in flocculation, and the flocculating particulate material forms a coagulum. The agglomeration process may or may not include the step of separating the coagulant from the liquid phase. In some embodiments, the coagulation process constitutes a partial, all, total purification process. In other embodiments, the flocculation process is separate and distinct from the purification process. Typically, the coagulation process is performed before the disinfection process.

The water treatment system may or may not contain aeration. In water treatment systems, aeration involves passing air and / or oxygen molecule streams into the water of the water treatment system. The aeration process promotes the oxidation of contaminants contained in the water treated in the water treatment system, and preferably the aeration promotes oxidation of biological contaminants, such as targets. In some embodiments, the aeration process converts the target species into a species that can be removed and / or detoxified by the rare earth-containing composition, additives, and / or particles or particulates. The water treatment system has one or more aeration processes. Typically, the disinfection process is followed by an aeration process.

The water treatment system may or may not have one or more heaters, coolers, and heat exchangers for heating and / or cooling the water treated by the water treatment system. The heater may be in any manner suitable for water heating. Non-limiting examples of suitable heat treatments include solar heating systems, electromagnetic heating systems (eg, induction heating, microwave heating and infrared), input heaters, and heat transfer heating systems (eg, combustion, streams, hot oils and others, where thermal The heating source is hotter than water and heats up by transferring heat to the water). The heat exchanger may be in any way capable of transferring thermal energy to or from water. The heat exchanger removes thermal energy from the water to cool the water and / or lower the temperature. In addition, the heat exchanger transfers thermal energy to water to raise the temperature of the heating and / or water. The cooler can be in any manner suitable for cooling the water. Non-limiting examples of suitable cooling methods include cooling processes, evaporative coolers, and thermoshear cooling systems (eg chillers, etc.) where the heat (cooling) source is lower than water and removes heat from the water to lower the temperature of the water. )to be. Any purification, disinfection, flocculation, aeration, filtration, sludge treatment, digestion, nutrient control, solid / liquid separation, and / or polish processes may also and / or before, after, or during one or both of the heating or cooling processes. Include. It will be appreciated that the heat exchanger typically includes at least one heating and cooling process.

The water treatment system may or may not include a digestion process. Typically, the digestion process is either anaerobic or aerobic digestion. In some configurations, the digestion process includes an anaerobic or aerobic digestion process followed by another anaerobic or aerobic digestion process. For example, one such configuration may be aerobic digestion followed by anaerobic digestion. Typically, digestion processes involve microorganisms that degrade biological degradants in water. In some embodiments, the biodegradant comprises a target material. The digestion process also converts the target species into a species that can be removed and / or detoxified by the rare earth-containing composition, additives, and / or particles or particulates. Anaerobic digestion for biodegradants proceeds in the absence of oxygen, and aerobic digestion for biodegradants occurs in the presence of oxygen. In some water treatment systems the digestion process is typically referred to as a biological stage / degradation tank or a biological treatment stage / degradation tank. Also, in some systems the disinfection process includes a fire extinguishing process.

Water treatment systems may or may not include nutrient control processes. The water treatment system also includes one or more nutrient control processes. Nutrient control processes typically include nitrogen and / or phosphorus control. In addition, nitrogen regulation usually includes nitrifying bacteria. Typically, phosphorus regulation is referred to as biological regulation and preferably regulates phosphorus used as algal impact. Nutrient control typically includes processes associated with the control of oxygen requirements, including nutrients, pathogens, and inorganic and synthetic organic compositions. The nutrient control process takes place either before or after disinfection. In some embodiments, the nutrient control process converts the target species into a rare earth-containing composition, additives, and / or species that can be removed and / or removed by particles or particulates.

The water treatment system may or may not include a solid / liquid separation process. Preferably, the water treatment system comprises one or more solid / liquid separation processes. Solid / liquid separation processes include any process of separating a solid phase from a liquid phase such as water. Non-limiting examples of suitable solid phase liquid phase separation processes include sedimentation (including water filtration), filtration (as above), vacuum and / or pressure filtration, cyclones (including liquid cyclones), flotation, precipitation (including gravity precipitation), flocculation (As above), precipitation (including but not limited to sedimentation tanks), and combinations thereof.

The water treatment system may or may not include a policy process. The policy process includes removing one or more fine particulates from water, an ion exchange process for softening the water, adjusting the pH of the water, or a combination thereof. Typically, the polishing process is after a disinfection step.

Water treatment systems typically include one or more sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and polishing processes, but the water treatment system may further comprise additional treatment facilities. Additional treatment facilities include, but are not limited to, storage tanks, reactors, septic tanks, treatment tanks or units, mixing tanks or elements, washing circuits, settling tanks, separation tanks or units, sedimentation tanks or tanks, reservoirs, pumps, aeration tanks, cooling towers, heat exchangers, Valves, boilers, gas phase liquid phase separators, nozzles, tenders, and the like. Water treatment systems also include but are not unitary pipes, hoses, channels, water pipes, drains, etc. Water is conveyed to and from the unit operation and / or further treatment facilities by conduit (s). In addition, each unit operation and / or additional processing facility is in fluid communication with other unit operations and / or additional processing facilities by conduits.

Target substance

The aqueous medium treated with the rare earth-containing composition, additives, and / or particles contains one or more targets. One or more target-containing species include various forms of metals (except scandium, yttrium and lanthanides), metalloids, and / or radioactive isotopes. In some aqueous media, target-containing species include, but are not limited to, hydrated metals (including but not limited to alkali metals, alkaline earth metals, actinium elements, transition metals, and post-transition metals and exclude scandium, yttrium and lanthanides) ), semi-metal, and / or a radioactive isotope, hydrated metal, metalloid, or, for negative ions, positive ions, or a net-free charges (for example, a radioactive isotope, M _a O _x ^{n +} or M _a O _x ⁰ wherein 0 Oxy species, positive, negative, or non-charged metals, metalloids, or radioisotope carbonates (eg, Mc (CO ₃ )) in the form <a ≦ 4, 0 <x ≦ 4, and 0 <n ≦ 6) _{y in} formula 0 <c ≤ 4 and 0 <y ≤ 4), or positive, negative, or non-charged metal, metalloid, or radioisotope hydroxide species (especially metal or metalloid hydroxides (e.g. M (OH) ) _z wherein 0 <z ≤ 8)), positive and negative, uncharged metal, metalloid, or a radioactive isotope oxy-hydroxide species and their souls It includes water. The target-containing species may be in solid, soluble species, or suspended form.

In some embodiments, the rare earth-containing composition removes a target that is anionic, cationic, oxy, hydroxide, hydrated, or a combination thereof, wherein the target “M” has an atomic number of 5, 13, 22 -33, 40-52, 72-84, and 89-94. Exemplary hydrated hydroxylated and hydrated oxycompounds (which may be anionic, neutral or cationic and are represented by the symbol “MS” below) include, but are not limited to M (H ₂ O) ₆ ⁿ , M (H ₂ O) ₅ OH ^{( n-1)} , M (OH) ^(n-1) , M (H ₂ O) ₄ (OH) ₂ ^(n-2) , M (OH) ₂ ^(n-2) , M (H ₂ O) ₃ (OH) ₃ ^(n-3) , M (OH) ₃ ^(n-3) , M (H ₂ O) ₂ (OH) ₄ ^(n-4) , M (OH) ₄ ^(n-4) , M (H ₂ O) (OH) ₅ ^(n-5) , M (OH) ₅ ^(n-5) , M (OH) ₆ ^(n-6) , M (H ₂ O) ₅ O ^(n-2) , MO ^(n-2) , M (H ₂ O) ₄ (O) ₂ ^(n-4) , MO ₂ ^(n-4) , M (H ₂ O) ₃ (O) ₃ ^(n-6) , MO ₃ ^(n-6) , M (H ₂ O) ₂ (O) ₄ ^(n-8) , MO ₄ ^(n-8) , M (H ₂ O) (O) ₅ ^(n-10) , MO ₅ ^(n-10) , MO ₆ ^(n-12) , M (H ₂ O) ₅ CO ₃ ^(n-2) , MCO ₃ ^(n-2) , M (H ₂ O) ₄ (CO ₃ ) ₂ ^(n-4) , M (CO ₃ ) ₂ ^(n-4) , M (H ₂ O) ₃ (CO ₃ ) ₃ ^(n-6) , M (CO ₃ ) ₃ ^(n-6) , M ( H ₂ O) ₂ (CO ₃ ) ₄ ^(n-8) , M (CO ₃ ) ₄ ^(n-8) , M (H ₂ O) (CO ₃ ) ₅ ^(n-10) , M (CO ₃ ) ₅ ^(n-10) , M (CO ₃ ) ₆ ^(n-12) , M (H ₂ O) ₄ ⁿ , M (H ₂ O) ₃ OH ^(n-1) , M (H ₂ O) ₂ ( OH) ₂ ^(n-2) , M (H ₂ O) (OH) ₃ ^(n-3) , M (H ₂ O) ₃ O ^(n-2) , M (H ₂ O) ₂ (O) ₂ ^(n-4) , M (H ₂ O) (O) ₃ ^{( n-6)} and M (O) ₄ ^(n-8) . Where n is a real number of 8 or less and represents the charge or oxidation state of the metal or metalloid “M” (eg n is 2 if M is Pb (II) and n is 4 if M is Pb (IV) to be). In general, M has a positive charge and “n” is about 8 or less.

Full bay diagrams for each of the metal, metalloid, and radioisotope are shown in FIGS. 2-47. 2-47 show the main species of target in aqueous solutions of different thermodynamic conditions. Referring to FIG. 39, the target substance lead has the following species: Pb (H ₂ O) ₆ ²⁺ , Pb (H ₂ O) ₄ (O) ₂ , Pb (H ₂ O) ₅ CO ₃ , Pb _{(H 2 O) 4 (CO} 3) 2 2-, Pb (H 2 O) 3 (OH) 3 -, Pb (H 2 O) 4 (OH) 2, Pb (H 2 O) 2 (OH) 4 ^2- , and Pb (H ₂ O) (O) ₃ ^2- . The state of the lead compound (solid (s) or aqueous (aq)) is shown in the lead full bay diagram. Typically, lead includes lead in the +2 oxidation state. Referring to Figure 27, the target antimony has the following species: Sb (H ₂ O) ₂ (OH) ₄ ^1- , Sb (H ₂ O) ₄ (OH) ₂ ¹⁺ , Sb (H ₂ O ) ₃ (OH) ₃ , Sb (H ₂ O) (OH) ₅ , and Sb (OH) ₆ ^1- . Typically, antimony includes antimony in either +5 or +3 oxidation state. Referring to FIG. 40, the target bismuth has the following species: Bi (H ₂ O) ₆ ³⁺ , Bi (H ₂ O) ₅ (OH) ²⁺ , Bi (H ₂ O) ₄ (OH) ₂ ^{1 +} , Bi (H ₂ O) ₃ (OH) ₃ , and Bi (H ₂ O) ₂ (OH) ₄ ^1- . Typically, bismuth is +5 or

Bismuth in one of the +3 oxidation states.

