水煤浆添加剂与煤之间的相互作用规律研究 Ⅰ. 复合煤颗粒间的相互作用对水煤浆流变性的影响

使用12种不同分散剂对14种不同变质程度的煤进行了成浆性实验，分析了182个水煤浆(CWS)样品的流变性。结果表明，低变质程度和高灰煤浆多呈屈服假塑性，煤的性质起主导作用；变质程度高且灰分较低煤浆的流变性，主要依赖于分散剂的结构与性质；分子结构单元立体空间效应大，疏水基团与亲水基团呈立体间隔分布的分散剂，易形成屈服假塑性CWS；分子线度长，亲水基团与疏水基团呈线性间隔分布的分散剂，易形成胀塑性CWS。复合煤粒间的相互作用方式是决定CWS流变特性的关键。     

聚合物分散剂对氟铃脲水悬浮剂流变性质的影响

采用控制应力流变仪研究了聚合物分散剂苯乙烯丙烯酸无规共聚物（MOTAS）用量、分子量及氟铃脲质量分数等对氟铃脲水悬浮剂流变性质的影响。 结果表明,以聚合物MOTAS为分散剂制备的氟铃脲水悬浮剂的流变行为符合Herschel-Bulkley模型。 在固定氟铃脲质量分数为20%时,当分散剂质量分数≤3.0%时,流动行为指数n≤1.0,悬浮体系表现为假塑性流体,当分散剂质量分数≥3.5%时,流动行为指数n≥1.0,悬浮体系具有胀塑性流体特征。 氟铃脲水悬浮剂的流变参数屈服值τH与分散剂MOTAS和氟铃脲的加入量有关。 分散剂MOTAS质量分数≤2.5%时,分散剂在氟铃脲颗粒界面吸附很少,裸露的氟铃脲颗粒界面间相互搭接,具有较大的屈服值τH;当分散剂加入质量分数为3.0%时,分散剂可在氟铃脲颗粒界面形成饱和吸附,若再增加分散剂用量,多余分散剂在悬浮的氟铃脲颗粒间形成搭接,使其屈服值τH增大。 在MOTAS分散剂的分子量在10 000~30 000范围内时,MOTAS分子量愈大,所制得的氟铃脲水悬浮剂的表观粘度和屈服值τH愈小,流变行为指数n虽略有增加,但均小于1,没有改变“剪切变稀”的假塑性特征。     

新疆褐煤疏水改性提高其成浆性能

针对新疆褐煤具有较高内水的问题,制备了阴离子AKD改性剂和非离子AKD改性剂,对褐煤颗粒进行疏水改性。研究了改性前后煤粒表面化学成分、孔隙分布、亲疏水性和Zeta电位等煤粒表面特性,并结合NSF分散剂在改性前后煤粒表面吸附量大小,探讨了改性前后褐煤水煤浆的成浆性、流变性和稳定性。结果表明,改性后煤粒孔隙结构降低,煤粒表面碳的相对含量增加,氧的相对含量降低,煤水界面接触角增加,煤粒疏水性能增强。NSF分散剂在改性煤表面吸附量增加,煤粒表面负电性增强。由阴离子AKD改性煤、非离子AKD改性煤制备的水煤浆最大成浆质量分数从原煤56.6%分别增加至61.0%、62.5%,浆体析水率从原煤13.97%分别降低至7.45%、7.89%,同时改性后煤粒制备的浆体均表现出剪切变稀的假塑性流体。因此,改性煤粒更容易制备高浓度、低黏度、高稳定性且易于储存和运输的水煤浆。     

壬基酚聚氧乙烯醚聚合度对水煤浆浆体性质的影响

研究了壬基酚聚氧乙烯醚型添加剂的聚合度对变质程度不同的8种煤所制得的水煤浆浆体性质的影响规律。结果表明,壬基酚聚氧乙烯醚添加剂的聚合度对于8种煤所制得的水煤浆的成浆性、流变性以及静态稳定性均有一定的影响,存在一最佳范围。研究还发现,用壬基酚聚氧乙烯醚型添加剂制备水煤浆时,该添加剂的作用与煤的分析基水分质量分数、丝质组分质量分数以及孔体积之间存在着相关性。     

