Determination of appropriate condition on replacing methane from hydrate with carbon dioxide

This paper is intended to determine the appropriate conditions for replacing CH4 from NGH with CO2. By analyzing the hydration equilibrium graphs and geotherms, the HSZs of NGH and CO2 hydrate, both in permafrost and under deep sea, were determined. Based on the above analysis and experimental results, it is found that to replace CH4 from NGH with gaseous CO2, the appropriate experimental condition should be in the area surrounded by four curves: the geotherm, (H-V)(CO2), (L-V)(CO2) and (H-V)(CH4), and to replace CH4 from NGH with liquid CO2, the condition should be in the area surrounded by three curves: (L-V)(CO2), (H-L)(CO2) and (H-V)CH4. For conditions in other areas, either CO2 can not form a hydrate or CH4 can release little from its hydrate, which are not desirable results.

Synthesis and characteristics of the human serum albumin-triazine chiral stationary phase

Human serum albumin (HSA) was successfully bonded to silica with s-triazine as activator. The coupling reaction by this method was rapid and effective. The triazine-activated silica is relatively stable and can be installed for at least 1 month without obvious loss of reactivity when stored below 30 degreesC, pH below 7. It was observed that the amount of bound HSA reached 120 mg/g silica calculated from the UV absorbance difference of the HSA solution. d,l-tryptophan was selected as the probe solute to characterize the properties of HSA bonded s-triazine chiral stationary phase, and separation factor of 9.4 was obtained for d,l-tryptophan. Furthermore, the amount of effective HSA on silica was measured by high-performance frontal analysis, and only 16.8 mg/g silica was responsible for the resolution of d,l-tryptophan. These results indicate that the amount of both the bound and effective HSA on silica with triazine as activator was much higher than those by the Schiff base coupling method. Different kinds of enantiomers were resolved successfully on the aminopropylsilica-bonded HSA s-triazine chiral stationary phase. (C) 2000 Wiley-Liss, Inc.

