DE19806001A1 - Dehalogenation of aqueous hydrocarbon solutions, e.g. ground- or waste water - Google Patents
Dehalogenation of aqueous hydrocarbon solutions, e.g. ground- or waste waterInfo
- Publication number
- DE19806001A1 DE19806001A1 DE1998106001 DE19806001A DE19806001A1 DE 19806001 A1 DE19806001 A1 DE 19806001A1 DE 1998106001 DE1998106001 DE 1998106001 DE 19806001 A DE19806001 A DE 19806001A DE 19806001 A1 DE19806001 A1 DE 19806001A1
- Authority
- DE
- Germany
- Prior art keywords
- dehalogenation
- ground
- waste water
- nickel
- zinc
- 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.)
- Withdrawn
Links
- 238000005695 dehalogenation reaction Methods 0.000 title claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 title abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 3
- 239000003673 groundwater Substances 0.000 title description 3
- 239000002351 wastewater Substances 0.000 title description 2
- 239000004215 Carbon black (E152) Substances 0.000 title 1
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910007567 Zn-Ni Inorganic materials 0.000 claims description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- -1 hydrogen halides Chemical class 0.000 claims 1
- 239000006069 physical mixture Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical compound Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- SORXVYYPMXPIFD-UHFFFAOYSA-N iron palladium Chemical compound [Fe].[Pd] SORXVYYPMXPIFD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010792 warming Methods 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
Description
Die Erfindung richtet sich auf ein Verfahren zur Zerstörung von in Wasser gelösten halogenierten Kohlenwasserstoffen mit Hilfe von nullwertigem vernickeltem Zink. Da bei findet an der Zink- Oberfläche eine Redox-Reaktion statt, bei der das Zink oxidiert und die HKW reduziert werden. Diese Reaktion läßt sich auch als Hydrierreaktion beschreiben, in der das Halogen durch eine Wasserstoffatom ersetzt wird. Das nur in geringen Mengen auf dem Zink-Körper gebrachte nullwertige Nickel fungiert dabei als Hydrierkatalysator. Nickel verbraucht sich in der Reaktion nicht. Wohingegen Zink als Reaktionspartner zu den halogenierten Stoffen gesehen wird.The invention relates to a method for the destruction of halogenated in water Hydrocarbons with the help of zero-value nickel-plated zinc. There takes place at the zinc A redox reaction takes place on the surface, in which the zinc is oxidized and the HKW is reduced. This reaction can also be described as a hydrogenation reaction in which the halogen is passed through a Hydrogen atom is replaced. That was only applied to the zinc body in small quantities Zero-valent nickel acts as a hydrogenation catalyst. Nickel is consumed in the reaction Not. Whereas zinc is seen as a reactant to the halogenated substances.
Die Erfindung baut auf das in DE 690 25 479T2 von Gillham patentierte Verfahren auf. Dort werden jedoch zur Zerstörung halogenierter Kohlenwasserstoffe im Wasser (resp. Grundwasser) Eisenpartikel eingesetzt.The invention is based on the method patented in DE 690 25 479T2 by Gillham. There are used to destroy halogenated hydrocarbons in water (or groundwater) Iron particles used.
Das Verfahren mit Zn-Ni-Körpern hat jedoch den außerordentlichen Vorteil, daß die Zerstörung wesentliche schneller von statten geht. Dadurch ist der Einsatzbereich dieser Reaktoren um ein vielfaches größer. Die Reaktordimensionen können klein gehalten und dadurch Kosten eingespart werden. Weiter wird wesentlich weniger Reaktionsmaterial gebraucht und somit können die Kosten nochmals reduziert werden.The method with Zn-Ni bodies has the extraordinary advantage that the destruction goes much faster. As a result, the area of application of these reactors is around one many times larger. The reactor dimensions can be kept small and thus costs be saved. Furthermore, much less reaction material is needed and therefore the costs can be reduced again.
