Working mechanism of poly(vinyl alcohol) cement fluid loss additive

The working mechanism of poly(vinyl alcohol) (PVA, M_w ～ 200,000 g mol^?1), a fluid loss control additive (FLA) applied in oil well cementing, was investigated. First, characteristic properties of PVA such as solubility and particle size in cold and hot water, minimum film forming temperature, adsorption on cement, viscosity of cement pore solution and static filtration properties of cement slurries treated with PVA were determined. It was found that the working mechanism of PVA relies on hydrated, but water‐insoluble PVA particles (d₅₀ ～ 2.4 μm). During cement slurry filtration, they coalesce into a polymer film. This film effectively plugs the pores of the cement filter cake. The sample studied here becomes water‐soluble at temperatures > 40°C (d₅₀ decreases to ～50 nm) and looses its effectiveness. Addition of highly anionic dispersants such as ß‐naphthalenesulfonate formaldehyde (BNS) or acetone formaldehyde sulfite (AFS) polycondensate extends the temperature range at which PVA works from 40°C to ～60°C. This effect is ascribed to lower solubility of PVA in the presence of these dispersants. The study reveals that decreased performance of PVA caused by higher temperatures is not the result of thermal degradation of the polymer, but is owed to its increasing water‐solubility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Mechanistic study on carboxymethyl hydroxyethyl cellulose as fluid loss control additive in oil well cement

The working mechanism of carboxymethyl hydroxyethyl cellulose (CMHEC, M_w 2.6 × 10⁵ g/mol) as fluid loss control additive (FLA) for oil well cement was investigated. First, characteristic properties of CMHEC such as anionic charge amount, intrinsic viscosity in cement pore solution, and static filtration properties of cement slurries containing CMHEC were determined at 27°C and 70 bar. Effectiveness of the FLA was found to rely on reduction of cement filter cake permeability. Consequently, the working mechanism is ascribed to constriction of cement filter cake pores. Zeta potential measurements confirm that at low CMHEC dosages (0–0.3% by weight of cement, bwoc), adsorption of the polymer onto the surface of hydrating cement occurs. However, at dosages of 0.4% bwoc and higher, an associated polymer network is formed. This was evidenced by a strong increase in hydrodynamic diameter of solved CMHEC molecules, an exponential increase in viscosity and a noticeable reduction of surface tension. Thus, the working mechanism of CMHEC changes with dosage. At low dosages, adsorption presents the predominant mode of action, whereas above a threshold concentration of ～ 10 g/L (the “overlapping concentration”), formation of associated polymer networks is responsible for effectiveness of CMHEC. Addition of anionic polyelectrolytes (e.g., sulfonated melamine formaldehyde polycondensate, M_w 2.0 × 10⁵ g/mol) to cement slurries containing CMHEC greatly improves fluid loss control. Apparently, the presence of such polyelectrolytes causes the formation of colloidal associates from CMHEC to occur at lower dosages. Through this mechanism, effectiveness of CMHEC as cement fluid loss additive is enhanced. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Modelling the Effect of Particle Size in Microfiltration

Abstract

Particle deposition at the filter surface in microfiltration is studied to better understand the effect of particle size on cake morphology and permeability reduction. Numerical simulations are carried out on a Hele Shaw cell which consists of a representative unit element of a two dimensional spatially periodic flat plate with pores. The particle concentration in the fluid is assumed to be low so that particles enter one by one into the computation domain. Particles follow the flow streamlines under creeping flow conditions from a random initial location until they are subjected to physico‐chemical interactions near the filter surface or a particle already deposited. The computational domain consists of two regions: a fluid region and a porous medium region, i.e. the particle cake. The flow over the two regions of the Hele Shaw cell is computed using the Darcy model, including the variations of the permeability field due to the cake formation. Results show that both the permeability and the filtration efficiency are affected significantly by particle size.     

