高温条件下AMPS类缓凝剂缓凝作用效果分析

缓凝剂的选配是高温水泥浆体系设计最关键的因素之一。为了合理地优选和适用缓凝剂,选用AMPS-IA共聚缓凝剂与大连G级油井水泥作用,通过高温高压稠化仪、X射线衍射仪、扫描电子显微镜和能谱仪等对水泥稠化性能、水化硬化产物的物质组成和微观结构特征进行检测,对其适用性进行分析。结果表明：AMPS类缓凝剂作为高温缓凝剂具有良好的缓凝效果,稠化线形好且稠化时间长。但是重复实验评价缓凝剂稳定性过程中有一定概率出现缓凝剂失效,稠化曲线出现波动,造成水泥浆异常胶凝。产生胶凝的原因是缓凝剂聚合物分子对阳离子产生螯合-吸附作用,在物理搅拌作用下使得大量聚合物分子与水泥熟料成胶联状聚集在搅拌轴外部。     

抗高温弹性固井水泥浆体系研究

为解决高温下水泥环完整性保障问题,根据高温复杂井对固井水泥浆体系要求,研究高温降失水剂、高温缓凝剂和抗高温弹性剂调节水泥浆的失水量、稠化时间和弹性模量,并构建了高温弹性水泥浆体系,对其性能进行评价。结果表明,研究的高温降失水剂HRW-4、高温缓凝剂HRT和高温弹性剂能有效调节水泥浆体系的各项性能,构建的水泥浆体系流变性满足固井施工要求,失水量33mL,稠化时间3～5h之间,抗压强度20 MPa以上且力学性能高温稳定性好,弹性模量低,有助于保障高温环境下水泥环完整性。     

HJH-1型高温油井水泥缓凝剂的合成及其性能评价

以MA、AMPS、AM为原料合成一种高温油井水泥缓凝剂HJH-1,通过正交实验确定最佳合成条件为:m(MA)∶m(AMPS)∶m(AM)=21∶9∶8、引发剂加量8%(以单体总质量计)、反应温度90℃和反应时间6 h,并对其应用性能进行评价。结果表明,HJH-1型缓凝剂在140℃的高温环境下仍具有很好的缓凝效果,4%加量时稠化时间为300 min,初始稠度低于30 Bc,稠化线形良好,直角稠化时间小于20 min;稠化时间可调性好,温度和加量敏感性低,综合性能满足固井施工安全要求;此外,将低场核磁共振分析技术应用于塑性水泥浆的研究,测试水泥浆体初凝前的横向弛豫时间T2分布,进一步分析了在初始水化阶段水泥浆体中水的存在状态及该缓凝剂对水泥浆初始阶段水化过程的影响。     

高温缓凝剂LY的合成及在低密度水泥浆中的应用

随着石油勘探开发向深部油气层发展,固井长度增加,井底温度升高,需要提高缓凝剂的抗温能力并降低其温敏性。本文首先以AMPS和IA(衣康酸)这两种单体为原料合成共聚物,通过单因素实验法优化合成条件,得出最优合成条件为n(AMPS):n(IA)=50:20,反应温度60℃,引发剂加量1%。再将AMPS/IA共聚物与一种多羟基羧酸盐复配得到新型高温缓凝剂LY,并将该缓凝剂LY应用于低密度水泥浆体系中,通过中、高温条件下的稠化时间对比说明缓凝剂LY对温度的敏感性,实验证实LY的温敏性较小;并通过缓凝剂LY对水泥浆流变性的影响说明缓凝剂的分散性及稳定性,结果证明缓凝剂LY的稳定性较好,并可改善水泥浆的流变性;通过125℃下的高温稠化曲线可知该缓凝剂可抗温度达到125℃,具备高温缓凝剂特性,能够满足固井的要求。再通过XRD谱图分析缓凝剂对低密度水泥石的影响,并最终探讨缓凝机理。     

