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WO2016154710A1 - Élimination de déversements de pétrole d'émulsions d'eau douce ou saumâtre au moyen de nanoparticules hydrophobes fonctionnalisées - Google Patents

Élimination de déversements de pétrole d'émulsions d'eau douce ou saumâtre au moyen de nanoparticules hydrophobes fonctionnalisées Download PDF

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Publication number
WO2016154710A1
WO2016154710A1 PCT/CA2015/000205 CA2015000205W WO2016154710A1 WO 2016154710 A1 WO2016154710 A1 WO 2016154710A1 CA 2015000205 W CA2015000205 W CA 2015000205W WO 2016154710 A1 WO2016154710 A1 WO 2016154710A1
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Prior art keywords
nanoparticles
functionalized
oil
nanoparticle
alumina
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PCT/CA2015/000205
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English (en)
Inventor
Nashaat N. NASSAR
Farid B. CORTÉS
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UTI LP
Universidad Nacional de Colombia
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UTI LP
Universidad Nacional de Colombia
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3289—Coatings involving more than one layer of same or different nature
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • 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
    • C02F2209/05—Conductivity or salinity
    • 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
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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
    • C02F2303/26—Reducing the size of particles, liquid droplets or bubbles, e.g. by crushing, grinding, spraying, creation of microbubbles or nanobubbles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination

Definitions

  • oil spills which are the release of different types of crude oil into the environment, are a form of pollution that is facing freshwater worldwide.
  • oil spills in the freshwater bodies involved significant volumes, they do not attract the attention of local or international media as do the marine oil spills.
  • Oil spills on freshwater can cause serious environmental and economic impacts, as they can influence the aquatic and nonaquatic life.
  • the properties and chemistry of the crude oil is strongly dependent on its origin and sources. Accordingly, its behavior in the water body is complex and cannot be easily predicted. For instance, some constituents of crude oil are noted for their tendency to float on water and vaporize; while others preferably bind to solid surfaces.
  • hydrocarbon compounds of oil constituents can form oil-in-water (o/w) emulsion due to flow turbulence like flow in rivers and consequently the emulsions change the properties and characteristics of oil spills, and hence can become dangerous substances with different toxicological effects on aquatic life and human beings.
  • o/w oil-in-water
  • Several physical, chemical and biological methods have been reported for removal of oil from produced water from onshore activities; including bioremediation, controlled burning, skimming, solidifying, and vacuum and centrifugation. These methods have proven to be expensive, time-consuming and/or ineffective in meeting stringent environment regulations. Owing to their simplicity and applicability at the industrial scale adsorption processes could be employed as an alternate technology for oil spill treatment and recovery.
  • adsorbents have been widely used for water treatment and recyclability, such as activated carbon, copolymers, organoclay, zeolite and resins.
  • an aim of this invention is to develop a low-cost nano-adsorbent that can be used in the adsorptive removal of oil from water, particularly oily emulsioned freshwater or saltwater (i.e., o/w stable emulsions).
  • the following variables have been investigated to enhance the removal efficiency namely, adsorption time, loading of VR, temperature, salinity and solution pH.
  • the invention provides adsorption materials and methods for making such materials useful for treatment of water contaminated with oil, e.g., oily water.
  • the materials of the invention are useful in methods for at least partial removal of oil from freshwater or salt water.
  • the materials and methods for oil removal are also useful for clean up of water, particularly briny water, contaminated with oil generated during various oil extraction and processing steps.
  • the materials and methods for oil removal are also useful for oil removal from water in which stable oil in water emulsions are present.
  • the invention provides nanoparticles functionalized by contact with complex hydrocarbon fractions, particularly those fractions of crude oil called residues, residuum or resid. Functionalization with such complex hydrocarbon fractions enhances adsorption of oil onto the nanoparticle.
  • Functionalized nanoparticles of the invention are particularly useful for removal or at least partial removal of oil or oily emulsions from fresh or salt water.
  • the nanoparticles are functionalized by contact with crude oil fractions, particularly with inexpensive waste oil fractions and more particularly with fractions that are residues from petroleum distillation.
  • nanoparticles are functionalized by contact with petroleum atmospheric distillation residue or petroleum vacuum distillation residue. More specifically, functionalization is carried out by contacting the nanoparticles with a solution of the residue in an appropriate organic solvent, such as toluene.
