活泼亚甲基类超支化甲醛捕获剂的合成及应用
本文选题:活泼亚甲基 + 超支化聚合物 ; 参考:《陕西科技大学》2017年硕士论文
【摘要】:随着国内环保工作的不断推进,国家对挥发性有机物(VOCs)的治理日益重视,甲醛作为VOCs的一种,已被列为致癌物质。目前常用的甲醛治理方法有:物理吸附、化学治理、生物技术、臭氧氧化以及光催化技术等方法。其中,化学治理法是一种高效且简单易行的方法。本研究以端羟基超支化聚合物为原料,对其进行改性制备活泼亚甲基类超支化甲醛捕获剂,并将其用于皮革复鞣及主鞣工序中,以降低成革中游离甲醛含量。首先,以端羟基超支化聚合物(HBP)为原料,采用乙酰乙酸乙酯(EAA)对其进行改性,制备活泼亚甲基类超支化甲醛捕获剂(HAMP),并通过傅里叶红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、纳米粒度表面电位分析仪、透射电子显微镜(TEM)等现代仪器分析方法对HAMP的分子结构、相对分子质量、粒径分布及形貌进行了分析表征。通过单因素实验和正交实验优化得到最佳合成条件:反应摩尔比n(HBP):n(EAA)为1:2.5,催化剂无水K2CO3用量为2.5%,反应温度为100℃,反应时间为4.5h。其次,以甲醛溶液为处理对象,通过单因素实验法分别研究了反应温度、HAMP用量、反应时间、甲醛溶液初始浓度以及溶液pH对甲醛去除过程的影响,结果表明HAMP对甲醛的去除率随着温度、时间以及捕获剂用量的增加而增加。最佳pH为碱性环境,最佳捕获温度为40℃;在最优pH及温度下,以20mL浓度为15μg/mL的甲醛溶液为研究对象,HAMP用量为0.12g时80min吸附即可达到平衡;HAMP对甲醛溶液的吸附容量随甲醛初始浓度的增加而增加,随着HAMP用量的增加而减小。以20mL浓度为15μg/mL的甲醛溶液为研究对象,对比研究了改性前后的端羟基超支化聚合物对甲醛的去除能力,结果表明HAMP对甲醛的去除能力比改性前提高了73.20%,吸附容量得到增加,甲醛去除效果显著增强。此外,研究了HAMP对甲醛溶液的吸附动力学和吸附热力学进行了研究,热力学研究表明不同温度下吸附甲醛等温线既符合Langmuir方程,又符合Freundlich方程,其中Freundlich方程拟合的相关性更高,由此说明HAMP对水体中的甲醛的吸附是以化学吸附为主,兼有物理吸附的多分子层吸附体系。动力学研究表明:二级动力学方程能更好地解释此类捕获剂吸附甲醛的过程。以绵羊皮蓝湿革为处理对象,将HAMP应用于绵羊皮服装革复鞣工艺,通过单因素实验得到HAMP应用的最佳工艺条件为:HAMP用量为4%,捕获时间为1h,此时皮革中游离甲醛含量由371mg/kg降至60mg/kg,甲醛去除率达到83.8%。加入HAMP的成革热力学性能、成革稳定性及表面粗糙度均增加,胶原纤维分散度增大。HAMP的加入使得皮革的物理机械性能发生改变,抗张强度降低了1.7%,撕裂强度降低了23.4%,柔软度提高了7.1%。以绵羊皮蓝湿革为原料,在常规皮革复鞣工艺条件下进行单因素实验,将端氨基超支化聚合物(NH2-HBP)与HAMP进行复配并应用于复鞣工艺,得到其最佳捕获工艺条件为:HAMP与NH2-HBP质量比m(HAMP):m(NH2-HBP)为1.5:1,捕获剂用量为4%,捕获时间为3h。此时皮革中游离甲醛含量低至31.32mg/kg,游离甲醛去除率达到89.95%。将HAMP应用于绵羊皮浸酸皮的主鞣工艺实验,结果表明,当HAMP用量为4%,捕获时间为2h时,醛鞣革中游离甲醛含量由2073mg/kg降至787mg/kg,甲醛去除率达到62.03%,坯革抗张强略微提高,撕裂强度提高了18.9%;有机膦鞣革中游离甲醛含量由488mg/kg降至214mg/kg,甲醛去除率达到56.13%,使用HAMP后坯革成革抗张强度提升了52.46%,撕裂强度升高了69.44%;VA唑烷鞣革中游离甲醛含量由615mg/kg降至110mg/kg,甲醛去除率达到81.97%,添加HAMP后坯革成革撕裂强度和抗张强度均有所增加。
[Abstract]:With the continuous promotion of domestic environmental protection work, the state has paid more and more attention to the treatment of volatile organic compounds (VOCs). As a kind of VOCs, formaldehyde has been listed as a carcinogen. At present, the commonly used methods of formaldehyde treatment are physical adsorption, chemical treatment, biotechnology, ozone oxidation and photocatalytic technology. Among them, chemical treatment is a kind of high method. In this study, the active methylene hyperbranched formaldehyde catcher was prepared with hydroxyl terminated hyperbranched polymer as raw material, and used in leather retanning and main tanning process to reduce the content of free formaldehyde in leather. First, acetoacetic acid was used with hydroxyl terminated hyperbranched polymer (HBP) as raw material. Ethyl (EAA) was modified to prepare active methylene hyperbranched formaldehyde capture agent (HAMP), and the molecular structure and relative molecular weight of HAMP were analyzed by modern instrumental analysis methods such as Fourier infrared spectroscopy (FT-IR), magnetic resonance hydrogen spectrum (1H-NMR), gel permeation chromatography (GPC), nano particle surface potential analyzer, transmission electron microscopy (TEM) and other modern instrument analysis methods. The optimum synthesis conditions were obtained by single factor experiment and orthogonal experiment. The reaction mole ratio n (HBP): n (EAA) was 1:2.5, the amount of K2CO3 was 2.5%, the reaction temperature was 100, and the reaction time was 4.5h., and the Formaldehyde Solution was used as the processing object, and the single factor experiment method was used respectively. The effects of reaction temperature, dosage of HAMP, reaction time, initial concentration of Formaldehyde Solution and pH on the removal of formaldehyde were investigated. The results showed that the removal rate of HAMP to formaldehyde increased with the increase of temperature, time and the amount of capture agent. The best pH was alkaline environment and the optimum capture temperature was 40. At the optimum pH and temperature, the concentration