16 research outputs found
Stakeholders Needs Requisite Analysis: Towards Croatian Marine Spatial Data Infrastructure Establishment
National Marine Spatial Data Infrastructure (MSDI) in the Republic of Croatia has not yet been implemented. This paper examines the requirements and needs of future MSDI stakeholders, using a multidisciplinary approach. The paper describes the testing procedures, how to use the interview method, survey and research results. Survey sample was made up of providers and users of marine spatial data in Croatia, considering also future MSDI stakeholders (government and private sector, research institutions and non-governmental organizations). The aim was to investigate the needs for the MSDI implementation, which in Croatia does not exist at the moment. However, results of our research show that the need for this kind of infrastructure is very high and justified. Results and collected information will be the basis for creation of the MSDI geoportal prototype
The removal of neonicotinoid insecticide imidacloprid in an annular photoreactor
Heterogeneous photocatalysis has recently attracted an increasing interest of scientists and experts who deal with the waste water and air treatment. An important area of application is removal of persistent organic pollutants, which can not be easily destroyed by conventional methods. Among these pollutants are neonicotinoid insecticides, which are widely used all over the world and currently are included in the watch list of substances of the European Commission within the Water Framework Directive. Therefore, there is a need to study their influence on the environment and to develop appropriate technologies for their removal. In this work, the photolytic and photocatalytic degradation of neonicotinoid insecticide imidacloprid in an annular photoreactor with recirculation under different working conditions (irradiation source, pH, type and concentration of the catalyst) was studied. The photolytic degradation was examined using lamps that emit UVA, UVC and simulated sun light. The photocatalytic experiments in the suspension involved the use of commercial titanium dioxide (TiO2 P25, Degussa/Evonik), commercial TiO2 P25 pre-treated with UVC irradiation prior to use in the catalytic system and nitrogen-doped TiO2 (CCR 200 N produced by Cinkarna Celje). The catalysts were characterized using XRD, UV/Vis-DRS and BET analysis. The most efficient photocatalyst was then immobilized on the glass woving fibre, using peroxotitanic acid (produced by Cinkarna Celje) as a binder. The degree of degradation of imidacloprid was determined using high performance liquid chromatography (HPLC). According to the obtained results, UVC-treated TiO2 showed the best efficiency among the examined catalysts in the slurry reactor while using lamp that simulates the sun irradiation. The imidacloprid degradation rate increases with the increase in the catalyst concentration. The immobilized UVC-treated catalyst gave satisfying results in terms of stability, activity and reuse
Doprinos transkranijske dupleks Dopplerove sonografije dijagnostici stenoze velikih moždanih arterija u djeteta
The contribution of pulsating duplex Doppler ultrasonography to the diagnosis of middle (MCA) and anterior (ACA) cerebral artery obstruction in one patient is reported. A 10year-old boy was admitted to the hospital for pulsating headaches (especially pronounced on physical training). He had no neurologic disabilities. His EEG and brain CT scan were normal, and so were his funduscopic examination, lumbar puncture, and laboratory tests. Transcranial color duplex Doppler ultrasonography showed very high velocities in both ACA and right MCA as a sign of suspected stenosis or spasm. Bilateral subtraction cerebral angiography performed after several months of recurrent headaches and unchanged Doppler ultrasonography findings produced an image of high degree stenosis of A1 segment of both ACA and right MCA, with signs of āsteal syndromeā through the posterior cerebral circulation. MRI performed one year later, after episodes of transient ischemic attacks, showed ischemic infarction in the right temporo-occipital region. The etiology of stenosis was supposed to include vasculopathy, i.e. early stage of moyamoya syndrome. Other vasculopathies were excluded by laboratory tests and clinical elaboration. It is concluded that transcranial Doppler ultrasonography is a very helpful method for detection and follow-up of the degree of stenosis of great cerebral arteries in children, and that it correlates well with cerebral angiography, yet it is not useful