SDS和THF对水合物法捕集模拟烟气中CO2的影响

采用搅拌式反应釜水合物生成实验装置研究动力学促进剂十二烷基硫酸钠(SDS)和热力学促进剂四氢呋喃(THF)对水合物法捕集CO_2的影响,用摩尔分数为25%的CO_2和75%的N_2混合气模拟烟气,分别探究不同浓度的SDS和THF对分离效果的影响;在此基础上,研究了不同初始压力、反应温度对分离效果的影响。结果表明,SDS和THF的存在都能提高CO_2回收率,但同时会降低分离因子。设定初始温度为3.5℃,初始压力为9.2 MPa时,加入质量分数为0.01%的SDS溶液后,CO_2回收率较纯水中增大了4.3%,分离因子较纯水中降低了44.8%;设定初始温度为6.5℃,初始压力为3.7 MPa时,加入摩尔分数为0.5%的THF溶液后,CO_2回收率较纯水中增大了30.4%,分离因子较纯水中降低了72.8%。在实验条件下,适宜的SDS质量分数为0.01%～0.05%,THF摩尔分数为0.5%～2%,初始压力的增加可以有效缩短水合反应的诱导时间,增大储气密度、CO_2回收率和分离因子,降低温度能有效提高分离效果。     

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.     

金属有机框架膜材料用于CO2分离过程的研究进展

金属有机框架材料(MOFs)具有孔隙率高、比表面积大、孔道可调节、结构多样等特点,将其添加到高分子膜中,可显著提升膜材料对CO₂的透过性和选择性。综述了近年来MOF膜材料用于CO₂分离过程的研究进展:①介绍了MOF膜材料的CO₂分离机理和合成工艺;②总结了几种主要的MOF膜材料在CO₂分离过程中的应用研究进展;③提出了MOF膜材料在CO₂分离领域的发展方向。      

CH4/N2在活性炭上吸附性能的研究

变压吸附是分离油田伴生气中N_2和CH_4的可行性方法,采用质量法测定了N_2、CH_4在活性炭WHXR-LB20上的吸附等温线,分离系数为2.87,满足工业应用要求且再生效果好;同时测定了油田伴生气中C_2H_6、C_3H_8,n-C_4H_(10)等对WHXR-LB20的影响,结果表明,C_2H_6、C_3H_8在WHXR-LB20上再生效果很好,而n-C_4H_(10)在WHXR-LB20上有积累,该积累量使N_2和CH_4在WHXR-LB20上的饱和吸附量降低。     

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。     

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.     

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...     

炼油厂燃料气中C_(3)+及H_(2)优化回收利用北大核心CSCD

目的回收利用炼厂燃料气中的C_(3)+及H_(2),提高经济效益。方法通过对不同来源的燃料气分析对比,找出其中富H_(2)、高C_(3)+燃料气。优化H_(2)利用及回收流程,增加脱氢膜面积,提高H_(2)回收量。利用催化装置和焦化装置的吸收稳定系统回收燃料气中的C_(3)+。结果技改总投资320万元,可回收C_(3)+1.23×10^(4) t/a,增效3000万元/年;H_(2)回收量可增加1050×10^(4) m^(3)/a,降低制氢成本1200万元/年。结论该方案充分利用炼厂现有吸收稳定系统及现有脱氢系统扩容,具有投资少、效益好、见效快的优点,对玉门炼化总厂高质量发展具有重要意义。     

Understanding aqueous foam with novel CO2-soluble surfactants for controlling CO2 vertical sweep in sandstone reservoirs

The ability of a novel nonionic CO₂-soluble surfactant to propagate foam in porous media was compared with that of a conventional anionic surfactant (aqueous soluble only) through core floods with Berea sandstone cores. Both simultaneous and alternating injections have been tested. The novel foam outperforms the conventional one with respect to faster foam propagation and higher desaturation rate. Furthermore, the novel injection strategy, CO₂ continuous injection with dissolved CO₂-soluble surfactant, has been tested in the laboratory. Strong foam presented without delay. It is the first time the measured surfactant properties have been used to model foam transport on a field scale to extend our findings with the presence of gravity segregation. Different injection strategies have been tested under both constant rate and pressure constraints. It was showed that novel foam outperforms the conventional one in every scenario with much higher sweep efficiency and injectivity as well as more even pressure redistribution. Also, for this novel foam, it is not necessary that constant pressure injection is better, which has been concluded in previous literature for conventional foam. Furthermore, the novel injection strategy, CO₂ continuous injection with dissolved CO₂-soluble surfactant, gave the best performance, which could lower the injection and water treatment cost.     

