DE2654843A1 - Purificn. of gas contg. sulphur di:oxide by washing - using an additive contg. a poly:carboxylic acid - Google Patents

Purificn. of gas contg. sulphur di:oxide by washing - using an additive contg. a poly:carboxylic acid

Info

Publication number
DE2654843A1
DE2654843A1 DE19762654843 DE2654843A DE2654843A1 DE 2654843 A1 DE2654843 A1 DE 2654843A1 DE 19762654843 DE19762654843 DE 19762654843 DE 2654843 A DE2654843 A DE 2654843A DE 2654843 A1 DE2654843 A1 DE 2654843A1
Authority
DE
Germany
Prior art keywords
contg
gas
washing
additive
purificn
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.)
Granted
Application number
DE19762654843
Other languages
German (de)
Other versions
DE2654843C2 (en
Inventor
Heinrich Gresch
Heinz Hoelter
Heinrich Igelbuescher
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.)
Individual
Original Assignee
Individual
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 DE2532373A external-priority patent/DE2532373C3/en
Application filed by Individual filed Critical Individual
Priority to DE19762654843 priority Critical patent/DE2654843C2/en
Priority to DE19772730845 priority patent/DE2730845A1/en
Priority to AT0783577A priority patent/AT367318B/en
Priority to NL7712450A priority patent/NL7712450A/en
Priority to SE7712900A priority patent/SE431939B/en
Priority to GB4849677A priority patent/GB1545175A/en
Priority to FR7735441A priority patent/FR2372651A1/en
Priority to AU31026/77A priority patent/AU515100B2/en
Priority to US05/855,268 priority patent/US4222993A/en
Priority to CH1461177A priority patent/CH630814A5/en
Priority to BE2056472A priority patent/BE861329A/en
Priority to IT30251/77A priority patent/IT1089312B/en
Priority to DK539277A priority patent/DK539277A/en
Priority to JP14492377A priority patent/JPS5370981A/en
Priority to CA292,308A priority patent/CA1100122A/en
Publication of DE2654843A1 publication Critical patent/DE2654843A1/en
Publication of DE2654843C2 publication Critical patent/DE2654843C2/en
Application granted granted Critical
Expired legal-status Critical Current

Links

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
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor

Landscapes

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

Abstract

In the purificn. of gas contg. SO2, the gas is brought into contact with a washing liq. contg. a strong mineral acid, partic. HCl, and circulating in a closed circuit, to which are added the carbonate and/or oxide and/or hydroxide and/or appropriate cpds. of Ca, the Ca ions in soln. fixing the SO2 during the washing. An additive contg. a polycarboxylic acid and if necessary a strong mineral acid, partic. HCl, are added to the closed circuit. The calcium-sulphur cpds. formed are oxidised into CaSO4 and removed from the system. The apparatus used for the process consists of a gas washer and an oxidn. appts. contg. several interconnected compartments including an oxidn. zone with an intake of air, a reaction zone with an intake of lime or lime-wash, and a zone in which the CaSO4 formed falls onto a conveyor and from which the clear washing liq. is pumped back to the gas washer. The amt. of washing liq. required to purify a given vol. of gas is lower than in previous processes, resulting in lower process costs.

Description

Beschreibung und Erläuterung zur ZusatzpatentDescription and explanation of the additional patent

anmeldung zum Aktenzeichen P 25 32 373.3 Waschflüssigkeit zur Reinigung von Abgasen aus Verbrennungsanlagenff In der Hauptanmeldung P 25 32 373.3 wird ein Verfahren und eine Vorrichtung zum Reinigen von Gasen beschrieben, vorzugsweise Rauchgasen, die mit Schwefeldioxyd und NOx angereichert sind, wobei die Waschflüssigkeit als Additiv Chlorionen und als zusätzliches Additiv Karbonsäuren, vorzugsweise Ameisensäure, enthält.registration for file number P 25 32 373.3 washing liquid for cleaning of exhaust gases from incineration plantsff In the main application P 25 32 373.3 is a Method and device for cleaning gases described, preferably Flue gases that are enriched with sulfur dioxide and NOx, with the scrubbing liquid as an additive chlorine ions and as an additional additive carboxylic acids, preferably formic acid, contains.

