WO2017136679A1 - Système et procédé destinés à désagréger des dépôts de scories et compositions utilisées - Google Patents

Système et procédé destinés à désagréger des dépôts de scories et compositions utilisées Download PDF

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Publication number
WO2017136679A1
WO2017136679A1 PCT/US2017/016439 US2017016439W WO2017136679A1 WO 2017136679 A1 WO2017136679 A1 WO 2017136679A1 US 2017016439 W US2017016439 W US 2017016439W WO 2017136679 A1 WO2017136679 A1 WO 2017136679A1
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WIPO (PCT)
Prior art keywords
expandable
hydrocarbon
disrupting
slag
deposit
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Ceased
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PCT/US2017/016439
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English (en)
Inventor
Mark D. Hughes
Daniel T. Smith
Kenneth W. Koch
Nathaniel J. SMOTER
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Liquid Minerals Group Ltd
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Liquid Minerals Group Ltd
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Publication of WO2017136679A1 publication Critical patent/WO2017136679A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B5/00—Treatment of  metallurgical  slag ; Artificial stone from molten  metallurgical  slag 
    • C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J3/00—Removing solid residues from passages or chambers beyond the fire, e.g. from flues by soot blowers
    • F23J3/02—Cleaning furnace tubes; Cleaning flues or chimneys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J7/00—Arrangement of devices for supplying chemicals to fire
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J9/00—Preventing premature solidification of molten combustion residues
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0209—Group I metals: Li, Na, K, Rb, Cs, Fr, Cu, Ag, Au
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0213—Group II metals: Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0218—Group III metals: Sc, Y, Al, Ga, In, Tl
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0231—Group VI metals: Cr, Mo, W, Po
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0236—Group VII metals: Mn, To, Re
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/024—Group VIII metals: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0245—Lanthanide group metals: La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0272—Silicon containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/06—Particle, bubble or droplet size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/02—Combustion or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
    • C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst

Definitions

  • Embodiments of the present invention generally relate to hydrocarbon-fired combustion apparatuses and, more specifically, to systems and methods for disrupting slag deposits formed on internal surfaces of hydrocarbon-fired combustion apparatuses (e.g., boilers), such as for easier removal thereof, and the treating compositions used therein.
  • hydrocarbon-fired combustion apparatuses e.g., boilers
  • the often preferred fuel is natural gas. Natural gas is preferred because it contains very few, if any, contaminants.
  • electric utilities are often forced to rely on less environmentally friendly fuels. These fuels may be derivatives of petroleum taken from various stages of the refining process of this increasingly expensive commodity. When price per unit of derived energy is considered, the chosen fuel is frequently coal when it is available as a viable option. Of all the fuels, coal has by far the greatest number and largest amounts of contaminants and, thus, has the greatest environmental impact when not properly and completely treated.
  • Contaminants often cause problems in the power generating industry.
  • the combustion of residual petroleum or other hydrocarbon fuels, e.g., coal in hydrocarbon-fired combustion apparatuses (e.g., boilers) produces an ash, which after fusion in the firing flames may remain sufficiently molten and adhere to the steam generating surfaces and superheater tubes, or elsewhere on fireside surfaces.
  • Substantial amounts of the molten ash may accumulate and solidify on those surfaces, upon cooling to a certain temperature, in the form of a slag deposit.
  • slag deposits can be extremely difficult to remove and generally require that a boiler, for example, be placed offline, which is undesirable, so as to remove the slag.
  • various slag removal techniques can be labor intensive and, thus, costly and time-consuming.
  • Such slag removal techniques include, for example, laser cutting, high pressure water or air nozzles or jets (including fire hoses), as well as the use of explosives, shotguns, or old-fashioned hammer and chisel techniques.
  • Embodiments of the present invention provide treating compositions including an effective amount of a slag deposit disrupting composition, where the slag deposit disrupting composition disrupts by weakening and/or reducing slag deposit integrity and/or reduces slag deposit formation in hydrocarbon-fired (e.g., coal-fired) boilers (or other hydrocarbon-fired combustion apparatuses).
  • the treating compositions also include an inhibiting amount of an emission and/or corrosion inhibiting composition that reduces hazardous emissions.
  • the slag deposit disrupting compositions and the emission and/or corrosion inhibiting compositions include particulate materials.
  • compositions/particulates are understood to combine or intermix with slag deposit forming materials formed during fuel combustion to co-deposit on boiler surfaces.
