United States Patent 19 Ramesh et al, UNINC 'US005330546A Patent Number: 5,330,546 Tul. 19, 1994 Date of Patent: oy 5) [54] HYDROPHOBIC POLYELECTROLYTE COAGULANTS FOR CONCENTRATING COAL TAILINGS, (75] Inventors: Manian Ramesh, Naperville; Ram A. ‘Venkatadri, South Chicago; Lawerence J. Connelly, Oak Lawn; Jeffrey R. Cramm, Winfield, all of I. Nalco Chemical Company, Naperville, Il 931,828 173] Assignee: [21] Appl. No. [22], Fitea: {51} Int. cs (2) Us.a. ‘Aug. 3, 1992 -. C1OL 9/10; CO2F 1/56 ~~ 44/620; 44/626, 210/734 [58] Field of Search -- 44/620, 626; 210/734 [56] References Cited US. PATENT DOCUMENTS 3,461,163 8/1969 Boothe .. 210/734 4151202 4/1979 Hunter et 524/381 4,855,329 11/1985. Sykes v= 209/5 4,619,669 10/1986 Jones et al 4/821 . 150 130 410 TURBIDITY WU) gy 70 50 0.20 0.65 1 10 4673511 6/1987 4,715,962 12/1987 4720346 1/1988, Richardson etal. Bhattocharyya etal. Fresher et al 4,835,206 5/1989 Farrar et al $869,829 9/1989 Casey cnn 210/735 4906386 3/1990 Vasconcelos etal 210/735 Primary Examiner—Margaret Medley ‘Attorney, Agent, or Firm-—Robert A. Miller; Joseph B. Barrett; Paul D. Greeley ts ABSTRACT ‘A method for concentrating coal tailings which com- prises steps of: feeding the coal tailings to a thickener, treating the coal tailings with a hydrophobic polyelec- trolyte copolymer coagulant which comprises diallyl- dimethylammonium chloride and a more hydrophobic ‘monomer, the coagulant is added tothe coal tailings in fan amount between about 0.05 to about 0.25 Ib/ton; treating the coal tailings with a loeculant in an amount between about 0.05 t0 about 0.25 Ib/ton; discharging substantilly concentrated tailing; and withdrawing substantially clarified liquid from the thickener. 7 Claims, 1 Drawing Sheet 1.55 2.00 2.45 2.90 DOSAGE (PPM) ==-0== POLY (DADMAC) —2— DADHAC/OMAEA. B00 v-+->++ DADHAC/OMAER,BCOUS. Patent July 19, 1994 5,330,546 TURBIOITY (NTU) 0.20 0.65 1.10 1.55 2.00 2.45 2.90 DOSAGE (PPH) ~--0-~~ POLY (DADMAC) —4— DADMAC/DHAEA..BCO sr-O-++- DADMAC/OMAEA.BCQ5,330,546 1 HYDROPHOBIC POLYELECTROLYTE COAGULANTS FOR CONCENTRATING COAL TAILINGS 5 ‘The present invention relates generally to the use of novel hydrophobic polyelectrolyte compositions. as coagulants for coal tailings thickening or concentrating. ‘These polyelectrolyte compositions are preferably hy- drophobically associating copolymers of diallyldime- thylammonium chloride (DADMAC) and either di- methylaminoethylacrylate. (DMAEA) or dime- thylaminoethylmethacrylate (DMAEM). BACKGROUND OF THE INVENTION Cosl is the most abundant natural energy source in the world. A significant portion of the U.S. domestic ‘energy requirements are met by burning coal as a fossil fuel. There are various types of coal found within the USS. ie, anthracite, semi-anthracite, low-volatile bitu- ‘minous coal, medium and high volatile bituminous coal, sub-bituminous coal, and lignite. Coals such as anthra- cite and semi-anthracite typically have high ash and sulfur contents and therefore require beneficiation prior to use ‘The primary purpose of coal beneficiation is to re- duce the incombustible ash content thus enhancing the heat content. Reduction in the ash content results in savings in transportation and ash disposal costs. Sulfur, mainly in the form of purite, is also reduced. ‘Another important economic factor to be considered in coal processing is the recovery and reuse of process water. Water is typically very expensive and there are often limits on total usage. Also, strict environmental controls prohibit or severely limit discharge of process 38 water. Thus, itis imperative that solids be efficiently removed from the process water and water recycled to the process stream, Beneficiation of coal is effected using two primary properties of coal, ic, (1) differences in specific gravity between coal and its impurities, and (2) differences in surface characteristics between coal and its impurities. Since the higher ash content fractions are usually found in the finer coal sizes, some plants only screen out these sizes to beneficiate the coal. However, since the quan- tity of such fine coal is on the rise, even this is treated. ‘A coal beneficiation plant may be broadly catego- rized into specific gravity separation and fine coal treat- ment. In gravity separation, cleaning units make use of the differences in specific gravity between coal and its {impurities to effect