WO2011015556A1 - Process for degrading organic pollutants in industrial wastewater and associated system - Google Patents

Process for degrading organic pollutants in industrial wastewater and associated system Download PDF

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Publication number
WO2011015556A1
WO2011015556A1 PCT/EP2010/061216 EP2010061216W WO2011015556A1 WO 2011015556 A1 WO2011015556 A1 WO 2011015556A1 EP 2010061216 W EP2010061216 W EP 2010061216W WO 2011015556 A1 WO2011015556 A1 WO 2011015556A1
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Prior art keywords
pollutants
concentration
present
cod
plant
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PCT/EP2010/061216
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German (de)
French (fr)
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WO2011015556A9 (en
Inventor
Alexander Hahn
Antje Knoppek
Wolfgang Schilling
Jochen Straub
Manfred Waidhas
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Siemens Aktiengesellschaft
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Publication of WO2011015556A1 publication Critical patent/WO2011015556A1/en
Publication of WO2011015556A9 publication Critical patent/WO2011015556A9/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C02F1/385—Treatment of water, waste water, or sewage by centrifugal separation by centrifuging suspensions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]

Definitions

  • the invention relates to a process for the degradation of organic pollutants in industrial wastewater.
  • the invention also relates to the associated system for carrying out the method.
  • Industrial wastewater is known to have a high content of organic pollutants. It is known to eliminate or at least reduce such pollutants by electrochemical oxidation.
  • the COD value can be lowered.
  • This process can be carried out in particular electrochemically, but also by adding chemicals or by introducing ozone gas.
  • the object is achieved according to the invention by the measures of patent claim 1.
  • An associated device / system is specified in claim 11. Further developments of the method and the associated system are the subject of the dependent claims.
  • a method is specified, which increases the energy efficiency of the electrochemical COD degradation, especially by a prior concentration of the liquid stream to be treated.
  • the different methodological approaches known per se can be used.
  • the concentration can be effected by membrane processes - such as ultrafiltration (UF), such as nanofiltration (NF), such as reverse osmosis (RO), and / or electrodialysis (ED).
  • UF ultrafiltration
  • NF nanofiltration
  • RO reverse osmosis
  • ED electrodialysis
  • This can be used to define procedures that significantly increase the energy efficiency of an electrochemical cell, especially for COD removal.
  • the conductivity of the medium increases in a known manner, as a result of which the cell voltage is reduced.
  • the efficiency of the process can be further increased.
  • there is the possibility of optimizing the cell structure For example, larger electrode distances simplify the mixing and it can thus be easier to clean the system. Even so, the effectiveness of the system according to the invention is increased.
  • Figure 1 is a scheme for a concentration of the organic
  • FIG. 2 shows the energy expenditure in the procedure according to FIG. 1 on the basis of a graphical representation.
  • the contaminated liquid is usually an industrial water, in particular contaminated with organic substances.
  • the sum of the impurities is defined by the so-called COD degradation.
  • COD degradation In practice, there are clear legal requirements for the value of a permissible COD contamination.
  • the COD value can be reduced electrochemically in practice, for example. This is usually done by concentrating the organically contaminated water.
  • the concentration of the organically contaminated water can be realized, for example, by membrane processes (UF, NF, RO, ED).
  • UF, NF, RO, ED membrane processes
  • the so-called concentration after the concentration must be treated electrochemically, wherein a so-called permeate is obtained as a by-product.
  • the permeate referred to in the relevant technology is the fluid freed by the filtration of, for example, bacterial hardening agents or heavy metals.
  • the retained substances during filtration are referred to as Retentad.
  • a concentrate with a COD value> 4000 mg / l is obtained.
  • This concentrate is subjected to electrolysis, the process being carried out in a specific manner, as described, for example, in applications of Applicant is described.
  • the permeate remaining at the individual concentration steps 1 and 2 can in turn be returned to the starting water.
  • the abscissa represents the COD value in mg / l and the percent power consumption is plotted on the cathode. It follows from this illustration, therefore, the power consumption as a function of the starting COD, with discontinuous, so batch experiments were performed.
  • the energy expenditure in the electrochemical treatment of the starting COD of the wastewater is shown in FIG. This results in the advantage of the method according to the invention.
