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Microbial H2S generation in hydrocarbon reservoirs: Analysis of mechanisms and recent remediation technologies 微生物在油气藏中产生H2S:机理分析及最新修复技术
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104729
Haithm Salah Hagar , Jalal Foroozesh , Sunil Kumar , Davood Zivar , Negar Banan , Iskandar Dzulkarnain

Sulphate reducing prokaryotes (SRP) cause hydrogen sulphide (H2S) generation in some waterflooded hydrocarbon reservoirs that is known as microbial reservoir souring or biosouring. The H2S generated in-situ by SRP is toxic and corrosive that adversely affects the quality, production, and economy of oil fields together with negative environmental impacts. Various chemical, biological, and microbial methods have been implemented to control such in-situ microbial reactions in the past few decades but still they are not fully controllable. This work aims to give deeper insight into microbial reservoir souring and its mitigations techniques. First, this review elaborates on the complex physics of souring and subsequently explores the latest modelling tools being used to capture the biochemistry of souring and the physics of H2S generation. Later, a critical discussion on the impact of governing parameters such as fluid composition, temperature, pressure, pH, and salinity on H2S biogeneration is added. Next, H2S-fluid-rock interactions leading to partitioning, adsorption, and scavenging phenomena are scientifically explained and their effects on H2S transport are elucidated. Various mitigation and control techniques are presented and critically compared in view of their suitability and applicability in different scenarios. Finally, some field cases are reported, and the key challenges and the forthcoming research requirements are highlighted. This insightful review provides necessary information on microbial activities in hydrocarbon fields that are important for chemical and petroleum engineers to tackle souring issue.

硫酸盐还原原核生物(SRP)在一些水淹油气藏中产生硫化氢(H2S),这被称为微生物油藏酸化或生物酸化。SRP在现场产生的H2S具有毒性和腐蚀性,会对油田的质量、产量和经济性产生不利影响,并对环境产生负面影响。在过去的几十年里,人们已经采用了各种化学、生物和微生物方法来控制这种原位微生物反应,但它们仍然不是完全可控的。这项工作的目的是更深入地了解微生物储层酸败及其缓解技术。首先,本文详细阐述了酸化的复杂物理过程,随后探讨了用于捕获酸化生物化学和H2S生成物理过程的最新建模工具。随后,对控制参数(如流体成分、温度、压力、pH和盐度)对H2S生物生成的影响进行了重要讨论。其次,科学地解释了H2S-流体-岩石相互作用导致的分配、吸附和清除现象,并阐明了它们对H2S运输的影响。介绍了各种缓解和控制技术,并对其在不同情况下的适宜性和适用性进行了严格比较。最后,报告了一些实地案例,并指出了主要挑战和未来的研究要求。这篇有见地的综述为油气领域的微生物活动提供了必要的信息,对化学和石油工程师解决酸化问题具有重要意义。
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引用次数: 7
Nano-CT measurement of pore-fracture evolution and diffusion transport induced by fracturing in medium-high rank coal 中高煤阶压裂孔隙-破裂演化及扩散输运的纳米ct测量
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104769
Qifeng Jia , Dameng Liu , Yidong Cai , Yuejian Lu , Rui Li , Hao Wu , Yingfang Zhou

