CATIONIC POLYMERIC MATERIAL FOR TREATING WATER, PREPARATION AND UTILISATION THEREOF

Abstract: A granular material having a cross-linked cationic polymer adhered to at least a portion of the surface thereof is very effective in separating oil dispersed in water. The material can be prepared by reacting a monomeric cationic component and a cross-linking agent at least partially in the presence of base material to adhere the polymer to the base.

Description: CATIONIC POLYMERIC MATERIAL FOR TREATING WATER, PREPARATION AND UTILISATION THEREOF This invention relates to material which can be employed in processes for separating organic materials from water and to processes for the preparation of such material. In particular the invention relates to materials-having excellent ability to separate from water organic matters or inorganic matters that are dispersed, emulsified or dissolved in water. A variety of processing methods have been proposed in regard to treating organic matters in water and, especially, in regard to treating oil-containing waste water. For example, there have been proposed mechanical separation methods utilizing the principle of gravitational separation such as natural flotation, forced flotation, filtration or centrifugal force, separation methods relying upon the electromagnetic means such as ultrasonic waves, electrolysis and electrophoresis, physical or chemical methods relying upon such means as adsoTption, absorption, ion-exchange, and coagulation, and methods utilizing microorganisms. Among the above-mentioned methods, a variety of adsorbing materials have been proposed in connection with the adsorption method which features relatively simple and stable operation. However, no adsorbing material has yet been found that is effective for treating finely dispersed oils and emulsified oils. With regard to the adsorbing materials which have now been proposed, for example, the hydrophobic synthetic resins or fine synthetic resin structures are mainly used for treating oils that are floating or coarsely dispersed oils. Activated carbon in the form of granules is effective to some extent for treating finely dispersed oils. The activated carbon, however, adsorbs the oils in very small amounts, and is not very effective for treating emulsified oils. Anion-exchange resins have large amounts of cationic groups on the surface thereof, have a large degree of swelling for water, and are effective for treating low molecular weight substances such as ions An an;ion-exchange resin, however, is not effective for oil droplets of the order of microns because the resin does not sufficiently exhibit a cationic effect in relation to such droplets. Further, since the true density depends upon the base resin, an anion-exchange resin cannot withstand the process of back washing. In recent years, there has been proposed a soft polyurethane fosm containing cationic groups. With the foem structure, however, the density tends to increase as it adsorbs oils and suspended materials. Moreover, the Zonm cannot be back washed. There has further been proposed treating materials comprising a surfactant, silicone oil or gamine that is held on the Surface of the base material such as fiber, fine resinous structure or silica alumina particles. Some of these exhibit good separating ability for fine oil droplets and emulsified oils during the initial stage of use. However, the adhesiveness is not sufficient between the base material and components held on the base material; the components are split off during use. Consequently, the materials cannot be substantial2 back washed, and are not capable of withstanding use for extended periods of time. As mentioned above, there has not yet been found a treating material that is effective for treating fine oil droplets and emulsified oils. Usually, a colloid which is stably dispersed in water, for example fine óil droplets or organic high molecules (hereinafter described as oil droplets) have a negative electric charge in the surface layer of the oil droplets. The stability of the oil droplets is dependent upon the diameter of oil droplets and the amount of electric charge. Therefore, it is preferable that a material for removing oil droplets neutralize the electric charge on the surface of the droplets so that they lose stability, possess electric charge of a polarity opposite to that of oil droplets so as to attract oil droplets, contain organic high molecular substances that are capable of adsorbing or embracing oils, be composed of a porous material having large surface areas, not be clogged by solid substances suspended in water, permit the passage of water without increasing the pressure, and release substances that are clogging the water-treating material when it is back washed, and/or have increased mechanical rigidity, swell only slightly in water, and sink in water. The object of the present invention is to provide watertreating materials having excellent ability to remove organic or inorganic substances that are dispersed, emulsified or dissolved in water, and to provide a process for preparing such water-treating materials. Particularly, the object of the present invention is to provide water-treating materials which are suited for treating waste water containing fine oil droplets, and to provide a process for preparing the water-treating materials. According to the invention there is provided a granular water-treating material having a cross-linked cationic polymer attached to at least a portion of the surface of a base material. There is also provided a process for preparing a granular water-treating material having a cross-linked cationic polymer on at least a portion of base material wherein a cationic component (A), and a cross-linking agent (B) are reacted together under conditions in which they are mixed together with the base material or in which they are adhered onto the base material, thereby to form a cross-linked cationic polymer adhered to at least a portion of the surface of such base material. In addition there is