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WO2003037442A1 - Procede de destruction de composes organiques halogenes dans des solides - Google Patents

Procede de destruction de composes organiques halogenes dans des solides Download PDF

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Publication number
WO2003037442A1
WO2003037442A1 PCT/CA2002/001584 CA0201584W WO03037442A1 WO 2003037442 A1 WO2003037442 A1 WO 2003037442A1 CA 0201584 W CA0201584 W CA 0201584W WO 03037442 A1 WO03037442 A1 WO 03037442A1
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WO
WIPO (PCT)
Prior art keywords
waste
solvent
asphaltic
solvent mixture
reactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CA2002/001584
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English (en)
Inventor
Keith Cheuklap Lee
Nicola Dominelli
Ian Gordon Norman Wylie
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Powertech Labs Inc
Original Assignee
Powertech Labs Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CA 2360408 external-priority patent/CA2360408C/fr
Application filed by Powertech Labs Inc filed Critical Powertech Labs Inc
Publication of WO2003037442A1 publication Critical patent/WO2003037442A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen

Definitions

  • the invention is in the field of processes for the destruction of hazardous compounds in solid wastes, particularly the chemical destruction of halogenated organic compounds.
  • halogenated organic compounds have been identified as being potentially hazardous to human health or to the environment. The safe destruction of these compounds in some waste materials is made particularly difficult by the nature of the waste, which may impede access to the hazardous compound for the purpose of treatment.
  • the present invention relates to the treatment of a variety of hazardous halogenated compounds in waste materials comprised of asphalt, an example of which is potting compound contaminated with polychlorinated biphenyls (PCBs).
  • PCBs are a family of very stable halogenated organic compounds of which there are more than 200 individual compounds (sometimes known as congeners, identified by IUPAC numbers 1-209). PCBs are the product of the chlorination of a biphenyl structure, wherein one or more of the ten hydrogen atoms of a biphenyl are replaced with chlorine atoms.
  • PCB were often produced in commercial mixtures, such as Aroclors
  • PCBs were often used in mixtures with other halogenated organic compounds, such as trichlorobenzene or tetrachlorobenzene, for example in insulating fluids for electrical equipment (such mixtures may be referred to by the tradename Askarels).
  • the present invention relates to processes for the decomposition of such compounds and mixtures.
  • PCBs are not easily destroyed by natural processes. Their use has been banned for environmental reasons due to the possible danger to the environment and inhabitants. PCBs are not easily biodegradable and will not disappear or decay to any extent by natural processes. Once they are formed, they can be destroyed only by special and generally expensive procedures.
  • PCBs Because they are stable, conduct heat well and are good electrical insulators while being fire resistant, PCBs have been used extensively in dielectric materials in electrical components such as transformers and capacitors. Although further use of PCBs for such purposes is generally prohibited by regulation in most jurisdictions, large quantities of these chemicals are present in existing equipment or in industrial waste, particularly in the electrical industry. In some jurisdictions, there are very large quantities of wastes in stockpiles awaiting disposal that have been identified as being contaminated with PCBs.
  • PCBs can be destroyed by incineration, high temperatures and controlled conditions are generally required, in order to avoid generation of PCB thermal decomposition byproducts that may be significantly more toxic than PCBs, such as polychlorinated dioxins and furans.
  • PCBs also have been disposed of by burial, but the stability of these compounds gives rise to concerns about approaches to disposal that do not destroy the compounds themselves.
  • Capacitors containing PCBs were used in electrical equipment such as fluorescent light ballasts until they were prohibited by regulations. Many of these capacitors leaked PCBs into the ballasts during malfunction, thus contaminating the internal components of the ballast, such as the potting compound.
  • the potting compound is typically a mixture of asphalt and sand (silica) that surrounds the electrical components in the ballast. Potting compounds may also include other ingredients such as waxes that modify properties such as the melt range of the potting compound and the adhesive characteristics of the asphalt. Asphalt is used primarily to provide an adhesive for the sand, which acts as an insulator and heat conductor. Some potting compounds may for example be made up of 35-50% silica for proper heat transfer, 50-65% percent asphalt and 0-10% wax.
  • the invention provides processes for destruction of PCBs in an asphaltic waste, wherein the processes may comprise steps A, B and C, as follows:
  • the waste, such as potting compound may for example encase an electrical component, and the electrical component may be treated in the process of the invention with the waste.
  • potting compound and the electrical components encased by the potting compound may first be separated, and the potting compound and electrical components may each be processed separately.
  • a hydrocarbon solvent may be selected that will facilitate dissolving the asphaltic waste at relatively mild temperatures.
  • a destructive reactant such as an alkali metal (such as sodium)
  • an alkali metal such as sodium
  • the halogenated organic compound such as a PCB
  • the alkali metal may for example be in an alkali metal dispersion in an alkali metal solvent.
