Hydraulic fracturing wastewater in Germany: composition, treatment, concerns

When studying technical methods and measures that could be applicable for flowback treatment, recycling and/or disposal, it is important to characterize the volumes and composition of hydraulic fracturing flowback. In this work, water volumes and water quality data are considered for investigating flowback at three selected drilling sites in Germany. The analysis highlighted an increase of chloride concentrations up to saturation limit over the time. High salinity concentrations were used as indicator for estimating the percentage of hydraulic fracturing fluid and formation water in flowback. For the studied shale gas well a proportion of formation water, 69 %, and hydraulic fracturing fluid, 31 %, in flowback were derived. Thus, 92 % of the hydraulic fracturing fluid remained in the formation. The physical/chemical properties of flowback were categorized in groups to enable the allocation of applicable treatment methods. The analysis revealed that no single technology can meet suitable effluent characteristics, thus two or more treatment systems might be used in series operation. In particular, for flowback containing high salinity concentrations the only treatment options are evaporation or crystallization. Hence, methodological distinctions need to be made between concentration, elimination, disposal and recycling, whereby for the existing concentrate treatment or disposal measures need to be completed and scaled up into the process.     

页岩储层-超临界CO2-模拟压裂液相互作用实验研究及其环境意义

近年来,页岩气作为一种重要的非常规天然气来源,逐渐成为国内外关注的热点。当前的研究工作总体侧重于页岩气开采技术的改进与环境监测,对页岩气开采过程中水岩相互作用还少有报道。本文采用模拟实验,选取储层页岩样品,在温度90 ℃、压力10 MPa环境下,开展了CO2压裂液页岩相互作用实验研究。主要探讨页岩气开采过程中,由于常规水力压裂液以及后期超临界CO2的增注,造成的储层岩石矿物的变化以及返排液成分的变化。实验结果显示：压裂液能使岩石矿物发生溶蚀,超临界CO2的存在会进一步加剧溶蚀反应的进行,促使孔隙变大并产生更多的微孔隙,为页岩气提供更多的运移通道,有利于油气的运移。但是,存在的环境威胁不容忽视：一方面,岩石中会溶解出大量的Ca、Mg、Si元素和少量Fe、Mn等金属元素,超临界CO2、富有机质页岩以及压裂液中表面活性剂等物质在高温高压酸性环境条件下,容易生成挥发性有机物残留在地层中,极有可能沿着岩石破碎的孔隙、断裂发生迁移或泄露,从而对地下含水层造成污染;另一方面,多种成分进入高矿化度溶液体系经返排回到地表,也会增大处理返排液的难度。本文取得的实验数据和成果有助于理解页岩气储层在开采过程中可能发生的水岩相互作用过程及其潜在的环境风险。     

Geochemical evaluation of flowback brine from Marcellus gas wells in Pennsylvania,USA

Large quantities of highly saline brine flow from gas wells in the Marcellus Formation after hydraulic stimulation (“fracking”). This study assesses the composition of these flowback waters from the Marcellus shale in Pennsylvania, USA. Concentrations of most inorganic components of flowback water (Cl, Br, Na, K, Ca, Mg, Sr, Ba, Ra, Fe, Mn, total dissolved solids, and others) increase with time from a well after hydraulic stimulation. Based on results in several datasets reported here, the greatest concentration of Cl⁻ in flowback water is 151,000 mg/L. For total Ra (combined ²²⁶Ra and ²²⁸Ra) in flowback, the highest level reported is 6540 pCi/L. Flowback waters from hydraulic fracturing of Marcellus wells resemble brines produced from conventional gas wells that tap into other Paleozoic formations in the region. The Br/Cl ratio and other parameters indicate that both types of brine formed by the evaporation of seawater followed by dolomitization, sulfate reduction and subsurface mixing with seawater and/or freshwater. Trends and relationships in brine composition indicate that (1) increased salt concentration in flowback is not mainly caused by dissolution of salt or other minerals in rock units, (2) the flowback waters represent a mixture of injection waters with highly concentrated in situ brines similar to those in the other formations, and (3) these waters contain concentrations of Ra and Ba that are commonly hundreds of times the US drinking water standards.     

贵州岑巩TX 1井牛蹄塘组页岩压裂效果评价

TX1井是四川盆地外围第一口针对牛蹄塘组页岩压裂的井,岩心现场解析含气量为1.00~3.06m3/t,含气性较好,展现了较好的勘探前景.但复杂构造以及下部含水层对后期储层改造提供了挑战.对TX1井进行了压裂改造,返排过程中气体点火2~3m,但后期一直出水,返排率大于100%.利用Meyer软件进行压裂拟合评价,结果显示TX1井在压裂过程中因沟通了底部高含水层,导致压后出水严重;压裂改造未形成复杂的裂缝网络,限制了储层改造的效果.因此认为直井压裂改造受体积的限制,只能作为对页岩储层含气性与产能的评价手段,页岩气商业性开发还需通过水平井钻井和大规模的分段压裂改造来实现.该井的钻探施工与压裂改造经验为本地区下一步勘探开发指明了方向.      

