Effects of acid-rock reaction on physical properties during CO_(2)-rich industrial waste gas(CO_(2)-rich IWG)injection in shale reservoirs

"Carbon peaking and carbon neutrality"is an essential national strategy,and the geological storage and utilization of CO_(2)is a hot issue today.However,due to the scarcity of pure CO_(2)gas sources in China and the high cost of CO_(2)capture,CO_(2)-rich industrial waste gas(CO_(2)-rich IWG)is gradually emerging into the public's gaze.CO_(2)has good adsorption properties on shale surfaces,but acidic gases can react with shale,so the mechanism of the CO_(2)-rich IWG-water-shale reaction and the change in reservoir properties will determine the stability of geological storage.Therefore,based on the mineral composition of the Longmaxi Formation shale,this study constructs a thermodynamic equilibrium model of water-rock reactions and simulates the regularity of reactions between CO_(2)-rich IWG and shale minerals.The results indicate that CO_(2)consumed 12%after reaction,and impurity gases in the CO_(2)-rich IWG can be dissolved entirely,thus demonstrating the feasibility of treating IWG through water-rock reactions.Since IWG inhibits the dissolution of CO_(2),the optimal composition of CO_(2)-rich IWG is 95%CO_(2)and 5%IWG when CO_(2)geological storage is the main goal.In contrast,when the main goal is the geological storage of total CO_(2)-rich IWG or impurity gas,the optimal CO_(2)-rich IWG composition is 50%CO_(2)and 50%IWG.In the CO_(2)-rich IWG-water-shale reaction,temperature has less influence on the water-rock reaction,while pressure is the most important parameter.SO2 has the greatest impact on water-rock reaction in gas.For minerals,clay minerals such as illite and montmorillonite had a significant effect on water-rock reaction.The overall reaction is dominated by precipitation and the volume of the rock skeleton has increased by 0.74 cm3,resulting in a decrease in shale porosity,which enhances the stability of CO_(2)geological storage to some extent.During the reaction between CO_(2)-rich IWG-water-shale at simulated temperatures and pressures,precipitation is the main reaction,and shale porosity decreases.However,as the reservoir water content increases,the reaction will first dissolve and then precipitate before dissolving again.When the water content is less than 0.0005 kg or greater than 0.4 kg,it will lead to an increase in reservoir porosity,which ultimately reduces the long-term geological storage stability of CO_(2)-rich IWG.

Study on Technology Clusters for Direct Utilization of CO2-Rich Natural Gas and Construction of Hybrid System for Energy and Chemicals Production

Based on industrial production with an annual capacity of million tons of methanol,ammonia/urea,etc.,a platform technology is developed for direct,green,efficient,and high-value mega-size utilization of the CO2-rich nature gas,which is the technology of CO2-rich natural gas dry reforming and hydrogen reaction.The following technologies are discussed,such as CO2-rich natural gas dry reforming integrated with the Fischer-Tropsch synthesis to olefins(FTO)technology for producing high value-added linear alpha olefins(LAO);CO2-rich natural gas dry reforming integrated with low carbon olefin linear hydroformylation technology to produce higher carbon alcohols;direct methanol production from CO2 and hydrogen;and the new cutting edge technology of photo-catalytic process.In addition,simple techno-economic evaluations of two technologies mentioned above are discussed.The CO2-rich natural gas dry reforming integrated with FTO technology can achieve about 30%of internal rate return(IRR),while the low carbon olefin linear hydroformylation technology could have a static payback period of 2.57 years when the capacity of 2-propylhexanol(2-PH)reaches 100 kt/a.Based on the mega-size green and high-efficient CO2-rich natural gas direct utilization technology,a hybrid energy and chemical production system framework with good prospects is preliminarily designed.A modern industry zone with an annual capacity of more than 10 Mt of CO2 converted to high value-added products is underway.

Zinc Oxide Nanostructure Thick Films as H₂S Gas Sensors at Room Temperature

The ZnO nanostructures have been synthesized and studied as the sensing element for the detection of H2S. The ZnO nanostructures were synthesized by hydrothermal method followed by sonication for different interval of time i.e. 30, 60, 90 and 120 min. By using screen printing method, thick films of synthesized ZnO nanostructure were deposited on glass substrate. Gas sensing properties of ZnO nanostructure thick films were studied for low concentration H2S gas at room temperature. The effects of morphology of synthesized ZnO nanostructure on gas sensing properties were studied and discussed. ZnO nanostructure synthesized by this method can be used as a promising material for semiconductor gas sensor to detect poisonous gas like H2S at room temperature with high sensitivity and selectivity.

