DE2654843C2 - Process for cleaning flue gases and other exhaust gases - Google Patents

Process for cleaning flue gases and other exhaust gases

Info

Publication number
DE2654843C2
DE2654843C2 DE19762654843 DE2654843A DE2654843C2 DE 2654843 C2 DE2654843 C2 DE 2654843C2 DE 19762654843 DE19762654843 DE 19762654843 DE 2654843 A DE2654843 A DE 2654843A DE 2654843 C2 DE2654843 C2 DE 2654843C2
Authority
DE
Germany
Prior art keywords
added
calcium
gas
liquid
washing
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.)
Expired
Application number
DE19762654843
Other languages
German (de)
Other versions
DE2654843A1 (en
Inventor
Heinrich 4600 Dortmund Gresch
Heinz 4390 Gladbeck Hölter
Heinrich 4390 Gladbeck Igelbüscher
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 US05/855,268 priority patent/US4222993A/en
Priority to AU31026/77A priority patent/AU515100B2/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 JP14492377A priority patent/JPS5370981A/en
Priority to DK539277A priority patent/DK539277A/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)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Description

Die Erfindung betrifft ein Verfahren zum Reinigen vorr Rauchgasen und anderen Abgasen, die Schwefeldioxyd enthalten, bei dem das Gas mit einer im Kreislauf gefahrenen Waschflüssigkeit in Kontakt gebracht wird, der Kalziumkarbonat und/oder Kalziumoxyd und/ock Kalziumhydroxyd zugesetzt werden und deren in Lösung befindliche Kalziumionen beim Waschvorgang das Schwefeldioxyd des Gases binden, und bei dem die gebildeten Verbindungen mittels Luftsauerstoff zu Kalziumsulfat oxydiert werden und aus dem Kreislauf ab geschieden werden, wobei der Waschflüssigkeit als Zusatz Salze und/oder eine Mineralsäure zugegeben werden und die Waschflüssigkeit vordem Kontakt mit dem Gas von Feststoffen befreit wird und der Waschflüssigkeit vor dem Kontakt mit dem Gas zusätzlich eine zur Pufferung dienende Karbonsäure und/oder deren Salz zugegeben wird nach Patent 25 32 373. The invention relates to a method for cleaning vorr flue gases and other exhaust gases containing sulfur dioxide, in which the gas is brought into contact with a circulating scrubbing liquid to which calcium carbonate and / or calcium oxide and / or calcium hydroxide are added and their calcium ions in solution bind the sulfur dioxide of the gas during the washing process, and in which the compounds formed are oxidized to calcium sulfate by means of atmospheric oxygen and are separated from the circuit, the washing liquid being added as an additive, salts and / or a mineral acid and the washing liquid before contact with the gas solids and is freed of the washing liquid prior to contact with the gas additionally serving for buffering carboxylic acid and / or salt thereof is added to Patent 25 32 373rd

Das Verfahren nach dem Hauptpatent hat sich bewährt. In Abhängigkeit von der Schwcfcldioxydkonzentration im Rauchgas werden außer bestimmten Mengen Salzsäure und Ameisensäure auch eine als Pufferung dienei.de einbasische Karbonsäurc und/oder deren Salze zugegeben.The procedure according to the main patent has proven itself. Depending on the low-carbon dioxide concentration In addition to certain quantities of hydrochloric acid and formic acid, the flue gas also acts as a buffer dienei.de monocarboxylic acids and / or their salts admitted.

Aufgabe der Erfindung ist die Verbesserung des Verfahrens nach dem Hauptpatent.The object of the invention is to improve the method according to the main patent.

Diese Aufgabe wird dadurch gelöst, daß die Waschflüssigkeit mit einem Additiv, das aus einer mehrbasischen Karbonsäurc und Chlorioncn besteht, versetzt wird.This object is achieved in that the washing liquid with an additive that consists of a polybasic Carboxylic acid and chlorine ions is added.

