WO2003006140A1 - Poudre d'adsorption a base de carbone contenant du chlorure cuivrique - Google Patents

Poudre d'adsorption a base de carbone contenant du chlorure cuivrique Download PDF

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Publication number
WO2003006140A1
WO2003006140A1 PCT/US2002/021120 US0221120W WO03006140A1 WO 2003006140 A1 WO2003006140 A1 WO 2003006140A1 US 0221120 W US0221120 W US 0221120W WO 03006140 A1 WO03006140 A1 WO 03006140A1
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Prior art keywords
weight percent
carbon
powder
carbons
cupric chloride
Prior art date
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PCT/US2002/021120
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English (en)
Inventor
Youssef El-Shoubary
Rudy Maes
Subash C. Seth
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Merck & Co., Inc.
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Publication date
Priority claimed from US09/408,361 external-priority patent/US6589318B2/en
Priority claimed from US09/902,293 external-priority patent/US6524371B2/en
Priority claimed from US09/902,285 external-priority patent/US6638347B2/en
Application filed by Merck & Co., Inc. filed Critical Merck & Co., Inc.
Priority to JP2003511940A priority Critical patent/JP2004534641A/ja
Priority to CA002451534A priority patent/CA2451534A1/fr
Priority to EP02748062A priority patent/EP1406718A4/fr
Publication of WO2003006140A1 publication Critical patent/WO2003006140A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B01D53/70—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—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
    • B01J20/0222—Compounds of Mn, Re
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/0203—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
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—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
    • B01J20/0262—Compounds of O, S, Se, Te
    • B01J20/0266—Compounds of S
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—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
    • 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
    • B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/04—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—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
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—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
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells

Definitions

  • the present invention relates to an adsorption powder useful for the removal of metal and organic pollutants from gas streams.
  • the adsorption powder is typically useful for treating solid waste contaminates, e.g. contaminated soil treatment by high efficiency incineration. More particularly, the invention relates to the capture of mercury and other metals, dioxins, furans and other organic compounds from high temperature, high moisture gas streams using an adsorption powder containing cupric chloride.
  • U.S. Patent No. 3,876,393 discloses passing mercury- containing vapors over activated carbon that has been impregnated with sulfuric acid. Selenium has also been used in the removal of mercury from a vapor.
  • U.S. Patent No. 3,786,619 discloses passing a mercury-containing gas over a mass containing as an active component, selenium, selenium sulfide or other selenium compounds. Electrostatic precipitators and various filters have traditionally been used for mercury removal, although complex apparatus have also been disclosed. (See e.g., U.S. Patent Nos. 5,409,522 and 5,607,496.)
  • LTTD low temperature thermal desorption
  • the hot gas stream is subsequently cooled.
  • the stream may be quenched with water, which cools the stream and concurrently increases the moisture content.
  • water quenching is a highly effective cooling method, this treatment increases the difficulty of removing mercury from the gas stream.
  • the gas stream is further treated to reduce and remove metals, HC1, NO ⁇ and SO ⁇ using acid scrubbers, carbon beds, condensation units and through the addition of adsorption powders.
  • metals HC1, NO ⁇ and SO ⁇
  • acid scrubbers acid scrubbers
  • carbon beds condensation units
  • condensation units through the addition of adsorption powders.
  • adsorption powders When adsorption powders are injected into the gas stream, mercury and other metals bind to moieties present in the powder, precipitating them from the gas stream.
  • the powder-bound mercury is ultimately collected in a bag house for appropriate disposal, while the clean gas stream is exhausted to the outside atmosphere.
  • LTTD and other methods suffer from the limitation that mercury removal from high moisture gas streams is much more difficult than mercury removal from dry streams.
  • Available adso ⁇ tion powders remove organics, metals and other contaminants, but they do not effectively remove mercury.
  • one available powder (Sorbalite TM) consisting of carbon, calcium hydroxide and sulfur removes HC1 from a gas stream, but it removed only about 55-65% of the mercury.
  • Another powder (WUELFRAsorb-C TM) consisting of alcohol saturated lime and activated carbon is also inefficient at removing mercury.
  • Some powders include sulfur or iodine impregnated carbon. At temperatures of 75°C or less, sulfur or iodine impregnated carbon based powders show a 95% mercury removal efficiency, however, powders formulated with sulfur impregnated carbon require that the gas stream to which they are added is dry. Lastly, the mercury removal efficiency of the powders described and other available powders is known to be very temperature dependent, placing an additional limitation on powder formulations.
  • an adsorption powder that effectively removes metals and other organic compounds, in general, and mercury, in particular, from high temperature, high moisture gas streams generated by the incineration of contaminated soils, treatment of hazardous materials, combustion of coal and other mercury liberating sources.
  • the powder must be inexpensive and easy to use.
  • such an adsorption powder can be employed at treatment facilities already in place and can take advantage of equipment already in position, without requiring retooling or reconfiguring existing equipment.
  • an adsorption powder and method for removing mercury, other metals, and contaminants from a gas stream comprising an adsorption powder, wherein the powder is characterized as containing a carbon-based powder selected from the group consisting of coal carbons, wood carbons, graphite carbons, activated carbons, coconut shell carbons, peat carbons, petroleum cokes, synthetic polymers, the like, and combinations thereof, and an effective amount (about 3 to about 10 weight percent) of cupric chloride.
  • a carbon-based powder selected from the group consisting of coal carbons, wood carbons, graphite carbons, activated carbons, coconut shell carbons, peat carbons, petroleum cokes, synthetic polymers, the like, and combinations thereof
  • an effective amount about 3 to about 10 weight percent
  • sulfur, potassium iodide and permanganate, calcium hydroxide, and combinations thereof may be added to the powder.
  • the invention also relates to a process for removing mercury and organic compounds from gaseous streams using an adsorption powder, characterized as containing a carbon-based powder selected from the group consisting of coal carbons, wood carbons, graphite carbons, activated carbons, coconut shell carbons, peat carbons, petroleum cokes, synthetic polymers, the like, and combinations thereof, and an effective amount (about 3 to about 10 weight percent) of cupric chloride, the process being characterized by the steps of: a) placing a solid phase mercury-containing contaminated soil feed into a rotary kiln/drum; b) heating said kiln/drum containing said soil feed to form gaseous and solid components of the sample; c) transferring the gaseous component of said soil feed to an exhaust cleaning unit/afterburner and the solid component of clean soil to a soil cooling unit; d) heating the gaseous component of said contaminated soil feed in said exhaust cleaning unit/afterburner;
  • Figure 1 is a view in elevation of a schematic diagram illustrating the design of an LTTD facility in which the claimed adsorption powder can be used to remove mercury from gas streams;
  • Figure 2 is a view in elevation of a schematic diagram illustrating the bench scale model of the LTTF facility.
  • an adsorption powder suitable for removing metals and organic compounds from high temperature, high moisture gaseous streams, wherein the metals are selected from the group consisting of mercury, lead, nickel, zinc, copper, arsenic, cadmium, other heavy metals, and combinations thereof, wherein the organic compounds selected from the group consisting of furans and dioxins.