  • the intermixed slag deposit disrupting compositions define an area or zone within the slag that weakens and/or reduces slag deposit integrity so that the slag deposits are more prone to flaking off, such as under their own weight, resulting in self-cleaning and/or are more easily removed using traditional cleaning or removal techniques.
  • the treating compositions include an emission and/or corrosion inhibiting composition, then the treating compositions also simultaneously reduce general deposit formation.
  • Embodiments of the present invention provide hydrocarbon-fired combustion apparatuses and systems, e.g., hydrocarbon-fired (e.g., coal-fired) boilers, including a
  • combustion unit which can have a fuel source, a fuel conduit, a fuel delivery assembly, burners, a combustion chamber, an oxidizing agent source, an oxidizing agent conduit, an oxidizing agent delivery assembly, a treating composition source, a treating composition conduit, a treating delivery assembly, a heat transfer fluid assembly, a flue gas exhaust assembly, and a unit for converting a portion of thermal energy associated with the heat transfer fluid to a usable form of energy such as electrical energy, mechanical energy, or a combination of the two.
  • the treating compositions are designed to disrupt slag deposit integrity by weakening and/or reducing slag deposit integrity of slag deposits that form on surfaces of the hydrocarbon-fired combustion apparatuses and/or systems, such as hydrocarbon-fired (e.g., coal-fired) boilers.
  • the treating compositions may also reduce hazardous emissions.
  • the treating delivery assembly includes at least one injector assembly, such as a high temperature injector assembly.
  • Each injector assembly includes at least one fluid injector and an injector feed device for feeding a treating composition of the present invention into the hydrocarbon-fired combustion apparatuses/systems, such as hydrocarbon-fired (e.g., coal) boilers, particularly at one location or a plurality of locations of the boiler at a sufficient rate to disrupt by weakening and/or reducing slag deposit integrity on internal surfaces of the boiler upon which slag deposits normally form and may also reduce hazardous emissions.
  • hydrocarbon-fired e.g., coal
  • the system further includes a treating composition source and a treating composition conduit for introducing the treating composition, which includes a deposit disrupting composition, to the hydrocarbon-fired combustion apparatus, and wherein the treating composition conduit introduces an effective amount of the treating composition into the hydrocarbon-fired combustion apparatus that is sufficient to disrupt slag deposits, which form as a result of combustion of the hydrocarbon fuel, by weakening and/or reducing slag deposit integrity on an internal surface of the hydrocarbon- fired combustion apparatus where slag formation occurs.
  • a treating composition source and a treating composition conduit for introducing the treating composition, which includes a deposit disrupting composition, to the hydrocarbon-fired combustion apparatus, and wherein the treating composition conduit introduces an effective amount of the treating composition into the hydrocarbon-fired combustion apparatus that is sufficient to disrupt slag deposits, which form as a result of combustion of the hydrocarbon fuel, by weakening and/or reducing slag deposit integrity on an internal surface of the hydrocarbon- fired combustion apparatus where slag formation occurs.
  • Embodiments of the present invention also provide methods for disrupting boiler slag deposits by weakening and/or reducing slag deposit integrity including injecting a treating composition of the present invention in a location or a plurality of locations of a hydrocarbon- fired combustion apparatus, such as a hydrocarbon-fired (e.g., coal-fired) boiler, at a rate sufficient to weaken, disrupt, and/or reduce deposits on surfaces of the apparatuses upon which deposits normally form.
  • the treating compositions also include an emission and/or corrosion inhibiting composition sufficient to reduce hazardous emissions.
  • Embodiments of the present invention also provide methods for making treating compositions including providing a treating composition comprising a deposit disrupting material/agent.
  • the methods include combining a plurality of deposit disrupting materials/agents to form a heterogeneous, substantially heterogeneous, homogeneous, or substantially homogeneous treating composition.
  • the methods may also include mixing the plurality of deposit disrupting materials/agents for a time and at a temperature and a pressure sufficient to form a substantially homogeneous or homogeneous treating composition.
  • the treating compositions are prepared by combining at least one deposit disrupting material/agent and at least one emission and/or corrosion inhibitor to form a heterogeneous, substantially heterogeneous, homogeneous, or substantially homogeneous treating composition.
  • the methods include mixing the at least one deposit disrupting material/agent and the at least one emission and/or corrosion inhibitor for a time and at a temperature sufficient to form a substantially homogeneous or homogeneous treating composition.
  • the methods may also include dispersing a treating composition in a suitable carrier to form a treating slurry composition.
  • the Figure depicts a hydrocarbon-fired (e.g., coal-fired) boiler.