provided a method of separating oil dispersed in water wherein the dispersion is treated with a granular water-treating material having a cross-linked cationic polymer attached to at least a portion of the surface of a base material. The gist of the present invention resides in a water-treating material holding a cross-linked cationic polymer at least a portion of the surface of base material. In a process for preparing water-treating materials a cationic component (A), and its cross-linking agent (B), and further a polymerization initiator or additive (C), if required, are reacted together under the condition in which they are mixed together with the base material or in which they are adhered onto the base material, thereby to form a cross-linked cationic polymer. The basic material and the components which can be used for preparing the cationic polymer and the process for preparing the water-treating material in the present invention will be explained below. Examples of the basic material which can be employed in the present invention include various inorganic materials, organic materials complexes of inorganic and organic materials or mixtures thereof. Blowing agent or additives can be added, as required, in the case of - molding process adopted. Examples of the inorganic material include granulated coal; anthracite, grass peat, silica, alumina, zeolite, purmice containing such elements as silicon, aluminum, calcium, magnesium and iron, foamed clay, slag, foamed slag, foamed glass, or natural granulated material such as pearlite, garret or sand. Non-carbonaceous inorganic materials are preferred because of the adhesion to the active components. Examples of the organic material include polymers or copolymers from such monomers as ethylene, propylene, styrene, vinyl acetate, vinyl chloride, acrylonitrile, (meth) acrylamide, (meth) acrylic acid, methyl (meth)acrylate, divinyl benzene, butadiene, isoprene and chloroprene, or polyurethane, polyurea, polyethylene terephthalate, nylon, aromatic polyamude, polycarbanate, polysulfone and polyether sulfone. The basic material can be a complex of components or a mixture of inorganic material and organic material and can include complexes or mixtures of inorganic granules such of the above-mentioned inorganic materials with barium sulfate, magnesium alumnate, iron oxide or magnesium oxide, and polymers or copolymers of the above-mentioned organic materials As to the proportions of these complexes or mixtures, a wide range is a-railable. Usually, however, the compositions containing 80 - 20% by weight of inorganic materials and 20 - 80% by weight of organic materials are preferable. Examples of the organic tationic component (A) include amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, vinylamine, ethyleneimine and aniline, amino alcohols such as N,N-diethylethanolamine, aminoethylethanolamine, N-methyl-N,N-diethanolamine, N,N-diisopropylethanolamine, N ,N-dibutyle- thanolamine, N-methylethanolamine, and triethanol amine, dialkylaminoethyl methacrylate, vinylpypridine, dicyan diamide, vinylimidazoline, or the quaternary ammonium salts of the above-mentioned compounds which are cationized with such a reagent as benzyl chloride, dimethyl sulfate or methyl chloride, or a monomer, a polymer or a copolymer such as 2-hydroxy-3-methacryloxypropyltrimethylammonium halide, or a polyester polyamine, polyamide polyamine, a cationic vinyl lactam/acryAamide copolymer, a cyclized polymer of drallyAammonium halide, a half-amide obtained by acting diamine upon a copolymer of isobutylene and maleic anhydride, a polycondensate of ammonia and epichlorohydrine, a quaternary ammoniate obtained by reacting diamine and methyl chloride upon a copolymer of styrene and maleic anhydride, a polycondensate of alkylene dichloride and alkylene polyamine, a polycondensate of aspartic acid and hexamethylene diamine, a polycondensate of aniline and formaldehyde, and polymers knows as a cationic high molecular coagulating agent such as chitosan. It is also allowable to use sulfonium compounds such as alkyldimethyl sulfonium and the like, and phosphonium compounds such as tetraalkyl phosphoniate and the like. Examples of the cross-linking agents (B) include epoxy compounds such as (poly) ethyleneglycol diglycidyl ether, (poly) propyleneglycol diglycidyl ether, neopentylglycol diglycidyl ether, (di)glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and epichlorohydrine, (meth) acrylates such as (poly) ethyleneglycoldi (meth) acrylate, tetrahydrofurfuryl (meth) - acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, and pentaerithritol acrylate, epoxy acrylates such as (di) ethyleneglycol diglycidylether dimethacrylate, propyleneglycol diglycidylether, diacrylate, glycerolpolyglycidylether polyacrylate, and phthalic acid diglycidylester diacrylate, isocyanates such as diphenylmethane dilsocyanate, tolylene diisocyanate and hexamethylene dii socyante, hydroxyl group-containing compounds such as polyester polyol, polyether polyol, acryl polyol, derivatives of castor oil, derivatives of tall oil and polybutadiene containing hydroxyl groups at the terminals, and prepolymers thereof. Examples of the polymerization initiator C include hydrogen preoxide, potassium persulfate, sulforous acid, sodium hydrogensulfite, benzoyl peroxide, azobisisobutyl nitryl, amines such as trialkylamine and tetraalkyldiamine, and organic metal compounds such as di-nbutyltin dilaurate. Further, examples of the additive will include ordinarily used stabilizers, emulsifiers, pigments and dyestuffs. In preparing the water-treating materials according to the present invention, the components A and B, or the components A, B and C can be adhered onto or mixed with the base material by any method, ald the cross-linked cationic polymer can also be formed by iirly method. For instance, the base material can be immersed for a predetermined period of tine in an aqueous solution, in an organic solvent solution, or in a mixture solution consisting of water and an organic solvent in which