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Современное состояние и проблемы аналитического контроля отработанных автомобильных катализаторов (обзор)


DOI: 10.26896/1028-6861-2017-83-11-05-14

Т. Ю. Алексеева, Ю. А. Карпов, О. А. Дальнова, В. В. Еськина, В. Б. Барановская, Л. Д. Горбатова; № 11 (83), 11.2017

Аннотация:

Отработанные автомобильные катализаторы (АК) занимают особое место среди вторичного сырья, содержащего драгоценные металлы (сырье ВДМ). Точное определение платиновых металлов в отработанных катализаторах имеет очень важное, а зачастую и решающее значение для оценки экономической эффективности процесса утилизации. В настоящей работе приведен обзор описанных в литературных источниках методов анализа отработанных АК, а также представлены методические разработки института «Гиредмет» совместно с центром «АНСЕРТЭКО» при НИТУ «МИСиС» по анализу АК. Основное внимание уделено применению автоклавного и микроволнового разложения для химической подготовки таких трудновскрываемых объектов, как АК. Отражены преимущества анализа АК с применением метода пробирного концентрирования на базе разработок Екатеринбургского завода по обработке цветных металлов. Разработаны и аттестованы атомно-эмиссионные, атомно-абсорбционные и химико-спектральные методики анализа АК, а также намечены пути их дальнейшего совершенствования.

Ключевые слова: аналитический контроль; отработанные автомобильные катализаторы; металлы платиновой группы.

Current State and Problems of Analytical Control of Waste Automotive Catalysts (Review)

T. Yu. Alekseeva, Yu. A. Karpov, O. A. Dalnova, V. V. Eskina, V. B. Baranovskaya, and L. D. Gorbatova

Spent autocatalysts hold a specific place among secondary raw materials containing precious metals. Precise determination of platinum metals in spent autocatalysts (SA) plays a very important role affecting the economic efficiency of the utilization process. We generalize the existing methods of analysis of spent autocatalysts presented in the literature and methodological developments of the Institute «Giredmet» in collaboration with the Center «ANSERTECO» and NUST «MISiS» regarding the same problem. The main emphasis is made on the use of modern tools for chemical preparation of hard-to-break object like spent autocatalysts: autoclave and microwave opening of the samples. The advantages of using the assay concentration method based on the developments of the Ekaterinburg Non-Ferrous Metals Processing Plant for analysis of spent autocatalysts are concidered. The atomic emission, atomic absorption and chemical spectroscopic methods of SA analysis have been developed and certified along with the guidelines of their further improvement.

Keywords: analytical control; spent autocatalysts; platinum group metals.

1. Popova N. M. Catalysts for exhaust gas cleaning vehicles. — Alma-Ata: Nauka, 1987. — 224 p. [in Russian].

2. Overview of the PGM markets 2016. — Johnson Matthey, 2017. — 56 p. [in Russian].

3. Dyachkova A. V., Malutina T. M., Karpov Yu. A., Alekseeva T. Yu. Chemical preparation of samples of dead automobile catalyzers for subsequent determination of platinum, palladium, and rhodium using atomic emission spectrometry with inductively coupled plasma / Inorg. Mater. 2012. Vol. 48. N 14. P. 1272 – 1278.

4. Brown J. A., Kunz F. W., Belitz R. K. Characterization of automotive catalysts using inductively coupled plasma mass spectrometry: sample preparation / J. Anal. Atom. Spectrom. 1991. Vol. 6. N 5. P. 393 – 395.

5. Borisov O. V., Coleman D. M., Oudsema K. A., Carter R. O. Determination of platinum, palladium, rhodium and titanium in automotive catalytic converters using inductively coupled plasma mass spectrometry with liquid nebulization / J. Anal. Atom. Spectrom. 1997. Vol. 12. N 2. P. 239 – 246.

