WO1993002965A1 - Method of processing untreated drinking water contaminated with organic substances - Google Patents
Method of processing untreated drinking water contaminated with organic substances Download PDFInfo
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- WO1993002965A1 WO1993002965A1 PCT/EP1992/001675 EP9201675W WO9302965A1 WO 1993002965 A1 WO1993002965 A1 WO 1993002965A1 EP 9201675 W EP9201675 W EP 9201675W WO 9302965 A1 WO9302965 A1 WO 9302965A1
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- Prior art keywords
- light
- drinking water
- wavelength
- lamp
- lamps
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003651 drinking water Substances 0.000 title claims abstract description 16
- 235000020188 drinking water Nutrition 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 title claims abstract description 12
- 239000011814 protection agent Substances 0.000 claims abstract description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000004202 carbamide Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 150000008163 sugars Chemical class 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002823 nitrates Chemical class 0.000 abstract 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004904 UV filter Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- -1 hydrogen peroxide Chemical compound 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
Definitions
- the present invention relates to a method of the type designated according to the preamble of claim 1 and a device according to the preamble of claim 8.
- Atrazine has become a major problem. Although it is possible to reduce the atrazine content by means of suitable treatment measures, this is predominantly to be carried out by means of filtration and adsorption with the correspondingly high outlay. These measures are all extremely expensive and involve high investments. In order to meet the guidelines laid down by the European Community with regard to the maximum exposure to, for example, atrazine, the water-producing companies must therefore make enormous efforts.
- DE-OS 27 35 550 discloses a method for cleaning, in particular for disinfection and disinfection of flowable media in a flow reactor with a predetermined minimum radiation, ie minimum dose, ultraviolet radiation predominantly in the wavelength range from 240-320 nm.
- the invention also relates to a device for Aus ⁇ Practice of such a method, consisting of one Radiation sources with at least one radiator which emits ultra violet radiation in the wavelength range from 240-320 nm, associated flow reactor with a feed line and a discharge line for the medium to be irradiated and with a monitoring device for the ultraviolet radiation passing through the flow reactor.
- the technical problem on which the invention is based is therefore to provide a method which makes it possible to avoid the disadvantages mentioned above.
- the process should be able to be carried out continuously and avoid subsequent oxidative treatment of the drinking water to be treated.
- the method should be able to be carried out by means of a device adapted to it.
- wavelengths in the range of in particular> 230 nm enables organic compounds, in particular crop protection agents such as atrazine, to be destroyed without the nitrate being converted to nitrite in the process.
- crop protection agents such as atrazine
- the wavelength range can advantageously be selected by means of UV filters. This is preferably done with filters that are made of high-purity quartz in large layer thicknesses such as. B. Heralux (20 mm) from Heraeus (Hanau) or cheaper materials such. B. Infralux M 235 / M 282 are made in sufficient layer thickness from Heraeus (Hanau).
- UV lamps that meet these requirements are particularly z.
- auxiliary chemicals for the treatment of the raw drinking water.
- auxiliary chemicals such as formic acid and its salts, acetic acid, ethanol, citric acid, tartaric acid, glucose and reducing sugars, other organic, reducing hydroxy compounds as well as ammonia, urea and amine derivative, such as amidosulfonic acid, into consideration, since these support the destruction of nitrite.
- UV light is used, which also has higher proportions of wavelengths less than 230 nm.
- a device suitable for carrying out the method according to the invention is proposed in P 40 25 078.4.
- the device described therein has a flow-through reactor, at least one UV lamp and supply and discharge lines and is characterized in that a surface which strongly reflects UV light is arranged in the reactor and a turbulent flow can be generated or stabilized. At flow rates which are below the critical Reynolds number, this can be ensured by means of devices which are arranged on or in front of the UV-reflecting surface.
- the devices can advantageously be arranged in the liquid flow both inside the reactor and before the medium to be treated enters the reactor.
- Another variant of the generation of the turbulent flow is based on a tangential inflow of the liquid flow into the reactor.
- the UV lamps to be used here can in particular be designed as UV immersion lamps.
- the figure shows a particularly preferred embodiment.
- the reactor 1 has feed and discharge lines.
- the UV lamp (2) is designed here as a diving lamp.