  • the nanoparticles are contacted with a solution of the residue in the organic solvent containing from about 1 to 6 wt% of residue with respect to the weight of nanoparticles being treated. More specifically, the organic solution for functionalization contains from 1.5 to 4.5 wt% of residue with respect to the weight of nanoparticles being treated. In more specific embodiments, functionalization solutions contain from about 2 to 4 wt% of residue with respect to the weight of nanoparticles being treated. In a specific embodiment, the nanoparticle are functionalized by contact with the solution of petroleum distillation residue for 1 -2 weeks at room temperature.
  • core-shell nanoparticles are those where the core is alumina or functionalized alumina and the shell is magnetic iron oxide. In a specific embodiment, core-shell nanoparticles are those where the core is magnetic iron oxide and the shell is alumina or functionalized alumina. In a specific embodiment, core-shell nanoparticles have an iron oxide magnetic core coated with silica and a shell of alumina or functionalized alumina.
  • the invention provides methods of making nanoparticle adsorbents by functionalization of nanoparticles employing crude oil or complex hydrocarbon fractions of crude oil.
  • the fractions employed for functionalization of nanoparticles are petroleum distillation residue fractions and more specifically are petroleum vacuum distillation residue fractions.
  • the invention provides methods for at least partially removing oil from water contaminated with oil.
  • the oil contaminating the water is crude oil originating form a crude oil spill.
  • the water may be fresh water or the water may be sea water or briny water generated by an oil extraction process.
  • Oil in the water to be treated can at least in part be in the form of an oil in water emulsion.
  • contaminated water is contacted with functionalized nanoparticles or functionalized composite nanoparticles until a desired level of oil is removed or until the fuctionalized nanoparticles are saturated with oil. Contact may be over minutes, hours, days or weeks dependent upon the level of contamination, environmental conditions, and nanoparticles used.
  • contaminated water is passed through one or more columns containing and retaining functionalized nanoparticles therein.
  • functionalized nanoparticles are added to a selected amount of contaminated water and after adsorption of oil, the nanoparticles are separated from the treated water.
  • any method for magnetic separation of the magnetic nanoparticles from water can be employed.
  • the process for water treatment optionally comprises regeneration of the adsorbents employed. Regeneration can be accomplished by application of heat, such as application of steam or by use of appropriate solvents, e.g., non-polar organic solvents, to remove at least a portion of adsorbed oil. Regeneration of used nanoparticles can provide value added products such as syngas or condensable hydrocarbons.
  • Figure 1 provides graphs showing the amount of oil adsorbed onto (a) virgin alumina, (b) AI/2VR and (c) AI/4VR nanoparticles at pH 7, for initial oil concentrations of 100 (o), 300 (0), and 500 ( ⁇ ) mg/L in fresh water.
  • Other experimental conditions Adsorbent dose, 2.5 g/L; shaking rate, 600 rpm; Temperature, 298 K.
  • Figure 2 provides graphs showing the amount of oil adsorbed onto (a) virgin alumina, (b) AI/2VR and (c) AI/4VR nanoparticles at pH 7, for initial oil concentrations of 100 (o), 300 (0), and 500 ( ⁇ ) mg/L in saltwater.
  • Other experimental conditions Adsorbent dose, 2.5 g/L; shaking rate, 600 rpm; Temperature, 298 K.
  • Figure 3 provides graphs showing the effect of pH on oil adsorption from freshwater onto (a) virgin alumina, (b) AI/2VR and (c) AI/4VR nanoparticles at pH values 4 ( ⁇ ), 7 (o) and 10 ( ⁇ ).
  • Other experimental conditions Adsorbent dose, 2.5 g/L; shaking rate, 600 rpm; Temperature, 298 K.
  • Figure 4 provides graphs showing adsorption isotherms for adsorption of oil from saltwater onto nanoparticles of virgin alumina, AI/2VR and AI/4VR at pH (a) 4, (b) 7 and (c) 10. Shaking rate, 600 rpm; temperature, 298 K; amount of adsorbent, 2.5 g/L.
  • Figure 5 provides graphs showing the effect of VR content on oil adsorption onto alumina ( ⁇ ), AI/2VR (0) and AI/4VR nanoparticles ( ⁇ ) at (a) pH 4, (b) pH 7 and (c) pH 10.