天然气净化厂低压尾气CO2回收技术研究

为了节能减排,降低天然气净化厂尾气中CO_2排放量,分别通过实验室实验、模拟试验、侧线试验逐步研究并验证了MEA和复合胺对CO_2的吸收性能。采用实验研究与现场测试、评价相结合的方法,开发出一套适合于普光天然气净化厂烟气排放工况的CO_2回收工艺,为实现天然气净化厂低碳生产与CO_2减排提供了技术支持。     

La-BiVO4催化剂的制备及其光催化还原CO2

为扩展广东惠州炼油厂和石油化工总厂二期工程,中国海洋石油总公司(中海油)选择了CB&I的4项技术。这是CB&I最近在中国的第一项关于电子油门气化技术的授权。电子油门气化技术可用来从煤和石油焦油中制备清洁的合成气体以供发电、制氢和炼油厂蒸汽使用,且可用于煤炭化工工业中制备从肥料到甲醇再到合成天然气的一系列产品。     

CO2泡沫驱体系筛选与评价

吉林油田CO₂驱油藏物性差,渗透率差异较大,裂缝相对发育,注入CO₂过程中出现气窜,严重影响气驱效果。为此开展CO₂泡沫体系研究,扩大气驱波及体积,提高气驱开发效果。室内建立泡沫体系的性能评价手段,优选一种由阴离子表面活性剂与非离子表面活性剂复配而成的CYL泡沫体系,确定现场CYL泡沫体系的最佳加量为0.3%、气液比1:1。物模试验结果表明：裂缝性低渗透岩心中CO₂泡沫驱采收率最高53.67%,CO₂气驱采收率次之（35.74%）,水驱采收率最低（23.42%）。CO₂泡沫驱的效果明显好于水驱、CO₂驱,现场开展CO₂泡沫驱试验,注气压力由措施前的6.0 MPa上升到措施后的8.1 MPa,井组日产油由措施前的7.7 m³增至措施后的10.8 m³,措施效果明显,有效提高气驱开发效果。     

Numerical simulation of enhancing coalbed methane recovery by injecting CO2 with heat injection

The technology used to enhance coalbed methane(CBM) recovery by injecting CO_2(CO_2-ECBM) with heat, combining heat injection with CO_2 injection, is still in its infancy; therefore, theoretical studies of this CO_2-ECBM technology should be perused. First, the coupling equations of the di usion–adsorption–seepage–heat transfer fields of gas are established. The displacement processes under di erent pressures and temperatures are simulated by COMSOL. Finally, the displacement effects, a comparison of the CO_2 storage capacity with the CH_4 output and the e ective influencing radius of CO_2 injection are analyzed and discussed. The results show that(1) the displacement pressure and temperature are two key factors influencing the CH_4 output and the CO_2 storage capacity, and the increase in the CO_2 storage capacity is more sensitive to temperature and pressure than the CH_4 output.(2) The gas flow direction is from the injection hole to the discharge hole during the displacement process, and the regions with high velocity are concentrated at the injection hole and the discharge hole.(3) A reduction in the CH_4 concentration and an increase in the CO_2 concentration are obvious during the displacement process.(4) The e ective influencing radius of injecting CO_2 with heat increases with the increase in time and pressure. The relationship between the e ective influencing radius and the injection time of CO_2 has a power exponential function, and there is a linear relationship between the functional coe cient and the injection pressure of CO_2. This numerical simulation study on enhancing CBM recovery by injecting CO_2 with heat can further promote the implementation of CO_2-ECBM project in deep coal seams.     

Optimal activated carbon for separation of CO_2 from(H_2 + CO_2) gas mixture

Seven types of activated carbon were used to investigate the effect of their structure on separation of CO_2 from(H_2 + CO_2) gas mixture by the adsorption method at ambient temperature and higher pressures. The results showed that the limiting factors for separation of CO_2 from 53.6 mol% H_2 + 46.4 mol% CO_2 mixture and from 85.1 mol% H_2 + 14.9 mol% CO_2 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 about2.07 lm for 53.6 mol% H_2 + 46.4 mol% CO_2 mixture and 1.41 lm for 85.1 mol% H_2 + 14.9 mol% CO_2 mixture. The effect of specific area and pore diameter of activated carbon on separation CO_2 from 53.6 mol% H_2 + 46.4 mol% CO_2 mixture was more significant than that from 85.1 mol% H_2 + 14.9 mol% CO_2 mixture. CO_2 in the gas phase can be decreased from 46.4 mol% to 2.3 mol%–4.3 mol% with a two-stage separation process.     