- the outer wall of the immersion tube (3) consists of a glass which acts as a UV filter for wavelengths ⁇ 230 nm.
- Infralux M 235 from Heraeus is used as the material for the wall of the immersion tube (3) in question.
- the supply and discharge lines (4, 5) are provided for the inlet and outlet of nitrogen. It has been shown that the use of an inert gas between the UV lamp (2) and the outer wall of the dip tube (3) prevents the formation of undesirable gaseous by-products.
- the device according to the figure has on the inner wall of the reactor, which is preferably made of polished stainless steel, devices in the form of protuberances which lead to turbulent flows within the reactor. At higher flow rates, the devices can be omitted if the critical Reynolds number is exceeded.
- An advantage of the process according to the invention is that continuous process control for the degradation of organic compounds, in particular crop protection agents such as atrazine, is made possible, without oxidizing substances such as H 2 O, for the re-oxidation of the nitrite formed by photo-chemical reactions to nitrate.
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- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Described is a method of processing untreated drinking water contaminated with organic substances, in particular water containing nitrates and plant-protection agents, by exposure to UV light. The method is characterized in that the untreated drinking water is either a) exposed to UV light at a wavelength greater than 230 nm or b) UV light with some of its wavelength components shorter than 230 nm is used in conjunction with nitrite-destroying substances. A particularly suitable device for carrying out the method comprises filters, located in the beampath between the UV lamp and the water, which allow UV light of wavelength 230 nm and above to pass. Also suitable are UV lamps which produce substantially no UV radiation of less than 230 nm.
Description
"Verfahren zur Aufbereitung von mit organischen Substanzen belastetem Rohtrinkwasser""Process for the treatment of raw drinking water contaminated with organic substances"
Gegenstand der vorliegenden Erfindung ist ein Verfahren der gemäß Oberbegriff des Anspruchs 1 und eine Vorrich¬ tung gemäß Oberbegriff des Anspruchs 8 bezeichneten Art.The present invention relates to a method of the type designated according to the preamble of claim 1 and a device according to the preamble of claim 8.
Die Verunreinigung des zur Gewinnung von Trinkwasser vor¬ gesehenen Rohtrinkwassers mit organischen Verbindungen, insbesondere Pflanzenschutzmitteln wie z. B. Atrazin ist zu einem großen Problem geworden. Es ist zwar möglich durch geeignete Aufbereitungsmaßnahmen den Atrazingehalt zu reduzieren, jedoch ist dies überwiegend durch Filtra¬ tionen und Adsorptionen mit dem entsprechend hohen Auf¬ wand durchzuführen. Diese Maßnahmen sind allesamt extrem kostspielig und mit hohen Investitionen verbunden. Um den von der Europäischen Gemeinschaft festgelegten Richtlinien bezüglich der Höchstbelastung mit beispielsweise Atrazin gerecht zu werden, müssen somit die wassererzeugenden Be¬ triebe enorme Anstrengungen entwickeln.Contamination of the raw drinking water provided for the production of drinking water with organic compounds, in particular pesticides such. B. Atrazine has become a major problem. Although it is possible to reduce the atrazine content by means of suitable treatment measures, this is predominantly to be carried out by means of filtration and adsorption with the correspondingly high outlay. These measures are all extremely expensive and involve high investments. In order to meet the guidelines laid down by the European Community with regard to the maximum exposure to, for example, atrazine, the water-producing companies must therefore make enormous efforts.
In Chemical Abstracts, Vol. 104, 1986, S. 422, Ref.Nr. 155599S, wird ein Verfahren zur Photolyse von pestizid- haltigen Lösungen mit UV-Licht bei einer Wellenlänge von 365-366 nm angegeben.In Chemical Abstracts, Vol. 104, 1986, p. 422, ref. No. 155599S, a method for the photolysis of pesticide-containing solutions with UV light at a wavelength of 365-366 nm is specified.