separation. Normally, the specific gravity ofthe clean coal is less than its impurities. Some commonly used equipment for gravity separation are: Jigs, heavy medium baths and cyclones, washing tables, water only cyclones and spirals. Fine coal treatment incorporates a flotation cells), clean coal filter and thickener. In the flotation cell, a collector and frother are added to the flotation feed. The collector (e.g., diesel oil #2) selectively imparts hydrophobicity to the coal particles. This increased 60 hydrophobicity makes the air bubbles more likely 10 attach to the coal particles. The frother (e2., an alcohol based product) reduces the surface tension of the air/- water interface, thus making a stable froth. ‘The concentrate (i.e, clean coal) from the flotation 65 cells goes to the clean coal filter and is dewatered. The tailings from the flotation cell go tothe thickener where they are thickened and discharged 2» 2 0 45 0 55 2 ‘The thickener is treated with coagulants and loccu- lants to enhance settling. Typically, the coagulants and flocculants are added at several points along the feed line to the thickener and in different sequences. Coagu- lation is the destabilization by surface charge neutralize- tion of stable negatively charged particles that are in suspension (ie,, settleable or dispersed) through the utilization of inorganic salts or cationic polyelectro- lytes. Flocculation is the aggregation of finely divided particles which are suspended in a liquid through the utilization of an entrapping agent (ie., an inorganic flocculant) or a bonding agent (ic., an organic floccu- lant) that brings the particles together. Although some inorganics, principally alum and iron salts, ae still used as coagulants, water soluble organic polymers are more commonly used as coagulants. Both naturally occurring and synthetic polyphers find use as, coagulants and floceulants in the mining industry. The principal natural polymers used are starch and guar, both of which are high-molecular weight polymers of simple sugars (i. polysaccharides). Starch is a poly- mer of glucose consisting of a mixture of linear (amy: Jose) and branched segments (amylopectin. Synthetic polymers have the advantage that they can be tailored to a specific application. This has resulted in ‘a wide range of commercially available coagulant and flocculants of varying charge, composition, and molec- ular weight. The most widely used synthetic coagulants are _polydiallyldimethylammonium chloride (poly- DADMAC or DADMAC) and condensation polymers of dimethylamine and epichlorohydrin (Epi/DMA). These structures vary greatly in molecular weight and are in the range of 20,000 to 100,000. The present inventors have developed various novel hydrophobic polyelectrolyte copolymers which may be ‘used as coagulants in the thickening process during coal beneficiation. These hydrophobic monomers exhibit improved performance or activity in coal tailings thick- ‘ening than do conventional inorganic and organic coag- ulants. Tn addition to the hydrophobicity, the hydro- phobic monomer used to synthesize the polyelectrolyte ‘copolymers according to the present invention produce copolymers with substantilly higher molecular ‘weights than conventional synthetic DADMAC homo- polymers prepared under the same conditions. Further- ‘more, the incorporation of a quaternary group, such as, benzyl, into the copolymer of the present invention reduces the bulk viscosity of the resultant copolymer relative homopolymers of DADMAC with comparable ‘molecular weights. As such, the hydrophobic polyelec- trolyte copolymers of the’ present invention exhibit ‘higher polymer concentrations than conventional or- ‘ganic coagulants. These hydrophobically associating, copolymers also demonstrate enhanced performance ‘with replacement ratios on the order of 0.45-0.50. ‘The present invention also provides many additional advantages which shall become apparent as described below. SUMMARY OF THE INVENTION ‘A method for concentrating coal tailings which in- clude liquid and colloidal particles. This method com- prises the steps of feeding the coal tailings to a thick- ‘ener; treating the coal tailings with a hydrophobic poly- electrolyte copolymer coagulant which comprises dial- lyldimethylammonium chloride (DADMAC) and a ‘more hydrophobic monomer selected from the group consisting of: quaternized dimethylaminoethylacrylates