have been dissolved ccmpollents A and B, or caiponents A, B and C, and aSter the solution is removed, the granular base material is treated with heat or irradiated with light. The granular base material coated with the components A and B, or with the components A, B and C, can be hefted with heat or irradiated with light. Immersing and coating can be used jointly. Visible rays, ultravoilet rays or electron rays can be used as a source of light irradiation. As for the immersing method, the concentration of immersing liquid and the irrimersing time will tary depending upon the type of components A, B and C and the type of solvent. Usually, however, the concentration of solute ranges from about 0.5 to 30% by weight, and the immersing time ranges from about 0.5 to 3 hours. As for the coating method, the components A, B (and) are adhered to the granular base material by dripping or spraying while the latter is being fluidized Usually the heat-treatment should be effected at a temperature of 50 to 200 C for 10 minutes to 20 hours. When the heat of reaction produced in cross-linked cationic polymer formation can be used, another heat-treatment is not necessary. When the base material is to be irradiated with light, the irradiation should be continued, usually, for not longer than 10 hours although it may vary depending upon the type of light and the itensity of light. Further, the water-treating material of the present invention can be obtained by mixing the components A and B, or the components A, B and C and base material and thereafter, molding the mixture by using an internal mixer, a Banbury mixer, a melt extruder or a granulating machine, followed, as required, by granulating through cutting or smash. Yor example, the water-treating material can be obtained by mixing the base material consisting of inorganic powder and organic polymer powder and further blowing agent or cross-linking agent, if required, and above-mentioned components and thereafter by kneading and cross-linking and molding to the cylindrical form with melt extruder and thereafter by granulating with pelletizer or granulator. Alternatively or in addition, the mixture of the above-mentioned base material and components can be melt kneaded and cross-linked and granulated at the same time by shearing action of these equipments. Because of the use of blowing agent and/or cross-linking agent, the surface of the water-treating material is increased and therefore its treating ability is increased. For a blowing agent, widely well knawn materials, for example azodicarbonamide and benzene suifonyl hydrazide, can be used. For a cross-linking agent, widely well known materials such as benzoylperoxide, dicumylperoxide or tert.-butyl peroxyhexane can be used. In the thus obtained water-treating material of the present invention, the cross-linked cationic polymer is held in any effective amount and preferably in an amount of from 0.05 to 50% by weight, and more preferably in an amount of from 0.1 to 30% by weight. When the cross-linked cationic polymer is present in an amount of less than 0.05% by weight, organic substances and inorganic substances may not be sufficiently removed from water. When the cross-linked cationic polymer is present in an amount greater than 50% by weight, on the other hand, the cationic groups may be embedded in the water-treating material, and no further increase in effect may result. Wken the cationic organic polymer is Åa nitrogen-containing compound, the content of nitrogen in the water-treating material should preferably range from 0.005 to 10% by weight, and more preferably from 0.01 to 5% by weight. Further, the capacity of ion-exchange of the watertreating material should preferably be fram 0.01 to 10 meg/g, and more preferably be from 0.02 to 2 meg/g. The water-treating material of the present invention is in a granular form. In order that the water-treating material does-not float in water during the use, it should most suitably have a true density of greater than 1.0 g/cm3, and particularly preferably greater than 1.2 glcm3. The water-treating material of the present invention can be effectively used for treating waste water containing a variety of mineral oils, animal oils and vegetable oils, alone or in a mixture. The water-treating material of the present invention removes these oils which may have been dispersed or emulsified in water The separating ability of the water-treating material is not affected by other solid components that are contained in water in addition to oils. The water-treating material of the present invention is effective for removing not only oils but also for removing negatively charged colloid such as silica colloid. The water-treating material features very excellent adhesiveness between the base material and the cross-linked cationic polymer, and is capable of being used for extended periods of time. The water-treating material of the present invention can be used not only as an adsorbing material but also as a coalescing agent. When the water-treating material is used as an adsorbing material, the adsorption system can employ the material in a slurry. Usually, however, it is preferred to use the system ofaSharged tower adsorption. The charged tower system can also be employed even when the watertreating material is used as a coalescing agent. The water-treating material of the present invention used as the adsorbing material or the coalescing agent for the charged tower system, can be back washed or can be washed for its surfaces, and is re-used. Water or the air can be used for washing the water-treating material. The water-treating material of the present invention is very effective for treating waste water containing emulsified or dispersed oils in a wide field of applications, that have hitherto been treated with difficulty, such as waste water containing cutting oil, waste water containing rolling oil, waste water produced from the washing of oil tanks, waste water produced from the washing of machines, waste water from paint factories, waste