含杂质CO2管道输送水合物形成规律研究

在延长油田产生的CO₂气体输送过程中,管线会发生水合物冰堵,影响气体输送流量,为了探究CO₂水合物在管道输送过程中的形成规律,利用PVTSIM软件生成了CO₂水合物的相平衡曲线,并通过OLGA软件对水平管和弯管输送的水合物形成规律进行了模拟分析。结果表明:在低温高压条件下,水平管和弯管输送过程中均会有水合物形成,其生成过程是一种类似于盐类的结晶过程,通常包括成核和生长两个阶段,然后依靠流体颗粒之间的黏附力致使水合物聚集,与直管段相比,弯管段更容易产生水合物;水合物生成速率均由小到大,然后快速进入稳定阶段,最后趋于0。现场管线的水合物也多发生在弯管处,从而进一步验证了CO₂水合物的形成规律。因此,在管道输送过程中应避免高压出口和低温入口条件,保证管道安全运营。      

N-甲基二乙醇胺溶液中CO2气体吸收与水合物生成特性实验研究

目的酸性气田开发气流中往往含有二氧化碳(CO₂)和硫化氢(H₂S)等酸性组分,易形成天然气水合物(简称水合物),引起管道堵塞。解决酸性组分吸收剂对水合物作用机制不明确问题,为脱除酸性气体组分并防治水合物生成提供理论依据。 方法 采用恒温恒容法研究了N-甲基二乙醇胺(MDEA)溶液质量分数、搅拌状态及初始压力对CO₂气体吸收规律的影响、MDEA溶液对CO₂水合物生长速率和宏观晶体形态的影响,并与传统热力学抑制剂乙二醇(EG)效果进行对比。 结果CO₂气体吸收量随MDEA溶液质量分数的增加表现为先增后减的趋势。开启搅拌和降低压力可加快CO₂气体的吸收速率,增加气体吸收量。在气液界面,水合物晶体以二维模式生长,并且MDEA可改变CO₂水合物的宏观形貌,增加其质量分数可显著增加CO₂水合物覆盖溶液表面的时间、降低CO₂水合物的生长速率。与EG相比,MDEA水合物的动力学抑制效果较差,但水合物膜覆盖时间较长,生长速率较慢。 结论MDEA可与溶液中水分子形成氢键,与水合物竞争水分子,减少水的活性,同时,MDEA分子可与CO₂分子结合,与水合物竞争CO₂,显著降低水合物生长速率。研究结果对酸性气体的分离捕获和天然气流动的安全保障具有理论指导意义。      

Kinetics of (TBAF + CO2) semi-clathrate hydrate formation in the presence and absence of SDS

In this communication, the impacts of adding SDS (sodium dodecyl sulfate), TBAF (tetra-n-butylammonium fluoride) and the mixture of SDS + TBAF on the main kinetic parameters of CO₂ hydrate formation (induction time, the quantity and rate of gas uptake, and storage capacity) were investigated. The tests were performed under stirring conditions at T = 5 ℃ and P = 3.8 MPa in a 169 cm³ batch reactor. The results show that adding SDS with a concentration of 400 ppm, TBAF with a concentration of 1–5 wt%, and the mixture of SDS + TBAF, would increase the storage capacity of CO₂ hydrate and the quantity of gas uptake, and decrease the induction time of hydrate formation process. The addition of 5 wt% of TBAF and 400 ppm of SDS would increase the CO₂ hydrate storage capacity by 86.1% and 81.6%, respectively, compared to pure water. Investigation of the impact of SDS, TBAF and their mixture on the rate of gas uptake indicates that the mixture of SDS + TBAF does not have a significant effect on the rate of gas uptake during hydrate formation process.     

