梳型聚羧酸盐分散剂化学结构与水煤浆流变相关性及与煤作用机理研究
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摘要
水煤浆技术是一种将煤炭液化的洁净利用技术。水煤浆具有燃烧率高、成本低的优势，容易达到节能减排的环保要求，是一种替代油的清洁燃料。水煤浆是一种固、液两相粗分散体系，为了使浆体具有较好的流动性、较低的粘度以便于运输，同时在静止时具有很好的稳定性，不易产生沉淀，在水煤浆的制备过程中必须加入分散剂。目前，现有工业使用的萘磺酸分散剂受气候变化影响大，浆稳定性降低，易析水产生硬沉淀，并具有一定的毒性，使生产和使用都不利于环保，需找出替代品。然而利用腐植酸制备水煤浆的稳定性较差、木质素分散剂降粘作用差，而且这两种分散剂成分复杂，会引入很多杂质。而聚羧酸盐分散剂作为水泥减水剂具有出色的性能，并且有广泛的适应性。梳型聚羧酸盐分散剂用在水煤浆中，具有较好的分散性能和浆体稳定性。它是一种人工合成的水溶性高分子，生产和使用环节都不会对环境造成污染。聚羧酸盐结构灵活可控，可设计、生产各种结构以适应各种煤种制水煤浆。
目前，梳型聚羧酸盐分散剂的分子设计、制备及结构与水煤浆流变相关性的系统研究比较欠缺。本论文通过分子结构设计、根据自由基聚合原理，制备基于聚醚大单体二元聚羧酸、基于聚醚大单体三元聚羧酸、基于聚酯聚羧酸以及两性离子聚羧酸分散剂共四类九种梳型聚羧酸盐分散剂，并系统讨论了梳型聚羧酸盐分散剂化学结构与水煤浆流变性能的相关性，揭示了聚羧酸盐分散剂与煤颗粒作用机理。
本论文设计、制备了基于聚醚大单体二元聚羧酸盐分散剂，使用不同链长（m=16,23,27,55）烯丙基聚氧乙烯醚（APEG）大单体分别与甲基丙烯酸（MAA）、烯丙基磺酸钠（SAS）、苯乙烯磺酸钠（SSS）共聚，合成了具有不同侧链长度的MAA-APEG、SAS-APEG和SSS-APEG三种二元聚羧酸分散剂。采用傅里叶红外光谱（FT-IR）和裂解气相质谱（Py-GCMS）及凝胶渗透色谱（GPC）表征了分散剂的结构，使用热失重（TGA）和差示扫描量热（DSC）测试了分散剂的热稳定性。讨论了聚合反应条件对神府煤水煤浆粘度的影响，通过单因素分析确定了各种分散剂的较佳合成条件为引发剂k2S2O8用量为单体总质量4%，反应温度80℃，MAA、SAS和SSS与APEG的反应摩尔比分别是1:1、1:1和0.5:1。并通过比较筛选出分散性能较好的分散剂MAA-APEG1200（m=27）、SAS-APEG1000（m=23）和SSS-APEG1000（m=23），它们的成浆稳定性均优于工业萘磺酸盐分散剂。
基于聚醚三元聚羧酸盐分散剂，使用不同链长（m=16,23,27,55）烯丙基聚氧乙烯醚（APEG）大单体，分别与甲基丙烯酸、烯丙基磺酸钠、丙烯酰胺和苯乙烯磺酸钠中的两种单体共聚，合成了具有不同侧链长度的三种三元聚羧酸分散剂，MAA-AM-APEG、MAA-SAS-APEG和SSS-AM-APEG。采用傅里叶红外光谱（FT-IR）和裂解气相质谱（Py-GCMS）及凝胶渗透色谱（GPC）表征了分散剂的结构，使用热失重和差示扫描量热测试了分散剂的热稳定性。讨论了聚合反应条件对水煤浆粘度的影响，通过单因素分析确定了各种分散剂的较佳合成条件为引发剂k2S2O8用量2%，反应温度80℃，MAA-AM-APEG、MAA-SAS-APEG和SSS-AM-APEG的反应摩尔比分别为2.5:1:1、2.0:1:1和0.5:1:1。通过比较筛选出分散性能较好的分散剂MAA-AM-APEG1000（m=23）、 MAA-SAS-APEG1000（m=23）和SSS-AM-APEG1000（m=23），其分散性能和稳定性能较好，成浆稳定性均优于工业萘磺酸分散剂。
基于聚酯大单体聚羧酸盐分散剂，论文使用自制的不同链长衣康酸聚乙二醇酯IAPEG （m=5,9,14,18,23,45）和马来酸聚乙二醇酯MaPEG（m=9,14,18,23,45）聚酯大单体，与甲基丙烯酸和苯乙烯磺酸钠共聚合成了具有不同侧链长度的MAA-IAPEG-SSS和MAA-MaPEG-SSS两种三元聚羧酸分散剂。采用傅里叶红外光谱（FT-IR）和裂解气相质谱（Py-GCMS）及凝胶渗透色谱（GPC）表征了分散剂的结构，使用热失重和差示扫描量热测试了分散剂的热稳定性。讨论了聚合反应条件对水煤浆粘度的影响，通过单因素分析确定了分散剂MAA-IAPEG-SSS的合成较佳条件为甲基丙烯酸、衣康酸聚乙二醇酯大单体和对苯乙烯磺酸钠摩尔比3:1.5:1，引发剂用量为单体总质量2%，反应温度为76℃，滴加物料时间2h，保温反应3h。MAA-MaPEG-SSS聚羧酸分散剂合成较佳条件为甲基丙烯酸、马来酸聚乙二醇酯大单体和对苯乙烯磺酸钠摩尔比3:1.5:1，引发剂用量为单体总质量2%，反应温度80℃，滴加物料时间2h，反应时间共计5h。通过比较，筛选出分散性能较好的分散剂MAA-IAPEG600-SSS （m=14）、MAA-MaPEG800-SSS（m=18）和SSS-AM-APEG1000（m=23），其分散性能和稳定性能较好，成浆稳定性均优于工业萘磺酸分散剂。
在前文研究的基础上，用聚乙二醇和丙烯酸酯化生成聚酯大单体，同时引入阳离子单体甲基丙烯酰氧乙基三甲基氯化铵（DMC），另外选苯乙烯磺酸钠为第三单体，设计、制备具有季铵阳离子、羧基和苯磺酸基的两性聚羧酸盐列分散剂SSS-DMC-AAPEG1000。采用傅里叶红外光谱（FT-IR）和裂解气相质谱（Py-GCMS）及凝胶渗透色谱（GPC）表征了分散剂的结构，使用热失重和差示扫描量热测试了分散剂的热稳定性。讨论了聚合反应条件对水煤浆粘度的影响，通过单因素分析确定了两性离子聚羧酸的较佳合成条件：苯乙烯磺酸钠与聚酯大单体的摩尔比为1:1，阳离子单体DMC用量为聚酯大单体和苯乙烯磺酸钠总质量的5%，引发剂过硫酸铵和亚硫酸钠（摩尔比4:1）用量为单体总质量的8%，反应温度80℃。两性离子聚羧酸分散剂所制备水煤浆（水煤浆浓度65%）稳定性高于萘磺酸（水煤浆浓度63%），其水煤浆析水率较低，稳定等级达到一级，静态和动态稳定性均较好，添加量0.5%时对神府煤最高制浆浓度为72%。