The Effect of Pressure on the Dissociation of H_2/CH_4Gas Mixture during Diamond Films Growth via Chemical Vapor Deposition

Monte Carlo simulations are adopted to study the electron motion in the mixture of H2 and CH4 during diamond synthesis via Glow Plasma-assisted Chemical Vapor Deposition (GPCVD). The non-uniform electric field is used and the avalanche of electrons is taken into account in this simulation. The average energy distribution of electrons and the space distribution of effective species such as CH3, CH+3, CH+ and H at various gas pressures are given in this paper, and optimum experimental conditions are inferred from these results.

Solubility and mass transfer of H2, CH4, and their mixtures in vacuum gas oil: An experimental and modeling study

In this work,the solubility data and liquid-phase mass transfer coefficients of hydrogen(H2),methane(CH4)and their mixtures in vacuum gas oil(VGO)at temperatures(353.15-453.15 K)and pressures(1-7 MPa)were measured,which are necessary for catalytic cracking process simulation and design.The solubility of H2 and CH4 in VGO increases with the increase of pressure,but decreases with the increase of temperature.Henry’s constants of H2 and CH4 follow the relation of In H=-413.05/T+5.27 and In H=-990.67/T+5.87,respectively.The molar fractions of H2 and system pressures at different equilibrium time were measured to estimate the liquid-phase mass transfer coefficients.The results showed that with the increase of pressure,the liquid-phase mass transfer coefficients increase.Furthermore,the solubility of H2 and CH4 in VGO was predicted by the predictive COSMO-RS model,and the predicted values agree well with experimental data.In addition,the gas-liquid equilibrium(GLE)for H2+CH4+VGO system at different feeding gas ratios in volume fraction(i.e.,H285%+CH415%and H290%+CH410%)was measured.The selectivity of H2 to CH4 predicted by the COSMO-RS model agrees well with experimental data.This work provides the basic thermodynamic and dynamic data for fuel oil catalytic cracking processes.

H_2S Gas Sensor Based on Nanocrystalline ZnO Synthesized by Electrochemical-Deposition

ZnO nanocrystals were prepared by a direct current electrochemical deposition process under 3.0V working voltage and 30A/m^2 current density using zinc sulfate as raw materials.The nanocrystals were characterized by X-ray diffraction (XRD)and transmission electron microscopy(TEM).The results indicated that the nanocrystals are hexagonal wurtzite ZnO with particle size range of 25nm～40nm without any treating.Gas sensing properties of the sensors were tested by mixing a gas in air at static state;the tested results showed that the sensors based on nanocrystalline ZnO had satisfied gas sensing properties to H_2S gas at rather low temperature.

A Thermoelectric Transducer Based on Bismuth Telluride Thin Films for H_2 Gas Sensing

We have developed a novel thermoelectric gas sensors based on bismuth telluride thin films.These sensors were employed for sensing different concentrations of H_2 gas.Radio frequency (R.F.) magnetron sputtering was employed to deposit the bismuth telluride (Bi_2Te_3) thin films.The morphology of such thin films was investigated and responses of the thermoelectric devices to H_2 were studied.

Experimental study on SO_2 recovery using a sodium-zinc sorbent based flue gas desulfurization technology

A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste products of calcium-based semi-dry and zinc-based flue gas desulfurization(Ca–SD-FGD and Zn–SD-FGD) technologies, respectively. It was found that Zn SO3·2.5H2 O first lost crystal H2 O at 100 °C and then decomposed into SO2 and solid Zn O at 260 °C in the air, while Ca SO3 is oxidized at 450 °C before it decomposed in the air. The experimental results confirm that Zn–SD-FGD technology is good for SO2 removal and recycling, but with problem in clogging and high operational cost. The proposed Na–Zn-FGD is clogging proof, and more cost-effective. In the new process, Na2CO3 is used to generate Na2SO3 for SO2absorption, and the intermediate product Na HSO3 reacts with Zn O powders, producing Zn SO3·2.5H2 O precipitate and Na2SO3 solution. The Na2SO3 solution is clogging proof, which is re-used for SO2 absorption. By thermal decomposition of Zn SO3·2.5H2 O, Zn O is re-generated and SO2 with high purity is co-produced as well. The cycle consumes some amount of raw material Na2CO3 and a small amount of Zn O only. The newly proposed FGD technology could be a substitute of the traditional semi-dry FGD technologies.

