DE4109872A1 - Removal of oxidisable nitrogen cpds. from water - by treatment with peroxy-di:sulphate and ultraviolet light - Google Patents
Removal of oxidisable nitrogen cpds. from water - by treatment with peroxy-di:sulphate and ultraviolet lightInfo
- Publication number
- DE4109872A1 DE4109872A1 DE19914109872 DE4109872A DE4109872A1 DE 4109872 A1 DE4109872 A1 DE 4109872A1 DE 19914109872 DE19914109872 DE 19914109872 DE 4109872 A DE4109872 A DE 4109872A DE 4109872 A1 DE4109872 A1 DE 4109872A1
- Authority
- DE
- Germany
- Prior art keywords
- treatment
- water
- oxidisable
- removal
- peroxy
- 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.)
- Ceased
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title description 10
- 229910052757 nitrogen Inorganic materials 0.000 title description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title 1
- 229910021653 sulphate ion Inorganic materials 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- -1 NH4(+) ions Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 5
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 23
- 239000003651 drinking water Substances 0.000 abstract description 12
- 235000020188 drinking water Nutrition 0.000 abstract description 12
- 229910002651 NO3 Inorganic materials 0.000 abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001678 irradiating effect Effects 0.000 abstract 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- 241000192041 Micrococcus Species 0.000 description 1
- 241000605159 Nitrobacter Species 0.000 description 1
- 241000605122 Nitrosomonas Species 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000011138 biotechnological process Methods 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2103/06—Contaminated groundwater or leachate
Abstract
Description
Die Erfindung betrifft ein Verfahren zum oxidativen Abbau von Ammoniak bzw. Ammoniumionen und/oder anderen oxidierbaren Stickstoffverbindungen, wie Hydrazin, Nitrit, Ethylendiamintetraacetat (EDTA) u. a., die in wäßrigen Lösungen in geringen Mengen vorkommen, insbesondere für die Trinkwasseraufbereitung.The invention relates to a method for oxidative Degradation of ammonia or ammonium ions and / or other oxidizable nitrogen compounds, such as Hydrazine, nitrite, ethylenediaminetetraacetate (EDTA) u. a. in small quantities in aqueous solutions occur, especially for the Drinking water treatment.
Der Ammoniumgehalt ist ein wichtiges Kriterium für die Wasserqualität. So fordert die WHO für Trinkwasser einen Grenzwert von 0,05 mg NH₄⁺/dm³. Die EG gibt einen Richtwert von 0,05-0,5 mg NH₄⁺/dm³ an. Die Reduktion von Nitrationen durch Mikroorganismen, hoher Düngereintrag und der Abbau organischer Stickstoffverbingungen sind Ursachen für den z. T. beträchtlichen Ammoniumgehalt des für die Trinkwasserversorgung vorgesehenen Wassers.The ammonium content is an important criterion for the water quality. So the WHO calls for Drinking water a limit of 0.05 mg NH₄⁺ / dm³. The EG gives a guideline value of 0.05-0.5 mg NH₄⁺ / dm³. The reduction of nitrate ions by microorganisms, high fertilizer input and organic degradation Nitrogen compounds are causes for the z. T. considerable ammonium content for the Drinking water supply provided water.
Für Abwasser sind je nach Herkunft im Abwassergesetz der Bundesrepublik Grenzwerte von 10 mg bis 50 mg NH₄⁺/dm³ vorgeschrieben.For wastewater, depending on the origin, in the wastewater law the Federal Republic of limit values from 10 mg to 50 mg NH₄⁺ / dm³ prescribed.
Zur Verringerung der Ammoniumbelastung wurden eine Reihe biotechnologischer Verfahren entwickelt. Diese beruhen im wesentlichen auf zwei Teilschritten. Im ersten, aeroben Schritt, der Nitrifikation, erfolgt die bakterielle Oxidation des Ammoniums durch die Stämme Nitrosomonas zum Nitrit und Nitrobacter weiter zu Nitrat; im zweiten Schritt, der Denitrifikation, erfolgt die Reduktion des Nitrats zu Stickstoff durch die Stämme Pseudomonas und Micrococcus.To reduce the ammonium pollution, a Developed a series of biotechnological processes. These are essentially based on two substeps. in the first, aerobic step, nitrification the bacterial oxidation of ammonium by the Strains of Nitrosomonas continue to nitrite and Nitrobacter to nitrate; in the second step, denitrification, the nitrate is reduced to nitrogen by the Pseudomonas and Micrococcus strains.
