含碱和表面活性剂的HPAM/Cr+3弱凝胶调驱剂的研制

从3种有机酸铬中选择一种烯基多元羧酸铬为交联剂,用于交联大庆油田三元复合驱油体系,制备弱凝胶调驱剂。以阻力系数(RF)特别是残余阻力系数(RRF)作为性能参数筛选调驱剂各组分的用量,得到了基本配方(以g/L计)如下:HPAM(M=1.2×107,HD=25%)0.9 交联剂(有效成分50%)0.18 表面活性剂(ORS41)3 碱(NaOH)8 稳定剂0.2,用大庆某三元复合驱试验区污水(矿化度3824mg/L)配液,其RRF值为清水(矿化度890mg/L)弱凝胶的～45%。基本配方弱凝胶45℃下7天时粘度18.3mPa·s,RF值81.2,RRF值8.2,随时间而减小,120天时分别为12.8mPa·s,66.1和7.3;油水界面张力仍在10-3mN/m数量级,只比常规三元复合体系略高;体系中表面活性剂在油砂上的静态吸附量为0.495mg/g油砂,比常规三元复合体系的相应值(0.462mg/g油砂)略高;岩心流动实验中测得的表面活性剂滞留量(0.067和0.070mg/g岩心)也高于常规三元复合体系的相应值(0.054和0.059mg/g岩心)。若用Na2CO3代替NaOH,则碱剂浓度可由6～8g/L提高到8～10g/L。表8参4。     

Evaluation of Interfacial Tension Between Zahra Oil and ASP Solution

Alkaline-surfactant-polymer (ASP) flooding has been proved to be an effective enhanced oil recovery (EOR) method. Reduction of interfacial tension (IFT) between crude oil and ASP solution is the main mechanism in ASP flooding. Evaluating IFT between crude oil and ASP solution is a key parameter for ASP flooding in laboratory experiments or field projects. In order to obtain good result of ASP flooding in the reservoir in Zahra field, the influence of the concentration of Na₂CO₃ on IFT between Zahra crude oil and ASP solution with three different surfactants, BHJC, SS-231, and SS-233, was researched. IFT was measured with surface tension meter SVT20N, Dataphysics Co. Germany, at 72°C. For the view of IFT result anionic surfactant BHJC is more suitable for the Zahra oil field. This research is helpful for practical application of ASP flooding in Zahra oil field.     

速溶聚合物及其Cr3+凝胶渗流特性

与陆地油田相比较,海上平台空间狭小,对聚合物配注设备工艺和聚合物溶解速度提出了更高要求。依据海上油田矿场实际需求,本文针对渤海主要油田油藏地质和流体条件,对“速溶”聚合物产品的溶解性及其聚合物溶液和Cr³⁺凝胶黏度特性、流变性、黏弹性、分子线团尺寸和渗流特性进行了实验研究。结果表明,在渤海主要油田油藏温度和溶剂水矿化度条件下,“速溶”聚合物溶解性优于“高分”聚合物,同时表现出较强的增黏性、流变性和黏弹性。与聚合物溶液中“线性支链状”聚集体相比较,Cr³⁺聚合物凝胶内聚合物分子以“局部网状”聚集体为主,柔性变差,刚性增强,渗流阻力增加。在后续水驱过程中,注入水稀释作用导致滞留岩心孔隙内Cr³⁺聚合物凝胶分子线团尺寸Dh增加,其增加的渗流阻力大于因部分滞留聚合物离开岩心而减小的渗流阻力,这导致Cr³⁺聚合物凝胶注入压力升高,残余阻力系数大于阻力系数,表现出与聚合物溶液不同的渗流特性。     

