聚合物-CO2泡沫压裂液性能研究及现场应用

针对目前常用的CO_2泡沫压裂液存在的与CO_2配伍性差、交联不易控制、耐温耐剪切性能差、残渣含量高等问题,采用丙烯酰胺类多元共聚物BCG-8为稠化剂,通过配套添加剂优选及用量优化,形成了的基础配方为0.3%~0.6%稠化剂BCG-8+0.2%~0.45%稠化增效剂(起泡剂)B-55+0.2%~0.3%调节剂B-14+1%KCl的聚合物-CO_2泡沫压裂液体系,研究了该压裂液体系的泡沫流变性、耐温耐剪切性能、携砂性能及破胶性能。研究结果表明,该体系泡沫质量在55%~75%时表观黏度保持在较高值,在140℃、剪切速率170 s~(-1)下剪切120 min后表观黏度保持在30 mPa·s以上,黏弹性的作用使其携砂性能明显优于HPG冻胶体系的,且该体系破胶液的表面张力低于24 mN/m、残渣含量低至0.1 mg/L。该压裂液体系在延长油田页岩气井中施工顺利,措施见效快,增产效果显著,可用于页岩气等非常规油气藏的储层改造。     

低伤害合成聚合物压裂液体系研究与应用

本文研发了一种新型低伤害合成聚合物压裂液体系,该体系主要由人工合成聚合物与金属交联剂交联组成。室内评价了该压裂液体系各项性能,结果表明:该压裂液体系聚合物使用浓度低、耐温耐剪切性能好、破胶彻底、耐矿化度性能好(高达20 000 mg/L)、残渣含量小(10.83 mg/L)、对岩心渗透率损害小(平均渗透率损害率为9.98%),相同条件下瓜胶压裂液残渣含量约为300 mg/L,岩心损害率为30%左右。该体系满足100℃以内储层压裂改造需求,尤其适用于淡水稀缺、配液水矿化度高的地区压裂改造。     

CO2泡沫压裂液性能评价

CO2泡沫压裂液是压裂液体系的一个重要组成部分,在低压、水敏地层的压裂改造中,CO2泡沫压裂液比其它压裂液体系优异.经优选,确定CO2泡沫压裂液实验基础配方为:(0.65%～0.70%)GRJ改性瓜胶 1.0%FL-36起泡剂 0.1%杀菌剂 0.3%DL-10助排剂 1.0%KCl粘土稳定剂 (0.003%～0.06%)过硫酸铵 1.5?-8酸性交联剂.并对泡沫质量为50%～70%压裂液体系的剪切性能、耐温性能、流变参数、粘温性能、破胶与残渣、破胶液的表观性能和岩心伤害进行了评价.结果表明,CO2泡沫压裂液体系具有良好的耐温耐剪切性能和流变性能,携砂能力强,对储层岩心伤害小,可以满足大多数泡沫压裂施工的需要.     

一种疏水缔合聚合物稠化剂的合成及压裂液性能评价

以AM、AMPS和阳离子疏水单体MD-18为单体,采用水溶液自由基聚合法合成了疏水缔合聚合物压裂液稠化剂HAPAM-18。研究了HAPAM-18的增黏性能、与表面活性剂的相互作用以及压裂液体系的相关性能。结果表明,HAPAM-18的表观黏度随质量浓度增加而增大,临界缔合浓度为0.15g/L;HAPAM-18与表面活性剂的相互作用符合三阶段模型,且SDBS与HAPAM-18的相互作用强于CTAB;ρ(HAPAM-18)0.6g/L+c(SDBS)0.5mmol/L+ρ(KCl)2g/L配制的压裂液体系的耐温性能达到101℃。耐剪切性实验和动态频率扫描表明,该压裂液体系具有良好的耐剪切性和黏弹性;过硫酸铵能使压裂液彻底破胶,破胶液残渣含量低至未检出,该压裂液是一种清洁压裂液。     

耐高温海水基压裂液聚合物稠化剂流变性能

为明确聚合物稠化剂分子量、功能单体种类及含量等参数对海水基压裂液流变性能的影响,选用分别具有强电解质单体2-丙烯酰胺-2甲基丙磺酸(AMPS)或可抑制酰胺基水解单体N-乙烯基吡咯烷酮(NVP)的超高分子量聚合物,研究了聚合物溶液的流变性能。对具有超高分子量及不同AMPS含量的5种聚合物进行了聚合物交联冻胶耐温耐剪切性能研究。实验结果表明,具有超高分子量及较低AMPS含量的聚合物黏弹性更好,具有超高分子量及高AMPS含量的聚合物在高温下耐剪切性能更好,具有超高分子量及NVP基团的聚合物在海水中增稠能力更好,具有高AMPS含量的聚合物耐温耐剪切性能更好;具有超高分子量(分子量不低于2×10⁷)、适宜的水解度(20%～23%)、低AMPS含量(3%～8%(w))的聚合物,更适于作为耐高温海水基压裂液稠化剂。     

