WO2006134227A1 - Method for preventing chlorine deposition on the heat- transferring surfaces of a boiler - Google Patents

Method for preventing chlorine deposition on the heat- transferring surfaces of a boiler Download PDF

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Publication number
WO2006134227A1
WO2006134227A1 PCT/FI2006/050252 FI2006050252W WO2006134227A1 WO 2006134227 A1 WO2006134227 A1 WO 2006134227A1 FI 2006050252 W FI2006050252 W FI 2006050252W WO 2006134227 A1 WO2006134227 A1 WO 2006134227A1
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WO
WIPO (PCT)
Prior art keywords
sulphate
chlorine
boiler
sulphur
fuel
Prior art date
Application number
PCT/FI2006/050252
Other languages
French (fr)
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WO2006134227B1 (en
Inventor
Martti Aho
Original Assignee
Kemira Oyj
Metso Power Oy
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Publication date
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Priority claimed from FI20055317A external-priority patent/FI20055317A0/en
Priority to BRPI0612821-1A priority Critical patent/BRPI0612821A2/en
Priority to CA2608028A priority patent/CA2608028C/en
Priority to US11/920,709 priority patent/US8052803B2/en
Priority to CN2006800214678A priority patent/CN101198679B/en
Application filed by Kemira Oyj, Metso Power Oy filed Critical Kemira Oyj
Priority to JP2008516358A priority patent/JP2008544202A/en
Priority to EP06755414.7A priority patent/EP1891187B1/en
Priority to DK06755414.7T priority patent/DK1891187T3/en
Priority to ES06755414.7T priority patent/ES2617730T3/en
Publication of WO2006134227A1 publication Critical patent/WO2006134227A1/en
Publication of WO2006134227B1 publication Critical patent/WO2006134227B1/en
Priority to NO20075680A priority patent/NO20075680L/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00—Other methods of preventing corrosion or incrustation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22G—SUPERHEATING OF STEAM
    • F22G3/00—Steam superheaters characterised by constructional features; Details of component parts thereof
    • F22G3/008—Protection of superheater elements, e.g. cooling superheater tubes during starting-up periods, water tube screens
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/003—Arrangements of devices for treating smoke or fumes for supplying chemicals to fumes, e.g. using injection devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/202—Single element halogens
    • B01D2257/2025—Chlorine
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a method for preventing chlorine deposition on the heat-transferring surfaces of a boiler, particularly on the superheater, in which boiler a fuel with a chlorine content, such as a biomass or waste fuel, is burned, and in which case a compound with a sulphate content, which forms a particular reagent to fix alkali compounds, is fed to the furnace, preferably in the superheater area.
  • a fuel with a chlorine content such as a biomass or waste fuel
  • a compound with a sulphate content which forms a particular reagent to fix alkali compounds
  • Both sulphur and aluminium silicate compounds can react with alkali chloride, in which case the chlorine forms hydrochloric acid, (the chlorine in which is not transferred to the deposition) , while the alkali remains attached to either the sulphate (sulphur) or aluminium silicate (AlO 3 * nSiO 2 * yH 2 0, the amount of silicon dioxide and crystal water may vary) .
  • the oxide form refers to all silicon compounds containing oxygen.
  • Publication US 2004/0068988 Al discloses a method, in which corrosion caused in heat exchangers by chlorine is reduced by adding an additive solution containing sulphur to the channel in which the heat exchangers are located. 5
  • Publication FI 823943 discloses a method for improving the combustion of fuels intended to produce energy. By means of the method, corrosion and fouling of the furnace surfaces are reduced.
  • a catalyser which contains at least 10 the elements Al, Mg, Mn, and Zn, is fed to the combustion zone.
  • Publication US6649135 discloses the use of aluminium silicates in a so-called dechlorination chamber 16, in a reaction fixing an alkali and releasing HCl.
  • Publication DE 19249022 also presents sulphur dioxide (SO 2 ) as a reagent for fixing alkali chlorides .
  • SO 2 sulphur dioxide
  • the publication also refers to sulphur trioxide (SO 3 ) , but the precise connection
  • Magnesium sulphate (MgSO 4 ) is presented as an economical compound that is a source of sulphur dioxide (SO 2 ) .
  • the invention is intended to create a new method, more advantageous than previous methods , for preventing chlorine deposition particularly in superheaters.
