新型有機(jī)衍生物緩蝕劑的制備與性能
發(fā)布時間：2018-08-22 09:22
【摘要】：緩蝕劑是一種以適當(dāng)?shù)臐舛群托问酱嬖谟诃h(huán)境(介質(zhì))中時,可以防止或減緩材料腐蝕的化學(xué)物質(zhì)或幾種化學(xué)物質(zhì)的混合物,在眾多腐蝕控制方法中,添加緩蝕劑成為了一種簡單,有效,適用性強(qiáng)的重要的防腐蝕手段,特別是在酸性腐蝕介質(zhì)中添加有機(jī)緩蝕劑已廣泛應(yīng)用于石油化工和鍋爐酸洗等行業(yè)。有機(jī)緩蝕劑分子結(jié)構(gòu)中常含有氮、氧、硫、不飽和鍵或芳香環(huán)的極性基團(tuán),它們可以通過靜電相互作用或通過配位共價鍵吸附在金屬表面,并形成一層保護(hù)膜。本論文主要合成了兩種有機(jī)小分子:三苯胺二醛(TD)和胞嘧啶-L-丙氨酸(CLAD),選用生物大分子脫氧核糖核苷酸(DNA)作為緩蝕劑,研究了三種有機(jī)分子作為碳鋼在強(qiáng)酸介質(zhì)中的緩蝕性能和機(jī)理,主要內(nèi)容如下:(1)本文將三苯胺進(jìn)行氧化反應(yīng)得到三苯胺二醛,并研究其與精氨酸,碘化鉀(KI)形成的復(fù)合物對碳鋼在1 MHC1溶液中的緩蝕性能。失重法發(fā)現(xiàn)當(dāng)配方為:50 mg·L-1三苯胺二醛+50 mg·L-1精氨酸+100 mg·L-1碘化鉀時,其緩蝕效率高達(dá)92%;該復(fù)合緩蝕劑作為混合型緩蝕劑在金屬表面吸附符合等溫吸附理論,EDS分析結(jié)果驗(yàn)證復(fù)合緩蝕劑吸附在金屬表面,形成一層良好的保護(hù)膜,同時對碘化鉀的協(xié)同作用機(jī)理也展開探討;量子化學(xué)計(jì)算結(jié)果表明,三苯胺二醛與精氨酸含有的極性基團(tuán)能夠起到穩(wěn)定地吸附作用,并通過建立簡易的吸附模型進(jìn)行解釋。(2)利用分子設(shè)計(jì)手段,將L-丙氨酸和胞嘧啶生物小分子通過脫水縮合反應(yīng)合成有機(jī)化合物胞嘧啶-L-丙氨酸,作為一種環(huán)境友好型緩蝕劑,用于X80鋼在0.5 M HC1溶液中。利用失重法、極化曲線法、電化學(xué)阻抗譜(EIS)和SEM法系統(tǒng)地研究胞嘧啶-L-丙氨酸的緩蝕性能。結(jié)果表明胞嘧啶-L-丙氨酸的最高緩蝕效率達(dá)到91%,遠(yuǎn)高于單獨(dú)使用丙氨酸的78%;形成的致密保護(hù)膜有效地阻礙電子的轉(zhuǎn)移,降低金屬溶解和腐蝕進(jìn)程;該有機(jī)緩蝕劑的吸附過程遵循等溫吸附理論,且吸附類型包含物理吸附和化學(xué)吸附;量子化學(xué)計(jì)算參數(shù)表明高緩蝕率主要源于胞嘧啶-L-丙氨酸較強(qiáng)的吸附能力。此外,當(dāng)胞嘧啶-L-丙氨酸與碘化鉀復(fù)合后,在進(jìn)一步提高緩蝕效率的同時還降低成本。(3)采用生物大分子DNA作為碳鋼在1 M HC1溶液中的緩蝕劑,并利用失重法和電化學(xué)方法研究其緩蝕效果,以吸附理論,紅外光譜,XPS和量子化計(jì)算探索其緩蝕機(jī)理。研究發(fā)現(xiàn),DNA緩蝕劑在濃度為20 mg·1-1時,緩蝕效率達(dá)到92%;同時DNA分子的吸附遵循朗格謬等溫吸附理論,紅外光譜結(jié)果表明DNA分子在成膜前后結(jié)構(gòu)發(fā)生了變化,原因是與金屬表面發(fā)生相互作用;XPS表征進(jìn)一步表明金屬表面含有DNA的元素,并與之形成Fe-N鍵和Fe-O鍵,量子化學(xué)計(jì)算結(jié)果進(jìn)一步表明DNA緩蝕劑分子向鐵原子d軌道提供孤對電子,形成穩(wěn)固的配位化學(xué)鍵。該研究證明了低用量DNA優(yōu)異的緩蝕性能和闡明了對應(yīng)緩蝕機(jī)理。
[Abstract]:An inhibitor is a chemical substance or a mixture of several chemicals that can prevent or slow down the corrosion of a material when it is present in the environment (medium) at an appropriate concentration and form, among many corrosion control methods, The addition of corrosion inhibitor has become a simple, effective and suitable way to prevent corrosion. Especially, the addition of organic corrosion inhibitor in acid corrosion medium has been widely used in petrochemical industry and boiler pickling industry. The molecular structures of organic corrosion inhibitors often contain polar groups of nitrogen, oxygen, sulfur, unsaturated bonds or aromatic rings, which can be adsorbed on the metal surface by electrostatic interaction or by coordination covalent bonds, and form a protective film. In this paper, two kinds of organic small molecules, trianiline dialdehyde (TD) and cytosine L-alanine (CLAD), were synthesized. The biomacromolecular deoxyribose nucleotides (DNA) were used as corrosion inhibitors. The corrosion inhibition properties and mechanism of three organic molecules used as carbon steel in strong acid medium were studied. The main contents are as follows: (1) Trianiline dialdehydes were prepared by oxidation of trianiline and arginine. Inhibition of corrosion of carbon steel by potassium iodide (KI) complex in 1 MHC1 solution. It