DE4321349C2 - Continuous process for the degradation of monochloroethene - Google Patents

Continuous process for the degradation of monochloroethene

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Publication number
DE4321349C2
DE4321349C2 DE4321349A DE4321349A DE4321349C2 DE 4321349 C2 DE4321349 C2 DE 4321349C2 DE 4321349 A DE4321349 A DE 4321349A DE 4321349 A DE4321349 A DE 4321349A DE 4321349 C2 DE4321349 C2 DE 4321349C2
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DE
Germany
Prior art keywords
monochloroethene
degradation
continuous process
bioreactor
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 - Fee Related
Application number
DE4321349A
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German (de)
Other versions
DE4321349A1 (en
Inventor
Hans-Georg Dr Edel
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.)
Ed Zueblin AG
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Ed Zueblin AG
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Publication date
Application filed by Ed Zueblin AG filed Critical Ed Zueblin AG
Priority to DE4321349A priority Critical patent/DE4321349C2/en
Priority to DE4345195A priority patent/DE4345195C2/en
Priority claimed from DE4345195A external-priority patent/DE4345195C2/en
Publication of DE4321349A1 publication Critical patent/DE4321349A1/en
Application granted granted Critical
Publication of DE4321349C2 publication Critical patent/DE4321349C2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/04—Aerobic processes using trickle filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Description

Im zunehmenden Maße werden alte Industriestandorte saniert, wobei auch das Grundwasser von Schadstoffen aus vormaliger Produktion oder Lagerung befreit werden muß. Grundwässer, deren Hauptverschmutzung aus chlorierten Kohlenwasserstoffen (CKW) besteht, können durch die verschiedenen, aus der Literatur bekannten Stripverfahren (z. B. GM 90 05 565, EP 0 242 665) gereinigt werden. Dem Stripverfahren ist dabei gewöhnlich eine Aktivkohleadsorption nachgeschaltet, die die Schadstoffe aus dem Stripgas, im allgemeinen der Stripluft, entfernen soll. Diese Verfahrenkombination eignet sich sehr gut für das Entfernen von Tri- und Tetrachlorethen aus dem Grundwasser, da die Aktivkohle eine hohe Absoprtionskapazität für diese Verbindungen besitzt.Old industrial sites are increasingly being renovated, whereby also the groundwater of pollutants from previous production or Storage must be exempt. Groundwater, its main pollution consists of chlorinated hydrocarbons (CHC), can by the various strip processes known from the literature (e.g. GM 90 05 565, EP 0 242 665). The strip process is included usually an activated carbon adsorption downstream, which the pollutants remove from the strip gas, generally the strip air. This Process combination is very suitable for the removal of tri and Tetrachlorethylene from the groundwater, because the activated carbon has a high Has absorption capacity for these compounds.

Bekannt ist aber auch, daß die Aufnahmekapazität der Aktivkohle für Stoffe wie Monochlorethen (Vinylchlorid), 1,1-Dichlorethen, cis- und trans- 1,2-Dichlorethen sowie Dichlormethan aufgrund deren physikalischer Eigenschaften (vor allem Polarität, niedriges Molekulargewicht) bei Raumtemperatur nur gering ist. Darüberhinaus ist aufgrund der chemisch­ physikalischen und toxischen Eigenschaften dieser Stoffe eine Regeneration von beladener Aktivkohle schwierig bzw. nicht möglich, da z. B Vinylchlorid cancerogen wirkt und in höherer Konzentration polymerisiert.But it is also known that the absorption capacity of the activated carbon for Substances such as monochloroethene (vinyl chloride), 1,1-dichloroethene, cis- and trans- 1,2-dichloroethene and dichloromethane due to their physical Properties (especially polarity, low molecular weight) Room temperature is only low. Furthermore, due to the chemical physical and toxic properties of these substances Regeneration of loaded activated carbon difficult or not possible because  e.g. B Vinyl chloride is carcinogenic and in higher concentrations polymerized.

Aus der Literatur (GWF-Wasser/Abwasser 129, 61-69, 1988 oder VDI- Berichte, 745, 911-926, 1989) ist bekannt, daß sich Monochlorethen mikrobiologisch bis zu CO2 und HCl abbauen läßt. Dabei erfolgt der Abbau der niedrig chlorierten CKW unter aeroben Bedingungen besser als unter anaeroben. Die Oxidation der Ethenderivate läuft über die Bildung eines Epoxids, das unter HCl-Abgabe spontan in Essigsäure zerfällt. Dieser Stoffwechselweg wird durch Oxygenasen katalysiert. Die Bakterien, die zu dieser Abbauleistung fähig sind, gehören den sogenannten methylotrophen Mikroorganismen an. Außerdem wurde nachgewiesen, daß die Oxidation der CKWs durch Nitrifikanten mit Hilfe des Enzyms Ammoniummonooxygenase erfolgen kann. Wichtig für die Abbauleistung im Bioreaktor ist, daß die methylotrophen Bakterien mit Methan, Erdgas und anderen C1- oder C2-Kohlenstoffverbindungen sowie mit NH4 + (Ammonium)-Verbindungen angereichert werden können und diese auch zum Abbau von halogenierten Kohlenwasserstoffen befähigt sind, ohne daß eine Anpassung an CKWs notwendig ist.From the literature (GWF water / waste water 129, 61-69, 1988 or VDI reports, 745, 911-926, 1989) it is known that monochloroethene can be microbiologically broken down to CO 2 and HCl. The degradation of the low chlorinated CHC is better under aerobic conditions than under anaerobic. The oxidation of ethene derivatives takes place through the formation of an epoxide, which spontaneously decomposes into acetic acid with the release of HCl. This pathway is catalyzed by oxygenases. The bacteria that are capable of this degradation belong to the so-called methylotrophic microorganisms. It has also been demonstrated that nitricants can oxidize the CHCs with the aid of the enzyme ammonium monooxygenase. It is important for the degradation performance in the bioreactor that the methylotrophic bacteria can be enriched with methane, natural gas and other C 1 or C 2 carbon compounds as well as with NH 4 + (ammonium) compounds and that they are also capable of degrading halogenated hydrocarbons, without having to adapt to CHCs.