Structural Characterization of Nanocrystalline La_1-xSr_xCrO₃Thick Films for H₂S Gas Sensors

The nanocrystalline of La1-xSrxCrO3 (x = 0.0, 0.1, 0.2, 0.3 & 0.4) were prepared by sol-gel method and their crystal structures & morphology were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). XRD patterns indicate that the average particle size of the nanocrystalline La0.7Sr0.3CrO3in the range of 30 - 35 nm. The gas sensing properties were studied towards reducing gases like Ammonia gas (NH3), liquefied petroleum gas (LPG), hydrogen sulphide (H2S) and H2 gas and it is observed that undoped LaCrO3 shows response to H2S gas at relatively high operating temperature 300°C. The La1-xSrxCrO3 based sensor with x = 0.3 shows better sensitivity towards H2S gas at an operating temperature 210°C. The effect of Sr doping on sensitivity, response time and recovery time of the sensor in the presence of H2S and other reducing gases were studied and discussed.

Simulation of CO₂and H₂S Removal Using Methanol in Hollow Fiber Membrane Gas Absorber (HFMGA)

Application of methanol solvent for physical absorption of CO2 and H2S from CO2/H2S/CH4 mixture in gas–liquid hollow fiber membrane gas absorber (HFMGA) was investigated. A computational mass transfer (CMT) model for simulation of HFMGA in the case of simultaneous separation of CO2 and H2S was developed. The membrane gas absorber model explicitly calculates for the rates of mass transfer through the membrane and components concentration profiles. Due to the lack of experimental data in the literature, the model was validated using available individual components’ water absorption data. The numerical predictions were in good agreement with the experimental data. The effects of operating conditions such as liquid velocity, gas velocity, temperature and pressure were analyzed. It is shown that methanol solvent can successfully be used for CO2 and H2S removal in membrane gas absorber. Also it is found that the concentration distribution of CO2 and H2S in the gas phase along the fiber length obeys plug flow model whereas in the methanol absorbent deeply affected by the interface concentration, absorbent velocity and diffusivity. In addition, it is shown that application of membrane gas absorber using methanol absorbents for H2S removal and at higher flow rate is more efficient. Moreover, at operating pressures above 10 atm even at low absorbent rate, H2S concentration depletion is relatively complete while at 1 atm this value is about 30%. This means that removal efficiency decreases with an increase in temperature and it is more important especially for H2S.

Distribution and treatment of harmful gas from heavy oil production in the Liaohe Oilfield, Northeast China

The distribution and treatment of harmful gas （H2S） in the Liaohe Oilfield, Northeast China, were investigated in this study. It was found that abundant toxic gas （H2S） is generated in thermal recovery of heavy oil. The H2S gas is mainly formed during thermochemical sulfate reduction （TSR） occurring in oil reservoirs or the thermal decomposition of sulfocompounds （TDS） in crude oil. H2S generation is controlled by thermal recovery time, temperature and the injected chemical compounds. The quantity of SO4^2- in the injected compounds is the most influencing factor for the rate of TSR reaction. Therefore, for prevention of H2S formation, periodic and effective monitoring should be undertaken and adequate H2S absorbent should also be provided during thermal recovery of heavy oil. The result suggests that great efforts should be made to reduce the SO4^2- source in heavy oil recovery, so as to restrain H2S generation in reservoirs. In situ burning or desulfurizer adsorption are suggested to reduce H2S levels. Prediction and prevention of H2S are important in heavy oil production. This will minimize environmental and human health risks, as well as equipment corrosion.

Hydrate-based carbon dioxide capture from simulated integrated gasification combined cycle gas

The equilibrium hydrate formation conditions for CO2/H2 gas mixtures with different CO2 concentrations in 0.29 mol% TBAB aqueous solution are firstly measured.The results illustrate that the equilibrium hydrate formation pressure increases remarkably with the decrease of CO2 concentration in the gas mixture.Based on the phase equilibrium data,a three stages hydrate CO2 separation from integrated gasification combined cycle （IGCC） synthesis gas is investigated.Because the separation efficiency is quite low for the third hydrate separation,a hybrid CO2 separation process of two hydrate stages in conjunction with one chemical absorption process （absorption with MEA） is proposed and studied.The experimental results show H2 concentration in the final residual gas released from the three stages hydrate CO2 separation process was approximately 95.0 mol% while that released from the hybrid CO2 separation process was approximately 99.4 mol%.Thus,the hybrid process is possible to be a promising technology for the industrial application in the future.

