The research on the thermal property of the hydrate has recently made great progress,including the understanding of hydrate thermal conductivity and effective thermal conductivity(ETC)of hydratebearing sediment.The th...The research on the thermal property of the hydrate has recently made great progress,including the understanding of hydrate thermal conductivity and effective thermal conductivity(ETC)of hydratebearing sediment.The thermal conductivity of hydrate is of great significance for the hydrate-related field,such as the natural gas hydrate exploitation and prevention of the hydrate plugging in oil or gas pipelines.In order to obtain a comprehensive understanding of the research progress of the hydrate thermal conductivity and the ETC of hydrate-bearing sediment,the literature on the studies of the thermal conductivity of hydrate and the ETC of hydrate-bearing sediment were summarized and reviewed in this study.Firstly,experimental studies of the reported measured values and the temperature dependence of the thermal conductivity of hydrate were discussed and reviewed.Secondly,the studies of the experimental measurements of the ETC of hydrate-bearing sediment and the effects of temperature,porosity,hydrate saturation,water saturation,thermal conductivity of porous medium,phase change,and other factors on the ETC of hydrate-bearing sediment were discussed and reviewed.Thirdly,the research progress of modeling on the ETC of the hydrate-bearing sediment was reviewed.The thermal conductivity determines the heat transfer capacity of the hydrate reservoir and directly affects the hydrate exploitation efficiency.Future efforts need to be devoted to obtain experimental data of the ETC of hydrate reservoirs and establish models to accurately predict the ETC of hydrate-bearing sediment.展开更多
Carbon emission reduction and clean energy development are urgent demands for mankind in the coming decades.Exploring an efficient CO_(2) storage method can significantly reduce CO_(2) emissions in the short term.In t...Carbon emission reduction and clean energy development are urgent demands for mankind in the coming decades.Exploring an efficient CO_(2) storage method can significantly reduce CO_(2) emissions in the short term.In this study,we attempted to construct sediment samples with different residual CH_(4) hydrate amounts and reservoir conditions,and then investigate the potentials of both CO_(2) storage and enhanced CH_(4) recovery in depleted gas hydrate deposits in the permafrost and ocean zones,respectively.The results demonstrate that CO_(2) hydrate formation rate can be significantly improved due to the presence of residual hydrate seeds;However,excessive residual hydrates in turn lead to the decrease in CO_(2) storage efficiency.Affected by the T-P conditions of the reservoir,the storage amount of liquid CO_(2) can reach 8 times that of gaseous CO_(2),and CO_(2) stored in hydrate form reaches 2-4 times.Additionally,we noticed two other advantages of this method.One is that CO_(2) injection can enhance CH_(4) recovery rate and increases CH_(4) recovery by 10%-20%.The second is that hydrate saturation in the reservoir can be restored to 20%-40%,which means that the solid volume of the reservoir avoids serious shrinkage.Obviously,this is crucial for protecting the goaf stability.In summary,this approach is greatly promising for high-efficient CO_(2) storage and safe exploitation of gas hydrate.展开更多
Natural gas hydrates,intricate crystalline structures formed by water molecules and small gas molecules,have emerged as a significant and globally impactful clean energy resource.However,their commercial exploitation ...Natural gas hydrates,intricate crystalline structures formed by water molecules and small gas molecules,have emerged as a significant and globally impactful clean energy resource.However,their commercial exploitation faces challenges,particularly operational disruptions caused by sand-related blockages.Understanding the rheological properties of hydrate slurry,especially in the presence of micron-sized sand particles,is imperative for ensuring the flow assurance of subsea hydrate exploitation.This study extensively investigates the rheological properties of sand-containing hydrate slurries.The findings reveal that these slurries exhibit non-Newtonian fluid characteristics,including yield stress,thixotropy,and shear-thinning behavior.Solid-like elastic features are observed in sand-containing hydrate slurries before yielding,transitioning to viscous behavior after yielding.Even with a minimal amount of sand,both static yield stress and yield strain experience substantial changes,correlating with the increase in sand concentration.The research conclusively establishes the thixotropic nature of sand-hydrate slurries,where the viscosity decay rate is directly influenced by the shear rate.These insights aim to contribute comprehensively to the development of effective flow assurance strategies,ensuring the safe and stable operation of subsea hydrate exploitation.展开更多
To date,the primary industrial carbon capture approach is still absorption using aqueous solutions of alkanolamines.Here,to pursue a substitute for the amine-based approach to improve the CO_(2) capture efficiency and...To date,the primary industrial carbon capture approach is still absorption using aqueous solutions of alkanolamines.Here,to pursue a substitute for the amine-based approach to improve the CO_(2) capture efficiency and decrease the energy cost further,we report a new carbon capture approach using a 2-methylimidazole(mIm)aqueous solution.The properties and sorption behaviors of this approach have been experimentally investigated.The results show that the mIm solution has higher CO_(2) absorption capacity under relatively higher equilibrium pressure(>130 kPa)and lower desorption heat than the methyldiethanolamine solution.91.6%sorption capacity of mIm solution can be recovered at 353.15 K and 80 kPa.The selectivity for CO_(2)/N_(2) and CO_(2)/CH_(4) can reach an exceptional 7609 and 4324,respectively.Furthermore,the pilot-scale tests were also performed,and the results demonstrate that more than 98%of CO_(2) in the feed gas could be removed and cyclic absorption capacity can reach 1 mol·L^(-1).This work indicates that mIm is an excellent alternative to alkanolamines for carbon capture in the industry.展开更多
The morphology characteristics of CH_(4),CO_(2),and CO_(2)+N_(2)hydrate film forming on the suspending gas bubbles are studied using microscopic visual method at supercooling conditions from 1.0 to 3.0 K.The hydrate f...The morphology characteristics of CH_(4),CO_(2),and CO_(2)+N_(2)hydrate film forming on the suspending gas bubbles are studied using microscopic visual method at supercooling conditions from 1.0 to 3.0 K.The hydrate film vertical growth rate and thickness along the planar gas-water interface are measured to study the hydrate formation kinetics and mass transfer process.Adding N_(2)in the gas mixture plays the same role as lowering the supercooling conditions,both retarding the crystal nucleation and growth rates,which results in larger single crystal size and rough hydrate morphology.N_(2)in the gas mixture helps to delay the secondary nucleation on the hydrate film,which is beneficial to maintain the porethroat structure and enhance the mass transfer.The vertical growth rate of hydrate film mainly depends on the supercooling conditions and gas compositions but has weak dependence on the experimental temperature and pressure.Under the same gas composition condition,the final film thickness shows a linear relationship with the supercooling conditions.The mass transfer coefficient of CH_(4)molecules in hydrates ranges from 4.54×10^(-8)to 7.54×10^(-8)mol·cm^(-2)·s^(-1)·MPa^(-1).The maximum mass transfer coefficient for CO_(2)t N_(2)hydrate occurs at the composition of 60%CO_(2)t 40%N_(2),which is 3.98×10^(-8)mol·cm^(-2)·s^(-1)·MPa^(-1).展开更多
The long hydrate induction time and limited gas-liquid contact area leads to slow hydrate formation rate and low water-hydrate conversion rate.Porous media are often used to promote hydrate formation because of their ...The long hydrate induction time and limited gas-liquid contact area leads to slow hydrate formation rate and low water-hydrate conversion rate.Porous media are often used to promote hydrate formation because of their large specific surface area.Consequently,we used 3A molecular sieve as a water-carrying solid in this work,and investigated the dynamic renewal of the gas-liquid interface and its effect on hydrate formation.The formation kinetics of ethane hydrate was first measured in an aqueous molecular sieve system.Then the separation of(H_(2)+CH_(4)+C_(2)H_(6)+C_(3)H_(8))gas mixture was conducted via hydrate formation.The results show that the formation rate and gas storage capacity of ethane hydrate can be greatly improved by using aqueous molecular sieve.Compared with a pure water system under the same temperature and pressure,aqueous molecular sieve has obvious advantages in separation effect and energy consumption for separating gas mixtures.展开更多
