本文選題：活潑亞甲基 + 超支化聚合物　； 參考：《陜西科技大學》2017年碩士論文

【摘要】：隨著國內環(huán)保工作的不斷推進,國家對揮發(fā)性有機物(VOCs)的治理日益重視,甲醛作為VOCs的一種,已被列為致癌物質。目前常用的甲醛治理方法有:物理吸附、化學治理、生物技術、臭氧氧化以及光催化技術等方法。其中,化學治理法是一種高效且簡單易行的方法。本研究以端羥基超支化聚合物為原料,對其進行改性制備活潑亞甲基類超支化甲醛捕獲劑,并將其用于皮革復鞣及主鞣工序中,以降低成革中游離甲醛含量。首先,以端羥基超支化聚合物(HBP)為原料,采用乙酰乙酸乙酯(EAA)對其進行改性,制備活潑亞甲基類超支化甲醛捕獲劑(HAMP),并通過傅里葉紅外光譜(FT-IR)、核磁共振氫譜(1H-NMR)、凝膠滲透色譜(GPC)、納米粒度表面電位分析儀、透射電子顯微鏡(TEM)等現(xiàn)代儀器分析方法對HAMP的分子結構、相對分子質量、粒徑分布及形貌進行了分析表征。通過單因素實驗和正交實驗優(yōu)化得到最佳合成條件:反應摩爾比n(HBP):n(EAA)為1:2.5,催化劑無水K2CO3用量為2.5%,反應溫度為100℃,反應時間為4.5h。其次,以甲醛溶液為處理對象,通過單因素實驗法分別研究了反應溫度、HAMP用量、反應時間、甲醛溶液初始濃度以及溶液pH對甲醛去除過程的影響,結果表明HAMP對甲醛的去除率隨著溫度、時間以及捕獲劑用量的增加而增加。最佳pH為堿性環(huán)境,最佳捕獲溫度為40℃;在最優(yōu)pH及溫度下,以20mL濃度為15μg/mL的甲醛溶液為研究對象,HAMP用量為0.12g時80min吸附即可達到平衡;HAMP對甲醛溶液的吸附容量隨甲醛初始濃度的增加而增加,隨著HAMP用量的增加而減小。以20mL濃度為15μg/mL的甲醛溶液為研究對象,對比研究了改性前后的端羥基超支化聚合物對甲醛的去除能力,結果表明HAMP對甲醛的去除能力比改性前提高了73.20%,吸附容量得到增加,甲醛去除效果顯著增強。此外,研究了HAMP對甲醛溶液的吸附動力學和吸附熱力學進行了研究,熱力學研究表明不同溫度下吸附甲醛等溫線既符合Langmuir方程,又符合Freundlich方程,其中Freundlich方程擬合的相關性更高,由此說明HAMP對水體中的甲醛的吸附是以化學吸附為主,兼有物理吸附的多分子層吸附體系。動力學研究表明:二級動力學方程能更好地解釋此類捕獲劑吸附甲醛的過程。以綿羊皮藍濕革為處理對象,將HAMP應用于綿羊皮服裝革復鞣工藝,通過單因素實驗得到HAMP應用的最佳工藝條件為:HAMP用量為4%,捕獲時間為1h,此時皮革中游離甲醛含量由371mg/kg降至60mg/kg,甲醛去除率達到83.8%。加入HAMP的成革熱力學性能、成革穩(wěn)定性及表面粗糙度均增加,膠原纖維分散度增大。HAMP的加入使得皮革的物理機械性能發(fā)生改變,抗張強度降低了1.7%,撕裂強度降低了23.4%,柔軟度提高了7.1%。以綿羊皮藍濕革為原料,在常規(guī)皮革復鞣工藝條件下進行單因素實驗,將端氨基超支化聚合物(NH2-HBP)與HAMP進行復配并應用于復鞣工藝,得到其最佳捕獲工藝條件為:HAMP與NH2-HBP質量比m(HAMP):m(NH2-HBP)為1.5:1,捕獲劑用量為4%,捕獲時間為3h。此時皮革中游離甲醛含量低至31.32mg/kg,游離甲醛去除率達到89.95%。將HAMP應用于綿羊皮浸酸皮的主鞣工藝實驗,結果表明,當HAMP用量為4%,捕獲時間為2h時,醛鞣革中游離甲醛含量由2073mg/kg降至787mg/kg,甲醛去除率達到62.03%,坯革抗張強略微提高,撕裂強度提高了18.9%;有機膦鞣革中游離甲醛含量由488mg/kg降至214mg/kg,甲醛去除率達到56.13%,使用HAMP后坯革成革抗張強度提升了52.46%,撕裂強度升高了69.44%;VA唑烷鞣革中游離甲醛含量由615mg/kg降至110mg/kg,甲醛去除率達到81.97%,添加HAMP后坯革成革撕裂強度和抗張強度均有所增加。
[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.

【學位授予單位】：陜西科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ424

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