WO2019213615A1 - Processes for reducing environmental availability of environmental pollutants - Google Patents

Processes for reducing environmental availability of environmental pollutants Download PDF

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Publication number
WO2019213615A1
WO2019213615A1 PCT/US2019/030729 US2019030729W WO2019213615A1 WO 2019213615 A1 WO2019213615 A1 WO 2019213615A1 US 2019030729 W US2019030729 W US 2019030729W WO 2019213615 A1 WO2019213615 A1 WO 2019213615A1
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Prior art keywords
halogen
containing sorbent
sorbent
process according
solid
Prior art date
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PCT/US2019/030729
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English (en)
French (fr)
Inventor
Qunhui Zhou
Gregory H. Lambeth
Jon Eric MILLER
Timothy Allen FROST
Sascha Joerg WELZ
Se Hye KIM
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Albemarle Corp
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Albemarle Corp
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Priority to US17/048,397 priority Critical patent/US12420259B2/en
Priority to AU2019262648A priority patent/AU2019262648B2/en
Priority to CN201980030354.1A priority patent/CN112135695B/zh
Priority to CN202410855989.8A priority patent/CN118988959A/zh
Priority to KR1020207031395A priority patent/KR20210006890A/ko
Priority to JP2020561647A priority patent/JP2021522994A/ja
Application filed by Albemarle Corp filed Critical Albemarle Corp
Priority to EP19728784.0A priority patent/EP3787810A1/en
Publication of WO2019213615A1 publication Critical patent/WO2019213615A1/en
Anticipated expiration legal-status Critical
Priority to JP2023132750A priority patent/JP2023154071A/ja
Priority to JP2025167140A priority patent/JP2026004495A/ja
Ceased legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid 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
    • B01J20/0262Compounds of O, S, Se, Te
    • B01J20/0266Compounds of S
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/0203Solid 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
    • B01J20/027Compounds of F, Cl, Br, I
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    • B01J20/08Solid 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 comprising aluminium oxide or hydroxide; comprising bauxite
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    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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    • B01J20/20Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
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    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3085Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204Inorganic carriers, supports or substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
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    • B09B3/70Chemical treatment, e.g. pH adjustment or oxidation
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • CCHEMISTRY; METALLURGY
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00Treatment of water, waste water, or sewage
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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 bio-accumulation 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 adding and/or applying a halogen-containing sorbent to the substance.
  • the halogen comprises one or more halogens selected from fluorine, chlorine, bromine, and/or iodine and one or more substrate materials.
  • Adding and/or applying the halogen-containing 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 equilibrium mercury adsorption isotherm data from Example 1.
  • 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 bio-accumulation.
  • environmental pollutant and “environmental pollutants” means a chemical element or compound or mixture thereof known be harmful 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.
  • halogen-containing sorbents sometimes referred to herein as "halogenated sorbents".
  • Halogen-containing sorbents are typically formed from one or more halogen-containing compounds, and one or more substrate materials. Many substrate materials, especially activated carbons, are available or obtainable in a wide range of particle sizes, from nanometer to centimeter.
  • Substrate materials include carbonaceous materials and inorganic materials. Suitable carbonaceous materials 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. Powdered activated carbon is a particularly preferred form of activated carbon.
  • Suitable inorganic materials 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; inorganic hydroxides such as iron hydroxide; mixed metal oxides such as hydrotalcites and metallated double layered clays; diatomaceous earth; cement dust; hydroprocessing catalysts including those on substrates such as alumina (
  • the halogen element in the halogen-containing sorbent can be fluorine, chlorine, bromine, iodine, or a mixture of any two or more halogens. Bromine is a preferred halogen.
  • Suitable halogen-containing compounds include, for example, without limitation, elemental iodine and/or iodine compounds, elemental bromine and/or bromine compounds, elemental chlorine and/or chlorine compounds, elemental fluorine and/or fluorine compounds, and other suitable halogen compounds, as will be known to those skilled in the art.
  • Types of halogen-containing compounds that can be used include hydrohalic acids, alkali metal halides, alkaline earth halides, and ammonium halides.
  • Hydrohalic acids include hydrogen chloride, hydrogen bromide, and hydrogen iodide.
  • 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 chloride, magnesium bromide, calcium chloride, and calcium bromide.
  • Ammonium halides include ammonium chloride, ammonium bromide, and ammonium iodide.
  • Preferred halogen-containing compounds include elemental bromine, hydrogen bromide, sodium chloride, sodium bromide, potassium iodide, and calcium bromide.