Hydraulic fracturing in unconventional gas reservoirs: risks in the geological system, part 2

Hydraulic fracturing is a method used for the production of unconventional gas resources. Huge amounts of so-called fracturing fluid (10,000–20,000 m³) are injected into a gas reservoir to create fractures in solid rock formations, upon which mobilised methane fills the pore space and the fracturing fluid is withdrawn. Hydraulic fracturing may pose a threat to groundwater resources if fracturing fluid or brine can migrate through fault zones into shallow aquifers. Diffuse methane emissions from the gas reservoir may not only contaminate shallow groundwater aquifers, but also escape into the atmosphere where methane acts as a greenhouse gas. The working group “Risks in the Geological System” as part of ExxonMobil’s hydrofracking dialogue and information dissemination processes was tasked with the assessment of possible hazards posed by migrating fluids as a result of hydraulic fracturing activities. In this work, several flow paths for fracturing fluid, brine and methane are identified and scenarios are set up to qualitatively estimate under what circumstances these fluids would leak into shallower layers. The parametrisation for potential hydraulic fracturing sites in North Rhine-Westphalia and Lower Saxony (both in Germany) is derived from literature using upper and lower bounds of hydraulic parameters. The results show that a significant fluid migration is only possible if a combination of several conservative assumptions is met by a scenario.     

煤层气井压后返排工艺

煤层气井压后返排,是关井待压力扩散一段时间后放喷,还是及时放喷,一直未能形成统一的认识。从压裂液、压力、关井时间等3个方面进行分析,认为煤层气井压裂后应及时放喷返排,建议时间控制在30 min内。同时根据煤层气井压裂后支撑剂立即沉降、颗粒之间出现胶结的特点,建立了压裂液返排模型。计算结果表明:压后返排时先用小油嘴控制放喷,然后逐步更换较大的油嘴放喷或者敞喷,及时返排压裂液,缩短返排时间。在煤层气井压后返排设计时,为定量选择放喷油嘴直径提供了重要的理论依据。      

Impact of water and nitrogen fracturing fluids on fracturing initiation pressure and flow pattern in anisotropic shale reservoirs

A numerical model is proposed to investigate the impact of water and nitrogen fracturing fluids on the fracturing initiation pressure and the flow pattern in anisotropic shale reservoirs. This model considers the anisotropy of shale deformation and permeability, the compressibility of fracturing fluid, and the fluid moving front. A crack initiation criterion is established with the stress intensity factor of mode I crack. Both crack initiation pressure and seepage area are verified and analyzed. These results show that shale deformation and permeability anisotropy, fracturing fluid compressibility, viscosity, and pressurization rate have significant impacts on fracturing initiation pressure and seepage area.     

Fracture closure modes during flowback from hydraulic fractures

Flowback analysis recently has been considered as a potential tool for assessing induced fractures through corresponding pressure analyses and rate transient analysis. In this paper, we study fracture closure mechanisms during the flowback of fracturing fluid after hydraulic fracturing treatments. Although it is known that flowback can be significantly affected by the geometry of the fractures and closure stress, there has not been any effort to understand the problem from the geomechanical point of view; rather, available studies assume that a fracture closes uniformly with constant fracture compressibility. The coupled geomechanics and fluid flow model presented in this paper help to elucidate how geostresses may affect fracturing fluid recovery under different conditions. We perform a scaling analysis to formulate the occurrence of different fracture closure modes and then use numerical analyses to verify our scaling parameters. The factors governing the flowback process include the mechanical and petrophysical properties of the rock as well as preexisting discontinuities such as natural fractures. Three different closure modes for fracture networks are described and numerically verified. The occurrence of each mode can dramatically affect fracturing fluid recovery. The role of fluid leakoff into the formation, fractures conductivity, and drawdown strategy are examined for each fracture closure scenario.     

