WO2003006383A1 - Method for purifying water - Google Patents
Method for purifying water Download PDFInfo
- Publication number
- WO2003006383A1 WO2003006383A1 PCT/DE2002/001915 DE0201915W WO03006383A1 WO 2003006383 A1 WO2003006383 A1 WO 2003006383A1 DE 0201915 W DE0201915 W DE 0201915W WO 03006383 A1 WO03006383 A1 WO 03006383A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lead
- water
- alkylene
- groundwater
- contaminated
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Definitions
- the invention relates to a process for the purification of water which is contaminated with lead alkylene.
- Lead tetraethyl and lead tetramethyl have been added extensively as anti-knock agents to petrol. Due to the toxicity and also the carcinogenicity of lead alkyls and the corresponding degradation products, use in Europe has been kept to a minimum. In some countries, regardless of lead alkyls continue to be used as an anti-knock agent.
- R is methyl or ethyl and LL corresponds to an inorganic acid residue, such as C0 3 or SO 4 2-
- the lead alkyls mainly affect the central nervous system in humans and can cause excitement, epileptic cramps and also Parkinsonism. Lead poisoning is also observed with chronic exposure. Contamination of the soil and thus the groundwater is particularly problematic because it can then be easily and permanently absorbed through the drinking water. Therefore, there is a need to remove the lead alkyl contaminant.
- the oxidation of lead alkylene with oxygen under the influence of UV light is described by Willemsens, LC in Intern. Lead Zinc Res. Org. Inc. New York, 1967.
- a similar process is disclosed in EP 0 714 712 AI, in which the lead alkyls contained in the water are decomposed with UV light with the addition of H 2 0 2 , which releases oxygen, and iron-III salts (Fenton's reagent) and then with Flocculant is precipitated.
- the contaminated water is activated carbon or inorganic silicates, e.g. B. Zeolite, cleaned.
- a disadvantage of this method is that only the lead tetraalkyls which are insoluble in water are removed by adsorption. Tri and dialkyls, which are very soluble in water, are not or only to a very small extent adsorbed. This measure does not make sense because the previous oxygen treatment essentially only contains the water-soluble tri- and dialkyls in the water. The cleaning effect is accordingly unsatisfactory.
- US Pat. No. 5,656,489 describes a process for the reduction of lead-organic compounds, in particular lead-ethyl, in contaminated, natural media, which uses microorganisms which degrade the compounds mentioned to form inorganic lead compounds.
- This process is economically and technically complex, since the population of the microorganisms in question must have a certain size in order to break down the lead compounds in a manageable time.
- the parameters according to the invention are observed, this is a very lengthy process in which the microorganisms have to be constantly supplied with additional nutrients in order to keep the population.
- the lead is not completely removed from the ground, but only converted into less toxic forms, which only offers a relative advantage.
- a method is provided according to the invention in which the water contaminated with lead alkylene is treated by means of organic cation exchangers.
- Cation exchangers with chelating groups e.g. the cation exchanger TP 207 from Bayer AG, but also water-softening ion exchangers, e.g. Amberlite from Rohm & Haas.
- the ion exchangers used are regenerated with acids, sodium chloride solution and hot water.
- the regeneration eluate is made according to known methods at elevated temperatures, i.e. > 60 ° C treated with ozone, the organic lead compounds being converted quantitatively into inorganic lead. This in turn can then be precipitated as sulfide.
- the method of purifying water according to the invention is of course not only for groundwater, but e.g. also suitable for water obtained for washing out contaminations according to known methods.
- Groundwater is drawn from a depth of 3 m on a company site that was used to manufacture the lead tetraethyl anti-knock agent. 350 1 of this water are mixed over 1 1 of a selective exchange resin TP 207 from Bayer AG cleaned. The exchange resin was in the Na + form.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Soil Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
Titel: Verfahren zur Reinigung von WasserTitle: Process for purifying water
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Reinigung von Wasser, das mit Bleialkylen verunreinigt ist.The invention relates to a process for the purification of water which is contaminated with lead alkylene.
