MEZINÁRODNÍ KONFERENCE projektu Partnerství pro chemii

MEZINÁRODNÍ KONFERENCE projektu Partnerství pro chemii Motto konference: MOZKY BUDOUCNOSTI aneb budoucí vývoj a výzvy technického vzdělání a jeho vazba na průmysl v EU Sborník příspěvků 19. 20.9. 2013, Pardubice

Mezinárodní konference projektu PARTNERSTVÍ PRO CHEMII Editor Petr Teplý Vědecký výbor doc. Ing. Libor Čapek, Ph.D. prof. Ing. Petr Kalenda, CSc. prof. Ing. Andréa Kalendová, Dr. Ing. Daniel Rubeš Ing. Petr Teplý, CSc. Ing. David Veselý, Ph.D. Univerzita Pardubice, 2013 ISBN 978-80-7395-672-1 Všechny příspěvky uvedené ve sborníku byly recenzovány Vědeckým výborem konference.

OBSAH. CONTENT. PARTNERSTVÍ PRO CHEMII PARTNERSHIP FOR CHEMISTRY 10 NOVÉ ANTIKOROZNÍ PIGMENTY NA BÁZI FERITŮ NEW ANTICORROSION PIGMENTS BASED ON FERRITE COMPOUNDS Petr Benda, Andréa Kalendová. 14 STUDIUM ODBOURÁVÁNÍ ORANŽE II ZA POUŽITÍ ODLIŠNÝCH ČÁSTIC S RŮZNÝMI FOTOAKTIVNÍMI VRSTVAMI THE STUDY OF PHOTOCHEMICAL DEGRADATION OF ACID ORANGE II ON DIFFERENT PARTICLES WITH VARIOUS PHOTOACTIVE LAYERS Nela Bendáková, Søren Poulsen. 16 DISTRIBUCE VANADOVÝCH ČÁSTIC NA MESOPORÉZNÍCH MATERIÁLECH S ROZÍLNÝM OBSAHEM ALUMINY A JEJICH KATALYTICKÁ AKTIVITA V OXIDATIVNÍ DEHYDROGENACI ETANU DISTRIBUTION OF VANADIUM SPECIES ON MESOPOROUS MATERIALS WITH DIFFERENT ALUMINA CONTENT AND THEIR ROLE ON CATALYTIC ACTIVITY IN ODH OF ETHANE Šárka Botková, Libor Čapek, Michal Setnička, Roman Bulánek, Arnošt Zukal..18 OXYCELULÓZA IDEÁLNÍ SORPČNÍ MATERIÁL OXYCELLULOSE IDEAL SORPTION MATERIAL Michaela Filipi, Miloslav Milichovský..20 TUHOST V OHYBU BUNIČINY Z ŘEPKOVÉ SLÁMY BENDING STIFFNESS OF RAPESED STRAW PULP Bijay Gurung, František Potůček..22 PŘÍPRAVA BUTYLESTERŮ TRANSESTERIFIKACÍ ŘEPKOVÉHO OLEJE BUTYL ESTERS PREPARATION BY TRANSESTERIFICATION OF RAPESEED OIL Martin Hájek, Robert Macura, František Skopal, Jaroslav Kocík.24

HYPERMOLEKULÁRNÍ VLASTNOSTI CELULÓZOVÝCH MATERIÁLŮ HYPERMOLECULAR PROPERTIES OF CELULLOSE MATERIALS Matěj Hájek, Michaela Filipi, Andréa Kalendová.26 NATRONOVÁ VÁRKA ŘEPKOVÉ SLÁMY SODA PULPING OF RAPESEED STRAW Kateřina Hájková, Bijay Gurung, František Potůček 28 ANTIKOROZNÍ VLASTNOSTI SMĚSNÝCH OXIDU MODIFIKOVANÝCH POLYANILINEM V NÁTĚRECH NA BÁZI ALKYDU ANTICORROSION PROPERTIES OF MIXED OXIDES SURFACE-MODIFIED WITH A POLYANILYNINE PHOSPHATE LAYER IN ALKYDE BASED COATINGS Tereza Hájková, Andréa Kalendová..30 PIGMENTY S OBSAHEM TITANU PRO ANTIKOROZNÍ ORGANICKÉ NÁTĚRY PIGMENTS WITH THE CONTENT OF TI FOR ANTICORROSION ORGANIC COATINGS Martina Hejdová, Andréa Kalendová...33 VLIV SKLADOVATELNOSTI NA AKRYLÁTOVÉ NÁTĚROVÉ HMOTY OBSAHUJÍCÍ ORGANICKÉ BIOCIDY INFLUENCE OF SHELF-LIFE STABILITY TO ACRYLIC COATINGS BASED ON ORGANIC BIOCIDES Veronika Jašková, Libuše Hochmannová, Jarmila Vytřasová, Andréa Kalendová 36 POTENCIÁL Mg/Al A Ca/Al SMĚSNÝCH OXIDŮ PRO PŘÍPRAVU BIONAFTY THE POTENCIAL OF Mg/Al AND Ca/Al MIXED OXIDE FOR BIODIESEL PREPARATION Jaroslav Kocík, Martin Hájek, Petr Kutálek, Lucie Smoláková, Libor Čapek, Ivana Troppová.38

