新型超支化大分子季铵型抑制剂的制备及性能评价

以二乙醇胺、丁二酸酐为原料,合成端羟基超支化大分子；用环氧丙基三甲基氯化铵进行末端基团改性，引入季铵盐阳离子基团制备了一种新型季铵盐抑制剂HBP-TAC，其结构经红外光谱、核磁和元素分析表征。考察了端基取代度与浓度对抑制膨润土水化膨胀性能影响，并对滚动回收率及与钻井液配伍性进行了评价、实验结果表明：该类抑制剂对膨润土的水化膨胀有一定抑制作用，加入1%多取代HBP-T2，抑制效果能达到95.31%；在高温130℃条件下，页岩滚动回收的一次回收率为91.8%，二次回收率为80.1%；抑制剂与水基钻井液体系相容性较好，并对滤失性有一定改善效果。      

微交联聚合物降滤失剂的合成与性能

针对深井、超深井钻井液体系中的降滤失剂受长时间高温、高矿化度作用易降解的问题，以氮丙啶与3-氯丙烯反应制得-N-烯丙基氮丙啶（ALAI）； ALAI与乙二胺反应制得四烯基交联剂单体（EAAD）； EAAD与丙烯酰胺（AM）和2 丙烯酰胺基-2-甲基丙磺酸（AMPS）发生水溶液自由基共聚反应，合成了微交联共聚物降滤失剂(PAAT)，其结构和性能经¹H NMR, IR和TG-DTG表征。结果表明：PAAT可抗220 ℃高温，在高温、高矿化度条件下可维持钻井液的滤失量与流变性能，API滤失量均低于4.0 mL，高温高压滤失量均小于13.0 mL。     

复合型改性木质素基钻井液用降粘剂的性能研究

以马尾松硫酸盐制浆黑液为原料,经化学改性制备复合型改性木质素基钻井液用降粘剂,并对其在钻井液中的降粘性能进行实验室评价。研究结果表明,该降粘剂既能发挥无机降粘剂良好的降粘作用,又具有木质素系降粘剂良好的抗温、抗盐效果,具有较好的协同作用。加入0.5%降粘剂的淡水基浆,降粘率可达96.7%。     

木质素脱甲基化改性及产物结构表征

通过对不同催化剂、催化剂量、反应温度和反应时间等反应条件下得到的改性木质素与甲醛反应活性的研究,确定了木质素脱甲基化反应条件,并通过FT-IR半定量、GPC1、H NMR对木质素脱甲基化前后结构进行表征。FT-IR半定量表明木质素甲氧基由反应前的0.990降至0.765,酚羟基由1.174增至1.529;GPC表明木质素脱甲基化后大分子木质素发生了降解,分子量小于2000的木质素含量由由改性前的38%增至改性后的51%;1H NMR表明木质素改性后脂肪族侧链与苯环分离,同时大量-βO-4醚键裂解。     

新型有机-无机复合型钻井液降滤失剂的制备及性能

以2-丙烯酰胺基-2-甲基丙磺酸、对苯乙烯磺酸钠和丙烯酰胺为共聚单体,氧化石墨烯为无机改性剂,采用水溶液聚合法制备了一种新型的水基钻井液降滤失剂(LC-1),其结构和性能经IR, GC和TG表征。结果表明:LC-1用量为1.6 wt%时,钻井液体系老化前后的滤失量分别为9.2 mL和9.8 mL,动切力为12.5 Pa和10.4 Pa,动塑比为0.30和0.26,钻井液体系的降滤失性、流变性和耐热性较好。页岩滚动回收两次,回收率大于90%。     

木质素磺酸盐表面活性剂的研究和应用进展

论述了木质素磺酸盐结构方面的研究、木质素磺酸盐的分离纯化和化学改性制备表面活性剂的方法、木质素磺酸盐表面活性剂应用取得的进展和研究面临的挑战。最后总结认为:进一步加强木质素磺酸盐结构和性能的基础研究,结合界面化学的最新理论成果和现代分析测试手段,通过改性解决木质素磺酸盐的颜色和活性问题,开发可用于日用领域的新型环保的木质素磺酸盐表面活性剂,是木质素磺酸盐这一绿色资源得到高值化利用的一个重要方向,同时木质素磺酸盐在导电高分子等先进材料制备领域具有重大的研究潜力。     

木质素活化改性制备酚醛树脂胶黏剂研究进展

木质素由于化学结构与苯酚相似,通过活化改性可部分替代苯酚制备木质素改性酚醛树脂胶黏剂。既可降低成本、达到生物质资源高效利用的目的,并且制备的木质素改性酚醛树脂胶黏剂有毒残余较低,具有环保意义,是合成制备生物质高分子材料的重要途径。本文综述了国内外研究人员在木质素活化改性制备酚醛树脂胶黏剂研究领域的最新进展,重点介绍了化学改性、物理改性、生物改性等木质素活化改性方法,比较了不同改性产物制备酚醛树脂胶黏剂的性能,并对影响木质素活化改性制备酚醛树脂胶黏剂实现工业化应用的主要因素进行了分析。     

木质素磺酸盐研究及其主要应用最新进展

木质素磺酸盐是造纸工业主要副产物之一,随着化石资源的日益枯竭和人们对环境保护的日益重视,人们对木质素磺酸盐的基础研究和应用开发研究渐趋活跃。为了能把握这一研究领域的新发展、新动向,本文综述了近几年来国内外科研工作者对木质素磺酸盐的分离与纯化、改性及其理化性质方面的研究进展,同时也综述了木质素磺酸盐近几年来在工业上的主要应用研究进展,具体包括其应用于混凝土减水剂、石油开采助剂、分散剂、高分子材料的改性剂等。     

高性能水基钻井液处理剂研究进展及发展趋势

钻井液是石油钻井工程的“血液”,具有清洁井眼、保护钻具、稳定井壁和平衡地层压力等重要作用。本文综述了高性能水基钻井液处理剂的研究进展,主要包括抑制剂、润滑剂、包被剂和降滤失剂,包含了国内外的最新研究成果,也涉及国外油服公司和化学品公司在工程现场已经规模应用的先进产品。最后在现有高性能水基钻井液处理剂研究及应用的基础上,对其发展趋势进行了展望。     

最小二乘法在聚合物有效物含量评价方法研究中的应用

为了彻底排除各种无机盐杂质的影响,真实地评价聚合物产品的有效成分含量,研究了醇酸共洗法测试钻井液用聚合物类降滤失剂有效物的可行性。该方法不但可有效地去除样品中的残留碱、水溶性无机盐类,同时还可以有效地去除样品中的酸溶性无机盐(如碳酸盐等)。在进行实验数据处理时,考虑标准碳酸钙的加入量与样品有效物含量测试结果间有较明显的线性关系,运用最小二乘法及加标回测外推法等统计学工具,最大限度地降低了测试结果的不确定度,提高了方法的准确度与可靠性,形成了较完善的钻井液用聚合物类降滤失剂产品有效物含量的评价方法。目前该方法已成功地应用于Q/SHCG 35-201《2钻井液用合成聚合物降滤失剂技术要求》等多个石化行业一级企业技术标准。     

Potential of Lignosulphonate of Eucalyptus Lignin from Pulp Plant as Dispersant in Gypsum Paste

Eucalyptus lignin was isolated from kraft black liquor through acidification by using H2SO4. To effectively utilize black liquor waste from pulp plant, lignin was converted into sulphonated hydroxymethylated phenolized sulphuric acid lignin compound (SHP-SAL), which is soluble in water. SHP-SAL was obtained through the sequence of (1) phenolation of sulphuric acid lignin (SAL) into phenolized sulphuric acid lignin (P-SAL), (2) hydroxymethylation of P-SAL into hydroxymethylated phenolized sulphuric acid lignin (HP-SAL), and (3) sulphonation of HP-SAL into SHP-SAL. The derived lignin of SHP-SAL characterized by infrared spectrometry showed a significant absorption at 630 cm^-1, which indicates the presence of S−O bond, and absorption at 1118 and 1059 cm^-1, which are characteristics of C−O bonds in lignosulphonates. Assessment of SHP-SAL as a dispersant in gypsum paste was done according to C230-90 ASTM standard. The synthesized SHP-SAL has approximately 60% higher dispersability than those of commercial sodium lignosulphonate (comm. SLS) and commercial calcium lignosulphonate (comm. CLS). It is equal to the dispersability of sulphonated naphthalene formaldehyde (SNF), one of the high-performing sulphonate compounds.     

Water-based drilling fluids: the contribution of xanthan gum and carboxymethylcellulose on filtration control

This study aimed mainly to evaluate the influence of xanthan gum (XG) and carboxymethylcellulose (CMC) in the filtration process of water-based drilling fluids, considering the conformational changes suffered by the polyelectrolyte with the addition of salt (NaCl) in different concentrations (0.17, 0.34 and 0.51 M). It was also evaluated the behavior of the fluid by the addition of calcite (calcium carbonate, CaCO₃). Sixteen drilling fluids were prepared with the same xanthan gum concentration (major application as thickener to transport the cuttings), but different salinities and having or not CMC and calcite at constant concentrations. This strategy was adopted to evaluate the real contribution of each additive in the control of filtration performance, frequently unclear in the papers. In general, the fluids prepared in all brines showed lower viscosities and higher filtrate loss compared to fluids of sweet water. This effect was more strong in fluids containing only XG. The addition of CMC enhanced the viscosity and reduced the filtrate loss. However, the best results were obtained when calcite was added. The results indicated that XG contribution as thickener is not enough to control efficiently the fluid filtration even in the presence of calcite. However, the addition of CMC and calcite to XG salt solution increased the viscosity and decreased significantly the filtrate loss. This result was attributed to synergistic interactions between XG, CMC and calcite.     

Synthesis and performance evaluation of a water-soluble copolymer as high-performance fluid loss additive for water-based drilling fluid at high temperature

Drilling fluids are widely used in the drilling of deep wells to clean and transport the rock cuttings, maintain the sidewall of oil well, lubricate and cool the drilling bit, and control the formation pressures. The present work aims at improving the high-temperature resistance of water-based drilling fluid by using the newly synthesized fluid loss additive named PAASD. This copolymer was obtained through the solution polymerization of four kinds of monomers. The synthesis conditions with the optimal API filtration were studied by single synthetic experiment, and the chemical structure of final product was confirmed by FTIR spectroscopy. The target product was carried out with thermal stability analysis, rheological property, filtrate property, temperature resistant capacity, salt tolerance capacity, micro-crosslink structure property, particle size distribution and the compatibility performance experiment. The results showed that PAASD was an efficient fluid loss additive, and the API filtration of fresh water drilling fluid containing 2% PAASD was only 5.2 mL, it was 10.6 mL after aging at the condition of 200°C and 16 h. Besides, PAASD has a good thermal stability, salt tolerance, and it could improve the rheological property of drilling fluid system obviously. Therefore, it could be used as fluid loss additive of water-based drilling fluid in salty and high-temperature environment.     

Emulsification properties of a star-shaped anionic surfactant in oil-based drilling fluid

A novel star-shaped sulfonate surfactant, synthesized with triethanolamine, was identified as a hydrophilic emulsifier which could form a stable water-in-oil emulsion. The interfacial film strength was measured by suspension drop method. The emulsification properties of emulsions were obtained by the emulsification rate experiment and demulsification voltage measurement. The emulsion shows an excellent emulsification effect when the addition of star-shaped anionic surfactant into oil-based drilling fluid was 2.0?wt%. In addition, the properties of surfactant in drilling fluid with different adding amounts were studied by rheological properties, thermal stability analysis and filtration experiments. The results show that star-shaped anionic surfactant used as emulsifier can improve the performance in oil-based drilling fluid, which maybe provides a new idea for this type of surfactant.     

苯乙烯-苯乙烯磺酸钠共聚物的制备及其流变性能

采用乳液聚合合成了一种可作为聚丙烯(PP)纤维可染改性添加剂的苯乙烯-苯乙烯磺酸钠共聚物P(St-co-NaSS)。通过傅里叶转换红外光谱仪(FT-IR)和核磁共振氢谱仪(~1 H-NMR)对共聚物的苯乙烯磺酸钠结构单元进行了表征,研究了反应条件对共聚物磺化度的影响;通过差示扫描量热仪(DSC)和热重分析仪(TG)研究了磺酸基团的引入对共聚物的玻璃化转变温度和起始分解温度的影响;通过旋转流变仪研究了磺化度对共聚物剪切黏度的影响;初步探讨了PP/P(St-co-NaSS)共混体系的染色性能。结果表明:当反应时间为2h,反应温度为70℃,引发剂质量分数为0.6%,苯乙烯磺酸钠的摩尔分数为0.01时,共聚物的磺化度f=6.68%(零切黏度η0=19 620Pa·s,属牛顿流体);在10~(-2)~10~(-1) s~(-1)的剪切速率范围内,P(St-co-NaSS)表现出假塑性流体的特征,具有较好的加工流动性。对于PP/P(St-co-NaSS)共混体系,使用阳离子染料染色时,染色深度(K/S值)为2.603 2,使用分散染料染色时,K/S值为10.168 8。P(St-co-NaSS)适合作为聚丙烯纤维的可染改性添加剂。     

Radical hydroxymethylation of alkyl iodides using formaldehyde as a C1 synthon

Radical hydroxymethylation using formaldehyde as a C1 synthon is challenging due to the reversible and endothermic nature of the addition process. Here we report a strategy that couples alkyl iodide building blocks with formaldehyde through the use of photocatalysis and a phosphine additive. Halogen-atom transfer (XAT) from α-aminoalkyl radicals is leveraged to convert the iodide into the corresponding open-shell species, while its following addition to formaldehyde is rendered irreversible by trapping the transient O-radical with PPh₃. This event delivers a phosphoranyl radical that re-generates the alkyl radical and provides the hydroxymethylated product.

Halogen-atom transfer (XAT) based on phosphoranyl radical chemistry enables the hydroxymethylation of alkyl iodides with formaldehyde.     

Experimental Investigation of the Rheological Behavior of an Oil-Based Drilling Fluid with Rheology Modifier and Oil Wetter Additives

Drilling issues such as shale hydration, high-temperature tolerance, torque and drag are often resolved by applying an appropriate drilling fluid formulation. Oil-based drilling fluid (OBDF) formulations are usually composed of emulsifiers, lime, brine, viscosifier, fluid loss controller and weighting agent. These additives sometimes outperform in extended exposure to high pressure high temperature (HPHT) conditions encountered in deep wells, resulting in weighting material segregation, high fluid loss, poor rheology and poor emulsion stability. In this study, two additives, oil wetter and rheology modifier were incorporated into the OBDF and their performance was investigated by conducting rheology, fluid loss, zeta potential and emulsion stability tests before and after hot rolling at 16 h and 32 h. Extending the hot rolling period beyond what is commonly used in this type of experiment is necessary to ensure the fluid’s stability. It was found that HPHT hot rolling affected the properties of drilling fluids by decreasing the rheology parameters and emulsion stability with the increase in the hot rolling time to 32 h. Also, the fluid loss additive’s performance degraded as rolling temperature and time increased. Adding oil wetter and rheology modifier additives resulted in a slight loss of rheological profile after 32 h and maintained flat rheology profile. The emulsion stability was slightly decreased and stayed close to the recommended value (400 V). The fluid loss was controlled by optimizing the concentration of fluid loss additive and oil wetter. The presence of oil wetter improved the carrying capacity of drilling fluids and prevented the barite sag problem. The zeta potential test confirmed that the oil wetter converted the surface of barite from water to oil and improved its dispersion in the oil.     

钻井液用交联-接枝淀粉的制备及性能

以N,N′-亚甲基双丙烯酰胺为交联剂,过硫酸铵为引发剂,采用“溶剂法”工艺合成了高粘度抗剪切丙烯酸钠接枝淀粉(St),考察了单体、引发剂和交联剂用量、丙烯酸中和度、反应时间及反应温度对合成交联丙烯酸钠接枝淀粉糊液粘度的影响。 结果表明,其优化反应条件为：m(淀粉)∶m(丙烯酸）=1∶1.5,乙醇质量分数为80%,过硫酸铵的用量为单体总质量的1%,交联剂为单体总质量的0.6%,反应时间2.5 h,反应温度为55 ℃,丙烯酸中和度为70%。 该交联接枝淀粉糊液具有良好的触变性,在4%盐水泥浆中的添加量为14.0 g/L时,表观粘度为26.0 mPa·s,滤失量为7.2 mL;在饱和盐水泥浆中添加量为23.5 g/L时,表观粘度为54.5 mPa·s,滤失量为3.1 mL;在80 ℃高温下老化16 h其表观粘度及滤失量等性能基本保持不变,表现出良好的增粘、降失水作用和抗盐、抗老化性能。     

甲基葡萄糖苷对钻井液性能的影响

甲基葡萄糖苷对钻井液性能的影响;甲基葡萄糖苷;抑制作用;膜效率;活度;钻井液     

Fabrication of ionic liquid-cellulose-silica hydrogels with appropriate thermal stability and good salt tolerance as potential drilling fluid

This paper investigates the rheological properties of methylcellulose-silica-ionic liquid nanocomposite (2-MCPS-MC) on the rheological properties (apparent viscosity (AV), plastic viscosity (PV), yield point (YP), 10-s gel strength, 10-min gel strength, and thixotropy according to API requirements) of water-based mud, and comparing these properties with the properties of the silica-free methylcellulose (MC) as drilling fluid additive. The physicochemical properties of the MC and 2-MCPS-MC compounds were studied using ¹H NMR, FTIR, Raman-spectroscopy, XRD, FE-SEM, AFM, and TGA. By FE-SEM and AFM, it is proven that the silica had an excellent dispersion in a spherical shape on the MC polymer. Three samples were prepared: the first is the commercial water-based mud, while the second and the third samples are MC and 2-MCPS-MC, respectively. The samples of MC were prepared in four concentrations (2%, 1.5%, 1.0% and 0.5% by weight). Throughout the test, density remained at 7.6 (lbs/gal) for mud fluid and 8.5 (lbs/gal) for MC and 2-MCPS-MC at pH 9.0. The results confirmed that the optimum concentration of MC and 2-MCPS-MC, which meet the required API code, was between 1 and 1.5%. The addition of 2-MCPS-MC to water-based mud enhances filtration properties. Response surface technique (RSM) with central composite design (CCD) was also used to optimize the drilling fluid properties to achieve the optimal response to AV, PV, YP, Gl, and Thixotropic using a Design expert software. The results obtained by RSM showed consistency between the experimental and theoretical data.