  • the process may include the addition of hydrogen donors or promoters, such as, but not limited to, water, alcohols or acids (as, for example, disclosed in United States Patent 5,185,488 to Hawari, European Patent EP0225849 to Burli et al, and Candian Electrical Association Report 153D253, "Scale-up of Chemical Reactions to Destroy Polychlorinated Biphenyls", Dominelli, N and Pugh, D.R., May 17, 1983).
  • a hydrolyzing reactant such as water, may be added to the treated waste-solvent mixture to hydrolyse an excess amount of the alkali metal remaining in the treated waste-solvent mixture.
  • the asphaltic waste may be a solid asphaltic waste with a particular melting temperature.
  • Solid asphaltic wastes containing PCBs may for example be crushed at a crushing temperature that is below the melting temperature of the solid asphaltic waste, for example, at temperatures well below the melting temperature to render the asphaltic material brittle and to facilitate breakage of the asphaltic material.
  • the crushed waste may be converted to a particulate waste with a relatively high surface area to enhance dissolution in the solvent.
  • the dissolving temperature, the reaction temperature and the melting temperature may for example be adjusted to be below the boiling point of the halogenated organic compound, which may for example help avoid evaporative loss of hazardous compounds such as PCBs during the processes of the invention.
  • the treated waste-solvent mixture may be distilled to separate the solvent, such as a hydrocarbon solvent, from the asphaltic waste, for example to produce a recyclable hydrocarbon solvent.
  • the distillation conditions may be adjusted, for example, so that the recyclable solvent may be substantially free of asphalt.
  • the recyclable solvent may in turn be reused as the solvent in the step of mixing with the asphaltic waste to produce the waste-solvent mixture.
  • an asphaltic waste is a waste material comprised of a substantial portion of asphalt, in which, for the purposes of the processes of the invention, halogenated organic compounds may be entrained by the cementitious nature of the asphalt.
  • asphalt generally includes bituminous substances derived as residua in refining from natural sources such as petroleum, shale oil, coal tar and pitches.
  • Asphalts are typically mixtures of hydrocarbons of natural and/or pyrogenous origin, accompanied by their derivatives, often prepared by distillation of crude oil.
  • asphalt is a mixture of paraffinic and aromatic hydrocarbons and heterocyclic compounds containing sulfur, nitrogen and oxygen.
  • Asphalt is a cementitious material having a solid or semi-solid consistency.
  • Halogenated organic compounds that may be treated in accordance with alternative aspects of the invention include aromatic and non-aromatic halides (bromides, chlorides, fluorides and iodides).
  • Representative halogenated organic compounds include PCBs and dioxins. In some embodiments, the invention is restricted to the destruction of PCBs.
  • processes for decontamination of electrical components encased in asphaltic compositions comprising the steps of: crushing the electrical components to form crushed fragments; adding a solvent to the crushed fragments to form a mixture; heating the mixture to a reaction temperature that is sufficient to dissolve the asphaltic material and thereby release the hazardous compounds from it; and reacting the mixture with a compound, such as an alkali metal dispersion, for a period of time sufficient to reduce the amount of the hazardous material in the waste mixture.
  • a compound such as an alkali metal dispersion
  • a process for decontamination of hazardous compounds such as halogenated organic compounds (including PCBs) found in electrical light ballasts, where the light ballasts are composed of asphaltic potting compound and electrical components.
  • Such processes of the invention may for example comprise the steps of: crushing the light ballasts to form crushed fragments; adding a solvent to the crushed fragments to form a mixture; heating the mixture to a reaction temperature that is sufficient to dissolve the potting compound; reacting the mixture with a reactant, such as an alkali metal dispersion, for a period of time sufficient to reduce the amount of the hazardous compound in the mixture.
  • a reactant such as an alkali metal dispersion
  • the invention provides an apparatus with means for carrying out the steps of the processes of the invention, such as: a) means for mixing an asphaltic waste entraining an organic halide with a solvent to produce a waste-solvent mixture; b) means for heating the waste-solvent mixture to a dissolving temperature for a dissolving time to produce a heated waste-solvent mixture in which the asphaltic waste is dissolved in the solvent so that the organic halide is released from the asphaltic waste; c) means for adding a destructive reactant to the heated waste-solvent mixture at a reaction temperature for a reaction time to produce a treated waste- solvent mixture in which the organic halide is substantially all reacted with the destructive reactant to destroy the organic halide.
  • the apparatus of the invention may include automated controls to adapt standard material handling equipment to carry out the processes of the invention in an automated fashion.
  • Such controls may for example adapt a mixer with a heating element and timer for mixing the waste with the solvent at the dissolving temperature for the dissolving time.
  • the controls may also adapt the mixer or a reaction vessel for reacting the heated waste-solvent mixture at the reaction temperature for the reaction time to produce the treated waste-solvent mixture.
  • the invention provides relatively mild processes for decontaminating electrical components using organic solvents.
  • Processes of the invention are disclosed that have surprisingly been found capable of dissolving asphaltic wastes to an extent that renders hazardous compounds, such as PCBs, amenable to destructive chemical treatment.
  • the electrical components may for example be capacitor windings entrained in an asphaltic potting compound, as may be found in fluorescent light ballasts.