  • Adsorbent dose 2.5 g/L; shaking rate, 600 rpm; temperature, 298 K.
  • Figure 6 provides graphs showing the effect of temperature on oil adsorption from freshwater onto (a) alumina, (b) AI/2VR and (c) AI/4VR nanoparticles at pH 7 and 283 K (o), 298 K ( ⁇ ), 313 K ( ⁇ ) and 328 K (0). Shaking rate, 600 rpm; amount of adsorbent, 2.5 g/L.
  • Figure 7 provides graphs showing the effect of temperature on oil adsorption from saltwater onto (a) alumina, (b) AI/2VR and (c) AI/4VR nanoparticles at pH 7 and 283 K (o), 298 K ( ⁇ ), 313 K ( ⁇ ) and 328 K (0). Shaking rate, 600 rpm; amount of adsorbent, 2.5 g/L.
  • Figure 8 is a graph showing the amount of NaCI adsorbed onto nanoparticles of virgin alumina, AI/2VR and AI/4VR at pH of 4, 7 and10, for initial NaCI concentration of 500 mg/L. Shaking rate, 600 rpm; temperature, 298 K; amount of adsorbent, 2.5 g/L.
  • Figure 9 is a graph showing oil adsorption isotherms from saltwater onto virgin alumina and silica nanoparticles at pH 7. Shaking rate, 600 rpm; temperature, 298 K; amount of adsorbent, 2.5 g/L.
  • Fig. 10 shows a comparison of FT-IR spectra of (a) VR, virgin alumina, AI/2VR (functionalized nanoparticles 2wt%) and AI/4VR (functionalized nanoparticles 4wt%) and (b) the difference spectra between AI/4R and virgin alumina and between AI4RV and virgin VR.
  • Figure 11 is a schematic illustration of the Adsorption and Subsequent Steam Catalytic Cracking of Oil Technology.
  • residues are complex mixtures of hydrocarbons, the composition of which depends upon the crude oil source, and the temperatures at which atmospheric or vacuum distillation is stopped. Additionally, such residues can be subjected to processes to remove components, for example asphaltene can be extracted from petroleum vacuum residue (VR). Such processed residues can be employed for functionalization. Elemental composition of such residues can be measured and certain art-known methods can provide compositional information on such residues. For example, SARA (saturates, asphaltenes, resins and aromatics) in such resides can be determined. Such residues can also be characterized by predominant carbon number and approximate boiling point. Compositions of such residues can be at least partially characterized by infrared spectroscopy and mass spectrometry methods, for example FT-IR and FT-ICR methods can be employed for such characterization.
  • infrared spectroscopy and mass spectrometry methods for example FT-IR and FT-ICR methods can be employed for such characterization.
  • Petroleum Distillation Residue or Residuum is a blend of components derived from crude petroleum oil.
  • Petroleum Atmospheric Distillation Residue is the fraction of petroleum that does not distill at atmospheric pressure. Typically, this residue has atmospheric boiling point of greater than about 344°C (650°F).
  • Petroleum Vacuum Distillation Residue (VR) is generally the fraction of petroleum, heavy oil or bitumen that does not distill under vacuum and represent the bottom product in a vacuum distillation column. The composition of a given VR depends upon the source of crude oil.
  • Vacuum Residues (petroleum) designated by CAS Registry Number 64741-56-6 is described as a complex residuum from the vacuum distillation of the residuum from atmospheric distillation of crude oil consisting of hydrocarbons having carbon numbers predominantly greater than C34 and boiling above approximately 495°C (923°F).
  • heavy gas oil and vacuum gas oil fractions from petroleum distillation can be employed for functionalization. See: Handbook of Petroleum Processing 2008 (Jones, D.S.J, and Pujado, P, eds) Springer , New York, N.Y. for information on petroleum distillation fractions.
  • Nanoparticles for use in the present method can range in average size generally from 5 nm to 500 nm. More specifically, nanoparticles for use in the present invention range in average size from 10 to 100 nm. Yet more specifically, nanoparticles useful for the present invention range in average size from 20-50 nm.
