Document 93Owjgy7QBgEzBQ4eYjrONee5

United States Patent [19] Azrak ct al. i'ii 3,928,278 [45] Dec. 23, 1975 [54] COUPLING AGENTS FOR CHRYSOTILE ASBESTOS AND THERMOPLASTIC POLYMERS [75] Inventors: Raymond George Azrak, Whitehouse Station; Fred Harpoth Ancker, Warren Township; Michael Dean Bertolucci, Martinsville, all of NJ. [73] Assignee: Union Carbide Corporation, New York, N.Y. [22] Filed: Nov. 29, 1973 [21] Appl. No.: 420,232 i [52] U.S. CL. 260/40 R; 117/126 AB; 117/126 AQ; 117/161 L; 260/37 N; 260/37 EP; 260/37 PC; 260/37 R; 260/42.14 [51] Int CL*..................... C03C 25/02; C0SK 3/34 [58] Field of Search..... 260/38, 37 PC, 37 N, 40 R, 260/42.14, 37 R, 37 EP; 117/126 AB, 126 AQ, 161 L [56] 2,653.886 References Cited UNITED STATES PATENTS 9/1953 Gentle et al..................... 117/161 L 3,003,990 3,039,894 3.519.593 3.519.594 10/1961 Umland et al........................... 260/38 6/1962 Raphael et al................ 117/126 AB 7/1970 Balger..................................26C/42.14 7/1970 Michael*............................ 260/42.47 FOREIGN PATENTS OR APPLICATIONS 1,287,166 8/1972 United Kingdom Primary Examiner--Donald E. Czaja Assistant Examiner--S. M. Person Attorney, Agent, or Firm--John S. Pisciteilo [57] ABSTRACT There is disclosed a novel class of coupling agents for chrysotile asbestos and thermoplastic polymers. The coupling agents comprise certain phenolic materials, and their use as coupling agents in chrysotile asbestosreinforced thermoplastic polymers serves to impart, at relatively low cost, a unique and valuable combination of properties to the said reinforced polymers. Pre ferred coupling agents are illustrated by 2.6-dimethylol-4-alkylphenols and oligomers and polymers thereof. 17 Claims, 1 Drawing Figure A08343 United States Patent Office 3,224,985 Patented Dec. 21, 19SS 12 While not wishing to be limited to the geographic deposit 3,224,965 WATER AMD WASTE TREATMENT Robert C. Woolery, Monroe, M.Y., assignor to Union Carbide Corporation, a corporation of Mew Yorlt at Coalinga, California, the type of asbestos recovered from ore such as found there is preferred in the present invention. This type of asbestos, i.e. having the proper No Drawing. Filed Sept. 10, 1963, Ser. No. 307,731 5 ties shown in Table I above, is intended wherever the 7 Claims. (Cl. 210--24) term "Coalinga-type" asbestos is used throughout the dis closure. This invention reiatss to a process for removing un WATER RETENTION desirable suspended and colloidal solid matter from liquids, especially from aqueous liquids. More particu 10 The water retention of the chrysotile asbestos is deter larly, the invention relates to a process for clarifying mined by taking 20 grams of dry opened chrysotile as water and removing solids from waste liquids by contact bestos fiber, slurrying the fiber in 500 ml. of water and ing such water and waste liquids with opened chrysotile asbestos. Water that is to be used for human consumption, home pouring the slurry onto a Buchner funnel provided with a disc of filter paper 6 inches in diameter. The slurry 15 is then filtered through the filter paper while maintain cooking and the like desirably should be clear for aesthetic ing a reduced pressure of 27 inches of mercury below the reasons as well as for health reasons. Colloidal and dis filter paper until the filtrate flowing from the stem of persed mineral and organic matter can affect the color, the Buchner funnel changes from a solid stream to drop- odor or taste of the water. Water that is to be used for industrial processes should be substantially free of col wise flow. The wet asbestos filter cake and filter paper 20 are then weighed. The tare weight of dry asbestos and loidal and suspended mineral and organic matter. Such contaminating materials can form objectionable scale in boilers and process piping as well as undesirably color the water. Waste liquid effluents from municipal sewage treatment plants and industrial processes should desirably contain minimum amounts of suspended and colloidal dry filter paper is then subtracted therefrom to compute the weight of water retained per 20 grams of asbestos. Distinctive Coalinga-type chrysotile asbestos useful ia the present invention must have a water retention of greater 25 than about 34 grams of water per 20 grams of asbestos or greater than about 