Natural gas hydrate is an energy resource for methane that has a carbon quantity twice more than all traditional fossil fuels combined.However,their practical application in the field has been limited due to the chall...Natural gas hydrate is an energy resource for methane that has a carbon quantity twice more than all traditional fossil fuels combined.However,their practical application in the field has been limited due to the challenges of long-term preparation,high costs and associated risks.Experimental studies,on the other hand,offer a safe and cost-effective means of exploring the mechanisms of hydrate dissociation and optimizing exploitation conditions.Gas hydrate decomposition is a complicated process along with intrinsic kinetics,mass transfer and heat transfer,which are the influencing factors for hydrate decomposition rate.The identification of the rate-limiting factor for hydrate dissociation during depressurization varies with the scale of the reservoir,making it challenging to extrapolate findings from laboratory experiments to the actual exploitation.This review aims to summarize current knowledge of investigations on hydrate decomposition on the subject of the research scale(core scale,middle scale,large scale and field tests)and to analyze determining factors for decomposition rate,considering the various research scales and their associated influencing factors.展开更多
The natural gas hydrate has become one of the most promising future green energy sources on the earth.The natural gas hydrates mostly exist in the sediments with porous structure, so a solid understanding of the hydra...The natural gas hydrate has become one of the most promising future green energy sources on the earth.The natural gas hydrates mostly exist in the sediments with porous structure, so a solid understanding of the hydrate formation and growth processes in the porous medium is of significance for the exploitation of natural gas hydrate. The micro-packed bed device is one of the efficient microfluidic devices in the engineering field, but it has been rarely used for the hydrate-based research. In this study, a transparent micro-packed bed device filled with glass beads was developed to mimic the porous condition of sediments, and used to in-situ visualize the hydrate formation and growth habits in the pore spaces under both static and dynamic conditions. For the static experiment, two types of hydrate growth patterns in porous medium were observed and identified in the micro-packed bed device, which were the graincoating growth and pore-filling growth. For the dynamic condition, the hydrate formation, growth,distribution habits and hydrate blockage phenomena in the pore spaces were in-situ visually captured.The impacts of flowrate and subcooling on the pressure variation of the micro-packed bed and the duration of the hydrate growth under dynamic flow condition in pores were in-situ monitored and analyzed. The higher flowrate could result in the faster hydrate growth and more severe blockage in pores, but the effect of subcooling condition might be less significant at the high flowrate.展开更多
The clathrate hydrate memory effect is a fascinating phenomenon with potential applications in carbon capture,utilization and storage(CCUS),gas separation,and gas storage as it can accelerate the secondary formation o...The clathrate hydrate memory effect is a fascinating phenomenon with potential applications in carbon capture,utilization and storage(CCUS),gas separation,and gas storage as it can accelerate the secondary formation of clathrate hydrate.However,the underlying mechanism of this effect remains unclear.To gain a better understanding of the mechanism,we conducted molecular dynamic simulations to simulate the initial formation and reformation processes of methane hydrate.In this work,we showed the evolution process of hydrate residual structures into hydrate cages.The simulation results indicate that the residual structures are closely related to the existence of hydrate memory effect,and the higher the contribution of hydrate dissociated water to the hydrate nucleation process,the faster the hydrate nucleation.After hydrate dissociation,the locally ordered structures still exist after hydrate dissociation and can promote the formation of cluster structures,thus accelerating hydrate nucleation.Additionally,the nucleation process of hydrate and the formation process of clusters are inseparable.The size of clusters composed of cup-cage structures is critical for hydrate nucleation.The residence time at high temperature after hydrate decomposition will affect the strength of the hydrate memory effect.Our simulation results provide microscopic insights into the occurrence of the hydrate memory effect and shed light on the hydrate reformation process at the molecular scale.展开更多
Ethylene-vinyl acetate copolymer(EVA) as a kind of effective polymeric pour point depressant has been extensively used in the pipeline transportation of crude oil to inhibit wax deposition and improve the low temperat...Ethylene-vinyl acetate copolymer(EVA) as a kind of effective polymeric pour point depressant has been extensively used in the pipeline transportation of crude oil to inhibit wax deposition and improve the low temperature fluidity of crude oil. In this work, molecular dynamics simulations were performed to investigate the effect of EVA on wax-hydrate coexistence system to evaluate the application potentiality of EVA to the flow assurance of deep-sea oil-gas-water multiphase flow system. Our simulation results reveal that wax molecules gradually stretched and stacked from random coiling to a directional and ordered crystalline state during the process of wax solidification. The strong affinity of polar vinyl acetate side chains of EVA to neighboring water molecules made the EVA molecule prefer being in a curly state,which disrupted the ordered crystallization of surrounding wax molecules and delayed the solidification rate of wax cluster. In addition, it is found that EVA cocrystallized with wax molecules to form eutectic when the wax was fully solidified. The simulation results of hydrate nucleation and growth show that the EVA molecule displayed a two-sided effect on gas adsorption of wax crystals, which was the key factor that affected the nucleation and growth of hydrates in the methane-water system. The nonpolar hydrocarbon backbone of EVA increased the diffusion rate of methane and water, allowing more methane to diffuse to the surface of wax crystals, reducing the methane concentration in aqueous solutions and inhibiting the hydrate formation. On the other hand, the nonpolar vinyl acetate chains had a repulsive effect on methane, which reduced the adsorption area of methane on the eutectic surface and decreased the adsorption threshold value of the wax crystal. The excluded methane molecules would continue dissociating in the aqueous phase and participating in the nucleation and growth process of hydrates.Therefore, the probability of hydrate formation would be increased. It was worth noting that the inhibition performance of EVA on hydrate formation mainly played a significant role in the system with small wax crystal, while its hydrate promotion effect played a dominant role in the system with lager wax crystal. In summary, EVA could significantly inhibit both of the wax and hydrate deposition for the waxgas-water multiphase system with low wax content. When the wax content in the system was high, the role of EVA was mainly played in the alleviation of wax crystallization rather than the gas hydrates. The results of the present work can contribute to a better understanding of EVA on wax deposition and hydrate formation, and provide theoretical support of the potential industrial applications of EVA.展开更多