Fracturing, as a common fracture-making technique, can improve the permeability of coal seams to enhance fluid transport efficiency. To quantitatively evaluate the microscopic characteristics of medium-high rank coal, the loaded pore-fracture system was characterized by computerized tomography (CT) scanning under triaxial loading, followed by the analysis of stress-strain evolution, stress sensitivity and three-dimensional (3D) fractal dimension. Combined with snow algorithm and incompressible steady laminar flow simulation, the heterogeneous distribution of fluid pressure is investigated, focusing on the diffusion effect of gas transport. The results show that the strain of the high-rank coal Chengzhuang (CZ) in the linear elastic stage increases from 0.25% to 1.25%, greater than that of the medium-rank coal Qiyi (QY) from 0.75% to 1.63%, demonstrating a slight lag of the high-rank coal from the linear elastic stage into the yielding stage. The porosity of CZ changes from 1.66% to 13.58% and that of QY varies from 1.74% to 22.28% after fracturing, reflecting that the primary and secondary pores of the medium- and high-rank coals form a complex network structure for fluid transport through continuous connection-expansion. When the strain is between 0.75% and 1.25%, the stress sensitivity coefficient of CZ decreases from 0.13 to 0.02. Moreover, there are many mutation points in the 3D fractal dimension of coal samples after fracturing, mainly due to the generation of new pore-fractures at different locations of the computational domain. For fluid transport, the pressure of QY after fracturing spreads in a wider range than CZ, accompanied by more distribution of high fluid pressure. The diffusion coefficient of the fractured CZ is 350 times higher than that of the original coal under the gas pressure condition of 0.5 MPa, which provides the possibility for more gas to be converted from Knudsen diffusion to transition diffusion or Fick diffusion in the channel.

压裂作为一种常用的造缝技术,可以提高煤层的渗透率,提高流体的输运效率。为了定量评价中高煤阶煤的微观特征,采用三轴加载下的CT扫描技术对加载后的孔隙-破裂系统进行了表征,并进行了应力-应变演化、应力敏感性和三维分形维数分析。结合积雪算法和不可压缩定常层流模拟,研究了流体压力的非均匀分布,重点研究了气体输运的扩散效应。结果表明:高煤阶程庄煤(CZ)在线弹性阶段的应变由0.25%增加到1.25%,高于中煤阶齐宜煤(QY)的应变由0.75%增加到1.63%,表明高煤阶煤从线弹性阶段进入屈服阶段有轻微滞后;压裂后CZ孔隙度变化范围为1.66% ~ 13.58%,QY孔隙度变化范围为1.74% ~ 22.28%,反映了中高阶煤的原生孔和次生孔通过不断的连接扩张形成复杂的网络结构,进行流体输送。当应变在0.75% ~ 1.25%之间时,CZ的应力敏感系数从0.13减小到0.02。此外,煤样在压裂后的三维分形维数中存在许多突变点,这主要是由于在计算域的不同位置产生了新的孔隙裂缝。在流体输运方面,压裂后QY区压力分布范围较CZ区大,高压分布较多。在0.5 MPa的瓦斯压力条件下,裂隙CZ的扩散系数比原煤的扩散系数高350倍,为通道内更多的瓦斯由Knudsen扩散向过渡扩散或Fick扩散转化提供了可能。
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引用次数: 3
Corrosion mechanism of X65 steel exposed to H2S/CO2 brine and H2S/CO2 vapor corrosion environments H2S/CO2卤水和H2S/CO2蒸气腐蚀环境下X65钢的腐蚀机理
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104774
Min Qin , Kexi Liao , Guoxi He , Qing Zou , Shuai Zhao , Shijian Zhang

Wet gas gathering and transportation in natural gas production has good economic benefits, but it also brings many risks. Due to the synergistic effect of corrosive gas and multi-phase flow in the wet gas pipeline, there are two corrosive environments, which leads to frequent accidents of pipeline corrosion failure. In this paper, the corrosion experiments of X65 steel in two environments (H2S/CO2 vapor; H2S/CO2-dissolved brine) were completed by a high-temperature and high-pressure reactor. Combined with SEM, EDS and XRD instruments, the morphology, elements and compounds of corrosion products were analyzed. The corrosion impact of temperature, flow rate, CO2 and H2S in both environments was determined. Finally, corrosion mechanism in two corrosion environments were established. When CO2 and H2S coexisted, both in two corrosive environments, the two gases were involved in the corrosion of X65 steel, and the corrosion products formed were FeCO3 and FeS in the liquid phase. The difference was that the corrosion product film in the gas phase was denser than that in the liquid phase and the corrosion rate in the gas phase was smaller than that in the liquid. There was a large amount of Cl and high shear force brought by the flowing, the corrosion product film fell off and formed local corrosion. In the gas phase, due to the H2S and CO2 higher concentration, a dense corrosion product film rapidly formed in the droplets. In the two environments, the order of corrosion factors is PH2SPCO2 Velocity > Temperature. But in the gas phase environment, H2S dominates in the gas phase more than in the liquid phase because it is more soluble in droplets.

