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WO1994020421A1 - Polymeres a base de silicone comme agents de traitement de fuites accidentelles de liquides - Google Patents

Polymeres a base de silicone comme agents de traitement de fuites accidentelles de liquides Download PDF

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Publication number
WO1994020421A1
WO1994020421A1 PCT/CA1994/000117 CA9400117W WO9420421A1 WO 1994020421 A1 WO1994020421 A1 WO 1994020421A1 CA 9400117 W CA9400117 W CA 9400117W WO 9420421 A1 WO9420421 A1 WO 9420421A1
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WO
WIPO (PCT)
Prior art keywords
hydrocarbon
oil
composition
general formula
carboxylic acid
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/CA1994/000117
Other languages
English (en)
Inventor
Emilien Pelletier
Robert Siron
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.)
Institut National de La Recherche Scientifique INRS
Original Assignee
Institut National de La Recherche Scientifique INRS
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 Institut National de La Recherche Scientifique INRS filed Critical Institut National de La Recherche Scientifique INRS
Priority to AU61524/94A priority Critical patent/AU6152494A/en
Publication of WO1994020421A1 publication Critical patent/WO1994020421A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water

Definitions

  • Crude oil, oil processing products and hydrocarbon residues are a major cause of severe environmental damage when spilled in the aquatic environment.
  • impacts of oil spills are the loss of shoreline habitat mainly for birds and aquatic mammals, the contamination of water and interstitial sediments with toxic hydrocarbons and, in some cases, major economic loss from the reduction of recreational and fisheries activities.
  • Only large oil spills capture public attention but small spills occurring daily in harbours, seaports and marinas or along navigation channels and waterways are very common and represent over 90% of the spilled oil products every year.
  • Oil spill recovering technologies can be divided in three major groups: 1) mechanical containment; 2) controlled burning and 3) spill- treating agents. The latter includes the use of solid adsorbents and dispersants.
  • Burning spilled oil from the surface of water is not currently a major spill recovering method, but could eventually be considered if the oil slick could be contained and thickened using fireproof booms. Igniting and keeping a slick ablaze can be contemplated, for example, if the oil is freshly spilled and the slick is at least >
  • Oil treating agents can be divided in four groups: dispersants, surface-washing agents, emulsion breakers or demulsifiers, and gelling agents or solidifiers.
  • Dispersants are chemical formulations of ionic and neutral surfactants usually dissolved in hydrocarbon-based solvents, and have the capability of decreasing the water/oil interfacial tension and promote the dispersion of tiny oil droplets into the underlying water mass.
  • dispersants are their unfavourable acceptance by the public as well as the relative toxicity of the oil-in-water dispersion. Furthermore, the effectiveness of dispersants significantly depend on environmental conditions, application techniques and chemical nature of spilled oiL
  • Surface-washing agents are surfactants mixtures which remove oil from solid surfaces such as beaches, rocks or boat hulls, by a "detergent" effect.
  • the efficiency of recuperation of most commercial surface-washing agents is below 50% and some of them exhibit an important dispersant effect.
  • Emulsion breakers or demulsifiers are chemical agents which can prevent the formation or break down water-in-oil emulsions.
  • the majority of these agents are hydrophillic surfactants which tend to leave quickly the oil and cannot be used on open water.
  • Recent oil spilled treating compositions using polymers instead of surfactants have been reported to treat emulsified oil successfully. US 5,004,559
  • gelling agents or solidifiers which facilitate the recuperation of the spilled oil from the water surface by lifting off.
  • These agents often consist of polymerization catalysts and cross-linking agents.
  • US 4,980,072 teaches that polyether containing isocyanate end groups added to hydrocarbons form a gel containing hydrocarbons which can be removed from seawater surface mechanically.
  • gelling agents usually suffer from a major field application restriction: the formation of the gel is not an instantaneous process and it requires vigorous and thorough agitation at the oil/water interface.
  • gelling agents historically have not been used or stored for use during oil spill recovery because of the large amount required, which is very often over 40% of the actual volume of the oil, to solidify the slick.
  • US 5,076,938 discloses a method for the encapsulation of hydrocarbons to produce a solid material which is easily removed from a spillage site.
  • the method involves the treatment of oil with a concentrated solution of surfactants to emulsify the oil followed by the addition of a silicate solution which immobilizes the resulting acidic mixture and produces a gel-like precipitate which can be dried, thus leading to a grey powder.
  • the method can be used on solid surfaces only since the application of emulsifying solution on oil floating on water would result in a dispersion of the oil in the water mass and subsequently the dilution of the silicate solution without any gelling effect.