The utilization of optimal orthodontic force is crucial to prevent undesirable side effects and ensure efficient tooth movement during orthodontic treatment.However,the sensitivity of existing detection techniques is ...The utilization of optimal orthodontic force is crucial to prevent undesirable side effects and ensure efficient tooth movement during orthodontic treatment.However,the sensitivity of existing detection techniques is not sufficient,and the criteria for evaluating optimal force have not been yet established.Here,by employing 3D finite element analysis methodology,we found that the apical distal region(A-D region)of mesial roots is particularly sensitive to orthodontic force in rats.Tartrate-resistant acidic phosphatase(TRAP)-positive osteoclasts began accumulating in the A-D region under the force of 40 grams(g),leading to alveolar bone resorption and tooth movement.When the force reached 80 g,TRAP-positive osteoclasts started appearing on the root surface in the A-D region.Additionally,micro-computed tomography revealed a significant root resorption at 80 g.Notably,the A-D region was identified as a major contributor to whole root resorption.It was determined that 40 g is the minimum effective force for tooth movement with minimal side effects according to the analysis of tooth movement,inclination,and hyalinization.These findings suggest that the A-D region with its changes on the root surface is an important consideration and sensitive indicator when evaluating orthodontic forces for a rat model.Collectively,our investigations into this region would aid in offering valuable implications for preventing and minimizing root resorption during patients’orthodontic treatment.展开更多
Insights into the mechanism of hydrate nucleation are of great significance for the development of hydrate-based technologies,hydrate relevant flow assurance,and the exploration of in situ natural gas hydrates.Compare...Insights into the mechanism of hydrate nucleation are of great significance for the development of hydrate-based technologies,hydrate relevant flow assurance,and the exploration of in situ natural gas hydrates.Compared with the thermodynamics of hydrate formation,understanding the nucleation mechanism is challenging and has drawn substantial attention in recent decades.In this paper,we attempt to give a comprehensive review of the recent progress of studies of clathrate hydrate nucleation.First,the existing hypotheses on the hydrate nucleation mechanism are introduced and discussed.Then,we summarize recent experimental studies on induction time,a key parameter evaluating the velocity of the nucleation process.Subsequently,the memory effect is particularly discussed,followed by the suggestion of several promising research perspectives.展开更多
Natural gas hydrate(NGH)is a highly efficient and clean energy,with huge reserves and widespread distribution in permafrost and marine areas.Researches all over the world are committed to developing an effective explo...Natural gas hydrate(NGH)is a highly efficient and clean energy,with huge reserves and widespread distribution in permafrost and marine areas.Researches all over the world are committed to developing an effective exploring technology for NGH reservoirs.In this paper,four conventional in-situ hydrate production methods,such as depressurization,thermal stimulation,inhibitor injection and CO2 replacement,are briefly introduced.Due to the limitations of each method,there has been no significantly breakthrough in hydrate exploring technology.Inspired by the development of unconventional oil and gas fields,researchers have put forward some new hydrate production methods.We summarize the enhanced hydrate exploiting methods,such as CO2/N2–CH4 replacement,CO2/H2–CH4 replacement,hydraulic fracturing treatment,and solid exploration;and potential hydrate mining techniques,such as self-generating heat fluid injection,geothermal stimulation,the well pattern optimization of hydrate exploring.The importance of reservoir stimulation technology for hydrate exploitation is emphasized,and it is believed that hydrate reservoir modification technology is a key to open hydrate resources exploitation,and the major challenges in the process of hydrate exploitation are pointed out.The combination of multiple hydrate exploring technologies and their complementary advantages will be the development trend in the future so as to promote the process of hydrate industrialization.展开更多
Coal bed methane has been considered as an important energy resource.One major difficulty of purifying coal bed methane comes from the similar physical properties of CH_4 and N_2.The ZIF-8/water-glycol slurry was used...Coal bed methane has been considered as an important energy resource.One major difficulty of purifying coal bed methane comes from the similar physical properties of CH_4 and N_2.The ZIF-8/water-glycol slurry was used as a medium to separate coal bed methane by fluidifying the solid adsorbent material.The sorption equilibrium experiment of binary mixture(CH_4/N_2)and slurry was conducted.The selectivity of CH_4 to N_2 is within the range of 2-6,which proved the feasibility of the slurry separation method.The modified Langmuir equation was used to describe the gas-slurry phase equilibrium behavior,and the calculated results were in good agreement with the experimental data.A continuous absorption-adsorption and desorption process on the separation of CH_4/N_2 in slurry is proposed and its mathematical model is also developed.Sensitivity analysis is conducted to determine the operation conditions and the energy performance of the proposed process was also evaluated.Feed gas contains 30 mol%of methane and the methane concentration in product gas is 95.46 mol%with the methane recovery ratio of 90.74%.The total energy consumption for per unit volume of product gas is determined as 1.846 kWh Nm^(-3).Experimental results and process simulation provide basic data for the design and operation of pilot and industrial plant.展开更多
In order to simulate the behavior of gas hydrate formation and decomposition,a 3-Dimension experimental device was built,consisting of a high-pressure reactor with an inner diameter of 300 mm,effective height of 100 m...In order to simulate the behavior of gas hydrate formation and decomposition,a 3-Dimension experimental device was built,consisting of a high-pressure reactor with an inner diameter of 300 mm,effective height of 100 mm,and operation pressure of 16 MPa.Eight thermal resistances were mounted in the porous media at different depthes and radiuses to detect the temperature distribution during the hydrate formation/decomposition.To collect the pressure,temperature,and flux of gas production data,the Monitor and Control Generated System(MCGS) was used.Using this device,the formation and decomposition behavior of methane hydrate in the 20 ~ 40 mesh natural sand with salinity of 3.35 wt% was examined.It was found that the front of formation or decomposition of hydrate can be judged by the temperature distribution.The amount of hydrate formation can also be evaluated by the temperature change.During the hydrate decomposition process,the temperature curves indicated that the hydrate in the top and bottom of reactor dissociated earlier than in the inner.The hydrate decomposition front gradually moved from porous media surface to inner and kept a shape of column form,with different moving speed at different surface position.The proper decomposition pressure was also determined.展开更多
Bone regeneration remains a great clinical challenge. Low intensity near-infrared(NIR) light showed strong potential to promote tissue regeneration, offering a promising strategy for bone defect regeneration. However,...Bone regeneration remains a great clinical challenge. Low intensity near-infrared(NIR) light showed strong potential to promote tissue regeneration, offering a promising strategy for bone defect regeneration. However, the effect and underlying mechanism of NIR on bone regeneration remain unclear. We demonstrated that bone regeneration in the rat skull defect model was significantly accelerated with low-intensity NIR stimulation. In vitro studies showed that NIR stimulation could promote the osteoblast differentiation in bone mesenchymal stem cells(BMSCs) and MC3T3-E1 cells, which was associated with increased ubiquitination of the core circadian clock protein Cryptochrome 1(CRY1) in the nucleus. We found that the reduction of CRY1 induced by NIR light activated the bone morphogenetic protein(BMP) signaling pathways, promoting SMAD1/5/9 phosphorylation and increasing the expression levels of Runx2 and Osterix. NIR light treatment may act through sodium voltage-gated channel Scn4a, which may be a potential responder of NIR light to accelerate bone regeneration. Together, these findings suggest that low-intensity NIR light may promote in situ bone regeneration in a CRY1-dependent manner, providing a novel, efficient and non-invasive strategy to promote bone regeneration for clinical bone defects.展开更多
