CA2439436A1 - Treatment of aqueous compositions containing contaminants - Google Patents

Abstract

There is disclosed methods and compositions for the preparation and use of aqueous dispersions of water insoluble polymers for waste water treatment and purification. An aqueous composition of the water insoluble polymer and the contaminant is prepared and the polymer undergoes phase inversion to flocculate the contaminant, which may be separated. The polymer can be recovered.

Description

TREATMENT OF AQUEOUS COMPOSITIONS CONTAINING
CONTAMINANTS
FIELD OF THE INVENTION
s The present invention relates to methods for the formulation, preparation and use of aqueous dispersions of insoluble polymer colloids and derivatives (many of which are believed to be new compositions of matter), which are particularly applicable to the treatment of aqueous compositions containing contaminants.
Such methods are particularly applicable to waste Water treatment and water io purification.
PRIOR ART
There are numerous prior art references relating to the use of various polymers in the field of contaminant removal from aqueous compositions. Typical of the is prior art are U.S. Patent Nos. 4,747,954; 3,798,194; 3,790,521 and 3,801,551.
As disclosed in one or more of these references, copolymers such as ethylene acrylic acid (EAA) are introduced into aqueous compositions in order to effect metal contaminant removal. None of these references utilize the concept of phase inversion for contaminant removal.
Zo SUMMARY OF PRESENT INVENTION
In accordance with one aspect of the present invention, methods have been developed involving the use of aqueous polymer dispersions ("APD") for the treatment of aqueous compositions, which methods can be adapted for a wide zs variety of uses for the removal of contaminants from a wide range of aqueous compositions.
In contrast to known solvated "monomeric" polymer units in a conventional aqueous polymer solution ("APS"), the colloidal structures of APD contain 3o hundreds or thousands of polymer units, with some of the characteristics of certain polymers of very high molecular weight ("MW") (up to tens of millions). It is known that APDs do not exhibit the high bulk viscosity and other undesirable characteristics associated with an APS of similar effective MW. There are literature reports of colloidal dispersions of polyacrylamides: these are distinguished from APD in that the colloidal polyacrylamide particles are water-soluble and form an APS upon dilution; APD retain their particulate characteristics even at low aqueous concentrations.
The structure and physicochemical behaviour of APD can be influenced by numerous variables including pH, temperature, salinity, zeta potential, multivalent rations, concentration of polymer, co-reagents and/or non-aqueous fluid phases (such as oils and gases), etc. Control of different variables allows 1o APD with varying properties to be prepared; these have utility in removing contaminants from aqueous mixtures via destabilisation ("phase inversion") of the APD to form polymer solids containing the contaminants or in forming solids with controlled properties. Other applications are also discussed below.
is In accordance with one aspect of the invention, there is provided an improved method for removing contaminants from aqueous mixtures. More particularly, in one embodiment, the invention provides a method of removing a contaminant from an aqueous mixture containing the contaminant, the improvement comprising the steps of:
Zo (A) forming an aqueous composition comprising (1 ) a dispersible substantially water insoluble polymer capable of undergoing phase inversion and (2) a contaminant; and (B) effecting phase inversion of the polymer in the aqueous composition to thereby form at least one contaminant precipitated phase and a treated 2s aqueous phase.
In the above method, a preferred aspect further comprises the steps of providing an aqueous mixture containing said contaminant; providing said polymer in an aqueous polymer dispersion; mixing said aqueous mixture and said aqueous so polymer dispersion to form said composition; and adding a precipitation agent to initiate phase inversion.

In another embodiment of the present invention, there is also provided a method of enhancing dewatering of a hydrous floc, in which the method includes the improvement comprising: forming an aqueous composition of (1 ) a dispersible substantially water insoluble polymer capable of undergoing phase inversion, and (2) a hydrous floc; and effecting phase inversion of said polymer in said aqueous composition to thereby form a second floc with improved dewatering properties.
In a still further embodiment of the present invention, there is provided a method io for treating an aqueous composition containing dispersed oil to flocculate the oil therein and provide an oil enriched phase relative to the oil in said aqueous composition, comprising the steps of: providing an aqueous composition containing oil; providing a polymer dispersion which is a dispersible substantially water insoluble polymer and is capable of undergoing phase is inversion; forming an admixture of said aqueous polymer dispersion and said aqueous composition containing oil; and effecting phase inversion of said polymer in said admixture to form a flocculated precipitate forming said oil enriched phase.
2o Another aspect of the present invention provides a method of separating a fluid mixture comprising the steps of: providing a fluid mixture; providing an aqueous polymer dispersion, said polymer being a dispersible substantially water insoluble polymer and said polymer being capable of undergoing a phase inversion; and mixing said dispersion with said fluid mixture to effect said phase zs inversion and form a solid polymer phase and at least one fluid phase.
A further embodiment of the present invention relates to a method of enhancing a flotation process in which a first phase is floated relative to a second phase, comprising the steps of adding an aqueous polymer dispersion to a composition 3o comprising said first phase and said second phase in which one of the phases is to be floated, said polymer of the dispersion being a dispersible substantially water insoluble polymer and being capable of undergoing phase inversion, and effecting phase inversion of said polymer to enhance floatation of at least one of said phases.
s fn a still further aspect of the present invention, there is disclosed a method of enhancing a sedimentation process comprising providing an aqueous composition containing a first fraction and a second fraction, one of said fractions being removable from said composition as a sediment by the step of adding an aqueous polymer dispersion to the composition mixture during said io process, said polymer of the dispersion being a dispersible substantially water insoluble polymer and being capable of undergoing phase inversion, effecting phase inversion of said polymer whereby enhanced sedimentation of one fraction of said composition is obtained.
is Another alternative aspect of the present invention is a method of treating bulk oil to provide a bulk oil product having improved properties comprising the steps of: providing bulk oil containing one or more undesirable components;
providing an aqueous polymer dispersion of a polymer capable of undergoing phase inversion, said polymer being a dispersible substantially water and oil insoluble 2o polymer; forming an admixture of said bulk oil and said aqueous polymer dispersion; effecting phase inversion of said polymer in said admixture whereby said polymer coalesces or flocculates at least one of said undesirable components to thereby obtain a treated bulk oil product having improved properties.
In various embodiments of the present invention, the polymer dispersions can be mixed by suitable means or steps with the aqueous mixture to form said composition, and separating a solid precipitate from the resulting treated phase.
Typical mixing methods include mechanical agitation, ultra-sonic mixing, 3o magnetic stirring, static mixers, etc. The intensity of mixing will depend on the nature of the admixture and whether or not high or low shear is employed will likewise depend on several factors, such as the nature of the contaminants, the characteristic properties of the resulting floc as to whether it is of a fragile or a robust nature. Suitable techniques are well known in the flocculating art for handling such floc types.
Another aspect of the present invention involves a method of removing a contaminant from an aqueous contaminant spill comprising the steps of:
locating an aqueous spill at a site containing the contaminant; providing an aqueous polymer dispersion, said polymer being capable of undergoing phase inversion io and being a substantially water insoluble polymer; applying said aqueous polymer dispersion to said aqueous spill and permitting said polymer dispersion to undergo a phase inversion to effect solidification and immobilization of said contaminant with said polymer and form a solid precipitate; and removing said solid precipitate from said spill. In this method, preferably there is included the is step of adding a precipitation agent to initiate said phase inversion.
The invention also provides, in another embodiment, a method of in-situ leak reparation comprising the steps of: providing an aqueous polymer dispersion, said polymer being capable of undergoing phase inversion and being a 2o substantially water insoluble polymer; injecting said aqueous polymer dispersion to a subsurface source having an aqueous contaminant leak, and in which the contaminant is contained within the aqueous mixture; effecting polymer phase inversion to form a solid precipitate of contaminant with said polymer; and permitting said solid precipitate to seal said leak. In this method, preferably 2s there is included the further step of adding a precipitation agent to initiate phase inversion.
In another aspect of the present invention, there is also provided a method of removing a contaminant from soil comprising the steps of: providing a soil 3o containing oil or other contaminant teachable therefrom; providing an aqueous polymer dispersion, said polymer being capable of undergoing phase inversion and being a substantially water insoluble polymer; mixing together, under conditions which substantially inhibit polymer phase inversion, said aqueous polymer dispersion, said soil containing said contaminant, water and a surfactant to cause said contaminant to enter the aqueous phase; and separating soil from the resulting aqueous phase.
In related aspects of the present invention, there is also provided a method of preparing an aqueous polymer dispersion with improved characteristics comprising the steps of: providing a first aqueous polymer dispersion in which ~o the polymer is substantially water insoluble; adding a substance at a controlled pH and temperature sufficient to form a second aqueous polymer dispersion having improved properties over said first aqueous polymer dispersion.
Desirably, the added substance is selected from the group consisting of acid, multivalent metal, cellulose, bitumen, rubber, oil, colloidal inorganic solid.
is The invention also provides novel products; one of these products is a stable aqueous dispersion composition containing multivalent metals of formulation M1 M2H P comprising: a substantially ionized ethylene-carboxylic acid copolymer P including ethylene-acrylic acid polymer of average molecular 2o weight from about 4,000 to about 15,000, and associated cation mixture M1 M2H; M1 being monovalent cations including ammonium and alkali metal, M2 being multivalent metal cations and H representing unionized carboxyl group, and where the ratio of equivalents of (M2 plus H) to equivalents of M1 is less than about 1:1.
In a still further development, there is also provided a method for the solvent extraction of metals from an aqueous mixture comprising the steps of:
providing an aqueous mixture containing metals and emulsified solvent-chelant; providing an aqueous polymer dispersion, said polymer being substantially water 3o insoluble and being capable of undergoing phase inversion; mixing said dispersion with said aqueous mixture; creating a polymer phase inversion; and separating the resulting polymer solid from the extracted solution.
Moreover, the present invention also provides a method for the selective extraction of metals from aqueous solution comprising the steps of: providing an s aqueous metal solution containing at least two different metals dissolved therein; providing an aqueous polymer dispersion of a substantially water insoluble polymer, said polymer being capable of phase inversion; mixing said dispersion with the said metal solution; inducing polymer phase inversion under conditions to preferentially incorporate a said one of said metals into polymer io solids resulting from phase inversion while the other metal remains substantially in dissolved form; and separating said polymer solids from the selectively extracted solution.
Another aspect of the present invention provides a method for enhancing a is solvent extraction process comprising: providing an aqueous solvent mixture;
providing an aqueous polymer dispersion, the polymer being capable of undergoing phase inversion and being substantially water insoluble; mixing said aqueous solvent mixture and said polymer dispersion to effect a polymer phase inversion and form a polymer solvent extract solid and extracted water phase Zo substantially free of solvent.
Still further, the present invention teaches a method for the extraction of a ' soluble substance from water comprising the steps of: providing an aqueous polymer dispersion, said polymer being substantially water insoluble and being is capable of phase inversion; providing an aqueous solution containing a substance to be extracted; mixing said dispersion and solution such that polymer phase inversion occurs; and producing a solid phase containing said substance and extracted water phase.
3o Moreover, there is also disclosed herein a method of purifying a dispensable polymer comprising the steps of: providing a dispensable polymer to be purified, - g said polymer being substantially water insoluble and being capable of undergoing phase inversion; preparing a dilute aqueous dispersion of said polymer; inducing a phase inversion in said dispersion; and separating purified polymer. Desirably, the preceding method includes the step of preparing an aqueous dispersion from said purified dispersable polymer.
The invention also provides for a new method for producing polymer-additive solids with improved dispersibility comprising the steps of: providing an aqueous polymer dispersion-additive mixture, said polymer being substantially water io insoluble and being capable of undergoing phase inversion; inducing a phase inversion under conditions to form a polymer-additive solid intermediate;
separating said intermediate solid; re-dispersing said intermediate solid;
removing undispersed material; inducing a phase inversion; and isolating the refined solid, said refined solid exhibiting improved dispersibility characteristics.
is In another embodiment, there is also provided a method for the manufacture of colourimetric pH-indicating solids comprising the steps of: providing an aqueous solution of at least one pH-indicating dye; providing an aqueous polymer dispersion or slurry; mixing said solution with said dispersion or slurry; and 2o separating the polymer-dye solid. Typically, the dye may comprise a compound which is known in this art, e.g. the substituted phenols and cresols. The products resulting from this method are long lasting pH indicators compared to ' conventional dyelpaper combinations. In addition, the products of the present invention are much simpler and more economical to manufacture and use.
For general purposes, the invention also provides a method of inducing a phase inversion in a mixture containing an aqueous polymer dispersion or flocculated slurry comprising: providing an aqueous polymer dispersion or flocculated slurry derived therefrom, said polymer being substantially water insoluble and being 3o capable of undergoing phase inversion, and adjusting the pH of said slurry to thereby form a polymer product having enhanced contaminant removal capability. In particular, such enhanced capabilities include properties such as increased contaminant removal, increased separation efficiency, increased selectivity for target contaminants. Thus, for example, selective removal of copper is enhanced by addition of calcium ions, metal removal capacity can be increased by addition of e.g. hydroxide ions.
The present invention also provides a method of forming a metastable or an activated aqueous polymer dispersion or slurry comprising: providing an aqueous polymer dispersion, said polymer comprising a water insoluble polymer io capable of undergoing phase inversion, providing an aqueous mixture containing at least one additive chosen from acids and multivalent metals, mixing said aqueous mixture and said dispersion, permitting said polymer to undergo phase inversion to thereby form said metastable or activated polymer dispersion. Such metastable dispersions can have an active lifetime of several is hours to several days thus permitting them to be formed at one site, and transported to a second use site where they can be activated.
Still further, one of the broader aspects of the present invention relates to the use of an aqueous polymer dispersion, the dispersion comprising a polymer ao which is substantially water-insoluble and which is capable of undergoing phase inversion, for removal of a contaminant from an aqueous mixture containing the contaminant.
Another embodiment of the present invention relates to a method of forming a is substantially water impermeable barrier in or on a substrate surface comprising the steps of: providing an aqueous dispersion of a dispersible substantially water insoluble polymer capable of undergoing phase inversion; applying said aqueous dispersion into or onto said substrate surface to form a zone of said polymer in or on said surface; and effecting phase inversion of said polymer 3o while said polymer is in or on said surface to thereby form a substantially continuous barrier layer of a polymer in or on said surface.

- to -The present invention also provides products which are believed to be new produced by different methods described above.
In the embodiments of the present invention such as those described above, s phase inversion is utilized to solidify the contaminants with the polymer and separating water from the solidified contaminants. In some cases, it may be desirable to add a solvent to increase extraction rate and or efficiency of the extraction.
In various methods of the present invention, it may be desirable to separate the precipitated phase from the aqueous phase; depending on the nature of the contaminant, the contaminant can be recovered for useful purposes (e.g. metal recovery).
is In various of the above methods, preferably there is included the step of separating a precipitated phase by a process selected from magnetic separation, sedimentation, flotation, centrifugation, hydrocyclone treatment, screening, filtration, differential pressure press-filtration and membrane permeation processes. Another aspect of this embodiment preferably Zo comprises the step of selectively heating or electromagnetically treating said precipitated phase prior to or simultaneous with the separation step.
In the above and subsequently described methods of the present invention, the invention may be used for treatment of a wide range of contaminants such as Zs colloidal solids, emulsified oil, free-phase oil or hydrocarbon, edible or essential oil, tar, bitumen, fat, dissolved metal, chelated metal, precipitated metal, dissolved organic substance, colloidal solid or liquid, surfactant, polymer, paint, carbon, clay, colour, protein, pharmaceutical agent, biocide, biological fluid fraction, fermentation fraction, blood, fertilizer, food residue, phenol or derivative 3o thereof, polynuclear aromatic hydrocarbon, chlorinated hydrocarbon, sulfonated hydrocarbon, carboxylic acid, soap, natural product, radionuclide; latex; and ore particles.
In various of the preceding methods, it is also possible in preferred s embodiments, to vary at least one process condition selected from pH, temperature, shear, mixing rate, residence time, addition rate, added soluble metal ration concentration, organic ration concentration.
If desired, following the various methods of the present invention described to herein above or hereinafter, the polymer can be recovered and used again.
Suitable recovery techniques include e.g. filtration, floatation, sedimentation, centrifugation, etc. Depending on the condition of the recovered polymer (e.g.
whether the polymer contains undesired contaminants, undesirable levels of such contaminants can be removed prior to re-use.
is In the embodiments of the present invention where a gas generating composition is employed, any suitable agent compatible with the aqueous composition or admixture may be employed. Such agents may be added as solids or liquids. Typical agents can be various carbonates and bicarbonates Zo such as ammonium carbonate, sodium carbonate, etc. The amount of agent added will vary depending on the intensity and amount of gas generation desired - typically such agents may be added from e.g. .5 wt % upwards.
In the above methods, where a precipitation or initiation agent for phase 2s inversion of the polymer is employed, the agent can be added, if desired, to the aqueous polymer dispersion, to thereby form an intermediate which in turn can then be added to the aqueous mixture. In other cases, the precipitation agent can be added directly to the aqueous compositional mixture made up of the aqueous polymer dispersion and aqueous mixture of contaminant. The choice 3o will depend on the nature of the aqueous contaminant and the specific type of polymer employed.