  • the term “substantially” means that the property is within 95% of its desired value. In other embodiments, “substantially” means that the property is within 97.5% of its desired value. In other embodiments, “substantially” means that the property is within 99% of its desired value. In other embodiments, “substantially” means that the property is within 99.9% of its desired value.
  • the term “substantially complete” as it relates to a coating means that the coating is at least 95% complete. In other embodiments, the term “substantially complete” as it relates to a coating, means that the coating is at least 97.5% complete.
  • the term "substantially” means that a value is within about +5% of the indicated value. In certain embodiments, the value is within about +2.5% of the indicated value. In certain embodiments, the value is within about +1% of the indicated value. In certain embodiments, the value is within about +0.5% of the indicated value. In certain embodiments, the value is within about +0.1% of the indicated value. In certain embodiments, the value is within about +0.01% of the indicated value.
  • the term "about” means that the value is within +10% of the indicated value. In certain embodiments, the value is within +5% of the indicated value. In certain embodiments, the value is within +2.5% of the indicated value. In certain embodiments, the value is within +1% of the indicated value. In certain embodiments, the value is within +0.5% of the indicated value. The term "about” means that the property is within +10% of the indicated value. In certain embodiments, the property is within +5% of the indicated value. In certain embodiments, the property is within +2.5% of the indicated value. In certain embodiments, the property is within +1% of the indicated value. In certain embodiments, the property is within +0.5% of the indicated value.
  • high flash point liquid additive means a liquid additive having a flash point that is at least about 65°C so that it is less hazardous around combustion equipment than liquid additives previously available. Liquid additives having a flash point of at least about 70°C are designed to be safer to use in coal-burning plants. In certain embodiments, liquid additives having a flash point of at least about 70°C will be referred to as a high flash point liquid additive. It is important to maintain high flash points to avoid or minimize the danger from fires. Flash point is directly related to vapor pressure of the product. The higher the flash point, the lower the vapor pressure of the material. Thus, even after a spill or leak, higher flash point products would not produce high concentrations of vapor that could travel over distances to spark or flame that could ignite them.
  • FP flash point
  • high temperature expandable material means a material that undergoes a rapid increase in volume after being subjected to an expansion temperature, but does not decompose at a combustion temperature of the boilers or other combustion systems to which the treating composition is added.
  • mixture means that two are more components have been mixed together to form a mixture before use.
  • Systems and methods are disclosed for disrupting slag deposits formed on internal surfaces of hydrocarbon-fired (e.g., coal-fired) boilers (or other hydrocarbon-fired combustion systems), such as for easier removal thereof.
  • hydrocarbon-fired e.g., coal-fired
  • the treating compositions for fuels used in these hydrocarbon-fired (e.g., coal-fired) boilers where the fuels tend to cause slag deposits on internal surfaces of the boilers and other hydrocarbon-fired (e.g. coal-fired) combustion systems, especially transfer fluid conduit surfaces.
  • Such treating compositions include a disrupting amount of a deposit disrupting composition and may also optionally include an inhibiting amount of an emission and/or corrosion inhibiting composition.
  • the treating compositions are injected into the fuel prior to the fuel being injected into the hydrocarbon-fired boiler (or other hydrocarbon-fired combustion system), while in other embodiments, the boiler includes at least one high temperature injector for injecting the additive compositions into a zone or zones of the boiler (or other combustion system).
  • the treating compositions are either present in the fuel in a sufficient amount or are injected at a sufficient rate to disrupt boiler slag deposits by combining or intermixing with slag deposit forming materials formed during fuel combustion to co-deposit on boiler surfaces, thereby weakening and/or reducing slag deposit integrity .
  • Embodiments of the present invention provide treating compositions including a disrupting amount of a slag deposit disrupting composition, where the slag deposit disrupting composition disrupts by weakening and/or reducing deposit integrity and/or reduces slag deposit formation.
  • the deposit disrupting compositions are believed to combine or intermix with slag deposit forming materials formed during fuel combustion to co-deposit on internal surfaces.
  • the intermixed slag deposit disrupting compositions define an area or zone within the slag that weakens and/or reduces slag deposit integrity so that the slag deposits are more prone to flaking off, such as under their own weight, resulting in self-cleaning and/or more easily removed using traditional cleaning or removal techniques.
  • the treating compositions also include an inhibiting amount of an inhibiting composition that inhibits corrosion and/or reduces hazardous emissions.
  • the treating compositions include at least one inhibitor modified deposit disrupting composition. If the treating compositions include an inhibiting composition, then the treating compositions also simultaneously reduce deposit formations that effect corrosion and/or emissions.
