WO2001023072A1 - Adsorption powder for removing mercury from high temperature, high moisture gas streams - Google Patents

Adsorption powder for removing mercury from high temperature, high moisture gas streams Download PDF

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Publication number
WO2001023072A1
WO2001023072A1 PCT/US2000/026217 US0026217W WO0123072A1 WO 2001023072 A1 WO2001023072 A1 WO 2001023072A1 US 0026217 W US0026217 W US 0026217W WO 0123072 A1 WO0123072 A1 WO 0123072A1
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Prior art keywords
carbon
powder
adsorption powder
adsorption
mercury
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PCT/US2000/026217
Other languages
French (fr)
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
Application filed by Merck & Co., Inc. filed Critical Merck & Co., Inc.
Priority to AU77127/00A priority Critical patent/AU7712700A/en
Publication of WO2001023072A1 publication Critical patent/WO2001023072A1/en

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    • 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
    • B01J20/04—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
    • 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
    • B01J20/0233—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
    • B01J20/0274—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
    • 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
    • B01J20/04—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
    • 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
    • B01J20/30—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
    • 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
    • B01J20/30—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
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases 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
    • 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
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Definitions

  • the present invention relates generally to removal of pollutants from high temperature, high moisture gas streams such as those found in devices designed to treat contaminated soil and in hazardous mate ⁇ al incinerators. More particularly, the invention relates to the capture of mercury and other metals, dioxms, furans and other organic compounds from high temperature, high moisture gas streams using an adsorption powder containing cup ⁇ c chlo ⁇ de.
  • St ⁇ ct standards exist for particulate and total mercury emissions by coal-fired power plants, petroleum refine ⁇ es, chemical refineries, coal fired furnaces, trash burning facilities, incinerators, metallurgical operations, thermal treatment units and other particulate and mercury emitting facilities. These same rest ⁇ ctions apply to mercury vapor, which can enter the atmosphere as a result of low temperature thermal desorption (LTTD) treatment of contaminated soils.
  • LTTD low temperature thermal desorption
  • 3,193, 987 discloses passing mercury- contammg vapor over activated carbon impregnated with a metal which forms an amalgam with mercury.
  • U.S. Patent No. 4,094,777 discloses passing a mercury- containing vapor over an adsorption mass consisting essentially of a support, sulfided copper and sulfided silver.
  • U.S. Patent No. 3,876,393 discloses passing mercury- containing vapors over activated carbon that has been impregnated with sulfu ⁇ c acid. Selenium has also been used in the removal of mercury from a vapor.
  • 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 x and SO x using acid scrubbers, carbon beds, condensation units and through the addition of adsorption powders.
  • metals, HC1, NO x and SO x using acid scrubbers, carbon beds, condensation units and 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 approp ⁇ ate 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 adsorption powders remove organics, metals and other contaminants, but they do not effectively remove mercury.
  • Sand TM one available powder
  • WUELFRAsorb-C TM Another powder 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 desc ⁇ bed 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 mate ⁇ als, 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 requmng retooling or reconfigu ⁇ ng existing equipment.
  • an adsorption powder and method for removing mercury and other metals and contaminants from a high temperature, high moisture gas stream comprising: about 1-97% carbon; about 1-97% of an alkaline material; about 1-97% cupric chloride and about 1-60% KI 3 impregnated carbon.
