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DE3531203A1 - Scrubbing water treatment for the simultaneous removal of SO2 and NOx from gases - Google Patents

Scrubbing water treatment for the simultaneous removal of SO2 and NOx from gases

Info

Publication number
DE3531203A1
DE3531203A1 DE19853531203 DE3531203A DE3531203A1 DE 3531203 A1 DE3531203 A1 DE 3531203A1 DE 19853531203 DE19853531203 DE 19853531203 DE 3531203 A DE3531203 A DE 3531203A DE 3531203 A1 DE3531203 A1 DE 3531203A1
Authority
DE
Germany
Prior art keywords
precipitation
scrubbing
water treatment
nox
calcium hydroxide
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.)
Withdrawn
Application number
DE19853531203
Other languages
German (de)
Inventor
Heinz Dipl Ing Hoelter
Heinrich Dipl Ing Igelbuescher
Heinrich Ing Grad Gresch
Heribert Dipl Ing Dewert
Manfred Dr Rer Nat Gross
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
Application filed by Individual filed Critical Individual
Priority to DE19853531203 priority Critical patent/DE3531203A1/en
Priority to EP86902811A priority patent/EP0217945A1/en
Priority to PCT/EP1986/000207 priority patent/WO1986005709A1/en
Publication of DE3531203A1 publication Critical patent/DE3531203A1/en
Withdrawn legal-status Critical Current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
    • B01D53/60—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
    • 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

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

Abstract

In the main application P 3526003.3, the scrubbing water treatment in the simultaneous removal of SO2 and NOx is described, a part-stream of the scrubbing circulation being treated with Ca(OH)2 at pH 12-pH 13, CaSO3 and CaSO4 being partly precipitated and iron being completely precipitated. In addition, the reduction of the Fe III ions and the formation of CaSO4 are described. It has now been found that the precipitation with Ca(OH)2 is performed particularly effectively by employing calcium hydroxide for the precipitation of a part-stream of the scrubbing water circulation and optimal precipitation conditions are achieved by establishing the sulphite concentration in the scrubbing circulation between 5 and 15 g/l and the sulphate concentration between 30 and 80 g/l and improving the gypsum quality by complexing agents. Flue gas and/or CO2 are introduced during the precipitation process. The calcium hydroxide can be added in solid form or as a suspension with fresh water and/or scrubbing liquid to the SO2/NOx purification for precipitation.

Description

In der Patentanmeldung P 3 52 60 033 wird die Waschwasseraufbereitung bei der simultanen SO2- und NO x - Entfernung beschrieben, wobei ein Teilstrom des Waschkreislaufes mit Ca(OH)2 bei pH 12 - pH 13 behandelt wird, wobei CaSO3 und CaSO4 partiell und Eisen total gefällt werden. Desweiteren wird die Reduktion der Fe-III-Ionen und die Bildung von CaSO4 beschrieben.Patent application P 3 52 60 033 describes the washing water treatment in the simultaneous removal of SO 2 and NO x , a partial stream of the washing circuit being treated with Ca (OH) 2 at pH 12 - pH 13, with CaSO 3 and CaSO 4 partial and total iron are felled. Furthermore, the reduction of Fe III ions and the formation of CaSO 4 are described.

Zur Optimierung dieser Prozeßstufen wurde gefunden, daß die Fällung mit Ca(OH)2 besonders effektiv dadurch erfolgt, daß das Ca(OH)2 in fester Form besonders intensiv verrührt wird oder als Suspension mit Frischwasser und/oder Waschwasser des Absorptionskreislaufes zudosiert wird. To optimize these process steps, it was found that the precipitation with Ca (OH) 2 takes place particularly effectively by stirring the Ca (OH) 2 particularly intensively in solid form or by metering it in as a suspension with fresh water and / or wash water from the absorption circuit.

Desweiteren wurde gefunden, daß die Fällung von CaSO3 begrenzt und die Fällung von CaSO4 erhöht werden kann, wenn im Waschkreislauf eine SO3 ---Konzentration von 5-15 g/l und eine SO4 ---Konzentration von 30-80 g/l eingestellt wird. Desweiteren führt eine Zuführung von CO2-haltigem Rauchgas und/oder reinem CO2 zu einer Absenkung des pH-Wertes infolge HCO3 --Bildung und die damit verringerte OH--Konzentration bewirkt eine Verbesserung des Reaktionsablaufes im Sinne einer erhöhten Fällrate insbesondere an CaSO4.Furthermore, it was found that the precipitation of CaSO 3 can be limited and the precipitation of CaSO 4 can be increased if an SO 3 - concentration of 5-15 g / l and an SO 4 - concentration of 30-80 in the washing cycle g / l is set. Furthermore leads a supply of CO 2 -containing flue gas and / or pure CO 2 in a lowering of the pH due to HCO 3 - concentration causes an improvement of the reaction process in the sense of an increased Fällrate particular CaSO - formation, and the thus decreased OH 4th

