OA19117A - Methods for Removing Contaminants from Aqueous Systems - Google Patents

Abstract

Methods for removing one or more contaminants from an aqueous stream comprising: adding one or more hydraulic binders and one or more promoters to the aqueous stream, and separating the contaminants from the aqueous stream are provided. The methods may be used for removing contaminants that are arsenic-based, seleniumbased, cadmium-based, zinc-based, mercurybased, iron-based, chromium-based and/or phosphate-based.

Description

METHODS FOR REMOVING CONTAMINANTS FROM AQUEOUS

SYSTEMS

Cross-reference to Related Applications

[0001] This application claims priority to U.S. Provisional Application No. 61/484,409, filed May 10, 2011; U.S. Provisional Application No. 61/484,413, filed May 10, 2011; and U.S. Provisional Application No. 61/539,757, filed September 27, 2011; ail of which are incorporated herein by reference.

Field of the Art

[0002] The embodiments described herein relate to a method for removing contaminants from aqueous streams, such as waste waters and the like.

Background

[0003] Industrial waste waters commonly include a variety of contaminants which require treatment or removal before the waste water can be discharged. Certain industrial processes, such as mining, generate waste water with oxyanion and/or métal contaminants. Oxyanions are negatively charged inorganic molécules with various degrees of oxidation, for example; CO_X, SO_X, NO_X, PO_X, CIO2, AsO_x, SeO_x, etc. Métal contaminants are toxic metals that may form poisonous water-soluble compounds, including for example mercury, cadmium, lead, chromium, molybdenum, and barium, among others. Both oxyanion and métal contaminants occur in various concentrations throughout the ecosystem and can be observed in elevated levels following various industrial processes, for example mining processes.

[0004] There are various commercial technologies for the removal of contaminants from an aqueous stream, including, for example: adsorption (e.g., adsorption on granular iron based media; adsorption on ion-exchange resins; and adsorption on activated alumina); chemical treatment (e.g., précipitation, cementation, coagulation, and flocculation methods); media filtration (filtering through sand, clay, titanium dioxide, ion exchange resins or membranes such as osmosis or nanofiltration membranes); and biomediated removal. Many of these methods require multiple steps to pretreat or chemically reduce the contamination. Many of these methods generate additional hazardous waste that must be further treated or handled.

[0005] The description herein of certain advantages and disadvantages of known methods is not intended to limit the scope of the present invention. Indeed the present embodiments may include some or ail of the features described above without suffering from the same disadvantages.

Brief Summary

[0006] Disclosed herein are methods for removing one or more contaminants from an aqueous stream comprising: adding one or more hydraulic binders and one or more promoters to the aqueous stream, and separating the one or more contaminants from the aqueous stream. Methods for removing one or more contaminants from an aqueous stream comprising: preparing a mixture of one or more hydraulic binders and one or more promoters, and passing an aqueous stream containing the one or more contaminants through the mixture are also provided.

Brief Description of the Drawings

[0007] In order to facilitate a fuller understanding of the exemplary embodiments, reference is now made to the appended drawings. These drawings should not be construed as limiting, but are intended to be exemplary only.

[0008] Figure 1 shows the results of decontamination of a solution containing 30000 ppb of cadmium using exemplary hydraulic binders with or without promoters.

[0009] Figure 2 shows the results of decontamination of a solution containing 11000 ppb of cadmium using various dosages of a commercially-available sodium aluminate coagulant.

[0010] Figure 3 shows the results of decontamination of a solution containing 11000 ppb of cadmium using various dosages of an exemplary hydraulic binder and promoter system.

Detailed Description

[0011] Methods for removing, or reducing the amount of, one or more types of contaminants from aqueous streams are provided, wherein the aqueous streams are treated with one or more hydraulic binders and one or more promoter compounds to form solids of the contaminants. After treatment, the solids can be separated from the aqueous stream, for example by gravity settling or mechanîcal séparation. In exemplary embodiments, the contaminants include metals and/or oxyanions.

[0012] According to the embodiments described herein, hydraulic binders can be used in combination with promoters, for example compounds with nucleophilic moieties, to provide an in-situ solidification, or in-situ chemisorption, method for treatment of contaminated process waters, in particular for mining process water. As described herein, hydraulic binders, for example inorganic aluminosilicate based materials, can be crosslinked in water, or in aqueous streams, to generate an insoluble amorphous sorbent with active sites for chemisorption of many types of contaminants, including metals and oxyanions.

[0013] Methods for removing, or reducing the amount of, one or more types of contaminants aqueous streams are provided, wherein the aqueous streams are treated with one or more hydraulic binders and one or more promoter compounds to form solids of the contaminants.

[0014] In an exemplary embodiment, the method may be used to encapsulate and/or immobilize one or more contaminants that are présent in water or aqueous streams. Encapsulated and/or immobilized species can go under common physical séparation and removal of suspended solids from the aqueous stream.

[0015] Aqueous Streams

[0016] The expression “aqueous stream” as used herein refers to any aqueous liquid feed that contains undesirable amounts of contaminants, for example metals or oxyanions. Exemplary aqueous streams include but are not limited to drinking water, ground water, well water, surface water, such as waters from lakes, ponds and wetlands, agricultural waters, wastewater, such as wastewater or leaching water from mining or industrial processes, geothermal fluids, water from mining processes associated with smelting, mine dewatering, tailing impoundment treatment, chemical induced leaching, flotation, autoclave, acid mine drainage, and the like. In certain embodiments, the method can be used to remove one or more contaminants from any aqueous stream containing greater than about 2.0 ppb of the one or more contaminants. In one embodiment, the method is effective for treating aqueous streams containing more than 500 ppb of one or more contaminants. In an exemplary embodiment, the method is effective in decreasing levels of one or more contaminants to below about 100, about 10, about 5, or about 2 ppb.

[0017] Depending on the composition of the aqueous stream, the hydraulic binders, promoters, and other additives may change, concentrations of the hydraulic binders, promoters, and additives may change, and the sequence of adding the hydraulic binders, promoters, and additives may change. Such changes would be understood by those skilled in the art and may be determined from expérience with different aqueous stream compositions.