一种适合于超高温油井水泥缓凝剂的研制

通过优选含有羟基、羧基和磷的单体进行水溶液聚合,合成了耐高温的油井水泥缓凝剂。讨论了单体的优选及合成的最佳条件;测试了超高温缓凝剂的抗高温性能、抗压性能及与其他外加剂的配伍性等。实验表明,该缓凝剂适用温度范围广(110℃~200℃);加量不敏感,与稠化时间具有良好的线性关系,有利于现场施工;在高温下48h强度发展迅速,对水泥石强度无影响;与其他水泥外加剂具有良好的配伍性,对水泥浆体系无不良影响,综合性能能满足固井现场的施工要求。     

超高温油井水泥缓凝剂的合成及评价

通过优选含有羟基、羧基和磷的单体进行水溶液聚合,合成了耐高温的油井水泥缓凝剂。讨论了单体的优选及合成的最佳条件;测试了超高温缓凝剂的抗高温性能、抗压性能及与其他外加剂的配伍性等。实验表明,该缓凝剂适用温度范围广(110℃²00℃);加量不敏感,与稠化时间具有良好的线性关系,有利于现场施工;在高温下48h强度发展迅速,对水泥石强度无影响;与其他水泥外加剂具有良好的配伍性,对水泥浆体系无不良影响,综合性能能满足固井现场的施工要求。     

高温缓凝剂AMPS-IA的性能及作用机理解释

针对深井固井高温环境下水泥浆稠化时间和抗温性能难以满足现场施工的问题,研制了一种抗高温缓凝剂AMPS-IA,并考察了高温缓凝性能、抗盐性能及它对水泥石抗压强度的影响。通过红外光谱分析,聚合物络合物中最明显的特征在于1405cm-1处吸收峰的出现。在溶液吸收光谱分析中,聚合物络合物中的最大吸收波长的变化代表了-C=O基团上发生了跃迁,-C=O基团的电子云密度降低。根据红外光谱及溶液吸收光谱分析,证实了缓凝剂中的配位体与水泥中的钙离子形成了金属螯合物,通过测试手段证实了AMPS-IA缓凝剂的作用机理。     

缓凝剂对氯氧镁水泥水化历程的影响

为了拓展氯氧镁水泥(MOC)的使用范围,研究了缓凝剂(柠檬酸、硼酸、葡萄糖酸钠)对氯氧镁水泥凝结时间、抗压强度、电阻率、水化热和耐水性的影响,同时采用X射线衍射仪分析了氯氧镁水泥改性后的水化产物。结果表明,掺入缓凝剂会延长氯氧镁水泥的凝结时间,当缓凝剂掺量达到0.75%(质量分数,下同)时,各组试样的28 d抗压强度较空白组分别下降了19.3%、16.7%和20.2%。缓凝剂的掺入降低了水泥浆体电阻率速率曲线和内部温度曲线的峰值,推迟了水化放热速率曲线第二峰值出现时间,即降低了氯氧镁水泥的水化速率,改善了氯氧镁水泥放热集中的现象。缓凝剂能提高氯氧镁水泥的耐水性,当硼酸掺量为0.75%时,软化系数可达到0.79。     

缓凝剂SN-3的制备及其对水泥浆横向弛豫时间T2分布的影响

首先合成了一种新型两性聚合物缓凝剂SN-3,然后采用红外光谱和元素分析等测试手段对其进行结构表征。其次,对其应用性能作了进一步研究,主要包括稠化时间、加量和温度敏感性等,实验结果表明应用性能满足现场施工要求。利用低场核磁共振测试技术重点研究了缓凝剂SN-3对油井水泥浆水化过程中横向弛豫时间T₂分布的影响,在相同的水灰比、温度和水化时间下,对纯水泥浆C和掺有缓凝剂SN-3的水泥浆CHN的横向弛豫时间进行测试和分析,借助迁移速率和峰形指数两个参数表征水泥浆T₂分布曲线的变化过程。最后,结合X衍射和扫描电镜（SEM）进一步探讨缓凝剂SN-3的缓凝作用原理。实验结果表明,缓凝剂使水泥浆中填充于絮凝结构之间的水的受缚程度减小,存在时间变长,转化为化学结合水所经历时间变长;缓凝剂SN-3主要通过沉淀和络合作用达到缓凝效果的。     