Bleitetraethyl und Bleitetramethyl wurden in großem Umfang als Antiklopfmittel Ottokraftstoffen zugesetzt. Aufgrund der Giftigkeit und auch der Carcinogenität der Bleialkyle bzw. der entsprechenden Abbauprodukte wurde u.a. in Europa die Verwendung auf ein Minimum beschränkt. In einigen Ländern werden des- sen ungeachtet Bleialkyle weiterhin als Antiklopfmittel eingesetzt .Lead tetraethyl and lead tetramethyl have been added extensively as anti-knock agents to petrol. Due to the toxicity and also the carcinogenicity of lead alkyls and the corresponding degradation products, use in Europe has been kept to a minimum. In some countries, regardless of lead alkyls continue to be used as an anti-knock agent.
In Fabriken zur Herstellung von Bleialkylen sind durch Leckverluste größere Mengen an Bleialkylen in den Boden und später durch Regenauswaschung in das Grundwasser gelangt.In factories in the production of lead alkylene, large amounts of lead alkylene have got into the ground due to leakage and later into the groundwater through washing out rain.
Im Boden und im Grundwasser findet über die Jahre hinweg ein langsamer Abbau der Bleialkyle von den Tetra- über die Tri- und Di-Verbindungen zu anorganischem Blei gemäß nachfolgendem Schema statt:In the soil and in the groundwater there is a slow degradation of the lead alkyls from the tetra- via the tri- and di-compounds to inorganic lead according to the following scheme:
PbR4 → PbR3 + → PbR2 2+ → Pb2+L2",PbR 4 → PbR 3 + → PbR 2 2+ → PbR 2+ L 2 " ,
wobei R Methyl oder Ethyl uunndd LL eeiinneem anorganischen Säurerest, wie C03 oder SO4 2- entsprichtwhere R is methyl or ethyl and LL corresponds to an inorganic acid residue, such as C0 3 or SO 4 2-
Die Bleialkyle wirken beim Menschen vorwiegend auf das Zentrale Nervensystem und können Erregungszustände, epileptische Krämpfe und auch Parkinsonismus hervorrufen. Bei chronischer Einwirkung werden auch Bleivergiftungen beobachtet. Die Verunreinigung von Boden und damit auch dem Grundwasser ist besonders problematisch, da es dann leicht und dauerhaft über das Trinkwasser aufgenommen werden kann. Daher besteht die Notwendigkeit, die Bleialkyl-Verunreinigung zu entfernen.The lead alkyls mainly affect the central nervous system in humans and can cause excitement, epileptic cramps and also Parkinsonism. Lead poisoning is also observed with chronic exposure. Contamination of the soil and thus the groundwater is particularly problematic because it can then be easily and permanently absorbed through the drinking water. Therefore, there is a need to remove the lead alkyl contaminant.
Zur Reinigung von Grundwasser bei Verunreinigung mit Bleialkylen liegen bisher nur relativ wenige Erfahrungen vor, wobei sich von vornherein auch nur Verfahren anbieten, die eine zusätzliche Kontamination des Wassers, z.B. durch die Verwendung von Halogenen, d. h. Fluor, Chlor und Brom, vermeiden (Schulze, Chem.Ztg.64, 47, 1940) .To date, there has been relatively little experience with the cleaning of groundwater in the event of contamination with lead alkylene, although from the outset only methods are available that involve additional contamination of the water, e.g. through the use of halogens, i.e. H. Avoid fluorine, chlorine and bromine (Schulze, Chem. Ztg. 64, 47, 1940).