6. Kirichenko A. S., Seregin A. N., Fedyunina N. N., et al. Some methods of determining the content of platinum group metals in spent automotive catalysts and products of their processing / Probl. Chern. Metallurg. Materialoved. 2014. N 1. P. 1 [in Russian].

7. Shaobo Shen, Liang Guishen, Tonglin Pan, et al. Selective adsorption of Pt ions from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion exchange resin Diaion WA21J / J. Colloid Interface Sci. 2011. Vol. 364. P. 482 – 489.

8. Bencs L., Ravindra K., van Grieken R. Methods for the determination of platinum group elements originating from the abrasion of automotive catalytic converters / Spectrochim. Acta. Part B. 2003. Vol. 58. P. 1723 – 1755.

9. Rauch S., Morrison G. M., Moldovan M. Scanning laser ablation-ICP-MS tracking of platinum group elements in urban particles / Sci. Total Environ. 2002. Vol. 286. P. 243 – 251.

10. Vanhaecke F.; Resano M.; Garcia-Ruíz E.; et al. Laser ablation-inductively coupled plasma-dynamic reaction cell-mass spectrometry (LA-ICP-DRC-MS) for the determination of Pt; Pd and Rh in Pb buttons obtained by fire assay of platiniferous ores / J. Anal. Atom. Spectrom. 2004. Vol. 19. P. 632 – 638.

11. Resano M., García-Ruiz E., McIntosh K. S., Vanhaecke F. Laser ablation-inductively coupled plasma-dynamic reaction cell-mass spectrometry for the determination of platinum group metals and gold in NiS buttons obtained by fire assay of platiniferous ores / J. Anal. Atom. Spectrom. 2008. Vol. 23. P. 1599 – 1609.

12. Vanhaecke F., Resano M., Koch J., et al. Femtosecond laser ablation-ICP-mass spectrometry analysis of a heavy metallic matrix: determination of platinum group metals and gold in lead fire-assay buttons as a case study / J. Anal. Atom. Spectrom. 2010. Vol. 25. P. 1259 – 1267.

13. Resano M., McIntosh K. S., Vanhaecke F. Laser ablation-inductively coupled plasmamass spectrometry using a double-focusing sector field mass spectrometer of Mattauch-Herzog geometry and an array detector for the determination of platinum group metals and gold in NiS buttons obtained by fire assay of platiniferous ores / J. Anal. Atom. Spectrom. 2012. Vol. 27. P. 165 – 173.

14. Alekseeva T. Yu., Filichkina V. A., Karpov Yu. A. Innovative research of the department of certification and analytical control in the field of chemical analysis of secondary metal-containing raw materials / Metallurg. 2010. N 5. P. 47 – 49 [in Russian].

15. Wayne D. M. Direct determination of trace noble metals (palladium, platinum and rhodium) in automobile catalysts by glow discharge mass spectrometry / J. Anal. Atom. Spectrom. 1997. Vol. 12. P. 1195 – 1202.

16. Resano M., García-Ruiz E., McIntosh K. S., et al. Comparison of the solid sampling techniques laser ablation-ICP-MS, glow discharge-MS and spark-OES for the determination of platinum group metals in Pb buttons obtained by fire assay of platiniferous ores / J. Anal. Atom. Spectrom. 2006. Vol. 21. P. 899 – 909.

17. Palesskii S. V., Nikolaeva I. V., Koz’menko O. A., Anoshchin G. N. Determination of platinum-group elements and rhenium in standard geological samples by isotope dilution with mass-spectrometric ending / Zh. Anal. Khimii. 2009. Vol. 64. N 3. P. 287 – 291 [in Russian].

18. Asimellis G., Michos N., Fasaki I., Kompitsas M. Platinum group metals bulk analysis in automobile catalyst recycling material by laser-induced breakdown spectroscopy / Spectrochim. Acta. Part B. 2008. Vol. 63. P. 1338 – 1343.

19. Lucena P., Vadillo J. M., Laserna J. J. Mapping of platinum group metals in automotive exhaust three-way catalysts using laser-induced breakdown spectrometry / Anal. Chem. 1999. Vol. 71. P. 4385 – 4391.