Die DE-OS 27 35 550 offenbart ein Verfahren zur Reinigung, insbesondere zur Entkeimung und Desinfektion fließfähiger Medien in einem Durchflußreaktor mit einer vorbestimmten Mindestbestrahlung, d.h. Mindestdosis, ultravioletter Strahlung überwiegend im Wellenlängenbereich von 240-320 nm. Die Erfindung betrifft auch eine Vorrichtung zur Aus¬ übung eines solchen Verfahrens, bestehend aus einem einer
Strahlungsguelle mit mindestens einem Strahler, der ultra¬ violette Strahlung im Wellenlängenbereich von 240-320 nm emittiert, zugeordneten Durchflußreaktor mit einer Zulei¬ tung und einer Ableitung für das zu bestrahlende Medium und mit einer Überwachungsreinrichtung für die den Durch¬ flußreaktor durchsetzende ultraviolette Strahlung.DE-OS 27 35 550 discloses a method for cleaning, in particular for disinfection and disinfection of flowable media in a flow reactor with a predetermined minimum radiation, ie minimum dose, ultraviolet radiation predominantly in the wavelength range from 240-320 nm. The invention also relates to a device for Aus ¬ Practice of such a method, consisting of one Radiation sources with at least one radiator which emits ultra violet radiation in the wavelength range from 240-320 nm, associated flow reactor with a feed line and a discharge line for the medium to be irradiated and with a monitoring device for the ultraviolet radiation passing through the flow reactor.
Eine photochemische Eliminierung organischer Substanzen, wie sie bereits in den Patentanmeldungen P 39 03 549 und P 40 16 514 beschrieben werden, sind nicht auf die Auf¬ bereitung von Trinkwasser übertragbar. Dies beruht auf der Tatsache, daß die Verunreinigungen die durch Atrazin- kontaminationen verursacht sind, überwiegend aus dem land¬ wirtschaftlichen Bereich stammen. Damit ist dann jedoch auch regelmäßig eine hohe Nitratbelastung des aufzube reitenden Trinkwassers verbunden. Durch photochemische Behandlung des Trinkwassers wird nun das Nitrat teilweise zum Nitrit reduziert. Dabei können die Grenzwerte der Trinkwasserverordnung (TVO) überschritten werden. Nitrit jedoch ist als kanzerogene Substanz bekannt. Um das Nitrit wiederum in das relativ unschädliche Nitrat zu überführen, müssen Oxidationsmittel zugesetzt werden, wie beispiels¬ weise Wasserstoffperoxid. Das führt dazu, daß dann über¬ schüssiges Wasserstoffperoxid gemäß TVO wieder dem Trink¬ wasser entzogen werden muß. Dies ist jedoch nicht nur aufwendig, sondern auch kostenintensiv.Photochemical elimination of organic substances, as already described in patent applications P 39 03 549 and P 40 16 514, cannot be transferred to the treatment of drinking water. This is based on the fact that the impurities caused by atrazine contamination mainly come from the agricultural sector. However, this is then also regularly associated with high nitrate pollution in the drinking water to be treated. The nitrate is now partially reduced to nitrite by photochemical treatment of the drinking water. The limits of the Drinking Water Ordinance (TVO) can be exceeded. However, nitrite is known to be a carcinogenic substance. In order to convert the nitrite into the relatively harmless nitrate, oxidizing agents, such as hydrogen peroxide, must be added. This means that excess hydrogen peroxide then has to be removed from the drinking water in accordance with TVO. However, this is not only complex, but also cost-intensive.
Das der Erfindung zugrundeliegende technische Problem ist es somit, ein Verfahren bereitzustellen, das es ermög¬ licht, die oben genannten Nachteile zu vermeiden. Das Verfahren soll insbesondere kontinuierlich durchführbar sein und eine nachträgliche oxidative Behandlung des auf¬ zubereitenden Trinkwassers vermeiden. Das Verfahren soll mittels einer daran angepaßten Vorrichtung durchgeführt werden können.The technical problem on which the invention is based is therefore to provide a method which makes it possible to avoid the disadvantages mentioned above. In particular, the process should be able to be carried out continuously and avoid subsequent oxidative treatment of the drinking water to be treated. The method should be able to be carried out by means of a device adapted to it.
Das der Erfindung zugrundeliegende technische Problem
wird mit einem Verfahren gemäß den Merkmalen des Anspruchs 1 gelöst. Die Unteransprüche betreffen bevorzugte Aus- führungsformen des erfindungsgemäßen Verfahrens. Eine dem erfindungsgemäßen Verfahren angepaßte Vorrichtung wird durch die Merkmale des Anspruchs 8 beschrieben.The technical problem underlying the invention is solved with a method according to the features of claim 1. The subclaims relate to preferred embodiments of the method according to the invention. A device adapted to the method according to the invention is described by the features of claim 8.
