&EPA United States Environmental Protection Agency Industrial Environmental Research - Laboratory Cincinnati OH 45268 Research and Development EPA-600/S2-82-065 August 1982 Project Summary Powdered Activated Carbon Adsorption Isotherms for Selected Tannery Effluents J. Vuceta and K. V. LaConde This project was initiated to gain a better understanding of powdered activated carbon (PAC) addition to secondary treatment of tannery efflu- ents. The purpose of this research was to obtain sufficient bench-scale data to select PACs for full-scale testing. Adsorption isotherms were developed for COO, BOD, TOC, total and specific phenols, oil and grease, and total chromium. Initially, two raw untreated tanning effluents, representing two different tanning subcategories, as classified by EPA, were tested using six individual PACs. Three of these carbons were thus excluded from further testing. The three remaining carbons (i.e., ICI- HDC, ICI-HDH, and Nuchar SA-15) were subsequently tested for the above parameters on eight additional tanning effluents (representing a total of six tanning subcategories). Final comparisons between the in- dividual carbons were performed in terms of their removal efficiencies (at a dose of 0.3 g/L) and ultimate capac- ities, using Freundlich adsorption iso- therms. COD, BOD, and TH A removal efficiencies of any of the three carbons at a dose of 0.3 g/L were found to be up to 30 percent for Tanneries 1,2,4, 5,6,7,8, and 9, while PAC treatment of effluents from Tanneries 0 and 3 resulted in more than 30 percent removal of COD and THA. In terms of ultimate surface capac- ities for COD, BOD, and THA within Tanneries 0, 2,3, 7, and 9. all three carbons exhibited differences equal to or less than one order of magnitude; for Tanneries 1, 4, 5, 6, and 8, differences between ultimate capac- ities were found to be greater than one order of magnitude. The presence and removal by PAC sorption of the four specific chloro- phenols considered in these investiga- tions were examined for Tannery 5 and 7 effluents only. Comparison of the wastewater char- acteristics of the four pairs of tanneries within the same subcategory indicated no similarities in the concentration of wastewater constituents. Analysis of the adsorption data indicated that the PACs have limited ability to bind COD, BOD, TOC, THA, chromium, and oil and grease in tannery effluents. Fur- thermore, there was no apparent cor- relation between final effluent charac- teristics and the nature of the tanning operations. Since data on the removal of specific phenols were insufficient to draw any general conclusions, the relationship between PAC dosage and specific phenols merits further investigation. However, any future related PAC research efforts should be conducted on an effluent-by-effluent basis. This report was submitted in fulfill- ment of Contract Nos. 68-03-2678, WD 7, and 68-03-3028, WA 11. by SCS Engineers under sponsorship of the U.S. Environmental Protection ------- Agency. This report covers the period from April 9, 1979, to December 8, 1981, and work was completed in October 1980. This Project Summary was devel- oped by EPA's Industrial Environmen- tal Research Laboratory, Cincinnati, OH, to announce key findings of the research project that is fully docu- mented in a separate report of the same title (see Project Report ordering information at back). Introduction Background Tanneries are pollution-intensive in- dustrial complexes which generate large volumes of highly concentrated waste- water. In implementing Best Available Technology Economically Achievable (BATEA) and Best Conventional Pollu- tant Control Technology (BCT) limita- tions, the U.S. Environmental Protection Agency (EPA) has recommended the use of powdered activated carbon (PAC) to enhance secondary biological treat- ment. Several studies have shown that when PAC is added to aeration basins, the carbon and microorganisms act synergistically to remove pollutants more effectively than conventional sec- ondary biological treatment systems. The addition of PAC to activated sludge systems has reduced aerator and efflu- ent foam, improved solids settling, in- creased effective digester capacity, adsorbed color, and increased the re- moval of COD, BOD, TOC, and selected organics. Under a separate EPA grant (Grant No. S804504), the A. C. Lawrence Company was to evaluate the effective- ness of adding PAC to its activated sludge system in Winchester, New Hampshire. This project was funded by the Effluent Guidelines Division (EGD) to gain a better understanding of PAC usage for full-scale testing. The devel- opment of adsorption isotherms was initiated under this grant to obtain a sufficient data base from which to select PACs for the full-scale testing program. While the results of these first isotherm tests are covered in a separate report, carbon selection, analytical parameters, and much of the testing protocol were developed during the early stages of the grant. The thrust of the project covered by this report, therefore, was a continua- tion and an expansion of the work started under the A. C. Lawrence grant. In addition, the results of this work were subsequently used to select PACs for the full-scale tests in Winchester. The objectives of this project were: • To develop adsorption isotherms for six individual PACs on two raw, untreated tanning effluents. Par- ameters to be investigated in- cluded COD, BOD5, TOC, total and specific phenols, oil and grease, and total chromium. • To select the three best PACs from the above and develop adsorption isotherms on eight additional tan- ning effluents for the parameters shown. • Based on the adsorption isotherm results, to recommend specific PACs for full-scale testing by the A. C. Lawrence Company. In the full project report, the conclu- sions of this study and the resulting recommendations are given in Sections 2 and 3. Section 4 outlines sampling, analytical, and experimental procedures employed during this study, with more details contained in Appendix B. Section 4 also contains a brief description of adsorption isotherm calculations. The results of this research are presented and interpreted in the form of adsorption isotherms in Section 5. More details on experimental data are given in Appendix A. Costs of PAC addition to biological treatment of tannery effluents, estima- ted from the results discussed in Section 5, are given in Section 6. Finally, for a better understanding of the processes which generate the wastes ultimately sampled. Appendix C provides a brief description of the subcategories within the tanning industry. Conclusions This section presents the conclusions of this study, involving the removal of different constituents from effluents generated by 10 tanneries, using the following six activated carbons: ICI-HDC, ICI-HDH, Nuchar SA-15, Norit FQA, Westates WO-841, and Amoco PX-21. For each tannery effluent, all of the carbons were examined in terms of their respective ultimate capacities and per- cent removals of each constituent at different carbon doses. In the delinea- tion that follows, the term "ultimate capacity" implies the theoretical weight of the constituent adsorbed per unit weight of carbon when the carbon is in equilibrium with the surrounding solu- tion. Ultimate capacities were deter- mined by the lines of best fit through each data set by performing a least squares linear regression using loga- rithms of the data points. Percent ad- sorption at different carbon doses was then calculated from the lines of best fit by using a computer program based on the method of flexible polyhedron search. PAC Initial tests were performed with six activated carbons on Tanneries 0 and 4. The results revealed that Westates WO- 841 and Norit FQA yield low removal efficiencies. These carbons were thus excluded from further testing. Although Amoco PX-21 is'very efficient m the treatment of tannery effluents, it was excluded from further testing, because it is not commercially available. Conse- quently, effluents from the other tan- neries were treated with only three carbons: ICI-HDC, ICI-HDH, and Nuchar SA-15. COD. BOD, and THA The removal efficiencies of any of the three carbons at a dose of 0.3 g/L are illustrated. Removal of COD, BOD, and THA at the above carbon dose (regard- less of carbon type) was found to be up to 30 percent from Tanneries 1, 2,4, 5, 6, 7, 8, and 9, while PAC treatment of effluents from Tanneries 0 and 3 re- sulted in more than 30 percent removal of COD and THA. Numerical values for COD removal efficiencies at a 0.3 g/L carbon dose were found to be in the