Classifications

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  • B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/0266—Compounds of S
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  • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
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  • B01J20/0288—Halides of compounds other than those provided for in B01J20/046
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/12—Naturally occurring clays or bleaching earth
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/16—Alumino-silicates
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  • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
  • B09B3/10—Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
  • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
  • B09B3/35—Shredding, crushing or cutting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
  • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/28—Treatment of water, waste water, or sewage by sorption
  • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/28—Treatment of water, waste water, or sewage by sorption
  • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/28—Treatment of water, waste water, or sewage by sorption
  • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/72—Treatment of water, waste water, or sewage by oxidation
  • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/72—Treatment of water, waste water, or sewage by oxidation
  • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
  • C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2220/00—Aspects relating to sorbent materials
  • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
  • B01J2220/42—Materials comprising a mixture of inorganic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09C—RECLAMATION OF CONTAMINATED SOIL
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• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2101/00—Nature of the contaminant
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  • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

• This invention relates to remediation of environmental pollutants to reduce their environmental availability.
• Mercury contamination can come from a variety of different sources such as mining and ore processes, chlor-alkali plants, and battery manufacturing processes. There also are many landfills contaminated with mercury-containing waste. Additionally, mercury pollutants are present in multiple forms including metallic mercury, organic mercury compounds, and inorganic mercury compounds, often at the same site. Different mercury forms and/or different substances often require different treating methods.
• Mercury contaminated substances are likely to also comprise multiple other environmental pollutants.
• some substances are also contaminated with organics and/or other heavy metals, and these other environmental pollutants provide similar challenges. Therefore, reducing the environmental availability of environmental pollutants at any particular site can be technically challenging and costly, depending on the substance that is contaminated, condition of the substance, waste types, mercury forms, and other contaminants or environmental pollutants present. Reducing the environmental availability of environmental pollutants, which in turn reduces the bio-availability of pollutants and thus their bio-accumulation, especially in substances such as soils, groundwaters, sediments, and slurries, is of particular interest.
• Toxicity Characteristic Leaching Procedure TCLP
• This invention provides processes for reducing environmental availability of at least a portion of one or more environmental pollutants in a substance comprising one or more environmental pollutants.
• a benefit provided by the processes of this invention is a reduction of environmental availability of toxic environmental pollutants in substances.
• toxic pollutants include mercury and methyl mercury, as well as heavy metals and ecologically toxic organic matter.
• An advantage provided by the processes of this invention is that by reducing environmental availability of environmental pollutants in substances, bio-availability and bioaccumulation of such pollutants is also reduced.
• the environmental pollutant is mercury
• another advantage is that the processes of the invention do not need sulfide to be present, and so reduction of environmental availability and thus reduction of bio-availability is not negatively affected by acidic conditions which permit sulfides to form sulfuric acid or sulfate compounds; this absence of sulfates in turn minimizes mercury methylation.
• Processes of this invention can be used as the sole process for reducing the environmental availability and/or the presence of environmental pollutants, such as mercury, in a substance, or can be used to complement and/or enhance the reduction in environmental availability and/or the amount of such environmental pollutants in the substance than is attained by existing technologies.
• environmental pollutants such as mercury
• An embodiment of this invention is a process for reducing environmental availability of at least a portion of one or more environmental pollutants in a substance comprising one or more environmental pollutants.
• This process comprises a) adding and/or applying an inorganic halide compound or an inorganic sulfide compound to the substance and b) adding and/or applying a sorbent to the substance.
• the inorganic halide compound comprises one or more inorganic fluorides, inorganic chlorides, inorganic bromides, and/or inorganic iodides. Adding and/or applying the inorganic halide compound or inorganic sulfide compound and the sorbent to the pollutant-containing substance reduces the environmental availability of at least a portion of one or more environmental pollutants in the substance.
• the Figure is a graph showing mercury adsorption as a function of bromide ion concentration from Example 1.
