Liquid purification or separation – Processes – Ion exchange or selective sorption
Reexamination Certificate
2001-04-24
2003-09-30
Dunn, Tom (Department: 1725)
Liquid purification or separation
Processes
Ion exchange or selective sorption
C210S690000, C502S061000, C502S064000, C502S080000, C502S401000, C502S407000
Reexamination Certificate
active
06627084
ABSTRACT:
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to organoclay compositions and methods of making them and for using them for removing impurities from contaminated liquids, and more particularly to organoclay compositions formed by contacting a microporous non-swelling aluminosilicate substrate with an alkylamine base.
(2) Description of the Related Art
Contaminated liquids are commonly produced as a result of industrial activities, transportation over land and water and storage and handling. Accidental releases, runoff, and the like are common problems that result in oil contaminated water, which is caused by spilling, leaking, or otherwise contacting the water with crude or refined oils, lubricants, fuels, or exhaust. The contaminants can render the liquid hazardous or unsuitable in terms of potability, industrial exposure, appearance, odor, growth of microorganisms, or environmental release. Methods of treating contaminated liquids are known, including the use of certain clays, treated clays, activated carbon and other materials as absorbents or adsorbents for the contaminants. Some of these materials have a high capacity for removing oils, for example, but may also absorb large amounts of water, or lose their structural integrity. Absorption of an excess amount of water can impair or limit the capacity of the material in removing the target impurities.
The modification and/or use of various types of clays as absorbents for contaminants has generated wide interest. General information on various clays and other aluminosilicates can be found, for example, in
The Industrial Minerals Handybook II
, Peter W. Harben, Ed., pp. 9-11 (attapulgite and sepiolite), pp. 21-25 (bentonite), and pp. 200-202 (zeolites), Industrial Minerals Division, Metal Bulletin PLC, London (1995).
In U.S. Pat. No. 2,367,384, Tymstra et al. described the use of a broad range of hydrophobic organic materials as coatings for a variety of fine particulate solids in order to obtain compositions capable of absorbing oil from water. Hauser, in U.S. Pat. No. 2,531,427, described the production of a swelling clay product that has been treated with an organic “onium” compound to form a material that formed a swollen gel upon contact with organic liquids.
Jordan, in U.S. Pat. No. 2,966,506, described the formation of modified clay complexes by reacting a swelling bentonitic clay, which had been ion exchanged, with an organic ammonium salt. The complexes were said to be useful for gelling an organic liquid.
U.S. Pat. No. 2,971,922 taught organophilic mineral compositions consisting of 25-70 parts of a clay and 30-75 parts of a fatty acid amide. These colloidal clay materials were used as gelling agents, foundry binders, and rheology modifiers.
U.S. Pat. No. 3,024,164 described monoethanolamine (MEA) coated clay compositions for use as a pesticide carrier.
U.S. Pat. No. 3,080,214 disclosed the treatment of attapulgite to make a filter aid by forming a dispersion, grinding, and drying the material.
U.S. Pat. No. 3,298,849 disclosed hydrating, swelling clays modified with alkanolamine acid salts.
In U.S. Pat. No. 3,487,928, Canevari taught the use of a montmorillionite clay that had been treated with an organic cationic agent, such as an amine or a glycol, for the removal of dispersed droplets of oil from water.
U.S. Pat. No. 3,617,561 disclosed the use of attapulgite with anionic polyacrylamide as a clarifying agent.
U.S. Pat. No. 3,901,818 disclosed a complex for binding hydrocarbons, comprising a solid hydroxyl-containing substrate, activated with an acid halide, then covalently bound with primary amines.
U.S. Pat. No. 4,054,515 disclosed the absorption of heavy metals from water using attapulgite or sepiolite.
U.S. Pat. No. 4,079,001 disclosed the purification of industrial effluents with an adsorptive material made from a cellulosic carrier treated with a clay-polyamidopolyamine complex.
U.S. Pat. Nos. 4,116,825 through 4,116,828 disclosed the use of attapulgite and sepiolite to adsorb hormones ('825), toxins ('826), viral microorganisms ('827), and pesticides ('828) from water.
