The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m-2 a-1, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 109 m3 MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.

Gas-bearing fluid influx sub-system for gas hydrate geological system in Shenhu Area, Northern South China Sea

Based on the comprehensive interpretation and study of the Neogene fracture system and diapiric structure, it can be concluded that the diapiric structures, high-angle fractures and vertical fissure system are the main gas-bearing fluid influx sub-system for gas hydrate geological system in Shenhu Area, northern South China Sea. The Neogene fractures widely developed in the study area may be classed into two groups: NW (NNW)-trending and NE (NNE)-trending. The first group was active in the Late Miocene, while the second one was active since the Pliocene. The NE (NNE)-trending fractures were characterized by lower activity strength and larger scale, and cut through the sediment layers deposited since the Pliocene. Within the top sediment layers, the high-angle fracture and vertical fissure system was developed. The diapiric structures display various types such as a turtle-back-like arch, weak piercing, gas chimney, and fracture (or crack, fissure). On the seismic profile, some diapiric structures show the vertical chimney pathway whose top is narrow and the bottom is wide, where some ones extend horizontally into pocket or flower-shaped structures and formed the seismic reflection chaotic zones. Within the overlying sediment layers of the diapiric structure, the tree branch, flower-shaped high-angle fractures and vertical fissures were developed and became the pathway and migration system of the gas-bearing fluid influx. In the study area, the diapiric structures indicate a high temperature/over pressure system ever developed. Closely associated and abundant bright-spots show the methane-bearing fluid influx migrated vertically or horizontally through the diapiric structures, high-angle fractures and vertical fissures. In the place where the temperature and pressure conditions were favor for the formation of gas hydrate, the hydrate reservoir deposition sub-system was developed.

Scale study of direct synthesis of dimethyl ether from biomass synthesis gas

We investigated the synthesis of dimethyl ether (DME) from biomass synthesis gas using a kind of hybrid catalyst consisting of methanol and HZSM-5 zeolite in a fixed-bed reactor in a 100 ton/year pilot plant. The biomass synthesis gas was produced by oxygen-rich gasification of corn core in a two-stage fixed bed. The results showed that CO conversions reached 82.00% and 73.55%, the selectivities for DME were 73.95% and 69.73%, and the space-time yields were 124.28 kg m- 3 h- 1 and 203.80 kg m- 3 h- 1 when gas hourly space velocities were 650 h- 1 and 1200 h- 1, respectively. Deoxidation and tar removal from biomass synthesis gas was critical to the stable operation of the DME synthesis system. Using single-pass synthesis, the H2/CO ratio improved from 0.98-1.17 to 2.12-2.22. The yield of DME would be increased greatly if the exhaust was reused after removal of the CO2.

Study on the Dissociation Behavior of Gas Hydrate in Porous Sediment Based on Fractal Theory

The dissociation process of gas hydrate was regarded as a gas-solid reaction without solid production layer when the temperature was above the zero centigrade. Based on the shrinking core model and the fractal theory, a fractional dimension dynamical model for gas hydrate dissociation in porous sediment was established. The new approach of evaluating the fractal dimension of the porous media was also presented. The fractional dimension dynamical model for gas hydrate dissociation was examined with the previous experimental data of methane hydrate and carbon dioxide hydrate dissociations, respectively. The calculated results indicate that the fractal dimensions of porous media acquired with this method agree well with the previous study. With the absolute average deviation (AAD) below 10%, the present model provided satisfactory predictions for the dissociation process of methane hydrate and carbon dioxide hydrate.

Synthesis Gas Generation by Chemical-Looping Reforming Using Ce-Based Oxygen Carriers Modified with Fe, Cu, and Mn Oxides

Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.

Effect of microwave on formation/decomposition of natural gas hydrate

Natural gas hydrate (NGH) reservoirs have been considered as a substantial future clean energy resource and how to recover gas from these reservoirs feasibly and economically is very important. Microwave heating will be taken as a promising method for gas production from gas hydrates for its advantages of fast heat transfer and flexible application. In this work, we investigate the formation/decomposition behavior of natural gas hydrate with different power of microwave (2450MHZ), preliminarily analyze the impact of microwave on phase equilibrium of gas hydrate,and make calculation based on van der Waals-Platteeuw model. It is found that microwave of a certain amount of power can reduce the induction time and sub-cooling degree of NGH formation, e.g., 20W microwave power can lead to a decrease of about 3A degrees C in sub-cooling degree and the shortening of induction time from 4.5 hours to 1.3 hours. Microwave can make rapid NGH decomposition, and water from NGH decomposition accelerates the decomposition of NGH with the decomposition of NGH. Under the same pressure, microwave can increase NGH phase equilibrium temperature. Different dielectric properties of each composition of NGH may cause a distinct difference in temperature in the process of NGH decomposition. Therefore, NGH decomposition by microwave can be affected by many factors.

Partial oxidation reforming of biomass fuel gas over nickel-based monolithic catalyst with naphthalene as model compound

With naphthalene as biomass tar model compound, partial oxidation reforming (with addition of O-2) and dry reforming of biomass fuel gas were investigated over nickel-based monoliths at the same conditions. The results showed that both processes had excellent performance in upgrading biomass raw fuel gas. Above 99% of naphthalene was converted into synthesis gases (H-2+CO). About 2.8 wt% of coke deposition was detected on the catalyst surface for dry reforming process at 750 degrees C during 108 h lifetime test. However, no Coke deposition was detected for partial oxidation reforming process, which indicated that addition of O-2 can effectively prohibit the coke formation. O-2 Can also increase the CH4 conversion and H-2/CO ratio of the producer gas. The average conversion of CH4 in dry and partial oxidation reforming process was 92% and 95%, respectively. The average H-2/CO ratio increased from 0.95 to 1.1 with the addition of O-2, which was suitable to be used as synthesis gas for dimethyl ether (DME) synthesis.