• the Figure illustrates embodiments of specific aspects of the invention, and are not intended to impose limitations on the scope of the invention.
• the present invention provides processes for reducing the environmental availability of environmental pollutants.
• reducing environmental availability refers to stabilizing, immobilizing, fixing, encapsulating, isolating, containing, destroying, detoxifying, decomposing, and decaying, reducing the amount of, reducing the mobility of, and/or reducing the migration ability of, at least one environmental pollutant.
• the stabilizing and/or immobilizing can be in a medium. Reducing the environmental availability of environmental pollutants in turn reduces the bio-availability of pollutants and thus their bioaccumulation.
• environmental pollutant and “environmental pollutants” means a chemical element or compound or mixture thereof known to be harmful to humans and/or to impact the environment (ecosystem).
• Environmental pollutants are typically regulated by one or more government agencies.
• environmental pollutants include mercury in all of its forms, e.g., elemental mercury, organic mercury compounds, and inorganic mercury compounds; other organic matter (including, for example, without limitation, hydrophobic organic compounds, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, dioxins, furans, and/or chlorinated pesticides); hazardous elements, organic and inorganic heavy metal compounds (including, for example, without limitation, compounds comprising As, Pb, Zn, Cu, Cr, and/or Cd); and other environmental pollutants known to those skilled in the art.
• other organic matter including, for example, without limitation, hydrophobic organic compounds, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, dioxins, furans, and/or chlorinated pesticides
• hazardous elements organic and inorganic heavy metal compounds (including, for example, without limitation, compounds comprising As, Pb, Zn, Cu, Cr, and/or Cd); and other environmental pollutants known to those skilled in the art.
• inorganic halide and the word “halide” are used throughout this document to refer to halide ions (fluoride, chloride, bromide, and iodide).
• the remediation agents in the practice of this invention comprise an inorganic halide compound and a sorbent or an inorganic sulfide compound and a sorbent; in the embodiments in which the substance comprises bromide ions in addition to one or more environmental pollutants, the remediation agents are bromine-containing carbonaceous materials.
• Sorbents include carbonaceous materials and inorganic materials. Suitable carbonaceous materials that can be used as sorbents in the practice of this invention include, for example, without limitation, activated carbon, carbon black, char, and coke. A preferred carbonaceous material is activated carbon, which can be used in many forms including, for example, without limitation, powdered, granular, or extruded; and high specific surface area.
• Suitable inorganic materials that can be used as sorbents in the practice of this invention include inorganic oxides such as alumina (amorphous and crystalline), silica, magnesia and titania; natural zeolites, such as chabazite, clinoptilolite, and faujasite; synthetic zeolites, such as synthetic chabazite, zeolites with high Si:Al ratios (ZSM-5, beta zeolites, sodalite), zeolites with moderate Si:Al ratios (Y zeolites, A zeolites), silica alumina phosphate (SAPO) zeolites, ion exchanged zeolites, uncalcined zeolites, clay minerals such as kaolin, kaolinite, bentonite, and montmorillonite; synthetic clays such as laponite, saponite, sauconite, stevensite, kaolinite, and hectorite; organo-clays
• sorbent material Another type of sorbent that can be used in the practice of this invention is a modified sorbent material, where "modified" indicates that a sorbent material has been contacted with a chemical to modify the sorbent material; the sorbent material may be a carbonaceous material or an inorganic material; preferences for carbonaceous materials and inorganic materials are as described above.
• the modified sorbent material comprises a modified carbonaceous material.
• Modified sorbent materials are usually halogen-containing sorbents and sulfur- containing sorbents, preferably halogen-containing carbonaceous materials and sulfur-containing carbonaceous materials, more preferably halogen-containing carbonaceous materials, especially bromine-containing carbonaceous materials.
• the halogen comprises one or more halogens selected from fluorine, chlorine, bromine, and/or iodine; bromine is a preferred halogen.