MgO超细颗粒水分散体系的稳定性研究

研究了影响MgO颗粒在水介质中的分散稳定性的因素,并通过降沉实验和测定颗粒的Zeta电势、颗粒粒度以及分散剂在颗粒/水界面的吸附等温线等来解释相关机理。研究发现,阴离子表面活性剂SDS和阳离子表面活性剂CTAB能够吸附在颗粒/水界面,提高颗粒表面的Zeta电势,增加颗粒间静电排斥效应,从而阻碍颗粒间发生絮凝,提高体系的分散稳定性。而阳离子高分子聚合物聚乙烯亚胺(PEI)在颗粒表面形成多点吸附,从而阻碍其它PEI分子在颗粒表面的吸附,对MgO微粒分散体系的稳定性贡献较小。     

Al2O3表面化学特性的研究

通过测量粉体在水溶液中的Ｚｅｔａ电位和颗粒大小,探讨了引入不同的分散剂如聚甲基丙烯酸氨（Ｄａｒｖａｎ Ｃ）、聚乙烯亚胺（ＰＥＩ）及 柠檬酸氨（ＤＡＣ）时Ａｌ２Ｏ３粉体表面带电状况及颗粒分散状况的变化。结果表明,在不同分散条件下的水溶液中,Ａｌ２Ｏ３表面的荷电会有非常显著的变化,Ａｌ２Ｏ３粉体的等电点会发生明显的偏移,并且在远离等电点处,Ａｌ２Ｏ３粉体呈单分散状态,在靠近等电点处,Ａｌ２Ｏ３呈现不同     

Cement cake properties in static filtration. On the role of fluid loss control additives on the cake porosity

The mechanism of the action of fluid loss control additives in cementing oilwell operations is principally the reduction of permeability of the cement filter cake. From filtration equations physical characteristics as porosity of the cement filter cake were investigated and compared with experimental data. A good correlation is observed when no adsorption is involved. The smallest pore diameter for obtaining an efficient control of fluid loss is shown to be of the same order of magnitude as the gyration radius of used macromolecular chains.     

Effect of different anchor groups on adsorption behavior and effectiveness of poly(N,N‐dimethylacrylamide‐co‐Ca 2‐acrylamido‐2‐methylpropanesulfonate) as cement fluid loss additive in presence of acetone–formaldehyde–sulfite dispersant

The impact of various anchor groups on adsorption behavior of AMPS® copolymers was studied. The anchor groups differ in anionic charge density. Copolymer adsorption and water retention of oil well cement slurries achieved from CaAMPS®‐co‐NNDMA in the presence of an acetone–formaldehyde–sulfite (AFS) dispersant were improved by incorporation of minor amounts (～ 1% by weight of polymer) of acrylic acid (CaAMPS®‐co‐NNDMA‐co‐AA), maleic acid anhydride (CaAMPS®‐co‐NNDMA‐co‐MAA), or vinyl phosphonic acid (CaAMPS®‐co‐NNDMA‐co‐VPA), respectively. Performance of these terpolymers was studied by measuring static filtration properties of oil well cement slurries at 27°C and 70 bar pressure. All fluid loss additives possess comparable molar masses and show the same adsorption behavior and effectiveness when no other admixture is present. In the presence of AFS dispersant, however, adsorption of CaAMPS®‐co‐NNDMA and hence fluid loss control is dramatically reduced, whereas effectiveness of CaAMPS®‐co‐NNDMA‐co‐AA is less influenced because of acrylic acid incorporated as additional anchor group. Even more, CaAMPS®‐co‐NNDMA‐co‐MAA combined with AFS allows simultaneous adsorption of both polymers and thus produces good fluid loss control. CaAMPS®‐co‐NNDMA‐co‐VPA no longer allows adsorption of AFS dispersant. This was also confirmed by rheological measurements. The results show that, in a binary admixture system, adsorption of the anionic polymer with anchor groups possessing higher charge density is preferred. Surface affinity of the anchor groups studied increase in the order ? SO → ? COO^? → vic‐(? COO^?)₂→ ? PO. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of entrapped air bubbles on fine coal dewatering via filtration

