WO2016057998A1 - Ajouts de matériaux argileux et constitués de scories à des chaudières brûlant du charbon - Google Patents

Ajouts de matériaux argileux et constitués de scories à des chaudières brûlant du charbon Download PDF

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Publication number
WO2016057998A1
WO2016057998A1 PCT/US2015/055163 US2015055163W WO2016057998A1 WO 2016057998 A1 WO2016057998 A1 WO 2016057998A1 US 2015055163 W US2015055163 W US 2015055163W WO 2016057998 A1 WO2016057998 A1 WO 2016057998A1
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Prior art keywords
coal
slag
additive
clay
weight percent
Prior art date
Application number
PCT/US2015/055163
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English (en)
Inventor
Wayne Fried
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Ash Improvement Technology Inc.
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Publication date
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Publication of WO2016057998A1 publication Critical patent/WO2016057998A1/fr

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Classifications

    • 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
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • C04B18/084—Flue dust, i.e. fly ash obtained from mixtures of pulverised coal and additives, added to influence the composition of the resulting flue dust
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C10/00—Fluidised bed combustion apparatus
    • F23C10/002—Fluidised bed combustion apparatus for pulverulent solid fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23K—FEEDING FUEL TO COMBUSTION APPARATUS
    • F23K1/00—Preparation of lump or pulverulent fuel in readiness for delivery to combustion apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23K—FEEDING FUEL TO COMBUSTION APPARATUS
    • F23K2201/00—Pretreatment of solid fuel
    • F23K2201/50—Blending
    • F23K2201/505—Blending with additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to the addition of clay and slag materials to coal combustion boilers to improve combustion, improve thermal heat transfer, remove or reduce heavy metals and/or deslag the coal combustion boilers.
  • An aspect of the present invention is to provide a method of combusting coal comprising combusting the coal in the presence of a clay additive and a slag additive, wherein the clay additive comprises from 1 to 50 weight percent of the weight of the coal, and the slag additive comprises from 1 to 50 weight percent of the coal.
  • Another aspect of the present invention is to provide a method of operating a coal combustion burner comprising introducing the coal, a clay additive, and a slag additive into the burner, and combusting the coal in the burner.
  • a further aspect of the present invention is to provide a combustion product of coal combusted in the presence of a clay additive and a slag additive, wherein the clay additive comprises from 1 to 50 weight percent of the weight of the coal, and the slag additive comprises from 1 to 50 weight percent of the coal.
  • Fig.1 schematically illustrates methods of adding clay and slag separately to coal combustion processes in accordance with an embodiment of the present invention.
  • Fig.2 schematically illustrates methods of adding clay and slag together to coal combustion processes in accordance with an embodiment of the present invention.
  • Fig.3 is a graph of kaolin flow versus time for combined injections of kaolin and slag to a coal combustion process in accordance with an embodiment of the present invention.
  • Fig.4 is a graph of slag flow versus time for combined injections of kaolin and slag to a coal combustion process in accordance with an embodiment of the present invention.
  • Fig.5 is a graph of coal flow versus time during a process of combined injections of kaolin and slag during a coal combustion process in accordance with an embodiment of the present invention.
  • Fig.6 is a graph of electric power generation versus time for combined injections of kaolin and slag into a coal combustion process in accordance with an embodiment of the present invention.
  • Fig.7 is a graph of boiler steam flow versus time during combined injections of kaolin and slag in a coal combustion process in accordance with an embodiment of the present invention.
  • Fig.8 is a graph of carbon monoxide versus time during combined injection of kaolin and slag into a coal combustion process in accordance with an embodiment of the present invention.
  • Fig.9 is a graph of limestone flow versus time during the combined injection of kaolin, slag and limestone into a coal combustion process in accordance with an embodiment of the present invention.
  • Fig.10 is a graph of coal flow versus time during a coal combustion process in which kaolin is injected during a portion of the coal combustion process in accordance with an embodiment of the present invention.
  • Fig.11 is a graph of steam flow versus time during a coal combustion process in which kaolin is injected during a portion of the coal combustion process in accordance with an embodiment of the present invention.
  • Fig.12 is a graph of coal, slag and limestone flow and electric power generation versus time during a coal combustion process for comparison purposes.