  • Processes for treating asphaltic wastes may involve heating the waste in the solvent and reacting the dissolved material with a reactant, such as an alkali metal in an organic solvent dispersion.
  • a reactant such as an alkali metal in an organic solvent dispersion.
  • PCB means that the concentration of the hazardous compound is reduced to a level at which it is not hazardous or toxic.
  • concentrations of hazardous compounds such as PCBs may for example be reduced in treated wastes to levels below about lOOppm, 90ppm, 80ppm, 70ppm, 60ppm, 50ppm, 40ppm, 30ppm, 20ppm, 10ppm, 5ppm, 2ppm, 1ppm, or 0.5ppm.
  • the waste to be treated may for example initially contain hazardous compounds such as PCBs at concentrations greater than the following values: about 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, lOOOppm, 2000ppm, 3000ppm, 4000ppm, 5000ppm, 6000ppm, 7000ppm, 8000ppm, 9000ppm, 10,000ppm, 100,000ppm or 200,000ppm (or any value between 100ppm and 200,000ppm).
  • Alternative embodiments of the invention may for example involve treating waste having a hazardous compound concentration greater than any one of the forgoing initial values, so that the treated waste has a hazardous compound concentration below any one of the foregoing treated waste values. Such treatments may for example be characterized as destroying a certain percentage of the hazardous compound, such as 80%, 90%, 95%, 99%, 99.9% or 99.99%.
  • fluorescent light ballasts may be separated into potting compound (composed mainly of asphalt and sand) and capacitor windings.
  • the potting compound and electrical components for example the capacitor windings, may be handled separately by the processes of the present invention, or the potting compound and the electrical components may be processed together. Segregation of waste streams may increase the available options for disposal of the products of the processes of the present invention, including the possibility of recycling.
  • Separation of potting compound from electrical components in a fluorescent light ballast may for example be carried out by manual or automated processes.
  • an asphaltic potting compound may be subjected to impact forces to promote the cracking of the potting compound, and thus the separation of the potting compound from the internal electrical components.
  • Method are for example disclosed in United States Patent No. 5, 230,140 (incorporated herein by reference) involving the cryogenic freezing of potting compound to the extent that the frozen potting compound becomes sufficiently brittle to enable it to be pulverized into small pieces that may be separated relatively cleanly away from the internal electrical components.
  • Wastes to be treated may be crushed.
  • the crushed waste may for example have a preferred particle size, such as an average particle size of less than approximately 2 inches (5 cm), 1 inch (2.5 cm) or V_ inch (1.25 cm) in size.
  • the process of separating a potting compound from electrical components may be adapted to yield potting compound fragments within the aforementioned particles size ranges, or additional steps of crushing the potting compound may be carried out.
  • Waste particle size reduction may for example be accomplished by processing the waste through an appropriate grinder for size reduction. A grinding or crushing process may be selected so that it will refine the waste without melting it.
  • a rotary shaft grinder design with a horizontal ram feed may be preferred where it minimizes cutting friction and heat build-up.
  • Waste such as crushed potting compound
  • a reaction vessel such as a mixer/evaporator, to which is added a solvent.
  • a horizontal mixer of the plough design may be used because where it disperses materials more efficiently than a ribbon or blade type mixer.
  • the solvent for dissolving the asphaltic waste may be chosen such that its boiling point is higher than the reaction temperature, such as by being approximately 5°C to 10°C higher than the reaction temperature.
  • reaction temperatures may for example be between 100°C to 170°C (as described below), so that in some embodiments a solvent may be selected with a boiling point of at least about 105°C to at least about 180°C (or any value in that range).
  • a solvent having an appropriate boiling point may reduce solvent evaporation during reaction with the waste, and may facilitate a more efficient recovery of the solvent by distillation at the end of the process, if desired.
  • the solvent is preferably chosen to be of a type that does not react with the reactant, such as solvents that do not react under the reaction conditions with an alkali metal.
  • suitable solvents for the processes of the invention may include mineral spirits, aliphatic hydrocarbons, paraffin oils, insulating oils or transformer oils.
  • suitable hydrocarbon solvents in some embodiments include VARSOLTM or ISOPAR KTM solvent (manufactured by Exxon Mobil Corporation).
  • Preferred solvents are low polarity liquids, such as hydrocarbon solvents, and preferred hydrocarbon solvents are oils.
  • solvent includes any substance which is a liquid at the dissolving temperature and the reaction temperature, and which is capable of dissolving the asphaltic waste and serving as a medium in which the organic halogen compound may be destroyed.
  • the waste-solvent mixture may be heated, for example in a mixer, to a temperature of between about 100°C to about 170°C until the asphaltic waste (such as potting compound) dissolves, thereby releasing the hazardous compounds (such as PCBs) into solution.
  • the temperature may be maintained at a selected reaction temperature throughout the reaction, or modulated over time.
  • the oxygen content in the reaction vessel may be maintained below a flammability limit of the solvent, to increase the safety of the process.
  • An inert gas atmosphere may be applied to increase safety.
  • the oxygen content of the atmosphere in a reaction vessel may be maintained below about 10%, 9%, 8%, 7% or preferably 6% at all times during the step of dissolving the waste, and less than about 5%, 4%, 3% or preferably below 2,5% when an alkali metal reactant is present, such as a sodium dispersion.
