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Efekti primene različitih postupaka remedijacije na imobilizaciju teških metala u sedimentu / The effects of remediation treatments application on the sediment heavy metal immobilizationPrica Miljana 25 March 2009 (has links)
<p>Predmet izučavanja ove disertacije, osim poređenja različitih metoda procene rizika na osnovu karakterizacije kvaliteta sedimenta vodotokova Vojvodine, bilo je i ispitivanje mogućnosti imobilizacije teških metalau sedimentu primenom različitih remedijacionih tehnika kao i određivanje njihove efikasnosti (npr. solidifikacija/stabilizacija silikatnim materijalima, portland cementom, kalcijum-oksidom itd.) u zavisnosti od brojnih faktora. Osim pseudo-ukupnog sadržaja metala određene su i specifičnije frakcije metala sa posebnim<br />osvrtom na određivanje potencijalno biodostupnih frakcija.</p><p>Rezultati su ukazali da je naosnovu holandskih preporuka sediment pojedinih vodotokova Vojvodine (Begej, DTD-kanal,Nadela, Sava-Šabac) zagađen metalima (klasa 4) i da je neohodno izmuljivanje i remedijacija. Prema USEPA i kanadskim preporukama, neki uzorci su potencijalno toksični, ali nije zabeležena akutna toksičnost za test vrste u pornoj vodi. Za neke uzorke, i pored visoke pseudo-ukupne koncentracije (klasa 4), nije potvrđena potencijalna toksičnost na osnovu odnosa kiselog volatilnog sulfida i simultano ekstrahovanih metala. Dok se ne primene skuplje metode remedijacije i tretmana sedimenta, najbolje rešenje je izolovano skladištenje na specijalnim deponijama. Naredni koraci bi trebali da budu usresređeni na kontrolu i sprečavanje zagađenja kako bi se obezbedilo da revitalizacija ovih vodotoka ima trajni pozitivan uticaj na životnu sredinu i nesmetanu i bezbednu plovidbu, kao i na primenu određenih remedijacionih metoda. Poređenje rezultata koji su dobijeni različitim procenama kvaliteta sedimenta pokazalo je da ponekad nije dovoljan jedan pristup i da je potrebno je uključiti metode procene biodostupnosti, biotestove i aspekt radioaktivnosti. U uzorku sedimenta koji je korišćen za ispitivanje efikasnosti remedijacionih tretmana, pokazano je da cink, nikal i olovo imaju visok rizik po okolinu, jer seprocenat metala u izmenljivoj i karbonatnoj fazi kretao od 40.1 do 45.2%. Cr i Cd imaju umeren rizik, dok je bakar prisutan u ovim frakcijama u koncentraciji koja predviđa nizak rizik (5.3%). Ovo je u skladu i sa rezultatima analize porne vode i simultano ekstrahovanih metala i kiselog volatilnog sulfida.</p><p>Istraživanje prikazano u radu je dalo odgovor na pitanje da li remedijacija može uspešno da ukloni zagađenje, u smislu imobilizacije metala u stanje kada oni više neće biti opasnost po okolinu. Svi primenjeni tretmani doveli su dosmanjenja procenta kumulativno izluženih metala iz S/S smeša, ali nijedna smeša tretiranog sedimenta i ispitivanih imobilizacionih agenasa ne pripada grupi inertnog otpada ukoliko se kumulativne izlužene koncentracije metala porede sa koncentracijama koje za otpad propisuje Evropska Unija (2003/33/EC). Ukoliko nam je cilj dobijanje nehazardnog otpada onda moramo primeniti u tretmanu sedimenta kontaminiranog metalima najmanje 30% imobilizaconih agenasa (cementa, kalcijum-oksida). Najveća efikasnost u imobilizaciji metala postignuta je korišćenjem cementa i kalcijum-oksida u smeši (30% cementa i 10% kalcijum-oksida) i primenom termičkog tretmana na višoj temperaturi (1100<sup>0</sup>C) sa glinom (20% gline) što je zaključeno na osnovu koeficijenata difuzije i indeksa izlužljivosti. Dominantan mehanizam izluživanjametala iz ovih smeša je difuzija.</p> / <p>This work is concerned with the comparison of the different methods of metal risk assessment in sediments based on examination of the qualityof water courses in Vojvodina. Besides, it deals with the possibility of applying remediation treatments of contaminated sediment and with the efficiency of the different methods, that is the techniques, for immobilization of sediment heavy metals by applying S/S and thermal treatments. A dominant mechanism is proposed for the process of leaching ofthe metals from treated mixtures.