  • FIGs.1 and 2 schematically illustrate processes in accordance with
  • clay and slag additions are introduced during coal combustion processes.
  • the clay and slag additives are introduced separately during the coal combustion process.
  • the clay and slag additives are introduced together into the coal combustion process.
  • the clay additive may be added directly into the coal combustion zone, such as the burner of a coal-fired electric power generating plant.
  • the clay additive may be mixed with the coal prior to their introduction into the coal combustion zone.
  • the slag additive may be added directly into the coal combustion zone.
  • the slag additive may be mixed with the coal prior to their introduction into the coal combustion zone.
  • the clay and/or slag are introduced into the coal combustion zone, they may be introduced in any suitable manner, for example, by a direct feed line into the burner.
  • the clay and/or slag additives are introduced into a recirculation loop that feeds back into the burner.
  • Fig.2 The embodiments shown in Fig.2 are similar to those of Fig.1, with the exception that the clay additive and the slag additive are mixed or otherwise combined together prior to their introduction into the coal combustion zone or their pre-mixture with the coal prior to introduction into the coal combustion zone.
  • the clay additive and slag additive are introduced into a recirculation loop that feeds back into the burner.
  • clay and slag additives are introduced during a coal combustion process, such as the combustion zone of a coal-fired power plant.
  • the clay and slag additives may be introduced into the burner, upstream from the burner and/or downstream from the burner in a recirculation loop back into the burner.
  • the clay and slag additives may be introduced separately into a coal stream, or may be pre-mixed together before their addition to the coal stream.
  • the clay and slag may be introduced separately, pre-mixed and introduced together and/or pre-mixed with the coal.
  • clay additive materials may comprise kaolin, talc, attapulgite, etc. and slag (such as metal slags) to coal-fired combustors. Furthermore, these combined additives have been shown to reduce the emission of heavy metals, such as mercury, while also deslagging the boiler components.
  • the clay additive materials may comprise kaolin,
  • the slag additive materials may comprise metallurgical slags such as ferrous slags, non-ferrous slags, aluminum slag, copper slag, recycled ground granulated blast furnace slag, and the like.
  • the slag additive may comprise stainless steel slag.
  • any suitable type or grade of coal may be used in accordance with the present invention.
  • the coal that is introduced into the burner may be low- grade coal, e.g., comprising waste or a by-product such as coal washings from coal processing operations.
  • Such coal washings are considered waste material that may be stored in large outdoor heaps or piles, which can result in unwanted water contamination and runoff in the surrounding areas, e.g., the water may have a pH as low as 1.
  • Certain types of power plants burn such coal washings as waste materials and may therefore be classified as waste treatment plants rather than conventional coal-fired power plants. All of these types of facilities are considered to be within the scope of the present invention, as well as other coal combustion facilities and processes.
  • Examples of clay additives include the kaolin, montmorillonite/smectite, illite and chlorite groups.
  • the kaolin group includes kaolinite, dickite and nacrite, and has a formula of Al 2 Si 2 O 5 (OH) 4 .
  • kaolin may include about 46 weight percent silica and about 28 weight percent alumina, with minor amounts of titanium (e.g., 1.5 weight percent), iron (e.g., 0.62 weight percent), calcium (e.g., 0.19 weight percent), magnesium (e.g., 0.14 weight percent), carbon (e.g., 0.01 weight percent) and sulfur trioxide (e.g., 0.02 weight percent), along with minor amounts of moisture.
  • the different minerals are polymorphs, i.e., they have the same chemistry but different structures.
  • the general structure of the kaolinite group is composed of silicate sheets (Si 2 O 5 ) bonded to aluminum
  • the montmorillonite/smectite group comprises several minerals including pyrophyllite, talc, vermiculite, sauconite, saponite, nontronite and monmorillonite, which differ mostly in chemical content.
  • the general formula is (Ca, Na, H)(Al, Mg, Fe, Zn) 2 (Si, Al) 4 O 10 (OH) 2 - xH 2 O, where x represents the variable amount of water that members of this group may contain.
  • the formula for talc is Mg 3 Si 4 O 10 (OH) 2 .
  • the gibbsite layers of the kaolinite group can be replaced in this group by a similar layer that is analogous to the oxide brucite (Mg 2 (OH) 4 ).
  • the structure of this group is composed of silicate layers sandwiching a gibbsite (or brucite) layer in between, in an s-g-s stacking sequence.
  • the variable amounts of water molecules may lie between the s-g-s sandwiches.
  • the illite group is basically a hydrated microscopic muscovite.
  • the mineral illite is the common mineral represented, however, it is a significant rock forming mineral being a main component of shales and other argillaceous rocks.
