聚天冬氨酸功能材料的研制及其缓蚀阻垢性能研究

发布时间：2018-05-11 20:23

本文选题：聚天冬氨酸 + 功能材料　；参考：《兰州交通大学》2016年博士论文

【摘要】：本论文旨在开发系列聚天冬氨酸功能材料,使其性能更优越,性质更稳定。研究多种形式的此类环境友好型功能材料,为我国聚天冬氨酸功能材料的国产化提供理论依据,为社会的可持续发展做出贡献。本文较深入地研究了系列聚天冬氨酸功能材料的合成以及它们在水处理行业中用作碳酸钙结晶过程抑制剂以及金属腐蚀过程抑制剂的效果,并对其抑制机理进行了一定的分析。研究的主要内容可以归纳为以下几点:(1)聚天冬氨酸的合成及其最优生产条件的确定。通过正交试验分别考察了聚天冬氨酸的阻垢缓蚀效果。通过综合平衡法得到同步缓蚀阻垢聚天冬氨酸的合成方案。并通过二次优选实验对该方案进行了验证。最终得到聚天冬氨酸的最优生产条件为:酐氨物料比摩尔为1:1.2,聚合温度为180℃,聚合时间为1.0h,碱解温度为40℃,碱解时间为90min。在碱解过程中,用4MNaOH控制溶液的质量分数为15%,即可以得到阻垢率为96.5%的PASP。(2)聚天冬氨酸复合缓蚀阻垢剂的研制及性能研究综合考虑模拟水的水质条件,针对A3碳钢的化学成分及缓蚀性能要求,以更大程度上发挥复合水处理化学品的缓蚀及阻垢效能为出发点,研制出以聚天冬氨酸为主剂的绿色缓蚀阻垢复合配方。该配方的组分为:聚天冬氨酸、D-葡萄糖酸钠、钼酸钠、硫酸锌及单宁。采用碳酸钙沉积法,分别考察了聚天冬氨酸复合材料单一组分、二元配方及三元配方的阻垢性能,结果显示,质量配比为PASP:D-SG:TA=2:1:2的配方对水质变化的适应能力最好;维持三组分质量比一定,当阻垢剂的加量达到PASP:20mg/L,葡萄糖酸钠:10 mg/L,单宁酸:20 mg/L时,阻垢率达到了95.7%,但增大复配阻垢剂的浓度时,阻垢率基本不再变化。说明该三元复合水处理剂具有低剂量效应。在研究缓蚀剂之间及阻垢剂之间的协同效应的基础上,通过复合配方优化实验,考察了复合水处理剂之间的协同效应。结果显示,复合水处理配方中的缓蚀与阻垢组分之间存在一定的协同效应。五元复合配方的腐蚀速率最低可达0.1083mm/a,缓蚀率为86.5%,阻垢率为94.2%。此时,药剂总量为:118mg/L。(3)接枝改性聚天冬氨酸功能材料PASP-EAA的研制及其性能研究利用β-二羰基化合物做亲核试剂,选择开环法合成接枝改性聚天冬氨酸功能材料。采用正交试验对接枝改性材料的合成条件进行了两次优化。得到了该材料合成的优方案为酐氨比1:1.4,聚合温度180℃,聚合时间1h,PASI:EAA的摩尔比1:1.0,EAA与醇钠的作用时间40min,反应时间24h。在这个条件下,产品的阻垢率为80.1%,腐蚀率为0.082170mm/a。对聚天冬氨酸功能材料性能的对比表明,聚天冬氨酸功能材料对碳酸钙垢的抑制情况较好。对聚天冬氨酸功能材料的性能进行了对比。结果表明,该材料对碳酸钙垢的抑制情况较好。通过物理改性及化学改性均可提高pasp的缓蚀性能。(4)聚天冬氨酸功能材料对碳酸钙垢抑制机理的分析探讨了该功能材料对碳酸钙晶体生长过程的抑制原理。研究的主要内容可以归纳为以下几点:(1)采用扫描电子显微镜技术对成垢的碳酸钙垢样进行了分析。通过对比碳酸钙结晶过程中是否存在聚天冬氨酸功能材料的电镜照片,可以发现,没有该材料时产生的caco3晶体大部分以方解石和针状的文石形态存在,有较为清晰的几何结构,形状规整,晶胞堆积紧密,排列规则;加入该材料后,碳酸钙晶体严重变形,形状不规整,边缘圆滑无棱角,且结构松散。其中,聚天冬氨酸复合材料主要是通过物理吸附,降低了固液界面附近的过饱和度,使碳酸钙晶核稳定地分散在介质中,形成微小的球霰石晶型。pasp及pasp-eaa主要依靠化学吸附,引起碳酸钙生长过程中产生晶格缺陷。(2)采用3dbuilder成像技术模拟了pasp功能材料存在下碳酸钙垢样的三维视图。结果显示,团聚部分及球形颗粒的内部结构极为松散、不规则,表面凹凸不平且存在若干晶体的孔眼。这说明碳酸钙的晶格已经被加入的抑制剂瓦解。(3)采用xrd粉末衍射技术对成垢的碳酸钙垢样做了分析。结果表明:加入聚天冬氨酸功能材料后,碳酸钙的x射线衍射图发生改变,方解石特征峰的强度明显降低,同时出现球霰石晶型的衍射峰。且三种类型的聚天冬氨酸功能材料都是很好的碳酸钙结晶抑制剂。(5)聚天冬氨酸功能材料在a3碳钢表面的缓蚀机理分析通过对比未添加缓蚀剂的空白实验与添加不同聚天冬氨酸功能材料的碳钢挂片的表面形貌可以看出,在介质中添加了聚天冬氨酸功能材料后,金属表面形成了一层保护层,在一定程度上抑制了金属的腐蚀过程。对腐蚀挂片清洗前后表面的sem分析可以看出:(1)由于加入了聚天冬氨酸功能材料,未清洗的碳钢表面形成了形态各异的保护层,阻止了腐蚀介质向金属表面的输送。清洗后仍可以看到较完整的金属基材表面;(2)未加入缓蚀剂的碳钢表面腐蚀严重,清洗后可见表面有麻面及凹凸不平的腐蚀坑。(3)加入pasp-eaa和pmzdt的金属基体比加入pasp的更完整。
[Abstract]:The purpose of this paper is to develop a series of polyaspartic acid functional materials to make their properties more advantageous and more stable in nature. To study various forms of such environmentally friendly functional materials, provide theoretical basis for the localization of the functional materials of polyaspartic acid in our country and contribute to the sustainable development of the society. This paper has studied a series of polyasparagus in a more deep study. The synthesis of functional materials of ammonia acid and the effect of their use as inhibitors of calcium carbonate crystallization process and inhibitors of metal corrosion process in water treatment industry and their inhibition mechanism are analyzed. The main contents of the study can be summarized as follows: (1) the synthesis of aspartic acid and the determination of the optimal production conditions. The effect of scale inhibition and corrosion inhibition of polyaspartic acid was investigated by over orthogonal experiments. The synthesis scheme of synchronized inhibition and scale inhibition of polyaspartic acid was obtained by the comprehensive