• the amount of halogen (or halogen content) on the sorbent material is typically equivalent to a total bromine content (or calculated as bromine) in the range of about 0.1 wt% to about 20 wt%, based on the total weight of the halogen-containing sorbent; here, the numerical value is calculated for bromine, even if the halogen is not bromine.
• Halogen- containing sorbents can be made from a sorbent material and one or more halogen-containing compounds as described in U.S. Pat. Nos. 6,953,494 and 9,101,907, and in International Patent Pub. No. WO 2012/071206.
• the modified sorbent material is a sulfur-containing sorbent
• the amount of sulfur (or sulfur content) on the sorbent material is typically in the range of about 0.1 wt% to about 15 wt%, based on the total weight of the sulfur-containing sorbent.
• Sulfur-containing sorbents can be made from a sorbent material and one or more sulfur-containing compounds or elemental sulfur as described in International Patent Pub. No. WO 2012/071206, Environ. Sci. Technol. 1998, 32, 531-538 (Liu et al.), and Int. ./. Environ. Sci. Technol, 2015, 12, 2511-2522 (Asasian et al.).
• the inorganic halide compound can be an inorganic fluoride, an inorganic chloride, an inorganic bromide, an inorganic iodide, or a mixture of any two or more halides.
• Inorganic chlorides and inorganic bromides are preferred inorganic halides; more preferred are inorganic bromides.
• the inorganic halides are provided by one or more inorganic halide compounds. Mixtures of inorganic halide compounds can be used; the mixtures may contain the same inorganic halide element and/or a different inorganic halide element.
• Types of inorganic halide compounds that can be used include hydrohalic acids, alkali metal halides, alkaline earth halides, other metal halide salts, and ammonium halides.
• Hydrohalic acids include hydrogen chloride, hydrogen bromide, and hydrogen iodide.
• Alkali metal halides include lithium halides, sodium halides, potassium halides, rubidium halides, and cesium halides; sodium halides and potassium halides are preferred.
• Suitable alkali metal halides include sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, and potassium iodide.
• Alkaline earth halides include magnesium halides, calcium halides, strontium halides, and barium halides; calcium halides are preferred.
• Suitable alkaline earth halides include magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, calcium fluoride, calcium chloride, calcium bromide, and calcium iodide.
• Other suitable metal halide salts include iron(III) fluoride, iron(III) chloride, iron(III) bromide, iron(III) iodide, manganese(II) fluoride, manganese(II) chloride, manganese(II) bromide, and manganese(II) iodide.
• Ammonium halides include ammonium chloride, ammonium bromide, and ammonium iodide.
• Preferred inorganic halide compounds include hydrogen bromide, sodium chloride, sodium bromide, potassium bromide, potassium iodide, calcium bromide, iron(III) bromide, and manganese(II) bromide; more preferred are hydrogen bromide, sodium chloride, sodium bromide, potassium bromide, potassium iodide, and calcium bromide; even more preferred are sodium bromide and calcium bromide, especially sodium bromide.
• the inorganic sulfide compound can be hydrogen sulfide, ammonium sulfide, an alkali metal sulfide, an alkaline earth sulfide, or another metal sulfide salt.
• Alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide; sodium sulfide and potassium sulfide are preferred.
• Alkaline earth sulfides include magnesium sulfide, calcium sulfide, strontium sulfide, and barium sulfide; calcium sulfide is preferred.
• Other suitable metal sulfide salts include iron(III) sulfide and manganese(II) sulfide.
• Preferred inorganic sulfide compounds include hydrogen sulfide, sodium sulfide, potassium sulfide, and calcium sulfide; more preferred are hydrogen sulfide and sodium sulfide, especially sodium sulfide.
• the inorganic halide compound or inorganic sulfide compound is used as a solid; if small particles are needed or desired, the solid inorganic halide compound or inorganic sulfide compound can be reduced to the needed or desired particle size.
• the inorganic halide compound or inorganic sulfide compound is used as a solution or slurry, normally and preferably as an aqueous solution.