班公湖带多不杂超大型富金斑岩铜矿床的成岩成矿年代学、岩石学及高氧化岩浆¬流体-成矿作用

Duobuza copper deposit, newly discovered typical gold-rich porphyry copper deposit with superlarge potential, is located in the Tiegelong Mesozoic tectonic -magmatic arc of the southern edge of Qiangtang block and the northern margin of Bangonghu-Nujiang suture. Quartz diorite porphyrite and grandiorite porphyry, occurred in stock, are the main ore-bearing porphyries. As the emplacement of porphyry stock, a wide range of hydrothermal alteration has developed. Within the framework of the ore district, abundant hydrothermal magnetite developed, and the relationship between precipitation of copper and gold and hydrothermal magnetite seems much close. Correspondingly, a series of veinlets and network veinlets occurred in all alteration zones. Therefore, systematic research on such a superlarge high-grade Duobuza gold-rich porphyry copper deposit can fully revealed the metallogenic characteristics of gold-rich porphyry copper deposits in this region, establish metallogenetic model and prospecting criteria, and has important practical significance on the promotion of regional exploration. In addition, this research on it can enrich metallogenic theory of strong oxidation magma-fluid to gold-rich porphyry copper deposit, and will be helpful to understand the metallogenic characteristics in early of subduction of Gangdese arc stages and its entire evolution history of the Qinghai-Tibet Plateau, the temporal and spatial distribution of ore deposits and their geodynamics settings. Northern ore body of Duobuza copper deposit have been controlled with width (north-south) about 100 ~ 400 m, length (east-west) about 1400 m, dip of 200 °, angle of dip 65 °~ 80 °. And controlled resource amount is of 2.7 million tons Cu with grade 0.94% and 13 tons Au with 0.21g/tAu. Overall features of ore body are large scale, higher grade copper, gold-rich. Ore occurred in the body of granodiotite porphyry and quartz diorite porphyrite and its contact zone with wall rock. Through the detailed mapping and field work studies, some typies of alteration are identificated as follows: albitization, biotititation, sericitization, silication, epidotization, chloritization, carbonatization, illitization, kaolinization and so on. The range of alteration is more than 10km2. Wall alteration zone can be divided into potassic alteration, moderate argillization alteration, argillization, illite-hydromuscovite or propylitization from ore-bearing porphyry center outwards, but phyllic alteration has not well developed and only sericite-quartz veins occurred in local area. Moreover, micro-fracture is development in ore district , and correspondingly a series of veinlets are development as follows: biotite vein (EB type), K-feldspar-biotite-chalcopyrite-quartz vein, magnetite-antinolite-K-feldspar vein, quartz-chalcopyrite-magnetite veins (A-type), quartz-magnetite-biotite-K-feldspar vein, chalcopyrite veinlets in potassic alteration zone; (2) chalcopyrite occurring in the center vein–quartz vein (B type), chalcopyrite veinlets, chalcopyrite-gypsum vein in intermediate argillization alteration; (3) chalcopyrite- pyrite-quartz vein, pyrite-quartz vein, chalcopyrite-gypsum veins, quartz-gypsum- molybdenite-chalcopyrite vein in argillization alteration; (4) gypsum veins, quartz-(molybdenite)-chalcopyrite vein, quartz-pyrite vein, gypsum- chalcopyrite vein, potassium feldspar veinlets, Carbonate veins, quartz-magnetite veins in the wall rock. In short, various veins are very abundant within the framework of the ore district. The results of electronic probe microscopy analysis (EMPA) indicate that Albite (Ab 91.5~99.7%) occurred along the rim of plagioclase phenocryst and fracture, and respresents the earliest stages of alteration. K-feldspar (Or 75.1~96.9%) altered plagioclase phenocryst and matrix or formed secondary potassium feldspar veinlets. Secondary biotite occurred mainly in phenocryst, matrix and veinlets, belong to magnesium-rich biotite formed under the conditions of high-oxidation magma- hydrothermal. Chloritization developed in all alteration zones and alterd iron- magnesium minerals such as biotite and hornblende and then formed chlorite veinlets. As the temperature rises, Si in the tetrahedral site of chlorite decreased, and chlorite component evolved from diabantite to ripiolite. The consistent 280℃~360℃ of formation temperature hinted that chlorite formed on the same temperature range in all alteration zones. However, formation temperature range of chlorite from the gypsum-carbonate-chlorite vein was 190℃~220℃, and it may be the product of the latest stage of hydrothermal activity. The closely relationship between biotite and rutile indicate that most of rutiles are precipitated in the process of biotite alteration and recrystallization. In addition, the V2O3 concentration of rutile from ore body in Duobuza gold-rich porphyry copper deposit is >0.4％, indicate that V concentration in rutile has important significance on marking main ore body of porphyry copper deposit. Apatites from Duobuza deposit all are F-rich. And apatite in the wall rock contained low MnO content and relatively high FeO content, which may due to the basaltic composition of the wall rocks. The MnO in apatite from altered porphyry show a strong positive correlation with FeO. In addition, Cl/F ratio of apatite from wall rock was highest, followed by the potassic alteration zone and potassic alteration zone overprinted by moderate argillization alteration was the lowest. SO2 in Apatite are in the scope of 0 to 0.66%, biotite in the apatite has the highest SO2, followed by the potassic alteration zone, potassic alteration zone overprinted by moderate argillization alteration, and the lowest in the