Study of the process of hydrophobization of carbonate rock with organic acids

UDK: 622.276.72
DOI: 10.24887/0028-2448-2022-3-73-76
Key words: hydrophobization of carbonate rock; organic acids; contact wetting angle; gas chromatography with pyrolytic cell
Authors: E.V. Tokareva (VNIIneft JSC, RF, Moscow), I.V. Tkachev (VNIIneft JSC, RF, Moscow), G.V. Sansiev (Zarubezhneft JSC, RF, Moscow), G.D. Fedorchenko (Zarubezhneft JSC, RF, Moscow), A.A. Ivanova (Skolkovo Institute of Science and Technology, RF, Moscow), P.A. Grishin (Skolkovo Institute of Science and Technology, RF, Moscow), S. Markovic (Skolkovo Institute of Science and Technology, RF, Moscow), I.G. Maryasev (SMA LLS, RF, Moscow), A.V. Kuzmin (SMA LLS, RF, Moscow)

The process of studying the hydrophobization of carbonate rock with organic acids includes the preparation of samples and their treatment with compositions of carboxylic and naphthenic acids. To reproduce reservoir conditions, adsorption was carried out at a temperature of 70 °C. During the study, the time of contact of the rock with acids was varied (1, 14 days); the operation of washing with toluene after aging in acids was used. The assessment of the change in the wetting properties was carried out by the static contact angle by two methods: scanning electron microscopy in the "natural environment" mode (ESEM) and sessile drop method on a DSA30S device from Kruss. The correctness of the contact angle measurement was confirmed on standard samples: glass (hydrophilic) and teflon (hydrophobic). A change in the wettability of carbonate plates from hydrophilic to hydrophobic after aging in solutions of palmitic and stearic acids has been achieved. In the case of palmitic acid, the wetting angle increases as the holding time increases. Washing samples with toluene after aging in acid has a hydrophilizing effect - the contact angle is reduced by 30% compared to samples without washing. It is possible that toluene washes away some of the acid molecules that have reacted with the molecules adsorbed on the rock surface and formed a monolayer. The fact of acid adsorption on the rock surface was confirmed by the method of pyrolitic two-dimensional chromatography – mass spectrometry (pyro-GC-GC-MS). An increase in the holding time in palmitic acid leads to an increase in the concentration of palmitate anions detected in the products of rock pyrolysis. After 14 days of exposure, a signal of decay products of aggregates of the palmitic acid molecule was recorded, which makes it possible to assume layer-by-layer adsorption of the acid on the rock surface. The obtained results became the basis for the method development for controlled calcite aging with solutions of carboxylic acids.


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