</p><p>Comparison of the results obtained by the different methods of sediment quality assessment showed that in some cases one approach to solving this problem is not sufficient. Metal concentrations in particular sediment samples (the Begej, the DTD Canal, the Nadela, the Sava at Šabac) indicate the presence of contamination, the analyzed samples being of Class 4. According to the Dutch regulations, a sedimentof Class 4 is of unacceptable quality and requires urgent intervention in the sense of sediment dredging, disposal into special depots, and, if possible, remediation. For some samples, despite a high pseudo-total concentration (Class 4), no potential toxicity was confirmed onthe basis of the ratioof the acidic volatile sulfide and simultaneously extracted metals. The results showed that, apart from chemical analyses, biological tests are also necessary, but also sequential extraction analysis, which can more clearly define the way of metal binding to the particular sediment fractions, to allow a more reliable prediction of metal mobility, potential toxicity and bioavailability. In the analysis of sediment quality it is also necessary toinclude the aspect of radioactivity, as it has been shown that the results of this analysis can, not only confirm some of the results of the other analyses, but also indicate the sediment age, origin of contamination and potential toxicity.The subsequent steps should be directed to the control and prevention of contamination, in order to ensure that the water course reviatalization has a lasting positive effect on the environment, an unimpared and safe navigation and application of remediation methods.</p><p>In the sediment sample (Class 4) that was usedfor the examination of the efficiency of it appeared that zinc, nickel and lead exhibit a high risk, as the percentages of these metals in the exchangeable and carbonate phases were in the range from 40.1 to 45.2%. On the other hand, chromium and cadmium exhibited a moderaterisk, whereas copperin these fractions was present at the levels corresponding to a low risk (5.3%). This is alsoin agreement with the results of pore water analysis and simultaneously extracted metals and acid volatile sulphide examinations.</p><p>The investigations presented in this work provided an answer to the question whetehr the remediation can successfully remove the contamination in the sense of the immobilization of metals in a state that will not be harmful tothe environment. All the treatments applied yielded a decrease of the percentage of cumulatively leached metals from the S/S mixtures, but none of the mixtures of treated sediments with the tested immobilization agents belongs to the group of inert materials if the cumulative leached concentrations are compared with the concntrations for the wastes given by the EU legislation (2003/33/EC). Ifthe goal is to obtain a non-hazardous material it is necessary to treat the contaminatedsediment with at least 30% of the immobilizing agent (cement or calcium oxide). Based on the diffusion coefficients and leachability index, the highest immobilization efficiency was achieved using a mixture of cement and calcium oxide (30% of cement and 10% of CaO) and by applying thermal treatment at a higher temperature (1100<sup>0</sup>C) with clay (20%). A dominant mechanism of leaching metals from these mixtures is diffusion.</p>
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Biosorpcija jona teških metala iz vode izluženim rezancima šećerne repe / Biosorption of heavy metal ions from water by sugar beet shredsKukić Dragana 18 November 2016 (has links)
<p>Cilj ove doktorske disertacije je bio da se ispita mogućnost primene izluţenih rezanaca šećerne repe i njihovih tretiranih oblika, nastalih u procesu proizvodnje bioetanola, kao biosorbenata za uklanjanje jona teških metala iz vode. U okviru eksperimenata, u laboratorijskim uslovima izvedeni su predtretman i hidroliza izluženih rezanaca kako bi se dobili tretirani oblici, a zatim je izvršena karakterizacija adsorbenata, ispitane njihove adsorpcione sposobnosti, utvrđeni najbolji uslovi za njihovu primenu i ispitana mogućnost njihove višestruke primene u obradi vode.<br />U okviru karakterizacije materijala određen je njihov sastav, specifiĉna površina i poroznost, ispitana površina primenom FTIR i EDS metode i kvantifikovana količina pojedinih funkcionalnih grupa prisutnih na površini primenom Boehm-ove titracije. Na osnovu FTIR metode pre i posle adsoprcije utvrđeno je koje grupe učestvuju u vezivanju jona metala.<br />Ispitan je i uticaj razliĉitih parametara na adsorpciju (vreme kontakta adsorbenta i adsorbata, veličina čestice, pH, temperatura, primenjena doza adsorbenta, jonska jačina, sušenje) radi utvrđivanja najboljih uslova za maksimalnu efikasnost.