in diagnosing the etiology of stenosis.Prikazan je sluÄaj 10-godiÅ”njeg djeÄaka koji je primljen na Kliniku zbog pulsirajuÄih glavobolja koje su se najÄeÅ”Äe javljale za vrijeme tjelesnog napora. DjeÄak je bio urednog somatskog i neuroloÅ”kog statusa. Njegov EEG i CT mozga bili su uredni, kao i pregled oÄnog dna, likvora i laboratorijske pretrage. Transkranijski obojeni dupleks Doppler pokazao je izrazito velike brzine u objema prednjim moždanim arterijama (ACA) i u desnoj srednjoj moždanoj arteriji (MCA), Å”to je moglo odgovarati stenozi krvnih aila. Subtrakcijska cerebralna angiografija uÄinjena je nakon nekoliko mjeseci opetovanih glavobolja i nepromijenjenog Doplerskog nalaza. Pokazala je veÄi stupanj stenoze prednjeg segmenta obiju ACA i poÄetnog dijela desne MCA, sa znacima āsindroma kraÄeā kroz stražnju moždanu cirkulaciju. MRI (uÄinjena godinu dana kasnije, nakon ponavljanih epizoda prolaznih ishemijskih napadaja) pokazala je ishemijski infarkt temporookcipitalno desno. Etiologija bolesti ostala je otvorenom. Pretpostavljeno je da se radi o vaskulopatiji, tj. ranom stadiju bolesti moyamoya. Ostale vaskulopatije iskljuÄene su laboratorijskim i kliniÄkim ispitivanjem. ZakljuÄuje se kako je transkranijski obojeni dupleks Doppler vrlo dobra metoda za otkrivanje i praÄenje stupnja stenoze moždanih arterija u djece i dobro korelira s cerebralnom angiografijom, ali joÅ” ne pomaže u otkrivanju etiologije stenoze
Importance of Circulating Platelet Aggregates and Haemodynamic Changes in Ophthalmic Artery and Progression of Visual Field Loss at Pseudoexfoliation Glaucoma
The aim of this work is to examine the role of circulating platelet aggregates (CPA) at pseudoexfoliation glaucoma
(PXG), haemodynamic changes in the ophthalmic artery by ultrasonic color Doppler, searching for visual field progression.
Vascular component at PXG and its role in VF progression dynamics has not been sufficiently explained, as well as
CPA influence to ischaemic events related to optic nerve damage and VF progression. The examination included 80 patients,
where of 35 (44%) men average age 68.3Ā±7.0 and 45 (56%) women average age 65.7Ā±7.0 (t=1.66; p=0.101). Forthy
of them suffered from primary open angle glaucoma (POAG) as a control group (healthy), and 40 from pseudoexfoliative
glaucoma (PXG) as an experimental group. All the examinees underwent complete ophthalmological examination: visual
acuity, ocular fundus, intraocular pressure measured, anterior eye segment biomicroscopy with gonioscopy performed.
Also VF examination was performed three times at 6 months intervals. Laboratory testing of CPA proportion values
was performed by means of Wu an Hoak method and ultrasonic measurement of blood perfusion in the carotid tree,
particularly concerning ophthalmic artery by means of color Doppler. Obtained decreased values of CPA proportion resulted
in hypercoagulability of blood in PXG group. At PXG were also found increased blood flow resistivity indexes in
ophthalmic artery (RI AO) and internal carotid artery (RI ACI), resulting with ischemia and hypoxia and finally progression
of the visual filed damage. In conclusion, our study shows that examining CPA and ultrasonic monitoring of
vascular parameters in ophthalmic artery with color Doppler may be the way of better understanding the vascular role in
PXG prognosis
Specific and Gender Differences between Hospitalized and out of Hospital Mortality due to Myocardial Infarction
In this paper, the authors evaluate gender related differences of myocardial infarction mortality before and after hospital
admittance. Myocardial infarction mortality in the Clinical Hospital Split in the seven years period between 2000
and 2006, have been analyzed together with out of hospital sudden death patients with acute myocardial infarction established
during autopsy. During the seven year period between 2000 and 2006, 3434 patients were treated for myocardial
infarction in the Split Clinical Hospital, 2336 (68%) males and 1098 (32%) females with a 12% total mortality (427
patients). The annual number of hospitalized persons has been increasing during that period (474 in yr. 2000 vs. 547 in
yr. 2006), while mortality decreased from 15% in 2000 to 9.6% in 2006. Female patients had significantly higher hospital
mortality than male patients, (228 or 21% vs. 202 or 9%, p<0.05). Women also had significantly higher total AMI mortality
(23.7% vs. 15,7%, p<0.05). Anterior myocardial infarction with ST elevation in precordial leads had significantly
higher mortality (19%) compared to patients with lateral (11%), inferior (10%) myocardial infarction with ST elevation
