Ilościowa ocena i wydzielenie różnych form siarki w próbkach geologicznych wraz z zastosowaniem do badań pochodzenia związków siarki w systemach naftowych

• Autorzy: Wencel Kinga , Bieleń Wojciech

Identyfikatory

DOI

10.18668/NG.2023.06.01

Warianty tytułu

EN

Quantitative assessment and isolation of various sulphur forms in geological samples and its application in investigation of sulphur compounds origin in petroleum systems

• Języki publikacji: PL

Abstrakty

PL

Siarka występuje w naturze w bogactwie form – jako siarka elementarna, siarczki, siarczany, organiczne związki siarki (OZS, ang. organic sulfur compounds, OSC). W pracy zbadano zależności pomiędzy występowaniem siarki w ropach i skałach macierzystych. Wydzielono siarkę pirytową, pierwiastkową, organiczną w kerogenie oraz OZS w bituminach. Do rozdzielenia siarki pirytowej pozostałej po izolacji kerogenu zastosowano metodę redukcji kwaśnym roztworem chlorku chromu (II) (ang. chromium reducible sulfur method, CRS), przeprowadzaną w inertnej atmosferze azotu w komorze rękawicowej. Zastosowanie CrCl2 w obecności HCl powoduje wydzielenie siarki pirytowej w postaci H2S. Siarkowodór jest następnie wprowadzany do roztworu AgNO3, gdzie zachodzi reakcja z wytrąceniem się czarnego osadu Ag2S. Ilość wytrąconej siarki była oznaczana wagowo, a kerogen i siarczek srebra (I) były poddawane badaniom izotopów siarki. Analiza elementarna badanego materiału przed usunięciem i po usunięciu siarki pirytowej oraz obliczenie stosunków atomowych H/C, O/C, N/C, S/C potwierdziły przydatność metody wykazanej w poprzednich badaniach i nie uwidoczniły istotnych zmian w badanym kerogenie. W pracy oddzielono siarkę pirytową od organicznej w kerogenie z wybranych próbek warstw menilitowych z zewnętrznych Karpat fliszowych oraz poddano obie formy tego pierwiastka badaniom izotopowym, a także skorelowano z danymi dotyczącymi innych form występowania siarki w skałach, bituminach i ropach. Co istotne, znaczną część siarki całkowitej w kerogenie stanowi siarka pirytowa, co implikuje konieczność rozdzielenia jej od siarki organicznej w celu sformułowania poprawnych wniosków dotyczących energii aktywacji kerogenu i tempa generacji węglowodorów. Badania izotopowe potwierdzają wcześniejsze interpretacje pochodzenia pirytu z procesu bakteryjnej redukcji siarczanów i euksynicznego środowiska depozycji oligoceńskich osadów w basenie Paratetydy.

EN

Sulphur occurs in nature in a variety of forms: as elemental sulphur, sulphides, sulphates, and organic sulphur compounds (OSC). The work investigated the relationship between the presence of sulphur in crude oil and source rocks. Pyritic and organic sulphur was isolated in kerogen, while OSC and elemental sulphur was isolated in bitumens. The chromium reducible sulphur method (CRS) carried out in an inert nitrogen atmosphere in a glove box was used to separate pyritic sulphur remaining after kerogen isolation. The use of a CrCl2 solution in HCl results in the release of pyritic sulphur in the form of H2S. Hydrogen sulphide is later introduced into the AgNO3 solution, where reaction occurs resulting in precipitation of black Ag2S. The amount of precipitated sulphur was determined by weight, while kerogen remains and silver (I) sulphide underwent sulphur isotope testing. The elemental analysis of the tested material before and after the removal of pyritic sulphur and the calculation of the atomic H/C, O/C, N/C, S/C ratios confirmed the usefulness of the method demonstrated in previous studies and did not show any significant changes in the tested kerogen. In the work, pyritic sulphur was separated from organic sulphur in kerogen from selected samples of Menilite Beds from the Outer Carpathians and subjected to isotope tests, and correlated with data on other forms of sulphur occurrence in rocks, bitumens and crudes. A significant part of the total sulphur in kerogen is pyritic sulphur, which without determining the content of organic sulphur may lead to incorrect assumptions regarding the activation energy of kerogen and the rate of hydrocarbon generation. Isotopic studies confirm earlier interpretations of the origin of pyrite by bacterial reduction of sulphates and the euxinic environment of the deposition of Oligocene sediments in the Paratethys Basin.

Słowa kluczowe

PL

kerogen; siarka redukowana chromem; CRS; warstwy menilitowe; bakteryjna redukcja siarczanów; analiza elementarna; izotopy siarki

EN

kerogen; chromium-reduced sulfur; CRS; Menilite Beds; bacterial sulfate reduction; elemental analysis; sulfur isotopes

• Wydawca: Instytut Nafty i Gazu - Państwowy Instytut Badawczy
• Czasopismo: Nafta-Gaz
• Rocznik: 2023
• Tom: R. 79, nr 6
• Strony: 371--384
• Opis fizyczny: Bibliogr. 60 poz.

Twórcy

autor

Wencel Kinga

• Instytut Nafty i Gazu – Państwowy Instytut Badawczy

autor

Bieleń Wojciech

• Instytut Nafty i Gazu – Państwowy Instytut Badawczy

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Uwagi

Opracowanie rekordu ze środków MEiN, umowa nr SONP/SP/546092/2022 w ramach programu "Społeczna odpowiedzialność nauki" - moduł: Popularyzacja nauki i promocja sportu (2022-2023).