Im Gegensatz zur mikrobiellen Behandlung von Abwasser besteht bei der Trinkwasseraufbereitung das Problem, daß keine Keime oder organische Stoffe ins Trinkwasser gelangen dürfen. Eine biologische Behandlung ist in dem Falle nur in Festbettreaktoren möglich, in denen die Mikroben durch Adsorption auf den Trägermaterialien festgehalten werden.In contrast to the microbial treatment of waste water there is a problem with drinking water treatment, that no germs or organic matter ins Drinking water. A biological one Treatment is only in fixed bed reactors possible in which the microbes are adsorbed on the carrier materials are held.
Ein wesentlicher Nachteil der mikrobiologischen Ammoniumoxidation ist ferner, daß sie bei niedrigen Temperaturen nicht oder nur ungenügend funktioniert. Bekannte chemische Verfahren zur Oxidation von Ammonium bzw. Ammoniak sind für die Trinkwasseraufbereitung nur bedingt einsetzbar. Die Oxidation mit Wasserstoffperoxid erfordert beispielsweise den Einsatz beträchtlicher Mengen toxischer Schwermetalle zur Katalyse [1]. Aus der Literatur ist weiterhin bekannt, daß sich Ammoniak bei Temperaturen <40°C durch Peroxodisulfat oxidieren läßt, wobei die Reaktionsgeschwindigkeit mit Temperaturerhöhung sowie Zusatz von katalytisch wirkenden Schwermetallsalzen wie Silber, Kupfer oder Nickel beschleunigt wird [2,3]. Bei Raumtemperatur erfolgt unter diesen Bedingungen keine Reaktion. Der Einsatz von Sauerstoff als Oxidationsmittel ist nur unter extremen Bedingungen, wie hohe Temperaturen und hoher Druck, möglich [4]. Die Komproportionierungs reaktion (1) mit Nitrit zu StickstoffA major disadvantage of the microbiological Ammonium oxidation is also low Temperatures do not work or work only insufficiently. Known chemical processes for the oxidation of Ammonium or ammonia are for the Drinking water treatment can only be used to a limited extent. The Oxidation with hydrogen peroxide required for example the use of considerable amounts toxic heavy metals for catalysis [1]. From the Literature is also known to be ammonia Oxidize with peroxodisulfate at temperatures <40 ° C lets, the reaction rate with Temperature increase and addition of catalytic acting heavy metal salts such as silver, copper or Nickel is accelerated [2,3]. At room temperature there is no reaction under these conditions. The Use of oxygen as an oxidizer is only under extreme conditions such as high temperatures and high pressure, possible [4]. The comproportionation reaction (1) with nitrite to nitrogen
NH₄⁺+NO₂-→N₂+2H₂O (1)NH₄⁺ + NO₂ - → N₂ + 2H₂O (1)
läuft nur in konzentrierten Lösungen mit merklicher Geschwindigkeit, so daß ein beträchtlicher Überschuß an toxischem Nitrit anfallen würde.only runs in concentrated solutions with noticeable Speed, so that a considerable excess of toxic nitrite.
Der in den Ansprüchen angegebenen Erfindung liegt das Problem zugrunde, insbesondere geringe Mengen oxidierbarer Stickstoffverbindungen auf technisch einfache Weise oxidativ zu entfernen, ohne daß dabei aus dem Reaktionsmittel resultierende toxische Stoffe in das zu behandelnde Wasser gelangen und durch aufwendige Verfahrensschritte wieder aus diesem entfernt werden müssen.The invention specified in the claims is Problem, especially small quantities oxidizable nitrogen compounds on technical easy way to remove oxidatively without doing toxic substances resulting from the reactant get into the water to be treated and through elaborate process steps again from this must be removed.
