Development of key additives for organoclay-free oil-based drilling mud and system performance evaluation

Traditional oil-based drilling muds(OBMs) have a relatively high solid content, which is detrimental to penetration rate increase and reservoir protection. Aimed at solving this problem, an organoclay-free OBM system was studied, the synthesis methods and functioning mechanism of key additives were introduced, and performance evaluation of the system was performed. The rheology modifier was prepared by reacting a dimer fatty acid with diethanolamine, the primary emulsifier was made by oxidation and addition reaction of fatty acids, the secondary emulsifier was made by amidation of a fatty acid, and finally the fluid loss additive of water-soluble acrylic resin was synthesized by introducing acrylic acid into styrene/butyl acrylate polymerization. The rheology modifier could enhance the attraction between droplets, particles in the emulsion via intermolecular hydrogen bonding and improve the shear stress by forming a three-dimensional network structure in the emulsion. Lab experimental results show that the organoclay-free OBM could tolerate temperatures up to 220 ?C and HTHP filtration is less than 5 m L. Compared with the traditional OBMs, the organoclay-free OBM has low plastic viscosity, high shear stress, high ratio of dynamic shear force to plastic viscosity and high permeability recovery, which are beneficial to penetration rate increase, hole cleaning and reservoir protection.

Development and applications of solids-free oil-in-water drilling fluids

The increasing application of near balanced drilling technology to low-pressure and depleted fractured reservoirs requires the use of low-density drilling fluids to avoid formation damage. Solidsfree oil-in-water （O/W） emulsion drilling fluid is one type of low-density drilling fluid suitable for depleted fractured reservoirs. In this paper, the solids-free O/W drilling fluid was developed and has been successfully used in the Bozhong 28-1 oil and gas field, by which lost circulation, a severe problem occurred previously when drilling into fractured reservoir beds, was controlled, thereby minimizing formation damage. The O/W emulsion drilling fluid was prepared by adding 20% （by volume） No. 5 mineral oil （with high flash point, as dispersed phase） into seawater （as continuous phase）. Surfactant HTO-1 （as a primary emulsifier） and non-ionic surfactant HTO-2 （as a secondary emulsifier） were added into the drilling fluid system to stabilize the emulsion; and YJD polymer was also added to seawater to improve the viscosity of the continuous phase （seawater）. The drilling fluid was characterized by high flash point, good thermal stability and high stability to crude oil contamination.

HI-OILFREE钻井液技术

大庆长垣外预探水平井具有油层物性和连续性差、储层辨识难度大、水平位移长、钻井周期长,储层含有大段泥页岩等技术难点。以往使用油包水钻井液施工,环境保护及成本压力较大,后期回收处理难度高。因此,室内优选出了HI-OILFREE钻井液,该钻井液利用胺基抑制剂AP-1对泥页岩及黏土的优良抑制作用及阳离子聚合物CAL-90对黏土的高效端面吸附作用控制水化及维护井眼稳定;利用极压润滑剂HLX-069、白油和乳化剂、固体润滑剂MRH的协同作用提高钻井液润滑性;用硅类表面活性剂作防水锁剂。室内评价及龙平1井的现场应用表明,HI-OILFREE钻井液抑制性强、流变性好、润滑效果好,荧光级别小于5,现场维护处理工艺简单,能够满足水平井钻井施工要求,储层保护效果显著,且成本与油包水钻井液相比下降了70%。