  • the inhibitor modified deposit disrupting compositions include at least one inhibitor modified expandable particulate material, at least one inhibitor modified non-expandable particulate material, at least one inhibitor modified hollow particulate material, or mixtures and combinations thereof.
  • the inhibitor modified deposit disrupting compositions include at least one inhibitor modified expandable particulate synthetic material, at least one inhibitor modified non-expandable particulate synthetic material, at least one inhibitor modified hollow particulate synthetic material, or mixtures and
  • the treating compositions include at least one inhibitor modified expandable particulate material, at least one unmodified non-expandable particulate material, and/or at least one corrosion inhibiting material.
  • the particulate materials have particle sizes ranging from about 0.01 microns or ⁇ to about 50,000 ⁇ , to about 25,000 ⁇ , to about 10,000 ⁇ , to about 5,000 ⁇ or to about 1,000 ⁇ . In other embodiments, the particulate materials have particle sizes ranging from about 0.1 ⁇ to about 50,000 ⁇ , to about 25,000 ⁇ , to about 10,000 ⁇ , to about 5,000 ⁇ or to about 1,000 ⁇ . In other embodiments, the particulate materials have particle sizes ranging from about 1 ⁇ to about 5,000 ⁇ to about 25,000 ⁇ , to about 10,000 ⁇ , to about 5,000 ⁇ or to about 1,000 ⁇ .
  • the particulate materials have particle sizes ranging from about 10 ⁇ to about 5,000 ⁇ to about 25,000 ⁇ , to about 10,000 ⁇ , to about 5,000 ⁇ or to about 1,000 ⁇ . In other embodiments, the particulate materials have particle sizes ranging from about 100 ⁇ to about 5,000 ⁇ to about 25,000 ⁇ , to about 10,000 ⁇ , to about 5,000 ⁇ or to about 1,000 ⁇ . In other embodiments, the particulate materials have particle sizes ranging from about 1,000 ⁇ to about 5,000 ⁇ to about 25,000 ⁇ , to about 10,000 ⁇ , to about 5,000 ⁇ or to about 1,000 ⁇ . In other
  • expandable particulate carbon based materials including expandable particulate coke, expandable particulate graphite, or mixtures and combinations thereof.
  • the expandable particulate carbon based materials include expandable synthetic particulate carbon based materials, such as expandable particulate synthetic coke, expandable particulate synthetic graphite, or mixtures and combinations thereof.
  • the expandable particulate materials comprise carbon-boron based materials, carbon-nitrogen based materials, or mixtures and combinations thereof.
  • the particulate compositions include expandable coke particles, which are synthetic.
  • the particulate compositions include expandable synthetic graphite particles.
  • the expandable synthetic coke or graphite particles when introduced into hydrocarbon-fired combustion systems, such as coal-fired boilers, will expand in volume instantaneously or substantially instantaneously upon heating to a given expansion temperature.
  • the expansion temperature can be at or greater than 100°C. In another example, the temperature can be at or greater than 150°C, or at or greater than 250°. In another example, the expansion temperature can be at or greater than 300°C, or at or greater than 600°C.
  • the particles will intermix with slag deposit forming materials formed during fuel combustion to co-deposit on internal boiler surfaces and expand to at least 150 times its initial volume to effectively define an area or zone within the slag that weakens and/or reduces slag deposit integrity.
  • the expanded volume is at least 175 times greater than its initial volume. In other embodiments, the expanded volume is at least 200 times greater than its initial volume.
  • compositions including inhibitor modified expandable particulate synthetic coke or graphite require smaller amounts of the compositions to achieve a desired leave of simultaneous slag deposit disruption and corrosion inhibition.
  • the amount of the composition required may be from about one tenth up to about one two hundredth compared to compositions including standard coke or graphite to achieve a desired degree of slat deposit disruption and corrosion inhibition.
  • inhibitor modified expandable cokes and graphite result in less of the treating compositions being required for a given degree of simultaneous slag deposit disruption and corrosion inhibition, more importantly, fewer particles require trapping by back end environmental controls.
  • expandable synthetic coke or graphite As expandable synthetic coke or graphite is heated and expands, it becomes softer. This allows the particles to occupy a greater volume, which means these particles will take up a greater volume within any slag deposit forming on the surfaces of the boiler systems thereby weakening and/or reducing slag deposit integrity. Any inhibitor remaining with the expanded coke or graphite, especially chemically attached inhibitors, will be intimately associated with the surface as slag deposits form on the surfaces.