In Abhängigkeit von der Schwefeldioxydkonzentration im Rauchgas werden bestimmte Mengen Salzsäure und Ameisensäure zugesetzt und zur Verbesserung der erfindungsgemäßen Ausführung, entsprechend der Hauptpatentanmeldung, wird weiterhin vorgeschlagen, der chlorionenhaltigen Waschflüssigkeit nicht eine einbasische Karbonsäure sondern eine mehrbasische Karbonsäure zuzusetzen.Depending on the sulfur dioxide concentration in the flue gas added certain amounts of hydrochloric acid and formic acid and to improve the inventive Execution, according to the main patent application, is still proposed, the washing liquid containing chlorine ions is not a monobasic carboxylic acid but rather add a polybasic carboxylic acid.

Dieser mehrbasischen Karbonsäure sollte vorzugsweise eine dreibasische, z. B. Zitronensäure, zugesetzt werden.This polybasic carboxylic acid should preferably be a tribasic, z. B. citric acid can be added.

Überraschenderweise hat sich gezeigt, daß beim erfindungsgemäßen Einsatz einer solchen aufbereiteten Waschflüssigkeit die Aufnahmefähigkeit von 502 etwa 3 x höher liegt, d. h. es können etwa 3 x soviel Calciumionen über das Calciumzitrat in Lösung gebracht werden als bei der Zugabe von z. B. einbasischer Ameisensäure mit HCl.Surprisingly, it has been shown that when used according to the invention of such a treated washing liquid the absorption capacity of 502 approximately 3 times higher, i.e. H. about 3 times as many calcium ions can get through the calcium citrate be brought into solution than with the addition of z. B. monobasic formic acid with HCl.

Das bedeutet einen wesentlich niedrigeren Waschflüssigkeitsfaktor (Liter Flüssigkeit zu m3 Rohgas), so daß eine wesentlich geringere Flüssigkeit zur Waschung in das Gaswaschsystem eingepumpt werden muß, somit nur ein Bruchteil der bisher erforderlichen Pumpenleistung.This means a much lower washing liquid factor (Liter of liquid to m3 of raw gas), so that a much smaller liquid for Washing must be pumped into the gas scrubbing system, thus only a fraction of the previously required pump capacity.

Die Waschflüssigkeitsbehälter, wie Sinkabscheider und Oxydationsgefäße, können wesentlich kleiner ausgelegt werden, da ja eine wesentlich geringere Waschflüssigkeitsmenge im Waschkreislauf gefahren wird.The washing liquid containers, such as sink separators and oxidation vessels, can be designed much smaller, since a much smaller amount of washing liquid is run in the washing cycle.

Die pH-Wert-Absenkung der aufgegebenen Waschflüssigkeit in den Waschprozeß von pH 12 bis auf pH 2,8 erfolgt ohne Ausfällung (keine Calciumsulfitbildung und Calciumcarbonatbildung). Es entstehen absolut keine Inkrustierungen innerhalb der Waschapparatur.The lowering of the pH value of the applied washing liquid in the washing process from pH 12 to pH 2.8 takes place without precipitation (no calcium sulfite formation and Calcium carbonate formation). There are absolutely no incrustations within the Washing apparatus.

Verluste durch Verdampfung beim Einsprühen in heiße Rauchgase um 2000 C entstehen nicht.Losses due to evaporation when spraying into hot smoke gases around 2000 C do not arise.

Die Zitronensäure liegt zur Dosierung in fester Form vor. Das Salz wird in Wasser gelöst der Waschflüssigkeit zugegeben.Citric acid is available in solid form for dosing. The salt is dissolved in water and added to the washing liquid.

Durch die Zugabe dieser dreibasischen Zitronensäure wird eine Waschlösung gebildet, die im alkalischen sowie im sauren Bereich als Pufferlösung wirkt.The addition of this tribasic citric acid creates a washing solution formed, which acts as a buffer solution in the alkaline as well as in the acidic range.

