Abstract:
This invention concerns a method of dewatering sludge comprising adding an effective amount of one or more cellulolytic enzymes and one or more peroxidases to the sludge.

Description:
TECHNICAL FIELD 
     This invention concerns the use of a combination of cellulolytic enzymes and oxidative enzymes to dewater municipal and industrial sludges. 
     BACKGROUND OF THE INVENTION 
     The dewatering of municipal and industrial sludges containing suspended organic solids is typically accomplished by mixing the sludge with one or more chemical reagents in order to induce a state of coagulation or flocculation of the solids which are then separated from the water using mechanical devices such as plate and frame filter presses, belt-filter presses, centrifuges, and the like. 
     For example, in a typical municipal sewage plant, waste water remaining after coarse solids are settled out of the incoming sewage influent is conveyed into a biological clarifying stage, where the dissolved and suspended organic material is decomposed by microorganisms in the presence or absence of air. These processes are referred to as aerobic fermentation and anaerobic fermentation, respectively. 
     The organic matter obtained as a result of this decomposition is largely bound in the form of a mass of microorganisms. This mass is precipitated as an activated sludge. The water may be released into waterways or allowed to seep away in sewage irrigation fields, but the activated sludge must be dewatered prior to disposal. 
     The objective of dewatering processes is to maximize the efficiency of water removal, as decreasing the amount of water retained in the dewatered solids leads decreased transport and disposal costs. Therefore, there is an ongoing need for improved dewatering technologies. 
     Dewatering of biologically-clarified sludges using a hydrolytic enzyme preparation containing cellulases followed by a high molecular weight cationic flocculant is disclosed in European Patent No. 291 665. 
     SUMMARY OF THE INVENTION 
     In its principal aspect, this invention is directed to a method of dewatering sludge comprising 
     i) adding an effective amount of one or more cellulases to the sludge; 
     ii) adding an effective amount of one or more peroxidases to the sludge to form a mixture of water and coagulated and flocculated solids and 
     iii) separating the coagulated and flocculated solids from the water. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The enzyme preparations used in the practice of this invention are commercially available enzymes obtained from microorganism cultures. The preparations may contain a single enzyme or a broad spectrum of enzyme activities. For example, in addition to the cellulolytic enzymes and peroxidases described herein, the enzyme preparations may also contain proteases, glycoproteinases, lipases, alpha-amylases, beta-glucanases, hemicellulases, laminarinases, etc. 
     The cellulolytic enzymes useful in the practice of this invention include one or more cellulases present in the enzyme system that hydrolyzes cellulose to glucose, including endo-1,4-beta-glucanase, exo-1,4-beta-glucanase and 1,4-beta-glucosidase. 
     The peroxidases useful in the practice of this invention are selected from the group of enzymes that use organic hydroperoxides or hydrogen peroxide as the oxidant to oxidize phenols to dimers via oxidative coupling. Representative peroxidases include peroxidases extracted from vegetables such soy bean and horseradish, as well as peroxidases from fruits such as apples and bananas and bacterial and fungal peroxidases. 
     The effective doses of cellulolytic enzyme and peroxidase depend on the properties of the sludge being treated and can be empirically determined by one of skill in the art. In general, the dose of cellulolytic enzyme is from about 20 to about 60 grams, preferably from about 40 to about 60 grams per dry ton of solids. 
     The effective dose of peroxidase is typically from about 17 to about 50 grams, more preferably from about 25 to about 50 grams per dry ton solids. 
     The cellulolytic enzyme and peroxidase are generally available as solutions in water, which can be further diluted. In the process of this invention, aqueous solutions having an enzyme concentration of from about 0.01 to about 100 grams of enzyme protein per liter are typically used. 
     Hydrogen peroxide is required to activate the peroxidase. Dosages of hydrogen peroxide are typically from about 300 to about 1,000, preferably from about 500 to about 1,000 milliliters (based on a 30% aqueous hydrogen peroxide solution) per dry ton of solids. 
     In a typical application, the sludge to be dewatered is warmed to about 30° C. to about 60° C., preferably about 30° C. to about 40° C. with mixing. An aqueous solution of the celluloytic enzymes, prepared as described above is then added. After a period of about 10 minutes to about one hour, an aqueous solution of peroxidase and hydrogen peroxide solution are added together to the mixed sludge. Mixing and heating are then continued for about 2 to about 72 hours, after which the sludge is cooled to ambient temperature and mechanically dewatered for example by devices such as plate and frame filter presses, belt-filter presses, centrifuges, and the like. 
     In a preferred aspect of this invention, the sludge is selected from the group consisting of municipal and industrial sludges. 
     In another preferred aspect, the sludge is a municipal sludge. 
     In another preferred aspect, the sludge is an activated sludge. 
     In another preferred aspect, one or more polymeric flocculants are added to the sludge after the enzyme treatment and before dewatering. 
     Flocculants useful in the process of this invention are typically acrylamide based cationic polymers with the molecular weights in excess of 1 million. The flocculant may be used in the solid form, as an aqueous solution, as water-in-oil emulsion, or as dispersion in water. Representative cationic polymers include copolymers and terpolymers of (meth)acrylamide with dimethylaminoethyl methacrylate (DMAEM), dimethylaminoethyl acrylate (DMAEA), diethylaminoethyl acrylate (DEAEA), diethylaminoethyl methacrylate (DEAEM) or their quaternary ammonium forms made with dimethyl sulfate, methyl chloride or benzyl chloride. 
     The dose of flocculant depends on the properties of the sludge being treated and can be empirically determined by one of skill in the art. In general, the flocculant polymer dose is from about 100 ppm to about 600 ppm, preferably from about 200 to about 600 ppm, based on polymer solids, per dry ton solids. 
     In another preferred aspect, one or more coagulants are added to the sludge after the enzyme treatment. Coagulants useful in the process of this invention are typically polyamines such as epichlorohydrin-dimethylamine having molecular weights in the range of 20,000 to 1 million. 
     In another preferred aspect, the cellulolytic enzyme is a mixture of endo-1,4-beta-glucanase, exo-1,4-beta-glucanase and 1,4-beta-glucosidase. 
     In another preferred aspect, the cellulolytic enzyme is endo-1,4-beta-glucanase. 
     The foregoing may be better understood by reference to the following examples, which are presented for purposes of illustration and are not intended to limit the scope of the invention. 
    