  • the method would be applicable to both damp surfaces and water surface and the treated hydrocarbon slick would be recovered by simple mechanical means. Such method would preferably trap and solidify the crude hydrocarbon, which could be easily recovered.
  • the hydrocarbon treating composition could also be used to prevent the contamination of the shores neighbouring the spill.
  • the hydrocarbon would preferably be easily extracted from the recovered hydrocarbon/hydrocarbon-treating composition residues.
  • the action of the hydrocarbon-treating composition would be independent from environmental conditions such as the ambient temperature, the nature of the hydrocarbon and the salinity of water, and would not further pollute the environment.
  • a method of recovering hydrocarbons such as crude oil, oil processing products, oil residues and the like, spilled on a watery environment which comprises contacting the hydrocarbon slick with a composition comprising the reaction products of at least one hydrolysable silane derivative reacted with a polyoxyethylenic surfactant, an aliphatic carboxylic acid, an aliphatic alcohol, or mixtures thereof.
  • the silane derivative reacts with the other components of the composition, and in the presence of water, a further reaction takes place to form an anti-adhesive polysiloxane matrix, thus trapping the hydrocarbon into the matrix.
  • the removal of the resulting silicone/hydrocarbon solid residues from the water or damp surface is performed by simple netting or conventional mechanical means. The residues are washed with hydrocarbon solvents leaving inert silicone polymers to be discarded and hydrocarbon solution to be recycled.
  • a method for protecting a damp surface against hydrocarbon spills which comprises contacting the surface with a composition comprising the reaction products of at least one hydrolysable silane derivative reacted with a polyoxyethylenic surfactant, an aliphatic carboxylic acid, an aliphatic alcohol, or mixtures thereof, to form an anti-adhesive polysiloxane matrix on the surface to prevent the adherence of the spilled hydrocarbon on the surface and facilitate the recuperation of the hydrocarbon.
  • composition for recovering spilled hydrocarbons such as crude oil, oil processing ⁇
  • watery environment is meant to include water or damp surface such as rocks, sand, shells, 10 wharfs, dams, river banks, cement, asphalt or any other material or surface susceptible of being contaminated by oil spills.
  • the method to prepare a preferred reactive composition is first to react a polyoxyethylenic surfactant of the general formula
  • suitable non-aromatic hydrocarbon solvents such as pentane, hexanes or petroleum ether as well as a mixture of light hydrocarbons.
  • silicon is defined in the present application as a synthetic polymer containing a repeating silicon-oxygen backbone and various organic groups, R and OR, attached to silicon atoms.
  • the Si-halogen bond is important in silicon chemistry and the hydrolysis of organochlorosilanes, for example, gives siloxane structures which are the basis of silicone products.
  • Halosilanes are reactive towards polar reagents and the first step of the reaction involves the displacement of one or more halogen atoms by a nucleophilic attack:
  • reactions of halosilanes with protic materials provide a number of intermediates (silanols, alkoxysilanes, siloxanes) that can be used as starting materials for polymer synthesis.
  • the first step usually involves the reaction of an excess of a trichlorosilane, thus containing 3 Si-Cl hydrolysable bonds, with a polyoxyethylenic surfactant such as polyoxyethylene stearyl ether, in a hydrocarbon solvent.
  • a polyoxyethylenic surfactant such as polyoxyethylene stearyl ether
  • the 1400-1000 cm" 1 region of the spectra of the polyoxyethylenic surfactant and the reactive composition are very similar. This is attributed to the superposition of stretching and bending modes of polyoxyethylenic groups which are not modified by the reaction.
  • the reactivity of this mixture can be adjusted according to the requirements of the application procedure by varying the molar ratio and the nature of the silane derivatives towards the surfactant. These adjustments can be easily determined by any man skilled in the art.
  • the reactive alkoxysilanes and siloxanes derivatives are readily obtained by stirring under c
  • the 5 polyoxyethylenic surfactant is replaced by an aliphatic alcohol as defined above, such as dodecyl alcohol, under similar conditions.
  • an aliphatic alcohol as defined above, such as dodecyl alcohol
  • the progress of the reaction and its completeness is monitored by the disappearance of 2 R-OH infrared absorption bands at 3630 and 1050 cm" 1 , and the formation of a new peak at 1100 cm" 1 corresponding to the vibration of the C-O-Si created.
  • the reactive alkoxysilanes and siloxanes derivatives are readily obtained by stirring under nitrogen atmosphere the aliphatic alcohol with the silane derivative(s) at room temperature for a few minutes.
  • the 15 polyoxyethylenic surfactant is replaced by an aliphatic carboxylic acid as defined above, such as stearic acid, under similar conditions.
  • an aliphatic carboxylic acid as defined above, such as stearic acid, under similar conditions.