  • Bromine-containing compounds are preferred halogen-containing compounds; more preferred are hydrogen bromide and elemental bromine, especially elemental bromine.
  • Halogen-containing sorbents can be made from the material and 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. In some embodiments, preferred halogen-containing sorbents are bromine-containing sorbents.
  • preferred halogen-containing sorbents are halogen-containing activated carbons.
  • preferred halogen-containing activated carbons are chlorine-containing activated carbons, bromine-containing activated carbons, and iodine-containing activated carbons.
  • the halogen-containing sorbents are chlorine- containing activated carbons and bromine-containing activated carbons.
  • the halogen-containing sorbents are bromine-containing activated carbons. Bromine-containing activated carbons are available commercially from Albemarle Corporation.
  • preferred halogen-containing sorbents are chlorine- containing activated carbons and iodine-containing activated carbons.
  • preferred halogen-containing sorbents are halogen-containing chabazites, halogen-containing bentonites, halogen-containing kaolinites, and halogen-containing silicas.
  • preferred halogen-containing sorbents include bromine- containing silica, bromine-containing kaolinite, and bromine-containing bentonite.
  • the amount of halogen (or halogen content) on the 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%, preferably equivalent to a total bromine content in the range of about 0.5 wt% to about 15 wt%, more preferably about 2 wt% to about 12 wt%, and still more preferably about 3 wt% to about 8 wt%, based on the total weight of the halogen- containing sorbent.
  • bromine As used throughout this document, the phrases "as bromine,” “reported as bromine,” “calculated as bromine,” and analogous phrases for the halogens refer to the amount of halogen, where the numerical value is calculated for bromine, unless otherwise noted. For example, elemental fluorine may be used, but the amount of halogen in the halogen-containing sorbent is stated as the value for bromine.
  • Bromine-containing 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; and other features as will be familiar to those skilled in the art.
  • Halogen-containing sorbents 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 halogen-containing sorbents 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 adsorbed by halogen-containing sorbents are stabilized such that desorption into the environment is substantially minimized.
  • halogen-containing sorbents especially bromine-containing activated carbon.
  • Different halogen (especially bromine) species can be formed on a halogen-containing sorbents, especially bromine-containing sorbents, particularly bromine-containing activated carbon.
  • bromine one of the bromine species, can oxidize elemental mercury and form mercuric bromide which can be adsorbed into pores of activated carbon; another species, bromide ion, can chemically bond with ionic mercury for adsorption onto the surface of activated carbon; another component might catalyze mercury oxidation and enhance the stabilization or adsorption of the oxidized mercury product.
  • halogen-containing sorbents particularly bromine-containing activated carbons, can physically and chemically adsorb mercury of different oxidation states including elemental mercury, oxidized mercury, and organic mercury.
  • Mercury adsorbed on bromine-containing activated carbon is stable in a wide range of pH values, where "stable" means that the mercury does not separate from the sorbent in appreciable amounts after adsorption.
  • 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 halogen-containing sorbent can be used in various forms, including as a dry sorbent or in combination with 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.
  • Bromine-containing 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 halogen-containing sorbent will remain in or with the substance.
  • the sorbent may be 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.
  • halogen-containing sorbent in some processes of this invention, whether applied to a substance comprising one or more solids, one or more liquids, or combinations of at least one solid and at least one liquid, use of the halogen-containing sorbent can be a stand-alone remedial approach or can complement the use of other remediation methods. In other processes according to the invention, the halogen-containing sorbent can be used in addition to one or more other remediation agents in the same remediation procedure.
  • Adding a halogen-containing sorbent into contaminated waste adsorbs one or more pollutants.
  • the halogen-containing sorbent remains in the substance to stabilize and/or solidify the substance.
  • the combined halogen-containing 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 the halogen-containing sorbent to the solid can comprise:
  • Combining the halogen-containing sorbent with the surface of the solid as in (c) above can be done by combining the halogen-containing sorbent with a portion of the solid, and then applying the combination of sorbent and solid to the surface of the solid, or by combining the halogen-containing sorbent with the surface of the solid.
  • Some preferred methods for adding and/or applying the halogen-containing sorbent to the solid are:
  • 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 halogen-containing sorbent, and (iii) heating some parts of the solid to migrate one or more environmental pollutants, e.g., mercury, toward the surface which has halogen-containing sorbent thereon.
  • one or more 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 halogen-containing 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 halogen-containing 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 a halogen-containing sorbent is present in the vacuum well as in (d) above, the halogenated sorbent can absorb the vaporized environmental pollutant(s).
