Alumina Supported Cu-Mn-Cr Catalysts for CO and VOCs Oxidation
This work studies the effect of chemical composition
on the activity and selectivity of γ–alumina supported CuO/
MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether
(DME) and methanol. The catalysts were prepared by impregnation
of the support with an aqueous solution of copper nitrate, manganese
nitrate and CrO3 under different conditions. Thermal, XRD and TPR
analysis were performed. The catalytic measurements of single
compounds oxidation were carried out on continuous flow equipment
with a four-channel isothermal stainless steel reactor. Flow-line
equipment with an adiabatic reactor for simultaneous oxidation of all
compounds under the conditions that mimic closely the industrial
ones was used. The reactant and product gases were analyzed by
means of on-line gas chromatographs.
On the basis of XRD analysis it can be concluded that the active
component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at
least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4,
Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio.
Chemical composition strongly influences catalytic properties, this
influence being quite variable with regards to the different processes.
The rate of CO oxidation rapidly decrease with increasing of
chromium content in the active component while for the DME was
observed the reverse trend. It was concluded that the best
compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and
Mn/Cr molar ratio from 1:3 to 1:4.
[1] X. Tang, B. Zhang, Y. Li, Y. Xu, Q. Xin, W. Shen, “Carbon monoxide
oxidation over CuO/CeO2 catalysts”, Catal. Today, 93-95, 191-198,
2004.
[2] D. R. Mechandjiev, P. G. Dimitrova, I. A. Tzolovski, A. B. Raevski,
“Cu/Co spinel containing exhaust gas catalyst and method of its
preparation”, WO Patent 03061821, 2003.
[3] G. J. Hutchings, A. A. Mirzaei, R. W. Joyner, M. R. H. Siddiqui, S.H.
Taylor, "Ambient temperature CO oxidation using copper manganese
oxide catalysts prepared by coprecipitation: effect of ageing on catalyst
performance", Catal. Lett., 42 (1-2), pp. 21-24, 1996.
[4] G. J. Hutchings, A. A. Mirzaei, R. W. Joyner, M. R. H. Siddiqui, S. H.
Taylor, "Effect of preparation conditions on the catalytic performance of
copper manganese oxide catalysts for CO oxidation", Appl. Catal. A:
Gen., 166 (1) pp. 143-152, 1998.
[5] L. S. Puckaber, H. Cheung, D. L. Cocke, A. Clearfield, “Reactivity of
copper manganese oxides”, Solid State Ionics, 32–33, pp. 206-213,
1989.
[6] S. Vepřek,D. L. Cocke, S. Kehl, H. R. Oswald, ”Mechanism of the
deactivation of Hopcalite catalysts studied by XPS, ISS, and other
techniques. J. Catal., 100 (1), pp.250-263, 1986.
[7] A. A. Mirzaei, H. R. Shaterian, M. Habibi, G. J. Hutchings, S. H. Taylor,
“Characterisation of copper-manganese oxide catalysts:effect of
precipitate ageing upon the structure and morphology of precursors and
catalysts”, Appl. Catal. A: Gen., 253, pp. 499–508, 2003.
[8] P. Larsson, A. Andersson, “Oxides of copper, ceria promoted copper,
manganese and copper manganese on Al2O3 for the combustion of CO,
ethyl acetate and ethanol”, Applied Catalysis B: Environmental, Vol. 24,
pp. 175–192, 2000.
[9] K. Qian, Z. Qian, Q. Hua, Z. Jiang, W. Huang, “Structure–activity
relationship of CuO/MnO2 catalysts in CO oxidation”, Applied Surface
Science, Vol. 273, pp. 357– 363, 2013.
[10] Y. Ren, Z. Ma, L. Qian, S. Dai, H. He, P. G. Bruce, “Ordered Crystalline
Mesoporous Oxides as Catalysts for CO Oxidation”, Catal. Lett. , 131,
pp. 146–154, 2009.
[11] Ferrandon, M., “Mixed Metal Oxide-Noble Metal Catalyst for Total
Oxidation of Volatile Organic Compounds and Carbon Oxide”,
Department of Chemical Engineering and Technology, Chemical
Reaction Engineering, Royal Institute of Technology, Stockholm.PhD
Thesis, 2011.
[12] R. McCabe and P. J. Mitchell, “Reactions of ethanol and acetaldehyde
over noble metal and metal oxide catalysts”, Ind. Eng. Chem. Prod. Res.
Dev., 23 (2), pp. 196–202, 1984.
[13] Y. Hasegawa, K. Fukumoto, T. Ishima, H. Yamamoto, M. Sano, T.