The initiation or precipitation agent can be for example, an acid. Typically, this may be an inorganic acid such as hydrochloric acid, sulphuric acid, phosphoric acid etc.; other acids such as an organic acid e.g acetic acid, propionic acid, sulphonic acids, etc. may be employed. Other types of precipitating or initiating s agents can be used such as an aqueous solution of a metal ion including Ca2+
and Fey'; colloidal solid particles with appropriate surface activity or any combination of the foregoing. The selection of the agent will depend on the nature of the dispersed polymer and aqueous phase as well as process conditions and desired solid-liquid separation method. The initiating agent may io be added to the aqueous solutions prior to the addition of the polymer in certain cases. The amount of initiating agent will vary depending on several factors -e.g. the amount and nature of the polymer used, the amount and nature of contaminant, pH and temperature conditions, etc.
is In some cases, addition of a precipitating agent or agent which initiates phase inversion may not be required where the mixture flocculates spontaneously after addition of the polymer dispersion.
While not being limited to any theory, it is thought that certain embodiments of 2o the present invention involve or are based on one or more of (1 ) contaminant micro- encapsulation by incorporation into the solid polymer lattice, (2) contaminant-polymer coalescence and flocculation induced by very high surface ' area polymer structures; (3) change in colloid surface tension and hydrophilic-oleophilic balance and (4) direct particulate entrapment within the polymer is structure.
TU ILITY
The present invention finds wide utility for numerous uses. One prominent use is the application of the method to remove contaminants from aqueous mixtures 3o for various purposes, such as plant stream clean up, purification of aqueous mixtures containing contaminants to recover the contaminants and provide a potential feed stream for re-use in various processes or industries, etc..
Other applications of the present invention relate to oil spill clean-ups, use of the methods of the present invention also finds application for land-based spills involving e.g. oil, which will provide a solidified oil fraction, which is then easily s removed from a spill site. In the case of contaminant spills such as oil spills into a body of water, utilization of the methods of the present invention will result in a polymer-contaminant solid which floats on the water body and thus may be removed by well-known surface skimming/screening techniques. In the case of oil spills in water bodies, the present invention also finds use where it has been io determined that the oil-water mixtures resulting from such a spill can be gelled using relatively small amounts of the polymers described herein, in combination with high shear mixing. In other words, a polymer is added to the oil-water mixture and after phase inversion together with high shear mixing gelled emulsions will result which will have the consistency of a stiff whipped froth.
is Such compositions can be stable for up to several days which would permit cleanup operations to be employed (e.g. using boom deployments). This particular technique has the advantage that many times the weight of the polymer in terms of contaminant, can be immobilized. Other uses of the methods of the present invention include metal removal from aqueous Zo compositions as well as use in providing in-situ leak reparations. The invention can also be used to prepare aqueous polymers dispersions having improved chemical andlor physical characteristics. Selective extraction of metals is also ' possible using the present invention as well as purification of dispersible polymer. The methods of the present invention provide significant Zs improvements over the prior art, particularly as to the efficiency of the present methods in removing contaminants from aqueous mixtures.
POLYMERS
In the present invention, the polymers which can be employed are those which 3o are substantially insoluble in water and are dispersible therein and which are capable of undergoing phase inversion. As used herein, the term "phase inversion" refers to a change in the dispersion from one continuity to another -and as illustrated in the examples hereinafter, includes precipitation, flocculation and coalescence. Such polymers can be chosen from a very wide range of known polymers, preferred classes of which are identified hereinafter.
s Alternatively, the substantially water insoluble polymer can be one which is capable of coalescing once mixed in an aqueous. solution containing a contaminant to undergo transformation to a non-dispersed form. As used herein, the term "dispersible polymer" refers to a polymer which when in an aqueous mixture, forms with the aqueous mixture, a two phase system in which io one phase is water with the other phase being composed of very small particles of polymer, either in a solid, liquid or gel state.
In many of the embodiments of the present invention, the dispersible polymer wilt be used in the form of an aqueous dispersion; in some embodiments, the is polymer may be used as a particulate solid which is added directly to an aqueous phase of the contaminant or the aqueous phase to be treated so that the polymer when in the aqueous contaminant, forms a dispersed polymer with the aqueous component containing the contaminant. The choice of whether an aqueous dispersion of the polymer is used, or whether the polymer is added to zo an aqueous contaminant phase, will depend on the ease of dispersion of the polymer into the aqueous contaminant phase, amongst other factors such as temperature, pH, etc.
It has been found that a wide variety of physical forms of polymers can be Zs employed in the present invention, provided such polymers are capable of forming an aqueous dispersion, such as a micro-emulsion or suspension of the polymer in an aqueous composition containing a contaminant. As such, the polymers which can be used in the present invention include liquid polymers such as paraffiins, silicones, polyglycols, latexes, and solid polymers including 3o cross-linked (resinous) polymers such as styrene-divinyl benzene, and a wide range of thermoplastic polymers some of which may also function as precursors to resinouslcross-linked polymers. With respect to solid polymers, preferably they are used in the present invention in finely divided particulate aqueous form.
A most preferred embodiment of the present invention utilizes nano sized particles for more desirable results - such particles may range in size from about 10 to 50,000 nanometers, desirably 15 to 10,000 nanometers, the most preferred range would be 20 to 2000 nanometers.
In general terms, the polymers which may be employed in the present invention can be various types of polyamides, polyolefins, and particularly polyethylene or io co-polymers of ethylene with one or more other monomers or polymers; in addition, oxidized polyolefins and in particular, highly oxidized poiyethylenes;
tefion polymers such as tetrafluoroethylene polymers and co-polymers, vinylacetate polymers such as polyvinyl acetate, or co-polymers of vinylacetate polymer; urethane polymers and precursors, e.g. polymers of isocyanate/polyol is having polymer backbones of aliphatic, ester, polycarbonate and polyether types; styrene polymers and co-polymers and particularly carboxylated styrenes;
acrylic acid polymers or co-polymers such as methacrylic acid co-polymers;
polymers and co-polymers containing diene groups such as polystyrene-butadiene, polychlorobutadiene, polystyrene-butadiene-vinylpyridine.
The choice of the individual polymer for use in the present invention will depend partially on the nature of the contaminant to be treated or removed from an ' aqueous solution. In some cases, various classes of polymers or co-polymers will find more application in solid flocculation while different polymers or co is polymers may be used for sludge de-watering or metal removal. Preferred classes of polymers for different purposes will become evident from the examples disclosed herein but it will be clearly understood by those skilled in the art that depending on other variables, such as the nature of individual contaminant (oil, metal ion, soluble organic, etc.), the polymer dispersions upon so phase inversion may be more suitable for certain types of contaminants compared to other contaminants.

By way of example, the present invention can utilize solid water-insoluble thermoplastic organic acid addition polymers which can be of a wide ranging chemical structure, provided that they have the physical properties and characteristics described above. Such typical polymers which may be acid s polymers which are addition polymers of ethylenically unsaturated monomers where the starting monomers include one having an acid group of the kind specified. For example, suitable polymers are the random copolymer products of copolymerization of mixtures of one or more polymerizable ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, malefic acid ~o and anhydride, itaconic acid, fumaric acid, citraconic acid and anhydride, methyl hydrogen maleate, and the like, and one or more non-acid polymerizable monomers, such as ethylene, propylene, butene-1, 1, 3-butadiene, and other aliphatic olefins; styrene, a-methylstyrene, vinyltoluene, chlorostyrene, and other aromatic olefins; ethyl acrylate, methyl methacrylate, vinyl acetate and is other unsaturated esters; vinyl and vinylidene chloride; vinyl ethers, acrylamide;
acrylonitrile; and the like.
One class of suitable copolymers for use in the present invention includes:
co-polymers of ethylene and from at least about 1 % to about 25% by weight of 20 one or more ethylenically unsaturated acids, such as acrylic acid, methacrylic acid, methyl hydrogen maleate, etc. as above recited; co-polymers of ethylene, from about 1 to about 25% by weight of one or more ethylenically unsaturated acids, and up to about 50% by weight of one or more other monomers such as ethyl acrylate, vinyl acetate, etc., as above recited; and co-polymers of styrene zs (andlor other substituted vinylaromatic compounds) and from about 1 °~ to about 25% by weight of one or more ethylenically unsaturated acids such acrylic acid, malefic anhydride, etc., as above recited.
In addition, other polymers which can be used include preformed and non-acid 3o polymers by subsequent chemical reaction carried out thereon. For example, the carboxylic acid group may be supplied by providing carboxylic anhydride, _ 17_ ester, amide, acyl halide, and nitrite groups which are then hydrolyzed to carboxylic acid groups.
Within the above defined groups of known polymers and co-polymers, reference s may be made specifically to ethylenelacrylic acid copolymers, ethylene/methacrylic acid copolymers, ethylene/itaconic acid copolymers, ethylenelmethyl hydrogen maleate copolymers, ethylenelmaleic acid copolymers, ethylenelacrylic acidlmethyl methacrylate (ternary) copolymers, ethylenelacrylic acidlethyl acrylate copolymers, ethylene /methacrylic acidlethyl xo acrylate copolymers, ethylenelitaconic acidelmethyl methacrylate copolymers, ethylenelmethyl hydrogen maleatelethyl acrylate copolymers, ethylenelacrylic acidlvinyl acetate copolymers, ethylenelmethacrylic acidlvinyl acetate copolymers, ethylene/acrylic acidlvinyl alcohol copolymers, ethylenelpropylenelacrylic acid copolymers, ethylenelacrylamidelacrylic acid is copolymers, ethylenelstyrenelacrylic acid copolymers, ethylene/methacrylic acidlacrylonitrile copolymers, ethylenelfumaric acidlvinyl methyl ether copolymers, ethylenelvinyl chloride/acrylic acid copolymers, ethylene/vinylidene chloridelacrylic acid copolymers, styrene/acrylic acid copolymers, styrenelmethacrylic acid copolymers, styrenelitaconic acid copolymers, Zo styrene/methyl methacrylate/acarylic acid copolymers, styrene/maleic anhydride copolymers, styrenelcitraconic anhydride copolymers, archlorostyrenelacrylic acid copolymers, ar-t-butylstyrenelacrylic acid copolymers, methyl ' methacrylate/isobutyi acrylatelacryiic acid copolymers.
Zs In general terms, the actual amount of polymer used will depend on numerous factors as will be understood by those skilled in the art, such as contaminant concentration, the type of contaminant, flocculating conditions, pH, etc..
Generally speaking, since the nature of different contaminants varies 3o considerably (e.g. contaminant oil removal vs. contaminant metal removal), it will be understood by those skilled in the art that determination of the amount of - Ig -polymer can be readily optimized by techniques well known to those skilled in the flocculating art.
BRIEF DESCRIPTION OF THE DRAWINGS
Having thus generally described the invention, reference will now be made to the accompanying drawings illustrating preferred embodiments only, and in which:
Figure 1 is a graphical representation of a dispersed polymer in an oily aqueous mixture;
io Figure 2 is an enlarged view of a portion of Figure 1;
Figure 3 is a representation of polymer-oil agglomeration;
Figure 4 is a representation of the condensed solid polymer-oil matrix;
Figure 5 is a representation of possible flocculation mechanisms for conventional vs MFD polymers; and is Figure 6A-B is a representation of surface structures of dispersed polymers.
DETAILED DESCRIPTION OF THE INVENTION
Preparation of Polymer Dispersion Zo In one preferred embodiment of the invention, a polymer dispersion is prepared from a solid polymer using hot aqueous alkali hydroxide, an amine or a chemical equivalent. Alternatively, for certain conventional polymers commercially available polymer dispersions (including eg. Michelman Inc's MICHEM~ tine of products) can be used. A third alternative involves preparation of 'metallized' is dispersions such as copper-EAA according to the teachings of the present invention.
Amongst the above outlined list of polymers, there are included known polymers which can be used in the present invention and which are "self-stabilizing"
(e.g.
so certain polyethylene acrylic acid (EAA) derivatives), or the polymer may be "non-self-stabilizing" (eg. certain polyfluorocarbons). The dispersions can be modified by methods exemplified herein to achieve desirable characteristics such as floc particle size, density, porosity, contaminant removal capacity, and the like.
Addition of polymer dispersion to aqueous solution containing contaminant In accordance with one embodiment of the invention, a polymer dispersion is mixed with an aqueous solution containing a contaminant to be treated.
Polymer Precipitation I Flocculation ("Phase Inversion") Mechanisms The interaction between the polymer dispersion and emulsified or dispersed oil io contaminant is illustrated in Figures 1 to 4. Figure 1 represents dispersed polymer particles (represented by numeral 2) and oil droplets, one of which is represented by numeral 4. Figure 2 represents an enlarged view of the surface of the oil droplet (numeral 4 in Figure 1 ). The initiation of polymer precipitation (phase inversion) enables polymer (numeral 8) penetration of the negatively is charged oil droplet surface (numeral 9), thought to be via the positively charged hydrogen or metal cation associated with polymer -COO groups. This is followed by flocculation to more extended structures (Figure 3) and subsequent contraction to a more dense and less porous polymer-oil solid (Figure 4).
Zo It has been noted that low MW dissolved anionic polymers are not effective as flocculating agents. Figure 5 depicts a possible conventional flocculating intermediate structure 14 and several possible structures 14' which may apply to ' flocculation by the polymers of the present invention. Structure 14 contains high MW (>1,000,000) dissolved polymer 13 bridging through electric double layers Zs represented by 11 between particles 12, allowing flocculation to proceed.
EAA polymers used herein may be of MW under 10,000 and thus possess less than 1/100th of the chain length of polymer 13. Thus, low MW EAA would not be expected to be effective as a flocculating agent. A polymer like 3M's THU-350C
30 (TM) polyfluorocarbon ("PFC") is essentially non-ionic and non-polar.
Therefore, one might expect minimal flocculating capability for PFC. However, low MW

EAA and PFC dispersions were both found effective as flocculating agents of the present invention.
Structure 14' depicts an equivalent arrangement to 14 involving either polymer s type.
A multi-chain polymer aggregate 15 acts to bridge between the particles as shown. The polymer surtace 16 is depicted in close-up in 16A and 16B for PFC
and EAA, respectively. 16A shows the compound nature of this dispersion type, io with the insoluble polymer surface (shaded portion) coated with surfactant molecules. 16B depicts the arrangement of polymer in dispersed EAA. Due to the random spacing of polar C00 groups (not shown), the groups cannot arrange themselves to form a generally hydrophobic inner structure surrounded by hydrophilic (polar) groups as is the case for structure 16A. The result for is some EAA polymers is a porous, water-swelled mixed hydrophilic and oleophilic structure 16B. This structure is very labile and may be manipulated by changing dispersion temperature, concentration, pH, ionic type andlor ionic strength and so forth.
zo Figure 6A depicts the surface of a surfactant-stabilized "inert" polymer dispersion and 6B that of a !ow MW EAA polymer in dispersed form. These represent two extremes of structural types; intermediate structures are easily ' envisioned. Interaction of these colloidal polymer structures with the aqueous phase leading to formation of more extended structures such as that depicted in as Fig 3 occurs under specific conditions of pH, ionicity, dispersed polymer concentration and temperature for each specific dispersion. These variables affect the relative strength of polymer-solvent interactions and thus the relative dispersed colloid stabilities, macroparticlelfloc formation rates, relative amounts) of liquid phases) retained by the floc, the amount and nature of 3o contaminants) retained and so forth.

This possibly could be one rationalization for the observed variation in dispersion behaviour: for example, PFC dispersion does not self-flocculate at low concentration even at pH< 4, while certain EAA dispersion formulations flocculate at pH>7. Not shown are a third class of dispersions where co-solvents are also present such as Adcote 50C30(TM) (referred to herein as "PE"
dispersion and thought to be a low-acid EAA polymer similar to polyethylene wax in dispersed form). When diluted with water, these appear stable for several days to months at alkaline pH. As evidenced by certain Examples herein, this type of dispersion may also be used in processes of the invention.
io The temperature of operation can affect the results of treatment and thus the selection of precipitating agent(s). The most preferred temperature in the case of low MW (6,000-8,000)EAA de-oiling applications may vary from about the freezing point to the boiling point of the aqueous mixture in the case of certain is metal-induced flocculative treatments, but only from about the solution freezing point to about 35°C to 55°C in the case of acid-induced flocculation.
The polymer type also determines the effective temperature range: unlike EAA, acid-induced PFC flocculation can be effective at over 100°C.
It is clear that the preferred ranges of temperature of operation and other variables will vary depending on the type of polymers) in dispersed form, the polymers) melting points) and melting points) of the contaminant-polymer solids among other considerations typical of conventional flocculating agents is such as mixing shear, residence time, separation method, etc. The effect of dispersed polymer type on flocculation behaviour is discussed below.
Chemistry of Polymer Dispersions:
Figure 6 represents a close-up of dispersed EAA vs (PFC-Surfactant) particles:
3o differences in activity are expected based on the different chemical compositions. For example, a monomeric RC00 anion possesses significant -zz-differences in acid-base-metal ion equilibrium constants and kinetics of reaction relative to a large anionic PCA cluster such as [(P(COO)xJ~,ooo . In addition, EAA
and PFC have different surface tension characteristics: solid EAA in the acid form has a surface tension of about 31 dlcm while typical polyfluorocarbon s polymers have lower surface tensions, eg. about 18 to 25 dlcm. Therefore, the dispersions respond differently to pH, temperature, concentration and other variables. For example, variations in the dispersion viscosity vs polymer type have been noted previously (Table 12).
io Some surfactants may have an unacceptably high residual solubility in certain applications. In these cases, in-situ or on-site generation of unstable (with respect to spontaneous re-agglomeration on storage) polymer dispersions would be possible. The prior art has employed certain "unstable" or "pH-splittable" polymers which operate due to chemical cleavage of the polymer is backbone. In contrast, the backbones of the polymers used in the present invention remains intact and grow due to cross-linking and remain substantially insoluble in the liquid phases) in the methods of the present invention.
In the case of ethylene-acrylic acid ("EAA") polymers, there are a variety of Zo commercially available MW ranges and acrylic acid contents; for example, two commercially available Dow "Primacor"TM products both have acrylic acid content in [P] approximating 20 wt.% and average polymer MW in PrimacorTM
5990 of about 6,000 ("EAA6000") and in PrimacorTM 5980 of about 8000 ("EAA8000") Lower acrylic acid contents (< 15 wt. %) are also available 2s commercially, e.g. those polymers present in dispersions such as Adcote(TM) products. The lower acrylic acid content polymers have increased polyolefinic and nonionic properties; for example the product Adcote(TM)50C30 is referred to in product literature and herein as polyethylene ("PE") dispersion. in the case of PFC ("Dyneon" (TM) terpolymer of tetrafluoroethylene, hexafluoropropylene 3o and vinylidene fluoride; 3M) dispersion, carboxylic acidlcarboxylate funtionality is present as added perfluorooctanoate surfactant.

It is known that EAA polymer dispersions are destabilized by Bronsted acids (HCI, acetic acid, etc.) and multivalent metal rations (Lewis acids). The art has not generally recognized that stable dispersions containing significant amounts of multivalent rations including Cu(II), Fe(III) and so forth can be prepared.
It is thought that the lower the ratio of multi- to mono- valent rations associated with the anionic dispersed polymer, the more stable the resulting product with respect to self-flocculation and precipitation of macroscopic solids.
Generally, the EAA dispersions become more unstable as the pH is lowered io from alkaline to acid. The exact conditions under which solids form is also dependent on the type and concentration of dissolved metal(s), polymer MW, acrylic acid content, temperature and so forth. Clearly, the types) of polymer(s), dispersion formulations) andlor additives will be selected for the desired performance under the conditions of use.
is Many of the effects observed in the behaviour of the sub-micron ethylene-carboxylic acid ("ECA") dispersions are thought to be due to the formation of distinctly different polymer micro structures. Of particular significance is the solvent-dependent behaviour of the precipitates. In the purification of glycol, Zo there is a difference in the activity of dispersed PE vs EAA showing that dispersion activity is altered by solvent characteristics.
Comparison of Commercial Polymers and Dispersions with Modified Formulations:
as Dispersion process performance may be enhanced by chemical manipulation.
The dispersions are readily modified in-situ by addition of inorganic reagents like Fe(lll) or AI(III), particulates such as carbon powders, emulsified bitumen, dispersed oils and so forth. These modifications confer the benefits of enhanced flocculation rates, polymer capacities andlor process efficiencies.
3a However, it may not be desirable or convenient to add such co-reagents in all situations. Thus,formulations not needing co-reagent addition will be preferred in certain instances. It has been found that cellulose-EAA, Fe-EAA and (chlorinated rubber)-EAA dispersions can exhibit better flocculation activity as compared to dispersions of commercially available EAA polymers under various conditions.
Metal-Polymer Dispersions:
It has been found that (multivalent metal)- polymer dispersions can be prepared.
These dispersions, some of which appeared stable for months, were useful for a io variety of applications including water treatment and preparation of porous solids.
Oil-Enhanced Production of Polymer Dispersion:
Addition of oil can facilitate the preparation of otherwise difficult to prepare is polymer dispersions which may require less precipitation agent during use.
The oil changes the properties of the dispersion such as average particle size, ion exchange selectivity andlor capacity, chemical reactivity and the like. Such enhancement of dispersion formation is known in the art. However, the technique is seldom practiced in the case of adding oil since oil interferes with zo use in for example coatings, adhesives, etc. Typically, alcohol andlor other volatile co-dispersants are used commercially in place of oils, since the alcohols can more readily evaporate from coatings and other products typically produced from the dispersions.
zs It is therefore a feature of one embodiment of the present invention to prepare oil-polymer-additive dispersions with improved properties over commercially available dispersions in the water treatment and purification processes described herein.
3o Separation Step:
The polymer-contaminant precipitate or condensate can be removed from the aqueous solution by eg. filtration, flotation or any other convenient process.
A
conventional filter such as a cellulose filter may be used. In another preferred embodiment of the invention, the contaminant-polymer precipitate or other suitable dispersion-additive mixture is used to produce filters optimized for the s separation required.
In accordance with the invention, the separation step is preceded by a "rest"
period (residence time) which may vary from about 0.1 min to several hours.
Preferred residence times will vary according to the feed composition, polymer io type, process conditions, separation method, etc. Further, the mixture may be treated by methods of the present invention to optimize the microstructure of the polymer floc solids for the selected separation method during the mixing andlor "rest" periods.
is Regeneration of Polymer:
In accordance with another aspect of the present invention, the contaminant and the polymer can be separated from each other, and the polymer regenerated for re-use in many cases. Separation may be achieved by a number of conventional methods, eg. aqueous leaching, solvent extraction, etc. The procedure chosen Zo will depend on the natures of the polymer and contaminant (and the floc resulting therefrom). Liquid oils may be recovered by squeezing the polymer-oil solids. The dispersion may then be regenerated from the purified solids via conventional means.
is Metal contaminants can be recovered using freshly prepared hydrous metal oxidelhydroxide-polymer flocs (which may be acid-leached) to yield a metal solution and extracted polymer to be re-dispersed. Alternatively" it may be regenerated directly by reaction with aqueous base yielding the dispersed polymer and hydrous metal oxidelhydroxide to be separated. Acid leaching of 3o aged slurry and dried-rewetted copper- and iron - EAA flocs of relatively high EAA content is not desirable. It has been found that the addition of oil to the mixture during the initial precipitation can facilitate solids leaching andlor polymer regeneration processes when contaminantslproducts such as metals are recovered. Without being limiting , it is believed to be possible that in the process of the present invention, the presence of oil prevents the condensation of the polymer-metal structure into the non-porous, non-teachable solids observed on drying or aqueous aging in the absence of oil.
Polishing Effluent:
In a further embodiment of the invention, effluent water or brine can be further io treated (polished) using known techniques such as employing activated carbon, vapour stripping, ion exchange, membrane technologies or the like.
Other Applications:
In further embodiments of the present invention, the aqueous polymer is dispersion, together with a precipitation initiator agent if required, may be applied onto spills to solidify and immobilize the contaminants, which may then be more easily recovered from a spill site. The aqueous polymer dispersion may also be injected with a precipitation initiator agent into subsurface sources of contamination including leaking landfills, underground fuel storage tanks or the zo like. Optionally, the polymer is injected at elevated temperature to form molten polymer which solidifies to a relatively impermeable mass on cooling, The polymer after flocculation andlor solidification acts to immobilize and solidify ' contaminants, while at the same time, forms a barrier to further leakage. In a preferred embodiment of the invention a water-soluble non-toxic acid or zs multivalent metal salt such as calcium or ferric chloride can be used as precipitation agent.
Advantages The technology of the present invention provides several advantages compared 3o to prior art techniques. Specifically, the present invention provides for the following: capability for on-site generation of polymer mixtures which allow selection of the optimal product to clean up of contaminant spills; porosity, oleophilidhydrophilic balance and other physicochemical properties of the polymer solids can be controlled by selection of process conditions and dispersionlactivator compositions; polymers can be varied and/or solvents, s reagents and colloidal solids can be easily formulated into dispersions to improve removal of specific contaminant types, higher absorptive capacity per weight; "activated" hydro-oleophilic polymer solids are capable of providing improved contaminant removal e.g. emulsified oil removal. The simplicity of the process of the present invention allows for the design of reliable automatic io systems for treating periodic andlor highly variable aqueous streams including storm runoff, effluents from process upsets, primary separator flooding.