pH值对适于页岩气储层的SDBS压裂液性能的影响研究

在低渗、低孔隙率页岩气储层压裂改造过程中,压裂液体系的pH值直接影响地层中的造缝、稳缝效果。pH值对阴离子表面活性剂压裂液的粘度、表面张力和页岩膨胀抑制性影响很大。通过改变阴离子表面活性剂的浓度,测定了在不同pH值条件下压裂液体系基本性能的变化。研究表明：SDBS压裂液体系的粘度随着pH值的增加先增大后减小,在pH值=9时达到最大;体系在pH值=5时降低体系表面张力的能力最好;页岩的膨胀量随着pH值的增大逐渐增大,在pH=7时膨胀量最大,且随着pH值的进一步增大,页岩膨胀量先减小后增大,在pH值=9时膨胀量最小;当体系的pH值一定时,SDBS在临界胶束浓度状态能够最大程度抑制页岩的膨胀。从化学微观角度上分析了pH值对SDBS压裂液性能的影响,有利于SDBS压裂液体系配方优化。     

Reductive weathering of black shale and release of barium during hydraulic fracturing

Hydraulic fracturing is an important technological advance in the extraction of natural gas and petroleum from black shales, but water injected into shale formations in the fracturing process returns with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium, Ba. It is generally assumed that high TDS comes from the mixing of surface water (injected fluid) with Na–Ca–Cl formation brines containing elevated Ba, but the mechanisms by which such mixing might occur are disputed. Here we show that Ba in water co-produced with gas could originate from water-rock reactions, with Ba levels observed in produced waters reached on a time scale relevant to hydraulic fracturing operations. We examined samples from three drill cores from the Marcellus Shale in Pennsylvania and New York to determine the possible water-rock reactions that release barium during hydraulic fracturing. Two samples, one containing microcrystalline barite (BaSO₄) and one without barite, contain elevated concentrations of Ba relative to the crustal average for shale rocks. A third sample is slightly depleted in Ba relative to the crustal average. Micro-XRF measurements and SEM/EDS analysis combined with chemical sequential extraction methods reveal that a majority of the Ba in all samples (55–77 wt.%) is present in clays and can only be leached from the rock by dissolution in hydrofluoric acid. Thus, a majority of barium in our samples is relatively inaccessible to leaching under hydraulic fracturing conditions. However, the balance of Ba in the rocks is contained in phases that are potentially leachable during hydraulic fracturing (e.g., soluble salts, exchangeable sites on clays, carbonates, barite, organics).We next studied how shale reacts with water at elevated temperatures (80 °C), low Eh (−100 to −200 mV), and a range of ionic strengths (IS = 0.85–6.4) that emulate conditions prevalent at depth during hydraulic fracturing. Our experimental results indicate that the amount of Ba released from the bulk rock has a positive correlation with the ionic strength of the reacting fluid. Between 5 and 25% of the total Ba in the rock can be leached from shale under ionic strength conditions and leachate compositions typical of produced waters over a contact time of just 7 days. We suggest that reductive weathering of black shale occurs during hydraulic fracturing due to: 1) Ba²⁺ in clays exchanging with Na⁺ and Ca²⁺ ions that are present in high concentrations in produced water, and 2) increased solubility and dissolution kinetics of barite under high ionic strength conditions. At the low Eh conditions prevalent during hydraulic fracturing the sulfate deficient water allows Ba to be dissolved into the produced water. Based on Ba yields determined from laboratory leaching experiments of Marcellus Shale and a reasonable estimate of the water/rock mass ratio during hydraulic fracturing, we suggest that all of the Ba in produced water can be reconciled with leaching directly from the fractured rock.     

裂缝参数对考虑滑脱效应页岩气水平井产能的影响

低渗透页岩气藏中,气体渗流时会受滑脱效应的影响。建立了考虑滑脱效应的气、水两相页岩气藏渗流数学模型,并建立了理想地质模型,采用数值模拟方法,研究了水力压裂的不同裂缝参数对水平井产能的影响。模拟结果表明:裂缝条数、长度和间距是影响页岩气井产能的重要参数,而裂缝宽度和渗透率对产能的影响相对较弱;页岩气井的产能随着裂缝条数和裂缝长度的增加而增大;水平井的水平段长度及裂缝条数一定时,可通过增大裂缝间距来减少裂缝间的相互干扰。      

