WO2003004136A1 - Procede de purification de gaz effluent - Google Patents

Procede de purification de gaz effluent Download PDF

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Publication number
WO2003004136A1
WO2003004136A1 PCT/FI2002/000602 FI0200602W WO03004136A1 WO 2003004136 A1 WO2003004136 A1 WO 2003004136A1 FI 0200602 W FI0200602 W FI 0200602W WO 03004136 A1 WO03004136 A1 WO 03004136A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel
boiler
flue gases
chamber
process according
Prior art date
Application number
PCT/FI2002/000602
Other languages
English (en)
Inventor
Ilari Ekman
Pauli Dernjatin
Marika RYYPPÖ
Marko Fabritius
Original Assignee
Fortum Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fortum Oyj filed Critical Fortum Oyj
Publication of WO2003004136A1 publication Critical patent/WO2003004136A1/fr

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Classifications

    • 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
    • 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
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • 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
    • 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
    • F23J15/006—Layout of treatment plant
    • 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 
    • F23J2215/00—Preventing emissions
    • F23J2215/20—Sulfur; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2217/00—Intercepting solids
    • F23J2217/10—Intercepting solids by filters
    • F23J2217/102—Intercepting solids by filters electrostatic

Definitions

  • This invention concerns a method for removing gaseous sulphur compounds and especially sulphur dioxide from the flue gases of a boiler burning sulphur- containing fuels.
  • the method is called a Bio-LIFAC process, and it is especially suitable for purification of the flue gases from power plant processes.
  • the sulphur dioxide content of flue gases can be reduced by various abso ⁇ tion methods outside the boiler.
  • One such method known as such is the so-called spray method, wherein the flue gases from the boiler are conducted into a separate reactor, into which aqueous slurry of calcium hydroxide is sprayed in the form of droplets through special nozzles.
  • the reactor is typically a rather big vessel, wherein the velocity of flue gases is allowed to slow down and aqueous slurry is sprayed downwards from the upper part of the vessel.
  • Chlorine In the process removal of chlorine (HC1) is also achieved. Chlorine can be removed easily with alkali and alkali earth metals at lower temperatures ( ⁇ 150°C). Chlorine is removed only slightly in limestone injection into the fire chamber.
  • FIG. 1 shows equipment according to the invention in connection with a boiler.
  • the boiler 10 is associated e.g. with a conventional steam power process, wherein fuel is burnt, supply water of the boiler is vaporized and the steam is conducted into a steam turbine, which further rotates an electric generator in order to produce electricity.
  • the boiler 10 may also function as such e.g. to heat district heating water or to produce steam for industrial use. This means that the pu ⁇ ose of use of the boiler 10 is not restricted herein.
  • fuel M is conducted into the fire chamber 11 of the boiler 10, and the combustion temperature in the fire chamber is in a range of 800 - 1350°C. Thus, the combustion temperature is within a certain exact range.
  • fuel M is used, which contains alkali or alkali earth metals in the following stoichiometric molar ratio: (Ca + 2K + 2Na) / (S + 2C1) > 0.5
  • Fuel M may be e.g. peat, biomass, lignite or waste-derived fuel.
  • the fuel to be burnt must have a certain composition; the stoichiometric molar ratio must be (Ca + 2K + 2Na) / (S + 2C1) > 0.5.
  • the combustion temperature in the fire chamber must be in a range of 800 - 1350°C.
  • water is sprayed into the flue gases after the fire chamber 11 in a separate humidification chamber 13, in order to convert the alkali and alkali earth metal oxides contained in the fuel into hydroxides, which will react further with sulphur dioxide or chlorine.
  • the Bio-LIFAC process according to the invention is suitable for fuels containing sufficiently alkali and alkali earth metals in themselves.