EXAMPLES
The following examples describe specific embodiments of the invention and are not meant to be limiting. All filtrations were done at a low pressure differential (about 4" H20 maximum) using a coarse cellulose No2 cone-type cellulose s filter, unless specified otherwise.

EXAMPLES
The following examples describe specific embodiments of the invention and are to not meant to be limiting. All filtrations were done at a low pressure differential (about 4" H20 maximum) using a coarse cellulose No2 cone-type cellulose filter, unless specified otherwise.

is Oily water emulsions were prepared and mixed with EAA8000 polymer as a 10%
aqueous dispersion, acidified to pH<4 using 5N aqueous HCI, and stirred for 5-minutes at 20 deg. C, resulting in substantially non-turbid filtrates..
Results are summarized in Table 1.
2o TABLE 1: TREATMENT OF EMULSIFIED OILS
Oil type IPA(g) Hz0 EAA (g) 5N HCI
(ml) (g) bilge oil (0.6 g) 2.5 450 0.3 2 LIX84T"" in kerosene' (2.5 g) 8 900 0.7 3.9 butter (3.3 g) 12.5 900 1 4.4 25 kerosene/crude oil b (8.3 g) 14.7 900 2 3.9 2-cycle engine oil (1 g) 0 400 0.3 1 waste oil from auto service station0 900 0.7 2 (1 g) waste oil from train yard (1 0 900 0.7 2 g) olive oil (1.7 ml) + sunflower 0 700 1 ~2 oil (1.7 ml) d As used herein: (a) 20% LIX84TM (from Henkel Corp.) in kerosene (b) kerosene/crude oil: 3!1 v/v (c) EAA added as a 15~° aqueous dispersion (d) liquid dish detergent added (~0.2 ml) EXAMPLE Z
"Polyethylene" dispersion to remove oil from water:
2.3 g of waste-crude-kerosene mixture (about 1:1:1 vol) was emulsified in 450 ml of water, 2.22 g of "polyethylene" (believed to contain acrylic acid as a co-s polymer) as a 30°~ dispersion from commercial source (7.4 g of Adcote(TM) 50C30) were added, mixed, and then 2 g of 10N HCI were added. A black oil-polymer precipitate floating over clear, colourless water was obtained. The press- dewatered precipitate weight obtained was 5.4 g. By following similar procedures, other oil types can be removed (eg. bilge oil and corn oil).
zo Preparation of Fluoropolymer and polyurethane Phase Inversion solids:
ml. of "fluoroplastic dispersion" in water (Dyneon (TM)3M terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride) containing is about 50 wt.% polymer and 0.5 wt.% ammonium pertluorooctanoate were added to 250 ml. water and the mixture acidified using 2 ml. 5N HCI, resulting in floc formation.
A similar preparation using "Armor Coat" water-based urethane- gloss (°UR"), zo yielded a floc upon acidification; dried weight corresponded to acid-precipitated solids content of about 30 wt %. The solid did not re-disperse in hot aqueous NaOH.

Zs Polyurethane dispersion tests:
The polyurethane dispersion ("UR") of Example 3 was used in the following examples.
4(i) 0.7 g of emulsified bitumen (0.84 g of "Orimulsion"TM) was added to 500 ml 3o water (10C) and stirred. 4.4 g UR {~1.3 g solids) was added to the stirred mixture, then 6 g of 16% HCI. Flocculation occurred rapidly (<1 min). The mixture was filtered after 5 minutes stirring. Crystal clear filtrate and 1.87 g of dried polymer-bitumen solids were obtained.
4(ii) 0.83 g of a 20-20-60 (wlw) Bunker "C"- diesel - kerosene mixture was s emulsified in 1000 ml water (10C; 21 ppm Ca) and 9.0 g UR (2.7g solids) were added. Then 6.4 g of 16°~ HCI were added and the mixture stirred. This yielded solids plus a cloudy aqueous phase.
4(iii) 0.5 g of oil specified in (ii) was emulsified in 600 ml water (10C; 21 ppm io Ca), then 5.2 g UR (1.6 g solids) were added , followed by 8 ml of 6N
AI(III).
This resulted in a large amount of floc containing solidified oil: the floc volume was presumably due to the large AI excess used. 10 ml 16% HCI was added and the mixture stirred 5 minutes then filtered, yielding crystal clear aqueous phase and brown solids.
is 4(iv) In qualitative tests using similar procedures to those described above, colored solids and partially decolorized aqueous phase Were obtained from acidification of mixtures of UR with cranberry juice or coffee.
Zo 4(v) EAA-UR co-flocculation and re-dispersion.
4v(a) 11.6 g of 16% HCI was added to a stirred mixture of EAA6000 (4.66 g) and UR (4.09 g; ~ 1.2 g non-volatiles) dispersed in 343 g water (15C, 21 ppm Ca). The resulting solids were filtered off and dried, resulting in 5.75 g of Zs crumbly off-white solid.
4v(b) A second preparation ((30.2g URI19.6 g EAA6000] plus water (1500 ml) to which was added 100 ml 2.2N HCI) was tested to determine floc characteristics.
3o Floc volume/time: 1300 ml/1 m; 800 mll4m; 700 ml/8m; 660 ml/15m;
580 mll53m 4v(c) The supernatant of Example 4v(b) was decanted and the floc filtered and press - dried, yielding 63.9 g of wet powder ("filter cake") 4v(d) A 33.6 g portion of filter cake of Example 4v(c) was air-dried at 60C
s yielding 19.0 g, for a calculated filter cake solids content of 56.5°~.
4v(e) An undried portion (~30g) of filter cake was added to 50 ml 1 N NaOH, swirled for 2m and then 100C water added to make a total volume of 225 ml;
immediate re-dispersion of the solids occurred. The dispersion deposited solids io on standing; these were easily re-dispersed by agitation. 85 ml of the dispersion was permitted to settle for 14 days, resulting in ~20 ml of white solid under 65 ml of slightly cloudy liquid.
4v(f) The dispersed product from Example 4v(e) (~7.5 g, 0.44 g solids) was is added to 1500 ml water (21 ppm Ca) at 100C resulting in a well-formed floc in <1 m with no apparent residual cloudiness.

Removal of crudelwaste oils from water:
Zo 0.5 g of a crudelwaste (1:1 ) oil mixture was emulsified in 250 ml water.
10 ml of fluoroplastic polymer dispersion were added, then 2 ml 5N HCI. Clear colourless filtrate was obtained. Similar results were detailed using kerosene, undiluted crude, waste and furnace oils.
Zs Titration was used to determine approximate concentrations needed for onset of flocculation using the above polymer.
To 0.5 g of kerosene emulsified in 10°C water containing 21 ppm Ca, 0.65 g of fluoroplastic polymer was added followed by high shear mixing for 10 sec so followed by 2 minutes low shear stirring. No flocculation was observed in the milky mixture. 1 g of 5 N HCI were added and mixed, no floc formed.

To the resulting mixture were added separately, with mixing three more 0.65 g aliquots of fluoroplastic followed by 1.6 g 5N HCI followed by two still further 0.65 g additions of fiuoroplastic. These additions resulted in formation of a visible floc; the solution remained cloudy. Totals of fluoroplastic polymer and 5N
s acid added were 3.9 g (2600 ppm) and 2.6 g, respectively.

High temperature de-oiling:
7 ml of a (1:1:1 vol) wastelcrude oillkerosene mixture was emulsified in 1500 ml io of 95°C water. 25 ml of fluoroplastic polymer dispersion was added, then 5 m!
N HCI. A solid precipitate containing the oil and clarified water resulted.
Similar experiments using EAA6000 polymer and EAA8000 polymer resulted in very milky aqueous phase which rapidly fouled a cellulose filter.
is EXAMPLE 7 Ethylene glycol purification:
200 ml of commercial automobile antifreeze (ethylene glycol) and water (50:50 v/v) was mixed with 5 ml ash particuiates and 2 ml of oil (corn oil). 1 g of EAA6000 polymer as a 10 wt% dispersion) and then 3 ml 5N HCI were added, Zo resulting in precipitate formation and substantially clear filtrate.
A similar experiment using undiluted ethylene glycol resulted in poor ~precipitationlflocculation. However, when 10 ml of mixed PEIEAA polymer dispersion (5 wt.% PE, 5 wt.% EAA6000) were added, satisfactory precipitate Zs formation then occurred. The filtrate was free of visible oil and turbidity.

Methanol-water treatment:
100 ml of windshield washer solution (about 50150 methanoll water mixture) was 3o mixed with 2 ml corn oil and 1 g EAA6000 polymer as a 10% dispersion, then ml 5 N HCI were added. The precipitate formed small dense particles and substantial residual free-phase oil was observed, indicative of reduced polymer-oil solidification capacity in the 50150 methanoilwater solution. Still, substantial clarification of the methanol/water mixture was achieved, since all emulsified oil had coalesced into a separate phase liquid layer during treatment.

De-oiling of CANDU heavy water samples:
Two oily heavy water samples were treated as described in the present invention with EAA8000 polymer as a 10% aqueous dispersion at 20° C. A
3 to io 5 min residence time was allotted prior to filtration. Gas chromatography-mass spectrometer (GCIMS) on the untreated samples gave data typical of lubelhydraulic oil contaminants and showed that both samples were contaminated by the same or similar lubricating or hydraulic oils. A first raw sample (referred to as type 1 ) was yellow and a second raw sample (referred to i5 as type 2) was black. After treatment described above, the filtrate colours of type 1 and 2 samples were yellow and faint yellow, respectively, and both were crystal clear. Table 2 summarizes the experimental data obtained.
TABLE 2: TREATMENT OF CANDU OILY N~O/D~O EFFLUENTS
20 Sample type Polymer TOC in TOC out Other resuns :

1 (a) 0.3 5500; 2000*;
: 1 initial titration(b) 0.7 2000 547** **oil not detected : 1 by gdms 1 1.1 : 5500 1320* 1.5 g (3 ml); press-de batch run A watered solids1100 ml sample 25 1 0.9 : 5500 1210* 0.9 g (2 ml) press-de batch run B watered solids/100 ml sample 2 (a) 0.5 4030; 1360*;
: 1 initial titration(b) 1 1360 482** **oil residues : 1 not detected 2 1 : 1 4030 652* 2.2 g (4.4 mi) press-de 3o batch run watered solids1100 ml sample = TOC" means total organic carbon; * no visible oil in filtrate; and '"' gas chromatography-mass spectrometry ("gclms") detection limit estimated at 100 ppm.

DISCUSSION OF DE-OILING RESULTS
It will be seen from the above example, as well as others - eg. Examples 10 and 19, that EAA, "PE", polyurethane and fluoroplastic dispersions are useful in removing oil from aqueous mixtures under various conditions. Selection of the s dispersion type to be used in a given situation will depend on specific feed type, process conditions and treatment efficiency requirements.
In addition to the direct flocculative oil removal benefits of the processes, there were other benefits were also found observed.
io it is clear from this Example 9 that soluble TOC (total organic carbon) removal by EAA8000 polymer was very effected given the absence of visible oii (65%
and 73% TOC removal, see Table 3). Thus, the EAA dispersion is very valuable as a soluble contaminant removal agent.
is With respect to de-oiling slurry formulations, in another feature of the present invention colloidal carbon can be used with phase inversion polymers in order to increase removal yields. It is believed when carbon is employed in conjunction with the polymers used in the present invention a colloidal porous oleophilic Zo "inorganic" solid together with a polymer colloid structure is obtained;
this structure will be different for identical slurries when exposed to different processing temperatures.

is Removal of organic contaminants from groundwater:
Stage 1: A 3 I sample of oil-groundwater emulsion from a site remediation project was treated with 25% EAA8000 polymer dispersion at 20°C, plus acid to pH<4. The polymer to oil (TPH) ratio observed was about 3 to 1. The results obtained are summarized in Table 2.
30 , Stage 2: A sample of the filtrate from stage 1 (1 liter) was further treated as follows: paraffin oil (0.25 g; BDH #829436) was added to the sample. The mixture was then subjected to 2 min of high shear. The resulting emulsion was treated using 0.25 g of EAA8000 polymer as a 25% aqueous dispersion, to final pH<4. The polymer to paraffin oil ratio observed was 1 to 1. The results are s summarized in Tables 3 and 4.
TABLE 3: TREATMENT OF OILY GROUNDWATER EMULSION
Compound Influent Effluent Removal (PPb) (PPb) Stage 1 TPH* 42700 1200 97 Total BTX* 180 48 73 Totat PAH* 175.6 1.8 99 Stage 2 TPH* 1200 590 50 Total BTX* 48 20 58 Total PAH* 1.8 1.2 34 "'TPH = total petroleum hydrocarbons; BTX = benzene toluene ethylbenzenes xylene; PAH =
polynuclear aromatic hydrocarbons TABLE 4: BTEX AND PAH COMPONENTS FROM EXAMPLE 10 2o Influent (ppb) Effluent Removal (ppb) (%) Benzene ND ND --Toluene ND ND --Ethylbenzene ND ND --Xylenes ND 4.213.1 --Higher Alkylbenzenes 180 48/20 89 Naphthalenes ND 22/12 --PAH

Total 175.63 1.7611.16 99 Naphthalene ND 22/12 --3o Acenaphthalene 0.2 ND >99 Acenaphthene 0.12 0.07/0.04 67 Fluorene 0.14 0.08/0.06 57 Phenanthrene 0.52 0.12/0.09 83 Influent (ppb) Effluent (ppb)Removal (96) Anthracene 1.09 0.1710.01 99 Fluoranthene 17.2 0.29/0.19 99 Pyrene 50.2 0.68/0.59 99 Bz(a)anthracene 9.44 0.08/0.04 >99 Chrysene/triphenylene 14.2 0.11!0.05 >99 Bz(b+k)fluoranthene 20.8 0.05/0.03 >99 Bz(e)pyrene 17.3 0.04/0.02 >99 Bz(a)pyrene 19.3 0.0410.02 >99 Indenopyrene 10 0.02/0.01 >99 to Bz(ghi)perylene 13.6 0.02/0.01 >99 Dibz(ah)anthracene 1.97 ND >99 ND= Not detected is This Example (stage 2) shows efficient (emulsified oil)-(polymer) extraction of dissolved aromatic hydrocarbons with 38% PAH, 50% TPH and 58% BTX
removals using mineral oil as extractant. Higher extractions may be expected using other oils or solvents with greater affinity for aromatics. Thus, the combination of emulsified oil (solvent) extraction and MFD to remove dissolved 2o contaminants from an aqueous phase is clearly effective.

Continuous De-oiling Process:
A 10 litre per minute feed of oily water was introduced into a 100 liter stirred Zs primary mixing tank with overflow level control to vary residence times.
Simultaneously into the stirred oily water were fed separate streams of ~10%
EAA6000 or 8000 polymer dispersion and 5N muriatic acid via peristaltic pumps.
The feed oil concentration was varied from about 85 to about 1,850 ppm, as well as the oil type. One oil type Was furnace oil recovered from a spill site plus used 3o auto engine oil mixture 80120 v/v, respectively. Other feeds contained bilge oils of density 0.87g1m1 or 0.85 g/ml. There was no apparent difference between - 37 _ EAA6000 and EAA 8000 polymer performance under the test conditions.
The amounts of polymer and acid added were adjusted to yield a wa11_ flocculated overflow stream into a second 100 I container: average residence s times were typically ~2 m in the primary mixer and 2 to 10 minutes in the second container. After a feed concentration or oil type change, adjustment of polymer and acid combined with visual observation of mixing tank turbidity were made;
this was found to restore stable operation , typically within 2-4 minutes. Oil residues Were determined from nephelometric measurements of effluent io turbidity after a residence time in the second tank and filtration through a coarse cellulose filter run at a low pressure differential (about 4" Hz0 maximum). No difference was found between the EAA6000 and EAA8000 polymers in the testing, nor did oil type seem to affect performance. System optimization -eg.;
combinations of varying acid addition rate, degree of aeration, mixer speed, is residence time and polymer to oil ratio avoided filter fouling and filtrate treating problems.
Oil concentrations in filtrate samples taken during normal operation varied from ~1 to ~ 6 ppm with average oil concentration of ~3 ppm. Typical data are zo presented in Tabie 5. It was noted that for polymer:oil ratios under approximately 1:1, the solids tended to release oil when pressed.
TABLE 5: CONTINUOUS MFD TREATMENT OF OILY WATER
Oil in (ppm) Oil out (ppm) Polymer : oil Removal (%) is 85 1 1.1 : 1 >99 814 4 1 : 1 99 1786 2 1 : 1 >99 101 3 0.9 : 1 97 126 4 0. 7 : 1 97 30 189 3 0.5 : 1 98 378 2 0.2 : 1 99 20 liter batch tests were carried out in the 50 liter mixing tank used in Example 11. Successfully de-oiled were mixtures including oillgasoline - in-groundwater emulsion (920 ppm feed, 1 ppm filtrate), diesel oil in fresh water (920 ppm feed, s 3 ppm filtrate), crude oil in saturated brine (1,000 ppm feed, 2 ppm filtrate) and various concentrations of kerosene and bilge oils in water and 1.2 glml brine.
Brine results sometimes exceeded 10 ppm, especially at lower mixing rates.

io Effect of temperature and dispersion type on de-oiling process:
Batch de-oiling experiments were run in the 50 liter mixed tank used in Example 11 at 20°C; 30°C and 45°C. Using EAA8000 polymer, a decrease in the percentage of removal of oil was observed going from 99.3% at 20°C to 98.6%
at 30°C and 96.3% at 45°C.
is In a subsequent flask- scale test run at 95C, 7 ml of a (1:1:1 vol) waste/crude oillkerosene mixture was emulsified (electric blender) in 1500 ml of 95°C water.
25 ml of THU 350C fluoroplastic dispersion was added, then 5 ml 10 N HCI. A
solid precipitate containing the oil, and clarified water, resulted. Similar 2o experiments using EAA6000 or EAA8000 polymers resulted in very milky aqueous phase which rapidly fouled the cellulose filter.