[0018] In exemplary embodiments, the aqueous stream comprises water and one or more contaminants, for example metals and/or oxyanions.

[0019] In exemplary embodiments, the aqueous stream is an industrial stream, process stream, wastewater from flue gas desulfurization units, runoff from wet fly ash ponds, groundwater stream, and the like. In exemplary embodiments, the aqueous stream is produced from a mining process, for example a smelting process, such a smelting process gold, copper, iron, nickel, silver, phosphate, coal or molybdenum; or processes associated with mine dewatering, tailing impoundment treatment, chemical induced leaching, flotation, autoclave, acid mine drainage, and the like. The embodiments described herein may be used to reduce or remove contaminants resulting from aqueous streams from various processes, încluding, for example, coal mining, industrial metals mining (e.g., phosphate, clays, white minerais, etc.), metals mining and processing (e.g., gold, copper, uranium, silver, nickel, etc.), metals smelting, municipal and industrial processes (e.g., coal burning power plants, and landfill leachate), oil processes (e.g., oil exploration, production, processing and/or refining).

[0020] Contaminants

[0021] The embodiments described herein may be used to reduce or remove a variety of metallic or non-metallic contaminants. As used herein, a “contaminant” refers to any substance which is not desirous, încluding those which may be considered harmful to humans or the environment, for example metals, non-metals, and/or oxyanions. The embodiments may remove métal contaminants, such as mercury, cadmium, zinc, manganèse, lead, copper, chromium, molybdenum, gallium, indium, thallium, barium, silver, and/or other métal contaminants, încluding the various oxidation states of these metals or compounds comprising these metals. The embodiments may remove nonmetallic contaminants such as, for example, antimony, arsenic, sélénium, phosphates, and/or other non-metallic contaminants, încluding the various oxidation states of these non-metals or compounds comprising these non-metals, or compounds comprising arsenic, sélénium, or phosphates.

[0022] An “oxyanion” or “oxoanion” is a chemical compound of the formula A_xO_y ^z_ (where A represents a chemical element and O represents an oxygen atom). Oxyanions are formed by many chemical éléments. Exemplary oxyanions include borate, carbonate, nitrate, phosphate, sulfate, chromate, arsenate, selenate, molybdate, nitrite, phosphate, sulfite, arsenite, selenite, hypophosphite, phosphate, hyposulfite, perchlorate, perbromate, periodate, permanganate, chlorate, chromate, bromate, iodate, chlorite, bromite, hypochlorite, and hypobromite.

[0023] In exemplary embodiments, the one or more contaminants may be any of the contaminants, or any mixture of the contaminants, described herein.

[0024] In an exemplary embodiment, the contaminant is a compound comprising arsenic or a mixture comprising arsenic-based compounds. Arsenic is a persistent, bioaccumulative toxin that is présent in high concentrations in metal-containing ores such as iron, gold, nickel or cobalt, and can be a significant component in mining process water. Arsenic is stable in several oxidation states, under different redox conditions in water. However, when présent in groundwater, arsenic occurs mostfy in the forms of arsenite, As(III), and arsenate, As(V). In one embodiment, the contaminant is arsenate or arsenite.

In one embodiment, the contaminant comprises arsenic, arsenite and/or arsenate, or a mixture comprising arsenic, arsenite and/or arsenate. In one embodiment, the arsenicbased contaminants in the aqueous stream are reduced to a level of less than about 100 ppb, about 50 ppb, about 20 ppb, about 10 ppb, or about 5 ppb. The US Environmental Protection Agency (EPA) recommends that levels of arsenic contaminants in water should be less than 10 ppb.

[0025] In an exemplary embodiment, arsenite is oxidized to arsenate prior to adding the hydraulic binder and promoter system, for example bleach or another oxidizing agent is added to the aqueous stream to oxidize arsenite. One of skill in the art would understand which oxidizing agents would be suitabie.

[0026] In an exemplary embodiment, the contaminant is a compound comprising sélénium or a mixture comprising selenium-based compounds. Sélénium is a naturally occurring element that in small quantities (e.g., 0.1 to 0.5 ppm) can be a micronutrient, but in concentrations above 3 ppm it can be toxic. Sélénium is présent in high concentrations in metal-containing ores such as copper, silver, uranium and lead, and can be a signifïcant component in mining process water. Sélénium can also be a signifïcant impurity in the production of sulfuric acid and mining/utilization of fossil fuels. In one embodiment, the contaminant is selenate (Se(VI)) or selenite (Se(IV)). In one embodiment, the contaminant comprises sélénium, selenite and/or selenate, or a mixture comprising sélénium, selenite and/or selenate. In one embodiment, the selenium-based contaminants in the aqueous stream are reduced to a level of less than about 100 ppb, about 50 ppb, about 20 ppb, about 10 ppb, or about 5 ppb. The EPA recommends that levels of selenates, selenites, or sélénium in water should be less than 5 ppb.

[0027] In an exemplary embodiment, selenate is reduced to selenate prior to adding the hydraulic binder and promoter system, for example hydrochloric acid or another reducing agent is added to the aqueous stream to oxidize selenite. One of skill in the art would understand which reducing agents would be suitabie.

[0028] In an exemplary embodiment, the contaminant is a compound comprising phosphores or a mixture comprising phosphores-based compounds. While phosphores is an element that is essential to life, at elevated concentrations in aqueous Systems it can lead to algal blooms that deplete the water’s oxygen levels, which can hâve detrimental effects on aqueous biota. Phosphores is frequently used in fertilizers in agriculture and faim production, which may contribute to increased concentrations of phosphores in the water supply. In one embodiment, the contaminant is phosphate or phosphite. In one embodiment, the contaminant comprises phosphores, phosphite and/or phosphate, or a mixture comprising phosphores, phosphite and/or phosphate. In one embodiment, the phosphores-based contaminants in the aqueous stream are reduced to a level of less than about 110 ppb, about 107 ppb, about 100 ppb, about 60 ppb, about 50 ppb, about 42 ppb, about 20 ppb, about 10 ppb, or about 5 ppb. In some areas, recommended levels of phosphorus-based contaminants in lakes, streams and canals are less than 50 ppb, less than

107ppb and less than 42 ppb, respectively.