Influence of Polycarboxylate Dispersants with Different Molecular Structures on the Performance of Coal Water Slurry

Polycarboxylate dispersants have variable structures and can be designed according to practical needs. Further study on the influence of molecular structures on the performance of coal-water slurry (CWS) has vital significance. A variety of polycarboxylate dispersants was designed and synthesized with different monomers. The performance of each dispersant for the low-rank China CWS (i.e., Shenfu coal) was evaluated. Results showed that sodium p-styrene sulfonate (SSS) was the most efficient monomer with better adsorption performance on the surface of coal particles and lower apparent viscosity (i.e., mole ratio of SSS and acrylic acid (AA) sodium 65:35, CWS concentration 63 wt%, dispersant dosage 0.5 wt%). Polyethylene glycol acrylate (PA) was also effective. In addition, 5 wt% cationic monomer methyl acryloyl oxygen ethyl trimethyl ammonium chloride (DMC) was introduced into the structure. The polycarboxylate dispersant with optimal molecular structure was applied in Shenfu coal. The performance of water slurry could meet the national standards well (i.e., apparent viscosity 920 mPa · s), displaying good rheological property and stability.     

聚对苯乙烯磺酸钠添加剂的分子量对水煤浆浆体性质的影响

选用了变质程度不同的八种煤和三种不同分子量的聚对苯乙烯磺酸钠（PSS）添加剂，详细考查了该添加剂的分子量对水煤浆浆体性质的影响。结果发现，在考查PSS相对分子量的范围内（质均分子量为5.34×104～33.39×104），八种煤的水煤浆成浆性随着分子量的增大而增加，水煤浆成浆性与PSS添加剂的平均分子量的关系可归因于添加剂在煤粒上的吸附，分子量小的PSS在煤粒上的吸附量大于分子量大的PSS；PSS分子量的增加有利于水煤浆的流变性由胀性向假塑性转变；PSS分子量的增加使水煤浆的静态稳定性得到显著的改善。     

Effect of the Interfacial Agents with Different Types of Hydrophilic Functional Groups on the Rheological Properties of Coal-Water Slurry

Five interfacial agents with different hydrophilic groups (DBS, SDS, SO, TX, CTAB) are used as model additives to prepare coal-water slurry (CWS). The effects of different interfacial agents on the rheological properties of CWS are systemically investigated, the microscopic aggregation behavior of coal particles in the suspensions and the zeta potentials in coal-water interface are also studied. Based on the interpretation of the results, the rheological behavior of CWS is greatly influenced by the adsorption pattern of the interfacial agents in coal-water interface. The adsorption patterns of anionic interfacial agents on coal surface are mainly influenced by the combining force between the anionic hydrophilic groups with Ca²⁺, the stronger combining force with Ca²⁺ leads to the apparent viscosity increase and heavier pseudo-plastic property of CWS. The adsorption pattern of nonionic interfacial agent on coal surface is seldom influenced by the hydrophilic polyoxyethylene chain, and the addition of nonionic interfacial agent reduces the apparent viscosity of CWS. The adsorption pattern of cationic interfacial agent on coal surface is determined by its cationic head, and the addition of cationic interfacial agent increases the apparent viscosity of CWS. The concluded adsorption models of the interfacial agents with different hydrophilic groups can be guidance for the molecular design of high-performance additives of CWS.      