<br />Kako bi se stekao bolji uvid u sam proces adsorpcije jona na površinu adsorbenata, na eksperimentalne podatke primenjeni su različiti modeli adsorpcionih izotermi, a mehanizam vezivanja je detaljnije razmotren primenom kinetiĉkih modela. Primenom termodinamičkih modela utvrđena je priroda procesa.<br />Radi višestruke primene ovih ekoloških biosorbenata ispitana je i mogućnost regeneracije materijala razliĉitim kiselinama kao desorbensima i utvrđeno optimalno vreme desorpcije. Ispitana je primena kroz više uzastopnih ciklusa adsorpcija – desropcija. Rezultati su pokazali da ispitani materijali imaju zadovoljavajući adsorpcioni kapacitet, ali da se mogu primenjivati i vlažni, odmah nakon procesa ekstrakcije šećera, depektinacije i hidrolize, bez utroška energije za sušenje. Pored toga, utvrđeno je da se mogu regenerisati i koristiti uspešno više puta, što otvara mogućnost za njihovu primenu u praksi.</p> / <p>The aim of this PhD thesis was to investigate the possibility of usage of sugar beet shreds and their treated forms from the bioethanol production for removal of heavy metal ions from water. In the context of experiments, pretreatment and hydrolysis of sugar beet shreds were performed in order to obtain treated forms. The characterization of biosorbents was conducted and their adsorption capacity was investigated. Also, the optimal conditions for their implementation and the possibility of their multiple applications for water treatment were determined.<br />Within the characterization of materials their composition, specific surface area and porosity were determined. The surface of biosorbents was investigated by using FTIR and EDS methods. The amount of the functional groups present on the surface was quantified by Boehm's titration. On the basis of the FTIR method before and after adsorption it was determined which functional groups participate in the binding process.<br />The influence of various parameters on the adsorption (contact time of the adsorbent and adsorbate, particle size, pH, temperature, adsorbent dose, ionic strength, drying process) were examined in order to determine the best conditions for maximum efficiency.<br />For better insight into the process of adsorption of ions on the surface of the adsorbents, different models of adsorption isotherms were applied to experimental data. Mechanism of adsorption was determined by applying different kinetic models. The nature of the process was investigated by determining thermodynamic parameters.<br />The multiple applications of these eco-friendly biosorbents was examined by regeneration investigation. The optimal time of desorption was determined and different acids were used for regeneration study. The multiple cycles adsorption – desorption was also conducted.<br />The results showed that the investigated materials have a satisfactory adsorption capacity. They can also be applied wet, immediately after the process of sugar extraction, depectination and hydrolysis, without the energy consumption for drying. In addition, it was found that they can be regenerated and successfully used several times. This opens up the possibility for their practical application.</p>
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Procena potencijala remedijacije sedimenta primenom imobilizacionih agenasa / Assessment of potential remediation of metal contaminated sediment using imobilisation agentsDalmacija Milena 28 June 2010 (has links)
<p>Predmet izučavanja ove disertacije je ispitivanje mogućnosti imobilizacije toksičnih metala u sedimentu primenom imobilizacione tehnike solidifikacije/stabilizacije portland cementom, kalcijum-oksidom, prirodnim zeolitom, letećim pepelom, kaolinitom, montmorilonitom, i različitim smešama ovih agenasa kao i određivanje njihove efikasnosti u zavisnosti od brojnih faktora. Efikasnost imobilizacionih postupaka praćena je korišćenjem tzv. testova izluživanja, odnosno određivanjem koncentracije metala koji su u toku određenog vremena iz imobilisane faze prešli u mobilnu fazu gde se smatraju potencijalno opasnim i biodostupnim. Krajnji cilj svakog testa izluživanja je mogućnost procene adekvatnosti primene određene imobilizacione, odnosno remedijacione tehnike. Efikasnost imobilizacionih postupaka zavisi i od određenih osobina: pH rastvora, dodatka imobilizacionog agensa što je istraživanjem ispitano. Na osnovu ovog testa, odnosno odnosa kumulativne frakcije metala koja je oslobođena iz imobilizacione smeše u mobilnu fazu i vremena određen je tip mehanizma koji