  • the invention is particularly suitable for application in fluid-bed boilers, or in other steam boilers with a similar flue-gas temperature range (600 - 1000 °C). Though the invention is of greatest importance in the corrosion protection of superheaters, the invention also assists in reducing the fouling of thermal surfaces .
  • ferric (III) sulphate Fe 2 (SO 4 J 3 disintegrates thermally to form ferric (III) oxide and sulphur trioxide, which fix alkali compounds very aggressively. This has a significant technical effect.
  • the literature on the field refers to the ferric (III) oxide SO 2 ⁇ SO 3 reaction as a catalyst, which also means that this oxide will effectively prevent the reduction of SO 3 that has already formed.
  • the compounds are used with or without the water of crystallization, singly, as mixtures, or as part of larger molecules (such as ammonium aluminium sulphate NH 4 Al (SO 4 ) 2 .
  • sulphur trioxide SO 3 effectively distroys alkali chlorides that have evaporated from the fuel, and which would otherwise condense onto the surfaces of the superheater, with resulting chorine corrosion.
  • the invention has the potential for worldwide application. It is necessary, when energy is produced from demanding chloritic biomasses and waste.
  • Figure 1 shows a comparison of reagents at a fixed dosage.
  • Figure 2 shows the effect of a known reagent at different dosages .
  • Figure 3 shows the effect of a reagent according to the invention, at different dosages.
  • the economical dosing of sulphur and aluminium-compound-based reagents will be sufficient to prevent the deposition of chlorine, if they are sprayed into the superheater area of a steam boiler.
  • the reagents will not spread in the lower parts of the furnace, so that they can be used to achieve an excellent effect/price ratio in the destruction of alkali compounds. Solubility in a liquid is a requirement if the reagents are to be added in a solution.
  • the reagent should be cheap, and in the case of a sulphur reagent there should be a large proportion of sulphur in the molecules .
  • Figure 1 shows the mass flows of the chlorine that travels with the finer fly ash ( ⁇ 4,1 ⁇ m) using a previously known reference reagent (ammonium sulphate, aforementioned WO publication) and two reagents according to the invention; Corr 1
  • Figure 2 shows the deposition of chlorine at the various sampling points using varying doses of a previously known reagent.
  • S/Cl ratio of the molar sulphur flow of the reagent and the molar chlorine flow of the fuel .
  • Figure 3 shows a comparison as in Figure 2, except that the reagent is aluminium sulphate according to the invention.
  • the first 'initial state' series of Figure 3 shows reference values, when an additive is not used. There was strong deposition of chlorine, except on the wind surfaces.
  • the dosing of the aluminium sulphate was linked to the sulphur/chlorine, i.e. S/Cl mol ratio, which means the mol ratio of the sulphur contained in the reagent and the chlorine contained in the fuel .
  • the experiment was carried out using mol ratios of 0,9; 1,5; 3; and 4,5.
  • the more advantageous dosing of sulphate is thus in the range 2 - 5 mols of sulphur to each mol of chlorine.
  • the compound used is sprayed in the direction of the flue-gas flow into the front side of the superheater area, as a water solution and in a drop size of 1 - 100 ⁇ m, preferably 10 - 20 ⁇ m.
  • This drop size can be carried out easily with commercial nozzles.
  • spraying technics which is known from SCR/SNCR technics.
  • the sulphates in question dissolve well in water (at least 30 weight-% and at most 80 weight-% of the weight of the solution. This depends on the reagent, more precisely CRC, Handbook of Chemistry and Physics. It is preferable to use the strongest possible solution, in order to avoid spraying excess water into the boiler. It will be seen from Figure 1 that many other factors than the dosage of the additive measured by the S/Cl ration affect the ability of the reagent to capture chlorine from alkali chlorides . The presence of alkali chlorides is revealed when analysing the fine fly ash (less than 4,1 ⁇ m) in which they are compressed in connection with sampling.
  • a cation (a cation of a commercial reagent, Fe3+ or A13+) plays an active role in promoting sulphating, or bringing increased power, for example, in the form of an aluminium-silicate reaction.
  • Figures 1, 2, and 3 also agree well with each other: It can be seen from Figure 1 that with aluminium (III) sulphate the alkali chloride content is much lower than with the reference reagents, if the S/CL is constant, while correspondingly with aluminium (III) sulphate the deposition of chloride is clearly weaker than with the reference reagents .

