Characterization of zirconia-magnesia-yttria materials used as catalysts for esters and alcohols fractions transformations by ketonization

• Autorzy: Klimkiewicz R. , Teterycz H. , Sikora E. , Rakoczy J. , Biskupski A. , Trawczyński J.
• Języki publikacji: EN

Abstrakty

EN

In former publications the application of the monophase material Zr(0.89)-Mg(0.10)-Y(0.01)-O as a catalyst of the waste alcohol and ester fractions ketonization was described. In the present work various compositions of the Zr-Mg-Y-O type respecting the reaction group: Zr(0.89)-Mg(0.10)-Y(0.01)-O(CL) synthesized from chlorides, Zr-Mg-Y-O(SULPH) from zirconium sulfate, mixed oxide ZrO2+Y2O(3BOG) and its derivative Zr-Mg-Y-O(BOG) are characterized. The catalytic properties of the materials were characterized with the use of n-butanol test, isopropanol test, cyclohexene + H2 test as well as TPD NH3, and FT-IR (pyridine) spectroscopy. Zr-Mg-Y-O(SULPH) catalyst obtained from the sulfate precursor, as compared to Zr(0.89)-Mg(0.10)-Y(0.01)-O(CL), revealed a much lower selectivity of the reaction of the primary and secondary alcohols into ketones. The surfaces of Zr(0.89)-Mg(0.10)-Y(0.01)-O(CL) and ZrO2 + Y2O(3BOG) materials, although they contained comparable numbers of the Lewis acidic centers (164 and 126 žmol Py/g, respectively), differed considerably as for the selectivity in the reaction of n-butyl alcohol condensation: ZrO2,+Y2O(3BOG) was not a selective catalyst of the ketonization. Under the conditions of the cyclohexene + H2 test over ZrO2 + Y2O(3BOG) the reaction proceeded towards isomerization and cracking, while Zr(0.89)-Mg(0.10)-Y(0.01)-O(CL) catalyzed hydrogenation. The application of Zr-Mg-Y-O(BOG) material of the lower Lewis acidity (62 žmol Py/g) did not result in the higher selectivity of the ketonization. However, the result of the cyclohexene + H2 test changed. Thus, a considerable number of the Lewis acidic centers (such as ZrO2+Y2O(3BOG) was not the only necessary condition for the bimolecular condensation of the primary alcohols and/or aldehydes or for esters transformation. The search for materials should be conducted towards the syntheses of the catalysts of the dehydrogenation properties and containing in their structure oxygen vacancies which could form the Lewis acidic centers.

Słowa kluczowe

EN

zirconia; magnesia; yttria; Lewis acid centers; bimolecular condensation of primary alcohols; ketones; waste esters; waste alcohols

PL

dwutlenek cyrkonu; tlenek magnezowy; tlenek itrowy; kwas Lewisa; ketony; alkohole odpadowe; estry odpadowe

• Wydawca: West Pomeranian University of Technology. Publishing House
• Czasopismo: Polish Journal of Chemical Technology
• Rocznik: 2005
• Tom: Vol. 7, nr 1
• Strony: 29--32
• Opis fizyczny: Bibliogr. 17 poz., tab., rys.

Twórcy

autor

Klimkiewicz R.

• Polish Academy of Sciences, Institute of Low Temperature and Structure Research, Wrocław

autor

Teterycz H.

• Wrocław University of Technology, Faculty of Microsystem Electronics and Photonics, Wroclaw, Poland

autor

Sikora E.

• Cracow University of Technology, Institute of Organic Chemistry and Technology, Kraków, Poland

autor

Rakoczy J.

• Cracow University of Technology, Institute of Organic Chemistry and Technology, Kraków, Poland

autor

Biskupski A.

• Wrocław University of Technology, Institute of Inorganic Technology and Mineral Fertilizers, Wrocław, Poland

autor

Trawczyński J.

