Carbon dioxide partial pressure and its diffusion flux in karst surface aquatic ecosystems:a review

Carbon dioxide(CO_(2))emissions from aquatic ecosystems are an important component of the karst carbon cycle process and also a key indicator for assessing the effect of karst carbon sinks.This paper reviewed the CO_(2)partial pressure(pCO_(2))and its diffusion flux(FCO_(2))in karst surface aquatic ecosystems,mainly rivers,lakes,and reservoirs,and their influencing factors summarized the methods for monitoring CO_(2)emissions in karst aquatic ecosystems and discussed their adaptation conditions in karst areas.The pCO_(2)and FCO_(2)decreased in the order of rivers>reservoirs>lakes,and the values in karst lakes were eventually significantly lower than those in global lakes.The pCO_(2)and FCO_(2)of karst aquatic ecosystems had patterns of variation with diurnal,seasonal,water depth and hydrological cycles,and spatial and temporal hetero-geneity.The sources of CO_(2)in karst waters are influenced by both internal and external sources,and the key spatial and temporal factors affecting the CO_(2)emissions from karst rivers,lakes,and reservoirs were determined in terms of physicochemical indicators,biological factors,and bio-genic elements;additionally,the process of human activity interference on CO_(2)emissions was discussed.Finally,a conceptual model illustrating the impacts of urban devel-opment,agriculture,mining,and dam construction on the CO_(2)emissions at the karst surface aquatic ecosystem is presented.Meanwhile,based on the disadvantages existing in current research,we proposed several important research fields related to CO_(2)emissions from karst surface aquatic ecosystems.

Kinetics and rate-limiting mechanisms of dolomite dissolution at various CO_2 partial pressures

Techniques of rotating-disk and catalyst were used in investigating the kinetics of dolomite dissolution in flowing CO2-H2O system. Experiments run in the solutions equilibrated with various CO2 partial pressures (PCO2) from 30 to 100000 Pa. It shows that dissolution rates ofdolomite are related with rotating speeds at conditions far from equilibrium. This was explained by modified diffusion boundary layer (DBL) model. In addition, the dissolution rates increase after addition of carbonic anhydrase (CA) to solutions, where the CA catalyzes CO2 conversion. However, great differences occur among various CO2 partial pressures. The experimental observations give a conclusion that the modified DBL model enables one to predict dissolution rates and their behaviour at various PCO2 with satisfactory precision at least far from equilibrium.

Effect of CO_2 partial pressure on SCC behavior of welded X80 pipeline in simulated soil solution

The stress corrosion cracking （SCC） behavior of welded X80 pipeline steel in simulated Ku＇erle soil solution was studied by means of electrochemical impedance spectroscopy （EIS） and slow strain rate tests （SSRT）. The microstructure of the welded steel was observed by optical microscopy （OM）. It is demonstrated that the microstructure of the weld metal consists of acicular ferrite and grain boundary ferrite, while that of heat affected zone （HAZ） is a mixture of acicular ferrite and bainitic ferrite micro- constituents. The microstructure of the base steel is composed of ferrite and pearlite. The anodic dissolution of X80 pipeline steel in simulated Ku＇erle soil solution could be enhanced and the SCC sensitivity increased with the increase of CO2 partial pressure. The SCC mechanism of X80 pipeline is a mixing mechanism of hydrogen embrittlement combined with anodic dissolution, and the hydrogen embrittlement plays a leading role. The higher SCC sensitivity of the weld metal was attributed to the metallurgical transformation, local hardening and residual stress.