• the inorganic halide compound or inorganic sulfide compound can be at a concentration up to its solubility limit in the solvent.
• the inorganic halide compound or inorganic sulfide compound in a solution or slurry is in an amount such that the halide or sulfide is about 0.5 wt% to about 45 wt% calculated as bromide relative to the total weight of the solution.
• the inorganic halide compound or inorganic sulfide compound in a solution or slurry is in an amount such that the halide or sulfide is about 1 wt% to about 30 wt%, more preferably about 5 wt% to about 20 wt%, calculated as bromide relative to the total weight of the solution or slurry.
• the phrases "as bromide,” “reported as bromide,” “calculated as bromide,” and analogous phrases for the halides and sulfide refer to the amount of halide or sulfide, where the numerical value is calculated for bromide, unless otherwise noted.
• an inorganic fluoride may be used, but the amount of halide relative to the weight of the solution or slurry is stated as the value for bromide.
• the relative amounts of halide or sulfide and sorbent can vary widely, as needed for the particular substance needing remediation. Often, the amount of sorbent relative to the halide or sulfide is very low, e.g., about 100 ppm to about 1000 ppm (about 0.01 wt% to about 0.1 wt%).
• Activated carbons suitable for use in processes of this invention can have a wide range of particle sizes and distributions, from nanometer to centimeter; and can be formed from activated carbon forms including, for example, without limitation, powdered, granular, or extruded; high specific surface area, a variety of unique pore structures, varying pore distributions; and other features as will be familiar to those skilled in the art.
• inorganic halide compounds and sorbents or inorganic sulfide compounds and sorbents when used together, especially inorganic bromide compounds, more especially inorganic bromide compounds and activated carbons, can reduce environmental availability of pollutants in substances through means including, for example, without limitation, oxidation and/or adsorption. Adsorption can reduce the environmental availability of environmental pollutants by reducing mobility of such pollutants.
• Other ways in which inorganic halide compounds and sorbents or inorganic sulfide compounds and sorbents when used together can reduce environmental availability of pollutants are by enhancing the degradation of such pollutants through surface reactions; and/or by inhibiting the formation of pollutants such as methyl mercury; and/or by other mechanisms.
• the environmental pollutants contacted by the inorganic halide compounds or inorganic sulfide compounds and/or adsorbed by the sorbents are stabilized such that desorption into the environment is substantially minimized.
• the inorganic halide compound or inorganic sulfide compound and sorbent are not mixed or combined prior to application to the substance to be remediated.
• the phrase "used together" means that both the inorganic halide compound or inorganic sulfide compound and sorbent are used in the process.
• the inorganic halide compound or inorganic sulfide compound and the sorbent can be added or applied to the substance to be remediated at the same time or at different times, and at the same location or at different locations.
• the periods of time for each may overlap, or there may not be overlap in the periods of time the inorganic halide compound or inorganic sulfide compound is added and/or applied and the sorbent is added and/or applied.
• the inorganic halide compound or inorganic sulfide compound and the sorbent can be added and/or applied to the substance to be treated via the same conduit or different conduits, or via the same mode of addition or via different modes of addition.
• the inorganic halide compound or inorganic sulfide compound and the sorbent may be injected through separate injection ports, and the inorganic halide compound or inorganic sulfide compound and the sorbent may be injected at different points in time. Preferences for adding and/or applying the inorganic halide compound or inorganic sulfide compound and the sorbent depend on various factors, which include the substance being treated and the remediation method being used.
• Mercury and other environmental pollutants can react with the inorganic halide compounds or inorganic sulfide compounds and/or become adsorbed onto or into sorbents, especially inorganic bromides and activated carbon when used together, effectively removing the pollutants.
• bromide ion can chemically bond with ionic mercury.
• inorganic halide compounds or inorganic sulfide compounds and sorbents when used together, particularly inorganic bromide compounds and activated carbons, capture mercury, and may allow physical and/or chemical adsorption of mercury.