  • Preferred nanoparticles for functionalization and use as adsorbents contain alumina. Nanoparticle mixtures of alumina and silica, particularly where alumina is the predominant component of the mixture can also be used. Composite nanoparticles comprising alumina are also useful for functionalization and use herein. In particular core/shell nanoparticles in which the core or shell is alumina are useful herein for functionalization and use herein. Combinations of functionalized alumina
  • nanoparticles and non-functionalized alumina nanoparticles can be employed as well. More particularly, core/shell nanoparticles comprising a core or shell of magnetic material, such as magnetic iron oxides, e.g., magnetite or maghemite and a shell or core of alumina are useful for functionalization and use herein. In a specific embodiment, nanoparticles having a magnetic iron oxide core coating with silica and having an alumina shell are useful herein for functionalization and use as adsorbents.
  • magnetic iron oxides e.g., magnetite or maghemite
  • nanoparticles having a magnetic iron oxide core coating with silica and having an alumina shell are useful herein for functionalization and use as adsorbents.
  • Any art recognized method can be employed for preparation of nanoparticles for use herein. Any art recognized method can be employed for preparation of magnetic nanoparticles for use herein. Any art recognized method can be used for
  • Functionalized nanoparticles can be provided as a coating on a substrate and contacting includes contacting the oil contaminated water with the coated substrate. It will be appreciated that the functionalized nanoparticle adsorbents herein can be combined with other materials known in the art to adsorb oil. In specific
  • any such combinations of adsorbents preferably comprise 50% or more by weight of a functionalized nanoparticle of this invention.
  • adsorbents After use as adsorbents, functionalized nanoparticles can be disposed of as appropriate.
  • used adsorbents can be treated to remove adsorbed oil components. Any art recognized method for such removal can be employed.
  • used adsorbents can be treated by steam injection or other form of heating to remove adsorbed oil components.
  • the invention provides a method for removing oil from water contaminated with oil which comprises contacting the contaminated water with nanoparticles comprising alumina wherein the nanoparticles are functionalized by contact with petroleum distillation residue.
  • the petroleum distillation residue is petroleum vacuum distillation residue.
  • the nanoparticles are functionalized alumina nanoparticles.
  • the nanoparticles are magnetic nanoparticles.
  • the magnetic nanoparticles further comprise alumina.
  • the contaminated water treated is fresh water. In an embodiment, the contaminated water treated is sea water. In an embodiment, the contaminated water treated is generated by an oil extraction process. In an embodiment, the contaminated water has pH of 10 or less. In an embodiment, the contaminated water has pH of 7 or less. In an embodiment, the contaminated water has pH of 4 to 7. In an embodiment, the contaminated water has pH of 6.5 to 8.
  • the method of treating contaminated water further comprising a step of measuring pH of the contaminated water prior to contact with the nanoparticles.
  • the method of treating contaminated water further comprises adjusting the pH of the contaminated water to a pH of 10 or less after measurement of pH and before contacting.
  • the method of treating contaminated water further comprises adjusting the pH of the contaminated water to a pH of 7 or less after measurement of pH and before contacting.
  • the method of treating contaminated water further comprises adjusting the pH of the contaminated water to a pH between 4-7 after measurement of pH and before contacting.
  • the method of treating contaminated water further comprises adjusting the pH of the contaminated water to a pH of 6 to 8 after measurement of pH and before contacting. In a related embodiment, the method of treating contaminated water further comprises adjusting the pH of the contaminated water to a pH of 6.5 to 7.5 after measurement of pH and before contacting.
  • pH of the contaminated water is adjusted to a pH of 10 or less before contacting. In an embodiment pH of the contaminated water is adjusted to a pH of 7 or less before contacting. In an embodiment pH of the contaminated water is adjusted to a pH between 4-7 before contacting. In an embodiment pH of the contaminated water is adjusted to a pH of 6 to 8 before contacting. In an embodiment pH of the contaminated water is adjusted to a pH of 6.5 to 7.5 before contacting.
  • the temperature of the contaminated water during contact with the functionalized nanoparticles ranges from 273 K to 325K. In an embodiment, the temperature of the contaminated water during contact with the functionalized nanoparticles is ambient temperature. In an embodiment, the temperature of the contaminated water during contact with the functionalized nanoparticles ranges from 280 K to 31 OK.
  • the invention provides a method for functionalizing nanoparticles to enhance adsorption of oil which comprises contacting the nanoparticle with a crude oil fraction.
  • the crude oil fraction is a petroleum distillate residue.