Miyake, “Preparation of copper-containing mesoporous manganese
oxides and their catalytic performance for CO oxidation”, Appl. Catal.
B: Environ. 89, pp. 420–424, 2009.
[14] Y. F. Yo-Yao, J. T. Kummer, “A study of high temperature treated
supported metal oxide catalysts”, J. Catal., 46, 1977, pp. 388 – 401.
[15] F. Severino, J. Brito, O. Carias, J. Laine, “Comparative study of
Alumina-Supported CuO and CuCr2O4 as catalysts for CO Oxidation”, J.
Catal., 102, pp. 172–179, 1986.
[16] Ch.-Ch. Chien, W.-P. Chuang, T.-J. Huang, “Effect of heat-treatment
conditions on Cu-Cr/γ-alumina catalyst for carbon monoxide and
propene oxidation”, Appl. Catal. A: Gen., 131, pp. 73-87, 1995.
[17] J. Laine, J. Brito, F. Severino, G. Castro, P. Tacconi, S. Yunes, J. Cruz,
“Surface copper enrichment by reduction of copper chromite catalyst
employed for carbon monoxide oxidation” Catal. Lett., 5, pp. 45-54,
1990. [18] J. R. Monnier, M. J. Hanrahan, G. Apai, “A study of the Catalytically
Active Copper Species in the Synthesis of Methanol Over Cu-Cr
Oxide”, J. Catal., 92, pp. 119-126, 1985.
[19] C. A. Leech, and L. E. Campbell, “Spinel Solid Solution Catalysts for
Automotive Applications”, Adv. Chem. Ser., 143, pp. 161-177, 1975.
[20] K. Ivanov, E. Kolentsova, D. Dimitrov, “Alumina Supported Copper-
manganese Catalysts for Combustion of Exhaust Gases: Effect of
Preparation Method”, XIII International Conference on Chemical
Engineering and Technology, Lisbon, Portugal, 2015, submitted for
publication.
[21] K. Ivanov, D. Dimitrov, B. Boyanov, “Deactivation of Cu - Cr/γ-
alumina catalysts for combustion of exhaust gases”, World Academy of
Science, Engineering and Technology, Volume 5, pp. 270 – 276, 2011.
[22] S. A. A. Sajadi, M. Khaleghian, “Study of thermal behavior of CrO3
using TG and DSC”, J. Therm. Anal. Calorim., 116, pp. 915–921, 2014.
[23] Z. Ding, W. Martens, R. L. Frost, “Thermal activation of copper nitrate”,
J. Mater. Sci. Letters, 21, pp. 1415-1417, 2002.
[24] K. Ivanov, E. Kolentsova, D. Dimitrov, Georgi V. Avdeev, Tatyana T.
Tabakova “Alumina Supported Copper-Manganese Catalysts for
Combustion of Exhaust Gases: Catalysts Characterization”, XIII
International Conference on Chemical Engineering and Applications,
Venice, Italy, 2015, Accepted for publication.
[25] J. R. Monnier, M. J. Hanrahan, G. Apai, A study of the Catalytically
Active Copper Species in the Synthesis of Methanol Over Cu-Cr Oxide,
J. Catal., 92, pp. 119-126, 1985.
[26] P. Wei, M. Bieringer, L.M. D. Cranswick, A. Petric, "In situ high-
temperature X-ray and neutron diffraction of Cu–Mn oxide phases." J.
Mater. Sci., 45 (4), pp. 1056–1064, 2010.
[27] Y. Tanaka, T. Utaka, R. Kikuchi, T. Takeguchi, K. Sasaki, K. Eguchi,
“Water gas shift reaction for the reformed fuels over Cu/MnO catalysts
prepared via spinel-type oxide”, J. Catal. 215, pp. 271-278, 2003.
[28] M. Morales, L. Barbero, L. Cadús, “Combustion of volatile organic
compounds on manganese iron or nickel mixed oxide catalysts”, Appl.
Catal. B: Envir., 67 (3–4), pp. 229–236, 2006.
[29] T. Tsoncheva, M. Jarn, D. Paneva, M. Dimitrov, I. Mitov, Copper and
chromium oxide nanocomposites supported on SBA-15 silica as
catalysts for ethylacetate combustion: Effect of mesoporous structure
and metal oxide composition."Micropor. Mesopor. Mater., 137, pp. 56–
64, 2011.
[1] X. Tang, B. Zhang, Y. Li, Y. Xu, Q. Xin, W. Shen, “Carbon monoxide
oxidation over CuO/CeO2 catalysts”, Catal. Today, 93-95, 191-198,
2004.