VLIV AMORFNÍCH CHALKOGENIDŮ NA KOROZNÍ VLASTNOSTI ORGANICKÝCH POVLAKŮ S VYSOKÝM OBSAHEM KOVOVÉHO ZINKU THE EFFECT OF AMORPHOUS CHALCOGENIDES ON CORROSIVE PROPERTIES OF ORGANIC COATINGS CONTAINING HIGH CONTENT OF ZINC METAL PARTICLES Miroslav Kohl, Andréa Kalendová 40 KATALYTICKÉ VLASTNOSTI NI-ČÁSTIC V NI-ALUMINA KATALYZÁTORECH PŘI OXIDATIVNÍ DEHYDROGENACI ETHANU A PROPANU ROLE OF NI-SPECIES ON THE CATALYTIC BEHAVIOUR OF NI-ALUMINA CATALYSTS IN THE OXIDATIVE DEHYDROGENATION OF ETHANE AND PROPANE Martin Kout, Lucie Smoláková, Peter Priecel, Agnieszka Soltysek, Libor Čapek...42 PROBLEMATIKA BIODEGRADABILNÍCH SAMOSEKVESTRUJÍCÍCH TENZIDŮ THE PROBLEM OF BIODEGRADABLE SELF-SEQUESTERING SURFACTANTS Lucia Krištofíková, Petra Bayerová, Ladislav Burgert..45 NÁTĚROVÉ HMOTY S NÍZKÝM OBSAHEM VOC OBSAHUJÍCÍ NETOXICKÉ ANTIKOROZNÍ PIGMENTY LOW VOC COATINGS PIGMENTED WITH ECO-FRIENDLY ANTICORROSIVE PIGMENTS Helena Kukačková, Andrea Vraštilová, Andréa Kalendová. 47 PŘÍPRAVA REDOXNÍCH NÍZKOROZMĚRNÝCH OXIDŮ TITANU PREPARATION OF REDOX LOW DIMENSIONAL TITANIUM OXIDE Zdeněk Kváča, Martin Mohyla, Petr Kalenda, Andrea Kalendová. 49

FUNKCIONALIZOVANÉ CORE-SHELL MIKROGELY PŘIPRAVENÉ EMULZNÍ POLYMERACÍ FUNCTIONALISED CORE-SHELL MICROGELS PREPARED BY EMULSION POLYMERISATION Jana Machotová, Jaromír Šňupárek, Miroslav Večeřa...52 POLITIKA ZAMĚSTNANOSTI EMPLOYMENT POLICY Jana Majerová.54 VLIV ATMOSFÉRY TVOŘENÉ OXIDY DUSÍKU NA PROCES STÁRNUTÍ PÓROVITÝCH MATERIÁLŮ NA CELULÓZOVÉ A LIGNOCELULÓZOVÉ BÁZI STUDY OF NITROGEN OXIDE ATMOSPHERE ON AGING PROCESS OF POROUS MATERIALS ON CELULOSE AND LIGNOCELLULOSE BASE Ondřej Mikala, Miloslav Milichovský, Michaela Filipi, Jan Gojný 56 POUŽITÍ POLYMERNÍCH STABILIZÁTORŮ PRO STABILIZACI HOUŽEVNATÉHO POLYSTYRENU THE USE OF POLYMER STABILIZERS FOR STABILIZING IMPACT POLYSTYRENE Zuzana Nádvorníková, Miroslav Večeřa, Lucie Zárybnická.58 UNIVERZITA, VĚDA, SPOLEČNOST UNIVERSITY, SCIENCE, SOCIETY Aleš Prázný.60