and also NSTEMI (4%) mortality p<0.05. Female patients more frequently die in hospital, 84% (230) than out of hospital
16% (43). From the total number of AMI deaths (388) in male patients, 56% (217) were in hospital and 44% (171) out
of hospital (p<0.001). Men had significantly higher prehospital mortality rate than women (81% vs. 19%, p<0.05). Men
also more frequently died from ventricular fibrillation (22% vs. 10%, p<0.05), while women died more frequently of
heart failure, cardiogenic shock, and myocardial rupture (33% vs. 15% p<0.05). Regarding the total number of deaths
from myocardial infarction men had significantly higher prehospital mortality compared to women (178 or 7.3% vs. 43
or 3.7%, p<0.05). Anterior myocardial infarction had a significantly higher rate in patients dying pre-hospital (58%), in
contrast to inferior (36%) and lateral myocardial infarction with ST elevation (6%) p<0,05.We have concluded that male
patients die more frequently within the first few hours of AMI mostly due to malignant arrhythmias, while female patients
died in sub acute stage due to heart failure while being hospitalized. Nevertheless total mortality of AMI remains
significantly higher in women
COMPARATIVE FOLLOW-UP STUDY OF UNSELECTED MALE POPULATION WITH CONGENITAL DEFECTIVE COLOR VISION FROM INLAND AND MEDITERRANEAN AREAS OF CROATIA
Cilj naÅ”eg desetogodiÅ”njeg istraživanja, provedenog od kraja 1998. do kraja 2008. godine, bio je ispitati zastupljenost kongenitalnih diskromatopsija neselektirane i zdrave muÅ”ke populacije u dobi od 15 do 45 godina na podruÄju dviju hrvatskih regija. Prva regija je kontinentalni dio Hrvatske (KH), a druga mediteranski dio Hrvatske (MH). Rezultati tih dviju regija su usporeÄivani, te su doneseni odgovarajuÄi zakljuÄci. Rezultati, tj. zakljuÄci se prvenstveno odnose na zastupljenosti kolornih poremeÄaja vida, te na njihove razlike prema glavnim kolornim skupinama (dikromati i anomalni trikromati) i podskupinama (protanopi, deuteranopi, protanomali, deuteranomali i dr.). Takav tip istraživanja tijekom dugog razdoblja i na tako velikom uzorku ispitanika nije dosada raÄen ni na Å”irem podruÄju jugoistoÄne Europe. Kolorni vid ispitivan je, poslije kompletnog oftalmoloÅ”kog pregleda, svakom muÅ”kom kandidatu koji se javio na pregled zbog pohaÄanja Å”kole za vozaÄe amatere. Kolorni vid se ispitivalo pseudoizokromatskim tablicama Ishihara, anomaloskopom Nagel II i Panel D-15 testom u ordinacijama medicine rada i klinikama za oÄne bolesti dviju regija. Broj ispitanika u KH iznosio je 12.974, a u MH 9.974. Rezultati su potvrdili ranije predviÄenu hipotezu ili kliniÄko zapažanje da u južnim dijelovima, tj. u MH ima manje kolornih poremeÄaja (8,50%), nasuprot sjevernom dijelu, tj. u KH (8,90%). ZakljuÄujemo i da je u MH naÄen veÄi broj dikromata (anopa) - 2,40% za razliku od KH gdje je naÄen veÄi broj anomalnih trikromata (anomala) - 6,93%. Važnost dobivenih rezultata je u doprinosu boljem uvidu u stanje kolornih poremeÄaja i eventualnim razlikama na uskom podruÄju Hrvatske, izmeÄu sjevera i juga.Aim: The aim of this ten-year study (from the end of 1998 to the end of 2008) was to assess the prevalence of congenital dyschromatopsia
in unselected healthy male population aged 15-45 from two Croatian regions, i.e. inland and Mediterranean parts of Croatia. Results collected in these two regions were compared and respective conclusions drawn. The results primarily referred to the prevalence of color vision disturbances and their differences according to the main color groups (dichromacy and anomalous trichromacy) and subgroups (protanopia, deuteranopia, protanomaly, deuteranomaly, and others). To our knowledge, no such a long-term study in a large population sample has been carried out in southeast Europe to date.
Methods: Color vision was examined after complete ophthalmologic examination in all subjects presenting for examination required for amateur driver license. Color vision examination was performed by use of pseudoisochromatic Ishihara tables, Nagel II anomaloscope and Panel D-15 color test at industrial medicine offices and ophthalmology departments in the two regions. There were 12,974 and 9,974 subjects in inland and Mediterranean Croatia, respectively.
Results: The results confirmed the hypothesis and clinical perception of a lower prevalence of color vision disturbances in southern parts, i.e. in Mediterranean Croatia (8.50%) as compared with inland Croatia (8.90%). The rate of dichromacy was higher in Mediterranean Croatia (2.40%), while the rate of anomalous trichromacy was greater in inland Croatia (6.93%).