Cr3+聚合物弱凝胶调驱剖面变化规律及改善方法

采用分子内交联为主的Cr³⁺聚合物弱凝胶,通过“分注分采”岩心驱替实验研究调驱剂段塞尺寸、岩石渗透率和原油黏度对储层吸液剖面和产液剖面的影响。针对渤海油田LD10-1区块渐新统东营组进行了“堵/调/驱”实验。研究结果表明：①调驱剂段塞尺寸对注采两端液流转向和剖面返转时机没有影响,但超过0.3 PV后单位体积段塞尺寸Cr³⁺聚合物弱凝胶提高原油采收率增幅减小,随储层渗透率级差和原油黏度增大,注采两端液流转向时机延后,剖面返转时机提前;②“有机/无机”复合凝胶体系封堵高渗透率层、聚合物微球调控微观非均质性和稠油流度改善剂提高驱油效率等3种措施同时实施,可提高聚合物弱凝胶调驱后的采收率;③“堵/调/驱”组合提高采收率机理为：封堵优势渗流通道扩大非均质储层宏观波及体积、聚合物微球在变径孔隙或喉道处发生桥堵实现微观液流转向、高效驱油剂可进入未波及孔喉区域发挥降黏原油、降低油水界面张力和高效驱替等3种作用。     

Research and Field Application of Polymer-Multiple Emulsion Crosslinker Gel for the Deep Profile Control

The authors describe a means to prolong gel time of Cr(Ac)₃-polyacrylamide gel system by coating the Cr(Ac)₃, forming the W₁/O/W₂ crosslinker. The white oil is the oil phase, and the sorbitol fatty acid esters are the water-in-oil emulsifier. The polyoxyethylene sorbitan monostearate is the oil-in-water emulsifier, which has a national patent (cf. Wang et al., 2009). The authors researched the effect of the reactants concentrations and reservoir environments are investigated to gelling behavior and plugging capacity such as temperature, salinity, and permeability. Compared to the Cr(Ac)₃ without coating, the multiple emulsion crosslinker obviously delays crosslinking and greatly increases gel time by about 3–4 times, so it is conducible to deep profile control. Reactant concentrations and temperature increase the gel strength and plugging capacity, but shorten gel time. Salinity causes gel time to shorten and lengthen, and gel strength weakens before it increases. Permeability reduces the plugging capacity and presents in linear relation in the log-log coordinate. Four wells were tested successfully in Shengli Oilfield from May to November 2008. The average injection pressure-added is 2.5 MPa, and approximately 3,200 tons of incremental oil was obtained with 6% water-cut decrease.     

Cr~(3+)聚合物凝胶与水交替注入调驱作用机理——以渤海LD10-1油田为例

针对渤海LD10-1油藏减缓吸液剖面反转技术需求,通过层内非均质岩心驱替实验,发现Cr~(3+)聚合物凝胶与水交替注入工艺具有较好的增油降水效果,运用并联岩心驱替实验,从驱替过程和驱油效果两方面探讨了交替注入增油机理。结果表明,相比整体凝胶段塞注入工艺,"Cr~(3+)聚合物凝胶+水"交替注入方式具有更好的封堵和驱替效应。凝胶前置段塞对高渗透层实施封堵后,后续水段塞一方面可使弱凝胶分子线团膨胀加强封堵效果,改善后续流体的转向能力,另一方面还可增强驱替效果,减缓吸液剖面反转现象。在实际设计交替轮次数时,应考虑水段塞过多易引起高渗透层突进的问题。     

濮城油田沙二上2+3油藏条件下体膨剂与聚合物混合调驱实验研究

报道了4个平行双岩心组合的体膨剂与聚合物混合调驱结果。所用体膨剂为工业品,代号HLP-02,为一种预交联凝胶颗粒,平均粒度200目,在自来水中24小时膨胀倍数80-90,在矿化度120 g/L的模拟地层水中配成5g/L的悬浮液。1.8 g/L聚合物HPAM溶液,黏度25 mPa·s。实验用储层洗油岩心表面弱亲水至中性,直径2.5cm、长7-8 cm,驱替温度80℃,0.1 PV体膨剂悬浮液与0.2 PV聚合物溶液混合注入,候凝12小时。kg0.330/0.0627μm^2双岩心组合,水驱至含水100%时原油采收率为74.0%/37.9%,注入混合调驱剂后采收率增值0/2.7%;kg0.345/0.0783μm^2双岩心组合上,水驱采收率为62.0%/45.7%,调驱增值为1.0%/2.9%。kg为0.0953/0.0512和0.0903/0.0280μm^2两个双岩心组合,水驱至含水80%时的采收率分别为32.0%/27.0%和30.3%/25.8%,调驱增值分别为34.0%/33.6%和37.2%/19.4%。对于所研究的濮城油藏,在目前含水80%条件下实施体膨剂/聚合物混合调驱较好,在水驱至残余油状态时调驱效果很差,高渗油层基本不出油,低渗油层出油很少,达不到应有的采收率。讨论了油层产水率与含水率的关系。图4表1参4。     