[0029] In an exemplary embodiment, the contaminant is a compound comprising cadmium or a mixture comprising cadmium-based compounds. Cadmium is a heavy métal in the same chemical family as zinc and mercury and prefers an oxidation state of +2 and is chemically similar to zinc. Cadmium typically is not found in an elemental pure state, but rather in zinc, lead, and copper ores as oxide, chloride or sulfide. Cadmium’s high vapor pressure contributes to its toxicity and mobility throughout the environment. During various processes, such as smelting, cadmium may be vaporized and, if not contained, it will oxidize in the environment with either oxygen or other environmental contaminants, such as SO_X, NO_X, CO_X, chloride, etc. Cadmium may enter the environment through volcanic activities, mining processes, industrial processes, as well as burning of coal. Cadmium contamination of aquatic environments can be caused, for example, by smelting of non-ferrous metals, such as from mine drainage water, mine process water, leaching from tailings ponds and the mine site. In one embodiment, the contaminant comprises cadmium or a mixture comprising cadmium and/or cadmium-based compounds. In one embodiment, the cadmium-based contaminants in the aqueous stream are reduced to a level of less than about 50 ppb, about 20 ppb, about 10 ppb, about 5 ppb, about 2 ppb, about 1 ppb, about 0.5 ppb, about 0.4 ppb, about 0.3 ppb, about 0.25 ppb, about 0.2 ppb, about 0.15 ppb, or about 0.1 ppb. The EPA currently recommends that levels of cadmium or cadmium-based compounds in water should be less than 0.25 ppb.

[0030] In an exemplary embodiment, the contaminant is a compound comprising mercury or a mixture comprising mercury-based compounds. In one embodiment, the mercury-based contaminants in the aqueous stream are reduced to a level of less than about 1 ppm, about 50 ppb, about 20 ppb, about 10 ppb, about 5 ppb, about 2 ppb, about 1 ppb, about 0.5 ppb, about 0.25 ppb, or about 0.1 ppb. The EPA recommends that levels of mercury or mercury -based compounds in water should be less than 0.7 ppb.

[0031] In an exemplary embodiment, the contaminant is a compound comprising zinc or a mixture comprising zinc-based compounds. In one embodiment, the contaminant is comprises zinc or a mixture comprising zinc and/or zinc-based compounds. In one embodiment, the zinc-based contaminants in the aqueous stream are reduced to a level of less than about 50 ppb, about 20 ppb, about 10 ppb, about 5 ppb, about 2 ppb, about 1 ppb, about 0.5 ppb, about 0.25 ppb, or about 0.1 ppb.

[0032] Hydraulic Binders

[0033] As used herein, the phrase “hydraulic binder” includes those inorganic materials which are distinguished from non-hydraulic binders by their capability to harden upon hydration by formation of an inorganic polymeric network with poor permeability. In exemplary embodiments, the hydraulic binder can be a complex mixture of inorganic phases, or adhesive substances capable of uniting fragments to form a compact whole. In one embodiment, the hydraulic binder is a synthetic or natural inorganic polymer with a silica and/or alumina backbone. Exemplary inorganic polymers are polymers with a skeletal structure that does not include carbon atoms. Examples of suitable hydraulic binders include but are not limited to hydraulic lime, naturally occurring cements, pozzolana cements, gypsum cements, phosphate cements, high alumina cements, slag cements, cernent kiln dust, silica cements, high alkalinity cements, Portland cements and combinations comprising at least one of the foregoing materials.

[0034] In exemplary embodiments, the hydraulic binder may be any of a variety of cements and pozzolanic materials. In one embodiment, the hydraulic binder cernent is a hydraulic cernent or mixture comprising one or more hydraulic cements. Exemplary hydraulic cements include Portland cernent, pozzolana cernent, gypsum cernent, high alumina cernent, slag cernent, silica cernent, kiln dust or mixtures thereof. Exemplary Portland cements may be those classified as class A, C, H and G cements according to American Petroleum Institute (API) spécification for materials and testing for well cements. They can also be classified by ASTM C150 or EN 197 in classes of I, II, III, IV and V. In one embodiment, the hydraulic binder is a hydraulic cernent that comprises calcium, aluminum, silicon, oxygen and/or sulfur which may set and harden by reaction with water. In one embodiment, the hydraulic binder is an alkaline cernent. In a particular embodiment, the hydraulic binder comprises a mixture of two or more hydraulic cements.

[0035] In one embodiment, the hydraulic binder comprises one or more types of Portland cernent. Portland cernent is the most common type of cementitious material used around the world. It consists mainly of calcium silicates and aluminates and some ironcontaining phases. When mixed with water, Portland cernent undergoes various hydration reactions resulting in raised pH as well as génération of new species including calcium silicate hydrates (CSHs). CSH may bind strongly to other minerai grains, resulting in a setting process.

[0036] Portland cernent (also referred to as Ordinary Portland Cernent or OPC) is a basic ingrédient of concrète, mortar, stucco and most non-specialty grout. Portland cernent is a mixture that results from the calcination of natural materials such as limestone, clay, sand and/or shale. In particular, Portland cernent comprises a mixture of calcium silicates, including Ca₃SiO5 and Ca2SiO4, which resuit from the calcination of limestone (CaCO₃) and silica (SiO₂). This mixture is known as cernent clinker. In order to achieve the desired setting qualities in the finished product, calcium sulfate (about 2-8%, most typically about 5%), usually in the form of gypsum or anhydrite, is added to the clinker and the mixture is finely ground to form the finished cernent powder. For example, a typical bulk chemical composition of Portland cernent is about 61 to about 67 wt% calcium oxide (CaO), about 12 to about 23 wt% silicon oxide (SiO₂), about 2.5 to about 6 wt% aluminum oxide (A1₂O₃), about 0 to about 6 wt% ferrie oxide (Fe₂O₃) and about 1.5 about 4.5 wt% sulfate. The properties of Portland cernent can be characterized by the mineralogical composition of the clinker. Major clinker phases présent in Portland cements include: Alite (3CaO.SiO₂), Belite (2CaO.SiO₂), Aluminate (3Cao.Al₂O3) and Ferrite (4CaO. Al₂O3.Fe₂O₃).