煤系非常规天然气一体化压裂液体系研究与应用

为了解决目前煤系非常规天然气压裂液体系应用灵活性差、性能不可调问题,研究了一体化压裂液体系。以3种一体化稠化剂为研究对象,结合现场黏土稳定剂、助排剂和破胶剂,开展一体化压裂液体系增黏、减阻、悬砂、耐温抗剪切、破胶、添加剂配伍性、防膨和表面张力实验评价,并分析一体化压裂液现场应用效果。结果表明,一体化压裂液体系黏度灵活可调,黏度随一体化稠化剂含量增加而增大,黏度调整区间为3~200 mPa·s,高黏液体悬砂性能优异,体积分数为1.0%的一体化压裂液在60℃、100 S?1剪切条件下黏度大于100 mPa·s;一体化压裂液体系与各类添加剂配伍性良好,易破胶,减阻率、防膨率均大于70%,表面张力小于28 mN/m。其一体化主要体现在功能性和应用性两个方面,功能上集滑溜水、线性胶、交联液压裂液体系于一体,能够满足各类气层压裂改造工艺对造缝、减阻、防膨、携砂、快速返排等性能的要求;应用上在鄂尔多斯盆地东缘现场煤层气、页岩气、致密砂岩气井均取得了成功应用。一体化压裂液推动了非常规气压裂工艺试验,提高了压裂改造效果,对各类气层以及压裂改造工艺具有良好的适应性。      

页岩水平井多段分簇压裂起裂压力数值模拟

页岩储层孔隙度和渗透率极低,天然裂缝和水平层理发育,常规压裂增产措施无法满足页岩气的开发要求,水平井多段分簇压裂是页岩气开发的关键技术之一,该技术能够大幅度提升压裂改造的体积、产气量和最终采收率。为确定页岩储层水平井多段分簇射孔压裂的起裂点和起裂压力,采用有限元方法建立了水平井套管完井（考虑水泥环和套管的存在）多段分簇射孔的全三维起裂模型。数值模型的起裂压力与室内试验结果吻合较好,证明了数值模型的准确性和可靠性。利用数值模型研究了页岩水平井多段分簇射孔压裂的起裂点和起裂压力的影响因素,研究发现：射孔孔眼附近无天然裂缝或水平层理影响,起裂点发生在射孔簇孔眼的根部;射孔簇间距越小,中间射孔簇的干扰越大,可能造成中间的射孔簇无法起裂;射孔密度和孔眼长度增大,起裂压力降低;天然裂缝的存在,在某些情况能够降低起裂压力且改变起裂位置,主要与天然裂缝的分布方位及水平主应力差有关;水平层理可能会降低起裂压力,但与垂向主应力与水平最小主应力的差值有关。获得的起裂压力变化规律,可作为进一步研究水平井多段分簇射孔条件下的裂缝扩展规律的基础,可以为压裂设计和施工的射孔参数确定及优化给出具体建议。     

湖北宜昌震旦系陡山沱组储层特征及复杂体积压裂效果评价

鄂阳页2 HF井是国内首口针对震旦系陡山沱组的页岩气水平井,该井钻遇的陡山沱组页岩厚度大,岩石脆性好,含气性好且天然裂缝发育,具备良好的压裂改造基础.针对陡山沱组储层"高云质、地层常压、水平应力差异大、隔夹层发育"等压裂改造难点,通过采用"密分切割、多簇射孔、转向压裂"等复杂裂缝体积压裂工艺,采取变排量、暂堵转向、停泵...     

对页岩气成因及工业前景的思考

页岩本身并不生气。以页岩为储层的油气藏,以裂缝为主要储集空间,即传统的裂缝性泥页岩油气藏。北美页岩气在以硅质胶结和以硅岩为主的储层中,产量偏高。这一现象从硅质的来源上,指出页岩气与碱性地幔流体的必然联系。阿巴拉契亚盆地深度3000m以下的页岩气,甲烷同系物碳同位素值完全反序排列,从地球化学角度证明页岩气来自地幔。如果页岩仅仅是储层而非气源岩,我国"页岩气十二五规划"探明页岩气储量6000×108m3和2015年产量65×108m3的目标将失去地质依据。因巨大的环境隐患,页岩气开发所必需的水力压裂法已在英、美、法、德、瑞士、保加利亚、澳大利亚等国立法禁止,在南非推迟发放所有的水力压裂法开采许可证。页岩气开采带来的环保问题不仅仅是有害气体向大气泄露,还有超过260种有害化学物质随着每次10000m3压裂液返排到地表,不断重复地向页岩气开采地区排放,将造成空前的污染。同时造成工业和民用供水短缺。美国页岩气被市场分析师称为"伪商业产品",价格在成本区间内。我国计划到2020年页岩气产量达600 108～1000 108m3,根据美国的经验,起码需要2万口页岩气井,10年内所需投资将达到4000亿～6000亿元。显然,页岩气即将成为吞噬中国几十年经济发展成果的黑洞,即将成为破坏我们生息环境的"切尔诺贝利"。     