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Incineration Of Waste (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Fuel Combustion (AREA)

Abstract

The invention relates to a method for preventing chlorine deposition on the heat- transferring surfaces of a boiler, particularly on the superheater, in which boiler a fuel with a chlorine content, such as a biomass or waste fuel, is burned. And to which steam boiler is fed, preferably in the superheater area, a compound with a sulphate content, which forms a particular reagent to fix alkali compounds . The said compound is ferric (III) sulphate, Fe2 (SO4)3 and/or aluminium (III) sulphate, Al2 (SO4)3 .

Description

METHOD FOR PREVENTING CHLORINE DEPOSITION ON THE HEAT- TRANSFERRING SURFACES OF A BOILER
The present invention relates to a method for preventing chlorine deposition on the heat-transferring surfaces of a boiler, particularly on the superheater, in which boiler a fuel with a chlorine content, such as a biomass or waste fuel, is burned, and in which case a compound with a sulphate content, which forms a particular reagent to fix alkali compounds, is fed to the furnace, preferably in the superheater area.
There has been a known attempt to prevent the deposition of chlorine, by mixing different fuels. Experiments have also been made with adding reagents to the fuel flow. During this research it has appeared that, among others, both sulphur and aluminium silicate compounds have the effect of preventing the deposition of chlorine. The best known are the following four sulphur reagents: (NH4) 2SO4, NH4HSO4, FeSO4, and H2SO4.
Both sulphur and aluminium silicate compounds can react with alkali chloride, in which case the chlorine forms hydrochloric acid, (the chlorine in which is not transferred to the deposition) , while the alkali remains attached to either the sulphate (sulphur) or aluminium silicate (AlO3 * nSiO2 * yH20, the amount of silicon dioxide and crystal water may vary) . This means that there must be sufficient silica present in the oxide form for the aluminium to act. Here, the oxide form refers to all silicon compounds containing oxygen.
Patent publications FI 93674 and DD294548 disclose some circulating-mass and fluid-bed boilers. Both of these publications disclose the addition of substances with a kaolin content (= aluminium silicate, kaolinite Al2Si2O5 (OH4) to the furnace. One intention is to prevent fouling and deposition on the hot surfaces . Publication US 2004/0068988 Al discloses a method, in which corrosion caused in heat exchangers by chlorine is reduced by adding an additive solution containing sulphur to the channel in which the heat exchangers are located. 5
Publication FI 823943 discloses a method for improving the combustion of fuels intended to produce energy. By means of the method, corrosion and fouling of the furnace surfaces are reduced. In the method, a catalyser, which contains at least 10 the elements Al, Mg, Mn, and Zn, is fed to the combustion zone.
The use of aluminium compounds in the high-temperature zone of an incinerator, in order to prevent depositions, is also known (Patent Abstracts of Japan, summary of publication JP 15 62261802) .
Publication US6649135 discloses the use of aluminium silicates in a so-called dechlorination chamber 16, in a reaction fixing an alkali and releasing HCl.
20
International patent application WO 02/059526 discloses in detail a method for capturing an alkali from alkali chlorides in combustion processes . In the method, a compound, which is one of the following ammonium sulphate (NH4) 2SO4, ammonium
25 bisulphate (NH4) HSO4, ferrous sulphate FeSO4, or sulphuric acid H2SO4, is fed to the furnace. The intention is to create sulphur trioxide (SO3) , which is formed indirectly through sulphur dioxide (SO2) from compounds. According to the publication, the compound is fed preferably in the flue-gas temperature range
30 600 - 1000 0C.
Publication DE 19249022 also presents sulphur dioxide (SO2) as a reagent for fixing alkali chlorides . The publication also refers to sulphur trioxide (SO3) , but the precise connection
35 between them is not explained. Magnesium sulphate (MgSO4) is presented as an economical compound that is a source of sulphur dioxide (SO2) .
The invention is intended to create a new method, more advantageous than previous methods , for preventing chlorine deposition particularly in superheaters.
The characteristic features of the present invention are stated in the accompanying Claims. It has been surprisingly observed that the compounds presented, ferric (III) sulphate, Fe2 (SO4) 3 and aluminium (III) sulphate, Al2 (SO4) 3, are more effective for the purpose of fixing alkali compounds than any compound suggested previously. The additives in question have a strong tendency to disintegrate in the furnace, in such a way that their sulphur is almost entirely converted to sulphur trioxide (SO3) . They should be added close to the superheater surfaces or similar in a liquid form in an efficient manner in drops, in order to produce a powerful effect.
The invention is particularly suitable for application in fluid-bed boilers, or in other steam boilers with a similar flue-gas temperature range (600 - 1000 °C). Though the invention is of greatest importance in the corrosion protection of superheaters, the invention also assists in reducing the fouling of thermal surfaces .
The excellent action of the compounds appears to be due, among other things, to the large proportion of effective sulphur in the compounds. For example, ferric (III) sulphate Fe2(SO4J3 disintegrates thermally to form ferric (III) oxide and sulphur trioxide, which fix alkali compounds very aggressively. This has a significant technical effect. As is known, the literature on the field refers to the ferric (III) oxide SO2 → SO3 reaction as a catalyst, which also means that this oxide will effectively prevent the reduction of SO3 that has already formed. The compounds are used with or without the water of crystallization, singly, as mixtures, or as part of larger molecules (such as ammonium aluminium sulphate NH4Al (SO4) 2. The economic dosing of sulphur and sulphur/aluminium-compound-based reagents will be enough to prevent the deposition of chlorine, if they are sprayed as a solution into the superheater area of fluid-bed boilers .