[0037] In an exemplary embodiment, the hydraulic binder is a fine powder mixture which contains more than 90% Portland cernent clinker, calcium sulfate and up to 5% minor constituents (see European Standard EN197.1).

[0038] During the préparation of the cernent, a grinding process may be controlled to obtain a powder with a broad particle size range, in which typically 15% by mass consists of particles below 5 pm diameter, and 5% of particles above 45 pm. The measure of particle fineness usually used is the spécifie surface area, which is the total particle surface area of a unit mass of cernent. The rate of initial reaction (up to 24 hours) of the cernent on addition of water is directly proportional to the spécifie surface area.

[0039] In an exemplary embodiment, supplementary cementitious materials, such as fly ash, silica fume or natural pozzolans may be used together with the hydraulic binder. As used herein, a pozzolan is a material which, when combined with calcium hydroxide, exhibits cementitious properties.

[0040] Promoters

[0041] In exemplary embodiments, the promoter is a compound that comprises nucleophilic functionality, e.g. a nucleophilic moiety. For example, elemental sulfur, sodium sulfide, thiols, organic sulfides, nitriles, amines, amides, organophosphines, alcohols, esters, acids, ethers, other sulfur-containing compounds, other hydroxylcontaining compounds, and mixtures thereof, can be used as promoter compounds in the embodiments described herein. One having ordinary skill in the art would understand which compounds would hâve sufficient nucleophilic fonction to provide a synergistic System.

[0042] In an exemplary embodiment, the promoter is elemental sulfur. In one embodiment, the promoter is elemental sulfur or a sulfur-containing compound. In one embodiment, the promoter is a mixture of promoter compounds, for example a mixture including elemental sulfur. In an exemplary embodiment, the promoter is sodium sulfide. In certain embodiments, the promoter is an amine. In other embodiments, the promoter is an organophosphine. In one embodiment, the promoter is an alcohol. In certain embodiments, the promoter is a sulfur-containing compounds, for example a sulfide, a polysulfide, hydrogen sulfide, dimethylthiolcarbamate, diethylthiolcarbamate, sodium sulfide, sodium thiosulfate, calcium polysulfide, and mixtures thereof.

[0043] In exemplary embodiments, the promoter is capable of interacting (e.g. cross-linking, coordinating, reducing or other modes of interacting) with contaminants, such as arsenic-based, selenium-based, cadmium-based, zinc-based, mercury-based, ironbased, chromium-based and/or phosphate-based contaminants. In one embodiment, the promoter is capable of cross-linking with contaminants. In another embodiment, the promoter is capable of coordinating with contaminants. In another embodiment, the promoter is capable of reducing contaminants.

[0044] In one embodiment, the promoter is sulfur or a sulfur-based compound and the contaminant is metal-based contaminant, for example cadmium or mercury. In another embodiment, the promoter is an amine, an organophosphine or an alcohol, and the contaminant comprises iron. In one embodiment, the promoter is an amine or an alcohol and the contaminant comprises chromium. As referred to herein, the term “organophosphine” refers to triorganophophorus compounds and does not include phosphane (PH₃).

[0045] Methods

[0046] A symbiotic system refers to the combination of the hydraulic binder and the promoter which by acting together surprisingly produce a synergistic effect. In exemplary embodiments, the interaction of the hydraulic binders and the promoters in water or aqueous streams is symbiotic.

[0047] In certain embodiments, the hydraulic binder, for example Portland cernent, when added to the aqueous stream in the absence of a promoter, may hâve little effect on concentration of the contaminants, for example cadmium and/or mercury. In comparison, when a promoter, for example elemental sulfur, is used in combination with the hydraulic binder, significant removal of various contaminants in the aqueous stream can be achieved. The use of the hydraulic binder and promoter in the methods described herein, facilitâtes the encapsulation and/or immobilization of the contaminants. The resulting amorphous solid mass, or suspended solids, may be separated by gravity settling, filtration or other conventional solid removal methods.

[0048] In exemplary embodiments, the one or more hydraulic binders and one or more promoters react in situ to generate a sorbent material. The contaminant species can be chemically adsorbed on the surface of the sorbent material, for example in the cavities of the sorbent material. The use of one or more hydraulic binders with one or more ίο promoters is extremely efficient for removing contaminants, for example cadmium or mercury species, from aqueous streams.

[0049] In exemplary embodiments, the ratio of the weight of the hydraulic binders to the weight of the promoter used in the methods is in the range of about 10:1 to about 5 1:1. For example, the ratio of the weight of the hydraulic binders to the weight of the promoter used in the methods is about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, or about 1:1.

[0050] In exemplary embodiments, the method may also comprise adding one or more additives to the aqueous stream. Exemplary additives include but are not limited to 10 aluminum-containing minerais or clays, or iron-containing minerais or clays, such as kaolinate, aluminate, ferrohydrate, hématite, bentonite, and the like. The additives may be added to the aqueous streams before, during or after addition of the hydraulic cernent and/or promoter. The additive may be added to the aqueous stream in an amount of about 0.1% to about 50%, about 0.1% to about 40%, about 0.1% to about 30%, about 0.1% to 15 about 20%, about 0.1% to about 10%, by weight of the one or more hydraulic binders.

[0051] In exemplary embodiments, the dosage of hydraulic binders used in the method is about 10 ppm to about 50,000 ppm, about 10 ppm to about 20,000 ppm, about 10 ppm to about 12,000 ppm, about 20 ppm to about 10,000 ppm, about 20 ppm to about 1000 ppm, about 20 ppm to about 500 ppm.