Die Oxidation von Bleialkylen mit Sauerstoff unter Einfluß von UV-Licht, wird von Willemsens , L. C. in Intern. Lead Zinc Res . Org . Inc. New York, 1967, beschrieben. Ein ähnliches Verfahren wird in der EP 0 714 712 AI offenbart, bei dem die im Wasser enthaltenden Bleialkyle mit UV-Licht unter Zusatz von H202, das Sauerstoff freisetzt, und Eisen -III- Salzen (Fentons Reagenz) zersetzt und anschließend mit Flok- kungsmitteln gefällt wird. Weiterhin wird das kontaminierte Wasser nach einer Ausführungsform des Verfahrens durch Aktivkohle oder anorganische Silicate, z. B. Zeolite, gereinigt. Nachteilig bei dieser Methode ist, daß durch Adsorption nur die in wasserunlöslichen Bleitetraalkyle entfernt werden. Tri- und Dialkyle, die in Wasser sehr gut löslich sind, werden nicht oder nur zu sehr geringen Teilen adsorbiert. Da durch die vorhergehende Sauerstoffbehandlung im wesentlichen nur die wasserlöslichen Tri- und Dialkyle im Wasser vorhanden sind, ist diese Maßnahme nicht sinnvoll. Der Abreinigungseffekt ist dementsprechend unbefriedigend.The oxidation of lead alkylene with oxygen under the influence of UV light is described by Willemsens, LC in Intern. Lead Zinc Res. Org. Inc. New York, 1967. A similar process is disclosed in EP 0 714 712 AI, in which the lead alkyls contained in the water are decomposed with UV light with the addition of H 2 0 2 , which releases oxygen, and iron-III salts (Fenton's reagent) and then with Flocculant is precipitated. Furthermore, according to one embodiment of the method, the contaminated water is activated carbon or inorganic silicates, e.g. B. Zeolite, cleaned. A disadvantage of this method is that only the lead tetraalkyls which are insoluble in water are removed by adsorption. Tri and dialkyls, which are very soluble in water, are not or only to a very small extent adsorbed. This measure does not make sense because the previous oxygen treatment essentially only contains the water-soluble tri- and dialkyls in the water. The cleaning effect is accordingly unsatisfactory.
Da die Behandlung von Bleitetraethyl mit Ozon im Abwasser in Gegenwart von Silicagel als Katalysator bekannt ist(Linch et al., Am. Ind. Hyg. Assoc. J. 25, 1964), läßt sich vermuten, daß bei vorhergehendem Verfahren die Adsorbentien nicht als solche, sondern als Katalysatoren zur Oxidation des Tetraethylblei verwendet werden sollen. Das Problem der im Wasser gelösten Abbauprodukte bleibt bestehen.Since the treatment of lead tetraethyl with ozone in the waste water in the presence of silica gel as a catalyst is known (Linch et al., Am. Ind. Hyg. Assoc. J. 25, 1964), it can be assumed that in the previous process the adsorbents are not considered as such, but should be used as catalysts for the oxidation of tetraethyl lead. The problem of the degradation products dissolved in the water remains.
Die vorgenannten Verfahren sind für die Reinigung von Abwässern sind überwiegend energetisch sehr aufwendig und teuer. Zudem führen diese nur bei Temperaturen > 50°C zur völligen Zersetzung der Bleialkyle. In kontaminiertem Grundwasser liegen die Bleialkylkonzentrationen üblicherweise um 1 - 3 Zehnerpotenzen niedriger als bei den in der Literatur beschriebenen Verfahren, so daß der Aufwand unvertretbar hoch wäre.The abovementioned processes for the purification of waste water are predominantly very complex and expensive in terms of energy. In addition, these lead to the complete decomposition of the lead alkyls only at temperatures> 50 ° C. In contaminated groundwater, the lead alkyl concentrations are usually 1 to 3 orders of magnitude lower than in the processes described in the literature, so that the effort would be unacceptably high.