基于Label-free组学研究南极磷虾油对脂代谢的影响

为了研究南极磷虾油对脂代谢的调节作用,利用非标记(Label-free)蛋白质定量技术,比较分析灌胃南极磷虾油对高脂模型小鼠肝脏蛋白的表达影响。结果表明,与模型组相比,灌胃磷虾油后,试验组和正常组中差异蛋白表达上调的分别有125个和109个,下调表达的分别有99个和95个。进一步分析脂代谢差异蛋白发现,在试验组和正常组中表达上调的分别是棕榈酰蛋白硫酯酶1 (PPT1)、载脂蛋白B100(APOB100)、短支链酰基辅酶A脱氢酶(ACADSB)、3-羟基酰基-CoA脱水酶3(HACD3)和磺基转移酶1A1(SULT1A1);表达下调的分别为酰基辅酶A合成酶中链家族成员3(ACSM3)和酰基辅酶A合成酶家族成员2(线粒体)(ACSF2)。结合脂代谢通路分析和蛋白质相互作用网络图进一步推测,ACADSB、ACSM3和ACSF2等蛋白质在南极磷虾油调节脂代谢中起着重要的调控作用。本研究结果为深入解析南极磷虾油的作用机理和调节脂代谢的分子机制提供了依据。

Occurrence mechanism of lacustrine shale oil in the Paleogene Shahejie Formation of Jiyang Depression, Bohai Bay Basin, China

To determine the occurrence mechanism and mobility of shale oil in the Shahejie Formation in the Jiyang Depression, organic geochemistry analysis, thin-section petrological observation, low-temperature nitrogen adsorption, high-pressure mercury intrusion porosimetry, field emission scanning electron microscopy experiments were conducted on shale samples to reveal its storage mechanism, including pore size, ratio of adsorbed oil to free oil, mobility and its influencing factors, and mode of storage. Residual shale oil is mainly present in pores less than 100 nm in diameter under the atmospheric temperature and pressure. The lower limit of pore size for free oil is 5 nm, and the lower limit of pore size for movable oil occurrence is about 30 nm. The light components, low TOC and high porosity are the main factors contributing to the high proportion of movable oil. Each type of pore can contain residual shale oil, but not all pores have shale oil. Pore connectivity and surface wettability are the determinants of shale oil enrichment degree and enrichment state.

A kinetic model for a single step biodiesel production from a high free fatty acid (FFA) biodiesel feedstock over a solid heteropolyacid catalyst

Production of biodiesel from yellow grease(waste cooking oil and waste animal fats) is fast emerging as a promising alternative to address the twin challenges before the biodiesel industry today-fluctuation in prices of vegetable oil and the food versus fuel debate. Yellow grease has a high percentage of free fatty acids(FFA) and proves to be an unsuitable feedstock for biodiesel production from commercially viable alkalicatalyzed production systems due to saponification problems.'Green' methodologies based on heterogeneous solid acid catalyzed reactions have the potential to simultaneously promote esterification and transesterification reactions of yellow grease to produce biodiesel without soap formation and offer easy catalyst separation without generation of toxic streams. This paper presents kinetic studies for the conversion of model yellow grease feeds to biodiesel using a heteropolyacid supported on alumina(HSiW/Al2O3) using a batch autoclave. Three model yellow grease feeds were prepared using canola oil with added FFA such as palmitic, oleic and linoleic acid. A pseudo homogeneous kinetic model for the parallel esterification and transesterification was developed. The rate constants and activation parameters for esterification and transesterification reactions for the model yellow grease feeds were determined. The rate constants for esterification are higher than the transesterification rate constants. The kinetic model was validated using the experimental biodiesel data obtained from processing a commercial yellow grease feed. The kinetic model could be used to design novel processes to convert various low-value waste oils, fats and non-food grade oils to sustainable biodiesel.

Biodiesel Production from Waste Cooking Oil Using Sulfuric Acid and Microwave Irradiation Processes

A comparative study of biodiesel production from waste cooking oil using sulfuric acid (Two-step) and microwave-assisted transesterification (One-step) was carried out. A two-step transesterification process was used to produce biodiesel (alkyl ester) from high free fatty acid (FFA) waste cooking oil. Microwave-assisted catalytic transesterification using BaO and KOH was evaluated for the efficacy of microwave irradiation in biodiesel production from waste cooking oil. On the basis of energy consumptions for waste cooking oil (WCO) transesterification by both conventional heating and microwave-heating methods evaluated in this study, it was estimated that the microwave-heating method consumes less than 10% of the energy to achieve the same yield as the conventional heating method for given experimental conditions. The thermal stability of waste cooking oil and biodiesel was assessed by thermogravimetric analysis (TGA). The analysis of different oil properties, fuel properties and process parametric evaluative studies of waste cooking oil are presented in detail. The fuel properties of biodiesel produced were compared with American Society for Testing and Materials (ASTM) standards for biodiesel and regular diesel.

