| PATENT ASSIGNEE'S COUNTRY | USA |
| UPDATE | 04.00 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 18.04.00 |
| PATENT TITLE |
Solid-liquid separation using phase transitional N-substituted pyrrolidones |
| PATENT ABSTRACT |
A process is disclosed for flocculating particles in a liquid suspension by mixing the suspension with a pyrrolidone having alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals from 1 to 18 carbon atoms to form a mixture at a temperature above a minimum flocculation temperature for the mixture. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 14.11.97 |
| PATENT REFERENCES CITED |
Flocculation/Dispersion of Suspensions by Controlling Adsorption and Conformation of Polymers and Surfactants, P. Somasundaran and Xiang Yu in Advances in Colloid and Interface Science, 53 1994, Month Unknown pp. 33-49. Adsorption Phenomena at the Surface of Silica Spheres in a Binary Liquid Mixture, D. Beysens and D. Esteve, in Physical Review Letters, May 13, 1985, pp. 2123-2126, vol. 54, No. 19. Wetting on Cylinders and Spheres, M. Gelfand and R. Lipowsky, Physical Review B, Dec. 1, 1987, pp. 8725-8735, vol. 36, No. 16. Specialty Pyrrolidones: Is this the solution you are looking for?, BASF Corporation, Date unknown. Critical Wetting, Flocculation of Silica Particles in Near-Critical Lutidine-Water Mixtures and Related Phenomena, Ernest A. Boucher, J. Chem. Soc. Faraday Trans., 1990, Month unknown, pp. 2263-2267. English Abstract of Savinchuk, Russian Patent No. 2,002,064, Derwent Abstract AN-94-073064, Class A41, week 9409, (WPI). English Language Translation of Russian Patent 2002064, dated Oct. 30, 1993 Applicants disclosed the Russian language version and corresponding English language abstract on Mar. 4, 1998. |
| PATENT CLAIMS |
What is claimed is: 1. A process for flocculating particles in a liquid suspension comprising: mixing the suspension with at least one pyrrolidone having a formula of: ##STR2## where R is a hydrocarbon radical selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals, having from 6 to 18 total carbon atoms; thereby forming a mixture whereby aggregation of the particles in the dispersion is induced by the pyrrolidone; and wherein the mixing occurs at a temperature above a minimum flocculation temperature for the mixture. 2. The process according to claim 1, wherein the liquid comprises water. 3. The process according to claim 2, wherein the particles comprise hydrophobic particles. 4. The process according to claim 3, wherein the particles comprise particles selected from the group consisting of graphite particles and coal particles. 5. The process according to claim 2, wherein the particles comprise hydrophilic particles. 6. The process according to claim 5, wherein the particles comprise kaolinite particles. 7. The process according to claim 1, wherein the concentration of particles in the liquid suspension is from 0.1 to 25 weight percent. 8. The process according to claim 1, wherein R is a hydrocarbon radical selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals having from 6 to 12 carbon atoms. 9. The process according to claim 1, wherein the pyrrolidone concentration of the mixture is from 0.1 to 20 weight percent. 10. The process according to claim 1, further comprising the step of adding a lower consolute temperature modifier selected from the group consisting of electrolytes, acids, and alkalis. 11. A process for flocculating particles in a liquid suspension comprising: mixing the suspension with at least one pyrrolidone having a formula of: ##STR3## where R is a hydrocarbon radical selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals, having from 6 to 18 carbon atoms; thereby forming a mixture whereby aggregation of the particles in the dispersion is induced by the pyrrolidone, and wherein the pyrrolidone is mixed in an amount exceeding the single phase solubility limit of the pyrrolidone in the liquid. 12. The process according to claim 11, wherein the liquid comprises water. 13. The process according to claim 12, wherein the particles comprise hydrophobic particles. 14. The process according to claim 13, wherein the particles comprise particles selected from the group consisting of graphite particles and coal particles. 15. The process according to claim 12, wherein the particles comprise hydrophilic particles. 16. The process according to claim 15, wherein the particles comprise kaolinite particles. 17. The process according to claim 11, wherein the particles are at a concentration in the mixture of from 0.1 to 25 weight percent. 18. The process according to claim 11, wherein R is a hydrocarbon radical selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals having from 6 to 12 carbon atoms. 19. The process according to claim 11, wherein the pyrrolidone is at a concentration in the mixture of from 0.1 to 20 volume percent. 20. The process according to claim 11, further comprising the step of adding a lower consolute temperature modifier selected from the group consisting of electrolytes, acids, and alkalis. 