  • the crude oil fraction is a petroleum atmospheric distillation residue.
  • the crude oil fraction is a petroleum vacuum distillation residue.
  • the nanoparticles functionalized are an alumina nanoparticles.
  • the nanoparticles functionalized are a mixture of alumina and silica nanoparticles.
  • the nanoparticles functionalized are core/shell nanoparticles.
  • the nanoparticle comprises alumina and magnetic iron oxide.
  • the nanoparticle consists of alumina and magnetic iron oxide.
  • the nanoparticle comprises alumina, silica and magnetic iron oxide. .
  • the nanoparticle consists of alumina, silica and magnetic iron oxide.
  • the method for functionalizing the nanoparticles comprises contacted the nanoparticle with a solution of a petroleum distillate residue in a non- polar organic solvent.
  • the non-polar organic solvent is cyclohexane, toluene or xylene.
  • the solution of a petroleum distillate contains residue in the amount of 1-5wt% with respect to the weight of nanoparticles to be treated.
  • functionalization is carried out by contacting the nanoparticles for at least one day. In an embodiment, the contacting is carried out for at least one week. In an embodiment, the contacting is carried out between about 280 K to 310 K.
  • the method further comprises washing the contacted nanoparticle with a non-polar organic solvent which does not absorb in the UV until the wash solvent exhibits no UV absorption.
  • the wash solvent is toluene or xylene.
  • the oil in water (o/w) emulsions were prepared using a Colombian crude oil (33°API) and freshwater.
  • the emulsions were prepared by mixing the oil and freshwater at 16000 rpm for 20 min at 298 K.
  • the mixture pH was around 7.
  • HNO 3 or NaOH was used to adjust pH in a range from 4 to 10.
  • the stability of the emulsions was monitored by the size of the oil drop using a RPL3B optical microscope with Rotating Stage Bertrand Lens Mica and Gypsum Plates (Microscopes INDIA, India) and the absorbance using UV-vis spectrophotometer Genesys 10S (Thermoscientific, USA).
  • Oil in saltwater emulsion 500 1.034 1.500 7.32
  • alumina surface can be considered an array of Bronsted acid-base sites
  • 5 ' 6 other mechanisms of VR anchoring on the alumina surface could be due to strong ionic interactions (i.e., Bronsted acid-base interactions) between the organic compounds present in the VR and the surface of alumina nanoparticles.
  • functionalized alumina nanoparticles were collected after decanting the supernatant. After that, the nanoparticle functionalized with VR were left to dry for a period of 6 h at 393 K to eliminate any remaining solvent and allow the dissolved VR transportation throughout the alumina surface.
  • Core-shell type particles where the core is composed of alumina nanoparticles functionalized with VR (e.g., 2 wt% or 4 wt%), and the shell is Fe 3 0 4 nanoparticles.
  • Fe 3 0 nanoparticles are prepared by co-precipitation of ferric and ferrous salts under N 2 gas. 8 For this purpose, 16.25 g of FeCI 3 and 6.35 g of FeCI 2 are dissolved in 200 ml_ of deoxygenated distilled water. After stirring for 60 minutes, chemical precipitation is achieved at 303 K under vigorous stirring by adding a stoichiometric solution of 2M NaOH under N 2 gas. The reaction system is kept at 343 K for 5 h with solution pH of about 12.
  • Fe 3 0 4 nanoparticles as synthetized above are then added in the desired amount (1 to 5 wt%) relative to the functionalized alumina nanoparticles and stirred for 4 hours at room temperature.
  • Core-shell nanoparticles are then washed 3 times with ethanol and centrifuged at 4500 rpm for 4 minutes in between each washing. Finally, the resultant core-shell particles are dried in oven at 343 K for 10 hours. 8
  • Fe 3 0 4 core/Alumina shell nanoparticles are prepared essentially as in Liu et al. (2008) 12 Fe 3 0 4 nanoparticles prepared as above are suspended in deionized water (0.2 g/40ml_) by sonication under nitrogen atmosphere. To this suspension, aqueous sodium silicate solution (0.6% by wt, pH 9, 40 mL) is added, and the resulting mixture is stirred for 24 h at 37 °C to provide a silica coating on the surface of the magnetic nanoparticles. The magnetic nanoparticles are rinsed with deionized water (3 x 40 mL) and resuspended in deionized water (40 mL).