天然气生产中的湿式集输具有良好的经济效益,但也带来了诸多风险。由于湿气管道中腐蚀性气体和多相流的协同作用,存在两种腐蚀环境,导致管道腐蚀失效事故频发。本文对X65钢在两种环境(H2S/CO2蒸气;H2S/ co2溶解盐水)在高温高压反应器中完成。结合扫描电镜(SEM)、能谱仪(EDS)和x射线衍射仪(XRD)对腐蚀产物的形貌、元素和化合物进行了分析。测定了两种环境下温度、流速、CO2和H2S对腐蚀的影响。最后,建立了两种腐蚀环境下的腐蚀机理。当CO2和H2S共存时,在两种腐蚀环境下,这两种气体都参与对X65钢的腐蚀,形成的腐蚀产物为液相的FeCO3和FeS。不同之处在于气相的腐蚀产物膜比液相的腐蚀产物膜密度大,气相的腐蚀速率比液相的腐蚀速率小。由于流动带来大量Cl−和较大的剪切力,腐蚀产物膜脱落,形成局部腐蚀。在气相中,由于H2S和CO2浓度较高,在液滴中迅速形成致密的腐蚀产物膜。在两种环境下,腐蚀因子的大小顺序为:PH2S > PCO2 Velocity >温度。但在气相环境中,H2S在气相中比在液相中更占优势,因为它更容易溶于液滴。
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引用次数: 1
Experimental study on hydraulic fracturing in clayey-silty hydrate-bearing sediments and fracability evaluation based on multilayer perceptron-analytic hierarchy process 黏性粉质含水沉积层水力压裂试验研究及基于多层感知器-层次分析法的可压性评价
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104735
Shuaishuai Nie , Xiuping Zhong , Jian Song , Guigang Tu , Chen Chen

Hydraulic fracturing is considered a promising stimulation technology for low-permeability hydrate reservoirs. To date, only a few studies have focused on hydraulic fracturing in hydrate-bearing sediments. However, the numerous factors that affect fracture initiation and propagation are not clearly understood, and the fracability of non-diagenetic geo-materials has not been systematically evaluated. In this study, a series of true triaxial hydraulic fracturing experiments are conducted on clayey-silty hydrate-bearing sediments to investigate the effects of the key reservoir and engineering parameters on fracture initiation and propagation. Based on the resulting data, a fracability index (FI) that considers multiple factors is developed using a novel method. The results indicate that fracture initiation pressure does not always increase with increasing hydrate saturation. Moreover, a maximum value of 14.92 MPa for the initiation pressure is observed at 40% hydrate saturation. This value is increased by 20.51 MPa when the effective horizontal in-situ stress increases from 1 to 4 MPa, which is in contrast to the tensile crack initiation law of elastic rocks. Additionally, owing to the inhomogeneous hydrate in sediments, fractures expand unevenly, and double fractures are able to form in an isotropic horizontal stress state. The horizontal stress difference is the primary parameter (weight 0.4) that governs the FI, followed by the coefficient of earth pressure at rest (weight 0.31), fracture toughness (weight 0.18), and hydrate saturation (weight 0.05), and vertical in-situ stress (weight 0.05). Increasing the injection rate and fracturing fluid viscosity is an effective method to promote fracture propagation, particularly when Qμ> 0.33 (defined by the normalised injection rate and fracturing fluid viscosity) and FI> 0.4. In such conditions, a considerable reconstruction area can be obtained.