Tensile strain of porous membrane materials can broaden their capacity in gas separation.In this work,using van der Waals corrected density functional theory(DFT)and molecular dynamics(MD)simulations,the performance a...Tensile strain of porous membrane materials can broaden their capacity in gas separation.In this work,using van der Waals corrected density functional theory(DFT)and molecular dynamics(MD)simulations,the performance and mechanism of CO2/CH4 separation through strain-oriented graphdiyne(GDY)monolayer were studied by applying lateral strain.It is demonstrated that the CO2 permeance peaks at 1.29×10^6 gas permeation units(GPU)accompanied with CO2/CH4 selectivity of 5.27×10^3 under ultimate strain,both of which are far beyond the Robeson’s limit.Furthermore,the GDY membrane exhibited a decreasing gas diffusion energy barrier and increasing permeance with the increase of applied tensile strain.CO2 molecule tends to reoriented itself vertically to permeate the membrane.Finally,the CO2 permeability decreases with the increase of the temperature from300 K to 500 K due to conserving of rotational freedom,suggesting an abnormal permeance of CO2 in relation to temperature.Our theoretical results suggest that the stretchable GDY monolayer holds great promise to be an excellent candidate for CO2/CH4 separation,owing to its extremely high selectivity and permeability of CO2.展开更多
The increasing concentration of CO_(2) in atmosphere is deemed the main reason of global warming.Therefore,efficiently capturing CO_(2) from various sources with energy conservation is of great significance.Herein,a s...The increasing concentration of CO_(2) in atmosphere is deemed the main reason of global warming.Therefore,efficiently capturing CO_(2) from various sources with energy conservation is of great significance.Herein,a series of experiments were carried out to successfully test the slurry-based ab-adsorption method for continuously capturing CO_(2) in the large-scale cycled separation unit with cost-effect taking into account the scale-up criteria.A bubble column(with height 4900 mm and inner diameter 376 mm)and a desorption tank(with volume 310 L)are the essential components of the separation unit.The novel slurry used in this study was formed with zeolitic imidazolate framework-8 and 2-methylimidazole-water solution.The influence of operation conditions was investigated systematically.The results show that increasing sorption pressure and slurry height level,decreasing gas volume flow and sorption temperature are beneficial for separation processes.The volume fraction of CO_(2) in the feed gas was also studied.Although the scale-up effect had been observed and it was found that it exerted a negative effect on CO_(2) capture,depending on experimental conditions,CO_(2) removal efficiency could still reach 85%-95%and the maximum CO_(2) loading in the recycled slurry could be up to0.007 mol·L-1·kPa-1.Furthermore,the slurry-based method could be operated well even under very moderate regeneration conditions(333 K and 0.05 MPa),which means that the novel approach shows greater energy conservation than traditional amine absorption methods.展开更多
The natural gas hydrate has been regarded as an important future green energy.Significant progress on the hydrate exploitation has been made,but some challenges are still remaining.In order to enhance the hydrate expl...The natural gas hydrate has been regarded as an important future green energy.Significant progress on the hydrate exploitation has been made,but some challenges are still remaining.In order to enhance the hydrate exploitation efficiency,a significant understanding of the effective thermal conductivity(ETC)of the hydrate-bearing sediment has become essential,since it directly controls the heat and mass transfer behaviors,and thereby determines the stability of hydrate reservoir and production rate.In this study,the effective thermal conductivities of various hydrate-bearing sediments were in-situ measured and studied.The impacts of temperature,particle size and type of sediment were investigated.The effective thermal conductivities of the quartz sand sediments before and after hydrate formation were in-situ measured.The results show the weak negative correlation of effective thermal conductivity of the quartz sand sediment on the temperature before and after the hydrate formation.The effective thermal conductivity of the hydrate-bearing sediment decreases with the increase of particle size of the sediment.The dominant effect of the type of porous medium on the characteristics of the effective thermal conductivity of hydrate-bearing sediment was highlighted.The results indicate that both the effective thermal conductivities of hydrate-bearing quartz sand sediment and hydrate-bearing silicon carbide sediment are weakly negatively correlated with temperature,but the effective thermal conductivity of hydrate-bearing clay sediment is weakly positively dependent on the temperature.In addition,the values of the effective thermal conductivities of various hydrate-bearing sediments are in the order of hydrate-bearing silicon carbide sediment>hydrate-bearing quartz sand sediment>hydrate-bearing clay sediment.These findings could suggest that the intrinsic thermal conductivity of porous medium could control the characteristics of effective thermal conductivity of hydrate-bearing sediment.展开更多
Although zeolitic imidazolate frameworks(ZIFs)have bright prospects in wide fields like gas storage/separation,catalysis and medicine,etc.,their large-scale applications are bottlenecked by the absence of their low-co...Although zeolitic imidazolate frameworks(ZIFs)have bright prospects in wide fields like gas storage/separation,catalysis and medicine,etc.,their large-scale applications are bottlenecked by the absence of their low-cost commercial production technique.Here,we report an uncon ventional method suitable for environmentally friendly and low-cost mass-production of ZIFs.In this method,taking the synthesis of ZIF-8 as an example,ZnO was used instead of Zn(NO_(3))_(2) in traditional solvent synthesis methods and CO_(2) was introduced to dissolve ZnO in aqueous solution of 2-methylimidazole(HMeim)and form water soluble salt([ZnMeim]^(+)[MeimCOO]^(-))at room temperature.Then,by removing CO_(2) through heating or vacuuming,Meim-ions are produced and instantaneously assemble with[ZnMeim]^(+)s to generate ZIF-8 without any by product.Due to the absence of strong acid anions(such as NO^(-)_(3) and Cl^(-) et al.)in solution,the washing of filter cake required in the conventional approaches could be omitted and the filtrate containing only water and HMeim could be reused completely.This method is really green as no waste gas or liquid generates because CO_(2) and water could be recycled perfectly.It overcomes almost all bottlenecks occurred in commercial production of ZIF-8 when using traditional methods.A pilot plant was established for mass-production of ZIF-8 and hundreds kilograms of ZIF-8 was produced,which indicates that the new method is not only environmentally friendly but also low cost and commercial accessibility.It is expected that the new method would open an avenue for commercial applications of ZIFs.展开更多
基金supported by the National Natural Science Foundation of China(U19B2005,21808238,U20B6005,22127812)the State Key Laboratory of Heavy Oil Processing,China University of Petroleumthe National Key Research and Development Program of China(2021YFC2800902)
文摘The research on the thermal property of the hydrate has recently made great progress,including the understanding of hydrate thermal conductivity and effective thermal conductivity(ETC)of hydratebearing sediment.The thermal conductivity of hydrate is of great significance for the hydrate-related field,such as the natural gas hydrate exploitation and prevention of the hydrate plugging in oil or gas pipelines.In order to obtain a comprehensive understanding of the research progress of the hydrate thermal conductivity and the ETC of hydrate-bearing sediment,the literature on the studies of the thermal conductivity of hydrate and the ETC of hydrate-bearing sediment were summarized and reviewed in this study.Firstly,experimental studies of the reported measured values and the temperature dependence of the thermal conductivity of hydrate were discussed and reviewed.Secondly,the studies of the experimental measurements of the ETC of hydrate-bearing sediment and the effects of temperature,porosity,hydrate saturation,water saturation,thermal conductivity of porous medium,phase change,and other factors on the ETC of hydrate-bearing sediment were discussed and reviewed.Thirdly,the research progress of modeling on the ETC of the hydrate-bearing sediment was reviewed.The thermal conductivity determines the heat transfer capacity of the hydrate reservoir and directly affects the hydrate exploitation efficiency.Future efforts need to be devoted to obtain experimental data of the ETC of hydrate reservoirs and establish models to accurately predict the ETC of hydrate-bearing sediment.