Überraschenderweise zeigte sich, daß Ammoniumionen bzw. Ammoniak unter Einwirkung von UV-Licht durch Peroxodisulfat rasch zu Stickstoff bzw. geringen Mengen Nitrat oxidiert werden. Die Peroxodisulfatkonzentration ist entsprechend der zu oxidierenden Stoffmengen und der Stöchiometrie zu wählen. Es laufen folgende Reaktionen (nebeneinander) ab:Surprisingly, it was found that ammonium ions or ammonia under the influence of UV light Peroxodisulfate quickly to nitrogen or low Amounts of nitrate are oxidized. The Peroxodisulfate concentration is corresponding to that oxidizing substances and stoichiometry choose. The following reactions are running (side by side) from:
NH₃+1,5 S₂O₈2-→0,5 N₂+3 SO₄2-+3 H⁺NH₃ + 1.5 S₂O₈ 2- → 0.5 N₂ + 3 SO₄ 2- +3 H⁺
NH₃+4 S₂O₈2-+3 H₂O→NO₃-+8 SO₄2-+9 H⁺NH₃ + 4 S₂O₈ 2- +3 H₂O → NO₃ - +8 SO₄ 2- +9 H⁺
Für die Oxidation von Ammoniak bzw. Ammoniumionen liegt die Peroxodisulfatkonzentration günstigerweise zwischen der 1,5-5fachen molaren Menge des Ammoniaks bzw. Ammoniums. Bei höheren Ammoniakkonzentrationen ist die Bildung von Stickstoff wesentlich begünstigt. Während der Reaktion entstehen je Mol Peroxodisulfat 2-2,5 Mol Wasserstoffionen. Die zur Neutralisation erforderliche Menge Lauge kann wahlweise vor, während oder nach der Reaktion zugesetzt werden. Der pH-Wert soll während der Reaktion zwischen 1 und 13 gehalten werden. Bei pH-Werten <8 ist für den Abbau von Ammoniumionen auf den geforderten Grenzwert die Anwesenheit von Chloridionen erforderlich. Im Alkalischen wird Ammoniak auch in chloridfreien Lösungen vollständig oxidiert. Da der pH-Wert während der Reaktion durch die Bildung von Wasserstoffionen ohnehin absinkt, ist es zweckmäßig, Peroxodisulfat und Lauge im geeigneten Verhältnis derart einzusetzen, daß die Lösung nach der Reaktion neutral ist. Die Oxidation von EDTA oder Nitrit läuft demgegenüber immer auch in chloridfreien Lösungen ab. For the oxidation of ammonia or ammonium ions the peroxodisulfate concentration is favorably between 1.5-5 times the molar amount of ammonia or ammonium. At higher ammonia concentrations the formation of nitrogen is significantly favored. Per mole of peroxodisulfate is formed during the reaction 2-2.5 moles of hydrogen ions. The one for neutralization required amount of lye can optionally be used before or added after the reaction. The pH should be kept between 1 and 13 during the reaction will. At pH values <8, the degradation of Ammonium ions to the required limit Presence of chloride ions required. in the Ammonia is also alkaline in chloride-free Solutions completely oxidized. Because the pH during the reaction by the formation of hydrogen ions sinks anyway, it is appropriate to use peroxodisulfate and lye in the appropriate ratio use that the solution is neutral after the reaction is. The oxidation of EDTA or nitrite is ongoing in contrast, always in chloride-free solutions.
Schwermetallionen wie Kupfer und Eisen, die in der Trinkwasseraufbereitung unbedenklich eingesetzt werden können, wirken im Konzentrationsbereich bis maximal etwa 10 µmol/dm³ katalytisch, sind jedoch nicht unbedingt notwendig.Heavy metal ions such as copper and iron, which in the Drinking water treatment used safely can act in the concentration range up to a maximum of about 10 µmol / dm³ are catalytic, however not absolutely necessary.
Die erforderliche Bestrahlungsdauer ist von der Ausgangskonzentration der zu oxidierenden Stoffe sowie der Strahlungsintensität des UV-Strahlers abhängig. Im allgemeinen wird eine Quecksilber- Hochdrucklampe verwendet.The required irradiation time is from Initial concentration of the substances to be oxidized as well as the radiation intensity of the UV lamp dependent. In general, a mercury High pressure lamp used.
Die Oxidation verläuft bei Normaltemperatur, aber auch eine Herabsetzung der Reaktionstemperatur auf 0- 5°C bewirkt nur eine geringfügige Verminderung der Reaktionsgeschwindigkeit.The oxidation proceeds at normal temperature, however also a reduction in the reaction temperature to 0- 5 ° C causes only a slight reduction in the Reaction speed.