    
     EXAMPLE 1 
     Treatment of Sludge with Enzymes 
     Fresh, anaerobically digested sewage sludge samples (1300 g in the form of a paste or slurry, containing about 26 g of solids) are obtained from midwestern suburban municipal treatment plants. The samples are heated at 40° C. When the temperature of the samples reaches 40° C., a cellulolytic enzyme having only endoglucanase activity (NS51008, 10% aqueous solution, available from Novozymes, North America, Inc., Franklinton, N.C.) is added. The dose of cellulolytic enzyme solution is about 0.17 liters for the treatment of sludge having about one ton solids (oven dried). The sludge with enzyme is well mixed for 10 minutes at 250 rpm and at 40° C. During the mixing, soy bean peroxidase (available from Biocatalytic, Inc, Pasadena, Calif.) is added. The dose of peroxidase is 0.5 mg of enzyme to treat sludge containing 26 grams solids (oven dried). Hydrogen peroxide (10 microliter of 30% aqueous solution) is also added to the sludge to activate the peroxidase. The enzyme treatment of the sludge is continued for about two hours. 
     EXAMPLE 2 
     Drainage Test 
     To perform the drainage test, 200 ml of the enzyme-treated sludge sample of Example 1 is placed in a 500 ml cylinder. Twenty mL of a 0.5% aqueous polymer flocculant solution is added to the sludge and mixed by inverting the cylinder. 
     The number of inversions is dependent upon the particular sludge utilized. Chemical and biological sludges are very fragile and do not require very many inversions before the floc breaks up and the sludge becomes liquid again. How thick the sludge is to begin with will determine the number of inversions. Sludges greater than 8% TSS may need to be diluted 50:50 with water in order to achieve good distribution of the polymer with the sludge. 
     Once a good floc is obtained and the inside of the cylinder is clean (indicating sufficient mixing with no excess of polymer), the sample is poured through a belt filter press cloth and the amount of water drained (in mL) in 20 seconds is utilized as a measure of dewatering effectiveness Flocculated sludge is then poured through a belt filter press cloth and the amount of water (in mL) drained in 10 seconds is utilized as a measure of the polymer performance. The results are shown in Tables 1-3. 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Drainage of an Anaerobic Municipal Sludge with a High Charge 
               
               
                 Flocculant Polymer, with Celluloytic Enzyme and with Celluloytic 
               
               
                 Enzyme and Peroxidase 
               
             
          
           
               
                   
                 Polymer 
                 Polymer + Cellulolytic 
                 Polymer + Cellulolytic 
               
               
                 Polymer Dose 1   
                 Alone 
                 Enzyme 
                 Enzyme + Peroxidase 
               
               
                   
               
             
          
           
               
                 200 
                 14 
                 12 
                 16 
               
               
                 250 
                 18.6 
                 14.2 
                 18.6 
               
               
                 300 
                 23.2 
                 31.5 
                 33.3 
               
               
                 375 
                 38.9 
                 50.3 
                 58.5 
               
               
                 450 
                 63.2 
                 59 
                 83.6 
               
               
                 500 
                   
                 87.8 
                 92 
               
               
                 550 
                   
                 96.6 
                 94.6 
               
               
                   
               
               
                   1 50 mole percent dimethylaminoethylacrylate methyl chloride quaternary salt/acrylamide copolymer, available from Ondeo Nalco Company, Naperville, IL.  
               
