Sinteza aditiva za snižavanje tecišta na osnovi maleinskog anhidrida za dizelsko i biodizelsko gorivo

master's thesis

• Title (english): Synthesis of pour point additives based on maleic anhydride for diesel and biodiesel fuel
• Author: Mislav Mišetić
• Mentor: Fabio Faraguna (mentor)
• Committee member: Fabio Faraguna (predsjednik povjerenstva)
• Committee member: Ante Jukić (član povjerenstva)
• Committee member: Mirela Leskovac (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2021-09-24, Croatia
• Scientific / art field, discipline and subdiscipline: TECHNICAL SCIENCES; Chemical Engineering

Abstract

Cilj ovog rada bio je provesti sintezu šest polimernih aditiva na osnovi maleinskog anhidrida i ispitati kako sintetizirani aditiv djeluje na niskotemperaturna svojstva dizelskog i biodizelskog goriva. Reakcijom polimerizacije sintetizirani su polimeri poli(maleinski anhidrid-ko-vinil-acetat) koristeći pri tome različite množinske omjere polaznih monomera (MA:VA=50:50 i 80:20). Nakon pročišćavanja uslijedila je funkcionalizacija polimernih molekula tijekom koje dolazi do otvaranja anhidridnog prstena i vezanja alkilnog lanca alkohola (heksanol, oktanol, dodekanol) na polimer reakcijom esterifikacije. Korištenjem triju alkohola ispitano je kako duljina alkilnog lanca alkohola utječe na topljivost polimernog aditiva u gorivu te na svojstva aditiviranog goriva. Čistoća polimernih aditiva nakon sinteze i tijekom pročišćavanja praćena je infracrvenom spektroskopijom s Fourierovom transformacijom (FTIR) i nuklearnom magnetskom rezonancijom (NMR). Kromatogafijom na propusnom gelu (GPC) određene su krivulje raspodjele molekulskih masa i prosjeci molekulskih masa pripremljenih aditiva. Diferencijalnom pretražnom kalorimetrijom (DSC) snimljeni su termogrami mješavina MAVA aditiva i goriva na temelju kojih je potvrđeno kako dodatak aditiva ima veći utjecaj na sniženje temperatura početka i maksimuma kristalizacije dizela u odnosu na biodizel. Prema standardiziranim ispitnim metodama izvršena su mjerenja temperature tečenja (ASTM D 5950) i filtrabilnosti (EN 116) aditiviranih goriva iz kojih se zaključuje kako polimerni aditivi s dodekanolom ne utječu na filtrabilnost, ali snižavaju tecište dizelskog goriva. Najveći utjecaj na niskotemperaturna svojstva vidljiv je u slučaju korištenja aditiva s omjerom monomera 80:20 i dodekanolom kao sredstvom za funkcionalizaciju koji je snizio temperaturu tečenja dizelskog goriva za 21 °C. U slučaju korištenja biodizela, izmjereno je kako aditiv može smanjiti točku tečenja i točku filtrabilnosti goriva za do 3 °C.

Abstract (english)

The aim of this study was to synthesize six polymer additives based on maleic anhydride in order to investigate how additives can improve low-temperature properties of diesel and biodiesel fuel. Polymerisation of poly(maleic anhydride-co-vinyl acetate) was performed with different molar ratios of monomers (MA:VA=50:50 and 80:20). After the synthesis and purification of polymers functionalization step was performed during which the anhydride ring opened and the alkyl chain of the alcohol (hexanol, octanol, dodecanol) was chemically bonded to the polymer. Three alcohols were used to examin how length of the alkyl chain of alcohol affects solubility of polymer additive in the fuel and also how it affects fuel properties. Purity of polymer additives after synthesis and during purification was examined by analysis of FTIR and 1H NMR spectrum. GPC analysis was used to determine the molecular weight distribution curves and the averages of molecular weights of prepared additives. DSC thermograms of mixtures of MAVA additives and fuels indicate that addition of additives has a greater impact on lowering the onset temperature and the temperature of first crystallization maximum of diesel fuel compared to biodiesel fuel. According to standardized test methods, measurements of pour point (ASTM D 5950) and cold filter plugging point (EN 116) were performed. It is concluded that polymer additives with dodecanol do not affect filterability, but they lower pour point of diesel fuel. The biggest influence on low-temperature properties is seen in the case of using additives with monomer ratio of 80:20 and dodecanol as a functionalization agent that lowered pour point of diesel fuel by 21 °C. In the case of biodiesel, it has been measured that additive can reduce pour point and cold filter plugging point by up to 3 °C.

• Keywords: polimerni aditivi; dizel; biodizel; funkcionalizacija; tecište; filtrabilnost
• Keywords (english): polymer additives; diesel; biodiesel; functionalization; pour point; cold filter plugging point
• Language: croatian
• URN:NBN: urn:nbn:hr:149:544246
• Project: Number: UIP-2019-04-5242; Title: Razvoj funkcionalnih biogoriva i (bio)aditiva te ispitivanje primjenskih svojstava mješavina s mineralnim gorivima; Title: Development of functional biofuels and (bio)additives and characterization of blends with mineral fuels; Acronym: FunBioFA; Leader: Fabio Faraguna; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: UIP
• Study programme: Title: Chemical Engineering - Graduate study; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra inženjer/inženjerka kemijskog inženjerstva (magistar/magistra inženjer/inženjerka kemijskog inženjerstva)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Access restricted to students and staff of home institution
• Created on: 2023-04-17 12:23:07