1.7 grams of water per gram of asbestos. solid matter. It has now been found that aqueous liquids can be OIL ADSORPTION purified through removal of substantially all of any sus pended and colloidal material by contacting such liquids 30 A 5 gram sample of dry' opened chrysotile asbestos is placed in a 500 ml. mortar. Di-octyl phthalate (DOP) with opened chrysotile asbestos. The suspended and col is added dropwise from a graduated burette to the as loidal material are, retained by the asbestos and the so- bestos in the mortar. The resulting mixture is ground purified aqueous liquid can then be easily separated from between the mortar and a pestle until sufficient DOP has the asbestos!' The'term "opened" refers to asbestos that has been at least partially broken up into individual 35 been added to cause formation of a paste that adheres to the pestle. The end point is taken at the time when all asbestos fibrils or small clusters of fibrils. Such opening of the asbestos-DOP mixture adheres to the pestle. Dis can be accomplished by mechanical means, such as a tinctive Coalinga-type chrysotile asbestos useful in the hammer mill. It is preferred that the opened asbestos present invention must have an oil adsorption greater employed in the present invention be in the short fiber 40 than about 1.4 milliliters DOP per gram of asbestos form having certain distinctive characteristics. This pre (greater than 0.7 grams DOP per gram of asbestos). ferred distinctive chrysotile asbestos, which for purposes of convenience will hereafter be referred to as "Coalinga- SPECIFIC SURFACE AREA type" asbestos, has the following properties in the dry The specific surface area of the dry opened asbestos form wherein the values are measured on chrysotile as 45 is measured conveniently by the Brunauer-Emmett-Teller bestos that has been opened, for example, by one pass (BET) method, using nitrogen. A sample of convenient through a laboratory size Mikropulverizer employing a size, such as 1-5 grams, is heated to about 250 C. under screen with 0.046-in. slots. pressure of less than 1 micron mercury for about 16 hours TABLE t Prior Art Chrysotile Asbestos ConllneaType Asbestos to drive off adsorbed gases and moisture. The sample 50 in its evacuated condition is then cooled to liquid nitrogen temperature. A measured amount of nitrogen gas is admitted to the sample chamber and the system allowed to come to equilibrium. The remaining gas is determined Water Retention (gm. watcr/jm. asbestos)----Oil Adsorption (pm. DOI'/jm. asbestos)......... l. 8--1. 7 0. 4-0. 5 1&-S0 9. J-9. 9 from temperature and pressure measurements. The dif 0.8-0.5 55 ference is the amount of nitrogen adsorbed by the sample. eo-so This is repeated at several adsorption pressures in order to obtain an isotherm. The isotherm data are then plotted The asbestos material preferred in the present inven and the surface area of the sample calculated by well tion is obtained from a deposit located near Coalinga, known techniques. This method is further described in California. This is a newly found deposit believed to be 60 "Physical Methods and Chemical Analyses," W. G. Berl, the largest single asbestos deposit in the world. Asbestos vol. 2. pp. 278, 301 (1951), Academic Press, New York. mined at this location is short tibered chrysotile asbestos Distinctive Coalinga-type chrysotile asbestos useful in the and would be classified between grade 5 and grade 7 present invention must have a specific surface area greater according to the Canadian Standards Classification. than about 35 square meters per gram. Coalinga asbestos, however, has a much more uniform 05 The distinctive Coalinga-type chrysotile asbestos use distribution of individual fiber lengths and diameters than ful in the present invention can be obtained in various do comparable grades of Canadian chrysotile asbestos. In addition, the surface area of Coalinga asbestos is sub ways. In general, bulk chry sotile asbestos can be broken up mechanically and then separated by well known clas stantially greater than that of any other type of asbestos. sification techniques into a fraction having the above As can be seen from the above table, refined asbestos 70 desired characteristics. Such classification can take place obtained from the Coalinga deposit has properties which in dry processing procedures