Effect of N_(2) partial pressure on comprehensive properties of antibacterial TiN/Cu nanocomposite coating

Foreign body reactions to the wear debris and corrosion products from the implants,and bacterial infections are the main factors leading to the implant failures.In order to resolve these problems,the antibacterial TiN/Cu nanocomposite coatings with various N_(2) partial pressures were deposited on 304 stainless steels(SS)using an arc ion plating(AIP)system,named TiN/Cu-x(x=0.5,1.0,1.5 Pa).The results of X-ray diffraction analysis,energy-dispersive X-ray spectroscopy,and scanning electron microscopy showed that the N_(2) partial pressures determined the Cu contents,surface defects,and crystallite sizes of TiN/Cu nanocomposite coatings,which further influenced the comprehensive abilities.And the hardness and wear resistances of TiN/Cu coatings were enhanced with increase of the crystallite sizes.Under the co-actions of surface defects,crystallite sizes,and Cu content,TiN/Cu-1.0 and TiN/Cu-1.5 coatings possessed excellent corrosion resistance.Besides,the biological tests proved that all the TiN/Cu coatings showed no cytotoxicity with strong antibacterial ability.Among them,TiN/Cu-1.5 coating significantly promoted the cell proliferation,which is expected to be a novel antibacterial,corrosion-resistant,and wear-resistant coating on the surfaces of medical implants.

In-situ coating and surface partial protonation co-promoting performance of single-crystal nickel-rich cathode in all-solid-state batteries

The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.

Analysis of pressure response at an observation well against pressure build-up by early stage of CO_(2)geological storage project

To ensure a safe and stable CO_(2)storage,pressure responses at an observation well are expected to be an important and useful field monitoring item to estimate the CO_(2)storage behaviors and the aquifer parameters during and after injecting CO_(2),because it can detect whether the injected CO_(2)leaks to the ground surface or the bottom of the sea.In this study,pressure responses were simulated to present design factors such as well location and pressure transmitter of the observation well.Numerical simulations on the pressure response and the time-delay from pressure build-up after CO_(2)injection were conducted by considering aquifer parameters and distance from the CO_(2)injection well to an observation well.The measurement resolution of a pressure transmitter installed in the observation well was presented based on numerical simulation results of the pressure response against pressure build-up at the injection well and CO_(2)plume front propagations.Furthermore,the pressure response at an observation well was estimated by comparing the numerical simulation results with the curve of CO_(2)saturation and relative permeability.It was also suggested that the analytical solution can be used for the analysis of the pressure response tendency using pressure build-up and dimensionless parameters of hydraulic diffusivity.Thus,a criterion was established for selecting a pressure transducer installed at an observation well to monitor the pressure responses with sufficient accuracy and resolution,considering the distance from the injection well and the pressure build-up at the injection well,for future carbon capture and storage(CCS)projects.

Analysis of impact pressure,rock-breaking effect,and ground vibration induced by the disposable CO_(2)fracturing tube

The technology of expansion fracturing with liquid CO_(2)(EFLCO_(2))has attracted increasing attention due to reduced vibration and damage.The disposable fracturing tube has been developed and is gradually replacing the Cardox tube.However,there is a lack of impact pressure testing of disposable tubes under real working conditions,selection of gas explosion design parameters,and systematic analysis of blasting vibration.This limitation has constrained the widespread application of disposable fracturing tubes in engineering.A joint monitoring of the pressure-time curves in the disposable tubes and boreholes was conducted.The rock-breaking effect of varying hole spacing parameters in the EFLCO_(2)design was analyzed,and a systematic study was carried out on the vibration peak value,frequency,and energy characteristics.The results show that(1)the pressure distribution characteristics,stress peak value,and duration in the disposable tubes are different from those of Cardox tubes,which show multi-peak distribution,low-pressure peak value,and short duration.The correlation between the pressure in the disposable tube,filling pressure,and liquid CO_(2)weight is established,and a theoretical calculation method for the borehole wall pressure is proposed;(2)The hole spacing in rocks of different hardness is suggested;and(3)At the same scale distance,the peak particle velocity(PPV)caused by EFLCO_(2)(PPVCO_(2))is significantly smaller than that caused by blasting(PPVexplosive).The ratio of PPVexplosive to PPVCO_(2)is a power function related to scale distance,and a distance-related zonality exist in this relationship.The frequency composition of the vibration signal caused by EFLCO_(2)is relatively simple with a narrow frequency band.Its PPV and energy are mainly concentrated in the low-frequency band.This research contributes to the optimization of disposable fracturing tubes,gas explosion design,and vibration hazard control.