An experimental study was conducted to obtain detailed information concerning entrapped air bubbles in fine coal filter cakes and their effects on filtration and the dewatering process. Four size fractions of coal samples (?80 mesh, ?42 mesh, ?82 mesh and ?100 +200 mesh) were investigated. An image analyzer with the aid of quantitative stereology was used to measure the entrapped air bubbles in relation to the microstructure of the filter cake (i.e., the particle and pore size distribution in the filter cake).The results show that the size and number of air bubbles entrapped in the filter cake can be controlled by the degree of aeration/deaeration of the coal slurry prior to filtration. Both the rate of filtration and the extent of dewatering are adversely affected by the presence of air bubbles in the filter cake. These adverse effects can best be understood in terms of the alteration of cake structure caused by air bubbles. Specifically, the reduction in connectedness of pores within the cake matrix tends to impede the flow of filtrate through the filter cake.     

Synthesis,effectiveness, and working mechanism of humic acid‐{sodium 2‐acrylamido‐2‐methylpropane sulfonate‐co‐N,N‐dimethyl acrylamide‐co‐acrylic acid} graft copolymer as high‐temperature fluid loss additive in oil well cementing

Monomers of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS®), N,N–dimethyl acrylamide (NNDMA) and acrylic acid (AA) were grafted on humic acid as backbone by aqueous free radical copolymerization in such a manner that a graft copolymer possessing lateral terpolymer chains was obtained. Molar ratios between AMPS®, NNDMA, and AA were found to be 1 : 1.54 : 0.02 and the ratio between backbone and graft chain was 20 : 80 wt %. The synthesized fluid loss additive (FLA) was characterized by size exclusion chromatography (SEC), charge titration, and Brookfield viscometry. Thermogravimetric and SEC analysis revealed stretched backbone worm architecture for the polymer whereby humic acid constitutes the backbone decorated with lateral graft chains. Grafting was confirmed by SEC data (R_g) and by ineffectiveness of a blend of AMPS®‐NNDMA‐AA copolymer with humic acid. Their performance as high temperature FLA was studied at 150°C by measuring static filtration properties of oil well cement slurries containing 35% bwoc of silica fume and 1.2% bwoc AMPS®‐co‐itaconic acid retarder. At this temperature, 1.0% bwoc graft copolymer achieves API fluid loss value of 40 mL, thus confirming high effectiveness. The graft copolymer viscosifies cement slurries less than other common synthetic FLAs. The working mechanism of the graft copolymer was found to rely on adsorption onto surface of hydrating cement, as was evidenced by adsorption and zeta potential measurements. Adsorption is hardly affected by temperature and results in constriction of the filter cake pores. The study provides insight into performance of cement additives under the harsh conditions of high temperature and high pressure. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

废弃玻璃粉对水泥石高温抗压强度和微观结构的影响

废弃玻璃粉作为一种高SiO₂含量的固体废弃物,可以有效防止油井水泥石在高温下的强度衰退,从而提升深井、超深井固井水泥环长期封隔完整性。本文研究了150 ℃、21 MPa下,不同粒径废弃玻璃粉对水泥石抗压强度、渗透率和微观结构的影响。结果表明:150 ℃、21 MPa下净浆水泥石180 d抗压强度为8.57 MPa,较1 d衰退76.04%;掺入废弃玻璃粉可以提高水泥石抗压强度的长期稳定性,在内掺40%(质量分数)粒径为45 μm的废弃玻璃粉情况下,水泥石在180 d时抗压强度为31.85 MPa,较1 d仅衰退3.95%,渗透率为1.28×10^-2 mD,较1 d降低16.88%;掺入废弃玻璃粉改变了水泥石150 ℃、21 MPa下的物相组成,净浆水泥石的主要结晶相为氢氧化钙和水硅钙石,掺入不同粒径废弃玻璃粉的水泥石主要结晶相为硬硅钙石和托贝莫来石;内掺40%粒径为45 μm的废弃玻璃粉的水泥石中托贝莫来石晶粒尺寸稳定;随龄期增加,净浆水泥石孔结构向大孔径发展,内掺40%粒径为45 μm的废弃玻璃粉的水泥石的孔结构更加致密,180 d内各龄期均以凝胶孔为主。     