  • the powder may be characterized as containing a carbon-based powder and an effective amount of cupric chloride, i.e. from about 90 to about 97 weight percent carbon-based powder and from about 3 to about 10 weight percent of cupric chloride. It has been found that the addition of cuprous and cupric chlorides to carbon-based powders provides suitable efficiency for removing metals and organic compounds from high temperature, high moisture vaporous streams.
  • the addition of other ingredients may enhance metal removal efficiency, dependent upon the operating conditions of the removal process
  • the addition of copper, in various salt forms, to a carbon-based powder will aid the efficiency of metals removal from various gas streams.
  • the performance of the carbon-based powder may be further enhanced, dependent upon the process of removal operating conditions, by the addition of calcium hydroxide, sulfur, potassium permanganate, potassium iodide and combinations thereof, and like compounds.
  • the adsorption powder is characterized as containing from 0 to about 62 weight percent of calcium hydroxide, from 0 to about 4 weight percent of sulfur, from 0 to about 15 weight percent of potassium permanganate, from 0 to about 10 weight percent of potassium iodide, from about 3 to about 10 weight percent of cupric chloride, and a balancing weight percent of carbon-based powder to provide 100, total, weight percent of adsorption powder.
  • a powder characterized as containing a carbon-based powder, calcium hydroxide, potassium iodide, and cupric chloride, characterized as containing from about 35 to about 38 weight percent of carbon-based powder, from about 52 to about 62 weight percent of calcium hydroxide, from about 5 to about 10 weight percent of potassium iodide, and from about 3 to about 10 weight percent of cupric chloride.
  • While another embodiment is a carbon-based, calcium hydroxide, potassium permanganate, and cupric chloride powder, characterized as containing from about 35 to about 38 weight percent of carbon-based powder, from about 52 to about 62 weight percent of calcium hydroxide, from about 5 to about 10 weight percent of potassium permanganate, and from about 3 to about 10 weight percent of cupric chloride.
  • the adsorption powder may contain from about 35 to about 38 weight percent of carbon, from about 52 to about 62 weight percent of calcium hydroxide, from 1 to about 4 weight percent of sulfur, from about 5 to about 10 weight percent of potassium permanganate, and from about 3 to about 10 weight percent of cupric chloride.
  • the adsorption powder may be characterized as containing from about 35 to about 38 weight percent of carbon, from about 52 to about 62 weight percent of calcium hydroxide, from about 0 to about 4 weight percent of sulfur, and from about 3 to about 10 weight percent of cupric chloride.
  • the powder is characterized as containing about 38 weight percent of carbon, about 58 weight percent of calcium hydroxide, about 4 weight percent of sulfur, and about 4 weight percent of cupric chloride.
  • the potassium permanganate- and potassium iodide-containing powders may be impregnated onto a carbon substrate as will become apparent to those skilled in the art.
  • One aspect of this embodiment is a powder characterized as containing from about 35 to about 38 weight percent of coal carbon, from about 52 to about 60 weight percent of calcium hydroxide, from about 5 to about 10 weight percent of potassium iodide impregnated onto a carbon substrate, and from about 5 to about 10 weight percent of cupric chloride.
  • the identical potassium iodide component may be in blended with other components to form the adsorption powder.
  • the invention is also directed to a process for removing mercury and organic compounds from gaseous streams using the adsorption powder described herein, the process being characterized by the steps of: a) placing a solid phase mercury-containing contaminated soil feed into a rotary kiln/drum; b) heating said kiln/drum containing said soil feed to form gaseous and solid components of the sample; c) transferring the gaseous component of said soil feed to an exhaust cleaning unit/afterburner and the solid component of clean soil to a soil cooling unit; -d) heating the gaseous component of said contaminated soil feed in said exhaust cleaning unit/afterburner; e) cooling the gaseous component of said contaminated soil feed; f) adding the adsorption powder to the gaseous component; g) transferring the powder-containing gaseous component to a baghouse; and h) releasing the substantially mercury-free gaseous component of said sample to the atmosphere.
  • An adsorption powder for the removal of mercury and other metals, dioxins, furans and other organic compounds must be efficient under a range of conditions.
  • Currently available powders do not function well at high temperatures and in high moisture environments, conditions that are favorable to mercury removal. High temperatures are necessary for effective removal of contaminants from soil. Temperatures of about 1800°F are necessary to volatize organic compounds, metals and other impurities from the contaminated soil. Mercury that is trapped in contaminated soil, however, is most efficiently adsorbed on carbon at about 300-500T. The most practical method of cooling a gas stream exiting an 1800°F oven is to inject water into the gas stream.
  • Water injection cools the gas stream to a temperature favorable to mercury removal, but also increases the moisture content of the sample, which decreases the efficiency of available mercury adsorption powders.
  • the mercury absorbing properties of available powders suffer dramatically in a high moisture environment.
  • the adso ⁇ tion powder of the invention operates effectively even in a higher moisture environment.
  • Cupric chloride was observed to significantly enhance the adso ⁇ tion of mercury from a gas stream and is the key to the instant invention. Cupric chloride supplies chlorine and activated copper to the elemental mercury in the exhaust stream. Elemental mercury reacts with the chlorine to form mercury chloride and the activated copper to form a stable mercury amalgam. Both forms of mercury are easily captured from the exhaust gas stream. KI 3 impregnated carbon was also found to increase mercury adso ⁇ tion when it was included in the powder.
  • FIG. 1 shows a schematic diagram of the actual process and equipment used to carry out the invention.
  • Prescreened contaminated feed soil ready to be processed 2 is placed within soil cleaning unit 4.