Improved combustion stability of biogas at different CO_(2) concentrations using inhomogeneous partially premixed stratified flames

Biogas is a renewable and clean energy source that plays an important role in the current environment of lowcarbon transition.If high-content CO_(2) in biogas can be separated,transformed,and utilized,it not only realizes high-value utilization of biogas but also promotes carbon reduction in the biogas field.To improve the combustion stability of biogas,an inhomogeneous,partially premixed stratified(IPPS)combustion model was adopted in this study.The thermal flame structure and stability were investigated for a wide range of mixture inhomogeneities,turbulence levels,CO_(2) concentrations,air-to-fuel velocity ratios,and combustion energies in a concentric flow slot burner(CFSB).A fine-wire thermocouple is used to resolve the thermal flame structure.The flame size was reduced by increasing the CO_(2) concentration and the flames became lighter blue.The flame temperature also decreased with increase in CO_(2) concentration.Flame stability was reduced by increasing the CO_(2) concentration.However,at a certain level of mixture inhomogeneity,the concentration of CO_(2) in the IPPS mode did not affect the stability.Accordingly,the IPPS mode of combustion should be suitable for the combustion and stabilization of biogas.This should support the design of highly stabilized biogas turbulent flames independent of CO_(2) concentration.The data show that the lower stability conditions are partially due to the change in fuel combustion energy,which is characterized by the Wobbe index(WI).In addition,at a certain level of mixture inhomogeneity,the effect of the WI on flame stability becomes dominant.

Reactions in a Mixture of CH_4 and CO_2 under the Action of Microwave Discharge at Atmospheric Pressure

Reactions between CH_4 and CO_2 under the action of continuous microwave discharge at atmospheric pressure were studied in a special homemade reactor. The main products were CO and H2, while acetylene and ethylene were also found in the products. Experimental results show that conversions of CH4 and CO2 could be higher than 90% without the presence of any catalyst. Effects of CO2/CH4 molar ratio and total flow rate of the feed gas on the reaction were also investigated.

A Numerical Simulation Study of Temperature and Pressure Effects on the Breakthrough Pressure of CO_(2)in Unsaturated Low-permeability Rock Core

Gas breakthrough pressure is a key parameter to evaluate the sealing capacity of caprock,and it also plays important roles in safety and capacity of CO_(2)geological storage.Based on the published experimental results,we present numerical simulations on CO_(2)breakthrough pressure in unsaturated low-permeability rock under 9 multiple P-T conditions(which can keep CO_(2)in gaseous,liquid and supercritical states)and thus,a numerical method which can be used to accurately predict CO_(2)breakthrough pressure on rock-core scale is proposed.The simulation results show that CO_(2)breakthrough pressure and breakthrough time are exponential correlated with P-T conditions.Meanwhile,pressure has stronger effects on experimental results than that of temperature.Moreover,we performed sensitivity studies on the pore distribution indexλ(0.6,0.7,0.8,and 0.9)in van Genuchten-Muale model.Results show that with the increase ofλ,CO_(2)breakthrough pressure and breakthrough time both show decreasing trends.In other words,the larger the value ofλis,the better the permeability of the caprock is,and the worse the CO_(2)sealing capacity is.The numerical method established in this study can provide an important reference for the prediction of gas breakthrough pressure on rock-core scale and for related numerical studies.