(η 3 -ALLYL)-(η 5 -CYKLOPENTADIENYL)-DIKARBONYLMOLYBDENATÝ KOMPLEX A JEHO DERIVÁTY JAKO NETOXICKÁ ADITIVA DO OXOPOLYMERAČNĚ ZASYCHAJÍCÍCH NÁTĚROVÝCH HMOT (η 3 -ALLYL)-(η 5 -CYKLOPENTADIENYL)-DIKARBONYLMOLYBDENIUM COMPLEX AND ITS DERIVATES AS NON TOXIC ADDITIVES TO OXOPOLYMERATION DRYING PAINTS Ondřej Preininger, Jan Honzíček, Jaromír Vinklárek, Milan Erben 63 MIKROENKAPSLOVANÁ BARVIVA A JEJICH VLIV NA BARVICÍ PROCES PŘI BARVENÍ USNÍ MICROENCAPSULATED DYESTUFFS AND THEIR EFFECT ON THE COLOURATION PROCESS IN THE LEATHER DYEING Nasanjargal Purev, Ladislav Burgert, Petr Přichystal, Michal Černý, Radim Hrdina, Jiří Kühn.66 CHARAKTERIZACE SPECIÁLNÍCH OXIDICKÝCH ANTIKOROZNÍCH PIGMENTŮ RENTGENOVOU ANALÝZOU CHARACTERIZATION OF SPECIAL OXIDIC ANTICORROSIVE PIGMENTS BY X - RAY ANALYSIS Petr Ryšánek, Petr Antoš, Andréa Kalendová..68 VLIV Ce JAKOŽTO PROMOTORU NA KATALYTICKÉ VLASTNOSTI Ni- ALUMINA KATALYZÁTORŮ V ODH REAKCI INFLUENCE OF DOPING CE PROMOTER TO THE NI-ALUMINA CATALYSTS ON THE ACTIVITY IN THE ODH REACTION Agnieszka Sołtysek, Lucie Smoláková, Šárka Botková, Libor Čapek, Peter Priecel, Martin Kout.71

MIGRACE ŽELEZO-ARENOVÉHO FOTOINICIÁTORU Z VYTVRZENÉHO POLYMERNÍHO FILMU MIGRATION OF IRONE-ARENE PHOTOINITIATOR FROM CURED POLYMER FILM Ondřej Škola, Bohumil Jašúrek, Petr Němec.73 BAZICKÉ VLASTNOSTI MG-AL HYDROTALCITŮ BASIC PROPERTIES OF MG-AL HYDROTALCITE-BASED MATERIALS Ivana Troppová, Libor Čapek, Petr Kutálek, Lucie Smoláková, Martin Hájek, Eva Frýdová, David Kubička 75 EKOLOGICKÉ PIGMENTY NA BÁZI SMĚSNÝCH OXIDU V ALKYDOVÝCH NÁTĚRECH ECOLOGICAL PIGMENTS BASED ON MIXED OXIDE PIGMENTS IN ALKYD BASED COATINGS Miroslav Ulbrich, Andréa Kalendová..78 MODIFIKOVANÉ PRYSKYŘICE KYANÁTOVÉHO TYPU MODIFIED CYANATE RESINS Ondřej Vodochodský, Miroslav Večeřa, Luboš Prokůpek 81 STUDIUM VLIVU MIKROENKAPSULACE TEXTILNÍCH KYSELÝCH BARVIV NA VYBARVENÍ POLYAMIDU STUDY OF THE INFLUENCE MICROENCAPSULATION OF THE TEXTILE S ACID DYES FOR DYEING POLYAMID Adam Vojtovič, Michal Černý, Petra Bayerová, Ladislav Burgert..83

ALTERNATIVNÍ MOŽNOSTI ODSTRAŇOVÁNÍ SLOUČENIN ZVYŠUJÍCÍCH PARAMETR AOX Z PRŮMYSLOVÝCH ODPADNÍCH VOD ALTERNATIVE POSSIBILITIES FOR REMOVAL OF HALOGENATED AROMATIC COMPOUNDS FROM INDUSTRIAL WASTE WATERS Tomáš Weidlich, Tereza Fulínová, Lenka Krchová, Lucie Josková.85 ANTIDEGRADANTY KOVALENTNĚ VÁZANÉ NA HOUŽEVNATÝ POLYSTYREN A POLYETHYLEN ANTIDEGRADANTS COVALENTLY BOUND TO HIGH IMPACT POLYSTYRENE AND POLYETHYLENE Lucie Zárybnická, Miroslav Večeřa, Zuzana Nádvorníková,Vladimír Špaček 87 RF SPUTTERED AMORPHOUS CHALCOGENIDE THIN FILMS FOR SURFACE ENHANCED INFRARED ABSORPTION SPECTROSCOPY F. Verger, V. Nazabal, F. Colas, P. Nemec, R. Chahal, B. Bureau, E. Rinnert, C. Cardinaud, I. Peron, S. Deputier, J.P. Guin, H. Lhermite, A. Moreac, C. Compère 89 RESEARCH ON NON-CONVENTIONAL GLASSES: RELATIONSHIPS WITH INDUSTRY AND FRENCH RESEARCH INSTITUTIONS Virginie Nazabal, Xiang-Hua Zhang and Jean-Luc Adam.91 POZNÁMKY.92

