Clathrate hydrate can be used in energy gas storage and transportation, CO2 capture and cool storage etc. However, these technologies are difficult to be used due to the low formation rate and long induction time of hydrate formation. In this paper, ZIF-61 (zeolite imidazolate framework, ZIF) was first used in hydrate formation to stimulate hydrate nucleation. As an additive of clathrate hydrate, ZIF-61 promoted obviously the acceleration of tetrahydrofuran (THF) hydrate nucleation. It shortened the induction time of THF hydrate formation from 2-5 h to 0.3-1 h mainly due to the template function of ZIF-61 by which the nucleation of THF hydrate has been promoted.
Coal bed methane (CBM) has a huge potential to be purified to relieve the shortage of natural gas meanwhile to weaken the greenhouse effect. This paper proposed an optimal design strategy for CBM to obtain an integrated process configuration consisting of three each single separation units, membrane, pressure swing absorption, and cryogenics. A superstructure model was established including all possible network configurations which were solved by MINLP. The design strategy optimized the separation unit configuration and operating conditions to satisfy the target of minimum total annual process cost. An example was presented for the separation of CH4/N2 mixtures in coal bed methane (CBM) treatment. The key operation parameters were also studied and they showed the influence to process configurations.
CO2 capture by hydrate formation is a novel gas separation technology, by which CO2 is selectively engaged in the cages of hydrate and is separated with other gases, based on the differences of phase equilibrium for CO2 and other gases. However. rigorous temperature and pressure, high energy cost and industrialized hydration separator dragged the development of the hydrate based CO2 capture. In this paper, the key problems in CO2 capture from the different sources such as shifted synthesis gas, flue gas and sour natural gas or biogas were analyzed. For shifted synthesis gas and flue gas, its high energy consumption is the barrier, and for the sour natural gas or biogas (CO2/CH4 system), the bottleneck is how to enhance the selectivity of CO2 hydration. For these gases, scale-up is the main difficulty. Also, this paper explored the possibility of separating different gases by selective hydrate formation and reviewed the progress of CO2 separation from shifted synthesis gas, flue gas and sour natural gas or biogas.
Gas hydrates now are expected to be one of the most important future unconventional energy resources. In this paper, researches on gas hydrate exploitation in laboratory and field were reviewed and discussed from the aspects of energy efficiency. Different exploiting methods and different types of hydrate reservoir were selected to study their effects on energy efficiencies. Both laboratory studies and field tests have shown that the improved technologies can help to increase efficiency for gas hydrate exploitation. And it also showed the trend that gas hydrate exploitation started to change from permafrost to marine. Energy efficiency ratio (EER) and energy return on energy invested (EROI) were introduced as an indicator of efficiency for natural gas hydrate exploitation. An energy-efficient hydrate production process, called "Hydrate Chain Energy System (HCES)", including treatment of flue gas, replacement of CH4 with CO2, separation of CO2 from CH4, and storage and transportation of CH4 in hydrate form, was proposed for future natural gas hydrate exploitation. In the meanwhile, some problems, such as mechanism of C02 replacement, mechanism of CO2 separation, CH4 storage and transportation are also needed to be solved for increasing the energy efficiency of gas hydrate exploitation.