Effects of the compound system of alkali and alkyl glycosides on the stability of oil-in-water emulsions

Abstract

The effects of Na₂CO₃, nonionic surfactant octyldecyl glucoside (APG0810), and inorganic salt addition on the water separation ratio and apparent viscosity of oil-in-water (O/W) emulsions were investigated. The influences of this compound system on the stability of the emulsion and its synergistic mechanism were also analyzed. Results revealed that in the first compound situation, when APG was selected as the main surfactant and had a concentration of 0.1%, the mass concentration of Na₂CO₃ was 0.4%, the emulsion exhibited the strongest stability, and the water separation ratio at 30?°C for 120?min was 20.3%. In the second compound situation, when Na₂CO₃ was used as the main surfactant and had a concentration of 0.1%, the mass concentration of APG was 0.4%, the emulsion displayed the strongest stability, and the water separation ratio at 30?°C for 120?min was 57.8%. The stability of the O/W emulsion increased with increased NaCl addition, and a higher salt concentration corresponded to a lower water separation ratio. After CaCl₂ addition, the apparent viscosity of the emulsion increased sharply, and the O/W emulsion underwent phase inversion to become an water-in-oil (W/O) emulsion. Within the set mass concentration range, increased salt concentration caused the apparent viscosity of the W/O emulsion measured at 50?°C and 30?rpm to decrease gradually but still exceeded 1500?mPa·s.     

Fe 3+x-TiO2/Shell光催化剂的制备及其对石油的光催化降解

 以自制的贝壳基规整吸附体为载体,采用浸渍煅烧法制备了Fe ³⁺_x-TiO₂/Shell光催化剂。采用XRD、SEM-EDS和UV-Vis等技术对制备的Fe ³⁺_x-TiO₂/Shell光催化剂进行表征。以石油为降解对象,考察了Fe³⁺掺杂量、Fe ³⁺_x-TiO₂/Shell的负载次数及光照时间对Fe ³⁺_x-TiO₂/Shell光催化活性的影响。结果表明,Fe³⁺掺杂量为0.7%(m(Fe³⁺ )/m(TiO₂)×100%)、Fe ³⁺_0.7-TiO₂负载次数为4次时,制备的Fe ³⁺_0.7-TiO₂/Shell光催化剂的光催化活性最高,300 W碘钨灯照射16 h,石油的光催化降解率达76%。     

Ca2+和Mg2+对Cr3+聚合物凝胶性能影响实验研究

为进一步探究Ca~(2+)和Mg~(2+)对弱凝胶调驱效果的作用机理,针对渤海某油藏地质特征和流体性质,以黏度、黏弹性、阻力系数、残余阻力系数以及采收率为评价指标,从增黏性、抗剪切性、耐温性、黏弹性、渗流特性和调驱效果等方面着手,开展了Ca~(2+)和Mg~(2+)对弱凝胶性能及其调驱效果影响研究。结果表明,与注入水相比,软化水虽然矿化度较高,但其几乎不含Ca~(2+)、Mg~(2+)二价阳离子,利用其所配制Cr~(3+)聚合物凝胶溶液中的聚合物分子链受阳离子影响较小,聚合物分子聚集体尺寸较大,其增黏性、抗剪切性、耐温性、黏弹性、渗流特性和调驱效果均强于注入水配制Cr~(3+)聚合物凝胶。对海上油田注入用水进行软化处理,即除去水中Ca~(2+)和Mg~(2+),有利于改善Cr~(3+)聚合物凝胶调驱效果,进一步提高原油采收率。     