There are many potential mechanisms for target removal. The exact mechanism may include the rare earth-containing compositions, additives, and / or specific forms and / or properties of the particles or particulates, the specific forms and / or properties of the target material, the pH of the medium 104, the Eh of the medium 104, the medium ( 104) many variables including temperature, medium 104 internal factors, and other factors known to those skilled in the art.

Without wishing to be bound by any theory, the target material in anionic form may be combined with the rare earth-containing composition with one or more absorption, precipitation, complexing, ionic bonds (any one or more hybrid or non-hybrid s, p, d or f orbitals Internal-atomic shell complexes, covalent bonds, or a combination thereof. Anionic forms include oxyanions, hydroxides, hydrates, or combinations thereof of a target substance with a net negative charge. Without wishing to be bound by any theory, the target material optionally interacts with the face or edge of the rare earth-containing composition microparticles. Another theory not wishing to be constrained is that the anionic target forms substantially insoluble products with rare earths. Rare earths are in the form of substantially water-soluble rare earth-containing salts or substantially water-insoluble substances which strongly absorb, bind, chemically react, or otherwise absorb anionic targets.

Without wishing to be bound by any theory, there are many mechanisms for removing target materials in cation form. Cations include complexing, hydroxylation, hydration, or a combination of targets with net positive charges. Without wishing to be bound by any theory, the target material in cationic form may be selected from the rare earth-containing compositions with one or more absorption, precipitation, complexation, ionic bonds (any one or more hybrid or non-hybrid s, p, d or f orbitals Of) inner-atomic cell complexes, covalent bonds, or a combination thereof. Without wishing to be bound by any theory, the target material optionally interacts with the face or edge of the rare earth-containing composition microparticles. Another theory not wishing to be bound is that cationic targets form substantially insoluble and / or stable products with rare earth cations.

Without wishing to be bound by any theory, other potential mechanisms for the removal of anionic, cationic, or non-charged species containing the target may include compounds, complexes, other attached species such as hydrated water, hydroxide radicals, Hydroxide ions, or carbonate species, function as chemical entities that attach, absorb, and / or chemically bond to the rare earth or rare earth-containing composition. Without being bound by theory and / or explanation, possible cationic metal or metalloid adsorption processes include those shown by Formula (2):

Rare earths may be in the form of substantially water-soluble rare earth-containing salts or substantially water insoluble materials that are strongly absorbed, bound, chemically reacted or otherwise attached to the cationic target, as shown in formula (3).

Wherein the atomic number of M is usually one of 5, 13, 22-33, 40-52, 72-84, and 89-94, more generally 5, 13, 22-33, 40-52, 56, 72 , 80-84, 88, to 90-94. Although the number of hydrated water for ceria oxide is indicated as "4", it can be understood that the number of hydrated water may vary according to the field.

Without being limited to theory and further examples, possible cationic lead adsorption processes include those shown by Formula (4):

The rare earth cations may be in the form of substantially water-soluble rare earth-containing salts or substantially water-insoluble materials that are strongly absorbed, bound, chemically reacted or otherwise attached to the cationic target, as shown in formula (5).

Without wishing to be bound by any theory, another possible mechanism is that rare earth-containing additives, such as cerium (IV) oxide, oxidize the target and / or target-containing species. The contact of the rare earth-containing oxidant and the target-containing species may be one or both of: a) chemical interaction with the target-containing species and b) reduced rare earth and / or rare earth-containing oxidants and oxidized Target and / or target-containing species formation. By way of example, a first cerium-containing composition having cerium in a +3 oxidation state is contacted with an oxidant (listed below) to form a second cerium-containing composition (or cerium (IV) oxidant) having cerium in a +4 oxidation state. The cerium (IV) oxidant is thereby formed. Typically, the second cerium-containing composition species is oxidized to form a first (reduced) cerium (III) -containing composition.

Regardless of the exact mechanism, the contact of the rare earth-containing additive and the target-containing species forms a rare earth- and target-containing product. The rare earth- and target-containing product may be in the form of a water-soluble substance or a solid substance contained in water or a solid phase separated from the water. Solid rare earth- and target-containing products may be precipitates, suspended solid particles in water, aggregated solid particles, and combinations thereof.

As shown in the preceding pullbay diagrams of FIGS. 2-47, the metal or metalloid major species in solution depends on pH and Eh. The values are usually chosen such that the water is electrochemically stable and the target is a soluble (not solid) species. For example, the cationic form of lead is typically present in an aqueous medium having, but not necessarily, an Eh of less than about pH 7 and less than about +1 V as the main species. As described below, treatment with rare earth-containing compositions, additives, and / or particles or particulates results in precipitation, adsorption or otherwise removal of the metal or metalloid forms present in solution, and thus the metal or metalloid forms from the aqueous medium. The efficiency and / or aqueous medium detoxification efficiency can be substantially increased by adjusting one or both of the pH and Eh of the medium. While the efficiency of precipitating, absorbing or removing targets is illustrated for various pH and Eh values, the concept of controlling one or both of pH and Eh is based on components including interferers that are not metal and / or metalloid-containing targets. It should be understood that the present invention can also be applied to effectively remove and / or detoxify an aqueous solution.

In some embodiments, the target material is removed from an aqueous medium having a selected pH value. Typically, the selected pH value of the aqueous medium is about pH 0 to about pH 14, more generally the pH of the aqueous medium is about pH 1 to about pH 13, even more generally the pH of the aqueous medium is about pH 2 to about pH 12. In general, the pH of the aqueous medium is about pH 3 to about pH 11, even more generally the pH of the aqueous medium is about pH 4 to about pH 10, and even more generally the pH of the aqueous medium is about pH 5 to about pH. 9, or even more generally, the pH of the aqueous medium can be from about pH 6 to about pH 8.

In one embodiment, the aqueous medium typically has about pH 6 to about pH 9 at a selected pH value, and more typically the aqueous medium has about pH 6.5 to about pH 8.5.

Typically in other embodiments, the aqueous medium is substantially acidic and the selected pH is about pH 0, more generally the selected pH is about pH 1, even more generally the selected pH is about pH 2, even more generally the selected pH is about pH 3, or even more generally the selected pH is about pH 4. Even more generally in other embodiments, the aqueous medium is substantially neutral and the selected pH is about pH 5, more generally the selected pH is about pH 6, even more generally the selected pH is about pH 7, even more generally The selected pH is about pH 8, or even more generally the selected pH is about pH 9. Typically in other embodiments, the aqueous medium is substantially basic and the selected pH is about pH 10, more generally the selected pH is about pH 11, even more generally the selected pH is about pH 12, even more generally the selected pH is About pH 13, or even more generally the selected pH is about pH 14.

In some embodiments, the target material is removed from an aqueous medium having an Eh value selected for a standardized reference electrode, such as a standard hydrogen electrode (SHE). Typically, the selected Eh of the aqueous medium is at least about -0.5 V, more generally at least about -0.4 V, more generally at least about -0.3 V, more generally at least about -0.2 V, more generally at least about -0.1 V, more generally at least about 0 V, more generally at least about 0.1 V, more generally at least about 0.2 V, more generally at least about 0.3 V, and more generally at least about 0.4 V, And more generally at least about 0.5 V. Typically, the selected Eh of the aqueous medium is below the level at which the water is not electrochemically stable, more generally at most about 1.7 V, more generally at most about

1.6 V, more typically about 1.5 V maximum, more typically about 1.4 V maximum, more typically about 1.3 V maximum, more typically about 1.2 V maximum, more typically about 1.1 V maximum, more general At most about 1.0 V, more generally at most about 0.9 V, more generally at most about 0.8 V, and more generally at most about 0.7 V.

The rare earth to target ratios of insoluble rare earth- and target-containing products may also vary with solution pH and / or Eh values. That is, rare earths having a rare earth ratio of 1 or less with respect to the target material have a greater molar removal performance of target material than rare earths having a rare earth ratio of 1 or more with respect to the target material. In some embodiments, the higher the pH value, the higher the rare earth ratio for the target material. In other embodiments, the higher the pH value, the lower the rare earth ratio for the target material. In another embodiment, the rare earth ratio for the target material is substantially constant over the range of pH values. In some embodiments, the rare earth ratio to target material is at most about 0.1, the rare earth ratio to target material is at most about 0.2, the rare earth ratio to target material is at most about 0.3, and the rare earth ratio to target material is at most about 0.4, the rare earth ratio for the target substance is about 0.5, the rare earth ratio for the target substance is about 0.6, the rare earth ratio for the target substance is about 0.7, the rare earth ratio for the target substance is about 0.8, The rare earth ratio for the target substance is at most about 0.9, the rare earth ratio for the target substance is at most about 1.0, the rare earth ratio for the target substance is at most about 1.1, the rare earth ratio for the target substance is at most about 1.2, and the target substance. The rare earth ratio for is about 1.3, and the rare earth ratio for the target is about 1.4, and the rare earth for the target is The ratio is about 1.5 at maximum, the rare earth ratio to the target substance is at most about 1.6, the rare earth ratio to the target substance is at most about 1.7, the rare earth ratio to the target substance is at most about 1.8, and the rare earth ratio to the target substance is At most about 1.9, the rare earth ratio to the target substance is at most about 1.9, or the rare earth ratio to the target substance is at least about 2.0, wherein the pH value is at most about pH -2, the pH value is at least about pH -1, the pH value Is about pH 0 or more, pH value is about pH 1 or more, pH value is about pH 2 or more, pH value is about pH 3 or more, pH value is about pH 4 or more, pH value is about pH 5 or more, pH value is about pH 6 or more, pH value about pH 7 or more, pH value about pH 8 or more, pH value about pH 9 or more, pH value about pH 10 or more, pH value about pH 11 or more, pH value about pH 12 In the above, the pH value is about pH 13 or more, or the pH value is about pH 14 or more.