  • a method for removing mercury and other metals, dioxins, furans and other organic compounds from high temperature, high moisture gas streams using the claimed powder is also disclosed.
  • Figure 1 is 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.
  • an adsorption powder for removing mercury and other metals from a gas stream comprising: a) about 1-97% carbon; b) about 1-97% of alkaline material; c) about 1-97% cupric chloride; and d) about 1-60% KI 3 impregnated carbon.
  • an adsorption powder for removing mercury and other metals from a gas stream comprising about 10-70% carbon, about 20-80% of alkaline material, about 1-50% cupric chloride and about 1-50% KI 3 impregnated carbon.
  • calcium hydroxide is the preferred alkaline material.
  • an adsorption powder for removing mercury and other metals from a gas stream comprising about 20-60% carbon, about 30-70% of alkaline material, about 1-30% cupric chloride and about 3-30% KI 3 impregnated carbon.
  • an adsorption powder for removing mercury and other metals from a gas stream comprising about 25-45% carbon, about 40-60% of alkaline material, about 1-15% cupric chloride and about 5-15% KI 3 impregnated carbon.
  • an adsorption powder for removing mercury and other metals from a gas stream comprising about 30% coal carbon, about 50% of alkaline material, about 10% cupric chloride and about 10% KI 3 impregnated carbon.
  • 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 organics, metals and other impurities from the contaminated soil. Mercury that is trapped in contaminated soil, however, is most efficiently adsorbed on carbon at about 300-500°F. 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 adsorption powder of the invention operates effectively even in a higher moisture environment.
  • Cupric chloride was observed to significantly enhance the adsorption 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 adsorption when it was included in the powder.
  • the powder of the invention contains from about 1-97% of alkaline material.
  • the alkaline material is used to treat SO x compounds and/or neutralize the acid content of the gas.
  • Alkaline materials that can be used in the powder of the invention include calcium hydroxide, calcium carbonate, calcium oxide, sodium hydroxide, sodium phosphates, sodium carbonate, barium hydroxide, magnesium hydroxide, barium phosphates, potassium hydroxide, potassium oxide, manganese hydroxide, soda ash, fly ash, boiler fines, kiln residues and other similar alkaline materials.
  • a combination of alkaline materials can be used as well as a single type.
  • the alkaline material used is calcium hydroxide, as shown in the following example.
  • Figure 1 shows a schematic diagram of the actual process and equip- ment 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 contaminates from the soil and generate a gas 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 adsorption 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 adsorption 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 adsorption powder mixture 20.
  • a se ⁇ es of field tests were performed employing a preferred adsorption powder formulation.
  • Three soil samples containing about 4.2 mg/kg of mercury were prepared by screening to 1 inch.
  • the coarse mate ⁇ al was discarded, and the remaining soil was fed into a soil cleaning unit and heated to about 900°F
  • the cleaned soil was transferred to a soil cooling unit and prepared for reuse.
  • the exhaust stream was sent to a dust remover and the precipitated mate ⁇ al was sent to the soil cooling unit.
  • the exhaust stream was then fed into an exhaust cleaning unit, which was heated to about 1850°F.
  • the exhaust gas was then cooled to about 360°F by quenching with water, and subsequently an adsorption powder comp ⁇ sing 30% coal carbon, 10% KI 3 impregnated carbon, 50% calcium hydroxide and 10% cup ⁇ c chlo ⁇ de was added.
  • the exhaust stream/adsorption powder mixture was fed into a baghouse, where the mercury-bound particulate was separated from the mercury-free exhaust gas.
  • the particulate mate ⁇ al was removed from the baghouse for analysis and disposal, while gas analyzers on the exhaust stack recorded mercury emission levels. The results of the three, two hour runs are reported in the following table.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treating Waste Gases (AREA)

