Аннотация
Техногенные сточные воды богаты ионами и сульфатами тяжелых металлов, являются обычным явлением, связанным с окислением сульфидов добытых рудных тел и обработанных отходов. Окисленные продукты попадают в водный организм, влияющий на качество воды за счет увеличения содержания металлов, концентрации растворенных солей и снижения потенциала водорода. Воздействие сульфата на окружающую среду ниже, чем растворенные металлы или кислотность, и контроль над сульфатом получил мало внимания во многих регулирующих юрисдикциях. Следует отметить, что литература по удалению сульфатов из техногенных сточных вод сравнительно небольшая, хотя используется и разработано несколько технологий для снижения концентраций растворенных ионов, включая сульфаты. Уровни контроля сульфатов основаны на требованиях предельно допустимых концентраций (ПДК) приблизительно 100 мг/л для промысловых водоемов и рекомендаций по вторичной питьевой воде приблизительно 500 мг/л. Методы удаления сульфатов из техногенных сточных вод подразделяются на два типа: удаление через полупроницаемое мембранное разделение; удаление путем осаждения соли посредством ионного обмена; проницаемый реактивный барьер; биологическое восстановление или образование нерастворимого минерального осадка. В статье представлен обзор основных вариантов удаления сульфатов для техногенных сточных вод, экономическое и техническое сравнение доступных технологий. На основе продемонстрированного сравнения и экономических выгод наиболее перспективными на сегодняшний день являются биологический и реагентные технологии. Эффективным вариантом недорогой и предварительной обработки для сульфата является обработка извести при условии, что концентрация сульфата превышает 2000 мг/л. Наиболее подходящий вариант для удаления сульфата будет определяться специфическими для конкретного участка условиями для конкретной операции добычи.
Ключевые слова
Методы очистки, кислые рудничные воды, сульфат-ионы, обратный осмос, реагентный способ, ионный обмен, биоочистка.
1. Federal Law No. 219-FZ dated July 21, 2014, “On amendments to the Federal Law “On Environmental Protection” and certain legislative acts of the Russian Federation”. (In Russ.)
2. Environmental impact charge: Calculation and collection rules, enacted by the decree No. 255 of the RF Government dated March 3, 2017. (In Russ.)
3. Masloboev V.A. Vigdergauz V.E. et al. Techniques for reducing the concentration of sulfates in mining wastewater. Vestnik Kolskogo nauchnogo tsentra RAN [Bulletin of Kolsky Science Centre of the Russian Academy of Sciences]. 1/2017 (9), pp. 99-115. (In Russ.)
4. Abdrakhmanova R.N., Orekhova N.N., Nefediev A.P. Understanding how to apply a double-action reagent to remove sulfates from the water and obtain an additional product. Sovremennye problemy kompleksnoy pererabotki trudnoobogatimykh rud i tekhnogennogo syrya (Plaksinskie chteniya – 2017): materialy Mezhdunarod. Nauch. Konf. [Current problems in the comprehensive processing of complex ores and manmade materials (Plaksin Readings-2017): Proceedings of the International Science Conference], Krasnoyarsk, 12-15 September 2017. Krasnoyarsk: Siberian Federal University, 2017, 452 p. (In Russ.)
5. Chappelle, F.M. 1993 Groandwater Microbiology and Geochemistry. Prentice-Hall.
6. Emlin E.F. Tekhnogenez kolchedannykh mestorozhdeniy Urala [Technogenesis of the pyrite deposits of the Urals]. Sverdlovsk: Publishing House of the Ural University, 1991. (In Russ.)
7. Shulenina Z.M., Plaul P. Acid drainage. Global Studies: Encyclopedia. Moscow: Raduga, 2003, pp. 440-442. (In Russ.)
8. Dytnersky Yu.I. Reverse osmosis and ultrafiltration. Moscow: Khimiya, 1978, 352 p. (In Russ.)
9. Kucera J. Reverse Osmosis. Industrial applications and processes. 2010, p. 393.
10. Pulles W., Juby G.J.G., and Busby R.W. 1992 Development of the Slurry Precipitation and Recycle Reverse Osmosis Technology for desalination technogenic waste waters. Water Science & Technology, 25, 25 pp.
11. Juby G.J.G. and Pulles W. 1990. Evaluation of Electrodialysis reversal for desalination of blackish mine water. WRC Report 179/1/90.
