聚合物驱后深部调剖提高采收率的实验研究

本项实验研究针对地温69～70℃、地层水矿化度4.5 g/L、注入水矿化度4.7 g/L的河南油田双河砂岩油藏.实验温度70℃,实验用原油70℃粘度12.1 mPa·s,选择单液法施工的交联聚合物冻胶为深部调剖剂,聚合物HPAM分子量1.62×166,水解度12.5%,交联剂有有机铬、无机铬[Cr(Ⅵ)化合物+还原剂]和酚醛树脂.根据三类聚合物/交联剂体系成冻时间等值线图选出了成冻时间分别为1、1、5、10、15天的5个配方,其突破真空度(强度)为69～40 kPa,Sydansk相对强度级别为G,注入0.2 PV时填砂管封堵率为99.23%～97.02%.渗透率级差～3的并联双填砂管饱和油之后注水驱油至含水98%,再注入0.30 PV 1.0 g/L HPAM溶液并再次注水,达到一定含水率(67.0%～98.0%范围,共7个值)和相应采收率(39.4%～45.3%)时,注入0.15 PV成冻时间1天、强度较高的调剖剂(HPAM/有机铬体系)并恢复注水,采收率增值(28.7%～12.5%)随调剖时机提前而加大.注入、采出口之间有高渗条带的可视平板填砂模型,依次饱和水,饱和油,注水驱油至含水98%,先后注入成冻时间1 d、强度不同的两种HPAM/有机铬体系(0.015+0.010 PV)并恢复注水,调剖剂注入顺序为先弱后强时的最终采收率(63.6%)高于注入顺序为先强后弱时的最终采收率(55.3%).图6表3参7.     

海上油田酚醛树脂冻胶调剖性能评价

适用于海上油田的酚醛树脂冻胶是由聚合物HPAM和酚醛树脂交联剂YG103交联形成的。通过室内实验,评价了聚合物、交联剂质量分数和剪切程度对酚醛树脂冻胶成冻时间和冻胶强度的影响,并绘制了成冻时间及强度等值图。结果表明,随着聚合物、交联剂质量分数的增加,酚醛树脂冻胶成冻时间缩短,冻胶强度增大,成冻时间在5～14d内可调;随着剪切强度的增加,其成冻时间延长,冻胶强度变弱。稳定性实验结果表明,此类冻胶的稳定性较好,强度保留率均大于90%,并且剪切对稳定性影响不大。物理模拟实验结果表明,随着聚合物、交联剂质量分数的增加,该冻胶的封堵能力增强,且封堵率均在90%以上。单管实验结果表明,酚醛树脂冻胶的注入性能较好,能实现在线注入;且该冻胶有很好的耐冲刷性能,成冻后水驱为10倍孔隙体积时,封堵率仍保持在94%以上。     

锆冻胶分散体调驱剂的制备与性能评价

为减弱地面剪切和吸附与稀释作用等因素对冻胶成冻性能的影响,将已成冻的锆本体冻胶经胶体磨的机械剪切制得锆冻胶分散体,室内研究了本体冻胶强度、剪切时间和剪切间距对锆冻胶分散体黏度和粒径的影响,考察了锆冻胶分散体的封堵调剖性能。结果表明,通过调整聚合物和有机锆交联剂的加量,可以调节锆本体冻胶体系的成冻时间和成冻强度,随着聚合物和交联剂加量的增大,交联越快,强度越大;锆冻胶分散体为粒径5.66数224.87μm的颗粒,黏度在1.8数41.0 m Pa·s内可调;随着本体冻胶强度和剪切间距的增大,锆冻胶分散体黏度和粒径增大;剪切时间越长,锆冻胶分散体黏度越低,粒径越小;驱油实验结果表明,随岩心渗透率增加,冻胶分散体对岩心的封堵率降低,锆冻胶分散体能有效调整渗流剖面,采收率增幅为46%。     

胜坨油田高温油藏深部调剖体系研究及矿场应用

实验评价了酚醛树脂交联剂与聚合物在地层温度下形成的冻胶的各项性能。结果表明,在100℃静态条件下,酚醛树脂冻胶作为深部调剖体系,成胶时间长,耐温抗盐能力强;调剖体系中适宜的聚合物质量浓度为1 500～3 000 mg/L,交联剂质量浓度为800～1 800 mg/L,体系适应的pH值在6～9之间。在动态条件下,酚醛树脂冻胶封堵率在90%以上,水驱10 PV后,封堵率保持在83%以上。矿场应用结果表明,使用酚醛树脂冻胶对胜坨油田坨143断块高温油藏实施深部调剖后,注水井启动压力得到有效改善,增油效果明显。     