  • the contaminated soil is heated to about 900°F or a temperature that will completely volatize the contaminants from the soil and generate a gaseous stream, as well as a clean/remediated solid soil component.
  • soil cleaning unit 4 is a rotary kiln.
  • the gas stream is then passed out of soil cleaning unit 4 to dust remover 6, while any solid fraction of the feed soil is transferred to clean soil cooling unit 8, where the soil is cooled and prepared for reuse.
  • Dust remover 6 is preferably a multi-tube dust collector.
  • the gas stream is passed into the Exhaust Cleaning Unit 10.
  • the Exhaust Cleaning Unit heats the volatilized contaminates to a temperature of about 1800°F for a minimum of two seconds retention time, which assures complete destruction of any remaining organic or other contaminants.
  • the gas stream then passes through cooling chamber 12 wherein a water pump (not shown) injects water into the cooling chamber 12 to lower the temperature of the sample to about 360°F. This cooling process consequentially increases the moisture content of the sample.
  • the high temperature, high moisture gas stream is then contacted to the adso ⁇ tion powder of the invention, which is stored in adsorbent storage silo 14 and injected into the gas stream.
  • This powder formulation is effective in removing metals, particularly mercury, and other contaminants.
  • baghouse 16 collects the particulate mercury- containing fraction of the adso ⁇ tion powder mixture, which is transported to a suitable bulk storage facility 20 and subsequently removed. The gaseous fraction is released to the outside atmosphere through vent 18, while the remaining dust particulate fraction is handled in a similar manner to the particulate mercury fraction of the adso ⁇ tion powder mixture 20.
  • EXAMPLES 1 -84 A bench-scale, batch rotary kiln system to simulate the system of Figure 1 was utilized to conduct and compare various powder mixtures for their capacity to adsorb vaporous mercury from a gaseous stream.
  • a schematic of the system 31 is shown in Figure 2.
  • a 4-inch diameter quartz rotary kiln 32 was utilized to contain the soil, and an insulated clamshell furnace 33 was utilized to indirectly heat the furnace.
  • the 4 inch diameter section of the kiln was 14 inches in length and contained raised dimples to provide mixing of the soil sample during rotation of the kiln.
  • a variable-speed electric motor 34 and controller rotated the kiln.
  • Purge gas 35 was metered to the kiln with calibrated rotameters from cylinders.
  • thermo oxidizer 36 another furnace containing a quartz tube.
  • the temperatures within the rotary kiln and thermal oxidizer were maintained with separate controllers.
  • quench water 37 was injected into the gaseous stream to lower the temperature of the hot gases.
  • the high moisture, quenched gases were passed through an adsorbent powder filter unit positioned inside a temperature-controlled oven 38, wherein vaporous mercury was efficiently adsorbed by the powder of the invention.
  • the gases were then directed to scrubbing unit 39 that consisted of 2 impingers containing acidic potassium permanganate.
  • Adsorbent mixtures were prepared by separately weighing each selected component thereof and blending them together. About 4.0 grms of adsorbent mixture per about 1 kg of soil was used in each batch measurement (1 kg of soil, as received basis, or about 0.88 kg of air-dried soil). The adsorbent mixture was then packed into a 1.5-inch diameter tube (Test Nos. 1-28) or, alternatively, loaded into a 102 mm x 1.6 mm filter holder (Test Nos. 29-84) and evenly distributed, and the tube or filter holder, respectively, was placed inside the filter oven.
  • the air-dried soil (about 0.88 kg) was loaded into the quartz kiln, gross and net weights were calculated therefor, and the kiln was positioned within the furnace.
  • a small amount quartz wool was inserted into the exhaust gas end of the system to filter and trap any dust that might be elutriated from the soil.
  • Behind the filter oven was placed 2 impingers, as final gas scrubbers to capture any mercury vapors that might pass through the adsorbent powder.
  • About 100 mis of acidic potassium permanganate solution was added to each impinger, they were placed in ice baths, and connected to the filter outlet with ground-glass connections so the gaseous stream would bubble through the solution.
  • Inlet gases were mixed to provide a composition of 10 vol. % oxygen, 3.2 vol.
  • Powder No. 1 38% carbon + 58% Ca(OH) 2 + 4% sulfur Powder No. 2 38% carbon + 58% Ca(OH) 2 + 4% sulfur + 10% KMnO 4 Powder No. 3 38% carbon + 62% Ca(OH) 2 + 10% KMnO 4 Additional components (in weight percent) added to the powders are listed in the tables. For each test run, the soil sample weight, amount of assay mercury contained therein, and the total amount of mercury in the sample was recorded. "Residue” refers to the amount of sample left in the kiln after the heating process, and mercury capture percent provides the efficiency of mercury removal from the sample. "Hg accountability” is the total amount of mercury calculated by material balance.
  • Test Numbers 29 and 62 utilized the a powder without additives (38 wt.% of carbon, 52 wt.% of calcium hydroxide, and 4 wt.% of sulfur), and the mercury capture results were 60 and 57.3%, respectively.
  • the addition of 5% cupric chloride (by weight) of Test Numbers 30, 39 and 40 resulted in mercury capture efficiency ranging from 86.5 to 90.0%.
  • Ten percent cupric chloride added to the kiln charge, Test Number 33 resulted in a mercury capture of 93%.
  • Test Number 32 containing additives of 5% potassium permanganate and 5% cupric chloride resulted in a mercury capture efficiency of 93.8%.
  • Test Numbers 54 through 58 were preformed using soil (containing no mercury) spiked with various mercury compounds to achieve approximately 4 to 5 milligrams of mercury in the kiln burden.
  • Spiking compounds included HgCl 2 , HgS, HgO, HgS0 4 , and elemental mercury
  • the adsorbent powder included a 5% cupric chloride additive.
  • the mercury removal efficiency for these examples ranged from 83 to 91%.
  • Test Numbers 37 and 69 (repeat examples) achieved mercury capture efficiencies of 99.3 and 99.6%, respectively, utilizing Westates coal carbon impregnated with potassium iodide.
  • Test Numbers 79A and 79B contained an adsorbent powder characterized as containing 38% Westates coal carbon impregnated with potassium iodide, 52% calcium hydroxide, and 10% cupric chloride, and the mercury capture increased to 99.6% with the addition of cupric chloride the powder.