20. Compernolle S., Wambeke D., De Raedt I., et al. Direct determination of Pd, Pt and Rh in fire assay lead buttons by laser ablation-ICP-OES: automotive exhaust catalysts as an example / J. Anal. Atom. Spectrom. 2011. Vol. 26. P. 1679 – 1684.

21. Malyutina T. M., D’yachkova A. V., Kudryavtseva G. S., et al. Determination of platinum and palladium in dead catalysts using inductively coupled plasma atomic emission spectrometry after sample digestion by high-temperature fusion / Inorg. Mater. 2010. Vol. 46. N 14. P. 1479 – 1482.

22. D’yachkova A. V., Kirillov A. D., Karpov Yu. A., Alekseeva T. Yu. Decomposition of samples of used ceramic-based automotive catalytic converters in analytical autoclaves with resistive heating / Inorg. Mater. 2013. Vol. 49. N 14. P. 1272 – 1276.

23. D’yachkova A. V., Alekseeva T. Yu., Es’kina V. V., Dal’nova O. A. Platinum, palladium and rhodium finding in metal-based dead automobile catalysts by atomic-emission spectrometry / Tsvet. Met. 2016. N 6. P. 55 – 61 [in Russian].

24. Bina Gupta, Indu Singh. Extraction and separation of platinum, palladium and rhodium using Cyanex 923 and their recovery from real samples / Hydrometallurgy. 2013. Vol. 134 – 135. P. 11 – 18.

25. Ramachandra Reddy B., Raju B., Jin Young Lee, Hyung Kyu Park. Process for the separation and recovery of palladium and platinum from spent automobile catalyst leach liquor using LIX 84I and Alamine 336 / J. Hazard. Mater. 2010. Vol. 180. P. 253 – 258.

26. Sun P. P., Lee M. S. Separation of Pt from hydrochloric acid leaching solution of spent catalysts by solvent extraction and ion exchange / Hydrometallurgy. 2011. Vol. 110. P. 91 – 98.

27. Krishan Kant Singh, Ritesh Ruhela, Amrita Das, et al. Separation and recovery of palladium from spent automobile catalyst dissolver solution using dithiodiglycolamide encapsulated polymeric beads / J. Environ. Chem. Eng. 2015. Vol. 3. P. 95 – 103.

28. Reddy T. Revathi, Meeravali N. N., Reddy A. V. R. Phase transfer catalyst assisted directly suspended droplet microextraction of platinum from geological and spent automobile converter samples prior to HRCS AAS determination / Anal. Methods. 2013. Vol. 5. N 9. P. 2343 – 2351.

29. Resano M., del Rosario Flórez M., Queralt I. T., et al. Determination of palladium, platinum and rhodium in used automobile catalysts and active pharmaceutical ingredients using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sample analysis / Spectrochim. Acta. Part B. 2015. Vol. 105. P. 38 – 46.

30. Potter N. M. Determination of rhodium in platinum-rhodium loaded automotive catalyst material by graphite furnace atomic absorption spectrometry / Anal. Chem. 1978. Vol. 50. N 7. P. 769 – 772.

31. Dal’nova O. A., Shiryaeva O. A., Karpov Yu. A., et al. Direct atomic-absorption determination of platinum, palladium, rhodium in dead ceramic-based autocatalysts / Inorg. Mater. 2010. Vol. 46. N 15. P. 1499 – 1502.

32. Puig A. I., Alvarado J. I. Evaluation of four sample treatments for determination of platinum in automotive catalytic converters by graphite furnace atomic absorption spectrometry / Spectrochim. Acta. Part B. 2006. Vol. 61. N 9. P. 1050 – 1053.

33. Dal’nova O. A., Shiryaeva O. A., Karpov Yu. A., et al. Sorption-atomic absorption determination of palladium and rhodium in used autocatalysts / Zavod. Lab. Diagn. Mater. 2009. Vol. 75. N 8. P. 18 – 22 [in Russian].

