Characterization of type III kerogen from Tyrolean shale (Hahntennjoch, Austria) based on its oxidation products
Karakterizacija kerogena tipa III Tirolskog škriljca (Hahntennjoch, Austrija) zasnovana na njegovim oksidacionim proizvodima
Апстракт
A 29-step alkaline permanganate degradation of type III kerogen from Tyrolean (Hahntennjoch, Austria) oil shale was performed. A high yield of oxidation products was obtained (93.7 % relative to the original kerogen): 0.5 % neutrals and bases, 19.5 % ether-soluble acids and 58.9 % of precipitated (PA). A substantial amount of kerogen carbon (14.8 %) was oxidized into carbon dioxide. The organic residue remaining after the final oxidation step was 6.9 %. The PA components were further oxidized and the total yields relative to original PA were 1.0 % neutrals and bases and 59.0 % ether-soluble acids, the non-degraded residue being 29.3 %. Detailed quantitative and qualitative analysis of all oxidation products suggested the Tyrolean shale kerogen to be a heterogeneous macromolecular substance consisting of three types of structures differing in composition and susceptibility towards alkaline permanganate: the first, resistant, presumably composed of aromatic structures linked by resorcino...l ethereal bonds; the second, combined in nature, the aliphatic part comprising methyl-substituents and short cross-links, both easily oxidized into CO2, water and low molecular weight acids and aromatic structures yielding aromatic diand tri-carboxylic acids as oxidation products; finally the third, composed of aliphatic cross-links and substituents, alicyclic (and/or heterocyclic) and some aromatic structures, bound into units moderately resistant towards oxidation. The overall yields of kerogen and PA oxidation products lead towards a balance between aromatic, alkane monoand dicarboxylic and alkanepolycarboxylic acids, suggesting a shift of the structure of Tyrolean shale kerogen from typical aromatic reference type III towards a heterogeneous aromatic-aliphaticalicyclic type structure.
Stupnjevitom degradacijom kerogena tirolskog škriljca pomoću alkalnog permanganata dobijeni su visoki prinosi oksidacionih proizvoda. Dobijene nerastvorne kiseline naknadno su degradovane u 8 stupnjeva. Detaljna GC-MS analiza kiselina rastvornih u etru, dobijenih degradacijom kerogena, potom intermedijarnih nerastvornih kiselina, pokazala je da je kerogen tirolskog škriljca heterogena makromolekularna supstanca i da se sastoji iz tri tipa strukture, različitog sastava i različite osetljivosti na primenjeno oksidaciono sredstvo. Prvi tip je aromatične prirode sa rezorcinolnim etarskim umreženjem, otporan prema alkalnom permanganatu. Drugi se vrlo lako oksiduje, a sastoji se od aromatičnih struktura umreženih kratkim alifatičnim nizovima i sa većim udelom metil-supstituenata. Ovaj tip strukture je pri oksidaciji dao visok prinos SO2, alifatične kiseline malih molekulskih masa i aromatične dii trikarboksilne kiseline u visokom prinosu. Treći tip strukture je srednje osetljivosti na perman...ganat, a sastoji se od alicikličnih i/ili heterocikličnih i aromatičnih jezgara povezanih alifatičnim nizovima srednjih dužina. Kvantitativan odnos alifatičnih, aromatičnih i alkan-polikarboksilnih kiselina u oksidacionim proizvodima pokazao je da struktura kerogena tirolskog škriljca odstupa od tipskih, dominantno aromatičnih struktura tipa III, kojima pripada po svom H/C-O/C atomskom odnosu, i da je pomerena ka heterogenim, aromatično-alifatično-alicikličnim strukturama tipa II.