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Abstract

L'invention concerne une poudre d'adsorption à base de carbone contenant une quantité efficace de chlorure cuivrique. Cette poudre peut être utilisée pour éliminer du mercure d'un flux gazeux à haute humidité et à haute température, la quantité efficace de chlorure cuivrique étant comprise entre environ 1 et environ 45 % en poids. Des additifs supplémentaires, tels que le permanganate de potassium, l'hydroxyde de calcium, l'iodure de potassium et le soufre, peuvent être ajoutés à cette poudre pour améliorer l'élimination du mercure du flux gazeux.
PCT/US2002/021120 1999-09-29 2002-07-05 Poudre d'adsorption a base de carbone contenant du chlorure cuivrique WO2003006140A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2003511940A JP2004534641A (ja) 1999-09-29 2002-07-05 塩化銅（ｉｉ）を含有する炭素ベースの吸着性粉体
CA002451534A CA2451534A1 (fr) 1999-09-29 2002-07-05 Poudre d'adsorption a base de carbone contenant du chlorure cuivrique
EP02748062A EP1406718A4 (fr) 1999-09-29 2002-07-05 Poudre d'adsorption a base de carbone contenant du chlorure cuivrique

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US09/408,361 US6589318B2 (en) 1999-09-29 1999-09-29 Adsorption powder for removing mercury from high temperature, high moisture gas streams
US09/902,293 2001-07-10
US09/902,285 2001-07-10
US09/902,293 US6524371B2 (en) 1999-09-29 2001-07-10 Process for adsorption of mercury from gaseous streams
US09/902,285 US6638347B2 (en) 1999-09-29 2001-07-10 Carbon-based adsorption powder containing cupric chloride

Publications (1)

Publication Number Publication Date
WO2003006140A1 true WO2003006140A1 (fr) 2003-01-23