Exploitation of fractured shale oil resources by cyclic CO2 injection

With shale oil reservoir pressure depletion and recovery of hydrocarbons from formations, the fracture apertures and conductivity are subject to reduction due to the interaction between stress effects and proppants. Suppose most of the proppants were concentrated in dominant fractures rather than sparsely allocated in the fracture network, the fracture conductivity would be less influenced by the induced stress effect. However, the merit of uniformly distributed proppants in the fracture network is that it increases the contact area for the injection gas with the shale matrix. In this paper, we address the question whether we should exploit or confine the fracture complexity for CO₂-EOR in shale oil reservoirs. Two proppant transport scenarios were simulated in this paper: Case 1—the proppant is uniformly distributed in the complex fracture system, propagating a partially propped or un-propped fracture network; Case 2—the proppant primarily settles in simple planar fractures. A series of sensitivity studies of the fracture conductivity were performed to investigate the conductivity requirements in order to more efficiently produce from the shale reservoirs. Our simulation results in this paper show the potential of CO₂ huff-n-puff to improve oil recovery in shale oil reservoirs. Simulation results indicate that the ultra-low permeability shales require an interconnected fracture network to maximize shale oil recovery in a reasonable time period. The well productivity of a fracture network with a conductivity of 4 mD ft achieves a better performance than that of planar fractures with an infinite conductivity. However, when the conductivity of fracture networks is inadequate, the planar fracture treatment design maybe a favorable choice. The available literature provides limited information on the relationship between fracture treatment design and the applicability of CO₂ huff-n-puff in very low permeability shale formations. Very limited field test or laboratory data are available on the investigation of conductivity requirements for cyclic CO₂ injection in shale oil reservoirs. In the context of CO₂ huff-n-puff EOR, the effect of fracture complexity on well productivity was examined by simulation approaches.     

氨基碳点/聚酰亚胺混合基质膜的制备及CO2分离性能研究

将水热合成法制备的氨基碳点与聚酰亚胺复合得到混合基质膜。通过SEM、FT-IR、XRD和DSC考查了氨基碳点掺杂质量分数对混合基质膜形貌和结构的影响。氨基碳点表面的氨基可以提供碱性环境,同时增加了膜内的自由体积,促进CO₂传递。当氨基碳点掺杂质量分数为0.3%时,混合基质膜的CO₂分离性能最佳,其CO₂、CH₄、N₂渗透通量分别为85.87 barrer、1.69 barrer、2.62 barrer,CO₂/CH₄、CO₂/N₂选择性分别为50.81和32.77。      

超声速喷管内CO2气体凝结特性研究

基于欧拉———欧拉双流体模型,建立气相及液相流动控制方程组,结合凝结成核与液滴生长理论,对喷管内CO_2气体的凝结特性进行了数值模拟研究。结果表明,采用的数学模型和数值计算方法可较准确地反映喷管内气体的凝结流动过程。CO_2气体凝结潜热较小,凝结冲波现象不明显;气体进入喷管特别是在经过喉部之后,在马赫数增大的同时,压力和温度降低,过冷度增加,最大可至30K左右,并于凝结发生后快速下降至约5K;CO_2气体成核过程在时间和空间上表现出急剧性。凝结起始位置距喉部约2.21mm,成核率由0激增至2.04×10~(21)m~(-3)·s~(-1),液滴数目达到10~(15)的数量级;凝结核心形成后,气体分子在一定的过冷度下在液滴表面团聚、液化,液滴半径和湿度迅速增加。成核过程结束后,已有凝结核心仍能不断生长,至喷管出口处液滴半径增至1.46×10~(-7 )m,湿度可达0.093 5。     

高含CO2天然气脱碳工艺中MDEA活化剂优选

国内高含CO_2天然气处理装置主要采用活化MDEA脱碳工艺。以DEA、MEA、PZ为活化剂,总胺物质的量浓度控制在4 mol/L。利用HYSYS软件建立运算模型,研究这3种活化MDEA溶液对CO_2的吸收性能和解吸性能,通过分析认为,高含CO_2天然气深度脱碳处理宜采用PZ为活化剂。对PZ的活化机理进行研究,发现PZ作为活化剂的效果远胜于DEA和MEA。最后,分析不同吸收温度及CO_2分压下PZ浓度变化对活化性能的影响,发现加入少量PZ即可大幅提高PZ活化MDEA溶液与CO_2反应速率,在不同CO_2分压和吸收温度的条件下均能满足高含CO_2天然气的脱碳处理要求,适应性较强,建议活化MDEA溶液中PZ的质量分数为3%~5%。     

二氧化碳在CH4-CO2二元体系中的冰点预测

采用深冷工艺回收天然气中的乙烷时,脱甲烷塔塔顶及冷箱处的温度较低,容易发生CO_2冻堵。研究固体CO_2在CH_4-CO_2二元体系中的形成规律,有助于优化深冷分离工艺,避免CO_2冻堵,同时降低冷能消耗。修正了纯组分CO_2的饱和蒸气压的通用关联式,以预测二元气相体系中固体CO_2的形成温度,并与陈赓良-朱利凯模型关联式计算、HYSYS软件计算及Aspen Plus软件计算的CO_2固体形成温度进行了比较。结果表明,修正后的计算模型准确度较高,与Agrawal的实验数据的平均偏差在2℃以内。同时,根据Kurata实验数据拟合出CH_4-CO_2二元液相体系中CO_2固体形成温度关联式,并与文献经验公式、HYSYS软件计算及Aspen Plus软件计算的CO_2固体形成温度进行了比较。结果表明,该计算模型与实验数据吻合度非常高,与Kurata的实验数据的平均偏差在1℃以内,且具有广泛的通用性。