Оптимизация режимов работы автономной фотоэлектрической станции

Цель работы: оптимизация режимов работы автономной фотоэлектрической станции. В результате исследования построены графики выработки и потребления электрической энергии, выбрано основное энергетическое оборудование миниФЭС, разработана схема, в соответствии со схемой, произведено сравнение тарифов миниФЭС с накопителями энергии и без них.Objective: operating mode optimization of stand- alone PV- station. The study graphs of production and consumption of electric energy, select the main power equipment mini PV-station, a scheme, in accordance with the scheme, a comparison of tariffs and mini PV-station with the storage system and without it

Preparation of Glycerol Carbonate Esters by using Hybrid Nafion-Silica Catalyst

Glycerol carbonate esters (GCEs), which are valuable biomass-deriv. compds., have been prepd. through the direct esterification of glycerol carbonate and long org. acids with different chain lengths, in the absence of solvent, and with heterogeneous catalysts, including acidic-org. resins, zeolites, and hybrid org.-inorg. acids. The best results, in terms of activity and selectivity towards GCEs, were obtained using a Nafion-silica composite. A full reaction scheme has been established, and it has been demonstrated that an undesired competing reaction results in the generation of glycerol and esters derived from a secondary hydrolysis of the endocyclic ester group, which is attributed to water formed during the esterification reaction. The influence of temp., substrate ratio, catalyst-to-substrate ratio, and the use of solvent has been studied and, under optimized reaction conditions and with the adequate catalyst, it was possible to achieve 95 % selectivity for the desired product at 98 % conversion. It was demonstrated that the reaction rate decreased as the no. of carbon atoms in the linear alkyl chain of the carboxylic acid increased for both p-toluenesulfonic acid and Nafion-silica nanocomposite (Nafion SAC-13) catalysts. After fitting the exptl. data to a mechanistically based kinetic model, the reaction kinetic parameters for Nafion SAC-13 catalysis were detd. and compared for reactions involving different carboxylic acids. A kinetic study showed that the reduced reactivity of carboxylic acids with increasing chain lengths could be explained by inductive as well as steric effects.The authors wish to acknowledge the Spanish Science and Innovation Ministry (Consolider Ingenio 2010, CTQ-2011-27550 and MULTICAT CSD2009-00050 projects) and the Generalitat Valenciana (Prometeo program) for their financial support. S.M. thanks the Ministerio de Educacion for a FPI fellowship.Climent Olmedo, MJ.; Corma Canós, A.; Iborra Chornet, S.; Martínez Silvestre, S.; Velty ., A. (2013). Preparation of Glycerol Carbonate Esters by using Hybrid Nafion-Silica Catalyst. ChemSusChem. 6(7):1224-1234. doi:10.1002/cssc.201300146S1224123467BUDRONI, G., & CORMA, A. (2008). Gold and gold–platinum as active and selective catalyst for biomass conversion: Synthesis of γ-butyrolactone and one-pot synthesis of pyrrolidone. Journal of Catalysis, 257(2), 403-408. doi:10.1016/j.jcat.2008.05.031Climent, M. J., Corma, A., & Iborra, S. (2011). Converting carbohydrates to bulk chemicals and fine chemicals over heterogeneous catalysts. Green Chemistry, 13(3), 520. doi:10.1039/c0gc00639dCorma, A., Iborra, S., & Velty, A. (2007). Chemical Routes for the Transformation of Biomass into Chemicals. Chemical Reviews, 107(6), 2411-2502. doi:10.1021/cr050989dMäki‐Arvela, P., Holmbom, B., Salmi, T., & Murzin, D. Y. (2007). Recent Progress in Synthesis of Fine and Specialty Chemicals from Wood and Other Biomass by Heterogeneous Catalytic Processes. Catalysis