omogućava transport metala (spiranje, difuzija, rastvaranje). Takođe su određeni i i parametri (koeficijenti difuzije, indeksi izlužljivosti) koji će poslužiti za ocenu efikasnosti prethodno primenjenih imobilizacionih tehnika. Primenjeni su i modifikovani testovi izluživanja sa ciljem što bolje simulacije realnih uslova. U modifikovanim testovima izluživanja korišćen je rastvor sa pH 3,25 da bi se simulirali uslovi koji oponašaju kisele kiše, odnosno uslovi u realnom sistemu. Takođe je koršćen i rastvor huminskih materija sa ciljem simulacije uslova velikog organskog opterećenja do kojeg bi moglo doći u slučaju akcidentnih situacija (na primer poplava) i generalno uslova koji se stvaraju u prirodi pri raspadanju organskog materijala (lišće, trava, itd.). Rezultati dobijeni simulacijom ovih uslova će dalje omogućiti modelovanje ponašanja metala u smislu dugoročnog "izluživanja" iz tretiranog sedimenta kao i procenu najefikasnijih agenasa za imobilizaciju različitih metala u sedimentu. Na osnovu dobijenih rezultata, zaključeno je da su optimalni agensi za imobilizaciju metala u sedimentu smeša cementa i kreča (5% cementa i 10% kreča), smeša montmorilonita i kreča (30% montmorilonita i 10% kreča), leteći pepeo (30%) i zeolit (30%). U ovim smešama dominantan mehanizam izluživanja je difuzija, a ove smeše se mogu smatrati inertnim otpadom po svim ispitivanim kriterijumima. Ovi rezultati se mogu upotrebiti za projektovanje i izgradnju pilot postrojenja na kome bi se ispitala efikasnost ovih agenasa za remedijaciju sedimenta u realnim uslovima. Dobijeni podaci su neprocenjivi sa aspekta ekonomski i ekološki prihvatljivog upravljanja sedimentom.</p> / <p>This work is concerned with exploring the possibilities of immobilization of toxic metals in sediments using solidification/stabilization as imobilization technique and using Portland cement, calcium oxide, natural zeolite, flying ash, kaolinite, montmorilonite, and various mixtures of these agents and determine their effectiveness depending on many factors. Performance of imobilization procedures was followed by the use of so-called leaching tests and determination of the metals concentration that are within a specified interval of time leached from the immobile phase and as such can be considered potentially hazardous and bioavailable. The ultimate goal of every leaching test is to assess the adequacy of the possibility of applying certain imobilization or remediation technique. Performance of imobilizaction procedures depends on certain characteristics: pH of solution, additon of imobilization agent, etc. Based on this test, ie relation between the cumulative fraction of metal leached from imobilization mixture and time, the type of leaching mechanism that allows the transport of metals (wash-off, diffusion, dissolution) was determined. Other parameters which will serve for evaluating the efficiency of the previously applied imobilization techniques (diffusion coefficients, leaching indices) were also determined. Modified leaching tests were applied with the aim of better simulation of real conditions on the field. In the modified leaching tests the solution with pH 3.25 was used to simulate conditions that mimic acid rain and conditions in the real system. The humic acid solution was also used with the aim to simulate high organic loads which could occur in the case accident situation (eg floods) and the general conditions that are created in naturewhen decaying organic material (leaves, grass, etc.). The results obtained by simulating these conditions will enable the modeling of behavior of metals in terms of long-term leaching period from the treated sediment and assess the most effective agents for the immobilization of various metals in the sediments. Based on these results, it was concluded that the optimal agents for immobilization of metals in the sediment mixture of cement and lime (5% cement and 10% lime), a mixture montmorilonite and lime (30% montmorilonite and 10% lime), fly ash (30%) and zeolite (30%). In these mixtures dominant leaching mechanism is diffusion, and these mixtures can be considered as inert waste by all tested criteria. These results can be used to design and builda pilot plant in which order to evaluate the effectiveness of these agents for remediation of sediment in real terms. The obtained data are invaluable from the aspect of economic and ecologically acceptable management of sediment.</p>
