WO2008132768A1 - Procédé d'élimination de composés organiques, en particulier d'hydrocarbures, de btex, de composés halogénés organiques et d'huiles minérales présents dans l'eau - Google Patents

Procédé d'élimination de composés organiques, en particulier d'hydrocarbures, de btex, de composés halogénés organiques et d'huiles minérales présents dans l'eau Download PDF

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Publication number
WO2008132768A1
WO2008132768A1 PCT/IT2007/000318 IT2007000318W WO2008132768A1 WO 2008132768 A1 WO2008132768 A1 WO 2008132768A1 IT 2007000318 W IT2007000318 W IT 2007000318W WO 2008132768 A1 WO2008132768 A1 WO 2008132768A1
Authority
WO
WIPO (PCT)
Prior art keywords
aqueous
hydrocarbon
hydrocarbon solvent
process according
pollutants
Prior art date
Application number
PCT/IT2007/000318
Other languages
English (en)
Inventor
Rita Mastromarino
Original Assignee
Rita Mastromarino
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rita Mastromarino filed Critical Rita Mastromarino
Priority to PCT/IT2007/000318 priority Critical patent/WO2008132768A1/fr
Publication of WO2008132768A1 publication Critical patent/WO2008132768A1/fr

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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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • C02F2101/006—Radioactive compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/322—Volatile compounds, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/325—Emulsions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/44—Time
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage

Definitions

  • the present invention relates to a method for decontaminating aqueous matrices polluted by organic compounds and in particular aqueous matrices contaminated by BTEX, halogenated organic compounds, MTBE, mineral oils and hydrocarbons in general.
  • Aqueous matrices polluted by organic compounds are, for example, groundwaters underlying various industrial plants such as refineries, plastic material manufacturing and/or processing plants, oil mills, etc. or groundwaters underlying commercial plants such as, for example, gas stations.
  • the hydrocarbon compounds produced and/or used in the production, processing and distribution processes in the above-mentioned plants if they come into contact with the soil, can permeate down to the aquifers thus polluting the water.
  • Particularly dangerous pollutants are for example BTEX (acronym of benzene, toluene, ethylbenzene an xylene), organic halogenated compounds, MTBE
  • patent US 5,282,974 discloses methods for removing benzene from process waters of the hydrocarbon industry by adding aluminium hydrochloride to water and subsequently separating benzene by solvent extraction. However, it is not specified which solvent can be used for extraction.
  • Patent US 6,045,696 discloses a process for purifying waste waters containing organic and inorganic sulphurous compounds, mercaptobenzothiazole, benzothiazole and/or derivatives of the last two, wherein waters are treated with an extraction agent which comprises salts of aliphatic amines and aliphatic and/or aromatic hydrocarbons. Kerosene and dodecane are mentioned as examples of aliphatic hydrocarbons which can be used for extraction.
  • Patent JP 61212380 discloses a treatment for waste waters which contain an organic chlorine compound, such as for example dichloroethane and trichloroethylene, with a high-boiling hydrocarbon, such as for example liquid paraffin.
  • the high-boiling hydrocarbon is introduced in a separation container wherein it sorbs the organic chlorine compound. Due to the difference of specific weight in the container two layers are formed: an upper layer containing the high-boiling hydrocarbons and the organic chlorine compounds, and a lower layer of decontaminated water. Decontaminated water is taken away, while the hydrocarbon layer is subjected to fractional distillation thus separating the organic chlorine compound from the high-boiling hydrocarbon which can be reused in the process.
  • Object of the present invention is thus to provide a method for decontaminating aqueous matrices which allows to effectively treat aqueous matrices polluted by a wide range of pollutants such as BTEX, organic halogenated compounds, MTBE, mineral oils, hydrocarbons and organic compounds in general.
  • Said object is achieved by a process which essentially consists of decontaminating aqueous matrices by means of an extraction by a hydrocarbon solvent which is insoluble in water and particularly suitable to dissolve the above-mentioned pollutants.
  • the main features of said process are specified in the first claim and other features are those specified in the following claims.
  • the main advantage of the process according to the present invention is the possibility to extract from aqueous matrices a wide range of organic pollutants by means of a single process and by using a single type of solvent.
  • Another advantage provided by the process according to the present invention is the possibility to easily reuse the solvent for subsequent extraction steps of the above- mentioned pollutants from aqueous matrices.
  • Aqueous matrices containing organic pollutants particularly belonging to the group comprising BTEX 5 organic halogenated compounds, MTBE, mineral oils and hydrocarbons are treated according to the present invention with a process comprising the following operative steps: a) adding to the aqueous matrix the hydrocarbon solvent capable of dissolving the pollutants contained in the aqueous matrix arranged in a ' suitable container, b) subsequently stirring the resulting blend, and c) finally separating the aqueous phase from the overlying hydrocarbon phase containing the above-mentioned hydrocarbon contaminants.
  • hydrocarbon solvents were tested for purifying the aqueous matrices containing, for example, BTEX, organic halogenated compounds, MTBE and mineral oils, and some hydrocarbon solvents were surprisingly found to be optimal for extracting any kind of contaminant and do not require to add other adjuvant agents for extraction.
  • Said solvents preferably have a density ranging from 0,5 to 2,0 g/cm 3 , a solubility in H 2 O ranging from 0 to 1000 mg/1 and a boiling temperature ranging from 40 to 300 0 C.
  • the most suitable hydrocarbon solvents for the purpose are those belonging to the group consisting of 1-decene, 1-octadecene, 1- hexadecene, n-decane or blends thereof.
  • the used hydrocarbon solvent is n-decane which, as it is evident from the examples below, allows to extract almost all hydrocarbon pollutants which are in the aqueous matrix.
  • Example 1 500 ml of n-decane under stirring at a speed of 200 rpm continuously for 5 minutes were added to 1000 ml of groundwater polluted by BTEX and other organic compounds coming from a production plant of plastic materials. A IKA RCT Basic type heating plate stirrer was used for this step.
  • the obtained blend was subsequently left to decant in a clear glass cylinder for 30 minutes, at the end of which the separation of the aqueous phase from the overlying hydrocarbon phase of the pollutants dissolved in n- decane looked evident and sharp.
  • the aqueous phase obtained after solvent extraction of the contaminants was subjected to analysis and the obtained results are reported in the following Table 1. In the fourth column of the table there is reported the percentage of abatement of the pollutants at the conclusion of the treatment thereof by the process according to the present invention.
  • n-decane 500 ml of n-decane were added to 1000 ml of groundwater containing concentrations of pollutants which are different from Example 1 and were stirred continuously for 5 minutes by the same stirrer as in Example 1.
  • the so-obtained blend was left to decant in a clear glass cylinder for 30 minutes and then the aqueous phase, once it had been separated from the hydrocarbon phase of the pollutants dissolved in n- decane, was subjected to analysis and the obtained results are reported in the following
  • Carrying out the process according to the present invention requires a time which substantially depends on the duration of the mixing step under stirring of the aqueous matrix and the hydrocarbon solvent. Said duration ranges from 1 to 60 minutes, preferably from 1 to 15 minutes. Further, it has been observed that the temperature positively influences the stirring step thus favouring the extraction process of the hydrocarbon. Suitable temperatures for maximizing the efficiency of the stirring step range from 5 to 80°C, preferably from 15 to 35 0 C.
  • the process according to the present invention may also comprise a step of decanting the blend of the aqueous matrix and the hydrocarbon solvent, in order to favour the step of demixing the aqueous phase from the hydrocarbon phase contained therein.
  • the step of separation of the hydrocarbon phase containing the contaminants from the aqueous phase may comprise a stage of centrifugation and/or addition of a chemical additive suitable to favour the demixing of the aqueous phase from the hydrocarbon phase.
  • a chemical additive suitable to favour the demixing of the aqueous phase from the hydrocarbon phase.
  • such chemical additive may be NaCl, which, by increasing the ionic strength of water, favours the demixing of the phases.
  • the process according to the present invention comprises a step of separation of the above-mentioned pollutants from the hydrocarbon solvent in order to reuse the latter in a further cycle of treatment of anew aqueous matrix.
  • the steps of adding the hydrocarbon solvent, stirring, decanting and separating included in the method according to the present invention may be repeated several times in order to reach a still higher purification grade. hi order to increase the purification efficiency the process according to the invention may also be performed as a continuous cycle.
  • the method according to the present invention is particularly suitable for purifying groundwaters containing organic pollutants, thus allowing to use said waters for an industrial use or household purposes or even for making them drinkable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de décontamination de matrices aqueuses contenant des polluants organiques, tels que le BTEX, des composés halogénés organiques, le MTBE, des huiles minérales et des hydrocarbures en général, lequel procédé consiste: à introduire un solvant hydrocarboné capable de dissoudre les polluants contenus dans la matrice aqueuse dans un conteneur approprié; à agiter le mélange résultant de ladite matrice aqueuse et dudit solvant hydrocarboné; à séparer la phase hydrocarbonée contenant les polluants de la phase aqueuse purifiée. Ledit solvant hydrocarboné a une densité se comprise entre 0,5 et2,0 g/cm3, une solubilité entre 0 et 1 000 mg/l et une température d'ébullition entre 40 et 300 °C. En particulier, ledit solvant est choisi dans le groupe constitué par le n-décane, le 1-decène, le 1-octadecène, le 1-hexadecène ou des mélanges de ceux-ci. Le procédé selon la présente invention permet d'extraire une large éventail de contaminants organiques à partir de matrices aqueuses au moyen d'un procédé simple, au moyen d'un solvant ou d'un mélange de solvants.
PCT/IT2007/000318 2007-04-27 2007-04-27 Procédé d'élimination de composés organiques, en particulier d'hydrocarbures, de btex, de composés halogénés organiques et d'huiles minérales présents dans l'eau WO2008132768A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IT2007/000318 WO2008132768A1 (fr) 2007-04-27 2007-04-27 Procédé d'élimination de composés organiques, en particulier d'hydrocarbures, de btex, de composés halogénés organiques et d'huiles minérales présents dans l'eau