Die starke Pufferwirkung der Waschlösung bewirkt auch in dem pH-Bereich von z. B. pH 5 bis pH 7 einen weitgehenden Korrosionsschutz für die Anlagenteile der Gaswascheinrichtung.The strong buffering effect of the washing solution also works in the pH range from Z. B. pH 5 to pH 7 an extensive corrosion protection for the system parts the gas scrubbing device.

Eine gute Oxydation von Calciumsulfit zu Calciumsulfat wird im pH-Wert-Bereich zwischen pH 6 bis pH 6,8 vorteilhaft erzielt.A good oxidation of calcium sulfite to calcium sulfate is in the pH range advantageously achieved between pH 6 to pH 6.8.

Als weiterer Vorteil darf gewertet werden, daß überraschenderweise die Kristallausbildung der Gipskristalle nach der Oxydation wesentlich größer ist, als bei den bekannten Waschflüssigkeiten, so daß hierdurch eine wesentlich bessere Absenkung des Wassergehaltes im abzufilternden CaSOq-Rückstand durch Trommelvakuumfilter oder Zentrifugen gewähleistet wird.Another advantage that can be seen is that, surprisingly the crystal formation of the gypsum crystals after the oxidation is much larger, than with the known washing liquids, so that this is a much better one Lowering of the water content in the CaSOq residue to be filtered off by means of a drum vacuum filter or Centrifuges is guaranteed.

Selbstverständlich ist die Erfindung nicht auf die vorstehend beschriebene Zusammensetzung begrenzt, sondern es sind zahlreiche Abänderungen möglich, ohne jedoch von dem Grundgedanken abzuweichen, eine Waschflüssigkeit zur Reinigung von Gasen, die mit z. B. SO2, HF und NO angex reichert sind, mit einem Additiv zu versehen, das mit einer mehrbasischen Karbonsäure und Chlorionen versetzt ist, vorzugsweise Zitronensäure.Of course, the invention is not limited to that described above Composition limited, but numerous amendments are possible without however to deviate from the basic idea of using a washing liquid for cleaning Gases with z. B. SO2, HF and NO are enriched with an additive, which is mixed with a polybasic carboxylic acid and chlorine ions, preferably Citric acid.

Patentanspruch.Claim.

Claims (1)

Patentanspruch: Waschflüssigkeit zur Reinigung von Gasen, die SO2, HF und NOx enthalten, dadurch gekennzeichnet, daß sie mit einem Additiv versetzt ist, das aus einer mehrbasischen Karbonsäure,vorzugsweise Zitronensäure und Chlorionen,besteht.Claim: washing liquid for cleaning gases containing SO2, Contain HF and NOx, characterized in that they are mixed with an additive which consists of a polybasic carboxylic acid, preferably citric acid and chlorine ions.
DE19762654843 1974-09-19 1976-12-03 Process for cleaning flue gases and other exhaust gases Expired DE2654843C2 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
DE19762654843 DE2654843C2 (en) 1975-07-19 1976-12-03 Process for cleaning flue gases and other exhaust gases
DE19772730845 DE2730845A1 (en) 1975-07-19 1977-07-08 Purificn. of gas contg. sulphur di:oxide by washing - using an additive contg. a poly:carboxylic acid
AT0783577A AT367318B (en) 1976-12-03 1977-11-03 METHOD FOR PURIFYING RAW GAS AND OTHER EXHAUST GASES CONTAINING SULFUR DIOXIDE AND DEVICE FOR CARRYING OUT THE METHOD
NL7712450A NL7712450A (en) 1976-12-03 1977-11-11 PROCESS FOR PURIFYING CRUDE GAS AND OTHER EXHAUST GASES CONTAINING SULFUR DIOXIDE AND EQUIPMENT FOR PERFORMING THIS PROCESS.
SE7712900A SE431939B (en) 1976-12-03 1977-11-15 SET TO CLEAN RAGAS AND OTHER EXHAUSTS INCLUDING SULFUR Dioxide AND DEVICE IMPLEMENTATION
GB4849677A GB1545175A (en) 1974-09-19 1977-11-22 Removal of noxious contaminants from gas
FR7735441A FR2372651A1 (en) 1976-12-03 1977-11-24 PROCESS FOR PURIFYING CRUDE GASES AND OTHER WASTE GASES WHICH CONTAIN SULPHUROUS ANHYDRIDE AND DEVICE FOR CARRYING OUT THIS PROCESS
US05/855,268 US4222993A (en) 1974-09-19 1977-11-28 Removal of noxious contaminants from gas
AU31026/77A AU515100B2 (en) 1976-12-03 1977-11-28 Gas washing process
CH1461177A CH630814A5 (en) 1976-12-03 1977-11-29 Process for cleaning waste gases containing sulphur dioxide, and appliance for carrying out the process
BE2056472A BE861329A (en) 1976-12-03 1977-11-30 METHOD AND DEVICE FOR PURIFYING CRUDE GASES AND OTHER RESIDUAL GASES CONTAINING SULPHUROUS ANHYDRIDE
IT30251/77A IT1089312B (en) 1976-12-03 1977-12-01 DEVICE TO PURIFY GEGGI GAS OR EXHAUST GASES, WHICH CONTAIN SULFUR DIOXIDE
DK539277A DK539277A (en) 1976-12-03 1977-12-02 PROCEDURE FOR PURIFICATION OF RAAGAS AND OTHER EXHAUST GASES CONTAINING SULFUR DIOXIDE AND APPLIANCE FOR PERFORMING THE PROCEDURE
JP14492377A JPS5370981A (en) 1976-12-03 1977-12-02 Method and apparatus for purifying raw gas and sulfur dioxideecontaining waste gas
CA292,308A CA1100122A (en) 1976-12-03 1977-12-02 Removal of noxious contaminants from gas