硼砂/三乙醇胺复合缓凝剂对磷酸钾镁水泥水化硬化性能的影响

磷酸钾镁水泥(MKPC)的速凝特性限制了其在更多工程领域的应用发展，有效延长凝结时间是其工程化应用的关键技术之一。本研究使用硼砂/三乙醇胺复合缓凝剂，深入研究了其对磷酸钾镁水泥凝结时间、抗压强度、物相组成、微观形貌、孔结构和水化放热等特性的影响，并探讨了缓凝机理。结果表明：在保障7 d抗压强度大于20 MPa条件下，复合缓凝剂的使用，可实现26～100 min的凝结时间调控；三乙醇胺分子包覆MgO颗粒，发挥阻水作用，从而显著降低水化反应的标准水化放热速率与标准水化放热量，达到缓凝效果；试样中K-鸟粪石含量的减少与大于10 nm孔隙体积的增加是削弱抗压强度的主要原因。     

SDJ2油井水泥降失水剂的室内研究

选用合适平均分子量的水溶性天然高分子改性产物羟乙基纤维素(HEC)合成一种油井水泥降失水剂SDJ2,并对添加SDJ2的水泥浆的性能进行了室内评价。这些性能包括水泥浆的流变性能、稳定性、稠化时间、失水量和水泥石的抗压强度等,并且将SDJ2与自制缓凝剂SDH-2进行了配方试验。结果表明,SDJ2对水泥浆有显著的降失水作用,流变性能和稳定性良好,与缓凝剂SDH-2有很好的相容性,稠化时间可调,水泥石抗压强度符合要求。     

油井水泥降失水剂(HCW-1)的合成及性能评价

研究了2-丙烯酰胺-2-甲基丙磺酸(AMPS）、丙烯酸(AA)和一种功能型单体(简称为SM)三元共聚物(HCW-1)的合成方法及在油井水泥浆中的降失水作用,并探讨了其降失水机理。实验结果表明,HCW-1对水泥浆稠化时间和水泥石抗压强度无不良影响,是一种良好的降失水剂。     

Adsorption behavior and effectiveness of poly(N,N‐dimethylacrylamide‐co‐Ca 2‐acrylamido‐2‐methylpropanesulfonate) as cement fluid loss additive in the presence of acetone‐formaldehyde‐sulfite dispersant

A copolymer of N,N‐dimethylacrylamide and Calcium 2‐acrylamido‐2‐methylpropanesulfonate was synthesized by free‐radical copolymerization. Its performance as anionic fluid loss additive (FLA) was studied by measuring static filtration properties of oil well cement slurries at 27°C and 70 bar pressure, respectively. It was found that cement filter cake permeability and API fluid loss decrease with increasing FLA dosage. Filtrate analysis revealed a linear correlation between fluid loss and the amount of FLA adsorbed on the cement surface. FLA adsorption on cement was determined by total organic carbon (TOC) analysis in cement filtrate and confirmed by ζ‐potential measurement. According to environmental scanning electron microscopy (ESEM) investigations, FLA does not alter the filter cake structure. In the presence of an anionic acetone–formaldehyde–sulfite (AFS) polycondensate dispersant, fluid loss control from FLA decreased and cement filter cake permeability increased because AFS reduces the amount of FLA adsorbed. In comparison to FLA, AFS shows stronger adsorption on the cement surface and succeeds in the competition with FLA. The different adsorption behavior of the two polymers is the reason for limited compatibility of this admixture com bination. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4341–4347, 2006     

Competitive adsorption between an AMPS®‐based fluid loss polymer and Welan gum biopolymer in oil well cement