Überraschenderweise hat sich gezeigt, daß dabei die Aufnahmefähigkeit von SO>etwa 3 χ höher liegt, d. h. es können etwa 3 χ soviel Kal/.iuininnen über d:is Kal/ium/ilial in Losung gebracht werden als bei der Zugabe von /.. H. einbasischer Ameisensäure mit HCI. Das beik-ulLt einen wesentlich niedrigeren Waschflüssigkeit*· f.iktor (l.iicr Hüssii'keit /u ni' Rohgas), so daß eine wesentlich geringere I liissigkeit zur Waschung in das Gaswaschsystem eingepumpt werden muß. somit nur einSurprisingly, it has been shown that the absorption capacity of SO is> about 3 higher, ie. H. it can have about 3 χ as many Kal / .iuininnen over d: is Kal / ium / ilial be brought into solution than with the addition of / .. H. monobasic formic acid with HCl. That beik-ulLt a much lower scrubbing liquid * · f.iktor (l.iicr Hüssii'keit / u ni 'raw gas), so that a substantially less liquid for washing in the gas washing system must be pumped in. thus only one

3030th Bruchteil der bisher erforderlichen Pumpenleistung. Die Waschflüssigkeitsbehälter, wie Sinkabscheider und OxydationsgefäBe, können wesentlich kleiner ausgelegt werden, da ja eine wesentlich geringere Waschflüssigkeitsmenge im Waschkreislauf gefahren wird.Fraction of the previously required pump output. the Washing liquid containers, such as sink separators and oxidation vessels, can be designed to be much smaller because 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 Kalziumsulfitbildung und Kalziumcarbonatbildung). Es entstehen absolut keine Inkrustierungen innerhalb der Wafchapparatur. Verluste durch Verdampfung beim Einsprühen in heiße Rauchgase um 200° C entstehen nichtThe 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 none Incrustations within the washing machine. Losses due to evaporation when spraying into hot Flue gases around 200 ° C do not arise

Die Zitronensäure liegt zur Dosierung in fester Form vor. Das Salz wird in Wasser gelöst der Waschflüssigkeit zugegeben. Durch die Zugabe dieser dreibasischen Zitronensäure wird eine Waschlösung gebiliet, die im alkalischen sowie im sauren Bereich als Pufferlösung wirkt 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. Eine gute Oxydation von Kalziumsulfit zu Kalziumsulfat wirr1; im pH-Wert-Bereich zwischen pH 6 bis pH 63 vorteilhaft erzieltCitric acid is available in solid form for dosing. The salt is dissolved in water and added to the washing liquid. The addition of this tribasic citric acid creates a washing solution that acts as a buffer solution in the alkaline and acidic range. B. pH 5 to pH 7 an extensive corrosion protection for the system parts of the gas scrubbing device. A good oxidation of calcium sulphite to calcium sulphate confused 1 ; advantageously achieved in the pH range between pH 6 to pH 63

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 CaSO*-Rückstand durch Trommelvakuumfilter oder Zentrifugen gewährleistet wird.Another advantage is that, surprisingly, the crystal formation of the gypsum crystals after the oxidation is significantly greater than that of the known washing liquids, so that this results in a much better lowering of the water content in the CaSO * residue to be filtered off is guaranteed by drum vacuum filters or centrifuges.

3535

4040

4545

5050

5555

Claims (2)

