EP2318489B1 - Targeted reagent injection for slag control from combustion of coals high in iron and/or calcium - Google Patents

Targeted reagent injection for slag control from combustion of coals high in iron and/or calcium Download PDF

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Publication number
EP2318489B1
EP2318489B1 EP09795277.4A EP09795277A EP2318489B1 EP 2318489 B1 EP2318489 B1 EP 2318489B1 EP 09795277 A EP09795277 A EP 09795277A EP 2318489 B1 EP2318489 B1 EP 2318489B1
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EP
European Patent Office
Prior art keywords
slag
coal
reagent
pounds
combustor
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.)
Not-in-force
Application number
EP09795277.4A
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German (de)
English (en)
French (fr)
Other versions
EP2318489A4 (en
EP2318489A1 (en
Inventor
Christopher R. Smyrniotis
Kent W. Schulz
Emelito P. Rivera
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Fuel Tech Inc
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Fuel Tech Inc
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Filing date
Publication date
Application filed by Fuel Tech Inc filed Critical Fuel Tech Inc
Priority to PL09795277T priority Critical patent/PL2318489T3/pl
Publication of EP2318489A1 publication Critical patent/EP2318489A1/en
Publication of EP2318489A4 publication Critical patent/EP2318489A4/en
Application granted granted Critical
Publication of EP2318489B1 publication Critical patent/EP2318489B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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 
    • F23C99/00—Subject-matter not provided for in other groups of this subclass
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • 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
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L2200/0254—Oxygen 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/18—Spraying or sprinkling

