Sulfonic acid catalysts based on porous carbons and polymers

SULFONIC ACID CATALYSTS BASED ON POROUS CARBONS AND POLYMERS TIAN XIAO NING NATIONAL UNIVERSITY OF SINGAPORE 2009 SULFONIC ACID CATALYSTS BASED ON POROUS CARBONS AND POLYMERS TIAN XIAO NING (M.Eng) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMICAL AND BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2009 Acknowledgement Acknowledgement I would like to convey my deepest appreciation to my supervisor, Assoc. Prof. Zhao X. S., George for his constant encouragement, invaluable guidance, patience and understanding throughout the whole period of my PhD candidature. This project had been a tough but enriching experience for me in research. I would like to express my heartfelt thanks to Assoc. Prof. Zhao for his guidance on writing scientific papers including this PhD thesis. In addition, I want to express my sincerest appreciation to the Department of Chemical and Biomolecular Engineering for offering me the chance to study at NUS with a scholarship. It’s my pleasure to work with a group of brilliant, warmhearted and lovely people, Dr. Su Fabing, Dr. Lv Lu, Dr. Zhou Jinkai, Dr. Li Gang, Dr. Wang Likui, Dr. Bai Peng, Ms. Lee Fang Yin, Ms. Liu Jiajia, Ms. Zhang Li Li, Ms. Wu Pingping, Mr. Cai Zhongyu, Mr. Dou Haiqing, and Mr. Zhang Jingtao. Particular acknowledgement goes to Mr. Chia Phai Ann, Mr. Shang Zhenhua, Dr. Yuan Zeliang, Mr. Mao Ning, Dr. Rajarathnam D., Madam Chow Pek Jaslyn, Mdm Fam Hwee Koong Samantha, Ms Lee Chai Keng, Ms Tay Choon Yen, Mr. Toh Keng Chee, Mr. Chun See Chong, Ms. Ng Ai Mei, Ms. Lum Mei Peng Sharon, and Ms. How Yoke Leng Doris for their kind supports. I thank my parents. It is no exaggeration to say that I could not complete the PhD work without their generous help, boundless love, encouragement and support. i Table of Contents Table of Contents Acknowledgement . i Table of Contents ii Summary . v Nomenclature vii List of Tables . viii List of Figures ix Chapter 1. Introduction . 1.1 Solid sulfonic acid catalysts 1.2 Objectives of thesis work 1.3 Structure of thesis . Chapter 2. Literature Review 2.1 Propylsulfonic-modified mesoporous silica . 2.2 Arenesulfonic-acid modified material 18 2.3 Perfluorosulfonic-acid modified mesopouous material 23 2.4 Organosulfonic-modified periodic mesoporous organosilica . 28 2.5 Sulfonic acid-modified carbon 37 2.6 Sulfonic acid-modified resin . 43 Chapter 3. Experimental Section 48 3.1 Reagents and apparatus . 48 3.2 Preparation of sulfonic acid catalysts . 49 ii Table of Contents 3.3 Characterization 53 3.4 Evaluation of conversion for acetic acid . 58 Chapter 4. Sulfonated Mesoporous Carbons and Carbon-silica Composites . 59 4.1 Introduction . 59 4.2 Catalyst preparation 60 4.3 Characterization of sulfonated mesoporous carbons and carbon-silica composites . 60 4.4 Catalytic properties in esterification . 71 4.5 Summary . 73 Chapter 5. Sulfonated Mesoporous Polymer Resins and Carbons . 74 5.1 Introduction . 74 5.2 Catalyst preparation 75 5.3 Characterization of sulfonated mesoporous polymers and carbons 75 5.4 Catalytic properties in esterification . 86 5.5 Summary . 88 Chapter 6. Sulfonated Polypyrrole and Carbon Nanospheres 90 6.1 Introduction . 90 6.2 Catalyst preparation 90 6.3 Characterization of sulfonated polypyrrole and carbon nanospheres . 91 6.4 Catalytic properties in esterification . 91 6.5 Summary . 104 iii Table of Contents Chapter 7. Sulfonated Polystyrene-Divinylnenzene Spheres . 105 7.1 Introduction . 105 7.2 Catalyst preparation 106 7.3 Characterization of sulfonated polystyrene spheres . 106 7.4 Catalytic properties in esterification . 117 7.5 Summary . 118 Chapter 8. Kinetics and Mechanism of Esterification Reaction over Sulfonated Polystyrene-Divinylbenzene Spheres . 120 8.1 Introduction . 120 8.2 Results and Discussion . 122 8.3 Summary . 133 Chapter 9. Conclusions and Recommendations 134 9.1 Conclusions . 134 9.2 Recommendations . 137 References . 