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Primena stabilizovanog nano nula valentnog gvožđa i komercijalnih imobilizacionih agenasa za remedijaciju sedimenta kontaminiranog toksičnim metalima / Application of stabilized nano zero valent iron and commercial immobilisation agents for remediation of sediment contaminated with toxic metalsTomašević Dragana 03 October 2013 (has links)
<p>Predmet istraživanja ove disertacije je mogućnost korišćenja nano nula<br />valentnog gvožđa stabilizovanog sa bentonitom, kaolinitom i karboksimetil<br />celulozom za imobilizaciju teških metala, kao i ponašanje i sudbina metala u<br />sedimentu. Istraživanja je usmero u dva pravca: prvi deo istraživanja ima za cilj,<br />pre svega da definiše bolje razumevanje ponašanja metala u sedimentu i<br />određivanje njihove potencijalne mobilnost, biodostupnost i potencijalne<br />toksičnost na osnovu metoda sekvencijalne ekstrakcione procedure, kiselo<br />volatilnog sulfida i simultano ekstrahovanih metalau netretiranim i tretiranim<br />uzorcima sedimenta. Takođe, određena je efikasnosti korišćenja nanomaterijala<br />za imobilizaciju metala u sedimentu iz tretiranih smeša korišćenjem tzv. testova<br />„izluživanja“ kao i definisanje dominantnog mehanizma izluživanja koji<br />omogućava transport metala. Drugi deo istraživanja ima za cilj ispitivanje<br />mogućnosti primene nano nula valentnog gvožđa obloženog sa bentonitom,<br />kaolinitom i karboksimetilcelulozom za tretman zagađenog sedimenta na lokaciji<br />(in-situ), uz određivanje potencijalnog rizika po okolinu na osnovu rezultata<br />sekvencijlane ekstrakcione procedure i ekstrakcija u jednom koraku nakon<br />tretmana. Primenjeni su i modifikovani testovi izluživanja sa ciljem što bolje<br />simulacije realnih uslova. Rezultati dobijeni simulacijom ovih uslova i daljom<br />karakterizacijom smeša, kako sa nanomaterijalom tako i smeša sa glinom,<br />omogućuju izradu modela ponašanja metala u smislu dugoročnog "izluživanja" iz<br />tretiranog (stabilizovanog) sedimenta kao i procenukoji materijali su efikasniji<br />za imobilizaciju toksičnih metala u sedimentu.</p> / <p>This thesis explores the possibility of using nano zero valent iron stabilized with<br />bentonite, kaolinite, and carboxymethyl cellulose for the immobilization of heavy<br />metals, as well as the behaviour and fate of metalsin sediments. Research is focused<br />in two directions: the first part of the study aimsto find a better understanding of the<br />behaviour of metals in sediments and to determine their potential mobility,<br />bioavailability and potential toxicity based on sequential extraction procedures and<br />acid volatile sulphides and simultaneously extracted metals methods, in untreated and<br />treated sediment samples. The efficacy of using nanomaterials for the immobilization<br />of metals in sediments is also determined, by applying "leaching" tests to the treated<br />mixtures and defining the dominant leaching mechanism that enables the transport of<br />metals. The second part of the study aims to examine the possibilities of applying<br />nano zero valent iron coated with bentonite, kaolinite and carboxymethyl cellulose for<br />the treatment of contaminated sediment in-situ, to determine the potential risk posed<br />to the environment after treatment, based on the results of sequential extraction<br />procedures and a single step extraction. Modified leaching tests were applied in order<br />to achieve better simulation of real conditions. The results of simulating these<br />conditions and further characterization of mixtureswith both nanomaterials and clay,<br />provide a long term "leaching" model for the behaviour of metals in the treated<br />(stabilized) sediments, as well as assessing which materials are most effective for the<br />immobilization of toxic metals in sediments.</p>
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Model procene uticaja raspodele katjona toksičnih metala u heterogenom sistemu tečno/čvrsto na kvalitet površinskih voda / Impact assessment model of toxic metal cations partitioning in heterogeneous system liquid/solid sistem for surface water qualityČavić Aleksandra 11 September 2018 (has links)