Reviews, 49(3), 197-340. doi:10.1080/01614940701313127Arias, K. S., Al-Resayes, S. I., Climent, M. J., Corma, A., & Iborra, S. (2013). From Biomass to Chemicals: Synthesis of Precursors of Biodegradable Surfactants from 5-Hydroxymethylfurfural. ChemSusChem, 6(1), 123-131. doi:10.1002/cssc.201200513Biodiesel Production 2004Vicente, G., Martı́nez, M., & Aracil, J. (2004). Integrated biodiesel production: a comparison of different homogeneous catalysts systems. Bioresource Technology, 92(3), 297-305. doi:10.1016/j.biortech.2003.08.014Behr, A., Eilting, J., Irawadi, K., Leschinski, J., & Lindner, F. (2008). Improved utilisation of renewable resources: New important derivatives of glycerol. Green Chem., 10(1), 13-30. doi:10.1039/b710561dPagliaro, M., Ciriminna, R., Kimura, H., Rossi, M., & Della Pina, C. (2007). Von Glycerin zu höherwertigen Produkten. Angewandte Chemie, 119(24), 4516-4522. doi:10.1002/ange.200604694Pagliaro, M., Ciriminna, R., Kimura, H., Rossi, M., & Della Pina, C. (2007). From Glycerol to Value-Added Products. Angewandte Chemie International Edition, 46(24), 4434-4440. doi:10.1002/anie.200604694Climent, M. J., Corma, A., De Frutos, P., Iborra, S., Noy, M., Velty, A., & Concepción, P. (2010). Chemicals from biomass: Synthesis of glycerol carbonate by transesterification and carbonylation with urea with hydrotalcite catalysts. The role of acid–base pairs. Journal of Catalysis, 269(1), 140-149. doi:10.1016/j.jcat.2009.11.001Schäffner, B., Schäffner, F., Verevkin, S. P., & Börner, A. (2010). Organic Carbonates as Solvents in Synthesis and Catalysis. Chemical Reviews, 110(8), 4554-4581. doi:10.1021/cr900393dSonnati, M. O., Amigoni, S., Taffin de Givenchy, E. P., Darmanin, T., Choulet, O., & Guittard, F. (2013). Glycerol carbonate as a versatile building block for tomorrow: synthesis, reactivity, properties and applications. Green Chem., 15(2), 283-306. doi:10.1039/c2gc36525aClements, J. H. (2003). Reactive Applications of Cyclic Alkylene Carbonates. Industrial & Engineering Chemistry Research, 42(4), 663-674. doi:10.1021/ie020678iR. B. Raether BASF SE 2012Studies in Surface Science and Catalysis 2001 135 (Zeolites and Mesoporous Materials at the Dawn of the 21st Century)Dibenedetto, A., Angelini, A., Aresta, M., Ethiraj, J., Fragale, C., & Nocito, F. (2011). Converting wastes into added value products: from glycerol to glycerol carbonate, glycidol and epichlorohydrin using environmentally friendly synthetic routes. Tetrahedron, 67(6), 1308-1313. doi:10.1016/j.tet.2010.11.070D. Balthasart 2010Mouloungui, Z., & Pelet, S. (2001). Study of the acyl transfer reaction: Structure and properties of glycerol carbonate esters. European Journal of Lipid Science and Technology, 103(4), 216-222. doi:10.1002/1438-9312(200104)103:43.0.co;2-jShaikh, A.-A. G., & Sivaram, S. (1996). Organic Carbonates†. Chemical Reviews, 96(3), 951-976. doi:10.1021/cr950067iHAMAGUCHI, S., YAMAMURA, H., HASEGAWA, J., & WATANABE, K. (1985). Biological resolution of racemic 2-oxazolidinones. Part IV. Enzymatic resolution of 2-oxazolidinone esters. Agricultural and Biological Chemistry, 49(5), 1509-1511. doi:10.1271/bbb1961.49.1509Oehlenschläger, J., & Gercken, G. (1978). Synthesis and mass spectrometry of 1-acyl and 3-acyl-sn-glycerol carbonates. Lipids, 13(8), 557-562. doi:10.1007/bf02533595Palaskar, D. V., Sane, P. S., & Wadgaonkar, P. P. (2010). A new ATRP initiator for synthesis of cyclic carbonate-terminated poly(methyl methacrylate). Reactive and Functional Polymers, 70(12), 931-937. doi:10.1016/j.reactfunctpolym.2010.08.005Katz, H. E. (1987). Preparation of soluble poly(carbonyldioxyglyceryl methacrylate). Macromolecules, 20(8), 2026-2027. doi:10.1021/ma00174a057Britz, J., Meyer, W. H., & Wegner, G. (2007). Blends