employing gases to aid in are substantially different from any prior art asbestos. separation or in wet processing procedures employing ,3 224,963 3 liquids to aid in separation. If desired, asbestos disper Aminco light scattering photometer. This value corre sion techniques may also be employed. Such dispersion sponds to the constant "k" in the equation; ///,,= techniques are described, for example, in British Patent where /h--initial light intensity, /slight intensity after No. 562,161 relating to mechanical wet dispersion and passing a distance "f" through a liquid. To this tap U.S. Patent Nos. 1,607,616; 2,626,213; 2,652,325 and 5 water was added 15 ml. of a water dispersion of asbestos 2,661,287 relating to chemical wet dispersion. Chrysolite containing 0.1 weight percent asbestos (about 0.015 gram) asbestos obtained from various raw material locations having the above-described distinctive characteristics. are useful in the present invention as long as the asbestos This asbestos dispersion was obtained by agitation of has the preferred distinctive properties. Typical short- a water-asbestos mixture containing lxlO"* gram moles fiber chrysolite asbestos per se does not have the above 10 of FcClj per gram of asbestos, such mixture having a preferred distinctive properties. Asbestos obtained from pH of 2.5 to 5. The asbestos dispersion and tap water deposits located near Coalinga, California is especially were stirred together for 5 minutes at 25* C. Sodium useful in the present invention because such deposits con carbonate was then added in an amount to raise the pH tain a high proportion of short-fiber.chrysotile asbestos to a value greater than 7 which caused flocculation of having the preferred distinctive properties. 13 the asbestos. The tap water was then separated from This invention can be employed to remove particulate the asbestos by gravity filtration. The filtrate had a solids from aqueous solutions as well as remove organics, turbidity of 15 as measured by the above method. A oils and non-biologically digestible material. The latter blank was run on the turbidity before and after filter contaminant is a special problem for waste treatment. ing and sodium carbonate addition and no change in Municipal sewage and waste treatment processes, as well 20. turbidity was noted. as the natural purifying action of streams and lakes, rely to a great extent on biological degradation of contaminat Example 2 ing material into non-harmful forms. Certain surface- Colloidal silica was added to 200 ml. of water until active materials and other chemicals used for domestic the turbidity as measured by an Aminco photometer was and industrial applications are not biologically digestible 23 470. To this mixture was added 0.015 gram of dis and their presence in waste effluents can seriously harm the persed asbestos prepared in the manner described in biological balance of streams and lakes as well as create Example 1 above. Additional FeClj was added to the a health hazard. Asbestos has been found useful to re mixture to form a 0.0005 molar solution. The FeClj duce the amount of non-biologically digestible material in tends to increase the electropositive charge on the sur- aqueous liquids. Asbestos can also neutralize dilute acids 30 face of the asbestos. The resulting mixture was slowly which may be present. stirred for five minutes and the pH adjusted between While not intending to be limited thereby, it is be 7 and 8 by addition of sodium carbonate. The result lieved that the asbestos purifies the aqueous liquids in the following manner. The electropositive surface charge ing mixture was allowed to stand for five minutes and then filtered through No. 41 grade filter paper. The on the asbestos fibrils attracts the generally electronega- 33 filtrate had a turbidity of 10. A blank was run on the tively charged suspended and colloidal solid matter and turbidity before and after sodium carbonate addition thus withdraws such matter from the liquid. The high absorbency aids in removing oils and other organics, in plus filtration and the turbidity decreased slightly from 470 to 430. cluding non-biologically digestible material. The nor ,, mally alkaline nature of asbestos aids in neutralizing dilute 40 Example 3 acids. The asbestos fibrils also can have a filtering action on the liquid