Habitat and hydrocarbon potential of the Kimmeridgian strata in the central part of the Polish Lowlands

The quantity, genetic type and maturity of organic matter dispersed in the Kimmeridgian strata of the central part of the Polish Lowlands were determined on the basis of results of Rock-Eval, stable carbon isotope composition of bitumen, their fractions and kerogen, biomarker distribution in saturate and aromatic hydrocarbon fraction, elemental composition of kerogen, vitrinite reflectance and maceral composition analyses of 225 rock samples collected from 32 boreholes. The study was conducted separately for Lower and Upper Kimmeridgian rocks in the Szczecin-Miechów and Kościerzyna-Puławy synclinoriums and Mid-Polish Anticlinorium. The best source rocks with TOC up to 6.8 wt.%, were found in the vicinity of Gostynin in the Mid-Polish Anticlinorium. Generally, the Upper Kimmeridgian strata are fair and good potential source-rocks whereas the Lower Kimmeridgian strata have much lower hydrocarbon potential. Gas-prone, terrigenous Type-III kerogen predominates in the Lower Kimmeridgian strata. The contribution of oil-prone, marine Type-II kerogen increases in the Upper Kimmeridgian rocks. In the whole profile, only low-sulphur kerogen was recorded, although the situation, when high-sulphur Type-IIS kerogen was mixed with re-worked, non-generative Type-IV kerogen supplied to the sedimentary basin with rocks from eroded land, cannot be excluded. Sedimentary conditions of organic material were variable, usually anoxic and suboxic with domination of siliclastic material in mineral matrix. The maturity of the dispersed organic matter refers mostly to the final phase of the microbial process, or to the initial phase of the low-temperature thermogenic process (oil window). The most mature rocks, corresponding up to 0.75% in the vitrinite reflectance scale, were recognised in the deepest buried parts of the basin (axial part of the Mogilno-Łódź Segment of the Szczecin-Miechów Synclinorium). The most prospecting source rocks were recognised in this area

Origin of liquid hydrocarbons accumulated in the Miocene strata of the Polish Carpathian Foredeep and its Palaeozoic–Mesozoic basement

Petroleum geochemical data of 34 oils and condensates accumulated in the Carpathian Foredeep and its Mesozoic and Palaeozoic basement were used to assess their origin and genetic type. The analysed liquid hydrocarbons are characterized by variable densities and sulphur contents. No relationship between these parameters and the reservoir rock age has been found. Secondary processes of evaporative fractionation and biodegradation are evidenced for some oils. These processes proceeded most intensively on the oil from Góra Ropczycka-1K well. The oils from Opaka-1, Lubaczów-157 and Góra Ropczycka-1K wells were generated from organic matter deposited in the Upper Jurassic carbonates. The oil from the inflow in Załazie-2 well originated from the Cambrian strata, but also contains biomarkers characteristic of Miocene strata. The next family, genetically connected with the Silurian and Ordovician source rocks, consists of oils accumulated in the Lower Carboniferous carbonates in Nosówka deposit and in the Upper Jurassic in the inflow into Łękawica-1 well. The condensates collected from the Miocene (Łękawica-1, Pilzno-37, Tarnów-39 and -45 wells) and Upper Jurassic strata (Łąkta-27 and Tarnów-5 wells) were generated by organic matter dispersed in the Middle Jurassic or Lower Carboniferous clastic facies. The remaining oils, from Grobla-Pławowice, Wierzchosławice, Jastrząbka Stara, Partynia-Podborze, Dąbrowa Tarnowska, Brzezówka and Zagorzyce deposits, and the inflows into Tarnów-47 and Pilzno-12 wells were generated from kerogen enriched in organic sulphur usually dispersed in carbonate rocks. Such a type of sediments occurs in the Devonian and Lower Carboniferous strata. Also, these strata as well as the underlying Silurian rocks have sufficient maturity for generation of the discussed oils. The oleanane in the discussed oils most probably originates from kerogen of the Upper Cretaceous or Miocene strata, through which these oils migrated and eluted this biomarker

Origin of oils accumulated in the Middle Cambrian reservoirs of the Polish part of the Baltic region