双河油田聚合物驱后深部调剖技术研究

聚合物驱后深部调剖技术弥补了聚合物溶液调剖作用有限的缺点,通过对地层充分调剖提高波及系数,最大限度提高地层的采收率.针对河南双河油田的情况,经研究发现：冻胶型深部调驱剂可根据需要配成不同成冻时间和强度的体系,体系成冻时间1d～15d,突破真空度0.04～0.062 MPa,具有较强的封堵能力.可视化模型研究表明,按照先弱后强的顺序注入组合调剖剂有利于提高采收率.采收率流动实验证明,调剖剂注入时机越早越有利于提高采收率.     

赵凹油田高温油藏冻胶泡沫调驱体系的研制及性能评价

针对赵凹油田安棚主体区主力油层水窜严重的开发现状,通过室内实验方法,研制了适用于其油藏条件的冻胶泡沫调驱体系,该体系主要包括耐高温起泡剂和冻胶稳泡体系,即由质量分数为0.2％～0.3％的HN-1起泡剂、0.25％～0.35％的KY-6梳形聚合物和0.6％～0.8％的YG103酚醛树脂交联剂复配而成,并优化了冻胶泡沫的注入方式、气液比和注气速度,评价了冻胶泡沫的驱油性能,形成了适用于赵凹油田油藏条件的耐高温冻胶泡沫调驱技术.评价结果表明:酚醛树脂冻胶体系作为耐高温冻胶泡沫的稳泡体系,具有较好的稳泡效果,能够大幅度提高泡沫的半衰期;与分段塞注入方式相比,气液混注方式产生的冻胶泡沫具有更好的封堵性能;冻胶泡沫的最佳气液比为1∶1,气液比过高或过低均会导致冻胶泡沫的阻力系数和封堵能力下降;最佳注气速度为0.5 mL/min,注气速度过高或过低均会使冻胶泡沫封堵能力下降.驱油实验结果表明,冻胶泡沫调驱体系具有良好的选择性封堵性能,剖面改善率达99％,采收率提高了44.6％.     

一种聚合物驱后深部调剖用HPAM/Cr3+冻胶体系

针对孤岛油田砂岩油藏的地质特点,用可延缓释放Cr3 的一种有机铬交联剂与延缓剂配合,研制了深部调剖用的一种聚合物(HPAM)/有机铬冻胶体系,由冻胶强度级别的划分定性地测定成冻时间和突破真空度的方法定量测定冻胶强度,并作出了成冻时间及强度等值图。实验结果表明HPAM/Cr3 冻胶交联时间可调,冻胶体系成冻时间可调1~18d,成冻后强度高。聚合物驱后,继续向地层中注入一定量的组合深部调剖剂,能有效地提高采收率。     

非均相复合驱油体系设计与性能评价

为进一步提高聚驱后油藏采收率,针对聚驱后油藏非均质性强、剩余油普遍分布的特点,提出了非均相复合驱油体系。非均相复合驱油体系包括黏弹性颗粒驱油剂（PPG）、表面活性剂和聚合物。通过研究黏弹性颗粒驱油剂的溶胀能力、黏弹性、滤过能力和在岩心中运移性能,及其与表面活性剂、聚合物之间相互作用,得到了适合于胜利高温高盐油藏和聚合物驱后油藏的非均相复合驱油体系1000 mg/L PPG＋1000 mg/L聚合物＋0.3％胜利石油磺酸盐＋0.1％非离子表面活性剂1709。结果表明,PPG可遇水溶胀,耐盐性能好,在油藏中具有封堵和运移性能,较单一聚合物能够更好地提高波及体积。在含水98％条件下注入0.3倍孔隙体积的非均相复合驱油体系,聚合物驱后提高采收率13.6%(OOIP)。该体系可应用于高温高盐油藏或聚合物驱后油藏大幅度提高采收率。     

冻胶泡沫体系室内实验研究

通过室内模拟实验,将聚合物ZWP与交联剂DY-1复配优选出性能较优的冻胶体系,加入起泡剂GX与氮气后形成冻胶泡沫体系,同时评价了不同因素对冻胶泡沫体系成冻性能和起泡性能的影响。冻胶泡沫体系配方(质量分数)为ZWP(0.3%)+DY-1(0.3%)+GX(0.6%),该体系的稳定性随温度的升高而下降,压力对起泡体积的影响较小,且随着压力的升高半衰期明显增加。在冻胶驱、聚合物驱、水基泡沫驱、冻胶泡沫驱四种驱替方式中,相同渗透率及注入速率下冻胶泡沫的封堵能力最强。     