  • the energy consumption is much higher with low COD initial concentrations than with waste water with high COD load.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Industrial wastewaters in particular frequently contain organic components as pollutants. Such organic pollutants are known to be able to be removed by employing electrochemical processes, for which purpose oxygen is required. A chemical oxygen demand (COD value) is defined for industrial practice, which value must be met by industry. According to the invention the organic pollutants are first concentrated (1, 2) and the liquid containing the concentrated pollutants is then subjected to an electrolysis (3).

Description

Beschreibung description
Verfahren zum Abbau von organischen Schadstoffen in industriellem Abwasser und zugehörige Anlage Process for the decomposition of organic pollutants in industrial waste water and associated plant
Die Erfindung bezieht sich auf ein Verfahren zum Abbau von organischen Schadstoffen in industriellem Abwasser. Daneben bezieht sich die Erfindung auch auf die zugehörige Anlage zur Durchführung des Verfahrens. The invention relates to a process for the degradation of organic pollutants in industrial wastewater. In addition, the invention also relates to the associated system for carrying out the method.
Industrielle Abwässer haben bekanntermaßen einen hohen Anteil an organischen Schadstoffen. Bekannt ist es, derartige Schadstoffe durch elektrochemische Oxidation zu beseitigen oder zumindest zu verringern. Industrial wastewater is known to have a high content of organic pollutants. It is known to eliminate or at least reduce such pollutants by electrochemical oxidation.
Vom Stand der Technik ist der oxidative Abbau von sauerstoffzehrenden organischen Verbindungen aus Industrieabwässern bekannt. Die Summe dieser organischen Verbindungen wird im so genannten CSB-Wert (CSB = Chemischer-S_auerstoff-Bedarf) er- fasst. Für diesen Summenparameter (CBS) existiert für die Industrie ein Einleitegrenzwert. The prior art discloses the oxidative degradation of oxygen-depleting organic compounds from industrial wastewater. The sum of these organic compounds is recorded in the so-called COD value (COD = chemical oxygen demand). For this sum parameter (CBS) there is an introduction limit value for the industry.
Durch Oxidation der organischen Schadstoffe kann der CSB-Wert gesenkt werden. Dieser Vorgang kann insbesondere elektroche- misch, aber auch durch Chemikalienzugabe oder durch Einleitung von Ozongas erfolgen. By oxidation of organic pollutants, the COD value can be lowered. This process can be carried out in particular electrochemically, but also by adding chemicals or by introducing ozone gas.
Beim elektrochemischen CBS-Abbau erfolgt die Oxidation der organischen Schadstoffe über OH-Radikale, die an der Anode generiert werden. Dieses Verfahren wird beispielsweise in den Patentdokumenten DE 10 2007 041 828 Al, In electrochemical CBS degradation, the oxidation of organic pollutants occurs via OH radicals generated at the anode. This method is described, for example, in the patent documents DE 10 2007 041 828 A1,
DE 10 2006 034 895 Al, DE 10 2004 023 161 Al, DE 10 2006 034 895 A1, DE 10 2004 023 161 A1,
WO 1991 018 837 Al und WO 2005 028 372 A2 beschrieben. Wie aus dem Stand der Technik ersichtlich ist, hängt die Effizienz des elektrochemischen CSB-Abbaus maßgeblich von der Stromausbeute und von der Zellspannung des Oxidationsvorgan- ges ab. Diese sind wiederum von vielen Faktoren abhängig, beispielsweise der angewandten Stromdichte, dem Elektrodenmaterial, dem Diffusionsweg zur Elektrodenoberfläche und der elektrischen Leitfähigkeit. Natürlich spielt auch der Abwasserinhalt, d.h. die Verunreinigung mit den Abwasserinhalts- Stoffen, in besonderer Weise eine Rolle. WO 1991 018 837 A1 and WO 2005 028 372 A2. As can be seen from the prior art, the efficiency of the electrochemical COD degradation depends largely on the current efficiency and on the cell voltage of the oxidation process. These in turn depend on many factors, for example, the applied current density, the electrode material, the diffusion path to the electrode surface and the electrical conductivity. Of course, the wastewater content, ie the contamination with the Abwasserinhalts- substances, plays a special role.
