WO1986006981A1 - PROCEDE PERMETTANT L'ELIMINATION SIMULTANEE PAR LAVAGE DE SO2, NOx ET LE CAS ECHEANT D'AUTRES SUBSTANCES NOCIVES CONTENUES DANS LES GAZ DE FUMEE DES INSTALLATIONS DE CHAUFFE ALIMENTEES PAR DES COMBUSTIBLES FOSSILES - Google Patents

PROCEDE PERMETTANT L'ELIMINATION SIMULTANEE PAR LAVAGE DE SO2, NOx ET LE CAS ECHEANT D'AUTRES SUBSTANCES NOCIVES CONTENUES DANS LES GAZ DE FUMEE DES INSTALLATIONS DE CHAUFFE ALIMENTEES PAR DES COMBUSTIBLES FOSSILES Download PDF

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Publication number
WO1986006981A1
WO1986006981A1 PCT/EP1986/000317 EP8600317W WO8606981A1 WO 1986006981 A1 WO1986006981 A1 WO 1986006981A1 EP 8600317 W EP8600317 W EP 8600317W WO 8606981 A1 WO8606981 A1 WO 8606981A1
Authority
WO
WIPO (PCT)
Prior art keywords
iron
washing liquid
calcium
iii
sulfate
Prior art date
Application number
PCT/EP1986/000317
Other languages
German (de)
English (en)
Inventor
Heinz HÖLTER
Heinrich IGELBÜSCHER
Heinrich Gresch
Heribert Dewert
Original Assignee
Hoelter Heinz
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
Priority claimed from DE19853518974 external-priority patent/DE3518974A1/de
Priority claimed from DE19853519198 external-priority patent/DE3519198A1/de
Priority claimed from DE19853520377 external-priority patent/DE3520377A1/de
Priority claimed from DE19853524047 external-priority patent/DE3524047A1/de
Priority claimed from DE19853525051 external-priority patent/DE3525051A1/de
Priority claimed from DE19853531968 external-priority patent/DE3531968A1/de
Application filed by Hoelter Heinz filed Critical Hoelter Heinz
Publication of WO1986006981A1 publication Critical patent/WO1986006981A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/48—Sulfites
    • 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
    • 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
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/464—Sulfates of Ca from gases containing sulfur oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to a method for simultaneously washing out S0 ? , NO and possibly other pollutants from the flue gases from combustion plants operated with fossil fuels.
  • So-called wet processes have become known for cleaning flue gases loaded with sulfur oxides, nitrogen oxides and possibly other pollutants, in which the flue gases are brought into contact with washing liquids which are enriched with appropriate absorbents for the pollutants.
  • washing liquids which are enriched with appropriate absorbents for the pollutants.
  • S0 soluble alkali or alkaline earth metal compounds.
  • calcium hydroxide calcium sulfate or calcium hydrogen sulfite is initially formed in an intermediate stage, which is oxidized to calcium sulfate with the addition of oxygen and is withdrawn from the system as a stable end product.
  • iron (II) complex compounds A disadvantage of using iron (II) complex compounds is the tendency of the iron (II) complexes to oxidize to iron (III) complexes under the prevailing absorption conditions, as a result of which the absorption capacity with regard to the nitrogen oxides and thus the efficiency of the NO separation deteriorates considerably.
  • the invention is based on the object of developing a method of the type mentioned at the outset which, with a constant high degree of efficiency, enables economical separation of sulfur oxides, nitrogen oxides and any other pollutants from flue gases.
  • this object is achieved in that a washing liquid is used which, in addition to alkali and / or alkaline earth ions and iron complex compounds of ethylenediaminetetraacetic acid (EDTA) and / or nitrotriscetic acid (NTA) at least one further substance which inhibits the oxidation of iron (II) to iron (III) and has a pH of between 3 and 10.
  • a single and / or polybasic carboxylic acid such as e.g. Formic acid and / or tartaric acid and / or citric acid can be used.
  • the reducing agent is thereby in short time intervals, pre preferably ⁇ l hour, mixed and the scrubbing 'üss i gkei t continuously fed and indeed expediently under complete exclusion of air, practically conditions under Inertgasbe ⁇ , and additional addition of high amounts of sulfite, for example 0.5 mol based on SO «.