  • the progress of the reaction and its completeness is monitored by the disappearance of the carbonyl (acid) infrared absorption band at 1705 cm" 1 , and the formation of a new peak at 1740 cm" 1 corresponding to the vibration of a carbonyl (ester) the CO-O-Si created.
  • a second optional step of the preparation procedure is the addition to the reactive solution of a variable amount of an alkylhalosilane or a mixture of alkyltrihalosilanes as a hydrophobic cross-linking polymerization reagent responsible for the three dimensional structure of the silicone polymer in contact with the hydrocarbon/water interface.
  • a preferred embodiment comprises the incorporation
  • a hydrocarbon spill-treating composition prepared as above contains a number of hydrolysable units (Si-X), its contact with water, seawater or any wet surface provokes a rapid but non violent hydrolysis of the reactive species in the composition, thus trapping the floating hydrocarbon and hydrocarbon residues into a semi-solid cross-linked silicone polymer.
  • Si-X hydrolysable units
  • the polyoxyethylenic surfactant, the carboxylic acid and the aliphatic alcohol possess a long hydrocarbon chain, which incidentally may be substituted. This is explained by the fact that compounds of these families having a shorter hydrocarbon chain are water-soluble and almost insoluble in hydrocarbon solvents. They are therefore undesirable for the purposes of the present invention.
  • the hydrocarbon spill-treating compositions of the present invention must obviously be stored under dry conditions to avoid undesirable hydrolysis.
  • the field application of these compositions to water or damp surfaces can be done by means of a slightly pressurized container equipped with a spray nozzle.
  • the composition is sprayed over and around the hydrocarbon slick and the silicone polymerization takes place within seconds to a few minutes.
  • a white flexible solid coating has been formed over the treated surface, which "envelops" the slick.
  • Hydrocarbon/silicone residues can be collected easily from the surface of water using a landing net having a small mesh size (1/16 to 1/8 inch), or any other mechanical means suitable for separating floating solids from water.
  • the compositions When applied to damp surfaces, the compositions also form a white solid coating "enveloping" the hydrocarbon and hydrocarbon residues easily collected with scrapers or any other appropriate mechanical means.
  • X is a halogen in the silane derivatives used in the composition
  • the hydrolysis reaction generates small concentrations of acid (hydrochloric, hydrofluoric etc.). Caution must therefore be taken up to that point, and neutralisation with a base such as calcium carbonate or any other neutralizing agent not causing damage to the environment, is recommended. This minor inconvenience is however minimized significantly in seawater due to the strong buffer capacity of the latter.
  • the alternative is to used silane derivatives wherein X is an alkoxy group to avoid the formation of such acid. After the collecting of hydrocarbon/silicone residues from the water surface or wet substrates, they are treated to recover the hydrocarbon.
  • the recovery of hydrocarbons can be done by washing or extracting the hydrocarbon/silicone residues with methylene chloride or a mixture of methylene chloride and a light non-aromatic hydrocarbon.
  • Methods of hydrocarbon recovery can vary from a simple agitation of residues into a large volume of solvent followed by centrifugation or decantation, to ultrasonic or soxhlet extractions. In all cases, unaltered hydrocarbons are quantitatively recovered and white-grey flaky silicone residues no longer showed any chemical reactivity.
  • An inert white plastic recipient was used to simulate the contact of a floating oil slick with solid substrates such as those found on a beach front.
  • Small rocks of various sizes and calcareous shells from different marine bivalves were placed on a rough flat surface tilted in the back and the box was filled with seawater so that all the rocks and the shells are covered with the seawater.
  • 50 mL of (Forties) crude oil was slowly poured until about 2/3 of the water surface was covered. After a few minutes, the oil slick was treated with a silicone oil spill- treating composition by spraying around and over the slick about 20 mL of a reactive solution prepared as indicated above and containing the following reagents in 15 ml of petroleum ether:
  • a round container was filled with fine beach sand and placed 30 in a plastic recipient.
  • the recipient was filled with seawater in order to wet the sand and cover its surface.
  • the water surface just above the sand was sprayed with about 20 mL of the silicone oil-treating composition prepared in example 1.
  • water was drained slowly and the polymer film was allowed to stick to the sand surface.
  • About 5 mL of crude oil was slowly poured over the white film. After about 5 minutes, tne recipient was filled again with seawater.
  • composition of the present invention To illustrate the ability of the composition of the present invention to clear oil from water surface and contribute to a rapid cleaning, a thin oil sheen was formed over the surface of a large cylindrical jar filled with seawater, by
  • the oil-treating agent used has the following composition dissolved in 15 mL of n-pentane:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Floating Material (AREA)

