Nuclear magnetic resonance cryoporometry is a newly developed technique that can characterize the pore size distribution of nano-scale porous materials. To date, this technique has scarcely been used for the testing of unconventional oil and gas reservoirs; thus, their micro- and nano-scale pore structures must still be investigated. The selection of the probe material for this technique has a key impact on the quality of the measurement results during the testing of geological samples. In this paper, we present details on the nuclear magnetic resonance cryoporometric procedure. Several types of probe materials were compared during the nuclear testing of standard nano-scale porous materials and unconventional reservoir geological samples from Sichuan Basin, Southwest China. Gas sorption experiments were also carried out on the same samples simultaneously. The KGT values of the probe materials octamethylcyclotetrasiloxane and calcium chloride hexahydrate were calibrated using standard nano-scale porous materials to reveal respective values of 149.3 Knm and 184 Knm. Water did not successfully wet the pore surfaces of the standard controlled pore glass samples; moreover, water damaged the pore structures of the geological samples, which was confirmed during two freeze-melting tests. The complex phase transition during the melting of cyclohexane introduced a nuclear magnetic resonance signal in addition to that from liquid in the pores, which led to an imprecise characterization of the pore size distribution. Octamethylcyclotetrasiloxane and calcium chloride hexahydrate have been rarely employed as nuclear magnetic resonance cryoporometric probe materials for the testing of an unconventional reservoir. Both of these materials were able to characterize pore sizes up to 1 μm, and they were more applicable than either water or cyclohexane.
Nuclear Magnetic Resonance Spectroscopy for In Situ Monitoring of Porous Materials Formation under Hydrothermal Conditions