In some embodiments, the rare earth ratio to the target substance is at most about 0.1, the rare earth ratio to the target substance is at most about 0.2, the rare earth ratio to the target substance is at most about 0.3, and the rare earth ratio to the target substance is at most about 0.4, Rare earth ratio for the target substance is about 0.5, Rare earth ratio for the target substance is about 0.6, Rare earth ratio for the target substance is about 0.7, Rare earth ratio for the target substance is about 0.8, Rare earth ratio for the target substance Is about 0.9, the rare earth ratio for the target substance is about 1.0, the rare earth ratio for the target substance is about 1.1, the rare earth ratio for the target substance is about 1.2, and the rare earth ratio for the target substance is about 1.3, the target Rare earth ratio to substance is about 1.4, Rare earth ratio to target substance is about 1.5, Rare earth ratio to target substance Approx. 1.6 at maximum, rare earth ratio to target material at most 1.7, rare earth ratio to target material at most about 1.8, rare earth ratio to target material at most about 1.9, rare earth ratio to target material at most about 1.9, or target The rare earth ratio to the substance is at least about 2.0, wherein the water pH value is at most about pH -2, the water pH value is at least about pH -1, the water pH value is at least about pH 0, the water pH value is at least about pH 1, The water pH value is about pH 2 or more, the water pH value is about pH 3 or more, the water pH value is about pH 4 or more, the water pH value is about pH 5 or more, the water pH value is about pH 6 or more, and the water pH value is about pH 7 or more, water pH value of about pH 8 or more, water pH value of about pH 9 or more, water pH value of about pH 10 or more, water pH value of about pH 11 or more, water pH value of about pH 12 or more, water The pH value is less than about 0.1 mg target / g REO ( eg CeO ₂ ). These are much better than two

Thin Rare Earth: Has a target mass ratio. For example, 0.1 mg is 0.0001 g, thus 1 g CeO ₂ /0.0001 g target = 10,000. In these embodiments, the rare earth ratio to target material is typically at most about 50,000, the rare earth ratio to target material is more generally at most about 47,500, and the rare earth ratio to target material is more generally at most about 45,000, on target material. The rare earth ratio for the target is more generally about 42,500, the rare earth ratio for the target substance is more generally about 40,000, the rare earth ratio for the target substance is about 37,500 and the rare earth ratio for the target substance is more generally Up to about 35,000, rare earth to target material more generally up to about 35,000, rare earth to target material more typically up to about 32,500, rare earth to target material more typically up to about 30,000, target Rare earth to material ratios are more generally about 37,500, target substances The rare earth ratio for the target material is more generally about 35,000, the rare earth ratio for the target substance is more generally about 32,500, the rare earth ratio for the target substance is more generally about 30,000, and the rare earth ratio for the target substance is more Generally about 27,500 maximum, rare earth ratio to target material more generally about 25,000, rare earth ratio to target material more generally about 22,500, or rare earth ratio to target material more generally maximum About 20,000, wherein the water pH value is at most about pH -2, the water pH value is at least about pH -1, the water pH value is at least about pH 0, the water pH value is at least about pH 1, and the water pH value is about pH 2 Water pH value is about pH 3 or more, water pH value is about pH 4 or more, water pH value is about pH 5 or more, water pH value is about pH 6 or more, water pH value is about pH 7 or more, water pH value Is about pH 8 or more, water pH value About pH 9 or more, water pH value about pH 10 or more, water pH value about pH 11 or more, water pH value about pH 12 or more, water pH value about pH 13 or more, or water pH value about pH 14 or more to be.

The concentrations of target substance and target-containing species vary with many factors. One or both concentrations are, for example, usually at least about 5 ppm, more generally at least about 50 ppm, more generally at least about 100 ppm, more generally at least about 500 ppm, more generally at least about 1,000 ppm, more generally at least about 5,000 ppm, more generally at least about 10,000 ppm, more generally at least about 100,000 ppm.

Medium pre-treatment

In step 108, the medium 104 is optionally pre-treated to produce selected major species of the target material. The selected major species are generally more effectively removed by the rare earth-containing composition, additives, and / or particles as compared to the main species in the medium 104. For example, one or more Eh and pH values are altered to more efficiently remove and / or detox the target. For example, when Eh is lower than about -0.3 (more negative), one or more species of Pb (H ₂ O) ₆ ²⁺ , Pb (H ₂ O) ₅ CO ₃ , Pb (H ₂ O) ₄ (CO ₃ ) ₂ ²⁺ , Pb (H ₂ O) ₅ (OH) ₂ , or Pb (H ₂ O) ₂ (OH) ₄ ^2- . As will be appreciated, pH is a measure of activity of hydrogen ions and Eh is a measure of electrochemical (oxidation / reduction) potential.

The type of pre-treatment applied depends on the field.

In one aspect, the pH can be adjusted to the desired pH value by addition of an acid, acid equivalent, base, or base equivalent. Exemplary acids or acid equivalents include single protic and diversity assets such as inorganic acids, sulfonic acids, carboxylic acids, vinyl carboxylic acids, nucleic acids, and mixtures thereof. Exemplary bases and base equivalents are strong bases (such as potassium hydroxide, barium hydroxide, cesium hydroxide, sodium hydroxide, strontium hydroxide, calcium hydroxide, magnesium hydroxide, lithium hydroxide, and rubidium hydroxide), superbases, carbonates, ammonia, hydroxides, metal oxides (Particularly alkoxides), and counterions of weak acids.

In one aspect, the Eh value can be adjusted by oxidation and reduction reactions. Eh is an oxidation or reduction potential measurement of the medium 104. The oxidation or reduction potential is commonly referred to as electromotive force or EMF. EMF is typically measured on standardized reference electrodes. Non-limiting examples of standardized reference electrodes are, to name a few, hydrogen electrodes (commonly referred to as SHE), copper sulfate electrodes, and silver / silver chloride.

In one variation, the target or target-containing species is contacted with an oxidant to oxidize the target or target-containing species. Oxidizers include chemical oxidants, oxidation processes, or a combination of both.

Chemical oxidants include chemical compositions in the form of elements or compounds. Chemical oxidants accept electrons from targets or target-containing species. Upon receipt of the former, the oxidant is reduced to form a reduced form of the oxidant. Non-limiting examples of preferred chemical oxidants include chlorine, chloroamine, chlorine dioxide, hypochlorite, trihalomethane, haloacetic acid, ozone, hydrogen peroxide, peroxygen compounds, hypobromic acid, bromoamine, hypobromite, hypochlorous acid, Isocyanurate, trichloro-s-triazinetrione, hydantoin, bromochloro-dimethyldantoin, 1-bromo-3-chloro-5,5- dimethyldantoin, 1,3-dichloro-5, 5-dimethyldantoin, sulfur dioxide, bisulfate, and combinations thereof. It is also believed that in some configurations one or more of the following chemical compositions oxidize the target or target-containing species: bromine, BrCl, permanganate, phenol, alcohol, oxyanion, arsenite, chromate, isotrisocyanuric acid, And surfactants. Chemical oxidants are also called "oxidants" or "oxidizers."

The oxidation process includes physical methods alone or in combination with chemical oxidants. The oxidation process facilitates the removal and / or removal of electrons from the target material or target-containing species. Non-limiting examples of oxidation processes are electromagnetic energy, ultraviolet light, thermal energy, ultrasonic energy, and gamma rays.

In another variation, the target or target-containing species is contacted with a reducing agent to reduce the target or target-containing species. Oxidizers include chemical oxidants, oxidation processes, or a combination of both.

Chemical reducing agents include chemical compositions in the form of elements or compounds. Chemical reducing agents provide electrons to the target or target-containing species. Upon donating an electron, the reducing agent is oxidized to form an oxidized form of the reducing agent. Non-limiting examples of preferred chemical reducing agents include: aluminum hydride, generator (atomic) hydrogen, sodium amalgam, sodium borohydride, divalent tin ion containing compounds, sulfite compounds, hydrazine, zinc-mercury amalgam, isobutyl aluminum hydride, lindral (Lindlar) catalyst, oxalic acid, formic acid, ascorbic acid, phosphite, hypophosphite, phosphoric acid, dithiothreitol, and divalent iron ion containing compounds. Chemical reducing agents are also referred to as “reducing agents” or “reducing agents”.

The redox method is a physical method of transferring electrons to or from a target or target-containing species, alone or in combination with chemical oxidants. Non-limiting examples of oxidation methods include electromagnetic energy, ultraviolet light, thermal energy, ultrasonic energy, gamma rays, and biological methods.

In one variation, the medium is contacted with halogenated species, such as chlorine, bromine, iodine, or acids, bases, or salts thereof. As will be appreciated, halogens affect the Eh of the medium. In some configurations, halogen affects the pH value of the aqueous medium.

Another type of pre-treatment is the removal of the target or target-containing species and / or species that adversely affect the pH and / or Eh control of the medium.

Pre-treatment includes one or more sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy processes. More specifically, the pre-treatment process is typically one of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment, more generally sedimentation, disinfection, flocculation, aeration, filtration in any order. , Any two species of solid-liquid separation, digestion, and policy treatment, and more generally any three of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment, more generally Is any four types of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment, and more generally, in any order, sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, Any five species of digestion, and policy treatment, even more generally in any order, any six species of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment, even more generally any sequence Furnace sedimentation, disinfection, flocculation, aeration , Any seven species of filtration, solid-liquid separation, digestion, and policy treatment, even more generally any of eight species of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment, Generally any of the nine types of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment in any order, and more generally, sedimentation, disinfection, flocculation, aeration, filtration, solids in any order Any 10 species of separation, digestion, and policy treatment, even more generally any sequence of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment, and more generally each Sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment of the medicaments are in any order. In some configurations, the pre-treatment may include or further include treatment by one or more additional treatment facilities of the water treatment system.

Contact of medium with rare earth-containing additives

In step 112, the optionally pre-treated medium is contacted with the rare earth-containing composition, additives, or particles or particulates to form the rare earth- and target-containing product. As described, the rare earth-containing compositions, additives, and / or particles or particulates chemically and / or physically react, absorb, precipitate, chemically modify, or otherwise inert or bind to the target or target-containing species. . In one configuration, the rare earth-containing additive is at least about 25%, more generally at least about 50%, more generally at least about 50%, more generally at least about 75%, and even more generally at least about 95% Reacts, absorbs, precipitates, chemically modifies, or otherwise inactivates or combines with a target or target-containing species of. The rare earth- and target-containing products, depending on the rare earth, the target, and the involved materials, potentially comprise one or more other components or elements of the rare earth-containing composition and / or target-containing species. Without wishing to be bound by any theory, the binding mechanism, in some processes, adheres to, and absorbs, hydrated water, hydroxide radicals, hydroxide ions, or carbonate species rare earth or rare earth-containing compositions that are compounded, complexed, or otherwise attached to the target material. And / or by acting as a chemically bound chemical entity.