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2532373A DE2532373C3 (en) 1975-07-19 1975-07-19 Method and device for cleaning flue gases and other exhaust gases containing sulfur dioxide
DE19762654843 DE2654843C2 (en) 1975-07-19 1976-12-03 Process for cleaning flue gases and other exhaust gases

Publications (2)

Publication Number Publication Date
DE2654843A1 true DE2654843A1 (en) 1978-06-08
DE2654843C2 DE2654843C2 (en) 1989-11-23

Family

ID=25769175

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19762654843 Expired DE2654843C2 (en) 1974-09-19 1976-12-03 Process for cleaning flue gases and other exhaust gases

Country Status (1)

Country Link
DE (1) DE2654843C2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2802622C1 (en) * 2022-12-09 2023-08-30 Федеральное государственное автономное образовательное учреждение высшего образования "Северо-Восточный федеральный университет имени М.К. Аммосова" Method for cleaning flue gases from acidic components

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632306A (en) * 1969-02-18 1972-01-04 Chemical Construction Corp Removal of sulfur dioxide from waste gases
DE2161476B2 (en) * 1970-12-29 1975-03-13 Mitsubishi Jukogyo K.K., Tokio Process for the cyclic countercurrent washing of combustion gases containing sulfur oxide by means of a clay slurry

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632306A (en) * 1969-02-18 1972-01-04 Chemical Construction Corp Removal of sulfur dioxide from waste gases
DE2161476B2 (en) * 1970-12-29 1975-03-13 Mitsubishi Jukogyo K.K., Tokio Process for the cyclic countercurrent washing of combustion gases containing sulfur oxide by means of a clay slurry

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DE-OS 24 44 781 Zusatzanmeldung zu DE-OS 24 15 693 *
Effect of organic acids on the kinetics of SO¶2¶-Absorption, veröffentlicht in der pol- nischen Zeitschrift Ochrona Powietrza, XI-1975, Nr. 3/47/S. 72-76 *
Removal of sulfur dioxide from stack gases by scrubbing with linestone slurry: use of organic acids. J.D. Hatfield, J.M. Poots, 2nd Interna- tional lime/limestone wet scrubbing symposium, New Orleans, Louisiana, 8.-12. November 1971, S. 263-267 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2802622C1 (en) * 2022-12-09 2023-08-30 Федеральное государственное автономное образовательное учреждение высшего образования "Северо-Восточный федеральный университет имени М.К. Аммосова" Method for cleaning flue gases from acidic components