  • expandable synthetic cokes and graphite including inhibitor modified expandable synthetic cokes and graphite are lubricating forms of carbon. This means, where the particles become incorporated with slag deposit forming materials, the slag deposits will have greater lubricity so that the slag deposits will be more prone to flaking out or dislodging during cleaning operations or fall under their own weight resulting in self-cleaning.
  • the thin film of carbon with or without inhibitors may also help in reducing the formation of future slag deposits on the metal surfaces as the surfaces may be slick and also may help reduce corrosion of the surface if inhibitors are also left on the surface with the carbon.
  • the thin film of carbon with or without inhibitors will also help insulate the surfaces of the metal parts. .
  • the treating compositions of the present invention may be introduced into the boilers using a carrier, such as a solvent.
  • a carrier such as a solvent.
  • the particulate compositions of the present invention may be formulated with aromatic solvents, surfactants, paraffinic solvents, or mixtures thereof.
  • the particulate compositions of the present invention may be dispersed into surfactant solutions, which may include, without limitation, fatty acids, sulfonic acids, organic carboxylic acids, polymeric materials, or mixtures thereof.
  • the particulate compositions of the present invention may be treated with suitable agents to enhance the ability for expandable particles, such as expandable synthetic coke or graphite particles, to expand or to allow easier application of the compositions for their intended role.
  • suitable agents such as expandable synthetic coke or graphite particles
  • the treating compositions of the present invention may be introduced directly into the combustion chamber (combustor) of hydrocarbon-fired (e.g., coal-fired) boilers (or other hydrocarbon-fired (e.g., coal-fired) combustion systems), and/or into the fuel stream, for example.
  • hydrocarbon-fired e.g., coal-fired
  • boilers or other hydrocarbon-fired (e.g., coal-fired) combustion systems
  • the inhibitor modified particles include a magnesium compound absorbed onto expandable coke or graphite particles.
  • the inhibitor modified particles include high purity magnesium nanoparticles absorbed onto expandable coke or graphite particles. [0053] In certain embodiments, the inhibitor modified particles include
  • magnesium/boron nanoparticles absorbed onto expandable coke or graphite particles magnesium/boron nanoparticles absorbed onto expandable coke or graphite particles.
  • the inhibitor modified particles include an aluminum compound absorbed onto expandable coke or graphite particles.
  • the inhibitor modified particles include a boron compound absorbed onto expandable coke or graphite particles.
  • the inhibitor modified particles include a magnesium compound and an aluminum compound absorbed onto expandable coke or graphite particles.
  • the amount is sufficient to disrupt slag deposits and simultaneously to reduce surface corrosion and reduce emissions.
  • Modified particulate agent comprising a particulate agent coated with, impregnated with, and/or chemically modified with at least one corrosion inhibiting agent and where the compositions simultaneously affect boiler slag deposits and corrosion inhibition during operation of the boiler.
  • the treating composition is either injected into the fuel on an intermittent, semi-periodic, semi-continuous, or continuous basis or into the boiler at the location(s) on an intermittent, semi-periodic, semi- continuous, or continuous basis.
  • Embodiments of the present invention also relate to methods for disrupting boiler slag deposits including introducing a treating composition of the present invention directly into a combustion chamber, into a fuel stream, and/or into an oxidizing agent stream of a hydrocarbon- fired combustion system, such as hydrocarbon-fired (e.g., coal-fired) boilers.
  • a hydrocarbon-fired combustion system such as hydrocarbon-fired (e.g., coal-fired) boilers.
  • treating compositions having expandable synthetic coke particles and/or expandable synthetic graphite particles are introduced into a hydrocarbon-fired (e.g., coal-fired) boiler and expand in volume instantaneously or substantially instantaneously upon heating to a given expansion temperature.
  • the particles will mix with the slag deposit forming materials formed during fuel combustion to co-deposit on internal boiler surfaces and expand, for example, to at least 150 times initial volume.
  • the expanded and intermixed particles define areas or zones within the slag that results in weakening and/or reducing slag deposit integrity so that the slag deposits are more prone to flaking off, such as under their own weight, resulting in self-cleaning and/or are more easily removed using traditional cleaning or removal techniques.
  • This procedure may remove on average 50% of the molten ash or slag deposits, resulting in a substantial regaining of the power lost.
  • the actual removal may be in the 25% to 75% range, but in some instances may be as low as 10%.
  • Higher firing temperature boilers will have ash deposits that are harder to remove than units that fire at lower temperatures.
  • a second or third charge may be necessary. It can also be repeated as deemed necessary based on operating modes.