  • scrubbing 'üss i gkei t continuously fed and indeed expediently under complete exclusion of air, practically conditions under Inertgasbe ⁇ , and additional addition of high amounts of sulfite, for example 0.5 mol based on SO «.
  • the free formic acid acts as a buffer medium so that the flue gas scrubbing can be carried out in a relatively wide pH range of the washing water between about 3 and 10, preferably between about 4.2 and 6.8.
  • the free formic acid formed reacts partly as an aldehyde, reducing the oxidation of iron (II) in the chelate complex to iron (III) caused by the oxygen content of the flue gas to be washed.
  • washing liquid according to the invention as has surprisingly been found, in particular at pH values below about 8, preferably between about 6 and 7.5, in addition to S0 ? and NO, depending on the type of firing, concentrations of 10-50 ppm in the flue gas always present NO (laughing gas) to residual concentrations of ⁇ 2 ppm, so that a harmful enrichment of the atmosphere or the stratosphere or a negative influence of the ozone belt surrounding the earth is largely avoided by this gas.
  • glycol preferably ethylene glycol 30 g / 1 vorzugswei se 18 g / 1
  • a wash water line 4 fed to the upper area of a flue gas scrubber 1 and brought into contact in countercurrent with the flue gas entering the scrubber via a line 2.
  • the flue gas leaves the scrubber from pollutants, in particular S0 2 and NO, freed as a clean gas via a line 3.
  • a partial amount of wash water from the wash water circuit is pumped via line 5 into a precipitation tank 6 and at pH values between 7 and 12.8, preferably between 7 and 8, 5, using calcium hydride 7, Cal ciu formi at 8 or a mixture of Calc iumformi at and Natri umformi at reacted to the in the water from the S0 ? / N0 removal available sodium sulfate / su lfat amounts as Calc iumsu lfi t or Cal c iu su 1fatd i hydrat - The water in the wash water at S0 ? / N0 wash formed free formic acid bound as sodium formate.
  • the water with the solids CaSO 1/2 H 2 O and CaSO 2 H 0 is fed via a line 9 to a gravity separator 10.
  • the thickened solids are fed via line 14 for dewatering a filtration 15 and then via line 16 to an oxidation container 17.
  • the proportionate calcium carbonate is oxidized to calcium sulfate with the addition of fresh water 18, sulfuric acid 19 and air 20.
  • the gypsum suspension is a Line 21 brought to a filter station 22 for dewatering and the solid CaS0 4 -2H 0 obtained via a line 13 as a marketable product, while the filtrate 24 can be discharged as waste water via a neutralization.
  • the pure water from the gravity separator 10 is introduced into a reduction tank 12 via a line 11; likewise the filtrate after the filtration 15 via a line 25.
  • the amount of water in the container 12 is added stoichiometrically to the iron (III) amount of reducing agent 13, preferably sodium diethylate, in order to maintain a pH between 7 and 9, preferably between 8 and 8.5 to reduce the iron (III) to iron (II).
  • the regenerated washing solution is then continuously deir via line 29. Wash water circuit of the scrubber 1 fed again.
  • a small amount of water for wastewater treatment and evaporation can be released via line 28
  • All containers 6, 10, 17 and 12 are connected to a cleaning line 26, which connects to the flue gas duct in front of the S0, in order to protect the washing liquid from air entry to prevent Fe (I l) oxidation «/ N0-Wash is connected.
  • a cleaning line 26 which connects to the flue gas duct in front of the S0, in order to protect the washing liquid from air entry to prevent Fe (I l) oxidation «/ N0-Wash is connected.
  • calcium formate or a mixture of calcium formate and sodium formate can also be used instead of sodium formate.
  • the washing liquid is dispensed via the containers 6, 10 and 12.
  • the reduction of iron (III) to iron (II) by supplying appropriate reducing agents can now be carried out directly in the bottom of the scrubber 1.
  • "of the pH value of the washing liquid is advantageously between 3 and 9, preferably between 4 and 5.5.
  • the pH of the liquid containing it is lowered to about 1.5 by adding sulfuric acid, whereby EDTA fails.
  • the reduction phase of iron (I ⁇ I) sulfate to iron (I ⁇ ) sulfate is then introduced by introducing a SO 2 -containing gas.
  • the liquid thus treated is then returned to the washing process.