  • an alkali metal such as a dispersion of sodium in a solvent
  • a dispersion of sodium in a solvent may be added to the reaction mixture and allowed to react with the halogenated organic compound for a period of time, for example 30 - 60 minutes. More or less time may be required depending in part on the amount of organic halide present in the starting material.
  • Sodium dispersions are generally commercially available. As well, there are a number of processes for the production of suitable sodium dispersions that are known. It may be preferable that a solvent used in the alkali metal dispersion have a boiling point similar to the solvent used to dissolve the asphaltic waste, and may in some embodiments be the same as the solvent used to dissolve the asphaltic waste.
  • Alkali metal solvents may for example be selected from the following non-exhaustive list: mineral oils, paraffinic oils, insulating oils, or transformer oils.
  • the particle size of the alkali metal dispersion may be less than about 100 microns, 50 microns, 40 microns, 30 microns, 20 microns, 10 microns or 5 microns.
  • PCB destruction processes may be used, such as base-catalysed decomposition processes or alkali metal hydroxide based decomposition processes (as, for example, disclosed in Unites States Patent 4,477,354 to Fessler, Unites States Patent 5,064,526 to Rogers et al., Unites States Patent 4,460,797 to
  • alkali metals such as potassium
  • excess alkali metal in the reaction mixture may be hydrolysed and neutralized, for example with the injection of water and carbon dioxide into the mixer. Hydrogen formed during this stage of the process may be captured for later use or it may be allowed to exhaust to the environment after passing through an appropriate exhaust filter, the purpose of which is to trap any liquid and solids that may be carried with the gas stream.
  • the solvent may be recovered for reuse, for example by distillation.
  • Distillation may be first carried out at atmospheric pressure or at reduced pressures. In some embodiments, the distillation pressure may be reduced during distillation to facilitate a near complete recovery of the solvent.
  • a decontaminated treated asphaltic waste product may be kept molten, for example by keeping potting compound at a temperature above the melting point of the compound, such as 120- 170°C. Treated asphaltic waste may be discharged from the reaction vessel into a collection bin.
  • electrical components such as capacitor windings obtained from a fluorescent light ballast, may be processed in a manner similar to that described above for asphaltic wastes. This may, for example, be advantageous when the components have asphaltic material still associated with them.
  • the reaction temperature may for example be in the approximate range of 150°C to 170°C.
  • Decontaminated electrical components may be discharged from a reaction vessel as a solid.
  • 200 g of the crushed potting compound was placed into a 750 mL glass reaction vessel fitted with a water cooled condenser, an inlet for nitrogen gas and an inlet for a dropping funnel.
  • 200 g of the solvent ISOPAR KTM was placed into the reaction vessel, and the mixture was agitated using a variable speed mechanical stirrer.
  • the mixture in the reaction vessel was heated to a reaction temperature of approximately 120°C under a nitrogen atmosphere.
  • a sample of the mixture was removed and the concentration of PCBs in the sample was measured to be 290 mg/kg (equivalent to 490 mg/kg in the feed material).
  • Capacitor windings from a PCB contaminated fluorescent light ballast was separated from the other components and crushed / as described above until the average particle size of the capacitor windings was less than V_" in size.
  • 30 g of the crushed capacitor windings and 550 g of the solvent ISOPAR KTM were placed into a 750 mL glass reaction vessel fitted with a water cooled condenser, an inlet for nitrogen gas and an inlet for a dropping funnel, and the mixture was agitated using a variable speed mechanical stirrer.
  • the mixture in the reaction vessel was heated to a reaction temperature of approximately 170°C under a nitrogen atmosphere.
  • a sample of the mixture was removed and the concentration of PCBs in the sample was measured to be 9,660 mg/kg (equivalent to 17.9% PCB in the feed material).
  • 30 g of sodium dispersion (20% by weight of sodium in insulating oil) was added to the mixture and allowed to react with the mixture while the temperature of the mixture was maintained near 170°C.
  • Another sample of the mixture was removed after approximately 30 minutes and again at 90 minutes after the addition of the sodium dispersion, and the concentration of PCBs in each case was measured to be below the detection limit. The mixture was then allowed to cool, and at below 100°C, 11 g of water was added to the mixture.
  • the potting compound and the internal electrical components from fluorescent light ballasts may be crushed simultaneously into the preferred particle sizes and processed together.
  • the crushed potting compound and electrical components may then be loaded into the reaction vessel to which is added the solvent, and the same general steps as described above may be carried out.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne des procédés de décontamination d'halogénures organiques dans des déchets contenant de l'asphalte, par exemple les biphényles polychlorés (BPC) dans les produits d'enrobage asphaltiques. Des solvants à base d'hydrocarbures peuvent être utilisés dans ces procédés pour dissoudre les déchets asphaltiques, ainsi qu'un réactif métallique alcali, par exemple une dispersion de sodium, pour détruire les halogénures organiques dans le mélange dissous.
PCT/CA2002/001584 2001-10-29 2002-10-18 Procede de destruction de composes organiques halogenes dans des solides Ceased WO2003037442A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CA2,360,408 2001-10-29
CA 2360408 CA2360408C (fr) 2001-10-29 2001-10-29 Procede de destruction de composes organiques halogenes dans des solides
US33772301P 2001-11-07 2001-11-07
US60/337,723 2001-11-07