Modeling CO2 miscible flooding for enhanced oil recovery

The injection of fuel-generated CO2 into oil reservoirs will lead to two benefits in both enhanced oil recovery (EOR) and the reduction in atmospheric emission of CO2. To get an insight into CO2 miscible flooding performance in oil reservoirs, a multi-compositional non-isothermal CO2 miscible flooding mathematical model is developed. The convection and diffusion of CO2-hydrocarbon mixtures in multiphase fluids in reservoirs, mass transfer between CO2 and crude, and formation damages caused by asphaltene precipitation are fully considered in the model. The governing equations are discretized in space using the integral finite difference method. The Newton-Raphson iterative technique was used to solve the nonlinear equation systems of mass and energy conservation. A numerical simulator, in which regular grids and irregular grids are optional, was developed for predicting CO2 miscible flooding processes. Two examples of one-dimensional (1D) regular and three-dimensional (3D) rectangle and polygonal grids are designed to demonstrate the functions of the simulator. Experimental data validate the developed simulator by comparison with 1D simulation results. The applications of the simulator indicate that it is feasible for predicting CO2 flooding in oil reservoirs for EOR.     

NH3作为CO2置换CH4水合物促进剂的分子动力学模拟研究

针对天然气水合物开采中CO₂置换面临的渗透性差、置换效率低的问题,采用分子动力学模拟方法,将对水合物相具有强穿透能力的NH₃作为促进剂,分别模拟了CO₂单组分和CO₂/NH₃混合组分置换水合物过程。结果表明:在模拟设定的温度压力范围内,245 K和255 K条件下,NH₃对CO₂置换水合物过程起到正向促进作用,而当温度升高至265 K时,则会对置换过程起到抑制作用;温度相同时,升高压力可以提高置换效率,但不会改变NH₃对置换过程的促进/抑制作用。该研究结果可为提高CO₂置换法的置换效率提供新的思路。      

超临界含杂质CO2管网停输再启动对水合物生成的影响

目的 在CO₂管道输送过程中,输送管网的工艺参数在停输再启动工况下会发生变化,容易生成水合物堵塞管网。预测和分析CO₂输送过程中水合物及水含量的生成规律,以保证管输的效率和安全性。方法 基于延长油田一期36×10⁴ t/a输送管网设计,利用OLGA软件建立超临界含杂质CO₂输送管网模型,在稳态输送下水合物生成的研究基础上,预测和分析停输再启动工况对水合物的生成位置和生成量等的影响。结果 在停输工况下,水合物生成温度和压力降低,水合物生成位置发生前移,在管网入口5 km处开始有质量浓度为0.18 kg/m³的水合物生成;而在再启动工况下,水合物生成温度增加,水合物生成量峰值为0.9 kg/m³,水合物生成区段减短且生成位置后移至管网20 km处。结论 模拟结果可以较好地指导延长油田管网设计,为管网的安全运行提供理论依据。     

富含CO_2天然气净化技术现状及研究方向

富含CO2天然气净化技术面临天然气气质和尾气排放标准的双重挑战,故在综述国内外富含CO2天然气脱除CO2技术现状的基础上,分析了现有净化技术存在的问题,即活化甲基二乙醇胺(aMDEA)法CO2吸收剂循环量大、装置能耗高,变压吸附法和膜分离集成法工艺不成熟等。进而提出了活化剂、工艺流程及其操作参数优化、变压吸附和膜分离集成技术等新的研究方向,以期形成适用于富含CO2天然气净化的系列配套技术,助推我国富含CO2天然气的高效开发。     

Vapor-hydrate phases equilibrium of （CH4＋C2H6） and （CH4＋C2H4） systems

Separation of the (C₁ + C₂) hydrocarbon system is of importance in natural gas processing and ethylene production. However it is the bottleneck because of its high refrigeration energy consumption, and needs to be urgently addressed. The technology of separating gas mixtures by forming hydrate could be used to separate (C₁ + C₂) gas mixtures at around 0 °C and has attracted increasing attention worldwide. In this paper, investigation of vapor-hydrate two-phase equilibrium was carried out for (C₁ + C₂) systems with and without tetrahydrofuran (THF). The compositions of vapor and hydrate phases under phase equilibrium were studied with model algorithm when structure I and structure II hydrates coexisted for the (methane + ethane) system. The average deviation between the modeled and actual mole fractions of ethane in hydrate and vapor phases was 0.55%, and that of ethylene was 5.7% when THF was not added. The average deviation of the mole fraction of ethane in vapor phase was 11.46% and ethylene was 7.38% when THF was added. The test results showed that the proposed algorithm is practicable.     