<p>U doktorskoj disertaciji evaluirani su interkorelacioni rezultati odnosa ključnih fizičko-hemijskih parametara i katjona metala u površinskoj vodi Dunava, Tise (na po tri selektovana reprezentativna lokaliteta) i kanala Dunav-Tisa-Dunav (na dva lokaliteta). U<br />Kanalu Dunav-Tisa-Dunav praćene su i rezidualne katjonske koncentracije metala u sedimentu. Na osnovu podataka prisutnosti katjona metala u heterogenom sistemu tečno/čvrsto izračunate su po prvi put konstante podeonih procesa za ispitivane katjone metala. Primenom multivarijantnih statističkih metoda analizirani su korelacioni odnosi između ključnih fizičko-hemijskih parametara i koncentracionih nivoa rezidula katjona teških, lakih i semimetala. Faktorskom analizom (PCA) i klaster analizom sa dendogramima tumačeni, analizirani i diskutovani su dobijeni rezultati. Za optimalnog uočavanja korelacionih odnosa primenjeno je unapređeno rangiranje određenih skupova podataka (interkorelacije ključnih fizičko-hemijskih parametara i rezidua katjona metala) i grafički prikazanih Haseovih dijagrama primenom DART softvera (Decision Analysis by Ranking Techniques) za definisani model procene uticaja raspodele katjona toksičnih metala u heterogenom sistemu tečno/čvrsto na kvalitet površinskih voda.</p> / <p>In the doctoral thesis are evaluated inter correlational results of key physicochemical parameters and metal cations in surface water of Danube, Tisa (on three selected representative sampling points) and canal Danube-Tisa-Danube (on two sampling sites). In the canal Danube-Tisa-Danube are also followed residual metal cations concentrations in sediment. Based on metal cations presence data in heterogeneous system liquid/solid for the first time partitioning processes constants are calculated for<br />selected metal cations. Appling multivariate statistical methods correlations between key physicochemical parameters and concentration levels of residual heavy, light and semimetals cations are analysed. Using factorial analyse (PCA) and cluster analyse with dendograms obtained results were interpreted, analysed and discussed. For optimal comprehension of correlations, advanced method ranking of finite order sets is applied (inter correlations key physicochemical parameters and residual metal cations) and graphically shown Hasse diagrams obtained by DART software (Decision Analysis by Ranking Techniques) for defined impact assessment model of toxic metal cations partitioning in heterogeneous system liquid/solid for surface water quality.</p>
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Fizičko-hemijske i katalitičke osobine ugljeničnih nanocevi sintetisanih metodom katalitičke hemijske depozicije iz gasne faze – korelacija sa osobinama primenjenih katalizatora na bazi prelaznih metala (Fe, Co, Ni) / Physico-chemical and catalytic properties of carbon nanotubes synthesized by catalytic chemical vapor deposition - correlation with the properties of the applied catalysts based ontransition metals (Fe, Co, Ni)Panić Sanja 31 October 2014 (has links)
<p>Postojanje ugljeničnih nanocevi (UNC), kao jedne od brojnih alotropskih modifikacija ugljenika, zabeleženo je još pre više od pola veka. Međutim, do prave eksplozije<br />interesovanja za ovu vrstu nanomaterijala je došlo tek 1991. godine kada ih je "ponovo" otkrio japanski naučnik S. Iijima. Od tada, zbog svojih izuzetnih fizičko-hemijskih osobina, UNC počinju da privlače pažnju naučne javnosti i spajaju istraživače iz različitih oblasti sa zajedničkim imeniteljem - nanotehnologija. Otkriće UNC je u znatnoj meri omogućilo razvoj visoke tehnologije u oblastima kao što su elektronika, optika, kompozitni materijali, kataliza, zaštita životne sredine, itd. Danas, primena nanocevi sve više doprinosi lakšoj implementaciji principa održivog razvoja u pomenute oblasti. Kataliza je polje od dvostrukog interesa, jer je jedan od načina dobijanja UNC upravo katalitički, a osim toga i same cevi su interesantne kao nosač novog katalizatora.<br />Istraživanje čiji su rezultati prikazani u okviru ove doktorske disertacije je obuhvatilo više oblasti proučavanja UNC, počevši od razvoja metode za njihovu sintezu, preko prečišćavanja i funkcionalizacije finalnog proizvoda, pa do primene nanocevi u dva procesa od značaja za oblast zaštite životne sredine.