equilibrium method. The scheme was verified by two optimum experiments. The optimum production conditions of polyaspartic acid were as follows: the specific content of ANHYDRIC aspartic acid was 1:1.2, and the polymerization temperature was 180. The polymerization time is 1.0h, the alkali solution temperature is 40 C, the alkali solution time is 90min. in the alkali solution process and the mass fraction of the solution is 15%, that is, the development and Performance Research of PASP. (2) polyaspartic acid complex corrosion inhibitor can be obtained by 4MNaOH, and the chemical composition of the A3 carbon steel is considered. In order to improve the corrosion inhibition and scale inhibition efficiency of the compound water treatment chemicals, a compound formula with polyaspartic acid, D- sodium gluconate, sodium molybdate, zinc sulfate, tannin and calcium carbonate was used as the starting point. The scale inhibition performance of the single component of polyaspartic acid composite material, two element formula and three element formula showed that the formula with the mass ratio of PASP:D-SG:TA=2:1:2 was the best to adapt to the change of water quality, and the mass ratio of three components was maintained, when the dosage of scale inhibitor reached PASP:20mg /L, sodium gluconate: 10 mg/L, tannic acid: 20 mg/L, scale inhibition The rate reached 95.7%, but the scale of scale inhibition was no longer changed when the concentration of the compound scale inhibitor increased. It showed that the three element composite water treatment agent had a low dose effect. On the basis of the synergistic effect between the inhibitors and the scale inhibitor, the synergistic effect between the compound water treatment agent was investigated by the compound formula optimization experiment. The results showed that the synergistic effect of the compound water treatment agent was observed. There is a certain synergistic effect between the corrosion inhibition and the scale inhibition components in the compound water treatment formula. The corrosion rate of the five element compound formula is lowest up to 0.1083mm/a, the corrosion inhibition rate is 86.5%, the scale of scale inhibition is 94.2%., and the total amount of the agent is: the development of the 118mg/L. (3) graft modified polyaspartic acid functional material PASP-EAA and its performance study using beta two. Carbonyl compounds were used as nucleophilic reagents and selected open loop method for the synthesis of modified polyaspartic acid functional materials. Orthogonal test was used to optimize the synthesis conditions of the graft modification materials two times. The optimum synthesis scheme of the material was anhydride Ammonia Ratio 1:1.4, polymerization temperature 180, polymerization time 1H, PASI:EAA molar ratio 1:1.0, EAA and sodium alcohol. Action time 40min, reaction time 24h. under this condition, the scale of scale inhibition of the product is 80.1%, the corrosion rate is 0.082170mm/a. to polyaspartic acid functional material performance comparison shows that polyaspartic acid function material has better inhibition of calcium carbonate scale. The performance of polyaspartic acid functional material is compared. The result shows that the material is the material. The inhibition of