In der US-PS 5,656,489 wird ein Verfahren zur Reduktion von bleiorganischen Verbindungen, insbesondere von Bleiteraethyl in verunreinigten, natürlichen Medien beschrieben, das von Mikroorganismen Gebrauch macht, die die genannten Verbindungen zu anorganischen Bleiverbindungen abbauen. Dieses Verfahren ist wirtschaftlich und technisch aufwendig, da die Population der betreffenden Mikroorganismen eine bestimmte Größe besitzen muß, um die Bleiverbindungen in überschaubarer Zeit abzubauen. Doch auch bei Einhaltung der erfindungsgemäßen Parameter ist dies ein sehr langwieriges Verfahren, bei dem ständig die Mikroorganismen mit zusätzlichen Nährstoffen versorgt werden müssen, um die Population zu halten. Zudem wird das Blei nicht vollständig aus dem Boden entfernt, sondern nur in weniger giftige Formen umgewandelt, was nur einen relativen Vorteil bietet.US Pat. No. 5,656,489 describes a process for the reduction of lead-organic compounds, in particular lead-ethyl, in contaminated, natural media, which uses microorganisms which degrade the compounds mentioned to form inorganic lead compounds. This process is economically and technically complex, since the population of the microorganisms in question must have a certain size in order to break down the lead compounds in a manageable time. However, even if the parameters according to the invention are observed, this is a very lengthy process in which the microorganisms have to be constantly supplied with additional nutrients in order to keep the population. In addition, the lead is not completely removed from the ground, but only converted into less toxic forms, which only offers a relative advantage.
Aus der US-PS 6,030,467 ist ein Verfahren zur Reinigung u.a. von Schlamm und Boden bekannt, bei dem bleiorganische Verbindungen mittels einer wäßrigen Lösung eines oberflächenaktiven Stoffes ausgewaschen werden. Dieses Verfahren ist nicht geeignet, um bereits- im Grundwasser befindliche Verunreinigungen zu entfernen. Zudem ist der Aufwand bei großflächigen Verunreinigungen sehr hoch.From US Pat. No. 6,030,467 a method for cleaning i.a. known from sludge and soil, in which lead organic compounds are washed out by means of an aqueous solution of a surface-active substance. This method is not suitable for removing contaminants that are already in the groundwater. In addition, the effort involved in large-scale contamination is very high.
Es ist daher Aufgabe der Erfindung, ein Verfahren zu schaffen, mit dem Bleialkyle einfach, kostengünstig und nahezu quantitativ aus verunreinigtem Wasser, insbesondere Grundwasser entfernt werden können.It is therefore an object of the invention to provide a method with which lead alkyls can be removed easily, inexpensively and almost quantitatively from contaminated water, in particular groundwater.
Diese Aufgabe wird durch ein Verfahren mit den Merkmalen des Anspruchs 1 gelöst.This object is achieved by a method with the features of claim 1.
Dazu ist erfindungsgemäß ein Verfahren vorgesehen, bei dem das mit Bleialkylen verunreinigte Wasser mittels organischen Katio- nentauschern behandelt wird.For this purpose, a method is provided according to the invention in which the water contaminated with lead alkylene is treated by means of organic cation exchangers.
Überraschend wurde nämlich festgestellt, daß nicht nur die in Ionenform vorliegenden niedrigalkylierten Bleiorganika PbR3 + und PbR2 2+ durch Ionenaustausch, sondern auch die ungeladenen hochalkylierten Verbindungen PbR adsorptiv gebunden werden, so daß es sich bei dem erfindungsgemäßen Verfahren um 'ein kombiniertes Adsorptions- und Ionenaustauscherverfahren handelt. Vorteilhafterweise werden durch die Anwendung des Verfahrens 99% der im Grundwasser vorhandenen organischen Bleikontaminationen entfernt. Ein wesentlicher und vorteilhafter Nebeneffekt der Erfindung ist dadurch gegeben, daß auch der überwiegende Teil des anorganischen Bleis im Ionenaustauscher verbleibt.Surprisingly, it has namely been found that not only present in ionic form niedrigalkylierten Bleiorganika PbR be bound 3 + and PbR 2 2+ by ion exchange, but also the uncharged highly alkylated compounds PbR adsorption, so that it is in the inventive method to 'a combined adsorption and ion exchange processes. Advantageously, 99% of the organic lead contamination present in the groundwater is removed by using the method. An essential and advantageous side effect of the invention is that the major part of the inorganic lead remains in the ion exchanger.