Integrated vacuum pressure swing adsorption and Rectisol process for CO_(2) capture from underground coal gasification syngas

An integrated vacuum pressure swing adsorption(VPSA) and Rectisol process is proposed for CO_(2) capture from underground coal gasification(UCG) syngas. A ten-bed VPSA process with silica gel adsorbent is firstly designed to pre-separate and capture 74.57% CO_(2) with a CO_(2) purity of 98.35% from UCG syngas(CH_(4)/CO/CO_(2)/H_(2)/N_(2)= 30.77%/6.15%/44.10%/18.46%/0.52%, mole fraction, from Shaar Lake Mine Field,Xinjiang Province, China) with a feed pressure of 3.5 MPa. Subsequently, the Rectisol process is constructed to furtherly remove and capture the residual CO_(2)remained in light product gas from the VPSA process using cryogenic methanol(233.15 K, 100%(mass)) as absorbent. A final purified gas with CO_(2) concentration lower than 3% and a regenerated CO_(2) product with CO_(2) purity higher than 95% were achieved by using the Rectisol process. Comparisons indicate that the energy consumption is deceased from 2.143 MJ·kg^(-1) of the single Rectisol process to 1.008 MJ·kg^(-1) of the integrated VPSA & Rectisol process, which demonstrated that the deployed VPSA was an energy conservation process for CO_(2) capture from UCG syngas. Additionally, the high-value gas(e.g., CH_(4)) loss can be decreased and the effects of key operating parameters on the process performances were detailed.

Thermokinetic and conductivity analyzes of the high CO2 chemisorption on Li5AlO4 and alkaline carbonate impregnated Li5AlO4 samples:Effects produced by the use of CO2 partial pressures and oxygen addition

The effect of COpartial pressure was evaluated during the COchemisorption in penta lithium aluminate（LiAlO）, using different COand Opartial pressures in the presence or absence of alkaline carbonates. Results showed that using low PO（0.1） did not affect the kinetic and final COchemisorption process. Moreover, small additions of oxygen（PO= 0.05） into the mixture flue gas, seemed to increase the COchemisorption. Additionally, the presence of alkaline carbonates modified the COcapture temperature range. COchemisorption kinetic parameters were determined assuming a double exponential model where direct COchemisorption and COchemisorption controlled by diffusion processes are considered.Finally, ionic diffusion was analyzed by ionic conduction analysis, where all the gravimetric and ionic measurements were in good agreement showing different diffusion processes depending on temperature.Finally, the oxygen and alkaline carbonate additions have positive effects during the COchemisorption process in LiAlO, and a possible reaction mechanism is presented.

Effect of N_2-Gas Partial Pressure on the Structure and Properties of Copper Nitride Films by DC Reactive Magnetron Sputtering

Copper nitride thin films were deposited on glass substrates by reactive direct current （DC） magnetron sputtering at various N2-gas partial pressures and room temperature. Xray diffraction measurements showed that the films were composed of Cu3N crystallites and exhibited a preferential orientation of the [111] direction at a low nitrogen gas （N2） partial pressure. The film growth preferred the [111] and the [100] direction at a high N2 partial pressure. Such preferential film growth is interpreted as being due to the variation in the Copper （Cu） nitrification rate with the N2 pressure. The N2 partial pressure affects not only the crystal structure of the film but also the deposition rate and the resistivity of the Cu3N film. In our experiment, the deposition rate of Cu3N films was 18 nm/min to 30 nm/min and increased with the N2 partial pressure. The resistivity of the Cu3N films increased sharply with the increasing N2 partial pressure. At a low N2 partial pressure, the Cu3N films showed a metallic conduction mechanism through the Cu path, and at a high N2 partial pressure, the conductivity of the Cu3N films showed a semiconductor conduction mechanism.

CO_(2)分注井气嘴节流特性及矿场应用

为了解决CO_(2)分注井节流压差建立困难,气嘴易冲蚀的技术难题,通过构建CO_(2)物性变化的流动-传热耦合模型,揭示2级和3级节流气嘴的流场演化机制,优化设计气嘴结构、建立了绕流气嘴节流图版并开展现场应用。结果表明:流量为10 m3/d时,2级嘴径1.4 mm和3级嘴径1.6 mm的绕流气嘴分别能产生将近6 MPa和8 MPa的节流压差,证明绕流气嘴结构合理、性能可靠、能够达到调整层间压差的技术要求;参照气嘴图版优选的节流气嘴,现场应用20口井,节流压差可达4 MPa左右,调整后注入压力上升2.4 MPa,加强层相对吸气比例由9.7%上升至50.7%,有效调整了层间差异,解决了分注井小层吸气不均的问题。研究结果指导现场测调,为CO_(2)分注规模化应用提供技术支撑。