Im allgemeinen ist die Reaktion z. B. für die Aufbereitung von Trinkwasser nach spätestens 2 Stunden beendet.In general, the reaction is e.g. B. for the Treatment of drinking water after 2 Hours ended.
Das erfindungsgemäße Verfahren ermöglicht es, ohne Temperaturerhöhung in einfacher Weise geringe Konzentrationen oxidierbarer Stickstoffverbindungen innerhalb kurzer Zeit aus dem Wasser zu entfernen. So können Konzentrationen von 5-20 mg NH₄⁺/dm³, wie sie häufig in für die Trinkwasserversorgung vorgesehenem Wasser vorkommen, auf den für Trinkwasser geforderten Wert von <0,5 mg NH₄⁺/dm³ verringert werden.The method according to the invention makes it possible without Low temperature increase in a simple manner Concentrations of oxidizable nitrogen compounds can be removed from the water within a short time. So can concentrations of 5-20 mg NH₄⁺ / dm³ as they often in those intended for drinking water supply Water occur on the required for drinking water Value of <0.5 mg NH₄⁺ / dm³ can be reduced.
Aber auch hohe Konzentrationen von <0,5 g NH₄⁺/dm³ können in nahezu derselben Zeit auf den entsprechenden Grenzwert verringert werden.But also high concentrations of <0.5 g NH₄⁺ / dm³ can be in the same time corresponding limit can be reduced.
Trotz des gegebenenfalls erfolgenden Zusatzes von Chlorid liegt die Fremdionenbelastung unter den für Trinkwasser zulässigen Werten und ist in toxikologischer Hinsicht unbedenklich.Despite the addition of The foreign ion load is below the chloride permissible values for drinking water and is in toxicologically harmless.
In Abb. 1 sind die Abbaukurven für eine Ausgangskonzentration von 200 mg NH₄⁺/dm³ im Alkalischen bzw. bei pH<7 angegeben. Fig. 1 shows the degradation curves for an initial concentration of 200 mg NH₄⁺ / dm³ in alkaline or at pH <7.
In Abb. 2 sind Abbaukurven verschiedener Mengen Ammonium bei unterschiedlicher Chloridkonzentration angegeben. Fig. 2 shows the degradation curves of different amounts of ammonium at different chloride concentrations.
In Abb. 3 werden Abbaukurven von 10 mg NH₄⁺/dm³ bei verschiedenen Chloridkonzentrationen gezeigt. Fig. 3 shows degradation curves of 10 mg NH₄⁺ / dm³ at different chloride concentrations.
Zu einer chloridfreien Lösung, die 10 mg NH₄⁺/dm³ enthielt, wurden 2,65 mmol/dm³ K₂S₂O₈ und 5,87 mmol/dm³ NaOH gegeben. Die Lösung wurde bei 5-10°C 1 Stunde mit einem 400 W-Hochdruck-Quecksilber brenner bestrahlt; danach hatte sie einen pH-Wert von 6 und einen Gehalt von 0,48 mg NH₄⁺/dm³.To a chloride-free solution, the 10 mg NH₄⁺ / dm³ contained, 2.65 mmol / dm³ K₂S₂O₈ and 5.87 given mmol / dm³ NaOH. The solution was at 5-10 ° C 1 hour with a 400 W high pressure mercury burner irradiated; after that she had a pH of 6 and a content of 0.48 mg NH₄⁺ / dm³.
In einem Galvanikbetrieb, in dem einerseits verbrauchte kupferhaltige Peroxodisulfat-Ätzlösungen und andererseits ammoniakhaltige Abwässer anfallen, lassen sich sowohl das Peroxodisulfat als auch Ammoniak gleichzeitig entsorgen, wenn die Abwässer im richtigen Verhältnis gemischt, mit Alkali versetzt und mit UV-Licht bestrahlt werden.In an electroplating shop, on the one hand used copper-containing peroxodisulfate etching solutions and on the other hand, waste water containing ammonia is produced, both the peroxodisulfate and Dispose of ammonia at the same time if the waste water in the correct ratio mixed, mixed with alkali and be irradiated with UV light.