We have examined 21 samples of crude oils accumulated in the Middle Cambrian sandstone reservoirs from the Polish part of the Baltic region. All the crude oils have similar parameters and indices, which suggests generation from the same source rock. Evaporative fractionation and biodegradation processes were detected in oil collected from the B4-N1/01 borehole. All crude oils have high gravities and low-sulphur contents, less than 0.3 wt.%, which suggests that their source rock contained low-sulphur kerogen deposited in a clastic environment. A low asphaltenes content (below 0.3 wt.%) and high saturate/aromatic hydrocarbon ratios indicate long migration distances or high thermal maturities. The longest migration distance was probably attained by oils from the arnowiec and B16 deposits. The biomarker data indicate an algal origin for the source organic matter deposited under conditions of clastic sedimentation. The stable carbon isotope data support this observation. The maturity of the oils analysed varies from ca. 0.75 to ca. 1.05% on the vitrinite reflectance scale. Unlike the B6, B16, Dbki and arnowiec accumulations, oils from the B3 and B4 accumulations reveal the lowest maturity

Estimation of hydrous-pyrolysis kinetic parameters for oil generation from Baltic Cambrian and Tremadocian source rocks with Type-II kerogen

Determining kinetic parameters for oil generation from a source rock by hydrous pyrolysis requires a considerable amount of sample (kilograms) and laboratory time (several weeks). In an effort to circumvent these requirements, hydrous-pyrolysis (HP) kinetic parameters for oil generation from Upper Cambrian and Tremadocian source rocks of the Baltic region are estimated by two methods: (1) organic sulfur content in kerogen and (2) HP experiments conducted at 330 and 355°C for 72 h. Estimates for the Upper Cambrian source rocks based on organic sulfur contents gave activation energies from 47 to 56 kcal/mole and frequency factors from 1.156 ' 1025>/sup> to 1.078 ' 1028 m.y.-1 . Tremadocian source rocks based on organic sulfur content gave estimated activation energies from 60 to 62 kcal/mole and frequency factors from 1.790 ' 1029 to 1.104 ' 1030 m.y.-1 . The estimates for the Tremadocian source rocks were less affected by thermal maturation because their low kerogen S/(S + C) mole fractions (>gt; 0.018) of the Upper Cambrian source rocks decreased with thermal maturation and resulted in overestimation of the kinetic parameters. The second method was designed to estimate kinetic parameters based on two HP experiments. The assumption that the maximum yield in calculating the rate constant at 330°C (k330°C could be determined by a second hydrous pyrolysis experiment at 355°C for 72 h proved not to be valid. Instead, a previously established relationship between Rock-Eval hydrogen index and maximum HP yield for Type-II kerogen was used to calculate k330°C from oil yields generated by the HP experiment at 330°C for 72 h assuming a first-order reaction. HP kinetic parameters were determined from relationships between k330°C and the HP kinetic parameters previously reported. These estimated HP kinetic parameters were in agreement with those obtained by the first method for immature samples, but underestimated the kinetic parameters for samples at higher thermal maturities. Applying these estimated HP kinetic parameters to geological heating rates of 1 and 10°C/m.y. indicated that the Upper Cambrian source rocks would generate oil notably earlier than the overlying Tremadocian source rocks. This was confirmed in part by available data from two neighboring boreholes in the Polish sector of the Baltic

Source rock characteristic of the selected flysch deposits in the transfrontier area of the Polish Outer Carpathians

Charakterystykę geochemiczną poziomów potencjalnie macierzystych utworów fliszowych jednostek alochtonicznych wschodniej części polskich Karpat Zewnętrznych wykonano dla dolnokredowych warstw wierzowskich, lgockich i spaskich, górnokredowych warstw istebniańskich i inoceramowych oraz oligoceńskich warstw menilitowych. W analizie wykorzystano wyniki badań geochemicznych 875 próbek skał z profili 11 odwiertów i 48 odsłonięć w polskiej i przygranicznej ukraińskiej części Karpat Zewnętrznych. Wyniki badań geochemicznych potwierdzają, że warstwy menilitowe są najlepszymi skałami macierzystymi. Ropotwórczy kerogen II typu jest generalnie niedojrzały lub dojrzały w fazie wczesnej "okna ropnego". Parametry kinetyczne kerogenu warstw menilitowych są zbliżone w jednostkach śląskiej i skolskiej oraz wyraźnie niższe w jednostce borysławsko-pokuckiej. Pozostałe analizowane kredowe wydzielenia litostratygraficzne lokalnie spełniają ilościowe kryterium macierzystości i mogą uzupełniać bilans węglowodorowy utworów fliszowych Karpat.Potential source rock horizons of the flysch cover were geochemically characterized in the eastern border area of the Polish flysch Carpathians: Lower Cretaceous Verovice, Lgota and Spas Beds, Upper Cretaceous Istebna and Inoceramian Beds as well as Oligocene Menilite Beds. The results of geochemical analyses of 875 rock samples collected from 11 boreholes and 48 outcrops in the Polish Outer Carpathians as well as from the adjacent Ukrainian were analyzed. The results indicate that Menilite Beds are the best source rocks of the Carpathian flysch cover in all analyzed tectonic units. The oil-prone Type II kerogen, deposited in marine environment of regular salinity, was proved to be usually immature or mature at an early stage of "oil window". Kinetic parameters of organic matter dispersed in the Menilite Beds, calculated based on organic sulphur content, are similar for the Silesian and Skole units and significantly lower in the Boryslav-Pokuttya Unit. The remaining lithostratigraphic divisions: Verovice, Lgota, Spas, Istebna and Inoceramian Beds, locally meet the source-rock requirements and can supplement the hydrocarbon balance of the Carpathians