following ranges: ICI-HDH, 3 to 17 percent; ICI-HDC, 4 to 18 percent; Nuchar SA-15, 7 to 36 percent. For 7 out of 10 cases (Tanneries 1, 2, 3, 5, 6, 7, 8, and 9), all three carbons yielded results that differed only up to 10 percent; for Tanneries 0,4, and 8, however, Nuchar SA-15 accom- plished removals that were 14 to 26 percent higher than those with 1C) carbons. In the case of BOD, all three carbons exhibited similar removal percentages (i.e., within a 10 percent range of difference) in 5 out of 10 cases (Tan- neries 1,3,4,7, and 9). For Tanneries 2, 5, 6, and 8, Nuchar SA-15 yielded 10 to 24 percent higher BOD removals than those accomplished using ICI carbons, while for Tannery 0, ICI carbons yielded 13 to 18 percent better removals than those with Nuchar SA-15. ------- With regard to THA removals, all three carbons yielded comparable results (equal to or less than 5 percent differ- ence) in 8 out of 10 cases (Tanneries 1, 2, 4, 5, 6, 7, 8, and 9). For Tannery 0, Nuchar SA-15 was apparently more effective, removing 11 to 19 percent more THA compounds than ICI carbons. In the case of Tannery 3, however, ICI carbons yielded 28 to 33 percent better THA removals than Nuchar SA-15. In terms of ultimate surface capacities, the following general observations can be made. The highest ultimate capacity for COD removal in Tannery 0 effluent was exhibited by Nuchar SA-15 (0.8 g COD/g carbon), followed by ICI-HDC (0.4 g COD/g carbon), and ICI-HDH (0.15 g COD/g carbon). The ultimate capacities of these carbons for BOD removal were found to be in the follow- ing descending order: ICI-HDC, ICI-HDH, and Nuchar SA-15, ranging from approx- imately 0.3 to 0.4 g BOD/g carbon. Those for THA removal were higher for Nuchar SA-15 and ICI-HDC (0.08 g THA/g carbon) than for ICI-HDH (0.04 g THA/g carbon). For Tannery 1 effluent, ultimate capac- ities of all three carbons for the removal of COD were found to range from approximately 0.9 to 1.3 g COD/g carbon, while those for BOD ranged from 0.75 to 1 g BOD/g carbon. Ultimate capacities for the removal of THA com- pounds, however, were estimated to be lower, ranging from 0.02 to 0.06 g THA/g carbon. For Tannery 2 effluent, the ICI carbons were found to be more efficient for COD removal than Nuchar SA-15, with ulti- mate capacities of approximately 0.6 and 0.45 g COD/g carbon, respectively. In terms of BOD removal, however, ICI carbons were found to be ineffective for this particular effluent, with ultimate capacities ranging from 0.04 to 0.05 g BOD/g carbon; Nuchar SA-15 exhibited an ultimate capacity of 0.4 g BOD/g carbon. Ultimate capacities of all three carbons for THA removal were estimated to be approximately 0.04 to 0.05 g THA/g carbon. In the treatment of Tannery 3 effluent, Nuchar SA-15 exhibited the highest ultimate COD removals (1.2 g COD/g carbon), while those of both ICI carbons were estimated to be approximately 0.6 g COD/g carbon. For BOD removal from this effluent, the experimental data indicated the following ultimate capac- ities: ICI-HDC, 0.09; ICI-HDH, 0.04; and Nuchar SA-15, 0.16 g BOD/g carbon. Ultimate capacities of all three carbons for THA removal were approximately 0.3 to 0.4 g THA/g carbon. At Tannery 4, the highest ultimate capacity for the removal of COD was exhibited by Nuchar SA-15 (1 g COD/g carbon), followed by the two ICI carbons (0.15 to 0.25 g COD/g carbon). Ultimate capacities for BOO removal were esti- mated to be higher for ICI-HDC and Nuchar SA-15 (0.05 to 0.04 g BOD/g carbon, respectively) than for ICI-HDH (less than 0.02 g BOD/g carbon). All three carbons were found to be quite ineffective for THA removal; their ulti- mate capacities ranged from 0.003 to 0.006 g THA/g carbon. Tests with Tannery 5 effluent revealed that Nuchar SA-15 had a slightly higher capacity (0.35 g COD/g carbon) for the removal of COD-contributing com- pounds than the ICI carbons(0.1 to0.2g COD/g carbon). In terms of BOD re- moval, the ultimate capacity of Nuchar SA-15 was estimated to be approxi- mately 1 g BOD/g carbon; those of ICI- HDC and ICI-HDH were 0.3 and 0.07 g BOD/g carbon, respectively. The ulti- mate capacities of all three carbons for THA removal were found to be approxi- mately 0.003 to 0.005 g THA/g carbon. Ultimate capacities of the carbons for the removal of COD from Tannery 6 effluent were