在实验结果基础上，研究各种聚羧酸分散剂对煤种的适应性能。研究表明，较适合于神府煤制水煤浆的分散剂有：SSS-DMC-AAPEG1000、MAA-IAPEG600-SSS、SSS-AM-APEG1000和MAA-SAS-APEG1000；较适合于彬长煤制水煤浆的分散剂有： SSS-DMC-AAPEG1000、SSS-AM-APEG1000、 MAA-IAPEG600-SSS、 MAA-AM-APEG1000和MAA-MaPEG800-SSS。采用了三种模型对聚羧酸盐分散剂水煤浆的流变曲线进行拟合，结果显示Bingham模型更适合于水煤浆流变曲线的拟合，模型方程式为：τ=τ0+μγ，拟合相关系数R2为0.9993。
通过表面接触角、Zeta电位仪、吸附量和扫面电镜等测试了分散剂对煤表面润湿性改善、煤表面Zeta电位、分散剂在煤表面的吸附性，研究了分散剂与煤颗粒相互作用。研究表明，梳型聚羧酸盐分散剂分子结构对水-煤界面作用有很好的改善，分散剂分子结构（主链长度、侧基种类和侧链长度）影响着水煤浆的体系吸附-分散稳定状态。煤吸附了梳型聚羧酸盐分散剂而形成特殊的胶团结构，梳型聚羧酸盐分散剂对煤的分散存在着双重作用，即静电斥力和立体位阻，为开发可用于生产实际的新型分散剂提供理论指导。梳型聚羧酸盐分散剂结构灵活可控，可以根据不同煤种的特点来改变梳型聚羧酸分散剂的分子结构，以生产出低掺量、高性能、适应强的分散剂。
CWS technology is a clean use of coal liquefaction technology. Coal-waterslurry has the advantages of high combustion rate and low cost, and it is easy forit to achieve the environmental requirements of energy saving and emissionreduction, so it is a clean fuel to replace the oil. CWS is a two-phase crudedispersion system with solid and liquid. In order to make the slurry have goodfluidity, low viscosity to facilitate transport and also good stability to producelittle precipitate, the dispersing agent should be added to the coal slurry in thepreparation process. At present, the available industrial naphthalene sulfonatedispersant is easy to be affected by climate. When the climate is changing, theslurry stability of the naphthalene sulfonate dispersant cuts down, then theprecipitate with certain toxicity appears. In short, the production and the use of itare not conducive to environmental protection. So, we should find somereplacements. However, the coal-water slurry, prepared by humic acid, is notstable and the lignin dispersant has poor viscosity reducing effect. Bothdispersants have complex ingredients, which mean a lot of impurities. As a waterreducing agent of cement, polycarboxylic acid dispersant shows excellentperformance, and has a wide range of applications. Also, it has good dispersionproperty and slurry stability when used in coal-water slurry. It is a syntheticwater soluble polymer; its production and use do not result in the environmentalpollution. Moreover, polycarboxylic acid has clear components and flexiblestructures, so it could be designed and produced to adapt to a variety of CWSmade for various kinds of coals.