Abstract

Selon la présente invention, on fournit un procédé pour récupérer les hydrocarbures tels que le pétrole brut, les produits de la transformation du pétrole, les résidus du pétrole et similiaire, répandus dans un environnement aqueux, qui consiste à mettre en contact la traînée d'hydrocarbures avec une composition renfermant les produits de réaction d'au moins un dérivé hydrolysable du silane avec un tensioactif polyoxyéthylénique, un acide aliphatique carboxylique, un alcool aliphatique ou un mélange de ceux-ci. Les produits de réaction de la composition réagissent en outre en présence d'eau pour former une matrice antiadhérente de polysiloxane, en piégeant ainsi l'hydrocarbure dans la matrice. L'élimination des résidus solides résultants silicone/hydrocarbure de la surface de l'eau s'effectue simplement à l'aide de filets ou par des moyens mécaniques classiques. Les résidus sont lavés avec des solvants hydrocarbonés en fournissant des polymères de silicone inertes que l'on peut jeter et une solution hydrocarbonée recyclable.
PCT/CA1994/000117 1993-03-02 1994-03-01 Polymeres a base de silicone comme agents de traitement de fuites accidentelles de liquides Ceased WO1994020421A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61524/94A AU6152494A (en) 1993-03-02 1994-03-01 Silicone based polymers as spill treating agent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2501693A 1993-03-02 1993-03-02
US08/025,016 1993-03-02

Publications (1)

Publication Number Publication Date
WO1994020421A1 true WO1994020421A1 (fr) 1994-09-15

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PCT/CA1994/000117 Ceased WO1994020421A1 (fr) 1993-03-02 1994-03-01 Polymeres a base de silicone comme agents de traitement de fuites accidentelles de liquides

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AU (1) AU6152494A (fr)
WO (1) WO1994020421A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998051422A1 (fr) * 1997-05-14 1998-11-19 Ingenieria Ambiental Mexicana, S.A. De C.V. Microencapsulation de contaminants organiques dangereux dans une matrice du sol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH475106A (de) * 1965-10-01 1969-07-15 Wacker Chemie Gmbh Verfahren zum Erzeugen lipophiler Oberflächen auf kleinteiligen festen Stoffen
US5076938A (en) * 1989-09-26 1991-12-31 Noonan William R Oil treatment method
JPH04202365A (ja) * 1990-11-29 1992-07-23 Kanegafuchi Chem Ind Co Ltd 吸油性樹脂組成物及び該組成物を用いた油の回収方法
EP0524674A1 (fr) * 1991-07-04 1993-01-27 ENICHEM ELASTOMERI S.r.l. Procédé pour éliminer des produits hydrocarbonés de la surface d'un milieu aqueoux

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH475106A (de) * 1965-10-01 1969-07-15 Wacker Chemie Gmbh Verfahren zum Erzeugen lipophiler Oberflächen auf kleinteiligen festen Stoffen
US5076938A (en) * 1989-09-26 1991-12-31 Noonan William R Oil treatment method
JPH04202365A (ja) * 1990-11-29 1992-07-23 Kanegafuchi Chem Ind Co Ltd 吸油性樹脂組成物及び該組成物を用いた油の回収方法
EP0524674A1 (fr) * 1991-07-04 1993-01-27 ENICHEM ELASTOMERI S.r.l. Procédé pour éliminer des produits hydrocarbonés de la surface d'un milieu aqueoux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9236, Derwent World Patents Index; Class A26, AN 92-295529 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998051422A1 (fr) * 1997-05-14 1998-11-19 Ingenieria Ambiental Mexicana, S.A. De C.V. Microencapsulation de contaminants organiques dangereux dans une matrice du sol

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Publication number Publication date
AU6152494A (en) 1994-09-26

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