21. A process for flocculating particles in a liquid suspension comprising: mixing the suspension with at least one pyrrolidone having a formula of: ##STR4## where R is a hydrocarbon radical selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals, having from 6 to 18 total carbon atoms; thereby forming a mixture, and heating the mixture to above a minimum flocculation temperature for the mixture whereby aggregation of the particles in the dispersion is induced by the pyrrolidone. 22. A process for flocculating particles in a liquid suspension comprising: mixing the suspension with at least one pyrrolidone having a formula of: ##STR5## where R is a hydrocarbon radical selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals, having from 6 to 18 total carbon atoms; thereby forming a mixture whereby aggregation of the particles in the dispersion is induced by the pyrrolidone, wherein the liquid suspension is at a temperature above the minimum flocculation temperature for the mixture. 23. A process for flocculating particles in a liquid suspension comprising: mixing the suspension with at least one pyrrolidone having a formula of: ##STR6## where R is a hydrocarbon radical selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals, having from 6 to 18 total carbon atoms; thereby forming a mixture whereby aggregation of the particles in the dispersion is induced by the pyrrolidone, wherein the pyrrolidone is at a temperature above the minimum flocculation temperature for the mixture. 24. A process of separating particles from at least part of a liquid suspension, comprising the process of flocculating according to claims 1, 11, 21, 22, or 23, to form at least one floc, and further comprising the step of separating the floc from the mixture. 25. The process according to claim 24, wherein the floc is allowed to settle by gravity before being separated from the mixture. 26. The process according to claim 24, further comprising a step of lowering the floc temperature below the phase transition temperature to reverse the flocculation and to provide a second suspension. 27. The process according to claim 26, further comprising centrifuging the second suspension. 28. A process of recovering at least some pyrrolidone from a pyrrolidone-particle floc, wherein the pyrrolidone has a formula of: ##STR7## where R is a hydrocarbon radical selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals, having from 6 to 18 total carbon atoms, comprising cooling the pyrrolidone-particle floc below a minimum flocculation temperature to form a suspension of particles in a liquid comprising the pyrrolidone; and separating the liquid from the particles to provide a supernatant comprising the pyrrolidone. 29. The process according to claim 28, further comprising steps of: heating the supernatant above a minimum phase separation temperature, thereby forming a pyrrolidone rich phase; and removing the pyrrolidone rich phase. 30. A process of recovering at least some pyrrolidone from a pyrrolidone-particle floc contained in a liquid mixture, comprising in the order recited, the steps of: separating the floc from at least part of the liquid; and the steps according to claim 29. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
BACKGROUND OF THE INVENTION The present invention relates generally to a process for the use of pyrrolidones for concentrating fine colloidal particles from liquid suspensions containing colloidal particles. Control and modification of interfacial properties of colloidal particles in liquid media have long been the subject of a great deal of attention. Controlling the stability and wettability of colloidal dispersions is often the key factor that determines the efficiency of various industrial processes such as effluent treatment and mineral and ceramic processing, and the quality of products such as cosmetics, pharmaceuticals, and foods, as described by P. Somasundaran and Xiang Yu in Advances in Colloid and Interface Science, volume 53, pages 31-49 (1994). Colloidal particles in liquid dispersion media exhibit Brownian motion resulting in frequent collisions. Stability and other dispersion characteristics are affected by the nature of the interactions between the particles during such collisions. When attractive forces dominate, the particles will aggregate and the dispersion may destabilize. When repulsive forces dominate, the system will remain in a dispersed state. Flocculation occurs by concentrating finely divided particles which are suspended in a liquid. Generally, flocculation occurs through the utilization of an inorganic coagulant or organic flocculant that brings the particles together, as described in U.S. Pat. No. 5,330,546, issued to Ramesh et al. Inorganic flocculants, such as alum and iron salts, may be used, however water soluble organic polymers are more commonly used to flocculate particles. Naturally occurring and synthetic polymers are also used as flocculants, especially in the mining industry. The principal natural polymer flocculants, such as starch and guar, are high-molecular weight polysaccharides consisting of a mixture of linear and branched segments. Synthetic polymers have the advantage that they can be tailored to specific applications, resulting in a wide