PARTNERSTVÍ PRO CHEMII Projekt číslo: CZ.1.07/2.4.00/31.0062 Operační program: Vzdělávání pro konkurenceschopnost, Prioritní osa: Terciární vzdělávání, výzkum a vývoj Oblast podpory: Partnerství a sítě Doba realizace: 1. 2. 2012 31. 1. 2014 Hlavní kordinátor: prof.ing.petr Kalenda,CSc., proděkan FChT Univerzity Pardubice Hlavní cíle projektu dlouhodobé a krátkodobé odborné stáže studentů Univerzity Pardubice, Fakulty chemicko-technologické u partnerů projektu propojení vědecko-výzkumné aktivity Univerzity Pardubice a průmyslových partnerů zvýšení uplatnitelnosti studentů na trhu práce (odborné praxe, kurzy) zvýšení odborné kvalifikace vysokoškolských zaměstnanců a garantů z praxe vznik interaktivního komunikačního portálu www.ceskachemie.cz rozvoj spolupráce mezi studenty, akademickými, výzkumnými a vývojovými pracovníky v daném oboru vytvoření Centra profesních kontaktů workshopy, semináře, konference zviditelňující výzkum i praxi chemického průmyslu Synthesia, a.s. společnost exportující větší část produkce, 90letá tradice v oblasti chemických výrobků 1600 zaměstnanců pracuje ve 4 základních segmentech (Pigmenty a barviva, Organika, Nitroceluóza, Energetika) držitel světově uznávaných standardů ISO 9001, ISO 14001 a OHSAS 18001 10

DEZA, a.s. společnost je světově významným podnikem v oboru zpracování černouhelného dehtu a benzolu, 120letá tradice produkty vznikající při koksování černého uhlí jsou zpracovávány na základní aromatické chemikálie (benzen, naftalen, fenoly, změkčovadla) přibližně 1000 zaměstnanců pracuje ve firmě certifikované dle ISO 9001 a usilující o ISO 14001 a ISO 16001 Fatra, a.s. exportně zaměřený výrobce s téměř 80letou tradicí v oblasti zpracování plastů s cca 1000 zaměstnanci se řadí mezi největší zpracovatele plastů (PVC, PE, PP, PET) ve střední Evropě pracovní procesy a vztah k životnímu prostředí se řídí standardy ISO 9001 a ISO 14001 PRECHEZA, a.s. téměř 120letá tradice výroby anorganických chemických produktů, 45 let výroby anorganických pigmentů přibližně se 600 zaměstnanci je firma největším výrobcem anorganických pigmentů (titanová běloba, železité pigmenty) v ČR držitel mezinárodních standardů ISO 9001, ISO 14001 a OHSAS 18001 Lovochemie, a.s. největší výrobce hnojiv v ČR s již téměř 110letou tradicí 650 zaměstnanců vyrábí dusíkatá i vícesložková hnojiva v tuhé i kapalné formě držitel světových standardů ISO 9001 a ISO 14001 PREOL, a.s. centrum pro vývoj a výrobu biopaliv, od roku 2009 největší výrobce MEŘO v ČR 11

řepkové semeno se zpracovává na potravinářský rostlinný olej, MEŘO, řepkový šrot a glycerin v současné době 118 zaměstnanců, mimo jiné certifikát ISO 9001 a GMP+B2 VÚOS, a.s. společnost vyvíjející aktivity zvláště v oblasti vývoje a výroby chemických specialit, 70letá tradice celkem 280 zaměstnanců je dále připraveno řešit problematiku dle legislativy REACH a provádět toxikologická testování akreditace dle ČSN EN ISO/IEC 17025 a ISO EN 45011, certifikace ISO 9001 ČTCAP, a.s. hlavní činností je výzkum a vývoj v oblasti anorganických pigmentů a jejich aplikací 24 zaměstnanců se věnuje především problematice titanové běloby, železitých pigmentů a nanomateriálů úzká spolupráce s akademickými výzkumnými pracovišti v tuzemsku i zahraničí EIRLZ, občanské sdružení rozvoj terciálního vzdělávání a vědecké a výzkumné činnosti s důrazem na podporu spolupráce mezi institucemi terciálního vzdělávání, výzkumnými organizacemi a podnikatelským, veřejným a neziskovým sektorem PARTNERSHIP FOR CHEMISTRY Project Number: CZ.1.07/2.4.00/31.0062 Operational Programme: Education for Competitiveness Priority axis: Tertiary Education, Research and Development Areas of Support: Partnerships and networks Period: 1. 2. 2012 31. 1. 2014 12