Of sulphur compounds, sulphur trioxide SO3 effectively distroys alkali chlorides that have evaporated from the fuel, and which would otherwise condense onto the surfaces of the superheater, with resulting chorine corrosion.
In principle, the invention has the potential for worldwide application. It is necessary, when energy is produced from demanding chloritic biomasses and waste.
In the following, the invention is examined in detail with reference to the accompanying drawings showing some embodiments of the invention.
Figure 1 shows a comparison of reagents at a fixed dosage. Figure 2 shows the effect of a known reagent at different dosages . Figure 3 shows the effect of a reagent according to the invention, at different dosages.
In these embodiments, the economical dosing of sulphur and aluminium-compound-based reagents will be sufficient to prevent the deposition of chlorine, if they are sprayed into the superheater area of a steam boiler. In that case, the reagents will not spread in the lower parts of the furnace, so that they can be used to achieve an excellent effect/price ratio in the destruction of alkali compounds. Solubility in a liquid is a requirement if the reagents are to be added in a solution. In addition, the reagent should be cheap, and in the case of a sulphur reagent there should be a large proportion of sulphur in the molecules . The aforementioned conditions are met by aluminium sulphate Al2 (SO4)3 and ferric (III) sulphate Fe2 (SO4) 3. From these sulphur trioxide SO3 is obtained, which immediately reacts with the alkali compounds .
If the alkali compounds are marked generally with the term MCl, their fixing will be based on the following chemical equation: 2 MCl + SO3 + H2O > 2 HCl + M2SO4
In the accompanying Figures 1 - 3, the deposition of chlorine on a deposit probe is shown using selected reagents and doses. The columns show the chlorine content of the deposition at different points. The chlorine content of the deposition was analysed after each combustion test. The experiment was made in a 20-kW research boiler, in which a mixture of bark and pelleted fuel from recycling was burned. The depositions were collected over a period of three hours and were measured on the probes 's wind and lee surfaces and at an angle of 50° relative to the intake direction of the flue gas .
Figure 1 shows the mass flows of the chlorine that travels with the finer fly ash (< 4,1 μm) using a previously known reference reagent (ammonium sulphate, aforementioned WO publication) and two reagents according to the invention; Corr 1
(aluminium (III) sulphate) and Corr 2 (ferric (III) sulphate) when burning described risky fuels. Dosage used: ratio of reagent molar sulphur flow to molar chlorine flow of the fuel = 3.
Figure 2 shows the deposition of chlorine at the various sampling points using varying doses of a previously known reagent. S/Cl = ratio of the molar sulphur flow of the reagent and the molar chlorine flow of the fuel .
Figure 3 shows a comparison as in Figure 2, except that the reagent is aluminium sulphate according to the invention. The first 'initial state' series of Figure 3 shows reference values, when an additive is not used. There was strong deposition of chlorine, except on the wind surfaces. In the other tests, the dosing of the aluminium sulphate was linked to the sulphur/chlorine, i.e. S/Cl mol ratio, which means the mol ratio of the sulphur contained in the reagent and the chlorine contained in the fuel . The experiment was carried out using mol ratios of 0,9; 1,5; 3; and 4,5. As a totality, the experiment shows that already at a molar dose of 1,5 - 2,0 the depositions of chlorine reduced so much that they were no longer detrimental. On a boiler scale, in which the conditions are not ideal, the range 2 - 3 appears to be sufficient.
The more advantageous dosing of sulphate is thus in the range 2 - 5 mols of sulphur to each mol of chlorine.
The precise addition of reagents prevents corrosion of the heat-transferring surfaces in steam boilers using biomass and waste fuels. Generally, soluble SO4 2" compounds are suitable for this purpose.
The compound used is sprayed in the direction of the flue-gas flow into the front side of the superheater area, as a water solution and in a drop size of 1 - 100 μm, preferably 10 - 20 μm. This drop size can be carried out easily with commercial nozzles. Here can be used for example spraying technics, which is known from SCR/SNCR technics.
The sulphates in question dissolve well in water (at least 30 weight-% and at most 80 weight-% of the weight of the solution. This depends on the reagent, more precisely CRC, Handbook of Chemistry and Physics. It is preferable to use the strongest possible solution, in order to avoid spraying excess water into the boiler. It will be seen from Figure 1 that many other factors than the dosage of the additive measured by the S/Cl ration affect the ability of the reagent to capture chlorine from alkali chlorides . The presence of alkali chlorides is revealed when analysing the fine fly ash (less than 4,1 μm) in which they are compressed in connection with sampling. In addition to sulphur, a cation (a cation of a commercial reagent, Fe3+ or A13+) plays an active role in promoting sulphating, or bringing increased power, for example, in the form of an aluminium-silicate reaction.
When comparing Figures 2 and 3, it will be noticed how much more effectively aluminium (III) sulphate (Fig. 3) prevents the deposition of chlorine, compared to a known reference reagent, if the dosing is constant. The capture of alkalis from alkali chlorides by sulphating is effective while, in addition, aluminium may have the ability to form alkali aluminium silicates in these conditions, because aluminium (III) sulphate clearly demonstrated itself to be also more effective than ferric (III) sulphate. Figures 1, 2, and 3 also agree well with each other: It can be seen from Figure 1 that with aluminium (III) sulphate the alkali chloride content is much lower than with the reference reagents, if the S/CL is constant, while correspondingly with aluminium (III) sulphate the deposition of chloride is clearly weaker than with the reference reagents .