Es hat sich gezeigt, daß die Verwendung von Wellenlängen im Bereich von insbesondere > 230 nm eine Zerstörung or¬ ganischer Verbindungen, insbesondere Pflanzenschutzmit¬ teln wie Atrazin, ermöglicht, ohne daß dabei das Nitrat zu Nitrit umgewandelt wird. Bei Verwendung der genannten Wellenlängen wird die Reduktion von Nitrat zu Nitrit ver¬ mieden, so daß auch eine Nachbehandlung des Wassers, wie sie bei Verwendung niedrigerer Wellenlängen erforderlich wird, nicht durchgeführt zu werden braucht.It has been shown that the use of wavelengths in the range of in particular> 230 nm enables organic compounds, in particular crop protection agents such as atrazine, to be destroyed without the nitrate being converted to nitrite in the process. When using the wavelengths mentioned, the reduction of nitrate to nitrite is avoided, so that post-treatment of the water, as is required when using lower wavelengths, does not have to be carried out.
In vorteilhafter Weise kann der Wellenlängenbereich mit¬ tels UV-Filtern ausgewählt werden. Dies geschieht vor¬ zugsweise mit Filtern, die aus hochreinen Quarzen in großen Schichtdicken wie z. B. Heralux (20 mm) der Fa. Heraeus (Hanau) oder preiswerteren Materialien wie z. B. Infralux M 235/M 282 in ausreichender Schichtdicke der Fa. Heraeus (Hanau) hergestellt sind.The wavelength range can advantageously be selected by means of UV filters. This is preferably done with filters that are made of high-purity quartz in large layer thicknesses such as. B. Heralux (20 mm) from Heraeus (Hanau) or cheaper materials such. B. Infralux M 235 / M 282 are made in sufficient layer thickness from Heraeus (Hanau).
Es ist ebenfalls möglich, mittels speziell ausgestalteter UV-Lampen dafür Sorge zu tragen, daß das Emissionsspek¬ trum der verwendeten Lampen keine wesentlichen Anteile mehr < 230 nm aufweist. UV-Lampen, die diese Anorderungen erfüllen, sind insbesondere z. B. dotierte UV-Tauch¬ strahler der Fa. Heraeus: ZI, Z2, Z3, Z4 oder allgemein Edelgas-Entladungslampen.It is also possible to use specially designed UV lamps to ensure that the emission spectrum of the lamps used no longer has any significant proportions <230 nm. UV lamps that meet these requirements are particularly z. B. doped UV immersion lamps from Heraeus: ZI, Z2, Z3, Z4 or generally noble gas discharge lamps.
Es ist mit dem erfindungsgemäßen Verfahren ebenfalls ver¬ einbar Hilfschemikalien zur Aufbereitung des Rohtrink¬ wassers einzubringen. Insbesondere kommen Hilfschemikalien wie Ameisensäure und deren Salze, Essigsäure, Ethanol, Citronensäure, Weinsäure, Glucose und reduzierende Zucker,
sonstige organische, reduzierend wirkende Hydroxyverbin- dungen sowie Ammoniak, Harnstoff und Aminderivat , wie Amidosulfonsäure, in Betracht, da diese die Zerstörung von Nitrit unterstützen. Dies ist dann zu empfehlen, wenn UV-Licht verwendet wird, das auch höhere Anteile an Wellenlängen kleiner 230 nm aufweist.It is also compatible with the method according to the invention to introduce auxiliary chemicals for the treatment of the raw drinking water. In particular, auxiliary chemicals such as formic acid and its salts, acetic acid, ethanol, citric acid, tartaric acid, glucose and reducing sugars, other organic, reducing hydroxy compounds as well as ammonia, urea and amine derivative, such as amidosulfonic acid, into consideration, since these support the destruction of nitrite. This is recommended if UV light is used, which also has higher proportions of wavelengths less than 230 nm.