Main goals of project practical training of students in chemical industry networking of research activity training courses, workshops, seminars, conferences www.ceskachemie.cz Professional contact centrum Partners Faculty of chemical technology, University of Pardubice Synthesia, a.s. DEZA, a.s. Fatra, a.s. PRECHEZA, a.s. Lovochemie, a.s. PREOL, a.s. VÚOS, a.s. ČTCAP, a.s. EIRLZ, občanské sdružení 13

NOVÉ ANTIKOROZNÍ PIGMENTY NA BÁZI FERITŮ NEW ANTICORROSION PIGMENTS BASED ON FERRITE COMPOUNDS Petr Benda, Andréa Kalendová Institute of Chemistry and Technology of Macromolecular Materials, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 532 10, Pardubice, Czech Republic Summary Paper describes ferrite and core-shell ferrite pigments and especially focuses on syntheses and anticorrosion properties of the prepared pigments. As a stating substances lamellar zinc, iron oxide, magnesium carbonate and calcium carbonate were used. Me x Zn 1-x Fe 2 O 4 /Zn and Me x Zn 1-x Fe 2 O 4 (Me = Mg or Ca) calcination products were dispersed into epoxyester binder and final paints applied on corrosion test panels. Prepared pigments anticorrosion and mechanical properties were tested and results discussed. On the field of anticorrosion protection these environmental friendly pigments are unique due to combination of anticorrosion effects, designed particle size distribution and anticorrosion mechanism. Key words: Core-shell pigment, zinc core, ferrite, core-shell ferrite, nonisometric lamellar pigment, anticorrosive coating Introduction Group of corrosion-inhibiting ferrite pigments includes the pigments that actively participate, in several ways, in extending the life of coating films. Our ferrite pigments have the general formula Me x Zn 1-x Fe 2 O 4 (Me = Mg or Ca) and a spinel structure [1 4]. Ferrites can act as barrier pigments if they are prepared as lamellar particles or can neutralize the action of corrosives substances that diffuse through the coating [5]. They also show willingness to react with the fatty acids present in the resin and form soaps which harden and seal the coating. Besides, the metallic substrate is passivated by the alkaline media generated by the hydrolysis of the pigment [1]. In the case of core-shell ferrite anticorrosion mechanism, there can simultaneously occur oxidation-reduction processes that are connected with the creation of new compounds with inhibitive effects. The primary particles of barrier 14

pigments have a non-isometric particle structure and assume a position that is parallel to the base. Experimental General ferrites can be synthetized by a classical high-temperature (above 1000 C) calcination process in a furnace. Starting substances used for their syntheses are iron oxide, zinc oxide and appropriate carbonate of rare earth metal. The core-shell ferrite pigments synthesis is based on modifying lamellar shaped zinc particles by reaction with iron oxide and an oxide of rare metal (Mg or Ca). The pigment composition and particle shape were investigated by the means of SEM, XRD and particle size distribution. Epoxyester coatings filled with the prepared pigments at 10% pigment volume concentration (PVC) were formulated. Using titanium white the coatings were adjusted to have quotient Q value equal to 35% ( Q = PVC/CPVC.100 = 35% ). Linear polarization of the final coatings was determined using a Bio-Logic SAS instrument, model VSP-300. Corrosion tests results & conclusion Comparison of all the results gave information that all the synthesized pigments enhance anticorrosion effect of prepared coatings. Core-shell pigment showed the highest degree of anticorrosion efficiency, when ZnFe 2 O 4 /Zn, Ca 0.2 Zn 0,8 Fe 2 O 4 and MgFe 2 O 4 showed the best results during testing. The core-shell ferrite coatings were highly resistive with polarization resistance values ranging from 1.4 x 10 10 Ohm to 1.2 x 10 11 Ohm in 0.5 M NaCl. The core-shell ferrites were effective in all the various environments where they were tested. The isometric particle pigments showed fare more different results for different environments. Combining anticorrosion mechanisms - active anticorrosion protection and barrier protection is the advantage of core-shell pigment. References [1] L. Chromy, E. Kaminska, Prog. Org. Coat. 18 (4) (1990) 319 324. [2] A. Kalendová, Pigment Res. Technol. 27 (4) (1998) 225 230. [3] M. Bota, D. Blându, L. Nábosnyi, G. Baciu, G. Varga, D. Stanciu, M. Balan, FATIPEC XXII, 15 19 May, Budapest, 1994. [4] C. Robu, N. Orban, G. Varga, PPCJ 5 (1987) 566 569. [5] A. Kalendová, Prog. Org. Coat. 38 (2000) 199 206. 15