Biodiesel Production from Unrefined Rice Bran Oil through Three-Stage Transesterification

Unrefined rice bran oil (UNRFRBO) with high free fatty acids (FFA) is used as a source for the production of unrefined rice bran oil methyl ester (UNRFRBOME). Three-stage transesterification process is successfully used. Initially, the FFA of UNRFRBO is reduced to 1% (0.8%) by using two stages esterification process with methanol in the presence of acid (H2SO4) as a catalyst. Finally, biodiesel has produced by alkaline (NaOH) catalyzed transesterification process which has designed according to the central composite design. 90% has obtained at the optimum values of CH3OH (20% v/v of oil), NaOH (1.0% w/v of oil), reaction time (60 minutes) and reaction temperature (55°C to 60°C).

济阳陆相断陷盆地页岩油研究进展

济阳陆相断陷盆地页岩油是现实的资源接替新领域,具有巨大勘探潜力,是胜利油田可持续发展的重要资源基础。结合近年来济阳陆相断陷盆地页岩油地质研究与勘探成效,系统梳理了济阳陆相断陷盆地页岩沉积、成储、成烃及页岩油富集理论认识、配套增产压裂技术等方面的新进展。研究表明:①提出了基于矿物组成、沉积构造、结晶程度和有机质丰度的“四要素三端元”页岩岩相划分方案,揭示了“四古控相”机制,明确了页岩岩相呈“环带状”有序分布。②集成岩心微纳米CT扫描、氩离子抛光扫描电镜、FIB-FESEM、核磁共振冻融、X射线小角散射等页岩多尺度孔缝系统量化表征技术,明确了济阳陆相断陷盆地页岩储集空间孔缝兼顾,以无机孔缝为主,揭示了方解石重结晶、溶蚀作用和伊/蒙混层向伊利石转化作用是最为主要的成储机制,构建了页岩孔缝网络储集模型。③研发了富有机质页岩含油率评价方法,揭示了咸化湖盆富有机质页岩古生产力高、早生、早富特点,初步估算济阳陆相断陷盆地页岩油资源量超过1010t。④纹层/层状页岩岩相成烃、成储时空耦合控制了页岩油富集,表现为“咸化源岩早生、无机孔缝储集、微观源储一体、二元耦合富集”模式。⑤创建了陆相断陷盆地页岩油勘探“四性”“四定”综合评价体系及目标优选流程。⑥研发了适合济阳陆相断陷盆地页岩的“组合缝网压裂”“水平井多级分段”增产压裂技术。结合胜利油田实际情况,确立了“主力洼陷增储上产、富油小洼陷探索新阵地、外围小洼陷落实资源、兼顾优化矿权”的勘探思路,有序推进济阳陆相断陷盆地页岩油规模增储建产,相关成果认识与配套技术对同类油田的页岩油勘探开发具有一定的借鉴和参考意义。

Rapid Extraction and Analysis of Essential Oil from Cinnamomum Cassia Presl.

An improved solvent-free microwave extraction（ISFME） was used for the extraction of essential oil from dried Cinnamomum cassia Presl. Two kinds of solid microwave absorption media[carbonyl iron powder（CIP） and graphite powder（GP）] were used. When ISFME was applied, the heating rate was enhanced and the extraction time was obviously shorter than that consumed in conventional solvent-free microwave extraction（CSFME）. Twenty-eight kinds of compounds in the essential oil were identified, and the total content fractions of the compounds obtained by CIP-ISFME, GP-ISFME, CSFME, and hydrodistillation（HD） were 96.65%, 96.06%, 97.22%, and 96.29%, respectively. The compounds in the essential oil obtained from Cinnamomum cassia Presl. by ISFME, CSFME, and HD were compared and the quantity of the essential oil was almost the same. The ISFME has been proved to be a feasible way to extract essential oil from dried samples, and there are several obvious advantages in ISFME over those of HD and CSFME, for example, shorter extraction time（30 min） and lower energy consumption.

