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WO1993004356A1 - Procede de selection de tensio-actifs pour l'extraction de polluants chimiques de sols - Google Patents

Procede de selection de tensio-actifs pour l'extraction de polluants chimiques de sols Download PDF

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Publication number
WO1993004356A1
WO1993004356A1 PCT/US1992/005176 US9205176W WO9304356A1 WO 1993004356 A1 WO1993004356 A1 WO 1993004356A1 US 9205176 W US9205176 W US 9205176W WO 9304356 A1 WO9304356 A1 WO 9304356A1
Authority
WO
WIPO (PCT)
Prior art keywords
soil
surfactant
pollutant
polar
surface tension
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
Application number
PCT/US1992/005176
Other languages
English (en)
Inventor
Lauren M. Purcell
Albert F. Lawrence
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Raytheon Co
Original Assignee
Hughes Aircraft Co
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 Hughes Aircraft Co filed Critical Hughes Aircraft Co
Priority to KR1019930701101A priority Critical patent/KR930702668A/ko
Priority to JP5504281A priority patent/JPH06502124A/ja
Publication of WO1993004356A1 publication Critical patent/WO1993004356A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N13/02—Investigating surface tension of liquids
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/24—Earth materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N13/02—Investigating surface tension of liquids
    • G01N2013/0275—Investigating surface tension of liquids involving surface-active agents