water from food factories, waste water containing emulsified oils such as drain from the compressors, ballast water of oil tankers, bilge. water, and waste water from the drilling of crude oil. The water-treating material is also effective for treating waste, water to such a degree that it can be reused. The invention will be explained below by way of working examples. Examples 1 to 4: Four base materials shown in Table 1 were introduced each in an amount of 300 g into a mixture solution consisting of 10 g of a polyethyleneimine (molecular weight 50,000; hereinafter referred to as component A), 10 g of a polyethyleneglycol diglycidylether (hereinafter referred to as component B) and 300 g of water, and were left to stand for 60 minutes such that the components A and B adhered on the base materials. Thereafter, the filtrate was removed by suction filtration the base materials on which have been adhered the components A and B were heat-treated with hot air heated at 80 C for 5 hours so that the components A and B reacted with each other on the surfare of the base materials and, thus, the water-treating materials of the present invention were obtained. Amounts of the cross-linked cationic polymer and nitrogen in the water-treating materials were as shown in Table 1. These water-treating materials were then charged into columns each having a diameter of 20 nin to a height of 800 mm, and a model water (oil content, 16 mg/) was allowed to flowdcwn through the each column at a flow speed of 4 m/hr for 50 hours. The model water was prepared in the following way. That is, 4 g of a crude oil (Arabian light) and 1 t of water was stirred together in a mixer for 5 minutes, and the mixture was diluted with water to a volume of 200 Q The diluted water was left to stand for more than 20 hours in a drum. Thereafter, 100 Q of water of the lower layer was used as the model water. Table 1 shows oil contents in the treated water after 10 hours and 50 hours have passed. To examine the adhesiveness between the base material component and the sub components, 300 g of the water-treating material and 10 of water were put in a beaker and washed by stirring at 1 hr/day for a week, and thereafter, charged into columns and the model water was < ¯¯ allowed to flow in the above-mentioned way. Oil contents in the treated water are shown in the right columns in Table 1. In the case of carbonaceous base material, the treating ability had decreased after the washing. The oil contents were measured in accordance with the extraction of oils with carbon tetrachloride - infrared ray analytical method specified under JIS X 0102 '18., Reference 1. --------------------------------------------------------------------------- Water-treating material Oil content in the treated water (mg/1) -------------------------------------------------------------------------------------------------- Cationic Nitrogen Unwashed material Washed material Example Base material organic content True ------------------------------------------ polymer (% by density After After After After (% by weight) (g/cm3) 10 jours 50 hours 10 hours 50 hours weight) ---------------------------------------------------------------------------------------------------------------- 1 Granulated activated carbon 3.1 0.5 2.1 0.9 1.1 2.8 4.3 (diameter (0,8 - 2.6 mm) ---------------------------------------------------------------------------------------------------------------- 2 Anthracite (diameter 1,8 0.3 2.0 0,5 0.9 4.9 6.8 O.B - 2.6 mm) ----------------------------------------------------------------------------------------------------------------- 3 Silica alumina-type pumice 1.7 0.3 2.4 0.3 1.0 0.2 0.3 (diameter 1.8 - 2.9 mm ----------------------------------------------------------------------------------------------------------------- 4 Composite material (note) (diameter 1.4 0.2 1.4 0.7 0.8 0.5 0.5 0.9 - 2.9 mm ------------------------------------------------------------------------------------------------------------------ EMI10.1 ------------------------------------------------------------------------------------------------------------------------- <SEP> Water-treating <SEP> material <SEP> Oil <SEP> content <SEP> in <SEP> the <SEP> treated <SEP> water <SEP> (mg/@) <tb> <SEP> ---------------------------------------------------------------------------------------------------------- <SEP> Cationic <SEP> Nitrogen <SEP> True <SEP> Unwashed <SEP> material <SEP> Washed <SEP> material <tb> Example <SEP> Base <SEP> material <SEP> organic <SEP> content <SEP> density <SEP> ------------------------------------------- <SEP> polymer <SEP> (% <SEP> by <SEP> After <SEP> After <SEP> After <SEP> After <tb> <SEP> (% <SEP> by <SEP> weight) <SEP> (g/cm3) <SEP> 10 <SEP> hours <SEP> 50 <SEP> hnours <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <tb> <SEP> weight) <tb> -------------------------------------------------------------------------------------------------------------------------- <SEP> 1 <SEP> Granulated <tb> <SEP> activated <tb> <SEP> carbon <SEP> 3.1 <SEP> 0.5 <SEP> 2.1 <SEP> 0.9 <SEP> 1.1 <SEP> 2.8 <SEP> 4.3 <tb> <SEP> (diameter <tb> <SEP> 0.8 <SEP> - <SEP> 2.6 <SEP> mm) <tb> --------------------------------------------------------------------------------------------------------------------------- <SEP> 2 <SEP> Anthracite <tb> <SEP> (diameter <SEP> 1.8 <SEP> 0.3 <SEP> 2.0 <SEP> 0.5 <SEP> 0.9 <SEP> 4.9 <SEP> 6.8 <tb> <SEP> 0.8 <SEP> - <SEP> 2.6 <SEP> mm <tb> --------------------------------------------------------------------------------------------------------------------------- <SEP> 3 <SEP> Silica <tb> <SEP> alumina-type <tb> <SEP> pumice <SEP> 1.7 <SEP> 0.3 <SEP> 2.4 <SEP> 0.3 <SEP> 1.0 <SEP> 0.2 <SEP> 0.3 <tb> <SEP> (diameter <tb> <SEP> 1.8 <SEP> - <SEP> 2.9 <SEP> mm) <tb> ---------------------------------------------------------------------------------------------------------------------------- <SEP> 4 <SEP> Composite <tb> <SEP> material <SEP> (note) <tb> <SEP> (diameter <SEP> 1.4 <SEP> 0.2 <SEP> 1.4 <SEP> 0.7 <SEP> 0.8 <SEP> 0.5 <SEP> 0.5 <tb> <SEP> 0.9 <SEP> - <SEP> 2.9 <SEP> mm <tb> ---------------------------------------------------------------------------------------------------------------------------- Note - Granular conposite material consisting of 50 parts by weeight of barium sulfate and 50 parts by weight of ethylne/vinyl acetate copolymer. Comparative Eamp ] es 1 to 6: Four base materials same as those used in Examples 1 to 4, a strongly basic anion-exchange resin (Diaion PA-316, a product of Mitsubishi Kasei Kogyo Co.) and a weakly basic anion-exchange resin (Diaion WA-20, a product of Mitsubishi Kasei Kogyo Co.) were charged into the column having a diameter of 20 mm to a height of 800 mm in the same way as in Examples 1 to 4, and the model water was allowed to flow. Oil contents in the treated water are shown in Table 2, from which it will be understood that the treated water contained oil components at considerably high concentrations compared with those of the treated water mentioned in Examples 1 to 4 of the present invention. Table 2 EMI11.1 <tb> <SEP> Oil <SEP> content <SEP> in <SEP> the <tb> treated <SEP> water <SEP> (mg/t) <SEP> <tb> Comparatlve <SEP> Charged <SEP> material <tb> <SEP> Example <SEP> After <SEP> After <SEP> <tb> <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <tb> <SEP> 1 <SEP> Granulated <SEP> activated <SEP> carbon <SEP> 8.5 <SEP> 76 <SEP> <tb> <SEP> 2 <SEP> Anthracite <SEP> : <SEP> 9 <SEP> 3 9.3 <SEP> 107 <SEP> <tb> <SEP> 3 <SEP> Silica <SEP> alumina-type <SEP> pumice- <SEP> 12,1 <SEP> 12.4 <SEP> <tb> <SEP> 4 <SEP> Composite <SEP> material <SEP> (note) <SEP> 8.0 <SEP> 8.3 <SEP> <tb> <SEP> 5 <SEP> Strongly <SEP> basic <SEP> cation-exchange <SEP> <tb> <SEP> resin <SEP> 2.1 <SEP> 5.3 <tb> <SEP> 6 <SEP> Weakly <SEP> basic <SEP> cation-exchange <tb> <SEP> resin <SEP> 11.1 <SEP> 8.6 <tb> Note - The same material as used in Example 4. Examples S to 8: Four base materials that were used in Examples 1 to 4 were introduced each in an amount of 300 g into a mixture solution consisting of 92 g of a methacrylic acid aminoethyltrimethylamrnonium chloride (hereinafter referred to as component A), 8 g of a polyethyleneglycol dimethacrylate (hereinafter referred to as component B), I g of pntassium persulfate (hereinafter referred to as component C), and 300 g of water, and were allowed to stand for 60 minutes so that the components A, B and C adhered on the base materials. Thereafter, the filtrate was removed by suction filtration, the base materials on which have been adhered the components A, B and C were heat-treated with hot air heated at 600C for 6 hours so that the components A, B and C reacted with each other on the surface of the base materials and, thus, the water-treating materials of the ?resent invention were obtained. Amounts of the cationic organic polymer and nitrogen in the water-trea-- ting materials were as shown in Table 3. The water-treating materials were then charged into the column having a diameter of 20 mm to a height of 800 mm in the same manner as in Examples 1 to 4, and the model water was allowed to flow. Table 3 shows oil contents in the treated water. Table 3 EMI13.1 ------------------------------------------------------------------------------------------------------- <SEP> Water-treating <SEP> material <SEP> Oil <SEP> dontent <SEP> in <SEP> the <tb> <SEP> -------------------------------------------------------------- <SEP> treated <SEP> water <SEP> (mg/@) <tb> Example <SEP> Crosslinked <SEP> Nitrogen <SEP> True <SEP> ---------------------- <SEP> Base <SEP> cationic <SEP> content <SEP> density <SEP> After <SEP> After <tb> <SEP> material <SEP> polymer <SEP> (% <SEP> by <SEP> weight) <SEP> (g/cm3) <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <tb> ------------------------------------------------------------------------------------------------------- <SEP> 5 <SEP> Granulated <tb> <SEP> activated <SEP> 8.6 <SEP> 0.5 <SEP> 2.0 <SEP> 1.2 <SEP> 1.4 <tb> <SEP> carbon <tb> ------------------------------------------------------------------------------------------------------- <SEP> 6 <SEP> Anthracite <SEP> 2.3 <SEP> 0.1 <SEP> 2.0 <SEP> 2.7 <SEP> 3.9 <tb> ------------------------------------------------------------------------------------------------------- <SEP> 7 <SEP> Silica <tb> <SEP> alumina-type <SEP> 5.1 <SEP> 0.3 <SEP> 2.3 <SEP> 0.8 <SEP> 1.1 <tb> <SEP> pumice <tb> ------------------------------------------------------------------------------------------------------- <SEP> 8 <SEP> Composite <tb> <SEP> material <SEP> 7.1 <SEP> 0.4 <SEP> 1.4 <SEP> 0.3 <SEP> o.5 <tb> <SEP> (note) <tb> -------------------------------------------------------------------------------------------------------- Note - The same material as used in Example 4. Examples 9 to 11 44 parts by weight of N-methyldiethanolamine, 46 parts by weight of benzyl chloride and 10 parts by weight of water were heated at 800C and reacted with stirring to synthesize a cationic compound (hereinafter referred to as component A). A mixture consisting of the component A and a tctraftctional polyetherpolyol (molecular weight 5,900; hereinafter referred to as component B-1) each in an equal @ amount, was adhered onto 1500 g of ench of three base materials shown in Table 4. While the base materials on which had been adhered the components A and B-1 were being fluidized by a blower, a mixture consisting of 1000 g of 2 olylene diisocyanate/2,6-tolylene diisocyanate (80:20) (hereinafter referred to as component B-2) and 15 ml of di-n-butyltin dilaurate (hereinafter referred to as component C), was sprayed, and thereafter, was heat-treated with the hot air heated at 800C for 20 minutes so that the components A, B-1, B-2 and C were reacted together on the surfaces of the base material and, thus the water-treating mateials of the present invention were obtained. The water-treating materials were then charged into the column in the same manner as in Examples 1 to 4, and the model water was allowed to flow. The results were as shown in Table 4. Table 4 EMI15.1 ---------------------------------------------------------------------------------------------------------------------------------------- <SEP> Raw <SEP> materials <SEP> Water-treating <SEP> material <SEP> Oil <SEP> content <SEP> in <SEP> the <tb> <SEP> ---------------------------------------------------------------------------------------------- <SEP> treated <SEP> water <SEP> (mg/L) <tb> Example <SEP> Base <SEP> material <SEP> Amount <SEP> of <SEP> Amount <SEP> of <SEP> Croeslinked <SEP> Ion-exchange <SEP> True <SEP> ---------------------- <SEP> mixture <SEP> of <SEP> mixture <SEP> of <SEP> cationic <SEP> capacity <SEP> density <SEP> After <SEP> After <tb> <SEP> A <SEP> and <SEP> B-1, <SEP> B-2 <SEP> and <SEP> C, <SEP> polymer <SEP> (neq/g) <SEP> (g/cm3) <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <tb> <SEP> adhered <SEP> adhered <SEP> (%) <tb> ---------------------------------------------------------------------------------------------------------------------------------------- <SEP> 9 <SEP> Garnet <SEP> (effective <tb> <SEP> diameter <SEP> 0,25 <SEP> mm) <SEP> 31 <SEP> g <SEP> 11g <SEP> 2.7 <SEP> 0.04 <SEP> 3.7 <SEP> 1.0 <SEP> 1.9 <tb> <SEP> 1500 <SEP> g <tb> ----------------------------------------------------------------------------------------------------------------------------------------- <SEP> 10 <SEP> Filter <SEP> sand <tb> <SEP> (effective <SEP> diameter <SEP> 56 <SEP> g <SEP> 20g <SEP> 4.8 <SEP> 0.06 <SEP> 2.4 <SEP> 0.9 <SEP> 1.3 <tb> <SEP> 0.5 <SEP> mm) <tb> <SEP> 1500 <SEP> g <tb> ----------------------------------------------------------------------------------------------------------------------------------------- <SEP> 11 <SEP> Composite <SEP> material <tb> <SEP> (note) <tb> <SEP> (diameter <SEP> 0.9 <SEP> - <SEP> 429 <SEP> g <SEP> 153g <SEP> 28.0 <SEP> 0.37 <SEP> 1.3 <SEP> 1.5 <SEP> 1.1 <tb> <SEP> 2.9 <SEP> mm) <tb> <SEP> 1500 <SEP> g <tb> ----------------------------------------------------------------------------------------------------------------------------------------- Note - Granular composite material consisting of 40 parte by weight of barum aulfate and 60 parts by weight of ethylene/vinyl acetate copolymer. Examples 12 to 13: A mixture consisting of 100 parts by weight of a crude diphenylmethanediisocyanate (containing 30.5% of NCO) (hereinafter referred to as component B-l) and 400 parts by weight of a tolylene diisocyanate prepolymer of liquid polybutadiene (Poly bd HTP-9, a product of Idernitsu Sekiyu Kagaku Co.) (hereinafter referred to as component B-2) was adhered in an amount of 250 g onto 1500 g of each of tBlo base materials shown in Table 5. While the base materials on which had been adhered the components B-l and B-2 were being fluidized by a blower, a mixture consisting of 10 ml of di-n-butyltin dilaurate (hereinafter referred to as component C) and 1000 g of a cationic compound (hereinafter referred to as component A) which is composed of 44 parts of Methyl diethanolamine, 46 parts of benzyl chloride and 20 parts of water, was sprayed in an amount of 180 g, and was heattreated with the hot air heated at 80 C for 20 minutes in the same manner as in Examples 9 to 11 so that the components B-l, B-2, A and C were reacted together on the surfaces of the base materials and, thus the water-treating materials of the present invention were obtained; ; The water-treating materials were then charged into columns lender the same conditions as in Examples 1 to 4, and the model water was allowed to flow therethrough. The results were as shown in Table 5. Table 5 EMI17.1 ---------------------------------------------------------------------------------------------------------------- <SEP> Water-treating <SEP> material <SEP> Oil <SEP> content <SEP> in <SEP> the <tb> <SEP> ------------------------------------------------------------------------ <SEP> treated <SEP> water <SEP> (mg/@) <tb> Example <SEP> Crosslinked <SEP> True <tb> <SEP> Base <SEP> cationic <SEP> Ion-exchange <SEP> density <tb> <SEP> material <SEP> polymer <SEP> capacity <SEP> After <SEP> After <tb> <SEP> (% <SEP> by <SEP> weight) <SEP> (meg/g) <SEP> (g/cm3) <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <tb> ---------------------------------------------------------------------------------------------------------------- <SEP> 12 <SEP> Composite <SEP> 22.3 <SEP> 0.30 <SEP> 1.4 <SEP> 1.1 <SEP> 1.4 <tb> <SEP> material <SEP> (note) <tb> ---------------------------------------------------------------------------------------------------------------- <SEP> 13 <SEP> Silica <tb> <SEP> alumina-type <tb> <SEP> pumioe <SEP> 22.3 <SEP> 0.31 <SEP> 1.8 <SEP> 1.0 <SEP> 1.0 <tb> <SEP> (diameter <tb> <SEP> 0.8 <SEP> - <SEP> 2.1 <SEP> mm) <tb> ---------------------------------------------------------------------------------------------------------------- Note - The same material as used in Example 11. Examples 14 to 15: while 300 g of e2ch two basic materials represented in Table 6 were being fluidized in a Henschel mixer (innerdiameter of the vessel 150 mm), N-methyl-N,N-diethanolamine (hereinafter referred to as component A) and crude diphenylmethane diisocyanate UNCO content 30.5%; hereinafter referred to as component B) were dripped in order. Thereby component A and B were reacted together on the surfaces of the base materials, and thus the water-treating materials of the present invention were obtained. The water-treating material were then charged into the column in the same manner as in Example 1, and the model water was allowed to flow. The results were as shown in Table 6. Table 6 EMI19.1 ------------------------------------------------------------------------------------------------------------------------ <SEP> Raw <SEP> materials <SEP> Water-treating <SEP> material <SEP> Oil <SEP> content <SEP> in <SEP> the <tb> <SEP> -------------------------------------------------------------------------------- <SEP> treated <SEP> water <SEP> (mg/1) <tb> Example <SEP> Crosslinked <SEP> --------------------- <SEP> Basic <SEP> Component <SEP> Component <SEP> cationic <SEP> Nitrogen <SEP> True <SEP> After <SEP> After <tb> <SEP> material <SEP> A <SEP> B <SEP> polymer <SEP> content <SEP> density <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <SEP> (% <SEP> by <SEP> (% <SEP> by <SEP> (g/cm3) <tb> <SEP> weight) <SEP> weight) <tb> ------------------------------------------------------------------------------------------------------------------------- <SEP> 14 <SEP> Silica <tb> <SEP> alumina-type <tb> <SEP> pumice <SEP> 20 <SEP> g <SEP> 32 <SEP> g <SEP> 14.8 <SEP> 0.67 <SEP> 2.0 <SEP> 0.3 <SEP> 1.0 <tb> <SEP> 300 <SEP> g <tb> <SEP> (0.8 <SEP> <SEP> 2.6 <SEP> mm) <tb> -------------------------------------------------------------------------------------------------------------------------- <SEP> 15 <SEP> Repelletized <tb> <SEP> polyester <tb> <SEP> (note) <tb> <SEP> 300 <SEP> g <SEP> 15 <SEP> g <SEP> 36 <SEP> g <SEP> 14.5 <SEP> 0.50 <SEP> 1.3 <SEP> 0.8 <SEP> 1.2 <tb> <SEP> (0.8 <SEP> <SEP> 2.9 <SEP> mm) <tb> -------------------------------------------------------------------------------------------------------------------------- Note - Granule made by heat bonding from polyester staple fibers. Examples 16 to 17: A mixture of a composition shown in Table 7 was mixed in a Henschel mixer for 15 minutes, and was melted; cross-linked and sheared using a vented melt extruder having a inner diameter of 50 mm at 1500 - 2000C of barrel temperature to obtain granules having diameters of 0.5 to 5.1 mm. Granules having diameters of 0.9 to 2.9 mm were taken out from the thus obtained water-treating materials, and were charged'into the column under the same condition as in Example 1. The model water was then allowed to flce through the column. ' The results were as shown in Table 7. Examples 18 to 20: A mixture of a composition shown in Table 8 was mixed in a Henschel mixer for 15 minutes, and was extruded using a vented melt extruder having an inner diameter of 30 mm at 1500 - 2000C of barrel temperature, and pelletized by pelletizer. Thus foamed and porous pellets having sizes of about 3 mm were obtained. Then the granules having diameters of 0.5 to 3,7 mm were obtained by granulating these pellets with a granulator. Granules having diameters of 0.9 to 2.9 mn were taken out from the thus obtained water-treating materials, and were charged into the column under the same conditions as in Example. The model water was then allowed to flow through the columns The results were as shown in Table S. Table 7 EMI21.1 --------------------------------------------------------------------------------------------------------------------------------------------- <SEP> Composition <SEP> of <SEP> raw <SEP> material <SEP> Water-treating <SEP> Oil <SEP> content <SEP> in <tb> <SEP> --------------------------------------------------------------------- <SEP> matrial <SEP> treated <SEP> water <tb> <SEP> Base <SEP> material <SEP> Components <SEP> --------------------------------------------- <SEP> --------------------------------------------------------------------------------- Example <SEP> EVA <SEP> Barium <SEP> Organic <SEP> Trimethylol- <SEP> Nitrogen <SEP> True <tb> <SEP> (note <SEP> 1) <SEP> sulfate <SEP> peroxide <SEP> Polyethyleneimine <SEP> propane <SEP> content <SEP> density <SEP> After <SEP> After <tb> <SEP> (parts <SEP> by <SEP> (parts <SEP> by <SEP> (note <SEP> 2) <SEP> (note <SEP> 3) <SEP> polyglycidyl <SEP> (% <SEP> by <SEP> (g/cm3) <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <tb> <SEP> weight) <SEP> weight) <SEP> (parts <SEP> by <SEP> (parts <SEP> by <SEP> weight) <SEP> ether <SEP> (parts <SEP> weight) <tb> <SEP> weight) <SEP> by <SEP> weight) <tb> ---------------------------------------------------------------------------------------------------------------------------------------------- <SEP> 16 <SEP> 50 <SEP> 50 <SEP> 2,0 <SEP> 4.0 <SEP> 2.0 <SEP> 1.1 <SEP> 1.6 <SEP> 0.6 <SEP> 0.9 <tb> ---------------------------------------------------------------------------------------------------------------------------------------------- <SEP> 17 <SEP> 40 <SEP> 60 <SEP> 1.5 <SEP> 2.0 <SEP> 1.0 <SEP> 0.6 <SEP> 1.8 <SEP> 0.7 <SEP> 0.9 <tb> ---------------------------------------------------------------------------------------------------------------------------------------------- Note 1 - Ethylene/vinyl acetate copolymer (vinyl acetate, 18 % by weight) Note 2 - 2,5-dimethyl-2,5-di (tertiary butylperoxy) hexane Note 3 - Molecular weight 1000 Table 8 EMI22.1 ------------------------------------------------------------------------------------------------------------------------------- <SEP> Composition <SEP> of <SEP> raw <SEP> material <SEP> Water-treating <SEP> Oil <SEP> content <SEP> in <SEP> the <tb> <SEP> --------------------------------------------------------- <SEP> material <SEP> treated <SEP> water <SEP> (mg/L) <tb> <SEP> Componente <SEP> --------------------------------------------- <SEP> ------------------------------- <SEP> Trimethylo- <SEP> Nitrogen <SEP> True <tb> Example <SEP> Base <SEP> material <SEP> Polyethleneimine <SEP> propane <SEP> content <SEP> deneity <SEP> After <SEP> After <tb> <SEP> (note) <SEP> polyglycidyl <SEP> (% <SEP> by <SEP> (g/cm3) <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <tb> <SEP> (Parts <SEP> by <SEP> weight) <SEP> ether <SEP> (parts <SEP> weight) <tb> <SEP> by <SEP> weight) <tb> -------------------------------------------------------------------------------------------------------------------------------- <SEP> 18 <SEP> EVA <SEP> Barium <SEP> Azodicerbon <SEP> 50 <SEP> parts <SEP> sulfate <SEP> amide <SEP> 3,0 <SEP> 1.5 <SEP> 0.9 <SEP> 1.6 <SEP> 0.9 <SEP> 1.8. <tb> <SEP> 50 <SEP> parts <SEP> 5 <SEP> parts <tb> -------------------------------------------------------------------------------------------------------------------------------- <SEP> 19 <SEP> EVA <SEP> Barium <tb> <SEP> 40 <SEP> parts <SEP> sulfate <SEP> - <SEP> ditto <SEP> - <SEP> 4.0 <SEP> 2.0 <SEP> 1.1 <SEP> 1.8 <SEP> 1.4 <SEP> 1.9 <tb> <SEP> 60 <SEP> parts <tb> -------------------------------------------------------------------------------------------------------------------------------- <SEP> 