  • Aluminum isopropoxide (alumina precursor, 20 mg) is then added to the suspension which is then sonicated for 30 min at room temperature.
  • the mixture is heated in a closed vial at 80 °C with vigorous stirring for 1 h.
  • the vial is then opened to release 2-propanol gas and the opened vial is then heated at 90 °C for 30 min.
  • the vial is loosely capped and heated at 90 °C for another 2.5 h.
  • the mixture is cooled to room temperature and the core/shell nanoparticles are collected by magnetic collection. Particles are rinsed with water several times and collected.
  • These core/shell nanoparticles are functionalized with hydrocarbons (e.g., VR) as described above.
  • Nanoparticles and functionalized nanoparticles were characterized by specific surface (S B ET), particle size, point of zero charge (pH pzc ) and the rmogravi metric analyses.
  • S B ET specific surface
  • the BET surface of the nanomaterials was measured by N 2 physisorption at 77 K using an Autosorb-1 from Quanta crome.
  • BET surface area (SBET) values were calculated using the model of Brunauer, Emmet and Teller (BET), and the mean crystallite size of the nanoparticles (dp) was estimated by applying Scherrer's equation to the main diffraction peak using a X ' Pert PRO MPD X-ray diffractometer (PANalytical, Almelo, Netherlands) with Cu Ka radiation operating at 60 kV and 40 mA with a ⁇ /2 ⁇ goniometer. The solid addition method was used to determine pH pzc .
  • thermogravimetric analyses were conducted with a TGA analyzer (Q50, TA Instruments, Inc., New Castle, DE) by heating the nanoparticles containing VR and the virgin alumina nanoparticles from 303 to 973 K at a rate of 288 K/min.
  • Table 2 lists the specifications and surface properties of the nanoparticles used in this study.
  • the functionalized nanoparticles were characterized by FT-IR, Panels a and b of Fig. 10 show (a) the FT-R spectra of virgin VR, virgin alumina nanoparticles, AI/2VR and AI/4VR nanoparticles and (b) the difference spectra between AI/4VR and virgin alumina nanoparticles and between AI/4VR and virgin VR.
  • AI/2VR and AI/4VR nanoparticles one can easily see the characteristic absorption signals of alumina, particularly around 3400 cm "1 where there is a big band corresponding to the presence of hydroxyl groups. As expected, this broad band is attributed to bonded hydroxyl groups, isolated OH groups and vibrations of adsorbed water.
  • the big absorption band appears between 00 cm 1 and 400 cm “1 corresponds to Al- O-AI vibration, the broadening of this band is believed due to the different vacancies in the octahedral and tetrahedral sites of alumina.
  • the FT-IR spectrum shows bands in the region of functional groups and the finger print region.
  • three bands are observed at 2926, 2850 and 1600 cm "1 .
  • the first two bands correspond to the region of hydrogen's stretching and are assigned to symmetric and asymmetric stretching vibration of the aliphatic CH 3 - and CH 2 -groups.
  • a band centered at 3456 cm “1 is observed and may corresponds to water adsorption on the sample surface or remaining toluene after the functionalization process.
  • four bands are observed at 1450, 1380, 1020 and 868 cm “1 corresponding to alkane C-H bending, symmetric (medium) nitro compounds, C-N single bond and meta aromatic out-of-plane (oop) C-H bending, respectively.
  • Bands between 1700 and 1000 cm "1 suggest the presence of various functional groups in the sample.
  • C-H stretching signal remains and a strong absorption band between 1100 and 1200 cm "1 , this signal is originated in the spectrum difference due to the narrower signal in AI/4VR compared to virgin alumina spectra probably due to changes in the vacancies in the alumina after deposition of VR.
  • FT-IR results show a high presence of non-polar compounds that have affinity with the non-polar molecules present in the oil-fresh water emulsion. Accordingly, a higher content of VR on the alumina surface is expected to increase the surface affinity to non-polar compounds.
  • Adsorption experiments were conducted at 283, 298, 313 and 328 K using a 50-mL glass beaker.
  • the batch adsorption isotherm experiments were performed at different initial concentrations of oil ranging from 100 to 500 mg/L and an initial NaCI concentration of 500 mg/L.
  • Solutions were prepared by diluting stock emulsions of oil at 500 mg/L and of NaCI at 500 mg/L. A total of 25 mg of nanoparticles was added to each emulsion sample (10 mL).