estimated to be approxi- mately 0.16 (ICI-HDC), 0.1 (ICI-HDH), and 0.35 g COD/g carbon (Nuchar SA- 15). For BOD removal, ICI-HDC was found to be essentially ineffective with an estimated ultimate capacity of less than 0.03 g BOD/g carbon. The ultimate capacity of ICI-HDH was found to be 0.2 g BOD/g carbon, and that of Nuchar SA-15 was approximately an order of magnitude higher. Ultimate capacities of all three carbons for the removal of THA from this particular effluent were estimated to be in the range of 0.03 to 0.04 g THA/g carbon. The ultimate capacities of the three carbons for the removal of COD from 1:10 dilution of Tannery 7 effluent were estimated to be as follows: ICI-HDC, 0.8 g COD/g carbon; ICI-HDH, 1 g COD/g carbon; and Nuchar SA-15,0.9 g COD/g carbon. Ultimate capacities of all three carbons for BOD removal from the same dilution of Tannery 7 effluent were found to be approximately 1 g BOD/g carbon; those for THA removal ranged from 0.2 to 0.5 g THA/g carbon. At Tannery 8, the experimental data revealed that the ultimate capacities of all three carbons for COD removal ranged from0.7to 1.4 g COD/g carbon; those for BOD removal ranged from 0.09 to 0.9 g BOD/g carbon. Saturation capacities of all three carbons for THA removal were approximately 0.01 g THA/g carbon. For Tannery 9 effluent, the experi- mental data yielded approximate ulti- mate capacities of 0.4 to 0.5 g COD/g carbon for all three carbons. Those for BOD removal were in the range of 0.3 to 0.4 g BOD/g carbon, while those for THA were estimated to be approximately 0.5 g THA/g carbon. It ca'n be generally concluded that within Tanneries 0, 2, 3, 7, and 9, all three carbons exhibited differences in ultimate capacities equal to or less than one order of magnitude; for Tanneries 1, 4, 5, 6, and 8, differences between ultimate capacities were found to be greater than one order of magnitude. The above observations indicate that the removals of COD, BOD, and THA were a function of carbon type and/or effluent characteristics; differences in removals may be attributed to factors such as effluent composition, speci- ation, total concentration of sorbates, competition of sorbates for the available adsorption sites, and carbon surface characteristics. The specific reasons for these differences cannot be determined at the present time. Specific Phenols Four specific chlorophenols were considered in these investigations: pentachlorophenol, 2,4,5-trichloro- phenol, tetrachlorophenol, and 2,4- dichlorophenol. Their presence and re- moval by PAC sorption were examined for Tannery 5 and 7 effluents only. All three carbons essentially removed most of the identified specific phenols from Tannery 5 effluent, but had no observ- able effect on the effluent from Tannery 7. TOO Accountable decreases in TOC con- centrations were observed only at high carbon doses, indicating low efficiencies of all three carbons for the removal of TOC from all effluents tested. Chromium Interpretation of the chromium results was not possible due to the lack of available information on both chemical speciation of chromium and detailed chemical characterization of the respec- tive effluents. » US QOVERNMENT PRINTING OFFICE-1982-559-017/0765 ------- Oil and Grease All of the PACs tested were essentially ineffective with respect to oil and grease removals. Cost Estimates The daily cost for PAC addition at doses of 300 mg/L to an existing biological treatment system at an as- sumed flow rate of 100,000 gal/day was estimated to be approximately $ 125 per day. Higher carbon doses (10 g/L) would increase daily costs up to $4,250 (for carbon only). J. Vuceta and K. V. LaConde are with SCS Engineers, Long Beach, CA 90807. Donald L. Wilson and Brian A. Westfall are the EPA Project Officers/see below). The complete report, entitled "Powdered Activated Carbon Adsorption Iso- therms for Selected Tannery Effluents," (Order No. PB 82-227 786; Cost: $13.50, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield. VA 22161 Telephone: 703-487-4650 The EPA Project Officers can be contacted at: Industrial Environmental Research Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Postage and Fees Paid Environmental Protection Agency EPA 335 Official Business Penalty for Private Use $300 RETURN POSTAGE GUARANTEED 0000329 ------- |