A mixture of auto spray paint in water (2.2 81500 ml) was clarified using 3.0 g of Zs EAA8000 polymer followed by acidification to pH<4 and filtration.

ml of oily water were drained from a can of tuna. Addition of 100 ml of water resulted in a cloudy mixture. 10 ml of a 10 wt % (50150 PE/EAA6000) dispersion 3o mixture were then added. Mixing and acidification (2 ml 5N HCI) resulted in clarified filtrate.

In-situ enhancement of gravity driven oil-water phase separation 16(a)Canola oil (13.4 g) was emulsified with water (500 ml) at 50°C.
The emulsion was poured into 10°C water and allowed to stand for 10 min, resulting s in a layer of oil floating on a very cloudy aqueous phase. EAA polymer (2.7 g) as a 10% aqueous dispersion and 2 mi of an aqueous solution of HCI (10N) were injected into the aqueous phase at 20°C below the oil layer. A gentle mixing was performed, without substantial mixing of the already separated oil layer. This resulted in liquid oil and solid precipitate floating over a slightly cloudy layer io after 5 min. After standing at 20°C overnight, complete clarification of the aqueous layer resulted, while the EAA polymer precipitate and liquid oil phase had combined to form a gelatinous solid.
16(b) (i) To 500 ml of tap water containing 21 ppm Ca were added 4.1 g of is dieseI/Bunker C oil and 31.0 g "varsol", followed by emulsification of the mixture using a blender.
(ii) In a separate flask were mixed 0.38 g AI2(S04)3*18H20 dissolved in 15 ml water and 1 g of EAA8000 (added as 100 ml of 1 °~ dispersion), resulting in a voluminous floc.
Zo (iii) The mixture was added to the emulsion described previously giving an oil:polymer ratio of ~35 : 1. The mixture was exposed to a brief (~2 second) pulse of mixing in a blender.
(iv) Cessation of mixing was followed by immediate (<30 sec) separation into a layer of black oil containing solids 0200 ml) over a slightly cloudy 2s water layer 0480 ml).
(v) EAA8000(0.01 g as a 1 % dispersion) was added to the water layer from (iv) and the mixture stirred for 2 minutes at low shear (magnetic stirrer, no aeration) resulting in clarified water plus a small amount of flocculated solids.
The oillsolids layer from (iv) was pressed through a cheesecloth filter, resulting in recovery of about 32 ml oil, 83m! clear water phase and 15 g wet solids retained by the cloth.

s In-situ gas flotation enhancement:
1 ) 12.73 g of diesel- Bunker C oil mixture was emulsified in 987.3 g water. To this was added 1.59 g EAA polymer as a 10% aqueous dispersion, and about 10 ppm of mixed phenoxy-polyoxyethanols as surfactant. Air was introduced while vigorously stirring the mixture.
~o Cessation of mixing and one minute settling time resulted in a black foamy oil layer floating on a dark brown aqueous layer.
2) 4.0 g of 5N HCI were then injected into the aqueous layer with gentle mixing. One minute of standing resulted in a slightly milky aqueous layer is under a layer of semi-solidified oil.
3) 700 ml of the aqueous layer from (2) was drained off and subjected to high shear mixing and aeration. 0.08 g (dry wt.) of frothy polymer.oil solids floated to the top immediately on cessation of mixing. The settled Zo water layer was nearly free of milkiness.
4) 461.1 ml of the unfiltered aqueous layer from (3) was filtered through a coarse cellulose filter: less than 0.01 g. of solids were recovered.
Zs EXAMPLE 18 Fiuoroplastic dispersion removal of EAA micro-particulate residues 2.5 g EAA
polymer dispersion was diluted in 250 ml with 50°C water and precipitated using 3 ml 5N HCI. A milky aqueous phase and a pliable spongy polymer mass were obtained. The milky aqueous phase (at --45°C) was separated and 0.2 g of THU
so 350C diluted to 10 ml with water was added over a 5-second period while stirring vigorously. Stirring was continued for about 10 seconds then ceased.
A

crystal clear, colorless aqueous phase and off-white polymer solids were obtained.

s Treatment of colloidal bitumen-water mixtures:
7.1 g of "Orimulsion" was diluted in 1,000 ml with water with dispersed EAA6000 polymer, then acidified. Orimulsion: polymer ratios of 2:1, 5:1, 10:1 and 13:1 all resulted in crystal clear filtrate. A similar test without added EAA
resulted in tar depositing on all surfaces and a brown aqueous phase which ao rapidly fouled the cellulose filter. The precipitates became more bitumen-like at the higher ratios: the 13:1 product adhered to surfaces similar to Orimulsion acidified in the absence of dispersed polymer; treatment of the surfaces with warm (60°C) dilute NaOH resulted in release of the adhering polymer-bitumen tar.
is Successful clarification was also obtained using 600 ml water with 0.9 g polyethylene (ca 1500 ppm) added as 30% dispersion (Adcote(TM)50C30) and 4.2 g dispersed bitumen added as 6.0 g "Orimulsion" (ca 7,000 ppm) plus 1.0 g 1:1 H2S04.
The bitumen-latex emulsion reaction of this example illustrates the use of a different colloidal polymer (a polymer) to remove an emulsified organic (bitumen) from water. Clarification was not as efficient as that from a . comparable dose of dispersed EAA but none the less was effective. In this 2s case, residual cloudiness was removed using a small amount of EAA
dispersion, at an EAA:contaminant (latex + bitumen) ratio of about 1 : 28 wlw.

Removal of DEET toluamides from water:
so About 0.1 g of Muskol(TM) liquid insect repellent was emulsified in water (20 ml). Addition of 0.1 g EAA6000 polymer as a 10°~ dispersion followed by 20wt%

HZS04 (0.2 ml) and mixing gave a white solid with the odour of toluamides and clarified water.

s Removal of epoxy from water:
About 1 g of Dow Epoxy Resin 331 was dissolved in 25 ml of isopropanol.
Addition of this solution to 1,000 ml of water resulted in a milky dispersion.
1.0 g of EAA6000 polymer as a 10% dispersion was added followed by 4 ml of 4 N
sulfuric acid. A white solid and clarified water phase were obtained.
io Treatment of drilling mud in water:
An aqueous organic-inorganic solids suspension was prepared by mixing 20 ml of drilling mud with 100 ml of water. 2 g of EAA8000 polymer as a 10%
is dispersion were added to the emulsion, then the mixture was acidified with HCI. After 3 min stirring, the mixture was filtered. A clear, colourless solution was obtained.

Zo De-oiling water containing metals:
An aqueous solution containing various metals was prepared by dissolution of correspondent metal salts in water as indicated in Table 10. An emulsion of kerosene in said aqueous solution was then treated with a 21.5% aqueous EAA8000 polymer dispersion at 20° C. The polymer to oil ratio was maintained Zs at 1 to 1, and a residence time of 5 min was observed in each case. Results are summarized in Table 10.
A sample of bilge water with a turbidity of ~160NTU was mixed with 18 ppm AI(III) followed by 2 m stirring, then 100 ppm EAA8000 polymer I 8 m stirring and 3o the mixture then filtered. Filtrate turbidity was 0.15 NTU. Similar results were obtained when Fe(III) was added prior to EAA.

TABLE 10: METALS EFFECT ON OIL REMOVAL
Aqueous phase Metal Feed Filtrate Removal 0.15 g Fe2(S0,~.3xH20 Fe(III) 173 ppm 36 ppm 79 in 925 g tot. oil oil wt.

0,99 g CuS0,.5H20 in 938 Cu(II) 149 ppm 20 ppm 87 g tot. wt. oil oil 0.27 g PbCl2 in 934 g Pb(II) 193 ppm 25 ppm 87 tot. wt. oi! oil 0.53 g Znf3rz in 934 g Zn(II) 171 ppm 4 ppm 98 tot. wt. oil oil 0.60 g CdCl2 in 915 g Cd(II) 197 ppm 27 ppm 86 tot. wt. oil oil 18 ppm AI plus bilge waterAI(III) 160 NTU 0.15 NTU 99.9 TREATMENT OF OIL SPILLS / FREE-PHASE OIL:
is Preamble to Example 24:
Preparation of solidified polymer products useful in remediation It has been discovered that polymer dispersions can be used to produce solids 2o useful as absorbents for the removal of free-phase oil from oil-water mixtures.
The porous solids had capacities of up to 5 or more times polymer weight in oil, depending on preparation conditions and therefore the porosity, absorbency , etc. of the resulting solids. Oil could be recovered from the solids by press-filtration.
In some embodiments of the present invention, it is obvious that the oil could be removed from the water surface by any convenient method and processed in a ship-mounted system. For example, on-ship bulk oil/water phase separation could be followed by de-oiling of the aqueous phase with MFD, to produce 3o separated oii, oil-polymer solids and purified water for discharge back into the water body. This could be a preferred option in situations where there are large amounts of oil to be recovered relative to the available polymer supply.
In a second embodiment useful for spill clean-up, dried porous polymer solids s may be applied directly to the spill surface. MFD-derived hydrophobic solids with oil capacities sometimes exceeding 5 times polymer weight and solid densities under 0.2 glml have been prepared. These solids are highly effective when applied to the oil surface. For recovery if finer polymer particles are present as a result of the treatment, addition of oil andlor fibrous binding agents io followed by an aqueous thermal annealing-quenching sequence can be used to produce more robust macroparticles. Such products are easier to collect from the surface of the treated water body.

is Free-phase oil removal:
This example provides a third embodiment (different from previously described embodiments) for spill treatments and which enhances polymer delivery capacity for a given vessel or other cleanup system. The embodiment involves the sequential production of precursor dispersion from polymer pellets and a Zo selected oil, followed by injection of the oil-dispersion mixture into hot carbonated or highly aerated water with mixing. This is followed by injection of the resulting slurry into cold water to "freeze" the polymer in highly porous form (chopping if necessary) and delivery of the resulting aqueous slurry through conduits onto the spill surface. Alternatively, the dispersionloil and hot water zs mixtures may be fed separately to nozzles and mixed immediately over the spill surface.
The following series of examples show selection of suitable formulation and activation conditions to produce highly porous, macroscopic hydrophobic 3o polymer solids useful for absorbing free-phase oils from, for example, an oil spill on a body of water.

(i) 16.76 g of EAA8000 polymer as a 13.3% dispersion and 5 g corn oil were combined with 50 ml water, emulsified and added with high shear mixing to 5 g CH3COOH and 25 ml 1 N HCI in water for a total volume of 500 ml.
s (ii) Immediately after mixing - (precipitation was complete), boiling water (~1 liter) and 6 g NaHC03 in 100 ml cold water were rapidly added with simultaneous mixing using a blender. Frothy solids floated to the surface which were immediately collected and immersed in cold (10°C) water.
(iii) The solid foam was added to 500 ml cold water, chopped and filtered:
io 97 g of wet solids were obtained.
(iv) The product from (iii) was tested for oil-absorbing characteristics as follows: 3.7g of a black oilltar mixture were poured onto the surface of 10°C water in a container with water surface area of 18x19.5 cm, resulting in a thin slick on the surface. A partridge feather (0.08 g) was is dipped quickly into the mixture and immediately (1 second) withdrawn:
the feather was black with oil and weighed 0.20 g. Subsequently, 10 g of wet solids (1.7 g dry wt calculated) were sprinkled onto the surface, with gentle mixing for about 5 seconds resulting in the solids absorbing apparently all of the oil with no visible residue. A second feather was Zo dipped under the surface of the mixture and swirled for a few seconds, then withdrawn. No discoloration of the feather was visible and a few small pieces of adhering polymer-oil solids were easily shaken off. The slightly water-wet feather weighed 0.17 g and was not discoloured by oil.
(v) A test similar to (iv) was run except that the oil type used was a is viscous mixture of Bunker"C" oil and diesel, which did not spread over the entire water surface. The oil appeared to absorb more slowly and the solids transferred black oil onto a feather dipped therein. Performance was improved by adding dispersed polymer (1 g of EAA6000), acidification and aeration-mixing. A second feather dipped under the 3o surface was only discoloured slightly. The in-situ - precipitated EAA floc solids tended to cling to the feather, and cause the surface to become water-wetted.
(vi) In another experiment, 50 ml of water were added to 0.7 g EAA
polymer as a 10% dispersion containing 0.7 g of 10% aqueous NaHC03.
3.5 ml of 5 N HCI were injected rapidly into the mixture and poured s immediately onto 1 g of oil floating on water. The precipitate absorbed the oil and had improved flotation characteristics relative to solid formed, without bicarbonate present.
(vii) In a series of experiments to determine the effects of thermal annealing on the porous polymer's oil vs water absorptive properties, io solids were isolated from 2:2:1 EAA6000 polymer:cellulose:corn oil mixture prepared in a manner similar to 24(i) and (ii), followed by air drying at 40°C. This was followed by either (a) 30 second immersion in 100C liquid water followed by quenching in 10°C water of pH 4 followed by drying at ~60°C or (b) brief (several seconds) exposure to 100°C
is steam followed by quenching in 10°C water of pH 4 and followed by air-drying at ~40°C. Solids (a) and (b) were found to exhibit variable properties as follows:
solid (a): d ~ 0.5 glml; well- annealed surfaces; easily water-wetted 2o Kerosene absorbed in 15 min: 1.2 glg; solid became crumbly Water absorbed in 14 min ~ 0.81 glg Water-wetted solids were immersed in kerosene immediately after removal from water and weighing; after a few seconds, kerosene was rapidly absorbed and air bubbled from the solid over a ~1 minute period;
is no water was released.
Kerosene secondary absorbtion data: total liquid weight gain ~ 210%;
kerosene absorbed in 1 min ~ 1.3 glg solid (b): d ~ 0.31 g/ml; highly macroporous surface; difficult to water-wet.
3o Kerosene: absorbed in < 5 seconds: 2.3 glg Water absorbed in 10 min: 1.1 g HZOIg** + kerosene = 2.3 g liquidlg "* This solid was then immersed in kerosene; after a few seconds, kerosene was rapidly absorbed and air bubbled vigorously from the solid surface; droplets of liquid water were also ejected.
EAA-corn oil solids prepared similarly to those described above but s without cellulose tended to disintegrate on handling when wetted with kerosene; EAA-cellulose solids prepared without corn oil tended to flake when wetted with water or kerosene.
(viii) Palletized MFD formulations io MFD dispersions may be formulated with compatible solids to form pastes, gels or pellets useful in water purification, as follows.
A variety of solid products were prepared which when added to acidic (pH< ~5) water were observed to sink to the bottom and then release C02 is bubbles and "activated" MFD solids at various rates (depending on formulation details). Such products have utility for example in the in-situ cleaning of contaminated sediments, ponds, tanks and the like.
Conventional compatible ingredients may be added for density control, pellet stability, rate of dissolution, etc.
2o Additionally, where the water body to be cleaned contains contaminants not efficiently removed by MFD polymers can be combined with suitable oils, co-reagents, complexing agents, etc. may be added to the formulation to supplement contaminant removal capacities of the MFD, if desired.
Where the contaminated water body is not sufficiently acidic to cause COZ release, acid may be added separately as a liquid or as a palletized solid. Alternatively, solid pellets which release acid when wetted with water may be admixed with the gel, paste or pellets, creating "self-3o starting" formulations.
Further, the pastes, gels or pellets may be adsorbed onto or admixed with inert solid carriers andlor coated or encapsulated by methods well-known in the art to provide desirable characteristics such as controlled particle size, stability, prevention of pellet agglomeration, easy admixing with other solids, controlled dissolution rate, optimal MFD release rate, C02 release rate, and the like. Thus, as one specific preparation example, a paste was prepared as follows:
24(a) 2 g corn oil was mixed with 24 g of MichemTM Prime 4983 HS,O. To this was added 25 g of Na HC03 powder with stirring. A putty-like paste was io obtained.
24(b) A 314-inch (2.6 g) spherical pellet was formed from an aliquot the paste from (a). The pellet was placed into a 130 ml glass cylinder containing a light red milky emulsion of ketchup (about 0.1 g), corn oil (0.2 g), vinegar (30 ml) and is water (to 120 ml).
24(c) The pellet over a 2-hour period released C02 and MFD solids and resulted in reddish solids floating over a substantially clarified solution.
Filtration yielded a clear, very pale red filtrate and red solids.
REVIEW OF FREE-PHASE OIL REMOVAL TESTS:
Using hydro-philiclphobic control of the activated floc solids, remediation ' efficiencies can be maximized for oil spill clean-up and other bulk oil removal applications including absorbtion and membrane phase processing. Generating 2s 'freshly hydrophobic' polymer macrosolids AT the instant of application to non-dispersed/floating oils increases the effective oil solidification rate and polymer oii solidification capacity. A spill clean up vessel may generate these solids either on-board for slurry application to the spill, or at the tips of mixing nozzles injecting directly into the spill surface.
It is clear that various methods of spill cleanup may be practiced according to the present invention. In-situ vs ex-situ polymer application and pre-treatment selected for the polymer dispersion, slurry or porous solid will depend on a variety of factors such as oil type, amount, location, availability of primary containment boomsl other separation equipment, etc.
It is also shown by Example 24(vii) that absorbent properties of the solids is readily manipulated by thermal treatment, and that the results of the treatment depend on variables including the nature of the heated fluid phase, solid composition and treatment time. It is noted that water-wetted solid (b) had i0 absorbed water displaced from the porous structure by liquid kerosene.

Metal removal from acidic mine water In ane test, 7.2 g EAA6000 polymer (20 mmol COO; added as a 10°~
dispersion, is Na salt) was mixed with 500 ml of acid mine drainage sample containing an unknown concentration of metals. The mixture was stirred 2 min and filtered (cellulose filter). The clear, colorless filtrate and the untreated drainage were analyzed for metals content. The results are summarized in Table 6.
2o TABLE 6: METAL REMOVALS
Metal Mefal IN: meq/ Metal out OUT: meql Removal (ppm) in 500 ml (ppm) 500 ml (ppm) AI(III) 112 6.2 0.4 ~0 >99 25 , Cu(II) 531 8.4 53.2 0.8 90 Zn(II) 511 7.8 293 4.5 43 Fe(III) 206 5.5 0.1 ~0 >99 , Pb(II) ' 81 ' ~0 0.25 ~0 93 Ca(II) 176 4.4 170 4.3 3 30 Total r~~eq'sM-in: M-out: delta[M] = [EAA] = d(M]:EAA=1.1 32.3 9.6 2Z.7 20 (a) Unit of measurement is ppb.

