發(fā)布時間：2018-05-11 20:23

  本文選題：聚天冬氨酸 + 功能材料��； 參考：《蘭州交通大學》2016年博士論文

【摘要】：本論文旨在開發(fā)系列聚天冬氨酸功能材料,使其性能更優(yōu)越,性質更穩(wěn)定。研究多種形式的此類環(huán)境友好型功能材料,為我國聚天冬氨酸功能材料的國產(chǎn)化提供理論依據(jù),為社會的可持續(xù)發(fā)展做出貢獻。本文較深入地研究了系列聚天冬氨酸功能材料的合成以及它們在水處理行業(yè)中用作碳酸鈣結晶過程抑制劑以及金屬腐蝕過程抑制劑的效果,并對其抑制機理進行了一定的分析。研究的主要內容可以歸納為以下幾點:(1)聚天冬氨酸的合成及其最優(yōu)生產(chǎn)條件的確定。通過正交試驗分別考察了聚天冬氨酸的阻垢緩蝕效果。通過綜合平衡法得到同步緩蝕阻垢聚天冬氨酸的合成方案。并通過二次優(yōu)選實驗對該方案進行了驗證。最終得到聚天冬氨酸的最優(yōu)生產(chǎn)條件為:酐氨物料比摩爾為1:1.2,聚合溫度為180℃,聚合時間為1.0h,堿解溫度為40℃,堿解時間為90min。在堿解過程中,用4MNaOH控制溶液的質量分數(shù)為15%,即可以得到阻垢率為96.5%的PASP。(2)聚天冬氨酸復合緩蝕阻垢劑的研制及性能研究綜合考慮模擬水的水質條件,針對A3碳鋼的化學成分及緩蝕性能要求,以更大程度上發(fā)揮復合水處理化學品的緩蝕及阻垢效能為出發(fā)點,研制出以聚天冬氨酸為主劑的綠色緩蝕阻垢復合配方。該配方的組分為:聚天冬氨酸、D-葡萄糖酸鈉、鉬酸鈉、硫酸鋅及單寧。采用碳酸鈣沉積法,分別考察了聚天冬氨酸復合材料單一組分、二元配方及三元配方的阻垢性能,結果顯示,質量配比為PASP:D-SG:TA=2:1:2的配方對水質變化的適應能力最好;維持三組分質量比一定,當阻垢劑的加量達到PASP:20mg/L,葡萄糖酸鈉:10 mg/L,單寧酸:20 mg/L時,阻垢率達到了95.7%,但增大復配阻垢劑的濃度時,阻垢率基本不再變化。說明該三元復合水處理劑具有低劑量效應。在研究緩蝕劑之間及阻垢劑之間的協(xié)同效應的基礎上,通過復合配方優(yōu)化實驗,考察了復合水處理劑之間的協(xié)同效應。結果顯示,復合水處理配方中的緩蝕與阻垢組分之間存在一定的協(xié)同效應。五元復合配方的腐蝕速率最低可達0.1083mm/a,緩蝕率為86.5%,阻垢率為94.2%。此時,藥劑總量為: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-二羰基化合物做親核試劑,選擇開環(huán)法合成接枝改性聚天冬氨酸功能材料。采用正交試驗對接枝改性材料的合成條件進行了兩次優(yōu)化。得到了該材料合成的優(yōu)方案為酐氨比1:1.4,聚合溫度180℃,聚合時間1h,PASI:EAA的摩爾比1:1.0,EAA與醇鈉的作用時間40min,反應時間24h。在這個條件下,產(chǎn)品的阻垢率為80.1%,腐蝕率為0.082170mm/a。對聚天冬氨酸功能材料性能的對比表明,聚天冬氨酸功能材料對碳酸鈣垢的抑制情況較好。對聚天冬氨酸功能材料的性能進行了對比。結果表明,該材料對碳酸鈣垢的抑制情況較好。通過物理改性及化學改性均可提高pasp的緩蝕性能。(4)聚天冬氨酸功能材料對碳酸鈣垢抑制機理的分析探討了該功能材料對碳酸鈣晶體生長過程的抑制原理。研究的主要內容可以歸納為以下幾點:(1)采用掃描電子顯微鏡技術對成垢的碳酸鈣垢樣進行了分析。通過對比碳酸鈣結晶過程中是否存在聚天冬氨酸功能材料的電鏡照片,可以發(fā)現(xiàn),沒有該材料時產(chǎn)生的caco3晶體大部分以方解石和針狀的文石形態(tài)存在,有較為清晰的幾何結構,形狀規(guī)整,晶胞堆積緊密,排列規(guī)則;加入該材料后,碳酸鈣晶體嚴重變形,形狀不規(guī)整,邊緣圓滑無棱角,且結構松散。其中,聚天冬氨酸復合材料主要是通過物理吸附,降低了固液界面附近的過飽和度,使碳酸鈣晶核穩(wěn)定地分散在介質中,形成微小的球霰石晶型。pasp及pasp-eaa主要依靠化學吸附,引起碳酸鈣生長過程中產(chǎn)生晶格缺陷。(2)采用3dbuilder成像技術模擬了pasp功能材料存在下碳酸鈣垢樣的三維視圖。結果顯示,團聚部分及球形顆粒的內部結構極為松散、不規(guī)則,表面凹凸不平且存在若干晶體的孔眼。這說明碳酸鈣的晶格已經(jīng)被加入的抑制劑瓦解。(3)采用xrd粉末衍射技術對成垢的碳酸鈣垢樣做了分析。結果表明:加入聚天冬氨酸功能材料后,碳酸鈣的x射線衍射圖發(fā)生改變,方解石特征峰的強度明顯降低,同時出現(xiàn)球霰石晶型的衍射峰。且三種類型的聚天冬氨酸功能材料都是很好的碳酸鈣結晶抑制劑。(5)聚天冬氨酸功能材料在a3碳鋼表面的緩蝕機理分析通過對比未添加緩蝕劑的空白實驗與添加不同聚天冬氨酸功能材料的碳鋼掛片的表面形貌可以看出,在介質中添加了聚天冬氨酸功能材料后,金屬表面形成了一層保護層,在一定程度上抑制了金屬的腐蝕過程。對腐蝕掛片清洗前后表面的sem分析可以看出:(1)由于加入了聚天冬氨酸功能材料,未清洗的碳鋼表面形成了形態(tài)各異的保護層,阻止了腐蝕介質向金屬表面的輸送。清洗后仍可以看到較完整的金屬基材表面;(2)未加入緩蝕劑的碳鋼表面腐蝕嚴重,清洗后可見表面有麻面及凹凸不平的腐蝕坑。(3)加入pasp-eaa和pmzdt的金屬基體比加入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.

【學位授予單位】：蘭州交通大學
【學位級別】：博士
【學位授予年份】：2016
【分類號】：TG174.42;TQ085.4

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