一种新型黏弹性清洁压裂液的合成及性能

合成了一种新型黏弹性清洁压裂液JL-K,通过实验确定最佳合成工艺为CM-A与CM-B质量比3∶2,催化剂E用量0.5%,反应温度为50℃,反应时间为60min,搅拌转速为280r/min。采用流变仪、表面张力仪等仪器对压裂液体系进行了耐温性能、耐剪切性能、悬砂性能、破胶性能的评价实验。性能测试结果表明:该压裂液体系具有较好的抗剪切性能,适合中温储层,破胶液无固相残渣、携砂性好、可降解、表观黏度低(5mPa·s以下),利于返排。     

BCG-1深井加重清洁压裂液体系

对于埋藏深、低渗透和温度高的储层进行压裂改造施工时,抗高温硼交联改性瓜胶压裂液体系存在摩阻高、残渣不能消除的问题。在实验室中合成了一种具有一定水解度的以丙烯酰胺和离子功能单体为主链的聚合物压裂液稠化剂,通过对添加剂进行优选,形成了一种BCG-1加重清洁压裂液体系。室内实验结果表明:BCG-1加重压裂液体系具有良好的耐温耐剪切性,在160℃、170 s-1条件下剪切120 min,压裂液黏度保持在57 mPa·s以上,且该压裂液配方实验重复性好。用自行设计并研制的多功能流动回路摩阻测试仪对BCG-1加重压裂液进行摩阻测试,实验采用8 mm测试管径,测试数据显示,体系增效剂ZJFA-1具有很好的降低BCG-1压裂液体系摩阻的特性;NaNO₃加重剂对该体系摩阻性能基本无影响;体系破胶性能好,破胶液黏度小于21 mPa·s,残渣含量小于5 mg/L,具备清洁压裂液的特性。      

耐高温清洁压裂液体系HT-160的研制及性能评价

针对目前聚合物压裂液破胶后残渣含量大且已有清洁压裂液耐温性差、稠化剂用量大、成本高等不足,通过分子结构设计、室内合成、性能评价及控制条件优化,制备了一种性能优越的Gemini型阳离子黏弹性表面活性剂,并将其作为稠化剂,然后通过配方优化,配制了由5.0%的稠化剂和少量无机盐（氯化钾和溴化钾）组成的清洁压裂液HT-160。室内试验显示,该压裂液体系表现出明显的弹性特征,具有很好的支撑剂悬浮性能,在160℃、170 s-1测试条件下剪切2 h后,黏度仍然保持在40 mPa·s左右,而且与煤油接触后能够彻底破胶、无残渣。研究结果表明,该压裂液体系能够满足深部储层压裂作业的要求,耐温可达160℃。      

胍胶清洁压裂液在延长气田的应用

延长气田属于典型低渗透储层,具有"低孔、低渗、低压"等特点,常规的胍胶压裂液体系胍胶用量大,残渣大,对裂缝导流能力的损害率高,对储层造成一定的伤害。针对延长气田储层特点,研发了一种胍胶清洁压裂液,该压裂液体系胍胶浓度低,相比常规胍胶压裂液,用量减少了30%,耐温耐剪切性能良好,残渣含量仅为145 mg/L,是一种低残渣、低伤害的压裂液。该压裂液在延长气田进行了现场实验,应用效果良好,具有很好的推广前景。     

低浓度聚合物压裂液体系研究与应用效果评价

聚合物压裂液冻胶体系在压裂施工过程中会在裂缝中和裂缝壁留下残渣造成储层伤害,降低聚合物浓度可以减轻这种伤害,但又会遇到冻胶体系黏弹性降低支撑剂沉降的问题,因此,研究优选满足携砂要求的低浓度聚合物压裂液体系具有实际意义.用实验方法研究了低浓度聚合物压裂液的增稠剂、交联剂及破胶剂.并评价了压裂液体系的抗温抗剪切性能、流变性能、携砂性能、破胶性能、低伤害性能、防膨性能和滤失性能.实验结果表明,低浓度聚合物压裂液的浓度为常规聚合物压裂液浓度一半时即可满足压裂时的携砂要求,抗温抗剪切性能优于清洁压裂液和常规聚合物压裂液,并且破胶后的残渣量明显减少,降低了对储层的伤害程度,是一种较为环保的低伤害压裂液.     