Abstract

There is disclosed an adsorption powder effective for capturing mercury from a high temperature, high moisture gas stream comprising: about 1-97 % carbon; about 1-97 % of alkaline material; about 1-97 % cupric chloride, and about 1-60 % carbon impregnated with KI3. Additionally, a method of removing mercury from high temperature, high moisture gas streams, using the adsorption powder of the invention, is disclosed.

Description

TITLE OF THE INVENTION
ADSORPTION POWDER FOR REMOVING MERCURY FROM HIGH
TEMPERATURE, HIGH MOISTURE GAS STREAMS
BACKGROUND OF THE INVENTION
The present invention relates generally to removal of pollutants from high temperature, high moisture gas streams such as those found in devices designed to treat contaminated soil and in hazardous mateπal incinerators. More particularly, the invention relates to the capture of mercury and other metals, dioxms, furans and other organic compounds from high temperature, high moisture gas streams using an adsorption powder containing cupπc chloπde.
Stπct standards exist for particulate and total mercury emissions by coal-fired power plants, petroleum refineπes, chemical refineries, coal fired furnaces, trash burning facilities, incinerators, metallurgical operations, thermal treatment units and other particulate and mercury emitting facilities. These same restπctions apply to mercury vapor, which can enter the atmosphere as a result of low temperature thermal desorption (LTTD) treatment of contaminated soils.
These stπngent standards exist in order to protect the environment and the community. When mercury-contammg gases are released, the gases disperse and mercury is deposited over a wide area. The dispersed mercury can accumulate in the soil or water supplies, where it may be incorporated into the food chain. Mercury is extremely harmful to aquatic life and ultimately to the humans who consume mercury-contaminated plants and animals. It is necessary, therefore, to have a safe and effective method of eliminating mercury from the environment. The problem of the capture and treatment of mercury vapor, typically in the context of coal-fired power plants and waste incinerators, has been previously considered. For example, U.S. Patent No. 3,193, 987 discloses passing mercury- contammg vapor over activated carbon impregnated with a metal which forms an amalgam with mercury. U.S. Patent No. 4,094,777 discloses passing a mercury- containing vapor over an adsorption mass consisting essentially of a support, sulfided copper and sulfided silver. U.S. Patent No. 3,876,393 discloses passing mercury- containing vapors over activated carbon that has been impregnated with sulfuπc 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.)
The problem of recaptuπng mercury from power plant gas streams is analogous to the need for recaptuπng mercury from incinerators that treat contaminated soils. A process currently in use at soil treatment facilities is known as low temperature thermal desorption (LTTD). LTTD is the mam process by which contaminated soils are treated to remove mercury and other contaminants. In this process, contaminated soils are fed into a heating furnace, most commonly a rotary kiln/drum, where the soil is heated by conduction. The heating volatizes the soil components and when a thermal oxidizer is added, the components are oxidized to manageable gases, such as CO , Cl2, NOx and SOx, where x is 1-3.
The hot gas stream is subsequently cooled. The stream may be quenched with water, which cools the stream and concurrently increases the moisture content. Although 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, NOx and SOx using acid scrubbers, carbon beds, condensation units and through the addition of 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 appropπate disposal, while the clean gas stream is exhausted to the outside atmosphere. The problem with standard LTTD methods is that some metals, such as mercury, are not removed from the stream at high efficiency and will move with the gas stream, ultimately into the environment. Other methods require the use of complex machinery and expensive adsorption beds. LTTD and other methods also suffer from the limitation that mercury removal from high moisture gas streams is much more difficult than mercury removal from dry streams. Available adsorption powders remove organics, metals and other contaminants, but they do not effectively remove mercury. For example, one available powder (Sorbalite ™) 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 ™) 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 descπbed and other available powders is known to be very temperature dependent, placing an additional limitation on powder formulations.
Accordingly, there is a need in the industry for 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 mateπals, combustion of coal and other mercury liberating sources. The powder must be inexpensive and easy to use. Ideally, such an adsorption powder can be employed at treatment facilities already in place and can take advantage of equipment already in position, without requmng retooling or reconfiguπng existing equipment.
SUMMARY OF THE INVENTION
There is disclosed an adsorption powder and method for removing mercury and other metals and contaminants from a high temperature, high moisture gas stream comprising: about 1-97% carbon; about 1-97% of an alkaline material; about 1-97% cupric chloride and about 1-60% KI3 impregnated carbon. A method for removing mercury and other metals, dioxins, furans and other organic compounds from high temperature, high moisture gas streams using the claimed powder is also disclosed.
BRIEF DESCRIPTION OF THE DRAWINGS
The instant invention will be more fully understood in the following detailed description, it being understood, however, that the invention is not confined to the precise disclosure. Changes and modifications may be made that do not affect the spirit of the invention, nor exceed the scope thereof, as expressed in the appended claims. Accordingly, the instant invention will now be described with particular reference to the accompanying drawings.