STUDIUM ODBOURÁVÁNÍ ORANŽE II ZA POUŽITÍ ODLIŠNÝCH ČÁSTIC S RŮZNÝMI FOTOAKTIVNÍMI VRSTVAMI THE STUDY OF PHOTOCHEMICAL DEGRADATION OF ACID ORANGE II ON DIFFERENT PARTICLES WITH VARIOUS PHOTOACTIVE LAYERS Nela Bendáková a, Søren Poulsen b a Synpo, akciová společnost, Pardubice; b Dyrup A/S, Søborg, Denmark Summary The paper deals with comparison of photocatalytic effectivity of prepared particles treated with titanium dioxide and zinc oxide. Particles with photoactive layers were prepared by two methods. Either wet deposition of a precursor metal with consecutive hydrolysis to the titanium dioxide or sol-gel method were used. Azo dye Acid Orange II was selected for determination of the photocatalytic effectivity. Key words: Photocatalytic degradation, titanium dioxide, zinc oxide Anatase titanium dioxide and zinc oxide are photoactive semiconductors and have similar photocatalytic properties. The irradiation with light of wavelength shorter than 385 nm leads to activation of TiO 2 crystals. ZnO absorbs ultraviolet radiation of wavelength shorter than 370 nm. The photocatalytic effect of both oxides is affected by the size, shape of the particles and the surface area. Absorption of light energy causes excitation of electrons from the valence to the conduction band. Both oxides in presence of water generate highly reactive hydroxyl radicals, which attack organic substrates [1]. The benefits TiO 2 include high photocatalytic activity, low cost, stability in water systems and low toxicity to the environment [2]. Wet deposition means a bounding of alkyl titanate on the surface of the particles, which hydrolyzes to TiO 2. After drying the treated particles are calcined. Sol-gel method comprises a reaction of particles with a colloidal solution. The particles are calcined after gelation of the blend and thin layers of TiO 2 or ZnO is form on their surface. Prepared particles are described in Table 1. Azo dye Acid Orange (C 16 H 11 N 2 NaO 4 S) is destroyed by photoactive particles in aqueous media under UV light. The lamps emit UV light between 315 nm and 400 nm with a peak at 352 nm. UV light intensity is 4.8 mw.cm -2 at a distance of 15 cm. It was found out that the Acid Orange meets model heterogeneous 16

photocatalysis, because it is stable under UV light. Its photolysis is monitored by bleaching of Acid Orange. The absorbance of the solutions is measured at a wavelength of 485 nm. Degradation level of Acid Orange is expressed as a change of the absorbance of the solution on time of UV exposure. Figure 1 shows the values of absorbance at a decline of 50, 75 and 99 % of the initial absorbance before UV exposure. The used spheres have a different composition, size and density. Therefore these particles differ in the photoactive layer. The spheres treated with ZnO are more effective compared to the spheres with TiO 2. Spheres treated with TiO 2 have various photocatalytic effectivity depending on the method used for the treatment. Table 1. Characterization of treated spheres. Spheres Density [g.cm -3 ] Average size [μm] A * 0.46 20 B * 0.60 16 C * 1.10 11 D * 2.50 4 E * 2.50 10 *) gel each of the spheres was treated by TiO 2, TiO 2 and ZnO gel Figure 1. The photocatalytic effectivity of different particles with various layers. References [1] Dušek L.: Čištění odpadních vod chemickou oxidací hydroxylovými radikály, Chem. Listy 104, 846-854 (2010) [2] Saggioro E. M., Oliveira A. S., Pavesi T., et al.: Use of Titanium Dioxide Photocatalysis on the Remediation of Model Textile Wastewaters Containing Azo Dyes, Molecules, 2011, vol. 16, no. 12, s. 10370-10386. 17

