DE4345195A1 - Process for eliminating chlorinated hydrocarbons which are difficult to absorb - Google Patents

Process for eliminating chlorinated hydrocarbons which are difficult to absorb

Info

Publication number
DE4345195A1
DE4345195A1 DE4345195A DE4345195A DE4345195A1 DE 4345195 A1 DE4345195 A1 DE 4345195A1 DE 4345195 A DE4345195 A DE 4345195A DE 4345195 A DE4345195 A DE 4345195A DE 4345195 A1 DE4345195 A1 DE 4345195A1
Authority
DE
Germany
Prior art keywords
difficult
absorb
air
chlorinated hydrocarbons
supply
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
DE4345195A
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German (de)
Other versions
DE4345195C2 (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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Filing date
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 DE4321349A external-priority patent/DE4321349C2/en
Publication of DE4345195A1 publication Critical patent/DE4345195A1/en
Application granted granted Critical
Publication of DE4345195C2 publication Critical patent/DE4345195C2/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
    • B01D53/85—Biological processes with gas-solid contact
    • 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
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor
    • C12N1/205—Bacterial isolates
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
    • C12P1/04—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes by using bacteria
    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/01—Bacteria or Actinomycetales ; using bacteria or Actinomycetales
    • 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

Abstract

Our invention relates to a process for the continuous degradation of chlorinated hydrocarbons using a biofilter which is colonised by methylotrophic bacteria.

Description

Im zunehmenden Maße werden alte Industriestandorte saniert, wobei auch das Grundwasser von Schadstoffen aus vormaliger Produktion oder Lagerung befreit werden muß. Grundwässer, deren Hauptver­ schmutzung aus chlorierten Kohlenwasserstoffen (CKW) besteht, können durch die verschiedenen, aus der Literatur bekannten Stripver­ fahren (z. B. GM 90 05 565, EP 0 242 665) gereinigt werden. Dem Stripverfahren ist dabei gewöhnlich eine Aktivkohleadsorption nach­ geschaltet, die die Schadstoffe aus dem Stripgas, im allgemeinen der Stripluft, entfernen soll. Diese Verfahrenskombination eignet sich sehr gut für das Entfernen von Tri- und Tetrachlorethen aus dem Grund­ wasser, da die Aktivkohle eine hohe Absorptionskapazität für diese Verbindungen besitzt.Old industrial sites are increasingly being renovated, whereby also the groundwater from pollutants from previous production or storage must be exempted. Groundwater, the main ver pollution consists of chlorinated hydrocarbons (CHC), can through the various stripver known from the literature driving (e.g. GM 90 05 565, EP 0 242 665). The The strip process is usually an activated carbon adsorption switched that the pollutants from the strip gas, generally the Strip air to remove. This combination of processes is very suitable good for removing tri and tetrachlorethylene on the ground water because the activated carbon has a high absorption capacity for this Has connections.

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 physikali­ scher Eigenschaften (vor allem Polarität, niedriges Molekulargewicht) bei Raumtemperatur nur gering ist. Darüber hinaus 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 Konzen­ tration 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 physi properties (especially polarity, low molecular weight) is only slight at room temperature. In addition, due to the chemical-physical and toxic properties of these substances regeneration of loaded activated carbon is difficult or not  possible because z. B. Vinyl chloride is carcinogenic and in higher concentrations tration polymerized.

Aus der Literatur (GWF-Wasser/Abwasser 129, 61-69, 1988 oder VDI-Berichte, 745, 911-926, 1989) ist bekannt, daß sich Monochlo­ rethen mikrobiologisch bis zu CO₂ und HCl abbauen läßt. Dabei er­ folgt der Abbau der niedrig chlorierten CKW unter aeroben Bedingun­ gen besser als unter anaeroben. Die Oxidation der Ethenderivate läuft über die Bildung eines Epoxids, das unter HCl-Abgabe spontan in Es­ sigsäure zerfällt. Dieser Stoffwechselweg wird durch Oxygenasen ka­ talysiert. Die Bakterien, die zu dieser Abbauleistung fähig sind, gehö­ ren 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 methylotro­ phen Bakterien mit Methan, Erdgas und anderen C₁- oder C₂-Koh­ lenstoffverbindungen sowie mit NH₄⁺ (Ammonium)-Verbindungen angereichert werden können und diese auch zum Abbau von haloge­ nierten Kohlenwasserstoffen befähigt sind, ohne daß eine Anpassung an CKWs notwendig ist.From the literature (GWF-Wasser / Abwasser 129, 61-69, 1988 or VDI reports, 745, 911-926, 1989) it is known that Monochlo rethen can be microbiologically broken down to CO₂ and HCl. Doing it follows the degradation of the low chlorinated CHCs under aerobic conditions better than under anaerobic. The oxidation of ethene derivatives is ongoing on the formation of an epoxide that spontaneously escapes with release of HCl acetic acid disintegrates. This metabolic pathway is caused by oxygenases talysed. The bacteria that are capable of this degradation performance belong ren the so-called methylotrophic microorganisms. also it was demonstrated that the oxidation of the CHCs by nitrifying bacteria can be done with the help of the enzyme ammonium monooxygenase. It is important for the degradation performance in the bioreactor that the methylotro phen bacteria with methane, natural gas and other C₁- or C₂-Koh lenstoffverbindungen as well as with NH₄⁺ (ammonium) compounds can be enriched and this also for the degradation of haloge nated hydrocarbons are capable without adjustment on CHCs is necessary.