to further aid in solids removal. Powdered kaolin clay was added to 200 ml. of water until the turbidity was 1980 as measured by Aminco The process of the present invention can be carded photometer. To this suspension was added 0.015 gram out in various ways. The liquid to be treated can be of dispersed asbestos prepared in the manner described passed through a bed of opened asbestos to form a puri 45 in Example 1 above. The resulting mixture was stirred fied effluent leaving the contaminants behind in the and the pH adjusted to a value above 7 by the addition asbestos bed. Alternatively, the liquid to be treated could of sodium carbonate solution. The resulting mixture be mixed with opened asbestos and the purified liquid was then filtered by gravity through No. 41 grade filter separated from the asbestos by filtration, by settling and paper. The filtrate had a turbidity of 17. A blank decantation, or by flotation removal of the asbestos. The 50 was run on the turbidity before and after sodium car asbestos purification process can be used alone to treat aqueous liquids or it can be used in conjunction with other purification treatments. For example, alum can bonate addition plus filtration and the turbidity decreased slightly from 1980 to 1870. The above examples clearly show that opened asbestos, be used to coagulate suspended matter and then the and especially dispersed asbestos having distinctive char- asbestos can be used to remove last traces of suspended 55 acteristics, can remove substantially all suspended and matter plus organics from the supernatant liquid. The colloidal particulate matter from cloudy water. asbestos can also be used in admixture with flocculating The present invention is also useful for purifying in agents, such as alum. Asbestos can- also be used either dustrial wastes, such as aqueous effluent from chemical as a pretreatment or post-treatment for activated sludge and food processing plants. It can also be used for sewage and waste treatment processes. The amount of go clean-up of the "white-water" from paper mills. A dis asbestos necessary to carry out the present process is not persion of distinctive asbestos in water having a 2 weigh: critical. It is preferred that the asbestos be present in percent asbestos solids content was used to treat in an amount sufficient to remove substantially all suspended dustrial wastes. Asbestos in amounts of at least about and colloidal matter from a given amount of aqueous 30 p.p.m. (parts by weight asbestos per million parts liquid to be treated. Such amounts of asbestos can 55 by weight waste liquid) substantially reduced the sus be readily determined by one skilled in the art of water pended solids content of the waste liquids. When used clarification and waste treatment. in combination with other treating materials, such as The invention is described in more detail with respect alum, the suspended solids content of waste liquids was to the following examples. reduced about 75 percent. 70 The following example describes use of asbestos in Example I combination with flocculating agents, such as organic flocculating agents, for the purification of aqueous in Water clarification was carried out in a 500 ml. glass dustrial wastes. Flocculating agents useful with asbestos beaker in which 200 ml. of tap water was ndJed. The arc well known in the art and arc exemplified by alum, tap water had a turbidity of 40 as determined by an 73 polyacrylamide and the like. A0835I 3,224,965 6 3. A process as claimed in claim 1 wherein the floc One liter of aqueous furnace dust slime from a steel culating agent is polyacrylamide. mill containing about 3500 p.p.m. solids (solids parts 4. A process for purifying an aqueous liquid by remov per million parts of liquid by weight) was placed in a ing suspended and colloidal matter therefrom which com one liter cylinder. The aqueous industrial waste was 5 prises contacting an impure aqueous liquid containing agitated with a plunger. During agitation 2 p.p.m. suspended and colloidal matter selected from the class '(parts by weight per million parts by weight of aqueous consisting of mineral and organic materials with chrysotile industrial waste) of Separan 2610. a polyacrylamide floc asbestos characterized by a specific surface area greater culating agent marketed by The Dow Chemical Co., was