Water‐soluble 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS®)‐based copolymers are commonly used to provide water retention (fluid loss control) for oil well cement slurries. Here, the fluid loss performance of a CaAMPS®‐N,N‐dimethylacrylamide copolymer (CaAMPS®‐co‐NNDMA) in the presence of Welan gum, an anionic microbial biopolymer produced by anaerobic fermentation using Alcaligenes ATCC 31555 bacteria was investigated at 80°C. Welan gum is used to control unwanted free water development at the surface of the cement slurry. The effectiveness of CaAMPS®‐co‐NNDMA fluid loss additive (FLA) solely relies on its high adsorption onto the positively charged surfaces of cement hydrates. Adsorption of the FLA is, however, perturbed by Welan gum. This anionic polysaccharide competes with CaAMPS®‐co‐NNDMA for adsorption sites on the cement surface. This effect is surprising because in cement pore solution, Welan gum exhibits a much lower specific anionic charge amount than CaAMPS®‐co‐NNDMA. The reason is that Welan gum possesses carboxylate functionalities, which are much stronger anchor groups than the sulfonate groups present in CaAMPS®‐co‐NNDMA. The superiority of the carboxylate groups regarding their affinity to the mineral surface, which possesses insufficiently coordinated Ca atoms is confirmed by a higher calcium binding capability for Welan gum than for the FLA. Thus, Welan gum can reduce effectiveness of CaAMPS®‐co‐NNDMA as fluid loss agent by preventing its adsorption or through displacement of already adsorbed FLA molecules from the surface of cement. In multiadmixture systems, which are commonly used in oil well cement, concrete or mortars, competitive adsorption between different additives for surface sites can negatively impact the performance of these additives. Understanding the reasons behind can help to develop more effective admixture systems. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of high temperature and the role of sulfate on adsorption behavior and effectiveness of AMPS®‐based cement fluid loss polymers

The fluid loss control performance of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS®)‐based copolymers added to cement slurries was studied at 27 and 100°C, respectively. It was found that effectiveness of these fluid loss additives solely relies on achievement of a high adsorbed amount on the surface of cement. At elevated temperature (100°C), CaAMPS®‐N,N‐dimethyl acrylamide copolymer (CaAMPS®‐co‐NNDMA) exhibits reduced adsorption and hence decreased fluid loss control of the cement slurry. The reason behind this behavior is poor calcium binding capability of the sulfonate anchor groups, which coordinate with calcium atoms present on the mineral surface. Whereas, an increase in the sulfate concentration present in cement pore solution instigates partial coiling of CaAMPS®‐co‐NNDMA and causes only a slight influence on the performance of this copolymer. The elevated sulfate content results from thermal degradation of ettringite, a cement hydrate mineral produced during the early stages of cement hydration. Incorporation of minor amounts (～ 1.3 mol %) of maleic anhydride into this copolymer produces a terpolymer, which exhibits higher and more stable adsorption, even at high temperature. This effect is owed to the presence of homopolymer blocks of polycarboxylates distributed along the polymer trunk. On mineral surfaces, they present much stronger anchor groups than sulfonate functionalities, as evidenced by their higher calcium binding capability. Consequently, fluid loss performance of CaAMPS®‐co‐NNDMA‐co‐MA is little affected by temperature. Understanding the influence of temperature on the physicochemical interactions occurring between additives and the mineral surface can help to design more effective admixtures suitable for high temperature applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

海上稠油热采井水泥浆体系研究

海上稠油热采井与陆地热采井对水泥浆性能要求基本相同,都要求水泥环在生产中要长期满足经受反复高温考验后仍具有稳定性的特点。针对海上平台作业条件,参照硅酸盐水泥浆体系耐高温特点和纤维材料的增韧效果,优化添加剂组合,配制出一套密度在1.50~1.90 g/cm~3、温度区间为40~90℃的新型水泥浆体系。室内试验结果表明:该水泥浆体系失水量小于50 mL,稠化时间在120~400 min范围内可控,水泥石高温养护24 h的抗压强度最高可达24.8 MPa,在经350℃高温条件下养护28 d,水泥石仍有32.9 MPa的抗压强度。表明该体系可以满足海上热采井固井的施工要求。     

水滑石插层降失水剂的制备和性能研究

随着石油开发逐渐转向陆地深层、超深层,固井工程对油井水泥降失水剂的要求越来越高,降失水剂在高温高盐地层依然需要具备良好的控水特性.为了满足油井水泥降失水剂耐高温的性能,将有机聚合物降失水剂与新型无机材料水滑石结合起来,研制出一种耐高温耐盐的新型油井水泥降失水剂.选择2-丙酰胺基-2-甲基丙磺酸(AMPS)、对苯乙烯磺酸...     