Figure 1 is 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.
DETAILED DESCRIPTION OF THE INVENTION
There is disclosed an adsorption powder for removing mercury and other metals from a gas stream comprising: a) about 1-97% carbon; b) about 1-97% of alkaline material; c) about 1-97% cupric chloride; and d) about 1-60% KI3 impregnated carbon.
In a preferred embodiment, there is disclosed an adsorption powder for removing mercury and other metals from a gas stream comprising about 10-70% carbon, about 20-80% of alkaline material, about 1-50% cupric chloride and about 1-50% KI3 impregnated carbon. In all prefeπed embodiments, calcium hydroxide is the preferred alkaline material. In a more prefeπed embodiment, there is disclosed an adsorption powder for removing mercury and other metals from a gas stream comprising about 20-60% carbon, about 30-70% of alkaline material, about 1-30% cupric chloride and about 3-30% KI3 impregnated carbon. In a further preferred embodiment, there is disclosed an adsorption powder for removing mercury and other metals from a gas stream comprising about 25-45% carbon, about 40-60% of alkaline material, about 1-15% cupric chloride and about 5-15% KI3 impregnated carbon.
In the most preferred embodiment, there is disclosed an adsorption powder for removing mercury and other metals from a gas stream comprising about 30% coal carbon, about 50% of alkaline material, about 10% cupric chloride and about 10% KI3 impregnated carbon.
There is also disclosed a process for removing mercury from a gas stream using the adsorption powder of the invention comprising 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 of Claim 1 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 organics, metals and other impurities from the contaminated soil. Mercury that is trapped in contaminated soil, however, is most efficiently adsorbed on carbon at about 300-500°F. 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 adsorption powder of the invention, however, operates effectively even in a higher moisture environment.
Experiments with carbon sources showed that coal carbon was superior to wood carbon for mercury adsorption. Many available adsorption powders use wood carbon as a component, rather than coal carbon. Cupric chloride was observed to significantly enhance the adsorption 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. KI3 impregnated carbon was also found to increase mercury adsorption when it was included in the powder.
The powder of the invention contains from about 1-97% of alkaline material. The alkaline material is used to treat SOx compounds and/or neutralize the acid content of the gas. Alkaline materials that can be used in the powder of the invention include calcium hydroxide, calcium carbonate, calcium oxide, sodium hydroxide, sodium phosphates, sodium carbonate, barium hydroxide, magnesium hydroxide, barium phosphates, potassium hydroxide, potassium oxide, manganese hydroxide, soda ash, fly ash, boiler fines, kiln residues and other similar alkaline materials. A combination of alkaline materials can be used as well as a single type. Preferably, the alkaline material used is calcium hydroxide, as shown in the following example.
Figure 1 shows a schematic diagram of the actual process and equip- ment 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 contaminates from the soil and generate a gas stream, as well as a clean/remediated solid soil component. Preferably, 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.
After dust remover 6 removes any particulate matter from the gas stream sample, 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. From the Exhaust Cleaning Unit 10, 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 adsorption 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.
After the gas stream has been contacted to the adsorption powder, the powder/gas stream mixture continues on to baghouse 16. The carbon component of the adsorption powder collects on the walls of bags and acts as a particulate filter for the gases leaving the baghouse. Baghouse 16 collects the particulate mercury- containing fraction of the adsorption 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 adsorption powder mixture 20. EXAMPLE 1
A seπes of field tests were performed employing a preferred adsorption powder formulation. Three soil samples containing about 4.2 mg/kg of mercury were prepared by screening to 1 inch. The coarse mateπal was discarded, and the remaining soil was fed into a soil cleaning unit and heated to about 900°F The cleaned soil was transferred to a soil cooling unit and prepared for reuse. The exhaust stream was sent to a dust remover and the precipitated mateπal was sent to the soil cooling unit. The exhaust stream was then fed into an exhaust cleaning unit, which was heated to about 1850°F. The exhaust gas was then cooled to about 360°F by quenching with water, and subsequently an adsorption powder compπsing 30% coal carbon, 10% KI3 impregnated carbon, 50% calcium hydroxide and 10% cupπc chloπde was added. The exhaust stream/adsorption powder mixture was fed into a baghouse, where the mercury-bound particulate was separated from the mercury-free exhaust gas. The particulate mateπal was removed from the baghouse for analysis and disposal, while gas analyzers on the exhaust stack recorded mercury emission levels. The results of the three, two hour runs are reported in the following table.
Figure imgf000009_0001
1 Removal Efficiency (%) = (Mass input - Stack Output- Clean Soil Output)/(Mass Input - Clean Soil Output)
The average mercury removal efficiency of 99.6% exceeds the current mercury control efficiency specification of 96.5% efficiency, set by NJDEP air permit legislation Mercury emissions were determined by EPA method 29-060. Although the adsorption powder and method descπbed and claimed are presented in the context of mercury removal from a gas stream, it should be appreciated that the powder and method are also useful for removing organics, metals and other contaminants from a gas stream