Durch gezielte Auswahl des Kationenaustauschers gelingt es, nur Schwermetalle aus dem Wasser zu eliminieren. Bevorzugt werden Kationenaustauscher mit Chelatbildnergruppen, wie z.B. der Kationenaustauscher TP 207 der Bayer AG, aber auch wasserenthärtende Ionenaustauscher, wie z.B. Amberlite der Fa. Rohm & Haas.By carefully selecting the cation exchanger, only heavy metals can be eliminated from the water. Cation exchangers with chelating groups, e.g. the cation exchanger TP 207 from Bayer AG, but also water-softening ion exchangers, e.g. Amberlite from Rohm & Haas.
Die Regenerierung der verwendeten Ionenaustauscher erfolgt mit Säuren, Natriumchloridlösung und heißem Wasser. Das Regenerie- rungseluat wird gemäß bekannten Verfahren bei erhöhten Temperaturen, d.h. > 60°C mit Ozon behandelt, wobei die organischen Bleiverbindungen quantitativ in anorganisches Blei überführt werden. Dieses wiederum kann anschließend als Sulfid gefällt werden .The ion exchangers used are regenerated with acids, sodium chloride solution and hot water. The regeneration eluate is made according to known methods at elevated temperatures, i.e. > 60 ° C treated with ozone, the organic lead compounds being converted quantitatively into inorganic lead. This in turn can then be precipitated as sulfide.
Das erfindungsgemäße Verfahren zur Reinigung von Wasser ist natürlich nicht nur für Grundwasser, sondern z.B. auch für Wasser, das zum Auswaschen von Kontaminierungen gemäß bekannter Verfahren anfällt, geeignet.The method of purifying water according to the invention is of course not only for groundwater, but e.g. also suitable for water obtained for washing out contaminations according to known methods.
Weitere vorteilhafte Ausgestaltungen der Erfindung sind in den Unteransprüchen gekennzeichnet.Further advantageous embodiments of the invention are characterized in the subclaims.
Nachstehend wird die Erfindung anhand eines Beispiels näher erläutert.The invention is explained in more detail below using an example.
Beispielexample
Auf einem Betriebsgelände, das der Herstellung des Antiklopfmittels Bleitetraethyl diente, wird aus 3 m Tiefe Grundwasser entnommen. 350 1 dieses Wassers werden über 1 1 eines Selektiv- austauscherharzes TP 207 der Fa. Bayer AG abgereinigt. Das Austauscherharz lag in der Na+-Form vor.Groundwater is drawn from a depth of 3 m on a company site that was used to manufacture the lead tetraethyl anti-knock agent. 350 1 of this water are mixed over 1 1 of a selective exchange resin TP 207 from Bayer AG cleaned. The exchange resin was in the Na + form.
