ОДЕРЖАННЯ СКЛАДНОЇ МАНГАН-НІКЕЛЬФОСФАТНОЇ КАТАЛІТИЧНОЇ СИСТЕМИ ТА ДОСЛІДЖЕННЯ ЇЇ ДЕЯКИХ ФІЗИКО-ХІМІЧНИХ ВЛАСТИВОСТЕЙ
DOI:
https://doi.org/10.24144/2414-0260.2018.2.65-74Ключові слова:
catalysis, catalyst, heterogeneous oxidation, partial oxidation of n-alkanes, C1-C4–hydrocarbons, ethane, ethylene, phosphatesАнотація
Individual phosphates of manganese and nickel and seven new complex oxide catalytic systems based on manganese phosphate have been synthesized by modifying it with Nі2+ type xMn2P2O7´yNi3(PO4)2 ions with different contents of both phosphates having acidic surface properties. The composition, structure and some physical and chemical parameters of all synthesized samples are investigated. The results of X-ray diffraction analysis of synthesized catalysts have shown that synthesized complex systems based on phosphate of chrome and nickel and roasted at T=393 K are characterized by a fine crystalline or X-ray amorphous state of a solid phase. The solid phase diffraction patterns after the heat treatment at an extreme temperature of 873 K differ significantly from the output and indicate the formation of new crystalline forms of phosphates. It was established that the characteristics of the group of catalysts of the type xMn2P2O7´yNi3(PO4)2 are the constancy of their chemical composition, the wide range of changes in the acidic properties of the surface, the synergistic effect of the modification, the developed specific surface, the small mobility of the oxygen of the crystalline lattice. The positive promotional role of nickel ions in terms of acidity is confirmed. It was established that due to the increase in the content of nickel phosphate in the structure of chromium phosphate, an increase in the total surface acidity of the total surface acidity is observed. In this case, the surface acidity of all synthesized complex catalytic systems xMn2P2O7´yNi3(PO4)2 is significantly higher than in individual phosphates due to their synergistic effect in the structure of synthesized oxide systems. As predicted, on the surface of almost all synthesized systems formed active centers of medium strength and weakly acidic centers. The relationship between the method of preparation, the composition of the oxide catalysts obtained and their physical and chemical parameters are established. The new complex modified acid mangan-nickel-phosphate catalytic systems can be used as effective catalysts for the partial oxidation of hydrocarbons in valuable products in the chemical industry.Посилання
Golodecz G.I. Geterogenno-kataliticheskie reakcii s uchastiem molekulyarnogo kisloroda. Kiev: Naukova dumka, 1977. S. 173 (in Russ.).
Gomonaj V.I. Avtoref. dis. dok. him. nauk: 02.00.04, IFX AN USSR. Kiev, 1990 (in Russ.).
Holub N.P. Avtoref. dis. kand. khim. nauk: 02.00.04, Kyivskyi natsionalnyi universytet im. Tarasa Shevchenka. Kyiv, 1996 (in Ukr.).
Golub N., Gomonay V., Gomonay P., Szekeresh K. Adsorption Science & Technology. 1999, 17(5), 403–406.
Holub Ye.O., Holub N.P., Homonai V.I., Sekeresh K.Iu., Borko V.O., Barenblat I.O. Kinetychni zakonomirnosti partsialnoho okysnennia nyzhchykh vuhlevodniv na fosfatnykh katalizatorakh. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2015, 2(34), 75–79 (in Ukr.).
Holub Ye.O., Holub N.P., Homonai V.I., Sekeresh K.Iu., Borko V.O., Barenblat I.O. Vplyv vidnovlennia poverkhni katalizatoriv na yikh katalitychni vlastyvosti v reaktsii partsialnoho okysnennia n-alkaniv. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2015, 1(33), 58–62 (in Ukr.).
Golodets G.I. Rol kislotnyih svoystv poverhnosti v reaktsiyah geterogennogo kataliticheskogo okisleniya. Kataliz i katalizatoryi. 1980, 18, 66–75 (in Russ.).