Patentansprüche:Patent claims: 1. Verfahren zum Reinigen von Rauchgasen und anderen Abgasen, die Schwefeldioxyd enthalten, bei dem das Gas mit einer im Kreislauf gefahrenen Waschflüssigkeit in Kontakt gebracht wird, der Kalziumkarbonat und/oder Kalziumoxyd und/oder Kalziumhydroxyd zugesetzt werden und deren in Lösung befindliche Kalziumionen beim Waschvorgang das Schwefeldioxyd des Gases binden, und bei dem die gebildeten Verbindungen mittels Luftsauerstoff zu Kalziumsulfat oxidiert werden und aus dem Kreislauf abgeschieden werden, wobei der Waschflüssigkeit als Zusatz Salze und/oder eine Mineral- säure zugegeben werden und der Waschflüssigkeit vor dem Kontakt mit dem Gas zusätzlich eine zur Pufferung dienende Karbonsäure und/oder deren Salz zugegeben wird, nach Patent 25 32 373, dadurch gekennzeichnet, daß die Waschflüs- sigkeit mit einem Additiv, das aus einer mehrbasischen Karbonsäure und Chlorionen besteht, versetzt wird.1. Procedure for cleaning flue gases and other exhaust gases containing sulfur dioxide to which the gas is brought into contact with a circulating scrubbing liquid, to which calcium carbonate and / or calcium oxide and / or calcium hydroxide are added and their calcium ions in solution during the washing process bind the sulfur dioxide of the gas, and in which the compounds formed by means of atmospheric oxygen are oxidized to calcium sulphate and separated from the circuit, with the washing liquid being added with salts and / or a mineral acid are added and the scrubbing liquid before contact with the gas in addition to Carboxylic acid and / or its salt serving as a buffer is added, according to Patent 25 32 373, characterized in that the washing liquid liquid with an additive consisting of a polybasic carboxylic acid and chlorine ions will. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als mehrbasischen Karbonsäure Zitro- nensäure eingesetzt wird.2. The method according to claim 1, characterized in that the polybasic carboxylic acid is nitro Nensäure is used.
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
AU31026/77A AU515100B2 (en) 1976-12-03 1977-11-28 Gas washing process
US05/855,268 US4222993A (en) 1974-09-19 1977-11-28 Removal of noxious contaminants from gas
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
JP14492377A JPS5370981A (en) 1976-12-03 1977-12-02 Method and apparatus for purifying raw gas and sulfur dioxideecontaining waste gas
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
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 DE2654843A1 (en) 1978-06-08
DE2654843C2 true 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)

Family Cites Families (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
JPS5017318B1 (en) * 1970-12-29 1975-06-19

Also Published As

Publication number Publication date
DE2654843A1 (en) 1978-06-08

Similar Documents

Publication Publication Date Title
DE68916104T2 (en) Process for the desulfurization of a gas stream containing sulfur dioxide.
DE2622197C2 (en) Process for cleaning flue gases and other exhaust gases containing sulfur dioxide
DE2502118A1 (en) PROCEDURE FOR REMOVING NITROGEN OXIDES FROM GASES CONTAINING NITROGEN
DE2408332A1 (en) PROCESS FOR THE REMOVAL OF SULFUR DIOXIDE FROM COMBUSTION GASES
DE2304496A1 (en) PROCEDURE FOR SO DEEP 2 REMOVAL
DE2847047A1 (en) PROCESS FOR DESULFURIZATION OF SULFUR-CONTAINING PROCESS GASES
CH616637A5 (en)
EP0324845B1 (en) Process for desulphurating flue gases from power station boiler furnaces
DE2654843C2 (en) Process for cleaning flue gases and other exhaust gases
DE2249874C3 (en) Process for removing sulfur dioxide from combustion exhaust gases
DE2822086C2 (en) Method of making an absorbent
DE2800994C2 (en) Process for shortening the oxidation of CaSO↓3↓ sludge resulting from the SO↓2↓ washing process
DE2726257C2 (en) Process for the desulfurization of exhaust gases containing sulfur oxides
DE3433396C2 (en) Process for the desulfurization of exhaust gas
DE2356139C3 (en) Process for removing sulfur dioxide from combustion exhaust gases
DE3507718C2 (en)
DE2707935C2 (en) Method and device for cleaning flue gases and other exhaust gases containing sulphur dioxide
DE3505488C2 (en) Process for NO↓x↓ separation from flue gases
DE2908322C2 (en) Process for cleaning flue gases and other waste gases containing sulphur dioxide
DE2752901C2 (en)
DE2519489A1 (en) Gas purification to remote sulphur dioxide - with calcium cpds in presence of sulphuric and other acids to prevent deposition of calcium carbonate
DE285617C (en)
DE3308648A1 (en) Scrubbing liquid for scrubbing acidic gases such as SO2, HCl, HF, NOx etc.
DE2915307C2 (en) Process for cleaning flue gases and other exhaust gases
DE2657970A1 (en) Sulphur dioxide removal from gases - by absorbing in soln. contg. a metal halide and hydroxide

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