Catalytic reforming

Catalytic reforming is a chemical process used to convert petroleum refinery naphthas distilled from crude oil (typically having low octane ratings) into high-octane liquid products called reformates, which are premium blending stocks for high-octane gasoline. The process converts low-octane linear hydrocarbons (paraffins) into branched alkanes (isoparaffins) and cyclic naphthenes, which are then partially dehydrogenated to produce high-octane aromatic hydrocarbons. The dehydrogenation also produces significant amounts of byproduct hydrogen gas, which is fed into other refinery processes such as hydrocracking. A side reaction is hydrogenolysis, which produces light hydrocarbons of lower value, such as methane, ethane, propane and butanes.

Continuous Catalytic reforming (CCR) unit

In addition to a gasoline blending stock, reformate is the main source of aromatic bulk chemicals such as benzene, toluene, xylene and ethylbenzene which have diverse uses, most importantly as raw materials for conversion into plastics. However, the benzene content of reformate makes it carcinogenic, which has led to governmental regulations effectively requiring further processing to reduce its benzene content.

This process is quite different from and not to be confused with the catalytic steam reforming process used industrially to produce products such as hydrogen, ammonia, and methanol from natural gas, naphtha or other petroleum-derived feedstocks. Nor is this process to be confused with various other catalytic reforming processes that use methanol or biomass-derived feedstocks to produce hydrogen for fuel cells or other uses.

These are the two main classes into which the catalysts utilised for the reforming processes fall.

  1. Supported noble metals
  2. non-noble transition metal
CCR
Continuous Catalytic Reforming / platforming

The best catalyst for the synthesis of syngas utilising various procedures has been the subject of several research. Rhodium,[1][2] ruthenium,[3][4] and platinum,[5][6] as well as palladium[7] and iridium[8] catalysts, have all been the subject of in-depth study on hydrogen production, catalytic thermal decomposition, and dry reforming catalysts.[9] Noble metals-based catalysts are much more effective and often less susceptible to deactivation by carbon production or oxidation, but because they are more expensive (costing 100–150 times more than nickel catalysts), they are less frequently used.[10] In industrial uses, catalysts depending on nickel are increasingly often utilised. However, due to carbon accumulation, their resilience is low. The most crucial issue for methane reforming, particularly in dry reforming, is the suppression of carbon deposition for non-noble metal catalysts. Increasing the surface basicity of catalysts and regulating the particle sizes of active ingredients are two techniques used to prevent carbon from depositing. The improvement of metal-support interaction, the creation of solid solutions, and plasma processes are only a few of the strategies that have been developed to manage the metal particle sizes. The surface basicity of catalysts was increased by using basic metal oxides as a support or promoter. Increased catalysts and processes as a consequence of the work of several authors have improved overall efficiency and environmental performance.[11][12]

  1. ^ Horn, R; Williams, K; Degenstein, N; Schmidt, L (2006-08-15). "Syngas by catalytic partial oxidation of methane on rhodium: Mechanistic conclusions from spatially resolved measurements and numerical simulations". Journal of Catalysis. 242 (1): 92–102. doi:10.1016/j.jcat.2006.05.008.
  2. ^ Salazar-Villalpando, Maria D.; Miller, Adam C. (March 2011). "Catalytic partial oxidation of methane and isotopic oxygen exchange reactions over 18O labeled Rh/Gadolinium doped ceria". International Journal of Hydrogen Energy. 36 (6): 3880–3885. doi:10.1016/j.ijhydene.2010.11.040.
  3. ^ Ishihara, A; Qian, E; Finahari, I; Sutrisna, I; Kabe, T (2005-04-27). "Addition effect of ruthenium on nickel steam reforming catalysts". Fuel. 84 (12): 1462–1468. doi:10.1016/j.fuel.2005.03.006.
  4. ^ Shamsi, Abolghasem (January 2009). "Partial oxidation of methane and the effect of sulfur on catalytic activity and selectivity". Catalysis Today. 139 (4): 268–273. doi:10.1016/j.cattod.2008.03.033.
  5. ^ Souza, Mariana M.V.M.; Macedo Neto, Octávio R.; Schmal, Martin (March 2006). "Synthesis Gas Production from Natural Gas on Supported Pt Catalysts". Journal of Natural Gas Chemistry. 15 (1): 21–27. doi:10.1016/S1003-9953(06)60003-0.
  6. ^ Salazar-Villalpando, Maria D.; Miller, Adam C. (January 2011). "Hydrogen production by methane decomposition and catalytic partial oxidation of methane over Pt/CexGd1−xO2 and Pt/CexZr1−xO2". Chemical Engineering Journal. 166 (2): 738–743. doi:10.1016/j.cej.2010.11.076.
  7. ^ Ryu, J; Lee, K; Kim, H; Yang, J; Jung, H (2008-05-08). "Promotion of palladium-based catalysts on metal monolith for partial oxidation of methane to syngas". Applied Catalysis B: Environmental. 80 (3–4): 306–312. doi:10.1016/j.apcatb.2007.10.010.
  8. ^ Richardson, J.T.; Paripatyadar, S.A. (May 1990). "Carbon dioxide reforming of methane with supported rhodium". Applied Catalysis. 61 (1): 293–309. doi:10.1016/S0166-9834(00)82152-1.
  9. ^ Barbero, J. (2003). "Support Effect in Supported Ni Catalysts on Their Performance for Methane Partial Oxidation". Catalysis Letters. 87 (3/4): 211–218. doi:10.1023/A:1023407609626. S2CID 91889442.
  10. ^ Zeppieri, M.; Villa, P.L.; Verdone, N.; Scarsella, M.; De Filippis, P. (2010-10-20). "Kinetic of methane steam reforming reaction over nickel- and rhodium-based catalysts". Applied Catalysis A: General. 387 (1–2): 147–154. doi:10.1016/j.apcata.2010.08.017. ISSN 0926-860X.
  11. ^ Ertl, Gerhard; Knözinger, Helmut; Schüth, Ferdi; Weitkamp, Jens, eds. (2008-03-15). Handbook of Heterogeneous Catalysis: Online. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA. doi:10.1002/9783527610044. ISBN 978-3-527-31241-2.
  12. ^ Molenbroek, Alfons M.; Helveg, Stig; Topsøe, Henrik; Clausen, Bjerne S. (September 2009). "Nano-Particles in Heterogeneous Catalysis". Topics in Catalysis. 52 (10): 1303–1311. doi:10.1007/s11244-009-9314-1. ISSN 1022-5528. S2CID 95513283.

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