The medium 104 temperature may vary in the contacting step. Typically, the aqueous solution temperature in the contacting step can vary. For example, the aqueous solution temperature may vary with water. Typically, the aqueous solution temperature is ambient temperature. Typically, the solution temperature range can be about −5 ° C. to about 50 ° C., more typically about 0 ° C. to about 45 ° C., even more typically about 5 ° C. to about 40 ° C. and even more typically about 10 ° C. to about 35 ° C. have. It is understood that each water treatment with respective sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and polishing treatments may have an optional treatment unit and / or operation to heat and / or cool one or more respective waters. It must be understood. In some configurations, each water is typically at least about 20 ° C, more typically at least about 25 ° C, even more typically at least about 30 ° C, even more typically at least about 35 ° C, even more typically at least about 40 ° C, even more typical At least about 45 ° C, even more typically at least about 50 ° C, even more typically at least about 60 ° C, even more typically at least about 70 ° C, even more typically at least about 80 ° C, even more typically at least about 90 ° C, even more typically at least About 100 ° C., even more typically at least about 110 ° C., even more typically at least about 120 ° C., even more typically at least about 140 ° C., even more typically at least about 150 ° C., or even more typically at least about 200 ° C. In some configurations, each water to be settled, disinfected, flocculated, aerated, filtered, solid-liquidized, digested, and polished, is typically at most about 110 ° C., more typically at most about 100 ° C., even more typically at most about. 90 ° C, even more typically at most about 80 ° C, even more typically at most about 70 ° C, even more typically at most about 60 ° C, even more typically at most about 50 ° C, even more typically at most about 45 ° C, even more typically at most about 40 ° C , Even more typically up to about 35 ° C., more typically up to about 30 ° C., more typically up to about 25 ° C., even more typically up to about 20 ° C., even more typically up to about 15 ° C., more typically up to about 10 ° C., even more Typically it may be cooled to at most about 5 ° C., or even more typically at most about 0 ° C.

Separation of Rare Earth- and Target-Containing Products from Media

In optional step 116, the product is removed from the medium 104 to form a treatment medium 124. In one configuration, typically at least about 25%, more generally at least about 50%, more generally more generally at least about 50%, more generally at least about 75%, and still more generally at least about 95% Rare earth- and target-containing products of are removed from the medium. In this case, it will be appreciated that the product consists of insoluble matter.

Solid rare earth- and target-containing products may be removed by any suitable technique, such as a liquid / solid separation system. Non-limiting examples of liquid / solid separation systems are filtration, suspension, precipitation, cyclones, and centrifugation. Alternatively, the rare earth-containing additive may be in the form of a particulate or supported porous and permeable matrix, such as a filter, through which the medium passes.

Alternatively, the water soluble rare earth- and target-containing products may be present in non-activated form in water. Non-limiting examples of non-activated rare earth- and target-containing products that remain dissolved are stable coordination complexes in the atmosphere of target-containing species and rare earth-containing compositions.

In some embodiments, the treatment medium 124 has a lower content of at least one target compared to the target-containing medium 104. Typically, the treatment medium 124 content is at least about 0.9 of the target-containing medium 104, more generally the treatment medium 124 content is at least about 0.8 of the target-containing medium 104, even more generally. The treatment medium 124 content is at least about 0.7 of the target-containing medium 104, even more generally the treatment medium 124 content is at least about 0.6 of the target-containing medium 104, even more generally the treatment medium. (124) The content is at least about 0.5 of the target-containing medium 104, even more generally the treatment medium 124 The content is at least about 0.4 of the target-containing medium 104, even more generally the treatment medium (124) ) Content is at least about 0.3 of the target-containing medium 104, even more generally the treatment medium 124 content is at least about 0.2, even more generally the treatment medium 124 content of the target-containing medium 104. Silver at least about 0.1 of the target-containing medium 104 And, more generally, the treated aqueous medium 124 content is at least about 0.05 of the target-containing medium 104, and even more generally the treated medium 124 content is at least about 0.01 of the target-containing medium 104, Even more generally, the treatment content 124 is at least about 0.005 of the target-containing medium 104, even more generally the treatment medium 124 content is at least about 0.001 of the target-containing medium 104, even more generally. The treatment medium 124 content is at least about 0.5 of the target-containing medium 104, even more generally the treatment medium 124 content is at least about 0.0005, even more generally the treatment of the target-containing medium 104. The medium 124 content is at least about 0.0001 of the target-containing medium 104, even more generally the treatment medium 124 content is at least about 5 × 10 ⁻⁵ , even more generally the treatment of the target-containing medium 104. Medium (124) content is the target - at least approximately in a medium containing 104 1x10 ^-5, still more generally, process medium 124, content of a target material - of at least about 5x10 ^-6, and even more generally treatment medium 124, the content of a medium containing 104 target ^substance-6 is ^at least about 1x10-containing medium (104). Typically, the target content in the treatment medium 124 content is at most about 100,000 ppm, more typically the target content in the treatment medium 124 content is at most about 10,000 ppm, even more typically the target material in the treatment medium 124 content. The content is at most about 1,000 ppm, even more typically the target content in the treatment medium (124) content is at most about 100 ppm, even more typically the target content in the treatment medium (124) content is at most about 10 ppm, even more typically the treatment medium. (124) The target content in the content is at most about 1 ppm, even more typically the treatment medium (124) The target content in the content is at most about 100 ppb, even more typically the target content in the treatment medium (124) content is at most about 10 ppb, even more typically, the target content in the treatment medium (124) content is at most about 1 ppb, even more typically the target content in the treatment medium (124) content is Of from about 0.1 ppb.

Step 116 includes optional processing steps.

This treatment includes one or more sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy treatment. More specifically, the treatment process is usually one of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy, more generally in any order, sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, Digestion, and any two of the policies, even more generally settled in any order, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and any three of the policies, even more generally settled in any order Any of four, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy, and more generally any of sedimentation, disinfection, agglomeration, aeration, filtration, solid-liquid separation, digestion, and policy in any order. Five, more generally in any order, any six of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy, and more generally in any order. Any seven of filtration, solid-liquid separation, digestion, and policy Or, more generally, in any order of sedimentation, disinfection, agglomeration, aeration, filtration, solid-liquid separation, digestion, and any of eight types, and more generally, in any order, sedimentation, disinfection, agglomeration, aeration, filtration, Any nine of solid-liquid separation, digestion, and policy, and more generally any of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy of any ten, more generally any Any 11 of sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy, and more generally each sedimentation, disinfection, flocculation, aeration, filtration, solid-liquid separation, digestion, and policy In any order.

Rare Earth Regeneration in Rare Earth- and Target-Containing Products for Recycling

The rare earth- and target-containing products are treated in a suitable process to remove the target from the rare earth and the rare earth is recycled to step 112. Regeneration processes include, for example, desorption, oxidation, reduction, heat treatment, irradiation, and the like.

Cerium (III) as used herein is also referred to as cerium (+3) and cerium (+3) is also referred to as cerium (III). Cerium (IV) as used herein is also referred to as cerium (+4) and cerium (+4) is also referred to as cerium (IV).

Examples

The following examples are intended to illustrate certain embodiments and should not be construed as limited to the embodiments set forth in the claims. Unless otherwise specified, all parts and percentages are by weight.

Example  One

A series of tests was performed to determine the maximum arsenic loading performance of soluble cerium (III) chloride CeCl ₃ to reduce the arsenic concentration in the arsenic-containing stream to less than 50 ppm. As shown in Table 1, the arsenic-containing stream to be tested (hereinafter alkaline leachate) has the following composition:

The initial pH of the seven alkaline leachates was approximately pH 11, the solution temperature was approximately 70 to 80 ºC, and the reaction time was approximately 30 minutes.

Seven alkaline leachates were prepared by varying the arsenic (V) concentrations as shown in Table 1 above. Each solution contained the same amount of sodium carbonate (20 g / L) and sodium sulfate (17.75 g / L). In a first test, 3.44 mL cerium chloride (CeCl ₃ ) was added to all isothermal solutions and adjusted to 0.918 g CeO ₂ (approximately 0.05 mole Ce). In the second test, 6.88 mL cerium chloride was added to all solutions and made up to 1.836 g CeO ₂ (approximately 0.1 mole Ce). Each isothermal test method is described below.

In the first step, the 200 mL solution was weighed and transferred to a 400 mL Pyrex beaker. The beaker was placed on a heating / stirring plate and heated to 70-80 ° C. with stirring.

In the second step, 3.44 mL of cerium chloride was weighed and added to the hot alkaline leachate and mixed. As soon as cerium chloride was added, a white precipitate formed. To ensure that the white precipitate is not cerium carbonate [Ce ₂ (CO ₃ ) ₃ .xH ₂ O], a third step was taken.

In the third step, 4.8 mL of concentrated HCl was slowly added dropwise. Bubbles The solution was continuously stirred for 30 minutes and then cooled for 4 hours before taking a sample.

The results are shown in Table 2:

Analysis using ICP-AES

FIG. 48 shows that the loading performance starts to level at the theoretical performance of 436 mg / g where cerium arsenate (CeAsO ₄ ) is formed, and it was determined that this was formed. 49 shows that the cerium molar ratio to arsenic necessary to lower the arsenic concentration to less than 50 ppm is between 1 and 2 molar ratios. However, at 2 molar ratios the loading performance achieved 217. 50 shows very similar results (substantially double CeCl ₃ addition); One

At molar ratios between 2 and 2, the soluble arsenic concentration is less than 50 ppm. This performance is improved by lowering the molar ratio and tighter pH control.

Example  2

In this example, it is shown that the cerium and arsenic products contain more arsenic than expected based on the gasparite stoichiometry of the cerium and arsenic prediction products. In addition, the X-ray diffraction pattern shows that the product is amorphous or nanocrystalline and consistent with ceria or, perhaps, gasparite. The amorphous or nanocrystalline phase is not only capable of recycling water treatment after arsenic sequestration but also has greater arsenic removal than other cerium-added forms, thus reducing treatment costs and reducing environmental risks.

Eight 50 mL centrifuge tubes each filled with 25 mL of fully oxidized arsenate / sulphate / NaOH solution and eight other 50 mL centrifuge tubes each with 25 mL complete reduction of molecular oxygen sparged for 2 hours. Nitrite / sulfide / NaOH solution was charged. Both solutions contained 24 g / L arsenic, 25 g / L NaOH, and equivalent 80 g / L sulfides. Each sample was treated with cerium (IV) nitrate or cerium (III) chloride. Cerium salt solution was added in 1, 2, 3, or 5 mL volumes. There was no pH adjustment and no temperature change at ambient 22ºC.