surrounding rocks, which may be caused by the decrease of oxygen fugacity of hydrothermal fluid and S exhaust by sulfide precipitation in potassic alteration. Magnetite in the wall rock have higher Cr2O3 and lower Al2O3 features compared with altered porphyry, this may be due to basalt wall rock generally has high Cr content. And magnetites have higher TiO2 content in potassic alteration than moderate argillization alteration overprinted by potassic alteration, argillization and wall rock, suggested that its formation temperature in potassic alteration was the highest among them. The ore minerals mainly are chalcopyrite and bornite, and Au contents of chalcopyrite, bornite, and pyrite are similar with chalcopyrite slightly higher. The Eu* negative anomaly of disseminated chalcopyrite was relatively lower than chalcopyrite in veinlets. Within a drill hole, the Eu* negative anomaly of disseminated chalcopyrite was gradually larger from bottom to top. Magnetite has the same distribution model, with obvious negative Eu* abnormal, and ΣREE in great changes. The gypsum has the highest ΣREE content and the obvious negative anomaly, and biotite obviously has the Eu* abnormal. Based on the petrographic and geochemical characteristics, five series of magmatic rocks can be broadly classified; they are volcanic rocks of the normal island arc, high-Nb basaltic rocks, adakites, altered porphyry and diorite. The Sr, Nd, Hf isotopes and geochemistry of various series of magmatic rock show that they may be the result of mixing between basic magma and various degrees of acid magma coming from lower crust melted by high temperature basic underplating from partial melting of the subduction sediment melt metasomatic mantle wedge. Furthermore S isotope and Pb isotope of the sulfide, ore-bearing porphyries and volcanic rocks indicated ore-forming source is the mantle wedge metasomatied by subduction sediment melt. Oxygen fugacity of magma estimated by Fe2O3/FeO of whole rock and zircon Ce4+/Ce3+ indicated that the oxidation of basalt-andesitic rocks is higher than ore-forming porphyry, and might imply high-oxidation characteristics of underplated basic magma. Its high oxidative mechanism is likely mantle sources metasomatied by subduction sediment magma, including water and Fe3+. And such high oxidation of basaltic magma is conducive to the mantle of sulfides in the effective access to melt. And the An component of dark part within plagioclase phenocryst zoning belong to bytownite (An 74%), and its may be a result of magma composition changes refreshment by basaltic magma injection. SHRIMP zircon U-Pb and LA-ICP-MS zircon U-Pb geochronology study showed that the intrusions and volcanic rocks from Duobuza porphyry copper deposit belong to early Cretaceous magma series (126~105Ma). The magma evolution series are as follows: the earliest diorite and diorite porphyrite → ore-bearing porphyry and barren grandiorite porphyry →basaltic andesite → diorite porphyrite → andesite → basaltic andesite, and magma component shows a evolution trend from intermediate to intermediate-acid to basic. Based on the field evidences, the formation age of high-Nb basalt may be the latest. The Ar-Ar geochronology of altered secondary biotite, K-feldspar and sericite shows that the main mineralization lasting a interval of about 4 Ma, the duration limit of whole magma-hydrothermal evolution of about 6 Ma, and possibly such a long duration limit may result in the formation of Duobuza super-large copper deposit. Moreover, tectonic diagram and trace element geochemistry of volcanic rocks and diorite from Duobuza porphyry copper deposit confirm that it formed in a continental margin arc environment. Zircon U-Pb age of volcanic rocks and porphyry fall in the range of 105~121Ma, and Duobuza porphyry copper deposit locating in the north of the Bangonghu- Nujiang suture zone, suggested that Neo-Tethys ocean still subducted northward at least early Cretaceous, and its closure time should be later than 105 Ma. Three major inclusion types and ten subtypes are distinguished from quartz phenocrysts and various quartz veins. Vapor generally coexisting with brine inclusions, suggest that fluid boiling may be the main ore-forming mechanism. Raman spectrums of fluid inclusions display that the content of vapor and liquid inclusion mainly contain water, and vapor occasionally contain a little CO2. In addition, the component of liquid inclusions mainly include Cl-, SO42-, Na+, K+, a small amount of Ca2+, F-; and Cl- and Na+ show good correlation. Vapor mainly contains water, a small amount of CO2, CH4 and C2H6 and so on. The daughter minerals identified by Laman spectroscopy and SEM include gypsum, chalcopyrite, halite, sylvite, rutile, potassium feldspar, Fe-Mn-chloride and other minerals, and ore-forming fluid belong to a complex hydrothermal system containing H2O-NaCl-KClFeCl2CaCl2. H and O isotopic analysis of quartz phenocryst, vein quartz, magnetite, chlorite and gypsum from all alteration zones show that the ore-forming fluid of Duobuza gold-rich porphyry copper deposit consisted mainly of magmatic water, without addition of meteric water. Duobuza gold-rich porphyry copper deposit formed by the primary magmatic fluid (600-950C), which has high oxidation, ultra-high salinity and metallogenic element-rich, exsolution direct from the magma, and it is representative of the typical orthomagmatic end member of the porphyry continuum. Moreover, the fluid evolution model of Duobuza gold-rich porphyry copper deposit has been established. Furthermore, two key factors for formation of large Au-rich porphyry copper deposit have been summed up, which are ore-forming fluids earlier separated from magma and high oxidation magma-mineralization fluid system.