Definitions

  • the invention relates to a process that increases the output of a combustor fired with coal having high iron and/or calcium content, by reducing the tendency of slag to form on heat exchange surfaces, changing the nature of the slag to make it easier to remove and actually removing slag.
  • the tendency to form slag and the properties of the slag for such high iron content coals have been a major concern of combustion engineers and plant operators for decades.
  • Slag accumulation is a problem that causes decreased heat transfer and often leads to long periods of downtime for cleaning.
  • US 2006/0121398 A1 deals with an additive atomizing system for injection into severe operating environments.
  • a yet further but more specific object is to provide a process to more effectively control slag by decreasing the amount of downtime associated with slag removal.
  • the invention provides a process for reducing slag cohesiveness and/or adhesiveness in a combustor, thereby decreasing the rate of fouling as defined in the claim.
  • the aluminum trihydroxide reagent is introduced in the form of an aqueous liquid and computational fluid dynamics is employed to determine flow rates and select reagent introduction rates, reagent introduction location(s), reagent concentration, reagent droplet size and/or reagent momentum.
  • Magnesium hydroxide is introduced as an aqueous slurry along with the slurry of aluminum trihydroxide.
  • Fig. 1 is a schematic view of one embodiment of the invention.
  • Fig. 1 shows a large combustor 10 of the type used for producing steam for electrical power generation, process steam, heating or incineration. Coal is fed by burners 20 and 20a and burned with air in a combustion zone 21 .
  • coal that is high in iron (e.g., iron contents of greater than 15%, e.g., from 20 to 35%, based on the weight of the ash and expressed as Fe 2 O 3 ) and/or calcium content (e.g., calcium contents of greater than 5%, e.g., from 10 to 25%, based on the weight of the ash and expressed as CaO).
  • iron e.g., iron contents of greater than 15%, e.g., from 20 to 35%, based on the weight of the ash and expressed as Fe 2 O 3
  • calcium content e.g., calcium contents of greater than 5%, e.g., from 10 to 25%, based on the weight of the ash and
  • Air for combustion supplied by fan 22 and ductwork 24, is preferably preheated by a gas-to-gas heat exchangers (not shown) which transfer heat from ductwork (not shown) at the exit end of the combustor.
  • Hot combustion gases rise and flow past heat exchangers 26, which transfer heat from the combustion gases to water for the generation of steam.
  • Other heat exchangers including an economizer (downstream and not shown) may also be provided according to the design of the particular boiler. Slag left untreated would tend to form on these heat exchanger surfaces, which are positioned within specific combustors based on design considerations important to individual locations.
  • modeling techniques such as computational fluid dynamics, are employed to initially direct treatment chemicals (especially, those identified as effective for particular types of coal according to the invention) to the optimum locations for reducing and/or controlling slag buildup and maintaining efficient operation of the boiler.
  • a series of suitable, preferably air assisted atomizing, nozzles in each of nozzle banks 30 and 30a are provided for introducing aluminum trihydroxide with magnesium hydroxide slurry from vessels 40 and 40a respectively. Both the ATH and the magnesium hydroxide are aqueous slurries.
  • Supply lines e.g., 41
  • Valves e.g., 42
  • temperature sensors e.g., 44
  • Both valves 42 and temperature sensors 44 are connected to controller 46 via electrical leads (e.g., 48) shown in dotted lines.
  • the controller 46 can be a general purpose digital computer programmed in accord with a predetermined control regimen with both feed forward and feedback features.
  • Aluminum trihydroxide (Al(OH) 3 ), which has been found effective according to the invention for greatly lessening the deposition of slag or cleaning deposited slag from troublesome coal types, is also known under other names such as ATH, aluminum hydroxide and hydrated alumina. Regardless of the form of aluminum trihydroxide raw material, it is preferred that it is mixed with water for introduction from tank 40 through associated lines 41, with or without chemical stabilizers, to concentrations suitable for storage and handling, e.g., at least 25%, and preferably at least 65%, solids by weight.
  • the concentration and flow rates will be initially determined by modeling to assure that the proper amount of chemical is supplied to the correct location in the combustor in the correct physical form to achieve the desired results of reduced slagging and ease of clean up.
  • it is diluted as determined, e.g ., by computational fluid dynamics (CFD) to within the range of from 0.1 to 10 %, more narrowly from 1 to 5 %.
  • CFD computational fluid dynamics
  • the aqueous aluminum trihydroxyde contacts the hot gases in the combustor, it is believed to be reduced to very small particles, e.g ., nano-sized particles, e.g ., under 200 nanometers and preferably below 100 nanometers.
  • Median particle sizes of from 50 to 150 nanometers are useful ranges for the process of the invention. To approach this size, it is important that the ATH be introduced with water. The small particles are believed to disrupt the normal crystalline or glass that forms the slag. Regardless of the mechanism involved it is a distinct advantage of the invention that the slag that does form is highly friable and breaks easily with brushing and can be crushed by hand.
  • the friability of slag that is formed is increased, making it easier to remove.
  • the invention also slows or eliminates the buildup of slag.
  • the invention can actually remove slag that has already formed.