二维核磁共振技术评价CO_(2)吞吐对不同状态页岩油的动用率

游离态和吸附互溶态页岩油动用的难易程度不同,不同状态页岩油动用程度的准确表征对于页岩油的高效开发具有重要意义。结合二维核磁共振技术和CO_(2)吞吐实验,建立了CO_(2)吞吐过程中不同赋存状态页岩油划分及动用率的评价方法。采用该方法处理得到的CO_(2)吞吐过程中页岩油总动用率与质量变化计算得到的总动用率基本一致,验证了该方法的准确性。此外,可以直观地看到吸附互溶态页岩油和游离态页岩油二维核磁共振图谱随吞吐轮次的变化,游离态页岩油的动用要比吸附互溶态页岩油更容易,而提高压力和吞吐轮次可以明显提高吸附互溶态页岩油的动用率,10 MPa吞吐5个轮次后,吸附互溶态页岩油的动用率和总动用率分别达到73.6%和91.1%。该方法可对吸附互溶态页岩油动用率进行定量评价,有助于优化页岩油CO_(2)吞吐增产工艺,大幅提高页岩油采收率。

基于油基钻屑制备压裂支撑剂的室内研究

针对热解析后脱油钻屑处理难和处理方式单一的问题,开展了将油基钻屑残渣制备成免烧压裂支撑剂的研究,研究了钻屑与水泥比、CMC添加量、石膏添加量和养护天数共4个因素对免烧压裂支撑剂性能影响。结果表明,在原料配比较优的情况下,制备工艺为钻屑水泥比0.67(质量比),石膏添加量为6%(质量分数),CMC添加量为4%(质量分数),养护时间28 d。该条件下制得的压裂支撑剂颗粒体积密度为1.47 g/cm^(3),视密度为2.52 g/cm^(3),35 MPa下颗粒破碎率为1.57%。经扫描电子显微镜与X射线衍射仪分析发现,此时压裂支撑剂内部结构致密,孔隙封闭,水化产物CaO·SiO_(2)·nH_(2)O凝胶和钙长石类物质有利于提高压裂支撑剂的综合物理性能。为脱油钻屑残渣利用提供新的方向。

The Antioxidant Activity of Barley Malt Rootlet Extracts in Heated Corn Oil at Frying Temperature

In this study the antioxidant activity of barley malt rootlet (BMR) extracts was evaluated in heat treated corn oil up to 5 hours at 185°C frying temperature. The antioxidant activity of BMR extracts was measured at 25, 50, 100 and 150 ppm concentrations. The free and bound antioxidant phenolics were extracted from BMR using three different extraction methods. Conventional solvent extraction (CSE), microwave assisted extraction (MAE) and autoclave assisted pretreated solvent extraction (APSE). In the present experiment, the total phenolic content and antioxidant activity of the various extracts were measured. Thiobarbituric acid reactive substances (TBARS) assay was used to evaluate the ability of the BMR to protect lipid peroxidation in corn oil at 185°C frying temperature. The formation of TBARS at 5 hours of heat treated corn oil has shown similar antioxidant levels in 150 ppm butylated hydroxytoluene (BHT) or MAE free phenolic extract added to corn oil. TBARS value for BHT was 1.896 ± 0.013 μg/mL of corn oil and for MAE was 1.896 ± 0.034 μg/mL of corn oil. The highest level of antioxidant activity was found for the free phenolic extracts. The order of inhibition of oxidation was found to be for free phenolics as follows: BHT (100 ppm) > APSE (50 ppm) > MAE (100 ppm) > CSE (100 ppm).