Conclusion: The results of this study provide better insight in the status of color vision disturbances and possible differences between the relatively close areas of north (inland) and south (Mediterranean) Croatia
RužiÄka days : International conference 16th RužiÄka Days āToday Science ā Tomorrow Industryā : Proceedings
Proceedings contains articles presented at Conference divided into sections: open lecture (1), chemical analysis and synthesis (3), chemical and biochemical engineering (8), food technology and biotechnology (8), medical chemistry and pharmacy (3), environmental protection (11) and meeting of young chemists (2)
Catalytic oxidation of toluene in a metal monolith reactor
Prekomjerne emisije hlapivih organskih spojeva (VOC) u okoliÅ”, koje uglavnom potjeÄu iz razliÄitih industrijskih postrojenja i motornih vozila, u velikoj mjeri naruÅ”avaju kvalitetu zraka, a samim time i kvalitetu života. Trenutno postoje brojne tehnologije kojima se koncentracija hlapivih organskih spojeva u zraku održava ispod dopuÅ”tenih granica. KatalitiÄka oksidacija hlapivih organskih spojeva intenzivno se izuÄava od 70-tih godina proÅ”log stoljeÄa s ciljem pronalaženja uÄinkovitog katalizatora i prikladne izvedbe reaktora. U novije vrijeme istraživanja u ovom podruÄju usmjerena su na primjenu metodologije intenzifikacije procesa, koja najÄeÅ”Äe podrazumijeva integriranje katalitiÄkih i adsorpcijskih procesa te razvoj i primjenu strukturiranih izvedbi katalizatora, a posebice monolitne izvedbe. Cilj ovog rada bio je razvoj metalnog monolitnog katalizatora/reaktora za katalitiÄku oksidaciju toluena kao predstavnika hlapivih organskih spojeva. Toluen je izabran kao modelna komponenta, jer se primjenjuje u razliÄitim industrijama (poput automobilske i farmaceutske industrije), a u okoliÅ” Äesto dospijeva i kao rezultat proizvodnje i uporabe organskih kemikalija, otapala, bojila i sliÄnih proizvoda. S obzirom da je jedan od specifiÄnih ciljeva istraživanja bio pronaÄi katalizator koji može poslužiti kao zamjena za skupe katalizatore na bazi plemenitih metala, posebna pažnja posveÄena je metalnim oksidima mangana i prijelaznih metala (kao Å”to su željezo, nikal i bakar) te njihovoj usporedbi sa srodnim tipovima katalizatora. Prvi dio rada ukljuÄuje pripremu i detaljnu karakterizaciju mijeÅ”anih manganovih oksida u praÅ”kastom obliku, ispitivanje njihovih fiziÄko-kemijskih i katalitiÄkih znaÄajki pri katalitiÄkoj oksidaciji toluena te usporedbu s perovskitnim katalizatorima (LaFeO3 i LaMnO3) i dopiranim cerijevim oksidima (CeO2 katalizator dopiran s ionima sljedeÄih metala: Cu, Mn, Al, Cd, Fe, Ni, Zn i Co). Kao pokazatelj uÄinkovitosti pripremljenih katalizatora koriÅ”ten je komercijalni katalizator Pt-Al2O3. Ispitan je utjecaj kemijskog sastava katalitiÄki aktivne tvari na znaÄajke pripremljenih katalizatora, kao i utjecaj radnih uvjeta, kao Å”to su temperatura, protok reakcijske smjese, ulazna koncentracija toluena te dimenzije zrna praÅ”kastog katalizatora na konverziju toluena. Ispitivanje katalitiÄke aktivnosti praÅ”kastih katalizatora provedeno je u reaktoru s nepokretnim slojem katalizatora pri razliÄitim radnim uvjetima, a u zavrÅ”nom dijelu istraživanja predloženi su odgovarajuÄi kinetiÄki i reaktorski modeli. Za tu svrhu provedeno je testiranje eksperimentalnih rezultata na jednodimenzijski (1D) pseudohomogeni model cijevnog reaktora i dvodimenzijski (2D) heterogeni model s unutarfaznom difuzijom. MijeÅ”ani oksidi mangana i prijelaznih metala koji su se u prethodnom dijelu istraživanja pokazali najboljim katalizatorima za oksidaciju toluena, u drugom dijelu istraživanja koriÅ”teni su za pripremu metalnih monolitnih katalizatora/reaktora. Tijekom istraživanja razvijena je metoda nanoÅ”enja katalitiÄki aktivnog sloja na povrÅ”inu prethodno oblikovanog metalnog monolitnog nosaÄa. Da bi se omoguÄila priprema stabilnog katalitiÄkog sloja provedena je obostrana anodizacija aluminijevih ploÄica koje su poslužile za pripremu metalnih monolitnih struktura. Ispitan je utjecaj uvjeta anodizacije i kemijskog sastava katalitiÄki aktivnog sloja na znaÄajke pripremljenih katalizatora, kao i utjecaj radnih uvjeta, kao Å”to su temperatura, protok reakcijske smjese, ulazna koncentracija toluena te utjecaj debljine katalitiÄkog sloja. Ustanovljeno je da je anodizacija Al ploÄica oksalnom kiselinom (C2H2O4) prikladniji naÄin anodizacije od anodizacije sumpornom kiselinom (H2SO4). Od izuÄavanih metalnih monolitnih katalizatora (Al/Al2O3-MnOx, Al/Al2O3-MnFeOx, Al/Al2O3-MnNiOx i Al/Al2O3-MnCuOx) najbolju aktivnost pokazivali su metalni monoliti koji sadrže mijeÅ”ani oksid mangana i bakra