Buyanov R.A. Nauchnyie osnovyi prigotovleniya i tehnologii katalizatorov. Kataliz i katalizatoryi. 1998, 151–152 (in. Russ.).
Kochubey D.I. Ispolzovanie kompleksa metodov dlya issledovaniya vyisokodispersnyih katalizatorov. Kataliz i katalizatoryi. 1998, 193–194 (in. Russ.).
Homonai V.I., Holub Ye.O., Holub N.P., Sekeresh K.Iu., Barenblat I.O. Faktory, shcho vplyvaiut na utvorennia kysnevmisnykh spoluk pry okysnenni С1-С2- vuhlevodniv. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2013, 2(30), 76-80 (in Ukr.).
Homonai V.I., Holub Ye.O., Holub N.P., Sekeresh K.Iu. Mekhanizm katalitychnoho okysnennia С1-С2- vuhlevodniv. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2013, 2(30), 84-88 (in Ukr.).
Mirkin L.I. Spravochnik po rentgenostrukturnomu analizu polikristallov. Pod red. prof. Umanskogo Ya. Moskva: Gos. izd-vo fiz.- mat. literaturyi, 1961, S. 860 (in Russ.).
Diller Ya.L. Tablitsyi mezhploskostnyih rasstoyaniy. T.2. Moskva: Nedra, 1966. S. 362 (in Russ.).
Nebola I.I. Rasshifrovka rentgenogramm poroshkov. Moskva: Metallurgiya, 1975. S. 247 (in Russ.).
Staszczuk P., Danielkiewicz T., Klinowski J. The investigations of the adsorbend layers and heterogeneous properties of the MCM-41 molecular sieve using the special thermal analysis method. IV Polish-Ukrainian Symposium “Theoretical and experimental studies of interfacial phenomena and their technological applications”. Lublin, Poland. 1999, Р.51.
Berg L.G. Vvedenie v termografiyu. Moskva: Nauka, 1969. S. 395 (in Russ.).
Berg L.G., Burmistrova N.P., Ozerova N.I., Tsurinov G.G. Prakticheskoe rukovodstvo po termografii. Kazan: Izd-vo Kazanskogo un-ta, 1967. S. 219 (in Russ.).
Nakamoto K. Infrakrasnyie spektryi neorganicheskih i koordinatsionnyih soedineniy. Moskva: Mir, 1982. S. 160 (in Russ.).
Nakamoto K. Atlas infrakrasnyih spektrov fosfatov. Ortofosfatyi. Moskva: Nauka, 1981. S. 247 (in Russ.).
Rubanik M.Ya., Gorohovatskiy Ya.B. Nepolnoe kataliticheskoe okislenie olefinov. Kiev: Tehnika, 1964. S. 35 (in Russ.).
Tanabe K. Tverdyie kislotyi i osnovaniya. Moskva: Mir, 1973. S. 125 (in Russ.).
Zanazzi P.F., Leavens P.B., White J.S. American Mineralogist. 1986, 71, 1224–1228.
Neeraj S., Noy M.L., Cheetham A.K. Solid State Sciences. 2002, 4, 397–404.
Chippindale A.M., Gaslain F.O.M., Bond A.D., Powell A.V. Journal of Materials Chemistry. 2003, 13, 1950–1955.
Lightfoot P., Cheetham A.K., Sleight A.W. Inorganic Chemistry. 1987, 26, 3544–3547.
Stefanidis T., Nord A.G. Acta Crystallographica C. 1984, 40, 1995–1999.
Vartanov A.A., Sekushova H.Z., Mehtiev K.M., Alhazov T.G. Sintez i termicheskie prevrascheniya geksagidrata ortofosfata margantsa. Zhurn. neorg. himii. 1978, 23(3), 616–620 (in Russ.).
Calvo C. Can. J. Chem. 1975, 53, 1516–1520.
Masse R., Guitel J.C., Durif A. Materials Research Bulletin. 1979, 14, 337–341.
