The palladium component influence on the catalytic activity of a catalyst was investigated based on transition-metal oxides deposited on α-Al2O3 carrier in the process of hydrocarbon catalytic thermal destruction. It has been determined that the value of surface concentrations of PdO deposited on Co3O4 doesn’t effect on the achievable conversion degree when using the obtained catalytic converter. It is suggested that PdO facilitates the interfacial diffusion of atomic oxygen on the catalyst oxide component due to support it in an oxidized state. Adsorbed on palladium oxygen migrates on cobalt oxide in the composition of this catalyst. At the expense of this process oxygen passivation of Pd-Co3O4/γ-Al2O3 catalyst is overcome and its high reaction activity is ensured. Our research is evidence that Co3O4 performs the role of active centers on a corundum carrier in the reaction of catalytic thermal hydrocarbon oxidation. Additionally injected PdO into the catalyst composition promotes to the cobalt phase enrichment by oxygen

Ponomarenko, A.

Saipov, A.

Satayev, M.

Ved, V. E.

Electronic National Technical University &quot;Kharkiv Polytechnic Institute&quot; Institutional Repository (eNTUKhPIIR)

Ponomarenko A., Ved V., Satayev M., Saipov A. PdO Impact on the Activity of Hydrocarbon Oxidation with Oxide Catalysts   36 Industrial Technology and Engineering. 2016, 2(19): 36-42  PdO IMPACT ON THE ACTIVITY OF HYDROCARBON OXIDATION WITH OXIDE CATALYSTS  Ponomarenko A.1, Ved V.1, Satayev M.2, Saipov A.2  1 National Technical University “Kharkiv Polytechnic Institute” 2 M.Auezov South Kazakhstan State University, Shymkent, Kazakhstan  E-mail: ponomarenko.anna@mail.ru  ABSTRACT   The palladium component influence on the catalytic activity of a catalyst was  investigated based on transition-metal oxides deposited on α-Al2O3 carrier in the process of hydrocarbon catalytic thermal destruction. It has been determined that the value of surface concentrations of PdO deposited on Co3O4 doesn’t effect on the achievable conversion degree when using the obtained catalytic converter. It is suggested that PdO facilitates the interfacial diffusion of atomic oxygen on the catalyst oxide component due to support it in an oxidized state. Adsorbed on palladium oxygen migrates on cobalt oxide in the composition of this catalyst. At the expense of this process oxygen passivation of Pd-Co3O4/γ-Al2O3 catalyst is overcome and its high reaction activity is ensured. Our research is evidence that Co3O4 performs the role of active centers on a corundum carrier in the reaction of catalytic thermal hydrocarbon oxidation. Additionally injected PdO into the catalyst composition promotes to the cobalt phase enrichment by oxygen.  Keywords: gas emissions, catalytic conversion, catalyst unit, hydrocarbon conversion, transition-metal oxides, palladium oxide.  INTRODUCTION Platinum group metals are widely used as catalysts in the chemical industry (ammonia oxidation [1, 2], methane combustion in gas turbines [3]) and also in exhaust gases’ converters of automobile transport [4-7]. The relatively low price of palladium among metals of this group and its high catalytic activity in reactions of hydrocarbon and CO oxidation, NOx reduction [8] at the same time determine the actuality of its compounds usage for the manufacture of gas purification catalysts. But precious metal reserves on the Planet are limited and demand for them increases year by year. More than 45% of all mined platinum group metals were spent to 1994 only for production of catalysts used to protect the environment [9]. Their cost steady growth is the reason for an active search of alternatives for effective catalyst synthesis. Therefore a certain tendency of increasing the research focused on the use of transition metals in the process of gas purification from toxic substances is observed [10-13]. Commercially produced gas emission cleaning catalysts can be divided into three main groups [14]: - catalysts containing platinum group metals; - catalysts based on transition-metal oxides; - mixed catalysts consisting of transition-element oxides and compounds of platinum group metals. Ponomarenko A., Ved V., Satayev M., Saipov A. PDO Impact on the Activity of Hydrocarbon Oxidation with Oxide Catalysts   Industrial Technology and Engineering. 