At present, a systematic research about the molecule design, the preparationof polycarboxylic acid dispersant and the relationship between its structure and the CWS rheological properties is still blank. My work is about: design themolecular structures to prepare four categories, nine kinds of comb-likepolycarboxylic acid dispersants, based on the polyether macromonomer binarypolycarboxylic acid, the polyether macromonomer ternary polycarboxylic acid,polyester polycarboxylic acid and zwitterionic polycarboxylic acid, according tothe principle of free radical polymerization; systematically discuss the relativitybetween chemical structures of polycarboxylic acid dispersants and CWSrheological properties; reveal the acting mechanism of polycarboxylic aciddispersants and coal particles.
This thesis designed and prepared binary polycarboxylic acid dispersantsbased on the polyether macromonomer. Methyl methacrylate (MAA), allylsulfonate (SAS), sodium styrene sulfonate (SSS) respectively, and allylpolyoxyethylene ether (APEG) macromonomer with different chain lengths(m=16,23,27,55) were used to copolymerize into three binary polycarboxylicacid dispersants, MAA-APEG, SAS-APEG and SSS-APEG. They had differentside chains. Using Fourier transform infrared spectroscopy (FT-IR), thepyrolysis-gas chromatography and mass spectrometry (Py-GCMS) and gelpermeation chromatography (GPC), the structures of the dispersing agents werecharacterized; using thermogravimetric （TGA） and differential scanningcalorimetry（DSC）, the thermal stabilities of the dispersants were tested. Theeffects on the viscosity of CWS from polymerization conditions were discussed.The optimal synthesizing conditions of the various dispersants were confirmedby univariate analysis. Dosage of k2S2O8as initiator for4%of the total mass ofmonomer, reaction temperature at80℃, reaction molar ratio of MAA, SAS, andSSS with APEG1:1,1:1and0.5:1respectively. And the preferred dispersantswere screened by comparing their dispersion performance. They were theMAA-APEG1200(m=27), the SAS-APEG1000(m=23), and theSSS-APEG1000(m=23). Besides, their slurrying stabilities were superior to theindustrial naphthalene sulfonate dispersing agent.
Three ternary polycarboxylic acid dispersants (MAA-AM-APEG,MAA-SAS-APEG and SSS-AM-APEG) based on the polyether macromonomerwere prepared, using the two monomers of methacrylic acid, sodiumallylsulfonate, acrylamide, sodium styrene sulfonate and allyl polyoxyethylene ether (APEG) macromonomer with different chain lengths (m=16,23,27,55) tocopolymerize. They had different side chains. Using Fourier transform infraredspectroscopy (FT-IR), the pyrolysis-gas chromatography and mass spectrometry(Py-GCMS) and gel permeation chromatography (GPC), the structures of thedispersing agents were characterized; using thermogravimetric and differentialscanning calorimetry, the thermal stabilities of the dispersants were tested. Andeffects on the viscosity of CWS from polymerization conditions were discussed.Also, through univariate analysis, the optimal synthesizing conditions of thevarious dispersants were confirmed. They were: dosage of k2S2O8as initiatorfor2%of the total mass of monomer, reaction temperature at80℃, reactionmolar ratios of MAA-AM-APEG, MAA-SAS-APEG and SSS-AM-APEG2.5:1:1,2.0:1:1and0.5:1:1respectively. And the preferred dispersants werescreened by comparing their dispersion performance. They were theMAA-AM-APEG1000（m=23）, the MAA-SAS-APEG1000（m=23）and theSSS-AM-APEG1000（m=23）. Besides, their slurrying stabilities were superior tothe industrial naphthalene sulfonate dispersing agent.