kao katalitiÄki aktivnu komponentu. TakoÄer su provedena istraživanja s ciljem dodatnog poboljÅ”anja uÄinkovitosti metalnih monolitnih katalizatora optimiranjem kemijskog sastava katalitiÄkog sloja, tj. omjera mangana i bakra. ZakljuÄeno je da se s poveÄanjem udjela mangana poboljÅ”avaju katalitiÄka svojstva mijeÅ”anog manganovog oksida te da uvoÄenje bakra rezultira sinergistiÄkim djelovanjem. Tijekom istraživanja katalitiÄka oksidacija toluena provoÄena je na monolitnim katalizatorima pri razliÄitim prostornim vremenima, pri Äemu su prostorna vremena mijenjana promjenom protoka reakcijske smjese uz konstantu duljinu monolitnog katalizatora, a provedena je i serija mjerenja u kojima su prostorna vremena mijenjana promjenom duljine monolita uz konstantan protok reakcijske smjese. Detaljna analiza rada monolitnih katalizatora/reaktora ukljuÄivala je i ispitivanje utjecaja unutarfazne i meÄufazne difuzije na ukupnu brzinu reakcije. Metalni monolitni katalizatori pripremljeni u ovom radu usporeÄeni su s keramiÄkim monolitnim katalizatorima koji su takoÄer sadržavali mijeÅ”ane okside mangana kao katalitiÄki aktivne komponente, kao i s dostupnim komercijalnim monolitnim katalizatorom (Purelyst PH ā 304) koji je sadržavao plemenite metale. U zavrÅ”nom dijelu istraživanja s ciljem detaljne analize rada i modeliranja monolitnog reaktora predložen je i razvijen jednodimenzijski (1D) heterogeni model koji je ukljuÄivao meÄufaznu difuziju. Provedena je ocjena prihvatljivosti predloženog modela te su procijenjeni kljuÄni parametri modela uz korijen srednjeg kvadratnog odstupanja kao kriterij slaganja. PotvrÄeno je da predloženi model dobro opisuje eksperimentalne rezultate te se stoga može uspjeÅ”no primijeniti za opisivanje metalnog monolitnog reaktora pri uvjetima koriÅ”tenim u ovom radu.Excessive emissions of volatile organic compounds (VOCs) into the environment, which mainly result from different industrial plants and motor vehicles, greatly affect the quality of the air and thus the quality of life. There are currently many technologies that keep the concentration of volatile organic compounds in the atmosphere below the allowed limits. The catalytic oxidation of volatile organic compounds has been intensively investigated since the 1970s with the aim of finding efficient catalysts and suitable reactors. More recently, research in this area is focused on the application of process intensification methodology, which most often involves the integration of catalytic and adsorption processes, and the development and application of structured catalysts, in particular monolith reactors. The aim of this dissertation was to develop a metal monolith catalyst/reactor for catalytic oxidation of toluene as a representative volatile organic compound. Toluene was chosen as a model component because it is used in various industries (such as the automotive and pharmaceutical industries), and is often emitted in the environment as a result of the production and use of organic chemicals, solvents, dyes and similar products. Since one of the specific research objectives was to find a catalyst that could serve as a substitute for expensive noble metal catalysts, special attention was given to manganese metal oxides mixed with transition metals (such as iron, nickel and copper) and their comparison to other similar catalyst types. The first part of the paper includes the preparation and detailed characterization of mixed manganese oxides in powder form. Catalytic properties of the prepared catalysts were tested in catalytic oxidation of toluene and the results were compared to results obtained with similar types of catalysts such as perovskite catalysts (LaFeO3 and LaMnO3) and doped cerium oxides (CeO2 catalyst doped with the following metal ions: Cu, Mn, Al, Cd, Fe, Ni, Zn and Co). Commercial catalyst Pt-Al2O3 was used as an indicator of the efficiency of the prepared catalysts. The influence of the chemical composition on the properties of the prepared catalysts was tested, as well as the influence of temperature, reaction mixture flow rate, toluene inlet concentration, and particle size of powder catalysts on toluene conversion. The catalytic activity of powder catalysts was tested in the fixed bed reactor at various working conditions. Appropriate kinetic and reactor models (one-dimensional (1D) pseudohomogenous model and a two-dimensional (2D) heterogeneous model with intra-phase diffusion) were proposed and tested in this part of the study. Mixed manganese and transition metal oxides, which in the previous part of the study showed the best catalytic properties, were used in the second