水力压裂被认为是一种很有前途的低渗透水合物增产技术。迄今为止,只有少数研究集中在含水合物沉积物的水力压裂上。然而,影响裂缝起裂和扩展的诸多因素尚不清楚,非成岩地物质的可裂性尚未得到系统评价。本研究通过对泥质粉质含水沉积层进行真三轴水力压裂试验,研究关键储层及工程参数对裂缝起裂扩展的影响。在此基础上,提出了一种考虑多种因素的压裂指数(FI)。结果表明,裂缝起裂压力并不总是随着水合物饱和度的增加而增加。水合物饱和度为40%时,起始压力最大值为14.92 MPa。当有效水平地应力从1 MPa增加到4 MPa时,该值增加了20.51 MPa,这与弹性岩石的拉裂起裂规律相反。此外,由于沉积物中水合物的不均匀性,裂缝扩展不均匀,在各向同性水平应力状态下可形成双裂缝。水平应力差是决定FI的主要参数(权重为0.4),其次是静土压力系数(权重为0.31)、断裂韧性系数(权重为0.18)、水合物饱和度系数(权重为0.05)和垂直地应力系数(权重为0.05)。增加注入量和压裂液粘度是促进裂缝扩展的有效方法,特别是当Qμ >0.33(由归一化注入速率和压裂液粘度定义)和FI>0.4. 在这种条件下,可以获得相当大的重建面积。
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引用次数: 7
Influences of diffusion-limited transport in the crystals and initial water on the gaseous CO2 dynamic replacement in CH4 hydrate 晶体和初始水的扩散限制输运对CH4水合物中气态CO2动态置换的影响
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104741
Yingfei Wang, Bo Dong, Lunxiang Zhang, Cong Chen, Weizhong Li, Yongchen Song, Yang Liu

CO2–CH4 dynamic replacement is a process of the CO2–CH4 replacement method. In this process, CO2 is injected into CH4 hydrate-bearing sediment continuously to recover CH4. The dynamic replacement process can be divided into the CO2 displacement stage and the subsequent dynamic replacement stage and is affected by the existence of initial water and diffusion-limited transport caused by the mixed hydrate layer. Effective fugacity is utilized to combine the thermodynamic model and kinetic model to investigate the effects of the above two factors on the CH4–CO2 dynamic replacement process. Initial water is assumed to distribute in the pore space. The CH4 hydrate decomposition due to the decrease of CH4 partial pressure in the gas phase during the CO2 displacement stage is considered. Our investigation results show that diffusion-limited transport is the main factor that restricts the replacement percent in the displacement stage, the effect of the existence of initial water on the replacement percent is more obvious than that of the diffusion-limited transport. CO2 storage efficiency is less than 10% during the entire dynamic replacement and is mainly affected by the existence of initial water rather than the diffusion-limited transport. The temperature increase is mainly due to newly formed hydrate. Finally, more CH4 hydrate is exploited near the outlet than that near the inlet. Therefore, the CH4–CO2 replacement method needs to be enhanced near the inlet. CO2 is mainly sequestrated in the CO2 hydrate formed through free water. CO2 sequestrated in the mixed hydrate is mainly distributed near the inlet, while the CO2 sequestrated in the CO2 hydrate is mainly distributed near the outlet.

CO2-CH4动态置换是CO2-CH4置换法的一个过程。在此过程中,向含CH4水合物的沉积物中不断注入CO2,以回收CH4。动态置换过程可分为CO2置换阶段和后续动态置换阶段,受初始水的存在和混合水合物层造成的扩散限制输运的影响。利用有效逸度结合热力学模型和动力学模型,考察上述两个因素对CH4-CO2动态置换过程的影响。假设初始水分布在孔隙空间中。考虑了CO2置换过程中气相CH4分压降低导致的CH4水合物分解。研究结果表明,在驱替阶段,扩散限制输运是制约置换率的主要因素,初始水的存在对置换率的影响比扩散限制输运的影响更为明显。在整个动态置换过程中,CO2储存效率小于10%,主要受初始水的存在而非扩散限制输运的影响。温度升高主要是由于新形成的水合物。出口附近的CH4水合物开采量大于进口附近的CH4水合物开采量。因此,需要在进口附近加强CH4-CO2置换方法。二氧化碳主要被封存在通过自由水形成的二氧化碳水合物中。混合水合物中固存的CO2主要分布在进口附近,而CO2水合物中固存的CO2主要分布在出口附近。
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引用次数: 1
A modeling approach to stress-dependent porosity and permeability decays of rocks 岩石应力相关孔隙度和渗透率衰减的建模方法
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104765
Teng Su , Hongwei Zhou , Jiawei Zhao , Zelin Liu , Huilin Deng