基金financially supported by the National Natural Science Foundation of China,China(22378424,52004136,22127812,U20B6005)the Science Foundation of China University of Petroleum Beijing(2462023BJRC017)Hunan Provincial Department of Education Scientific Research Project(22B0310).
文摘Carbon emission reduction and clean energy development are urgent demands for mankind in the coming decades.Exploring an efficient CO_(2) storage method can significantly reduce CO_(2) emissions in the short term.In this study,we attempted to construct sediment samples with different residual CH_(4) hydrate amounts and reservoir conditions,and then investigate the potentials of both CO_(2) storage and enhanced CH_(4) recovery in depleted gas hydrate deposits in the permafrost and ocean zones,respectively.The results demonstrate that CO_(2) hydrate formation rate can be significantly improved due to the presence of residual hydrate seeds;However,excessive residual hydrates in turn lead to the decrease in CO_(2) storage efficiency.Affected by the T-P conditions of the reservoir,the storage amount of liquid CO_(2) can reach 8 times that of gaseous CO_(2),and CO_(2) stored in hydrate form reaches 2-4 times.Additionally,we noticed two other advantages of this method.One is that CO_(2) injection can enhance CH_(4) recovery rate and increases CH_(4) recovery by 10%-20%.The second is that hydrate saturation in the reservoir can be restored to 20%-40%,which means that the solid volume of the reservoir avoids serious shrinkage.Obviously,this is crucial for protecting the goaf stability.In summary,this approach is greatly promising for high-efficient CO_(2) storage and safe exploitation of gas hydrate.
基金supported by the National Natural Science Foundation of China(52104069,U20B6005)Beijing Municipal Natural Science Foundation(3232030)Science Foundation of China University of Petroleum,Beijing(2462023BJRC018,2462020YXZZ045).
文摘Natural gas hydrates,intricate crystalline structures formed by water molecules and small gas molecules,have emerged as a significant and globally impactful clean energy resource.However,their commercial exploitation faces challenges,particularly operational disruptions caused by sand-related blockages.Understanding the rheological properties of hydrate slurry,especially in the presence of micron-sized sand particles,is imperative for ensuring the flow assurance of subsea hydrate exploitation.This study extensively investigates the rheological properties of sand-containing hydrate slurries.The findings reveal that these slurries exhibit non-Newtonian fluid characteristics,including yield stress,thixotropy,and shear-thinning behavior.Solid-like elastic features are observed in sand-containing hydrate slurries before yielding,transitioning to viscous behavior after yielding.Even with a minimal amount of sand,both static yield stress and yield strain experience substantial changes,correlating with the increase in sand concentration.The research conclusively establishes the thixotropic nature of sand-hydrate slurries,where the viscosity decay rate is directly influenced by the shear rate.These insights aim to contribute comprehensively to the development of effective flow assurance strategies,ensuring the safe and stable operation of subsea hydrate exploitation.
基金The financial supports received from National Natural Science Foundation of China (U20B6005, 22178378, and 22127812)
文摘To date,the primary industrial carbon capture approach is still absorption using aqueous solutions of alkanolamines.Here,to pursue a substitute for the amine-based approach to improve the CO_(2) capture efficiency and decrease the energy cost further,we report a new carbon capture approach using a 2-methylimidazole(mIm)aqueous solution.The properties and sorption behaviors of this approach have been experimentally investigated.The results show that the mIm solution has higher CO_(2) absorption capacity under relatively higher equilibrium pressure(>130 kPa)and lower desorption heat than the methyldiethanolamine solution.91.6%sorption capacity of mIm solution can be recovered at 353.15 K and 80 kPa.The selectivity for CO_(2)/N_(2) and CO_(2)/CH_(4) can reach an exceptional 7609 and 4324,respectively.Furthermore,the pilot-scale tests were also performed,and the results demonstrate that more than 98%of CO_(2) in the feed gas could be removed and cyclic absorption capacity can reach 1 mol·L^(-1).This work indicates that mIm is an excellent alternative to alkanolamines for carbon capture in the industry.
基金financially supported by the National Natural Science Foundation of China(52106002,22378424)Natural Science Foundation of Hunan Province(2023JJ40026)+2 种基金Hunan Provincial Department of Education Scientific Research Project(22B0310)Natural Science Foundation of Guangdong Province(2021A1515010578,2020A1515110693)Shanghai Key Laboratory of Multiphase Materials Chemical Engineering(MMCE2023001).
文摘The morphology characteristics of CH_(4),CO_(2),and CO_(2)+N_(2)hydrate film forming on the suspending gas bubbles are studied using microscopic visual method at supercooling conditions from 1.0 to 3.0 K.The hydrate film vertical growth rate and thickness along the planar gas-water interface are measured to study the hydrate formation kinetics and mass transfer process.Adding N_(2)in the gas mixture plays the same role as lowering the supercooling conditions,both retarding the crystal nucleation and growth rates,which results in larger single crystal size and rough hydrate morphology.N_(2)in the gas mixture helps to delay the secondary nucleation on the hydrate film,which is beneficial to maintain the porethroat structure and enhance the mass transfer.The vertical growth rate of hydrate film mainly depends on the supercooling conditions and gas compositions but has weak dependence on the experimental temperature and pressure.Under the same gas composition condition,the final film thickness shows a linear relationship with the supercooling conditions.The mass transfer coefficient of CH_(4)molecules in hydrates ranges from 4.54×10^(-8)to 7.54×10^(-8)mol·cm^(-2)·s^(-1)·MPa^(-1).The maximum mass transfer coefficient for CO_(2)t N_(2)hydrate occurs at the composition of 60%CO_(2)t 40%N_(2),which is 3.98×10^(-8)mol·cm^(-2)·s^(-1)·MPa^(-1).