聚合物凝胶用Cr3+交联剂检测方法探讨

胜利油田交联聚合物驱、封堵大孔道中使用Cr3+交联的HPAM凝胶。探讨了Cr3+交联剂的检测方法。将4种商品HPAM和6种商品Cr3+交联剂在矿化度5727mg/L、钙镁含量108mg/L的胜利盐水中配制成24个HPAM/Cr3+成胶溶液,根据70℃下反应72h后在70℃测定的凝胶相对强度(要求在代码C以上),确定使用分子量1.11×107、水解度28.8%的一种HPAM,配液浓度为1300mg/L。推荐采用在70℃、振荡频率f=0.422s-1测定的复数粘度η 和储能模量G′表示凝胶的强度,给出了HPAM浓度不同、各Cr3+交联剂浓度为最低需要量的6种凝胶的η 和G′值;推荐取G′值达到0.1Pa的时间为成胶时间,由上述6种体系的G′ t曲线求出成胶时间在98～300min范围。提出其他应测定的性能包括:成胶溶液抗剪切性,凝胶热稳定性(抗热老化性),凝胶抗温性,凝胶抗盐性及岩心堵水率,对测定方法作了详略不等的讨论。特别指出,用于热老化实验的成胶溶液必须彻底除氧,否则粘时曲线的变化将无规律(给出了实例)。图7表7参3。     

Facile preparation of Cr2O3 nanoparticles and their use as an active catalyst on the thermal decomposition of ammonium perchlorate

ABSTRACT

Cr₂O₃ nanoparticles were prepared by repeated wet mechanical milling technique. Three drying methods, oven drying, vacuum drying, and vacuum freeze-drying were comparatively used to dry Cr₂O₃ nanoparticles. These processes can be easily scaled up to 10-kg quantities. It took only 2–3 h to cut bulk size to nanometer by milling. The obtained Cr₂O₃ nanoparticles are semi-spherical and homogeneous with an average size of 30 nm measured by SEM and TEM and show similar diffraction peak positions to bulk one investigated by XRD. The TG/DSC study indicated that, compared with bulk Cr₂O₃, Cr₂O₃ nanoparticles obtained by oven drying and vacuum drying, the catalytic performance of Cr₂O₃ nanoparticles obtained by vacuum freeze-drying is the best in lowering the peak temperature of high temperature decomposition and the activation energy, while increasing the apparent decomposition heat and the reaction rate constant of ammonium perchlorate (AP) due to their good dispersion and large specific surface area. The possible catalytic mechanism of Cr₂O₃ on the thermal decomposition of AP was proposed by TG-MS analysis. These findings showed that wet mechanical milling technique combined with vacuum freeze-drying technology is suitable for efficient preparation of Cr₂O₃ nanoparticles, which could be a promising additive for accelerating the thermal decomposition of AP.     

HPAM/Cr3+交联暂堵技术在堵水封窜中的应用

研发了一种聚合物铬凝胶类暂堵剂用于油水井堵水封窜,其组成为：0.6%-0.8%聚合物HPAM＋0.003%-0.004%交联剂乙酸铬＋0.010%-0.025%破胶剂过硫酸铵。该剂45℃成胶时间〈16小时,16小时成胶黏度5.8-8.2 Pa.s（可超过10 Pa.s）,72小时破胶剂液黏度240-280 mPa.s,可用于40-80℃地层。在原始水测渗透率0.45-5.0μm^2的人造岩心上,该剂封堵物的突破压力≥12.5 MPa/30 cm,暂堵率≥97.9%,破胶后恢复率≥85.2%。该剂已成功用于大庆采油一厂2口斜井的堵水封窜作业。详细介绍了井口严重反冒的高150斜41注水井的暂堵封窜作业：在注水层段以上补孔;注入12 m^3暂堵剂封堵注水层段（10.5 m＋3.6 m）,注入压力5 MPa,套压3.8 MPa;依次注入速凝堵剂8 m^3（注入压力14 MPa,套压8 MPa）、强凝胶堵剂10 m^3（23,9 MPa）封堵窜流层段（10.5 m）,36小时后注水压力13 MPa,注水量5 m^3/d,以后逐渐升至20 m^3/d,井口无反冒水,封窜成功,注水层暂堵保护有效。图3表4参2。     