of 20mL was at the concentration of 20mL. The Formaldehyde Solution of 15 mu g/mL is the research object. When the amount of HAMP is 0.12g, 80min adsorption can reach the balance. The adsorption capacity of HAMP to Formaldehyde Solution increases with the increase of the initial concentration of formaldehyde, and decreases with the increase of the amount of HAMP. With the 20mL concentration of the Formaldehyde Solution as the research object, the hydroxyl end hyperbranched before and after the modification is compared and studied. The removal ability of the polymer to formaldehyde showed that the removal ability of HAMP to formaldehyde was 73.20% higher than that before the modification, the adsorption capacity was increased and the removal efficiency of formaldehyde was significantly enhanced. In addition, the adsorption kinetics and adsorption thermodynamics of Formaldehyde Solution were studied by HAMP. The thermodynamics study showed that the adsorption of formaldehyde at different temperatures and so on was shown. The temperature line not only conforms to the Langmuir equation, but also conforms to the Freundlich equation, in which the correlation of the Freundlich equation is higher. Thus, the adsorption of formaldehyde in the body of HAMP is mainly chemical adsorption and the adsorption system of the multi molecular layer with physical adsorption. The kinetic study shows that the two stage kinetic equation can better explain the absorption of this kind of capture agent. HAMP was applied to the Retanning Process of sheep skin garment leather with sheep skin blue wet leather as the treatment object. The optimum technological conditions for the application of HAMP were obtained by single factor experiment. The amount of HAMP was 4% and the capture time was 1H. At this time the content of free formaldehyde in leather was reduced from 371mg/kg to 60mg/kg, and the removal rate of formaldehyde reached 83.8%. to HAMP. The thermodynamic properties of the leather, the stability and the surface roughness of the leather are all increased. The physical and mechanical properties of the leather are changed by the addition of.HAMP, the tensile strength is reduced by 1.7%, the tear strength is reduced by 23.4%, the softness increases 7.1%. with the wet leather of the sheep skin blue as raw material and under the conventional leather retanning process. A single factor experiment was carried out to compounded the hyperbranched polymer (NH2-HBP) with HAMP and used in the retanning process. The optimum conditions for the capture were as follows: the mass ratio of HAMP to NH2-HBP was m (HAMP), m (NH2-HBP) was 1.5:1, the amount of the capture agent was 4%, the free formaldehyde content in the leather was low to 31.32mg/kg, and the free formaldehyde removal rate was found when the capture time was 3h.. The results showed that when the amount of HAMP was 4% and the capture time was 2h, the content of free formaldehyde in the tanning leather was reduced from 2073mg/kg to 787mg/kg, the removal rate of formaldehyde was 62.03%, the tensile strength was increased by 18.9%, and the content of free formaldehyde in organic phosphine tanning leather was increased by 18.9% when the amount of HAMP was 4% and the capture time was 2H. From 488mg/kg to 214mg/kg, the removal rate of formaldehyde reached 56.13%. After the use of HAMP, the tensile strength of the leather leathers was raised by 52.46% and the tear strength increased by 69.44%. The free formaldehyde content in the tanning leather of VA was reduced from 615mg/kg to 110mg/kg, the removal rate of formaldehyde reached 81.97%, and the tearing strength and tensile strength of the leather leather leather were increased after the addition of HAMP.
【学位授予单位】:陕西科技大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:TQ424
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