Eine zur Durchführung des erfindungsge äßen Verfahrens geeignete Vorrichtung wird in der P 40 25 078.4 vorge¬ schlagen. Die dort beschriebene Vorrichtung weist einen durchströmten Reaktor, mindestens eine UV-Lampe sowie Zu- und Ableitungen auf und ist dadurch charakterisiert, daß im Reaktor eine stark UV-Licht reflektierende Oberfläche angeordnet ist und eine turbulente Strömung erzeugt bzw. stabilisiert werden kann. Dies kann bei Durchflußgeschwin¬ digkeiten, die unterhalb der kritischen Reynolds-Zahl liegen, durch Einrichtungen gewährleistet werden, die auf oder vor der UV-reflektierenden Oberfläche angeordnet sind. Die Einrichtungen können in vorteilhafter Weise sowohl innerhalb des Reaktors wie auch vor Eintritt des zu behandelnden Mediums in den Reaktor im Flüssigkeits¬ strom angeordnet sein.A device suitable for carrying out the method according to the invention is proposed in P 40 25 078.4. The device described therein has a flow-through reactor, at least one UV lamp and supply and discharge lines and is characterized in that a surface which strongly reflects UV light is arranged in the reactor and a turbulent flow can be generated or stabilized. At flow rates which are below the critical Reynolds number, this can be ensured by means of devices which are arranged on or in front of the UV-reflecting surface. The devices can advantageously be arranged in the liquid flow both inside the reactor and before the medium to be treated enters the reactor.
Eine andere Variante der Erzeugung der turbulenten Strömung beruht auf einer tangentialen Einströmung des Flüssigkeitsstroms in den Reaktor.Another variant of the generation of the turbulent flow is based on a tangential inflow of the liquid flow into the reactor.
Wird die Reynolds-Zahl, die von der Geometrie des Reaktors und der jeweiligen Durchflußgeschwindigkeit des zu behan¬ delnden Mediums abhängt, überschritten, wird eine turbu¬ lente Strömung im Flüssigkeitsström auch ohne diese unter¬ stützenden Einrichtungen erzeugt. Die dabei zu verwenden¬ den UV-Lampen können insbesondere als UV-Tauchlampen aus¬ gebildet werden.If the Reynolds number, which depends on the geometry of the reactor and the respective flow rate of the medium to be treated, is exceeded, a turbulent flow in the liquid flow is generated even without these supporting devices. The UV lamps to be used here can in particular be designed as UV immersion lamps.
Die Figur zeigt eine besonders bevorzugte Ausführungs- form. Der Reaktor 1 weist Zu- und Ableitungen auf. Die
UV-Lampe- (2) ist hier als Tauchlampe ausgebildet. Die Außenwand des Tauchrohres (3) besteht in einer besonders bevorzugten Ausführungsform aus einem Glas, welches als UV-Filter wirkt für Wellenlängen < 230 nm. Als Material für die Wand des Tauchrohres (3) kommt insbesondere In- fralux M 235 der Fa. Heraeus in Frage. Die Zu- und Ab¬ leitungen (4, 5) sind für den Einlaß bzw. Auslaß von Stick¬ stoff vorgesehen. Es hat sich gezeigt, daß die Verwendung eines inerten Gases zwischen der UV-Lampe (2) und der Außenwand des Tauchrohrs (3) die Bildung unerwünschter gasförmiger Nebenprodukte verhindert. Die Vorrichtung gemäß der Figur weist auf der Innenwand des Reaktors, der vorzugsweise aus poliertem Edelstahl besteht, Einrich¬ tungen in Form von Protuberanzen auf, die zu turbulenten Strömungen innerhalb des Reaktors führen. Bei höheren Durchflußraten können die Einrichtungen entfallen, sofern die kritische Reynolds-Zahl überschritten wird.The figure shows a particularly preferred embodiment. The reactor 1 has feed and discharge lines. The UV lamp (2) is designed here as a diving lamp. In a particularly preferred embodiment, the outer wall of the immersion tube (3) consists of a glass which acts as a UV filter for wavelengths <230 nm. In particular, Infralux M 235 from Heraeus is used as the material for the wall of the immersion tube (3) in question. The supply and discharge lines (4, 5) are provided for the inlet and outlet of nitrogen. It has been shown that the use of an inert gas between the UV lamp (2) and the outer wall of the dip tube (3) prevents the formation of undesirable gaseous by-products. The device according to the figure has on the inner wall of the reactor, which is preferably made of polished stainless steel, devices in the form of protuberances which lead to turbulent flows within the reactor. At higher flow rates, the devices can be omitted if the critical Reynolds number is exceeded.