calcium carbonate scale is better. The corrosion inhibition performance of PASP can be improved by physical modification and chemical modification. (4) the inhibition mechanism of calcium carbonate scale inhibition by polyaspartic acid functional materials is discussed. The main contents of the study can be summed up as follows: (1) the use of scavenging is the following. By contrasting the electron microscope photographs of the functional materials of polyaspartic acid in the crystallization of calcium carbonate, it is found that most of the CaCO3 crystals produced without this material exist in calcite and acicular aragonite, with a clearer geometric structure and shape. After adding this material, the crystal of calcium carbonate is seriously deformed, the shape is irregular, the edge is smooth and the structure is loose, and the structure is loose. Among them, the polyaspartic acid composite material is mainly through physical adsorption, which reduces the supersaturation near the solid liquid interface, and makes the calcium carbonate nucleus disperse in the medium steadily. The tiny spherite crystal type.Pasp and pasp-eaa mainly rely on chemical adsorption to produce lattice defects in the growth of calcium carbonate. (2) the three-dimensional view of calcium carbonate scale in PASP functional materials is simulated by 3DBuilder imaging technology. The results show that the internal structure of the aggregate and spherical particles is very loose, irregular and concave and convex. This shows that the lattice of a number of crystals has been disintegrated. (3) the scale samples of calcium carbonate were analyzed by XRD powder diffraction technique. The results showed that the X ray diffraction pattern of calcium carbonate was changed and the strength of calcite characteristic peak was obviously reduced after adding the functional material of polyaspartic acid. In addition, the three types of polyaspartic acid functional materials are good calcium carbonate crystallization inhibitors. (5) the corrosion inhibition mechanism of polyaspartic acid functional materials on the surface of A3 carbon steel is compared with the blank test of not adding corrosion inhibitors and the addition of carbon steel plates with different aspartic acid functional materials. The surface morphology shows that after adding the polyaspartic acid functional material in the medium, the metal surface forms a layer of protective layer, which inhibits the corrosion process of the metal to a certain extent. The SEM analysis of the surface before and after the cleaning of the corrosion sheet can be seen as follows: (1) the surface of the uncleaned carbon steel is formed due to the addition of polyaspartic acid functional material. Different protective layers have prevented the transport of corrosion medium to the metal surface. After cleaning, more complete metal substrate surface can be seen. (2) the surface of carbon steel without corrosion inhibitor is seriously corroded, and the surface has surface and uneven corrosion pit on the surface. (3) the metal matrix added to pasp-eaa and pmzdt is more complete than that of PASP. Whole.

【学位授予单位】：兰州交通大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TG174.42;TQ085.4

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