Landscapes

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

Abstract

Le procédé ci-décrit utilise un liquide laveur contenant, outre des ions alcalins et/ou alcalino-terreux et des composés complexes ferreux, une autre substance destinée à empêcher l'oxydation des composés complexes de fer (II) en composés complexes de fer (III), de préférence un acide carboxylique monobasique et/ou polybasique et/ou un alcool supérieur, de préférence de l'éthylène glycol, ainsi que le cas échéant un réducteur, de préférence du dithionite de sodium, pour réduire le fer (III) en fer (II).
PCT/EP1986/000317 1985-05-25 1986-05-24 PROCEDE PERMETTANT L'ELIMINATION SIMULTANEE PAR LAVAGE DE SO2, NOx ET LE CAS ECHEANT D'AUTRES SUBSTANCES NOCIVES CONTENUES DANS LES GAZ DE FUMEE DES INSTALLATIONS DE CHAUFFE ALIMENTEES PAR DES COMBUSTIBLES FOSSILES WO1986006981A1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
DE19853518974 DE3518974A1 (de) 1985-05-25 1985-05-25 Waschloesung zur simultanen waschung von so(pfeil abwaerts)2(pfeil abwaerts) und no(pfeil abwaerts)x(pfeil abwaerts) in rauchgasen hinter kraftwerken und anderen fossilen verbrennungsanlagen
DEP3518974.6 1985-05-25
DEP3519198.8 1985-05-29
DE19853519198 DE3519198A1 (de) 1985-05-25 1985-05-29 Waschfluessigkeit zur waschung von so(pfeil abwaerts)2(pfeil abwaerts) und no(pfeil abwaerts)x(pfeil abwaerts) aus rauchgasen hinter fossil-kraftwerken
DE19853520377 DE3520377A1 (de) 1985-05-25 1985-06-07 Reduktionsmittelbevorratung fuer die waschloesung zur simultanen waschung von so(pfeil abwaerts)2(pfeil abwaerts) und no(pfeil abwaerts)x(pfeil abwaerts)
DEP3520377.3 1985-06-07
DEP3524047.4 1985-07-05
DE19853524047 DE3524047A1 (de) 1985-05-25 1985-07-05 Waschfluessigkeit und verfahren zur abscheidung von so(pfeil abwaerts)2(pfeil abwaerts) und no(pfeil abwaerts)x(pfeil abwaerts) aus rauchgasen von fossil-kraftwerken mit gleichzeitiger n(pfeil abwaerts)2(pfeil abwaerts)o-abscheidung
DEP3525051.8 1985-07-13
DE19853525051 DE3525051A1 (de) 1985-07-13 1985-07-13 Verfahren zur entfernung von hcl, hf, so(pfeil abwaerts)3(pfeil abwaerts), so(pfeil abwaerts)2(pfeil abwaerts) und oxiden des stickstoffs aus verbrennungsabgasen durch eine simultane nasswaesche
DEP3531968.2 1985-09-07
DE19853531968 DE3531968A1 (de) 1985-07-13 1985-09-07 Simultane waschung von so(pfeil abwaerts)2(pfeil abwaerts) und no(pfeil abwaerts)x(pfeil abwaerts) mit intermediaerem schritt

Publications (1)

Publication Number Publication Date
WO1986006981A1 true WO1986006981A1 (fr) 1986-12-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1986/000317 WO1986006981A1 (fr) 1985-05-25 1986-05-24 PROCEDE PERMETTANT L'ELIMINATION SIMULTANEE PAR LAVAGE DE SO2, NOx ET LE CAS ECHEANT D'AUTRES SUBSTANCES NOCIVES CONTENUES DANS LES GAZ DE FUMEE DES INSTALLATIONS DE CHAUFFE ALIMENTEES PAR DES COMBUSTIBLES FOSSILES

