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United States Patent 19 [11] 3,909,406 Lang (45) Sept United States Patent 19 [11] 3,909,406 Lang (45) Sept. 30, 1975 54 CLARIFYING AGENTS FOR WATER 3,101.317 8/1963 Starry............................., 21.0/52 76) Inventor: John L. Lang, P.O. Box 1242, 3,285,849 l/1966 Watanabe et al.,...,,,,,,,,,,,,,,,,, 210/52 Midland, Mich, 48.640 FOREIGN PATENTS OR APPLICATIONS 22 Filed; Feb. 22, 1972 227,429 l/1926 United Kingdom................., 20152 (2ll Appl. No.: 228,336 Related U.S. Application Data Primary Evanliner-Thomas G. Wyse (63) Continuation-in-part of Ser, No. 144,416, May 17, 57 ABSTRACT 1971, abandoned, The use of compounds of polyvalent cations with alu minate, borate, and aluminosilicate anions has been (52) U.S. C. ... 210/47 found to provide improved clarification methods for 5 i Int, Cl,'................ ......................... CO2B 1/20 aqueous suspensions. The use of these materials is 58) Field of Search..................., 210/43, 47, 51-53, much more effective than that of the corresponding 210/42 conventional mono-valent cation compounds. A par ticularly effective form of these clarifying agents re (56) References Cited sults when preparation is carried out by high tempera UNITED STATES PATENTs ture methods, including the fusion of the reactants. l,604,125 10/1926 Kern........... .a 20/47 Recycling of the used clarifying agents is possible 1872,262 8/1932 Evans. ... 210/51 using these materials, especially when the flocculated 1872,263 8/1932 Evans., 210/53 X solids are incinerated during the ultimate disposal 1940,409 12/1933 Fink.......,. ..., 210/47 step. 2,310,009 2/1943 Baker et al. .......................... 210/51 2,416,007 21947 Joachim..........................., 210/53 X 1 Claim, No Drawings 3,909,406 1 2 CLARIFYING AGENTS FOR WATER those of polyvalent cations with anions such as alumi nate, poly-aluminate, aluminosilicate, poly aluminosil CROSS REFERENCES TO RELATED icate, borate, poly borate, and the like. APPLICATIONS: , , Group II of the Periodic Table of Elements includes This is a continuation-in-part of S.N. 144,416 filed 5 magnesium, calcium, strontium, barium, zinc, and cad May 17, 1971, entitled “Clarifying Agents for Water.” mium. Group VIII-Series 4 includes iron, cobalt, and abandoned. r nickel. The preferred embodiment of the invention com BACKGROUND OF THE INVENTION prises the use of finely ground fusion-formed com The problems involved in the purification of water, 10 pounds of calcium, magnesium, and barium with alumi particularly that containing suspended solids, has been nate, aluminosilicate, poly aluminosilicate, and poly the subject of much investigation for an extended per borate anions. iod. This is especially true in the cases of municipal Many of these materials are prepared by calcining, water supply, sewage treatment, treatment' of dis i.e., heating attemperatures at which water and carbon charges from mineral dressing operations, food pro dioxide are at least partly expelled, of such raw materi cessing plants, breweries, and many other operations als as limestones, dolostones, dolomites, argillaceous which are directed toward man's existence and en limestones, argillaceous dolostones, marls, clays, deavor. Many materials have been used to aid in the shales, metallurgical slags, and other materials contain purification of water and wastes from such operations. ing silica, alumina, calcium, magnesium, barium, bo Some of these are relatively old; the use of alum, ferric 20 ron, iron, and chemically analogous elements. or ferrous salts alone or in conjunction with lime, so An especially advantageous clarification agent of this dium aluminate, soluble starches, water soluble natu type may be prepared by “clinkering," i.e., fusion reac ral, modified, and synthetic polymers, and the like are tion, of a mixture of limestone, clay and bauxite, so as examples of such flocculating agents. Recently, much, to prepare a material containing 28% or more of cal attention has been given to the use of natural gums and 2 5 cium aluminate, followed by pulverization of the synthetic high molecular weight polyelectrolytes, as cooled clinker. typified by poly(acrylic acid ) and salts thereof, poly(vi The use of these new clarifying agents is easily car nylbenzene sulfonic acid) and salts thereof, poly(- ried out, usually by simply mixing the untreated water maleic acid) and salts thereof, the water dispersible re with either the dry pulverized clarifying agent or a action products of nucleophilic reagents with polymers slurry thereof in water, allowing flocculation to take containing vinyl benzylchloride and -bromide; poly(e- place in a quiescent or gently agitated settling Zone, thyleneimine), and many others. Relatively non-ionic and the purified water removed by decantation, siphon polymers, as poly(acrylamide) have also found wide ing, pumping off, filtration or any of the known meth application for use in water clarification. Most of these ods or combinations thereof. materials must be used in certain pH ranges, and in pro An effective procedure involves the addition to the portion to the solids content of the waste, etc., the mixture of untreated water and clarifying agent of a : maintenance of which parometers may be difficult dur ground mineral which has some ion-exchange capacity ing continuous-basis operation. or characteristics. Alternatively, the untreated water can be mixed with SUMMARY OF THE INVENTION ... 