Кључне речи:
Tyrolean shale / type III kerogen / structural characterization / alkaline permanganate degradation / oxidation productsИзвор:
Journal of the Serbian Chemical Society, 2008, 73, 4, 463-478Издавач:
- Serbian Chemical Society
Институција/група
IHTMTY - JOUR AU - Bajc, S. AU - Cvetković, Olga AU - Ambles, A. AU - Vitorović, Dragomir PY - 2008 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/407 AB - A 29-step alkaline permanganate degradation of type III kerogen from Tyrolean (Hahntennjoch, Austria) oil shale was performed. A high yield of oxidation products was obtained (93.7 % relative to the original kerogen): 0.5 % neutrals and bases, 19.5 % ether-soluble acids and 58.9 % of precipitated (PA). A substantial amount of kerogen carbon (14.8 %) was oxidized into carbon dioxide. The organic residue remaining after the final oxidation step was 6.9 %. The PA components were further oxidized and the total yields relative to original PA were 1.0 % neutrals and bases and 59.0 % ether-soluble acids, the non-degraded residue being 29.3 %. Detailed quantitative and qualitative analysis of all oxidation products suggested the Tyrolean shale kerogen to be a heterogeneous macromolecular substance consisting of three types of structures differing in composition and susceptibility towards alkaline permanganate: the first, resistant, presumably composed of aromatic structures linked by resorcinol ethereal bonds; the second, combined in nature, the aliphatic part comprising methyl-substituents and short cross-links, both easily oxidized into CO2, water and low molecular weight acids and aromatic structures yielding aromatic diand tri-carboxylic acids as oxidation products; finally the third, composed of aliphatic cross-links and substituents, alicyclic (and/or heterocyclic) and some aromatic structures, bound into units moderately resistant towards oxidation. The overall yields of kerogen and PA oxidation products lead towards a balance between aromatic, alkane monoand dicarboxylic and alkanepolycarboxylic acids, suggesting a shift of the structure of Tyrolean shale kerogen from typical aromatic reference type III towards a heterogeneous aromatic-aliphaticalicyclic type structure. AB - Stupnjevitom degradacijom kerogena tirolskog škriljca pomoću alkalnog permanganata dobijeni su visoki prinosi oksidacionih proizvoda. Dobijene nerastvorne kiseline naknadno su degradovane u 8 stupnjeva. Detaljna GC-MS analiza kiselina rastvornih u etru, dobijenih degradacijom kerogena, potom intermedijarnih nerastvornih kiselina, pokazala je da je kerogen tirolskog škriljca heterogena makromolekularna supstanca i da se sastoji iz tri tipa strukture, različitog sastava i različite osetljivosti na primenjeno oksidaciono sredstvo. Prvi tip je aromatične prirode sa rezorcinolnim etarskim umreženjem, otporan prema alkalnom permanganatu. Drugi se vrlo lako oksiduje, a sastoji se od aromatičnih struktura umreženih kratkim alifatičnim nizovima i sa većim udelom metil-supstituenata. Ovaj tip strukture je pri oksidaciji dao visok prinos SO2, alifatične kiseline malih molekulskih masa i aromatične dii trikarboksilne kiseline u visokom prinosu. Treći tip strukture je srednje osetljivosti na permanganat, a sastoji se od alicikličnih i/ili heterocikličnih i aromatičnih jezgara povezanih alifatičnim nizovima srednjih dužina. Kvantitativan odnos alifatičnih, aromatičnih i alkan-polikarboksilnih kiselina u oksidacionim proizvodima pokazao je da struktura kerogena tirolskog škriljca odstupa od tipskih, dominantno aromatičnih struktura tipa III, kojima pripada po svom H/C-O/C atomskom odnosu, i da je pomerena ka heterogenim, aromatično-alifatično-alicikličnim strukturama tipa II. PB - Serbian Chemical Society T2 - Journal of the Serbian Chemical Society T1 - Characterization of type III kerogen from Tyrolean shale (Hahntennjoch, Austria) based on its oxidation products T1 - Karakterizacija kerogena tipa III Tirolskog škriljca (Hahntennjoch, Austrija) zasnovana na njegovim oksidacionim proizvodima VL - 73 IS - 4 SP - 463 EP - 478 DO - 10.2298/JSC0804463B ER -