H_2S Sensing Characteristics of Thin Film SnO_2 Sensor with N_2 Treatment

<正>SnO_2 thin film sensors were fabricated by a thermal evaporation method.The sensors were heated for thermal oxidation.For high porosity,SnO_2 thin film sensors were treated in a N_2 atmosphere.The sensors that were treated with O_2 after being treated with N_2 showed 70 % sensitivity for 1×10~ -6) of H_2S,which is higher than the sensors that were only treated with O_2.The Ni metal,as a catalyst,was evaporated on the thin film Sn on the Al_2O_3 substrate.The sensor was heated to grow the Sn nanowire in a tube furnace with N_2 flow.Sn nanowire was heated for oxidation.The sensitivity of SnO_2 nanowire sensor was measured for 500×10~ -9) of H_2S.The selectivity of the SnO_2 nanowire sensor was compared with the thin film and the thick film SnO_2.Each sensor was measured for H_2S,CO,and NH_3 in this study.

Geochemical characteristics of ultra-deep natural gas in the Sichuan Basin, SW China

The natural gas components and geochemistry of 38 ultra-deep gas wells(burial depth greater than 6 000 m) in the Sichuan Basin were analyzed to determine the genesis of ultra-deep natural gas in the basin. The ultra-deep natural gas components of the basin have the following characteristics: Methane has an absolute advantage, which can be up to 99.56% with an average of 86.6%; ethane is low, with an average of 0.13%; there is nearly no propane and butane. So it is dry gas at over-mature thermal stage. The content of H2 S can be up to 25.21%, with an average of 5.45%. The alkane gas isotopes are: the carbon isotope varies from-32.3‰ to-26.7‰ for methane and from-32.9‰ to-22.1‰ for ethane. There is nearly no carbon isotopic reversal among methane and its homologues. Hydrogen isotope varies from-156‰ to-114‰ for methane, and from-103‰ to-89‰ for some ethane. The carbon isotope of CO_2 varies from-17.2‰ to 1.9‰ and most of them fall within the range of 0±3‰. According to the δ^(13)C_1-δ^(13)C_2-δ^(13)C_3 plot, except some wells, all other ultra-deep gas wells are dominated by coal-derived gas. Based on the CO_2 origin distinguishing plot and δ^(13)C_(CO_2), except some individual wells, most of the ultra-deep CO_2 are of carbonate metamorphic origin. H2 S in the ultra-deep layer of Longgang and Yuanba gas fields belongs to thermochemical sulfate reduction(TSR), while H2 S from Well Shuangtan belongs to thermal decomposition of sulfides(TDS).

Hydrogen and Ozone SAW Based Gas Sensors with RF Magnetron Sputtered InO_x and Electron Beam Evaporated SiN_y

Layered Surface Acoustic Wave (SAW) devices with an InO_x/SiN_u/36°YX LiTaO_3 structure were investigated for sensing low concentrations of hydrogen (H_2) and ozone (O_3) at different operating temperatures.The sensor consists of a 1μm thick silicon nitride (SiN_y) intermediate layer deposited by electron beam evaporation on a 36°Y-cut X-propagating piezoelectric lithium tantalate (LiTaO_3) substrate and a 100 nm thin indium oxide (InO_x) sensing layer deposited by R.F.magnetron sputtering.The device fabrication is described and the performance of the sensor is analyzed in terms of response magnitude as a function of operating temperature.Large frequency shifts of 360 kHz for 600μg/g of H_2 and 92 kHz for 40 ng/g O_3 were recorded.In addition,the surface morphology of the deposited films were investigated by Atomic Force Microscopy (AFM) and the chemical composition by X-Ray Photoelectron Spectroscopy (XPS) to correlate gas-sensing behavior to structural characteristics of the thin film.

Low temperature H_2S sensor based on copper oxide/tin dioxide thick film

Nanostructured tin dioxide （SnO2） powders were prepared by a sol-gel dialytic process and and the doping of CuO on it was completed by a deposition-precipitation method.The thick film sensors were fabricated from the CuO/SnO2 polycrystalline powders.Sensing behavior of the sensor was investigated with various gases including CO,H2,NH3,hexane,acetone,ethanol,methanol and H2S in air.The as-synthesized gas sensor had much better response to H2S than to other gases.At the same time,the CuO/SnO2 sensor had enough sensitivity,together with fast response and recovery,to distinguish H2S from those gases at 160 and 210 ℃.Therefore,it might have promising applications in the future.