Influence of A-type Zeolite on Methane Hydrate Formation

The porous medium has an important effect on hydrate formation. In this paper, the formation process and the gas storage capacity of the methane hydrate were investigated with A-type zeolite and Sodium Dodecyl Sulfate (SDS) existing in the system. The results show that A-type zeolite can influence methane hydrate formation. At the temperature of 273.5 K and pressure of 8.3 MPa, the distilled water with A-type zeolite can form methane hydrate with gaseous methane in 12 hours. The formation process of the system with A-type zeolite was quite steady and the amount of A-type zeolite can influence the gas storage capacity significantly. The adding of A-type zeolite with 0.067 g.(g water)(-1) into 2 x 10(-3) g.g(-1) SDS-water solution can increase the gas storage capacity, and the maximum increase rate was 31%. Simultaneously the promotion effect on hydrate formation of 3A-type zeolite is much more obvious than that of 5A-type zeolite when the water adding amounts are 0.033 g.g(-1) and 0.067 g.g(-1) at the experimental conditions.

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.

Replacement of methane from quartz sand-bearing hydrate with carbon dioxide-in-water emulsion

The replacement of CH4 from its hydrate in quartz sand with 90:10, 70:30, and 50:50 (W-CO2:W-H2O) carbon dioxide-in-water (C/W) emulsions and liquid CO2 has been performed in a cell with size of empty set 36 x 200 mm. The above emulsions were formed in a new emulsifier, in which the temperature and pressure were 285.2 K and 30 MPa, respectively, and the emulsions were stable for 7-12 h. The results of replacing showed that 13.1-27.1%, 14.1-25.5%, and 14.6-24.3% of CH4 had been displaced from its hydrate with the above emulsions after 24-96 It of replacement, corresponding to about 1.5 times the CH4 replaced with high-pressure liquid CO2. The results also showed that the replacement rate of CH4 with the above emulsions and liquid CO2 decreased from 0.543, 0.587, 0.608, and 0.348 1/h to 0.083, 0.077, 0.069, and 0.063 1/h with the replacement time increased from 24 to 96 h. It has been indicated by this study that the use of CO2 emulsions is advantageous compared to the use of liquid CO2 in replacing CH4 from its hydrate.

Use of electrical resistance to detect the formation and decomposition of methane hydrate

The changes of electrical resistance (R) were studied experimentally in the process of CH4 hydrate formation and decomposition, using temperature and pressure as the auxiliary detecting methods simultaneously. The experiment results show that R increases with hydrate formation and decreases with hydrate decompositon. R is more sensitive to hydrate formation and decompositon than temperature or pressure, which indicates that the detection of R will be an effective means for detecting natural gas hydrate (NGH) quantitatively.