Auf diese Weise gelingt es, das Ziel dieser Fällstufe - relativ geringe Fällung an CaSO3 nur in dem Maße, wie es für die nachfolgende Fe-III-Reduktion erforderlich ist und relativ hohe Fällung von CaSO4 - technisch und ökonomisch attraktiv zu erreichen, da außerdem infolge des geringeren Anteiles von CaSO3 gegenüber CaSO4 und Fe(OH)3 eine bessere Filtration der Suspension möglich ist.In this way it is possible to achieve the goal of this precipitation stage - relatively low precipitation of CaSO 3 only to the extent that is required for the subsequent Fe III reduction and relatively high precipitation of CaSO 4 - because it is technically and economically attractive better filtration of the suspension is also possible due to the lower proportion of CaSO 3 compared to CaSO 4 and Fe (OH) 3 .

Erfahrungsgemäß enthält das bei der Waschwasserbehandlung gebildete CaSO4 Spuren von Eisenoxid und ggf. anderen Spurenverunreinigungen, so daß der Weißheitsgrad des CaSO4 beeinträchtigt sein kann.Experience has shown that the CaSO 4 formed in the wash water treatment contains traces of iron oxide and possibly other trace impurities, so that the whiteness of the CaSO 4 can be impaired.

Diese Erscheinung tritt besonders dann auf, wenn die erforderlichen Schritte der Waschwasseraufbereitung nicht vorschriftsmäßig durchgeführt werden.This phenomenon occurs especially when the necessary steps of the washing water treatment not carried out in accordance with regulations.

Es wurde nun gefunden, daß ein Überschuß an EDTA im Waschkreislauf dazu führt, daß Eisen oder andere kationische Spurenverunreinigungen komplex gebunden werden und so der Weißheitsgrad des CaSO4 sichergestellt werden kann.It has now been found that an excess of EDTA in the washing cycle leads to the fact that iron or other cationic trace impurities are bound in a complex manner and the whiteness of the CaSO 4 can thus be ensured.

Claims (5)

Anspruch 1
Waschwasseraufbereitung für die simultane SO2- und NOx-Entfernung aus Gasen dadurch gekennzeichnet, daß für die Fällung eines Teilstromes des Waschwasserkreislaufes Kalciumhydroxyd verwendet wird und optimale Fallbedingungen erreicht werden, indem die Sulfitkonzentration im Waschkreislauf zwischen 5 und 15 g/l und die Sulfatkonzentration zwischen 30 und 80 g/l eingestellt wird und die Gipsqualität durch Komplexbildner verbessert wird.Claim 1
Washing water treatment for the simultaneous removal of SO 2 and NO x from gases, characterized in that calcium hydroxide is used for the precipitation of a partial flow of the washing water circuit and optimal conditions are achieved by the sulfite concentration in the washing circuit between 5 and 15 g / l and the sulfate concentration between 30 and 80 g / l is set and the gypsum quality is improved by complexing agents. Anspruch 2
Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß während des Fällvorganges Rauchgas und/oder CO2 eingeleitet wird.Claim 2
A method according to claim 1, characterized in that flue gas and / or CO 2 is introduced during the precipitation process. Anspruch 3
Verfahren nach Anspruch 1 und 2 dadurch gekennzeichnet, daß das Kalciumhydroxyd in fester Form oder als Suspension mit Frischwasser und/oder Waschflüssigkeit der SO2/NO x - Reinigung zur Fällung zudosiert wird.Claim 3
Process according to Claims 1 and 2, characterized in that the calcium hydroxide is added to the SO 2 / NO x cleaning for precipitation in solid form or as a suspension with fresh water and / or washing liquid. Anspruch 4
Verfahren nach Anspruch 1-3 dadurch gekennzeichnet, daß im Waschkreislauf oder im Teilstrom davon, der zur Ca(OH)2-Fällstufe geht, mit einem Überschuß an EDTA oder NTA als für 1 : 1 - molare Fe/Chelat-Bildung erforderlich, versehen wird, um die Gipsqualität zu verbessern.Claim 4
Process according to Claims 1-3, characterized in that in the washing circuit or in the partial stream thereof which goes to the Ca (OH) 2 precipitation stage, it is provided with an excess of EDTA or NTA as required for 1: 1 molar Fe / chelation formation to improve the quality of the plaster. Anspruch 5
Verfahren nach Anspruch 1-4 dadurch gekennzeichnet, daß zusätzlich an anderen geeigneten Stellen des Waschwasseraufbereitungsprozesses EDTA oder NTA im Überschuß zugegeben wird.Claim 5
Process according to Claims 1-4, characterized in that EDTA or NTA is additionally added in excess at other suitable points in the wash water treatment process.
DE19853531203 1985-04-06 1985-08-31 Scrubbing water treatment for the simultaneous removal of SO2 and NOx from gases Withdrawn DE3531203A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE19853531203 DE3531203A1 (en) 1985-08-31 1985-08-31 Scrubbing water treatment for the simultaneous removal of SO2 and NOx from gases
EP86902811A EP0217945A1 (en) 1985-04-06 1986-04-05 Process for the cleansing of fumes
PCT/EP1986/000207 WO1986005709A1 (en) 1985-04-06 1986-04-05 Process for the cleansing of fumes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19853531203 DE3531203A1 (en) 1985-08-31 1985-08-31 Scrubbing water treatment for the simultaneous removal of SO2 and NOx from gases