</p><p>Razvoj katalitičke metode sinteze UNC započet je primenom vertikalnog cevnog kvarcnog reaktora, iz CO i CH4 kao izvora ugljenika, pri čemu su u reakciji testirani<br />monometalni katalizatori na bazi Fe, Co i Ni na Al2O3 kao nosaču (I serija katalizatora). Rezultati ovih preliminarnih eksperimenata su pokazali malu aktivnost I serije monometalnih katalizatora, što se može pripisati, kako neadekvatnoj hidrodinamici reaktora i loše odabranim reakcionim parametrima, tako i neodgovarajućoj veličini katalitičkih čestica i načina njihovog pakovanja u vertikalnom<br />reaktoru. Shodno tome, u cilju postizanja boljeg prinosa nanocevi, dalji eksperimenti sinteze izvedeni su u horizontalnom reaktoru u struji C2H4 i u prisustvu II serije<br />monometalnih katalizatora sa Al2O3 i SiO2 kao nosačima, koji se u odnosu na I seriju razlikuju po udelu aktivne faze i veličini čestica katalizatora (praškast oblik). Katalizatori II serije su pokazali zadovoljavajuću aktivnost u reakciji sinteze UNC, a rezultati karakterizacije dobijenih uzoraka nanocevi ukazuju na različit uticaj nosača katalizatora na morfologiju sintetisanih nanocevi. Shodno ostvarenom prinosu ugljenika, a u cilju optimizacije reakcionih parametara, katalizator na bazi Fe sa SiO2 kao nosačem je odabran kao reprezentativan za ispitivanje uticaja vremena trajanja sinteze UNC, kao i zapreminskog udela C2H4 u smeši sa azotom, na prinos<br />nanocevi i selektivnost procesa. Optimizacija reakcionih uslova je u daljoj fazi rada dovela do uvođenja bimetalnih katalizatora sa istim tradicionalnim nosačima – Al2O3 i SiO2. Najveći prinos ugljenika ostvaren je na katalizatorima sa Fe i Co kao aktivnom fazom, bez obzira na vrstu nosača. UNC sintetisane na pomenutim katalizatorima su karakterisane u cilju<br />ispitivanja uticaja primenjenih nosača na njihove fizičkohemijske osobine, pa je shodno tome i predložen vršni mehanizam njihovog rasta. Rezultati ispitivanja kvaliteta sintetisanih UNC su ukazali da primena SiO2, kao nosača katalizatora, za razliku od Al2O3, favorizuje rast UNC boljeg površinskog i ukupnog kvaliteta. S obzirom na raznolikost mogućnosti primene UNC, istraživanja u tom smeru zahtevaju čiste UNC, pa su shodno tome proizvodi sinteze prečišćeni metodom tečne oksidacije. Rezultati fizičko-hemijske karakterizacije prečišćenih UNC su ukazali na efikasnost primenjene metode sa aspekta uklanjanja prisutnog katalizatora, ali i na njen različit uticaj na strukturu, odnosno kvalitet prečišćenih uzoraka. Kao posledica promena unutar strukture UNC, kao i različitog stepena njihove funkcionalizacije, ukupni kvalitet prečišćenih nanocevi je, u zavisnosti od primenjenog nosača katalizatora, promenjen u odnosu na odgovarajuće neprečišćene uzorke.<br />Poslednjih godina se posebna pažnja poklanja nanomaterijalima koji se mogu primeniti za uklanjanje različitih polutanata iz životne sredine, kako u funkciji adsorbenata, tako i u funkciji katalizatora. U okviru ove doktorske disertacije obuhvaćena je primena UNC kao adsorbenta za uklanjanje insekticida tiametoksama iz vode, kao i njihova primena kao nosača katalizatora u reakciji<br />denitracije vode. Rezultati eksperimenata adsorpcije su pokazali da UNC, prethodno tretirane u ccHNO3, predstavljaju dobar adsorbent za uklanjanje insekticida tiametoksama iz vodenog rastvora. Odabir procesnih parametara za proučavanje kinetike adsorpcije, adsorpcione ravnoteže, kao i termodinamike procesa izvršen je primenom frakcionog faktorskog dizajna na dva nivoa, 5 1 V 2 , a dobijeni rezultati su ukazali da je pomenuti proces adsorpcije spontan i kontrolisan uglavnom unutrašnjom difuzijom molekula insekticida u mezopore uzorka UNC. Performanse katalizatora sa UNC kao nosačem su testirane u reakciji katalitičke denitracije, pri čemu su dobijeni rezultati pokazali da se novoformirani katalizator karakteriše zadovoljavajućom disperznošću sa udelombimetalnih Pd-Cu nanočestica koje omogućavaju 60% konverzije nitratnog jona.</p> / <p style="text-align: justify;">The existance of carbon nanotubes (CNTs), as one of the carbon allotropes, was noted over half century ago. However, the true interest for these nanomaterials appeared at 1991, when they were "redescovered" by Japanese scientist S. Iijima. Since then, due to their unique physico-chemical properties, CNTs begin to attract attention of the scientific community and to gather researchers from different areas within the common field of interest – nanotechnology. The CNTs discovery substantially enabled the high technology development in the fields such as electronics, optics, composite materials, catalysis, environmental protection, etc. Nowdays, the application of nanotubes is increasingly contributing to easier implementation of sustainable development principles in the above mentioned areas. Catalysis is the field of double interest – one of the CNTs synthesis method is catalytical, and the nanotubes can also be used as the support of the new catalyst.