Claims

1. Method for preventing chlorine deposition on the heat- transferring surfaces of a boiler, in particular on the superheater, in which boiler a fuel with a chlorine content, such as a biomass or waste fuel, is burned, and to which steam boiler is fed, preferably in the superheater area, a compound with a sulphate content, which forms a particular reagent to fix alkali compounds, characterized in that the said compound is ferric (III) sulphate, Fe2 (SO4)3 and/or aluminium (III) sulphate, Al2 (SO4) 3.
2. Method according to Claim 1, characterized in that the compounds are with or without the water of crystallization, by themselves, as mixtures, or as part of larger molecules.
3. Method according to any of Claims 1 - 2, characterized in that the said compound is sprayed on the front side of the superheater or other thermal surface to be protected, as a water solution and in a drop size of 1 - 100 μm, preferably 10 - 20 μm.
4. Method according to any of Claims 1 - 3 , characterized in that the dosage of the sulphate is in such that the sulphur contained in the reagent is the range 2 - 5 mols for every mol of chlorine contained in the fuel, in a case in which the fuel does not contain sulphur.
PCT/FI2006/050252 2005-06-16 2006-06-12 Method for preventing chlorine deposition on the heat- transferring surfaces of a boiler WO2006134227A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
ES06755414.7T ES2617730T3 (en) 2005-06-16 2006-06-12 Method to avoid the deposition of chlorine on the superheater of a boiler
DK06755414.7T DK1891187T3 (en) 2005-06-16 2006-06-12 Procedure for preventing chlorine deposition on the boiler's superiors
CA2608028A CA2608028C (en) 2005-06-16 2006-06-12 Method for preventing chlorine deposition on the heat- transferring surfaces of a boiler
US11/920,709 US8052803B2 (en) 2005-06-16 2006-06-12 Method for preventing chlorine deposition on the heat-transferring surfaces of a boiler
CN2006800214678A CN101198679B (en) 2005-06-16 2006-06-12 Method for preventing chlorine deposition on the heat- transferring surfaces of a boiler
BRPI0612821-1A BRPI0612821A2 (en) 2005-06-16 2006-06-12 method to prevent chloride deposition on heat transfer surfaces of a burner
JP2008516358A JP2008544202A (en) 2005-06-16 2006-06-12 Method for preventing chlorine accumulation on the heat transfer surface of a boiler
EP06755414.7A EP1891187B1 (en) 2005-06-16 2006-06-12 Method for preventing chlorine deposition on the superheater of a boiler
NO20075680A NO20075680L (en) 2005-06-16 2007-11-07 Process for preventing chlorine deposition on the heat transferring surfaces of a cooker.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FI20055317A FI20055317A0 (en) 2005-06-16 2005-06-16 Prevention of chlorine deposition in sludge boilers
FI20055317 2005-06-16
FI20065045 2006-01-23
FI20065045A FI117631B (en) 2005-06-16 2006-01-23 A method of preventing the deposition of chlorine on the heating surfaces of a boiler