Also Published As

Publication number Publication date
DE2654843C2 (en) 1989-11-23

Similar Documents

Publication Publication Date Title
DE2619145C3 (en) Process for separating nitrogen oxides or nitrogen oxides and sulfur oxides from exhaust gases
DE2622197C2 (en) Process for cleaning flue gases and other exhaust gases containing sulfur dioxide
DE2847047A1 (en) PROCESS FOR DESULFURIZATION OF SULFUR-CONTAINING PROCESS GASES
DE2412372B2 (en) PROCESS FOR THE REMOVAL OF SULFUR DIOXIDE FROM Gout or SMOKE GAS PRODUCTION OF PLASTER
DE2363793A1 (en) Removal of sulphur oxides from industrial waste gases - in a continuous process, using sol. sulphates
DE2654843A1 (en) Purificn. of gas contg. sulphur di:oxide by washing - using an additive contg. a poly:carboxylic acid
DE2822086C2 (en) Method of making an absorbent
DE3433396C2 (en) Process for the desulfurization of exhaust gas
DE3507718C2 (en)
DE3445163C2 (en)
DE2913867A1 (en) Sulphur di:oxide removal from exhaust gas streams - having scrubbing liquor in which pH is controlled by use of mineral and organic acid(s) and to which calcium carbonate is added
DE2730845A1 (en) Purificn. of gas contg. sulphur di:oxide by washing - using an additive contg. a poly:carboxylic acid
DE2519489A1 (en) Gas purification to remote sulphur dioxide - with calcium cpds in presence of sulphuric and other acids to prevent deposition of calcium carbonate
DE3308648A1 (en) Scrubbing liquid for scrubbing acidic gases such as SO2, HCl, HF, NOx etc.
DE3230352A1 (en) Process for purification of flue gas from SO2, HCl, HF and preferably NOx downstream of coal-fired or oil-fired power stations and refuse incineration plants or other fired plants
DE2607716C2 (en)
DE2509788A1 (en) Gas purification to remote sulphur dioxide - with calcium cpds in presence of sulphuric and other acids to prevent deposition of calcium carbonate
DE2707935A1 (en) Purificn. of gas contg. sulphur di:oxide by washing - using an additive contg. a poly:carboxylic acid
DE2752901C2 (en)
DE3139991A1 (en) Limestone scrubbing for scrubbing waste gases, preferably from coal power stations
DE545331C (en) Process and device to avoid corrosion of the scrubbing metal in generator systems
DE2519939A1 (en) Gas purification to remote sulphur dioxide - with calcium cpds in presence of sulphuric and other acids to prevent deposition of calcium carbonate
DE2335520A1 (en) METHOD FOR TREATMENT OF DESULFURIZED WASTEWATER WITH OZONE
DE3409526A1 (en) Simultaneous separating out of NOx and further associated flue gas pollutants
DE2447165A1 (en) Gas purification to remote sulphur dioxide - with calcium cpds in presence of sulphuric and other acids to prevent deposition of calcium carbonate

Legal Events

Date Code Title Description
8110 Request for examination paragraph 44
AF Is addition to no.

Ref country code: DE

Ref document number: 2532373

Format of ref document f/p: P

AF Is addition to no.

Ref country code: DE

Ref document number: 2532373

Format of ref document f/p: P

AG Has addition no.

Ref country code: DE

Ref document number: 2730845

Format of ref document f/p: P

D2 Grant after examination
8363 Opposition against the patent
Q176 The application caused the suspense of an application

Ref document number: 2730845

Country of ref document: DE

8366 Restricted maintained after opposition proceedings
8305 Restricted maintenance of patent after opposition
AF Is addition to no.

Ref country code: DE

Ref document number: 2532373

Format of ref document f/p: P

AG Has addition no.

Ref country code: DE

Ref document number: 2730845

Format of ref document f/p: P

D4 Patent maintained restricted
AG Has addition no.

Ref country code: DE

Ref document number: 2730845

Format of ref document f/p: P