  • the general formula is (K, H)Al 2 (Si, Al) 4 O 10 (OH) 2 - xH 2 O, where x represents the variable amount of water that this group may contain.
  • the structure of this group is similar to the montmorillonite group with silicate layers sandwiching a gibbsite-like layer in between, in an s-g-s stacking sequence.
  • the variable amounts of water molecules may lie between the s-g-s sandwiches as well as the potassium ions.
  • the chlorite group has a general formula of X 4-6 Y 4 O 10 (OH, O) 8 , where the X represents one or more of aluminum, iron, lithium, magnesium, manganese, nickel, zinc or rarely chromium, and the Y represents either aluminum, silicon, boron or iron but mostly aluminum and silicon.
  • the clay additive may include particle size fractions that are not typically desirable for certain types of industrial applications such as use in paper or cosmetic products.
  • the clay may have a smaller and/or larger average particle size than the clay typically used in various industries.
  • approximately one-third may be sized appropriately for use in the paper or cosmetic industries, while the remaining approximately two-thirds of the mined kaolin may include ultrafine particles and/or coarse particles that may remain unused.
  • Such unused fractions may be dumped into storage areas such as pits, abandoned mines, etc.
  • such discarded kaolin is useful as the kaolin additive component in the coal combustion process.
  • recycled clays from various sources such as waste paper may be recovered and used as the clay additive in accordance with the present invention.
  • waste paper containing clay the entire waste product may be combusted in the burner, thereby providing a source of clay as well as an additional combustible fuel for the combustion process.
  • the clay additives typically comprise from 1 or 2 to 50 percent of the weight of the coal, for example, from 3 to 30 percent.
  • slag additives include metallurgical slags such as stainless steel slags, ferrous slags, non-ferrous slags, aluminum slag, copper slag, recycled ground granulated blast furnace slag, and the like.
  • the slag additives typically comprise from 1 or 2 to 50 percent of the weight of the coal, for example, from 3 to 30 percent.
  • the total combined weight of the clay and slag is typically from 2 to 60 percent of the weight of the coal, for example, from 5 to 40 percent.
  • Other optional additives include limestone, waste concrete such as recycled Portland cement concrete, shale, recycled crushed glass, recycled crushed aggregate fines, silica fume, cement kiln dust, lime kiln dust, weathered clinker, clinker, granite kiln dust, zeolites, limestone quarry dust, red mud, fine ground mine tailings, oil shale fines, bottom ash, dry stored fly ash, landfilled fly ash, ponded flyash, lithium-containing ores and other waste or low-cost materials containing calcium oxide, silicon dioxide and/or aluminum oxide.
  • waste concrete such as recycled Portland cement concrete, shale, recycled crushed glass, recycled crushed aggregate fines, silica fume, cement kiln dust, lime kiln dust, weathered clinker, clinker, granite kiln dust, zeolites, limestone quarry dust, red mud, fine ground mine tailings, oil shale fines, bottom ash, dry stored fly ash, landfilled fly ash,
  • limestone may be injected along with the clay and slag additives during the coal combustion process.
  • the amount of limestone may be selected in order to control emissions such as SO X while producing a combustion product with desirable properties when added to cement.
  • the amount of limestone may range from zero to 5 weight percent based on the weight of the coal, or the limestone may range from 0.5 to 4 weight percent, or from 1 to 3 weight percent, based on the weight of the coal.
  • Tests were performed in a conventional fluidized bed coal fired boiler of an electrical power generation plant.
  • combined injections of clay and slag were made to the coal combustion zone by adding the clay and slag into the recirculation loop of the fluidized bed boiler.
  • the clay additive comprised kaolin
  • the slag additive comprised stainless steel slag.
  • the coal was a low grade coal, i.e., waste coal.
  • the kaolin and slag were added, the amount of limestone added to the coal fired burner was significantly decreased from the conventional amounts of limestone typically used to control emissions from the boiler.
  • the results of the tests are graphically shown in Figs.3-9.
  • Fig.3 is a graph of kaolin flow versus time for combined injections of kaolin and slag to the coal combustion zone. As shown in Fig.3, during the combined kaolin and slag injection, the rate of kaolin injection was within a range of from about 6,000-8,000 pounds per hour. In addition to the data plot shown in Fig.3, a straight line has been superimposed thereon, as well as in subsequent figures, to show the general increase in flow during the injection period.
  • Fig.4 is a graph of slag flow versus time for combined injections of kaolin and slag to the coal combustion zone. As shown in Fig.4, during the combined injection of kaolin and slag, the flow of slag generally ranged between 7,000 and 15,000 pounds per hour. A straight line is superimposed on the actual flow plot to illustrate the generally increasing flow rate during the test period.