Claims

WHAT IS CLAIMED IS:
1. An adsorption powder for removing mercury and other metals, dioxins, furans and other organic compounds from a gas stream compπsing: a) about 1-97% carbon; b) about 1-97% of alkaline mateπal; c) about 1-97% cupπc chloπde; and d) about 1-60% KI3 impregnated carbon.
2. The adsorption powder of claim 1 wherein the alkaline mateπal is selected from calcium hydroxide, calcium carbonate, calcium oxide, sodium hydroxide, sodium phosphates, sodium carbonate, baπum hydroxide, magnesium hydroxide, baπum phosphates, potassium hydroxide, potassium oxide, manganese hydroxide or combinations thereof.
3. The adsorption powder of claim 2 wherein the alkaline mateπal is calcium hydroxide.
4. The adsorption powder of claim 3 wherein the adsorption powder compπses about 10-70% carbon, about 20-80% calcium hydroxide, about
1-50% cupπc chloπde and about 1-50% KI3 impregnated carbon.
5. The adsorption powder of claim 4 wherein the adsorption powder compπses about 20-60% carbon, about 30-70% calcium hydroxide, about 1-30% cupπc chloπde and about 3-30% KI impregnated carbon.
6. The adsorption powder of claim 5 wherein the adsorption powder compπses about 25-45% carbon, about 40-60% calcium hydroxide, about 1-15% cupπc chloπde and about 5-15% KI3 impregnated carbon.
7. The adsorption powder of claim 6 wherein the adsorption powder compπses about 30% carbon, about 50% calcium hydroxide, about 10% cupπc chloπde and about 10% KI3 impregnated carbon.
8. The adsorption powder of claim 1 wherein the carbon is coal carbon.
9. A method for removing mercury and other metals, dioxins, furans and other organic compounds from a gas stream using the adsorption powder of claim 1 compπsing the steps of:
a) placing a solid phase mercury-containing contaminated soil feed into a rotary
Figure imgf000011_0001
b) heating said kiln/drum containing said soil feed to form gaseous and solid components of the sample; c) transferπng 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 of Claim 1 to the gaseous component, g) transferπng the powder-containing gaseous component to a baghouse; and h) releasing the substantially mercury-free gaseous component of said sample to the atmosphere.
10. The method of Claim 9 wherein the adsorption powder used in step f) compπses a) about 1-97% carbon; b) about 1-97% of alkaline mateπal; c) about 1-97% cupπc chloπde; and d) about 1-60% KI3 impregnated carbon.
11. The method of Claim 10 wherein the adsorption powder used in step f) comprises about 10-70% carbon, about 20-80% calcium hydroxide, about 1-50% cupric chloride and about 1-50% KI3 impregnated carbon.
12. The method of Claim 11 wherein the adsorption powder used in step f) comprises about 30% carbon, about 50% calcium hydroxide, about 10% cupric chloride and about 10% KI3 impregnated carbon.
AMENDED CLAIMS
[received by the International Bureau on 24 January 2001 (24.01.01); original claims 1, 3-7 and 9 amended; remaining claims unchanged (3 pages)]
1. An adsorption powder for removing mercury and other metals, dioxins, furans and other organic compounds from a gas stream comprising: a) carbon; b) alkaline material; c) cupric chloride; and d) KI3 impregnated carbon.
2, The adsorption powder of claim 1 wherein the alkaline material is selected from calcium hydroxide, calcium carbonate, calcium oxide, sodium hydroxide, sodium phosphate, sodium carbonate, barium hydroxide, magnesium hydroxide, barium phosphates, potassium hydroxide, potassium oxide, manganese hydroxide or combinations thereof.
3. The adsorption powder of claim 2 wherein the alkaline material is calcium hydroxide.
4. The adsorption powder of claim 3 wherein the powder compπses about 10-70% carbon, about 20-80% calcium hydroxide, about 1-50% cupric chloride and about 1-50% KI3 impregnated carbon.
5. The adsorption powder of claim 4 wherein the powder comprises about 20-60% carbon, about 30-70% calcium hydroxide, about 1-30% cupric chloride and about 3-30% I3 impregnated carbon.
6. The adsorption powder of claim 5 wherein the powder comprises about 25-45% carbon, about 40-60% calcium hydroxide, about 1-15% cupric chloride and about 5-15% KI3 impregnated carbon.
7. The adsorption powder of claim 6 wherein the powder comprises about 30% carbon, about 50% calcium hydroxide, about 10% cupric chloride and about 10% KI3 impregnated carbon.
8. The adsorption powder of claim 1 wherein the carbon is coal carbon.
9. A method of removing mercury and other metals, dioxins, furans and other organic compounds from a gas stream using adsorption powder, wherein the powder is characterized as containing a) carbon; b) calcium hydroxide; c) cupric chloride; and d) KI3 impregnated carbon, the method comprises 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; c) transferring the gaseous component of said soil feed to un exhaust cleaning unit/afterbumer, and transferring the solid component 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 to collect the carbon component of the powder on the walls of the baghouse and filter solid component from the gaseous component to provide a substantially mercury-free gaseous component; and h) releasing the substantially mercury-free gaseous component to the atmosphere.
10. The method of claim 9 wherein the adsorption powder used in step f) comprises: a) about 1-97% carbon; b) about 1-97% alkaline material; c) about 1-97% cupric chloride; and d) about 1-60% KI3 impregnated carbon.
11. The method of claim 10 wherein the adsorption powder used in step f) comprises about 1-70% carbon, about 20-80% calcium hydroxide, about 1-50% cupric chloride and about 1-50% KI impregnated carbon.
12. The method of claim 11 wherein the adsorption powder used in step f) comprises about 30% carbon, about 50% calcium hydroxide, about 10% cupric chloride and about 10% I3 impregnated carbon.
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