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1385621A2 (fr) * 2001-03-29 2004-02-04 Merck & Co., Inc. Poudre d'adsorption contenant du chlorure cuivrique
GB2444397A (en) * 2006-11-30 2008-06-04 Gen Electric Catalyst composition and method of use of the catalyst composition for removal of mercury from emissions stream of a power plant
GB2475932A (en) * 2009-12-07 2011-06-08 Michael Schlitt Disposable catheter with reinforcement rod
CN103958030A (zh) * 2011-11-28 2014-07-30 Ada碳解决方案有限责任公司 用于从烟道气中快速除汞的多官能组合物
CN105467040A (zh) * 2015-12-30 2016-04-06 乌鲁木齐谱尼测试科技有限公司 土壤中对氨基苯甲醚和对硝基苯甲醚残留量的检测方法
CN107737581A (zh) * 2017-11-09 2018-02-27 东南大学 一种制备改性石油焦基脱汞吸附剂的方法

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CN103056157A (zh) * 2013-01-25 2013-04-24 贵州省环境科学研究设计院 汞污染土壤的低温热解处理修复方法及装置
BR112023005462B1 (pt) 2020-09-25 2024-03-12 Carbon Technology Holdings, LLC Composição para reduzir um minério metálico
CN117015514A (zh) 2021-02-18 2023-11-07 卡本科技控股有限责任公司 碳负冶金产品
WO2022232311A1 (fr) 2021-04-27 2022-11-03 Carbon Technology Holdings, LLC Compositions de biocarbone avec carbone fixe optimisé et leurs procédés de production
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US3193987A (en) * 1962-02-23 1965-07-13 Pittsburgh Activated Carbon Co Mercury vapor removal
US3194629A (en) * 1962-02-23 1965-07-13 Pittsburgh Activated Carbon Co Method of removing mercury vapor from gases
US3956458A (en) * 1973-11-16 1976-05-11 Paul Brent Anderson Method and apparatus for air purification
US4094777A (en) * 1975-12-18 1978-06-13 Institut Francais Du Petrole Process for removing mercury from a gas or a liquid by absorption on a copper sulfide containing solid mass
US4889698A (en) * 1986-07-16 1989-12-26 A/S Niro Atomizer Process for removal or mercury vapor and/or vapor of noxious organic compounds and/or nitrogen oxides from flue gas from an incinerator plant
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US5575982A (en) * 1993-12-23 1996-11-19 Metallgesellschaft Aktiengesellschaft Process of purifying exhaust gases produced by combustion of waste materials
US5659110A (en) * 1994-02-03 1997-08-19 Metallgesellschar Aktiengeselschaft Process of purifying combustion exhaust gases
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1385621A2 (fr) * 2001-03-29 2004-02-04 Merck & Co., Inc. Poudre d'adsorption contenant du chlorure cuivrique
EP1385621A4 (fr) * 2001-03-29 2008-04-16 Merck & Co Inc Poudre d'adsorption contenant du chlorure cuivrique
GB2444397A (en) * 2006-11-30 2008-06-04 Gen Electric Catalyst composition and method of use of the catalyst composition for removal of mercury from emissions stream of a power plant
GB2444397B (en) * 2006-11-30 2010-09-15 Gen Electric Method for removal of mercury from the emissions stream of a power plant and an apparatus for achieving the same
GB2475932A (en) * 2009-12-07 2011-06-08 Michael Schlitt Disposable catheter with reinforcement rod
CN103958030A (zh) * 2011-11-28 2014-07-30 Ada碳解决方案有限责任公司 用于从烟道气中快速除汞的多官能组合物
CN103958030B (zh) * 2011-11-28 2016-04-20 Ada碳解决方案有限责任公司 用于从烟道气中快速除汞的多官能组合物
CN105467040A (zh) * 2015-12-30 2016-04-06 乌鲁木齐谱尼测试科技有限公司 土壤中对氨基苯甲醚和对硝基苯甲醚残留量的检测方法
CN107737581A (zh) * 2017-11-09 2018-02-27 东南大学 一种制备改性石油焦基脱汞吸附剂的方法

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EP1406718A1 (fr) 2004-04-14
EP1406718A4 (fr) 2005-10-19
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CA2451534A1 (fr) 2003-01-23

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