Da die Reaktionen bereits bei niedrigen Temperaturen ablaufen ist der Einsatz auch in insitu im Grundwasser oder Abwasserstrom ohne vorherige Aufwärmung des Systems einsetzbar.Since the reactions take place at low temperatures, use is also possible in situ Groundwater or wastewater flow can be used without prior warming up of the system.
In der Patentschrift PCT US95/16529 werden paladisierte Eisenkörper zur Dehaloginierung eingesetzt. Dieses System hat jedoch den Nachteil, daß diese Stoffe sehr teuer in der Anschaffung sind. Der Zink-Nickel-Körper ist billig in der Anschaffung und hat daher große Vorteile gegenüber der Eisen-Palladium-Methode.In the patent specification PCT US95 / 16529 paladized iron bodies are used for dehalogenation used. However, this system has the disadvantage that these substances are very expensive to produce Purchase. The zinc-nickel body is inexpensive to purchase and therefore has a large size Advantages over the iron palladium method.
Die Reaktion läuft bei Zimmertemperatur und darunter ab. Um etwa 40 mg/l Tetrachlorethen vollkommen zu zerstören werden weniger als 4 Stunden benötigt. Zerstört werden mit diesem Verfahren bevorzugt die Stoffe, Trichlorethen, Trichlorethan, Tetrachlorethen und cis-1,2 Dichlorethen.The reaction takes place at room temperature and below. Around 40 mg / l tetrachloroethene completely destroy it takes less than 4 hours. Be destroyed with this Process prefers the substances, trichlorethylene, trichloroethane, tetrachlorethylene and cis-1,2 Dichloroethene.
Das Zink ist in Form eines Pulvers bzw. Granulates von Korngrößen von 0,01 mm bis 3 mm und wurde mittels einer Nickelchlorid-Lösung mit Nickel teilweise galvanisch überzogen. Das Nickel ist fest auf die Zinkoberfläche gebunden und nimmt an der Hydrierfunktion nur in sofern teil, als daß es die eigentliche Reaktion auf katalytischem Wege begünstigt.The zinc is in the form of a powder or granulate with grain sizes from 0.01 mm to 3 mm and was partially electroplated with nickel using a nickel chloride solution. The nickel is firmly bound to the zinc surface and only takes part in the hydrogenation function insofar as that it favors the actual reaction catalytically.
Die mit halogenierten Kohlenwasserstoffen versehene wäßrige Lösung wird durch den Zink- Nickel-Körper geleitet, so daß eine möglichst große Kontaktfläche zwischen Wasser und Zink- Nickel-Körper vorhanden ist. Die Dimension des Zink-Nickel-Körpers ist abhängig von den Gehalten an halogenen Kohlenwasserstoffen und von der erforderlichen Abreinigungsleistung.The aqueous solution provided with halogenated hydrocarbons is Nickel body so that the largest possible contact area between water and zinc Nickel body is present. The dimension of the zinc-nickel body depends on the Contained in halogenated hydrocarbons and the required cleaning performance.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998106001 DE19806001A1 (en) | 1998-02-16 | 1998-02-16 | Dehalogenation of aqueous hydrocarbon solutions, e.g. ground- or waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998106001 DE19806001A1 (en) | 1998-02-16 | 1998-02-16 | Dehalogenation of aqueous hydrocarbon solutions, e.g. ground- or waste water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19806001A1 true DE19806001A1 (en) | 1999-08-19 |
Family
ID=7857674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1998106001 Withdrawn DE19806001A1 (en) | 1998-02-16 | 1998-02-16 | Dehalogenation of aqueous hydrocarbon solutions, e.g. ground- or waste water |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19806001A1 (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382865A (en) * | 1978-09-14 | 1983-05-10 | Envirogenics Systems Company | Treatment of reducible halohydrocarbon containing aqueous stream |