range of commercially available flocculants of varying charge, composition, and molecular weight. The most widely used synthetic coagulants include polydiallydimethylammonium chloride (poly-DADMAC or DADMAC) and condensation polymers of epichlorohydrin and dimethylamine (Epi/DMA). These structures vary greatly in molecular weight. Colloidal silica particles have been found to flocculate in a solution of water and 2,6-lutidine at close to the phase transition or demixing temperature, as described in D. Beysen and D. Esteve, 54 Physics Review Letters 2123 (1985). The flocculation was found to be reversible. Upon lowering the temperature below the lower critical solution temperature, the particles were re-dispersible. This flocculation phenomenon was thought to be caused by capillary condensation, i.e., the coexistence curve being displaced between two particles as a result of wetting, as described in M. P. Gelfand and R. Lipowsky, B36 Physics Review 8725 (1987). Polyvinylpyrrolidones have been used to flocculate kaolinite and montmorillonite, as described by A. M. Gad, M. A. Khattab, W. Kotb and F. F. Assaad, 34 Alexandria Engineering Journal D119 (1995) and S. Smimabayashi, M. Okuda, and M. Nakagaki, 36 Chemical and Pharmaceutical Bulletin 1257 (1988). N-alkyl pyrrolidones have found wide commercial acceptance as non-toxic, aprotic chemical solvents. Similar to other members of the lactam family, pyrrolidones are resonance stabilized by the lactam oxygen and adjacent ring nitrogen. Among many of their advantageous characteristics are solubility in both polar and non-polar solvents and an ability to participate in hydrogen bonding. The properties of pyrrolidones have attracted increasing industrial interest for a wide variety of applications, such as solvents in cleaning printing presses, coating strippers in the electronics industry and formulating agents for many crop protection products, as described in a Technical Brochure, Specialty Pyrrolidones, BASF Corporation, Mount Olive, N.J. 07828. For example, U.S. Pat. Nos. 5,093,031 and 5,294,644, incorporated herein by reference, describe surface active properties of N-alkyl pyrrolidones, such as solubility, wetting, viscosity building, emulsifying and/or complexing. However, the use of N-alkyl pyrrolidones for the concentration of colloidal particles is heretofore unknown. Known flocculants generally suffer from low settling rates, high sediment volume, and a difficulty in reclaiming the flocculant after sedimentation. In addition, many available flocculants are not biodegradable and emit noxious odors. Other disadvantages of a number of available flocculants include high vapor pressure and toxicity. SUMMARY OF THE INVENTION Accordingly, it is an object of the invention to provide enhanced flocculation and/or separation of hydrophobic and hydrophilic fine particles suspended in a liquid media with low settlement volumes. Another object of the invention is to concentrate fine colloidal particles from a liquid suspension using a flocculant which is biodegradable, odor free, has low vapor pressure and low toxicity and is partially or completely miscible with water. A further object of the invention is to concentrate fine colloidal particles from a liquid suspension using a nonpolymeric flocculant which is more effective for solid-liquid separation, provides higher settling rates and lower sediment volume and offers more options for reagent recovery than polymeric flocculants. These and other objects of the invention are obtained by flocculating colloidal particles in a liquid suspension by mixing the suspension with a pyrrolidone defined by the formula: ##STR1## where R is a hydrocarbon radical selected from alkyl, alkenyl, aryl, alkylaryl, and arylalkyl radicals having from 1 to 18 total carbon atoms. As used herein, the term "mixing" includes everything from mere contacting to complete homogenization. The mixture temperature should be above a minimum flocculation temperature for the pyrrolidone and the suspension. In contrast to the use of polymeric flocculants of the prior art, the process of the instant invention uses non-polymeric pyrrolidones as the flocculating agents resulting in substantially more effective flocculation, bigger floc size, higher settling rates, and lower settlement volumes. N-substituted pyrrolidones also have many additional advantages which shall become apparent upon detailed consideration of the invention with reference to the accompanying drawings. DETAILED DESCRIPTION As used herein, the minimum flocculation temperature is defined as the lower temperature at which two liquid phases form in the suspension and pyrrolidone. This minimum flocculation temperature can be approximated by the lower consolute temperature, which is the lowest temperature at which two phases form in the pyrrolidone and the suspending liquid. Preferably, the pyrrolidone concentration exceeds its single phase solubility limit in the mixture. The liquid may be either aqueous or non-aqueous; preferably it is water. The colloidal particles may be either hydrophilic or hydrophobic. Preferred hydrophobic colloidal particles are graphite or