139 Appendix: List of publications 152 iv Summary Summary Liquid sulfuric acid is a widely used homogeneous catalyst in many important chemical processes. However, liquid sulfuric acid has a number of problems, such as corrosion, toxicity, and disposal problem. Therefore, solid sulfonic acid catalysts are strongly desired. Over the past few years, solid sulfonic acid materials have been investigated, aimed to replace the liquid sulfuric acid catalyst. The preparation of such solid sulfonic acid materials generally includes functionalization of porous silica, carbon and polymer materials with propylsulfonic acid, arenesulfonic acid, perfluorosulfonic acid and sulfonic acid groups. Carbon in its chemical allotropes of graphite and diamond occurs in a great variety of species and has been developed to a large number of applications as structural and functional materials. The underlying reason for this unique manifold of species is twofold: (1) the co-ordination chemistry of carbon is flexible in allowing continuous mixtures of C=C and C-C bonding in one structure. This leads to an infinite possibility of 3-dimensional structures (e.g.: carbon nanotubes, graphene, C60) and to continuous tenability of structural and physical properties, (2) carbon accepts foreign elements such as hydrogen, boron, oxygen, nitrogen, and sulfur both on its surfaces and within structural framework. This leads to tunable physical and chemical properties. Porous carbons such as activated carbons and carbon fibers have long been used as sorbents, catalyst supports and electrode materials because of their unique properties, such as high surface area, good electric conductivity, tunability of surface chemistry, stability against various chemical environments, and low cost. Their high surface area ensures a high density of catalytic active sites when used as catalysts and catalyst supports. v Summary In this thesis work, carbon materials were prepared and subsequently sulfonated. First, mesoporous carbon was prepared using the hard template method. It was found that a high carbonization temperature resulted in the formation of large carbon sheets, unfavorable for the subsequent functionalization of sulfonic acid groups. On the other hand, sulfonated mesoprorous carbon-silica composites exhibited a better catalytic performance than sulfonated mesoporous carbons. Second, mesoporous phenol resins were synthesized by a soft template method and subsequently carbonized to form mesoporous carbons. Sulfonations were conducted on both mesoporous resins and carbons. Temperature was again found to play an important role in both carbonization and sulfonation. Sulfonated mesoporous phenol resins exhibited a higher conversion and stability than sulfonated mesoporous carbons. Third, polypyrrole nanospheres were synthesized and carbonized to carbon nanospheres. Both polypyrrole and carbon nanospheres were sulfonated. It was found that polypyrrole nanospheres were easier to be sulfonated than carbon nanospheres. Fourth, both linear-linked and cross-linked polystyrene spheres were synthesized and sulfonated. Sulfonated cross-linked polystyrene spheres showed a higher conversion and stable recyclability than linearlinked spheres. Finally, the kinetics and mechanism of esterification reaction of methanol with acetic acid over sulfonated cross-linked polystyrene spheres were investigated. The reaction mechanism was experimentally studied and the reaction kinetics in the micro-kinetic region was modeled. The adsorption equilibrium constants of acetic acid, methanol, and water were found to be 0.2, 0.5, and 4.1 L/mol respectively. The initial rate decreased with the increase of water concentration, showing the inhabitation effect of water. vi Nomenclature Nomenclature DI Deionized C0 Initial concentration (mol/L) ro Initial Reaction Rate (mol/min*L) t Time (min) CVD Chemical vapor deposition CHNS-O BET Elemental analysis Brunauer-Emmett-Teller FESEM Field emission scanning electron microscopy FTIR Fourier Transform Infrared HREM High-Resolution Electron Microsocopy MAS Magic Angle Spinning NMR Nuclear Magnetic Resonance HMS Hexagonal Mesoporous Silica PS Polystyrene SBA Santa Babara SEM Scanning electron microscopy TEM Transmission electron microscopy TEOS Tetraethyl orthosilicate UV Ultraviolet XPS X-ray Photoelectron Spectroscopy XRD X-ray Diffraction vii List of Tables List of Tables Table 3.1 Chemicals used for synthesis of sulfonic acid catalysts. Table 3.2 Apparatus. Table 4.1 Texture parameters of samples before and after sulfonation. Table 4.2 Compositions of samples according to elemental analysis. Table 4.3 Surface compositions of samples according to XPS analysis. Table 5.1 Textural parameters of mesoporous resins and carbons. Table 5.2 The composition of samples analyzed using elemental analysis. Table 6.1 Elemental compositions of samples analyzed using the CHN-S technique. Table 6.2 Surface compositions according to XPS analysis and surface areas of samples. Table 7.1 The acidity titration results. Table 7.2 Composition of samples analyzed using elemental analysis. Table 7.3 Decomposition temperatures of samples. Table 7.4 The preparation parameters and diameter of polymer