The rock porosity or permeability highly depends on stress, a crucial property in resource exploitation and geological storage engineering. However, due to factors such as rock types, loading paths, and loading ranges, the stress-porosity/permeability relationships are pretty different, exhibiting linear, nonlinear, or even heavy-tailed characteristics. The exponential and power-law models, two mainstream empirical relationships for describing the rock permeability and porosity decays, are used to fit the data with “heavy tail” characteristics but yield poor fitting or outrageous predictions for specific stress ranges. Based on the physical interpretation of the compaction-induced microstructural evolution inside the rock, this paper proposes fractional-order relaxation equations, which consider the memory effect of permeability/porosity variations with stress, leading to accurate descriptions of effective stress-porosity/permeability relationships by the Mittag-Leffler (ML) law. The fitting on low-permeability shales and relatively high-permeability sandstones shows that the ML law agrees better with the experimental data, especially with “heavy tail” characteristics than the two classical laws. Moreover, the numerical solutions for the proposed ML models are presented via the predictor-corrector algorithm. The relationship between the ML, exponential, and power laws is also discussed.

岩石的孔隙度或渗透率在很大程度上取决于应力,这是资源开发和地质储存工程中的一个重要性质。然而,由于岩石类型、加载路径和加载范围等因素的影响,应力-孔隙度/渗透率关系存在较大差异,表现为线性、非线性甚至重尾特征。指数和幂律模型是描述岩石渗透率和孔隙度衰减的两种主流经验关系,用于拟合具有“重尾”特征的数据,但对特定应力范围的拟合效果不佳或预测结果令人难以置信。在对压实作用下岩石内部微观结构演化进行物理解释的基础上,提出了考虑渗透率/孔隙度随应力变化的记忆效应的分数阶松弛方程,利用Mittag-Leffler (ML)定律准确描述了有效的应力-孔隙度/渗透率关系。对低渗透页岩和相对高渗透砂岩的拟合表明,ML规律与实验数据吻合较好,特别是“重尾”特征优于两个经典规律。此外,通过预测校正算法给出了所提出的机器学习模型的数值解。还讨论了ML、指数律和幂律之间的关系。
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引用次数: 3
Modeling of natural gas self-diffusion in the micro-pores of organic-rich shales coupling sorption and geomechanical effects 富有机质页岩微孔中天然气自扩散耦合吸附与地质力学效应模拟
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104757
Clement Afagwu , Saad Alafnan , Mohamed Mahmoud , I. Yucel Akkutlu

A significant amount of the natural gas in shale formations is contained in the micro- and mesopores as dissolved (absorbed) phase and on the surfaces of associated microcracks as (adsorbed) phase. The transport of natural gas in such confined spaces is primarily governed by self-diffusion as could be deduced from Knudsen number. Self-diffusion is governed by the pressure and the space confinement. In this study, realistic kerogen structures possessing both tortuous micropores and larger microcracks were formed and used to assess self-diffusion behavior during the depletion of shale reservoirs through some comprehensive molecular simulation workflow. Analysis of the transport modes revealed transition self-diffusion as the primary transport mechanism in these micropores. The sorption behavior and the mechanical properties were analyzed and incorporated to derive a transition diffusion model that is sensitive to changes in the pore pressure and the stress field. The proposed model was compared and validated against similar work in the literature. The results showed that during a typical production span, a pressure drop influences the sorption profile, the net overburden stress on the pores, and the mean free path, altering the magnitude of self-diffusivity. The calibrated pore scale model produced decent predictive ability with a relative error of 2.5–16%. The implications of structure tortuosity, sorption profile, and pore pressure on the effective diffusion coefficient and gas desorption are discussed in depth. This work provides a novel methodology for studying the effect of coupled multiphysics processes on methane transport in a realistic kerogen geometry, which could be used to calibrate a suitable pore scale model for upscaled reservoir simulation applications and accurate assessment of reservoir dynamics and ultimate recovery.