Methacrylic acid, sodium styrene sulfonate and alternatively itaconic acidpolyethylene glycol ester, IAPEG （m=5,9,14,18,23,45） and maleic acidpolyethylene glycol ester, MaPEG（m=9,14,18,23,45）were copolymerized intotwo ternary polycarboxylic acid dispersants with different side chains,MAA-IAPEG-SSS and MAA-MaPEG-SSS. Using Fourier transform infraredspectroscopy (FT-IR), the pyrolysis-gas chromatography and mass spectrometry(Py-GCMS) and gel permeation chromatography (GPC), the structures of thedispersing agents were characterized; using thermogravimetric and differentialscanning calorimetry, the thermal stabilities of the dispersants were tested. Andeffects on the viscosity of CWS from polymerization conditions were discussed.Also, through univariate analysis, the optimal synthesizing conditions of the twodispersants were confirmed. For MAA-IAPEG-SSS, the conditions were:reaction molar ratio of methacrylic acid, maleic acid polyethylene glycol esterand sodium styrene sulfonate3:1.5:1, dosage of k2S2O8as initiator for2%ofthe total mass of monomer, reaction temperature at76℃, dropping time2hours,reactive time totally5hours. And preferred dispersants were screened bycomparing their dispersion performances. They were the MAA-IAPEG600-SSS （m=14）, the MAA-MaPEG800-SSS（m=18）and the SSS-AM-APEG1000（m=23）. In all, their slurrying stabilities were better than the industrialnaphthalene sulfonate dispersing agent.
On the basis of previous research, amphiprotic polycarboxylic aciddispersing agent (SSS-DMC-AAPEG) with quaternary ammonium cations,carboxyl group and sulfobenzoic acid group was prepared, using cationicmonomer methyl acrylic acid ethyltrimethyl chloride ammonium(DMC), sodiumstyrene sulfonate and polyester monomer esterified by polyethylene glycol andacrylic acid. Using Fourier transform infrared spectroscopy (FT-IR), thepyrolysis-gas chromatography and mass spectrometry (Py-GCMS) and gelpermeation chromatography (GPC), the structures of the dispersing agents werecharacterized; using thermogravimetric and differential scanning calorimetry, thethermal stabilities of the dispersants were tested. And effects on the viscosity ofCWS from polymerization conditions were discussed. Also, through univariateanalysis, the optimal synthesizing conditions of the amphiprotic poly carboxylicacid dispersing agent were confirmed. They were: reaction molar ratio of sodiumstyrene sulfonate and polyester monomer1:1, dosage of cationic monomer DMCfor5%of the total mass of sodium styrene sulfonate and polyester monomer,dosage of ammonia sulfate and sodium sulfite (molar ratio4:1) as initiator for8%of the total mass of monomer, reaction temperature at80℃. The stability ofCWS (concentration65%)produced by Amphiprotic poly carboxylic aciddispersing agents was better than that(concentration63%) made by naphthalenesulfonate dispersants. Also the former has lower water separating rate. And itsstability reached to grade one; its dynamic and static stabilities were fine. Whenits additive amount ran up to0.5%, the highest concentration of CWS was72%.
According to the experimental results, adaptive properties of polycarboxylicacid dispersants to different coals were studied. It indicated thatSSS-DMC-AAPEG1000, MAA-IAPEG600-SSS, SSS-AM-APEG1000andMAA-SAS-APEG1000were suitable for shenfu coal to prepare CWS; whileSSS-DMC-AAPEG1000, SSS-AM-APEG1000, MAA-IAPEG600-SSS,MAA-AM-APEG1000and MAA-MaPEG800-SSS were suitable for binchangcoal. There were three models used to fit the CWS rheological curve ofpolycarboxylic acid dispersants. It showed that the Bingham model was much suited to the CWS rheological curve fitting. The model equation was τ=τ0+μγ;fitting correlation coefficient R2was0.9993.