Impact of the composition of absorption blend on the efficiency of CO2 removal

Wykonano badania równowag oraz kinetyki absorpcji CO2 w roztworach zawierających różnego typu aminy, takie jak: aminy pierwszorzędowe (np. MEA), poliaminy (np. piperazyna) oraz aminy z zawadą steryczną (np. AMP) oraz dodatek cieczy organicznych. Przebadano, pod kątem wpływu ilości cieczy organicznej i wody na zdolności absorpcyjne, roztwory bazujące na układzie amin pierwszorzędowa/amina z zawadą steryczną/aktywator/ciecz organiczna/ woda. Określono również wpływ ilości aktywatora na parametry, takie jak: szybkość absorpcji oraz pojemność absorpcyjna dla roztworów aminy trzeciorzędowej.Analysis was performed of the equilibriums and kinetics of CO2 absorption in solutions containing various types of amines, such as: primary amines (e.g. MEA), polyamines (e.g. piperazin) and amines with steric hindrance (e.g. AMP), and an addition of organic liquids. The solutions based on the primary amine/amine with steric hindrance/activator/organic liquid/water compounds were tested in terms of the impact of the volume of organic liquid and water on the absorption capability. Also assessed was the impact of the volume of activator on parameters such as: absorption rate and absorption capacity for tertiary amine solutions

Laboratory research on selection of optimal operating conditions of CO₂ separation plant – progress of work

W artykule przedstawiono wyniki badań prowadzonych nad doborem optymalnych warunków pracy instalacji separacji CO2 dla wychwytu ditlenku węgla z gazów o zwiększonej jego zawartości. Skupiono się zarówno na wytypowaniu jak najlepszego sorbentu jak i doborze optymalnych warunków prowadzenia procesu absorpcji, co ogranicza energochłonność wychwytu CO2. W ramach prowadzonych badań wykonano testy, mające na celu wybór optymalnego sorbentu pod kątem kinetyki absorpcji, pojemności absorpcyjnej i uzyskiwanych parametrów podczas pracy w rzeczywistym układzie absorber–desorber. Pod kątem kinetyki absorpcji i pojemności absorpcyjnej zostały przebadane czyste roztwory aktywatorów oraz roztwory aminy z zawadą steryczną z dodatkiem aktywatorów na bazie wytypowanego we wcześniejszym etapie badań najlepszego roztworu. Roztwór ten porównano również z innymi badanymi wcześniej roztworami pod kątem sprawności wychwytu CO2 oraz zużycia energii na kg wychwyconego CO2 w badaniach procesowych. Przeprowadzono dodatkowo badania nad doborem wypełnienia kolumny absorpcyjnej zapewniającego nie tylko jak najlepszą absorpcję CO2, ale również najniższe opory przepływu gazu przez złoże.The article presents results of researches carried out on the selection of optimal operating conditions of CO2 separation plant for carbon dioxide removal from gases with increased content of CO2. Researches were focused on both: the selection of the best sorbent as well as the selection of the optimal absorption process parameters, which reduces energy consumption of carbon dioxide removal. In this study were carried out tests on the selection of optimal paying special attention to absorption kinetics, absorption capacity and parameters obtained during operation in a real absorber-desorber system. For the absorption kinetics and absorption capacity there were tested activators water solutions and the solution containing sterically hindered amines with the addition of activators on the basis of best solution selected at an earlier stage of research. This solution was compared with other previously tested solutions for CO2 removal efficiency and energy consumption per kg of CO2 captured in the process researches. Researches were also carried out for the selection of the optimal absorption column packing, not only ensuring the best possible absorption of CO2, but also the lowest possible pressure drop in the packed bed

Laboratory research on optimal operating conditions of CO₂ separation plant treating flue gases with high CO₂ content