基金supported by National Natural Science Foundation of China (22278424, 22127812)Distinguished Youth Foundation of the Tianshan Program of Xinjiang Uygur Autonomous Region (2022TSYCJC0013)Science Foundation of China University of Petroleum-Beijing (2462023YJRC002)
文摘The long hydrate induction time and limited gas-liquid contact area leads to slow hydrate formation rate and low water-hydrate conversion rate.Porous media are often used to promote hydrate formation because of their large specific surface area.Consequently,we used 3A molecular sieve as a water-carrying solid in this work,and investigated the dynamic renewal of the gas-liquid interface and its effect on hydrate formation.The formation kinetics of ethane hydrate was first measured in an aqueous molecular sieve system.Then the separation of(H_(2)+CH_(4)+C_(2)H_(6)+C_(3)H_(8))gas mixture was conducted via hydrate formation.The results show that the formation rate and gas storage capacity of ethane hydrate can be greatly improved by using aqueous molecular sieve.Compared with a pure water system under the same temperature and pressure,aqueous molecular sieve has obvious advantages in separation effect and energy consumption for separating gas mixtures.
基金Financial support received from the National Natural Science Foundation of China(22178379)the National Key Research and Development Program of China(2021YFC2800902)is gratefully acknowledged.
文摘Natural gas hydrate is an energy resource for methane that has a carbon quantity twice more than all traditional fossil fuels combined.However,their practical application in the field has been limited due to the challenges of long-term preparation,high costs and associated risks.Experimental studies,on the other hand,offer a safe and cost-effective means of exploring the mechanisms of hydrate dissociation and optimizing exploitation conditions.Gas hydrate decomposition is a complicated process along with intrinsic kinetics,mass transfer and heat transfer,which are the influencing factors for hydrate decomposition rate.The identification of the rate-limiting factor for hydrate dissociation during depressurization varies with the scale of the reservoir,making it challenging to extrapolate findings from laboratory experiments to the actual exploitation.This review aims to summarize current knowledge of investigations on hydrate decomposition on the subject of the research scale(core scale,middle scale,large scale and field tests)and to analyze determining factors for decomposition rate,considering the various research scales and their associated influencing factors.
基金supported by the National Natural Science Foundation of China(21808238,U19B2005,U20B6005,22127812)the National Key Research and Development Program of China(2021YFC2800902)。
文摘The natural gas hydrate has become one of the most promising future green energy sources on the earth.The natural gas hydrates mostly exist in the sediments with porous structure, so a solid understanding of the hydrate formation and growth processes in the porous medium is of significance for the exploitation of natural gas hydrate. The micro-packed bed device is one of the efficient microfluidic devices in the engineering field, but it has been rarely used for the hydrate-based research. In this study, a transparent micro-packed bed device filled with glass beads was developed to mimic the porous condition of sediments, and used to in-situ visualize the hydrate formation and growth habits in the pore spaces under both static and dynamic conditions. For the static experiment, two types of hydrate growth patterns in porous medium were observed and identified in the micro-packed bed device, which were the graincoating growth and pore-filling growth. For the dynamic condition, the hydrate formation, growth,distribution habits and hydrate blockage phenomena in the pore spaces were in-situ visually captured.The impacts of flowrate and subcooling on the pressure variation of the micro-packed bed and the duration of the hydrate growth under dynamic flow condition in pores were in-situ monitored and analyzed. The higher flowrate could result in the faster hydrate growth and more severe blockage in pores, but the effect of subcooling condition might be less significant at the high flowrate.
基金Financial support from the National Natural Science Foundation of China(22208329,22178378,22127812,21908116 and U19B2005)Jiangxi Provincial Natural Science Foundation of China(20232BAB213044)。
文摘The clathrate hydrate memory effect is a fascinating phenomenon with potential applications in carbon capture,utilization and storage(CCUS),gas separation,and gas storage as it can accelerate the secondary formation of clathrate hydrate.However,the underlying mechanism of this effect remains unclear.To gain a better understanding of the mechanism,we conducted molecular dynamic simulations to simulate the initial formation and reformation processes of methane hydrate.In this work,we showed the evolution process of hydrate residual structures into hydrate cages.The simulation results indicate that the residual structures are closely related to the existence of hydrate memory effect,and the higher the contribution of hydrate dissociated water to the hydrate nucleation process,the faster the hydrate nucleation.After hydrate dissociation,the locally ordered structures still exist after hydrate dissociation and can promote the formation of cluster structures,thus accelerating hydrate nucleation.Additionally,the nucleation process of hydrate and the formation process of clusters are inseparable.The size of clusters composed of cup-cage structures is critical for hydrate nucleation.The residence time at high temperature after hydrate decomposition will affect the strength of the hydrate memory effect.Our simulation results provide microscopic insights into the occurrence of the hydrate memory effect and shed light on the hydrate reformation process at the molecular scale.
基金financial support received from National Natural Science Foundation of China(22178378 and 22127812)"Tianchi Talent"Recruitment Program,Xinjiang Tianshan Innovation Team(2022TSYCTD0002)Xinjiang Uygur Region"One Case,One Policy"Strategic Talent Introduction Project(XQZX20240054)are gratefully acknowledged.
文摘Ethylene-vinyl acetate copolymer(EVA) as a kind of effective polymeric pour point depressant has been extensively used in the pipeline transportation of crude oil to inhibit wax deposition and improve the low temperature fluidity of crude oil. In this work, molecular dynamics simulations were performed to investigate the effect of EVA on wax-hydrate coexistence system to evaluate the application potentiality of EVA to the flow assurance of deep-sea oil-gas-water multiphase flow system. Our simulation results reveal that wax molecules gradually stretched and stacked from random coiling to a directional and ordered crystalline state during the process of wax solidification. The strong affinity of polar vinyl acetate side chains of EVA to neighboring water molecules made the EVA molecule prefer being in a curly state,which disrupted the ordered crystallization of surrounding wax molecules and delayed the solidification rate of wax cluster. In addition, it is found that EVA cocrystallized with wax molecules to form eutectic when the wax was fully solidified. The simulation results of hydrate nucleation and growth show that the EVA molecule displayed a two-sided effect on gas adsorption of wax crystals, which was the key factor that affected the nucleation and growth of hydrates in the methane-water system. The nonpolar hydrocarbon backbone of EVA increased the diffusion rate of methane and water, allowing more methane to diffuse to the surface of wax crystals, reducing the methane concentration in aqueous solutions and inhibiting the hydrate formation. On the other hand, the nonpolar vinyl acetate chains had a repulsive effect on methane, which reduced the adsorption area of methane on the eutectic surface and decreased the adsorption threshold value of the wax crystal. The excluded methane molecules would continue dissociating in the aqueous phase and participating in the nucleation and growth process of hydrates.Therefore, the probability of hydrate formation would be increased. It was worth noting that the inhibition performance of EVA on hydrate formation mainly played a significant role in the system with small wax crystal, while its hydrate promotion effect played a dominant role in the system with lager wax crystal. In summary, EVA could significantly inhibit both of the wax and hydrate deposition for the waxgas-water multiphase system with low wax content. When the wax content in the system was high, the role of EVA was mainly played in the alleviation of wax crystallization rather than the gas hydrates. The results of the present work can contribute to a better understanding of EVA on wax deposition and hydrate formation, and provide theoretical support of the potential industrial applications of EVA.
