Sorpcija imitanata bojnih otrova na prirodnom i sintetskom zeolitu

doctoral thesis

• Title (english): Sorption of imitants of warfare agents on natural and synthetic zeolites
• Author: Dragutin Tušek
• Mentor: Danijela Ašperger (mentor)
• Committee member: Sandra Babić (predsjednik povjerenstva)
• Committee member: Jelena Macan (član povjerenstva)
• Committee member: Lidija Ćurković (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2017-06-12, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Cilj ovog rada je razvoj ekološki prihvatljivih dekontaminanata kemijskog oružja i drugih toksičnih kemikalija što je važno iz sigurnosnih, ekonomskih, zdravstvenih, političkih i ekoloških razloga. Istraživani imitanti bojnih otrova su: dimetil metilfosfonat (DMMP) kao najviše istraživani imitant živčanih bojnih otrova, 2-kloroetiletil sulfid (2-CEES) kao najviše istraživani imitant sumpornih iperita te dietil 2-[(dimetoksifosforotiol)sulfanil]butandioat (malation) kao najviše istraživani imitant za O-etil-S-[2-(diisopropilamino)etil]metilfosfonotioat (VX). Ispitivanja su provedena na slijedećim sorbensima: prirodnom zeolitu klinoptilolitu, sintetskom zeolitu MCC Na i Ca forme, smjesi prirodnog i sintetskog zeolita, na metalnim oksidima - magnezija, aluminija, titanija i cinka, na smjesama metalnih oksida sa sintetskim zeolitom, na smjesi aluminijevog i magnezijevog oksida te na aktivnom ugljenu. Istraživanja na sorbensima obuhvaćala su: ispitivanje djelotvornosti sorpcije imitanata na sorbense iz organske faze pomoću plinske kromatografije vezane na spektrometar masa, ispitivanje djelotvornosti sorpcije imitanana na sorbense iz vodene faze tekućinskom kromatografijom ultra visoke djelotvornosti vezane na detektor s nizom dioda, određivanje volumena prodora za organske otopine imitanata na istraživanim sorbensima pomoću plinske kromatografije vezane na spektrometar masa, detekciju sorpcijskih mehanizama pomoću infracrvene spektrometrije te karakterizaciju istraživanih sorbensa korištenjem pretražne elektronske mikroskopije. Rezultati ispitivanja djelotvornosti sorpcije imitanata na sorbense iz organske i vodene otopine pokazali su vrlo dobra sorpcijska svojstva istraživanih sorbensa u sorpciji svih triju imitanata bojnih otrova, znatno bolja u sorpciji DMMP i malationa, nego u sorpciji 2-CEES. Temeljem rezultata ispitivanja volumena prodora iz organske otopine najveći potencijal u sorpciji sva tri imitanta bojnih otrova pokazao je aluminijev oksid, zatim smjesa aluminijevog oksida s magnezijevim oksidom i sintetskim zeolitom te aktivni ugljen, najslabija sorpcijska svojstva pokazali su cinkov oksid, sintetski zeolit te njihova smjesa. Dominantan mehanizam sorpcije DMMP-a i 2-CEES kod svih sorbensa je preko Lewisove baze, a kod malationa dominantna je pojava kemisorpcije malationa preko Lewisove i Brönstedove baze. Temeljem rezultata analize moguće je dizajnirati djelotvorne sorbense, jeftine, dostupne i ekološki prihvatljive koji se mogu djelotvorno koristiti kao sorbensi i/ili dekontaminanti najtoksičnijih organskih spojeva poput bojnih otrova i pesticida.

Abstract (english)

The aim of this doctoral thesis is development of environmentally acceptable decontaminants of chemical weapons and other highly toxic chemicals, which is important for the reasons related to security, economics, health, politics, and environment. The investigated imitants of chemical warfare agents were included: dimethyl methylphosphonate (DMMP), as the most commonly studied chemical warfare agent simulant for nerve agents; 2-chloroethylethyl sulfide (2-CEES), as the most commonly studied chemical warfare agent simulant for sulfur mustard; and diethyl 2-[(dimethoxyphosphoro thioyl)sulfanyl]butanedioate (malathion), as the most commonly studied chemical warfare agent simulant for 2-(diisopropylamino)ethyl]-O-ethylmethylphosphonothioate (VX). Research was performed on the following sorbents: natural zeolite clinoptilolite, synthetic zeolite MCC Na and Ca form, mixture of natural and synthetic zeolites, metal oxides of magnesium, aluminum, titanium and zinc, mixtures metal oxides with synthetic zeolite, mixtures of aluminum and magnesium oxide and activated carbon. Research on the investigated sorbents involved: efficiency testing of the investigated sorbents from the organic phase by gas chromatography coupled with mass spectrometry, efficiency testing of the investigated sorbents from aqueous phase by ultra-high performance liquid chromatography associated with a diode array detector, determination of the breaktrough volume from the organic phase on the studied sorbents by gas chromatography coupled with mass spectrometry, detection of sorption mechanisms by infrared spectrometry, and characterization of the investigated sorbent using scanning electron microscopy.
The results of the performed analysis of sorption efficiency from the organic and aqueous solution indicated very good sorption properties of all investigated sorbents in sorption of all three imitants of chemical warfare agents. Sorption of DMMP and malathion was significantly better than sorption of 2-CEES. Based on the results of the testing of breaktrough volume from the organic solution, the greatest potential for sorption of all three imitants of chemical warfare agents showed aluminum oxide, then mixture of aluminum oxide with magnesium oxide and then mixture of aluminum oxide with synthetic zeolite and activated carbon.
The lowest sorption properties were showed zinc oxide, synthetic zeolites and their mixture. The dominant mechanism for sorption of DMMP and 2-CEES on all sorbents, was through the Lewis base, whereas for malathion was chemisorption of malathion through the Lewis and Brönsted bases. It is possible, according to the results of the analysis, to design efficient, cheap, accessible, and environmentally friendly sorbents that can be used efficiently as sorbents and / or decontaminants for the most toxic organic compounds such as chemical warfare agents and pesticides.

• Keywords: dimetil metilfosfonat (DMMP); 2-kloroetiletil sulfid (2-CEES); dietil 2-[(dimetoksifosforotiol)sulfanil]butandioat (malation); zeoliti; metalni oksidi; volumen prodora; plinska kromatografija vezana sa spektrometrijom masa (GC-MS); Fourierova infracrvena transformacijska spektrometrija (FTIR); pretražna elektronska mikroskopija (SEM)
• Keywords (english): dimethyl methylphosphonate (DMMP); 2-chloroethylethyl sulfide (2-CEES); diethyl 2-[(dimethoxyphosphorothioyl)sulfanyl]butanedioate (malathion); zeolites; metal oxides; breaktrough volume; gas chromatography mass spectrometry (GC-MS); Fourier transform infrared spectrometry (FTIR); scanning electron microscopy (SEM)
• Language: croatian
• URN:NBN: urn:nbn:hr:149:503297
• Promotion: 2017
• Study programme: Title: Engineering Chemistry - Doctoral Course; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
• Type of resource: Text
• Extent: 197 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2023-12-06 13:33:15