阻燃性油水分离泡沫状材料的制备及其性能研究

发布时间：2018-05-18 15:35

本文选题：层层自组装 + 聚合物材料　；参考：《中国地质大学》2017年博士论文

【摘要】：随着石油工业的发展,石油管道运输及跨海运输的增加使溢油事故频发,海上石油泄漏不仅会对环境造成严重影响,也会对人的健康造成威胁;此外,在石油化工、火力发电等行业使用的储油罐,常发生油罐泄漏、火灾、爆炸事故,造成严重的人员伤亡、环境破坏和经济损失。无论海上溢油事故,还是陆上油罐泄漏事故,都必须采取紧急安全应急措施,防止油料向更大范围扩散造成破坏环境,或蒸发遇火导致火灾或爆炸事故。采用油水分离及吸油材料既可以进行海上溢油事故的油水分离吸油,也可以进行油罐泄漏油料的吸收,是一种处置溢油或泄漏事故的安全技术措施。而现有油水分离及吸油材料大多为高分子聚合物材料,而高分子聚合物材料有机化学成分的特点使得其中的绝大部分具有显著的可燃性,因而,在储存、运输过程中存在着极大的火灾安全性问题,而溢油或泄漏事故中石油中可燃气体的挥发也可能引发火灾,油水分离及吸油材料的火灾安全性问题在某种程度上限制了其应用,因此,在制备油水分离及吸油材料,赋予材料基体良好的油水分离及吸油性能的同时需要兼顾其阻燃性能,以降低其火灾危险性。三维多孔泡沫状材料一般具有大的比表面积、高的开孔率和互通的孔洞结构,是制备高效油水分离及吸油材料的理想基体。本文以商业化的软质聚氨酯(FPU)泡沫和三聚氰胺泡沫(MF)为基体,提出利用层层自组装的方法,将具有阻燃作用的物质和不同表面能的改性剂构筑于泡沫基体的表面,使其在具备良好的油水选择浸润性的同时赋予其阻燃性能的思路,制备出阻燃性高效油水分离及吸油材料。围绕上述思路,论文主要开展了软质聚氨酯泡沫和三聚氰胺泡沫的表面改性及其油水分离性能和阻燃性能的研究,具体研究内容及成果如下:1.以软质聚氨酯泡沫为基体,采用层层自组装的方法,分别将具有高表面能的聚乙烯亚胺(PEI)/海藻酸钠(SA)和纤维素磷化衍生物(PC)/壳聚糖(CH)成功构筑于泡沫基体的表面,赋予其表面亲水、水下疏油性能,接触角测试结果显示所制得的样品水接触角达到0°,具有超亲水性,油水分离测试结果显示PEI/SA和PC/CH改性的样品均能有效地分离油水混合物。热失重分析结果显示PC/CH改性的样品其热稳定性在285°C-700°C范围内有大幅提升,锥形量热仪测试结果显示,组装了15层PC/CH的样品相较纯样其峰值热释放速率下降了60.3%,总热释量相较于纯样下降了30.3%。热稳定性和阻燃性能效果的显著提升主要归因于含磷化合物的催化成炭作用。2.采用层层自组装的方法分别将包含氢氧化镁(Mg(OH)_2)和蒙脱土(MMT)的组装层成功构筑于软质聚氨酯泡沫的表面,以增加其表面粗糙度,进一步利用低表面能的十二硫醇(DDT)对泡沫基体进行改性,使其具有疏水亲油性能,经Mg(OH)_2/DDT和MMT/DDT改性的聚氨酯泡沫的水接触角分别达到了136°和135°,所得样品对不同油品和有机溶剂的吸油倍率在16至64倍之间,在50次重复吸油后仍能够保持良好的吸油倍率。所得改性样品的热稳定性较纯样得到了大大的提升。锥形量热仪测试结果显示,组装了8层MMT填充涂层改性的样品及最高Mg(OH)_2涂层含量的样品峰值热释放速率和总热释放量均有下降,这可归因于氢氧化镁(Mg(OH)_2)和蒙脱土(MMT)对泡沫基体发挥了优异的阻燃作用。3.首先,采用层层自组装的方法将MMT构筑于软质聚氨酯泡沫,之后采用有机硅氧烷(PDMS)对其进行进一步表面改性,制得的油水分离材料其水接触角超过150°,表现出超疏水超亲油性能。所制得的样品能有效吸附水面油层,对不同的油品和有机溶剂的吸油倍率在20至70倍之间。热失重分析结果显示6层MMT填充的涂层改性的样品700°C时的残炭量相较于纯样提升了8.73个百分点,锥形量热仪测试结果显示该样品峰值热释放速率较纯样下降了70%。4.以三聚氰胺泡沫为基体,首先采用层层自组装的方法将典型的阻燃性二维片层纳米粒子MMT和α-磷酸锆分别构筑于三聚氰胺泡沫的表面,增加了其表面粗糙度,并分别采用二甲基二氯硅烷和甲基三氯硅烷对其进行进一步改性。制备所得样品的水接触角均超过150°,表现出超疏水超亲油性能,其对不同油品和有机溶剂的吸油率能达到自身重量的28-131倍,在各种环境下均能展现出良好的油水分离性能。制备所得样品的在高温阶段的热稳定性较纯样有较大的提高,其在500℃高温处理后的体积收缩程度明显小于纯样,炭渣也更为完整。5.对本文中制得的各种油水分离及吸油材料的应用装置及事故处理提出了设想并进行了探讨,也为未来此类材料的大规模使用提出展望。
[Abstract]:With the development of the oil industry, the oil pipeline transportation and the increase of trans sea transportation make the oil spill frequent. The offshore oil leakage will not only cause serious impact on the environment, but also threaten the health of people. In addition, oil tanks used in such industries as petrochemical and thermal power generation often occur oil tank leaks, fires and explosions. Casualties, environmental damage and economic losses, whether oil spill accidents, or oil tank leakage accidents on land, must take emergency safety emergency measures to prevent oil from spreading to a larger range to cause damage to the environment, or to evaporate and cause fire or explosion accidents. Oil and water separation and oil absorption materials can be carried out at sea oil spill. Therefore, oil and water separation and oil absorption can also be used for the absorption of oil tank leaked oil. It is a safe and technical measure to deal with oil spills or leakage accidents. Most of the existing oil and water separation and oil absorption materials are polymer materials, and the special points of organic chemical composition of polymer materials make the vast majority of them have significant combustible. Therefore, there is a great fire safety problem in the process of storage and transportation, and the volatilization of combustible gas in oil or leakage accidents may also cause fire. The fire safety of oil and water separation and oil absorption materials is limited to some extent. Therefore, the materials for oil and water separation and oil absorption are prepared and given to the material. The good oil and water separation and oil absorption properties of the matrix should take into account the flame retardancy and reduce the fire risk. The three-dimensional porous foam material has large specific surface area, high opening rate and interconnected pore structure. It is an ideal matrix for the preparation of high efficiency oil and water separation and oil absorption materials. This paper is based on commercialized soft polyurethane (FPU) foam and melamine foam (MF) as the substrate, a method of layer self assembly is proposed to construct a flame retardant substance and a modifier with different surface energy on the surface of the foam base, so that the flame retardant and high efficiency oil water separation is prepared by the idea that it has good oil water selection and wettability. In this paper, the surface modification