[2] D. R. Mechandjiev, P. G. Dimitrova, I. A. Tzolovski, A. B. Raevski,
“Cu/Co spinel containing exhaust gas catalyst and method of its
preparation”, WO Patent 03061821, 2003.
[3] G. J. Hutchings, A. A. Mirzaei, R. W. Joyner, M. R. H. Siddiqui, S.H.
Taylor, "Ambient temperature CO oxidation using copper manganese
oxide catalysts prepared by coprecipitation: effect of ageing on catalyst
performance", Catal. Lett., 42 (1-2), pp. 21-24, 1996.
[4] G. J. Hutchings, A. A. Mirzaei, R. W. Joyner, M. R. H. Siddiqui, S. H.
Taylor, "Effect of preparation conditions on the catalytic performance of
copper manganese oxide catalysts for CO oxidation", Appl. Catal. A:
Gen., 166 (1) pp. 143-152, 1998.
[5] L. S. Puckaber, H. Cheung, D. L. Cocke, A. Clearfield, “Reactivity of
copper manganese oxides”, Solid State Ionics, 32–33, pp. 206-213,
1989.
[6] S. Vepřek,D. L. Cocke, S. Kehl, H. R. Oswald, ”Mechanism of the
deactivation of Hopcalite catalysts studied by XPS, ISS, and other
techniques. J. Catal., 100 (1), pp.250-263, 1986.
[7] A. A. Mirzaei, H. R. Shaterian, M. Habibi, G. J. Hutchings, S. H. Taylor,
“Characterisation of copper-manganese oxide catalysts:effect of
precipitate ageing upon the structure and morphology of precursors and
catalysts”, Appl. Catal. A: Gen., 253, pp. 499–508, 2003.
[8] P. Larsson, A. Andersson, “Oxides of copper, ceria promoted copper,
manganese and copper manganese on Al2O3 for the combustion of CO,
ethyl acetate and ethanol”, Applied Catalysis B: Environmental, Vol. 24,
pp. 175–192, 2000.
[9] K. Qian, Z. Qian, Q. Hua, Z. Jiang, W. Huang, “Structure–activity
relationship of CuO/MnO2 catalysts in CO oxidation”, Applied Surface
Science, Vol. 273, pp. 357– 363, 2013.
[10] Y. Ren, Z. Ma, L. Qian, S. Dai, H. He, P. G. Bruce, “Ordered Crystalline
Mesoporous Oxides as Catalysts for CO Oxidation”, Catal. Lett. , 131,
pp. 146–154, 2009.
[11] Ferrandon, M., “Mixed Metal Oxide-Noble Metal Catalyst for Total
Oxidation of Volatile Organic Compounds and Carbon Oxide”,
Department of Chemical Engineering and Technology, Chemical
Reaction Engineering, Royal Institute of Technology, Stockholm.PhD
Thesis, 2011.
[12] R. McCabe and P. J. Mitchell, “Reactions of ethanol and acetaldehyde
over noble metal and metal oxide catalysts”, Ind. Eng. Chem. Prod. Res.
Dev., 23 (2), pp. 196–202, 1984.
[13] Y. Hasegawa, K. Fukumoto, T. Ishima, H. Yamamoto, M. Sano, T.
Miyake, “Preparation of copper-containing mesoporous manganese
oxides and their catalytic performance for CO oxidation”, Appl. Catal.
B: Environ. 89, pp. 420–424, 2009.
[14] Y. F. Yo-Yao, J. T. Kummer, “A study of high temperature treated
supported metal oxide catalysts”, J. Catal., 46, 1977, pp. 388 – 401.
[15] F. Severino, J. Brito, O. Carias, J. Laine, “Comparative study of
Alumina-Supported CuO and CuCr2O4 as catalysts for CO Oxidation”, J.
Catal., 102, pp. 172–179, 1986.
[16] Ch.-Ch. Chien, W.-P. Chuang, T.-J. Huang, “Effect of heat-treatment
conditions on Cu-Cr/γ-alumina catalyst for carbon monoxide and
propene oxidation”, Appl. Catal. A: Gen., 131, pp. 73-87, 1995.
[17] J. Laine, J. Brito, F. Severino, G. Castro, P. Tacconi, S. Yunes, J. Cruz,
“Surface copper enrichment by reduction of copper chromite catalyst
employed for carbon monoxide oxidation” Catal. Lett., 5, pp. 45-54,
1990. [18] J. R. Monnier, M. J. Hanrahan, G. Apai, “A study of the Catalytically
Active Copper Species in the Synthesis of Methanol Over Cu-Cr
Oxide”, J. Catal., 92, pp. 119-126, 1985.