页岩地层中大量的天然气以溶解(吸收)相的形式存在于微孔和中孔中,以吸附(吸附)相的形式存在于相关的微裂缝表面。天然气在这种密闭空间中的输运主要受自扩散控制,这可以从克努森数中推断出来。自扩散受压力和空间约束的制约。在本研究中,形成了具有弯曲微孔和较大微裂缝的真实干酪根结构,并通过一些综合的分子模拟工作流程来评估页岩储层衰竭过程中的自扩散行为。输运模式分析表明,过渡自扩散是这些微孔中的主要输运机制。通过对吸附行为和力学性能的分析,建立了对孔隙压力和应力场变化敏感的过渡扩散模型。提出的模型与文献中的类似工作进行了比较和验证。结果表明,在一个典型的生产跨度内,压降会影响吸附剖面、孔隙的净覆盖应力和平均自由程,从而改变自扩散系数的大小。校正后的孔隙尺度模型具有较好的预测能力,相对误差为2.5-16%。深入讨论了结构弯曲度、吸附剖面和孔隙压力对有效扩散系数和气体解吸的影响。这项工作为研究真实干酪根几何结构中耦合多物理场过程对甲烷运移的影响提供了一种新的方法,可用于校准适合的孔隙尺度模型,用于大规模油藏模拟应用,并准确评估油藏动态和最终采收率。
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引用次数: 9
A new technology to enhance gas drainage in the composite coal seam with tectonic coal sublayer 构造煤亚层复合煤层加强瓦斯抽采新技术
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104760
Rong Zhang , Ping Wang , Yuanping Cheng , Longyong Shu , Yinfu Liu , Zhiyang Zhang , Hongxing Zhou , Liang Wang

Composite coal seam is a kind of special coal seam that is formed after complex geological structure action, including a tectonic coal sublayer. Gas can't be drained easily from this coal seam, which cause coal and gas outburst accidents (CGOA) occur frequently. A new hydraulic flushing technology was proposed in this paper to improve gas drainage. Accordingly, a new set of mechanical equipment, technology process, roadway layout system and gas extraction monitoring system are provided by drawing lessons from the Guhanshan coal mine. The stress variation and damage failure were investigated by numerical simulation on the basis of flushed-out coal and borehole geometry. The gas drainage effect, coal seam permeability and outburst risk-sensitive indexes of the special coal seam were obtained by field measurements. According to the results, hydraulic flushing can enlarge the stress unloading and plastic damaged zone around boreholes dramatically, and the coal seam permeability can be increased largely.