of soft polyurethane foam and melamine foam, the performance of oil and water separation and the flame retardancy are studied in this paper. The specific research content and results are as follows: 1. using the soft polyurethane foam as the matrix and the method of layer self-assembly, the polyethylene with high surface energy is used respectively. Imide (PEI) / sodium alginate (SA) and cellulose phosphating derivatives (PC) / chitosan (CH) were successfully constructed on the surface of the foam substrate, which gave the surface hydrophilic and underwater oil repellency. The contact angle test results showed that the water contact angle of the samples reached 0 degrees, with super hydrophile properties, and the results of oil and water separation test showed that all the samples of PEI/SA and PC/CH modified were all. The results of thermal weight loss analysis show that the thermal stability of the PC/CH modified samples has a significant increase in the range of 285 degrees C-700 C. The cone calorimeter test results show that the peak heat release rate of the 15 layers of PC/CH has decreased by 60.3% compared with the pure sample, and the total thermoluminescence is more stable than the pure sample. The significant improvement of qualitative and flame retardant properties is attributed to the catalytic carbonization of phosphorus compounds..2. by layer self-assembly method, including magnesium hydroxide (Mg (OH) _2) and montmorillonite (MMT), was successfully constructed on the surface of the soft polyurethane foam to increase the surface roughness and further use ten of the low surface energy. Two thiol (DDT) modified the foam matrix to make it hydrophobic. The water contact angle of the polyurethane foam modified by Mg (OH) _2/DDT and MMT/DDT was reached 136 and 135 degrees respectively. The oil absorption ratio of the samples to different oil and organic solvents was between 16 and 64 times, and the oil absorption doubled after 50 repeated oil absorption. The results of the conical calorimeter showed that the peak heat release rate and total heat release rate of the samples assembled with 8 layers of MMT filled coating and the highest Mg (OH) _2 coating content decreased, which could be attributed to the bubbles of magnesium hydroxide (Mg (OH) _2) and montmorillonite (MMT). The foam matrix plays an excellent flame retardancy.3. first. First, MMT is constructed in the soft polyurethane foam by layer self assembly, and then organosiloxane (PDMS) is used to further surface modification. The water contact angle of the prepared oil and water separation material is over 150 degrees, showing super hydrophobic super hydrophobic property. The samples obtained can be effective. The oil absorption rate of different oil and organic solvents is between 20 and 70 times. The thermal weight loss analysis shows that the residual carbon content of the 6 layer MMT filled coated samples 700 C is 8.73 percentage points compared to the pure sample, and the cone calorimeter test results show that the peak heat release rate of the sample is decreased by 70%.4 than that of the pure sample. With melamine foam as the matrix, the typical flame retardant two-dimensional lamellar nanoparticles MMT and alpha zirconium phosphate were constructed on the surface of melamine foam by layer layer self-assembly. The surface roughness was increased, and two methyl two chlorosilane and methyl three chlorosilane were further modified. The water contact angle of the sample is more than 150 degrees, showing the super hydrophobic super parent oil performance. The oil absorption rate of different oil and organic solvents can reach 28-131 times of its own weight, and the good oil and water separation performance can be displayed in various environment. The thermal stability of the prepared samples is higher than that of the pure sample at the high temperature stage, and it is 500. The degree of volume contraction after temperature treatment at high temperature is obviously smaller than that of pure sample, and carbon slag is more complete.5.. The application device and accident treatment of various oil and water separation and oil absorption materials obtained in this paper are proposed and discussed, and the prospect of the large-scale use of such materials in the future is also put forward.
【学位授予单位】：中国地质大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ328;TB34

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