Für die elektrochemische CSB-Reduzierung sind unterschiedlichste Zellgeometrien und Elektrodenanordnungen bekannt. Diese Reaktoren können sowohl im Batch-Betrieb, d.h. diskon- tinuierlich, aber auch kontinuierlich betrieben werden. Des Weiteren kann dabei mit fester Anode bzw. Kathode oder aber mit wechselnd polarisierten Elektroden gearbeitet werden. Zum apparativen Aufbau sind den Druckschriften DE 36 400 20 Cl, US 3,923,630 A, DE 10 2004 023 161 Al und der For the electrochemical COD reduction, a wide variety of cell geometries and electrode arrangements are known. These reactors can be run in batch mode, i. be operated continuously, but also continuously. Furthermore, it is possible to work with a fixed anode or cathode or with alternating polarized electrodes. For the apparatus construction are the documents DE 36 400 20 Cl, US 3,923,630 A, DE 10 2004 023 161 Al and the
DE 10 2006 046 808 Al Einzelheiten zu entnehmen. DE 10 2006 046 808 A1 for details.
Ausgehend von obigen Ausführungen und insbesondere dem dort angegebenen Stand der Technik ist es Aufgabe der Erfindung, eine Steigerung der Energieeffizienz beim Abbau der organi- sehen Schadstoffe herbeizuführen. Dazu soll sowohl das Verfahren verbessert werden als auch zugehörige Vorrichtungen bzw. Anlagen geschaffen werden. Based on the above statements and in particular the state of the art given there, it is an object of the invention to bring about an increase in energy efficiency in the degradation of the organic pollutants. For this purpose, both the method should be improved as well as associated devices or systems are created.
Die Aufgabe ist erfindungsgemäß durch die Maßnahmen des Pa- tentanspruches 1 gelöst. Eine zugehörige Vorrichtung/Anlage ist im Patentanspruch 11 angegeben. Weiterbildungen des Verfahrens bzw. der zugehörigen Anlage sind Gegenstand der Unteransprüche . Mit der Erfindung ist ein Verfahren angegeben, welches die Energieeffizienz des elektrochemischen CSB-Abbaus speziell durch eine vorherige Aufkonzentration des zu behandelnden Flüssigkeitsstromes steigert. Dabei können die an sich bekannten unterschiedlichen methodischen Ansätze verwendet wer- den. Beispielsweise kann die Aufkonzentration durch Membranprozesse - wie Ultrafiltration (UF) , wie Nanofiltration (NF) , wie Reverse Osmose (RO) , und/oder Elektrodialyse (ED) erfolgen. Insbesondere können derartige unterschiedliche methodi- sehe Ansätze miteinander kombiniert werden. Damit lassen sich Verfahren definieren, durch welche die Energieeffizienz einer elektrochemischen Zelle speziell für den CSB-Abbau deutlich steigern lässt. Da der CSB-Abbau durch Oxidation an der Ano- denoberflache geschieht, muss im Rahmen der Erfindung ein effektiver Stoffumsatz gewährleistet sein, so dass sich immer genügend organischer CSB im Bereich der Elektrode befindet. Dies erfolgt erfindungsgemäß durch die vorgeschaltete Aufkonzentration, wobei mit der vorgeschalteten Aufkonzentrati- onsstufe des zu behandelnden Flüssigkeitsstromes die mittleren Diffusionswege zur Elektrode reduziert werden. Dies bedeutet, dass bei höherer CSB-Konzentration statistisch deutlich mehr organische Moleküle auf die Elektrode treffen und somit ein erheblich gesteigerter CSB-Abbau stattfindet. The object is achieved according to the invention by the measures of patent claim 1. An associated device / system is specified in claim 11. Further developments of the method and the associated system are the subject of the dependent claims. With the invention, a method is specified, which increases the energy efficiency of the electrochemical COD degradation, especially by a prior concentration of the liquid stream to be treated. The different methodological approaches known per se can be used. For example, the concentration can be effected by membrane processes - such as ultrafiltration (UF), such as nanofiltration (NF), such as reverse osmosis (RO), and / or electrodialysis (ED). In particular, such different methodological see approaches combined with each other. This can be used to define procedures that significantly increase the energy efficiency of an electrochemical cell, especially for COD removal. Since the COD degradation by oxidation takes place at the anode surface, an effective material turnover must be ensured in the context of the invention, so that there is always enough organic COD in the region of the electrode. This is done according to the invention by the upstream concentration, wherein with the upstream Aufkonzentrati- onsstufe the liquid stream to be treated, the average diffusion paths are reduced to the electrode. This means that at higher COD concentration statistically significantly more organic molecules hit the electrode and thus a significantly increased COD degradation takes place.