[19] C. A. Leech, and L. E. Campbell, “Spinel Solid Solution Catalysts for
Automotive Applications”, Adv. Chem. Ser., 143, pp. 161-177, 1975.
[20] K. Ivanov, E. Kolentsova, D. Dimitrov, “Alumina Supported Copper-
manganese Catalysts for Combustion of Exhaust Gases: Effect of
Preparation Method”, XIII International Conference on Chemical
Engineering and Technology, Lisbon, Portugal, 2015, submitted for
publication.
[21] K. Ivanov, D. Dimitrov, B. Boyanov, “Deactivation of Cu - Cr/γ-
alumina catalysts for combustion of exhaust gases”, World Academy of
Science, Engineering and Technology, Volume 5, pp. 270 – 276, 2011.
[22] S. A. A. Sajadi, M. Khaleghian, “Study of thermal behavior of CrO3
using TG and DSC”, J. Therm. Anal. Calorim., 116, pp. 915–921, 2014.
[23] Z. Ding, W. Martens, R. L. Frost, “Thermal activation of copper nitrate”,
J. Mater. Sci. Letters, 21, pp. 1415-1417, 2002.
[24] K. Ivanov, E. Kolentsova, D. Dimitrov, Georgi V. Avdeev, Tatyana T.
Tabakova “Alumina Supported Copper-Manganese Catalysts for
Combustion of Exhaust Gases: Catalysts Characterization”, XIII
International Conference on Chemical Engineering and Applications,
Venice, Italy, 2015, Accepted for publication.
[25] J. R. Monnier, M. J. Hanrahan, G. Apai, A study of the Catalytically
Active Copper Species in the Synthesis of Methanol Over Cu-Cr Oxide,
J. Catal., 92, pp. 119-126, 1985.
[26] P. Wei, M. Bieringer, L.M. D. Cranswick, A. Petric, "In situ high-
temperature X-ray and neutron diffraction of Cu–Mn oxide phases." J.
Mater. Sci., 45 (4), pp. 1056–1064, 2010.
[27] Y. Tanaka, T. Utaka, R. Kikuchi, T. Takeguchi, K. Sasaki, K. Eguchi,
“Water gas shift reaction for the reformed fuels over Cu/MnO catalysts
prepared via spinel-type oxide”, J. Catal. 215, pp. 271-278, 2003.
[28] M. Morales, L. Barbero, L. Cadús, “Combustion of volatile organic
compounds on manganese iron or nickel mixed oxide catalysts”, Appl.
Catal. B: Envir., 67 (3–4), pp. 229–236, 2006.
[29] T. Tsoncheva, M. Jarn, D. Paneva, M. Dimitrov, I. Mitov, Copper and
chromium oxide nanocomposites supported on SBA-15 silica as
catalysts for ethylacetate combustion: Effect of mesoporous structure
and metal oxide composition."Micropor. Mesopor. Mater., 137, pp. 56–
64, 2011.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:70436", author = "Krasimir I. Ivanov and Elitsa N. Kolentsova and Dimitar Y. Dimitrov and Petya Ts. Petrova and Tatyana T. Tabakova", title = "Alumina Supported Cu-Mn-Cr Catalysts for CO and VOCs Oxidation", abstract = "This work studies the effect of chemical composition
on the activity and selectivity of γ–alumina supported CuO/
MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether
(DME) and methanol. The catalysts were prepared by impregnation
of the support with an aqueous solution of copper nitrate, manganese
nitrate and CrO3 under different conditions. Thermal, XRD and TPR
analysis were performed. The catalytic measurements of single
compounds oxidation were carried out on continuous flow equipment
with a four-channel isothermal stainless steel reactor. Flow-line
equipment with an adiabatic reactor for simultaneous oxidation of all
compounds under the conditions that mimic closely the industrial
ones was used. The reactant and product gases were analyzed by
means of on-line gas chromatographs.
On the basis of XRD analysis it can be concluded that the active
component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at
least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4,
Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio.
Chemical composition strongly influences catalytic properties, this
influence being quite variable with regards to the different processes.
The rate of CO oxidation rapidly decrease with increasing of
chromium content in the active component while for the DME was
observed the reverse trend. It was concluded that the best
compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and
Mn/Cr molar ratio from 1:3 to 1:4.", keywords = "Copper-manganese-chromium oxide catalysts, CO,
deep oxidation, volatile organic compounds.", volume = "9", number = "5", pages = "651-8", }