Escobal J., Pizarro J.L., Mesa J.L., Rojo J.M., Bazan B., Arriortua M.I., Rojo T. Journal of Solid State Chemistry. 2005, 178, 2626–2634.
Jin Shouwen, Wang Daqi, Gao Xinjun, Wen Xianhong, Zhou Jianzhong Poly. Acta Crystallographica E. Structure Reports Online. 2008, 64(1), m259.
Essehli R., Lachkar M., Svoboda I., Fuess H., El Bali B. Acta Crystallographica E, Structure Reports Online. 2005, 61, 64–66.
Blachnik R., Wiest T., Duelmer A., Reuter H. Zeitschrift fuer Kristallographie. 1979, 149, 20–23.
Jouini A., Dabbabi M., Durif A. J. of Solid State Chemistry. 1985, 60, 6–34.
Escobal J., Pizarro J.L., Mesa J.L., Rojo J.M., Bazan B., Arriortua M.I., Rojo T. J. of Solid State Chemistry. 2005, 178, 2626–2634.
Schegrov L.N., Pechkovskiy V.V., Eschenko L.S. Termicheskaya degidratatsiya Ni3(PO4)2•8H2O. Dokladyi Akademii nauk SSSR. 1969, 184(2), 391–394 (in Russ.).
Massa W., Yakubovich O.V., Dimitrova O.V. A Novel. Solid State Sciences. 2005, 7, 950–956.
Syichev M.M., Komlev V.G. Tverdenie zhelezo-, kobalt- i nikel-fosfatnyih tsementov. Izv. AN SSSR. Neorganicheskie materialyi. 1971, 7(9), 1612–1615 (in Russ.).
Holub N.P., Holub Ye.O., Barenblat I.O., Homonai V.I., Sekeresh K.Iu. Dyferentsiino-termichnyi analiz skladnoi katalitychnoi systemy typu хСо3(РО4)2•уNi3(РО4)2. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2018, 1(39), 83–88 (in. Ukr.)
Homonai V.I. Shliakhy partsialnoho peretvorennia С1-С4 vuhlevodniv. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 1997, 2, 81–86 (in. Ukr.).
Holub Ye.O., Holub N.P., Homonai V.I., Sekeresh K.Iu., Barenblat I.O., Kozma A.A. Doslidzhennia mekhanizmu peretvorennia etanu na deiakykh skladnykh systemakh impulsnym metodom. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2016, 36, 60–64 (in. Ukr.).
Gomonay V., Barenblat I., Golub N., Szekeresh K. The mechanism formation of ethylene and monooxide of carboneum at heterogenous oxidation of ethane. VI Ukrainian-Polish Symposium “Theoretical and experimental studies of interfacial phenomena and their technological applications”. Odessa, Ukraina. 2001, P. 73–75.
Sekeresh K.Iu. Avtoref. dis. kand. khim. nauk: 02.00.04, Instytut fizychnoi khimii AN URSR. Kyiv, 1978 (in. Ukr.).
Homonai V.I., Sekeresh K.Iu., Holub Ye.O., Holub N.P., Barenblat I.O. Osoblyvosti heterohennoho peretvorennia n-alkaniv na deiakykh skladnykh oksydnykh katalizatorakh. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2013, 1(29), 64–66 (in. Ukr.).
Holub Ye.O., Holub N.P., Homonai V.I., Sekeresh K.Iu., Barenblat I.O. Vplyv poverkhnevykh vlastyvostei skladnoi oksydnoi systemy typu хАl2О3.уР2О5 na katalitychnu aktyvnist v reaktsii partsialnoho okysnennia lehkykh vuhlevodniv. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2014, 2(32), 59–63 (in. Ukr.).
Holub Ye.O., Holub N.P., Barenblat I.O., Homonai V.I., Sekeresh K.Iu. Vplyv kontsentratsii etanu ta kysniu na kinetyku partsialnoho okysnennia etanu na deiakykh skladnykh oksydnykh katalizatorakh. Nauk. visnik Uzhgorods'kogo un-tu. Serіya «Khimiya». 2014, 2(32), 64–69 (in. Ukr.).