Eine verbrauchte Ätzlösung, die 100 g/dm³ Peroxodisulfat und ca. 20 g/dm³ Kupfer enthält, wird zum 51fachen Volumen eines Abwassers mit 100 mg NH₄⁺/dm³ gegeben. Zur neutralen Lösung werden 2,4 kg Ca(OH)₂/m³ zugesetzt, wobei Cu(OH)₂ und CaSO₄ ausfallen und abfiltriert werden können.A used etching solution, the 100 g / dm³ Contains peroxodisulfate and approx. 20 g / dm³ copper to 51 times the volume of waste water with 100 mg NH₄⁺ / dm³ given. 2.4 kg becomes the neutral solution Ca (OH) ₂ / m³ added, with Cu (OH) ₂ and CaSO₄ precipitate and can be filtered off.
Das Filtrat wird ca. 1,5 h mit UV-Licht bestrahlt. Danach enthält das Abwasser noch etwa 0,1 mg NH₄⁺/dm³ und 30 mg NO₃-/dm³; der pH-Wert ist annähernd 7. The filtrate is irradiated with UV light for about 1.5 hours. Then the wastewater still contains about 0.1 mg NH₄⁺ / dm³ and 30 mg NO₃ - / dm³; the pH is approximately 7.
[1] Ott, D.; OS DE 36 44 080 A1 (1985) C02F1/00
[2] Gmelin Handbuch der anorganischen Chemie, Bd. 23
(Ammonium), S. 12 ff.
[3] Ball, R. E., Chako, A., Edwards, J. O., Levey, G.;
Inorg. Chim. Acta 1985, 99, S. 49-58
[4] Kakihara, N., Harada, Y., Uedono, N., Yamazaki, K.,
Ueda, T., Fujitani, H.; PS DE 29 50 710 C2 (1979)
C02F1/74[1] Ott, D .; OS DE 36 44 080 A1 (1985) C02F1 / 00
[2] Gmelin Handbook of Inorganic Chemistry, Vol. 23 (Ammonium), p. 12 ff.
[3] Ball, RE, Chako, A., Edwards, JO, Levey, G .; Inorg. Chim. Acta 1985, 99, pp. 49-58
[4] Kakihara, N., Harada, Y., Uedono, N., Yamazaki, K., Ueda, T., Fujitani, H .; PS DE 29 50 710 C2 (1979) C02F1 / 74
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914109872 DE4109872A1 (en) | 1991-03-26 | 1991-03-26 | Removal of oxidisable nitrogen cpds. from water - by treatment with peroxy-di:sulphate and ultraviolet light |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914109872 DE4109872A1 (en) | 1991-03-26 | 1991-03-26 | Removal of oxidisable nitrogen cpds. from water - by treatment with peroxy-di:sulphate and ultraviolet light |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4109872A1 true DE4109872A1 (en) | 1992-10-01 |
Family
ID=6428216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19914109872 Ceased DE4109872A1 (en) | 1991-03-26 | 1991-03-26 | Removal of oxidisable nitrogen cpds. from water - by treatment with peroxy-di:sulphate and ultraviolet light |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4109872A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999005065A1 (en) * | 1997-07-23 | 1999-02-04 | Crc For Waste Management & Pollution Control Limited | Photo-assisted oxidation of inorganic species in aqueous solutions |
| CN101699352B (en) * | 2009-11-06 | 2011-10-19 | 常州瑞择微电子科技有限公司 | Method for removing sulfate radicals from photomask |
| FR2981924A1 (en) * | 2011-10-27 | 2013-05-03 | Univ Provence Aix Marseille 1 | REACTOR USED FOR DECONTAMINATION OF FLUIDS AND METHOD OF USE |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1517675A1 (en) * | 1963-11-13 | 1969-10-16 | Kernforschungsanlage Juelich | Process for the clarification of faecal waste, especially those that are radioactively contaminated |
| DE2054123A1 (en) * | 1970-01-29 | 1971-08-05 | Air Liquide | Process for the detoxification of wastewater contaminated with organic cyano compounds |
| EP0059978A1 (en) * | 1981-03-10 | 1982-09-15 | BAYROL Chemische Fabrik G.m.b.H. | Process for the chemical treatment and disinfection of waters and aqueous systems |
| US4774026A (en) * | 1986-01-22 | 1988-09-27 | Hitachi, Ltd. | Process and apparatus for oxidizing or reducing dissolved substance |