  • a higher proportion of adsorbent and adsorbate could not be used because the high rates of oil removal made the determination of the adsorption isotherms impossible.
  • Emulsions were stirred at 600 rpm for 2 h to reach adsorption equilibrium.
  • Time dependent experiments were performed at 298 K and pH of 7 to determine the oil removal rate from the oily emulsion at oil initial concentrations of 100, 300 and 500 mg/L for virgin alumina nanoparticles and functionalized alumina nanoparticles with different loadings of VR.
  • Panels a-c of Fig. 1 show the amount adsorbed as a function of contact time for (a) virgin alumina nanoparticles, (b) AI/2VR and (c) AI/4VR samples.
  • the adsorbed amount of oil increased with time and leveled off after approximately 25 min of shaking. This time-invariant concentration was considered as the equilibrium time for adsorption.
  • the solution pH plays a significant role in adsorption as it affects the functional groups present in both oil molecules and nanoparticle surfaces.
  • Adsorption of oil as a function of pH was studied at pH of 4, 7 and 10 and a temperature of 298 K.
  • Adsorption isotherms of oil from fresh and saltwater by three nanoparticles (i.e., virgin alumina, AI/2VR and AI/4VR) for pH values of 4, 7 and 10 are presented in panels a-c of Fig. 3 and Fig. 4, respectively.
  • oil adsorption is pH dependent and adsorption isotherms exhibited Type III behavior according to the lUPAC.
  • nanoparticles in a solution with a pH higher than pH pzc were negatively charged, and nanoparticles in a solution with a pH lower than pH pzc were positively charged; i.e., the cationic behavior of nanoparticles became stronger as the pH of a solution decreased.
  • aromatic nitrogen compounds in the VR structure of pyrrolic and pyridinic type and structures having carbonyl groups that can be altered with pH changes according to their acidity constant.
  • the amount of oil adsorbed at pH values lower than pH pzc increased because the nanoparticles have less cationic behavior.
  • the highest amount adsorbed was found at pH 7 and the lowest at pH 10. Accordingly, one would anticipate that reducing the point of zero charge of the nanoparticle surface would favor the adsorption of oil.
  • Panels a-c of Fig. 5 show the adsorption isotherms of oil from freshwater on virgin alumina nanoparticles and alumina functionalized with 2 wt% and 4 wt% VR at (a) pH 4, (b) pH 7 and (c) pH 10.
  • adsorption increased as the amount of VR loading on nanoparticle surface increased. This indicates that increasing the VR on the alumina surface favors the affinity of the nanoparticles to the non-polar compounds in the emulsioned water.
  • Na + and CI can compete with oil molecules and interfere with the adsorption efficiency. Therefore, the effect of NaCI on oil removal was studied for different initial concentrations of oil and a fixed initial concentration of NaCI of 500 mg/L at pH values of 4, 7 and 10.
  • the amount of NaCI adsorbed onto the nanoparticle surface was independent of the initial oil concentration, but highly dependent on the solution pH.
  • Fig. 8 shows the amount of NaCI adsorbed onto alumina, AI/2VR and AI/4VR at pH values of 4, 7 and 10 and an initial NaCI concentration of 500 mg/L.
  • the amount of NaCI adsorbed also increased as the amount of VR on the alumina surface increased. For virgin alumina and AI/2VR, the adsorbed amount of NaCI increased as the solution pH decreased.
  • the amount adsorbed was similar at pH values of 4 and 10, with the highest occurring at a pH of 7.
  • the amount of NaCI adsorbed was always significantly lower than the amount of oil adsorbed, which shows that the presence of NaCI does not impact the adsorption capacity of the nanoparticles.
  • ASSCCOT is a highly efficient system and process for cleaning of wastewater from the petroleum industry.
  • Figure 11 shows a scheme of ASSCCOT.
  • the system (10) has at least two columns, for example a first column (11 ) and a second column (12).
  • the system also has at least two column positions C1 for water cleaning based on the adsorptive removal of oil, particularly using functionalized alumina nanoparticles, and C2 for the regeneration of the adsorbent and steam catalytic cracking of the adsorbed oil to generate syngas (exiting at 15).
  • This system allows cleaning the water in a continuous flow by operating the at least two columns between the at least two column positions.