• Mercury that has been captured by a combination of activated carbon and one or more inorganic bromides is stable in a wide range of pH values, where "stable" means that the mercury is not released from the combination of activated carbon and one or more inorganic bromides in appreciable amounts after capture.
• the inorganic halide compounds or inorganic sulfide compounds and sorbents used in processes of this invention can be combined with other optional components such as pH buffers (including, for example, without limitation, carbonates and phosphates); carriers (including, for example, without limitation, sand and mud); binders (including, for example, without limitation, mud, clay, and polymers); and/or other additives (including, for example, without limitation, iron compounds and sulfur compounds).
• pH buffers including, for example, without limitation, carbonates and phosphates
• carriers including, for example, without limitation, sand and mud
• binders including, for example, without limitation, mud, clay, and polymers
• additives including, for example, without limitation, iron compounds and sulfur compounds.
• the inorganic halide compound or inorganic sulfide compound and the sorbent can be used in various forms, including as a dry sorbent and a dry inorganic halide compound, or one or both of the inorganic halide compound or inorganic sulfide compound and the sorbent can be in a suitable fluid, for example, in a slurry.
• suitable fluid means fluids such as water, and other fluids.
• Thermal desorption and retorting are two common ex situ methods of thermal treatment for mercury remediation.
• the technology heats contaminated medium to volatilize mercury, followed by condensing vapors into liquid elemental mercury.
• An inorganic halide compound or inorganic sulfide compound and the sorbent preferably an inorganic bromide and activated carbon, may be used to adsorb mercury as a replacement of the liquid mercury condenser or to remove mercury in off-gasses exiting the condenser.
• the inorganic halide compound or inorganic sulfide compound and/or the sorbent will remain in or with the substance.
• the inorganic halide compound or inorganic sulfide compound and/or sorbent may be collected after use. When the collected after use, the sorbent can be disposed of, or regenerated and re-used.
• the substances containing one or more environmental pollutants are solids, liquids, or combinations of a solid and a liquid, or combinations of one or more solids and one or more liquids.
• the substance When the substance is a solid, it may comprise more than one solid.
• the substance When the substance is a liquid, it may comprise more than one liquid.
• use of the inorganic halide compound or inorganic sulfide compound and sorbent can be a standalone remedial approach or can complement the use of other remediation methods.
• the inorganic halide compound or inorganic sulfide compound and sorbent can be used in addition to one or more other remediation agents in the same remediation procedure.
• Adding an inorganic halide compound or inorganic sulfide compound and a sorbent into contaminated waste adsorbs one or more pollutants.
• the inorganic halide compound or inorganic sulfide compound and the sorbent remain in the substance to stabilize and/or solidify the substance.
• the combined inorganic halide compound or inorganic sulfide compound, sorbent, and substance are placed in landfill, often with a binder and other compounds.
• solid and/or “solids”, include without limitation, soil, debris, waste and other such substances known to those skilled in the art.
• Soil is a preferred solid to treat in the practice of this invention.
• Processes of the invention are provided for reducing environmental availability of at least a portion of one or more environmental pollutants in a solid comprising one or more environmental pollutants. Substances which are solids are sometimes referred to herein as solid substances.
• the adding and/or applying of an inorganic halide compound or inorganic sulfide compound and a sorbent to the solid can comprise:
• Some preferred methods for adding and/or applying an inorganic halide compound or inorganic sulfide compound and a sorbent to the solid are:
• More preferred methods for adding and/or applying an inorganic halide compound or inorganic sulfide compound and a sorbent to the solid are:
• Combining an inorganic halide compound or inorganic sulfide compound and a sorbent with the surface of the solid as in (c) above can be done by combining the inorganic halide compound or inorganic sulfide compound and the sorbent with a portion of the solid, and then applying the mixture of the inorganic halide compound or inorganic sulfide compound, sorbent, and portion of the solid to the surface of the solid, or by combining the inorganic halide compound or inorganic sulfide compound and the sorbent with the surface of the solid.