Titration of EAA with mixed metals:
A sample of acidified metal sulfide ore tailings filtrate ("concentrateu) containing various metals (25.19g) was diluted to 500 ml with water. Aliquots of EAA as a s 10% aqueous polymer dispersion were added at 20° C, stirred 5 min then filtered prior to addition of the next Stage (aliquot of EAA). Amounts of 10°r6 EAA
added were as follows: Stage A, 12 ml (3.2 meq); Stages B to F, 3 ml (0.83 meq); Stage G, 11 ml (3.1 meq); Stage H, 7.6 ml (2.1 meq). Selected polymer-metal precipitates were analysed for metals content. The results are io summarised in Table 7. Sequential precipitate colours (y-brown to blue to colorless) and analyses were indicative of selective metals removal, consistent with analyses.
TABLE 7:
is ANALYSES OF EAA-MIXED METAL SOLIDS FROM MULTISTAGE
TITRATION*
Metal Feed'"* Stage A Stage B Stage F Stage H

' AI 102.1 1650 5480 9390 54 Zo Sb 0.153 2.8 17.5 1.2 < 0.3 As 1.013 25 13 7 3 Ba 0.0012 <0.3 <0.3 <0.3 7 Be 0.009 < 0.3 0.6 2.1 < 0.3 Bi 0.001 12 1.1 <0.3 <0.3 Zs B 0.088 11 < 0.3 < 0.3 < 0.3 Cd 0.206 3.1 3.2 7.1 3.4 Ca 29.32 1120 1420 2180 14600 Cr 0.0036 6 5 10 < 3 Co 0.463 4.1 4.3 6.9 85.9 3o Cu 98.74 992 1570 3760 205 Fe 113.4 19000 9290 200 < 60 Metal Feed""' Stage A Stage B Stage F Stage H

Pb 0.138 8.6 4.4 9.5 0.9 Mg 53.9 190 230 330 430 Mn 30.53 296 293 631 6650 Mo 0 0.8 0.9 0.4 < 0.3 s N i 0.25 < 3 4 4 43 Se 0.002 4 9 39 23 12 Ag <0.0001 < 0.3 < 0.3 < 0.3 < 0.3 Sr 0.023 5 5 8 43 Te 0 1.3 0.6 < 0.3 < 0.3 io TI <0.0001 1.2 0.5 < 0.3 0.4 Sn 0.001 1.2 1.1 0.5 0.5 U 0.026 1.4 7.9 2.1 < 0.3 V 0.007 < 0.3 < 0.3 < 0.3 < 0.3 Zn 13 1320 1350 2550 11400 is * All values are in ppm. ** Calculated from concentrate analysis divided by dilution factor 19.85 Stoichiometry of copper-EAA flocs:
Zo EAA6000 as an 8.7% dispersion was added in 0.087 g aliquots to a 420 ppm copper solution with stirring. Precipitation became very sluggish as the equivalent ratio for 2(EAA) to 1 (Cu(il)) was approached. Thus, the precipitate stoichiometry in this case was 2 polymer -COONHd groups to one Cu(II), giving the precipitate a calculated 8 wt% copper content.
2s Enhancement of solubiiityldispersion of copper-organic floc:
A suspension of finely divided blue floc-precipitate was prepared by adding 10 ml of 1,000 ppm Cu(II) solution to 30 ml of unbleached paper towel- water 30 leachate. To a first 20 ml of this suspension were added 10 ml of 10% Dow 5990-Na dispersion; a second 20 mls was mixed with a further 10 ml water.
The dispersion -floc mixture was substantially solids-free and the solution a much bluer colour as compared to the water-only sample, which was a s colourless liquid containing a light blue solid floc.

Reaction of dispersed latex with copper and iron solutions:
To 600 ml of 1,000 ppm "Eimer's Squeeze 'N Caulk" TM siliconized acrylic latex io in water was added 0.195 g of Cu(II) in 12 g water for a resulting concentration of 320 ppm Cu. Stirring 2 min. and settling ~30 min. gave a light blue sinking floc and clear colourless supernatant. The pH was ~8.5. Residual copper was <
1 ppm, for > 99.7% removal of copper. Latex removal was apparently quantitative; no residual turbidity was observed. The blue solids released is copper at pH -5.5 (as evidenced by formation of a blue solution and colorless solids).
Similar results were obtained with Fe(III)- and Fe(III)ICu(II)- latex mixtures.The metal-latex solids also absorbed kerosene from a waterlkerosene mixture.

Metal oxide-hydroxide floc treatment:
'Voluminous iron (11,111) flocs were produced by adding sufficient NaOH to acidic Fe(II,III) solutions to induce precipitation(Floc 1 was at pH 9, Floc 2 at pH

5.5).
2s EAA followed by acetic acid were added to aliquots of the samples such that the resulting concentrations in the "treated" samples were 87 ppm EAA6000 and 100 ppm acetic acid. Treated Floc 1 filtered at about twice the rate of untreated Floc 1; untreated Floc 2 was filterable while treated Floc 2 clogged the cellulose filter. Treatment of Floc 2 with 8.7 ppm EAA and no acetic acid 3o resulted in a product which filtered at about three times the rate of untreated Floc 2.

The iron flocs referred to above and mixed metal flocs prepared from mine tailings leachate (Fe, AI, Cu, Zn as principal metal components) were treated with EAA at higher temperatures (> 40°C), resulting in rapidly (<1 min) floating, compact metal-polymer solids. It was also observed that the voluminous Floc 1 s and 2 polymer-metal solids formed at 15°C described above rapidly collapsed into similarly compact, easily separated solids on heating to >40 ° C.
Other metal-EAA flocs formed at various temperatures were observed to sink as opposed to floating.
io The mixed metal flocs were added to 100°C dilute NaOH solution; re-dispersion occurred. Brown particulates were observed in the dispersions. Addition of this mixture to a second aliquot of acidic metal leachate resulted in formation of a more intensely brown polymer-metal precipitate and a blue solution, indicative of iron uptake at the expense of copper; i.e. selectivity for iron over copper. This is re-dispersionl re- precipitation cycle was repeated five times and resulted in increasingly brown precipitate, while the filtrates were blue, indicating the presence of non-precipitated copper.

Zo Comparison of present invention and prior art EAA-copper removal:
31(i) Prior art method: In a procedure similar to that described in U.S. Pat.
4,747,954, 1,000 ml of DI water containing 3.6 ppm Cu(II) was stirred at 25°C for 'S minutes with 0.042 g of EAA6000 (approx. a 7% excess). The filtered solution contained substantial unremoved copper. Similar results were observed when a Zs cellulose-EAA6000 polymer dispersion was used.
31 (ii) Comparative example: In a comparison of copper removal capacity, 0.13g Cu(II) in 1000 ml of DI water was mixed with 4 meq NaOH then 0.022 g of EAA6000 polymer, giving blue solids and colourless filtrate. In a comparative 3o test of the method according to Vaughn, addition of 0.022 g a EAA6000 polymer to 0.138 Cu/1000 ml produced only a trace of blue solid and the filtrate was blue, indicating the presence of substantial unremoved copper.
31 (iii) The following is an example of copper removal by emulsified solvent extraction followed by EAA polymer de-oiling, 1100 ml of 3.6 ppm Cu(II) in DI
s water was emulsified with 0.48 g of 1:1 wlw tri-n-octyl amine in kerosene.
0.4 g of EAA6000 was added as a 10% dispersion; a voluminous pale blue floc formed; addition of 1.44 g of 1 N HCI resulted in a less voluminous floc.
31 (iv) In a typical example of copper removal by acid-promoted polymer phase io inversion, 4 ppm Cu(II) in 1,000 ml DI water and 0.08 g of EAA6000 (77%
excess) were stirred 1 min at 25° C, then adjusted to pH ~4 using 1 ml 1 N HCI.
Pale blue floc and a filtrate substantially free of copper were obtained.
31 (v) This example illustrates copper removal by metal ion-promoted phase is inversion: 1 ppm Cu(II) in 10,000 ml of water containing 21 ppm Ca was stirred at 22°C with 20 ppm of EAA6000 for 10 min. A green (copper-containing) floc was obtainead. A similar preparation without addition of Cu(II) yielded colourless solids.
Zo 31 (vi) Use of iron-caustic-EAA for the selective removal of copper from dilute solution followed by dilute acid leaching for the selective recovery of copper. To 2,000 ml of 20 ppm Cu(II) and 21 ppm Ca were added Fe(III) (~20ppm), then . NaOH (2.5 meq), then EAA8000(25ppm). 2 min stirring followed by 20 min settling resulted in circa 55 ml of green floc under substantially clear, colorless Zs aqueous phase. The settled floc was isolated and HCI (0.5 meq) added, resulting in substantial solubiliZation of the copper from the floc.
Filtration yielded ~ 53 ml of pale blue filtrate and 1.45 g of press-dried filter cake containing iron.
3o RESULTS OF METALS REMOVAL
Flocs from EAA plus NaOH- treated tailings leachate rapidly collapsed into compact, easily separated solids on warming. The solids after re-dispersion using hot aqueous NaOH were found useful in removal of dissolved iron.
The results of Examples 25 and 26, summarized in Tables 6 and 7, may be compared with the results reported in U.S. 4,747,954 (Vaughn; 1988): a generally similar observation of the present work was that even excess of polymer carboxyl: (total multivalent metal ion) equivalents did not result in complete metal removals. Other generally similar results were observed with respect to removal of multiple multivalent metals. However, in contrast to the io results reported in '954, some products were not easily separated by filtration:
flocs formed from excess polymer rapidly fouled even coarse cellulose filters.
The influence of temperature and other variables on floc properties is outlined below, and in other examples.
is It will be noted from the examples and disclosure herein that some dilute metal solutions do not form visible flocs with EAA under certain conditions. This behaviour is reflected by the observation that relatively concentrated (>1,000 ppm) (multivalent metal)-(EAA) dispersions of varying stability can be prepared under some conditions and (polymer): (metal) ratios. U.S. (*") reveals that the Zo presence of cellulostic materials aids retention of low level metaIlEAA
dispersion. In some circumstances, however, it may be impractical or inconvenient to add cellulose to the process mixture.
In the case of copper, Example 31 (i) shows that 3.6 ppm copper is not removed 2s by 40 ppm EAA polymer dispersions when processed by the method of Vaughn.
In contrast to this observation, 31 (iii to v) show that addition of appropriate amounts of co-additive andlor co-reagent including oil-chelant mixture, acid, andlor suitable non-target metal ion resulted in substantial removal of such copper levels.
A preferred option for removal of copper With reduced polymer consumption relative to the method of Vaughn and of Examples 31 (iii to v) is summarized in Example 31 (ii), where precipitation of metal hydroxide is followed by EAA
polymer addition. This is an example of a pre-treatment designed to minimize polymer consumption by contaminant precipitation followed by precipitate flocculation at much lower polymer dose than required for the ion exchange (IX) method of Vaughn. For example, the 0.022 g a EAA polymer dose successful in flocculating the copper hydroxide solids in Example 31 (ii) is only 1/66th the dose needed for "complete" copper complexation by IX.
io Processes of the present invention for substantial low-ppm copper removal include Example 31 (iii) emulsified solvent extraction followed by removal of oil phase via EAA polymer treatment, Example 31 (iv) addition of excess EAA
followed by acidification and Examples 31 (v) and 31 (vi) addition of suitable metal ion co-reagent. Example 31 (vi) further illustrates selective recovery of is copper from the floc via dilute acid leaching of the floc; it is obvious that the acid-leached residue containing iron and EAA could be re-dispersed and recycled similar to the method of Example 30 thus accomplishing a selective extraction and recovery of a metal accompanied by polymer recycle. The results exemplify advantages between the methods and results of the present ao invention as compared to those of Vaughn.
Example 29 shows reaction of dispersed commercial latex of unknown . formulation with copper and iron solutions. 99% metals (copper, iron) removal was achieved. Copper-latex solids readily released copper on exposure to is dilute (<1 %) acetic acid, in contrast to freshly prepared EAA-metal solids, which required very strong (>1 N) hydrochloric acid as leachant. Metal-latex solids also absorbed kerosene from a kerosene-water mixture.
Therefore, it is possible to substantially remove low levels of multivalent metals 3o by a variety of heretofor unrecognized combination of techniques as applied to metal-polymer disperson mixtures.

The results of Example 30 show that EAA dispersion can also be useful in the flocculative processing of metal oxidelhydroxide particulates.
The selectivity characteristics shown in Examples 25 and 26 are also noted to s be of utility in for example metal production processes where it is desired to separate soluble metals into component metal streams. It will be obvious that the methods of the present invention shown in these examples can optionally include other known conventional procedures (such as known in the metal processing industries), and as otherwise outlined in this disclosure.
io Treatment of tar sands process water:
Samples of process water from tar sands refining were used; the samples (pH
~8.5) contained finely divided suspended solids with no visible oil present.
is EAA8000 polymer was added as a 1 % dispersion at 1, 2.5, 5 and 10 ppm and gently stirred for 5 minutes. The 1 ppm dosage gave poor flocculation, 2.5 ppm caused flocculation but settling time was >10 m; 5 and 10 ppm each gave excellent flocs which settled within 10 m yielding clear supernatant solutions.
Zo EXAMPLE 33 Suspended solids flocculation with removal of soluble colour:
33(a) A slurry of 0.83 g ground, partially carbonized coffee beans and 1.50 g 'tobacco ash was prepared in 2,000 ml water.
is 33(b) To 1,000 ml of slurry from (a) were added 4 ml 1 N NaOH, 10 ml of 0.5%
Fe(lll) solution and 5 ml of 1 % EAA6000 polymer. The mixture was swirled for minutes and allowed to settle for 2 minutes; a few small floc particles remained suspended. The supernatant was yellow.
30 33(c) 900 ml of supernatant from (b) were passed through a coffee filter giving crystal clear, slightly yellow filtrate. To this were added 2 ml of 0.5%
Fe(III) and ml of 1 °~ EAA6000 polymer. The pH was adjusted to ~6 by addition of 1 N HCI
and the sample shaken vigorously for 30 seconds then filtered through a coffee filter, yielding a slightly less yellow filtrate.
s 33(d) 600 ml of filtrate from (c) were mixed with 0.5 ml of 0.5% Fe(III) and 12 ml of 1 % EAA6000 polymer. The pH was adjusted to about 5, then the mixture shaken vigorously for 30 seconds, then filtered. A crystal clear, very slightly yellow filtrate was obtained.
io EXAMPLE 34 Flocculation of carbon powder:
34(a) A mixture of activated carbon pellets and powder (20 g) with water (700 ml) were pureed in a blender for 2 min, resulting in an opaque black slurry.
EAA
(2 g) as a 10% aqueous dispersion was added and mixed, then 1 ml of an is aqueous solution of HCI (10N) was added. The resulting mixture rapidly (30 sec) formed an agglomerated carbon-polymer precipitate (density > 1 glcc). A
cellulose coffee filter ("c.filter") was used for filtration. The filtrate obtained was a crystal clear and colourless solution.
20 34(b) A mixture of powdered charcoal (0.10 g) in 100 ml 10°C tap water containing 20 ppm Ca was titrated with 0.001 g aliquots of EAA6000 polymer added as 1 % dispersion . After each polymer addition, rapid magnetic stirringlaeration for 20 sec was followed by 160 sec stirring at low speed.
Under these conditions, C:EAA ratios of 100:1 and 50:1 did not flocculate; 33:1 gave is small floc particles but did not settle well; 25:1 yielded a good floc with a few fine black floc particles; 20:1 yielded a well-formed floc which settled in seconds with no trace of black particles in supernatant. However, the supernatant was hazy with excess of polymer; 0.5 ml of 2000 ppm AI solution was added and the mixture stirred for 10 seconds, resulting in removal of the haziness.
34(c) 400 ml of brewed coffee was cooled and stirred at 20°C with 10 g ground ~ 02439436 2003-09-03 activated carbon for 10 min., then 0.3 g EAA8000 polymer in 300 ml water was added to a total aqueous volume of 750 ml. Acidification and filtration gave a yellow filtrate "Y" and a separated black solid. A similar experiment without EAA
gave a brown filtrate. The yellow solution "Y" was stirred with 1.25 g activated s carbon powder for 10 minutes. The resulting black slurry contained particles fine enough to pass through a c. filter; settling for 15 minutes did not substantially clarify the solution. A c. filter was wetted with 1 % EAA6000 polymer and immersed in 0.01 N HCI, then rinsed. This treated filter gave significantly lighter-colored filtrate (less fine carbon particles passed through).
io The bulk of the mixture was adjusted to pH~8 and 0.0025 g of EAA6000 polymer as 1 % dispersion was added; the fine particles flocculated. Most of the floc settled within 5 minutes leaving a few fine, neutral-buoyancy grey particles.
Addition of a further 0.0075 g EAA gave somewhat larger particles and faster-~s settling floc, but neutral-buoyancy particles remained. A clear, colorless solution was obtained when filtered through an untreated c. filter.

35(A) Latex Removal:
Zo In one series of tests, 2 g of 50wt°~ acrylic latex (Rhoplex Fastrack 2706; Rohm and Haas) in 1,000 ml of distilled water samples were treated with varying amounts of EAA8000 polymer added as a ~10% dispersion for the 13:1 and 50:1 latex: polymer ratios and as a 1 % dispersion for the higher latex:polmyer ratios.

After EAA addition, the mixture was stirred at medium in a magnetic stirrer without aeration for 2 minutes. 1 N HCI was then added dropwise over ~30 seconds until a pH of 4 was attained. Mixing speed was then adjusted to slow, and mixing continued for a further 5 minutes. 250 ml of mixture were then gravity 3o filtered through a coarse coffee filter and the volume of filtrate collected in 2 minutes recorded. Turbidity of the filtrate decreased with amount filtered through the paper; for example, in the case of the 100:1 Iatex:EAA filtrate, the first ml had a turbidity of 7.8 NTU while the fraction 95-120 ml had a turbidity of 0.34 NTU. The remainder of the mixtures were gravity settled for 15 minutes:
supernatant clarity decreased markedly at higher latex: polymer ratios. Table s summarizes the filtration data.
35(B): Flocculation and De-watering of Cellulose:
In a typical test, No-Name (TM) toilet paper (0.42 g) and 1 ml of 1 N NaOH
were added to 1700 ml water containing 21 ppm Ca at ~25C and subjected to high-io shear stirring. To the resulting slurry was added 0.04 ml of EAA6000 polymer as 16% dispersion. Stirring for --2 minutes and settling for ~7 minutes resulted in less than 100 ml of (sinking) floc. The supernatant was decanted and the floc screened off and pressed : wet weight = 0.84 g, dry wt.= 0.40 g; thus the pressed floc contained 48% solids. Calculated weight (0.42 g paper + 0.04 g is EAA) = 0.46 g, thus an 87 % recovered yield of dried cellulose-polymer solids was realized.
35(C) i and ii Flocculation and De-watering of Yeast:
(i) "Direct" EAA-solids flocculation: In a typical test, 1.0 g of Fleischmann's (TM) zo yeast was added to 1 meq NaOH in 1,000 ml of water and stirred until a cloudy dispersion was obtained. Addition of 0.08 g EAA6000 polymer as a 16 dispersion followed by 2 m stirring, 3 m settling, decantation, filtration and ' press-drying yielded 2.57 g filter cake analyzing at ~31 % solids.ln a similar test, time:floc volume was : 5m: 40 mi, 15m: 20 ml, 30m: 20m1.
as (ii) Inorganic coagulant/hydroxide co-flocculation: In a typical test, 4 ml of 0.6N
AI(III) was added to 1.00 g yeast dispersed in 900m1 DI water. Stirring yielded fine particulates. Addition of 3 meq NaOH, 1 m stirring , addition of 0.005g EAA6000 polymer, slow stirring for 15m then 30m settling produced 3o substantially clarified supernatant over about 20 ml floc layer.