Through surface contact angle, zeta potential analyzer, adsorption quality ofdispersant on coal and scanning electron microscope, tests of coal surfacewettability improvement from dispersants, Zeta potential of coal surface,adsorption of dispersants on coal surface were made; interactions betweendispersants and coal particles were studied. The research indicated that themolecular structure of comb-like polycarboxylic acid dispersants improvedactions of the water-coal interface. The molecular structures of the dispersants(main chain length, the type of side groups and side chain length) affected thestable systematic adsorption–dispersion status with the CWS. Coal adsorbedcomb-like polycarboxylic acid dispersants to form special micelle structure. Andcomb-like polycarboxylic acid dispersants on the dispersion of coal had dualroles, namely electrostatic repulsion and sterical hindrance, providing theoreticalguidance for new dispersants applied for actual production. The structures ofcomb-like polycarboxylic acid dispersants were flexible. And the molecularstructures of comb-like polycarboxylic acid dispersants could be changedaccording to characteristics of different coals to produce dispersants of lowdosage, high performance and strong adaptation.
目前，梳型聚羧酸盐分散剂的分子设计、制备及结构与水煤浆流变相关性的系统研究比较欠缺。本论文通过分子结构设计、根据自由基聚合原理，制备基于聚醚大单体二元聚羧酸、基于聚醚大单体三元聚羧酸、基于聚酯聚羧酸以及两性离子聚羧酸分散剂共四类九种梳型聚羧酸盐分散剂，并系统讨论了梳型聚羧酸盐分散剂化学结构与水煤浆流变性能的相关性，揭示了聚羧酸盐分散剂与煤颗粒作用机理。
本论文设计、制备了基于聚醚大单体二元聚羧酸盐分散剂，使用不同链长（m=16,23,27,55）烯丙基聚氧乙烯醚（APEG）大单体分别与甲基丙烯酸（MAA）、烯丙基磺酸钠（SAS）、苯乙烯磺酸钠（SSS）共聚，合成了具有不同侧链长度的MAA-APEG、SAS-APEG和SSS-APEG三种二元聚羧酸分散剂。采用傅里叶红外光谱（FT-IR）和裂解气相质谱（Py-GCMS）及凝胶渗透色谱（GPC）表征了分散剂的结构，使用热失重（TGA）和差示扫描量热（DSC）测试了分散剂的热稳定性。讨论了聚合反应条件对神府煤水煤浆粘度的影响，通过单因素分析确定了各种分散剂的较佳合成条件为引发剂k2S2O8用量为单体总质量4%，反应温度80℃，MAA、SAS和SSS与APEG的反应摩尔比分别是1:1、1:1和0.5:1。并通过比较筛选出分散性能较好的分散剂MAA-APEG1200（m=27）、SAS-APEG1000（m=23）和SSS-APEG1000（m=23），它们的成浆稳定性均优于工业萘磺酸盐分散剂。
基于聚醚三元聚羧酸盐分散剂，使用不同链长（m=16,23,27,55）烯丙基聚氧乙烯醚（APEG）大单体，分别与甲基丙烯酸、烯丙基磺酸钠、丙烯酰胺和苯乙烯磺酸钠中的两种单体共聚，合成了具有不同侧链长度的三种三元聚羧酸分散剂，MAA-AM-APEG、MAA-SAS-APEG和SSS-AM-APEG。采用傅里叶红外光谱（FT-IR）和裂解气相质谱（Py-GCMS）及凝胶渗透色谱（GPC）表征了分散剂的结构，使用热失重和差示扫描量热测试了分散剂的热稳定性。讨论了聚合反应条件对水煤浆粘度的影响，通过单因素分析确定了各种分散剂的较佳合成条件为引发剂k2S2O8用量2%，反应温度80℃，MAA-AM-APEG、MAA-SAS-APEG和SSS-AM-APEG的反应摩尔比分别为2.5:1:1、2.0:1:1和0.5:1:1。通过比较筛选出分散性能较好的分散剂MAA-AM-APEG1000（m=23）、 MAA-SAS-APEG1000（m=23）和SSS-AM-APEG1000（m=23），其分散性能和稳定性能较好，成浆稳定性均优于工业萘磺酸分散剂。
基于聚酯大单体聚羧酸盐分散剂，论文使用自制的不同链长衣康酸聚乙二醇酯IAPEG （m=5,9,14,18,23,45）和马来酸聚乙二醇酯MaPEG（m=9,14,18,23,45）聚酯大单体，与甲基丙烯酸和苯乙烯磺酸钠共聚合成了具有不同侧链长度的MAA-IAPEG-SSS和MAA-MaPEG-SSS两种三元聚羧酸分散剂。采用傅里叶红外光谱（FT-IR）和裂解气相质谱（Py-GCMS）及凝胶渗透色谱（GPC）表征了分散剂的结构，使用热失重和差示扫描量热测试了分散剂的热稳定性。讨论了聚合反应条件对水煤浆粘度的影响，通过单因素分析确定了分散剂MAA-IAPEG-SSS的合成较佳条件为甲基丙烯酸、衣康酸聚乙二醇酯大单体和对苯乙烯磺酸钠摩尔比3:1.5:1，引发剂用量为单体总质量2%，反应温度为76℃，滴加物料时间2h，保温反应3h。MAA-MaPEG-SSS聚羧酸分散剂合成较佳条件为甲基丙烯酸、马来酸聚乙二醇酯大单体和对苯乙烯磺酸钠摩尔比3:1.5:1，引发剂用量为单体总质量2%，反应温度80℃，滴加物料时间2h，反应时间共计5h。通过比较，筛选出分散性能较好的分散剂MAA-IAPEG600-SSS （m=14）、MAA-MaPEG800-SSS（m=18）和SSS-AM-APEG1000（m=23），其分散性能和稳定性能较好，成浆稳定性均优于工业萘磺酸分散剂。