陆相页岩层系岩心中气态烃井场测定技术初步应用及展望

陆相页岩层系的流体分析是页岩油甜点评价的重要基础,针对岩心样品中气态烃易于散失的特性和页岩油钻井现场的需求,研发了井场岩心气态烃快速采集测定装置及方法,探讨了基于岩心气态烃分析和热解含油性分析资料快速计算视气油比和估算游离油损失的方法。研究表明,该装置适用于全直径岩心和块状样品的气态烃检测,既可以实现全直径岩心在常温、常压下逸散气态烃的采集测定,也可以测定块状岩心样品的气态烃总量,气态烃检测相对误差10%,测试结果可以转换为单位质量岩样气态烃含量。全直径岩心逸散气分析可实现岩心气态烃的非破坏式采集和测定,反映了页岩层系垂向上含油气性及其非均质性的变化特征。视气油比可反映页岩层系含油气性和可流动性的趋势,视气油比越大,代表相应页岩层系页岩油可流动性越好。利用视气油比可估算岩心经历降压降温脱气过程中游离烃的损失量,在建立岩心降温降压脱气过程的热解游离烃损失恢复方法中具有较大应用潜力。岩心气态烃井场测定技术丰富了适用于井场的岩心流体分析实验技术手段和方法,为陆相页岩层系流体评价及甜点确定提供数据支撑。

页岩油赋存特征、可动性实验技术及研究方法进展

赋存特征与可动性是页岩油评价及勘探开发的一项重要内容,但由于页岩非均质性强,孔隙结构及流体性质较为复杂,页岩油赋存特征及可动性的表征仍存在较大挑战。近些年,随着中外页岩油勘探开发的进行,一些新的研究方法和实验技术不断涌现。为此,针对页岩油赋存特征及可动性评价方面的研究方法和实验技术进展进行了梳理,并提出了页岩油赋存特征及可动性研究需要考虑的问题。现有技术中,利用先进的高分辨率成像技术进行图像观察是定性评价页岩油赋存特征的最直接方法;基于统计分析的油饱和度指数法和分级评价方法在成熟探区评价页岩油可动性具有优势;多温阶热解参数法是目前快速高效定量表征不同赋存状态页岩油量的方法,在页岩含油性、页岩油可动性及资源量评价方面具有较好的应用前景。在未来页岩油赋存特征及可动性研究时,需要充分考虑以下问题:①开发高仿真的页岩油富集、流动及开发模拟实验,保证实验条件与地下地质条件的相似性。②开展微纳米尺度下页岩油微观流动实验,探索页岩油微观流动机理及控制因素。③详细剖析不同基础薄层中页岩油赋存特征及可动性的差异性,以及不同基础薄层对页岩含油性及页岩油可动性的贡献。④将页岩油微观赋存形式、流体机理与宏观地质参数结合,确定评价页岩油可动性的宏观地质条件及参数。

增效型无土相仿生油基钻井液技术的研究与应用

针对深井超深井钻井过程中钻遇高温高压、井壁失稳及井下复杂情况的难题,基于仿生学、超分子化学以及岩石表面润湿性理论,通过优选仿生增效剂、仿生提切剂及仿生降滤失剂,配套相关处理剂,最终形成了一套适用于深井、超深井地层钻探的增效型无土相仿生油基钻井液体系。研究发现,建立的增效型无土相仿生油基钻井液体系可抗220℃高温,配制密度为2.4 g/cm^(3),破乳电压大于400 V,高温高压滤失量为3.2 mL,人造岩心在该体系中220℃下老化后的抗压强度达到7.1 MPa,平均渗透率恢复值为93.9%。现场应用情况表明,体系流变性能稳定,平均机械钻速比邻井提高16%,平均井径扩大率仅为1.25%,可有效解决深井超深井钻井过程中出现的井壁失稳难题,为我国深井超深井的钻探提供了技术保障。