DISTRIBUCE VANADOVÝCH ČÁSTIC NA MESOPORÉZNÍCH MATERIÁLECH S ROZÍLNÝM OBSAHEM ALUMINY A JEJICH KATALYTICKÁ AKTIVITA V OXIDATIVNÍ DEHYDROGENACI ETANU DISTRIBUTION OF VANADIUM SPECIES ON MESOPOROUS MATERIALS WITH DIFFERENT ALUMINA CONTENT AND THEIR ROLE ON CATALYTIC ACTIVITY IN ODH OF ETHANE Šárka Botková a, Libor Čapek a, Michal Setnička a, Roman Bulánek a, Arnošt Zukal b a Department of Physical Chemistry, University of Pardubice, CZ 532 10 Pardubice, b J. Heyrovsky Institute of Physical Chemistry AS CR, CZ 182 23 Prague Summary This work contributes to the analysis of the vanadium species supported on mesoporous materials of M41S family, i.e. HMS, SBA-15 and MCM-41. The attention is focused on both mesoporous silica based materials and the Al-doped mesoporous materials. A combination of UV-Vis spectroscopy, H 2 -TPR, N 2 -adsorption, Raman, XRD and SEM provided complex analytical information of the vanadium species. The present contribution also deals with (i) the activity of single V-based catalysts in the ODH of ethane, (ii) the role of Si/Al ratio at V-Al-HMS, V-Al-MCM-41 and V-Al-SBA-15 materials on the distribution of vanadium species and the ODH activity, and (iii) the relation between the structure of vanadium species and its relation to the ODH of ethane. Key words: ODH of ethane, mesoporous materials, vanadium species The analysis of vanadium species is important with respect to many oxidation reactions. The oxidative dehydrogenation (ODH) of light alkanes such as ethane and propane is an attractive way for the production of corresponding olefins. A large number of catalysts have been studied in the ODH of ethane. They encompass: (i) mixed oxide catalysts containing, for example, vanadium, molybdenum and niobium, and (ii) metal species such as vanadium and nickel supported on inorganic solids or micro- and mesoporous materials [1]. The most important vanadium species on the catalyst supports are monomeric VO x species with tetrahedral coordination (O=V (O-Sup) 3 ), vanadate dimeric or oligomeric chain- or sheet-like structures, polyvanadate anions, and 3-D nano- and microstructures of V 2 O 5 at higher V-loadings. To achieve a high activity and selectivity in oxidative dehydrogenation of ethane, vanadium atoms should be highly dispersed up to vanadium content as high as possible. The optimum catalytic 18

efficiency in ODH of ethane is achieved in V-loading between 2 and 4 wt. % V, when highly dispersed species are prevailing [2]. V-HMS, V-MCM-41 and V-SBA-15 catalysts exhibited approximately similar distribution of vanadium species and the activity in the ODH of ethane in the region of 0-8 wt. % V [3]. Textural properties and structure of supporting materials were preserved after the impregnation of vanadium species. In contrast to the V-silica based materials, V-materials doped with Al contained higher population of Td coordinated oligomeric species that population increased with increasing Si/Al ratio. On the other hand, V-Al-HMS, V-Al-MCM-41 and V-Al-SBA-15 materials exhibited higher selectivity in the ODH of ethane in comparison with V-HMS, V-MCM-41 and V- SBA-15, respectively. Acknowledgement The authors gratefully thank to the Grant Agency of Czech Republic for financial support (projects No. P106/10/0196) and Ministry of Education, Youth and Sports (MSM0021627501). References [1] F. Cavani, N. Ballarini and A. Cericola, Catal. Today, 2007, 127, 113. [2] T. Grygar, L. Čapek, J. Adam, V. Machovič., J. Electroanal. Chem., 2009, 633,127. [3] L. Capek, J. Adam, T. Grygar, R. Bulanek, L. Vradman, G. Kosova-Kucerova, P. Cicmanec and P. Knotek, Appl. Catal., A, 2008, 342, 99. 19

OXYCELULÓZA IDEÁLNÍ SORPČNÍ MATERIÁL OXYCELLULOSE IDEAL SORPTION MATERIAL Michaela Filipi, Miloslav Milichovský Ústav chemie a technologie makromolekulárních látek, Univerzita Pardubice Summary The article deals with the oxycellulose and its separation properties, which are studied on the base of the basic dyes separation from its aquaeous solutions and from the model mixture. The concentrations of these ions, which are adsorbed on the fibres of oxycellulose, and concentrations in the filtrate remained after adsorption, are determined for the different reaction times. After the spectrophotometric determination of these values, the adsorption isotherms are constructed and help us to evaluate separation efficiency of the oxycellulose for Fe 2+ ions. Key words: oxycellulose, adsorption, separation, basic dyes, adsorption isotherms, standard addition INTRODUCITON Basic dyes are cationic soluble salts of coloured bases. This a class of synthetic dyes, that act as bases and when made soluble in water, they form a colored cationic salt, which can react with the anionic sites on the surface of the substrate. They are applied to substrate with anionic character where electrostatic attractions are formed. The dyes produce bright shades with high tinctorial values, on textile materials and they react on the basic side of the isoelectric points. [1] Oxycellulose as well as cotton linters suspension was prepared by weighing out of 20g of air dried oxycellulose followed by its dissolution in 1 L of distilled water. The fibres were stirred up in 1 L of distilled water. Before stirring up, the oxycelluloses No. 242, No. 247 and linters were refined in order to reach better homogenization of fibrous suspension. 20

