功能单体对聚羧酸盐水煤浆分散剂的结构与性能影响研究

发布时间：2018-03-25 00:29

  本文选题：水煤浆　切入点：分散剂　出处：《陕西科技大学》2016年硕士论文

【摘要】：陕西彬长煤和内蒙霍林河煤的煤质差,氧/碳比和内水含量较高,变质程度低,成浆性差。本文针这两种煤,制备了新一代水煤浆分散剂,聚羧酸盐水煤浆分散剂。该类分散剂分散性能优异,制浆浓度高,添加量小、其制备工艺简单。但是由于各单体价格昂贵导致制备成本高,还未被广泛应用。制备出性能优良,价格低廉的聚羧酸盐分散剂是发展该类分散剂的关键。本文制备了一系列聚羧酸盐分散剂,旨在降低合成成本,筛选出最经济有效的功能单体,提高聚羧酸盐分散剂的应用价值。本文的第一部分以甲基丙烯酸(MAA)和烯丙基磺酸钠(SAS)为单体,以质量分数为10%的次亚磷酸钠为链转移剂,以4%(质量分数)的过硫酸氨为引发剂,反应温度为80℃,反应时间约为5h,通过自由基反应共聚制得两元聚羧酸盐(PMAS)系列聚羧酸盐分散剂。单体MAA:SAS的摩尔比分别为20.83,9.21,4.60,3.63,2.22的两元分散剂,分别记为PMAS-0、 PMAS-1、PMAS-2、PMAS-3、PMAS-4。并通过水相电位滴定法测得-COO-1-SO3-1的实际摩尔比分别为15.67,6.93,3.23,1.78,0.94。并通过红外光谱(FT-IR)、凝胶渗透色谱(GPC)表征了其分子结构。将其作用于陕西彬长煤制浆,在用量为0.4wt%,水煤浆浆浓为65%时,考察了浆体的表观粘度与-COO-1-SO3-1比值的关系,在不同浓度下的Zeta电位以及pH对水煤浆制浆应用的影响等。结果表明当-COO-1-SO3-1比值为约3.23时,浆体的表观粘度最低,稳定性理想,此时浆体的Zeta能达到-38mV,水煤浆粘度随着pH的增大逐渐降低,当pH大于10时水煤浆粘度趋于稳定。第二部分在二元分散剂的基础上引入聚醚大单体,并改变磺酸盐单体的种类,考察其应用性能。用甲基丙烯酸(MAA)、烯丙基醇聚氧乙烯醚(APEG500)分别和苯乙烯磺酸钠(SSS)、烯丙基磺酸钠(SAS)、甲基烯丙基磺酸钠(SMAS).2-丙烯酰胺-2-甲基丙磺酸(AMPS)按照一定比例,通过共聚反应制得4种三元分散剂,分别记为PCSS、PCS、PCSM、 PCSA。通过红外光谱(FT-IR)、凝胶渗透色谱(GPC)表征了结构。以热失重(TA)和差示扫描(DSC)分析,考察了其热性能。将4种分散剂分别作用于霍林河煤制浆,分析了大单体APEG500的最佳用量。并考察了4种分散剂制浆时的表观粘度、稳定性、流变性、最大成浆浓度、最佳添加量等性能,筛选出性能最佳的磺酸盐单体对应的聚羧酸盐分散剂。通过Zeta电位、吸附性能及其和煤的接触角等作用机理,分析了几种分散剂与煤的作用特点。结果表明,在MAA:S(磺酸盐单体):APEG500=4:1.3:2时,霍林河煤的最佳制浆浓度为57%,最佳添加量为0.4%。其中分散剂：PCSS的分散性能最好,制浆的表观粘度和稳定性俱佳,且PCSS的流变模型优于其他三元分散剂制浆流变模型。分散齐PCSS在煤表面的吸附量最大,可达3.32mg/g,浆浓在57%时,表观粘度在644mPa·s, Zeta电位为-41mV,接触角有34.11°。筛选出带苯环的苯乙烯磺酸钠是该三元分散剂的最佳磺酸盐类单体。第三部分以甲基丙烯酸(MAA)、烯丙基醇聚氧乙烯醚(APEG500)、苯乙烯(St)分别和烯丙基磺酸钠(SAS)、甲基烯丙基磺酸钠(SMAS)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)共聚制得3种四元聚羧酸盐分散剂。分别记为PCST、PCSMT、PCSAT。通过红外光谱、热重、凝胶渗透色谱等手段对分散剂的结构、热性能和相对分子质量及其分布进行了表征和分析。作用于霍林河煤,讨论了St的最佳用量,考察了浆体的表观粘度、稳定性、流变性、最大成浆浓度、最佳添加量等性能。最后考察了分散剂的Zeta电位、吸附性能及其和煤的接触角等作用机理。结果表明,在St用量为3.5Wt%时,四元分散剂PCST的分散性能最好。此时,霍林河煤的最佳制浆浓度为57%,最佳添加量为0.4%。其中分散剂PCST的分散性能最好,表观粘度和稳定性俱佳,流变模型为假塑型。分散齐IJPCST的的分散性能最好,浆浓在57%时,表观粘度在503.7 mPa·s,吸附量最大,可达3.19mg/g, Zeta电位为-36mV,接触角有49.84°。
[Abstract]:Coal Shaanxi Binchang coal and Inner Mongolia Huolinhe Coal poor oxygen / carbon ratio and high water content, low degree of metamorphism, the pulp is poor. These two kinds of coal in this paper, the preparation of a new generation of water coal slurry dispersing agent, polycarboxylic acid salt water coal slurry dispersing agent. The dispersion agent with excellent performance the high concentration of the pulp, and add a small amount of the preparation process is simple. But because of the expensive monomer in the preparation of high cost, has not been widely used. The preparation of excellent performance, low price of polycarboxylate dispersant is the key to the development of dispersing agent. In this paper, the preparation of a series of polycarboxylate dispersant, in order to reduce the cost of synthesis, screening out the most economical and effective functional monomer, improve the application value of polycarboxylate dispersant. The first part of this paper using methacrylic acid (MAA) and sodium allyl sulfonate (SAS) as the monomer mass fraction of sodium hypophosphite as the chain 10% transfer agent, with 4% ( The mass fraction of) ammonium persulfate as the initiator, the reaction temperature is 80 DEG C, the reaction time is about 5h, prepared by the free radical reaction of 2 polycarboxylate (PMAS) series of polycarboxylate dispersant. The molar ratio of monomer MAA:SAS were 20.83,9.21,4.60,3.63,2.22 binary dispersant, respectively PMAS-0, PMAS-1. PMAS-2, PMAS-3, PMAS-4. and the actual molar ratio by an aqueous potentiometric titration of -COO-1-SO3-1 were measured by IR and 15.67,6.93,3.23,1.78,0.94. (FT-IR), gel permeation chromatography (GPC) to characterize the molecular structure. Its effect on Shaanxi Binchang coal slurry. When the dosage is 0.4wt%, the water coal slurry concentration is 65%. Explores the relationship between the apparent viscosity and the ratio of -COO-1-SO3-1 slurry table, under