无碱二元体系的黏弹性和界面张力对水驱残余油的作用

三元复合驱含碱驱油体系会大幅度降低聚合物溶液的黏弹性,引起地层粘土分散和运移、形成碱垢及导致地层渗透率下降。为此提出利用不加碱可形成超低界面张力的聚合物/甜菜碱表面活性剂二元复合体系驱油。通过流变性实验及微观模型驱油实验,分析了表面活性剂对聚合物表面活性剂二元复合体系黏弹性的影响和聚合物表面活性剂二元复合体系的黏弹性及界面张力对采收率的影响。对聚合物表面活性剂二元复合体系提高水驱后残余油采收率机理的研究表明:在驱替水驱后残余油过程中,聚合物表面活性剂二元复合体系利用了聚合物溶液的黏弹特性和表面活性剂的超低张力界面特性,水驱后残余油以油丝和乳状液形式被携带和运移,随着二元驱油体系的黏弹性的增加和界面张力的降低,水驱后二元驱后的采收率增加,降低界面张力的驱油效果(指达到超低)比提高体系的黏弹性的效果更明显。     

Effect of CO<Subscript>2</Subscript> on the oxidation of cyclohexene by H<Subscript>2</Subscript>O<Subscript>2</Subscript> using Co<Subscript>1.5</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript> catalyst

Oxidation of cyclohexene by cheap and environmentally friendly oxidants, namely H₂O₂ and CO₂ has been catalyzed by Co_1.5PW₁₂O₄₀. It has been found that the main products of the oxidation are 2-cyclohexen-l-one (enone), 2-cyclohexen-l-ol (enol) and 1, 2-cyclohexanediol (diol) with the enone as the major product. Oxidation by CO₂ along with H₂O₂ remarkably increased the conversion compared to that by CO₂ and H₂O₂ separately. This might be due to the fact that CO₂ increases the percarbonate species (HCO₄ ^?) responsible of the oxidation by oxygen transfer, which indicated that the CO₂/H₂O₂ mixture is a useful reagent system. The decrease of both the selectivity of the enone and epoxide in favor of that of diol at higher conversions indicated that the diol was formed from the epoxide by consecutive reaction and/or directly from cyclohexene.     

Kinetics of cyclohexene hydrocarbalkoxylation with cyclohexanol catalyzed by the Pd(PPh<Subscript>3</Subscript>)<Subscript>2</Subscript>Cl<Subscript>2</Subscript>-PPh<Subscript>3</Subscript>-<Emphasis Type="Italic">p</Emphasis>-toluenesulfonic acid system

The reaction kinetics of cyclohexene hydrocarbalkoxylation with cyclohexanol catalyzed by the Pd(PPh₃)₂Cl₂-PPh₃-p-toluenesulfonic acid system was studied over the temperature range 363–393 K. The reaction rate was found to be a nonlinear function of the Pd(PPh₃)₂Cl₂ concentration or a nonmonotonic function of the PPh₃ and cyclohexanol concentrations or p _CO. The experimental data were interpreted in terms of a mechanism that involves ion pairs containing alkyl and acyl palladium complexes of the cationic type as intermediates. Based on the quasi-steady-state approximation, a rate equation was obtained to adequately describe the experimental data. The rate equation parameters were estimated using the least squares technique. The apparent activation energies of these parameters were determined. The heats of formation of Pd(PPh₃)₂(C₆H₁₁OH)₂, Pd(PPh₃)₂(CO)₂, and Pd(PPh₃)₄ complexes from Pd(PPh₃)₂(C₆H₅CH₃)₂ were estimated. A symbatic change in these values with the donor-acceptor properties of ligands was demonstrated.     

Dissociation behavior of （CH4 ＋ C2H4） hydrate in the presence of sodium dodecyl sulfate

Separation of a mixture of CH4+C2H4 gas by forming hydrate in ethylene production has become of interest,and the dissociation behavior of(CH4+C2H4) hydrate is of great importance for this process. The hydrate formation rate could be increased by adding a small amount of sodium dodecyl sulfate(SDS) into water. In this work,the kinetic data of CH4(18.5 mol%) +C2H4(81.5 mol%) hydrate decomposition in the presence of 1000 mg·L-1 SDS at different temperatures and pressures were measured with the depressurizing m...     