34. Eskina V. V., Dalnova O. A., Filatova D. G., et al. Separation and concentration of platinum, palladium and rhodium from exhausted automobile catalysts solutions using heterochain polymer S,N-containing sorbent with subsequent theirs determination by high-resolution continuum source graphite furnace atomic absorption spectrometry / Talanta. 2016. Vol. 159. P. 103 – 110.

35. Van Meel K., Smekens A., Behets M., et al. Determination of platinum, palladium, and rhodium in automotive catalysts using high-energy secondary target X-ray fluorescence spectrometry / Anal. Chem. 2007. Vol. 79. P. 6383 – 6389.

36. Kuzin A. Yu., Zablotskii A. V., Lyamina O. I., et al. An x-ray fluorescence determination of platinum and rhodium in autocatalysts on a ceramic base / Measur. Tech. 2013. Vol. 56. N 9. P. 1088 – 1091.

37. Antonova Yu. V., Bukhryakov V. A., Karpov Yu. A., et al. Direct x-ray fluorescence determination of platinum and rhodium in used ceramic-based autocatalysts / Inorg. Mater. 2014. Vol. 50. N 14. P. 1431 – 1434.

38. Chen Xiaoli, Wang, Wang Yaming, Zhao Yunkun, et al. Comparison and Research of Acid Digestion Technique for Pt, Pd and Rh in Catalysts / Rare Metal Mater. Eng. 2011. Vol. 40. N 10. P. 1867 – 1870.

39. Anran Chen, ShixingWang, Libo Zhang, Jinhui Peng. Optimization of the microwave roasting extraction of palladium and rhodiumfromspent automobile catalysts using response surface analysis / Int. J. Mineral Proc. 2015. Vol. 143. P. 18 – 24.

40. Welz B., Morés S., Carasek E., et al. High-resolution continuum source atomic and molecular absorption spectrometry — a review / Appl. Spectrosc. Rev. 2010. Vol. 45. P. 327 – 354.

41. Resano M., García-Ruiz E. High-resolution continuum source graphite furnace atomic absorption spectrometry: is it as good as it sounds? A critical review / Anal. Bioanal. Chem. 2011. Vol. 399. P. 323 – 330.

42. Resano M., Flórez M. R., García-Ruiz E. High-resolution continuum source atomic absorption spectrometry for the simultaneous or sequential monitoring of multiple lines. A critical review of current possibilities / Spectrochim. Acta. Part B. 2013. Vol. 88. P. 85 – 97.

43. Resano M., Flórez M. R., García-Ruiz E. Progress in the determination of metalloids and non-metals by means of high-resolution continuum source atomic or molecular absorption spectrometry. A critical review / Anal. Bioanal. Chem. 2014. Vol. 406. P. 2239 – 2259.

44. Welz B., Vale M. G. R., Pereira Й. R., et al. Continuum source atomic absorption spectrometry: past, present and future aspects — a critical review / J. Braz. Chem. Soc. 2014. Vol. 25. P. 799 – 821.

45. Resano M., Aramendía M., Belarra M. A. High-resolution continuum source graphite furnace atomic absorption spectrometry for direct analysis of solid samples and complex materials: a tutorial review / J. Anal. Atom. Spectrom. 2014. Vol. 29. P. 2229 – 2250.

46. Ginzburg S. I., Ezerskaya N. A., Prokof’eva I. V., Fedorenko N. V. Analytical chemistry of platinum metals. — Moscow: Nauka, 1972. — 616 p. [in Russian].

47. Simpson L. A., Hearn R., Catterick T. The Development of a High Accuracy Method for the Analysis of Pd, Pt and Rh in Auto Catalysts Using a Multi-Collector ICP-MS / J. Anal. Atom. Spectrom. 2004. Vol. 19. P. 1244 – 1251.