煤中超临界CO_(2)解吸滞后机理及其对地质封存启示

将CO_(2)注入不可采煤层地质封存既是降低温室气体效应最理想选择之一,也是煤炭工业降低CO_(2)排放、实现低碳化可持续发展的必由之路,然而,煤层CO_(2)地质封存悬而未决的关键问题是:“注入煤层中的CO_(2)到底能否长期停留而安全封存?”。鉴于此,在弄清煤体CO_(2)解吸滞后规律的基础上,揭示超临界CO_(2)解吸滞后机理,建立煤层CO_(2)地质封存量化模型,探讨利用解吸滞后实现煤层CO_(2)长期安全封存。研究表明:煤中超临界态CO_(2)解吸滞后程度大于亚临界态CO_(2),在超临界阶段,吸附与解吸等温线形成近似“平行线”的稳定滞后特征;解吸滞后的本质原因是煤中微纳米级亲水性孔隙形成弯液面、产生强大毛细压力、渗吸液态水、截断并固定超临界CO_(2)流体、最终形成了CO_(2)残余封存,例如,煤中直径40~10 nm圆柱形无机孔隙可产生7.30~29.12 MPa毛细压力,足以封堵超临界态CO_(2);以九里山煤样解吸等温线数据为例,采用基于煤层CO_(2)解吸滞后的地质封存量化模型,评估出900~1500 m深部二1煤层封存总量稳定在35~37 m^(3)/t,其中,吸附封存约占80%,残余封存约占15%,而结构封存仅占5%;解吸滞后启示应尽可能采取措施提高煤层残余封存CO_(2)比例,原因是毛细堵塞的残余封存CO_(2)较围岩密封的游离和吸附CO_(2)更安全且没有泄露风险,煤层灰分、水分、孔隙尺寸和形貌等物性参数是影响残余封存效率的主要因素。

胜利油田CO_(2)高压混相驱油与封存理论技术及矿场实践

针对胜利油田开展CO_(2)驱油与封存面临的原油轻烃含量低混相难、储层非均质性强波及效率低、易气窜全过程调控难等问题,通过室内实验、技术攻关和矿场实践,形成CO_(2)高压混相驱油与封存理论及关键技术。研究发现,提高地层压力至1.2倍最小混相压力之上,可以提高原油中的中重质组分混相能力,增大小孔隙中的原油动用程度,均衡驱替前缘,扩大波及体积。通过超前压驱补能实现快速高压混相,采用梯级气水交替、注采耦合、多级化学调堵等技术全过程动态调控渗流阻力,实现采收率与封存率的协同最优。研究成果应用于高89-樊142 CCUS(二氧化碳捕集、利用与封存)示范区,区块日产油由254.6 t提高至358.2 t,预计实施15年可提高采出程度11.6个百分点,为CCUS规模化应用提供理论和技术支撑。

不同流向上小流道加热管内超临界CO_(2)的压降特性

针对不同流动方向上超临界CO_(2)流体在小流道加热管径为0.75mm内的压降特性进行了实验研究。结果表明,不同流动(水平流动、垂直向上流动以及垂直向下流动)方向上,实验总压降、摩擦压降以及加速度压降均随着系统压力的升高而逐渐减小,而随着质量流量的增大、加热功率以及进口温度的升高而增大。然而,在垂直流动方向上重力压降随着系统压力的升高以及质量流量的增大而逐渐增大,但随着加热功率以及进口温度的升高而逐渐减小。当系统压力、质量流量、加热功率以及进口温度保持恒定时,不同流动方向上超临界CO_(2)流体的摩擦压降均在实验总压降中所占有的比例最大,而重力压降在实验总压降中所占有的比例最小。通过两种测试管径的压降数据比较可知,超临界CO_(2)流体在不同流动方向上实验总压降的变化趋势始终保持一致,并且小管径的实验总压降远大于大管径的实验总压降,从而说明测试管径的尺寸大小对实验总压降的变化有着显著影响。