在前文研究的基础上，用聚乙二醇和丙烯酸酯化生成聚酯大单体，同时引入阳离子单体甲基丙烯酰氧乙基三甲基氯化铵（DMC），另外选苯乙烯磺酸钠为第三单体，设计、制备具有季铵阳离子、羧基和苯磺酸基的两性聚羧酸盐列分散剂SSS-DMC-AAPEG1000。采用傅里叶红外光谱（FT-IR）和裂解气相质谱（Py-GCMS）及凝胶渗透色谱（GPC）表征了分散剂的结构，使用热失重和差示扫描量热测试了分散剂的热稳定性。讨论了聚合反应条件对水煤浆粘度的影响，通过单因素分析确定了两性离子聚羧酸的较佳合成条件：苯乙烯磺酸钠与聚酯大单体的摩尔比为1:1，阳离子单体DMC用量为聚酯大单体和苯乙烯磺酸钠总质量的5%，引发剂过硫酸铵和亚硫酸钠（摩尔比4:1）用量为单体总质量的8%，反应温度80℃。两性离子聚羧酸分散剂所制备水煤浆（水煤浆浓度65%）稳定性高于萘磺酸（水煤浆浓度63%），其水煤浆析水率较低，稳定等级达到一级，静态和动态稳定性均较好，添加量0.5%时对神府煤最高制浆浓度为72%。
在实验结果基础上，研究各种聚羧酸分散剂对煤种的适应性能。研究表明，较适合于神府煤制水煤浆的分散剂有：SSS-DMC-AAPEG1000、MAA-IAPEG600-SSS、SSS-AM-APEG1000和MAA-SAS-APEG1000；较适合于彬长煤制水煤浆的分散剂有： SSS-DMC-AAPEG1000、SSS-AM-APEG1000、 MAA-IAPEG600-SSS、 MAA-AM-APEG1000和MAA-MaPEG800-SSS。采用了三种模型对聚羧酸盐分散剂水煤浆的流变曲线进行拟合，结果显示Bingham模型更适合于水煤浆流变曲线的拟合，模型方程式为：τ=τ0+μγ，拟合相关系数R2为0.9993。
通过表面接触角、Zeta电位仪、吸附量和扫面电镜等测试了分散剂对煤表面润湿性改善、煤表面Zeta电位、分散剂在煤表面的吸附性，研究了分散剂与煤颗粒相互作用。研究表明，梳型聚羧酸盐分散剂分子结构对水-煤界面作用有很好的改善，分散剂分子结构（主链长度、侧基种类和侧链长度）影响着水煤浆的体系吸附-分散稳定状态。煤吸附了梳型聚羧酸盐分散剂而形成特殊的胶团结构，梳型聚羧酸盐分散剂对煤的分散存在着双重作用，即静电斥力和立体位阻，为开发可用于生产实际的新型分散剂提供理论指导。梳型聚羧酸盐分散剂结构灵活可控，可以根据不同煤种的特点来改变梳型聚羧酸分散剂的分子结构，以生产出低掺量、高性能、适应强的分散剂。
CWS technology is a clean use of coal liquefaction technology. Coal-waterslurry has the advantages of high combustion rate and low cost, and it is easy forit to achieve the environmental requirements of energy saving and emissionreduction, so it is a clean fuel to replace the oil. CWS is a two-phase crudedispersion system with solid and liquid. In order to make the slurry have goodfluidity, low viscosity to facilitate transport and also good stability to producelittle precipitate, the dispersing agent should be added to the coal slurry in thepreparation process. At present, the available industrial naphthalene sulfonatedispersant is easy to be affected by climate. When the climate is changing, theslurry stability of the naphthalene sulfonate dispersant cuts down, then theprecipitate with certain toxicity appears. In short, the production and the use of itare not conducive to environmental protection. So, we should find somereplacements. However, the coal-water slurry, prepared by humic acid, is notstable and the lignin dispersant has poor viscosity reducing effect. Bothdispersants have complex ingredients, which mean a lot of impurities. As a waterreducing agent of cement, polycarboxylic acid dispersant shows excellentperformance, and has a wide range of applications. Also, it has good dispersionproperty and slurry stability when used in coal-water slurry. It is a syntheticwater soluble polymer; its production and use do not result in the environmentalpollution. Moreover, polycarboxylic acid has clear components and flexiblestructures, so it could be designed and produced to adapt to a variety of CWSmade for various kinds of coals.