Die Erfindung betrifft ein Verfahren, das es ermöglicht, auch die leichtflüchtigen CKW aus der Strippung oder allgemein aus jeder Abluft zu entfernen und die Schadstoffe im Anschluß sofort abzubauen. Gerade die Tatsache, daß Substanzen wie Ethanol und Ether, C2- Kohlenstoffverbindungen und NH4 +-Verbindungen, als Cosubstrat für methylotrophe Bakterien dienen können, führt zu der erfindungsgemäßen Idee, Monochlorethen mit Ethanol oder Ether auszuwaschen und anschließend dieses CKW mikrobiologisch abzubauen. The invention relates to a method which also makes it possible to remove the volatile CHCs from the stripping or in general from any exhaust air and to immediately dismantle the pollutants. The very fact that substances such as ethanol and ether, C 2 carbon compounds and NH 4 + compounds can serve as a cosubstrate for methylotrophic bacteria leads to the idea according to the invention of washing out monochloroethene with ethanol or ether and then degrading this CHC microbiologically.

Dazu wird ein Wäscher mit einer geeigneten Waschflüssigkeit, die gleichzeitig als Anzuchtsubstrat für die Mikroorganismen dienen kann, verwendet. Die Aufbereitung der Waschflüssigkeit erfolgt über einen Bio- Reaktor, dessen Population an Mikroorganismen die Schadstoffe in der Flüssigkeit abbaut. Abgebaute und zersetzte Waschflüssigkeit muß ersetzt werden.For this purpose, a washer with a suitable washing liquid, the can also serve as a growth substrate for the microorganisms, used. The washing liquid is processed using a bio Reactor, whose population of microorganisms contains the pollutants in the Degrades liquid. Degraded and decomposed washing liquid must be replaced.

Fig. 1 zeigt den schematischen Aufbau einer zweistufigen Reinigungsanlage für Monochlorethen-haltige Abluft. Fig. 1 shows the schematic structure of a two-stage purification system for exhaust air containing monochloroethene.

Die monochlorethenhaltige Abluft aus der Strippung oder Bodenluft- Absaugung wird über die Abluftzuführung (3) in den Wäscher (1) geleitet. Im Wäscher (1) wird die Waschflüssigkeit, bei der es sich um eine wässrige Lösung von Ethanol oder Ether handelt, über die Ausströmöffnung (7) und den Rieselkörper (6), versprüht. Luft und Waschlösung werden im Gegenstrom geführt, so daß es zu einem innigen Austausch von wässrigem und gasförmigen Medium kommt. Auf diese Weise geht die Verunreinigung von der Abluft auf die Waschflüssigkeit über. Die gereinigte Abluft verläßt über die Öffnung (4) den Wäscher. Die jetzt mit Monochlorethen beladene wässerige Ethanol- oder Etherlösung sammelt sich im Bereich (5) des Wäschers und wird von der Schmutzwasserpumpe (8) in den Bioreaktor (2) gepumpt. Auf dem Trägermaterial (10) wurden bereits vor dem Prozeßbeginn mit Hilfe der wässrigen Ethanollösung und einer gepufferten Nährstofflösung und durch ein eventuelles Vorwärmen der Flüssigkeiten methylotrophe Bakterien angezüchtet. Über die Verrieselung (12) wird am Bioreaktor das mit Monochlorethen beladene Waschwasser eingebracht. Die Mikroorganismen bauen das Monochlorethen über Essigsäure zu CO2 und HCl ab. Die entstehenden Säuren müssen abgepuffert werden. The monochloroethene-containing exhaust air from the stripping or soil air extraction is passed through the exhaust air supply ( 3 ) into the scrubber ( 1 ). In the washer ( 1 ), the washing liquid, which is an aqueous solution of ethanol or ether, is sprayed through the outflow opening ( 7 ) and the trickle ( 6 ). Air and washing solution are passed in countercurrent, so that there is an intimate exchange of aqueous and gaseous medium. In this way, the contamination passes from the exhaust air to the washing liquid. The cleaned exhaust air leaves the scrubber through the opening ( 4 ). The aqueous ethanol or ether solution now loaded with monochloroethene collects in the area ( 5 ) of the scrubber and is pumped into the bioreactor ( 2 ) by the dirty water pump ( 8 ). Before the start of the process, methylotrophic bacteria were grown on the carrier material ( 10 ) with the aid of the aqueous ethanol solution and a buffered nutrient solution and by preheating the liquids. The washing water loaded with monochloroethene is introduced into the bioreactor via the sprinkler ( 12 ). The microorganisms break down the monochloroethene via acetic acid to CO 2 and HCl. The resulting acids must be buffered.