Definitions

  • the present invention is directed to the extraction of chemical pollutants from the soil, and, more particularly, to the selection of specific surfactants to extract specific pollutants from a given soil.
  • surfactant treatment also has its advantages and disadvantages. It is inexpen- sive, non-toxic, and removes and concentrates pollutants before destruction. However, although extraction takes place, there is no destruction of the contaminant, the in situ extraction process can be slow, and removal of large contaminant concentrations can be impeded unless large scale earthmoving, grinding, and mixing operations are performed. Many experiments rely on solubility to predict performance, only to find that upon application to a real site, solubilization of pollutants varies dramatically with soil conditions. Thus, some surfactants are not as effec- tive in the field as expected based on lab analysis. Other problems which emerge in field tests are enough to stop pursuits with this technology.
  • a method for selecting the appropriate surfactant, or surfactants, for the removal of a given contaminant from a specific soil.
  • surfactant selection There are three aspects to surfactant selection: characterization of the soil, contact angle measurements to determine the surface energies of pollutants on soils, and estimation of the chemical nature of the surfactant which would provide effective removal.
  • FIG. 1 is a schematic diagram depicting the solubility and formation of micelles
  • FIG. 2 is a cross-sectional view, depicting a drop of liquid on a solid surface, and showing the contact angle
  • FIGS. 3a and 3b are schematic diagrams depicting the significance of contact angles in oil removal. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • FIG. 1 schematically depicts the roll-back mechanism for removal of oil 10 which is adhered to rock 12.
  • the oil 10 is surrounded by surfactant molecules 14 oriented so that the lipophilic end 14a lines up towards the oil 10, while the hydrophilic end 14b is surrounded by water (which surrounds the assembly shown in FIG. 1, but which is not depicted).
  • the surfactant 14 acts to initiate drop formation, followed by necking and eventual oil removal and the formation of micelles.
  • the present invention is directed to the initial release rather than the formation of micelles in solution.
  • the present invention is directed to the selection of one or more appropriate surfactants to remove contaminant(s) from a given soil.
  • surfactant selection There are three aspects to surfactant selection: characterization of the soil, contact angle measurements to determine the surface energies of pollutants on soils, and estimation of the chemical nature of the surfactant which would provide effective removal.
  • test surfaces may be the same as those for determining the interaction energy between the contaminant and the soil or they may be different. The important aspect is to obtain well-defined values.
  • Interfacial tension between surfactants and the soil can be computed to assist in evaluating whether selected surfactants may adhere to soils.
  • Surfactant non-polar and polar surface tension contributions are evaluated in terms of the total free energy of interaction between the contaminant and surfactant versus contaminant and soil to predict the performance of existing and novel surfactant molecules.
  • the surfactant selection methodology is described below. It includes contributions from surface chemistry and applies them to surfactant performance for the remediation of soils.
  • the method of the invention provides for both the determination of the surface adhesive forces between the contaminant of interest and the soils in which the contaminant(s) lie, and the determination of the surface adhesive forces between the surfactant and contaminant and between the surfactant and soils.
  • any of the well-known in situ and on-site reactor soil remediation processes and apparatus may be employed to treat the contaminated soil.
  • These extraction processes and apparatus are well-known and do not form a part of this invention, which is directed to the selection of the surfactant(s) used to treat the contaminated soil.
  • the first step is to determine the mineral character of the soil. Mineralogy is needed to determine the adhesive energy between the soil and the pollutant. The adhesive energy is the force which must be overcome by the surfactant to remove the contaminant.
  • X-ray diffraction can be found in typical mineralogy laboratories.
  • minerals are identified, together with how their composition varies with particle size. For example, there are coarse, medium, and fine grained silicas; however, in soils, clays are typically finer grained than silicas.
  • a Siemens D-500 diffractometer driven by a DEC Microvax computer and equipped with a copper anode X- ray tube operating at 40 KV and 30 mA, is suitably employed in soil analysis.
  • a graphite diffracted-beam monochromator is positioned between the sample and the detector. Analysis is done grinding the soil sample to pass a 350 mesh screen and then recording the diffraction pattern. The patterns are identified through a JCPDS (Joint Committee on Powder Diffraction Standards) Powder Diffraction File stored on computer. Search is both automatic using Siemens software and manual by visual inspection. Each constituent mineral phase present in quantities greater than 5% by volume can be identified.
  • a sample from a PCB-contaminated site was taken and dispersed in distilled water. Two fractions of soil were taken based on particle size which were, roughly, the clay (fine) fraction and the coarser fraction. The fine fraction was deposited on a glass slide using a conventional technique for clay mineral analysis. The coarse fraction was packed in a bulk sample container. The diffraction patterns for both were similar, indicating that both contain essentially the same minerals, but not necessarily in the same proportions.
  • the dominant mineral was quartz, with minor amounts of other silicates.
  • This mineralogy listed in Table II, is typical of a soil derived from glacial sediments and reflects the igneous rock types in Canada, the source of these sediments.
  • the inventors have discovered that the foregoing procedures can be applied to the treatment of contaminated soil with surfactants.