Preparation and property of 2‐acrylamide‐2‐methylpropanesulfonic acid/acrylamide/sodium styrene sulfonate as fluid loss agent for oil well cement

A novel terpolymer 2‐acrylamide‐2‐methylpropanesulfonic acid/acrylamide/sodium styrene sulfonate (AMPS/AM/SSS), used as fluid loss agent for oil well cement under high temperature, was prepared with initiator of azobisisobutryamide chloride. The optimum reaction conditions of polymerization were obtained from the orthogonal experiments, reaction temperature 40°C, initiator 0.1 wt%, molar ratio of monomers AMPS/AM/SSS 20/5/1. The structure and performance of terpolymer was characterized with Fourier transform infrared spectrometer, nuclear magnetic resonance hydrogen spectrum, thermogravimetric and simultaneous differential thermal analysis, high‐temperature and high‐pressure water loss meter, and rotational viscometer, indicating that the terpolymer was perfectly synthesized and started to decompose at 350°C and showed good performance of fluid loss control up to 160°C. The ζ‐potential instrument and scanning electron microscopy were used to investigate the mechanisms of fluid loss control, indicating that the terpolymer can prevent the generation of flocculated structure in the cement and reduce the porosity of the filter cake. These results have important referential value for developing new high‐temperature‐resisting fluid loss agents. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

松南地区低密度水泥浆体系的研究与应用

松南地区地层破裂压力梯度较低,井底循环温度较低,油气层分布十分广泛,注水泥后易造成漏失,发生环空气窜等问题,给固井施工带来了很大的困难,严重影响了固井质量。为解决这些问题,研究并应用了漂珠一微硅低密度水泥浆体系,该体系具有低失水、流变性能好、稠化过渡时间短、抗压强度高等优点,能够满足松南地区固井要求。     

Modification of the molar anionic charge density of acetone–formaldehyde–sulfite dispersant to improve adsorption behavior and effectiveness in the presence of CaAMPS®‐co‐NNDMA cement fluid loss polymer

Sulfonated aldol polycondensates were synthesized from acetone, formaldehyde, and different amounts of sodium sulfite, resulting in polymers with varying degrees of sulfonation (DS). The anionic charge amount of these macromolecules measured by polyelectrolyte titration decreased with lower DS. The effectiveness of the acetone–formaldehyde–sulfite (AFS) polycondensates as cement dispersant was found to depend on the amount of polymer adsorbed on cement. AFS adsorption decreases with lower DS. Interaction and compatibility between AFS and CaAMPS®‐co‐NNDMA fluid loss additive was studied by formulating binary additive systems composed of one of the modified AFS polymers and CaAMPS‐co‐NNDMA. At high DS, AFS adsorbs strongly and prevents CaAMPS‐co‐NNDMA from adsorbing in sufficient amounts on the cement surface. The result is poor fluid loss control of the cement slurry. AFS polymers with lower DS, however, allow simultaneous adsorption of both polymers in sufficient quantities to provide good fluid loss control and low rheology at the same time. Thus, effectiveness of both additives was retained. Obviously, effectiveness of such multi‐admixture systems depends on the adjustment of the adsorption behavior of the individual components relative to each other. Molar anionic charge density of the polymers was found to be a major parameter influencing their relative adsorption behavior. The AFS polymer with DS = 0.2 possesses a molar anionic charge density comparable to CaAMPS‐co‐NNDMA. Thus, when admixtures with similar molar anionic charge densities are used, the performance of one component is not negatively influenced by the other. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009