复合煤层是在复杂地质构造作用下形成的一种特殊煤层,包括构造煤亚层。该煤层瓦斯不容易排出,导致煤与瓦斯突出事故频发。提出了一种新的液压冲洗技术,以改善瓦斯抽放。据此,借鉴古寒山煤矿的经验,提供了一套新的机械设备、工艺流程、巷道布置系统和瓦斯抽采监测系统。基于冲刷煤层和井眼几何形状,采用数值模拟方法研究了井壁的应力变化和破坏破坏规律。通过现场实测,获得了特殊煤层瓦斯抽放效果、煤层渗透性和突出危险性敏感指标。结果表明,水力冲洗能显著扩大钻孔周围的应力卸荷区和塑性破坏区,显著提高煤层渗透率。
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引用次数: 4
A process for CO2 capture and brine salinity reduction through reaction with potassium hydroxide: A multi-stage evaluation 一种通过氢氧化钾反应捕获二氧化碳和降低盐水盐度的工艺:多阶段评价
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104756
Aya A-H. Mourad , Ameera F. Mohammad , Ali H. Al-Marzouqi , Mohammednoor Altarawneh , Mohamed H. Al-Marzouqi , Muftah H. El-Naas
<div><p><span>Solvay and modified Solvay processes are facing a major challenge in reducing brine salinity<span> to a level suitable for agriculture and industry. This challenge arises as a result of competing reactions and mixing limits between CO</span></span><sub>2</sub><span> gas and brine. Another challenge is the high solubility of sodium bicarbonate (NaHCO</span><sub>3</sub><span><span>), which results in a low overall desalination efficiency. Previous studies established the effectiveness of a modified Solvay process based on </span>potassium<span> hydroxide (KOH). The first objective of this study is to evaluate a multi-stage treatment for a modified Solvay process on the basis of potassium hydroxide (KOH) to achieve an additional reduction in ion removal from high-salinity brines and an increase in CO</span></span><sub>2</sub><span> capture as compared to previously obtained under optimal operating conditions. Three different methods were investigated. The first method evaluated the effectiveness of adding ammonium bicarbonate (NH</span><sub>4</sub>HCO<sub>3</sub>) in reducing the solubility of NaHCO<sub>3</sub>. Even though the <span><math><mrow><msup><mtext>Na</mtext><mo>+</mo></msup></mrow></math></span> and <span><math><mrow><msup><mtext>Cl</mtext><mo>−</mo></msup></mrow></math></span> concentrations were reduced by 56.2% and 40%, respectively, the total CO<sub>2</sub> uptake slightly improved by 1.2% (67.8 g CO<sub>2</sub>/1000 ml of treated brine). In the second method, the addition of extra KOH in subsequent stages was investigated to overcome the pH reduction observed in the first method. There was an <span><math><mrow><mo>∼</mo></mrow></math></span> 47.3% improvement in CO<sub>2</sub> uptake from the first method. Furthermore, the percentages of <span><math><mrow><msup><mtext>Na</mtext><mo>+</mo></msup></mrow></math></span> and <span><math><mrow><msup><mtext>Cl</mtext><mo>−</mo></msup></mrow></math></span> removal were increased to 65% and 64.5%, respectively. In the third method, the recovery of <span><math><mrow><msup><mtext>Ca</mtext><mrow><mn>2</mn><mo>+</mo></mrow></msup></mrow></math></span> and <span><math><mrow><msup><mtext>Mg</mtext><mrow><mn>2</mn><mo>+</mo></mrow></msup></mrow></math></span> was approximately 76.3% and 94.6%, respectively, following the pre-treatment step (filtration), followed by the same stages as in the second method. Reducing these ions decreased the competitive reactions and thus increased CO<sub>2</sub> solubility and reactivity with KOH, resulting in higher cumulative CO<sub>2</sub> uptake from all stages to 108.2 g CO<sub>2</sub>/1000 ml, which was 8.3% more than the second method. Additionally, solid products were characterized using scanning electron microscopy, X-ray diffraction, FTIR and Raman analysis. Finally, the dynamic behaviour of the reactor was evaluated using step changes in the inlet gas and liquid flow rate. The results are promising in terms of the reactor system's adaptabilit
Solvay和改进的Solvay工艺在将盐水盐度降低到适合农业和工业的水平方面面临着重大挑战。这一挑战是由于二氧化碳气体和盐水之间的竞争反应和混合限制而产生的。另一个挑战是碳酸氢钠(NaHCO3)的高溶解度,这导致整体脱盐效率较低。先前的研究证实了基于氢氧化钾(KOH)的改进溶剂法的有效性。本研究的第一个目标是评估基于氢氧化钾(KOH)的改进Solvay工艺的多阶段处理,与之前在最佳操作条件下获得的结果相比,该工艺可以进一步减少高盐度盐水中的离子去除,并增加二氧化碳捕获。研究了三种不同的方法。第一种方法评价了加入碳酸氢铵(NH4HCO3)降低NaHCO3溶解度的有效性。尽管Na+和Cl−浓度分别降低了56.2%和40%,但CO2的总吸收量却略微提高了1.2% (67.8 g CO2/1000 ml处理盐水)。在第二种方法中,研究了在后续阶段添加额外的KOH以克服第一种方法中观察到的pH降低。与第一种方法相比,CO2吸收量提高了~ 47.3%。此外,Na+和Cl−去除率分别提高到65%和64.5%。在第三种方法中,Ca2+和Mg2+的回收率分别约为76.3%和94.6%,经过预处理步骤(过滤),然后进行与第二种方法相同的步骤。减少这些离子减少了竞争反应,从而增加了CO2的溶解度和与KOH的反应性,导致所有阶段的累积CO2吸收量增加到108.2 g CO2/1000 ml,比第二种方法多8.3%。利用扫描电镜、x射线衍射、红外光谱和拉曼光谱对固体产物进行了表征。最后,利用进气液流量的阶跃变化对反应器的动态特性进行了评价。结果表明,该反应器系统对大规模过程的适应性是有希望的。
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引用次数: 2
Performance assessment of control strategies with application to NGL separation units 控制策略的性能评价及其在NGL分离装置中的应用
IF 4.965 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2022-10-01 DOI: 10.1016/j.jngse.2022.104763
Marta Mandis , Roberto Baratti , Jorge Chebeir , Stefania Tronci , José A. Romagnoli