<br />The research, which results are shown within this PhD Thesis, includes few different CNTs research fields, starting from the synthesis method development, over the purification and functionalization of the final product, to the application of<br />nanotubes in two processes of significance for the field of environmental protection.<br />The development of the CNTs catalytic synthesis method was started by the use of vertical quartz tube reactor, in the flow of CO and CH4 as the carbon source, and in the presence of monometallic catalysts based on Fe, Co and Ni at Al2O3 as the support (the first series of catalysts). The results of these preliminary experiments have shown the low activity of these monometallic catalysts, which can be attributed to the inadequate reactor hydrodynamics and selected reaction parameters, as well as the inadequate size of the catalytic particles and the type of their packing in the vertical reactor. Consequently, in order to achieve the higher nanotubes yield, further synthesis experiments were carried out in a horizontal reactor in the flow of C2H4 as the carbon source, and in the presence of the second series of monometallic catalysts with Al2O3 and SiO2 as the supports. The catalysts of the second series have shown satisfactory activity in the CNTs synthesis reaction, and the results of the obtained samples characterization idicate a different influence of the catalyst support on the synthesized CNTs morphology. In order to optimize the reaction parameters, Fe/SiO2 catalyst was chosen as a representative to examine the effect of the CNTs synthesis duration, as well as the volume percentage of C2H4 in the mixture with nitrogen to the CNTs yield and process selectivity. In a further phase of work, the optimization of thereaction parameters led to the introduction of the bimetallic catalysts with the same traditional supports, Al2O3 and SiO2. The highest carbon yield was achieved over Fe, Co based catalysts, regardless of the type of the catalyst support. CNTs synthesized over the above mentioned catalysts were characterized in order to study the effect of the used supports on their physico-chemical properties, and consequently the CNTs tip growth mechanism was proposed. The results of quality examination of the synthesized CNTs showed that the use of SiO2, as a catalyst support, unlike Al2O3, favors the growth of nanotubes of better surface and overall crystalline quality. In view of the diversity of possible CNTs applications, investigation in that direction requires purified CNTs and accordingly the final CNTs products were purified by liquid oxidation method. The results of physico-chemical characterization of the purified CNTs showed that the applied purification method was effective in terms of removing the present catalyst, but on the other hand it had different influence on the structure and quality of the purified samples. As a consequence of CNTs structural changes, as well as their different degree of functionalization, the overall crystalline quality of the purified nanotubes, originating from different catalyst supports, was changed in comparison to the corresponding unpurified samples. Over the past few years, special attention was focused on<br />nanomaterials that can be applied as adsorbents or catalysts for the removal of various pollutants from the environment. This PhD Thesis considers the use of CNTs, as adsorbent, for the removal of insecticide thiamethoxam from water, as well as their use as catalyst support for water denitration reaction. The results of adsorption experiments have shown that the CNTs, pretreated in ccHNO3, represent a good adsorbent for the removal of thiamethoxam from the aqueous solutions. The<br />selection of the process parameters in order to study the adsorption kinetics and equilibrium, as well as the thermodynamics of the process, was conducted using the<br />fractional factorial design at two levels, 5 1 V 2 . The obtained results showed that the adsorption process is spontaneous and controlled mainly by an internal diffusion of molecules of insecticide in the mesopores of CNTs. The performance of the catalyst with the CNTs as the support were tested in catalytic water denitration reaction, whereby the results showed that the newly formed catalyst is characterized by satisfactory dispersion of Pd-Cu bimetallic nanoparticles which enable the 60% conversion of nitrate ions.</p>
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