  • Fig.5 is a graph of coal flow versus time during a process of combined injections of kaolin and slag during the coal combustion zone. As shown in Fig.5, during the combined injection of kaolin and slag, the coal flow was maintained at a substantially constant flow rate of 90,000 pounds per hour. Although a sharp dip in the coal flow rate is shown during a short portion of the test period, the sharp dip may be due to a measurement anomaly, and the overall coal flow rate was maintained substantially constant, as shown by the straight line in Fig.5.
  • Fig.6 is a graph of electric power generation versus time for combined injections of kaolin and slag into the coal combustion zone. As shown in Fig.6, during the combined injection of kaolin and slag, the electric power generation from the power plant was within the general range of from 75 to 81 megawatts.
  • Fig.7 is a graph of boiler steam flow versus time during combined injections of kaolin and slag in the coal combustion zone. As shown in Fig.7, the steam flow generated by the coal fired boiler during the combined injection of kaolin and slag ranged generally from 350,000 to 380,000 pounds per hour.
  • Fig.8 is a graph of carbon monoxide versus time during combined injection of kaolin and slag into the coal combustion zone. As shown in Fig.8, during the combined injection of kaolin and slag, carbon monoxide emissions range from about 0.05 to 0.08 pounds per MMBtu, with a significant drop during the injection process.
  • Fig.9 is a graph of limestone flow versus time during the combined injection of kaolin and slag into the coal combustion zone.
  • Fig.9 illustrates limestone flow during the combined injection of kaolin and slag, as well as limestone flow before and after the kaolin and slag injections.
  • limestone flow averaged about 5,000 pounds per hour, while during the injection period limestone flow was reduced to about 2,500 pounds per hour.
  • the reduced limestone flow resulted from an automatic limestone injection system in which SO X emissions were measured and the amount of limestone was adjusted to maintain the SO X emissions at a substantially constant level, e.g., the system reduced limestone injections when the SO X emissions were lowered.
  • Fig.10 is a graph of coal flow versus time during the coal combustion process in which kaolin, but not slag, is injected during a portion of the coal combustion process.
  • Fig.11 is a graph of steam flow versus time during the coal combustion process in which kaolin, but not slag, is injected during a portion of the coal combustion process.
  • coal flow was maintained at a substantially constant rate before, during, and for a period of time after the period in which the kaolin was injected.
  • Fig.11 tracks the boiler steam flow.
  • the injection of kaolin, as opposed to the combined injection of kaolin and slag results in lower flue gas outlet temperatures.
  • Fig.12 is a graph of coal, slag and limestone flow and electric power generation versus time during the coal combustion process in which slag, but not kaolin, was injected. As shown in Fig.12, during the period of slag injection, power output (in kilowatts) was maintained at a constant level, but coal flow was increased.
  • the test results indicate that combined injections of kaolin and slag together provide improvements such as greater output for the same amount of coal (e.g., greater steam output from the boiler and greater electric power output from the power generation plant) and increased boiler efficiency (e.g., decreased carbon monoxide production).
  • improvements such as greater output for the same amount of coal (e.g., greater steam output from the boiler and greater electric power output from the power generation plant) and increased boiler efficiency (e.g., decreased carbon monoxide production).
  • heavy metal emissions may be reduced or eliminated and limestone injections may be reduced or eliminated while maintaining SO X emission levels below target levels.
  • Tables 1 and 2 show compressive strengths for base Portland cement (Sample No.1), base Portland cement with various substitutions of unmodified flyash from a conventional coal-fired power plant (Sample Nos.2 and 3), and Portland base cement with various substitutions of the combined coal/clay/slag combustion products of the present invention produced in-situ in a fluidized bed coal fired boiler, as described above (Sample Nos.4-7). As shown in Table 1, the combustion products of the present invention exhibit favorable 7-day and 28-day compressive strengths. Table 1
  • Test Material A comprised coal with limestone injections.
  • Test Material B comprised coal with clay injections.
  • Test Material C comprised coal with combined slag and clay injections in which the clay was present in a relatively small amount.
  • Test Material D comprised coal with slag and clay injections in which the clay was present in a relatively large amount. Injections were made as a liquid slurry into a hot zone prior to the bag house. The combined slag and clay injections significantly reduced mercury levels. Mercury levels were reduced by 40% or more. Table 4