• Wrocław University of Technology, Institute of Chemistry and Technology of Petroleum and Coal, Wrocław, Poland

Bibliografia

• (1) Miura N., Raisen T., Lu G., Yamazoe N., Highly selective CO sensor using stabilized zirconia and a couple of oxide electrodes, Sensors and Actuators B, 1988, 47, 84.
• (2) Teterycz H., Licznerski B.W., Klimkiewicz R., Wiśniewski K., Nitsch K., Zgł. Pat. P 338306, 2000.
• (3) Teterycz H., Licznerski B.W., Klimkiewicz R., Wiśniewski K., Nitsch K., Zgł. Pat. P 338307, 2000.
• (4) Teterycz H., Klimkiewicz R., Grabowska H., CeO2 and stabilized ZrO2 as potential catalysts of waste alcohols ketonization (in Polish), Chem. Inż. Ekol., 2002, 9/5 - 6, 655.
• (5) Teterycz H., Klimkiewicz R., Łaniecki M., The role of Lewis acidic centers in stabilized zirconium dioxide, Appl. Catal. A: Gen., 2003, 249, 313.
• (6) Klimkiewicz R., Teterycz H., Grabowska H., Rakoczy J., Biskupski A., Syper L., Wrzyszcz J., Nitsch K., Wiśniewski K., Licznerski B.W., Zgł. Pat. P 348382, 2001.
• (7) Klimkiewicz R., Biskupski A., Grabowska H., Teterycz H., Rakoczy J., Frakcje alkoholowe z produkcji cykloheksanonu - zagospodarowanie przez ketonizację V Konferencja „Technologie Bezodpadowe i Zagospodarowanie Odpadów w Przemyśle Chemicznym i Rolnictwie, Łukęcin, 2001, Streszczenia, p. 93.
• (8) Klimkiewicz R., Biskupski A., Grabowska H., Teterycz H., Syper L., Rakoczy J., Utilization of alcohol fractions from the production of cyclohexanone by ketonization, Pol. J. Chem. Technol., 2001, 3/3, 10.
• (9) Klimkiewicz R., Grabowska H., Teterycz H., Application of Zr-Mg-Y-O catalyst for ketonization of ester and alcohol type industrial wastes, Pol. J. Environmental Stud., 2003, 12/1, 67.
• (10) Klimkiewicz R., Syper L., Morawski I., Grabowska H., Teterycz H., Biskupski A., waste technical fats as potential source for receiving gemini surfactants. The application of zirconium catalyst at the level of ketonization, in: Chemical Products in Agriculture and Environment, Chemistry for Agriculture - Vol. 3, Górecki H., Dobrzański Z. (Eds.), Czech-Pol Trade, Prague-Brussels-Stockholm, 2002, 102.
• (11) Klimkiewicz R., Morawski I., Syper L., Biskupski A., Teterycz H., Isobutyraldehyde - a potential material for ketonization (in Polish), Przem. Chem., 2003, 82/8 - 9, 608
• (12) Molnár Á., Bartók M., Dehydration of alcohols, in: R.A. Sheldon, H. van Bekkum (Eds.), Fine Chemicals through Heterogeneous Catalysis, Wiley-VCH, Weinheim, 2001, 295.
• (13) Hölderich W.F., Roberge D.M., Dehydrogenati ibid. 427.
• (14) „Zirconium in Catalysis", ed. by P.J. Moles, in: Ca Today, 1994, 20.
• (15) Tanabe K., Yamaguchi T., Acid-base bifunctional catalysis by ZrO2 and its mixed oxides, Catal. Today, 1994 20, 185.
• (16) Datka J., Dehydroxylation of NaHY zeolites studied by Infrared Spectroscopy, J. Chem. Soc, Faraday Trans. I, 1981, 2877.
• (17) Kotsarenko N.S., Shmachkova V.P., Catalytic properties of the thermal decomposition products of Zr(S04)2-H20, Kinet. Katal., 2002, 43/2, 280.