| US4861484A (en) * | 1988-03-02 | 1989-08-29 | Synlize, Inc. | Catalytic process for degradation of organic materials in aqueous and organic fluids to produce environmentally compatible products |
| DE3836850A1 (en) * | 1988-10-28 | 1990-05-03 | Guenther O Prof Dr Schenck | Process and apparatus for purifying waters of oxidisable carbon compounds contained therein |
| EP0436922A2 (en) * | 1990-01-09 | 1991-07-17 | Layer + Knödler Abwassertechnik + Kunststoffbau Gmbh | Method and apparatus for treating effluent |
-
1991
- 1991-03-26 DE DE19914109872 patent/DE4109872A1/en not_active Ceased
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1517675A1 (en) * | 1963-11-13 | 1969-10-16 | Kernforschungsanlage Juelich | Process for the clarification of faecal waste, especially those that are radioactively contaminated |
| DE2054123A1 (en) * | 1970-01-29 | 1971-08-05 | Air Liquide | Process for the detoxification of wastewater contaminated with organic cyano compounds |
| EP0059978A1 (en) * | 1981-03-10 | 1982-09-15 | BAYROL Chemische Fabrik G.m.b.H. | Process for the chemical treatment and disinfection of waters and aqueous systems |
| US4774026A (en) * | 1986-01-22 | 1988-09-27 | Hitachi, Ltd. | Process and apparatus for oxidizing or reducing dissolved substance |
| US4861484A (en) * | 1988-03-02 | 1989-08-29 | Synlize, Inc. | Catalytic process for degradation of organic materials in aqueous and organic fluids to produce environmentally compatible products |
| DE3836850A1 (en) * | 1988-10-28 | 1990-05-03 | Guenther O Prof Dr Schenck | Process and apparatus for purifying waters of oxidisable carbon compounds contained therein |
| EP0436922A2 (en) * | 1990-01-09 | 1991-07-17 | Layer + Knödler Abwassertechnik + Kunststoffbau Gmbh | Method and apparatus for treating effluent |
Non-Patent Citations (9)
| Title |
|---|
| BALL, Richard E. et.al.: "Mechanism of Oxidation...", Inrganica Chimica Acta 99 (1985), S. 49-58 * |
| CHRISTENSEN, P.A. er.al.: A Pulse-radiolytic...", J. Chem. Soc. Foraday Traus. 80(1984)2, S. 145191464 * |
| HIRKAMP, S. et.al.: "Online Verfahren...", * |
| HOUSE, D.A.: "Kiretics and Mechanism...", Chem. Reviews, 62(1962) 3, S. 185-203 * |
| NEUMÜLLER, O.A.: "Römpps Chemie-Lexikon", 7. Aufl. Franck'sche Verlagshandlung, Stuttgart 1974, "Persulfate", Peroxodisulfate" * |
| Referat aus Chemical Abstracts, Vol. 112, 1990, S. 606, Nr. 112:207585w * |
| Referat aus Chemical Abstracts, Vol. 96, 1982, S. 444, Nr. 96:110869e * |
| Referat aus Chemical Abstracts, Vol. 96, 1982, S. 639, Nr. 96:94840f * |
| Referat aus Chemical Abstracts, Vol. 99, 1983, S. 151, Nr. 99:41026a * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999005065A1 (en) * | 1997-07-23 | 1999-02-04 | Crc For Waste Management & Pollution Control Limited | Photo-assisted oxidation of inorganic species in aqueous solutions |
| US6884391B1 (en) | 1997-07-23 | 2005-04-26 | Crc For Waste Management & Pollution Control Limited | Photo-assisted oxidation of inorganic species in aqueous solutions |
| CN101699352B (en) * | 2009-11-06 | 2011-10-19 | 常州瑞择微电子科技有限公司 | Method for removing sulfate radicals from photomask |
| FR2981924A1 (en) * | 2011-10-27 | 2013-05-03 | Univ Provence Aix Marseille 1 | REACTOR USED FOR DECONTAMINATION OF FLUIDS AND METHOD OF USE |
| WO2013061007A3 (en) * | 2011-10-27 | 2013-10-24 | Universite D'aix Marseille | Reactor usable for decontamination of fluids and method of use |
| US9981862B2 (en) | 2011-10-27 | 2018-05-29 | Universite D'aix Marseille | Reactor usable for decontamination of fluids and method of use |
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| OP8 | Request for examination as to paragraph 44 patent law | ||
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