Mono- and Bimetallic Mo(W)S<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Mo(W)S<Subscript>2</Subscript>/SBA-15 Hydrotreating Catalysts Based on SiMo<Subscript>12</Subscript> and SiW<Subscript>12</Subscript> Heteropoly Acids

Mono- and bimetallic Mo(W)S₂ catalysts supported on γ-Al₂O₃ and SBA-15 have been prepared using the Keggin heteropoly acids (HPAs) H₄SiMo₁₂O₄₀ and H₄SiW₁₂O₄₀. The catalyst samples have been analyzed by temperature-programmed reduction with hydrogen, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. Catalytic properties have been examined in the joint hydrotreating of dibenzothiophene and naphthalene on a flow-through unit. It has been shown that the use of mesoporous silica SBA-15 as a support can reduce the average length of Mo(W)S₂ particles from 4.9 to 3.7 nm and increase the average number of layers and the particle size of the active phase, changes that lead to an increase in catalytic activity by a factor of ~3 relative to the alumina-supported counterparts. The use of a mixture of SiMo₁₂HPA and SiW₁₂HPA for preparing MoW catalysts leads to a significant enhancement of catalytic activity, which is apparently due to the formation of mixed active sites.     

Study of a mass transfer-reaction model for SO<Subscript>2</Subscript> absorption process using LAS/H<Subscript>2</Subscript>SO<Subscript>4</Subscript> solution

A regenerative absorption process for removal of SO_x from FCC off-gas using LAS/H₂SO₄ solution as absorbant was studied and pilot-plant experiments were carried out. A mass transferreaction model for the SO₂ absorption process was established based on pilot-plant experiments, and the concentration distribution of components in the liquid film, and the partial pressure and mass transfer rate of SO₂ along the height of the absorption tower, was calculated from this model. The numerical simulation results were compared with the experimental results and proved that the model can be used for describing the SO₂ absorption process.     

Exhaustive schemes for refining C<Subscript>3</Subscript>-C<Subscript>4</Subscript> hydrocarbon fractions

Exhaustive schemes for efficient refining of the C₃-C₄ hydrocarbon fraction using zeolite type Y catalysts to obtain a high-octane additive are proposed. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5, pp. 6–7, September–October, 2008.     

Catalytic Cracking of <Emphasis Type="Italic">n</Emphasis>-Hexane and <Emphasis Type="Italic">n</Emphasis>-Heptane over ZSM-5 Zeolite: Influence of SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ratio

The performance of two types of ZSM-5 zeolite catalysts (MFI-type zeolite, SiO₂/Al₂O₃ = 50 and 300) was studied in the catalytic cracking of n-hexane and n-heptane as a model compound of light naphtha for production of light olefins at 500, 550, and 600°C. The physicochemical properties of ZSM-5 catalysts were characterized by means of XRD, BET, SEM and NH₃-TPD. The influence of SiO₂/Al₂O₃ molar ratio was investigated on conversion and product selectivity. ZSM-5 zeolite yielded higher conversion in the cracking of n-hexane compared to n-heptane and maximum conversion was achieved over ZSM-5(50) at 600°C. ZSM-5(50) showed higher alkane selectivity rather than olefins. It was found that ZSM-5(300) was more desirable in terms of having significant selectivity to light olefins as well as producing high propylene to ethylene ratio. The maximum propylene to ethylene ratio of 2.7 and 2.48 was observed over ZSM-5(300) at 500°C for n-hexane and n-heptane cracking, respectively.     

Composite catalysts for selective catalytic reduction of NO<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript> and oxidation of residual NH<Subscript>3</Subscript>

A comprehensive study has been performed on the catalytic properties of composite catalysts [Mn/support + FeBeta] and their individual components (Mn/support and FeBeta) in the selective catalytic reduction of nitrogen oxides and the ammonia oxidation reaction. It has been shown that mixing the oxide component with the zeolite not only leads to an increase in NO_x conversion, but also improves the selectivity in the oxidation of residual ammonia, thus making it possible to conduct both processes in a single catalytic unit.     

Ethylene oligomerization in the presence of ZrO(OCOR)<Subscript>2</Subscript>-Al(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>2</Subscript>Cl-Modifier catalytic system

The kinetics of ethylene oligomerization and molecular-mass distribution of resulted oligomers on ZrO(OCOR)₂-Al(C₂H₅)₂Cl and ZrO(OCOR)₂-Al(C₂H₅)₂Cl-modifier catalyst systems, where the modifier was CCl₄, vinyl acetate, or zinc stearate, were studied depending on the modifier: ZrO(OCOR)₂ and Al(C₂H₅)₂Cl: ZrO(OCOR)₂ molar ratios, ethylene pressure, temperature, and modifier nature.