| EP0361581A1 (en) * | 1988-09-26 | 1990-04-04 | Solvay | Process for the purification of aqueous acid effluents containing halogenated compounds |
| DE3839329A1 (en) * | 1988-11-22 | 1990-05-31 | Basf Ag | METHOD FOR THE REDUCTIVE ENTHALOGENATION OF AROMATES |
| US4959155A (en) * | 1989-05-23 | 1990-09-25 | Luis Gomez | Method for the purification of fluids such as water, aqueous fluids and fuel fluids |
| EP0389650A1 (en) * | 1987-05-26 | 1990-10-03 | The Dow Chemical Company | Process and catalyst for the dehydrohalogenation of halogenated hydrocarbons or alkylene halohydrins |
| DE3941813C2 (en) * | 1989-12-19 | 1992-01-30 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De | |
| US5276240A (en) * | 1991-10-18 | 1994-01-04 | Board Of Regents, The University Of Texas System | Catalytic hydrodehalogenation of polyhalogenated hydrocarbons |
| DE4236724A1 (en) * | 1992-10-30 | 1994-05-05 | Schering Ag | Process for the recovery of iodine from iodinated organic compounds |
| US5411664A (en) * | 1992-09-28 | 1995-05-02 | W. R. Grace & Co.-Conn. | Method for dehalogenation and degradation of halogenated organic contaminants |
| DE4407057A1 (en) * | 1994-03-03 | 1995-09-07 | Dechema | Electrochemical degradation of halogenated hydrocarbon(s) in polluted water |
| EP0677501A1 (en) * | 1994-04-14 | 1995-10-18 | The Dow Chemical Company | Hydrodechlorination process |
-
1998
- 1998-02-16 DE DE1998106001 patent/DE19806001A1/en not_active Withdrawn
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382865A (en) * | 1978-09-14 | 1983-05-10 | Envirogenics Systems Company | Treatment of reducible halohydrocarbon containing aqueous stream |
| EP0389650A1 (en) * | 1987-05-26 | 1990-10-03 | The Dow Chemical Company | Process and catalyst for the dehydrohalogenation of halogenated hydrocarbons or alkylene halohydrins |
| EP0361581A1 (en) * | 1988-09-26 | 1990-04-04 | Solvay | Process for the purification of aqueous acid effluents containing halogenated compounds |
| DE3839329A1 (en) * | 1988-11-22 | 1990-05-31 | Basf Ag | METHOD FOR THE REDUCTIVE ENTHALOGENATION OF AROMATES |
| US4959155A (en) * | 1989-05-23 | 1990-09-25 | Luis Gomez | Method for the purification of fluids such as water, aqueous fluids and fuel fluids |
| DE3941813C2 (en) * | 1989-12-19 | 1992-01-30 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De | |
| US5276240A (en) * | 1991-10-18 | 1994-01-04 | Board Of Regents, The University Of Texas System | Catalytic hydrodehalogenation of polyhalogenated hydrocarbons |
| US5411664A (en) * | 1992-09-28 | 1995-05-02 | W. R. Grace & Co.-Conn. | Method for dehalogenation and degradation of halogenated organic contaminants |
| DE4236724A1 (en) * | 1992-10-30 | 1994-05-05 | Schering Ag | Process for the recovery of iodine from iodinated organic compounds |
| DE4407057A1 (en) * | 1994-03-03 | 1995-09-07 | Dechema | Electrochemical degradation of halogenated hydrocarbon(s) in polluted water |
| EP0677501A1 (en) * | 1994-04-14 | 1995-10-18 | The Dow Chemical Company | Hydrodechlorination process |
Non-Patent Citations (3)
| Title |
|---|
| 6- 72900 A.,C-1214,June 20,1994,Vol.18,No.322 * |
| JP Patents Abstracts of Japan: 3-114589 A.,C- 856,Aug. 6,1991,Vol.15,No.306 * |
| SATO,Fumie, et.al.: Debromination of vic- Dibromides with Zinc and a Catalytic Amount of Titanium(IV) Chloride in Tetrahydrofuran. In: Synthesis 1982, H.12, S.1025,1026 * |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OM8 | Search report available as to paragraph 43 lit. 1 sentence 1 patent law | ||
| 8139 | Disposal/non-payment of the annual fee |