Publications (1)

Publication Number Publication Date
DE3531203A1 true DE3531203A1 (en) 1987-03-05

Family

ID=6279874

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19853531203 Withdrawn DE3531203A1 (en) 1985-04-06 1985-08-31 Scrubbing water treatment for the simultaneous removal of SO2 and NOx from gases

Country Status (1)

Country Link
DE (1) DE3531203A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3641170A1 (en) * 1986-12-02 1988-06-09 Hoelter Heinz Simultaneous SO2/NOx wet scrubbing process with scrubbing water treatment for purifying combustion exhaust gases
DE4010321A1 (en) * 1990-03-30 1991-10-02 Aquamot Ag METHOD FOR ELIMINATING ACID AND HEAVY METAL IMPURITIES FROM LIQUIDS
EP1129997A3 (en) * 1999-05-17 2002-08-28 Mitsubishi Heavy Industries, Ltd. Flue gas desulphurisation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2460231A1 (en) * 1973-12-27 1975-07-03 Chisso Eng Co Ltd PROCESS FOR THE REMOVAL OF NITROGEN OXIDES FROM INDUSTRIAL EXHAUST GASES AND SUITABLE AQUATIC TREATMENT SOLUTIONS
DE2554584A1 (en) * 1974-12-28 1976-07-01 Chisso Corp METHOD OF REGENERATING AN ABSORBENT SOLUTION THAT HAS BEEN USED TO CLEAN EXHAUST GAS
DE2619145A1 (en) * 1975-05-06 1976-11-25 Fuji Kasui Eng Co Ltd PROCESS FOR SEPARATING NITROGEN OXYDES AND SIMULTANEOUSLY SEPARATING NITROGEN OXYDE AND SULFUR OXYDE FROM EXHAUST GASES

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2460231A1 (en) * 1973-12-27 1975-07-03 Chisso Eng Co Ltd PROCESS FOR THE REMOVAL OF NITROGEN OXIDES FROM INDUSTRIAL EXHAUST GASES AND SUITABLE AQUATIC TREATMENT SOLUTIONS
DE2554584A1 (en) * 1974-12-28 1976-07-01 Chisso Corp METHOD OF REGENERATING AN ABSORBENT SOLUTION THAT HAS BEEN USED TO CLEAN EXHAUST GAS
DE2619145A1 (en) * 1975-05-06 1976-11-25 Fuji Kasui Eng Co Ltd PROCESS FOR SEPARATING NITROGEN OXYDES AND SIMULTANEOUSLY SEPARATING NITROGEN OXYDE AND SULFUR OXYDE FROM EXHAUST GASES

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3641170A1 (en) * 1986-12-02 1988-06-09 Hoelter Heinz Simultaneous SO2/NOx wet scrubbing process with scrubbing water treatment for purifying combustion exhaust gases
DE4010321A1 (en) * 1990-03-30 1991-10-02 Aquamot Ag METHOD FOR ELIMINATING ACID AND HEAVY METAL IMPURITIES FROM LIQUIDS
EP1129997A3 (en) * 1999-05-17 2002-08-28 Mitsubishi Heavy Industries, Ltd. Flue gas desulphurisation

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