12. Helfferich F. 1962 Ion Exchange. McGraw-Hill, San Francisco: 624 pp.
13. Adlem C.J.L. 1997 Treatment of sulfate-rich effluents with the barium sulfide process. MSc. thesis. University of Pretoria, South Africa.
14. Adlem C.J.L., Maree J.P., and Pleiss P.Du. 1991. Treatment of sulfate-rich mining effluents with the Barium Hydroxide process and recovery of valuable by-products. In.: 4th International Mine Water association Congress, Ljubljana (Slovenia) – Portschach (Austria), September 1991, pp. 211--221.
15. Frank Yu.A., Lushnikov S.V. Biochemical potential of sulfate-reducing bacteria. Ekologiya i promyshlennost [Ecology and industry], 2006, no. 1, pp. 10-13. (In Russ.)
16. Dill S., Du Preez L., Graff M. and Mare J. 1994 Biological sulfate removal from acid mine drainage utilizing producer gas as carbon and energy source. 5th Internetional Mine Water Congress, September 1994, pp. 631--641.
17. Henze M., Herremoes P., La Cour-Jansen., Arvan E. Ochistka stochnykh vod. Biologicheskie i khimicheskie protsessy [Wastewater treatment. Biological and chemical processes]. Moscow: Mir, 2004. (In Russ.)
18. Morozova K.M. Biological wastewater treatment systems: Design principles. Vodosnabzhenie i sanitarnaya tekhnika [Water supply and sanitary engineering], 2009, no. 1. (In Russ.)
19. Kim M.P., Molodchik G.L. Sposob ochistki stochnykh vod ot sulfat-ionov [Technique for removing sulfate-ions from wastewater]. Patent RF, no. 2236384. Applied: 2003. Published: 2004. (In Russ.)
20. Kim M.P., Molodchik G.L., Agapov A.E., Azimov B.V., Navitny A.M. Sposob ochistki stochnykh vod ot sulfat-ionov [Technique for removing sulfate-ions from wastewater]. Patent RF, no. 2322398. Applied: 2006. Published: 2008. (In Russ.)
21. Kim M.P., Molodchik G.L., Agapov A.E., Azimov B.V., Navitny A.M. Sposob ochistki stochnykh vod ot sulfat-ionov [Technique for removing sulfate-ions from wastewater]. Patent RF, no. 2323164. Applied: 2006. Published: 2008. (In Russ.)
22. Grishin V.P., Makarov O.V., Nekryachenko S.G. Pat. Sposob ochistki stochnykh vod ot sulfat-ionov [Technique for removing sulfate-ions from wastewater]. Patent RF, no. 2559489. Applied: 2014. Published: 2015. (In Russ.)
23. Kim M.P., Molodchik G.L. Sposob ochistki stochnykh vod ot sulfat-ionov [Technique for removing sulfate-ions from wastewater]. Patent RF, no. 2233802. Applied: 2003. Published: 2004. (In Russ.)
24. Nurkeev S.S., Ozerov A.I., Kospanov M.M., Musina U.Sh. Sposob ochistki stochnykh vod ot sulfat-ionov [Technique for removing sulfate-ions from wastewater]. Patent USSR, no. 1724597 A1. Applied: 1989. Published: 1992. (In Russ.)
25. Buchanan J. 1987 Basics of filtration. Water Sewage & Effluent. September 1987; 35-36.
26. Chappelle F.M. 1993 Groundwater Microbiology and Geochemistry. Prentice-Hall.
27. Cravotta C.A. III 1994 Secondary iron-sulfate minerals as sources of sulfate and acidity. In: Environmental Geochemistry of Sulfate Oxidation (eds. C.N. Alpers and D.W. Blowes). American Chemical Society Symposium Series, 550. 1994. 345-364.
28. Du Pleiss G.H. and Swartz J.A. 1992 Tubular Reverse Osmosis treatment of Secunda mine water: a pilot plant investigation. Water Science Technology, 25, 193-201.
29. Du Preez L.A., Maree J.P., and Jackson-Moss C.A. 1992 Biological sulfate removal from industrial effluents. Environmental Technology, 13: 875-882.