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2007/000318 WO2008132768A1 (fr) 2007-04-27 2007-04-27 Procédé d'élimination de composés organiques, en particulier d'hydrocarbures, de btex, de composés halogénés organiques et d'huiles minérales présents dans l'eau

Publications (1)

Publication Number Publication Date
WO2008132768A1 true WO2008132768A1 (fr) 2008-11-06

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PCT/IT2007/000318 WO2008132768A1 (fr) 2007-04-27 2007-04-27 Procédé d'élimination de composés organiques, en particulier d'hydrocarbures, de btex, de composés halogénés organiques et d'huiles minérales présents dans l'eau

Country Status (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2501261A (en) * 2012-04-17 2013-10-23 Statoil Canada Ltd A method of cleaning water to remove hydrocarbon
WO2013156535A1 (fr) * 2012-04-17 2013-10-24 Statoil Canada Limited Procédé de purification de l'eau visant à en éliminer les hydrocarbures

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3412018A (en) * 1965-11-15 1968-11-19 Ct Tech De L Ind Des Papiers Water purifying process
US6045696A (en) * 1997-07-25 2000-04-04 Bayer Ag Process for the purification of waste waters containing organic and inorganic sulphur compounds
US6433163B1 (en) * 2000-04-03 2002-08-13 Commodore Separation Technoligies, Inc. Combined supported liquid membrane/strip dispersion process for the removal and recovery of penicillin and organic acids
US20040188355A1 (en) * 2002-08-23 2004-09-30 Hal Alper Method for separating low HLB contaminants from an aqueous dispersion of a high HLB oil

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3412018A (en) * 1965-11-15 1968-11-19 Ct Tech De L Ind Des Papiers Water purifying process
US6045696A (en) * 1997-07-25 2000-04-04 Bayer Ag Process for the purification of waste waters containing organic and inorganic sulphur compounds
US6433163B1 (en) * 2000-04-03 2002-08-13 Commodore Separation Technoligies, Inc. Combined supported liquid membrane/strip dispersion process for the removal and recovery of penicillin and organic acids
US20040188355A1 (en) * 2002-08-23 2004-09-30 Hal Alper Method for separating low HLB contaminants from an aqueous dispersion of a high HLB oil

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2501261A (en) * 2012-04-17 2013-10-23 Statoil Canada Ltd A method of cleaning water to remove hydrocarbon
WO2013156535A1 (fr) * 2012-04-17 2013-10-24 Statoil Canada Limited Procédé de purification de l'eau visant à en éliminer les hydrocarbures

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