人工裂缝参数对CO2-ESGR中CO2封存和CH4开采的影响

目的 页岩储层中的裂缝系统对CH₄产量和CO₂封存量有着重要的影响,不同的储层地质特征有其对应的最优压裂方案。对鄂尔多斯盆地延长组页岩储层人工裂缝参数对CO₂封存和CH₄开采的影响进行分析。方法 基于鄂尔多斯盆地延长组页岩储层地质条件建立了页岩基质-裂缝双孔双渗均质模型,分析CO₂增强页岩气开采技术(CO₂-ESGR)中人工裂缝半长、裂缝宽度、裂缝高度、裂缝间距和裂缝数量对CO₂封存量和CH₄产量的影响。结果 CO₂封存量和CH₄产量与裂缝半长、裂缝宽度和裂缝高度呈正相关,其中裂缝宽度的影响最大,从5 mm增加到25 mm时,最多可使CO₂封存量和CH₄产量分别增加112.69%和87.11%。裂缝间距和裂缝数量增加可提高CO₂封存量和CH₄产量,但水平井长度相同时裂缝数量增加对CO...     

Optimal activated carbon for separation of CO2 from (H2 + CO2) gas mixture

Seven types of activated carbon were used to investigate the effect of their structure on separation of CO₂ from (H₂ + CO₂) gas mixture by the adsorption method at ambient temperature and higher pressures. The results showed that the limiting factors for separation of CO₂ from 53.6 mol% H₂ + 46.4 mol% CO₂ mixture and from 85.1 mol% H₂ + 14.9 mol% CO₂ mixture were different at 20 C and about 2 MPa. The best separation result could be achieved when the pore diameter of the activated carbon ranged from 0.77 to 1.20 nm, and the median particle size was about 2.07 lm for 53.6 mol% H₂ ? 46.4 mol% CO₂ mixture and 1.41 lm for 85.1 mol% H₂ + 14.9 mol% CO₂ mixture. The effect of specific area and pore diameter of activated carbon on separation CO₂ from 53.6 mol% H₂ ? 46.4 mol% CO₂ mixture was more significant than that from 85.1 mol% H₂ ? 14.9 mol% CO₂ mixture. CO₂ in the gas phase can be decreased from 46.4 mol% to 2.3 mol%–4.3 mol% with a two-stage separation process.     

二氧化碳甲烷自热重整计算分析与中试

运用Gibbs自由能最小化方法和耦合详细反应动力学的计算流体力学(CFD)方法对CO_2-CH_4自热重整进行了相关的计算分析。结合自主研发的反应器和催化剂,在山西省潞安集团煤制油低碳循环经济园区进行了原料气处理量10 000m~3/h、运行压力2MPa、新型镍基催化剂装填量约5t的中试实验,获得合成气中甲烷摩尔分数小于1%、n(H_2)/n(CO)=1.1、有效气摩尔分数为60.7%的合成气。其中,CO_2-CH_4自热重整反应器设计主要尺寸为:内径1.6m,燃烧高度3.0m,催化剂装填高度2.8m,反应器总体高度约13.8m。     

Modelling of CO2 capture and separation from different gas mixtures using semiclathrate hydrates

In this work we present a model for predicting hydrate formation condition to separate carbon dioxide (CO₂) from different gas mixtures such as fuel gas (H₂+CO₂), flue gas (N₂+CO₂), and biogas gas (CH₄+CO₂) in the presence of different promoters such as tetra-n-butylammonium bromide (TBAB), tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium fluoride (TBAF), tetra-n-butyl ammonium nitrate (TBANO₃), and tetra-n-butylphosphonium bromide (TBPB). The proposed method was optimized by genetic algorithm. In the proposed model, hydrate formation pressure is a function of temperature and a new variable in term of Z, which used to cover different concentrations of studied systems. The study shows experimental data and predicted values are in acceptable agreement.     