  • the compositions include inhibitor modified particles, the particles not only disrupt slag deposits on boiler surfaces but also can reduce or prevent corrosion of the surfaces.
  • the corrosion inhibitors coated on, impregnated in, or chemically attached to expandable or non-expandable particles may be water soluble or oil soluble magnesium corrosion inhibitors.
  • the magnesium corrosion inhibitors include a minimum of 30% magnesium.
  • Such formulations would include a sufficient amount of the corrosion inhibitors coating, impregnating and/or chemically attached to the particulate materials to cause both adequate treating and adequate corrosion protection and emission suppression. With these formulations, sufficient expandable synthetic coke and/or graphite or other material would be available to maintain the boiler in a boiler slag disrupting condition.
  • the treating composition of the present invention may require a smaller amount of modification of the particulate materials with corrosion inhibitors or the inhibitor modified particulate materials may be "cut" with unmodified particulate materials, because these fuels normally contain lesser quantities of vanadium and consequently require less magnesium corrosion inhibitor additive for treatment. In some instances, not enough treating composition is added under normal treatment requirements. Thus a supplemental treatment may be needed to provide the desired amount of treating composition to ensure the boiler is maintained in a boiler slag disrupting state.
  • the advantage of using synthetic expandable and/or non-expandable coke and/or graphite materials instead of more common nutshells or even graphite is the synthetic coke and/or graphite materials will not oxidize in the flame as readily as nutshells or standard coke or graphite materials. Thus, the synthetic coke and/or graphite may persist post flame to perform its disrupting and, if modified with inhibitors, inhibiting functions. The expandable nature of the particles will lead to larger (volume) particles to impact even more surface area.
  • Embodiments of the present invention broadly relate to methods for making the treating compositions of the present invention including step of contacting at least one disrupting particulate material with at least one optional corrosion inhibitor under conditions to form an inhibitor modified disrupting compositions including at least one particulate treating agent coated with, impregnated with, and/or chemically modified by at least one corrosion inhibiting agent via any chemical and/or physical interaction including covalent bonding, ionic bonding, hydrogen bonding, electrostatic interactions, or any other chemical and/or physical interaction.
  • inhibitor modified particles are made by spraying a corrosion inhibitor comprising nano-particles of a corrosion inhibitor in a carrier onto a fluidized particulate agent, such as expandable synthetic coke and/or graphite, so that the particulate agent becomes coated with and/or impregnated with the nano-particles.
  • a fluidized particulate agent such as expandable synthetic coke and/or graphite
  • inhibitor modified particles are made by spraying a corrosion inhibitor comprising nano-particles of a corrosion inhibitor and a coupling agent in a carrier onto a fluidized particulate agent, such as expandable synthetic coke and/or graphite, so that the particulate agent becomes coated with, impregnated with and/or chemically modified by the nano-particles.
  • a fluidized particulate agent such as expandable synthetic coke and/or graphite
  • the treating compositions include 100 wt.% of a deposit disrupting composition. In other embodiments, the treating compositions include between about 99 wt.% and about 1 wt.% of a deposit disrupting composition and between about 1 wt.% and about 99 wt.% of an inhibiting composition. In other embodiments, the treating compositions include between about 95 wt.% and about 5 wt.% of a deposit disrupting composition and between about 5 wt.% and about 95 wt.% of an inhibiting composition.
  • the treating compositions include between about 60 wt.% and about 40 wt.% of a deposit disrupting composition and between about 40 wt.% and about 60 wt.% of an inhibiting composition. In other embodiments, the treating compositions include about 50 wt.% of a deposit disrupting composition and about 50 wt.% of an inhibiting composition.
  • the disrupting composition includes between about 95 wt.% and about 5 wt.% of a non-expandable particulate disrupting material or a plurality of non- expandable particulate disrupting materials and between about 5 wt.% and about 95 wt.% of an expandable particulate disrupting material or a plurality of expandable particulate disrupting materials.
  • the disrupting composition includes between about 90 wt.% and about 10 wt.% of a non-expandable particulate disrupting material or a plurality of non- expandable particulate disrupting materials and between about 10 wt.% and about 90 wt.% of an expandable particulate disrupting material or a plurality of expandable particulate disrupting materials.
  • the disrupting composition includes between about 80 wt.% and about 20 wt.% of a non-expandable particulate disrupting material or a plurality of non- expandable particulate disrupting materials and between about 20 wt.% and about 80 wt.% of an expandable particulate disrupting material or a plurality of expandable particulate disrupting materials.