基金funded by the National Natural Science Foundation of China for Key Program Projects(No.82030070,to L.C.)Hubei Provincial Natural Science Fund for Creative Research(No.2020CFA014,to L.C.)+1 种基金the National Natural Science Foundation of China(No.82100960,to S.Y.)Chinese Orthodontic Society Basic Research Fund(COS-B2021-01,to M.X.).
文摘The utilization of optimal orthodontic force is crucial to prevent undesirable side effects and ensure efficient tooth movement during orthodontic treatment.However,the sensitivity of existing detection techniques is not sufficient,and the criteria for evaluating optimal force have not been yet established.Here,by employing 3D finite element analysis methodology,we found that the apical distal region(A-D region)of mesial roots is particularly sensitive to orthodontic force in rats.Tartrate-resistant acidic phosphatase(TRAP)-positive osteoclasts began accumulating in the A-D region under the force of 40 grams(g),leading to alveolar bone resorption and tooth movement.When the force reached 80 g,TRAP-positive osteoclasts started appearing on the root surface in the A-D region.Additionally,micro-computed tomography revealed a significant root resorption at 80 g.Notably,the A-D region was identified as a major contributor to whole root resorption.It was determined that 40 g is the minimum effective force for tooth movement with minimal side effects according to the analysis of tooth movement,inclination,and hyalinization.These findings suggest that the A-D region with its changes on the root surface is an important consideration and sensitive indicator when evaluating orthodontic forces for a rat model.Collectively,our investigations into this region would aid in offering valuable implications for preventing and minimizing root resorption during patients’orthodontic treatment.
基金Supported by the National Key Research and Development Program of China(2016YFC0304003,2017YFC0307302)the National Natural Science Foundation of China(21636009,51576209,21522609)the Innovative Talents Support Program for Postgraduates(BX201700288)
文摘Insights into the mechanism of hydrate nucleation are of great significance for the development of hydrate-based technologies,hydrate relevant flow assurance,and the exploration of in situ natural gas hydrates.Compared with the thermodynamics of hydrate formation,understanding the nucleation mechanism is challenging and has drawn substantial attention in recent decades.In this paper,we attempt to give a comprehensive review of the recent progress of studies of clathrate hydrate nucleation.First,the existing hypotheses on the hydrate nucleation mechanism are introduced and discussed.Then,we summarize recent experimental studies on induction time,a key parameter evaluating the velocity of the nucleation process.Subsequently,the memory effect is particularly discussed,followed by the suggestion of several promising research perspectives.
基金Supported by the National Key Research and Development Program of China(2017YFC0307302,2016YFC0304003)the National Natural Science Foundation of China(21636009,51576209,51676207,21522609)
文摘Natural gas hydrate(NGH)is a highly efficient and clean energy,with huge reserves and widespread distribution in permafrost and marine areas.Researches all over the world are committed to developing an effective exploring technology for NGH reservoirs.In this paper,four conventional in-situ hydrate production methods,such as depressurization,thermal stimulation,inhibitor injection and CO2 replacement,are briefly introduced.Due to the limitations of each method,there has been no significantly breakthrough in hydrate exploring technology.Inspired by the development of unconventional oil and gas fields,researchers have put forward some new hydrate production methods.We summarize the enhanced hydrate exploiting methods,such as CO2/N2–CH4 replacement,CO2/H2–CH4 replacement,hydraulic fracturing treatment,and solid exploration;and potential hydrate mining techniques,such as self-generating heat fluid injection,geothermal stimulation,the well pattern optimization of hydrate exploring.The importance of reservoir stimulation technology for hydrate exploitation is emphasized,and it is believed that hydrate reservoir modification technology is a key to open hydrate resources exploitation,and the major challenges in the process of hydrate exploitation are pointed out.The combination of multiple hydrate exploring technologies and their complementary advantages will be the development trend in the future so as to promote the process of hydrate industrialization.
基金The financial supports received from the National Natural Science Foundation of China(21522609,21636009 and 21878328)the National Key Research and Development Program of China(Nos.2017YFC0307302,2016YFC0304003)+1 种基金the Science Foundation of China University of Petroleum,Beijing(No.2462018BJC004)Beijing Science and Technology Program,China(No.Z181100005118010)。
文摘Coal bed methane has been considered as an important energy resource.One major difficulty of purifying coal bed methane comes from the similar physical properties of CH_4 and N_2.The ZIF-8/water-glycol slurry was used as a medium to separate coal bed methane by fluidifying the solid adsorbent material.The sorption equilibrium experiment of binary mixture(CH_4/N_2)and slurry was conducted.The selectivity of CH_4 to N_2 is within the range of 2-6,which proved the feasibility of the slurry separation method.The modified Langmuir equation was used to describe the gas-slurry phase equilibrium behavior,and the calculated results were in good agreement with the experimental data.A continuous absorption-adsorption and desorption process on the separation of CH_4/N_2 in slurry is proposed and its mathematical model is also developed.Sensitivity analysis is conducted to determine the operation conditions and the energy performance of the proposed process was also evaluated.Feed gas contains 30 mol%of methane and the methane concentration in product gas is 95.46 mol%with the methane recovery ratio of 90.74%.The total energy consumption for per unit volume of product gas is determined as 1.846 kWh Nm^(-3).Experimental results and process simulation provide basic data for the design and operation of pilot and industrial plant.
基金supported by the National Natural Science Foundation of China (Grant numbers: 20676145, U0633003)973 program (No. 2009CB219504)NCET-07-0842
文摘In order to simulate the behavior of gas hydrate formation and decomposition,a 3-Dimension experimental device was built,consisting of a high-pressure reactor with an inner diameter of 300 mm,effective height of 100 mm,and operation pressure of 16 MPa.Eight thermal resistances were mounted in the porous media at different depthes and radiuses to detect the temperature distribution during the hydrate formation/decomposition.To collect the pressure,temperature,and flux of gas production data,the Monitor and Control Generated System(MCGS) was used.Using this device,the formation and decomposition behavior of methane hydrate in the 20 ~ 40 mesh natural sand with salinity of 3.35 wt% was examined.It was found that the front of formation or decomposition of hydrate can be judged by the temperature distribution.The amount of hydrate formation can also be evaluated by the temperature change.During the hydrate decomposition process,the temperature curves indicated that the hydrate in the top and bottom of reactor dissociated earlier than in the inner.The hydrate decomposition front gradually moved from porous media surface to inner and kept a shape of column form,with different moving speed at different surface position.The proper decomposition pressure was also determined.
