Kinetics of (TBAF + CO_2) 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 CO_2 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 cm~3 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 CO_2 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 CO_2 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.     

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。      

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.     

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。     

不同压力下冻土区水合物法封存CO2的实验研究

目的水合物法封存CO₂稳定性良好、储气密度高,是一种极具潜力的碳封存方式,利用冻土区的地层条件更具独特优势,将CO₂气体注入冻土区地层中,在一定的温度和压力条件下,形成固态CO₂水合物实现封存。 方法依据国内冻土地区地层深度对应的温度和压力条件,选取不同地层深度(150 m和200 m)对应温度(1.27 ℃和2.72 ℃)和有效孔隙含水率(40%),研究不同注气压力(3.5 MPa、4.5 MPa和5.5 MPa)下的封存特征。分析封存过程的温度和压力变化、封存速率、最终水转化率和最终封存率等动力学规律。 结果封存压力越高,水合物法封存所需的诱导时间越短,压力降幅越大。较高的封存压力导致初期封存速率较慢,缓慢封存期的持续时间减少,且封存压力越高,封存率、最终水转化率和水合物相饱和度越高。封存温度越高,压力对封存率的影响效果越明显。 结论在地层深度150 m(对应地层平均温度1.27 ℃)、5.5 MPa及有效孔隙含水率(40%)的条件下,CO₂封存效果最佳。      

TBAC+Tween80+CO2体系下水合物生成动力学

四丁基氯化铵(TBAC)作为一种热力学促进剂,被广泛应用在促进水合物生成方面,但由于单一的TBAC促进效果有限,因此开展了TBAC和聚氧乙烯脱水山梨醇单油酸酯(Tween80)复配体系下水合物生成动力学实验,探究了不同复配比对水合物生成过程中诱导时间、总耗气量、生成速率的影响及机理。实验结果表明,在复配体系下,水合物生成的诱导时间相比纯TABC体系大幅度减少,其中在10%(w)TBAC+2000 mg/L的Tween80体系中,促进作用达到最大,相比纯TBAC体系诱导时间减少59%;5%,10%(w)TBAC+Tween80都会使得体系的总耗气量略微的减少,而15%(w)TBAC+Tween80则会使溶液中的总耗气量略微增加;在生成速率影响方面,复配体系下气-水合物转化率均有明显提高。     

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...     

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.     

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.     

Phase equilibrium modeling of semi-clathrate hydrates of the CO2+H2/CH4/N2+TBAB aqueous solution system

In this study, the semi-clathrate hydrate dissociation pressure for the CO₂+N₂, CO₂+H₂, CO₂+CH₄, and pure CO₂ systems in the presence of different concentrations of TBAB aqueous solutions is predicted using a strong machine learning technique of multi-layer perceptron neural network (MLP-NN). The developed model, with an overall correlation coefficient (R²) of 0.9961 and mean square error (MSE) of 5.96E?02, presented an excellent accuracy in prognosticating experimental data. A complete statistical evaluation performed to promise the strength and generality of the multi-layer perceptron artificial neural network (MLP-ANN). In addition, the applicability of the proposed network and quality of experimental data was assessed through the Leverage approach.     

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.     

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。     

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。     

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.     

高岭石与CO2溶液反应实验研究

目的 高岭石是沉积岩重要的黏土矿物,为明确高岭石在CO₂水溶液中化学行为与变化历程,探究CO₂与高岭石反应规律。方法 在10 MPa、60℃下,利用XRD、XRF、ICP、SEM等手段系统评价了高岭石与CO₂在不同反应阶段的状态,重点对比了高岭石粉末反应前后固相元素、晶体结构及反应液中离子含量变化,结合高岭石结构特征,明确高岭石在酸中的变化规律。结果 液相中新增加了Al³⁺、Si⁴⁺,Mg²⁺含量先上升后趋于平稳,固相粉末中Si/Al(质量比)变化较小,衍射曲线峰形稳定,高岭石集合体未见明显溶蚀,单体边缘有轻微溶蚀。结论 高岭石与CO₂反应后总体变化较小,在CO₂溶液中相对稳定存在。实验结果为注CO₂对储层特征的影响以及气/水交替驱的可行性研究提供重要参数和依据。     

Experimental study and modeling of the kinetics of gas hydrate formation for acetylene,ethylene, propane and propylene in the presence and absence of SDS

The kinetics of hydrate formation of the hydrocarbons acetylene, ethylene, propane, and propylene were investigated using a fully stirred batch reactor. In relation to hydrate formation, a kinetic model was used to determine the induction time, the rate of hydrate formation, the apparent hydration rate constant, water-to-hydrate conversion associated with hydrate growth as well the storage capacity. This was done for all gases investigated in this study. Experiments were performed in the temperature and pressure ranges of (273.7–280.0) K and (0.5–4.12) MPa, respectively. Furthermore, the effect of sodium dodecyl sulfate (SDS) on the gas hydrate formation rate was examined. A substantial growth in the hydrate nucleation rate was observed in the presence of SDS.     

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。     

Nanofluid-assisted gas to hydrate (GTH) energy conversion for promoting CO2 recovery and sequestration processes in the petroleum industry

In this work the enhancement of gas to hydrate conversion employing the nanographene oxide (NGO)–based nanofluid regarding CO₂ capture and sequestration recovery is investigated. A new series of experiments are carried out at different pressures, temperatures, agitation intensities and NGO promoter concentrations by using a newly developed fully automated GTH (gas to hydrate) energy converter. According to the presented results at the 3 MPa and 275.15 K and in the presence of 30 ppm NGO, it is possible to reach a CO₂ gas to hydrate conversion of 95% at a low impeller speed in less than 2.5 h, which is quite interesting from an energy consumption standpoint. The presented approach can have potential application for development of low cost hydrate-based carbon dioxide recovery plants in petroleum industry.     

氧化石墨烯作为新型促进剂加速CO_2水合物生成实验

为了解决气体水合物生成速率慢、储气密度低、生成条件苛刻等难题,利用高压反应釜生成实验装置,探究了添加质量浓度为0.2 g/L的氧化石墨烯对CO_2水合物生成的诱导时间、气体消耗量及CO_2水合物相平衡压力的影响,揭示了温度和压力的变化规律,与去离子水中CO_2水合物生成实验进行了比较并分析了其促进机理。结果表明:①氧化石墨烯具有动力学促进和热力学促进的双重作用,能够加快CO_2水合物体系的传热传质效率,促进气体溶解,提高成核速率和气体消耗量,降低相平衡压力;②与去离子水相比,氧化石墨烯体系下CO_2水合物生成诱导时间缩短了74%~85%;③温度为6℃时,随着初始压力的不同氧化石墨烯均能提高气体消耗量,在4 MPa时气体消耗量增长幅度最大,达17.2%,提高了水合物储气密度;④氧化石墨烯降低CO_2水合物相平衡压力的最大降幅为20%。结论认为,该新型促进剂能够提高CO_2水合物的生成速率和储气密度。