Eli Tannenbaum

Role of minerals in the thermal alteration of organic matter--I: generation of gases and condensates under dry condition.

Pyrolysis experiments were carried out on Monterey formation kerogen and bitumen and Green River formation kerogen (Type II and I, respectively), in the presence and absence of montmorillonite, illite and calcite at 200 and 300 degrees C for 2-2000 hours. The pyrolysis products were identified and quantified and the results of the measurements on the gas and condensate range are reported here. A significant catalytic effect was observed for the pyrolysis of kerogen with montmorillonite, whereas small or no effects were observed with illite and calcite, respectively. Catalytic activity was evident by the production of up to five times higher C1-C6 hydrocarbons for kerogen with montmorillonite than for kerogen alone, and by the dominance of branched hydrocarbons in the C4-C6 range (up to 90% of the total amount at any single carbon number). This latter effect in the presence of montmorillonite is attributed to cracking via a carbonium-ion [carbocation] intermediate which forms on the acidic sites of the day. No catalytic effect, however, was observed for generation of methane and C2 hydrocarbons which form by thermal cracking. The catalysis of montmorillonite was significantly greater during pyrolysis of bitumen than for kerogen, which may point to the importance of the early formed bitumen as an intermediate in the production of low molecular weight hydrocarbons. Catalysis by minerals was also observed for the production of carbon dioxide. These results stress the importance of the mineral matrix in determining the type and amount of gases and condensates forming from the associated organic matter under thermal stress. The literature contains examples of gas distribution in the geologic column which can be accounted for by selective mineral catalysis, mainly during early stages of organic matter maturation.

The role of minerals in the thermal alteration of organic matter—III. Generation of bitumen in laboratory experiments☆

A series of pyrolysis experiments, utilizing two different immature kerogens (from the Monterey and Green River Formations) mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the impact of the mineral matrix on the bitumen that was generated. Calcite has no significant influence on the thermal evolution of bitumen and also shows virtually no adsorption capacity for any of the pyrolysate. In contrast, montmorillonite and illite, to a lesser extent, alter bitumen during dry pyrolysis. Montmorillonite and illite also display strong adsorption capacities for the polar constituents of bitumen. By this process, hydrocarbons are substantially concentrated within the pyrolysate that is not strongly adsorbed on the clay matrices. The effects of the clay minerals are significantly reduced during hydrous pyrolysis. The strong adsorption capacities of montmorillonite and illite, as well as their thermocatalytic properties, may in part explain why light oils and gases are generated from certain argillaceous source-rock assemblages, whereas heavy immature oils are often derived from carbonate source rocks.

Steranes and triterpanes generated from kerogen pyrolysis in the absence and presence of minerals

Steranes and triterpanes generated from pyrolysis of immature Monterey Formation kerogen in the presence and absence of calcite, illite and montmorillonite reveal results that are both consistent and divergent with published data that reflect the use of these biological markers as maturation indicators. The extent of isomerization of biomarkers generated from pyrolysis of kerogen at 300 degrees C for 2 hours, at C-20 in 14 alpha(H), 17 alpha(H)-steranes, at C-22 in 17 alpha(H),21 beta(H)-hopanes and of 17 beta(H),21 beta(H)-hopanes correspond to early diagenetic stages in rock extracts from sedimentary basins. Isomerization increases with heating time and, after 1000 hours, attains values which correspond to the catagenetic stage in sedimentary basins, or equivalent to that of mature oil. Stepwise pyrolysis of the kerogen indicates faster isomerization rates for steranes and triterpanes in the bitumen than those retained in the kerogen structure, confirming earlier studies. Presence of a mineral matrix can influence the isomerization of steranes and triterpanes considerably. Comparisons with results from kerogen heated alone, for a given maturation stage, show that calcite inhibits, illite catalyzes slightly and montmorillonite has a pronounced catalytic effect on these reactions. This effect results in early isomerization of steranes and hopanes corresponding to the catagenetic stage in the presence of montmorillonite, while kerogen or kerogen with calcite held at the same temperature (300 degrees C) and time (10 hours) only yield isomerized products which correspond to a diagenetic stage. Further, illite and montmorillonite affect various isomerization reactions differently. The fastest reaction is the isomerization at C-20 in 14 alpha(H),17 alpha (H)-steranes followed by that at C-22 in 17 alpha(H),21 beta(H)-hopanes and the slowest is the formation of 14 beta(H),17 beta(H) steranes. These results show that maturation measurements of rock or oil samples from basins which use biological markers have to take into account the mineral matrix effects, which have been largely ignored until present.

Role of Minerals in Thermal Alteration of Organic Matter--II: A Material Balance

Pyrolysis experiments were performed on Green River and Monterey Formation kerogens (Types I and II, respectively) with and without calcite, illite, or montmorillonite at 300 degrees C for 2 to 1,000 hours under dry and hydrous conditions. Pyrolysis products were identified and quantified, and a material balance of product and reactants resulted. Significant differences were found in the products generated by pyrolysis of kerogens with and without minerals. Both illite and montmorillonite adsorb a considerable portion (up to 80%) of the generated bitumen. The adsorbed bitumen is almost exclusively composed of polar compounds and asphaltenes that crack to yield low molecular weight compounds and insoluble pyrobitumen during prolonged heating. Montmorillonite shows the most pronounced adsorptive and catalytic effects. With calcite however, the pyrolysis products are similar to those from kerogen heated alone, and bitumen adsorption is negligible. Applying these results to maturation of organic matter in natural environments, we suggest that a given type of organic matter associated with different minerals in source rocks will yield different products. Furthermore, the different adsorption capacities of minerals exert a significant influence on the migration of polar and high molecular weight compounds generated from the breakdown of kerogen. Therefore, the overall accumulated products from carbonate source rocks are mainly heavy oils with some gas, whereas light oils and gases are the main products from source rocks that contain expandable clays with catalytic and adsorptive properties.

Role of Minerals in Formation of Hydrocarbons During Pyrolysis of Organic Matter--a Material Balance Approach: ABSTRACT

Monterey Formation and Green River Formation kerogens (types II and I, respectively) were isolated, mixed with common sedimentary minerals, and pyrolyzed under dry and hydrous conditions for various times and temperatures. Analysis of all the pyrolyses products were conducted to perform a material balance and to infer reaction kinetics and mechanisms. Material balance of the pyrolyses products, in the presence and absence of minerals, reveals that the kerogen degradation results in the formation of bitumen rich in high molecular weight compounds in the initial stages, followed by additional cracking of kerogen and bitumen. However, amount and type of hydrocarbons in the pyrolyses products of kerogen in the presence of montmorillonite are markedly different from those produced by heating kerogen alone or with other minerals. The initial amount of products in the presence of montmorillonite, and in particular the quantities of low molecular weight hydrocarbons, are higher than those in the presence of illite, calcite, and kerogen alone. The composition of these low molecular weight compounds is dominated by branched hydrocarbons, ind cating catalytic cracking via carbonium ion mechanism, which is initiated on acidic sites of the clay. Compositional differences are evident also in the distribution of n-alkanes and in the pristane/phytane ratio. The catalytic effect of montmorillonite, however, disappears in the presence of excess water. These differences may have important implications for the composition and quantities of petroleum generated from source rocks with different mineralogies. End_of_Article - Last_Page 310------------