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Title:Isolation of chitin from marine biomass with deep eutectic solvents and kinetics study of n-deacetylation to chitosan : doctoral disertation
Authors:ID Bradić, Bojana (Author)
ID Likozar, Blaž (Mentor) More about this mentor... New window
Files:.pdf DOK_Bradic_Bojana_2020.pdf (4,52 MB)
MD5: 9B6B53EBF60849F3A5F53B36610FDC57
PID: 20.500.12556/dkum/ccc2c983-2a19-4999-a03e-737e2b675bcd
 
Language:English
Work type:Doctoral dissertation
Typology:2.08 - Doctoral Dissertation
Organization:FKKT - Faculty of Chemistry and Chemical Engineering
Abstract:Namen disertacije je predstaviti razvoj nove metodologije z uporabo zelenih alternativnih rešitev, ki predstavljajo izboljšanje v primerjavi s tradicionalnim naĉinom pridobivanja komponent iz odpadne morske biomase. Frakcioniranje morske biomase, v našem primeru lupine škampov v sestavne dele, z glavnim hitinom, ki je eden prvih in najbolj komercialno pomembnih biopolimerov, je bilo doseženo s selektivno optimizacijo pogojev ekstrakcije z uporabo evtektiĉnih topil, kar je imelo za posledico zelo visok izkoristek hitina. Mehanizem frakcioniranja je razložen s kvantitativno analizo tekoĉih in trdnih frakcij, dobljenih po raztapljanju lupin škampov v DES. Evtektiĉna topila so se reciklirana in ponovno uporabila za hitinsko izolacijo, pri ĉemerto ni imelo velik vpliv na izkoristek hitina. Štiri najbolj obetavna in komercialno dostopna NADES, ki jih sestavljajo mešanice holin-klorid-mleĉna kislina (CCLA), holin-kloridmalonska kislina (CCMA), holin-klorid-seĉnina (CCUR) in holin-klorid-citronska kislina (CCCA), so bili preizkušeni. Najvišji izkoristek ekstrakcije hitina je bil <90% z uporabo CCLA, s ĉistostostjo izoliranega hitina nad 98%. Študija o modeliranju heterogenega koraka N-deacetilacije α-hitina, dobljenega iz odpadkov škampov, z uporabo katalitiĉne alkalne raztopine pri razliĉnih delovnih temperaturah in koncentracijah je prinesla nova mehanistiĉna spoznanja. Porazdelitve velikosti delcev za dva loĉena eksperimenta z manjšim prahom ali veĉjimi morfologijami hitina dobijene so sistemom sledenja v realnem ĉasu.Mehanizem pretvorbe verige biopolimerov je bil opisan preko matematiĉnega modela reakcijsko-difuzijske rešetke, rešen za vse intervale frakcij. Kinetika reakcije je bila predposatvljena drugega reda, ker koncentracija hidroksilnih ionov v porah ni bila konstantna. Izbrani matematiĉni model je omogoĉil razmeroma dober dogovor za kumulativne eksperimentalne podatke glede kinetike v zaĉetni fazi , kot tudi naknadno difuzijo za OH−. V tej študiji je bil nadelje tudi razvit en trajnostni pristop k raztapljanju hitina z vkljuĉitvijo zelene tehnologije v predelavo hitina, da bi odpravili pomanjkljivosti s pomoĉjo konvencialnih naĉinov raztapljanja hitina in kemijske deacetilacije. V tej študiji so bila preizkušena številna razliĉna evtektiĉna topila za raztaplanje hitina, kjer so se štiri izkazala kot zelo uĉinkovita. CCLA ( holin hlorid-mleĉna kislina) je bilo najbolj obetavno topilo za raztapljanje hitina. Alkalna in nevtralna evtektiĉna topila, so lahko vplivali na vodikove vezi v strukturi hitina, hkrati pa so vzpostavili novo in omogoĉili hitrejšo reakcijsko kinetiko N.-deacetilacijo ob uporabi manjše koncetracije NaOH. Tako so najuĉinkovitejši: CCLA, GLBT (glicerol-betain) in CCUR (holin klorid-urea) , uporabljeni za izvajanje N-deacetilacije s 30% raztopino NaOH pri 80°C in reakcijskim ĉasom do 18h. Dobljeni rezultati so pokazali DDA za približno 44-55% višjo od obstojeĉih literaturinih rezultatov, kjer je potekala homogena reakcija N deacetilacije hitina.
Keywords:hitin, hitozan, model z vkljuĉevanjem reakcijske kinetike in transporta, frakcionacija biomase, loĉevanje mineralov, evetktĉna topila
Place of publishing:Maribor
Place of performance:Maribor
Publisher:[B. Bradić]
Year of publishing:2020
Number of pages:121 str.
PID:20.500.12556/DKUM-75981 New window
UDC:604.4:662.6:579(043.3)
COBISS.SI-ID:38979075 New window
NUK URN:URN:SI:UM:DK:W3NCPC7G
Publication date in DKUM:23.11.2020
Views:1433
Downloads:133
Metadata:XML DC-XML DC-RDF
Categories:KTFMB - FKKT
:
BRADIĆ, Bojana, 2020, Isolation of chitin from marine biomass with deep eutectic solvents and kinetics study of n-deacetylation to chitosan : doctoral disertation [online]. Doctoral dissertation. Maribor : B. Bradić. [Accessed 3 April 2025]. Retrieved from: https://dk.um.si/IzpisGradiva.php?lang=eng&id=75981
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Licences