Die Erfindung betrifft ein Verfahren, das es ermöglicht, auch die leichtflüchtigen CKW aus der Strippung oder allgemein aus jeder Ab­ luft 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 erfindungs­ gemäßen Idee, Monochlorethen mit Ethanol oder Ether auszuwaschen und anschließend dieses CKW mikrobiologisch abzubauen. The invention relates to a method that also makes it possible volatile CHC from stripping or generally from any ab remove air and then immediately dismantle the pollutants. The very fact that substances such as ethanol and ether, C₂- Carbon compounds and NH₄⁺ compounds, as a cosubstrate can serve for methylotrophic bacteria leads to the invention modern idea to wash out monochloroethene with ethanol or ether and then break down this CHC microbiologically.  

Dazu dient eine biologische Abluftreinigung zum Abbau von schwer­ absorbierbaren CKWs. Dabei wird anstatt eines Wäschers ein Biofil­ ter eingesetzt, dessen Trägermaterial mit den oben genannten Bakte­ rien besiedelt wird (Nitrifikanten oder C₂-Abbauer). Als Substrat für diese Organismen dient Ethanol oder eine andere C₂-Verbindung, die der Zuluft zugemischt werden. Nach erfolgter ausreichender Besied­ lung des Trägermaterials wird auf die zu reinigende Rohluft mit dem schwer absorbierbaren CKW umgestellt. Die zu reinigende Stripluft oder Abluft wird in den Biofilter eingeleitet. Die Schadstoffe können anschließend sofort von den methylotrophen Bakterien, die im Trä­ germedium angesiedelt sind, abgebaut werden.Biological exhaust air purification is used to break down heavy absorbable CHCs. Instead of a scrubber, it becomes a biofil ter used, the carrier material with the above-mentioned bacteria rien is populated (nitrificants or C₂ miners). As a substrate for these organisms serve ethanol or another C₂ compound that be added to the supply air. After sufficient colonization The carrier material is applied to the untreated air to be cleaned with the CHC that is difficult to absorb. The strip air to be cleaned or exhaust air is introduced into the biofilter. The pollutants can then immediately from the methylotrophic bacteria in Trä germ medium are located, dismantled.

Claims (5)

1. Kontinuierliches Verfahren zum Abbau von CKW in einem Gas durch den Einsatz eines Biofilters, gekennzeichnet durch
  • a) die Ansiedlung von methylotrophen Bakterien auf dessen Trägerma­ terial mit Hilfe der Zuführung von ethanolhaltiger oder anderer C₂- Kohlenstoffverbindung-haltiger Zuluft
  • b) anschließende Reinigung von schadstoffbefrachteter Luft durch die methylotrophen Bakterien.
1. Continuous process for the decomposition of CHC in a gas by using a biofilter, characterized by
  • a) the settlement of methylotrophic bacteria on its carrier material with the aid of the supply of ethanol-containing or other C₂-carbon compound-containing supply air
  • b) subsequent cleaning of polluted air by the methylotrophic bacteria.
2. Verfahren nach Anspruch 1, gekennzeichnet durch die Behandlung von Abgas oder Abluft, die mit an Aktivkohle schwer absorbierbaren CKWs belastet ist.2. The method according to claim 1, characterized by the treatment of exhaust gas or exhaust air that are difficult to absorb on activated carbon CHCs is charged. 3. Verfahren nach Anspruch 1, gekennzeichnet durch die Behandlung von Abgas, das mit Monochlorethen belastet ist.3. The method according to claim 1, characterized by the treatment of exhaust gas contaminated with monochloroethene. 4. Verfahren nach Anspruch 1, gekennzeichnet durch eine kontinuierli­ che Zufuhr von Nährstoffen, Puffersubstanzen und Gasen in den Bio­ filter.4. The method according to claim 1, characterized by a continuously The supply of nutrients, buffer substances and gases in the bio filter. 5. Verfahren nach Anspruch 1, gekennzeichnet durch den Einsatz von C₁- oder C₂-Kohlenstoffverbindungen haltiger Zuluft zur Besiedlung des Biofilters mit methylotrophen Bakterien.5. The method according to claim 1, characterized by the use of C₁ or C₂ carbon compounds containing supply air for settlement of the biofilter with methylotrophic bacteria.
DE4345195A 1993-06-26 1993-06-26 Process for the elimination of chlorine hydrocarbons which are difficult to absorb Expired - Fee Related DE4345195C2 (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
DE4345195A1 true DE4345195A1 (en) 1995-01-12
DE4345195C2 DE4345195C2 (en) 1996-08-22

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DE4345195A Expired - Fee Related DE4345195C2 (en) 1993-06-26 1993-06-26 Process for the elimination of chlorine hydrocarbons which are difficult to absorb

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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

Also Published As

Publication number Publication date
DE4345195C2 (en) 1996-08-22

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