of Poly(meth)acrylates with 2-Oxo-(1,3)dioxolane Side Chains and Lithium Salts as Lithium Ion Conductors. Macromolecules, 40(21), 7558-7565. doi:10.1021/ma0714619G. F. D′Alelio Scott Paper Co. 1965D’Alelio, G. F., & Huemmer, T. (1967). Preparation and polymerization of some vinyl monomers containing the 2-oxo-1,3-dioxolane group. Journal of Polymer Science Part A-1: Polymer Chemistry, 5(2), 307-321. doi:10.1002/pol.1967.150050208D. Grahe D. Lachowicz Dainippon Ink Chemical Industry Co. 1989J. J. Whelan R. J. Cotter 1963I. Frischinger J. Cotting J. Finter J. François 2003Ochiai, B., Ootani, Y., Maruyama, T., & Endo, T. (2007). Synthesis and properties of polymethacrylate bearing cyclic carbonate through urethane linkage. Journal of Polymer Science Part A: Polymer Chemistry, 45(24), 5781-5789. doi:10.1002/pola.22327J. C. Fang E. I. du Pont de Nemours & Co. 1961B. Schmitt M. Caspari 2008Ramaiah, M. (1985). A new convenient method for esterification using the Ph3P/CCl4 system. The Journal of Organic Chemistry, 50(24), 4991-4993. doi:10.1021/jo00224a076J. M. Renga F. D. Coms E. R. Humphreys Henkel Corp. 1993G. Brindoepke Hoechst A.-G., Fed. Rep. Ger. 1987Jana, S., Yu, H., Parthiban, A., & Chai, C. L. L. (2010). Controlled synthesis and functionalization of PEGylated methacrylates bearing cyclic carbonate pendant groups. Journal of Polymer Science Part A: Polymer Chemistry, 48(7), 1622-1632. doi:10.1002/pola.23928A. Lachowicz G. F. Grahe Dainippon Ink Chemical Industry Co. 1991Yadav, G. ., & Thathagar, M. . (2002). Esterification of maleic acid with ethanol over cation-exchange resin catalysts. Reactive and Functional Polymers, 52(2), 99-110. doi:10.1016/s1381-5148(02)00086-xCorma, A. (1995). Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions. Chemical Reviews, 95(3), 559-614. doi:10.1021/cr00035a006Corma, A., Hamid, S. B. A., Iborra, S., & Velty, A. (2008). Surfactants from Biomass: A Two-Step Cascade Reaction for the Synthesis of Sorbitol Fatty Acid Esters Using Solid Acid Catalysts. ChemSusChem, 1(1-2), 85-90. doi:10.1002/cssc.200700109CHU, W., YANG, X., YE, X., & WU, Y. (1996). Vapor phase esterification catalyzed by immobilized dodecatungstosilicic acid (SiW12) on activated carbon. Applied Catalysis A: General, 145(1-2), 125-140. doi:10.1016/0926-860x(96)00109-3Sepúlveda, J. H., Yori, J. C., & Vera, C. R. (2005). Repeated use of supported H3PW12O40 catalysts in the liquid phase esterification of acetic acid with butanol. Applied Catalysis A: General, 288(1-2), 18-24. doi:10.1016/j.apcata.2005.03.038Jermy, B. R., & Pandurangan, A. (2005). Catalytic application of Al-MCM-41 in the esterification of acetic acid with various alcohols. Applied Catalysis A: General, 288(1-2), 25-33. doi:10.1016/j.apcata.2005.03.047Kirumakki, S. R., Nagaraju, N., Chary, K. V. R., & Narayanan, S. (2003). Kinetics of esterification of aromatic carboxylic acids over zeolites Hβ and HZSM5 using dimethyl carbonate. Applied Catalysis A: General, 248(1-2), 161-167. doi:10.1016/s0926-860x(03)00152-2Izumi, Y., & Urabe, K. (1981). CATALYSIS OF HETEROPOLY ACIDS ENTRAPPED IN ACTIVATED CARBON. Chemistry Letters, 10(5), 663-666. doi:10.1246/cl.1981.663Mauritz, K. A., & Moore, R. B. (2004). State of Understanding of Nafion. Chemical Reviews, 104(10), 4535-4586. doi:10.1021/cr0207123Harmer, M. A., Farneth, W. E., & Sun, Q. (1996). High Surface Area Nafion†Resin/Silica Nanocomposites:  A New Class of Solid Acid Catalyst. Journal of the American Chemical Society, 118(33), 7708-7715. doi:10.1021/ja9541950Harmer, M. A., Sun, Q., Vega, A. J., Farneth, W. E., Heidekum, A., & Hoelderich, W. F. (2000). Nafion resin–silica nanocomposite solid acid catalysts. Microstructure–processing–property correlations. Green