Feasibility of Protein a for the Oriented Immobilization of Immunoglobulin on Silicon Surface for a Biosensor with Imaging Ellipsometry

The feasibility of using protein A to immobilize antibody on silicon surface for a biosensor with imaging ellipsometry was presented in this study. The amount of human IgG bound with anti-IgG immobilized by the protein A on silicon surface was much more than that bound with anti-IgG immobilized by physical adsorption. The result indicated that the protein A could be used to immobilize antibody molecules in a highly oriented manner and maintain antibody molecular functional configuration on the silicon surface. High reproducibility of the amount of antibody immobilization and homogenous antibody adsorption layer on surfaces could be obtained by this immobilization method. Imaging ellipsometry has been proven to be a fast and reliable detection method and sensitive enough to detect small changes in a molecular monolayer level. The combination of imaging ellipsometry and surface modification with protein A has the potential to be further developed into an efficient immunoassay protein chip.

Quantifying Cell Binding Kinetics Mediated By Surface-Bound Blood Type B Antigen To Immobilized Antibodies

Cell adhesion is crucial to many biological processes, such as inflammatory responses, tumor metastasis and thrombosis formation. Recently a commercial surface plasmon resonance (SPR)-based BIAcore biosensor has been extended to determine cell binding mediated by surface-bound biomolecular interactions. How such cell binding is quantitatively governed by kinetic rates and regulating factors, however, has been poorly understood. Here we developed a novel assay to determine the binding kinetics of surface-bound biomolecular interactions using a commercial BIAcore 3000 biosensor. Human red blood cells (RBCs) presenting blood group B antigen and CM5 chip bearing immobilized anti-B monoclonal antibody (mAb) were used to obtain the time courses of response unit, or sensorgrams, when flowing RBCs over the chip surface. A cellular kinetic model was proposed to correlate the sensorgrams with kinetic rates. Impacts of regulating factors, such as cell concentration, flow duration and rate, antibody-presenting level, as well as pH value and osmotic pressure of suspending medium were tested systematically, which imparted the confidence that the approach can be applied to kinetic measurements of cell adhesion mediated by surface-bound biomolecular interactions. These results provided a new insight into quantifying cell binding using a commercial SPR-based BIAcore biosensor.

Measuring Binding Kinetics Of Surface-Bound Molecules Using The Surface Plasmon Resonance Technique

Surface plasmon resonance (SPR) technology and the Biacore biosensor have been widely used to measure the kinetics of biomolecular interactions in the fluid phase. In the past decade, the assay was further extended to measure reaction kinetics when two counterpart molecules are anchored on apposed surfaces. However, the cell binding kinetics has not been well quantified. Here we report development of a cellular kinetic model, combined with experimental procedures for cell binding kinetic measurements, to predict kinetic rates per cell. Human red blood cells coated with bovine serum albumin and anti-BSA monoclonal antibodies (mAbs) immobilized on the chip were used to conduct the measurements. Sensor-grams for BSA-coated RBC binding onto and debinding from the anti-BSA mAb-immobilized chip were obtained using a commercial Biacore 3000 biosensor, and analyzed with the cellular kinetic model developed. Not only did the model fit the data well, but it also predicted cellular on and off-rates as well as binding affinities from curve fitting. The dependence of flow duration, flow rate, and site density of BSA on binding kinetics was tested systematically, which further validated the feasibility and reliability of the new approach. Crown copyright (c) 2008 Published by Elsevier Inc. All rights reserved.

Influence Of Different Amount Of Au On The Wetting Behavior Of Pdms Membrane

Polydimethylsiloxane (PDMS) has been widely used as a base material for bio-MEMS/NEMS devices. It is difficult for PDMS to transfer and spread aqueous solution as a kind of highly hydrophobic material. Therefore, surface modification is necessary for PDMS to make it hydrophilic. In this paper, a method of hydrophilization of PDMS surface is proposed. Gold is sputtered to the PDMS substrate by sputter coater in different average thicknesses. Relationship between the average thickness of gold on the PDMS substrate and the contact angle of the surface was studied. It was found that even gold of average thickness less than 1 nm can result in about 25 degrees change of contact angle. AFM is also used to get topographic information of PDMS surface coated with gold. Three cases are classified with different amount of Au: (1) Heterogeneous zone; (2) Transition zone; (3) Film zone. For heterogeneous zone, a simple model about heterogeneous phase wetting is put forward to interpret this phenomenon.