Petroleum Hydrocarbons Extraction Efficiency of Carbon Tetrachloride and Trichlorotrifluoroethane: A Comparative Study

Abstract

Petroleum hydrocarbons (PHC) contaminated water samples, prepared in laboratory, were analyzed using infrared spectroscopy to compare PHC extraction efficiency of carbon tetrachloride (CCl₄) and trichlorotrifluoroethane (C₂Cl₃F₃) solvents. The comparison of the results illustrated that PHC extraction efficiency of CCl₄ was greater than C₂Cl₃F₃. The higher extraction efficiency of CCl₄ was ascribed to its more non-polar nature and higher polarity index. This study supported the selection and use of CCl₄ for extraction and quantification of PHC of groundwater samples of the projects carried out in the department.     

H6P2W18O62/MCM-48催化剂的制备、表征及催化绿色合成己二酸

以MCM-48为载体,通过浸渍法制备了H6P2W18O62/MCM-48催化剂,并采用FT-IR、XRD、SEM、EDS对催化剂进行表征。以微波促进30%(质量分数)H2O2氧化环己酮合成己二酸反应为探针,考察了H6P2W18O62/MCM-48的催化性能,并通过正交实验确定了优化的工艺条件。结果表明,采用H6P2W18O62负载量40%的H6P2W18O62/MCM-48催化剂,在优化的合成己二酸的工艺条件下,即催化剂质量分数(以环己酮质量计)5.1%、n(C6H10O)∶n(H2O2)∶n(H2C2O4.2H2O)=100∶450∶1.88、反应温度95℃、微波功率300 W、反应时间3.5h,己二酸收率可达81.3%;催化剂重复使用5次,己二酸收率仍可达到64.6%。     

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.     

Nanosized Platinum-Loaded H-ZSM-5 Zeolite Catalysts for n-Hexane Hydroconversion

Abstract

A series of nanosized platinum-containing catalysts was successfully loaded on/in zeolite H-ZSM-5 via exchanging the zeolitic proton with platinum from Pt tetramine dichloride complex. Another series of Pt/H-ZSM-5 catalysts was prepared via wet impregnation of H₂PtCl₆ solution for comparison. The latter series was found to produce lower Pt dispersion. Pt dispersion was determined by H₂ chemisorption. Catalyst characterization via ammonia temperature-programmed desorption (TPD), temperature-programmed reduction (TPR), and transmission electron microscopy (TEM) was examined for all catalysts and showed large differences in particle sizes. The data on n-hexane reactions of the catalysts of both series confirmed the formation of Pt nanoparticles in the exchanged catalysts. The relatively lower density and strength of acid sites acquired by Pt-exchanged catalysts contributed to this difference; stronger acid sites in the impregnated catalysts are in favor of hydrocracking reactions, which inhibit isomerization selectivity.     

Characterization of Al2O3–ZrO2 Mixed Oxide Supported Mo Hydrotreating Catalyst

Abstract

A series of molybdenum catalysts supported on Al₂O₃–ZrO₂ mixed oxide containing 50% ZrO₂ and 50% Al₂O₃ were prepared by incipient wetness technique and characterized by BET surface area, X-ray diffraction, temperature programmed reduction and oxygen chemisorption. The catalytic activities for hydrodesulphurization (HDS), hydrogenation (HYD), and hydrocracking (HYC) were determined using thiophene, cyclohexene, and cumene as model compounds, respectively. Results indicate that up to 8 wt% Mo loading, the catalyst is well dispersed and crystallite growth occurred beyond this loading. Also both oxygen uptake and catalytic activities increase with Mo loading up to 8 wt% and then decreases at higher loading. A linear correlation was obtained between oxygen uptake and all catalytic activities and the correlation coefficients obtained suggest that the order of catalytic activities for HDS, HYD, and HYC is: HDS > HYD > HYC. Furthermore, the catalytic activities of the mixed oxide supported catalyst for HDS, HYD, and HYC were higher than those supported on pure alumina and pure zirconia. The incorporation of 3% Co on 8% Mo catalyst was determined to result in enhanced activity for HDS, HYD, and HYC.     