• An embodiment of treatment of solids to reduce environmental availability of one or more environmental pollutants involves (i) drilling holes, wells, and/or channels into the solid, (ii) covering a surface of the solid with a layer of inorganic halide compound or inorganic sulfide compound and sorbent, and (iii) heating some parts of the solid to migrate one or more environmental pollutants, e.g., mercury, toward the surface which has an inorganic halide compound or inorganic sulfide compound and a sorbent thereon.
• environmental pollutants e.g., mercury
• Another embodiment of treatment of solids to reduce environmental availability of one or more environmental pollutants involves (i) drilling holes, wells, and/or channels into the solid, (ii) filling some holes or channels with an inorganic halide compound or inorganic sulfide compound and a sorbent, and (iii) purging heated air into holes or channels to migrate one or more environmental pollutants, e.g., mercury, toward the holes filled with the inorganic halide compound or inorganic sulfide compound and the sorbent.
• one or more environmental pollutants e.g., mercury
• the solid is heated to vaporize the environmental pollutant, e.g., mercury, in a vacuum well; when an inorganic halide compound or inorganic sulfide compound and a sorbent are present in the vacuum well as in (h) above, the inorganic halide compound or inorganic sulfide compound and/or sorbent can absorb the vaporized environmental pollutant(s).
• the inorganic halide compound or inorganic sulfide compound is placed with the substance being treated and the sorbent is placed in contact with the vapor produced in the vacuum well at one or more locations before the vapor exits to atmosphere.
• SVE Soil Vapor Extraction
• inorganic halide compounds or inorganic sulfide compounds and sorbents especially inorganic bromides and activated carbons, can be used in the vacuum well to adsorb mercury.
• an inorganic halide compound or inorganic sulfide compound and a sorbent can be utilized to immobilize mercury prior to, or during stabilization and solidification (S/S) of soil in situ and/or ex situ treatment.
• One ex situ process adds an inorganic halide compound or inorganic sulfide compound and a sorbent, one or more binders, and other components into a contaminated substance and mixes them together in a reactor. The mixture is then stabilized and cemented or placed in landfill.
• an inorganic bromide and powdered activated carbon can be used in S/S treatment processes. Mercury adsorbed by inorganic bromides and powdered activated carbon is stable during making and curing of concrete; see for example U.S. Pat. Nos. 8,404,038 and 8,420,033. This is advantageous because fly ash and cement are typical binders used in S/S technologies.
• inorganic halide compounds or inorganic sulfide compound and sorbents especially inorganic bromides and powdered activated carbons
• the inorganic halide compound or inorganic sulfide compound and sorbent are spread on top of the contaminated soil.
• the soil is not disturbed and the inorganic halide compound or inorganic sulfide compound and sorbent, especially an inorganic bromide and activated carbon, are present in the top layer of soil and block migration of mercury from the soil.
• Either or both of the inorganic halide compound or inorganic sulfide compound and the sorbent, preferably inorganic bromide compounds and activated carbons, can be mixed with another agent to create a mixture that improves penetration of the inorganic halide compound or inorganic sulfide compound and/or the sorbent into the solid, especially soil.
• a pH adjustment agent is also applied, either separately or in admixture with the inorganic halide compound or inorganic sulfide compound and/or the sorbent, optionally along with an agent that improves penetration of the inorganic halide compound or inorganic sulfide compound and/or the sorbent into the solid.
• Processes of the invention are provided for reducing environmental availability of at least a portion of one or more environmental pollutants in a liquid comprising one or more environmental pollutants.
• liquid and/or “liquids”, include without limitation, groundwater, wastewater, surface water, salt water, fresh water (e.g., lakes, ponds), and other such substances known to those skilled in the art. Substances which are liquids are sometimes referred to herein as liquid substances.