part of the study for the preparation of metal monolith catalysts/reactors. Deposition method of stabile catalytically active layer on the surface of the corrugated metal monolith support was developed during the research. In order to prepare metal monolith structures for a stable catalytic layer deposition, two-sided anodization of aluminum tiles was used. The influence of the anodization parameters and the chemical composition of the catalytically active layer on the properties of the prepared catalysts were tested, as well as the influence of the working conditions, such as temperature, reaction mixture flow rate, toluene inlet concentration and the effect of the thickness of the catalytic layer. It was concluded that the anodization of aluminum tiles with oxalic acid (C2H2O4) was more successful than the anodization with sulfuric acid (H2SO4). Out of the studied metal monolith catalysts (Al/Al2O3-MnOx, Al/Al2O3-MnFeOx, Al/Al2O3-MnNiOx and Al/Al2O3-MnCuOx) the metal monoliths with mixed manganese and copper oxides exhibited the best catalytical activity in toluene oxidation. Further research was carried out to improve the efficiency of the metal monolith catalysts by optimizing the chemical composition of the catalytic layer, i.e. the ratio of manganese and copper. It was concluded that with the increase in the manganese share, the catalytic properties of the mixed manganese oxides were improved and the introduction of copper resulted in synergistic effect. The catalytic tests with monolith catalysts/reactors were carried out at different space times, changing the space times by changing the reaction mixture flow rate over constant monolith length, and also, by changing the length of the monolith at constant reaction mixture flow rate. Detailed analysis of monolith catalyst/reactor activity involved testing the influence of both the inter-phase and intra-phase diffusion on the overall reaction rate. Metal monolith catalysts, prepared in this study, were compared to the ceramic monoliths, as well as to the commercial monolith catalyst (Purelyst PH ā 304) with noble metals (Pt and Pd) as catalytically active substances. In the final part of the research a one-dimensional (1D) heterogeneous model with inter-phase diffusion was proposed and developed. The proposed model assessment was carried by the root mean square deviation as the criterion, and the key parameters of the model were estimated. It was confirmed that the proposed model describes experimental results well, and can therefore be successfully applied to describe the metal monolith reactor under the conditions used in this research
Catalytic oxidation of toluene in a metal monolith reactor
Prekomjerne emisije hlapivih organskih spojeva (VOC) u okoliÅ”, koje uglavnom potjeÄu iz razliÄitih industrijskih postrojenja i motornih vozila, u velikoj mjeri naruÅ”avaju kvalitetu zraka, a samim time i kvalitetu života. Trenutno postoje brojne tehnologije kojima se koncentracija hlapivih organskih spojeva u zraku održava ispod dopuÅ”tenih granica. KatalitiÄka oksidacija hlapivih organskih spojeva intenzivno se izuÄava od 70-tih godina proÅ”log stoljeÄa s ciljem pronalaženja uÄinkovitog katalizatora i prikladne izvedbe reaktora. U novije vrijeme istraživanja u ovom podruÄju usmjerena su na primjenu metodologije intenzifikacije procesa, koja najÄeÅ”Äe podrazumijeva integriranje katalitiÄkih i adsorpcijskih procesa te razvoj i primjenu strukturiranih izvedbi katalizatora, a posebice monolitne izvedbe. Cilj ovog rada bio je razvoj metalnog monolitnog katalizatora/reaktora za katalitiÄku oksidaciju toluena kao predstavnika hlapivih organskih spojeva. Toluen je izabran kao modelna komponenta, jer se primjenjuje u razliÄitim industrijama (poput automobilske i farmaceutske industrije), a u okoliÅ” Äesto dospijeva i kao rezultat proizvodnje i uporabe organskih kemikalija, otapala, bojila i sliÄnih proizvoda. S obzirom da je jedan od specifiÄnih ciljeva istraživanja bio pronaÄi katalizator koji može poslužiti kao zamjena za skupe katalizatore na bazi plemenitih metala, posebna pažnja posveÄena je metalnim oksidima mangana i prijelaznih metala (kao Å”to su željezo, nikal i bakar) te njihovoj usporedbi sa srodnim tipovima katalizatora. Prvi dio rada ukljuÄuje pripremu i detaljnu karakterizaciju mijeÅ”anih manganovih oksida u praÅ”kastom obliku, ispitivanje njihovih fiziÄko-kemijskih i katalitiÄkih znaÄajki pri katalitiÄkoj oksidaciji toluena te usporedbu s perovskitnim katalizatorima (LaFeO3 i LaMnO3) i dopiranim cerijevim oksidima (CeO2 katalizator dopiran s ionima sljedeÄih metala: Cu, Mn, Al, Cd, Fe, Ni, Zn i Co). Kao