Folgende Resultate wurden erzielt:The following results were achieved:
Claims
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02749015A EP1406842A1 (en) | 2001-07-13 | 2002-07-12 | Process for the extraction of an organic heavy metal compound from an aqueous medium |
| PCT/GB2002/003215 WO2003008339A1 (en) | 2001-07-13 | 2002-07-12 | Process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10133570A DE10133570C1 (en) | 2001-07-13 | 2001-07-13 | Purification of water, especially ground water, contaminated with lead alkyls, especially lead methyl and lead ethyl, comprises passing water through organic cation exchanger |
| DE10133570.9 | 2001-07-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2003006383A1 true WO2003006383A1 (en) | 2003-01-23 |
Family
ID=7691329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DE2002/001915 Ceased WO2003006383A1 (en) | 2001-07-13 | 2002-05-23 | Method for purifying water |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE10133570C1 (en) |
| WO (1) | WO2003006383A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8025899B2 (en) | 2003-08-28 | 2011-09-27 | Abbott Laboratories | Solid pharmaceutical dosage form |
| US9107830B2 (en) | 1999-11-12 | 2015-08-18 | Abbvie, Inc. | Inhibitors of crystallization in a solid dispersion |
| CN107651783A (en) * | 2017-11-07 | 2018-02-02 | 长沙埃比林环保科技有限公司 | A kind of method of ion-exchange treatment lead waste water |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3308061A (en) * | 1965-03-05 | 1967-03-07 | Du Pont | Ozone treatment of waste aqueous effluent from alkyllead manufacture |
| DE2344279A1 (en) * | 1972-09-05 | 1974-03-21 | Rohm & Haas | REDUCTION OF LEAD IN ORGANIC LIQUIDS |
| DE2452571A1 (en) * | 1973-11-09 | 1975-05-15 | Ass Octel | PROCESS FOR REDUCING THE LEAD CONTENT OF AQUATIC MEDIA CONTAINING ORGANIC LEAD IONS IN SOLUTION |
| US3919077A (en) * | 1972-12-29 | 1975-11-11 | Darrell Duayne Whitehurst | Sorbent for removal of heavy metals |
| US4070282A (en) * | 1975-04-15 | 1978-01-24 | Ppg Industries, Inc. | Method of removing dissolved organo-lead compounds from water |
| US4592843A (en) * | 1984-10-03 | 1986-06-03 | Morton Thiokol, Inc. | Method for removal of organometallics from wastewater |
| EP0714712A1 (en) * | 1994-11-28 | 1996-06-05 | Degussa Aktiengesellschaft | Method of decontaminating soil |
| GB2350356A (en) * | 1998-11-18 | 2000-11-29 | Univ Northumbria Newcastle | Removal of organometallic material from liquids |
-
2001
- 2001-07-13 DE DE10133570A patent/DE10133570C1/en not_active Expired - Fee Related
-
2002
- 2002-05-23 WO PCT/DE2002/001915 patent/WO2003006383A1/en not_active Ceased
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3308061A (en) * | 1965-03-05 | 1967-03-07 | Du Pont | Ozone treatment of waste aqueous effluent from alkyllead manufacture |
| DE2344279A1 (en) * | 1972-09-05 | 1974-03-21 | Rohm & Haas | REDUCTION OF LEAD IN ORGANIC LIQUIDS |
| US3919077A (en) * | 1972-12-29 | 1975-11-11 | Darrell Duayne Whitehurst | Sorbent for removal of heavy metals |
| DE2452571A1 (en) * | 1973-11-09 | 1975-05-15 | Ass Octel | PROCESS FOR REDUCING THE LEAD CONTENT OF AQUATIC MEDIA CONTAINING ORGANIC LEAD IONS IN SOLUTION |
| US4070282A (en) * | 1975-04-15 | 1978-01-24 | Ppg Industries, Inc. | Method of removing dissolved organo-lead compounds from water |
| US4592843A (en) * | 1984-10-03 | 1986-06-03 | Morton Thiokol, Inc. | Method for removal of organometallics from wastewater |
| EP0714712A1 (en) * | 1994-11-28 | 1996-06-05 | Degussa Aktiengesellschaft | Method of decontaminating soil |
| GB2350356A (en) * | 1998-11-18 | 2000-11-29 | Univ Northumbria Newcastle | Removal of organometallic material from liquids |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9107830B2 (en) | 1999-11-12 | 2015-08-18 | Abbvie, Inc. | Inhibitors of crystallization in a solid dispersion |