• the adding and/or applying of an inorganic halide compound or inorganic sulfide compound and a sorbent to the liquid can comprise:
• Combining an inorganic halide compound or inorganic sulfide compound and a sorbent with the liquid as in (c) above can be done by combining the inorganic halide compound or inorganic sulfide compound and the sorbent with the bulk liquid, or by combining the inorganic halide compound or inorganic sulfide compound and/or sorbent with a portion of the liquid to form a slurry, and then combining the slurry with the remaining liquid.
• Some substances are combinations of at least one solid and at least one liquid, and include sludge, slurries, sediments, pore water (e.g., soil pore water or sediment pore water) and other combinations of solids and liquids. Sediment, soil pore water, and sediment pore water are preferred combination substances to treat in the practice of this invention. These combinations are sometimes referred to as multiphasic substances. Processes of the invention are provided for reducing environmental availability of at least a portion of one or more environmental pollutants in a combination comprising one or more environmental pollutants. Substances which are combinations are sometimes referred to herein as combination substances. [0063] The adding and/or applying of an inorganic halide compound or inorganic sulfide compound and a sorbent to the combination can comprise:
• Some preferred methods for adding and/or applying an inorganic halide compound or inorganic sulfide compound and a sorbent to the combination are: (a) injecting an inorganic halide compound or inorganic sulfide compound and a sorbent into the combination, optionally through holes and/or wells and/or channels that are present in the substance, whether already present or manually created, e.g., by drilling into the combination; and/or
• More preferred methods for adding and/or applying an inorganic halide compound or inorganic sulfide compound and a sorbent to the combination are:
• Combining the inorganic halide compound or inorganic sulfide compound and the sorbent with the combination as in (d) above can be done by combining the inorganic halide compound or inorganic sulfide compound and sorbent with the combination, or by combining the inorganic halide compound or inorganic sulfide compound and/or sorbent with a portion of the combination to form a mixture, and then combining the mixture with the surface of the combination.
• the inorganic halide compound and the sorbent can comprise, for example, without limitation, an inorganic chloride or inorganic bromide and an activated carbon, preferably an inorganic bromide and a carbonaceous material, more preferably sodium bromide and/or calcium bromide and an activated carbon.
• Another embodiment of this invention is a process for reducing environmental availability of at least a portion of one or more environmental pollutants in a substance comprising one or more environmental pollutants and bromide ions.
• the process comprises adding and/or applying a bromine-containing carbonaceous material to said substance, thereby reducing environmental availability of at least a portion of one or more environmental pollutants in the substance.
• an inorganic halide compound does not need to be added or applied because bromide ions are present in the substance with the environmental pollutant(s); the remediation agents in this embodiment of the invention comprise a bromine-containing carbonaceous material.
• the amount of bromine in the bromine- containing carbonaceous material is in the range of about 0.1 wt% to about 20 wt%, based on the total weight of the bromine-containing carbonaceous material.
• a feature of this embodiment is that adding and/or applying only the bromine-containing carbonaceous material is necessary, and the treatments of the substance and considerations therefor are the same as described above in regard to the sorbent. In this embodiment, applying an inorganic halide compound or an inorganic sulfide compound is optional.
• the adding and/or applying of a bromine-containing carbonaceous material to the solid containing one or more environmental pollutants and bromide ions can comprise:
• More preferred methods for adding and/or applying a bromine-containing carbonaceous material to the solid are:
• Combining a bromine-containing carbonaceous material with the surface of the solid as in (c) above can be done by combining the bromine-containing carbonaceous material with a portion of the solid, and then applying the mixture of the bromine-containing carbonaceous material and portion of the solid to the surface of the solid, or by combining the bromine- containing carbonaceous material with the surface of the solid.