@article{ author = "Bajc, S. and Cvetković, Olga and Ambles, A. and Vitorović, Dragomir", year = "2008", abstract = "A 29-step alkaline permanganate degradation of type III kerogen from Tyrolean (Hahntennjoch, Austria) oil shale was performed. A high yield of oxidation products was obtained (93.7 % relative to the original kerogen): 0.5 % neutrals and bases, 19.5 % ether-soluble acids and 58.9 % of precipitated (PA). A substantial amount of kerogen carbon (14.8 %) was oxidized into carbon dioxide. The organic residue remaining after the final oxidation step was 6.9 %. The PA components were further oxidized and the total yields relative to original PA were 1.0 % neutrals and bases and 59.0 % ether-soluble acids, the non-degraded residue being 29.3 %. Detailed quantitative and qualitative analysis of all oxidation products suggested the Tyrolean shale kerogen to be a heterogeneous macromolecular substance consisting of three types of structures differing in composition and susceptibility towards alkaline permanganate: the first, resistant, presumably composed of aromatic structures linked by resorcinol ethereal bonds; the second, combined in nature, the aliphatic part comprising methyl-substituents and short cross-links, both easily oxidized into CO2, water and low molecular weight acids and aromatic structures yielding aromatic diand tri-carboxylic acids as oxidation products; finally the third, composed of aliphatic cross-links and substituents, alicyclic (and/or heterocyclic) and some aromatic structures, bound into units moderately resistant towards oxidation. The overall yields of kerogen and PA oxidation products lead towards a balance between aromatic, alkane monoand dicarboxylic and alkanepolycarboxylic acids, suggesting a shift of the structure of Tyrolean shale kerogen from typical aromatic reference type III towards a heterogeneous aromatic-aliphaticalicyclic type structure., Stupnjevitom degradacijom kerogena tirolskog škriljca pomoću alkalnog permanganata dobijeni su visoki prinosi oksidacionih proizvoda. Dobijene nerastvorne kiseline naknadno su degradovane u 8 stupnjeva. Detaljna GC-MS analiza kiselina rastvornih u etru, dobijenih degradacijom kerogena, potom intermedijarnih nerastvornih kiselina, pokazala je da je kerogen tirolskog škriljca heterogena makromolekularna supstanca i da se sastoji iz tri tipa strukture, različitog sastava i različite osetljivosti na primenjeno oksidaciono sredstvo. Prvi tip je aromatične prirode sa rezorcinolnim etarskim umreženjem, otporan prema alkalnom permanganatu. Drugi se vrlo lako oksiduje, a sastoji se od aromatičnih struktura umreženih kratkim alifatičnim nizovima i sa većim udelom metil-supstituenata. Ovaj tip strukture je pri oksidaciji dao visok prinos SO2, alifatične kiseline malih molekulskih masa i aromatične dii trikarboksilne kiseline u visokom prinosu. Treći tip strukture je srednje osetljivosti na permanganat, a sastoji se od alicikličnih i/ili heterocikličnih i aromatičnih jezgara povezanih alifatičnim nizovima srednjih dužina. Kvantitativan odnos alifatičnih, aromatičnih i alkan-polikarboksilnih kiselina u oksidacionim proizvodima pokazao je da struktura kerogena tirolskog škriljca odstupa od tipskih, dominantno aromatičnih struktura tipa III, kojima pripada po svom H/C-O/C atomskom odnosu, i da je pomerena ka heterogenim, aromatično-alifatično-alicikličnim strukturama tipa II.", publisher = "Serbian Chemical Society", journal = "Journal of the Serbian Chemical Society", title = "Characterization of type III kerogen from Tyrolean shale (Hahntennjoch, Austria) based on its oxidation products, Karakterizacija kerogena tipa III Tirolskog škriljca (Hahntennjoch, Austrija) zasnovana na njegovim oksidacionim proizvodima", volume = "73", number = "4", pages = "463-478", doi = "10.2298/JSC0804463B" }
Bajc, S., Cvetković, O., Ambles, A.,& Vitorović, D.. (2008). Characterization of type III kerogen from Tyrolean shale (Hahntennjoch, Austria) based on its oxidation products. in Journal of the Serbian Chemical Society Serbian Chemical Society., 73(4), 463-478. https://doi.org/10.2298/JSC0804463B
Bajc S, Cvetković O, Ambles A, Vitorović D. Characterization of type III kerogen from Tyrolean shale (Hahntennjoch, Austria) based on its oxidation products. in Journal of the Serbian Chemical Society. 2008;73(4):463-478. doi:10.2298/JSC0804463B .
Bajc, S., Cvetković, Olga, Ambles, A., Vitorović, Dragomir, "Characterization of type III kerogen from Tyrolean shale (Hahntennjoch, Austria) based on its oxidation products" in Journal of the Serbian Chemical Society, 73, no. 4 (2008):463-478, https://doi.org/10.2298/JSC0804463B . .