Hierzu muß die Pufferlösung von Zeit zu Zeit ebenso wie die Nährlösung über die Zuleitung (11) ergänzt werden. Ebenfalls über die Zuleitung (11) erfolgt die Belüftung des Reaktors. Die gereinigte Waschlösung wird dann über die Umwälzpumpe (9) wieder dem Wäscher zugeführt, wobei verbrauchte Waschlösung wieder ersetzt werden muß.For this purpose, the buffer solution as well as the nutrient solution must be supplemented from time to time via the feed line ( 11 ). The reactor is also vented via the feed line ( 11 ). The cleaned washing solution is then fed back to the scrubber via the circulation pump ( 9 ), the used washing solution having to be replaced again.

Claims (5)

1. Kontinuierliches Verfahren zum Abbau von Monochlorethen in einem Gas durch den Einsatz einer geeigneten Waschlösung und deren anschließenden Behandlung durch methylotrophe Bakterien, dadurch gekennzeichnet, daß man die Waschlösung im Kreislauf führt, wobei diese in einem Wäscher (1) mit Schadstoff beladen wird und in einem Bioreaktor (2) der Schadstoffabbau stattfindet.1. Continuous process for the degradation of monochloroethene in a gas by using a suitable washing solution and its subsequent treatment by methylotrophic bacteria, characterized in that the washing solution is circulated, this being loaded with pollutant in a washer ( 1 ) and in a bioreactor ( 2 ) the pollutant degradation takes place. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man einen Gegenstromwäscher einsetzt.2. The method according to claim 1, characterized in that a countercurrent washer is used. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man dem Bioreaktor kontinuierlich Nährstoffe, Puffersubstanzen und Gase zuführt (11).3. The method according to claim 1, characterized in that the bioreactor is continuously fed with nutrients, buffer substances and gases ( 11 ). 4. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß man Ethanol und Ether als Waschflüssigkeit einsetzt.4. The method according to claim 1 to 3, characterized in that ethanol and ether as Wash liquid is used. 5. Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß man eine Waschflüssigkeit einsetzt, die zugleich als Anzuchtsubstrat für die abbauenden Bakterien dient.5. The method according to claim 1 to 4, characterized in that a washing liquid is used which also serves as a growing substrate for the degrading bacteria.
DE4321349A 1993-06-26 1993-06-26 Continuous process for the degradation of monochloroethene Expired - Fee Related DE4321349C2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE4321349A DE4321349C2 (en) 1993-06-26 1993-06-26 Continuous process for the degradation of monochloroethene
DE4345195A DE4345195C2 (en) 1993-06-26 1993-06-26 Process for the elimination of chlorine hydrocarbons which are difficult to absorb

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4321349A DE4321349C2 (en) 1993-06-26 1993-06-26 Continuous process for the degradation of monochloroethene
DE4345195A DE4345195C2 (en) 1993-06-26 1993-06-26 Process for the elimination of chlorine hydrocarbons which are difficult to absorb

Publications (2)

Publication Number Publication Date
DE4321349A1 DE4321349A1 (en) 1995-01-05
DE4321349C2 true DE4321349C2 (en) 1999-03-18

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DE4321349A Expired - Fee Related DE4321349C2 (en) 1993-06-26 1993-06-26 Continuous process for the degradation of monochloroethene

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4009109A1 (en) * 1990-03-21 1991-09-26 Fraunhofer Ges Forschung METHOD FOR THE MICROBIOLOGICAL CLEANING OF EXHAUST AIR FLOWS CONTAMINATED WITH HALOGENATED ETHENES AND / OR WITH HALOGENATED BUTADIENES
DE4104756A1 (en) * 1991-02-15 1992-08-20 Envicon Eng Gmbh Purificn. of water contg. chlorinated or halogenated hydrocarbon(s) - comprises extn. of hydrocarbon(s) by bubbling air through water and air is then purified using a biological treatment procedure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4009109A1 (en) * 1990-03-21 1991-09-26 Fraunhofer Ges Forschung METHOD FOR THE MICROBIOLOGICAL CLEANING OF EXHAUST AIR FLOWS CONTAMINATED WITH HALOGENATED ETHENES AND / OR WITH HALOGENATED BUTADIENES
DE4104756A1 (en) * 1991-02-15 1992-08-20 Envicon Eng Gmbh Purificn. of water contg. chlorinated or halogenated hydrocarbon(s) - comprises extn. of hydrocarbon(s) by bubbling air through water and air is then purified using a biological treatment procedure

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Publication number Publication date
DE4321349A1 (en) 1995-01-05

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