different concentrations of Zeta and the potential influence of pH on the preparation of coal water slurry application. The results show that when the -COO-1-SO3-1 ratio is about 3.23, paste table The lowest viscosity and stability of this ideal, paste Zeta can reach -38mV, coal water slurry viscosity gradually decreased with the increase of pH, when more than 10 pH coal water slurry viscosity tends to be stable. The second part is dispersed in two yuan agent is introduced based on the polyether macromonomer, and change the type of sulfonate monomer, the application performance. Using methacrylic acid (MAA), allyl alcohol polyoxyethylene ether (APEG500) and sodium styrene sulfonate (SSS), sodium allyl sulfonate (SAS), methyl allyl sulfonate (SMAS).2- acrylamide -2- methyl propane sulfonic acid (AMPS) according to a certain proportion, through the copolymerization reaction system 4 three Yuan dispersant, respectively PCSS, PCS, PCSM, PCSA. (FT-IR) by infrared spectroscopy, gel permeation chromatography (GPC) to characterize the structure. By thermogravimetry (TA) and differential scanning calorimetry (DSC) analysis, the thermal properties were investigated. The 4 kinds of dispersants were used to Huolinhe Coal Slurry. Analysis of the The optimal dosage of APEG500 monomer. And the effects of viscosity, 4 dispersant pulp surface stability, rheology, maximum slurry concentration, the optimal amount of performance, selected the best performance of the sulfonate monomer corresponding polycarboxylate dispersant. By Zeta potential, adsorption properties and coal and contact angle mechanism, analyzes several characteristics of dispersion agent and coal. The results showed that in MAA:S (sulfonate monomer): APEG500=4:1.3:2, the best concentration of pulp and Huolinhe Coal is 57%, the best dosage is 0.4%. the dispersant: PCSS dispersion can be the best, the apparent viscosity and good stability and table. And the PCSS rheological model is better than the other three yuan dispersant pulp rheological model. The maximum PCSS in homogeneous dispersion, adsorption of the coal surface can reach 3.32mg/g, pulp concentration is 57%, the apparent viscosity of 644mPa, s, Zeta potential is -41mV, the contact angle is 34.11 DEG. Screening With benzene sulfonic acid sodium is the three best dispersant sulfonate monomers. The third part of the methacrylic acid (MAA), allyl alcohol polyoxyethylene ether (APEG500), styrene (St) and sodium allyl sulfonate (SAS), methyl allyl sulfonate (SMAS), 2- -2- methyl acrylamide propane sulfonic acid (AMPS) prepared 3 yuan of four kinds of polycarboxylate dispersant. They were recorded as PCST, PCSMT, PCSAT. by infrared spectroscopy, thermogravimetry, gel permeation chromatography and other means of structure of dispersant, thermal properties and relative molecular mass and its distribution were characterized and analyzed. In Huolinhe Coal, discussion the optimal dosage of St, investigated the slurry apparent viscosity, stability, rheology, maximum slurry concentration, the optimal amount of performance. Finally we investigated the potential of Zeta dispersant, adsorption properties and the contact angle of coal and its mechanism. The results show that when the dosage of St is 3.5 Wt%, four yuan of dispersant PCST the best dispersant. At this time, the optimal pulping concentration Huolinhe Coal is 57%, the best dosage is 0.4%. the dispersion stability of disperse agent PCST best, apparent viscosity and stability and rheological model of pseudoplastic. Dispersion homogeneous IJPCST dispersion can be the best, in the pulp consistency 57%, the apparent viscosity at 503.7 mPa - s, the maximum adsorption amount, up to 3.19mg/g, the Zeta potential is -36mV, the contact angle is 49.84 degrees.

【学位授予单位】：陕西科技大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TQ536;O631
，

本文编号：1660752