Liquid nitrogen freezing, which is an effective permeability enhancement technology, has been applied to the extraction of oil, shale gas, and coalbed methane (CBM). This study is aimed at revealing the effect of liquid nitrogen mass transfer on the temperature variation and pore structure evolution within coal. To achieve this aim, first, temperature measurement tests under the action of liquid nitrogen freezing were conducted on saturated and dried coal samples, respectively. Next, the coal samples were subjected to nuclear magnetic resonance and computer tomography tests before and after liquid nitrogen cold soaking to further explore the mechanism of coal temperature variation from a microscopic perspective. The results show that the action of liquid nitrogen mass transfer can accelerate coal temperature variation through coal pore structure and pore water phase change. The thermal stress and frost heave force generated by liquid nitrogen cold soaking exceed the tensile strength of the coal sample, which directly causes crack initiation, expansion, and connection. The mass transfer of liquid nitrogen has a significant promoting effect on pore development. This study provides the technical support necessary for the efficient exploitation of CBM resources and the improvement of CBM extraction rate.

To determine the unfrozen water content variation characteristics of coal from the low temperature freezing based on the good linear relationship between the amplitude of the nuclear magnetic resonance (NMR) signal and movable water, pulsed NMR technology was used to test water-saturated coal samples and analyze the relationship between the unfrozen water content, the temperature and pore pressure during freeze–thaw from a microscopic perspective. Experimental results show that the swelling stress of the ice destroys the original pore structure during the freezing process, causing the melting point of the pore ice to change, so the unfrozen water content during the melting process presents a hysteresis phenomenon. When phase equilibrium has been established in the freezing process, the unfrozen water is mainly the film water on the pore surface and pore water in pores with pore radius below 10 nm. At this time, the freezing point of the water in the system decreases exponentially as the temperature increases. The micropores of the coal samples from the Jiulishan Coalmine are well-developed, and the macropores and fractures are relatively small, with most pores having a pore radius between 0.1 and 10 nm. The pore water freezing point gradually decreases with the pore radius. When the pore radius decreases to 10 nm, the freezing point of pore water starts to decrease sharply with the decreasing pore radius. When the pore radius reaches 1.54 nm, the pore water freezing point changes as fast as 600 ℃/nm.

Due to its advantages such as environmental friendliness and remarkable permeability enhancement effect, the technology of liquid nitrogen cold soaking (LNCS) cracking coal has become a hot spot in the research on coal seam permeability enhancement in recent years. The frost heave force generated by water-ice phase transformation and the temperature stress are the main mechanisms of LNCS cracking water-containing coal. This paper focuses on the effect of LNCS on the temperature variations and seepage characteristics of coal. To further this purpose, the temperature measurement test and the permeability test were conducted on coal samples with different moisture contents under LNCS, respectively. In addition, by comparing the computer tomography test results of coal samples before and after LNCS, the internal pore structure changes of coal samples were further analyzed from a three-dimensional perspective. The test results show that the coal sample with a higher moisture content consumes a shorter time to reach internal temperature equilibrium and experiences faster temperature changes. LNCS can enhance coal permeability, and the growth rate of permeability increases exponentially with the increase of moisture content. After the LNCS treatment, the dried coal sample is mainly sprouting new pores on the basis of primary pores; in contrast, for water-containing coal samples, new pores are sprouted while primary pores will penetrate each other spatially to form a fracture network. In the process of LNCS, moisture has a significant effect on the seepage characteristics of coal, so appropriately increasing the moisture content of the coal seam conduces to achieving a better permeability enhancement effect.

An experimental system for liquid nitrogen soaking and real-time temperature measurement was designed and implemented to investigate the characteristics of temperature field changes in coal under liquid nitrogen soaking. Then, the heat conduction law of the coal in the process of liquid nitrogen soaking and room temperature recovery for dry and water-saturated coal were examined. The microstructure characteristics of the coal before and after liquid nitrogen soaking were analyzed with nuclear magnetic resonance (NMR) technology. The results showed that, during the liquid nitrogen cold soaking process, the heat transfer law of the dry and water-saturated coal samples exhibited a notable three-stage distribution. For the room temperature recovery process, the dry and water-saturated coal samples exhibited rapid heating characteristics, and the cooling rate gradually decreased to zero. NMR test results indicated that the liquid nitrogen soaking increased the number of micro and small pores in the coal. Thermal stress analysis revealed that the thermal stress generated by the dry coal was larger than that produced by the saturated coal, and the damage was primarily caused by thermal stress. However, the permeability of the saturated coal was better than that of the dry coal. The damage on the saturated coal was caused by the volume expansion of pores and fissures caused by water-ice phase transition.

This study examines the evolution law of the coal temperature field under low-temperature freezing conditions. The temperature inside coal samples with different water contents was measured in real-time at several measurement points in different locations inside the sample under the condition of low-temperature medium (liquid nitrogen) freezing. The temperature change curve was then used to analyse the laws of temperature propagation and the movement of the freezing front of the coal, which revealed the mechanism of internal water migration in the coal under low-temperature freezing conditions. The results indicate that the greater the water content of the coal sample, the greater the temperature propagation rate. The reasons for this are the phase change of ice and water inside the coal during the freezing process; the increase in the contact area of the ice and coal matrix caused by the volume expansion; and the joint action of the two. The process of the movement of the freezing front is due to the greater adsorption force of the ice lens than that of the coal matrix. Thus, the water molecules adsorbed in the unfrozen area of the coal matrix migrate towards the freezing front and form a new ice lens. Considering the temperature gradient and water content of the coal samples, Darcy’s permeation equation and water migration equation for the inside of the coal under freezing conditions were derived, and the segregation potential and matrix potential were analysed. The obtained theoretical and experimental results were found to be consistent. The higher the water content of the coal samples, the smaller the matrix potential for the hindrance of water migration. Furthermore, the larger the temperature gradient, the larger the segregation potential, and the faster the water migration rate.