Zapewnienie dostaw energii elektrycznej i ciepła na potrzeby gospodarki i społeczeństwa jest warunkiem dla utrzymania odpowiedniego tempa rozwoju polskiej gospodarki. Niestety, z klasycznymi procesami wytwarzania energii związana jest emisja gazów cieplarnianych, m.in. CO2. Dostępne metody ograniczania emisji CO2 z procesów produkcji energii elektrycznej z paliw kopalnych możemy podzielić na trzy główne grupy: separacja ditlenku węgla przed procesem spalania, spalanie w atmosferze tlenowej bądź separacja ditlenku węgla po procesie spalania. Podczas spalania w atmosferze tlenowej (tzw. oxyspalanie) powstają spaliny składające się w głównej mierze z CO2 i pary wodnej oraz niewielkich ilości tlenu i azotu. W okresie przejściowym przed opracowaniem i wprowadzeniem komercyjnych rozwiązań technologii oxyspalania należy brać pod uwagę również możliwość spalania w powietrzu wzbogaconym w tlen w wyniku czego otrzymujemy spaliny o podwyższonej zawartości CO2 i konieczne staje się jego odseparowanie od reszty gazów jedną z metodpost-combustion. W artykule przedstawiono wyniki badań prowadzonych nad doborem optymalnych warunków pracy instalacji separacji CO2 ze spalin o podwyższonym stężeniu ditlenku węgla w porównaniu ze składem spalin z klasycznych procesów spalania. W ramach prowadzonych badań wykonane zostały testy nad doborem jak najlepszego sorbentu do wychwytu ditlenku węgla oraz testy nad określeniem wpływu parametrów procesowych na sprawność oraz energochłonność procesu. Dla określenia przydatności poszczególnych sorbentów przeprowadzono badania szybkości oraz wyznaczono izotermy absorpcji CO2 w roztworach aminowych. W ramach tych testów przebadano roztwory MDEA ze zmienną zawartością aktywatora, roztwory poliamin oraz roztwory amin z zawadą steryczną. Badania procesowe obejmowały testy nad wpływem natężenia przepływu sorbentu, natężenia przepływu spalin oraz ilości energii dostarczonej do regeneratora na sprawność usuwania CO2 oraz ilość energii zużytej na separację 1 kg CO2. Badania te zostały przeprowadzone na roztworach 30%MEA oraz 30%MDEA + 6%PZ.Available methods for reducing C02 emissions resulting from the production of electricity from fossil fuels can be divided into three main groups the separation of carbon dioxide before combustion, combustion in an oxygen atmosphere, and separation of carbon dioxide after combustion. During combustion in an oxygen atmosphere, the flue gases consist mainly of C02, water vapor, and small amounts of oxygen and nitrogen. However, the possibility of burning in air enriched in oxygen should also be taken into account, as it then becomes necessary to separate the C02 gas from the rest of the gases via one of the post-combustion methods. This paper presents the results of research conducted for the selection of the optimum operating conditions of a C02 separation plant. In this study, tests were performed for the selection of the best sorbent for carbon dioxide capture and for determination of the influence of process parameters on energy consumption and carbon dioxide capture efficiency. To test the usefulness of various sorbents, research was conducted to determine C02 absorption speed and C02 absorption isotherms in different amine solutions. MDEA solutions were tested containing differing activator amounts, polyamines solutions, and sterically amine solutions. The process research included tests on the influence of sorbent flow rate, gas flow rate, and the amount of energy supplied to the regenerator on C02 removal efficiency and the amount of energy used for the separation of 1kg of C02. These tests were carried out on a 30% MEA solution and a 30% MDEA + 6% PZ solution

Fluid inclusions in halite and bitumens in rock salt from Miocene evaporites in the Ukrainian Fore-Carpathian region: as indicators of hydrocarbon accumulations in the underlying strata

Fluid inclusions in halite from Miocene rock salt of the Ukrainian Carpathian Foredeep Basin in locations where evaporites overlie oil and gas reservoir rocks are characterized by their high methane content and the presence of oil droplets in some of them. They are thus similar to fluid inclusions reported from geochemical aureoles around oil and gas accumulations in the Zechstein (Upper Permian) of western Poland (Kovalevych et al., 2008). Geochemical analyses of bitumen in bulk samples of rock salt (including content and distribution of n-alkanes and isoprenoids, carbon isotope ratios) suggest a varied origin: hydrocarbon extracted from halite from boreholes located in proximity (proved or assumed) of oil and gas deposits (Lopushna-7, Grynivka-525) are probably related to organic material dispersed within the rock salt itself, and those from the barren areas (Verkhniy Strutyn-29) are most probably cogenetic with oil accumulated in the deposits of the Boryslav-Pokuttya Nappe