Nano CoO-Cu-MgO catalyst for vapor phase simultaneous synthesis of ortho-chloroaniline and γ-butyrolactone from ortho-cholonitrobenzne and 1,4-butanediol

Hari Prasad Reddy Kannapu 1,2,3, Young-Woong Suh2,3, Veeralakshmi Vaddeboina 1, Anand Narani 1, David Raju Burri 1, Seetha Rama Rao Kamaraju 1

Abstract


Aiming at developing an efficient catalysts for simultanoius hydrogenation of o-chloronitrobenzene to o-chloroaniline and 1,4-butanediol dehydrogenation to  γ-butyrolactone. A series of CoO-Cu-MgO catalysts, composed of 10 wt% of copper, various amount of cobalt loadings (1, 5 and 10 wt%) and remaining of MgO were developed by co-precipitation followed by thermal treatment. o-Chloroaniline and γ-butyrolactone were the main products with high yield of 85% and 90%, respectively. The advantage of the coupling process is that the hydrogenation reaction was conducted without external hydrogen, indicating minimise the hydrogen consumption which is also known as hydrogen economy route. From N2O characterization results, the high activtiy of 5CoO-10Cu-MgO was found to have high amount of Cu species (Cu0/Cu+1) species and govern the stable activity and selectivity on time on stream study in presence of cobalt in Cu-MgO.


Keywords


Transfer Hydrogenation; Ortho-chloro Aniline; γ-Butyrolactone; Atomic H2; Basic Sites; Nano CoO-Cu-MgO

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References


Yang XL, Deng ZL, Liu HF. Modification of metal complex on hydrogenation of ortho -chloronitrobenzene over polymer-stabilized platinum colloidal clusters. Journal of Molecular CatalysisA: Chemical. 1999; 144:123.

Khilnani VL, Chandalia SB. Selective Hydrogenation. I. para- Chloronitrobenzene to para-Chloroaniline Platinum on Carbon As Catalyst Organic Process Research and Development. 2001; 5: 257.

Yang XL, Wang XD, Liu HQ, Liu HC and Wang Y. Excellent catalytic properties over nanocomposite catalysts for selective hydrogenation of halonitrobenzenes. Journal of Catalysis. 2008; 255: 335.

Motoyama Y, Kamo K, Nagashima H. Catalysis in polysiloxane gels: platinum-catalyzed hydrosilylation of polymethylhydrosiloxane leading to reusable catalysts for reduction of nitroarenes. Organic Letter. 2009; 11: 1345.

Yuan X, Yan N, Xiao C X, Li C N, Fei ZF, Cai ZP, Kou Y, Dyson PJ. Highly selective hydrogenation of aromatic chloronitro compounds to aromatic chloroamines with ionic-liquid-like copolymer stabilized platinum nanocatalysts in ionic liquids. Green Chemistry. 2010;12: 228.

Yang XL, Liu HF, Zhong H. Hydrogenation of ortho-chloronitrobenzene over polymer-stabilized palladium–platinum bimetallic colloidal clusters. Journal of Molecular Catalysis A: Chemical. 1999; 147: 55.

Sreedhar B, Reddy PS, Devi DK. Direct One-Pot Reductive Amination of Aldehydes with Nitroarenes in a Domino Fashion: Catalysis by Gum-Acacia-Stabilized Palladium Nanoparticles. Journal of Organic Chemistry. 2009; 74: 8806.

Liu MH, Yu WY, Liu HF. Selective hydrogenation of ortho-chloronitrobenzene over polymer-stabilized ruthenium colloidal catalysts. Journal of Molecular Catalysis A: Chemical 1999; 138: 295.

Kratky V, Kralik M, Mecarova M, Stolcova M, Zalibera L, Hronec M. Effect of catalyst and substituents on the hy

Nagaraja BM, Padmasri AH, Seetharamulu P, Reddy KHP, David Raju B, Rao KSR. A highly active Cu-MgO-Cr2O3 catalyst for simultaneous synthesis of furfuryl alcohol and cyclohexanone by a novel coupling route—Combination of furfural hydrogenation and cyclohexanol dehydrogenation. Journal of Molecular Catalysis A: Chemical. 2007; 278: 29.

Reddy KHP, Mullen CA, Elkasabi Y, Boateng AA. Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates: Reduction of p-cresol and furfural over bimetallic Ni–Cu catalysts using isopropanol. Fuel Processing Technology. 2015; 137: 220–228.