CO2准干法压裂技术研究及应用

致密砂岩气藏普遍具有储层物性差、孔喉细、黏土矿物含量高的特征,水力压裂易导致储层产生水敏、水锁等液相伤害,影响增产效果。针对此问题,研究了CO₂准干法压裂技术,重点开展了准干法压裂工作液组成、携砂性能、耐温耐剪切性能等方面的研究,形成了一种液态CO₂中含有少量水基压裂液的均匀混合相体系,具有液相伤害小、造缝携砂性能好、现场操作性强等特点,可满足大砂量、高砂比压裂施工要求。该技术在冀东油田南堡5号构造深层致密砂岩气藏进行先导试验,压后单井日增油2.5倍,日增气8.6倍,增产效果理想。      

Kinetics of CO2-induced asphaltene precipitation from various Saskatchewan crude oils during CO2 miscible flooding

A molar CO₂ programmed titration technique was used to evaluate the kinetics of CO₂-induced asphaltene precipitation from three Saskatchewan crude oils (namely Steelman, 12-25-6-14w2 and D8-12-6-14w2) under isothermal (in the range of 300–338 K) and isobaric (at 17.2 MPa) reservoir conditions in a solids detection system (SDS) consisting essentially of a mercury-free, variable volume, fully visual, JEFRI PVT cell. The results show that the rate of asphaltene precipitation depends on, both, the asphaltene and CO₂ contents of the oil. This work represents the first attempt at obtaining kinetic data for asphaltene precipitation from crude oil without any pretreatment of the oil as well as formulating a kinetic model that fits the data. Different values for the reaction order (m) of asphaltene, and the reaction order (n) for CO₂ were obtained for the same oil at different temperatures. This shows that the mechanism for CO₂-induced asphaltene precipitation was temperature dependent. Also, the values of n for all the oils at all the temperatures were much larger than the corresponding values for m. This shows that asphaltene precipitation is extremely more sensitive to CO₂ content than asphaltene content, even though the contribution from asphaltene content in the oil cannot be ignored. The large overall reaction order (m+n>4) also provides the experimental evidence to confirm that asphaltene precipitation is not an elementary process.     

Coupled THMC modeling of CO2 injection by finite element methods

Geological CO₂ sequestration has been proposed to mitigate greenhouse gas emissions. Massive CO₂ injection into subsurface formation involves interactions among pressure and temperature change, chemical reactions, solute transport, and the mechanical response of the rock; this is a coupled thermal–hydraulic–mechanical–chemical (THMC) process. Numerical modeling of CO₂ injection around the wellbore area can provide information such as changes in rock properties as well as stress and pressure changes, and this helps better predict injectivity evolution and leakage risk. In this paper, a fully coupled THMC model based on finite element methods is presented to analyze the transient stress, pressure, temperature and chemical solute concentration changes simultaneously around an injection well. To overcome these numerical oscillations in solving the transient advection–diffusion equations involved in the heat transfer and solute transport processes, we employ a stabilized finite element approach, the subgrid scale/gradient subgrid scale method (SGS/GSGS). A hypothetical numerical experiment on CO₂ saturated water injection into a carbonate aquifer is conducted and preliminary results show that the fully coupled model can successfully analyze stress and pressure changes in the rock around a wellbore subjected to thermal and chemical effects.     

含杂质超临界-密相CO2管道输送工艺参数优化

CO_2输送作为CCUS技术实现的中间环节,承担着将CO_2从捕获地输送到封存点的重要任务,结合原油、天然气管道的经验可知,由于管道输送具有输量大、安全可靠性高、连续性强等优势,是目前最主要的CO_2输送方式。根据国外40多年的CO_2管道输送经验,由于超临界-密相CO_2具有类似于液体的高密度和类似于气体的高扩散性与低黏度,被认为是最经济的管道输送方式。以国内某油田30×10~4 t/a CCUS项目为例,采用Pipephase模拟软件对不同管径的超临界-密相CO_2管道在相同入口参数下进行模拟计算,分析研究不同管径下的管道压力、温度、密度与输送距离之间的变化规律,得出含杂质超临界-密相CO_2最优管道输送工艺参数,为后续我国CCUS项目推广和发展提供理论依据。     