was found by weightlessness that when the formula was 1: 50 mg L-1 trianiline dialdehyde 50 mg L-1 arginine 100 mg L-1 potassium iodide, The corrosion inhibition efficiency is as high as 92.The composite inhibitor acts as a mixed inhibitor to adsorb on the metal surface in accordance with the isothermal adsorption theory and EDS analysis results show that the composite inhibitor adsorbs on the metal surface and forms a good protective film. At the same time, the synergistic mechanism of potassium iodide was also discussed. The results of quantum chemical calculation showed that the polar groups contained in trianiline dialdehydes and arginine could be adsorbed stably. A simple adsorption model was established. (2) the organic compound cytosine L-alanine was synthesized by dehydration and condensation reaction of L-alanine and cytosine biological small molecules by molecular design as an environment-friendly corrosion inhibitor. It is used in X80 steel in 0.5m HC1 solution. The corrosion inhibition of cytosine L-alanine was systematically studied by weightlessness method, polarization curve method, electrochemical impedance spectroscopy (EIS) and SEM method. The results show that the highest corrosion inhibition efficiency of cytosine L-alanine is 91%, which is much higher than that of 78% alanine alone, and the dense protective film can effectively block the electron transfer and reduce the process of metal dissolution and corrosion. The adsorption process of the organic corrosion inhibitor follows the isothermal adsorption theory, and the adsorption types include physical adsorption and chemical adsorption, and the quantum chemical calculation parameters show that the high corrosion inhibition rate is mainly due to the strong adsorption capacity of cytosine-L-alanine. In addition, when cytosine -L-alanine was combined with potassium iodide, the corrosion inhibition efficiency was further improved and the cost was also reduced. (3) Biomacromolecule DNA was used as corrosion inhibitor for carbon steel in 1m HC1 solution. The inhibition effect was studied by weightlessness method and electrochemical method. The corrosion inhibition mechanism was explored by adsorption theory, IR XPS and quantization calculation. It was found that the inhibition efficiency reached 92when the concentration of DNA inhibitor was 20mg 1-1. Meanwhile, the adsorption of DNA molecules followed Langermal isotherm adsorption theory, and the IR spectra showed that the structure of DNA molecules changed before and after the film formation. The reason is that the interaction between DNA and metal surface further indicates that the metal surface contains the elements of DNA and forms Fe-N bond and Fe-O bond. The quantum chemical calculation further indicates that the DNA inhibitor molecule provides lone pair electrons to the d orbital of iron atom. Form a solid coordination chemical bond. This study proved the excellent corrosion inhibition performance of low dosage DNA and explained the corresponding corrosion inhibition mechanism.