[0052] In certain embodiments, the contaminant is selenium-based and the dosage of the hydraulic binders used in the method is about 100 ppm to about 50,000 ppm, or about 6000 ppm to about 20,000 ppm. In certain embodiments, the contaminant is arsenicbased and the dosage of the hydraulic binders used in the method is about 50 ppm to about 50,000 ppm, or about 500 ppm to about 5000 ppm. In certain embodiments, the 25 contaminant is phosphorus-based and the dosage of the hydraulic binders used in the method is about 50 ppm to about 20,000 ppm, or about 50 ppm to about 1000 ppm. In certain embodiments, the contaminant is cadmium- and/or zinc-based and the dosage of the hydraulic binders used in the method is about 50 ppm to about 50,000 ppm, or about 300 ppm to about 12,000 ppm. In certain embodiments, the contaminant is mercury-based 30 and the dosage of the hydraulic binders used in the method is about 50 ppm to about 50,000 ppm, or about 300 ppm to about 12,000 ppm.

[0053] In an exemplary embodiment, the amount of the one or more hydraulic binders and one or more promoters added during the process is the amount necessary to reduce the concentration of the one or more contaminants to below about 100 ppb, about 35 50 ppb, about 40 ppb, about 30 ppb, about 20 ppb, about 10 ppb, about 5 ppb, about 4 ppb, about 3 ppb, about 2 ppb, about 1 ppb, about 0.5 ppb, about 0.4 ppb, about 0.3 ppb, about 0.25 ppb, about 0.2 ppb, about 0.15 ppb, or about 0.1 ppb, in total or per species.

[0054] In certain embodiments, the one or more hydraulic binders and one or more promoters may be added to the aqueous stream in one or more doses as needed or in intervals, in a stepwise fashion, or in a continuous fashion.

[0055] In exemplary embodiments, the method for removing one or more contaminants from an aqueous stream comprises: adding one or more hydraulic binders and one or more promoters to the aqueous stream, and separating the contaminants from the aqueous stream. In other embodiments, the method for removing one or more contaminants from an aqueous stream comprises: preparing a mixture of one or more hydraulic binders and one or more promoters, and passing an aqueous stream containing 10 contaminants through the mixture.

[0056] In exemplary embodiments, the one or more hydraulic binders and the one or more promoters can be added to the aqueous stream simultaneously or sequentially. In certain embodiments, the one or more hydraulic binders and the one or more promoters may be premixed before being added to the aqueous stream or before the aqueous stream 15 containing contaminants is passed through the mixture.

[0057] In an exemplary embodiment, the hydraulic binders and promoters, and optionally other additives, are mixed in water and allowed to settle. The resulting solid can be processed, for example milled, into a controlled particle size, for example about 200 to about 1000 micron, these solid particles can be applied as a filter media wherein the 20 aqueous stream containing contaminants is run through the bottom of the filter media, through the top of the filter media, or into a closed circuit.

[0058] In exemplary embodiments, the hydraulic binders and promoters can be added to, or applied to, the aqueous stream in a process that may be a batch process, a continuous process or a semicontinuous process. Such processes can include settling or 25 filtering processes. In exemplary embodiments, the hydraulic binders and promoters can be added as dry materials or as dispersions, for example dispersions in water.

[0059] In exemplary embodiments, the hydraulic binders and promoters are added to an aqueous stream, for example in a reactor or mixing tank, and the aqueous stream is stirred or agitated. In one embodiment, after adding the hydraulic binders and promoters, 30 the aqueous stream is stirred or agitated for a period of time from about 5 minutes to about hours, or about 1 hour to about 3 hours. In exemplary embodiments, after adding the hydraulic binders and promoters, the aqueous stream is stirred for at least about 15 minutes, about 30 minutes, about one hour, about two hours, or about 3 hours. There is no particular limit on the amount of time that the aqueous stream may be stirred after adding 35 the hydraulic binders and promoters.

[0060] In exemplary embodiments, after agitation of the aqueous stream, the stream may be transferred to a thickener or settling tank, or may be allowed to settle where it is.

In certain embodiments, a flocculant may be added to assist in settling.

[0061] In exemplary embodiments, the method may further comprise adding a flocculant. Any suitable flocculant or mixture of flocculants may be used in the method described herein. In certain embodiments, the one or more flocculants added to the aqueous stream comprise one or more polymer flocculants. In exemplary embodiments, the polymer flocculants may be anionic, nonionic, or cationic, for example an acrylamide flocculant. Any polymer flocculants known in the art may be used in the processes described herein. Nonlimiting examples of exemplary polymer flocculants include, for example, flocculant-grade homopolymers, copolymers, and terpolymers prepared from monomers such as (meth)acrylic acid, (meth)acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, and ethylene oxide. In one embodiment, the polymer flocculant is an anionic polymer. In one embodiment, the polymer flocculant is a nonionic polymer. In one embodiment, the polymer flocculant is a mixture of an anionic polymer and a nonionic polymer. In an exemplary embodiment, the one or more flocculants comprises a polyacrylamide flocculant.

[0062] As used herein, the terms “polymer,” “polymers,” “polymeric,” and similar terms are used in their ordinary sense as understood by one skilled in the art, and thus may be used herein to refer to or describe a large molécule (or group of such molécules) that contains recurring units. Polymers may be formed in various ways, including by polymerizing monomers and/or by chemically modifying one or more recurring units of a precursor polymer. A polymer may be a “homopolymer” comprising substantially identical recurring units formed by, e.g., polymerizing a particular monomer. A polymer may also be a “copolymer” comprising two or more different recurring units formed by, e.g., copolymerizing two or more different monomers, and/or by chemically modifying one or more recurring units of a precursor polymer. The term “terpolymer” may be used herein to refer to polymers containing three or more different recurring units.

[0063] In the exemplary embodiments, the dosage of the one or more flocculants can be any dosage that will achieve a necessary or desired resuit. In one embodiment, the dosage of the one or more flocculants is about 5 ppm to about 100 ppm; about 10 ppm to about 70 ppm; or about 20 ppm to about 50 ppm. In one embodiment, the dosage of the one or more flocculants is less than about 100 ppm, about 70 ppm, or about 50 ppm.

[0064] In certain embodiments, the method may further comprise the step of adding one or more absorbents and/or one or more coagulants.

[0065] In an exemplary embodiment, the method further comprises the step of adding one or more additional absorbents before the addition of the one or more flocculants. An “absorbent” as referred to herein includes silica-based compounds, for example an inorganic silica-based polymer, a clay-based material, cellulose, aluminacased adsorbents, ferrohydrate adsorbents, carbon, for example carbon black, or a mixture thereof.