Chemistry, 2(1), 7-14. doi:10.1039/a907892dHarmer, M. A., & Sun, Q. (2001). Solid acid catalysis using ion-exchange resins. Applied Catalysis A: General, 221(1-2), 45-62. doi:10.1016/s0926-860x(01)00794-3Botella, P., Corma, A., & López-Nieto, J. M. (1999). The Influence of Textural and Compositional Characteristics of Nafion/Silica Composites on Isobutane/2-Butene Alkylation. Journal of Catalysis, 185(2), 371-377. doi:10.1006/jcat.1999.2502Heidekum, A., Harmer, M. A., & Hoelderich, W. F. (1999). Addition of Carboxylic Acids to Cyclic Olefins Catalyzed by Strong Acidic Ion-Exchange Resins. Journal of Catalysis, 181(2), 217-222. doi:10.1006/jcat.1998.2300Heidekum, A., Harmer, M. A., & Hoelderich, W. F. (1999). Nafion/Silica Composite Material Reveals High Catalytic Potential in Acylation Reactions. Journal of Catalysis, 188(1), 230-232. doi:10.1006/jcat.1999.2656Török, B., Kiricsi, I., Molnár, Á., & Olah, G. A. (2000). Acidity and Catalytic Activity of a Nafion-H/Silica Nanocomposite Catalyst Compared with a Silica-Supported Nafion Sample. Journal of Catalysis, 193(1), 132-138. doi:10.1006/jcat.2000.2869Laufer, M. (2003). Synthesis of 7-hydroxycoumarins by Pechmann reaction using Nafion resin/silica nanocomposites as catalysts. Journal of Catalysis, 218(2), 315-320. doi:10.1016/s0021-9517(03)00073-3Beltrame, P., & Zuretti, G. (2003). The reaction of naphthalene with benzyl alcohol over a Nafion-silica composite: a kinetic study. Applied Catalysis A: General, 248(1-2), 75-83. doi:10.1016/s0926-860x(03)00149-2Ledneczki, I., & Molnár, Á. (2004). Efficient and Selective Formation of Mixed Acetals by Nafion‐H SAC‐13 Silica Nanocomposite Solid Acid Catalyst. Synthetic Communications, 34(20), 3683-3690. doi:10.1081/scc-200032419Ledneczki, I., Darányi, M., Fülöp, F., & Molnár, Á. (2005). SAC-13 silica nanocomposite solid acid catalyst in organic synthesis. Catalysis Today, 100(3-4), 437-440. doi:10.1016/j.cattod.2004.09.076Chézeau, J.-M., Delmotte, L., Guth, J.-L., & Soulard, M. (1989). High-resolution solid-state 29Si and 13C n.m.r. on highly siliceous MFI-type zeolites synthesized in nonalkaline fluoride medium. Zeolites, 9(1), 78-80. doi:10.1016/0144-2449(89)90013-4Rönnback, R., Salmi, T., Vuori, A., Haario, H., Lehtonen, J., Sundqvist, A., & Tirronen, E. (1997). Development of a kinetic model for the esterification of acetic acid with methanol in the presence of a homogeneous acid catalyst. Chemical Engineering Science, 52(19), 3369-3381. doi:10.1016/s0009-2509(97)00139-5Fujimoto, H., Mizutani, Y., Endo, J., & Jinbu, Y. (1989). Theoretical study of substituent effects. Analysis of steric repulsion by means of paired interacting orbitals. The Journal of Organic Chemistry, 54(11), 2568-2573. doi:10.1021/jo00272a021Charton, M. (1975). Steric effects. I. Esterification and acid-catalyzed hydrolysis of esters. Journal of the American Chemical Society, 97(6), 1552-1556. doi:10.1021/ja00839a047LIU, Y., LOTERO, E., & GOODWINJR, J. (2006). Effect of carbon chain length on esterification of carboxylic acids with methanol using acid catalysis. Journal of Catalysis, 243(2), 221-228. doi:10.1016/j.jcat.2006.07.013Fujita, T., Takayama, C., & Nakajima, M. (1973). Nature and composition of Taft-Hancock steric constants. The Journal of Organic Chemistry, 38(9), 1623-1630. doi:10.1021/jo00949a001Datta, D., & Majumdar, D. (1991). Steric effects of alkyl groups: A ?cone angle? approach. Journal of Physical Organic Chemistry, 4(10), 611-617. doi:10.1002/poc.610041005Eder, F., Stockenhuber, M., & Lercher, J. A. (1997). Brønsted Acid Site and Pore Controlled Siting of Alkane Sorption in Acidic Molecular Sieves. The Journal of Physical Chemistry B, 101(27), 5414-5419. doi:10.1021/jp9706487Corma, A. (1997). Organic