40 the clarifying agent in proper proportions, clarification The object of this invention is to provide a new water allowed to take place, the supernatant clarified water purification system. ; ; removed, and the mixture of the thus-concentrated Another object of this invention is to provide an inex solid contaminant water, and clarifying agent recycled pensive, easy method for removal of suspended solids by mixing with another portion of untreated water. This from water, either by separation of clarified superna 45 procedure may be repeated several times; the number tant, or by providing a more easily filtrable mixture. of cycles being dependent upon the degree of contami A further object of this invention is to provide a pro nation of the untreated water and upon whether or not cess which uses a new flocculating system which settles additional make-up increments of clarifying agent are suspended solids from water at a rapid rate, and pro added at each recycling stage. This recycle procedure duces a satisfactorily clear supernatant portion which produces extra volumes of clarified water, when using may be readily removed as purified water, thus greatly any of the separation procedures between cycles. Use increasing the overall capacity of existing water purifi of this procedure increases the solids content of the cation installations. flocculated residue several fold, thus increasing the ef Another object of this invention is to provide floccu fective capacity of water treating plants when com lating and settling agents which are physiologically in pared to conventional operation, also minimizing the ert, and non-contaminants in terms of the effects of volume of settled solids that must be dewatered, wet them upon plants and animals. incincrated, dried or transported for ultimate disposal. Other objects will become apparent to those skilled In the case of municipal waste treatment plants, this in the art upon reading the specification and claims of method of operation converts, for practical purposes, this instrument. a secondary treatment plant into a tertiary stage treat In accordance with the invention, the water contain ment plant with little or no added capital costs, and also ing undesirable suspended solids is treated with an oxy reduces the volume of sludge requiring de-watering, gen compound, with aluminum, of oxygen with alumi wet- or dry-incineration, or transportation for ultimate num and silicon, of oxygen and boron and the like, disposal. which also contains a cation of at least one element se 65 Because of the inorganic nature of the material lected from Groups II and VIII-Series 4 of the Periodic herein taught to be effective clarification agents, they Table of Elements. These compounds are essentially can be recycled in another way; when incineration is 3,909,406 3 4 used as the means for ultimate disposal, the ash there treatment plant was added 0.14 g of powdered trical from contains the flocculating agent in rejuvenated or cium aluminate (fused). The solids in the activated regenerated form. In some cases, the material is still in sludge flocculated. In similar tests, dicalcium alumi the form of particles sufficiently small as to be immedi nate, zinc aluminate, magnesium aluminate, sodium ately re-useable at high levels of effectiveness; in other ferrite, calcium ferrite, and dicalcium silicate were cases it may be fused into larger nodules which are nev used to treat activated sludge. ertheless effective, but re-grinding restores the material EXAMPLE III to its original level of effectiveness when re-used. The mixture of water and clarifying agent can be A series of experiments were carried out using some readily filtered, or can be de-watered by other methods of the flocculating agents herein concerned, as tri in order to separate the clarified water from the resid calcium aluminate, and a powdered cement containing ual solids. The settled solids may be wet-incineratcd, 40% calcium aluminante, in comparison with known dried, dry-incinerated, etc., used for land-fill, fertilizer, flocculating agents, viz.: alum, ferric chloride, ferric soil-builder, or otherwise used. They can be trans chloride plus lime, sodium aluminate and ferric chlo ported for ultimate disposal in a now-concentrated 5 ride - sodium hydroxide, as settling agents for the solids form, recycled in the same or other process, or other in activated sludge as above described in Example II. wise discarded. One hundred milliliters of the treated sludge containing In the case of municipal waste water treatment, the these agents was allowed to settle for 10 minutes (600 settled solids and/or dewatered solids may be readily seconds) and the volume of clear supernatant recover converted into an acceptable form of soil nutrient.
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