阴离子型添加剂的分子结构特征对水煤浆浆体性质的影响

选用分子结构特征不同的三类共七种添加剂和变质程度不同的八种煤,对添加剂的分子结构特征与煤质及水煤浆浆体各性质间的匹配规律进行研究。结果表明,以多核芳烃为缩聚单体的磺酸盐类添加剂中甲基取代基的引入对煤的成浆性不利,但有利于浆体向塑性流体转变和静态稳定性的提高;苄基取代基的引入能提高分析基氧体积分数低的煤种的成浆性,但是其浆体的静态稳定性较差。富含极性含氧官能团且变质程度较低的煤种在使用磺化程度较高的腐植酸盐类添加剂制浆时,可以制备出较高定黏浓度的水煤浆。腐植酸类添加剂磺化度较高时改善了浆体的流变性。对于腐植酸类和木质素类添加剂,磺化度较高的添加剂有利于挥发分较高的煤种所制浆体的静态稳定性的提高。     

Effect of solvent composition on dispersing ability of reaction sialon suspensions

This work focuses on the optimization of the rheological behavior of suspensions considering different solvent compositions. The effects of methyl ethyl ketone (MEK)/ethanol (E) solvent mixtures on reaction sialon suspensions were investigated by measuring sedimentation behavior, adsorption of dispersant, and flow behavior. It was shown that both the flow behavior and the sedimentation behavior strongly depended on selection of solvent composition. Using 3 wt% KD1 as dispersant, well-dispersed colloidal suspensions could be obtained in MEK-rich solvents. The suspensions with 60 vol% MEK/40 vol% E as solvent could be fitted to the Bingham model with very low yield stress, while suspensions with pure MEK or ethanol-rich mixtures as solvent showed pseudo plastic behavior with relatively high yield stress values. A model was proposed to explain the different flow behaviors of suspensions considering the different configurations of dispersant at particles' surfaces.     

Adsorption of sodium dodecyl benzenesulfonate onto coal

The adsorption behavior of sodium dodecyl benzenesulfonate (NaDDBS) on a raw (as received) coal sample and its demineralized variety with 11.3% and 1.2% ash contents respectively has been studied. The samples have been characterized by their proximate analysis, particle size distribution, surface area, porosity, density, points of zero charge, etc. Adsorption of NaDDBS on these two samples has been studied as a function of concentration of NaDDBS, temperature, pH, and presence of indifferent electrolyte in the medium. It has been observed that the isotherm exhibits two adsorption plateaus below and above the critical micelle concentration (CMC) of NaDDBS. Low heats of adsorption suggest weak hydrophobic bonding between adsorbent and adsorbate. The present work aims to correlate the adsorption of surfactant onto coal particles with the rheological behavior of coal-water slurry (CWS). The results reveal that addition of a very small amount of NaDDBS (0.3 wt% of coal) to 60% (w/w) CWS results in a marked reduction of the apparent viscosity of the CWS at a shear rate of 100 s(-1). The effect of pH on the apparent viscosity of CWS with and without the presence of the surfactant is also investigated.     

Effect of Polycarboxylic Acid Used as High-Performance Dispersant on Low-Rank Coal-Water Slurry

A new polycarboxylic (PC) acid was prepared from copolymerization of 2-methyl-1-butylene alcohol polyoxyethylene ether (HPEG), acrylic acid (AA), and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and used as a high-performance dispersant in low-rank coal-water slurry (CWS). The optimized conditions are as follows: the reaction temperature is 80°C, the mole ratio of HPEG, AA, and AMPS is 1:3:0.3, and the inherent viscosity of PC polymer is 49.26 ml/g. The molecule structure of PC polymer was characterized by means of FTIR. Moreover, the apparent viscosity, static stability, and rheological property of CWS with the concentration of 63.0 and 65.0 wt% were all determined by adding PC hyper-dispersant or naphthalene sulfonate-formaldehyde (NSF) condensate dispersant at 0.5 wt% dosage. The result shows that PC dispersant has better properties than commercial NSF product in low-rank CWS. The effect was well rationalized by a combination of electrostatic repulsion force, wetting property, and steric hindrance provided by PC polymer.     