  • a first column 11 is charged with functionalized adsorbent and positioned at C1 , oily water enters C1 at inlet 13 (with column 11 functioning as the adsorption column) at a desired inlet hydraulic loading (1.4-6.8 LJm 2 .s) from bottom to top and at desired pressure and temperature, preferably atmospheric pressure and temperatures lower than 673 K.
  • desired inlet hydraulic loading (1.4-6.8 LJm 2 .s) from bottom to top and at desired pressure and temperature, preferably atmospheric pressure and temperatures lower than 673 K.
  • desired pressure and temperature preferably atmospheric pressure and temperatures lower than 673 K.
  • the amount of oil remaining in the water as it passes through the column at C1 will be monitored continually at the column outlet (14).
  • the column (11 ) swings to the regeneration process position C2 which is set up for oil removal.
  • Column 11 at the regeneration position C2 will operate at selected temperature (lower than 673 K, e.g., 523 to 673K) in order to perform catalytic decomposition of the crude oil adsorbed.
  • the decomposition is instituted by injecting hot steam into the column at the regenerating position C2, for example via heat source 18 resulting in generation of syngas.
  • syngas (at outlet 15) is generated and can optionally be used for feeding (via conduit 16) the heat source (18) or generated as a by-product of the process.
  • a given system can be implemented with additional columns, e.g., a third and a fourth, etc., swinging between positions C1 and C2. It will also be appreciated that a given system can be implemented with multiple C1 and C2 positions. A given system may have the same or different number of C1 and C2 positions.
  • the ASSCCOT technology can optionally be implemented as ASSTCCOT (Adsorption and Subsequent Steam Catalytic Cracking of Oil Technology) by submitting the swing process to an inert atmosphere (e.g., N 2 ) in order to obtain condensable hydrocarbons as the product of the regeneration process.
  • ASSTCCOT Adsorption and Subsequent Steam Catalytic Cracking of Oil Technology

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Abstract

L'invention porte sur des adsorbants, sur des procédés permettant de fabriquer et d'utiliser des adsorbants et permettant le traitement de l'eau contaminée par du pétrole. Des adsorbants sont des nanoparticules fonctionnalisées qui sont hydrophobes. Des adsorbants sont utiles dans des procédés permettant une élimination au moins partielle du pétrole de l'eau douce ou de l'eau salée. Des adsorbants sont également utiles pour nettoyer l'eau, en particulier l'eau saumâtre, contaminée par du pétrole produit au cours de diverses étapes de traitement et d'extraction du pétrole. Des adsorbants sont également utiles pour permettre l'élimination du pétrole de l'eau dans laquelle des émulsions huile dans l'eau stables sont présentes. Des adsorbants spécifiques sont des nanoparticules comprenant de l'alumine fonctionnalisée avec des résidus de distillation du pétrole.
PCT/CA2015/000205 2015-03-31 2015-03-31 Élimination de déversements de pétrole d'émulsions d'eau douce ou saumâtre au moyen de nanoparticules hydrophobes fonctionnalisées Ceased WO2016154710A1 (fr)

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FRANCO, C. A. ET AL.: "Removal of Oil from Oil-in-Saltwater Emulsions by Adsorption onto Nano-Alumina Functionalized with Petroleum Vacuum Residue »", J. COLLOID AND INTERFACE SCIENCE, vol. 433, 22 July 2014 (2014-07-22), pages 58 - 67, XP029054879 *
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11511258B2 (en) 2018-04-04 2022-11-29 King Fahd University Of Petroleum And Minerals Using porous activated asphaltenes as effective adsorbents for the removal of heavy metals in water
US11701634B2 (en) 2018-04-04 2023-07-18 King Fahd University Of Petroleum And Minerals Method for forming a porous activated asphaltene material
CN111330539A (zh) * 2018-12-19 2020-06-26 丰益(上海)生物技术研发中心有限公司 一种复合型固体吸附剂以及一种纯化油脂的方法
CN111330539B (zh) * 2018-12-19 2022-08-26 丰益(上海)生物技术研发中心有限公司 一种复合型固体吸附剂以及一种纯化油脂的方法
CN111644159A (zh) * 2020-05-25 2020-09-11 哈尔滨工业大学 一种基于改性蛋壳的磁性吸附剂及其制备方法和应用
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