U.S. Pat. No. 4,167,481 disclosed a process for metals removal using cation exchangers (tectosilicate and phyllosilicate clays) in the presence of polyamines.
U.S. Pat. No. 4,386,010 disclosed compositions of attapulgite treated with quaternary ammonium or phosphonium surfactants.
U.S. Pat. No. 4,444,665 disclosed a method of purifying aqueous liquids with calcined attapulgite treated with quaternary cationic surfactants.
Beall, In U.S. Pat. No. 4,473,477, described a method for absorbing organic wastes onto an organoclay formed by reacting a quaternary ammonium salt and a smectite-type clay. In U.S. Pat. No. 4,517,094, the same inventor described a two-stage method for removing organic contaminants from aqueous liquids, where the first step of the method involved passing the waste through a column packed with an organoclay.
U.S. Pat. No. 4,769,078 disclosed organophilic clays made by reacting smectic clays with quaternary ammonium compounds and a betaine.
U.S. Pat. Nos. Re. 34,041 and 4,781,860 disclosed a method of disposal of radioactive or hazardous liquid wastes, by adding attapulgite or sepiolite clay and stirring until the mixture solidified.
U.S. Pat. No. 4,802,985 disclosed a water treatment material of organic thermoplastic polymer, inorganic particulate material, and organic cationic crosslinked polymer.
U.S. Pat. No. 5,028,388 taught an immobilizing process for metallic and organic pollutants, by absorbing them on a layered clay mineral modified with a quaternary ammonium compound.
U.S. Pat. No. 5,057,467 described the use of polyalkylenepolyamine and an optional latex to improve the filtration rate and viscosity of clay slurries.
U.S. Pat. No. 5,071,587 disclosed a composition for removing turbidity, metals, and organics from drinking water, comprising clay, coagulant or flocculent, biocide, and activated charcoal.
U.S. Pat. No. 5,231,063 taught a composite adsorbent for odors, comprising salts of aromatic amino acids, an acid, and a transition metal.
U.S. Pat. No. 5,238,575 described a method of absorbing hydrocarbons, using acid leached bentonite modified with an alkyl ammonium salt that is protonated with an organic aliphatic acid. Optional co-additives were also listed.
U.S. Pat. No. 5,320,773 disclosed a method of making a dry solid water purification composition, by impregnating a mineral with a biocide and a coagulant or flocculant.
U.S. Pat. No. 5,407,879 taught a method of absorbing contaminated liquids with smectite clays impregnated with a water soluble polymer.
U.S. Pat. No. 5,454,955 disclosed a method of clarifying deinking waste with hectorite clay, cationic coagulant, and anionic flocculant.
U.S. Pat. No. 5,554,288 described the use of filter papers impregnated with additives to remove halogen, organic, and metal cation wastes.
U.S. Pat. No. 5,556,547 disclosed the use of polymer modified smectite clays to thicken or solidify sludges.
U.S. Pat. No. 5,667,694 disclosed a method of heavy metals removal using an organoclay formed from a smectite clay and a quaternary ammonium salt.
U.S. Pat. No. 5,670,435 disclosed a composition of bentonite with acid for treating waste water.
U.S. Pat. No. 6,080,319 taught a method of removing inorganic ionic contaminants from water using a mineral modified with an organic ionic compound and an amphoteric surfactant.
Despite the advances that have been made in the area of organoclay compositions for treating liquid wastes, there remains a need for economical, effective compositions that can be used in different types of treatment settings. Specifically, for inline treatment settings, a non-swelling composition would be preferable for cartridge containment. It would also be useful if such compositions provided low resistance to liquid flow, and were capable of maintaining structural integrity while demonstrating low water absorption and a high capacity for organics. There is also a need for new methods of purification of c
Fabri Jonathan M.
Mahoney Robert P.
Murphy Christopher B.
Ildebrando Christina
Nelson Mullins Riley & Scarborough LLP
Polymer Ventures, Inc.
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