  • increase the friability of the slag it is meant that the slag after treatment requires less force per unit area to crush than slag formed under the same conditions without the treatment.
  • remove slag it is meant that the weight of the slag adhering to boiler, particularly heat exchange, surfaces is reduced from initial values by the treatment of the invention.
  • the process for most coals works best with a combination of ATH and magnesium hydroxide. While some coals, e.g ., with low silicate compositions can be burned with reduced problems attributed to slag, the use of magnesium hydroxide, at least initially, is preferred.
  • the magnesium hydroxide reagent can preferably be prepared from brines containing calcium and other salts, usually from underground brine pools or seawater. Dolomitic lime is mixed with these brines to form calcium chloride solution and magnesium hydroxide which is precipitated and filtered out of the solution. This form of magnesium hydroxide can be mixed with water, with or without stabilizers, to concentrations suitable for storage and handling, e.g ., from 25 to 65% solids by weight.
  • CFD computational fluid dynamics
  • it is diluted as determined by computational fluid dynamics (CFD) to within the range of from 0.1 to 10%, more narrowly from 1 to 5%.
  • CFD computational fluid dynamics
  • nano-sized particles e.g ., under 200 nanometers and preferably below 100 nanometers.
  • Median particle sizes of from 50 to 150 nanometers are useful ranges for the process of the invention.
  • Other forms of MgO can also be employed where necessary or desired, e . g ., "light burn” or "caustic” can be employed where it is available in the desired particle size range.
  • the invention will preferably take advantage of CFD to project initial flow rates and select initial reagent introduction rates, reagent introduction location(s), reagent concentration, reagent droplet size and reagent momentum.
  • CFD is a well understood science, and it is utilized with full benefit in this case, where it is desired to supply a minimum amount of chemical for maximum effect.
  • the initial feed rate for the best economics for combustors operating similar to the one exemplified below can be up to 2.7 kg (6 pounds) of ATH(as dry active ATH) or 3.6 kg (8 pounds) (as a 65-70% slurry) per ton of coal.
  • amounts of from 0.45 to 2.7 kg (1 to 6 pounds) of slurry will be effective (more narrowly, e.g ., 0.9 to 1.36 kg (2 to 3 pounds) of slurry).
  • amounts of from 0.23 to 0.9 kg (0.5 to 2 pounds) of Mg(OH) 2 slurry per ton of coal, e.g ., from 0.3 to 0.45 kg (0.7 to 1 pounds) of Mg(OH) 2 slurry per ton of coal can be utilized.
  • the slurries are diluted as necessary, typically to a solids concentration of from about 5% for smaller applications to 35% or more.
  • the weight of the slag adhering to a combustor, particularly heat exchange, surfaces is effectively reduced from initial values by the treatment of the invention, especially when the ATH and Mg(OH) 2 are used at high concentrations within the above ranges, i.e. from 1.36 to 2.7 kg (3 to 6 pounds) of ATH per ton of coal and 0.45 to 0.9 kg (1 to 2 pounds) of Mg(OH) 2 per ton of coal.
  • This ability to remove slag provides the ability to provide a cleaning and maintenance regimen wherein the initial dosing is as just mentioned for removing slag, with the dosing then reduced to from 10 to 50% of the initial values for maintaining the combustor clean and operating efficiently.
  • combustion catalysts and or effluent treatment chemicals can be added to the fuel, combustion zone or otherwise as described, for example in U. S. Patent No. 7,162,960 to Smyrniotis, et al.
  • Al(OH) 3 aluminum trihydroxide slurry or ATH for short
  • aqueous slurry at a rate of 2.3 kg (5 pounds) slurry per ton of coal consumed from two banks of three air-cooled nozzles positioned on the wall opposite of two banks of pulverized coal burners - one bank at an elevation between the two burners and one bank at an elevation above the uppermost coal burners.
  • the slurry is diluted to a concentration of 35 weight % ATH.
  • the density of the ATH slurry before dilution is 6.3 kg/3.8 1 (14 pounds/gallon), meaning that the feed rate is 730.6 1 (193 gallons) per day (2.3 kg (5 pounds) per ton of coal) for ATH slurry.
  • an effective feed rate for this particular combustor will be from 0.45 to 2.7 kg (1 to 6 pounds) of ATH slurry per ton of coal, e.g., 0.9 to 1.36 kg (2 to 3 pounds) per ton.
  • Example 2 This example illustrates the effect of introducing Mg(OH) 2 (magnesium hydroxide) into a furnace burning 540 tons of coal per day in addition to the aluminum trihydroxide fed in Example 1.
  • the coal was a blend of Illinois basin and Appalachian bituminous coals, as illustrated in Example 1.
  • the magnesium hydroxide was fed as a slurry at 0.9 kg (2 lbs) of 50 to 60 weight % slurry per ton of coal consumed. Density of the magnesium hydroxide slurry was approximately 5.4 kg/3.8 1 (12 lbs/gallon). Therefore, the feed rate was about 340.7 1 (90 gallons) per day for the Mg(OH) 2 slurry. As before, we fed the aluminum trihydroxide slurry at 2.3 kg (5 pounds) of slurry per ton of coal consumed. The density of the ATH was 6.3 kg/3.8 1 (14 pounds/gallon), making the feed rate 730.6 1 (193 gallons) per day for ATH.
  • Fig . 2 is a photograph of a slag sample obtained after operation for 24 hours of ATH feed only. The slag was unexpectedly friable.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Incineration Of Waste (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Air Supply (AREA)
  • Gasification And Melting Of Waste (AREA)
EP09795277.4A 2008-07-11 2009-07-13 Targeted reagent injection for slag control from combustion of coals high in iron and/or calcium Not-in-force EP2318489B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09795277T PL2318489T3 (pl) 2008-07-11 2009-07-13 Ukierunkowane wtryskiwanie reagenta do kontroli żużla ze spalania węgli o wysokiej zawartości żelaza i/lub wapnia