考虑压敏效应的低渗透油藏CO_(2)辅助重力驱合理配产方法

高倾角低渗透油藏在进行水驱开发时,在油藏高部位存在大量剩余油,采收率较低,采用CO_(2)辅助重力驱,可以充分利用高倾角的地质特征,有效提高该类油藏的采出程度。但是由于CO_(2)对原油物性影响要远大于水对原油物性的影响,CO_(2)驱替过程中流体的渗流过程更加复杂,因此有必要对低渗透油藏CO_(2)重力驱合理配产优化进行研究。首先,依据油藏中任意一点压力与最小混相压力的关系,分别建立了考虑压敏效应的低渗透油藏CO_(2)重力驱混相和非混相模型;其次,运用Python对模型进行求解,同时分析了压敏系数、地层倾角、注采井距和注气速度对油藏配产的影响;最后,结合现有工作制度法和增产倍数法,对比本模型计算结果,运用tNavigtor软件对3种方法进行采收率预测。研究结果表明:运用本文方法对油藏进行合理配产具有较好的开发效果,油藏采收率相对较高,研究结果对该类低渗油藏的开发具有较好的借鉴意义。

CO_(2)-EOR过程中油藏储层构造封存能力的模拟

为应对日益严峻的能源危机和温室效应,CO_(2)提高采收率技术脱颖而出,因此CO_(2)提高采收率后的地质封存安全性和相应的封存能力评估引起了广泛关注。借助数值模拟方法,基于吉林油田某区块油藏的实际储层条件,构建了注入CO_(2)含量为10%~90%的9个模型,分别探究了含水饱和度为30%,50%和90%以及储层压力为10 MPa,20 MPa和30 MPa时油藏各相组分的分布规律;基于前人对封存CO_(2)安全储存状态划分的研究,最终明确了CO_(2)的安全封存量。结果表明:1)当含水饱和度(30%)和压力(10 MPa)一定时,增加CO_(2)含量(10%~90%)可大幅提高CO_(2)的有效封存体积分数(26%~93%);2)压力的提升(10~30 MPa)促进了CO_(2)在油相中的溶解,从而略微降低了储层的封存能力(18%~7%);3)含水饱和度对储层封存CO_(2)的能力的影响微乎其微。该研究旨在阐明不同条件下CO_(2)的构造埋存量,为相关研究提供借鉴。

不同CO_(2)压力下黄铁矿与煤制气耦合机制研究

目的为了研究不同CO_(2)压力下黄铁矿与煤制气的耦合机制,方法利用压力为1,3,5 MPa的高压罐进行煤和黄铁矿厌氧发酵产气试验。结果结果表明:(1)压力1 MPa时产气量较好,最终产气量为1.26 mmol/g;压力增加,罐中产气量减少,压力5 MPa时产气量仅0.02 mmol/g。(2)随着压力增加,水溶液中HCO-3质量浓度和氧化还原电位(Eh)逐渐上升,pH逐渐下降,5 MPa试验组反应末期pH最低,为4.02,1 MPa压力罐内总铁有消耗,波动较大;反应前期,3,5 MPa压力罐中总铁质量浓度持续增加,说明反应前期3,5 MPa压力下黄铁矿溶解量增加较多;(3)高压条件下,化学需氧量(chemical oxygen deman,COD)和短链脂肪酸浓度水平的显著减少反映了厌氧发酵程度的减弱和黄铁矿酸化程度的增强;(4)压力增加,功能菌种丰度和多样性降低,硫杆菌属逐渐处于优势地位,厌氧发酵过程基本停滞。结论适宜的CO_(2)压力条件可促进煤储层条件下的微生物生长代谢,同时添加黄铁矿发生氧化产生的铁离子,可促进菌群酶活,使煤生物产气反应顺利进行。研究结果可为原位条件富集营养液注入后的产气机制研究提供理论支撑。