  • fuels are lignite, peat and bio fuels.
  • the first requirement is that the fuel in itself contains alkali and alkali earth metals in the following molar ratio:
  • the molar ratio of fuel is typically in a class of 2.5, due to the natural occurrence of alkali and alkali earth metals in the fuel.
  • the following requirement on the Bio-LIFAC process according to the invention is a low combustion temperature.
  • the temperature window required for the process is in a range of 800 - 1350°C. At these temperatures the alkali metals are released as oxides in the fire chamber.
  • the residence time of oxides and sulphur dioxide is very short especially in power plants using peat and bio fuel. The probable reason for this is the long combustion time of these fuels in the fire chamber, whereby oxides and dioxides occur only in the upper part of the fire chamber and they have only a short time to react in the right temperature window.
  • Bio-LIFAC process according to the invention is suitable for combustion processes at lower temperatures and for such boilers, wherein the combustion temperature is within the above-mentioned window.
  • Such combustion devices are, for example, Bubbling Fluidized Bed boilers (BFB) and Circulating Fludized Bed boilers (CFB) and lignite boilers.
  • Calcination into oxide (CaO) of the calcium carbonate (CaCO 3 ) in the fuel ash takes place when the temperature of the ash particle exceeds 800°C.
  • the sodium and potassium in the ash will form sodium and potassium carbonates (Na2CO 3 and K2CO 3 ), which do not calcinate.
  • Sodium and potassium carbonates react with sulphur oxides in the upper part of the fire chamber forming sodium and potassium sulphates (Na2SO 4 and K2SO ).
  • Calcium oxide reacts partly with sulphur oxides in the upper part of the fire chamber forming calcium sulphate (CaSO 4 ).
  • the activation reactor or the humidification chamber is an essential part of the Bio-LIFAC process according to the invention.
  • Water is sprayed into the flue gases in the humidification chamber.
  • the alkali metal oxides in the flue gas react quickly, and the following reactions take place in the humidification chamber 13: CaO + H 2 O -> Ca(OH) 2 Ca(OH) + SO 2 -> CaSO 3 + H 2 O
  • the sprayed quantity of water will vaporize in the reactor and the final product is separated in the solid phase together with the fly ash, as is the case in the original LIFAC process.
  • the following test run was carried out at the power plant.
  • the peat used as fuel had a sulphur content of 0.14 w-% of the dry matter and a chlorine content of 0.04 w-%.
  • the fuel contained 0.46 w-% of calcium, 0.02 w-% of sodium and 0.03 w-% of potassium.
  • the main alkali metal was calcium and the molar ratio Ca/S of the fuel was 2.6 and its Ca/Cb molar ratio was 5.1.
  • the fuel was burnt in a 295 MW BFB boiler. From the flue gas a secondary flow was taken into a 1000 nm 3 /h test humidification reactor. Test results
  • an additional CaCO 3 injection may block e.g. the air pre- heaters.
  • the simple Bio-LIFAC process is suitable for burning taking place at a low temperature, such as is normally the case e.g. when burning peat, lignite, biomass and waste-derived fuel, due to the burning technology and/or the low heat value of the fuel. At the same time these fuels often contain sufficient alkalis and alkali earth metals. Under these circumstances, the Bio-LIFAC process according to the invention may well be used in certain processes.
  • the invention and its technology may be utilised advantageously to meet the stricter emission standards, which can be expected within the EU area and outside it.
  • a moderate SO2 retention (less than 50 %) is achieved by injecting only limestone into the fire chamber. This is due to the fact that the particles have too short a residence time in the correct temperature window in the fire chamber. Should the emission limit of 200 mg/nm come into force for SO2, then limestone injection alone is not sufficient and wet desulphurisation would cause additional costs in the power plant process. Since the costs of the humidification reactor system are low, the Bio-LIFAC process according to the invention would be one of the best exploitable techniques when aiming at low emission values.
  • HC1 dechlorination