• An embodiment of treatment of solids to reduce environmental availability of one or more environmental pollutants involves (i) drilling holes, wells, and/or channels into the solid, (ii) covering a surface of the solid with a layer of bromine-containing carbonaceous material, and
• Another embodiment of treatment of solids to reduce environmental availability of one or more environmental pollutants involves (i) drilling holes, wells, and/or channels into the solid, (ii) filling some holes or channels with a bromine-containing carbonaceous material, and (iii) purging heated air into holes or channels to migrate one or more environmental pollutants, e.g., mercury, toward the holes filled with the bromine-containing carbonaceous material.
• bromine-containing carbonaceous materials are remediation agents for mercury contaminated soil
• the bromine-containing carbonaceous material is spread on top of the contaminated soil. In this method, the soil is not disturbed and the bromine-containing carbonaceous material is present in the top layer of soil and blocks migration of mercury from the soil.
• the adding and/or applying of a bromine-containing carbonaceous material to the liquid containing one or more environmental pollutants and bromide ions can comprise:
• Combining a bromine-containing carbonaceous material with the liquid as in (c) above can be done by combining the bromine-containing carbonaceous material with the bulk liquid, or by combining the bromine-containing carbonaceous material with a portion of the liquid to form a slurry, and then combining the slurry with the remaining liquid.
• the adding and/or applying of a bromine-containing carbonaceous material to the combination containing one or more environmental pollutants and bromide ions can comprise:
• More preferred methods for adding and/or applying a bromine-containing carbonaceous material to the combination are:
• Combining the bromine-containing carbonaceous material with the combination as in (d) above can be done by combining the bromine-containing carbonaceous material with the combination, or by combining the bromine-containing carbonaceous material with a portion of the combination to form a mixture, and then combining the mixture with the surface of the combination.
• the bromine-containing carbonaceous material can be a bromine-containing activated carbon.
• the amount of mercury present in a sample was determined in an atomic absorption spectrometer with a mercury vapor analyzer via cold vapor atomic absorption (CVAA; Atomic Absorption Mercury Spectrometer with Zeeman background correction, Ohio Lumex Co., model no. RA 915+).
• Powdered activated carbon (PAC) was added to several reactor bottles, followed by 50 mL of a solution of mercury, which solution had a pH of 2, and contained about 50 ppm mercury from Hg(N03)2; the amount of PAC in each reactor bottle was 0.4 g/L.
• Solid NaBr was dissolved in deionized water to form a solution containing bromide ion at 2 wt%; an amount of the NaBr solution was pipetted into each reactor bottle.
• the activated carbon capacity was 100 mg Hg/g activated carbon (sorbent) at a steady state concentration of bromide ion of about 16 ppm, significantly larger than the mercury adsorption of activated carbon without bromide ion present.
• the Figure is a graph showing mercury adsorption as a function of bromide ion concentration, where the x axis is the bromide ion concentration in mg/L, and the y axis is the Hg adsorbed in mg/g sorbent.
• Example 2 More samples prepared as in Example 1 were prepared and tested; one set of runs used powdered activated carbon formed from palm shells. Results are summarized in Table 2.
• This PAC was formed from palm shells.
• Example 3 More samples prepared as in Example 1 were prepared and tested. In these runs, the initial mercury concentration was varied. Results are summarized in Table 3.
• counterions are bromide for NaBr; chloride for NaCl; iodide for Nal; and sulfide for Na2S. Amounts of the counterions listed in this column are reported as the particular counterion.
• a process for reducing environmental availability of at least a portion of one or more environmental pollutants in a substance comprising one or more environmental pollutants comprises adding and/or applying an inorganic halide compound or inorganic sulfide compound to said substance, wherein the inorganic halide compound is sodium bromide or calcium bromide and wherein the inorganic sulfide compound is hydrogen sulfide or sodium sulfide, and adding and/or applying a sorbent to said substance wherein the sorbent is an activated carbon or a bromine-containing carbonaceous material, thereby reducing environmental availability of at least a portion of one or more environmental pollutants in the substance.
• the invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.
• the term "about" modifying the quantity of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
• the term about also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about”, the claims include equivalents to the quantities.

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