| US8025899B2 (en) | 2003-08-28 | 2011-09-27 | Abbott Laboratories | Solid pharmaceutical dosage form |
| US8268349B2 (en) | 2003-08-28 | 2012-09-18 | Abbott Laboratories | Solid pharmaceutical dosage form |
| US8309613B2 (en) | 2003-08-28 | 2012-11-13 | Abbvie Inc. | Solid pharmaceutical dosage form |
| US8333990B2 (en) | 2003-08-28 | 2012-12-18 | Abbott Laboratories | Solid pharmaceutical dosage form |
| US8399015B2 (en) | 2003-08-28 | 2013-03-19 | Abbvie Inc. | Solid pharmaceutical dosage form |
| US8691878B2 (en) | 2003-08-28 | 2014-04-08 | Abbvie Inc. | Solid pharmaceutical dosage form |
| CN107651783A (en) * | 2017-11-07 | 2018-02-02 | 长沙埃比林环保科技有限公司 | A kind of method of ion-exchange treatment lead waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10133570C1 (en) | 2002-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0818421B1 (en) | Process and apparatus for treatment of swimmingpool water and for keeping it clean | |
| DE1517526C3 (en) | Process for the production of potable water from wastewater | |
| EP3599226B1 (en) | Method and device for enriching silicate in drinking water | |
| DE2608408A1 (en) | METHOD AND DEVICE FOR TREATMENT OF DRINKING WATER | |
| EP0371187B1 (en) | Process for removing substances for plant treatment from raw water | |
| WO2006002054A2 (en) | Hydrogen peroxide based water treatment system and method | |
| DE69404734T2 (en) | Process and device for decontaminating liquids containing ionic metals | |
| DE602004002271T2 (en) | BIOLOGICAL REMOVAL OF OXYANIONES-LIKE PERCHLORATE ON ION EXCHANGE RESINS | |
| DE3903549A1 (en) | UV light for the degradation of pollutants, in particular of halogenated hydrocarbons | |
| DE3742063A1 (en) | METHOD FOR DETOXIFYING SEWAGE CONTAINING ELEMENTAL MERCURY | |
| DE10133570C1 (en) | Purification of water, especially ground water, contaminated with lead alkyls, especially lead methyl and lead ethyl, comprises passing water through organic cation exchanger | |
| DE68906119T2 (en) | Process for the treatment of waste water containing amine. | |
| DE4339887A1 (en) | Process for the treatment of waste water containing organic and inorganic compounds | |
| DE4016514A1 (en) | Destruction of organic substances - esp. aromatic and/or halogenated cpds. in liq. or gases by irradiation with UV | |
| DE102010020105A1 (en) | Method for photocatalytic treatment of wastewater containing oxidizing component with iron ions, comprises supplying a compound containing oxidation agent and iron(II)ions to wastewater and adjusting the pH-value of the mixture | |
| DE4442248A1 (en) | Soil decontamination process | |
| Yeh et al. | The fate of dissolved organics in water purification processes treating polluted raw water | |
| DE19624982A1 (en) | Use of humic acid or derivatives in purifying waste water, exhaust gas etc | |
| DE2826107A1 (en) | METHOD AND DEVICE FOR TREATING DRINKING WATER | |
| DE2408778C2 (en) | Process for the degradation of pseudohalides contained in waste water | |
| JPH06285368A (en) | Regenerating method of zeolite for removing ammonia | |
| Provin et al. | What's in My Water? | |
| DE202005019293U1 (en) | Apparatus for removing particles and dissolved materials from swimming bath water has prefiltration unit, flocculating agent injection point and ultrafiltration unit, some filtrate being dechlorinated and treated by reverse osmosis | |
| WO2003008339A1 (en) | Process | |
| WO2001004062A1 (en) | Method and device for treating water, especially drinking water, and for maintaining the purity thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: JP |
|
| WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |