用作弱凝胶交联剂的水溶性酚醛树脂的合成

对用作聚合物弱凝胶交联剂的水溶性酚醛树脂合成工艺进行了系统的实验研究。实验弱凝胶体系由1.5 g/L的HPAM(M-=1.8×107,HD=25%)和酚醛树脂组成,二者质量比6∶1,配液用水为矿化度19334 mg/L、含Ca2 Mg2 4145 mg/L的胜利标准盐水。以85℃下成胶的弱凝胶粘度(85℃,7.3 1/s)作为评价酚醛树脂对HPAM交联性能的参数。两步碱催化法树脂的游离甲醛含量低,羟甲基含量高,交联HPAM的性能明显优于一步碱催化法树脂,其粘度随甲醛、苯酚摩尔比的增加而持续增大,羟甲基含量和弱凝胶粘度随甲醛、苯酚摩尔比、最终缩聚温度、合成反应时间的增加而变化的规律一致,均经过最大值,由此求得用作聚合物弱凝胶交联剂的水溶性酚醛树脂的最佳合成条件为:苯酚、甲醛摩尔比1∶2~1∶3,pH值9~10,最终缩聚温度85℃,最终缩聚时间30 min。这种树脂的红外光谱中不出现表征交联的强吸收峰。图8表2参10。     

改进型酚醛树脂交联剂的合成与成胶性能

通过对活性酚醛树脂交联剂的合成方法进行改进,制得改进型酚醛树脂交联剂.该交联剂的的毒性低,稳定性高;而且从制备的凝胶体系性能来看,其成胶强度、热稳定性及抗盐性能均优于常规酚醛交联剂,适用范围更广.     

九、胶粘剂

TQ433 JSH9806901酚醛树脂化合物的缩醛衍生物=Acetal derivatives ofresole compounds:U.S.US 5677414[专,英]/LordCorp.,USA(Spaltenstein Esther…).—1997.10.14.—329634(1994.10.26);IPC C08G8/04 题述环缩醛衍生物含邻位酚醛树脂化合物与羰基化合物或羰基化合物衍生物的反应产物,且至少含一个环嵌段苯酚单元。此环缩醛衍生物能交联,在其加热时可作交联剂。此酚醛树脂化合物的环缩醛衍生物具有增进的贮存稳定性且在高温时易于活化以便制备酚基胶粘剂及涂料。2,4,6—三羟甲基苯酚与乙醛二乙基     

耐贮存改性酚醛树脂交联剂的合成及性能评价

目前国内油田剖面调整作业中常用的酚醛树脂交联剂贮存有效期短,无法满足长周期施工作业需求,为此,采用水杨酸类改性剂合成了改性酚醛树脂交联剂,并应用核磁共振氢谱表征了改性酚醛树脂的分子结构。通过室内试验考察了改性剂加量、催化剂加量及高温对改性酚醛树脂的贮存有效期及凝胶强度的影响,研究了交联剂加量、温度和矿化度对改性酚醛树脂交联体系成胶时间及凝胶强度的影响,评价了改性酚醛树脂交联体系的热稳定性能、封堵性能及提高采收率效果。试验结果表明,改性酚醛树脂分子上引入了具有空间位阻效应的酯基结构,其贮存有效期大幅延长,常温条件下贮存有效期达到234 d,45℃恒温条件下贮存有效期大于90 d;改性酚醛树脂交联体系在60~100℃及矿化度小于20 000 mg/L条件下可生成高强度凝胶;改性酚醛树脂交联体系180 d黏度保留率大于88%,封堵率大于98%,采收率可提高14.6百分点。研究表明,耐贮存改性酚醛树脂交联剂不仅具有良好的交联性能,还具有良好的耐贮存性能,满足长周期施工作业的需要,具有较好的应用前景。      

液相色谱法测定酚醛交联剂中残余苯酚含量

建立高效液相色谱法测定酚醛树脂交联剂中苯酚含量。方法采用C18柱（150mm×4．6mm，5μm），流动相为甲醇-水（60：40），流速为1．0mL／min，检测波长为270nm。结果表明：苯酚线性范围为10．922～65．532mg／L，r=0．99998（n=6），平均回收率为99．96％，RSD=0．432％（n=9）。交联剂样品测定结果表明：与滴定法相比，本方法相对误差小于5．4％。该法操作简便，结果准确，可用于酚醛交联剂中残余苯酚的含量测定。     

低盐水配制酚醛树脂冻胶在高盐水中的稳定性北大核心CSCD

目的塔河碳酸盐岩油藏地层温度高(110℃以上)、地层水盐质量浓度高(22×10^(4) mg/L,其中,钙镁离子近2×10^(4) mg/L)。针对塔河油田高温、高盐的苛刻油藏条件,现有堵剂选择性单一,封堵时间较短,需研发新类型堵剂进行封堵。方法设计在低盐含量模拟注入水中,以AM-AMPS共聚物为成胶剂,以水溶性酚醛树脂为交联剂,加入纳米SiO_(2)做稳定剂配制成胶液,测定成胶时间和冻胶强度,并将130℃形成的冻胶老化3天后放于高盐含量模拟水浸泡,考查其长期稳定性。另外,为探索冻胶的稳定性和脱水收缩机理,将在高盐含量水中老化前后的冻胶逐级脱水并干燥后进行了SEM和IR、XPS分析。结果在相同的交联剂与聚合物用量下,增加纳米SiO_(2)的含量,冻胶稳定性增加,可在高盐含量模拟水中保持60天脱水率低于10%;脱水程度随交联剂质量分数的增加而降低。冻胶在高盐水中浸泡后,由于伯酰胺的水解及其生成的羧酸根与地层水中钙镁离子的交联作用,冻胶网格变密,储能模量增加。结论在低盐水中制备的AM-AMPS40-水溶性酚醛树脂满足塔河油田堵水的要求,该结果可为高温高盐油藏用堵剂选择提供指导。     

植物胶压裂液循环利用的制约因素分析

为实现压裂液的循环利用,节约水资源,减少环境污染,研究了植物胶压裂液返排液中残余交联剂硼和稠化剂对循环利用的影响。以均相状态为评价标准,采用拉曼光谱测定不同多羟基化合物与硼交联剂的结合形态,对体系中残余交联剂硼的最小无作用量进行研究;测定了破胶过程中稠化剂的相对分子质量、总糖含量和pH值的变化。结果表明,破胶液内部残留的交联剂和稠化剂均为制约返排液循环利用的制约因子。硼砂-甘露醇络合性能稳定,甘露醇可作为高效掩蔽剂,交联剂硼的最小无作用量为5 mg/L;过硫酸盐破胶时可以将稠化剂胍胶大分子部分降解,随破胶时间延长,小分子比例增加,体系中总糖含量下降。溶剂总糖含量低于1800 mg/L时所配制的压裂液可以满足循环利用要求,但残渣伤害风险增加。     

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。     

深部调剖驱油交联剂的研究

为提高非均质性严重的地层原油采出率 ,合成了用于聚合物驱油的 4种交联剂 ,并对聚合物种类、用量和其与交联剂组成的体系进行了评价。 4 0℃下铝交联剂凝胶粘度低 ,酚醛树脂交联剂低温下不成胶 ,而有机铬交联剂 (J2 )和有机复合胺 (J3)交联效果好。当选用HPAM/有机铬交联剂 /有机酸交联体系时 ,其中HPAM相对分子质量为 2 1× 10 7,可通过改变体系pH值调节成胶速度 ,pH值 6 5时 ,14 0 0mg/LHPAM和 4 0 0mg/LJ2组成的体系在 4 0℃、30d可形成粘度为12 0mPa·s以上的凝胶 ,且热稳定性好 ,成胶时间能满足现场施工需要。 14 0 0mg/LHPAM和10 0 0mg/LJ3交联剂组成的体系 ,成胶时间长 ,有利于油田深部调剖驱油     

汽油中氮化物的定性定量方法研究与应用

采用预富集技术提取汽油中的氮化物,结合气相色谱-质谱(GC-MS)定性,对照标准样品的色谱保留时间确定汽油中氮化物的形态。以气相色谱-氮化学发光检测法(GC-NCD)为分析手段,对汽油中氮化物进行定量分析,单组分化合物的检出限为0.6 mg/L。用该方法分析得出催化裂化汽油中氮化物的类型主要包括腈类、吡啶类、吡咯类、苯胺类。对市售车用汽油中氮化物的形态进行识别并定量分析,大部分常规车用汽油样品中氮化物的含量小于60 mg/L,其中几个车用汽油样品中苯胺类氮化物含量大于100 mg/L。     

Chemical analysis of resin fraction of Nigerian bitumen for organic and trace metal compositions

Studies of organics and trace metals of the resin fraction of Nigerian bitumen were carried out with an opinion to establish the environmental consequences of the fossil fuel and as well as characterize them. Bitumen samples were extracted from oil sands via Soxhlet extraction procedure using toluene as the extracting solvent. The bitumen samples were deasphaltened to obtain maltene by dissolving the samples in n-pentane (1:40). Column chromatography was used to fractionate the maltene into its components (saturates, aromatics, and resin) using silica gel as adsorbent and dissimilar solvents of varying polarity (n-hexane for saturates, toluene for aromatics, and methanol for resins). The organic compounds of the resin fraction were examined using Fourier Transform Infrared Spectrophometry (FTIR) and the elemental concentrations were determined using Inductively Coupled Plasma Optical Emission Spectrophotometry (ICP-OES). The infrared spectra of all the resin samples presented distinctive bands including expected polar functional groups which confirmed that the resin was cleanly eluted from the bitumen samples. The concentrations of the analyzed trace metals in the resin fraction were found to be high compared to other fractions and this was confirmed by their T-test values. Fe had the highest average concentration of 34.81 ± 14.37 mg/kg and a range of 19.35–47.48 mg/kg, while Mn had the least mean concentration of 0.94 ± 0.71 mg/kg and a range of 0.35–1.88 mg/kg. The result of cross-plot analysis revealed that resin fraction has strong and positive inter elemental correlation with the NSO and asphaltene fraction of the same bitumen samples. The overall results indicated that processing of the bitumen and/or its resin may cause catalyst poisoning and fouling, corrosion of equipment and pipelines, and particulate emissions into the environment and therefore adequate demetalisation of the fossil fuel must be done before processing.     

离子淌度-飞行时间质谱测定减压蜡油芳香分及胶质中的碱性氮化物

采用柱层析法将减压蜡油（VGO）分离为饱和分、芳香分和胶质,然后用电喷雾电离源（ESI）离子淌度-飞行时间质谱（IMS-TOF MS）对其芳香分与胶质中的碱性氮化物进行了表征,对不同来源的VGO中碱性氮化物的结构差异进行了分析。结果表明：对于不同来源的VGO样品,即使碱性氮化物不饱和程度接近,其芳环的连接方式也存在明显差异;而对于同一样品的芳香分和胶质,则存在碳数相近,但胶质中等效双键数稍低的现象。以核磁共振波谱仪异核单量子相干试验和加氢脱氮反应评价作为辅证,进一步推测了VGO中碱性氮化物的芳环侧链长度与其脱除难度之间的关联。将柱层析分离技术与ESI IMS-TOF MS联用,可以解决高蜡含量样品难以溶解的问题,并减弱强极性组分的离子化抑制作用,得到比直接进样更为全面的质谱信息。     

Study of resin fraction of Nigerian crude oil using spectroscopic/spectrometric analytical techniques

Organics and trace metals of the resin fraction of Nigerian crude oil were analysed in order to characterise the fossil fuel. The crude oil samples were deasphaltened by n-pentane, while maltene fraction was fractionated into its components (saturates, aromatics and resin) using column chromatography. The organic compounds and elemental concentrations of the resin fraction were investigated using Fourier Transform Infrared Spectroscopy and Inductively Coupled Plasma Optical Emission Spectrometry respectively. The infrared spectra showed characteristic bands containing polar functional groups expected confirming that the resin was purely eluted. The elemental concentrations were found to be high compared to other fractions and was confirmed by their T-test values. Zinc had the highest mean concentration of 32.13 ± 35.66 mg/kg, while Mn had the least (1.14 ± 0.17 mg/kg). Results indicated that processing of the crude oil resin may cause catalyst poisoning/fouling, corrosion of equipment/pipelines. Therefore, adequate consideration of these trace metals must be taken before processing.     

冷热水管材用PP-R混配料的开发

参照GB/T18742-2017新国标要求制定了中石化PP-R管材混配料的性能指标,利用核磁共振碳谱、凝胶渗透色谱对混配料基础树脂的分子结构进行了表征,通过小试试验确定了混配料的配方体系及生产工艺条件,在此基础上实现了工业化开发。工业化产品的物理性能优、卫生性能好、静液压强度高,由其制备的管材通过了静液压状态下的长期热稳定性试验,综合性能达到国外同类产品的先进水平。     

CHEMICAL CHARACTERISTICS OF SUPERCRITICAL TOLUENE EXTRACTS FROM TWO TURKISH LIGNITES

Samples from two major deposits of Turkish lignites were subjected to supercritical toluene extraction at 325°C and 14.1 MPa in an autoclave. The resultant extracts were separated into pre-asphaltene, asphaltene, saturates, aromatics and resin fractions by column chromatography. The fractions were characterized by ¹H-NMR, ¹³C-NMR, IR. and elemental analysis in order to compare the chemical composition of extracis from the two coal samples. The results show that the extracts from the Tungbiiek (T-coal) deposits contain aliphatic constituent which is composed of mostly long chain unbranched alkyl compounds while the extracts from the Soma Mcrkeg (S-coal) deposits contain a significant amount of branched paraffinic compounds. The resin fractions from both samples were found to contain a significant amount of single ring aromatic compounds.     

多孔莫来石基低密度高强度支撑剂的制备及性能

目前常用的树脂复合型压裂支撑剂多存在圆球度差、抗破碎能力低、树脂用量大、成本高等不足,为解决该问题,研制了多孔莫来石基复合型低密度高强度陶粒支撑剂。通过测试支撑剂用FT酚醛环氧树脂改性前后的性能,确定了制备该支撑剂的最佳树脂质量分数和树脂含量;采用压汞分析和扫描电子显微镜对该支撑剂的显气孔率、气孔孔径分布和微观形貌进行了分析,讨论了该支撑剂的增强作用机制。结果表明:树脂的质量分数为35%时,陶粒浸渍体的体积密度最大(1.18 g/cm3),树脂的充填效果最佳,显气孔率与浸渍前的陶粒相比下降了约62%,树脂与陶粒基体相互穿插构成了网络结构,使其抗破碎能力提高;当陶粒浸渍体包覆树脂含量为5%时,颗粒表面包覆的树脂层可完全封闭陶粒浸渍体,显气孔率降低至1.06%,其视密度为1.90 g/cm3,在52和69 MPa闭合压力下的破碎率分别为2.17%和2.81%,达到行业和企业标准的技术要求。      

Upper Cretaceous Duwi Formation shale’s oil potentiality Safaga-Quseir,Red Sea,Egypt

Duwi Formation shale deposits at Safaga – Quseir area were assessed by rock eval pyrolysis for its shale oil potentiality. The studied shale’s organic matter are mainly of type I, type II, mixed type I/II in addition to some of type III. The studied shale is described as very good source rock with total organic carbon (TOC?>?2?wt%). The kerogen maturation in the studied samples is immature according to PI and Tmax. Extracted shale oil from the studied samples as bitumen was fractionated by liquid chromatography (LG) into saturated hydrocarbon, aromatic hydrocarbon, resin and asphaltene. The saturated hydrocarbon was described by gas chromatography (GC), the pristane/phytane, isoprenoids/n-alkane and CPI ratios show that, samples were deposited in marine environment with some input of terrestrial environment and are characterized by immature level.The X-Ray Diffraction (XRD) analysis for the studied shale samples show their bulk minerals are mainly quartz, calcite, dolomite, gypsum, hematite and pyrite in addition to apatite and fluorapatite. While their clay minerals are mainly smectite and kaolinite. The chemical composition of the studied samples showed high concentration of trace elements such as Co, Cr, Cu, Ni, V and Zn which in turn through more lights on the depositional environment of the organic matter.     

石油树脂代替C_9增粘树脂的应用

试验研究石油树脂在载重斜交轮胎胎圈钢丝包布胶中的应用。结果表明,在胎圈钢丝包布胶中以石油树脂等量代替C_9增粘树脂,胶料的硫化特性、工艺性能及硫化胶的物理性能变化不大,载重斜交轮胎的胎圈问题退赔率由原来的1.3%降为1.0%以下,且生产成本降低。     

高温高盐油藏环氧树脂／酚醛树脂复合堵水调剖剂的性能研究

针对国内高温高盐油藏,使用环氧树脂胶黏剂和酚醛树脂,选择合适的固化剂、增韧剂,制备环氧树脂／酚醛树脂复合调剖体系,确定了复合词剖剂最佳配方：100g环氧树脂和酚醛树脂混合物（环氧树脂与酚醛树脂质量比为6：4）,稀释剂40mL,固化剂六次甲基四胺0．1％,中试纤维2．0％。对复合调剖体系进行了性能评价,试验结果表明,堵水调剖体系在14．5℃下养护30d,抗压强度仍达7．76MPa;在矿化度160g／t,中养护24h,7d后封堵率在96％以上;在145℃下养护时间在2．5h内,黏度均在1000mPa·s内;4000min以搅拌30min后,黏度下降8．33％,24h后抗压强度为2．36MPa;后续水驱中注水量达30PV时,堵水率基本不变。此复合调剖体系能满足高温高盐油藏堵水调剖的要求。     

3种注塑专用高密度聚乙烯树脂的性能对比

采用凝胶渗透色谱、差示扫描量热等方法分析测试了3种注塑专用高密度聚乙烯树脂(HDPE,进口2种,国产1种)的分子结构及物理机械性能。结果表明,HDPE的相对分子质量分布、密度、支化度、支化类型、拉伸屈服强度、断裂伸长率、冲击强度、弯曲弹性模量、熔点、热变形温度和维卡软化点、氧化诱导期、耐环境应力开裂时间分别为:(1)国产,5.36,951.9 kg/m3,4.1,乙基支化,26.5 MPa,1 100%,98.6 J/m2,1 160 MPa,131.1℃,76.9℃,127℃,28 min,18 h;(2)进口,4.95～5.05,949.0 kg/m3,3.9～6.8,甲基支化,24.5～25.1 MPa,598%～950%,88.6～123.8 J/m2,762～825 MPa,132.6～132.9℃,77.1～77.2℃,126～126℃,14～18 min,10～37 h。