pokazatelj uÄinkovitosti pripremljenih katalizatora koriÅ”ten je komercijalni katalizator Pt-Al2O3. Ispitan je utjecaj kemijskog sastava katalitiÄki aktivne tvari na znaÄajke pripremljenih katalizatora, kao i utjecaj radnih uvjeta, kao Å”to su temperatura, protok reakcijske smjese, ulazna koncentracija toluena te dimenzije zrna praÅ”kastog katalizatora na konverziju toluena. Ispitivanje katalitiÄke aktivnosti praÅ”kastih katalizatora provedeno je u reaktoru s nepokretnim slojem katalizatora pri razliÄitim radnim uvjetima, a u zavrÅ”nom dijelu istraživanja predloženi su odgovarajuÄi kinetiÄki i reaktorski modeli. Za tu svrhu provedeno je testiranje eksperimentalnih rezultata na jednodimenzijski (1D) pseudohomogeni model cijevnog reaktora i dvodimenzijski (2D) heterogeni model s unutarfaznom difuzijom. MijeÅ”ani oksidi mangana i prijelaznih metala koji su se u prethodnom dijelu istraživanja pokazali najboljim katalizatorima za oksidaciju toluena, u drugom dijelu istraživanja koriÅ”teni su za pripremu metalnih monolitnih katalizatora/reaktora. Tijekom istraživanja razvijena je metoda nanoÅ”enja katalitiÄki aktivnog sloja na povrÅ”inu prethodno oblikovanog metalnog monolitnog nosaÄa. Da bi se omoguÄila priprema stabilnog katalitiÄkog sloja provedena je obostrana anodizacija aluminijevih ploÄica koje su poslužile za pripremu metalnih monolitnih struktura. Ispitan je utjecaj uvjeta anodizacije i kemijskog sastava katalitiÄki aktivnog sloja na znaÄajke pripremljenih katalizatora, kao i utjecaj radnih uvjeta, kao Å”to su temperatura, protok reakcijske smjese, ulazna koncentracija toluena te utjecaj debljine katalitiÄkog sloja. Ustanovljeno je da je anodizacija Al ploÄica oksalnom kiselinom (C2H2O4) prikladniji naÄin anodizacije od anodizacije sumpornom kiselinom (H2SO4). Od izuÄavanih metalnih monolitnih katalizatora (Al/Al2O3-MnOx, Al/Al2O3-MnFeOx, Al/Al2O3-MnNiOx i Al/Al2O3-MnCuOx) najbolju aktivnost pokazivali su metalni monoliti koji sadrže mijeÅ”ani oksid mangana i bakra kao katalitiÄki aktivnu komponentu. TakoÄer su provedena istraživanja s ciljem dodatnog poboljÅ”anja uÄinkovitosti metalnih monolitnih katalizatora optimiranjem kemijskog sastava katalitiÄkog sloja, tj. omjera mangana i bakra. ZakljuÄeno je da se s poveÄanjem udjela mangana poboljÅ”avaju katalitiÄka svojstva mijeÅ”anog manganovog oksida te da uvoÄenje bakra rezultira sinergistiÄkim djelovanjem. Tijekom istraživanja katalitiÄka oksidacija toluena provoÄena je na monolitnim katalizatorima pri razliÄitim prostornim vremenima, pri Äemu su prostorna vremena mijenjana promjenom protoka reakcijske smjese uz konstantu duljinu monolitnog katalizatora, a provedena je i serija mjerenja u kojima su prostorna vremena mijenjana promjenom duljine monolita uz konstantan protok reakcijske smjese. Detaljna analiza rada monolitnih katalizatora/reaktora ukljuÄivala je i ispitivanje utjecaja unutarfazne i meÄufazne difuzije na ukupnu brzinu reakcije. Metalni monolitni katalizatori pripremljeni u ovom radu usporeÄeni su s keramiÄkim monolitnim katalizatorima koji su takoÄer sadržavali mijeÅ”ane okside mangana kao katalitiÄki aktivne komponente, kao i s dostupnim komercijalnim monolitnim katalizatorom (Purelyst PH ā 304) koji je sadržavao plemenite metale. U zavrÅ”nom dijelu istraživanja s ciljem detaljne analize rada i modeliranja monolitnog reaktora predložen je i razvijen jednodimenzijski (1D) heterogeni model koji je ukljuÄivao meÄufaznu difuziju. Provedena je ocjena prihvatljivosti predloženog modela te su procijenjeni kljuÄni parametri modela uz korijen srednjeg kvadratnog odstupanja kao kriterij slaganja. PotvrÄeno je da predloženi model dobro opisuje eksperimentalne rezultate te se stoga može uspjeÅ”no primijeniti za opisivanje metalnog monolitnog reaktora pri uvjetima koriÅ”tenim u ovom radu.Excessive emissions of volatile organic compounds (VOCs) into the environment, which mainly result from different industrial plants and motor vehicles, greatly affect the quality of the air and thus the quality of life. There are currently many technologies that keep the concentration of volatile organic compounds in the atmosphere below the allowed limits. The catalytic oxidation of volatile organic compounds has been intensively investigated since the 1970s with the aim of finding efficient catalysts and suitable reactors. More recently, research in this area is focused on the application of process intensification methodology, which most often involves the integration of catalytic and adsorption processes, and the development and application of structured catalysts, in particular monolith reactors. The aim of this