than 60 m.s/gm., a water retention greater than 1.7 grams added followed by 50 p.p.m. of opened chemically dis 10 of water per gram of asbestos, and an oil adsorption persed asbestos (parts asbestos per million parts of indus greater than 0.7 gram of dioctyl phthalate per gram of trial waste by weight). The asbestos was added in the form of an asbestos-water slurry containing 10 grams of .dry opened distinctive asbestos Fr lirer of slurry. Agita tion was continued for one minute. The treated industrial waste was allowed to stand without agitation for 20 minutes. The supernatant clear liquid was decanted and 'its light transmission properties were measured by well 15 asbestos, whereby the suspended and colloidal matter are retained by said asbestos, and then separating said asbestos and retained matter from the sopurified aqueous liquid. 5. A process for purifying an aqueous liquid by remov ing suspended and colloidal matter therefrom which com prises contacting an impure aqueous liquid containing -known techniques; Using the light transmission of dis tilled water as a standard of 100 percent, the clear liquid obtained above had a light transmission of 94.5 percent. If untreated furnace dust slime is allowed to settle for 20 minutes, the supernatant liquid has a light transmission of only about 28 percent. This clearly shows the im 20 suspended and colloidal matter selected from the class consisting of mineral and organic materials with opened Coalinga-type chrysotile asbestos characterized by a spe cific surface area greater than 60 m.3/gm., a water reten tion greater than 1.7 grams of water per gram of asbestos, and an oil adsorption greater than 0.7 gram of dioctyi proved clarification that is obtained by the combination 25 phthalate per gram of asbestos, whereby the suspended of asbestos and a flocculating agent. Such clarification is and colloidal matter are retained by said asbestos, and an improvement over the results obtained by either asbestos or flocculating agent used alone. The asbestos then separating said asbestos and retained matter from the so-purifled aqueous liquid. also results in flocculated material which is more stable and more resistant to dispersion by agitation than that 30 6. A process as claimed in claim 4 wherein the impure aqueous liquid has a cloudy appearance. obtained by prior art flocculating agents without the presence of opened chrysotile asbestos. 7. A process as claimed in claim 5 wherein the impure aqueous liquid has a cloudy appearance. The above examples all employed opened chrysotile References Cited by the Examiner asbestos that has been chemically dispersed in water suspension. It should be understood that other forms of 35 UNITED STATES PATENTS opened chrysotile asbestos which have not been chem 1,364,337 1/1921 Landreth............................ 210--*2 ically dispersed are also useful in the present invention. 2,158,954 5/1939 Zigerli................................ 210--17 What is claimed is: 2,593,125 4/1952 Eaton et al.__________ 252--315 1. A process for removing suspended and colloidal 40 2,661,237 12/1953 Barbaras 252--313 matter from aqueous liquids which comprises contacting _OTHER REFERENCES an impure aqueous liquid with a flocculating agent and opened Coalinga-type chrysotile asbestos to flocculate Dow: Separan 2610 in Waste and Sewage Treatment, and retain the suspended and colloidal matter, wherein a publication of The Dow Chemical Co., Midland, Mich., said asbestos is characterized in the dry form by a specific October 1956, 16 pp. and 7 additional pp. appendix, surface area greater than 60 square meters per gram, a 45 pp. 1-5 and 13 particularly relied on. water retention greater than 1.7 grams of water per gram of asbestos, and an oil adsorption greater than 0.7 gram of dioctyl phtbalate per gram of asbestos, and then sepa Liu: Asbestos as Filter Aid in Sugar Refining, Ind. and Eng. Chem., vol. 33, May 1946, pp. 521-524. Pundsack: The Properties of Asbestos, I. Phys. Chem., vol. 59 (1955), pp. S92-S95. rating the asbestos, flocculating agent and retained matter 50 Rosa to: Asbestos, Its Industrial Applications, 1959, from the so-purifled aqueous liquid. Reinhold, New York, pp. 41 and 135 relied on. 2. A process as claimed in claim 1 wherein the floc culating agent is alum. MORRIS O. WOLK, Primary Examiner. A 08352