spheres. Table 8.1 Initial reaction rate by using catalyst with/without swelling in methanol. Table 8.2 Initial reaction rate for the determination of apparent reaction orders of acetic acid and methanol in sulfonated cross-linked polystyrene catalyzed esterification at 55ºC. Table 8.3 Initial reaction rate by using catalyst with/without pre-adsorption in acetic acid. Table 8.4 Pyridine adsorption experiment. Table 9.1 Acid density and conversion of acetic acid for prepared catalysts. viii Charpter 9. Conclusions and Recommendations adding of divinylbenzene the hard core-shell structure inhibited the attachment of sulfonic acid groups, which caused the decrease of acetic acid conversion. The appropriate increase of sulfonation temperature are benefit for the amount and stability of attached –SO3H groups, which are helpful for improvement of the catalytic performance. • For the esterification reaction of acetic acid with methanol catalyzed by sulfonated cross-linked polystyrene-divinylbenzene spheres both reactants had positive affects on the reaction rate with increasing reactant concentration. And single active site was involved in the heterogeneous reaction. Sulfuric acid and sulfonated cross-linked polystyrene-divinylbenzene spheres exhibit the same trend for the whole reaction run process and water deactivation profile. And the mechanistic route involved in esterification reaction catalyzed by sulfonated cross-linked polystyrene-divinylbenzene spheres resembles that of H2SO4. The adsorption equilibrium constants of acetic acid, methanol, and water are 0.2, 0.5, and 4.1L/mol respectively. Initial rate decreased with the increase of added water concentration, which indicates the inhabitation behavior of water. 9.2 Recommendations The present work suggests that solid sulfonic acid catalysts show quite promising results for the esterification reaction of methanol with acetic acid. The quality and stability of attached –SO3H groups play a significant role for improving activity as well as recyclability over esterification reaction. Compared with polymer based sulfonic acid catalysts carbon material based sulfonic acid catalysts can stand for high temperature reaction, because the carbon material was normally produced by high temperature carbonization process. However, the number of attached –SO3H groups is 137 Charpter 9. Conclusions and Recommendations limited and the stability of supported –SO3H groups is not good. For polymer based sulfonic acid catalysts the number and stability of attached –SO3H groups are greatly improved. Therefore polymer based solfonic acid catalysts show higher activity and recyclability in the esterification reaction. However, polymer backbones are not suitable for high temperature reaction, which limits their application. Therefore, much work is still need to be conducted to find out high performance sulfonic aicd catalyst material and efficient way for introducing –SO3H groups. Some recommendations are proposed in following section: • Polymer based sulfonic acid catalysts show high catalytic activity and recyclability over esterification reaction of methanol with acetic acid. Therefore polymer based material is a good choice for sulfonic acid catalyst support. 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Chem., 15, pp.25692574. 2005. 151 Appendix APPENDIX List of publications coming from this thesis work Papers published (or accepted) in international referred journal (1) Tian XN, Su F and Zhao XS. Sulfonated polypyrrole nanospheres as a solid acid cataslyst. GreenChemistry, 2008, 10, 951-956. (2) Xiao Ning Tian, X.S. Zhao. Sulfonated mesoporous carbons as a solid sulfonic acid catalyst. Studies in Surface Science and Catalysis, 2008, Volume 174, Part 2, 13471350. (3) Su F, Zhou Z, Guo W, Liu J, Tian XN and Zhao XS. Template Approaches to Synthesis of Porous Carbon. Chemistry and Physics of Carbon, Vol. 30, Ed: L. R. Radovic, 2008, Vol. 30, 63-128; (4) Liu J, Tian XN, Su F, Lv L and Zhao XS. Hydrogenation of glucose over Ru nanoparticles embedded in templated porous carbon. Australian Journal of Chemistry 2009, in press. Papers submitted to international referred journal (5) Tian XN, Zhang Lili, Bai Peng, and Zhao X.S. Sulfonation of mesoporous polymer and carbon. Submitted to Microporous and Mesoporous Materials, 2009. (6) Tian XN, Zhang Xinhui, Wang Likui, and Zhao X.S. Sulfonated Polystyrene as Strong sulfonic acid catalyst. Submitted to Industrial & Engineering Chemistry Research, 2009. 152 [...]