Publications (1)

Publication Number Publication Date
WO2003037442A1 true WO2003037442A1 (fr) 2003-05-08

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PCT/CA2002/001584 Ceased WO2003037442A1 (fr) 2001-10-29 2002-10-18 Procede de destruction de composes organiques halogenes dans des solides

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0225849A1 (fr) * 1985-12-06 1987-06-16 Ciba-Geigy Ag Procédé pour déshalogéner les composés halogénés aliphatiques et aromatiques
DE4206308A1 (de) * 1991-02-28 1992-09-03 Jade Stahl Gmbh Verfahren und vorrichtung zum reinigen und/oder entsorgen von pcb-belasteten elektrischen bzw. elektronischen bauelementen
EP0503831A1 (fr) * 1991-03-15 1992-09-16 Ontario Hydro Destruction des biphényles polychlorés
US5230140A (en) * 1991-10-24 1993-07-27 Anthony Nardella Process for environmentally safe disposal of used fluorescent lamp potted ballast assemblies with component part reclamation and/or recycling
DE4429391A1 (de) * 1994-08-11 1996-02-15 Boehme Elektr Recycling Gmbh Verfahren und Vorrichtung zur Aufbereitung PCB-haltiger Kondensatoren

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0225849A1 (fr) * 1985-12-06 1987-06-16 Ciba-Geigy Ag Procédé pour déshalogéner les composés halogénés aliphatiques et aromatiques
DE4206308A1 (de) * 1991-02-28 1992-09-03 Jade Stahl Gmbh Verfahren und vorrichtung zum reinigen und/oder entsorgen von pcb-belasteten elektrischen bzw. elektronischen bauelementen
EP0503831A1 (fr) * 1991-03-15 1992-09-16 Ontario Hydro Destruction des biphényles polychlorés
US5230140A (en) * 1991-10-24 1993-07-27 Anthony Nardella Process for environmentally safe disposal of used fluorescent lamp potted ballast assemblies with component part reclamation and/or recycling
DE4429391A1 (de) * 1994-08-11 1996-02-15 Boehme Elektr Recycling Gmbh Verfahren und Vorrichtung zur Aufbereitung PCB-haltiger Kondensatoren

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