Simple Preparation of Spherical Activated Carbon with Mesoporous Structure from Phenolic Resol and Associated Catalytic Performance in Isobutane Dehydrogenation

Abstract

This study provides a detailed report on the synthesis of spherical activated carbon with mesoporous structure using a soluble low molecular weight phenolic resol precursor through an ammonium alginate assisted sol–gel method. The effects of calcinating temperature and the addition of CaCO₃ as a pore-enlarging agent on texture structure and catalytic performance in isobutane dehydrogenation to isobutene were investigated. Characterization of N₂ sorption, mechanical strength tests, and optical photographs confirmed that the obtained carbon materials had high mechanical strength, a good degree of sphericity, and a large surface area. Introducing CaCO₃ as a pore-enlarging agent during the preparation process promoted the formation of a mesoporous structure of carbon spheres and evidently increased the surface area and oxygen content, which can improve isobutane conversion and isobutene selectivity of these carbon spheres. The conversion of isobutane reached up to 28% for this spherical activated carbon, and the selectivity of isobutene reached up to 96%. Isobutane conversion increased with an increase in calcination temperature due to an increase in the oxygen content, whereas the selectivity of isobutene decreased due to the slight decrease in the specific surface area.

Keywords

Spherical activated carbon / Pore-enlarging agent / Isobutane dehydrogenation / Isobutene

References

[1] Casella ML, Siri GJ, Santori GF, et al. Surface characterization of Li-modified platinum/tin catalysts for isobutane dehydrogenation. Langmuir, 2000, 16: 5639-5643.

[2] Siri GJ, Casella ML, Santori GF, et al. Tin/platinum on alumina as catalyst for dehydrogenation of isobutane. Influence of the preparation procedure and of the addition of lithium on the catalytic properties. Ind Eng Chem Res, 1997, 36: 4821-4826.

[3] Pisduangdaw S, Praserthdam P, Panpranot J, et al. One-step preparation of Pt–Ce and Pt–Sn–Ce/Al₂O₃ catalysts by flame spray pyrolysis in propane dehydrogenation. React Kinet Mech Catal, 2014, 113: 149-158.

[4] Minh CL, Alanazi AK, Miron DJ, et al. Carbon-carbon bond cleavage and dehydrogenation of isobutane over HZSM-5 at low pressures and temperatures. Catal Lett, 2012, 142: 1470-1473.

[5] Ding J, Shao R, Wu J, et al. Coupling dehydrogenation of isobutane to produce isobutene in carbon dioxide over NiO/γ-Al₂O₃ catalyst. React Kinet Mech Catal, 2010, 101: 173-181.

[6] Ogonowski J, Skrzynska E. Deactivation of VMgO _x catalysts by coke in the process of isobutane dehydrogenation with carbon dioxide. Catal Lett, 2008, 121: 234-240.

[7] Airaksinen SMK, Krause AOI. Effect of catalyst prereduction on the dehydrogenation of isobutane over chromia/alumina. Ind Eng Chem Res, 2005, 44: 3862-3868.

[8] Sun G, Huang Q, Li H, et al. Different supports-supported Cr-based catalysts for oxidative dehydrogenation of isobutane with CO₂. Chin J Catal, 2011, 32: 1424-1429 (in Chinese)

[9] Tasbihi M, Feyzi F, Amlashi MA, et al. Effect of the addition of potassium and lithium in Pt–Sn/Al₂O₃ catalysts for the dehydrogenation of isobutane. Fuel Process Technol, 2007, 88: 883-889.

[10] Zhang Y, Zhou Y, Sheng X, et al. Effect of the competitive adsorbates on the catalytic performances of PtSnK/γ-Al₂O₃ catalyst for isobutane dehydrogenation. Fuel Process Technol, 2012, 104: 23-30.

[11] Zangeneh FT, Sahebdelfar S, Bahmani M. Propane dehydrogenation over a commercial Pt–Sn/Al₂O₃ catalyst for isobutane dehydrogenation: optimization of reaction conditions. Chin J Chem Eng, 2013, 21: 730-735.

[12] Zheng C, Qian W, Cui C, et al. Carbon nanotubes for supercapacitors: consideration of cost and chemical vapor deposition techniques. J Nat Gas Chem, 2012, 21: 233-240.

[13] Lee JK, Gould GL, Rhine W. Polyurea based aerogel for a high performance thermal insulation material. J Sol Gel Sci Technol, 2009, 49: 209-220.

[14] Prabhakaran K, Singh PK, Gokhale NM, et al. Processing of sucrose to low density carbon foams. J Mater Sci, 2007, 42: 3894-3900.

[15] Valentin R, Horga R, Bonelli B, et al. Acidity of alginate aerogels studied by FTIR spectroscopy of probe molecules. Symp Macromol, 2005, 230: 71-77.

[16] Malaika A, Wower K, Kozłowski M. Chemically modified activated carbons as catalysts of oxidative dehydrogenation of n-butane. Acta Phys Pol A, 2010, 118: 459-464.

[17] Rao R, Ling Q, Dong H, et al. Effect of surface modification on multi-walled carbon nanotubes for catalytic oxidative dehydrogenation using CO₂ as oxidant. Chem Eng J, 2016, 301: 115-122.

[18] Liang C, Xie H, Schwartz V, et al. Open-cage fullerene-like graphitic carbons as catalysts for oxidative dehydrogenation of isobutane. J Am Chem Soc, 2009, 131: 7735-7741.

[19] Huang R, Liang CH, Su DS, et al. The difference between borate and phosphate modified carbon nanotubes in isopentane oxidative dehydrogenation. Catal Today, 2015, 249: 161-166.

[20] Takita Y, Kurosaki K, Mizuhara Y, et al. Novel catalysts for oxidative dehydrogenation of iso-butane to iso-butene. Chem Lett, 1993, 22: 335-338.

[21] Dong AH, Wang K, Zhu SZ, Yang GB, Wang XT. Facile preparation of PtSn-La/Al₂O₃ catalyst with large pore size and its improved catalytic performance for isobutane dehydrogenation. Fuel Process Technol, 2017, 158: 218-225.

[22] Han JX, Duan JZ, Chen P, et al. Carbon-supported molybdenum carbide catalysts for the conversion of vegetable oils. Chem Sus Chem, 2012, 5: 727-733.

[23] Haug A, Larsen B, Smidsrod O. A study of the constitution of alginic acid by partial acid hydrolysis. Acta Chem Scand, 1996, 20: 183-190.

[24] Raymundo-Pinero E, Leroux F, Béguin F. A high-performance carbon for supercapacitors obtained by carbonization of a seaweed biopolymer. Adv Mater, 2006, 18: 1877-1882.

[25] Pandi K, Viswanathan K. A novel metal coordination enabled in carboxylated alginic acid for effective fluoride removal. Carbohydr Polym, 2015, 118: 242-249.

[26] Centi G, Perathoner S, Su D. Nanocarbons: opening new possibilities for nano-engineered novel catalysts and catalytic electrodes. Catal Surv Asia, 2014, 18: 149-163.

[27] Ermakova MA, Ermakov DY, Plyasova LM. XRD studies of evolution of catalytic nickel nanoparticles during synthesis of filamentous carbon from methane. Catal Lett, 1999, 62: 93-97.

[28] Liu X, Chen J, Zhang J. Hydrodechlorination of chlorobenzene over silica-supported nickel phosphide catalysts. Ind Eng Chem Res, 2008, 47: 5362-5368.