Durch die erfindungsgemäße Aufkonzentration steigt in bekannter Weise die Leitfähigkeit des Mediums, wodurch sich die Zellspannung reduziert. Damit kann im erfindungsgemäßen Sinne die Effizienz des Verfahrens weiter gesteigert werden. Außer- dem besteht dadurch die Möglichkeit, den Zellaufbau zu optimieren. Beispielsweise vereinfachen größere Elektrodenabstände die Durchmischung und es kann dadurch eine leichtere Reinigung der Anlage erfolgen. Auch damit wird die Effektivität der erfindungsgemäßen Anlage gesteigert. As a result of the concentration according to the invention, the conductivity of the medium increases in a known manner, as a result of which the cell voltage is reduced. Thus, in the context of the invention, the efficiency of the process can be further increased. In addition, there is the possibility of optimizing the cell structure. For example, larger electrode distances simplify the mixing and it can thus be easier to clean the system. Even so, the effectiveness of the system according to the invention is increased.
Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der nachfolgenden Figurenbeschreibung eines Ausführungsbeispiels anhand der Zeichnung in Verbindung mit den Patentansprüchen. Es zeigen Further details and advantages of the invention will become apparent from the following description of an embodiment with reference to the drawing in conjunction with the claims. Show it
Figur 1 ein Schema für eine Aufkonzentration der organischen Figure 1 is a scheme for a concentration of the organic
Schadstoffe in einem Abwasserstrom und  Pollutants in a sewage stream and
Figur 2 anhand einer graphischen Darstellung den Energieaufwand bei der Vorgehensweise gemäß Figur 1.  FIG. 2 shows the energy expenditure in the procedure according to FIG. 1 on the basis of a graphical representation.
Es sollen aus einer verunreinigten Flüssigkeit Schadstoffe beseitigt werden. Im industriellen Bereich ist die verunreinigte Flüssigkeit meist ein Industriewasser, das insbesondere mit organischen Substanzen belastet ist. Die Summe der Verunreinigungen wird durch den so genannten CSB-Abbau definiert. Für die Praxis existieren klare gesetzliche Vorgaben für den Wert einer zulässigen CSB-Verunreinigung. Der CSB-Wert kann in der Praxis beispielsweise elektrochemisch verringert werden. Dazu erfolgt üblicherweise eine Aufkonzentration des organisch belasteten Wassers. Die Aufkonzentration des organisch belasteten Wassers kann beispielsweise durch Membranverfahren (UF, NF, RO, ED) realisiert werden. Dazu muss in diesem Fall die so genannte Konzentration nach der Aufkonzentration elektrochemisch weiterbehandelt werden, wobei ein so genanntes Permeat als Nebenprodukt anfällt. Als Permeat wird in der einschlägigen Technologie das durch die Filtration von beispielsweise Bakterienhärtebildnern oder Schwerme- tallen befreite Fluid bezeichnet. Die bei der Filtration zurückgehaltenen Stoffe werden dagegen als Retentad bezeichnet. It should be removed from a contaminated liquid pollutants. In the industrial sector, the contaminated liquid is usually an industrial water, in particular contaminated with organic substances. The sum of the impurities is defined by the so-called COD degradation. In practice, there are clear legal requirements for the value of a permissible COD contamination. The COD value can be reduced electrochemically in practice, for example. This is usually done by concentrating the organically contaminated water. The concentration of the organically contaminated water can be realized, for example, by membrane processes (UF, NF, RO, ED). For this purpose, in this case, the so-called concentration after the concentration must be treated electrochemically, wherein a so-called permeate is obtained as a by-product. The permeate referred to in the relevant technology is the fluid freed by the filtration of, for example, bacterial hardening agents or heavy metals. The retained substances during filtration are referred to as Retentad.