基金funded by the National Key Research and Development Program of China(2021YFC2400404,to L.C.)the Key Program of National Natural Science of China(82030070,to L.C.)+1 种基金the National Science Foundation for Excellent Young Scholars of China(31725011,to L.C.)the Youth Clinical Research Fund of Chinese Stomatological Association(CSA-O2020-10,to Q.T.)。
文摘Bone regeneration remains a great clinical challenge. Low intensity near-infrared(NIR) light showed strong potential to promote tissue regeneration, offering a promising strategy for bone defect regeneration. However, the effect and underlying mechanism of NIR on bone regeneration remain unclear. We demonstrated that bone regeneration in the rat skull defect model was significantly accelerated with low-intensity NIR stimulation. In vitro studies showed that NIR stimulation could promote the osteoblast differentiation in bone mesenchymal stem cells(BMSCs) and MC3T3-E1 cells, which was associated with increased ubiquitination of the core circadian clock protein Cryptochrome 1(CRY1) in the nucleus. We found that the reduction of CRY1 induced by NIR light activated the bone morphogenetic protein(BMP) signaling pathways, promoting SMAD1/5/9 phosphorylation and increasing the expression levels of Runx2 and Osterix. NIR light treatment may act through sodium voltage-gated channel Scn4a, which may be a potential responder of NIR light to accelerate bone regeneration. Together, these findings suggest that low-intensity NIR light may promote in situ bone regeneration in a CRY1-dependent manner, providing a novel, efficient and non-invasive strategy to promote bone regeneration for clinical bone defects.
基金financial support received from the National Natural Science Foundation of China(21776301)the Science Foundation of China University of Petroleum,Beijing(2462018BJC004)。
文摘Tensile strain of porous membrane materials can broaden their capacity in gas separation.In this work,using van der Waals corrected density functional theory(DFT)and molecular dynamics(MD)simulations,the performance and mechanism of CO2/CH4 separation through strain-oriented graphdiyne(GDY)monolayer were studied by applying lateral strain.It is demonstrated that the CO2 permeance peaks at 1.29×10^6 gas permeation units(GPU)accompanied with CO2/CH4 selectivity of 5.27×10^3 under ultimate strain,both of which are far beyond the Robeson’s limit.Furthermore,the GDY membrane exhibited a decreasing gas diffusion energy barrier and increasing permeance with the increase of applied tensile strain.CO2 molecule tends to reoriented itself vertically to permeate the membrane.Finally,the CO2 permeability decreases with the increase of the temperature from300 K to 500 K due to conserving of rotational freedom,suggesting an abnormal permeance of CO2 in relation to temperature.Our theoretical results suggest that the stretchable GDY monolayer holds great promise to be an excellent candidate for CO2/CH4 separation,owing to its extremely high selectivity and permeability of CO2.
基金The authors gratefully acknowledge the financial supports received from the National Natural Science Foundation of China(21776301,21636009)the Science Foundation of China University of Petroleum,Beijing(2462018BJC004).
文摘The increasing concentration of CO_(2) in atmosphere is deemed the main reason of global warming.Therefore,efficiently capturing CO_(2) from various sources with energy conservation is of great significance.Herein,a series of experiments were carried out to successfully test the slurry-based ab-adsorption method for continuously capturing CO_(2) in the large-scale cycled separation unit with cost-effect taking into account the scale-up criteria.A bubble column(with height 4900 mm and inner diameter 376 mm)and a desorption tank(with volume 310 L)are the essential components of the separation unit.The novel slurry used in this study was formed with zeolitic imidazolate framework-8 and 2-methylimidazole-water solution.The influence of operation conditions was investigated systematically.The results show that increasing sorption pressure and slurry height level,decreasing gas volume flow and sorption temperature are beneficial for separation processes.The volume fraction of CO_(2) in the feed gas was also studied.Although the scale-up effect had been observed and it was found that it exerted a negative effect on CO_(2) capture,depending on experimental conditions,CO_(2) removal efficiency could still reach 85%-95%and the maximum CO_(2) loading in the recycled slurry could be up to0.007 mol·L-1·kPa-1.Furthermore,the slurry-based method could be operated well even under very moderate regeneration conditions(333 K and 0.05 MPa),which means that the novel approach shows greater energy conservation than traditional amine absorption methods.
基金This work was supported by the National Natural Science Foundation of China(U19B2005,21808238,U20B6005,22127812)the National Key Research and Development Program of China(2021YFC2800902).
文摘The natural gas hydrate has been regarded as an important future green energy.Significant progress on the hydrate exploitation has been made,but some challenges are still remaining.In order to enhance the hydrate exploitation efficiency,a significant understanding of the effective thermal conductivity(ETC)of the hydrate-bearing sediment has become essential,since it directly controls the heat and mass transfer behaviors,and thereby determines the stability of hydrate reservoir and production rate.In this study,the effective thermal conductivities of various hydrate-bearing sediments were in-situ measured and studied.The impacts of temperature,particle size and type of sediment were investigated.The effective thermal conductivities of the quartz sand sediments before and after hydrate formation were in-situ measured.The results show the weak negative correlation of effective thermal conductivity of the quartz sand sediment on the temperature before and after the hydrate formation.The effective thermal conductivity of the hydrate-bearing sediment decreases with the increase of particle size of the sediment.The dominant effect of the type of porous medium on the characteristics of the effective thermal conductivity of hydrate-bearing sediment was highlighted.The results indicate that both the effective thermal conductivities of hydrate-bearing quartz sand sediment and hydrate-bearing silicon carbide sediment are weakly negatively correlated with temperature,but the effective thermal conductivity of hydrate-bearing clay sediment is weakly positively dependent on the temperature.In addition,the values of the effective thermal conductivities of various hydrate-bearing sediments are in the order of hydrate-bearing silicon carbide sediment>hydrate-bearing quartz sand sediment>hydrate-bearing clay sediment.These findings could suggest that the intrinsic thermal conductivity of porous medium could control the characteristics of effective thermal conductivity of hydrate-bearing sediment.
基金supports received from the National Natural Science Foundation of China (21776301,21636009)are gratefully acknowledged.
文摘Although zeolitic imidazolate frameworks(ZIFs)have bright prospects in wide fields like gas storage/separation,catalysis and medicine,etc.,their large-scale applications are bottlenecked by the absence of their low-cost commercial production technique.Here,we report an uncon ventional method suitable for environmentally friendly and low-cost mass-production of ZIFs.In this method,taking the synthesis of ZIF-8 as an example,ZnO was used instead of Zn(NO_(3))_(2) in traditional solvent synthesis methods and CO_(2) was introduced to dissolve ZnO in aqueous solution of 2-methylimidazole(HMeim)and form water soluble salt([ZnMeim]^(+)[MeimCOO]^(-))at room temperature.Then,by removing CO_(2) through heating or vacuuming,Meim-ions are produced and instantaneously assemble with[ZnMeim]^(+)s to generate ZIF-8 without any by product.Due to the absence of strong acid anions(such as NO^(-)_(3) and Cl^(-) et al.)in solution,the washing of filter cake required in the conventional approaches could be omitted and the filtrate containing only water and HMeim could be reused completely.This method is really green as no waste gas or liquid generates because CO_(2) and water could be recycled perfectly.It overcomes almost all bottlenecks occurred in commercial production of ZIF-8 when using traditional methods.A pilot plant was established for mass-production of ZIF-8 and hundreds kilograms of ZIF-8 was produced,which indicates that the new method is not only environmentally friendly but also low cost and commercial accessibility.It is expected that the new method would open an avenue for commercial applications of ZIFs.