Country Status (2)

Country Link
EP (1) EP0223803A1 (fr)
WO (1) WO1986006981A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0531726A1 (fr) * 1991-08-29 1993-03-17 Dravo Lime Company Procédé pour éliminer l'anhydride sulfureux et les oxydes d'azote des gaz de fumée
WO1995015806A1 (fr) * 1993-12-08 1995-06-15 Lkab Procede d'epuration de gaz brules
WO2000002646A1 (fr) * 1998-07-10 2000-01-20 Biostar Development Cv Procede de nettoyage d'un gaz de combustion
CN102583735A (zh) * 2011-01-17 2012-07-18 株式会社东芝 废水的生物学处理方法及废水处理装置
CN102824824A (zh) * 2012-09-11 2012-12-19 浙江天蓝环保技术股份有限公司 一种氨基湿法联合脱硫脱硝装置及工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2353528A1 (de) * 1972-10-25 1974-05-16 Hitachi Ltd Verfahren zur behandlung von abgasen
JPS5013581A (fr) * 1973-06-14 1975-02-13
JPS5013582A (fr) * 1973-06-14 1975-02-13
US4087372A (en) * 1973-10-31 1978-05-02 Kureha Kagaku Kogyo Kabushiki Kaisha An absorbing solution for the removal of nitrogen oxide form a gas containing same
JPS5335863B2 (fr) * 1974-12-28 1978-09-29
US4418044A (en) * 1982-01-15 1983-11-29 Conoco Inc. Nitric oxide and sulfur oxide absorption by scrubbing with Fe++ /S.sub. O3-

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2353528A1 (de) * 1972-10-25 1974-05-16 Hitachi Ltd Verfahren zur behandlung von abgasen
JPS5013581A (fr) * 1973-06-14 1975-02-13
JPS5013582A (fr) * 1973-06-14 1975-02-13
US4087372A (en) * 1973-10-31 1978-05-02 Kureha Kagaku Kogyo Kabushiki Kaisha An absorbing solution for the removal of nitrogen oxide form a gas containing same
JPS5335863B2 (fr) * 1974-12-28 1978-09-29
US4418044A (en) * 1982-01-15 1983-11-29 Conoco Inc. Nitric oxide and sulfur oxide absorption by scrubbing with Fe++ /S.sub. O3-

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Japanese Patents Gazette , No. X37, 20 October 1976, Chemical Engineering, page 7, Derwent & JP,A,50 013 581 (Kawasaki Jukogyo K.K.) 31 January 1975 *
Japanese Patents Gazette, No. X37, 20 October 1976, Chemical Engineering, page 7, Derwent & JP,A,50 013 582 (Kawasaki Jukogyo K.K.) 31 January 1975 *
Japanese Patents Report, Vol. 78, No. 40, 30 November 1978, Chemical Engineering page 2, Derwent & JP,B,53 035 863 (Kawasaki Jukogyo) 29 September 1978, see Abstract *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0531726A1 (fr) * 1991-08-29 1993-03-17 Dravo Lime Company Procédé pour éliminer l'anhydride sulfureux et les oxydes d'azote des gaz de fumée
US5200160A (en) * 1991-08-29 1993-04-06 Dravo Lime Company Process for removing sulfur dioxide and nitrogen oxides from flue gases
TR27881A (tr) * 1991-08-29 1995-10-11 Dravo Lime Co Baca gazlarindan kükürt dioksit ve azot oksitleri uzaklastirmaya mahsus yöntem.
WO1995015806A1 (fr) * 1993-12-08 1995-06-15 Lkab Procede d'epuration de gaz brules
WO2000002646A1 (fr) * 1998-07-10 2000-01-20 Biostar Development Cv Procede de nettoyage d'un gaz de combustion
CN102583735A (zh) * 2011-01-17 2012-07-18 株式会社东芝 废水的生物学处理方法及废水处理装置
CN102824824A (zh) * 2012-09-11 2012-12-19 浙江天蓝环保技术股份有限公司 一种氨基湿法联合脱硫脱硝装置及工艺

Also Published As

Publication number Publication date
EP0223803A1 (fr) 1987-06-03

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