[0066] In exemplary embodiments, the dosage of the one or more absorbents can be any dosage that will achieve a necessary or desired resuit. In one embodiment, the dosage of the one or more absorbents is about 1 to about 10,000 ppm; about 50 to about 5000 ppm; or about 100 to about 1000 ppm. In one embodiment, the dosage of the one or more absorbents is less than about 10,000 ppm, about 5000 ppm, or about 1000 ppm.

[0067] In an exemplary embodiment, the method further comprises the step of adding one or more coagulants before the addition of the one or more flocculants. A “coagulant” as referred to herein includes iron compounds or salts, for example ferrie or ferrous compounds or salts; aluminum compounds or salts; hydrated lime; magnésium carbonate; a polymer that contains one or more quaternized ammonium groups or mixtures thereof. Iron coagulants include, for example, ferrie sulfate, ferrous sulfate, ferrie chloride and ferrie chloride sulfate. Aluminum coagulants include, for example, aluminum sulfate, aluminum chloride and sodium aluminate. Polymer coagulants that contain one or more quaternized ammonium groups include, for example acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, and acrylamidopropyltrimethylammonium chloride.

[0068] In the exemplary embodiments, the dosage of the one or more coagulants can be any dosage that will achieve a necessary or desired resuit. In one embodiment, the dosage of the one or more coagulants is about 1 to about 15 times the amount of the contaminants by mass (e.g. Fe:As mass ratio). In one embodiment, the dosage of the one or more coagulants is less than about 15 times the amount of the contaminants by mass.

[0069] According to the embodiments, the immobilized or solidified contaminants may then be recovered and removed by using any suitable method known in the art. In exemplary embodiments, the séparation step may be accomplished by any means known to those skilled in the art, including but not limited to gravity settling, centrifuges, hydrocyclones, décantation, filtration, thickeners or another mechanical séparation method.

[0070] In exemplary embodiments, the contaminants, once treated with the hydraulic binders and promoters, may be handled or processed in any manner as necessary or desired. In one embodiment, the contaminants should be handled in compliance with govemmental régulations. In some embodiments, the contaminants may be disposed of, sent to a landfill, or when solids are a concentrated source of minerais, the solids may be used a raw materials or feed to produce compounds for commercial products.

[0071] In certain embodiments, the method comprises adding one or more reducing agents, for example a sulfur-containing compound, sodium borohydride, aiuminum hydride, sodium bisulfite, hydrochloric acid or another reducing agent. One of skill in the art would understand what reducing agents could be used. The sulfur-containing compound can be, for example, a sulfide, a polysulfide, hydrogen sulfide, dimethylthiolcarbamate, diethylthiolcarbamate, sodium sulfide, sodium thiosulfate, calcium polysulfide, and mixtures thereof. The amount of the reducing agent to be added to the aqueous stream is dépendent on the amount of contaminant present in the aqueous stream. In one embodiment, the amount of the one or more reducing agents to be added is in the range of about 1.0 mole to about 4.0 moles, about 1.0 mole to about 3.0 moles, or about 1.0 mole to about 2.0 moles, per mol of contaminants. In exemplary embodiments, the amount of the reducing agent added to the aqueous stream is an amount sufficient to maintain a reducing environment.

[0072] In exemplary embodiments, the methods may be used to remove contaminants in non-ferrous métal processes, such as mining and smelting of non-ferrous metals, for example zinc production; iron and/or steel production; fuel combustion, such as coal, oil or wood; cernent manufacturing; phosphate fertilizer manufacture; or sewage sludge incinération.

[0073] In an exemplary embodiment, the method can be easily incorporated into common water treatment practices in the form of in-line addition.

[0074] In exemplary embodiments, the methods described herein can be used to provide an economical and versatile solution for treatment of contaminated mining process waters within an operational and environmental friendly process.

[0075] In exemplary embodiments, the method is useful for solidification/stabilization (S/S) treatment of solid wastes. S/S treatment of waste involves mixing a binder into contaminated media or waste to immobilize contaminants within the treated material. The chemical properties of the binder may be used to lower the solubility of toxic contaminants in the waste and may also be used to lower the toxicity of a hazardous constituents. S/S is used to treat industrial solid waste to make it safe for land disposai. S/S is also used to treat contaminated soil, sédiment or sludge at clean-up (remediation) sites.

[0076] The following examples are presented for illustrative purposes only, and are not intended to be limiting.

Examples

[0077] In the following examples, the cements referenced include: Cernent A: API

Class A Cernent (similar to construction grade Portland cernent), Cernent B: API Class G

Cernent (Standard Oilwell Cernent), Cernent C: ReezCEM 800 (a blended microfine cernent based on Cernent A + Fly Ash).

[0078] In each example, the concentration of the contaminants referenced refers to total ion concentrations.

[0079] The components of the hydraulic binder compositions as referred to in the following examples are provided in the table below. The amounts provided are those amounts mixed as a dry blend and then added to 500 ml of water except as noted otherwise.

[0080] Table 1. Treatment Compositions

Sample Name	Hydraulic Binder (amount in grams)	Promoter	Other additives	Notes
IP-1	Portland Cernent (0.3 g)	-	-	dry blend
IP-2	Portland Cernent (0.3 g)	-	Bentonite (0.02 g)	dry blend
IP-1*	Portland Cernent (0-3 g)	Sulfur (0.06 g)		dry blend
IP-2*	Portland Cernent (0-3g)	Sulfur (0.06 g)	Bentonite (0.02 g)	dry blend
IP-l-N	Portland Cernent (0-3 g)	Sulfur (0.06 g)	Sodium Sulfide (0.02 g)	pre-wet; 70g of the mixture is added to 150 mis water and mixed for 3 hours before use

[0081] Example 1:

[0082] In this example, and in Examples 2, 3, and 4, cadmium chloride (CdCE) was purchased from Aldrich and used as received with no further purification. Lab-made aqueous solutions containing cadmium were prepared by dissolution of the chemical in city of Atlanta tap water. A Thermo Scientific ICP-AES system model iCAP 6200 equipped with a charge injection device (CID) detector and a CETAC ASX-520 autosampler was used for détermination of cadmium species in water samples. Low détection limits (0.2 ppb for cadmium) were achieved by pre-concentration of 100 ml aqueous samples. Quantitative elemental analysis of trace éléments was conducted on a

Broker S4 Explorer wavelength-dispersive X-ray fluorescence spectrometer.