  • the halogen-containing sorbent is placed in the vacuum well 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
  • halogen- containing sorbents, especially bromine-containing activated carbons can be placed in the vacuum well to adsorb mercury.
  • halogen-containing sorbents can be utilized to immobilize mercury prior to, or during stabilization and solidification (S/S) of soil in situ and/or ex situ treatment.
  • S/S stabilization and solidification
  • One ex situ process adds halogen-containing 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.
  • bromine-containing powdered activated carbon can be used in S/S treatment processes. Mercury adsorbed by bromine-containing 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.
  • halogen-containing sorbents especially bromine-containing powdered activated carbons
  • the halogen-containing sorbent is spread on top of the contaminated soil.
  • the soil is not disturbed and the halogen-containing sorbent, especially a bromine-containing activated carbon, is present in the top layer of soil and blocks migration of mercury from the soil.
  • Halogenated sorbents can be mixed with another agent to create a mixture that improves penetration of the halogen- containing sorbent into the solid, especially soil.
  • the amount of halogen-containing sorbent added may be less than 10% of the top layer of soil, and the top layer of soil may be up to 10 cm thick.
  • a pH adjustment agent is also applied, either separately or in admixture with the halogen-containing sorbent, optionally along with an agent that improves penetration of the halogen-containing 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 the halogen-containing sorbent and the liquid can comprise:
  • Combining the halogen-containing sorbent with the liquid as in (c) above can be done by combining the halogen-containing sorbent with the bulk liquid, or by combining the halogen-containing 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.
  • the adding and/or applying of the halogen-containing sorbent and the combination can comprise adding and/or applying the halogen-containing sorbent to the combination.
  • adding and/or applying the halogen-containing sorbent to the combination can comprise:
  • Combining the halogen-containing sorbent with the combination as in (d) above can be done by combining the halogen-containing sorbent with the combination, or by combining the halogen-containing sorbent with a portion of the combination to form a mixture, and then combining the mixture with the surface of the combination.
  • the halogen-containing sorbent can comprise, for example, without limitation, a halogen-containing activated carbon sorbent, preferably a bromine-containing carbon sorbent, more preferably a bromine-containing activated carbon sorbent.
  • Some preferred methods for adding and/or applying the halogen-containing sorbent to the combination are:
  • 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+).
  • a powdered activated carbon (average particle size 15 pm) was treated with gas phase Br 2 at elevated temperature in a procedure as described in U.S. Pat. No. 6,953,494 to form a bromine-containing powdered activated carbon with a bromine content of 8 wt%.
  • the bromine-containing activated carbon sorbents were used to remove mercury from synthetic mercury-containing solutions.
  • Bromine-containing powdered activated carbon (0.4 g/L) was placed in several reactor bottles. Solutions were prepared with Hg(N0 3 ) 2 at a pH of 2 and added to the reactor bottles containing sorbent; each reactor bottle contained a constant volume of solution prepared with a different Hg 2+ concentration.
  • Both the Br-PAC and the untreated powdered activated carbon (PAC) adsorption isotherms fit a Langmuir equation; the calculated Langmuir equilibrium adsorption capacities agree with the experimental data.
  • the Figure is a graph showing equilibrium mercury adsorption isotherms for both the set of runs, with the data shown as squares and the calculated Langmuir isotherms as lines for both Br-PAC (solid squares and solid line) and the comparative runs with untreated activated carbon (open squares and dashed line); where the x axis is the aqueous equilibrium Hg concentration in mg/L, and the y axis is the Hg adsorbed in mg/g sorbent.
  • a granular activated carbon with a particle size range of 0.6 mm to 2.4 mm was treated with gas phase Br 2 at elevated temperature in a procedure as described in U.S. Pat. No. 6,953,494 to form a bromine-containing granular activated carbon with a bromine content of 3 wt%.
  • the bromine-containing granular activated carbon was packed into several quartz columns of 15 cm height and 1.5 cm diameter.
  • a synthetic wastewater solution was made by adding Hg 2+ as HgCl 2 or Hg(N0 3 ) 2 into deionized water to an Hg 2+ concentration of -4000 ng/l at a pH of 6.8+0.2.
  • the synthetic wastewater solution was passed through each column from top to bottom at different flow rates, 0.1, 0.3, 0.5, and 1.0 BV/min (BV is bed volume). Influent and effluent samples were taken every three hours from each column, and the samples were analyzed for mercury content in the atomic absorption spectrometer using U.S. EPA Method 1631.