Ein Vorteil des erfindungsgemäßen Verfahrens besteht da¬ rin, daß eine kontinuierliche Verfahrensführung zum Abbau von organischen Verbindungen, insbesondere Pflanzenschutz¬ mitteln wie Atrazin ermöglicht wird, ohne dabei oxidieren- de Substanzen wie H20, zur Rückoxidation des durch photo¬ chemische Reaktionen gebildeten Nitrits zu Nitrat anzu¬ setzen. Es ist zur Anwendung des erfindungsgemäßen Ver¬ fahrens möglich, bereits vorhandene Anlagen so umzurüsten, daß Wellenlängen des UV-Lichts von etwa 230 nm oder größer eingesetzt werden können. Dies ist in besonders einfacher Weise möglich durch Einsetzen der entsprechenden UV-Tauch¬ lampen oder Anordnungen von Filtern im Strahlengang, bei¬ spielsweise zwischen Tauchrohr und der zu behandelnden Flüssigkeit. Wird UV-Licht mit Wellenlängenanteilen kleiner 230 nm verwendet, kann das entstehende Nitrit nach der erfindungsgemäßen Verfahrensweise b) zerstört werden.
An advantage of the process according to the invention is that continuous process control for the degradation of organic compounds, in particular crop protection agents such as atrazine, is made possible, without oxidizing substances such as H 2 O, for the re-oxidation of the nitrite formed by photo-chemical reactions to nitrate. To use the method according to the invention, it is possible to retrofit existing systems in such a way that wavelengths of UV light of approximately 230 nm or greater can be used. This is possible in a particularly simple manner by inserting the corresponding UV immersion lamps or arranging filters in the beam path, for example between the immersion tube and the liquid to be treated. If UV light with wavelength components smaller than 230 nm is used, the resulting nitrite can be destroyed by the procedure b) according to the invention.
Claims
1. Verfahren zur Aufbereitung von mit organischen Sub¬ stanzen belastetem Rohtrinkwasser, insbesondere von nitrathaltigem Rohtrinkwasser, das mit Pflanzen¬ schutzmitteln belastet ist durch Behandlung mit UV- Licht, dadurch gekennzeichnet, daß die Aufbereitung des Rohtrinkwassers entweder a) mit ultraviolettem Licht einer Wellenlänge > 230 nm erfolgt oder b) UV-Licht auch mit Anteilen kürzerer Wellenlänge als 230 nm in Verbindung mit Nitrit zerstörenden Sub¬ stanzen verwendet wird.1. Process for the treatment of raw drinking water contaminated with organic substances, in particular nitrate-containing raw drinking water which is contaminated with crop protection agents by treatment with UV light, characterized in that the treatment of the raw drinking water is either a) with ultraviolet light of a wavelength> 230 nm takes place or b) UV light is also used with portions of shorter wavelength than 230 nm in connection with nitrite-destroying substances.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Wellenlänge durch Verwendung eines Filters, der nur UV-Licht > 230 nm durchläßt, ausgewählt wird.2. The method according to claim 1, characterized in that the wavelength is selected by using a filter that only allows UV light> 230 nm.
3. Verfahren nach Anspruch 1 und/oder 2, dadurch ge¬ kennzeichnet, daß zur Erzeugung des ultravioletten Lichts eine Lampe verwendet wird, die zwar eine Emission im Bereich von 230 nm aufweist, jedoch we¬ nig UV-Licht mit Wellenlängen < 230 nm emitiert.3. The method according to claim 1 and / or 2, characterized ge indicates that a lamp is used to generate the ultraviolet light, which has an emission in the range of 230 nm, but little UV light with wavelengths <230 nm emitted.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß als Lampen UV-Tauchlampen (dotiert) der Fa. Heraeus ZI, Z2, Z3, Z4 oder allgemein Edelgas-Ent¬ ladungslampen verwendet werden.4. The method according to claim 3, characterized in that UV immersion lamps (doped) from Heraeus ZI, Z2, Z3, Z4 or generally noble gas discharge lamps are used as lamps.
5. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß als Filter solche aus Infralux M 235 der Fa. Heraeus verwendet werden.5. The method according to claim 2, characterized in that those made of Infralux M 235 from Heraeus are used as filters.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß in der Verfahrensalternative b) als Nitrit zer¬ störende Substanzen organische Säuren oder deren 1-6. The method according to claim 1, characterized in that in the process alternative b) as nitrite zer¬ disruptive substances organic acids or their 1-
Salze, Alkohole, reduzierend wirkende Hydroxyverbin- dungen, Ammoniak, Harnstoff sowie Aminderivate sowie deren Kombinationen verwendet werden.Salts, alcohols, reducing hydroxy compounds, ammonia, urea and amine derivatives and their combinations can be used.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß Ameisensäure, Essigsäure, Zitronensäure, Wein¬ säure oder Salze dieser Säuren, Ethanol, Glucose und reduzierende Zucker, Amidosulfonsaure und deren Salze allein oder in Kombination verwendet werden.7. The method according to claim 6, characterized in that formic acid, acetic acid, citric acid, tartaric acid or salts of these acids, ethanol, glucose and reducing sugars, amidosulfonic acid and their salts are used alone or in combination.
8. Vorrichtung zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 5, mit mindestens einer UV-Lampe, gegebenenfalls als UV-Tauchlampe ausge¬ staltet, einem durchströmten Reaktionsgefäß, das innen eine stark UV-Licht reflektierende Oberfläche besitzt und eine turbulente Strömung zu erzeugen vermag, dadurch gekennzeichnet, daß die UV-Lampe im wesentlichen UV-Licht einer Wellenlänge > 230 nm emittiert und/oder durch in den Strahlengang ge¬ schaltete Filtereinrichtungen UV-Licht der Wellen¬ länge > 230 nm erzeugt wird.8. Device for carrying out the method according to one of claims 1 to 5, with at least one UV lamp, optionally configured as a UV immersion lamp, a flow-through reaction vessel which has a highly UV-reflecting surface on the inside and a turbulent flow capable of generating, characterized in that the UV lamp emits essentially UV light of a wavelength> 230 nm and / or UV light of the wavelength> 230 nm is generated by filter devices connected in the beam path.
9. Vorrichtung nach Anspruch 8, dadurch gekennzeichnet, daß die Filtereinrichtungen aus hochreinem Quarz¬ glas bestehen. 9. The device according to claim 8, characterized in that the filter devices consist of high-purity Quarz¬ glass.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP92916380A EP0597928A1 (en) | 1991-07-26 | 1992-07-22 | Method of processing untreated drinking water contaminated with organic substances |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4124843.0 | 1991-07-26 | ||
DE4124843A DE4124843A1 (en) | 1991-07-26 | 1991-07-26 | Purifying raw drinking water loaded with organic matter - by exposure to long wave UV radiation |
DEP4212604.5 | 1992-04-15 | ||
DE19924212604 DE4212604A1 (en) | 1992-04-15 | 1992-04-15 | Treating drinking water contg. organic substances esp. pesticides |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993002965A1 true WO1993002965A1 (en) | 1993-02-18 |
Family
ID=25905858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1992/001675 WO1993002965A1 (en) | 1991-07-26 | 1992-07-22 | Method of processing untreated drinking water contaminated with organic substances |
Country Status (2)
Country | Link |
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EP (1) | EP0597928A1 (en) |
WO (1) | WO1993002965A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996020136A2 (en) * | 1994-12-28 | 1996-07-04 | Egner, Andrea | Process and device for reducing the nitrate content of water |
EP0721920A1 (en) * | 1995-01-16 | 1996-07-17 | OTV Omnium de Traitements et de Valorisation S.A. | UV irradiation reactor for the treatment of liquids |