dissertation was to develop a metal monolith catalyst/reactor for catalytic oxidation of toluene as a representative volatile organic compound. Toluene was chosen as a model component because it is used in various industries (such as the automotive and pharmaceutical industries), and is often emitted in the environment as a result of the production and use of organic chemicals, solvents, dyes and similar products. Since one of the specific research objectives was to find a catalyst that could serve as a substitute for expensive noble metal catalysts, special attention was given to manganese metal oxides mixed with transition metals (such as iron, nickel and copper) and their comparison to other similar catalyst types. The first part of the paper includes the preparation and detailed characterization of mixed manganese oxides in powder form. Catalytic properties of the prepared catalysts were tested in catalytic oxidation of toluene and the results were compared to results obtained with similar types of catalysts such as perovskite catalysts (LaFeO3 and LaMnO3) and doped cerium oxides (CeO2 catalyst doped with the following metal ions: Cu, Mn, Al, Cd, Fe, Ni, Zn and Co). Commercial catalyst Pt-Al2O3 was used as an indicator of the efficiency of the prepared catalysts. The influence of the chemical composition on the properties of the prepared catalysts was tested, as well as the influence of temperature, reaction mixture flow rate, toluene inlet concentration, and particle size of powder catalysts on toluene conversion. The catalytic activity of powder catalysts was tested in the fixed bed reactor at various working conditions. Appropriate kinetic and reactor models (one-dimensional (1D) pseudohomogenous model and a two-dimensional (2D) heterogeneous model with intra-phase diffusion) were proposed and tested in this part of the study. Mixed manganese and transition metal oxides, which in the previous part of the study showed the best catalytic properties, were used in the second part of the study for the preparation of metal monolith catalysts/reactors. Deposition method of stabile catalytically active layer on the surface of the corrugated metal monolith support was developed during the research. In order to prepare metal monolith structures for a stable catalytic layer deposition, two-sided anodization of aluminum tiles was used. The influence of the anodization parameters and the chemical composition of the catalytically active layer on the properties of the prepared catalysts were tested, as well as the influence of the working conditions, such as temperature, reaction mixture flow rate, toluene inlet concentration and the effect of the thickness of the catalytic layer. It was concluded that the anodization of aluminum tiles with oxalic acid (C2H2O4) was more successful than the anodization with sulfuric acid (H2SO4). Out of the studied metal monolith catalysts (Al/Al2O3-MnOx, Al/Al2O3-MnFeOx, Al/Al2O3-MnNiOx and Al/Al2O3-MnCuOx) the metal monoliths with mixed manganese and copper oxides exhibited the best catalytical activity in toluene oxidation. Further research was carried out to improve the efficiency of the metal monolith catalysts by optimizing the chemical composition of the catalytic layer, i.e. the ratio of manganese and copper. It was concluded that with the increase in the manganese share, the catalytic properties of the mixed manganese oxides were improved and the introduction of copper resulted in synergistic effect. The catalytic tests with monolith catalysts/reactors were carried out at different space times, changing the space times by changing the reaction mixture flow rate over constant monolith length, and also, by changing the length of the monolith at constant reaction mixture flow rate. Detailed analysis of monolith catalyst/reactor activity involved testing the influence of both the inter-phase and intra-phase diffusion on the overall reaction rate. Metal monolith catalysts, prepared in this study, were compared to the ceramic monoliths, as well as to the commercial monolith catalyst (Purelyst PH ā 304) with noble metals (Pt and Pd) as catalytically active substances. In the final part of the research a one-dimensional (1D) heterogeneous model with inter-phase diffusion was proposed and developed. The proposed model assessment was carried by the root mean square deviation as the criterion, and the key parameters of the model were estimated. It was confirmed that the proposed model describes experimental results well, and can therefore be successfully applied to describe the metal monolith reactor under the conditions used in this research