高邮凹陷花庄地区阜二段烃源岩有机地化特征与含油性

利用最近钻探的几口页岩油探井资料,开展苏北盆地高邮凹陷花庄地区古近系阜宁组二段烃源岩有机地化特征和含油性研究。通过对有机碳含量、氯仿沥青“A”、总烃含量和生烃潜量(S_(1)+S_(2))等指标的分级评价,以及对干酪根显微组分、镜质体反射率(R_(o))、岩石热解最高峰温(T_(max))、正构烷烃分布和生物标志物组成等参数分析,有机质丰度总体上达到好烃源岩-优质烃源岩标准;有机质类型主要为Ⅰ型、Ⅱ_(1)型和Ⅱ_(2)型,且从下往上,有机质类型变好;有机质成熟度总体到达成熟—高成熟阶段。采用两种方法(游离油含量法和含油饱和指数法)对花庄地区阜二段烃源岩含油性进行评价,认为其含油性到达Ⅰ类或Ⅱ类标准,具有较大的勘探潜力。研究结果对高邮凹陷下一步页岩油勘探地质甜点的选择起到一定的指导作用。

页岩油藏各赋存态油相体积的计算理论与方法

页岩油是赋存于富有机质页岩层系中的石油,勘探开发潜力巨大。页岩油赋存状态多样,油相主要以游离态赋存于无机矿物孔隙和有机质内部发育的孔隙中,以及以溶解态存在于有机质高分子缩聚物内部的溶解态油相,准确劈分不同赋存状态的油相体积对页岩油藏储量精细评价具有重要意义。目前,页岩油储层含油量主要是在孔径分析法、流体饱和实验、热解法或氯仿沥青“A”法等实验测试的基础上计算得到,但受限于测试原理和条件,这些方法无法准确表征不同赋存态页岩油体积。现基于页岩储集特征和流体赋存状态分析,建立页岩油藏各赋存态油相体积的理论计算模型,模型能够根据页岩物性参数定量计算页岩无机孔隙中的游离态油相体积、有机孔隙中的游离态油相体积、有机质内部的溶解态油相体积和总含油量,并能够得到页岩无机矿物介质和有机质的非常规物性参数,实现页岩各赋存态油相体积和总含油量的准确计算。结果表明:总有机碳含量主要影响有机质内部的有机游离态油相体积与溶解态油相体积,有机质溶解度主要对溶解态油相体积产生影响,页岩总孔隙度主要受无机孔隙度的影响,对于总孔隙度较高的页岩,其内部的无机游离态油相含量越高,有利于弹性开采。研究成果为页岩油藏的储层表征和储量准确评价提供了理论依据。

含双温敏单体的耐220℃高温降失水剂

针对目前油井水泥降失水剂高温条件下耐温性差的问题,通过分子结构设计,以丙烯酰胺(AM)、对苯乙烯磺酸钠(SSS)、双温敏单体N,N-二甲基丙烯酰胺(DMAA)与N,N-二乙基丙烯酰胺(DEAA)为原料,通过水溶液自由基聚合法制备了一种耐高温降失水剂(LHF-1L)。以失水量为评价指标,对合成条件进行了优选,同时对LHF-1L进行了结构表征和性能评价。结果表明,在AM、SSS、DMAA、DEAA物质的量比为4∶6∶2∶0.5,引发剂为单体总质量0.75%的过硫酸钾(KPS)溶液,反应物溶液pH值为7,反应温度为65℃,反应时间为4 h的条件下制得的LHF-1L的降滤失性能最佳。在220℃、7%加量下的失水量为42 mL。FT-IR、TG和GPC测试结果表明,4个单体均成功参与聚合并生成目标产物。当温度达到273℃后,LHF-1L才出现明显的热损失,其多分散系数为1.396,数均分子量为171 351 g/mol。此外,LHF-1L对水泥浆流动度和水泥石抗压强度发展的影响较小。在220℃下,在水泥浆中加入7%LHF-1L后的失水量仍能控制在50 mL以内。在150℃、94.4 MPa下,LHF-1L不会使水泥浆急剧增稠和超缓凝,稠化曲线正常,未发生异常胶凝现象。采用双温敏单体制备LHF-1L,增强了其在高温下的温敏疏水缔合作用,从而提高了高温降滤失性能,可以满足高温条件下的固井技术需求。