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8000408P 2008-07-11 2008-07-11
PCT/US2009/050354 WO2010006325A1 (en) 2008-07-11 2009-07-13 Targeted reagent injection for slag control from combustion of coals high in iron and/or calcium

Publications (3)

Publication Number Publication Date
EP2318489A1 EP2318489A1 (en) 2011-05-11
EP2318489A4 EP2318489A4 (en) 2013-05-15
EP2318489B1 true EP2318489B1 (en) 2015-09-02

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EP09795277.4A Not-in-force EP2318489B1 (en) 2008-07-11 2009-07-13 Targeted reagent injection for slag control from combustion of coals high in iron and/or calcium

Country Status (18)

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US (1) US20100006014A1 (zh)
EP (1) EP2318489B1 (zh)
JP (1) JP5657533B2 (zh)
KR (1) KR101298932B1 (zh)
CN (1) CN102089413B (zh)
AR (1) AR072502A1 (zh)
AU (1) AU2009268391C1 (zh)
CA (1) CA2729959C (zh)
CL (1) CL2009001571A1 (zh)
CO (1) CO6300873A2 (zh)
ES (1) ES2554165T3 (zh)
HK (1) HK1157810A1 (zh)
MX (1) MX2011000275A (zh)
MY (1) MY156010A (zh)
PL (1) PL2318489T3 (zh)
RU (1) RU2493240C2 (zh)
TW (1) TWI482852B (zh)
WO (1) WO2010006325A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009091539A1 (en) 2008-01-15 2009-07-23 Environmental Energy Services, Inc. Process for operating a coal-fired furnace with reduced slag formation
KR101773019B1 (ko) 2011-01-14 2017-08-30 인바이런멘탈 에너지 서비시즈, 인크. 역청탄을 이용한 퍼니스 작동 프로세스 및 슬래그 형성물 감소 방법
US9920929B2 (en) * 2011-06-13 2018-03-20 Ecolab Usa Inc. Method for reducing slag in biomass combustion
WO2017053499A1 (en) * 2015-09-25 2017-03-30 Fuel Tech, Inc. Process and apparatus for reducing plume

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Also Published As

Publication number Publication date
CA2729959A1 (en) 2010-01-14
EP2318489A4 (en) 2013-05-15
CL2009001571A1 (es) 2010-03-12
WO2010006325A1 (en) 2010-01-14
RU2493240C2 (ru) 2013-09-20
CA2729959C (en) 2015-09-01
EP2318489A1 (en) 2011-05-11
AR072502A1 (es) 2010-09-01
MY156010A (en) 2015-12-31
US20100006014A1 (en) 2010-01-14
JP2011527000A (ja) 2011-10-20
CN102089413B (zh) 2013-12-18
CN102089413A (zh) 2011-06-08
RU2011103846A (ru) 2012-08-20
PL2318489T3 (pl) 2016-03-31
AU2009268391C1 (en) 2014-12-11
AU2009268391B2 (en) 2014-05-08
AU2009268391A1 (en) 2010-01-14
MX2011000275A (es) 2011-03-02
KR101298932B1 (ko) 2013-08-22
KR20110043656A (ko) 2011-04-27
TW201009067A (en) 2010-03-01
TWI482852B (zh) 2015-05-01
ES2554165T3 (es) 2015-12-16
HK1157810A1 (zh) 2012-07-06
CO6300873A2 (es) 2011-07-21
JP5657533B2 (ja) 2015-01-21

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