2016, 2(19): 36-42 37  The effect of palladium component addition on the activity of an oxide catalyst deposited on a carrier - molten corundum (α-Al2O3) in a process of catalytic thermal hydrocarbon destruction was studied in the present research. MATERIALS AND METHODS Corundum grains of 0.3-0.4 mm fraction were used as a carrier; the grains were subjected to a multi-stage impregnation with saturated water solutions of nitrates Co(NO3)2·6H2O, Cr(NO3)3·9H2O, Cu(NO3)2·3H2O, Ni(NO3)2·6H2O. The catalyst active centers on the carrier were formed in the subsequent two-hour drying at 130°C and heat treatment for 4 hours at the temperature of 400°C [12]. The identification of formed active centers, conducted by X-ray phase analysis using DRON-2.0 diffractometer showed that the nitrate salts were subjected to decomposition with Co3O4, Cr2O3, CuO, and NiO formation (Fig. 1) on the corundum surface[13].   Fig. 1. The XRD of coated samples on the corundum: peaks proper to 1 – Со3О4; 2 – α-Al2O3  The carrier α-Al2O3 samples with supported catalysts of given compositions and without them were treated with Pd(NO3)2 saturated water solution of 2 g/cm3 density by the same method. The samples were also subjected to thermal decomposition. The results of X-ray analysis (Fig. 2) showed that palladium nitrate destruction on corundum grains led to PdO formation.   Ponomarenko A., Ved V., Satayev M., Saipov A. PdO Impact on the Activity of Hydrocarbon Oxidation with Oxide Catalysts   38 Industrial Technology and Engineering. 2016, 2(19): 36-42   Fig. 2. The XRD of coated samples on the corundum: 1 – peaks proper to PdO; 2 – α-Al2O3  The effectiveness of using a certain type of gas purification catalyst was determined by studying the process of catalytic thermal hydrocarbon destruction (Fig. 3-6) on the lab bench [15]. Benzene vapors in air medium were used as a model hydrocarbon mixture [16].   Fig. 3. Temperature dependences of benzene vapor conversion degree (%) obtained using compositions Co3O4 - PdO with surface concentration on the carrier (mg/cm2): Со3О4 –5, PdО − 1 (1); Со3О4 – 10, PdО − 1 (2); PdО – 1 (3)  Ponomarenko A., Ved V., Satayev M., Saipov A. PDO Impact on the Activity of Hydrocarbon Oxidation with Oxide Catalysts   Industrial Technology and Engineering. 2016, 2(19): 36-42 39   Fig. 4. Temperature dependences of benzene vapor conversion degree (%) obtained  using compositions Сr2О3 – PdО with surface concentration on the carrier (mg/cm2): Сr2О3 – 10; PdО – (1); PdО − 1 (2)    Fig. 5. Temperature dependences of benzene vapor conversion degree (%) obtained using compositions СuО – PdО with surface concentration on the carrier (mg/cm2): СuО – 3, PdО - 1 (1); СuО - 5, PdО - 1 (2); СuО - 7, PdО - 1 (3); СuО - 10, PdО - 1 (4); PdО - 1 (5)  Ponomarenko A., Ved V., Satayev M., Saipov A. PdO Impact on the Activity of Hydrocarbon Oxidation with Oxide Catalysts   40 Industrial Technology and Engineering. 2016, 2(19): 36-42    Fig. 6. Temperature dependences of benzene vapor conversion degree (%) obtained using compositions NiО – PdО with surface concentration on the carrier (mg/cm2): NiО – 10;  PdО − 1 (1); PdО − 1 (2)     RESULTS AND DISCUSSION Temperature dependences (Fig. 2-5) show maximum values of benzene vapor conversion degrees, presented in Table 1.   Table 1. Values of surface concentrations of catalyst active centers and maximum benzene vapor conversion degree Surface concentrations of catalyst active centers, mg/cm2 Maximum benzene vapor conversion degree, % Со3О4 – 5; PdО – 1 46 Со3О4 – 10; PdО – 1 68 Сr2О3 – 10; PdО − 1 70 СuО – 3; PdО – 1 46 СuО – 5; PdО − 1 60 СuО – 7; PdО – 1 66 СuО – 10; PdО – 1 66 NiО – 10; PdО − 1. 49 PdО − 1 75  Data in Table 1 testifies that the highest degree of catalytic neutralization is reached using PdО catalyst active centers with surface concentration of 1 mg/cm2. Pre-coating of Ponomarenko A., Ved V., Satayev M., Saipov A. PDO Impact on the Activity of Hydrocarbon Oxidation with Oxide Catalysts   Industrial Technology and Engineering. 2016, 2(19): 36-42 41  transition-metal oxides (in amounts specified by surface concentration limits) on the carrier decreases the catalyst activity.  