At present, a systematic research about the molecule design, the preparationof polycarboxylic acid dispersant and the relationship between its structure and the CWS rheological properties is still blank. My work is about: design themolecular structures to prepare four categories, nine kinds of comb-likepolycarboxylic acid dispersants, based on the polyether macromonomer binarypolycarboxylic acid, the polyether macromonomer ternary polycarboxylic acid,polyester polycarboxylic acid and zwitterionic polycarboxylic acid, according tothe principle of free radical polymerization; systematically discuss the relativitybetween chemical structures of polycarboxylic acid dispersants and CWSrheological properties; reveal the acting mechanism of polycarboxylic aciddispersants and coal particles.
This thesis designed and prepared binary polycarboxylic acid dispersantsbased on the polyether macromonomer. Methyl methacrylate (MAA), allylsulfonate (SAS), sodium styrene sulfonate (SSS) respectively, and allylpolyoxyethylene ether (APEG) macromonomer with different chain lengths(m=16,23,27,55) were used to copolymerize into three binary polycarboxylicacid dispersants, MAA-APEG, SAS-APEG and SSS-APEG. They had differentside chains. Using Fourier transform infrared spectroscopy (FT-IR), thepyrolysis-gas chromatography and mass spectrometry (Py-GCMS) and gelpermeation chromatography (GPC), the structures of the dispersing agents werecharacterized; using thermogravimetric （TGA） and differential scanningcalorimetry（DSC）, the thermal stabilities of the dispersants were tested. Theeffects on the viscosity of CWS from polymerization conditions were discussed.The optimal synthesizing conditions of the various dispersants were confirmedby univariate analysis. Dosage of k2S2O8as initiator for4%of the total mass ofmonomer, reaction temperature at80℃, reaction molar ratio of MAA, SAS, andSSS with APEG1:1,1:1and0.5:1respectively. And the preferred dispersantswere screened by comparing their dispersion performance. They were theMAA-APEG1200(m=27), the SAS-APEG1000(m=23), and theSSS-APEG1000(m=23). Besides, their slurrying stabilities were superior to theindustrial naphthalene sulfonate dispersing agent.
Three ternary polycarboxylic acid dispersants (MAA-AM-APEG,MAA-SAS-APEG and SSS-AM-APEG) based on the polyether macromonomerwere prepared, using the two monomers of methacrylic acid, sodiumallylsulfonate, acrylamide, sodium styrene sulfonate and allyl polyoxyethylene ether (APEG) macromonomer with different chain lengths (m=16,23,27,55) tocopolymerize. They had different side chains. Using Fourier transform infraredspectroscopy (FT-IR), the pyrolysis-gas chromatography and mass spectrometry(Py-GCMS) and gel permeation chromatography (GPC), the structures of thedispersing agents were characterized; using thermogravimetric and differentialscanning calorimetry, the thermal stabilities of the dispersants were tested. Andeffects on the viscosity of CWS from polymerization conditions were discussed.Also, through univariate analysis, the optimal synthesizing conditions of thevarious dispersants were confirmed. They were: dosage of k2S2O8as initiatorfor2%of the total mass of monomer, reaction temperature at80℃, reactionmolar ratios of MAA-AM-APEG, MAA-SAS-APEG and SSS-AM-APEG2.5:1:1,2.0:1:1and0.5:1:1respectively. And the preferred dispersants werescreened by comparing their dispersion performance. They were theMAA-AM-APEG1000（m=23）, the MAA-SAS-APEG1000（m=23）and theSSS-AM-APEG1000（m=23）. Besides, their slurrying stabilities were superior tothe industrial naphthalene sulfonate dispersing agent.