             
          
         
       
     
     As shown in Table 1, dewatering efficiency is increased by treatment with polymer and enzymes relative to polymer treatment alone. The data further show that use of cellulase and peroxidase results in a further increase in drainage over treatment with cellulase alone. Treatment of a different sample from the same facility shows similar results. 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Drainage of an Anaerobic Municipal Sludge with a Low Charge 
               
               
                 Flocculant Polymer, with Celluloytic Enzyme and with Celluloytic 
               
               
                 Enzyme and Peroxidase 
               
             
          
           
               
                   
                 Polymer 
                 Polymer + Cellulolytic 
                 Polymer + Cellulolytic 
               
               
                 Polymer Dose 1   
                 Alone 
                 Enzyme 
                 Enzyme + Peroxidase 
               
               
                   
               
             
          
           
               
                 200 
                 7.7 
                 14 
                 10 
               
               
                 250 
                 12.2 
                 16 
                 12 
               
               
                 300 
                 15 
                 16.4 
                 15.4 
               
               
                 375 
                 18.3 
                 22.6 
                 25.7 
               
               
                 450 
                 30 
                 38 
                 39 
               
               
                 500 
                 37.6 
                 43.5 
                 44.8 
               
               
                 550 
                 50 
                 54 
                 60 
               
               
                 625 
                 69.2 
                 69.9 
                 84.4 
               
               
                 700 
                 81.2 
                 78 
                 90.3 
               
               
                 750 
                   
                 99.5 
                 98.4 
               
               
                   
               
               
                   1 10 mole percent dimethylaminoethylacrylate methyl chloride quaternary salt/acrylamide copolymer, available from Ondeo Nalco Company, Naperville, IL.  
               
             
          
         
       
     
     As shown in Table 2, the drainage is higher when sludge is treated with flocculant and a combination of cellulase and peroxidase compared with only flocculant and cellulase. Similar results are obtained when a different batch of sludge from the same facility is tested. 
     
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Drainage of an Anaerobic Municipal Sludge with a Combination of Low Charge and High 
               
               
                 Charge Flocculant Polymers, with Celluloytic Enzyme and with Celluloytic Enzyme and 
               
               
                 Peroxidase 
               
             
          
           
               
                   
                   
                   
                 Polymer A 1  + Cellulase + 
                 Polymer B 2  + Cellulase + 
               
               
                 Polymer Dose 
                 Polymer A 
                 Polymer B 
                 Peroxidase 
                 Peroxidase 
               
               
                   
               
             
          
           
               
                 200 
                 14 
                 7.7 
                 16 
                 10 
               
               
                 250 
                 18.5 
                 12.2 
                 18.6 
                 12 
               
               
                 300 
                 23.2 
                 15 
                 33.3 
                 15.4 
               
               
                 375 
                 38.9 
                 18.3 
                 58.5 
                 25.7 
               
               
                 450 
                 63.2 
                 30 
                 83.6 
                 39 
               
               
                 500 
                   
                 37.6 
                 92 
                 44.8 
               
               
                 550 
                   
                 50 
                 94.6 
                 60 
               
               
                 625 
                   
                 69.2 
                   
                 84.4 
               
               
                 700 
                   
                 81.2 
                   
                 90.3 
               
               
                 750 
                   
                   
                   
                 98.4 
               
               
                   
               
               
                   1 50 mole percent dimethylaminoethylacrylate methyl chloride quaternary salt/acrylamide copolymer, available from Ondeo Nalco Company, Naperville, IL.  
               
               
                   2 30 mole percent dimethylaminoethylacrylate methyl chloride quaternary salt/acrylamide copolymer, available from Ondeo Nalco Company, Naperville, IL.  
               
             
          
         
       
     
     As shown in Table 3, Polymer A (50 mole percent) alone or in combinations with enzymes performed better than Polymer B (30 mole percent). Similar results are obtained when the experiment is repeated using a different batch of sludge from the same facility. 
     In sludge dewatering application synthetic polymers are used. Most synthetic polymers are synthesized using acrylamide monomers known to be neurotoxic. Therefore, their release in environment are regulated. Enzymes are protein and known to be environmentally friendly. Use of enzymes in combination with polymers may help in improving dewatering with simultaneous reduction in polymer dose. This invention discloses the advantages of enzymes with polymers for sludge dewatering and dry solids. 
     Various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. It is therefore intended that such changes and modifications be covered by the appended claims.