【學(xué)位授予單位】：西南石油大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TG174.42
本文編號：2196675
[Abstract]:An inhibitor is a chemical substance or a mixture of several chemicals that can prevent or slow down the corrosion of a material when it is present in the environment (medium) at an appropriate concentration and form, among many corrosion control methods, The addition of corrosion inhibitor has become a simple, effective and suitable way to prevent corrosion. Especially, the addition of organic corrosion inhibitor in acid corrosion medium has been widely used in petrochemical industry and boiler pickling industry. The molecular structures of organic corrosion inhibitors often contain polar groups of nitrogen, oxygen, sulfur, unsaturated bonds or aromatic rings, which can be adsorbed on the metal surface by electrostatic interaction or by coordination covalent bonds, and form a protective film. In this paper, two kinds of organic small molecules, trianiline dialdehyde (TD) and cytosine L-alanine (CLAD), were synthesized. The biomacromolecular deoxyribose nucleotides (DNA) were used as corrosion inhibitors. The corrosion inhibition properties and mechanism of three organic molecules used as carbon steel in strong acid medium were studied. The main contents are as follows: (1) Trianiline dialdehydes were prepared by oxidation of trianiline and arginine. Inhibition of corrosion of carbon steel by potassium iodide (KI) complex in 1 MHC1 solution. It was found by weightlessness that when the formula was 1: 50 mg L-1 trianiline dialdehyde 50 mg L-1 arginine 100 mg L-1 potassium iodide, The corrosion inhibition efficiency is as high as 92.The composite inhibitor acts as a mixed inhibitor to adsorb on the metal surface in accordance with the isothermal adsorption theory and EDS analysis results show that the composite inhibitor adsorbs on the metal surface and forms a good protective film. At the same time, the synergistic mechanism of potassium iodide was also discussed. The results of quantum chemical calculation showed that the polar groups contained in trianiline dialdehydes and arginine could be adsorbed stably. A simple adsorption model was established. (2) the organic compound cytosine L-alanine was synthesized by dehydration and condensation reaction of L-alanine and cytosine biological small molecules by molecular design as an environment-friendly corrosion inhibitor. It is used in X80 steel in 0.5m HC1 solution. The corrosion inhibition of cytosine L-alanine was systematically studied by weightlessness method, polarization curve method, electrochemical impedance spectroscopy (EIS) and SEM method. The results show that the highest corrosion inhibition efficiency of cytosine L-alanine is 91%, which is much higher than that of 78% alanine alone, and the dense protective film can effectively block the electron transfer and reduce the process of metal dissolution and corrosion. The adsorption process of the organic corrosion inhibitor follows the isothermal adsorption theory, and the adsorption types include physical adsorption and chemical adsorption, and the quantum chemical calculation parameters show that the high corrosion inhibition rate is mainly due to the strong adsorption capacity of cytosine-L-alanine. In addition, when cytosine -L-alanine was combined with potassium iodide, the corrosion inhibition efficiency was further improved and the cost was also reduced. (3) Biomacromolecule DNA was used as corrosion inhibitor for carbon steel in 1m HC1 solution. The inhibition effect was studied by weightlessness method and electrochemical method. The corrosion inhibition mechanism was explored by adsorption theory, IR XPS and quantization calculation. It was found that the inhibition efficiency reached 92when the concentration of DNA inhibitor was 20mg 1-1. Meanwhile, the adsorption of DNA molecules followed Langermal isotherm adsorption theory, and the IR spectra showed that the structure of DNA molecules changed before and after the film formation. The reason is that the interaction between DNA and metal surface further indicates that the metal surface contains the elements of DNA and forms Fe-N bond and Fe-O bond. The quantum chemical calculation further indicates that the DNA inhibitor molecule provides lone pair electrons to the d orbital of iron atom. Form a solid coordination chemical bond. This study proved the excellent corrosion inhibition performance of low dosage DNA and explained the corresponding corrosion inhibition mechanism.
【學(xué)位授予單位】：西南石油大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TG174.42
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