  • the disrupting composition includes between about 70 wt.% and about 30 wt.% of a non-expandable particulate disrupting material or a plurality of non- expandable particulate disrupting materials and between about 30 wt.% and about 70 wt.% of an expandable particulate disrupting material or a plurality of expandable particulate disrupting materials.
  • the disrupting composition includes between about 60 wt.% and about 40 wt.% of a non-expandable particulate disrupting material or a plurality of non- expandable particulate disrupting materials and between about 40 wt.% and about 60 wt.% of an expandable particulate disrupting material or a plurality of expandable particulate disrupting materials.
  • the disrupting composition includes about 50 wt.% of a non- expandable particulate disrupting material or a plurality of non-expandable particulate disrupting materials and about 50 wt.% of an expandable particulate disrupting material or a plurality of expandable particulate disrupting materials.
  • the non-expandable and/or expandable particulate disrupting material may be a synthetic carbon, such as synthetic coke and/or graphite.
  • the disrupting composition includes 100 wt.% of an inhibitor modified non-expandable particulate disrupting material or a plurality of inhibitor modified non-expandable particulate disrupting materials. In other embodiments, the disrupting composition includes 100 wt.% of an inhibitor modified expandable particulate disrupting material or a plurality of inhibitor modified expandable particulate disrupting materials.
  • the disrupting composition includes between about 99 wt.% and about 1 wt.% of an inhibitor modified non-expandable particulate disrupting material or a plurality of inhibitor modified non-expandable particulate disrupting materials and between about 1 wt.% and about 99 wt.% of an inhibitor modified expandable particulate disrupting material or a plurality of inhibitor modified expandable particulate disrupting materials.
  • the disrupting composition includes between about 95 wt.% and about 5 wt.% of an inhibitor modified non-expandable particulate disrupting material or a plurality of inhibitor modified non- expandable particulate disrupting materials and between about 5 wt.% and about 95 wt.% of an inhibitor modified expandable particulate disrupting material or a plurality of inhibitor modified expandable particulate disrupting materials.
  • the disrupting composition includes between about 90 wt.% and about 10 wt.% of an inhibitor modified non-expandable particulate disrupting material or a plurality of inhibitor modified non-expandable particulate disrupting materials and between about 10 wt.% and about 90 wt.% of an inhibitor modified expandable particulate disrupting material or a plurality of inhibitor modified expandable particulate disrupting materials.
  • the disrupting composition includes between about 80 wt.% and about 20 wt.% of an inhibitor modified non-expandable particulate disrupting material or a plurality of inhibitor modified non-expandable particulate disrupting materials and between about 20 wt.% and about 80 wt.% of an inhibitor modified expandable particulate disrupting material or a plurality of inhibitor modified expandable particulate disrupting materials.
  • the disrupting composition includes between about 70 wt.% and about 30 wt.% of an inhibitor modified non-expandable particulate disrupting material or a plurality of inhibitor modified non-expandable particulate disrupting materials and between about 30 wt.% and about 70 wt.% of an inhibitor modified expandable particulate disrupting material or a plurality of inhibitor modified expandable particulate disrupting materials.
  • the disrupting composition includes between about 60 wt.% and about 40 wt.% of an inhibitor modified non-expandable particulate disrupting material or a plurality of inhibitor modified non-expandable particulate disrupting materials and between about 40 wt.% and about 60 wt.% of an inhibitor modified expandable particulate disrupting material or a plurality of inhibitor modified expandable particulate disrupting materials.
  • the disrupting composition includes about 50 wt.% of an inhibitor modified non- expandable particulate disrupting material or a plurality of inhibitor modified non-expandable particulate disrupting materials and about 50 wt.% of an inhibitor modified expandable particulate disrupting material or a plurality of inhibitor modified expandable particulate disrupting materials.
  • the non-expandable and/or expandable particulate disrupting material may be a synthetic carbon, such as synthetic coke and/or graphite.
  • the disrupting composition includes 100 wt.% of an inhibitor modified particulate material or a plurality of inhibitor modified particulate materials. [0074] In other embodiments, the disrupting composition includes 100 wt.% of an unmodified particulate material or a plurality of unmodified particulate materials.
  • the disrupting composition includes between 99 wt.% and
  • the disrupting composition includes between 95 wt.% and 5 wt.% of an inhibitor modified particulate material or a plurality of inhibitor modified particulate materials and between 5 wt.% to 95 wt.% of an unmodified particulate material or a plurality of unmodified particulate materials.