[0083] Two hydraulic binder compositions (IP-1 and IP-2) were evaluated for their effectiveness in the treatment of cadmium contaminated water samples. Water samples were prepared having 3000 ppb cadmium. The water samples were treated with IP-1 or IP-2 and mixed for 2-3 hours. Resulting suspensions were then left for gravity settling. Filtration of supernatant on a Whatman qualitative filter paper No. 5 (pore size of 2.5 pm) provided a clear, visible solid free water sample for ICP analysis. As shown in Figure 1, the hydraulic binder alone reduced the cadmium concentration to 17 ppb (for IP-1) or 5.6 ppb (for IP-2).

[0084] Example 2:

[0085] Water samples were treated with compositions containing a hydraulic binder and a sulfur promoter. Water samples were prepared having 30,000 ppb cadmium. The water samples were treated with IP-1* or IP-2* and mixed for 2-3 hours. Resulting suspensions were then left for gravity settling. Filtration of supernatant on a Whatman qualitative filter paper No. 5 (pore size of 2.5 pm) provided a clear, visible solid free water sample for ICP analysis. As shown in Figure 1, hydraulic binder plus promoter samples (IP-1* and IP-2*, respectively), the cadmium was further reduced, for example, to 1.7 ppb in the case of IP-1* treatment.

[0086] Example 3:

[0087] Water samples were treated with compositions containing a hydraulic binder and a sulfur promoter, were subsequently flocculated using a commercial flocculant to accelerate the settling of suspended solids instead of gravity settling. Water samples were prepared having 30,000 ppb cadmium. The water samples were treated with IP-1* or IP2*, and were mixed for 2-3 hours. Using a plastic syringe, a flocculant (Superfloc A130HMW, Kemira Oyj) was added to each sample solution to obtain 0.5 to 7.5 ppm weight/weight in the sample. The samples were stirred for one minute, and allowed to settle for at least five minutes. The beaker contents were filtered using vacuum filtration or syringe filtration with 0.45 micron filters. As shown in Figure 1, in these treatments (IP-1* -(-Flocculation and IP-2* -(-Flocculation, respectively), the cadmium level was even further reduced to 0.8 ppb (for IP-1*) and 0.5 ppb (for IP-2*). This indicated the presence of fine solids in the sample fluid which may pass through the filter paper at the first trails.

[0088] Example 4:

[0089] In this comparative example, traditional ferrons chloride and sodium aluminate coagulants were evaluated under lab conditions and cadmium contaminated water having 11000 ppb cadmium. Treatment with ferrous chloride did not lead to any réduction in cadmium, but treatment with sodium aluminate showed a réduction in cadmium level in contaminated water. As shown in Figure 2, cadmium level can be reduced from 11000 ppb to 380 ppb when 520 ppm of aluminate coagulant is used.

[0090] Example 5:

[0091] The hydraulic binder and promoter system, IP-2*, was evaluated at varying concentrations, and it was found that it could provide higher efficiency than the aluminate coagulant. As illustrated in Figure 3, IP-2* provided a réduction in the cadmium level from 11000 ppb to 11.80 ppb by using only 24 ppm of the hydraulic binder and promoter system. Further réduction was achieved by increasing the hydraulic binder and promoter concentration. At a level of 240ppm, the residual cadmium concentration in the treated water was below 1 ppb.

[0092] Example 6:

[0093] In this example, several treatment methods were evaluated for efficacy of reducing zinc contaminants in water. The starting zinc contaminated water samples contained 697 ppb of zinc. The water samples were treated with IP-1* or IP-l-N. The treatment conditions are the same as described above for Example 2. The results are provided in Table 2, below. For comparison, some water samples were treated with two commercial coagulants, ferrous chloride and sodium aluminate. The treatment conditions are the same as described above for Example 4. The results are provided in Table 3.

Table 2. Effect of the treatment composition on Zn concentration (ppb) in the contaminated water

Treatment (PPm)	60	200	600	900	1200	1500
IP-1*	26.1	12.7	<10	<10	<10	15.3
IP-l-N	22.9	20.8	<10	<10	<10	<10

Table 3. Effect of the treatment composition on Zn concentration (ppb) in the contaminated water

Treatment (PPm)	100	200	600	1000	2000	3000	4000	6000
Ferrous	621	679	647	726	n/a	n/a	n/a	n/a

Chloride
Sodium Aluminate	105	135	32.7	30.9	41.2	42.3	48.8	53.7

[0094] Example 7:

[0095] In this example, the dry blended hydraulic binder and promoter compositions were added to water containing 25 ppm sélénium contaminants. Prior to adding the hydraulic binder and promoter, the pH of the contaminated water sample was adjusted to pH 4 with the addition of HCl to reduce the selenate compounds to selenite compounds. The solutions were agitated for 3 hours to promote mixing. The solids are then allowed to settle and are subsequently removed through gravitational filtration. The dry blended hydraulic binder and promoter compositions are provided in Table 4. The promoter in each experiment was elemental sulfur. The amount of sélénium removed was determined by analyzing the liquids with ICP and/or the solids with XRF analysis.

Table 4. Effect of treatment composition on Se concentration in the contaminated water

Experiment No.	1	2	3	4	5	6
Sélénium Removal	49.44%	15.36%	5.50%	49.62%	100.00%	34.90%
Hydraulic Binder Type	Cernent A	Cernent B	Cernent C	Cernent A	Cernent A	Cernent A
Dosage of Treatment System (ppm)	1200	1200	1000	2200	1400	600
Weight Ratio (Hydraulic Binder: Promoter)	1:0.2	1:0.2	1:0	1:0.1	1:0.4	1:0.2

[0096] Example 8:

[0097] In this example, the dry blended hydraulic binder and promoter compositions were added to water containing 25 ppm arsenic. Prior to adding the hydraulic binder and promoter, 20 ppm of commercial bleach was added to the contaminated water to oxidize the arsenite compounds to arsenate compounds. The solutions were agitated for 3 hours to promote mixing. The solids are then allowed to settle and are subsequently removed through gravitational filtration. The dry blended hydraulic binder and promoter compositions are provided in Table 5. The promoter in each experiment was elemental sulfur. The amount of arsenic removed was determined by analyzing the liquids with ICP.