.. ......, CA 02439436 2003-09-03 Table 8 (B) summarizes trials run without AI(III) addition.
TABLE 8A: EAA-LATEX RATIO VS FILTRATION RATE
35(A); Latex:EAA Filtrate/2 min (ml) Turbidity , NTU
s 8000 13. 3 : 1 92 --50:1 40 --100:1 32 0-25 ml = 7.8 ; 95-120 ml =
0.34 200:1 29 --io 500:1 28 (hazy) -TABLE 8 (B): EAA -CELLULOSE AND EAA - YEAST FLOC DATA
X:Plm/ ml 1 N NaOH Filter cake % solidsRecovery, Cel: EAA= 10 : 1 48 87 is Yeast:EAA / NaOH

5:1 /1 34 91 10:1/1 28 80 20:1/2 45 72 Zo Other results using a Bayer polymer identified as a "dispersion" and marketed by Bayer under the designation "CBD" (polychlorobutadiene) also provided extremely high de-watering effects, yielding 2.4 times more solids content than other commercially available polymers such as Dow 1410 (17% versus 7°r6), when using procedures such as those described above in Example 35.
REVIEW OF SOLIDS TREATMENT
Example 29 demonstrates results of the reaction of dispersed latex with copper and iron solutions. The metal-latex solids also absorbed kerosene from a waterlkerosene mixture; capacity was not determined. Other Examples of metal and oil removal show flocculation of polymer residues, latexes, metal oxide/hydroxide solids and drilling mud. In Examples 33 other tests were run on solids removal via flocculation : flocculation of tar sands tailing fines is described in Example 32, charred organiclash treatment is described in Example 33, carbon in Example 34 and acrylic latex, cellulose and yeast in Example 35.
Press-dewatered filter cakes from 35(B and C) containing 25 to 50°~ dry wt were readily obtained thus the de-watering qualities of the flocs formed via the ~o procedures were judged to be satisfactory.
Thus, it has been demonstrated that aqueous dispersions containing low molecular weight and/or water-insoluble polymers in colloidal form can function as flocculating agents for a number of solid types under certain conditions.
is Extractions of coloured compounds from water:
36(a): Removal of colour from river water: 200 ml of river water samples were prepared containing 0, 5, 10, 20 and 50 ppm EAA. Acidification to pH<3 (10 N
Zo HCI), 5 min stirring then filtration through micro porous hollow fibre membrane of 0.1 micron nominal pore size yielded substantially colourless water for all samples except 0 ppm, the filtration of which did not remove substantial colour from the sample.
Zs 36(b) Coffee partial decofourization: Coffee grinds (15 ml) were mixed with boiling water (400 ml) and filtered. 200 ml of this brown extract was cooled to about 25°C by adding ice to a final volume of 250 ml. Addition of a first aliquot of 0.5g EAA as 10°~ dispersion followed by acidification using 0.5 ml 5 N
HCI
resulted in a brown precipitate and yellow filtrate. Addition of a further 1 g EAA
3o as 1 % dispersion to the yellow filtrate resulted in a colourless precipitate and yellow filtrate, i.e, no apparent further extraction of the compounds) responsible for the yellow coloration. This residue was found removable via activated carbon-EAA treatment.
36(c) Tea partial decolourization: 250 ml of water of initial temperature of s 100°C was poured over 1 bag (about 4 g) of tea. Steeping for 5 minutes followed by removal of tea bag resulted in 200 ml of brown tea extract. The solution was cooled to about 15°C using 100 g of ice, then 175 ml of this solution was treated with 1 g of EAA as 10wt% dispersion, then 1 ml 5N HCI, resulting in light brown precipitate and yellow filtrate.
io A second 1 g EAA as 1 % dispersion was added to 125 ml of this yellow filtrate:
light brown precipitate formed only after further acidification using 20 ml of 5°~
acetic acid; the filtrate remained light yellow. A third extraction similar to the second resulted in colourless precipitate and yellow solution, i.e. no further is apparent extraction.
36(d) Separation of dye components: 0.1 g each of commercial blue and yellow brand liquid food colours were added to 125 ml of water, resulting in a green solution. 1.0 g of NaH-90 as 16% dispersion was added, then 1.7 g of 10 ao N HCI. A blue solid immediately formed and was filtered off. The soluble portion was yellow, thus the yellow and blue dyes were separated by the treatment.
36(e) Reaction of Fr4A and pH-indicating dyes: A number of qualitative tests were performed on acidification of EAA6000-polymer and EAA 8000 -polymer is (pH indicating dye) mixtures in water. Dyes included bromocresol purple, chlorophenol red, metacresol purple, dimethyl yellow, bromophenol blue and methyl violet. Acidification of the mixtures resulted in formation of coloured polymer solids. The degree of colour removal from the aqueous phase depended on factors such as polymer:dye ratio, final pH, temperature and so 3o forth. The removal of colour was substantially complete in some tests on about ppm dyel 1,000 ppm polymer and pH <4. The polymer solids underwent colour changes upon exposure to different pH's, all released dye when mixed with water at pH > 8; release rate was variable depending on polymer porosity, surface area, pH and so forth. At acidic pH's and appropriate dye components, the solids were found to act as solid pH-indicating products.
36(f) Reaction of PE and pH-indicating dyes: Tests were run similar to 36(e) except that the dispersed polymer was "polyethylene" from Adcote (TM) 50C30.
The resulting solids were much less intensely coloured that those from 36(e) at equal pH values.
io 36(g) Reaction of polystyrene-divinyl benzene) and pH-indicating dyes:
Methanol-hydrophilicized Amberlite TM XAD-2 non-ionic macroporous co-polymer beads absorbed a variety of PH indicating dyes from aqueous solutions. These solids retained the dyes even after repeated rinsing.
is In addition to the above, other commercial polymers such as that marketed by Bayer and known as "SBD", a styrene butadiene latex, was particularly effected in removing phenolic dyes.
20 36(h) Colour removal from commercial effluent: To 500 ml of blue-coloured dyeing plant effluent were added 5.5 meq Fe(III) followed after 1 min stirring by 0.25 g (500 ppm) of Na-EAA6000 as 1 % dispersion followed after 2 min stirring ' by a further 1.1 meq Fe(III). Stirring was continued for 5 min, resulting in a blue solid and substantially colourless filtrate.
36(i) In addition to the tests described above, commercial APD"s including Pyratex(styrene-butadiene-vinyl pyridine polymer), Bapren(chlorobutadiene polymer), Alberdingck 595 Styrene-Acrylic dispersion, Bastal SX8678 (carboxylated styrene-butadiene polymer) and other formulations were found to 3o remove Fe(III)-activated dyes at various efficiencies, depending on APD:dye:Fe(III) ratios, pH and so forth.

REVIEW OF DISSOLVED ORGANICS REMOVAL
The results of the above examples demonstrate that EAA and other APD's may be used to facilitate reduction in coloured contaminant concentrations. In s combination with colloidal carbon (Example 33) superior decolorization results were achieved as compared to either carbon or EAA alone. In Example 36, bromocresol purple, chlorophenol red, metacresol purple, dimethyl yellow, bromophenol blue, methyl violet, and coloured compounds from coffee and tea were removed at various efficiencies depending on process variables discussed io herein. It is noted that functional groups including (substituted aromatic hydrocarbon), (phenol), (cresol), (halogen), (sulfur-oxygen), (carboxylic acid) etc. are contained in these compounds. Additionally, blue and yellow food dyes were separated via selective precipitation.
is EXAMPLE 37 Treatment of a micellar dispersion (soap removal from water) 37(A) Soap: A mixture of household soap (1.14 g) dispersed in 650 ml of water plus 1.39 g EAA8000 was stirred at RT. Addition of 11 ml 1 N HCI, 5 minutes stirring, filtration and drying yielded 2.51 g of solids. Wt calculated = 2.53 g;
2o removal ~ 98%.
37(B) Phenol-EO: 440 g of water containing circa 0.2% TritonX-45 (TM) and ~5 ppm of phenol red gave a hazy orange-red aqueous mixture. The mixture was stirred for 5 m with 0.55 g of powdered carbon, 0.5 g EAA6000 and 1 mez 2s Fe(lll). The filtrate was colorless thus a water-soluble phenolic dye was also removed by the procedure. COD's (ppm) were determined: Feed = 1120;
Coarse filtrate = 46, Fine (0.45 um) filtrate = 17, for ~ 96°r6 and 98%
reduction in COD, for C and F filtrates respectively.
3o EXAMPLE 38 Egg yolk (5 ml) was mixed with 200 ml water, resulting in a cloudy yellowish liquid. 5 g of EAA6000 as a 10% dispersion were added, followed by mixing and acidification (10 ml of 5% acetic acid). The filtrate was clear and colourless.
The presence of residual organic compounds) was inferred by the slight foaming tendency of the filtrate on shaking. The near-white precipitate turned yellow when air-dried.

Clarificationlextraction of food residues from water:
(acidification to pH about 4.5 was done using 5% acetic acid (household vinegar)) io (i) 12 g. carrot peel soluble extract diluted to 100 ml. with water + 0.5 g EAA
-------> 0.54 g orange solids (air-dried) + clear colourless water (ii) 15 ml tomato juice diluted to 100 ml with water + 1.0 g EAA
-----> red precipitate + clear water is (iii) 5 ml vanilla extract diluted to 100 ml with water + 1.0 g EAA
------> brown ppt + yellowish water (iv) 20 ml chicken-rice-noodle soup diluted to 100 ml with water + 3.0 g EAA -----> yellow ppt + clear colourless water (v) 1.0 g powdered cocoa was mixed with 100 ml water (~ 100°C). Cooling to Zo 20°C gave a brown solution which quickly clogged the pores of a coffee filter on attempted filtration. A similar sample was treated with 0.5 g EAA: the resulting brown precipitate did not clog the filter; clear very slightly yellow-brown filtrate was obtained.
Zs EXAMPLE 40 Clarification of blood-water mixture:
1.5 ml blood in 50 ml water was clarified using 0.2 g EAA Dow 5990 acidified with 5 ml 5% acetic acid followed by filtration; the filtrate was clear and colourless.
Example 38 shows partial adsorption and selective separation of proteins from water. Example 39 shows removal of food residues from water, while Example 40 shows removal of blood. Thus, complex aqueous mixtures may be successfully treated by the methods of the present invention. It has also been shown in various examples using emulsified oils, bitumen, particulate carbon, etc., that liquid emulsions and colloidal mixtures may be rendered useful in s purifying water by addition of a polymer dispersion and that selection of additive(s), sequential processes and conditions can minimize polymer consumption.
EFFECT OF SELECTED VARIABLES
io The preceding Examples show that the results of dispersed polymer processes are dependent on a variety of factors. The following Examples illustrate the effect of certain variables into polymer treatments in the processes of the invention.

is Floc filtration vs dispersion and process variables:
Table 9 summarizes the results of filtration tests performed generally as follows:
To 1500 ml of 10°C water containing 21 ppm Ca was added the selected dose of polymer and optional oil or aeration with mixing at a selected shear generated by a magnetic stirring bar or an electric mixer (referred to as "h. shear" in Table 20 9) TABLE 9: FLOC FILTERABILITY VARIABLES
All tests: Calcium = 21 ppm MI to MI to MI to MI to fouling fouling fouling fouling P TYPE; P Conc. 100ppm 300ppm 380ppm 530 ppm Mix time P:Ca,wlw(eq:eq) 4.8(0.3) 14(0.8) 24(1.3) Zs 5 min.; I. shear; T = 10 C
Na90 & NaH90; N.A. 275 350 --Cellulose-EAA6000 'sol'; N.A. 450 400'" --AIO/EAA6000 slurry; N.A. 600 290'~* --NaPE; N.A. 500; -- --30 (ibid) + Oil @ 1:1 O:P ratio 600 1 min.,T=10C

All tests: Calcium = 21 ppm MI to MI to MI to MI to fouling fouling fouling fouling NaH90-80 h. shear, N.A.;
70**; <50**;
--(Ibid) + C @ 0.5:1 B:P ratio 160 50-100**

Non-aerated EAA6000, h. shear ~ 50 90 1: Aerated @ 1:1 EAA: K, h. shear >300 300;

s 2: (1) to pH<4, !. shear, N.A. 1,000 PE, h. shear, N.A. 70 1: PE, h. shear, N.A., 1:1 EAA:K 110;

2: (1 ) to pH< 4, I. shear, N.A. 400;

3: (2) aerated, h. shear 10 sec >1500 to * 20um #2 size cellulose conical coffee filter; Oil type added (B) = bilge oil; (K) _ kerosene; N.A. = Not Aerated ** = dispersion residue observed in filtrate (cloudy when acidified) Filterability vs. mixing time:
21 ppm Ca plus 100 ppm NaH90 were stirred (medium speed magnetic stirrer setting) without aeration for the desired interval at 20°C and filtered, yielding the 2o following data:
Mix time (min : sec) 0:05 0:15 0:30 0:45 1:00 2:00 5:00 10:00 15:00 30:00 Filtrate volume (ml) 45 52 68 89 115 240 490 960 1,310 >2,000 Comparison of different polymer flocs:
temperaturelvolume effects so 43(i): 1.5 g (4.17 meq) of EAA8000 was acidified using 2 ml of 5N HCI
(10meq), resulting in white voluminous precipitate. The mixture was allowed to stand at 15°C: the apparent volume of polymer solids floating within the water decreased over time.
3s 43(ii): Procedure 38(i) was repeated using EAA6000 polymer.

43(iii): 43(i) was repeated using (0.75g EAA6000 polymer plus 0.75 g PE) dispersed in 150 ml water.
43(iv): 43(i) was repeated except 3 ml corn oil was also added to the mixture.
s 43(v): 43(ii) was repeated except 3 ml corn oil was also added to the mixture.
43(vi): 43(iii) was repeated except 3 ml corn oil was also added to the mixture.
io 43(vii): 43(i) was repeated using 1.9 g EAA8000 polymer as ~1 % (190 ml) and the stoichiometric equivalent to polymer carboxyl groups (0.1 g Fe(III), in 10m1 water. The floc completely filled the 200 ml volume and did not decrease in volume over 10 minutes. The floc volume decreased to 100 ml on heating to ~45°C. On heating to ~85°C, the floc became more compact (volume not is measureable due to convection) but fibrillous structure was still visible unlike that for H-EAA or Ca-EAA flocs at 85°C. On further heating to >90°C, the floc particles further contracted but did not melt. Floc volumes are recorded in Table 10. The particles were very fine so a further 1.5 g EAA6000 polymer and ~0.3 g Fe(Ill) were added to the hot mixture. After 3 minutes low shear mixing, the 2o mixture was filtered: 1,250 ml of filtrate was collected thus the particulates were non-fouling. The filtered solids were of a sludge-like consistency and analysis showed 85% water. The sludge was subsequently dewatered using EAA as described in Example 46.
Zs 43(viii) Cu-EAA6000 polymer was prepared similarly to 43(vii) and its volume vs temperature properties were measured.
43(ix) AI-EAA6000 polymer was prepared similarly to 43(vii) and its volume vs temperature properties measured Results are summarized in Table 10.

_70_ TABLE 10: VOLUME VS TIME COMPARISON FOR
DIFFERENT POLYMER COMPOSITIONS
Relative floc volumes (ml/g) vs time, polymer type and additives Time(m); T~15C 43(i)43(ii)43(iii)43(iv)43(v)43(vi)43(vii)43(viii) 43(ix) - - - - - - 100* 88* 88* *stable 10 30 33 67 60 2.7 5 3.3 - 25*" - ** ~ite~

cake 60 27 50 47 2.7 3.3 2.7 - - -240 10 17 14 2.7 3.3 2.7 - - -Temperature IS 50C 2.7 4 3.3 2.7 3.3 2.7 50 17 65 100C __ __ __ __ __ __ ~ g g __ Zo Ca-EAA floc interactions:
A voluminous floc was prepared by extended shaking/aeration (about 10 min.) of 0.36 g EAA8000 polymer (added as a 13 % dispersion) in 1 liter of water containing about 21 ppm of Ca. Floc volumes ware monitored after ~15 min.
' settling as temperature and NaOH concentration were varied. A similar trial was as run with PE dispersion. Results are summarized in Table 11.
TABLE 11: FLOC VOLUMES VS PH, T AND DISPERSION TYPE
3o Temperature(deg ml 1 N NaOH floc volume (ml) C) Ca-EAA8000 Ca-"PE"

0 200 ~45 33 0 400 ~45 40 0 300 ~45 35 45 0 200 ~45 50 0 100 ~45 50 1 150 floc disintegration Preparation of cellulose-EAA and Rubber-EAA Dispersions (1) (a) A dispersed cellulose-EAA derivative was prepared from 94.3 g of 15.9°~
EAA6000 + 2 ml 1 N NaOH + 1 g bleached cellulose, stirred 5 min at 100°C, s then filtered. The dispersion assayed at 15.5% solids.
(I) (b) A second preparation using 8.8 g unbleached cellulose, 540.5 g of 15.9%
EAA6000(86.0 g polymer), 40.4 g of 1 N NaOH and about 50 ml of water, heating to 85°C for 30 min, filtering through a polyester fibre scrubbing pad and io rinsing the pulp with water yielded 752.4 g of light brown hazy filtrate containing a small amount of visible solid and undispersed cellulose pulp.
(II) A dispersed "GOOP"(TM) chlorinated rubber - EAA formulation was prepared as follows: 31.36 g of "GOOP"(TM) was added to 30 g of methylene is chloride and stirred until homogeneous. The mixture was then added to 250 ml water plus 200 g of 15.9% Na90. The mixture was stirred using an electric hand-held blender while 50 ml of concentrated HCI was added over a 30 second period. Filtration and air-drying for 24 hr at 25°C gave 40.6 g of solids. This solid was mixed with 3.4 g NaOH and water to a total of 400 g, then heated to 20 ~85°C with stirring. Not all solids dispersed; 18.3 ml of 1 N NaOH
were added and heating/stirring continued for a further few minutes. There were still solids present in the dispersion; separation by filtration yielded 7.9 g of non-dispersed solids and 310 g of dispersion assaying at 8.2 % acid-precipitated solids.
2s The above products were then used in the methods of the present invention for contaminant removal.

EAA as dewatering agent:
3o An iron-EAA-water paste from Example 43(vii) was partly de-watered using EAA
as follows: 14.73 g sludge of ~85% water content was slurried with water to 50 ml, 0.2 g of EAA6000 polymer as 16% dispersion were added and the mixture stirred for 30 sec. then acidified to pH<4 and stirred for 1 m. To the 50 ml of mixture were added 250 ml of boiling water resulting in compact flocculated solids. Filtration yielded a solid which could be press-dewatered. This wet solid (10.6 g) was air-dried at ~60°C to 3.15 g, thus the solids content of the starting s sludge of 15% had been increased to 30%, a 100% increase.

Effect of solids production temperature:
Typically, the polymer dispersion and desired additives) were mixed in water io and the phase inversion ("P.I.") step induced. Some of these P.I. solids were stored up to 18 months at 25°C before being further processed. Results and observations are discussed following.
47(a): Preparation of polymer powders: Generally, in the absence of oils or is other impurities, powders or porous granules resulted from acidification of relatively dilute (~ 0.1 wt.%) dispersed polymer concentrations at <35°C. THV
350C produced powders at all temperatures investigated (15 to 95°C).
47(b): Preparation of sponge-like agglomerates: Generally, dispersed EAA, PE
2o and EAAIPE mixtures precipitated at > about 40°C formed pliable porous agglomerates on air-drying at about 25°C. Powders from 47(a) were also easily agglomerated by heating to ~60°C. These agglomerates when dried had densities from <0.2 to >0.5 g/cc and absorbed up to 6 times their weight in liquid phase oil.
EAA solids tended to crumble when wetted with oil; it was found that addition of emulsified linseed oil to the liquid mixture prior to solids formation, drying and curing (linseed polymer formation) yielded porous rubbery products with better handling properties.
47(c): Preparation of polymer films: (i) Addition of relatively concentrated (>5N) aqueous acid to concentrated (> 5 wt.%) polymer dispersion at 20°C

resulted in formation of hydrophobic polymer "skins" at the acid-dispersion interface. Obvious variations in addition methods would enable preparation of membranes and films of controllable thickness, porosity and other parameters.
s EXAMPLE 48 Polymer purification and recycle tests:
48(i) Polymer purification In a first step (1 ), 360g of a 10% aqueous polymer dispersion were diluted to 3,600 ml (about 10,000 ppm polymer) with process water. This was followed by ~o addition of excess (200 ml) muriatic acid with continuous mixing. A clear aqueous filtrate containing 13.4 ppm total organic carbon (TOC) [99.87 polymer removal) and a wet polymer precipitate were obtained.
In a second step (2), the wet polymer was rinsed with water and re-dispersed in is process water. No undispersed polymer was observed. The procedure in step 1 was repeated. This time the filtrate contained 5.6 ppm TOC [99.94 % polymer removal]. No baseline value for TOC contribution from the process water was established, thus calculated polymer removals are minimum values.
2o Thus, the procedure gave a product more suited to applications where very low TOC values are required.
The precipitate was rinsed and air-dried: 36.5 g of polymer were obtained, thus quantitative polymer recovery was realized.
2s 48(ii): Polymer recycle (A) 20.95 g of Teresso 32 TM lubricating oil was emulsified in 2000 ml HZO.
g of EAA as a 10 wt% solution and 10N HCI (10 ml) were added. Press-dewatered precipitate weight was 38.8 g.
(B) 30.35 g of the precipitate from (A) was then thoroughly mixed with 50 ml of hexane. Press-filtration of this mixture gave 18.21 g of hexane-wet solid.