... with Sulfonic Acid Groups (Wang et al., 2007) Figure 4.1 Nitrogen adsorption-desorption isotherms of mesoporous carbons before sulfonation(A), BJH-PSD curves of mesoporous carbons before sulfonation(B), nitrogen adsorption-desorption isotherms of mesoporous carbons after sulfonation(C), BJH-PSD curves of mesoporous carbons after sulfonation(D), nitrogen adsorption-desorption isotherms of sulfonated... preparation of mesoporous phenol resin P123 was adopted as the template Mesoporous carbons were obtained through the carbonization of mesoporous polymer resin Sulfonic acid catalysts based on both mesoporous resin and carbon were prepared The conversion of acetic acid and recyclability for resultant catalysts were affected by the catalyst structure, which was formed under different sulfonation and carbonization... carbonization temperature 3 Chapter 1 Introduction • Polypyrrole nanospheres were prepared and sulfonated to produce polymer based sulfonic acid catalysts Through the carbonization process polypyrrole nanospheres transferred to carbon nanospheres, which were also sulfonated to prepare carbon based sulfonic acid catalysts The conversion of acetic acid and recyclability for sulfonated polypyrrole and carbon... template method was used to prepare mesoporous carbons with high surface area and porous structure Sulfonic acid groups (-SO3H) were then introduced on the carbon surface by using sulfonation reaction Incompletely carbonized carbon-silica composites were prepared The composites facilitated the introduction of sulfonic acid groups due to the presence of small carbon sheets • Porous structure can also be introduced... carbon-silica composites are discussed The effect of carbonization temperature on the physical, chemical and catalytic properties of the resultant solids is presented Chapter 5 discusses sulfonated mesoporous resins and carbons, with an emphasis on the influence of sulfonation and carbonization effects on the materials structural and catalytic properties Chapter 6 describes the esterification reaction... FriedelCrafts, hydration, esterification, and hydrolysis reactions Many of these reactions are still carried out by using conventional liquid acid catalysts like H2SO4 Such liquid catalysts create many inevitable problems, such as high toxicity, corrosion, generation of solid wastes, and difficulty in separation and recovery In comparison, solid acid catalysts have a number of advantages over the liquid ones, such... preparation of silica based sulfonic acid catalysts (Melero et al., 2006) Works dealing with the preparation of organosulfonic-modified silica date from 1998, which are based on the covalent attachment of alkylsulfonic acid groups to the surface of MCM and HMS type materials Pierre A Jacobs and co-workers first functionalized calcined MCM and HMS samples with propane-thiol groups by reaction of the... in-situ oxidation procedure to prepare propylsulfonicmodified hexagonally mesostructured materials (van Grieken et al., 2002) They tailored the pore size of these sulfonic mesoporous materials from 30Å to 110Å conveniently modifying the synthesis conditions using Pluronic 123 as template and acid conditions The catalytic applications for propylsulfonic-modified silica by in-suit oxidation method were... process And the oxidation of thiol groups concurred with the silica preparation Sulfonic acid functionalized porous silicas with uniform pores, high surface area and good stability have been found to exhibit excellent catalytic activities in many reactions, such as esterification (Bossaert et al., 1999; Diaz et al., 2001 b), condensation and addition reactions (Das et al., 2001; Shimizu et al., 2005), and. .. arenesulfonic acid groups They assumed that the oxime rearrangement and hydrolysis were catalyzed on different active sites of –SO3H and Si–OH, respectively In comparison with other porous acid catalysts such as SBA-prSO3H, H-ZSM-5, Al-MCM-41 and Al-SBA-15, the mesoporous arenesulfonicmodified SBA-15 showed higher catalytic activity and lactam selectivity due to the strong acid strength Dual-functionalized . SULFONIC ACID CATALYSTS BASED ON POROUS CARBONS AND POLYMERS TIAN XIAO NING NATIONAL UNIVERSITY OF SINGAPORE 2009 SULFONIC ACID CATALYSTS BASED ON POROUS. template. Mesoporous carbons were obtained through the carbonization of mesoporous polymer resin. Sulfonic acid catalysts based on both mesoporous resin and carbon were prepared. The conversion of. adsorption-desorption isotherms of mesoporous carbons after sulfonation(C), BJH-PSD curves of mesoporous carbons after sulfonation(D), nitrogen adsorption-desorption isotherms of sulfonated carbon-silicate