复合SiO2-WO3催化剂的制备、表征及氧化脱除苯并噻吩性能

 采用溶胶-凝胶法制备了SiO₂-WO₃催化剂,并采用XRD、FT-IR、BET、TG-DTA等方法对催化剂进行表征。以苯并噻吩(BT)为模型化合物,H₂O₂为氧化剂,考察了催化剂的活性元素、制备方法、n(W)/n(Si)和焙烧温度对其催化氧化脱硫活性的影响。结果表明,W的引入降低了SiO₂的比表面积,SiO₂-WO₃催化剂中W的主物相为WO₃。在以W为活性组元,且n(W)/n(Si)为0.1时,500℃焙烧得到的SiO₂-0.1WO₃催化剂具有最好的催化脱硫活性。在模拟油20 mL、催化剂SiO₂-0.1WO₃用量0.04 g、n(H₂O₂)/n(S)为15.9、乙腈/模拟油体积比0.3、65℃反应60 min的条件下,苯并噻吩模拟油脱硫率可达99.3%。     

Design of Catalyst Support for Deep Hydrodesulfurization of Gas Oil

Abstract

Alumina-silica (Al₂O₃-SiO₂) composite supports were examined to find the optimum state of support (i.e., composition and morphology). SiO₂ content in the Al₂O₃-SiO₂ support induced a shift of the main peak to higher frequency ascribed to an increased amount of Mo₈O₂₆ ^4?. A 75 wt% Al₂O₃-25 wt% SiO₂ support had homogeneously dispersed alumina particles of smaller size with high crystallinity. Hydrodesulfurization (HDS) of straight-run gas oil and its conventionally hydrotreated straight-run gas oil was performed over NiMo sulfides supported on Al₂O₃-SiO₂ composites. The high crystallinity of NMASA2-27 may be related to the high HDS and hydrogenation activity of NiMo sulfides due to its moderate interaction with the alumina surface.     

Production of olefins from syngas over Al2O3 supported Ni and Cu nano-catalysts

The most important products that can be produced from syngas are methanol, dimethyl ether and light olefins (ethylene and propylene). The light olefins are the most important syngas products, because many of the chemicals are produced from them. The aim of this work was to study the olefins production from syngas over Al₂O₃-supported Ni-Cu nano-catalysts. In addition, the effect of various factors such as catalyst on olefin production and CO conversion has been investigated. The concentration of heavier olefins (C5) was greater than the remaining olefins, since the rate of reactions must be increased to form C1 to C4. In the case of a Ni/Al₂O₃ catalyst, C1 and C4 was initially increased and then decreased with an increase in Ni loading from 0% to 15%.     

Application of Light Hydrocarbon (C7+) and Biomarker Analyses in Characterizing Oil from Wells in the North and North Central Sinai,Egypt

Abstract

Seven representative oil show samples from wells in the north and north central Sinai have been characterized by means of a variety of organic geochemical techniques (C₇ hydrocarbon and biomarker analyses), to illustrate origin, differences, and similarity among oils. These oils were obtained from Cretaceous and Jurassic reservoirs. The C₇ oil correlation star diagram (OCSD) suggests closely related oils, derived mainly from similar source rocks, while the C₇ oil transformation star diagram (OTSD) and C₇ light hydrocarbon analyses indicate a minor degree of transformation of some oils, as Misri-1, Halal-1, and Nakhl-1 oils were subjected to evaporative fractionation. Moreover, the studied oils show no sign of water washing and biodegradation. Molecular characteristics suggest pre-Tertiary shales and carbonate source rocks, deposited under a saline oxic environment, rich in terrigeneous organic sources with significant bacterial and algal input. Since the studied oils are of mixed marine and terrestrial origin, C₇ signature of these oils is not representative of their origin and should be supported by other geochemical evidence (e.g., biomarkers) to predict their origin.     

氧化镁改性微米TS-1催化丙烯环氧化

合成了粒径在1~2 μm的廉价微米TS-1,并经MgO改性,杀灭其上少量的酸中心;采用SEM、XRD、BET对MgO改性前后的TS-1进行了表征,并考察了其在甲醇溶剂体系丙烯环氧化的催化性能。结果表明,TS-1催化剂经MgO改性后,可以显著提高其催化丙烯环氧化反应的环氧丙烷(PO)选择性,减少副反应的发生;在最优化反应条件CH₂O₂ =1.0 mol/L, θ = 60℃, t = 60 min, p_C3↓H6↓ = 0.6 MPa,以及按每1 gTS-1需80 mL CH₃OH的比例下,H₂O₂转化率达到99.5%,环氧丙烷选择性达到96.7%,环氧丙烷收率比未改性的微米TS-1也有明显提高。