(C) The solid from (B) was added to 100 ml dilute(about 3%) NaOH solution at 95°C, resulting in vaporization of the residual hexane from the solids, and re-dispersion of the EAA.
s (D) The dispersion from (C) was added to 10 g Teresso 32 emulsified in 2400 ml H°O. Acidification (10 g of 10 N HCI) and filtration gave a clear aqueous filtrate.
(E) Steps (B) to (D) were repeated on the solids from (D), again resulting in a clear aqueous filtrate and solids (17.8 g).
io (F) The solids from (E) were allowed to stand at 20°C for 14 days, then roll-pressed between sheets of absorbent paper giving 9.8 g of solid while liquid oil was released into the paper. The solids were re-dispersed as in (C), then added to 2000 ml H20 containing 5.0 g kerosene. The resulting solids were is then roll-pressed between sheets of absorbent paper, giving 10.1 g of solid.
Liquid water and kerosene were released into the paper.
(G) The 10.1 g of solids were dispersed and used to remove a further 5.0 g of kerosene as in (F). Roll-pressing of the wet precipitate gave 10.6 g of solids.
(H) Step (G) was repeated twice more, for a total of 7 dispersion-precipitation cycles. The final yield of roll-pressed solids was 10.6 g.

2s 49(a) Simultaneous production of purified oil and dispersible polymer derivatives:
(i) A 50/25/25 wt% (Bunker "C" / diesel / kerosene) mixture (10 g) was emulsified in water (800 g). 1.25 g EAA6000 polymer as a 16% Na dispersion was added with stirring.
(ii) A solution of aq. Fe(III) 0.1 g in 50 ml water was than added followed by ~ 2 second stir resulting in a rapidly floating floc layer (substantially separated in under 5 seconds) (iii) The floc was screened off and pressed: Water was released from the black waxy solids under minimal pressing force. As the force was increased, mixed s oil water then oil only were released.
(iv) The weight of pressed, air-dried (at 60°C) solids was 3.34 g. The calculated weight of 1.35 g for Fe-EAA indicates that ~2 g of particulates and tars were removed from the oil mixture.
io (v) The solid from (iv) was wetted with 3.8 ml 1 N NaOH, then 100 ml of 100°C
water were added. Magnetic stirring for ~2 minutes resulted in substantial dispersion of the solids into the aqueous phase.
is (vi) The product from (v) was added to 12.2 g (BC/D/K-20/20/60) emulsified in 300 ml water (vii) Procedures (ii) to (iii) were repeated. The screen-recovered floc weighed 22.5 g and readily released liquid oil on handling.
(viii) 2 g of pressed dried solids from (vii) were tested as per Procedures (v) to (vi); only about 50 % of the solids dispersed and the dispersed product showed poor oil flocculation.
2s 49(b) Oil production via dispersion-catalyzed phase coalescence (i) 25.08 g of the oil mixture used in 49 (A) was emulsified into 1 liter of water containing 21 ppm Ca. The temperature of the aqueous phase was about 10°C.
Settling the mixture for 5 minutes resulted in a few coalesced oil droplets floating over an opaque black water layer.
(ii) 0.448 g of EAA6000 polymer (18% excess relative to the Ca content of the starting water phase) was added as 16°~ dispersion, Na salt, and the mixture stirred on a magnetic stirrer for 1 minute. Cessation of stirring gave a well-coalesced oil phase containing polymer solids over a cloudy light brown aqueous phase containing floc particles.
s (iii) 500 ml of water containing 21 ppm Ca was added to the aqueous phase and the mixture stirred for 1 minute, resulting in substantial clarification of the aqueous layer and a floating oil layer containing solids.
io 49(c) Precipitation agent: In a test similar to 49(A), steps (i-iii) except that HCI
instead of Fe(III) was used to induce solid formation, the recovered polymer solids were not found to reproduce the results from 49(a)(v-viii), i.e. the solids did not re-disperse well nor did the re-dispersed product function well in emulsified oil-water phase coalescence.
is DISCUSSION OF EXAMPLE 49:
Example 49 A and B demonstrate methods of flocculative processing of concentrated (thousands of ppm) oil-in-water mixtures. The results may also provide further insight into the mechanisms underlying MFD liquid phase Zo coalescence and processing.
Example 49 A also demonstrates the removal of heavy components from an oil to give a refined oil plus a dispersible solid polymer derivative in 260%
yield relative to EAA added. The derivative formed a dispersion useful in flocculative Zs oil removal from water. We note that the acid-solidified product from 49(C) did not re-disperse well; this may be due to chemical reaction of polymer COON
groups with heavy oil components andlor formation of non-porous polymer-contaminant structures andlor other factors.

_ 77 Example 49 B demonstrates that the dispersed polymer is capable of catalytic oil-water phase coalescence in the absence of acid or other demulsifiers. The only multivalent metal ions present in appreciable quantity were Ca(II) at 21 ppm , 0.005M concentration. Ca ions would be expected to substantially react s with impurities in the oil during pre-emulsification so the effective concentration was significantly less than 0.005M.
According to the electrical double layer (EDL) theory of emulsion stability, divalent ions of concentration 0.01 or greater are required for substantial io emulsion destabilization, thus metal ions were present in insufficient concentration to catalyze the observed coalescence. The polymer carboxyl group plus counter-ion concentration of 0.001 M relative to water is also far too low to induce emulsion destabilization according to EDL theory (greater than ~0.1 M is required).
~s Combination of the methods described in 49A and 49B with each other and/or with any other suitable technology would be obvious to one skilled in the art to produce the desired balance of overall separation rate, raw material consumption, water effluent quality, degree of oil purification, amount of 2o dispersible solids produced and demand therefor among other technical and market considerations.
Known techniques including but not limited to any one or more of the following are anticipated to be useful in enhancing the results of the above flocculative is MFD oil water processes in certain circumstances: gravity settling, absorption, adsorption, precipitation, electrostatic precipitation, heating, cooling, chemical addition, filtration, hydrocyclone treatment, centrifuging, gravity flotation, gas flotation, hollow fibre phase separation (US Pat 6,146,535), coalescence, exposure to ultrasonic energy, exposure to microwaves, microfiltration, 3o nanofiltration, distillation, freezing, solvent extraction . In addition, rocesses reported herein may be beneficially combined with procedures 49 A and/or B

include membrane-induced coalescence, preferential phase membrane permeation and any other convenient flocculative treatment similar to those described in the Examples herein.
s Clearly, the processes of 49A and B could be carried out on various oil types and concentrations of aqueous phase. It would thus be clearly within the purview of the present invention to apply processes) similar to 49 A andlor 49 B, alone or in suitable combination with other techniques noted previously, to separate/refine various oils and other hydrocarbons including crude oil, waste io oil, heavy oils, bitumen, oil shales, coal, oily mixtures containing suspended solids and so forth.

Soil extraction process enhancement:
is General Procedure: A sandy soil containing 5 wt.% mixed oils (heavy crude:
train yard waste: used lubricating oil = 1:1:1 (wt.)) was used as "soil" feed.
Aliquots of this soil were then extracted by stirring (magnetic stirring bar;

minutes) in a 250 ml Erlenmeyer flask using the aqueous phase formulations indicated in the Table. The treated soil was then separated from the liquid 2o extract phase(s), dried and extracted with excess methylene chloride to determine hydrocarbon residues in the soil. For extracts to which EAA
. dispersion was added (Numbers 5,6 and 9-12), acidification of the hydrocarbon-rich liquid leachate/extract resulted in formation of an EAA- hydrocarbon precipitate, and clarified water, except where the amount and type of surfactant is present interfered with precipitate formation, e.g. Surfactant A at about ppm and Surfactant B at all doses tested.
Results are summarized in Table 13.

TABLE 13: SOIL EXTRACTIONS
Run # soil, g Surf*., gasoline, EAA, g % extraction g g 1 (i) 13.7 0 0 0 50 1 (ii) 16.5 0** 26 1 (iii) 17.8 0 (20 min.) 2(i) 16.0 0 0.5 0 57;

2(ii) 15.9 1.0 0 94;

2(iii) 17.2 0.1 0** 22 3A 13.4 1.53 A; 0 0 33;

l0 3B 16.3 1.0 B 55 4A(~ 14.0 1.5 A; 0.1; 0 59 4A(ii) 16.4 3.85 A ; 0.03 ; 33 4A(iii) 13.6 1.6 A; 1.0; 106 4B 16.1 0.9 B 0.1 63 5(i) 16.7 0 0 1.0 66;

5(ii) 16.5 1.0** 50 6 16.5 3.0 A 0 1.0'""" 38 7 17 4.9 A 0 0"* 24 8 16 1.0 B 0.1 0** 30 9 16.6 1.0 B 0 1 26 10(I) 16.1 1.5 A 0.1 1.0** 88;

10(ii) 16.4 2.7 A 0.1 0.88 68 11 (i) 16.5 2.0 A 0.1 0.35**

11 (ii) 11 (i)solid4.6 A 0.1 0.46** 108 12 16.6 6.5 A 0.1 1.0** 92 150 mt aqueous phase extracted at about 15°C except (12); run at 44-50°C.
* A = phenoxy-polyoxyalkanol, 2.75% in water; B = Sunlight TM liquid dish detergent ** = 0.1 g NaOH added De-gassing catalyst: 5 ml of 8.7% EAA6000 Na salt were added to 100 ml of carbonated sugar- water-lemon-lime soda mixture. Solids formed within 30 seconds, accompanied by rapid gas bubble evolution.
s Enhancement of aqueous leaching of organic compounds from solids ml of Amberlite XAD-2 non-ionic adsorbent polymer beads onto which metacresol purple and bromocresol purple had been adsorbed were added to to each of (a) 250 ml of water + 0.1 g NaOH, and (b) 8.7 wt% EAA6000, Na salt in water.
Sample (a) water remained colourless while sample (b) liquid phase became purple, i.e. the cresols had been leached off the polymer bead surfaces.

De-inking agent: A plastic 3-ml eyedropper stained with 2-year old dried ink was used. The dropper was repeatedly washed with hot (60°C) soapy water followed by multiple rinsing: traces of colour remained on the plastic surface.
Immersion Zo in 8.7% EAA6000 for 5 minutes at 25°C gave complete transfer of colour from the plastic surface into the aqueous phase.

Preparation of stable Na-PE-EAA aqueous dispersions is A mixture of Adcote(TM, Morton) 50C30 "PE" dispersion (containing alcohols, water and 30 wt % polymer) and EAA6000 with PE:EAA wt ratio of 1:1 and total polymer concentration of about 1 % was acidified (pH<4) and the solids filtered off , rinsed and air-dried at 25°C. The dried solids (10 g) were mixed with 100 ml of water containing 0.75 g NaOFt and heated to 100°C with stirring for 30 - gl -min. Cooling to 25°C resulted in a translucent dispersion. Similarly, dispersions containing up to 15 wt% of the Na salt of PE solids could be prepared without added EAA.
s EXAMPLE 55 Dispersions containing copper (II) toil Dispersions containing copper(II) were prepared by adding copper sulfate solution (from 5 % to 50 % of the equivalent weight required for a 1:1 Cu:EAA
equivalent ratio) to heated (100°C) stirred EAA6000 dispersion (10 %) io containing corn oil (0.5 g oil/ g polymer). The resulting blue dispersions were cooled to 20°C and any solids formed were removed. One dispersion was stored over a two-month period: a small amount of blue polymer solid separated but the dispersed phase was still blue, indicating that stable dispersions containing multivalent metal rations can be prepared.
is Oil-enhanced production of polymer dispersion (a) A mixture of dispersed EAA (1.5g) and PE (1.5g) in H20 (27g) was prepared and partially acidified using dilute acetic acid (-3ml). This resulted in formation Zo of fluffy white solids within the milky liquid.
(b) After 2 hr at 15°C ., corn oil (2ml) was added to the mixture from (a).
Shaking resulted in apparently complete re-dispersion of the solids:
filtration (coffee filter) resulted in no observed solids retained by the filter.
(c) The mixture from (b) was then allowed to stand 1 hour at about 50°C: a few Zs corn oil droplets, about 0.1 ml, separated as a top layer. The remainder of the milky dispersion appeared stable and free of solids.

Aqueous extraction of oil:
(a) Corn oil was mixed with Salon Pro "Ultra Care" nail polish remover (10:1v/v) resulting in an intensely sweet smelling milky liquid. Components listed in NUltra s Care": ° ethyl acetate, alcohol, water, glycerine, isopropyl alcohol, gelatin, fragrance, castor oil, propyl acetate, benzophenone-1, Denatonium benzoate, Red 17".
(b) The milky emulsion from (a) (water-in-oil type, as opposed to the oil-in-water io types of previous Examples) was solidified by adding water, EAA6000 polymer and acetic acid.
(c) The intensely sweet-smelling solid from (b) was washed with about 20: 1 v/v excess of soapy water at 50°C (vigorous shaking was used to mix); an is unmeasured amount of oil was released. The solids were separated and water-rinsed/drained three times. The entire procedure was completed in 30 minutes and resulted in an odorless solid.
(d) A portion of the waxy solid from (c) was placed in 100°C water.
Clear 20 odorless oil was released as the solid melted.
(e) An odorless water-oil mixture was obtained from a second portion of the solids by press-filtration at 20°C. The pressed solids were powdery, had a waxy feel and agglomerated and floated readily after vigorous stirring with water is (flotation was complete in 5-10 seconds settling time).

Removal of ink from water using EAA or fluoroplastic:
0.2 ml of Carter's black stamp pad ink was added to 200 ml. water. 1 g EAA6000 polymer was added as 10% solution followed by 2 ml 5N HCI. A
clear, colorless filtrate was obtained.
A similar experiment using 3 g fluoroplastic as 50% dispersion also resulted in s complete colour removal.
While there have been shown and described what are considered to be the preferred embodiments of the invention, it will be understood by persons skilled in the art to which this invention relates that various modifications and changes io in form or detail can readily be made without departing from the spirit of the invention. It is therefore intended that the invention not be limited to the exact form and detail herein shown and described nor to anything less than the whole of the invention herein disclosed as hereafter claimed.
is EXAMPLE 89 In-situ Leak Repair In one test, 74g of soil was poured into a 3.5 cm ID X 41 cm L tube. The resulting bed had a thickness of approximately 10 cm and a water permeation rate of 400 ml/min at 31 cm water head pressure. The water level was drained Zo to soil surface, then about 0.2 g CBD as an approximate 1 °r6 dispersion and approximately 1 meq Fe(lll) were added simultaneously with mixing and allowed to permeate into the soil bed.
Flow decreased immediately to about 20m1/13 hr. After six days, the drainage is rate was measured at <10 ml/d (a 99.998% decrease in water flux rate).
Thus, the application of CBD - Fe was an effective method of reducing water permeability of soil.

APD Types: EAA Co-Flocculation tests The following data in Table 14 illustrates that EAA-APD mixtures according to the present invention may be co-flocculated resulting in substantial removal of s both APD types.
TABLE 14: APD1IAPD2 FORMULATION SCREENING: POLYMER TYPES
Aqueous mixture: 500ppm APD1,V=500 ml/ Ca=21ppm; +20ppm AI; +EAA6000;
+ acid (opt) io APD 1 ml HCI APD2 *NTU: **NTU Other observations in out %

1 PCBD'""' 0 116EAA733 0.41 >99.9 2 ML156 0 233EAA375 2.71, 99.3 5min=10.2 NTU

15 APD 1 ml HCI APD2 *NTU: *"NTU Other observations in out %

3 ML110 0 " 150 1.02 99.3 + 100ppm MFD90 = 12.13 NTU

4 SBA 0 " 468 0.31 99.9 10 AI = 23 NTU

ME27720 0 " 1174 0.24 >99.9 10 AI = 411 NTU

6 BSVP 0 " 193.5 0.50 99.7 10 AI = ~21 NTU

20 7 BSAA 0 " 209 1.36 99.3 10 AI = 18.75 NTU

8 EAA 1410 0 " 755 1.6 99.8 9 AF 315 0 " 1057 6.3;3.799.4;
99.6 Flbond 325 " 842 0.2 >99.9 13.2 NTU pre- HCI

11 AF 4500 1 " 347 6.24 98.2 14 NTU pre-HCI

25 12 AF 4530 2 " 423 0.83 99.8 13 430Em 2 " 576 0.50 99.9 . 14 MP4983R " S/F 0.47 (>99) S/F; 19NTU pre- HCI

ME68725 2 " NIA 2.04; (>98) 17.45 NTU pre- HCI

16 Mic05940 2 " 128.1 1.16 99.1 30 17 Fastr 2774 " 678 0.67 99.9 18 90/AP820 0 " S/F 0.17 (>99.9) 19 EAA-Rubber " SlF 0.50 (>99.5) urethane 2 " 91.7 0.39 99.6 21 Soap (6.4~) " S/F 0.15 ---35 *Denotes nephelometric turbidity units '~'Denotes reduction ometric nits in nephel turbidity u SF denotes self flocculating APD Polymer compositions Trade Name Polymer Type PCBD polychlorylbutidiene polymer PrimacorTM series EAA MW 6000-8000, pH~9; 25-90 nm; NS;
(SSS' EAA6000 derivatives) Various BAYPREN-LATEX T 58%: Chlorobutadiene, NS
BAYSTAL S X 8678 50%: Styrene - Butadiene; NS
ACRALEN BS 40%: Butadiene-Styrene-acrylamide-acrylonitrile-methacrylic acid ; NS
LIPATON AE 4620 50%: Styrene- n-butyl acrylate; NS
PYRATEX 241: Styrene-butadiene-Vinyl pyridine; NS
Trade Name Polymer Type ABK: - AS 6800VP50%: Styrene-modified Acrylic-Methacrylic acid ester; Anionic ABK: - H 595 30%: Styrene-modified Acrylic-methacrylic acid-MA ester;

Anionic 30 nm ABK: - AC548 50%: Acrylic-MethacrylicAcid ester; Anionic 60nm ML110, 25%: #1 Carnauba wax, PE, anionic; 60 nm, pH ~9 2o ML180, 25%: #1 camauba wax, paraffin; 180 nm; anionic;

MG15, 40%: PTFE, 12,000 nm; anionic surfactant;
pH8.5 ME05940,40%: Paraffin; 90nm; nonionic ME27720,20%: Polyamide; 500nm; nonionic ME68725, 25%: PE type AC(TM)629, nonionic, 45nm; pH~10 ME39235, 35%: AC(TM)392 high density oxidized polyethylene;
35nm, nonionic ML156, 25%: #3 Camauba wax; 130 nm; nonionic; pH~S

AP: 4500 Poly Ethylene-Vinyl Chloride 4530 Poly Ethylene-Vinyl Chloride 315 Poly Vinyl acetate 325 Poly Vinyl acetate 430 Poly Ethylene-VinylAcetate-VinyIChloride INCOREZ W830I140 Polyurethane; Polycarbonate backbone;
7.3% co-solvent INCOREZ W830/177 Polyurethane; Polyester backbone INCOREZ W830/256 Polyurethane; Polycarbonate backbone;
8.4% co-solvent INCOREZ W830/397 Polyurethane; Polyether backbone (NS = no surfactant; "anionic" = anionic surfactant; "nonionic" = nonionic surtactant) (ML = Michem Lube; ME = Michem Emulsion; MP = Michem Prime; MG = Michem Glide;
ABK = ALBERDINGK; AP = Air Products) TABLE 15: APD11APD2 OIL REMOVAL TESTS
*** Test 22-31 base sofn = 100ppm Crude Oil Emulsion + 20 ppm AI + 500ppm APD1 + 233 ppm APD2 Test PD1 HCI PD2 Turb1*Turb2NTU Observations (EAA type) reduction,%