MTC技术提高固井二界面胶结强度实验研究

本文对MTC固井液二界面胶结强度进行了实验研究。研究表明：与常规水泥石相比,MTC固化体能够与残余钻井液、钻井液泥饼实现整体固化胶结,MTC固化体体积收缩率较小,井壁界面条件特别是有泥饼时对常规水泥石的二界面胶结强度影响较大,但对MTC固化体的二界面胶结强度影响较小,MTC固井液可以有效地提高固井二界面胶结强度,从而提高固井质量。     

高灰细泥对煤泥水处理系统的影响

分析了升平煤矿选煤厂煤泥粒度组成,发现浮选入料中高灰细泥含量高,增加了煤泥脱水的难度。在论述颗粒直径与浮选特性、药剂消耗关系的基础上,对选煤厂浮选精煤粒度组成进行了分析,说明细粒煤对浮选精煤污染严重。浮选入料细粒煤泥过多造成了选煤厂滤饼水分、滤液浓度高,煤泥水性质恶化,过滤机吸料差,处理能力低,并针对上述问题,将原有PG78-8圆盘真空过滤机更换为GPJ-96加压过滤机对选煤厂进行了改造。改造完成后,GPJ-96加压过滤机的入料质量分数和滤液质量分数均低于PG78-8圆盘真空过滤机,且滤饼质量分数远大于PG78-8圆盘真空过滤机,可见GPJ-96加压过滤机煤泥压滤效果较好;GPJ-96加压过滤机的固体产率由原来的61.53%增加到67.06%,脱水率由原来的92.34%增加到94.86%,降低了循环水浓度,有利于生产的稳定进行。     

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     

Dewatering of coal plant tailings: Flocculation followed by filtration

A sustainable alternative to tailings dam disposal of coal refuse is mechanical dewatering of tailings, which provides fast production of dry solids and water reuse. In this study, flocculation followed by filtration of coal plant tailings, a new concept in tailings dewatering is investigated in detail. This paper focuses on the effect of preconditioning tailings with varying flocculants and dosages on filtration kinetics and the resultant moisture content of the filter cake. The results show that the cationic flocculant, MAGNAFLOC LT 425, requires a high dosage to produce a low moisture content filter cake and clear filtrate. Optimal sized flocs were produced with the anionic flocculant, MAGNAFLOC 5250, even though the particles are negatively charged. The kinetics of the filtration was dependent on the composition of process water as indicated by supporting sedimentation tests. The concentration of divalent alkali earth metals such as Ca²⁺ and Mg²⁺ allow for large floc growth by a bridging mechanism, which involves binding of the polymer and the negativity charged particle. Filtration and settling curves at this dosage were also supported by filter cake analysis using Darcy plots. It was found that the large floc size significantly increases the permeability of the filter cake. Floc size measurements and fractal dimension showed that while the large flocs were produced with anionic flocculant, the flocs produced with the cationic flocculant were small and weak. The results indicate that the optimum dosage and flocculant type for effective and efficient filtration of coal plant tailings is approximately 350 g/t of anionic flocculant at a 35% solids content and 40 kPa filtration pressure.     