Thermal performance of a micro-combustor for micro-gas turbine system

Premixed combustion of hydrogen gas and air was performed in a stainless steel based micro-annular combustor for a micro-gas turbine system. Micro-scale combustion has proved to be stable in the micro-combustor with a gap of 2 mm. The operating range of the micro-combustor was measured, and the maximum excess air ratio is up to 4.5. The distribution of the outer wall temperature and the temperature of exhaust gas of the micro-conbustor with excess air ratio were obtained, and the wall temperature of the micro-combustor reaches its maximum value at the excess air ratio of 0.9 instead of 1 (stoichiometric ratio). The heat loss of the micro-combustor to the environment was calculated and even exceeds 70% of the total thermal power computed from the consumed hydrogen mass flow rate. Moreover, radiant hunt transfer covers a large fraction of the total heat loss. Measures used to reduce the heat loss were proposed to improve the thermal performance of the micro-combustor. The optimal operating status of the micro-combustor and micro-gas turbine is analyzed and proposed by analyzing the relationship of the temperature of the exhaust gas of the micro-combustor with thermal power and excess air ratio. The investigation of the thermal performance of the micro-combustor is helpful to design an improved microcombustor.

Transient flow patterns and bubble slug lengths in parallel microchannels with oxygen gas bubbles produced by catalytic chemical reactions

Transient flow patterns and bubble slug lengths were investigated with oxygen gas (O-2) bubbles produced by catalytic chemical reactions using a high speed camera bonded with a microscope. The microreactor consists of an inlet liquid plenum, nine parallel rectangular microchannels followed by a micronozzle, using the MEMS fabrication technique. The etched surface was deposited by the thin platinum film, which is acted as the catalyst. Experiments were performed with the inlet mass concentration of the hydrogen peroxide from 50% to 90% and the pressure drop across the silicon chip from 2.5 to 20.0 kPa. The silicon chip is directly exposed in the environment thus the heat released via the catalytic chemical reactions is dissipated into the environment and the experiment was performed at the room temperature level. It is found that the two-phase flow with the catalytic chemical reactions display the cyclic behavior. A full cycle consists of a short fresh liquid refilling stage, a liquid decomposition stage followed by the bubble slug flow stage. At the beginning of the bubble slug flow stage, the liquid slug number reaches maximum, while at the end of the bubble slug flow stage the liquid slugs are quickly flushed out of the microchannels. Two or three large bubbles are observed in the inlet liquid plenum, affecting the two-phase distributions in microchannels. The bubble slug lengths, cycle periods as well as the mass flow rates are analyzed with different mass concentrations of hydrogen peroxide and pressure drops. The bubble slug length is helpful for the selection of the future microreactor length ensuring the complete hydrogen peroxide decomposition. Future studies on the temperature effect on the transient two-phase flow with chemical reactions are recommended.

Hydrate dissociation conditions for gas mixtures containing carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons using SAFT

A new method, a molecular thermodynamic model based on statistical mechanics, is employed to predict the hydrate dissociation conditions for binary gas mixtures with carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons in the presence of aqueous solutions. The statistical associating fluid theory (SAFT) equation of state is employed to characterize the vapor and liquid phases and the statistical model of van der Waals and Platteeuw for the hydrate phase. The predictions of the proposed model were found to be in satisfactory to excellent agreement with the experimental data.

Control mechanisms for gas hydrate production by depressurization in different scale hydrate reservoirs

The methane hydrate was formed in a pressure vessel 38 mm in id and 500 mm in length. Experimental works on gas production from the hydrate-bearing core by depressurization to 0.1, 0.93, and 1.93 MPa have been carried out. The hydrate reservoir simulator TOUGH-Fx/Hydrate was used to simulate the experimental gas production behavior, and the intrinsic hydration dissociation constant (K-0) fitted for the experimental data was on the order of 104 mol m(-2) Pa-1 s(-1), which was one order lower than that of the bulk hydrate dissociation. The sensitivity analyses based on the simulator have been carried out, and the results suggested that the hydrate dissociation kinetics had a great effect on the gas production behavior for the laboratory-scale hydrate-bearing core. However for a field-scale hydrate reservoir, the flow ability dominated the gas production behavior and the effect of hydrate dissociation kinetics on the gas production behavior could be neglected.

Hydrogen-rich gas production from biomass air and oxygen/steam gasification in a downdraft gasifier

Biomass gasification is an important method to obtain renewable hydrogen, However, this technology still stagnates in a laboratory scale because of its high-energy consumption. In order to get maximum hydrogen yield and decrease energy consumption, this study applies a self-heated downdraft gasifier as the reactor and uses char as the catalyst to study the characteristics of hydrogen production from biomass gasification. Air and oxygen/steam are utilized as the gasifying agents. The experimental results indicate that compared to biomass air gasification, biomass oxygen/steam gasification improves hydrogen yield depending on the volume of downdraft gasifier, and also nearly doubles the heating value of fuel gas. The maximum lower heating value of fuel gas reaches 11.11 MJ/ N m(3) for biomass oxygen/steam gasification. Over the ranges of operating conditions examined, the maximum hydrogen yield reaches 45.16 g H-2/kg biomass. For biomass oxygen/steam gasification, the content of H-2 and CO reaches 63.27-72.56%, while the content Of H2 and CO gets to 52.19-63.31% for biomass air gasification. The ratio of H-2/CO for biomass oxygen/steam gasification reaches 0.70-0.90, which is lower than that of biomass air gasification, 1.06-1.27. The experimental and comparison results prove that biomass oxygen/steam gasification in a downdraft gasifier is an effective, relatively low energy consumption technology for hydrogen-rich gas production.