Table 5. Effect of treatment composition on As concentration in the contaminated water

Experiment No.	1	2	3	4	5	6
Arsenic Removal	87.00%	65.00%	66.00%	100.00%	100.00%	71.90%
Hydraulic Binder Type	Cernent A	Cernent B	Cernent C	Cernent A	Cernent A	Cernent A
Dose of Treatment System (ppm)	600	600	600	1200	1100	300
Weight Ratio (Hydraulic Binder: Promoter)	1:0.2	1:0.2	1:0.2	1:0.2	1:0.1	1:0.2

[0098] Example 9:

[0099] In this example, the dry blended hydraulic binder and promoter compositions were added to lab generated water containing 600 ppb phosphorus (sodium phosphate). The water sample was prepared by the addition of sodium phosphate to lab generated water. The solutions were agitated for 3 hours to promote mixing. The solids are then allowed to settle and are subsequently removed through gravitational filtration, results are shown in Table 6. The amount of phosphorus removed was determined by analyzing the liquids with ICP. It was observed that the phosphorus concentration was reduced to 3 ppb when the hydraulic binder and promoter System was applied.

Table 6. Effect of treatment composition on phosphorus concentration (ppb) in the contaminated water

Dosage (ppm)	20	60	200	600	1200	2000
Treatment: IP-l-N	571	29.2	6.3	8.3	5.8	3.6
Treatment: IP-1*	496	8.5	14.4	5.1	3	3

[00100] Example 10:

[00101] In this example, the dry blended hydraulic binder and promoter compositions were added to water containing 15.5 ppm phosphorus. The solutions were agitated for 3 hours to promote mixing. The solids are then allowed to settle and are subsequently removed through gravitational filtration. The results are shown in Table 7. The amount of phosphorus removed was determined by analyzing the liquids with ICP.

Table 7. Effect of treatment composition on phosphorus concentration (ppm) in the contaminated water

Dosage (ppm)

200

600

1200

2000

Treatment: IP-1*	0.12	0.14	0.12	0.09
Treatment: IP-1*	0.11	0.11	0.13	0.08
Treatment: IP-l-N	0.13	0.09	0.01	0.09

[00102] Example 11:

[00103] In this comparative example, the ferrons chloride or sodium aluminate compositions were added to water containing 26.4 ppm phosphorus. The solutions were 5 agitated for 3 hours to promote mixing. The solids were then allowed to settle and were subsequently removed through gravitational filtration. The results are shown in Table 8. The amount of phosphorus removed was determined by analyzing the liquids with ICP.

Table 8. Effect of treatment composition on phosphorus concentration (ppm) in the 10 contaminated water

Dosage (ppm)	100	200	600	1000
Treatment: Ferrous chloride	0.71	0.1	0.02	0.05
Treatment: Sodium aluminate	0.07	0.07	0.06	0.06

[00104] In the preceding spécification, various embodiments hâve been described with reference to the examples. It will, however, be évident that various modifications and changes may be made thereto, and additional embodiments may be implemented, 15 without departing from the broader scope of the exemplary embodiments as set forth in the claims that follow. The spécification and drawings are accordingly to be regarded in an illustrative rather than restrictive sense.

Claims (12)

1. We Claim:

   1. A method for removing one or more contaminants from an aqueous stream comprising: adding one or more hydraulic binders and one or more promoters to the aqueous stream, and separating the contaminants from the aqueous stream.
2. 2. The method of claim 1, wherein the contaminants are selected from the group consisting of mercury, cadmium, zinc, manganèse, lead, copper, chromium, molybdenum, gallium, indium, thallium, other métal contaminants, including the various oxidation states of these metals and compounds comprising these metals.
3. 3. The method of claim 1, wherein the contaminants is selected from the group consisting of antimony, arsenic, sélénium, phosphates, other non-metallic contaminants, and compounds comprising arsenic, sélénium, phosphates, including the various oxidation states of these non-metals and compounds comprising these non-metals.
4. 4. The method of claim 1, wherein the contaminants comprise arsenic-based, selenium-based, cadmium-based, zinc-based, mercury-based, iron-based, chromium-based and/or phosphate-based contaminants.
5. 5. The method of claim 1, wherein the hydraulic binders are selected from the group consisting of hydraulic lime, naturally occurring cements, pozzolana cements, gypsum cements, phosphate cements, high alumina cements, slag cements, cernent kiln dust, silica cements, high alkalinity cements, Portland cements and combinations thereof.
6. 6. The method of claim 1, wherein the promoters are selected from compounds that comprise a nucleophilic moiety.
7. 7. The method of claim 6, wherein the nucleophilic moiety is selected from the group consisting of elemental sulfur, sodium sulfide, thiols,organic sulfides, nitriles, amines, amides, organophosphines, alcohols, esters, acids, ethers, other sulfur-containing compounds, and other hydroxyl-containing compounds.
8. 8. The method of claim 1, wherein the promoter is elemental sulfur.
9. 9. The method of claim 1, wherein the aqueous stream is selected from industrial streams, process streams, wastewater from flue gas, desulfurization units, runoff from wet fly ash ponds, and groundwater streams.
10. 10. The method of claim 1, wherein the séparation step is accomplished by gravity settling, filtration, or another mechanical séparation method.
11. 11. The method of claim 1, wherein the method further comprises stirring or agitating the aqueous stream after the binders and promoters hâve been added.
12. 12. A method for removing contaminants from an aqueous stream comprising: preparing a mixture of one or more hydraulic binders and one or more promoters, and passing an aqueous stream containing one or more contaminants through the mixture.