三偏磷酸钠交联黄原胶的制备及其溶液流变性

以三偏磷酸钠(STMP)为交联剂,合成了水溶性低交联度黄原胶(XG),依据其溶液粘度优化出了最佳合成条件;考察了电解质质量分数、pH值及温度对STMP交联黄原胶(简记为SP-c-XG)溶液流变性的影响,并与XG溶液进行了对比。 结果表明,在所研究的电解质(NaCl和CaCl₂)质量分数(0~5.0%)、pH值(2~11)和温度(20~70 ℃)范围内,SP-c-XG和XG溶液的流变曲线均为假塑型,符合Herschel-Bulkley模型;其屈服值、表观粘度和动力学模量随电解质质量分数增大均先下降后上升,而随pH值的升高先升高后降低,随温度升高而降低。 SP-c-XG和XG溶液具有相似的流变性,但与XG溶液相比,SP-c-XG溶液具有更高的屈服值和表观粘度,特别是具有更强的弹性和耐温性,在油田强化采油领域具有重要应用前景。     

阴离子分散剂对酸化膨润土流变性的影响

研究了阴离子分散剂聚丙烯酸钠对质量分数为10%的酸化膨润土分散体系流变性的影响. 结果表明, 添加0.4%分散剂的分散体系的剪切应力、表观黏度和屈服应力最低. 其它体系流体均表现为从假塑型到胀流型流体的转变, 而含0.4%分散剂的体系始终表现为胀流型流体. 采用Herschel-Bulkley模型对各体系的流变曲线进行了拟合, 得到较好的拟合曲线, 同时探讨了酸化膨润土分散体系的流变机理.     

褐煤水热提质改善水煤浆的成浆性、流变性和稳定性的实验研究

采用水热法对小龙潭褐煤进行提质处理,从煤质特性、含氧基团、表面亲水性和粒度分布等因素,探究了水热提质对褐煤水煤浆成浆浓度、流变特性以及稳定性的影响。结果表明,水热提质脱除了褐煤中的水分,氧含量降低,煤阶升高。水热提质脱除了褐煤中含氧基团,煤水表面接触角增大,褐煤表面亲水性得到改善。小龙潭褐煤颗粒粒度呈现双峰分布,水热提质后褐煤颗粒粒径减小且趋于规则。水热提质改善了水煤浆的成浆性能,成浆浓度由提质前的44.09%,最高可提升到61.94%。在相近的表观黏度下,水热提质后水煤浆的稠度系数K减小,流变指数n增大,水热提质在降低浆体黏度的同时,仍保持假塑性流体特征。水热提质降低水煤浆的析水率,延缓了浆体出现硬沉淀的时间,改善浆体的稳定性。水热提质从理化特性对褐煤进行深度改性,从而获得高浓度,假塑性以及稳定性良好的符合工业应用的水煤浆。     

新型刺激响应性纤维素基含能凝胶的流变性能

研究了以不同基团含量的羧甲基纤维素硝酸酯(CMCN)为胶凝剂的含能凝胶细微结构与流变行为的关系.探讨了凝胶的形成机理,并采用线性的流变学方法研究了凝胶的屈服性、触变性、蠕变性及温敏性等动态黏弹性质,分别利用Herschel-Bulkley模型、Burger模型及Carreau-Yasuda模型对凝胶的流动曲线、蠕变曲线和频率曲线进行了数据拟合.研究发现,CMCN凝胶是由其分子结构上两亲性基团通过分子链间氢键及疏水键等非共价键相互作用形成的一种结构均匀的物理交联网络型凝胶.凝胶的非牛顿系数n均小于0.5.随着亲水性羧酸基团含量的增加,凝胶的屈服应力逐渐增大,触变恢复性逐渐增强,弹性与黏性柔量均减小,但其比值增加,蠕变的黏性响应性逐渐减弱而弹性响应性逐渐增强.凝胶的温敏性变化有一个力学松弛转变区,随着羧酸基团含量的增加,松弛转变区愈发明显,凝胶的温敏性也逐渐增强.     