coal; preferred hydrophilic particles are kaolinite. Other appropriate particles include zeolites, bentonite, montmorillonite, and other clays; substances containing copper sulfide particles, for example chalcopyrite ore, zinc sulfide particles, for example sphalerite ore, iron sulfide particles, lead sulfide particles, for example galena ore, and nickel sulfide particles; and paint particles, including pigments. Preferably, the concentration of the colloidal particles is from 0.1 to 25 weight percent of the suspension. The optimum concentration of pyrrolidone in the mixture depends on the pyrrolidone, the liquid, the temperature, and the type and concentration of colloidal particles; but preferably the concentration of the pyrrolidone is from 0.1 to 20 weight percent of the mixture. Preferably the value of R is from 4 to 12 carbon atoms, most preferably from 6 to 12 carbon atoms. The flocs may be separated after allowing the them to settle, with or without assistance. The particles may be separated from the flocs by lowering the temperature below the phase transition temperature to reverse flocculation and to provide a suspension from which the particles may be separated by centrifugation. Recovery of the pyrrolidone after separating the particles can be accomplished by raising the temperature to induce phase separation. The pyrrolidone can then be skimmed from the surface. The following specific examples are intended to illustrate certain aspects of the present invention; they are not to be construed as limitations thereof. Alkyl substituted pyrrolidones can be made using the methods described in U.S. Pat. Nos. 5,093,031 and 5,294,644, issued to Login et al., incorporated herein by reference, but in the following examples the alkyl substituted pyrrolidones were obtained from International Specialty Products, Inc. Synthetic graphite powder having a purity greater than ninety-eight percent and an average diameter of 1 .mu.m was obtained from Aldrich Chemical Company. Pittsburgh No. 8 coal of 200 mesh was used in the examples described herein. Well-crystallized Georgia Kaolinite was obtained from the clay depository at the University of Missouri. The Kaolinite described herein had an estimated specific surface area of 9.4 m.sup.2 /g as characterized by nitrogen adsorption. Flocculation was determined using the following procedure: 0.5 gram of solid and a desired amount of water were added into a 15 ml graduated cylinder and the suspension was subjected to ultrasonication for 5 minutes in a Fisher Scientific FS-9 ultrasonic bath for mixing purposes. Following 15 minutes of shaking, a calculated amount of pyrrolidone was added into the suspension to produce a known concentration of pyrrolidone in solution, and the flocculation was then evaluated. The settling rate in centimeters per minute (cm/min) was determined by measuring the descent of the upper interface between the floc and the liquid. The volume of sediment after a given time of settling was also recorded. Phase diagrams of the N-substituted pyrrolidone and the water solutions were obtained in the following manner: 10 ml of pyrrolidone-water mixture of known concentration in a glass vial was placed into a Brinkman Lauda RM 6 water bath and phase separation was visually observed. Temperature was controlled at an accuracy of .+-.0.1.degree. C. Table 1 list data for a phase diagram of cyclohexyl(a), hexyl(b), octyl(c) pyrrolidones mixed with water. TABLE 1 ______________________________________ Data for Phase Diagram of Alkyl Pyrrolidones HP conc., Temp., CHP conc., Temp., OP conc., Temp., volume % .degree. C volume % .degree. C volume % .degree. C ______________________________________ 1.1 43 8 80 0.01 30 2 24 9 60 0.05 10 4.5 20 13 50 0.1 0 8.1 19 20 43 12 19 30 40 18 19 40 43 24 19 60 59 31 20 65 75 38 22 44 24 52 30 63 41 ______________________________________ At laboratory temperatures, cyclohexyl pyrrolidone ("CHP") is fully miscible. Cyclohexyl pyrrolidone and hexyl pyrrolidone ("HP") show two-phase co-existence with lower consolute temperatures (hereinafter "LCT") of 40 and 19.degree. C. respectively. The shape of the co-existence curves for cyclohexyl pyrrolidone and hexyl pyrrolidone are rather flat-bottomed. The complete phase diagram of octyl pyrrolidone ("OP") and water were not determined because the LCT of octyl pyrrolidone apparently falls below the freezing point of that solution. It can be seen from the phase diagrams of pyrrolidones that at a given temperature, the concentration range for the coexistence of two separate phases decreases with an increase in alkyl chain length. The shape of the co-existence curves and LCT can be shifted upon the addition of electrolytes, acids, and alkalis. For example, addition of 1 Molal of NaCl increases the lower consolute temperature of hexyl-pyrrolidone by ten degrees centigrade (10.degree. C.), whereas the lower consolute temperature decreases by thirteen degrees (13.degree. C.) centigrade with the addition of 1 Molal of HCl. |
| PATENT EXAMPLES | This data is not available for free |
| PATENT PHOTOCOPY | Available on request |
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