Fifteen of the 16 test samples showed rapid precipitate formation, accounting for a total of 25 mL. The reaction between the two concentrated solutions took place almost immediately, and the total solution volume was filled with gel-like precipitates. The 16th sample containing 5 mL cerium (IV) was light yellow and an additional 5 mL 50% NaOH formed a purple solid.

Solids formed by the cerium and arsenic reactions stabilized for one hour but hardly settling. Samples were centrifuged at 50% speed for 5 minutes. At this time, the total solution volume and settled solid volume were recorded and a 5 mL sample was taken for analysis. Since at most 5 mL supernatant was available (arsenic concentration was 24 g / L, which means that the cerium concentration was also very high), the samples were filtered with 0.45 micron paper. Four samples with 5 mL cerium salt were not filtered. The supernatant was recovered and the volume recorded.

The resulting filter cake was left in a dry weight plastic weight boat for the weekend. After 72 hours, each boat content was weighed to confirm that the pellets were still very humid (more content than was added to the sample as a soluble solid). The semi-dried solid of the sample with 2 mL cerium salt solution was treated for 1 hour in a 130ºC dry oven and analyzed by XRD.

XRD results are shown in FIG. 51. XRD results for gasparite (predicted product) and various systems that were present during the experiment are shown, and “ceria” corresponds to cerium dioxide. As shown in FIG. 51, XRD analysis does not show any crystalline peaks or phases of arsenic and cerium solids in various systems. The only crystalline material present was identified as Na ₂ SO ₄ which was present in the sample from NaCl, NaNO ₃ (introduced with rare earth solution) or Na ₂ SO ₄ . However, broad diffraction peaks at about 29, 49, and 57 degrees 2-theta can mean very small particles of ceria or, perhaps, gasparite.

Arsenic content of the supernatant was determined by ICP-AES. Both cerium (IV) and cerium (III) were shown to be effectively arsenic removed from the system to approximately the same extent.

As can be seen in Table 3 below and in FIG. 52, a greater difference in arsenic removal was between the fully oxidized system and the fully reduced system prior to molecular oxygen sparging. FIG. 52 depicts an “oxidized” system starting with arsenate and arsenic micromolar starting with a arsenite and subsequently removed from a “molecular oxygen sparged” system that is oxidized to arsenate by molecular oxygen sparging.

FIG. 52 shows arsenic consumption by precipitation solids formation as a function of cerium addition. Soluble arsenic concentrations according to this experiment are classified into two groups: samples containing completely oxidized arsenate and sulfates and samples containing arsenites and sulfites that are sparged with molecular oxygen. The oxidation state of cerium used as a soluble binder did not significantly affect process efficiency, and both Ce (III) and Ce (IV) data for each test solution met a single regression line. In the case of a fully oxidized solution, it will stick to arsenic as a solid.

Example  3

A series of experiments were undertaken, with the addition of a soluble cerium salt in Ce (III) state from an extremely concentrated wastewater stream below pH 2 followed by titration with sodium hydroxide (NaOH) solution in the pH range from 6 to 10 Arsenic precipitation in the (V) state.

In a first test, a 400 mL solution containing 33.5 mL 0.07125 mol / L NaH ₂ AsO ₄ solution was stirred in a beaker at room temperature. After adjusting the pH to approximately pH 1.5 by adding 4.0 mol / L HNO ₃ , 1.05 g of Ce (NO ₃ ) ₃ .6H ₂ O was added. There was no discoloration or any precipitate formation following the addition of the cerium (III) salt. NaOH (1.0 mol / L) was added dropwise to the stirred solution to adjust the pH to pH 10.1. The pH was maintained at pH 10.2 ± 0.2 for 1.5 hours while stirring with a magnet. After the reaction, the solution was taken out of the stirring plate and allowed to stand for 12 to 18 hours. The supernatant was collected by tilting and stored for ICP-MS analysis of Ce and As. The solid was filtered through 0.4 μm cellulose membrane and washed thoroughly with 500-800 mL of deionized water. The solid was dried in air and analyzed by X-ray diffraction.

In a second test, a simulated wastewater stream solution was prepared with the following components: As (1,200 ppm), F (650 ppm), Fe (120 ppm), S (80 ppm), Si (50 ppm), Ca (35 ppm), Mg (25 ppm), Zn (10 ppm), and less than 10 ppm Al, K, and Cu. The solution pH was titrated to pH 0.4 with concentrated HCl (12.1 mol / L) and the solution was heated to 70 ºC. CeCl ₃ solution (6.3 mL, 1.194 mol / L) was added to the hot solution and the pH was gradually raised to pH 7.5 by dropwise addition of NaOH (20 wt.%, 6.2 mol / L). The solution was then aged for 1.5 h at 70 ° C. with magnetic stirring and the pH was maintained at pH 7.5 ± 0.2. The solution was taken out and left to stand for 12-18 hours. The supernatant was collected by tilting and stored for ICP-MS analysis of Ce and As. The precipitated solid was centrifuged and washed twice, then the solid was filtered through 0.4 μm cellulose membrane and washed thoroughly with 500-800 mL of deionized water. The solid was dried in air and analyzed by X-ray diffraction.

In a third test, low-pH leaching test stability was tested on solid powders of new Ce-As compounds. 0.5 g fresh Ce-As compound was added to 10 mL of an acetic acid solution at pH 2.9 or pH 5.0. The vessel was sealed and rotated 30 ± 2 times per minute for 18 ± 2 hours at an ambient temperature of 22 ± 5 ° C. After the required rotation time, the solution was filtered through a 0.2 micron filter and analyzed for Ce and As leached from the solid by ICP-MS. Less than 1 ppm of As was detected by ICP-MS.

53 is a new compound CeAs X- ray for the light and Gaspar (both experimental and simulated) (trigonal crystal system (trigonal) CeAs O ₄ and (H ₂ O) X (Experimental and simulated both) as shown) diffraction ( " XRD ”) results. FIG. 9 compares the XRD results for trigonal CeAs O _4. (H ₂ O) X (both experimental and simulated) and trigonal BiP O _4. (H ₂ O) 0.67 (simulated). XRD results show that the precipitated crystalline compound is structurally different from gasparite (CeAsO4), which crystallizes in monoclinic space groups with a monazite structure, and is very similar to trigonal BiP O _4. (H2O) 0.67.

Experiments with Ce and As in different oxidation states show that the new Ce-As compounds require Ce (III) states and arsenic As (V) states. PH titration with a strong base such as sodium hydroxide appears to be necessary. PH titration with sodium carbonate produces gasparite, a known naturally occurring compound or gasparite, and a combination of trigonal CeAsO _4. (H ₂ O) X. Both cerium chloride and cerium nitrate show that new compounds can be successfully synthesized. The presence of other metal species, such as magnesium, aluminum, silicon, calcium, iron, copper, and zinc, did not appear to interfere with new compound synthesis. The presence of fluorides competes with arsenic removal to produce insoluble CeF ₃ precipitates. A solution containing only arsenic and cerium showed that a Ce: As atomic ratio of 1: 1 is preferred for the formation of new compounds, while solutions containing excess cerium produced cerium oxide (CeO ₂ ) precipitates in addition to the new compounds. The new compounds also appear to be stable in leaching tests requiring arsenic less than 1 ppm soluble in pH 2.9 and pH 5.0 solutions.

Example  4

In this example, a test solution containing 1.0 ppmw chromium, calculated as Cr, was prepared by dissolving reagent grade potassium dichromate in distilled water. The solution contains Cr ⁺⁶ in the form of oxyanions and no other metal oxyanions. A mixture of 0.5 grams of lanthanum oxide (La ₂ O ₃ ) and 0.5 grams of cerium dioxide (CeO ₂ ) was suspended in a glass container with 100 milliliters of test solution. The resulting slurry was stirred for 15 minutes with a Teflon applied magnetic stir bar. After stirring, water was filtered from the solid through Whatman # 41 filter paper and chromium was analyzed with an inductively coupled plasma atomic emission spectrometer. This procedure was repeated twice, but instead of suspending a mixture of lanthanum oxide and cerium dioxide with 100 milliliters of test solution, 1.0 grams each was used. The results of these tests 1-3 are shown in Table 4.

Thus lanthanum oxide, cerium dioxide and the same amount of each were effective in removing chromium from the test solution by more than 98 percent.

Test 4-6

The procedure of Test 1-3 was repeated except that a 1.0 ppmw antimony-containing test solution was used when calculated as Sb instead of a chromium test solution. The antimony test solution was 100 ppmw with 100 ppmw of As, Be, Ca, Cd, Co, Cr, Fe, Li, Mg, Mn, Mo, Ni, Pb, Se, Sr, Ti, Tl, V, and Zn, respectively. The antimony containing verification standard solution was prepared by diluting with distilled water. The test results are shown in Table 4 and show that the two rare earth compounds alone or in combination are effective at removing 90% or more of antimony from the test solution.

Test 7-9

The procedure of Test 1-3 was repeated except that 1.0 ppmw molybdenum containing test solution was used when calculated as Mo instead of chromium test solution. Molybdenum test solution is 100 ppmw with 100 ppmw of As, Be, Ca, Cd, Co, Cr, Fe, Li, Mg, Mn, Ni, Pb, Sb, Se, Sr, Ti, Tl, V, and Zn, respectively. Molybdenum-containing verification standard solutions were prepared by dilution with distilled water. The test results are shown in Table 4 and are shown to be effective for removal with lanthanum oxide, cesium dioxide.

Test 10-12

The procedure of Test 1-3 was repeated except that a 1.0 ppmw vanadium containing test solution was used when calculating V instead of the chromium test solution. The vanadium test solution is 100 ppmw with 100 ppmw of As, Be, Ca, Cd, Co, Cr, Fe, Li, Mg, Mn, Mo, Ni, Pb, Sb, Se, Sr, Ti, Tl, and Zn, respectively. The vanadium containing verification standard solution was prepared by diluting with distilled water. The test results are presented in Table 4 and show that lanthanum oxide and a mixture of equal weight lanthanum oxide and cerium dioxide are effective at removing vanadium above 98 percent from the test solution, and cerium dioxide removes vanadium at about 88 percent.

Test 13-15

The procedure of Tests 1-3 was repeated except that a 2.0 ppmw uranium containing test solution was calculated as U instead of the chromium test solution. Uranium test solutions were prepared by diluting a 1,000 ppmw uranium containing verification standard solution with distilled water. The solution did not contain other metals. The test results are shown in Table 4 and show that, like Test 10-12, lanthanum oxide and a mixture of equal weight lanthanum oxide and cerium dioxide are effective at removing significant amounts of uranium from the test solution. However, as in these examples, cerium dioxide removes uranium by about 75 percent and is not effective.