Methacrylic acid, sodium styrene sulfonate and alternatively itaconic acidpolyethylene glycol ester, IAPEG （m=5,9,14,18,23,45） and maleic acidpolyethylene glycol ester, MaPEG（m=9,14,18,23,45）were copolymerized intotwo ternary polycarboxylic acid dispersants with different side chains,MAA-IAPEG-SSS and MAA-MaPEG-SSS. Using Fourier transform infraredspectroscopy (FT-IR), the pyrolysis-gas chromatography and mass spectrometry(Py-GCMS) and gel permeation chromatography (GPC), the structures of thedispersing agents were characterized; using thermogravimetric and differentialscanning calorimetry, the thermal stabilities of the dispersants were tested. Andeffects on the viscosity of CWS from polymerization conditions were discussed.Also, through univariate analysis, the optimal synthesizing conditions of the twodispersants were confirmed. For MAA-IAPEG-SSS, the conditions were:reaction molar ratio of methacrylic acid, maleic acid polyethylene glycol esterand sodium styrene sulfonate3:1.5:1, dosage of k2S2O8as initiator for2%ofthe total mass of monomer, reaction temperature at76℃, dropping time2hours,reactive time totally5hours. And preferred dispersants were screened bycomparing their dispersion performances. They were the MAA-IAPEG600-SSS （m=14）, the MAA-MaPEG800-SSS（m=18）and the SSS-AM-APEG1000（m=23）. In all, their slurrying stabilities were better than the industrialnaphthalene sulfonate dispersing agent.
On the basis of previous research, amphiprotic polycarboxylic aciddispersing agent (SSS-DMC-AAPEG) with quaternary ammonium cations,carboxyl group and sulfobenzoic acid group was prepared, using cationicmonomer methyl acrylic acid ethyltrimethyl chloride ammonium(DMC), sodiumstyrene sulfonate and polyester monomer esterified by polyethylene glycol andacrylic acid. Using Fourier transform infrared spectroscopy (FT-IR), thepyrolysis-gas chromatography and mass spectrometry (Py-GCMS) and gelpermeation chromatography (GPC), the structures of the dispersing agents werecharacterized; using thermogravimetric and differential scanning calorimetry, thethermal stabilities of the dispersants were tested. And effects on the viscosity ofCWS from polymerization conditions were discussed. Also, through univariateanalysis, the optimal synthesizing conditions of the amphiprotic poly carboxylicacid dispersing agent were confirmed. They were: reaction molar ratio of sodiumstyrene sulfonate and polyester monomer1:1, dosage of cationic monomer DMCfor5%of the total mass of sodium styrene sulfonate and polyester monomer,dosage of ammonia sulfate and sodium sulfite (molar ratio4:1) as initiator for8%of the total mass of monomer, reaction temperature at80℃. The stability ofCWS (concentration65%)produced by Amphiprotic poly carboxylic aciddispersing agents was better than that(concentration63%) made by naphthalenesulfonate dispersants. Also the former has lower water separating rate. And itsstability reached to grade one; its dynamic and static stabilities were fine. Whenits additive amount ran up to0.5%, the highest concentration of CWS was72%.
According to the experimental results, adaptive properties of polycarboxylicacid dispersants to different coals were studied. It indicated thatSSS-DMC-AAPEG1000, MAA-IAPEG600-SSS, SSS-AM-APEG1000andMAA-SAS-APEG1000were suitable for shenfu coal to prepare CWS; whileSSS-DMC-AAPEG1000, SSS-AM-APEG1000, MAA-IAPEG600-SSS,MAA-AM-APEG1000and MAA-MaPEG800-SSS were suitable for binchangcoal. There were three models used to fit the CWS rheological curve ofpolycarboxylic acid dispersants. It showed that the Bingham model was much suited to the CWS rheological curve fitting. The model equation was τ=τ0+μγ;fitting correlation coefficient R2was0.9993.
Through surface contact angle, zeta potential analyzer, adsorption quality ofdispersant on coal and scanning electron microscope, tests of coal surfacewettability improvement from dispersants, Zeta potential of coal surface,adsorption of dispersants on coal surface were made; interactions betweendispersants and coal particles were studied. The research indicated that themolecular structure of comb-like polycarboxylic acid dispersants improvedactions of the water-coal interface. The molecular structures of the dispersants(main chain length, the type of side groups and side chain length) affected thestable systematic adsorption–dispersion status with the CWS. Coal adsorbedcomb-like polycarboxylic acid dispersants to form special micelle structure. Andcomb-like polycarboxylic acid dispersants on the dispersion of coal had dualroles, namely electrostatic repulsion and sterical hindrance, providing theoreticalguidance for new dispersants applied for actual production. The structures ofcomb-like polycarboxylic acid dispersants were flexible. And the molecularstructures of comb-like polycarboxylic acid dispersants could be changedaccording to characteristics of different coals to produce dispersants of lowdosage, high performance and strong adaptation.
引文
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