添加剂分子结构特征与灵武煤水煤浆浆体各性质间匹配规律研究

研究了分子结构特征不同的十六种添加剂与灵武煤成浆性、流变特征以及静态稳定性间的匹配规律。实验结果表明，添加剂的主结构特征、取代基的性质、磺化度及聚合度与灵武煤浆体各性质间存在明显的匹配规律，其中，主结构特征、聚合度和磺化度对灵武煤浆体各性质的影响最为显著。分散性能强的添加剂不利于灵武煤煤浆流变特性的改善，而在一定范围内磺化度的增加能明显改善浆体的流变特性；添加剂的聚合度是影响灵武煤浆体的成浆性和稳定性的重要因素。     

分散剂分子结构特征对煤浆流变特性的影响

系统考察了具有不同分子结构特片系列分散剂对高浓度煤浆性质的影响。发现煤的成浆性、浆体的流变特性和稳定化作用与分散剂的分子结构特征密切相关。就本研究所涉及的分散剂种类和煤种而言，分散剂单体结构中多核芳烃结构所占比例较小时易于使浆体呈屈服假塑性，相反，则使浆体呈屈服胀塑性。分散剂单体的侧链结构对煤成浆性和浆体流变性的影响不很突出，而分散剂的第二单体结构的影响却非常显著。结果还同时表明，分散剂的高分散性能是导致浆体呈屈服胀塑性流体和弱化浆体稳定化作用的重要因素。     

Effects of Modified Sodium Lignosulfonate on Rheological Properties of Coal–Water Slurry with Low-Rank Coal

Coal–water slurry (CWS) is a new type of oil-replaceable liquid fuel with low pollution. The cost of CWS preparation will be greatly reduced if low-rank coal is used as the preparation material. In this work, chemical modification was used to prepare the modified sodium lignosulfonate (SL-M) hyper-dispersant, having larger molecular weight and more sulfonic groups than sodium lignosulfonate (SL), which was widely used for preparation of CWS from low-rank Shenhua coal due to its rich source and lower price. Effects of preparation conditions and molecular structure of SL-M on rheological properties of CWS were studied by using Haak rheometer. Results showed that the CWS transfered from viscous fluid to swelling fluid when the coal particle size decreased. The consistency coefficient of CWS decreased with the increase of additive dosage. The rheological properties of CWS became much better with the addition of the stabilizer, sodium carboxymethyl cellulose (CMC), compared with that of CWS without CMC. The prepared CWS changed from yield viscous fluid into yield swelling fluid with the increase of the molecular weight of SL-M. The rheological index was lower than 1 when the sulfonic group content was low, then it was increased with the increase of the sulfonic group content.     

混合煤制浆对水煤浆性质的影响

实验选用三种性能较差，不适宜制浆的煤作为原料煤，选用成浆性、稳定性或流变性较好的三种煤作为配煤进行混合煤制备水煤浆。实验结果表明，在相同的制浆条件下，加入成浆性、稳定性较好的煤种，使得水煤浆性质较差的煤成浆性、稳定性均有不同程度的提高，浆体流变性得到改善，煤浆粘度明显降低。根据配煤加入量的不同，煤的成浆浓度可提高约2%～3%，浆体稳定性增加，产生软沉淀的时间由1 d提高到10 d。加入成浆性较差的褐煤，亦可明显提高难制浆煤种的稳定性和改善浆体的流变性，使得浆体由胀塑性流体变为假塑性流体。煤的表面性质分析表明，配入表面性质差异较大的煤种，有利于改善难制浆煤种的水煤浆性质。     

油焦浆流变特性的研究

利用减压不同和石油焦制备成浆体燃料,然后考察了其流变性及温度、浓度和原料油对流变性的影响。结果表明,浆体为屈服假塑性流体并具有触变性,屈服应力值和粘度随着温度升高、浓度的降低而减小。原料油中的胶质和沥青质组分对浆体的流变特性和度有很大的影响,含有较多的胶质和沥青质原料油的浆体表现出更强的屈服假塑性和更高的粘度。