Simulation of Natural Gas Production in Hydrate Reservoirs

This paper simulates a one-dimensional physical model of natural gas production from hydrate dissociation in a reservoir by depressurization. According to the principles of solid hydrate decomposition in stratum and flow of natural gas in porous medium, the pressure governing equations for both gas zone and hydrate zone are set up based on the physical production model. Using the approximation reported by N. N. Verigin et al. (1980), the nonlinear governing equations are simplified and the self-similar solutions are obtained. Through calculation, for different reservoir parameters, the distribution characters of pressure are analyzed. The decline trend of natural gas production rate with time is also studied. The simulation results show that production of natural gas from a hydrate reservoir is very sensitive to several reservoir parameters, such as wellbore pressure and stratum porosity and permeability.

Study on the Mechanical Properties of the Tetrahydrofuran Hydrate Deposit

Pure tetrahydrofuran hydrate and tetrahydrofuran hydrate deposits with different materials as the skeleton are synthesized in our laboratory. A series of experiments are carried out to study the mechanical properties. The stress-strain curve, strength of pure tetrahydrofuran hydrate and hydrate deposit are obtained. Some phenomenon is explained.

Surface-Bound Selectin-Ligand Binding Is Regulated By Carrier Diffusion

Two-dimensional (2D) kinetics of receptor-ligand interactions governs cell adhesion in many biological processes. While the dissociation kinetics of receptor-ligand bond is extensively investigated, the association kinetics has much less been quantified. Recently receptor-ligand interactions between two surfaces were investigated using a thermal fluctuation assay upon biomembrane force probe technique (Chen et al. in Biophys J 94:694-701, 2008). The regulating factors on association kinetics, however, are not well characterized. Here we developed an alternative thermal fluctuation assay using optical trap technique, which enables to visualize consecutive binding-unbinding transition and to quantify the impact of microbead diffusion on receptor-ligand binding. Three selectin constructs (sLs, sPs, and PLE) and their ligand P-selectin glycoprotein ligand 1 were used to conduct the measurements. It was indicated that bond formation was reduced by enhancing the diffusivity of selectin-coupled carrier, suggesting that carrier diffusion is crucial to determine receptor-ligand binding. It was also found that 2D forward rate predicted upon first-order kinetics was in the order of sPs > sLs > PLE and bond formation was history-dependent. These results further the understandings in regulating association kinetics of surface-bound receptor-ligand interactions.

The Experimental and Numerical Studies on Gas Production from Hydrate Reservoir by Depressurization

A set of experimental system to study hydrate dissociation in porous media is built and some experiments on hydrate dissociation by depressurization are carried out. A mathematical model is developed to simulate the hydrate dissociation by depressurization in hydrate-bearing porous media. The model can be used to analyze the effects of the flow of multiphase fluids, the kinetic process and endothermic process of hydrate dissociation, ice-water phase equilibrium, the variation of permeability, convection and conduction on the hydrate dissociation, and gas and water productions. The numerical results agree well with the experimental results, which validate our mathematical model. For a 3-D hydrate reservoir of Class 3, the evolutions of pressure, temperature, and saturations are elucidated and the effects of some main parameters on gas and water rates are analyzed. Numerical results show that gas can be produced effectively from hydrate reservoir in the first stage of depressurization. Then, methods such as thermal stimulation or inhibitor injection should be considered due to the energy deficiency of formation energy. The numerical results for 3-D hydrate reservoir of Class 1 show that the overlying gas hydrate zone can apparently enhance gas rate and prolong life span of gas reservoir.