Figure 1: The sorption isotherm of metylen blue on oxycelluloses and cellulose merely in the distilled water. T = 21±1 o C. Result and discussion The adsorption isotherms (Figure 1) shows that the results are highly volatile due to the accompanying colloid-chemical process between adduct dyes with soluble particles oxycellulose which happened in the supernatant. Followed by filtration of fiber suspension, more or less we will separate these colloidal particles according to their size, affinity for the emerging porosity fibrous bed and porosity characteristics from other particles that remain in the filtrate, and which we consider as not adsorbed. It is therefore a complex process, where in addition to the sorption process underway and colloidal interactions influenced by dissolved oxycellulose particles, as already mentioned above. References [1] Komers K.: Základy koloidní chemie, Pardubice 1996. [2] Tockstein A: Fyzikální chemie, 1.díl, Pardubice 1982. [3] Hnětkovský V: Papírenská příručka, Praha 1983. [4] Arient J : Přehled barviv, Praha 1968. [5] Matouš V: Chemie organických barviv, Praha 1987. [6] Milichovský M, Češek B: Surface flocculation as a new tool for controlling adsorption processes, Adsorption, Science Technology, volume 20, number 9, 2002. 21

TUHOST V OHYBU BUNIČINY Z ŘEPKOVÉ SLÁMY BENDING STIFFNESS OF RAPESED STRAW PULP Bijay Gurung, František Potůček University of Pardubice, Faculty of Chemical Technology, Institute of Chemistry and Technology of Macromolecular Materials, 532 10 Pardubice Summary The objective of this work was to determine the potential application of rapeseed straw in the chemi-mechanical pulping process. The influence of caustic soda charge applied in the leaching process upon the bending stiffness, bending modulus of elasticity, maximum curvature in the region of reversible deformation, and critical curvature in the region of plastic deformation was investigated by using three-point loading method. The results obtained for rapeseed straw were compared with those measured for unbleached spruce groundwood and for moulded fibre products, which were published in preceding papers. Key words: Chemi-mechanical pulping, rapeseed straw, bending stiffness Nowadays, non-woody plants are receiving more attention in order to fulfil the shortage of wood fibres in pulp and paper industry due to its abundance and cost effectiveness. Among various sources of non-wood fibres, straw has been utilised in huge quantity and contributes as the largest source of non-wood raw material for the paper industry [1]. Rapeseed is the third most important oilseed crop after soybean and palm. Hence, the objective of this work was to prepare pulp from rapeseed straw by chemi-mechanical pulping and to investigate the influence of the varying alkaline dosage in the leaching process on the strength properties like bending stiffness. Rapeseed straw (Brassica napus L. convar. napus, in our case linie genotype Ontario) from Bohemian-Moravian Highlands was used for forming chemi-mechanical pulp. The chemi-mechanical pulping comprises four main operations, viz. chipping, grinding, leaching, and beating. The accepts after grinding were leached into aqueous solution of caustic soda with different dosage of caustic soda, ranging from 0 to 15.9 % of Na 2 O on oven dry straw, for 20 h at a laboratory temperature. Using a laboratory conical beater, the wet material after leaching process was beaten to 50 58 SR. Handsheets of two different levels of grammage, approximately 260, and 520 g m -2, were prepared. 22

Bending stiffness is a property of paper and board which expresses its rigidity or resistance to bending. The results obtained showed that the bending stiffness is apparently higher for specimen with higher thickness whereas, in contrast, the bending modulus is somewhat lower for the higher thickness. Figure 1 shows the dependence of bending stiffness on the caustic soda charge used in the leaching Figure 1. Bending stiffnes as a function of Na 2 O-charge on oven process. For the specimens with lower dry straw. basis weight (245 266 g m -2 ), it is evident that the bending stiffness increases slightly with increasing caustic soda charge. However, in the case of specimens with higher basis weight (508 554 g m -2 ), the effect of caustic soda charge is ambiguous. The stiffness results obtained for rapeseed straw were compared with those measured for unbleached spruce groundwood and for moulded fibre products, which were published earlier [2, 3]. At almost constant thickness of the handsheets, the bending stiffness and bending modulus of elasticity in the region of reversible deformation measured for highest charge of caustic soda are comparable to those measured for unbleached spruce groundwood and are much greater in comparison with those obtained for moulded fibre products made from waste paper. In conclusion, the preliminary results obtained offer a possibility to utilize rapeseed straw, at least partial, in the pulp and paper industry, e. g., in a blend with softwood or hardwood pulps to manufacture moulded fibre products. References [1] F. POTŮČEK, M. MILICHOVSKÝ, Cellul. Chem. Technol. 2011, 45(1 2), 23. [2] F. POTŮČEK, B. ČEŠEK, M. MILICHOVSKÝ, Cellul. Chem. Technol. 2008, 42(7 8), 413. [3] F. POTŮČEK, B. ČEŠEK, P. DOMIN, M. MILICHOVSKÝ, Cellul. Chem. Technol. 2007, 41(4 6), 277. 23