48. Palacios M. A., Gomez M. M., Moldovan M., Morrison G. Platinum-group elements quantification in collected exhaust fumes and studies of catalyst surfaces / Sci. Total Environ. 2000. Vol. 257. P. 1 – 15.

49. Rao C. R. M., Reddy G. S. Platinum group metals (PGM); occurrence, use and recent trends in their determination / TrAC-Trends Anal. Chem. 2000. Vol. 19. N 9. P. 565 – 586.

50. Kylander M. E., Rauch S., Morrison G. M., Andam K. Impact of automobile emissions on the levels of platinum and lead inAccra, Ghana / J. Environ. Monit. 2003. N 5. P. 91 – 95.

51. Dubakin V. A., Zotov V. S., Kuznetsov S. D. Neutralization of exhaust gases of automobile engines. — Moscow: Kompaniya «Ékomash-KN», 2008. — 141 p. [in Russian].

52. Kuz’min N. M., Zolotov Yu. A. Concentration of traces of elements. — Moscow: Nauka, 1988. — 268 p. [in Russian].

53. Markhol M. Ion exchangers in analytical chemistry. Part 2. — Moscow: Mir, 1985. — 280 p. [Russian translation].

54. Simanova S. A., Kukushkin Yu. N. / Izv. Vuzov. Khimiya Khim. Tekhnol. 1985. Vol. 28. N 8. P. 3 [in Russian].

55. Pechenyuk S. I. Sorption-hydrolytic deposition of platinum metals on the surface of inorganic sorbents. — Leningrad: Nauka, 1991. — 248 p. [in Russian].

56. Zolotova Yu. A., Varshal G. M., Ivanova V. M. (eds.). Analytical chemistry of platinum group metals. — Moscow: URSS, 2003. — 592 p. [in Russian].

57. Ginzburg S. I., Gladyshevskaya K. A., Ezerskaya N. A., et al. Guide to the chemical analysis of platinum metals and gold. — Moscow: Nauka, 1965. — 315 p. [in Russian].

58. Fraser J., Beamish F. E., McBryde W. / Anal. Chem. 1954. Vol. 26. P. 495.

59. Akimov V. K. Abstracts of the VI meeting on the analysis of precious metals. — Moscow: 1963. P. 6 [in Russian].

60. Kasikov A. G., Petrova A. M. Processing of deactivated platinum-rhenium catalysts / Khim. Tekhnol. 2008. Vol. 9. N 8. P. 376 – 385 [in Russian].

61. Smirnov I. V., Karavan M. D., Efremova T. I., et al. Extraction of americium, europium, technetium and palladium with phosphorylated calixarenes from nitric acid media / Radiokhimiya. 2007. Vol. 49. N 5. P. 423 – 431 [in Russian].

62. Kalimgulova A. N., Parfenova M. A., Ulendeeva A. D., et al. Sulfides based on tert-dodecyl mercaptan and their extraction properties with respect to palladium (II) and gold (III) / Zh. Prikl. Khimii. 2006. Vol. 79. N 11. P. 1818 – 1821 [in Russian].

63. The successes of analytical chemistry: to the 75th anniversary of Academician Yu. A. Zolotov. — Moscow: Nauka, 2007. — 391 p. [in Russian].

64. RF Pat. No. 2205237. Method for extracting precious and heavy metals from solutions / Dal’nova Yu. S., Kovtunenko S. V., Ivashchenko A. A., Alekseev S. V., Zhirnov B. S.; applicant and owner OOO Nauchno-proizvodstvennaya firma «Pallada»; appl. 08.06.2001; publ. 27.05.2003 [in Russian].

65. Baranovskaya V. B., Alekseeva T. Yu., Mar’ina G. E., et al. Features of analytical control of waste automotive neutralizers containing precious metals / Collection of reports of the III International Scientific and Practical Conference «Materials in the Automotive Industry», June 19 – 20, 2008, Tol’yatti – Samara, Russia [in Russian].