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un procédé de purification de gaz effluent. Le combustible (M) est brûlé dans une chambre de combustion (11) d'une chaudière (10). A partir de la chaudière (10), les gaz effluents sont conduits à travers un conduit (12) dans une chambre d'humidification (13), et continuent pour sortir à travers une cheminée (16). Tout le Ca, K, et le Na utilisé dans le procédé provient du combustible. Le combustible (M) est brûlé dans la chambre de combustion (11) de la chaudière (10) à l'intérieur d'une plage de température comprise entre 800° et 1 350° C. Après la chaudière, les gaz effluents sont amenés par le conduit (12) dans la chambre d'humidification (13) dans laquelle de l'eau est vaporisée à partir d'un conduit de buse (14) ou analogue.
PCT/FI2002/000602 2001-07-05 2002-07-03 Procede de purification de gaz effluent WO2003004136A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20011469 2001-07-05
FI20011469A FI111608B (fi) 2001-07-05 2001-07-05 Savukaasujen puhdistusprosessi

Publications (1)

Publication Number Publication Date
WO2003004136A1 true WO2003004136A1 (fr) 2003-01-16

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2002/000602 WO2003004136A1 (fr) 2001-07-05 2002-07-03 Procede de purification de gaz effluent

Country Status (2)

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FI (1) FI111608B (fr)
WO (1) WO2003004136A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101596398B (zh) * 2009-05-08 2012-05-23 朱学智 一种基于循环流化床锅炉烟道的再脱硫方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50117805A (fr) * 1974-03-04 1975-09-16
JPS5319307A (en) * 1976-08-07 1978-02-22 Daihatsu Motor Co Ltd Method of removing sulfur oxide in exhast gas of internal combustion engine
DE3234315A1 (de) * 1982-09-16 1984-03-22 Klöckner-Humboldt-Deutz AG, 5000 Köln Verfahren zur verringerung der schwefelemission
GB2174082A (en) * 1985-04-24 1986-10-29 Tampella Oy Ab A process for removing gaseous sulphur compounds, particularly sulphur dioxide, from the flue gases of a furnace
SE460362B (sv) * 1988-05-31 1989-10-02 Nycol Ab Saett att tillverka ett torrt kolpulverbraensle
EP0857777A1 (fr) * 1997-02-07 1998-08-12 Ethyl Petroleum Additives Limited Utilisation d'un système de mélange de métaux alcalino-terreux-alcalin comme agent réducteur des émissions dans les moteurs à allumage par compression
US6200358B1 (en) * 1998-04-24 2001-03-13 Daimlerchrysler Ag Additive for a fuel to neutralize sulfur dioxide and/or sulfur trioxide in the exhaust gases

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50117805A (fr) * 1974-03-04 1975-09-16
JPS5319307A (en) * 1976-08-07 1978-02-22 Daihatsu Motor Co Ltd Method of removing sulfur oxide in exhast gas of internal combustion engine
DE3234315A1 (de) * 1982-09-16 1984-03-22 Klöckner-Humboldt-Deutz AG, 5000 Köln Verfahren zur verringerung der schwefelemission
GB2174082A (en) * 1985-04-24 1986-10-29 Tampella Oy Ab A process for removing gaseous sulphur compounds, particularly sulphur dioxide, from the flue gases of a furnace
SE460362B (sv) * 1988-05-31 1989-10-02 Nycol Ab Saett att tillverka ett torrt kolpulverbraensle
EP0857777A1 (fr) * 1997-02-07 1998-08-12 Ethyl Petroleum Additives Limited Utilisation d'un système de mélange de métaux alcalino-terreux-alcalin comme agent réducteur des émissions dans les moteurs à allumage par compression
US6200358B1 (en) * 1998-04-24 2001-03-13 Daimlerchrysler Ag Additive for a fuel to neutralize sulfur dioxide and/or sulfur trioxide in the exhaust gases

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 197814, Derwent World Patents Index; Class C10, AN 1978-26220A, XP002957947 *
DATABASE WPI Week 197851, Derwent World Patents Index; Class C10, AN 1977-72986Y, XP002957948 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101596398B (zh) * 2009-05-08 2012-05-23 朱学智 一种基于循环流化床锅炉烟道的再脱硫方法

Also Published As

Publication number Publication date
FI111608B (fi) 2003-08-29
FI20011469A (fi) 2003-01-06
FI20011469A0 (fi) 2001-07-05

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