In this contribution, the problem of NGL separation control is addressed by dealing with the most common process schemes. The main goal is to achieve a specified ethane recovery as well as maintaining certain levels of methane impurity in the demethanizer column. An indirect control of composition through the temperature control in the column is proposed. A cascade arrangement between the column temperature control and the controller that maintains a constant ratio of boil-up to column bottom product is proposed for the improvement of methane impurity levels. Additionally, an “inferential” control approach based on Antoine's law is formulated and tested to enhance the ethane recovery control. The performance indexes calculated for ethane recovery and methane impurity show the superiority of the proposed control structure in each NGL separation process scheme. When the feed flowrate is reduced by 10%, the proposed control strategy allows a lower deviation from the target and a smaller offset with a reduction of 73.7% for ethane recovery and 72.7% for the methane concentration in the conventional process, 86.6% for ethane recovery and 96.4% for methane concentration in the GSP, and 97.1% for ethane recovery and 91.1% for methane concentration in the CRR process. In case of sinusoidal variations of inlet flowrate, the integral square error is reduced by 99.33% for methane bottom concentration in the GSP process scheme, while ethane recovery shows a reduction of 82.69% in the CRR scheme.

在这篇文章中,通过处理最常见的工艺方案来解决NGL分离控制的问题。主要目标是实现特定的乙烷回收率,并在脱甲烷塔中保持一定水平的甲烷杂质。提出了一种通过塔内温度控制间接控制组分的方法。为了提高甲烷杂质水平,提出了在塔温控制装置和保持沸腾产物与塔底产物恒定比的控制器之间采用级联布置的方法。此外,提出了一种基于Antoine定律的“推理”控制方法,并进行了测试,以增强乙烷采收率控制。计算的乙烷回收率和甲烷杂质性能指标表明,所提出的控制结构在各NGL分离工艺方案中具有优越性。当进料流量降低10%时,该控制策略与目标偏差较小,常规工艺的乙烷回收率降低73.7%,甲烷浓度降低72.7%;GSP工艺的乙烷回收率降低86.6%,甲烷浓度降低96.4%;CRR工艺的乙烷回收率降低97.1%,甲烷浓度降低91.1%。在进口流量呈正弦变化的情况下,GSP工艺方案的甲烷底浓度积分平方误差减小了99.33%,CRR工艺方案的乙烷回收率减小了82.69%。
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引用次数: 1
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Journal of Natural Gas Science and Engineering
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