reactions catalyzed over solid acids. Catalysis Today, 38(3), 257-308. doi:10.1016/s0920-5861(97)81500-1Omota, F., Dimian, A. ., & Bliek, A. (2003). Fatty acid esterification by reactive distillation: Part 2—kinetics-based design for sulphated zirconia catalysts. Chemical Engineering Science, 58(14), 3175-3185. doi:10.1016/s0009-2509(03)00154-4Melián-Cabrera, I., Kapteijn, F., & Moulijn, J. A. (2006). Tooling up Heterogeneous Catalysis through Fenton’s Chemistry. Detemplation and functionalization of micro- And mesoporous materials. Scientific Bases for the Preparation of Heterogeneous Catalysts, 37-46. doi:10.1016/s0167-2991(06)80888-8Melián-Cabrera, I., Osman, A. H., van Eck, E. R. H., Kentgens, A. P. M., Polushkin, E., Kapteijn, F., & Moulijn, J. A. (2007). Fenton detemplation of ordered (meso)porous materials. Studies in Surface Science and Catalysis, 648-654. doi:10.1016/s0167-2991(07)80904-9Leonowicz, M. E., Lawton, J. A., Lawton, S. L., & Rubin, M. K. (1994). MCM-22: A Molecular Sieve with Two Independent Multidimensional Channel Systems. Science, 264(5167), 1910-1913. doi:10.1126/science.264.5167.1910Corma, A., Corell, C., Llopis, F., Marti´nez, A., & Pe´rez-Pariente, J. (1994). Proposed pore volume topology of zeolite MCM-22 based on catalytic tests. Applied Catalysis A: General, 115(1), 121-134. doi:10.1016/0926-860x(94)80382-xCorma, A., Fornes, V., Pergher, S. B., Maesen, T. L. M., & Buglass, J. G. (1998). Delaminated zeolite precursors as selective acidic catalysts. Nature, 396(6709), 353-356. doi:10.1038/24592H. A. Goldsmith Colgate-Palmolive-Peet Co. 195

Organische Reaktionen an stark sauren Nafion-Silica nanokompositen Katalysatoren

This paper decribes the study on several organic reactions over highly acidic Nafion/Silica catalysts. Via embedding nano-sized Nafion particles within a highly porous silica matrix, a nano-composite catalyst is manufactured, which got tremendously improved desorption and adsorption properties. This implies improvements in the catalytic activity. Due to the rigid silica framework, the acidic composite catalyst is even able to catalyze gaseous organic reactions. The scope of the explored organic reactions implies the dimerization of alpha-methlystyrene, Friedel Crafts acylation reactions, Fries rearrangements, electrophilic additions of carboxylic acids or water to monocyclic unsaturated carbohydrates, Pinacolon rearrangements and especially reactions in the vapour phase. In all studied reactions the impact of the solvent has been thoroughly discussed. The results were evaluated in comparison to alternative catalysts like acidic ion-exchange resins as well as to zeolithes e.g. H-BEA

Organische Reaktionen an stark sauren Nafion-Silica nanokompositen Katalysatoren

This paper decribes the study on several organic reactions over highly acidic Nafion/Silica catalysts. Via embedding nano-sized Nafion particles within a highly porous silica matrix, a nano-composite catalyst is manufactured, which got tremendously improved desorption and adsorption properties. This implies improvements in the catalytic activity. Due to the rigid silica framework, the acidic composite catalyst is even able to catalyze gaseous organic reactions. The scope of the explored organic reactions implies the dimerization of alpha-methlystyrene, Friedel Crafts acylation reactions, Fries rearrangements, electrophilic additions of carboxylic acids or water to monocyclic unsaturated carbohydrates, Pinacolon rearrangements and especially reactions in the vapour phase. In all studied reactions the impact of the solvent has been thoroughly discussed. The results were evaluated in comparison to alternative catalysts like acidic ion-exchange resins as well as to zeolithes e.g. H-BEA