WO1997007059A1 (en) * | 1995-08-18 | 1997-02-27 | Lenzing Aktiengesellschaft | Method of processing an aqueous solution in the amine oxide process |
US5847129A (en) * | 1995-08-18 | 1998-12-08 | Lenzing Aktiengesellschaft | Process for the regeneration of an aqueous process liquid of the amine-oxide process |
US6440928B1 (en) | 1988-12-06 | 2002-08-27 | Colorado State University Research Foundation | Method for treating diabetic neuropathy with NGF |
WO2008011650A2 (en) * | 2006-07-26 | 2008-01-31 | Vtu Holding Gmbh | Method for the reduction of nitrate |
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US4144152A (en) * | 1978-03-27 | 1979-03-13 | Atlantic Research Corporation | Dehalogenation of halogenated compounds |
EP0334078A2 (en) * | 1988-03-23 | 1989-09-27 | ENIRICERCHE S.p.A. | Process of photocatalytic degradation of bentazon |
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 |
DE3903549A1 (en) * | 1989-02-07 | 1990-08-09 | Int Biotech Lab | UV light for the degradation of pollutants, in particular of halogenated hydrocarbons |
DE4025078A1 (en) * | 1990-08-08 | 1992-02-13 | Ibl Umwelt Und Biotechnik Gmbh | DEVICE FOR CARRYING OUT PHOTOCHEMICAL REACTIONS |
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1992
- 1992-07-22 WO PCT/EP1992/001675 patent/WO1993002965A1/en not_active Application Discontinuation
- 1992-07-22 EP EP92916380A patent/EP0597928A1/en not_active Withdrawn
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US4144152A (en) * | 1978-03-27 | 1979-03-13 | Atlantic Research Corporation | Dehalogenation of halogenated compounds |
EP0334078A2 (en) * | 1988-03-23 | 1989-09-27 | ENIRICERCHE S.p.A. | Process of photocatalytic degradation of bentazon |
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 |
DE3903549A1 (en) * | 1989-02-07 | 1990-08-09 | Int Biotech Lab | UV light for the degradation of pollutants, in particular of halogenated hydrocarbons |
DE4025078A1 (en) * | 1990-08-08 | 1992-02-13 | Ibl Umwelt Und Biotechnik Gmbh | DEVICE FOR CARRYING OUT PHOTOCHEMICAL REACTIONS |
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CHEMICAL ABSTRACTS, vol. 104, no. 18, 5. Mai 1986, Columbus, Ohio, US; abstract no. 155599s, GRECHKO ET AL. 'Detoxication of aqueous pesticide solution by photolysis' Seite 422 ;Spalte 1 ; in der Anmeldung erwähnt * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6440928B1 (en) | 1988-12-06 | 2002-08-27 | Colorado State University Research Foundation | Method for treating diabetic neuropathy with NGF |
WO1996020136A2 (en) * | 1994-12-28 | 1996-07-04 | Egner, Andrea | Process and device for reducing the nitrate content of water |
WO1996020136A3 (en) * | 1994-12-28 | 1996-09-06 | Egner Siegfried | Process and device for reducing the nitrate content of water |
EP0721920A1 (en) * | 1995-01-16 | 1996-07-17 | OTV Omnium de Traitements et de Valorisation S.A. | UV irradiation reactor for the treatment of liquids |
FR2729382A1 (en) * | 1995-01-16 | 1996-07-19 | Omnium Traitement Valorisa | UV IRRADIATION REACTOR FOR THE TREATMENT OF LIQUIDS |
US5725757A (en) * | 1995-01-16 | 1998-03-10 | Otv Omnium De Traitements Et De Valorisation (Societe Anonyme) | Reactor for UV radiation for the treatment of liquids |
WO1997007059A1 (en) * | 1995-08-18 | 1997-02-27 | Lenzing Aktiengesellschaft | Method of processing an aqueous solution in the amine oxide process |
AU698554B2 (en) * | 1995-08-18 | 1998-10-29 | Lenzing Aktiengesellschaft | Process for the regeneration of an aqeous process liquid of the amine-oxide process |
US5847129A (en) * | 1995-08-18 | 1998-12-08 | Lenzing Aktiengesellschaft | Process for the regeneration of an aqueous process liquid of the amine-oxide process |
WO2008011650A2 (en) * | 2006-07-26 | 2008-01-31 | Vtu Holding Gmbh | Method for the reduction of nitrate |
WO2008011650A3 (en) * | 2006-07-26 | 2008-04-24 | Vtu Engineering Planungs Und B | Method for the reduction of nitrate |
Also Published As
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