  • FIG. 2 shows the contact angle ⁇ which a drop 20 of liquid makes with a surface 22.
  • FIG. 3a shows that in a water-oil-silica system (the water is not shown in the drawing, but surrounds the assembly), oil 10 does not spread on (wet) the substrate 12, but will form a finite contact angle in water.
  • FIG. 3b shows that the surfactant solution (again, not shown) in place of water reduces the surface tension between the substrate 12 and the oil 10 , enough to pull the oil into solution .
  • the surfactant bath will spontaneously displace the oil from the substrate when the contact angle is 180°; if the contact angle is less than 180° but more than 90°, the contaminant will not be displaced spontaneously but might be removed by hydraulic currents in the bath.
  • ⁇ LW Lifshitz-van der Waals contribution
  • ⁇ + Lewis acid surface tension contribution (electron acceptor)
  • ⁇ - Lewis base surface tension contribution (electron donor).
  • the total surface tension of liquids can be measured or found in published tables. If measured, three different surfaces are employed, such as a polytetrafluoroethylene material for the non-polar component and polymethylmethac- rylate for the polar (Lewis base) component). There are no reliable solid surfaces with a large polar (Lewis acid) component. Thus, the Lewis acid component of the liquid must be computed from measurements on another surface with a different Lewis base value, such as polystyrene.
  • the desired surfaces will be in either a solid, smooth crystal form or prepared in a pressed cake with a smooth surface which can be reliably reproduced. All surfaces must have known ⁇ LW , ⁇ + , and ⁇ - values.
  • the ⁇ L LW can be found by one of two methods.
  • One method is that of Lif- shitz as described by D.B. Hough et al, "The Calculation of Hamaker Constants from Lifshitz Theory with Applications to Wetting Theory", Advances in Colloid and Interface Science, Vol. 14, pp. 3-41 (1980), where the dispersion forces between bulk materials is found from the dielectric of the materials in question,, the refractive index, etc.
  • polar interactions are essentially asymmetrical and can only be satisfactorily treated by taking that asymmetry into account, dividing up the polar component ⁇ AB of the surface tension into electron acceptor ⁇ + and electron donor ⁇ - parameters.
  • ⁇ G SL TOT ⁇ G SL LW + ⁇ G SL AB (7) is the total free energy of interaction between a solid and a liquid.
  • the polar and non-polar components of the free energy of interaction are:
  • ⁇ LW The Lifshitz-van der Waals component of the surface tension, ⁇ LW , was determined from contact angle measurements on a smooth fluoroethylene polymer surface. Several drops were measured and multiple measurements of each drop were made. The average contact angle was found to be 81.3°.
  • the Young's equation for an apolar solid is:
  • Polystyrene is less useful than PMMA because it has a small ⁇ -; both are monopolar substances. This monopolarity makes it possible to solve for ⁇ + and ⁇ - for Aroclor 1248 given the value of ⁇ AB .
  • the average contact angle on polystyrene was 17.9° and a similar calculation was done. The results of these calculations based on the contact angles of Aroclor 1248 on these two substrates are set forth in Table IV below.
  • the solubility (S) is approximately 1 ppm, the molecular weight (MW) is approximately 360, the contactable surface area (Sc) is approximately 0.8 nm 2 (estimated from twice the Sc value for glucose).
  • S solubility
  • MW molecular weight
  • Sc contactable surface area
  • ⁇ 12 [( ⁇ Pcb LW ) 1 ⁇ 2 - (Y water LW )1 ⁇ 2 ] 2 + 2[( ⁇ pcb + ⁇ pcb -) 1 ⁇ 2
  • ⁇ 12 [(43.4) 1 ⁇ 2 - (21.8) 1 ⁇ 2 ] 2 + 2 [ ( 0 X ⁇ pcb - ) 1 ⁇ 2 +
  • the next part of the method of the invention is to determine the interfacial energy of the surfactant and the pollutant of interest.
  • the interfacial tension between two liquids is measured by a variety of approaches, such as hanging drop, spinning drop, and drop weight method.
  • Surfactant polar ( ⁇ + and ⁇ -) and non-polar ( ⁇ LW ) surface tension components are then listed based upon chemical structure. This methodology, shown below, reveals the three surface tension components required for both the polar (hydrophilic) and the non-polar (lipophilic) parts of the surfactant molecule. Thus, if the surface tension values for N polar groups and M non-polar groups are known, then estimates for N*M surfactant combinations can be made. This gives one the ability to fine-tune surface tension requirements and to design surfactants for contaminant removal.
  • the ⁇ G p/m TOT between the contaminant, or pollutant (p), and soil, or mineral (m), is computed from Eqn. (7) or each combination.
  • the ⁇ G S/P TOT between the surfactant (s) and pollutant can also be determined.
  • Aroclor 1248 to quartz in the presence of (a) water and (b) hexane.
  • Table VI one can see that there is a substantial adhesion energy between the Aroclor 1248 and quartz, a common constituent in soils, in the presence of water. If the water were replaced by hexane, the adhesion energy is substantially reduced, but is still negative, which means that the Aroclor will still bind to the quartz.
  • the surface tension components which have been determined by contact angle measurements give parameters for the co-surfactant.
  • a desirable combination of surfactant and oil-soluble co-surfactant would be a surfactant which is largely basic in nature and a co-surfactant which is largely acidic in nature.
  • the surfactant-co-surfactant pair must be chosen in such a way that the soil-contaminant contact angle goes to 180° when the surfactant solution is added to the contaminant soil, thus lifting the contaminant off the soil completely.
  • the co-surfactant provides an additional set of parameters whereby this might be accomplished.
  • the method of the invention is expected to find use in the extraction of chemical pollutants from contaminated soils.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Immunology (AREA)
  • Biochemistry (AREA)
  • Pathology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Remote Sensing (AREA)
  • Food Science & Technology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Soil Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Detergent Compositions (AREA)