Test 16-18

The procedure of Tests 1-3 was repeated except that a 1.0 ppmw tungsten containing test solution was used when counting W instead of the chromium test solution. The tungsten test solution was prepared by diluting 1,000 ppmw tungsten containing verification standard solution with distilled water. The solution did not contain other metals. The test results are shown in Table 4 and show that lanthanum oxide, cerium dioxide, and a mixture of equal weight lanthanum oxide and cerium dioxide are effective at removing 95 percent or more of tungsten from the test solution.

Example  5

This example shows halogen affinity for rare earth metals. A series of tests was performed to determine whether certain halogens, particularly fluorine (and other halogens), compete with arsenic for binding to cerium chloride. Arsenic is known to bind strongly with cerium chloride in aqueous media when water-soluble cerium chloride (CeCl ₃ ) is used. This halogen binding affinity was determined by comparing the differences between the stock solutions with or without fluorine. The materials used were as follows: CeCl ₃ (1.194 M Ce or 205.43 g / L (rare earth oxides or REO) and 400 mL stock solution. The stock components were prepared according to NSF P231 “General Test Water 2” (“NSF”). 5 and 6: Table 5 shows the additive reagent contents.

The stock initial pH was approximately 0-1. The stock solution temperature was raised to 70 deg. The reaction or residence time was approximately 90 minutes.

Cerium arsenate precipitation procedure with or without fluorine is as follows:

Step 1:

Two 3.5L synthetic stocks with and without fluorine were prepared. Both solutions contained the compounds listed in Table 5.

Step 2:

A 400 mL synthetic stock was aliquoted (402.41 g) and transferred to a 600 mL Pyrex beaker. The beaker was placed on a heating / stirring plate and heated to 70 ° C. with stirring.

Step 3:

Sufficient cerium chloride was added to the stock to meet the desired cerium molar ratio to arsenic. For example, 5.68 mL of cerium chloride was weighed (7.17 g) and added to the stirred solution to achieve a molar ratio of 1 mole of ceria to 1 mole of arsenic. When cerium chloride is added, a yellow / white precipitate is formed immediately, and the pH is lowered since the cerium chloride solution normal concentration is 0.22. The pH was adjusted to approximately 7 with 20% sodium hydroxide.

Step 4:

Cerium chloride was added to a 70 ° C. solution and allowed to react for 90 minutes before taking a sample.

Step 5:

Steps 2-4 were repeated for all desired molar ratios with or without fluorine solution.

The results are shown in Table 7 and FIGS. 55 and 56.

Table 7. Residual Arsenic Concentration in Supernatants After Precipitation with Cerium Chloride Solution

Comparing the loading performance for the fluorine-free solution shows a strong affinity for halogens and halogenated compounds. 55 shows cerium III affinity for fluorine in the presence of arsenic. FIG. 56 shows that loading performance (defined as As mg per ₂ grams of CeO) for fluorine free solutions is significantly higher when the cerium molar ratio to arsenic is low. Sequestration of rare earth metals, and especially fluorinated organic compounds, in particular fluorinated pharmaceutical compounds with cerium, is clearly indicated.

For solutions with cerium to arsenic molar ratios of approximately 1.4 to 1 or higher, there was no significant difference in loading performance between solutions with and without F ⁻ . Thus fixing F ⁻ ; It was determined that excess 40% cerium was needed for the remaining cerium to react with arsenic.

These results confirm that the presence of fluorine effectively interferes with arsenic and other target substance fixation. Interference occurs in a CeF ₃ forming competition reaction with fairly good Ksp. As a result of these, fluorine and other halogens must be removed before the addition of the rare earth-containing additives.

Example  6

This example shows successful removal of sulfate-containing compounds, halogenated compounds, carbonate-containing compounds, and phosphate-containing compounds using cerium dioxide powder. Cerium powder with 400 ppb arsenic removal performance was contacted with various solutions containing arsenic (III) as arsenite and arsenic (V) as arsenate and high concentrations of compounds competing with known binding affinity between arsenic and cerium. Competing organic compounds included sulfate, fluorine, chlorine, carbonate, silicate, and phosphate ions at approximately 500% of the corresponding ion NSF concentration. Cerium dioxide powder was also contacted with arsenic-contaminated distillation and NSF P231 “General Test Water 2” (“NSF”) water. Distilled water provided a baseline measurement.

The results are shown in FIG. 55. As shown in FIG. 55, NSF aquatic ions reduce cerium dioxide performance for both arsenite and arsenate compared to distilled water, indicating successful bonding of these compounds with rare earth metals. The presence of carbonate ions further reduces the cerium dioxide removal performance for the arsenate than for the arsenite. The presence of silicate ions substantially reduces the cerium dioxide removal performance for both arsenite and arsenate. Finally, phosphate ions have the greatest drop in cerium dioxide removal performance for arsenite (10X NSF concentration) and arsenate (50X NSF concentration), with the greatest reduction in removal performance for arsenite.

Example  7

Many tests were performed to evaluate solution phase or soluble cerium ion precipitation.

Test 1:

The 250 ppm Cr (VI) containing solution was changed to molar equivalents of cerium provided as Ce (III) chloride or Ce (IV) nitrate. The addition of Ce (III) to the chromate shows no immediate visible effect on the solution, but after 24 hours a fine precipitate of dark solids is formed. Conversely, addition of Ce (IV) immediately forms a large amount of solids.

As in the previous example, the portion was filtered and the pH was adjusted to pH 3 for Ce (IV) and to pH 5 for Ce (III). Ce (III) addition did not significantly affect Cr solubility, but Ce (IV) removed almost 90% of Cr at pH 3 from the solution.

Test 2:

A solution containing 50 ppm molybdenum Spex ICP standard, possibly molybdate, was changed to molar equivalents of Ce (III) chloride. Like the electrical sample, a solid was formed after cerium addition and the portions were filtered through a 0.45 micron syringe filter for ICP analysis. At pH 3, almost 30 ppm Mo remained in the solution, but when the pH rose to 5, the Mo concentration dropped to 20 ppm and at nearly pH 7, the Mo concentration was only 10 ppm.

Example  8

These examples examine the adsorption and desorption of a series of non-arsenic anions in a manner similar to that set up in the arsenic test.

Permanganate:

Two examples were performed. In the first example, 40 g ceria powder was added to 250 mL of 550 ppm KMnO ₄ solution. In a second example, 250 mL of 20 g ceria powder

Was added to a 500 ppm KMnO ₄ solution and the pH was lowered with 1.5 mL of 4 N HCl. Slurry pH

Lowering resulted in a four-fold increase in Mn loading in ceria.

In two examples the ceria was contacted with permanganate for 18 hours and then filtered to give a solid. Mn was analyzed by ICP-AES on the filtrate and the solid was washed with 250 mL DI water. The pH unadjusted solid was washed again.

The filtered and washed Mn-contacted solid weight was measured and classified into a series of three extraction test groups and a control group. The three test groups were intended to investigate the extent to which manganese was recovered from the ceria surface when contacted with 1 N NaOH, 10% oxalic acid, or 1 M phosphate compared to DI numbers in the same conditions.

Permanganate-loaded ceria powder samples were contacted with water as a control and showed less than 5% Mn release. As with the arsenate, NaOH effectively desorbed the permanganate from the ceria surface. It is shown that basic pH levels, or basicization, act as interferers in the permanganate removal by ceria. For the second example where the pH was lowered, the NaOH effect was greater than the first case where permanganate was adsorbed at higher pH conditions.

Phosphates induce permanganate desorption more effectively than induction of arsenate desorption. Phosphate was the most effective desorption accelerator investigated for permanganate. That is, the ceria powder performance of removing permanganate in the presence of phosphate is relatively low since the ceria powder performance for phosphate is much higher than that for permanganate.

Oxalic acid caused significant discoloration in the permanganate solution, which meant that Mn (VII) was reduced to Mn (II) or Mn (IV), where MnO or MnO2 precipitates formed and were not removed or removed from ceria. No additional Mn can be found. The reducing agent is therefore an interferer in the removal of ceria for Mn (VII). In samples that were not pH adjusted, no desorbed Mn was detected. However, significant amounts of Mn were recovered from the ceria surface in samples prepared by slightly acidifying the slurry.

Chromate

A 250 mL solution was prepared using 0.6 g sodium dichromate, and the solution was contacted with 20 g cerium powder for 18 hours without pH adjustment. The slurry was filtered and the solid was washed with DI water and then divided into 50 mL centrifuge tubes to test the chromium extraction capability of the three solutions on the ceria surface.

The ceria performance for the chromate was significant and loading was achieved to> 20 mg Cr / g ceria without any pH adjustment or system optimization (filtrate pH approximately 8). Similarly, extraction of adsorption chromate was also easily accomplished. Raising the chromate-containing ceria-containing slurry pH to 1 N NaOH is the most effective desorption method for the chromium to be tested. Very little chromate was desorbed using phosphate and a smaller amount desorbed using oxalic acid. This means that phosphate and oxalic acid are not powerful interferers in chromate removal compared to permanganate removal. In the control sample, only 5% of the chromates were recovered when the loading solids contacted with distilled water.

antimony

Antimony solubility is relatively low and these reactions are limited by the antimony content dissolved. In this case, 100 mg antimony (III) oxide was added with 10 mL concentrated HCl in 1 L distilled water, allowed to equilibrate for several days and filtered through a 0.8 micron polycarbonate membrane to remove insoluble antimony. The antimony solution was contacted with 16 g ceria powder, which was effective in removing antimony in the solution, but there was little soluble Sb (III) which would cause high loading on the surface. In part due to the low adsorption rate and strong surface-anion interaction, the extraction test showed little Sb recovery. Even if hydrogen peroxide, which is expected to convert Sb (III) to the less easily adsorbed species Sb (V), was used, the Sb recovery was not large.

arsenic

Table 8-11 shows test parameters and results.

Table 8: Cerium oxide surface loading of arsenate and arsenite showing arsenic desorption methods

Table 9: Arsenic Desorption Methods Visible arsenate  Oxide surface loading of ferric and arsenite

Table 10: Redox  And competitive reactions Ceria  Arsenic Extraction from Surface

Table 11: Ceria  Loading and Extraction of Other Adsorption Elements from Surfaces (Extracted as a Recovered Loading 'Percentage for Each Method Is shown )

Example  9

NH ₄ MgPO ₄ · CeCl ₃ were mixed to a molar ratio of the NH ₄ MgPO ₄ · 6H ₂ O of struvite particles consisting of 6H ₂ O to the CeCl ₃ solution was about 0.8, 1.0, 1.2 and 1.5. In each case, the struvite weight was about 0.2 g and the CeCl ₃ concentration was about 0.5 mole / L. In addition, about 0.2 grams of struvite control in about 0.1 L deionized water were prepared. Each solution pH value was adjusted to about pH 4.3 ± 0.2. Each sample solution was stirred with a magnetic stir bar. After stirring for at least about 16 hours, the solids were filtered from the solution. The filtered solid was analyzed by x-ray diffraction and the solution was analyzed by ICP-MS. Final solution pH values ranged from about pH 4.6 to about pH 8.0. The results are summarized in Table 12.