  • the disrupting composition includes between 90 wt.% and 10 wt.% of an inhibitor modified particulate material or a plurality of inhibitor modified particulate materials and between 10 wt.% to 90 wt.% of an unmodified particulate material or a plurality of unmodified particulate materials. In other embodiments, the disrupting composition includes between 80 wt.% and 20 wt.% of an inhibitor modified particulate material or a plurality of inhibitor modified particulate materials and between 20 wt.% to 80 wt.% of an unmodified particulate material or a plurality of unmodified particulate materials.
  • the disrupting composition includes between 70 wt.% and 30 wt.% of an inhibitor modified particulate material or a plurality of inhibitor modified particulate materials and between 30 wt.% to 70 wt.% of an unmodified particulate material or a plurality of unmodified particulate materials. In other embodiments, the disrupting composition includes between 60 wt.% and 40 wt.% of an inhibitor modified particulate material or a plurality of inhibitor modified particulate materials and between 40 wt.% to 60 wt.% of an unmodified particulate material or a plurality of unmodified particulate materials.
  • the disrupting composition includes about 50 wt.% of an inhibitor modified particulate material or a plurality of inhibitor modified particulate materials and from about 50 wt.% of an unmodified particulate material or a plurality of unmodified particulate materials.
  • the treating compositions of the present invention are used at an effective amount, where the effective amount is an amount sufficient to disrupt slag deposits on internal surfaces of the hydrocarbon-fired boilers (or other hydrocarbon-fired combustion systems) in which the treating compositions are used. In other embodiments, the effective amount is an amount sufficient to simultaneously disrupt boiler slag deposits on internal surfaces thereoof and reduce or prevent corrosion of the surfaces and/or emissions of the boiler in which the treating compositions are used.
  • the effective amount of the treating composition is injected into the boiler of the present invention via the fuel, the oxidizing agent, and/or via independent injectors in an amount of at least 1 wt.% based on the fuel burned. In other embodiments, the effective amount of the treating composition used is at least 5 wt.% . In other embodiments, the effective amount used includes at least 10 wt.%. In other embodiments, the treating compositions include at least 20 wt.%. In other embodiments, the treating compositions include at least 30 wt.%.
  • Suitable deposit disrupting materials include, without limitation, expandable materials, inhibitor modified expandable materials, non-expandable materials, inhibitor modified non-expandable materials, hollow materials, inhibitor modified hollow materials, or mixtures and combinations thereof.
  • the deposit disrupting materials are non- oxidizable at the operating temperature of the boiler or other combustion apparatus during the time of treatment.
  • Suitable deposit disrupting materials include synthetic carbons, such as coke and graphite.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
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  • Ceramic Engineering (AREA)
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Abstract

La présente invention concerne des systèmes et des procédés destinés à désagréger des dépôts de scories formés sur les surfaces internes d'appareils de combustion d'hydrocarbures (par exemple, de chaudières), de façon à faciliter l'élimination de ces derniers, et les compositions de traitement utilisées dans les systèmes. Selon certains modes de réalisation, les compositions de traitement comprennent un carbone synthétique ne se dilatant pas et/ou se dilatant et éventuellement une composition inhibant la corrosion qui réduit les émissions dangereuses. Les compositions/particules désagrégeant le dépôt de scories sont censées se combiner ou se mélanger aux matériaux formant un dépôt de scories formés pendant la combustion de carburant de manière à se co-déposer sur les surfaces de la chaudière. Les compositions désagrégeant le dépôt de scories mélangées définissent une aire ou une zone dans les scories qui affaiblit et/ou réduit l'intégrité des dépôts de scories de sorte que les dépôts de scories sont plus enclins à l'écaillage, comme sous l'effet de leur propre poids, résultant en un auto-nettoyage et/ou sont éliminés plus facilement à l'aide de techniques d'élimination ou de nettoyage classiques.
PCT/US2017/016439 2016-02-04 2017-02-03 Système et procédé destinés à désagréger des dépôts de scories et compositions utilisées Ceased WO2017136679A1 (fr)

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CN110467954A (zh) * 2019-07-03 2019-11-19 南通汉森农业科技有限公司 秸秆混合燃料及其制备方法
CN111548840A (zh) * 2020-04-24 2020-08-18 宁波市北仑环保固废处置有限公司 一种危险废物焚烧炉专用结焦抑制剂及其制备方法和应用

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CN111548840A (zh) * 2020-04-24 2020-08-18 宁波市北仑环保固废处置有限公司 一种危险废物焚烧炉专用结焦抑制剂及其制备方法和应用

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