Effect of Plastic Deformation and H_2S on Dynamic Fracture Toughness of High Strength Casing Steel

The effects of plastic deformation and H2 S on fracture toughness of high strength casing steel（C110 steel） were investigated. The studied casing specimens are as follows： original casing, plastic deformation（PD） casing and PD casing after being immersed in NACE A solution saturated with H2S（PD＋H2S）. Instrumented impact method was employed to evaluate the impact behaviors of the specimens, meanwhile, dynamic fracture toughness（JId） was calculated by using Rice model and Schindler model. The experimental results show that dynamic fracture toughness of the casing decreases after plastic deformation. Compared with that of the original casing and PD casing, the dynamic fracture toughness decreases further when the PD casing immersed in H2 S, moreover, there are ridge-shaped feature and many secondary cracks present on the fracture surface of the specimens. Impact fracture mechanism of the casing is proposed as follows： the plastic deformation results in the increase of defect density of materials where the atomic hydrogen can accumulate in reversible or irreversible traps and even recombine to form molecular hydrogen, subsequently, the casing material toughness decreases greatly.

Model for Reduction of Iron Oxide Pellet with a C-O-H-N Gas Mixture Considering Water Gas Shift Equilibrium in the Gas While It Diffuses through the Product Layer

In metallurgical processes, more and more usage of hydrocarbons is encouraged to bring down the carbon emissions. In this regard, numerous investigations on reduction of oxides by C-O-H-N gas mixture have been reported. Attempts to simulate these reduction processes using shrinking core model, one of the common models used for such studies, have under predicted the reduction rates. This may be owing to the fact that the homogeneous reaction in the gas phase is not being considered. If the reaction temperatures are above 1,000 K, generally so for many reduction processes, the homogeneous gas reaction rates are expected to be high enough that local equilibrium in the gas phase can be assumed. In the present study, reduction of wustite in a C-O-H-N gas mixture has been modeled using shrinking core model considering the water gas shift equilibrium in the gas while it diffuses through the product layer.

Long-Term H2O and CO2 Trends in Conifer Disc Tree Rings and Meteorological Parameters

Results of investigations into the CO2 content in tree disc rings by the method proposed here have shown that a considerable part of CO2 generated under cell respiration is found in tree stems. Besides, annual CO2 distribution in tree rings exhibits a well-defined cyclicity. Results obtained from investigations into long-term CO2 and H2O variations in tree discs performed by different methods are presented. Wavelet and spectral analyses of the relationship between CO2 and H2O variations in a Siberian stone pine disc and meteorological parameters were made. The CO2 annual distributions of seven spruce tree discs were examined by the Caterpiller-SSA method. Wood samples of Siberian stone pine and spruce trees were taken from the same site in Tomsk region （Siberia, Russia） that characterized by an optimum growth habitat. Conclusions are made regarding the response of the annual CO2 and H2O conifer disc tree ring distributions to different climatic factors.

Role of CuO-ZnO Heterojunctions in Gas Sensing Response of CuO-ZnO Thick Films

The CuO-doped ZnO thick films were prepared by the screen printing technique. The CuO doped ZnO composite materials were obtained by mixing AR grade （99.9% pure） Zinc Oxide powder mechanochemically in acetone medium with various weight percentages of Copper Chloride （CulCI2.2H20） powder （1, 3, 5, 7 and 9wt.%）. The prepared materials were sintered at 1,000 ℃ for 12 h in air ambience and ball milled to ensure sufficiently fine particle size. The films were characterized by different techniques with respect to their surface morphology and compositional property by means of SEM （scanning electron microscope） and EDXA （energy dispersive x-ray analysis）. The surface morphology of the films was studied by SEM and it shows the films are porous in nature and petal-shaped grains of sizes varies from 220 nm to 250 nm were observed. The final composition of each film was determined by the EDXA analysis. The gas response of undoped ZnO and CuO doped ZnO films was studied for different gases such as CO, C12, NH3, Ethanol, H2S and LPG at operating temperature ranging from 50 ℃ to 400 ℃. The 7wt.% CuO-doped ZnO film shows good response to H2S gas （100 ppm） at 250 ℃.