Publications (2)

Publication Number Publication Date
WO2006134227A1 true WO2006134227A1 (en) 2006-12-21
WO2006134227B1 WO2006134227B1 (en) 2007-02-08

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Country Status (15)

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US (1) US8052803B2 (en)
EP (1) EP1891187B1 (en)
JP (1) JP2008544202A (en)
KR (1) KR20080016641A (en)
CN (1) CN101198679B (en)
BR (1) BRPI0612821A2 (en)
CA (1) CA2608028C (en)
DK (1) DK1891187T3 (en)
ES (1) ES2617730T3 (en)
FI (1) FI117631B (en)
NO (1) NO20075680L (en)
PL (1) PL1891187T3 (en)
PT (1) PT1891187T (en)
RU (1) RU2393205C2 (en)
WO (1) WO2006134227A1 (en)

Cited By (9)

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EP2071239A2 (en) 2007-12-10 2009-06-17 Metso Power Oy A method for preventing corrosion on the heat exchange surfaces of a boiler, and a supply means for additional material
EP2071239A3 (en) * 2007-12-10 2014-03-26 Metso Power Oy A method for preventing corrosion on the heat exchange surfaces of a boiler, and a supply means for additional material
DE102009007783B3 (en) * 2009-02-06 2010-08-26 Karlsruher Institut für Technologie Method for reducing the pollutant potential in exhaust gases and residues of incinerators
EP2216598A2 (en) 2009-02-06 2010-08-11 Karlsruher Institut für Technologie Method for reducing the polluting potential of waste gases and residues of combustion installations
RU2518593C2 (en) * 2009-06-17 2014-06-10 Метсо Пауэр Ой Monitoring composition of flue gases brought about by thermal processes
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WO2011131842A2 (en) 2010-04-23 2011-10-27 Metso Power Oy A boiler and a superheater, as well as a method
EP2381169A2 (en) 2010-04-23 2011-10-26 Metso Power OY Boiler equipped with a superheater
GB2525776B (en) * 2013-03-31 2017-09-20 Drax Power Ltd Biomass combustion
WO2018059715A1 (en) * 2016-09-30 2018-04-05 Cemex Research Group Ag Process enabling the use alternative fuels with high chlorine content in clinker production
KR20200071719A (en) 2017-10-25 2020-06-19 스미도모쥬기가이고교 가부시키가이샤 Circulating fluidized bed boiler and its operation method

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CA2608028A1 (en) 2006-12-21
KR20080016641A (en) 2008-02-21
PT1891187T (en) 2017-03-13
US20090038310A1 (en) 2009-02-12
PL1891187T3 (en) 2017-06-30
FI117631B (en) 2006-12-29
US8052803B2 (en) 2011-11-08
CN101198679A (en) 2008-06-11
EP1891187B1 (en) 2016-12-07
BRPI0612821A2 (en) 2010-11-30
EP1891187A4 (en) 2012-05-30
ES2617730T3 (en) 2017-06-19
JP2008544202A (en) 2008-12-04
FI20065045A0 (en) 2006-01-23
CN101198679B (en) 2012-10-10
WO2006134227B1 (en) 2007-02-08
RU2008101678A (en) 2009-07-27
RU2393205C2 (en) 2010-06-27
NO20075680L (en) 2008-02-22
EP1891187A1 (en) 2008-02-27
CA2608028C (en) 2014-01-07

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