Example  10

Struvite, NH ₄ MgPO ₄ .6H ₂ O particles were mixed with about 0.1 L solution containing different rare earth chlorides. The rare earth chloride solution was LaCl ₃ , CeCl ₃ , PrCl ₃ and NdCl _{3 in a} solution of about 0.15 mol / L. The struvite weight added to each rare earth chloride solution was about 0.2 g and the rare earth chloride molar ratio to struvite was about 1.0. Rare earth chloride solution pH was adjusted to about pH 4.3 ± 0.2. Each sample solution was stirred with a magnetic stir bar. After stirring for at least about 16 hours, the solids were filtered from the solution. The filtered solid was analyzed by x-ray diffraction and the solution was analyzed by ICP-MS. Final solution pH values ranged from about pH 4.6 to about pH 8.0. The results are summarized in Table 13.

Example  11

Example 11 A control having about 0.1 L of 0.15 mol / L acidic ferric chloride, about 0.2 g of struvite mixed with FeCl ₃ solution, NH ₄ MgPO ₄ .6H ₂ O, particles. The ferric chloride molar ratio to struvite was about 1.0 and the initial pH of the solution was about pH 2.5. The initial pH of the control solution was low enough to dissolve struvite in the absence of ferric chloride. The control solution was stirred with a magnetic stir bar. After stirring for at least about 16 hours, the solids were filtered from the solution. The filtered solid was analyzed by x-ray diffraction and the solution was analyzed by ICP-MS. The final solution pH value was about pH 2.3. The results are summarized in Table 14.

Examples 9-11 show that struvite can be removed more effectively with rare earth-containing compositions than with other removal materials such as ferric chloride.

Example  12

Table 15 summarizes the accumulated material removal performance for cerium dioxide from deionized water and NSF water.

Example  13

Metal and metalloid removal experiments were performed with cerium-containing compositions from deionized water and NSF standard water (see Table 16).

As shown in Table 16, the cerium-containing compositions are effective at removing species comprised of the targets of Table 16.

Example  14

Metal and Quasi of Cerium-containing Additives from Deionized Water and NSF Standard Water (see Table 17)

Experiments were performed to quantitatively measure metal removal performance.

As can be seen from Table 16, the cerium-containing composition is effective in removing species comprised of the targets of Table 17.

Example  15

Experiments were performed to quantitatively measure the removal of organic, metal, metalloid and non-metallic contaminants from deionized water and NSF standard water (see Tables 18 and 19).

CeO ₂ is in powder form and agglomerated CeO ₂ is agglomerated with the polymerizable binder.

The insoluble form of lead is removed by the rare earth-containing composition from an aqueous medium containing one or both of the soluble and insoluble forms of lead. Insoluble lead can be in the form of colloidal and / or particulate lead such as, but not limited to, lead oxide, lead hydroxide, and / or lead oxy (hydroxide). The insoluble lead composition may be in hydrated form with one or more hydrated waters.

NSF test water composition as defined in one or more of the following documents: “NSF / ANSI 42-2007a NSF International Standard / American National Standard for Drinking Water Treatment Units-Drinking Water Treatment Units-Aesthetic Effects” Standard Developer-NSF International, Designated as a ANSI Standard, October 22, 2007, American National Standards; “NSF / ANSI 53-2009e NSF International Standard / American National Standard Drinking Water Treatment Units-Health Effects” Standard Developer-NSF International, designated as an ANSI Standard, August 28, 2009; and “NSF / ANSI 61-2009 NSF International Standard / American National Standard for Drinking Water Additives-Drinking Water System Components-Health Effects” Standard Developer NSF International, designated as an ANSI Standard, August 26, 2009.

Example  16

High surface area (“HAS”) ceria (surface area: 130 ± 10 m ² / g) of about 20 mg loading was contacted with an analyte of NSF 53 water with about 0.5 mg / L reagent of interest. NSF water components are provided in Table 20 below:

Analyte pH was pH 12.25 ± 0.25 and temperature was 20-25 ° C. (ambient room temperature).

The analyte was contacted with HSF ceria for approximately 24 hours.

Reagents of interest were bismuth, chromium, cobalt, manganese, zinc and zirconium species. Under these conditions, the main species were determined in colloidal form.

Medium was prepared by weighing 20 mg HSA ceria in a plastic weightboat and wetting the HAS ceria medium with deionized water for at least 30 minutes.

Analytes were prepared in a 2.0 L batch of NSF 53 water. Lead-free lead remover. A 1,000 mg / L SPEX nitric acid based standard was obtained and used to prepare 0.5 mg / L influent of the reagent of interest. The solution was mixed for 30 seconds with a high shear mixer (Ninja Model: BL500 30). The pH was adjusted to pH 12.25 ± 0.25 with 3M NaOH and mixed for an additional 60 seconds. Previous tests at higher concentrations showed the presence of particulates at pH 12.25 ± 0.25.

An isotherm was prepared by pouring 500 mL inlet into 4 500 mL bottles. Pre-wetted media was placed in each 500 mL sample bottle. The bottle cap was closed and sealed with electrical tape. Each bottle was placed in a rotating container containing 10 bottles. The vessel was sealed with duct tape and placed in the rotator. Samples and controls were rotated for 24 hours. After 24 hours, the rotator was taken out of the device and the bottles were removed from the container.

For each metal sample, 5 mL sample was taken, diluted with 3 mL concentrated nitric acid and filtered through a 0.2 μm filter. The samples were acidified to ensure that all metals were in soluble form. Metal samples were analyzed by inductively coupled plasma-weight spectrometry (ICP-MS). To confirm the presence of colloidal metal, the sample was first filtered to remove any particulates and then acidified to ensure that the metal was in soluble form. These test analyzes were below the analytical metal detection limit. All isotherms were prepared and tested in the same manner to facilitate comparison.

As shown in Table 21, colloidal bismuth, chromium, manganese, and zinc were all removed with HSA ceria in NSF 53 water. The reagent removal ability of interest is based on at least 10% removal of the reagent of interest from the influent.

* Final concentration, removal performance, and% removal are the average of three samples

Table 22 shows the individual cases of cobalt and zirconium.

Colloidal Bismuth, Chromium, Manganese, and Zinc from NSF 53 Water to HSA Ceria

All removed. As a result of this, in ideal control, these reagents apply HSA ceria

It can be seen that it can be removed.

Example  17

This example compares the results of various tests to draw conclusions about whether temperature, surface area, specification, and concentration changes affect the arsenic loading performance of ceria. The experimental procedure is as follows:

Material: CeO ₂ : LOI-4.6%, SA-140 m ² / g;

CeO ₂ : LOI- 6.3%, SA-210 m / g

Loading: 40 g

Test solution component (20 L Add to DI water ):

2244.45 g NiSO ₄ 6H ₂ O

119.37 g CuSO ₄ · 5H ₂ O

57.81 H ₃ BO ₃

406.11 NaCl

15.01 FeSO ₄ 7H ₂ O

4.79 g CoSO ₄ · 7H ₂ O

70 con HCl

Test solution condition:

pH: 1.63

Density: 1.08 mL / g

Column influent :

pH: pH 1.1 to 1.2 for all columns

Density: 1.08 g / mL for all columns

Temperature: All columns operate at ambient room temperature ~ 21 ° C or 70 ° C

Flow rate: 1 to 1.8 mL / min, or 2.2% -4.0% commercial (Bed Volume)

Approximate amount of flocculant used: 22 drops of 1% Nalco 7871

Column Top Dimensions: 8.5-9 cm X 2.54 cm ID for all columns

media:

150 g ACS validation NaCl was added to 1 L. The salt was then diluted to 1 L notation using DI water. The salt was transferred to a 2 L beaker and boiled. Next, 15 mL concentrated HCl was added to boiling water and stirred with a magnetic stir bar. Immediately after addition of HCl, 40.00 g dry CeO ₂ was slowly added to the mixed acidic salt solution. The solution was stirred for 5 minutes. Next, 22 drops of 1% Nalco 7871 were added to purify the solution and inhibit material separation when added to the column.

Column loading :

Aggregated CeO ₂ media was flowed at 12 mL / min until the bed was completely dry to 8.5 cm. The DI water on the bed was tilted off and replaced with the influent solution, then the stopper was closed and sealed.

As can be seen in Table 23 and FIG. 57, the arsenic species loading performance of cerium (IV) oxide loading is affected by temperature, surface area, species, and arsenic species concentration changes.

Example  18

This example determines whether colloidal metal removal from NSF 53 water is possible by high surface area (“HSA”) cerium (IV) oxide. The test parameters are as follows:

Arguments:

Substance: HSA Ceria Oxide (Surface Area: 130 ± 10 m ² / g)

Loading: 20 mg

Analyte concentration: 0.5 mg / L NSF 53 in water Reagent of interest

pH: variable

Temperature: 20-25 C ambient room temperature

Contact time: 24 hours

Test metal bismuth, chromium, cobalt, manganese, zinc, zirconium, aluminum, and copper

Media Production:

20 mg HSA ceria oxide was measured on a plastic weightboat. The medium was wetted for at least 30 minutes with DI water.

Influent Production :

The influent was prepared in a 2.0 L batch of lead free NSF 53 water with no lead added. A 1,000 mg / L SPEX nitric acid based standard was obtained and used to prepare 0.5 mg / L influent of reagent of interest. The solution was mixed for 30 seconds with a high shear mixer (Ninja Model: BL500 30), then the pH was adjusted with 3M NaOH or concentrated HCl and mixed for an additional 30 seconds. And the redox potential (“ORP”) value was adjusted using solid sodium sulfite or 12.5% NaClO solution (see Table 25).

** I did not get the correct ORP value

Test procedure:

Isothermal Manufacturing Procedure:

Four 500 mL bottles were each filled with 500 g influent. Pre-wetted media was placed in each 500 mL sample bottle. The bottle cap was closed and sealed with electrical tape. Each bottle was placed in a rotating container containing 10 bottles. The vessel was sealed with duct tape and placed in the rotator. Samples were rotated for 24 hours. After 24 hours, the rotator was taken out of the device and the bottles were removed from the container.