Reddy KHP, Prasad NCK, Rao KSR, Kalevaru VN, Martin A, Raju BD.Unusual effect of cobalt on Cu–MgO catalyst for the synthesis of γ-butyrolactone and aniline via coupling reaction. Catalysis Science and Technology. 2016; 6: 5494.

Reddy KHP, Rahul R, Reddy SS, Raju BD, Rao KSR. Coupling of 1,4-butanediol dehydrogenation reaction with the hydrogenation of nitrobenzene over Cu/MgO catalysts. Catalysis Communication. 2009; 10: 879.

Reddy KHP, Anand N, Venkateswarlu V, Rao KSR, Raju BD. A selective synthesis of 1-phenylethanol and γ-butyrolactone through coupling processes over Cu/MgO catalysts. Journal of Molecular Catalysis A: Chemical. 2012; 355:180.

Reddy KHP, Young-Woong S, Anand N, David Raju B, Rama Rao KS. Coupling of 1,4-Butanediol Dehydrogenation with Nitrobenzene Hydrogenation for Simultaneous Synthesis of γ-Butyrolactone and Aniline over Promoted Cu-MgO Catalysts: Effect of Promoters. Catalysis Letters. 2017; 147, 90–101.

Reddy KHP, Young-Woong S, Anand N, David Raju B, Rama Rao KS. Coupling of ortho-chloronitrobenzene hydrogenation with 1, 4-butanediol dehydrogenation over Cu-MgO catalysts: A hydrogen free process. Catalysis Communications. 2017; 95: 21–25.

Reddy KHP, Young-Woong S, Anand N, Veeralakshmi V, David Raju B, Rama Rao KS, One-pot Synthesis of Ethylbenzene/1-Phenylethanol and γ-Butyrolactone from Simultaneous Acetophenone Hydrogenation and 1,4-Butanediol Dehydrogenation over Copper Based Catalysts: Effect of support. RSC Advances. 2017; 7: 35346-35356.

Reddy KHP, Anand N, Sai Prasad PS, Rama Rao KS, David Raju B.

Daage MRR. Chianelli. Structure-Function Relations in Molybdenum Sulfide Catalysts: The "Rim-Edge" Model. Journal of Catalysis. 1994; 149: 414.

Vradman L, Landau MV, Herskowitz M, Ezersky V, Talianker M , Nikitenko S, Koltypin Y, Gedanken A. High loading of short WS2 slabs inside SBA-15: promotion with nickel and performance in hydrodesulfurization and hydrogenation. Journal of Catalysis. 2003; 213: 163.

Ning G, Liu Y, Wei F, Wen Q, Luo G. Porous and Lamella-like Fe/MgO Catalysts prepared under Hydrothermal Conditions for High-Yield Synthesis of Double-Walled Carbon Nanotubes. Journal of Physical Chemistry C. 2007; 11:1969.

Shaheen WM, Ali AA, haracterization of solid–solid interactions and physicochemical properties of copper–cobalt mixed oxides and CuxCo32xO4 spinels. Materials Research Bulletin. 2001; 36: 1703.

Omata K, Nukui N, Hottai T, Yamada M, Cobalt–magnesia catalyst by oxalate co- precipitation method for dry reforming of methane under pressure. Catalysis communications. 2004; 5: 771.

Wang HY, Ruckenstein E. CO2 reforming of CH4 over Co/MgO solid solution catalysts effect of calcination temperature and Co loading. Applied Catalysis A: General. 2001; 209: 207.

Ago H, Nakamura K, Uehara N, Tsuji M. Roles of Metal−Support Interaction in Growth of Single- and Double-Walled Carbon Nanotubes Studied with Diameter-Controlled Iron particles Supported on MgO. Journal of Physical Chemistry B. 2004; 108: 18908.

Furusawa T, Tsutsumi A. Comparison of Co/MgO and Ni/MgO catalysts for the steam reforming of naphthalene as a model compound of tar derived from biomass gasification Applied Catalysis A: General. 2005; 278: 207.

Stoyanova D, Christova M, Dimitrova P, Marinova J, Kasabova N, Panayotov D.Copper–cobalt oxide spinel supported on high-temperature aluminosilicate carriers as catalyst for CO–O2 and CO–NO reactions. Applied Catalysis B. 1998; 17: 233.

Cesar C.A. Perez, Schmal M, Salim VMM. Quantitative XPS analysis of silica-supported Cu–Co oxides. Applied Surface Science. 2000; 157: 159.




DOI: http://dx.doi.org/10.24294/can.v2i3.523

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