Enthält das zu behandelnde Abwasser derartige Fest- bzw. Does the wastewater to be treated contain such solid or
Schwebstoffe, kann die Aufkonzentration der Schadstoffe durch Zentrifugieren erfolgen. Des Weiteren können die Inhaltsstoffe des Abwassers durch thermisches Eindampfen oder Verdunsten aufkonzentriert werden, wenn der CSB-Stoff in Form von hochsiedenden organischen Verbindungen vorliegt. Letzteres ist in Figur 1 verdeutlicht. Dargestellt ist schematisch eine mögliche Aufkonzentration der organischen Schadstoffe des Abwasserstroms durch eine Kombination au Nano- filtration und Reverse Osmose vor der eigentlichen elektrochemischen CSB-Reduzierung. Dazu bedeuten Verfahrensschritt gemäß Bezugszeichen 1 die Nanofiltration und Verfahrensschritt gemäß Bezugszeichen 2 die Reverse Osmose. Wenn das Abwasser einen CSB-Wert von beispielsweise 1000 mg/1 enthält, kann nach dem Verfahrensschritt 1 eine Konzentration mit CSB = 1500 mg/1 enthalten werden. Nach der 'Reverse Osmose' gemäß Funktionsschritt 2 wird ein Konzentrat mit einem CSB- Wert > 4000 mg/1 erhalten. Dieses Konzentrat wird einer Elektrolyse unterzogen, wobei der Verfahrensablauf in spezifischer Weise erfolgt, wie er beispielsweise in Anmeldungen der Anmelderin beschrieben ist. Das bei den einzelnen Aufkon- zentrationsschritten 1 und 2 zurückbleibende Permeat kann wiederum in das Ausgangswasser zurückgeführt werden. In Figur 2 ist auf der Abszisse der CSB-Wert in mg/1 und ist auf der Kathode der Leistungsaufwand in Prozent aufgetragen. Es ergibt sich aus dieser Darstellung also der Leistungsaufwand in Abhängigkeit der Ausgangs-CSB, wobei diskontinuierliche, also Batch-Versuche, durchgeführt wurden. Insgesamt ist der Figur 2 der Energieaufwand bei der elektrochemischen Behandlung vom Ausgangs-CSB des Abwassers zu entnehmen. Daraus ergibt sich der Vorteil des erfindungsgemäßen Verfahrens. Der Energieaufwand ist bei geringen CSB-Ausgangskonzentrationen um ein Vielfaches höher als bei Abwassern mit hoher CSB- Belastung. Suspended matter, the concentration of the pollutants can be done by centrifuging. Furthermore, the constituents of the wastewater can be concentrated by thermal evaporation or evaporation if the COD material is in the form of high-boiling organic compounds. The latter is illustrated in FIG. Shown schematically is a possible concentration of the organic pollutants of the wastewater stream by a combination of nano-filtration and reverse osmosis before the actual electrochemical COD reduction. For this purpose, the process step according to reference numeral 1, the nanofiltration and process step according to reference numeral 2 reverse osmosis. If the wastewater contains a COD value of, for example, 1000 mg / l, a concentration with COD = 1500 mg / l can be contained after process step 1. After the reverse osmosis according to functional step 2, a concentrate with a COD value> 4000 mg / l is obtained. This concentrate is subjected to electrolysis, the process being carried out in a specific manner, as described, for example, in applications of Applicant is described. The permeate remaining at the individual concentration steps 1 and 2 can in turn be returned to the starting water. In FIG. 2, the abscissa represents the COD value in mg / l and the percent power consumption is plotted on the cathode. It follows from this illustration, therefore, the power consumption as a function of the starting COD, with discontinuous, so batch experiments were performed. Overall, the energy expenditure in the electrochemical treatment of the starting COD of the wastewater is shown in FIG. This results in the advantage of the method according to the invention. The energy consumption is much higher with low COD initial concentrations than with waste water with high COD load.

Claims

Patentansprüche claims
1. Verfahren zur Aufbereitung von mit organischen Schadstoffen belasteten Flüssigkeiten, insbesondere von industriellen Abwassern, bei dem die organischen Bestandteile elektrochemisch beseitigt werden und der so genannte CBS-Wert verringert wird, mit folgenden Verfahrensschritten: 1. A process for the treatment of polluted with organic pollutants liquids, especially of industrial wastewater, in which the organic constituents are removed electrochemically and the so-called CBS value is reduced, comprising the following process steps:
- die organischen Schadstoffe in der Flüssigkeit werden in einem ersten Schritt aufkonzentriert und - The organic pollutants in the liquid are concentrated in a first step and
- anschließend wird die mit den Schadstoffen aufkonzentrierte Flüssigkeit einer Elektrolyse unterzogen. - Then the liquid concentrated with the pollutants is subjected to electrolysis.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass bei der Aufkonzentration der Schadstoffe ein CBS-Wert von > 4000 mg/1 erreicht wird. 2. The method according to claim 1, characterized in that at the concentration of the pollutants, a CBS value of> 4000 mg / 1 is achieved.