The experiments for determination of the effect of palladium oxide amount in the complex catalyst Co3O4-PdO/α-Al2O3 composition on its activity were conducted in parallel. Data of surface concentrations of supported catalysts on corundum grains and reached maximum benzene vapor conversion degree at their usage is given in Table. 2. Table 2. Dependences of values of maximum benzene vapor conversion degree on surface concentrations of catalyst active elements  Surface concentrations of catalyst active centers, mg/cm2 Maximum benzene vapor conversion degree, % PdО – 0.1 28 Со3О4  – 10 56 Со3О4– 10, PdО – 0.1 67  Data in Table 2 testifies that the lowest benzene vapor conversion degree is reached using PdО as catalyst active centers with 0.1 mg/cm2 surface concentration on the carrier. Using Co3O4 catalyst with 10 mg/cm2 surface concentration allows to reach maximum benzene vapors conversion degree of 56%. The conversion degree increases up to 67% upon subsequent PdO depositing with the surface concentration of 0.1 mg/cm2 (Table 2). However according to the Table 1 maximum benzene vapor conversion degree equal to 68% was obtained when depositing on the corundum Co3O4 surface with surface concentration of 10 mg/cm2 and PdO 1 mg/cm2. Thus it is established that at subsequent PdO compound deposition on Co3O4 with the surface concentration in the range 0.1-1 mg/cm2 the maximum conversion degree is not significantly changed when using the catalyst of such compositions.  CONCLUSIONS PdO role in the composition of Co3O4-PdO/α-Al2O3 catalyst is shown, apparently, in increasing Co3O4 phase stability. This may be conditioned by the fact that PdO facilitates interfacial diffusion of atomic oxygen on catalyst oxide component and maintains it in oxidized state. This provision is confirmed by the results of NO and CO catalytic conversion research [17] on the Pd-Co3O4/γ-Al2O3 catalyst. The research [17] showed that oxygen adsorbed on palladium migrates on cobalt oxide in the composition of this catalyst. At the expense of this process oxygen passivation of Pd-Co3O4/γ-Al2O3 catalyst is overcome and its high reaction activity is ensured. Our research is evidence that Co3O4 performs the role of active centers on a corundum carrier in the reaction of catalytic thermal hydrocarbon oxidation. Additionally injected PdO into the catalyst composition promotes to the cobalt phase enrichment with oxygen.  REFERENCES  1. Ryabchikov  А.А. e.a. (Ukraine). A catalyst for ammonia oxidation. Patent RF, no. 2333794, 2008. 2. Kosyakov А.А. (Russia). A catalyst for ammonia oxidation reactor. Patent RF no. 2248935. 2003. 3. Ismagilov Z.R. (Russia), Shikina N.V. (Russia). The method of hydrocarbon fuel combustion (versions) and catalysts for its implementation. Patent RF, no. 2372556. 2009.   Ponomarenko A., Ved V., Satayev M., Saipov A. PdO Impact on the Activity of Hydrocarbon Oxidation with Oxide Catalysts   42 Industrial Technology and Engineering. 2016, 2(19): 36-42  5. Miura Masahide (Japan). Catalyst for Emission Gas Purification. Patent USA, no. 922456, 2010. 6. Morisaka Hideaki (Japan); Wakamatsu Hironori (Japan); Nakamaura Masanori (Japan). Сatalyst for purification of exhaust gas. Patent USA, no. 861644, 2010. 7. Matsubara Hiroyuki (Japan). Catalyst Support Particle, Exhaust Gas Purifying Catalyst and Production Processes Thereof. Patent USA, no. 084419, 2011. 8. Elvin B. Stiles. Carriers and supported catalysts. Theory and и practice, 1991,  240p. (Russ. ed.: Elvin B. Stails. Nositeli i nanesennyie katalizatoryi. Teoriya i praktika. Moscow, Nauka, 1991. 240 p.). 9. Review of the Market of Industrial Catalysts in Russia. 2010, 304p. Infomain – research group. Association of independent experts in the field of mineral resources, metallurgy and chemical industry. 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PdO impact on the activity of hydrocarbon oxidation with oxide catalysts

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PdO impact on the activity of hydrocarbon oxidation with oxide catalysts

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PdO impact on the activity of hydrocarbon oxidation with oxide catalysts

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