EP0223803A1 - PROCEDE PERMETTANT L'ELIMINATION SIMULTANEE PAR LAVAGE DE SO 2?, NO x? 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 SO 2?, NO x? ET LE CAS ECHEANT D'AUTRES SUBSTANCES NOCIVES CONTENUES DANS LES GAZ DE FUMEE DES INSTALLATIONS DE CHAUFFE ALIMENTEES PAR DES COMBUSTIBLES FOSSILES

Info

Publication number
EP0223803A1
EP0223803A1 EP86903350A EP86903350A EP0223803A1 EP 0223803 A1 EP0223803 A1 EP 0223803A1 EP 86903350 A EP86903350 A EP 86903350A EP 86903350 A EP86903350 A EP 86903350A EP 0223803 A1 EP0223803 A1 EP 0223803A1
Authority
EP
European Patent Office
Prior art keywords
iron
washing liquid
calcium
iii
sulfate
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.)
Ceased
Application number
EP86903350A
Other languages
German (de)
English (en)
Inventor
Heinrich IGELBÜSCHER
Heinrich Gresch
Heribert Dewert
Heinz HÖLTER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Holter Heinz Dipl-Ing
Original Assignee
Holter Heinz Dipl-Ing
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 Holter Heinz Dipl-Ing filed Critical Holter Heinz Dipl-Ing
Publication of EP0223803A1 publication Critical patent/EP0223803A1/fr
Ceased legal-status Critical Current

Links

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).
EP86903350A 1985-05-25 1986-05-24 PROCEDE PERMETTANT L'ELIMINATION SIMULTANEE PAR LAVAGE DE SO 2?, NO x? ET LE CAS ECHEANT D'AUTRES SUBSTANCES NOCIVES CONTENUES DANS LES GAZ DE FUMEE DES INSTALLATIONS DE CHAUFFE ALIMENTEES PAR DES COMBUSTIBLES FOSSILES Ceased EP0223803A1 (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
DE3518974 1985-05-25
DE3519198 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
DE3520377 1985-06-07
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)
DE3524047 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
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
DE3525051 1985-07-13
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
DE3531968 1985-09-07

Publications (1)

Publication Number Publication Date
EP0223803A1 true EP0223803A1 (fr) 1987-06-03

Family

ID=27544399

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86903350A Ceased EP0223803A1 (fr) 1985-05-25 1986-05-24 PROCEDE PERMETTANT L'ELIMINATION SIMULTANEE PAR LAVAGE DE SO 2?, NO x? 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)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5200160A (en) * 1991-08-29 1993-04-06 Dravo Lime Company Process for removing sulfur dioxide and nitrogen oxides from flue gases
SE9304082L (sv) * 1993-12-08 1995-06-09 Lkab Förfarande för rening av rökgaser
NL1009612C1 (nl) * 1998-07-10 2000-01-11 Biostar Bv Werkwijze voor het reinigen van een afgas.
JP5238830B2 (ja) * 2011-01-17 2013-07-17 株式会社東芝 廃水処理装置
CN102824824B (zh) * 2012-09-11 2015-02-25 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

Family Cites Families (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
JPS5142193B2 (fr) * 1973-06-14 1976-11-13
JPS5140151B2 (fr) * 1973-06-14 1976-11-01
GB1482643A (en) * 1973-10-31 1977-08-10 Kureha Chemical Ind Co Ltd Method for removing oxides of nitrogen from a gas
JPS5177575A (ja) * 1974-12-28 1976-07-05 Kawasaki Heavy Ind Ltd Haigasuchunoiosankabutsu oyobi chitsusosankabutsuno dojijokyoho
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 (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8606981A1 *

Also Published As

Publication number Publication date
WO1986006981A1 (fr) 1986-12-04

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