3. Verfahren nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass die Aufkonzentration in zwei Schritten erfolgt, wobei im ersten Schritt ein CSB-Wert von etwa 1000 bis 1500 mg/1 erreicht wird. 3. The method according to claim 1 or claim 2, characterized in that the concentration takes place in two steps, wherein in the first step, a COD value of about 1000 to 1500 mg / 1 is achieved.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass im ersten Schritt eine Nanofiltration (NF) durchgeführt wird. 4. The method according to claim 3, characterized in that in the first step, a nanofiltration (NF) is performed.
5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass im ersten Schritt eine Ultrafiltration (UF) durchgeführt wird. 5. The method according to claim 3, characterized in that in the first step, an ultrafiltration (UF) is performed.
6. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass im zweiten Schritt eine so genannte Reverse Osmose (RO) durchge- führt wird. 6. The method according to claim 3, characterized in that in the second step, a so-called reverse osmosis (RO) is performed.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass in Kombination eine Nanofiltration, eine Reverse-Osmose und eine Elektrodialyse durchgeführt wird. 7. The method according to any one of the preceding claims, characterized in that in combination a nanofiltration, a reverse osmosis and an electrodialysis is performed.
8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass im ersten Schritt mehrere Membranverfah- ren mit steigender Trennwirkung hintereinander durchgeführt werden . 8. The method according to any one of the preceding claims, characterized in that in the first step several Membranverfah- be carried out successively with increasing separation effect.
9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Aufkonzentration durch Zentrifugieren erfolgt. 9. The method according to claim 1, characterized in that the concentration is carried out by centrifugation.
10. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Aufkonzentration durch thermisches Eindampfen erfolgt. 10. The method according to claim 1, characterized in that the concentration is carried out by thermal evaporation.
11. Verfahren nach Anspruch 8 und Anspruch 9, dadurch gekennzeichnet, dass die Verfahrensschritte des Zentrifugierens und des Eindampfens miteinander kombiniert werden. 11. The method according to claim 8 and claim 9, characterized in that the process steps of centrifuging and evaporation are combined with each other.
12. Anlage zur Durchführung des Verfahrens nach Anspruch 1 oder einem der Ansprüche 2 bis 10, gekennzeichnet durch eine12. Plant for carrying out the method according to claim 1 or one of claims 2 to 10, characterized by a
Einrichtung zur Erhöhung des CSB-Wertes und eine daran gekoppelte EIektrodialyse-Einrichtung. Device for increasing the COD value and an electrodialysis device coupled thereto.
13. Anlage nach Anspruch 11, dadurch gekennzeichnet, dass eine Einrichtung zur Nano-Filtration vorhanden ist. 13. Plant according to claim 11, characterized in that a device for nano-filtration is present.
14. Anlage nach Anspruch 11, dadurch gekennzeichnet, dass eine Einrichtung zur Ultrafiltration vorhanden ist. 14. Plant according to claim 11, characterized in that a device for ultrafiltration is present.
15. Anlage nach Anspruch 11, dadurch gekennzeichnet, dass eine Einrichtung zur Reverse-Osmose vorhanden ist. 15. Plant according to claim 11, characterized in that a device for reverse osmosis is present.
16. Anlage nach Anspruch 11, dadurch gekennzeichnet, dass eine Einrichtung zum Zentrifugieren vorhanden ist. 16. Plant according to claim 11, characterized in that a device for centrifuging is present.
17. Anlage nach Anspruch 11, dadurch gekennzeichnet, dass eine Einrichtung zum thermischen Eindampfen vorhanden ist. 17. Plant according to claim 11, characterized in that a device for thermal evaporation is present.
18. Anlage nach einem der Ansprüche 11 bis 15, dadurch ge- kennzeichnet, dass Mittel zum Bestimmen des CSB-Wertes vorhanden sind. 18. Installation according to one of claims 11 to 15, character- ized in that means for determining the COD value are present.
19. Anlage nach Anspruch 15, dadurch gekennzeichnet, dass die Analyse Mittel jeweils den einzelnen Einrichtungen zum Aufkonzentrieren nachgeschaltet sind. 19. Plant according to claim 15, characterized in that the analysis means are each followed by the individual means for concentrating.
PCT/EP2010/061216 2009-08-04 2010-08-02 Process for degrading organic pollutants in industrial wastewater and associated system WO2011015556A1 (en)

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