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。     

孔径双峰分布γ-Al2O3负载NiMoP催化剂的制备及对蜡油加氢催化性能

在氢氧化铝干胶挤条成型时,调节纳米炭黑的加入量和水/粉质量比,制备了孔径呈双峰分布、具有较大孔容和比表面积的γ-Al2O3载体。当炭黑加入质量分数为13%、水/粉质量比1.15时,制备的孔径呈双峰分布的γ-Al2O3载体的孔容为0.80mL/g、比表面积为309m2/g,4～10nm和10～15nm孔径分别占总孔容50.8%和35.1%(体积分数),采用该载体制备的NiMoP/γ-Al2O3催化剂的孔径呈明显的双峰分布。在反应温度370℃、氢分压10MPa、氢/油体积比700、体积空速1.5h-1的条件下,制备的NiMoP/γ-Al2O3催化剂可使减压和焦化混合蜡油的硫质量分数由25600μg/g降至2070μg/g,脱硫率为91.9%,而参比催化剂仅可使减压和焦化混合蜡油硫质量分数降至3450μg/g,脱硫率为86.5%。     

岔河集油田岔15、39断块黄原胶调剖先导试验

为解决低渗透断块油田开发后期层间,层内矛盾引起的油井水淹问题,华北油田公司二采油厂于1998－1999年在岔河集油田的岔15,39断块开展了黄原胶调驱结合的先导性试验,室内总结了两个调剂配方,在岔15,39两个新块上进行了先导性矿场试验,结果表明两种配方都具有较好的改善注水井吸水剖面与增油降水效果,可以提高注水的利用率和油藏的油水采收率。     

Nanocatalysts: Effect of Active-phase and Promoter on Catalytic Properties and Performance in the Hydrodesulfurization Reaction

The influence of various amounts of phosphorus addition on performance of NiMoP/Al₂O₃ and CoMoP/Al₂O₃ nanocatalysts was examined in hydrodesulfurization of thiophene. The nanocatalysts were synthesized via sonochemical technique. The prepared samples were characterized by XRD, FESEM, BET, and FTIR analysis. The catalytic activity in hydrodesulfurization reaction was investigated in a batch stirred slurry reactor at 160°C and atmospheric pressure. The characterizations confirmed highly dispersion of active phase and formation of amorphous AlPO₄ species on the support surface. The results obtained from thiophene hydrodesulfurization showed the nanocatalysts contained 1 wt% of phosphorus had the highest activity. The CoMoP/Al₂O₃ and NiMoP/Al₂O₃ nanocatalysts with optimum phosphorus loading nearly gave 100% conversion of thiophene, so that the sulfur compound concentration in final solution was less than 50 ppm.     

渤海油田多轮次凝胶调驱参数优化实验研究——以LD5-2油田A22井为例

LD5-2油田经过多年开发,地层非均质性逐渐增强,亟待采取强化液流转向措施来扩大波及体积,改善水驱开发效果。为了适应油田开发需要,以油藏工程和物理化学理论为指导,以仪器检测和物理模拟方法为技术手段,以LD5-2油藏地质和流体性质为实验平台,开展了多轮次调驱效果实验研究。结果表明,在三种水配制Cr3+聚合物凝胶中,除垢水凝胶黏度较大,液流转向能力较强,调驱增油效果较好;随聚合物浓度增加,Cr3+聚合物凝胶黏度增大,液流转向能力增强,采收率增幅增加;在Cr3+聚合物凝胶段塞尺寸相同条件下,采用多个凝胶小段塞与水交替注入方式可以减少驱油剂用量,获得了较好的驱油效果。     

弱凝胶调驱技术在濮城油田西区沙二上2+3层系的应用

弱凝胶调驱是通过延缓交联技术、控制聚合物与交联剂的反应时间，使得凝胶溶液可以大剂量注入并达到地层深部，且在较高压差下可以流动的“可动”凝胶。它进入地层后，不仅可以改善纵向非均质性，达到“调”的目的，而且可以改善水驱油流度比，解决油藏的层内及平面矛盾，达到“驱”的目的，是一种提高注入水波及效率的综合技术。结合濮城油田西区沙二上2＋3油藏的地持特点、存在问题，详细介绍了弱凝胶调驱技术的原理、施工工艺以及在该区块的现场应用情况。