22 AF4530 0 6000 >500 7.01 >98.6 23 W830/256 0 6000 23.8 5.10 79 24 W830/256 0 8000 23.8 12.0649 25 W830/140 2 6000 15.4 0.47 97 26 W830/177 2 6000 31.1 0.13 99.6 Test PD1 HCI PD2 Turb1Turb2NTU Observations *

(EAA type) reduction,%

27 W830/397 2 6000 91.4 0.48 99.5 28 AirFlex 325 2 8000 911 0.55 >99.9 13.07 NTU before HCI

29ME68725 2 8000 14.010.40 97 33.0 NTU before HCI

30 ME68725 2 MP4983 14.010.68 95 49.8 NTU before HCI

31 ME68725 2 EAA-Rubber14.010.67 95 55.3 NTU before HCI

* measured for APD1+
oil aqueous mixture For polymer identification, see above.
2s It will be seen from the above Table 15, based on the results obtained, that a wide variety of APD mixtures according to the present invention may be used to remove emulsified crude oil from water.
APD Types: Suspended Solids Flocculation Tests 3o CARBON-APD
TABLE 16: APD-CARBON FLOCCULATION
Mixture composition: 500 ml pre-settled carbon suspension / approximately 200ppm APD / 0.8 meq Fe 35 APD monomer composition Visual observations Filtrate*Settled'"' % removal vs control NTU NTU;+/-1 Filtrate Settled APD monomer composition Visual observationsFiltrate*Settled** % removal vs control none (control) black suspension14.6 20 --F~1A6000 fine fragile 0.53 11 9645 floc Chlorobutadiene fine fragile 0.75 15 9525 floc Styrene-butadiene-vinyl pyridine large robust 0.34 6 9870 floc ' 20 min settle, filter measure turbidity 30m; decant 2 X 100 ml, of second 100 top ml aliquot;
** settle 100 ml In the above compositions used for Tables 14, 15 and 16, dispersions were prepared according to the teachings of earlier examples except as otherwise noted.
TABLE 17: CARBON-APD FLOC SETTLING VS APD DOSE
Mixture composition: 1,000 ppm carbon suspension I indicated APD dose I
approximately 20 ppm Ca; Feed turbidity approximately152 NTU
2o APD monomers) : APD dose; ppm settled; % turbidity removal none 0 0 S-BD-vinyl pyridine(SBDVP) 5 92 ' Chlorobutadiene (CBD) 5 90 F~4A MP4983R 10 99 TABLE 18: FLOC DEWATERING
Contaminant: Polymer RatioPressed Filter cake;Recovery, ~
% solids Cellulose:EAA= 10 : 1 48 87 Yeast***"(lr7:F~4A = 5:1 34 91 Y: F~1A = 10:1 28 80 Y: EAA = 20:1 45 72 Y:SBDVP:EAA = 60:5:1;+0.4Fe/1.2Cu48 --Cu:SBDVP = 0.6:1 * 36 --0.3 Fe(III) : 11.6 CBD* 71 95 1 Fe(III) : 39 FAA 25 --1 Fe (III) : 39 (1:1 FJ~A:CBD)26 - -1 Fe (III) : 39 CBD* 71 95 _ 88 -Contaminant: Polymer RatioPressed Filter cake;Recovery, 96 ~ solids carbon:EAA = 10:1 40 --carbon:SBDVP = 10:1 45 --carbon:PCBD = 10:1 42 --* no metal observed in filtrate '""""(Y) denotes yeast used as a model contaminant in these examples SBDVP denotes a styrenebutidienevinyl pyridine copolymer The above Table 18 clearly illustrates that procedures of the present invention can be used to dewater flocs, in some cases up to 95%, using various APD's to and flocculation /filtration conditions. Variations in yields will be seen to depend on the polymer type as well as contaminant type and their relative concentrations. Thus, it is demonstrated that selection of the appropriate APD
type and control of floccluationlfiltration conditions may be useful in maximizing the de-watering characteristics of specific contaminant-APD solids.
IS

Preparation of New APD Derivatives:
It has been found that treatment of suitable APD mixtures with metals and/or heat andlor microwaves may be used to produce new compositions of polymers, Zo where APD1 and APD 2 are linked via colloid-colloid surface bonding and/or are substantially permeated each throughout the other, in either case forming a third colloid composition APD3.
Aqueous dispersions of CBD and EAA6000 in 1:2 ratio were prepared. Two Zs aliquots were treated via addition of 50% of total EAA equivalents in (acid : iron) (2:1 eq. ratio) then a portion heated to 1 OOC via microwaves or thermally. A
third untreated aliquot was used as control. The dispersions produced were subjected to phase inversion; both treated samples gave much better clarity than the untreated aliquot when tested for phase inversion efficiency. There was 3o no apparent difference between the treated samples.

Preparation of Carbon-APD solids:
(A) In a first test, a ~10% aqueous slurry of 20 g carbon and 6.67g dispersed EAA6000 was briefly (seconds) heated to 100C using microwave energy, cooled and filtered. The filtrate was acidified to pH<3; no polymer floc was observed, s indicating substantially complete combination of the carbon and EAA.
(B) In a second test similar to (A) except that ~5 meq Fe(III) and polychlorobutadiene dispersion (2.23g) were added , a very cloudy aqueous phase and compact carbon-APD floc of settled volume ~75 ml was obtained.
io (C) In a third test similar to (B) except that the mixture was not heated, a less cloudy supernatant and greater floc volume (125 ml) were obtained.

Claims (60)

1. In a method of removing a contaminant from an aqueous mixture containing the contaminant, the improvement comprising the steps of:
(a) forming an aqueous composition comprising:
(1) a dispersible substantially water insoluble polymer capable of undergoing phase inversion or coalescence; and (2) a contaminant;
(b) effecting phase inversion or coalescence of said polymer in said aqueous composition to thereby form at least one contaminant precipitated phase and a treated aqueous phase.

2. A method as defined in claim 1, further comprising the steps of:
providing an aqueous mixture containing said contaminant;
providing said polymer in an aqueous polymer dispersion;
mixing said aqueous mixture and said aqueous polymer dispersion to form said composition; and adding a precipitation agent to initiate phase inversion.

3. In a method of enhancing dewatering of a hydrous floc, the improvement comprising:
(a) forming an aqueous composition of:
(1 ) a dispersible substantially water insoluble polymer capable of undergoing phase inversion or coalescence, and (2) a hydrous floc (b) effecting phase inversion of said polymer in said aqueous composition to thereby form a second floc with improved dewatering properties.

4. A method for treating an aqueous composition containing dispersed oil to flocculate the oil therein and provide an oil enriched phase relative to the oil in said aqueous composition, comprising the steps of:

providing an aqueous composition containing oil;
providing a polymer dispersion which is a dispersible substantially water insoluble polymer and is capable of undergoing phase inversion;
forming an admixture of said aqueous polymer dispersion and said aqueous composition containing oil; and effecting phase inversion of said polymer in said admixture to form a flocculated precipitate forming said oil enriched phase.

5. A method of separating a fluid mixture comprising the steps of:
providing a fluid mixture;
providing an aqueous polymer dispersion, said polymer being a dispersible substantially water insoluble polymer and said polymer being capable of undergoing a phase inversion; and mixing said dispersion with said fluid mixture to effect said phase inversion and form a solid polymer phase and at least one fluid phase.

6. A method as defined in claim 2, wherein said precipitation agent is added to said aqueous polymer dispersion to form an intermediate prior to addition of said intermediate to said aqueous mixture.

7. A method as defined in any one of claims 1 to 6, which includes the step of separating a precipitated phase by a process selected from magnetic separation, sedimentation, flotation, centrifugation, hydrocyclone treatment, screening, filtration, differential pressure press-filtration and membrane permeation processes.

8. A method as defined in claim 5, further comprising the step of selectively heating or electromagnetically treating said precipitated phase prior to or simultaneously with the separation step.

9. A method as defined in any one of claims 1 to 3, wherein said contaminant is at least one contaminant which is emulsified oil, free-phase oil or hydrocarbon, edible or essential oil, tar, bitumen, fat, dissolved metal, chelated metal, precipitated metal, dissolved organic substance, colloidal solid or liquid, surfactant, polymer, paint, carbon, clay, colour, protein, pharmaceutical agent, biocide, biological fluid fraction, fermentation fraction, blood, fertilizer, food residue, phenol or derivative thereof, polynuclear aromatic hydrocarbon, chlorinated hydrocarbon, sulfonated hydrocarbon, carboxylic acid, soap, natural product, radionuclide, latex, and ore particle.

10. A method as defined in any one of claims 1 to 9, wherein at least one process condition selected from pH, temperature, shear, mixing rate, residence time, addition rate, added soluble metal cation concentration, organic cation concentration, is controlled during said method.

11. A method as defined in any one of claims 4 to 10, further comprising the step of recovering said polymer from said solid precipitate, and if desired, recycling recovered polymer.

12. A method as defined in claim 1 or 2, further comprising the step of separating precipitated phase from treated aqueous phase.

13. A method as defined in claim 4, wherein said gas generating composition containing a water-activated solid or paste having an alkyl amine, carbonate or bicarbonate.

14. A method as defined in claim 4, further incorporating the step of including an acid in said aqueous composition.

15. A method of enhancing a flotation process in which a first phase is floated relative to a second phase, comprising the steps of adding an aqueous polymer dispersion to a composition comprising said first phase and said second phase in which one of the phases is to be floated, said polymer of the dispersion being a dispersible substantially water insoluble polymer and being capable of undergoing phase inversion, and effecting phase inversion of said polymer to enhance floatation of at least one of said phases.

16. A method of enhancing a sedimentation process comprising providing an aqueous composition containing a first fraction and a second fraction, one of said fractions being removable from said composition as a sediment by the step of adding an aqueous polymer dispersion to the composition mixture during said process, said polymer of the dispersion being a dispersible substantially water insoluble polymer and being capable of undergoing phase inversion, effecting phase inversion of said polymer whereby enhanced sedimentation of one fraction of said composition is obtained.

17. A method of treating bulk oil to provide a bulk oil product having improved properties comprising the steps of:
providing bulk oil containing one or more undesirable components;
providing an aqueous polymer dispersion of a polymer capable of undergoing phase inversion, said polymer being a dispersible substantially water and oil insoluble polymer;
forming an admixture of said bulk oil and said aqueous polymer dispersion;
effecting phase inversion of said polymer in said admixture whereby said polymer coalesces or flocculates at least one of said undesirable components to thereby obtain a treated bulk oil product having improved properties.

18. A method as defined in claim 1, including the step of intimately mixing said polymer dispersion with said aqueous mixture to form said composition.

19. A method of removing a contaminant from an aqueous contaminant spill comprising the steps of:
locating an aqueous spill at a site containing the contaminant;
providing a polymer capable of undergoing phase inversion, said polymer being a dispersible substantially water insoluble polymer;
forming an aqueous polymer dispersion with said aqueous spill;
enabling said polymer dispersion to undergo phase inversion to effect solidification and immobilization of said contaminant with said polymer to form a solid precipitate; and removing said solid precipitate from said spill.

20. A method as defined in claim 19, further comprising the step of adding a precipitation agent to initiate said phase inversion.

21. A method of in-situ leak reparation comprising the steps of:
providing an aqueous polymer dispersion, said polymer being capable of undergoing phase inversion and being a dispersible substantially water insoluble polymer;
injecting a subsurface source having an aqueous contaminant leak, and in which the contaminant is contained within the aqueous mixture with said aqueous polymer dispersion;
effecting polymer phase inversion to form a solid precipitate of contaminant with said polymer; and sealing said leak with said solid precipitate.

22. A method as defined in claim 21, further comprising the step of adding a precipitation agent to initiate phase inversion.

23. A method of removing a contaminant from soil comprising the steps of:
providing a soil containing oil or other contaminant teachable therefrom;
providing an aqueous polymer dispersion, said polymer being capable of undergoing phase inversion and being a dispersible substantially water insoluble polymer;
mixing together, under conditions which substantially inhibit polymer phase inversion, said aqueous polymer dispersion, said soil containing said contaminant, water and a surfactant to cause said contaminant to enter the aqueous phase; and separating treated soil from the resulting aqueous phase.

24. A method according to claim 19 further comprising initiating a phase inversion to solidify the contaminants with the polymer and separating water from the solidified contaminants.

25. A method as defined in claim 23, further comprising the step of adding a solvent.

26. A method of preparing an aqueous polymer dispersion with improved characteristics comprising the steps of:
providing a first aqueous polymer dispersion in which the polymer is substantially water insoluble;
adding a substance at a controlled pH and temperature sufficient to form a second aqueous polymer dispersion having improved properties over said first aqueous polymer dispersion.

27. A method according to claim 26 wherein the added substance is at least one substance selected from the group consisting of soluble polymer flocculating agent, aqueous polymer dispersion, acid, base, multivalent metal, cellulose, bitumen, rubber, oil, carbon, colloidal inorganic solid.

28. A stable aqueous dispersion composition containing multivalent metals of the formulation M1M2HP comprising:
a substantially ionized ethylene-carboxylic acid copolymer P including ethylene-acrylic acid polymer of average molecular weight from about 4,000 to about 15,000 and associated ration mixture M1M2H;
M1 being monovalent rations including ammonium and alkali metal, M2 being multivalent metal rations and H representing unionized carboxyl group; and where the ratio of equivalents of (M2 plus H) to equivalents of M1 is less than about 1:1.

29. A method for the solvent extraction of metals from an aqueous mixture comprising the steps of:
providing an aqueous mixture containing metals and an emulsified solvent-chelant;
providing an aqueous polymer dispersion, said polymer being substantially water insoluble and being capable of undergoing phase inversion;
mixing said dispersion with said aqueous mixture;
creating a polymer phase inversion; and separating a resulting polymer solid from the extracted solution.

30. A method for the selective extraction of metals from aqueous solution comprising the steps of:
providing an aqueous metal solution containing at least two different metals dissolved therein;
providing an aqueous polymer dispersion of a dispersible substantially water insoluble polymer, said polymer being capable of phase inversion;
mixing said dispersion with the said metal solution;
inducing polymer phase inversion under conditions to preferentially incorporate a said one of said metals into polymer solids resulting from phase inversion while the other metal remains substantially in dissolved form; and separating said polymer solids from the selectively extracted solution.

31. A method for enhancing a solvent extraction process comprising:
providing an aqueous solvent mixture;
providing an aqueous polymer dispersion, the polymer being capable of undergoing phase inversion and being substantially water insoluble; and mixing said aqueous solvent mixture and said polymer dispersion to effect a polymer phase inversion and form a polymer solvent extract solid and extracted water phase substantially free of solvent.

32. A method for the extraction of a soluble substance from water comprising the steps of:
providing an aqueous polymer dispersion, said polymer being substantially water insoluble and being capable of phase inversion;
providing an aqueous solution containing a substance to be extracted;
mixing said dispersion and solution such that polymer phase inversion occurs; and producing a solid phase containing said substance and extracted water phase.

33. A method of purifying a dispensable polymer comprising the steps of:
providing a dispensable polymer to be purified, said polymer being substantially water insoluble and being capable of undergoing phase inversion;
preparing a dilute aqueous dispersion of said polymer; inducing a phase inversion in said dispersion; and separating purified polymer.

34. A method according to claim 33, including the step of preparing an aqueous dispersion from said purified dispensable polymer.

35. A method for producing polymer-additive solids with improved dispersibility comprising the steps of:

providing an aqueous polymer dispersion-additive mixture, said polymer being substantially water insoluble and being capable of undergoing phase inversion;
inducing a phase inversion under conditions to form a polymer-additive solid intermediate;
separating said intermediate solid;
re-dispersing said intermediate solid as a further aqueous phase;
removing undispersed material from said further aqueous phase;
inducing phase inversion of said intermediate polymer in said further aqueous phase; and isolating from said further aqueous phase a refined solid comprising polymer and said additive wherein said refined solid exhibits improved dispersibility characteristics relative to said intermediate solid and said aqueous polymer dispersion-additive mixture.

36. A method for the manufacture of colourimetric pH-indicating solids comprising the steps of:
forming a composition comprising an aqueous composition of a mixture of at least one pH-indicating dye and a dispersible water insoluble polymer capable of undergoing phase inversion;
effecting phase inversion of said polymer in said aqueous solution;
and separating a polymer-dye solid from said solution.

37. A method of inducing a phase inversion in a mixture containing an aqueous polymer dispersion or flocculated slurry comprising:
providing an aqueous polymer dispersion or flocculated slurry derived therefrom, said polymer being substantially water insoluble and being capable of undergoing phase inversion; and adjusting at least one of the pH or ionic strength of said slurry to effect phase inversion of said polymer and form a polymer product having enhanced contaminant removal capability.

38. A method of particulate flocculation comprising:
providing an aqueous mixture containing particulates;
providing an aqueous polymer dispersion of a water insoluble polymer capable of undergoing phase inversion;
mixing said polymer dispersion with said aqueous mixture; and effecting phase inversion of said polymer in the resulting mixture to thereby permit particulate flocculation.

39. A method of forming a metastable or an activated aqueous polymer dispersion or slurry comprising:
providing an aqueous polymer dispersion, said polymer comprising a water insoluble polymer capable of undergoing phase inversion;
providing an aqueous mixture containing at least one additive chosen from acids and multivalent metals;
mixing said aqueous mixture and said dispersion; and permitting said polymer to undergo phase inversion to thereby form said metastable or activated polymer dispersion.

40. Use of an aqueous polymer dispersion, the dispersion comprising a polymer which is substantially water-insoluble and which is capable of undergoing phase inversion, for removal of a contaminant from an aqueous mixture containing the contaminant.

41. A method of forming a substantially water impermeable barrier in or on a substrate surface comprising the steps of:
providing an aqueous dispersion of a dispersible substantially water insoluble polymer capable of undergoing phase inversion;
applying said aqueous dispersion into or onto said substrate surface to form a zone of said polymer in or on said surface; and effecting phase inversion of said polymer while said polymer is in or on said surface to thereby form a substantially continuous barrier layer of a polymer in or on said surface.

42. A method as defined in claim 17, wherein said bulk oil to be treated contains at least one of particulate matter, metals, water, sulphur or sulphur containing compounds and nitrogen containing compounds.

43. A novel product produced by any of the methods of claims 1 to 18, 26, 27 and 33 to 37, wherein said novel product is a polymer solid or gel.

44. As a new composition of matter, an aqueous polymer dispersion formed from a dispersable substantially water insoluble polymer which has undergone phase inversion.

45. The composition of claim 44 comprising two of said water insoluble polymers each having undergone phase inversion.

46. A method as defined in claim 3, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said aqueous composition.

47. A method as defined in claim 4, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said admixture.

48. A method as defined in claim 5, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said fluid mixture.

49. A method as defined in claim 15, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said composition.

50. A method as defined in claim 16, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said composition.

51. A method as defined in claim 17, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said admixture.

52. A method as defined in claim 20 or 24, wherein said precipitation agent is added to said aqueous polymer dispersion to form an intermediate prior to addition of said intermediate to said aqueous spill.

53. A method as defined in claim 22, wherein said precipitation agent is added to said aqueous polymer dispersion to form an intermediate prior to addition of said intermediate to said aqueous mixture.

54. A method as defined in claim 29, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said aqueous mixture.

55. A method as defined in claim 30, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said metal solution.

56. A method as defined in claim 31, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said aqueous solvent mixture.

57. A method as defined in claim 32, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said solution.

58. A method as defined in claim 36, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said aqueous solution.

59. A method as defined in claim 38, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to addition of said intermediate to said aqueous mixture.

60. A method as defined in claim 41, wherein said phase inversion is initiated by adding a precipitation agent to said polymer to form an intermediate prior to application of said intermediate to said substrate surface.