20 <SEP> Poly- <SEP> Silica <tb> <SEP> ethylene <SEP> 50 <SEP> parts <SEP> - <SEP> dittö <SEP> - <SEP> 4.0 <SEP> 2.0 <SEP> 1.1 <SEP> 1.6 <SEP> 1.1 <SEP> 2.0 <tb> <SEP> 50 <SEP> parts <tb> --------------------------------------------------------------------------------------------------------------------------------- Note - Molecular weight 1000 Examples <RTI ID=23.1> 21 to 24: The water-treating materials of the present invention prepared in Examples 1, 3, 4 and 14 were charged into colt having a diameter of 20 nin to a height of, 800 mm, and the model water was allowed to flow through these coltmns at a flow speed of 4 m/hr for 50 hours. The model water was prepared in the following way. That is, 4 g of a , special turbin oil (produced by Maruzen Sekiyu Co.), 0.2 g of polyoxy ethylenenonylphenyl ether and 1 liter of water were stirred together in a mixer for 5 minutes. The mixture was then diluted with water to a volume of 200 Q, and the thus obtained water containing emulsified oil was used as the model water. Turbidity of the model water and the treated water was measured using a turbidimeter. The results were as shown in Table 9. Table 9 EMI23.1 <tb> <SEP> Turbidity <SEP> of <tb> Example <SEP> Water-treating <SEP> Turbidity <SEP> of <SEP> treated <SEP> water <SEP> (ppm) <SEP> <tb> <SEP> matellai <SEP> moder <SEP> w@ler. <SEP> After <SEP> After <tb> ----------------------------------------------------------------------------- <SEP> 10 <SEP> hours <SEP> 50 <SEP> hours <tb> ----------------------------------------------------------------------------------- <SEP> 21 <SEP> Material <SEP> of <tb> Example <SEP> 1 <SEP> 21 <SEP> 1.2 <SEP> 0.8 <tb> <SEP> 22 <SEP> Material <SEP> of <tb> Example <SEP> 3 <SEP> 21 <SEP> 1.@ <SEP> 1.@ <tb> 23 <SEP> Material <SEP> of <SEP> 21 <SEP> 0.9 <SEP> 1.2 <tb> <SEP> Example <SEP> 4 <tb> .24 <SEP> Material <SEP> of <SEP> 21 <SEP> 0.8 <SEP> 1.1 <tb> <SEP> Example <SEP> 14 <tb> Example 25: : The water-treating material of the present invention prepared in Example 4 was charged into a column having a diameter of 20 mm to a height of 800 mm, and the model water was allowed to flow through the column. The model water was prepared in the following way. That is, 4 g of a crude oil (Arabian light) and 1 liter of water were stirred together in a mixer for 5 minutes. The mixture was then diluted with water to a volume of 200 & The water-treating material exhibited good behaviour during the back washing; and the back wash developing factor at this moment was 29%. After the back wash has been finished, city water was allowed to flow downwards at a flow speed, of 4 m/hr for 10 minutes and, then the model water was allowed to flow again. The results were as shown in Table 10. Table 10 EMI24.1 <tb> <SEP> Water-treating <SEP> material <SEP> Oil <SEP> content <SEP> of <SEP> treated <SEP> water <SEP> (melt) <SEP> <tb> <SEP> Chtionic <SEP> Nitrogen <SEP> True <SEP> Before <SEP> back <SEP> washed <SEP> After <SEP> back <SEP> washed <tb> <SEP> @@@@@ir <SEP> <SEP> content <SEP> density <SEP> ----------------------------------------- <tb> <SEP> @@@lymer <SEP> (% <SEP> by <SEP> (g/cm3) <SEP> After <SEP> <SEP> After <SEP> After <SEP> After <tb> (% <SEP> by <SEP> weight) <SEP> (g/cm3) <SEP> 50 <SEP> hours <SEP> 100 <SEP> hours <SEP> 50 <SEP> hours <SEP> 100 <SEP> hours <tb> <SEP> weight) <tb> <SEP> 1.6 <SEP> 0.37 <SEP> . <SEP> 1.4 <SEP> . <SEP> 0.9, <SEP> 1.0 <SEP> oils <SEP> 1.0 <tb>

Claims: CLAIMS 1. A granular water-treating material having a crosslinked cationic polymer attached to at least a portion of the surface of a base material. 2. A granular water-treating material according to claim 1, wherein the base material is an organic polymer, a non-carbonaceous inorganic compound or a mixture or a complex thereof. 3. A granular water-treating material according to either of claims 1 and 2, wherein the cross-linked cationic polymer is attached in an amount of 0.1 to 308 by weight on the base material. 4. A process for preparing a granular water-treating material having a cross-linked cationic polymer on at least a portion of base material wherein, a cationic component (At, and a cross-linking agent tB) are reacted together under conditions in which they are mixed together with the base material or in which they are adhered onto the base material, thereby to form a cross-linked cationic polymer adhered to at least a portion of the surface of such base material. 5. A process according to claim 4. wherein the reactants include at least one of a polymerization initiator or a polymer additive. 6. A process according to either of claims 4 or 5 wherein the base material is an organic polymer, a non-carbonaceoos inorganic compound or a mixture or a complex thereof. 7. A process according to any one of claims 4 to 6, wherein the components (A) and (B) are adhered onto the surface of granular base material, then cross-linked to the final cationic polymer adhered to the base material. 8. A process according to claim 7, wherein the components (A) and (B) are adhered to the granular base material while the base material is being fluidized. 9. A process according to claim 7, wherein the components (A) and (B) are adhered to the surface of the granular base material in a solution. 10. A process according to claim 4, wherein the base material and the components (A) and (B) are mixed and thereafter molded in a melt extruder to form a granular material. 11. A process according to claim 10, wherein the base material comprises a non-carbonaceous inorganic powder and an organic polymer and a cross-linking agent end/or a blowing agent. 12. A method of separating oil dispersed in water wherein the dispersion is treated with a granular water-treating material having a cross-linked cationic polymer attached to at least a portion of the surface of a base material.

Inventors: KAWAMURA, TOMIHIKO, MATSUDA, TADASHI, NAKANO, SHINTARO, SUGIMORI, SHUICHI
Applicants: MITSUBISHI RAYON CO. LTD.
Application year: 1982
Main classification: B01D17
IPC codes: B01D17, B01J20, B01D21, C02F1, C09K3