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)

Abstract

L'invention concerne un procédé de combustion de charbon en présence d'un additif argileux et d'un additif constitué de scories. La combustion peut se produire dans un brûleur de combustion de charbon d'une centrale électrique au charbon. Des co-injections d'argile et de scories améliorent l'efficacité de fonctionnement de chaudières au charbon par l'amélioration de la combustion, du transfert thermique, de la production de vapeur et/ou de la production d'énergie électrique. Des co-injections d'argile et de scories peuvent également réduire des émissions non voulues. Le produit de combustion peut être utilisé comme additif pouzzolanique pour du ciment.
PCT/US2015/055163 2014-10-10 2015-10-12 Ajouts de matériaux argileux et constitués de scories à des chaudières brûlant du charbon WO2016057998A1 (fr)

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US201462062442P 2014-10-10 2014-10-10
US62/062,442 2014-10-10

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016138308A1 (fr) * 2015-02-25 2016-09-01 Ash Improvement Technology Inc. Ajout d'argile et de laitier dans des chambres de combustion fonctionnant au charbon
WO2018204331A1 (fr) * 2017-05-01 2018-11-08 Fuel Tech, Inc. Régulation de la scorification et/ou de l'encrassement dans des fours à combustion de biomasse
CN110386769A (zh) * 2019-07-26 2019-10-29 中建商品混凝土有限公司 一种基于搅拌站废渣活化技术的复合掺合料及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
US20130125791A1 (en) 2009-09-24 2013-05-23 Ash Improvement Technology, Inc. In-process addition of property-enhancing additives to coal combustion products used in cementicious materials
US20130125792A1 (en) * 2009-09-24 2013-05-23 Ash Improvement Technology, Inc. Production of coal combustion products for use in cementitious materials
US20130125799A1 (en) 2009-09-24 2013-05-23 Ash Improvement Technology, Inc. Systems and methods for comminuting and recirculating coal combustion products
US20140141380A1 (en) * 2005-03-17 2014-05-22 Nox Ii, Ltd. Reducing Mercury Emissions From The Burning of Coal
US8741054B2 (en) 2009-09-24 2014-06-03 Ash Improvement Technology, Inc. Production of cement additives from combustion products of hydrocarbon fuels and strength enhancing metal oxides

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Publication number Priority date Publication date Assignee Title
US20140141380A1 (en) * 2005-03-17 2014-05-22 Nox Ii, Ltd. Reducing Mercury Emissions From The Burning of Coal
US20130125791A1 (en) 2009-09-24 2013-05-23 Ash Improvement Technology, Inc. In-process addition of property-enhancing additives to coal combustion products used in cementicious materials
US20130125792A1 (en) * 2009-09-24 2013-05-23 Ash Improvement Technology, Inc. Production of coal combustion products for use in cementitious materials
US20130125799A1 (en) 2009-09-24 2013-05-23 Ash Improvement Technology, Inc. Systems and methods for comminuting and recirculating coal combustion products
US8741054B2 (en) 2009-09-24 2014-06-03 Ash Improvement Technology, Inc. Production of cement additives from combustion products of hydrocarbon fuels and strength enhancing metal oxides
US8961684B2 (en) 2009-09-24 2015-02-24 Ash Improvement Technology Inc. Production of coal combustion products for use in cementitious materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016138308A1 (fr) * 2015-02-25 2016-09-01 Ash Improvement Technology Inc. Ajout d'argile et de laitier dans des chambres de combustion fonctionnant au charbon
WO2018204331A1 (fr) * 2017-05-01 2018-11-08 Fuel Tech, Inc. Régulation de la scorification et/ou de l'encrassement dans des fours à combustion de biomasse
CN110386769A (zh) * 2019-07-26 2019-10-29 中建商品混凝土有限公司 一种基于搅拌站废渣活化技术的复合掺合料及其制备方法和应用
CN110386769B (zh) * 2019-07-26 2021-09-21 中建商品混凝土有限公司 一种基于搅拌站废渣活化技术的复合掺合料及其制备方法和应用

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