Preparation of anionic ion exchange latex particles via heteroaggregation

To prepare relatively large negatively charged polymer particles in a size range from 0.3 μm to 0.5 μm, having high surface charge densities, the heteroaggregation of small (50–100 nm), highly charged (185 and 421 μeq/g) anionic polystyrene particles onto the surface of larger (317–466 nm) poly(vinylbenzyl choride)‐based cationic (10, 614, and 830 μeq/g) particles was carried out. As a result, particles with different surface charges, having a core‐shell structure, were successfully prepared. First, aggregated particles were formed via heteroaggregation of the lowest surface charge density anionic particles (185 μeq/g) with the lowest surface charge density cationic particles (10 μeq/g). However, the anionic particles in the shell layer desorbed with time owing to the relatively weak interaction between the two particles. Second, aggregated particles comprised of the highest surface charge density cationic (830 μeq/g) and anionic latex particles (421 μeq/g) were formed. However, to prepare a stable system, an excess of the small anionic particles was required, leaving a large number of small particles present in the aqueous phase, which proved difficult to remove. Finally, aggregated particles were formed by heteroaggregation of cationic particles with an intermediate surface charge density (614 μeq/g) with the highest surface charge anionic particles (421 μeq/g). As a result, not only were core‐shell particles formed, but few free small anionic particles remained in the aqueous phase. In this article, the preparation and characterization of each of these aggregates are discussed in terms of particle size, morphology, and extent of incorporation of the functional groups. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

流化床与固定床耦合反应器中的颗粒磨损

在直径50mm的冷模流化床与固定床耦合反应器中,考察了活性炭颗粒在130～150℃及不同气速下的磨损情况,得到了不同气速下固定床中圆柱状颗粒的磨损率随时间的变化关系,同时分析了滞留在流化床、固定床及袋滤器中的细颗粒在不同气速下的粒径分布与质量分布.结果表明,颗粒在该耦合反应器中磨损严重,在0.212～0.424m/s气速下,固定床中颗粒质量损失可达3%～4%,流化床中颗粒平均粒径由200μm降至100μm以下.     

Law of substance separation on cross-flow filtration in turbulent flow

Cross-flow filtration is a filtration process for separation of a disperse phase from liquids. Suspension flows tangentially to a membrane and the filtrate is drawn off perpendicular to the direction of flow. Formation of a filter cake on the membrane is thus prevented, reduced, or its composition, modified. The principle of the separation is based on tow opposing effects: on the one hand, the particles are transported by the filtration flux to the membrane where they cause and increase in concentration; on the other hand, concentration differences are again reduced by the turbulence of the cross-flow and by Brownian motion of the particles. The two mechanisms compete with each other and depend upon particle size in different ways. An energetic comparison of the two effects yields the separation law of cross-flow filtration as a steady state solution of the Fokker-Planck equation. The separation law has an exponential form and assigns each particle size a separation probability with which it reaches the membrane. Once on the membrane the particles may form a filter cake, flow through the pores or return to the bulk flow. If the particles remain on the membrane the ranges of layer-free and cake-forming filtration can be calculated from the hydro-dynamic and geometric conditions of the cross-flow filter. Conventional cake filtration is regarded as limiting case. In continuous cross-flow filtration process a low separation probability through the filtration pressure on selection of the filter medium resistance.     

Controlling attractive interparticle forces via small anionic and cationic additives in kaolin clay slurries

Interparticle forces govern slurry behavior in flow, mixing, sedimentation and thickening. This study evaluates the use of small anionic and cationic additives with pH to control the interparticle forces in kaolin slurry via the yield stress parameter. Both phosphate and citrate additives were found to reduce the interparticle attractive force or yield stress in the moderate pH region of 4–12. These relatively low charged additives were unable to impart a sufficiently strong repulsive interparticle force to completely disperse the slurry. Three linear relationships between yield stress and the square of zeta potential were observed in slurry with and without these additives, indicating that the yield stress–DLVO force model is obeyed in each linear region. The mid-range zeta potential region yielded a positive slope which was attributed to heterogeneous charge attraction between clay particles. It is this heterogeneous charge attraction that was weakened by the adsorbed additives. In contrast, cationic Polyethylenimine (PEI) of Mw 70,000 increases the yield stress at all pH level via bridging. Charge reversal was also observed at high PEI concentrations. In two cases, the pH of maximum yield stress and zero zeta potential coincided. A single linear yield stress–zeta potential squared relationship was observed despite particle bridging interaction being the dominant interparticle force.