页岩气开采压裂液技术进展

页岩气是一种分布广泛且储量丰富的非常规能源,但由于其储层具有孔隙度小及渗透率低等特性,一直以来页岩气未得到大规模开采。直到近20年,页岩气开采技术才得到飞速发展,这主要得益于水力压裂技术的进步。压裂液是水力压裂的重要组成部分,其性能的优劣直接影响水力压裂施工的成败。通过调研国内外文献,结合国内外压裂液技术的发展历程,分析了页岩气开采中几种常用压裂液的优点、适应性及存在的问题,综述了两类新型的无水压裂技术。结合我国页岩气储层的特殊性及压裂技术发展的现状,提出了适于我国页岩气开采的压裂液技术发展的建议,并特别强调了在页岩气开发初期重视环保的重要性。     

FixAl及同位素方法在EGS返排液研究中的应用

增强地热系统(EGS)是开采低渗透率热岩体中热能的技术,属于广义的地热储工程。其中,作为换热介质被注入岩体并在换热后返回地表的返排液,不仅是岩体地球化学特征的信息载体,而且其物理化学行为直接影响着EGS系统的运行效果。FixAl化学热力学模拟和水同位素十三线图解在天然水热系统评价中得到了广泛应用,对返排液研究的实用性则是文章的核心问题。文中收集了全球主要EGS项目的返排液资料,基于FixAl方法分析矿物与返排液的化学平衡状态,并计算了流体在深部的热交换温度,用同位素模型验证了EGS系统中原生卤水的驱替过程。研究结果表明,上述方法在EGS返排液研究中是适用的。此外,返排液的化学特征对EGS的指示意义还包括厘定原生卤水在返排液中所占比例,识别岩浆挥发分溶解及储层改造时的添加剂残留,预测结垢趋势和流体腐蚀性等。未来需要通过更多的实验和模拟方法深入研究返排液的化学特征,建立EGS的热-水-力-化学(THMC)耦合模型,为科学开发深层地热能提供依据。     

A Fully Coupled Chemo-Poroelastic Analysis of Pore Pressure and Stress Distribution around a Wellbore in Water Active Rocks

Water active rocks consist of minerals that hold water in their crystalline structure and in pore spaces. Free water from drilling fluid can be attracted by the formation depending on the potential differences between pore space and drilling fluid. The fluid movement into the formation or out of the formation can lead to a change in effective stress, thus causing wellbore failures. In all previous studies it is found that the solute transport from or to the formation is primarily controlled by diffusion process and the effect of advection on solute transfer is negligible for a range of very low permeable shale formations (>10⁻⁵ mD). In this study a range of permeable shale formations (10⁻⁵ to 10⁻³ mD) commonly encountered in drilling oil and gas wells are considered to investigate the solute transfer between drilling fluid and formation due to advection. For this purpose a finite element model of fully coupled chemo-hydro-mechanical processes was developed. Results of this study revealed that the solute transfer between the drilling fluid and the shale formation is controlled primarily by permeability of the shale formations. For the range of shale formations studied here, there exists a threshold permeability below which the solute transfer is dominated by diffusion process and above which by fluid in motion (fluid flow). Results from the numerical experiments have shown that when the permeability of shales is greater than this threshold permeability, the chemical potential gradient between the pore fluid and drilling fluid reaches equilibrium faster than that when the permeability of shales is below this threshold value. Also it has been found that when advection is taken into account, effective radial and tangential stresses decrease around the wellbore, particularly near the wellbore wall where the solute concentration has reached near equilibrium.     

页岩气开发钻完井技术探讨

我国广泛分布着丰富的页岩气资源,开发应用远景良好。通过借鉴、转化、应用常规油气开发的成熟技术,可集成配套形成页岩气开发钻完井技术系列。水平井已成为页岩气开发的主要钻井方式,结合旋转导向、MWD/LWD、三维地震和欠平衡钻井等工艺技术的集成应用可提高开发效率。水力压裂工艺已成为页岩气开发的主要技术,随着清水压裂、重复压裂、同步压裂等技术的发展,页岩气的勘探开发更具发展潜力。     

页岩气开发水力压裂技术综述

世界页岩气资源丰富,但由于页岩地层渗透率很低,目前还没有广泛开发。水力压裂技术是页岩气开发的核心技术之一,广泛用于页岩储层的改造。介绍了水力压裂作业的压裂设计、裂缝监测、压裂液配制和添加剂选择,以及常用的压裂技术,包括多级压裂、清水压裂、同步压裂、水力喷射压裂和重复压裂。结合国外页岩气开发的实例和国内压裂技术的应用情况,分析了各种压裂技术的适用性。研究认为,清水压裂是现阶段中国页岩气开发储层改造的适用技术,开采长度(厚度)大的页岩气井,可以使用多级分段清水压裂技术。同步压裂技术是规模化的页岩气开发的客观需要。