30. Eckenfelder W.W. 1989 Industrial Water Pollution Control. McGraw Hill, 400 p.
31. Eriksson P. 1988 Nanofiltration extends the range of membrane filtration. Environmental Progress, 7: 58-62.
32. Everrtt D.J., Du Plessis J. and Gussman H.W. (1994) The removal of salt from underground technogenic waste waters. Mining Environmental Management, March 1994: 12-14.
33. Feng D., Aldrich C., and Tan H. 2000. Treatment of acid mine water by use of metal precipitation and ion exchange. Minerals Engineering, 13(6), 623-642.
34. Geldenhuys A.J., Maree J.P., de Beer M. and Hlabela P. 2001 An integrated limestone/lime process for partial sulfate removal. Proceedings of Environmentally Responsible Mining in South Africa, September 2001. CSIR, Pretoria, South Africa.
35. Gould W.D., Bechard G. and Lortie L. 1994 The nature and role of microorganisms in mine drainage. In: Environmental Geochemistry of Mine Waste, (eds: J.L.Jambor and D.W. Blowes). 185-199, MAC.
36. Gussman H.W. and Nagy P. 1993 The development and operation of the GYPCIX pilot plant, JCI MPRL, Johannesburg, SA, July 1993.
37. Harries R.C. 1985 A field trial of Seeded Reverse Osmosis for desalination of a scaling type mine water. Desalination, 56: 227-236.
38. Juby G.J.G. 1989 Membrane desalination of mine water. WISA Conference. March 1989.
39. Kleinmann R.L.P. and Pacelli R.R. 1991 Biogeochemistry of acid mine drainage. Mining. Engineering, 33, 300-6.
40. Kun L.E. 1972 A report on the reduction of the sulfate content of acid mine drainage by precipitation with barium carbonate. Anglo American Research Laboratories. D/3/W/1.
41. Lorax 2003 A review of sulfate treatment. Report to INAP by Lorax consultants. Electronic document, INAP website.
42. Marree J.P. 1989 Sulfate removal from Industrial effluents. PhD thesis. University of the Orange Free State.
43. Maree J.P., Bosman D.J. and Jenkins G.R. 1989 Chemical removal of sulfate, calcium and metals from mining and power station effluents. Water Sewage and Effluent, 9: 10-25.
44. Marree J.P. and Du Plessis P. 1994 Neutralization of acid mine water with calcium carbonate. Water Science & Technology, 29: 285-296.
45. Marree J.P., Hulse G., Dods D. and Schutte C.E. 1991 Pilot plant studies on biological sulfate removal. Water Pollution Research and Control, part 3. CSIR.
46. Nordstrom D.K. 1982 Aqueous pyrite oxidation and the consequent formation of secondary minerals. In: Acid Sulfate Weathering, 37-56. Soil Science Society of America.
47. Pulles W., Juby G.J.G., and Busby R.W. 1992 Development of the Slurry precipitation and Recycle Reverse Osmosis Technology for desalinating technogenic waste waters. Water Science & Technology, 25. 25 p.
48. Robins R.G. et al. 1997 Chemical, physical and biological interaction at the Berkerley Pit, Butte, Montana. Tailings and Mine Waste 97. 529-541. Balkema, Rotterdam.
49. Robertson A.M., Everett D., Du Plessis P. 1993 Sulfate removal by GYPCIX process following lime treatment. In: SUPERFUND XIV Conference, 30/11-2/12/93, Washington USA.
50. Smit J.P. 1999 The cleaning of polluted mine water. Proceedings of the International Symposium on Mine Water & Environment for the 21st Century, Seville, Spain.
51. Trudinger A., Chambers L.A., and Smith J.W. 1985 Low temperature sulfate reduction: biological versus abiological. Canadian Journal of Earth Sciences, 22, 1910-1918.
52. Trusler G.E., Edwards R.I. Brouckaert C.J., and Buckley C.A. 1988 The chemical removal of sulfates. Proceedings of the 5th National Meeting of the South Africal Institute of Chemical Engineers, Pretoria, W3-0-W3-11.
53. Wilsenbach I. 1986 Cost estimate for barium sulfate reduction. Internal report of the Division of Water Technology, CSIR, 620/2616/6.
54. Abdrakhmanova R.N., Nefedjev A.P., Abdrakhmanov R.N. Overview of methods for removing sulfates from mine waters. Actual problems of mining, 2018, no. 5, pp. 38–43. (In Russ.)