H2S与CO2共存条件下气田地面集输系统内腐蚀影响因素分析方法研究

CO2和H2S是最常见的两种管道内腐蚀介质,当系统中H2S和CO2共存时,其腐蚀行为远比H2S或CO2单独作用时复杂得多,即便是少量的H2S也会对CO2的腐蚀产生明显的影响,对气田开采与管输设备造成严重的破坏,甚至引发设备失效与安全事故。CO2/H2S共存体系下的金属腐蚀规律十分复杂且难于把握,与两种因素单一存在时截然不同。国外早期的研究始于20世纪80年代末,国内起步相对较晚。经过近30年的研究,发现腐蚀过程受CO2或H2S的控制取决于两者的含量、介质温度、压力、流速等因素。根据川东气田的气质和工况环境,进行实验研究与深入的理论归纳分析,得出川东气田H2S与CO2共存条件下地面集输系统内腐蚀影响因素及其交互作用的腐蚀影响权重。在此基础上,利用归一化方法,计算出重庆气矿中高含硫气井的腐蚀风险权重值,筛选出腐蚀敏感度较高的需要重点关注的气井及其采气管线。     

氨基改性吸附剂在低CO2分压下吸附CO2的热力学研究

为了减少温室效应,应采取有效措施减少温室气体CO2的排放。氨基改性吸附剂是捕获烟道气中CO2的重要吸附材料。建立了描述氨基改性MCM-41吸附剂在低CO2压力下吸附等温线的平衡模型,并计算了吸附热力学参数。该模型基于Dual-site Langmuir模型,同时假设CO2吸附具有两种独立的吸附机理,分别是氨基基团的化学吸附和吸附剂表面的物理吸附,提出了一种基于未改性介孔材料吸附容量和比表面积计算改性材料的物理吸附量方法。结果表明,该模型能较好地拟合吸附等温线,计算得到的物理化学吸附热分别为-25.4kJ/mol和-41.9kJ/mol,总吸附热为-67.3kJ/mol,与实验数据一致,且氨基改性MCM-41-TEPA饱和吸附容量可达到7.79mmol/g。     

延长油田致密砂岩油藏CO2驱油机理研究

CO_2驱是提高低渗透油田产量、缓解温室效应的有效途径。针对鄂尔多斯盆地油藏压力系数低、原油轻质组分含量高的特点,通过PVT和最小混相压力等测试分析方法,揭示了低压、低孔、低渗油藏CO_2驱提高采收率主要机理。开展了CO_2注入储层与无机、有机物作用后的沉淀研究,表明CO_2在无机盐溶液中不会形成沉淀堵塞孔隙,CO_2与有机质作用后沉积点高于油藏压力,且注入压力越高,CO_2在地层原油中的溶解能力越强,目标区块CO_2注入后不易形成沥青质沉淀。物模驱替实验结果表明,均质岩心的采出程度明显高于非均质岩心,且随着岩心非均质性的增加,水驱采出程度、气驱采出程度及最终采出程度均明显下降。     

CO2 sequestration through enhanced oil recovery in a mature oil field

Recent advances in enhanced oil recovery (EOR) technology create new opportunities for CO₂ sequestration. This paper proposes a technical–economic model for underground storage of CO₂ emitted by a fertilizer industry in the Northeast of Brazil, in a hypothetical mature oil reservoir through EOR operation. Simulations based on mass, energy and entropy balances, as well as economic analysis, were assessed for the process of CO₂ sequestration combined with EOR. This model takes into account the energy requirements for the whole CO₂ sequestration process, as well as the emissions inherent to the process. Additionally, a breakdown cost methodology is proposed to estimate the main financial determinants of the integrated EOR with CO₂ sequestration (costs of CO₂ purchase, compression, transportation and storage). Project evaluation is derived from a cash flow model, regarding reservoir production profile, price and costs, capital expenditures (CAPEX), operating expenditures (OPEX), carbon credits, depreciation time, fiscal assumptions etc. A sensitivity analysis study is carried out to identify the most critical variables. Project feasibility, as expected, is found to be very sensitive to oil price, oil production, and CAPEX. Moreover, there is the contribution from the mitigation of the greenhouse gas (GHG) by storing a significant amount of CO₂ in the reservoir where it can remain for thousands of years.