Analytical Sample Preparation Procedures:

For each metal sample, 5 mL sample was taken, diluted with 5 mL 10% nitric acid and filtered through a 0.2 μm filter. The samples were acidified to ensure that all metals were in soluble form. Metal samples were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). To confirm the presence of insoluble metals, the samples were first filtered through a 0.2 μm filter to remove any insoluble metals and then acidified to ensure that all samples were identical. All isotherms were prepared and tested in the same manner to facilitate comparison.

result:

As shown in Tables 26-27, Cr ₂ O ₃ (S), Mn ₃ O ₄ (S) Al ₂ O ₃ (H ₂ O) (S), Cu (OH) ₂ (S), and Cu ₂ O (S) All were removed with HSA ceria from NSF 53 water. Reagent removal of interest was based on at least 10% removal of the reagent of interest from the influent.

* Final concentration, removal performance, and% removal were averages taken from three samples.

** I did not get the correct ORP value

conclusion:

Colloidal chromium, aluminum, and copper were all removed from NSF 53 water with HSA ceria. Some experiments have shown that cobalt, zinc, and zirconium are also removed. The ability of HAS ceria to remove manganese was not clear.

Example  19

This example determined whether a high surface area (“HSA”) cerium (IV) oxide can remove colloidal metals from NSF 53 water. The test parameters are as follows:

Arguments:

Substance: HSA ceria (surface area: 130 ± 10 m ² / g).

Loading: 20 mg.

Analyte concentration: 0.5 mg / L NSF 53 in water Reagent of interest, see Table 34.

pH, ORP: variable, see Table 28.

Temperature: 20-25 C ambient room temperature.

Contact time: 24 hours.

Test metals: bismuth, chromium, cobalt, manganese, zinc, zirconium, aluminum, and copper.

Media Production:

20 mg HSA ceria was measured on a plastic weightboat. The medium was wetted for at least 30 minutes with DI water.

Influent Production :

The influent was prepared in a 2.0 L batch of lead free NSF 53 water with no lead added. A 1,000 mg / L SPEX nitric acid based standard was obtained and used to prepare 0.5 mg / L influent of reagent of interest. The solution was mixed for 30 seconds with a high shear mixer (Ninja Model: BL500 30), then the pH was adjusted with 3M NaOH or concentrated HCl and mixed for an additional 30 seconds. The ORP value was then adjusted using solid sodium sulfite or 12.5% NaClO solution.

** ORP values are estimated, exact values for Bi _(S) have not been obtained and recorded values correspond to BiO ⁺ .

step:

Isothermal Manufacturing Procedure:

Four 500 mL bottles were each filled with 500 g influent. Pre-wetted media was placed in each 500 mL sample bottle. The bottle cap was closed and sealed with electrical tape. Each bottle was placed in a rotating container containing 10 bottles. The vessel was sealed with duct tape and placed in the rotator. Samples were rotated for 24 hours. After 24 hours, the rotator was taken out of the device and the bottles were removed from the container.

Analytical Sample Preparation Procedures:

For each metal sample, 5 mL sample was taken, diluted with 5 mL 10% nitric acid and filtered through a 0.2 μm filter. The samples were acidified to ensure that all metals were in soluble form. Metal samples were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). To confirm the presence of insoluble metals, the samples were first filtered through a 0.2 μm filter to remove any insoluble metals and then acidified to ensure that all samples were identical. All isotherms were prepared and tested in the same manner to facilitate comparison.

result

The results are shown in Table 29-30.

* Final concentration, removal performance, and% removal were averages taken from three samples

* Not included in this table due to negative removal performance or negative final concentration of insoluble cobalt, manganese, zinc, and zirconium.

conclusion

All metal solutions were prepared in NSF 53 arsenic test water without As. All of these solutions were tested for HSA cerium oxide (CeO 2). Bi (target species BiOOH _(S) , BiO ⁺ ) was certainly removed. Cr (target species Cr ₂ O _{3 (S)} ), Mn (target species MnO _{2 (S)} , Mn ₂ O _{3 (S)} , and Mn ₃ O _{4 (S)} ), Zn (target species Zn (OH) _{2 (S)} ), Al (target species Al ₂ O ₃ (H ₂ O) _(S) ), Cu (target species Cu (OH) _{2 (S)} and Cu ₂ O _(S) ), and Zr (target species ZrO _{2 (S)} ) was certainly removed. In attempt 2AA, Co (target species CoO _{2 (S)} ) was clearly removed. These results show that, under controlled conditions, insoluble compounds of Al, Co, Cr, Cu, Mn, Zn, and Zr can be removed using HSA cerium oxide (CeO ₂ ).

58-65 show a preceding pullbay diagram for the material.

Example  20

This example determines whether the selected soluble metal can be removed from NSF 53 water using HAS cerium (IV) oxide.

Arguments:

Substance: HSA ceria (surface area: 130 ± 10 m ² / g).

Loading: 20 mg.

Analyte concentration: 0.5 mg / L NSF 53 in water Reagent of interest, see Table 31.

pH, ORP: variable, see Table: 32.

Temperature: 20-25 C ambient room temperature.

Contact time: 24 hours.

Test metals: aluminum (Al ^{3 +} ), barium (Ba ^{2 +} ), cadmium (Cd ^{2 +} ), chromium (Cr ^{3 +} ), cobalt (Co ^{2 +} ), copper (Cu ^{2 +} ), iron (Fe ^{2 +} ), manganese (Mn ^{+ 2),} and nickel (Ni ^{+ 2).}

Media Production:

20 mg HSA ceria was measured on a plastic weightboat. The medium was wetted for at least 30 minutes with DI water.

Influent Production :

The influent was prepared in a 2.0 L batch of lead-free NSF 53 water without addition of arsenic. A 1,000 mg / L SPEX nitric acid based standard was obtained and used to prepare 0.5 mg / L influent of reagent of interest. The solution was mixed using a stir plate and then pH adjusted with 3M NaOH or concentrated HCl. The ORP value was then adjusted using solid sodium sulfite or 12.5% NaClO solution.

step:

Isothermal Manufacturing Procedure:

Four 500 mL bottles were each filled with 500 g influent. Pre-wetted media was placed in each 500 mL sample bottle. The bottle cap was closed and sealed with electrical tape. Each bottle was placed in a rotating container containing 10 bottles. The vessel was sealed with duct tape and removed from ash and the bottles were removed from the vessel.

Analytical Sample Preparation Procedures:

For each metal sample, 6 mL sample was taken, diluted with 0.667 mL concentrated nitric acid and filtered through a 0.2 μm filter. The samples were acidified to ensure that all metals were in soluble form. Metal samples were analyzed by ICP-MS. All isotherms were prepared and tested in the same manner to facilitate comparison.

result:

The results are shown in Tables 32-33.

* Final concentration, removal performance, and% removal were averages taken from three samples

conclusion:

By HSA ceria-soluble or water-soluble Al ^{3 +} from the NSF 53 ^{water, Ba 2+, Cd 2+, Cr} 3+, Co 2 +, Cu 2 +, Fe 2 +, Mn 2 +, Ni ^{2 +,} and certainly removed It became.

3A-E (aluminum), 6A-E (chrome), 7A-F (manganese), 8A-F (iron), 9A-E (cobalt), 10A-E (nickel), 11A-E (copper), 24A-C (cadmium), 66A-E (barium), and 67A-E (radium) are the preceding pullbay diagrams for the metal.

Many variations and modifications of the invention can be applied. That is, any embodiment alone or combinations and substitutions thereof may be applied. It may be possible to provide some features of the invention without providing other features.

In various embodiments, configurations, or aspects the invention includes substantially the elements, methods, processes, systems and / or devices described and described herein, which include various embodiments, configurations, Aspects, sub-combinations, and sets. After understanding the present invention, those skilled in the art may apply or use various embodiments, configurations, or aspects. In various embodiments, configurations, and aspects, the invention includes devices and methods of element members not described and / or described herein or in various embodiments, configurations, or aspects, and the absence of such elements. Includes, for example, the absence of elements used in electrical devices or methods for reducing performance, ease of implementation and / or cost of implementation.

The above discussion has been presented for the purposes of description and description. The discussion is not intended to limit the invention to the form or forms disclosed herein. For example, in the foregoing Detailed Description, various features of the invention have been classified into one or more embodiments, configurations, or aspects for the purpose of streamlining the invention. Embodiments, configurations, or aspects of the invention may be combined with alternative embodiments, configurations, or aspects other than those described above. This method of disclosure should not be construed as reflecting the intention that any claim and / or combinations require more features than are explicitly recited in each claim. Rather, as the following claims reflect, inventive aspects are recited less than all features of the embodiments, configurations, or aspects disclosed above alone. Accordingly, the following claims are incorporated into the Detailed Description, with each claim standing on its own as a separate preferred embodiment.

In addition, the description of the present invention includes descriptions of one or more embodiments, configurations, or aspects, but certain changes and variations, other modifications, combinations, and variations are within the scope of the present invention, for example After understanding the present invention, it is within the skill and knowledge of those skilled in the art. Is intended to obtain the right to include alternative embodiments, configurations, or aspects to an acceptable extent, including alternatives, interchanges, and / or equivalent structures, functions, ranges, or steps to those claimed, and such alternatives, Interchange and / or equivalent structures, functions, ranges, or steps are intended to obtain such rights without intention of focusing on any patentable subject matter, regardless of what is disclosed herein and in public.

Claims (39)

Contacting at least one of the lead hydroxide and lead carbonate in a liquid medium with a rare earth-containing additive in the form of a CeO ₂ to remove at least one of lead hydroxide and lead carbonate.
delete delete delete The method of claim 1, wherein the contacting step comprises the following sub-steps (a)-(d):
(a) introducing an oxidizing agent into the medium to oxidize a target-containing species comprising at least one of lead hydroxide and lead carbonate to a major species of at least one form of other lead hydroxide and lead carbonate;
(b) introducing a reducing agent into the medium to reduce a target-containing species comprising at least one of lead hydroxide and lead carbonate to a major species of at least one form of other lead hydroxide and lead carbonate;
(c) introducing a base and / or a base equivalent into the medium to convert the target-containing species comprising at least one of lead hydroxide and lead carbonate to a major species of at least one form of other lead hydroxide and lead carbonate; ;
(d) introducing an acid and / or an acid equivalent into the medium to convert the target-containing species comprising at least one of lead hydroxide and lead carbonate into a major species of one or more forms of other lead hydroxide and lead carbonate; ; And
Then contacting the rare earth-containing additive with at least one of lead hydroxide and lead carbonate in the medium to remove at least one of lead hydroxide and lead carbonate.
The method of claim 1, wherein the rare earth-containing additive is water soluble or water insoluble. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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