Abstract

La physique de l'adhérence est appliquée pour sélectionner des tensio-actifs qui possèdent une base d'acide de Lewis et des valeurs d'interaction de force de dispersion exigées pour extraire de façon optimale des polluants (10) des sols (12). Cette application est nouvelle dans le sens qu'elle prédit une efficacité d'un tensio-actif dans l'extraction de contaminants toxiques. De plus, la base d'acide de Lewis et les forces de dispersion sont appliquées pour sélectionner un co-tensio-actif afin d'améliorer l'adhérence entre un tensio-actif et un polluant.
PCT/US1992/005176 1991-08-13 1992-06-22 Procede de selection de tensio-actifs pour l'extraction de polluants chimiques de sols Ceased WO1993004356A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019930701101A KR930702668A (ko) 1991-08-13 1992-06-22 토양으로부터 화학적 오염물질의 추출을 위한 계면활성제의 선택법
JP5504281A JPH06502124A (ja) 1991-08-13 1992-06-22 土壌から化学的汚染物の抽出のための界面活性剤選択方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US74723991A 1991-08-13 1991-08-13
US747,239 1991-08-13

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WO1993004356A1 true WO1993004356A1 (fr) 1993-03-04

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PCT/US1992/005176 Ceased WO1993004356A1 (fr) 1991-08-13 1992-06-22 Procede de selection de tensio-actifs pour l'extraction de polluants chimiques de sols

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EP (1) EP0552327A1 (fr)
JP (1) JPH06502124A (fr)
KR (1) KR930702668A (fr)
CA (1) CA2089639A1 (fr)
WO (1) WO1993004356A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012105756A1 (de) * 2012-06-29 2014-01-02 Conti Temic Microelectronic Gmbh Verfahren zur Ermittlung der Oberflächenspannung einer Flüssigkeit
KR20140064937A (ko) * 2011-10-14 2014-05-28 제이에프이 스틸 가부시키가이샤 코크스의 제조 방법
CN109085095A (zh) * 2018-08-08 2018-12-25 长安大学 一种土壤接触角测试装置及方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6319882B1 (en) 1998-12-31 2001-11-20 George A. Ivey Air, soil and ground water remediation compositions and methods
US6447207B1 (en) 1999-11-22 2002-09-10 George A. Ivey Air, soil and ground water remediation compositions and methods
CN113702246B (zh) * 2021-08-25 2023-02-03 河海大学 一种充填裂隙网络中污染物迁移的监测装置及监测方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2624272A1 (fr) * 1987-12-02 1989-06-09 Univ Alsace Procede pour determiner les energies de surface de solides par mouillabilite et dispositif pour la mise en oeuvre de ce procede
WO1990006795A1 (fr) * 1988-12-22 1990-06-28 Ensr Corporation PROCEDE ET APPAREIL D'EXTRACTION DE PCBs DU SOL ET DE BOUES
EP0379261A1 (fr) * 1989-01-17 1990-07-25 Tauw Infra Consult B.V. Procédé de nettoyage de la terre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2624272A1 (fr) * 1987-12-02 1989-06-09 Univ Alsace Procede pour determiner les energies de surface de solides par mouillabilite et dispositif pour la mise en oeuvre de ce procede
WO1990006795A1 (fr) * 1988-12-22 1990-06-28 Ensr Corporation PROCEDE ET APPAREIL D'EXTRACTION DE PCBs DU SOL ET DE BOUES
EP0379261A1 (fr) * 1989-01-17 1990-07-25 Tauw Infra Consult B.V. Procédé de nettoyage de la terre

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEM. REV., Vol. 88, 1988 Carel J. Van Oss et al: "Interfacial Lifshitz-van der Waals and Polar Interactions in Macroscopic Systems ", *
J. ADHESION SCI. TECHNOL., Vol. 4, No. 4, 1990 P.M. Costanzo et al: "Determination of the acid-base characteristics of clay mineral surfaces by contact angle measurementsimplications for the adsorption of organic solutes from aqueous media ", *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140064937A (ko) * 2011-10-14 2014-05-28 제이에프이 스틸 가부시키가이샤 코크스의 제조 방법
KR101580855B1 (ko) 2011-10-14 2015-12-29 제이에프이 스틸 가부시키가이샤 코크스의 제조 방법
DE102012105756A1 (de) * 2012-06-29 2014-01-02 Conti Temic Microelectronic Gmbh Verfahren zur Ermittlung der Oberflächenspannung einer Flüssigkeit
WO2014000739A1 (fr) * 2012-06-29 2014-01-03 Conti Temic Microelectronic Gmbh Procédé pour déterminer la tension superficielle d'un liquide
CN109085095A (zh) * 2018-08-08 2018-12-25 长安大学 一种土壤接触角测试装置及方法
CN109085095B (zh) * 2018-08-08 2021-07-23 长安大学 一种土壤接触角测试装置及方法

Also Published As

Publication number Publication date
EP0552327A1 (fr) 1993-07-28
KR930702668A (ko) 1993-09-09
CA2089639A1 (fr) 1993-02-14
JPH06502124A (ja) 1994-03-10

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