License:CC BY-NC-ND 4.0, Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
Link:http://creativecommons.org/licenses/by-nc-nd/4.0/
Description:The most restrictive Creative Commons license. This only allows people to download and share the work for no commercial gain and for no other purposes.
Licensing start date:27.03.2020

Secondary language

Language:Slovenian
Title:Izolacija hitina iz morske biomase z uporabo evtektičnih topil in študija kinetike n-deacetilacije do hitozana
Abstract:The purpose of the dissertation is to present the development of a new methodology using green alternative solutions that represent an improvement over the traditional method of extracting components from marine biomass. The fractionation of marine biomass, in our case, the shrimp shell into components, with main chitin, which is one of the first and most commercially important biopolymers, was achieved by selectively optimizing the extraction conditions using eutectic solvents, resulting in very high chitin efficiency. The fractionation mechanism is explained by the quantitative analysis of the liquid and solid fractions obtained after dissolving the shrimp shells in DES. Eutectic solvents were recycled and reused for chitin isolation, showing slight impact on chitin recovery yield. The highest yield of chitin extraction was <90% using CCLA, with an isolated chitin purity greater than 98%. A study on the modeling of the heterogeneous N-deacetylation step of α-chitin obtained from shrimp waste using a catalytic alkaline solution at different operating temperatures and concentrations has provided new mechanistic insights. Particle size distributions for two separate experiments with smaller dusts or larger chitin morphologies were obtained in real-time. The biopolymer chain conversion mechanism was described via a mathematical reaction-diffusion lattice model solved for all fraction intervals. The reaction kinetics was second order reaction since the concentration of hydroxyl ions in the pores was not constant. The chosen mathematical model provided relatively good agreement for the cumulative experimental data on the kinetics in the initial phase as well as the subsequent diffusion for OH−. This study also developed one sustainable approach to chitin dissolution by incorporating green technology into chitin processing, to avoid negative drawbacks using conventional methods of chitin dissolution and chemical deacetylation. In this study, a variety of different eutectic chitin dissolution solvents were tested, where four proved to be very effective. CCLA (choline chloride-lactic acid) was the most promising solvent for dissolving chitin. Alkaline and neutral eutectic solvents were able to disturb the hydrogen bonds in the chitin structure, while establishing a new one and allowing faster reaction kinetics of N-deacetylation using a lower NaOH concentration. Thus, the most effective are: CCLA, GLBT (glycerol-betaine) and CCUR (choline chloride-urea), used to perform N-deacetylation with 30% NaOH solution at 80 ° C and reaction time up to 18h. The results obtained showed a DDA approximately 44-55% higher than the existing literature results where a homogeneous reaction of chitin N deacetylation took place.
Keywords:chitin, chitosan, fractionation of biomass, reaction-diffusion model, in-line monitoring, heterogeneous N deacetylation of chitin, homogeneous N deacetylation of chitin, deep eutectic solvents


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