  • the bromine-containing granular activated carbon used in this Example is much more efficient than a commercially-available activated carbon with a particle size of 0.8 to 1.0 mm (Filtrasorb ® 300, Calgon Corp.), which was tested on mercury-contaminated water near the Y-12 plant in Oak Ridge, Tennessee.
  • the data generated for the Filtrasorb ® 300 sorbent is reported in T&N Associates, Mercury Treatability Study Final Report: Oak Ridge Y-12 Plant, Report BJC/OR-46, prepared for the U.S. Department of Energy, Office of Environmental Management under subcontract 395064- 14-AMU, Oak Ridge, Tennessee, June 1998. Results are summarized in Table 2 below.
  • Hg in leachate of the acetic acid solution minus Hg in extract solvent see below for explanation.
  • the data in Table 3 show that mercury in leachates of samples containing fly ash and bromine-containing powdered activated carbon at various pH values is minimal.
  • the negative values in the "Difference" column in Table 3 indicate not only that the mercury adsorbed by bromine-containing activated powdered carbon was not released, but also that the bromine-containing powdered activated carbon removed mercury present in the extract solvent of acetic acid.
  • Stability ratio was calculated as: [Hg adsorbed into sorbent, mg/g sorbent] ⁇ [Hg desorbed, mg/g sorbent]
  • Br-PAC was made as described in U.S. Pat. No. 6,953,494.
  • Several halogen- containing sorbents were prepared by either (1) adding an aqueous halide salt solution to the activated carbon or inorganic material, mixing very well, and then drying the mixture; or (2) blending a powdered halide salt with carbon or inorganic material until a relatively uniform mixture was obtained.
  • These bromine-containing sorbents were tested to study their capacity to absorb mercury from synthetic mercury-containing solutions.
  • Halogenated sorbents were placed in reactor bottles. Solutions were prepared with HgCl 2 or Hg(N0 3 ) 2 and added to the reactor bottles containing sorbent; each reactor bottle contained the same concentration of Hg 2+ . The samples were rotated for 24 hours at 32+2 rpm, and each of the resulting mixtures was passed through a syringe filter (0.45 pm pore membrane) to separate the sorbent from the liquid. A comparative run was conducted in parallel using untreated (plain) activated carbon. The mercury concentration of the filtered liquid from each solution was then determined. Parameters have not been optimized, especially for the halogenated sorbents made from inorganic halide salts. Results are summarized in Table 7.
  • 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 which process comprises
  • halogen-containing sorbent is a bromine-containing activated carbon sorbent, a chlorine-containing activated carbon sorbent, an iodine-containing activated carbon sorbent, a bromine-containing chabazite, a bromine-containing bentonite, a bromine-containing kaolinite, or a bromine-containing silica,
  • halogen content is about 0.5 wt% to about 15 wt%, preferably about 2 wt% to about 12 wt%, more preferably about 3 wt% to about 8 wt%, calculated as bromine and based on the total weight of the halogen-containing sorbent.
  • the sorbent is a bromine-containing chabazite, a bromine-containing bentonite, a bromine-containing kaolinite, or a bromine-containing silica, wherein the halogen content is about 0.1 wt% to about 20 wt%, calculated as bromine and based on the total weight of the halogen-containing sorbent, and wherein the substance is soil, sediment, soil pore water, or sediment pore water.
  • the sorbent is a chlorine-containing activated carbon, wherein the halogen content is about 0.1 wt% to about 20 wt%, calculated as bromine and based on the total weight of the halogen-containing sorbent, and wherein the substance is soil, sediment, soil pore water, or sediment pore water.
  • 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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CN115551620A (zh) * 2020-05-11 2022-12-30 雅宝公司 用于从流动相减少环境污染物的工艺、系统和设备
JP2023526191A (ja) * 2020-05-11 2023-06-21 アルベマール コーポレーション 移動相から環境汚染物質を減らすためのプロセス、システム、及び装置
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US12605693B2 (en) * 2020-05-11 2026-04-21 Albemarle Amendments, Llc Process, system, and apparatus for reducing environmental pollutants from a mobile phase
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CN115768447A (zh) * 2020-05-28 2023-03-07 雅宝公司 减少环境甲基汞并限制它被摄入植物和生物体中的方法
JP2023528193A (ja) * 2020-05-28 2023-07-04 アルベマール コーポレーション 環境のメチル水銀を減らす方法、ならびに、環境のメチル水銀の植物及び生体への取り込みを制限する方法
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AU2019262648B2 (en) 2024-09-19
JP2021522994A (ja) 2021-09-02
CN112135695B (zh) 2024-07-19
KR20210006890A (ko) 2021-01-19
US20210146335A1 (en) 2021-05-20
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