羧基烷基硫代丁二酸的合成及其缓蚀阻垢机理研究
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摘要
油田进入后期开发后,普遍采用注水采油的工艺,为减轻注采系统的腐蚀和结垢问题,一般采用加入缓蚀阻垢剂的方法。然而适合油田高温高压高矿化度等条件的缓蚀阻垢剂种类较少,并且一般都含有磷。羧基烷基硫代丁二酸是近年来为了满足环保要求而开发的一类新型助剂,其合成报道最早见于1999年法国Elf Atochem S.A.公司申请的专利,然而关于其性能尤其是缓蚀阻垢性能的研究在国内外均为少见。
本论文主要以羧甲基硫代丁二酸和羧乙基硫代丁二酸为研究对象,通过对羧乙基硫代丁二酸合成反应体系进行热力学计算与分析得出适宜的反应温度,通过实验筛选出适宜的溶剂和催化剂,以3-巯基丙酸和马来酸合成了羧乙基硫代丁二酸,以巯基乙酸和马来酸合成了羧甲基硫代丁二酸。适宜的反应条件为:反应物配比为1:1,溶剂为水,催化剂为D301-R,在常压,100℃下进行,产物收率为84%,纯度为90%左右。试验出一种产物提纯的方法,并用1HNMR、IR、熔点测定和碱熔试验等手段对产物进行了表征。
参照行业标准SY/T5673-93和模拟某油田水质两种方法对合成产物的阻垢性能进行了评价,并与几种常用缓蚀阻垢剂的阻垢性能进行了对比。结果表明在模拟油田水质的高温高压高矿化度条件下,100mg/L提纯羧甲基硫代丁二酸的阻垢率达90%,优于POCA、HPMA两种常用缓蚀阻垢剂和羧乙基硫代丁二酸。并考察了浓度、温度、压力和流速等条件对羧甲基硫代丁二酸在模拟某油田水质中的阻垢性能影响。通过羧甲基硫代丁二酸溶解碳酸钙的实验表明,羧甲基硫代丁二酸对钙离子具有螯合作用。对加入不同缓蚀阻垢剂制备的CaSO4垢样和CaCO3垢样进行SEM和XRD分析表明,羧甲基硫代丁二酸的阻CaSO4垢机理主要是使晶格发生畸变作用,阻CaCO3垢机理主要是螯合增溶作用。
参照SY/T5273-2000中常压静态腐蚀速率及缓蚀率测定方法对羧甲基硫代丁二酸的缓蚀性能进行了评价,结果表明100mg/L提纯羧甲基硫代丁二酸对A3钢在模拟某油田水质中的缓蚀率为49.6%。并考察了浓度和温度对羧甲基硫代丁二酸缓蚀性能的影响。通过对A3钢在加入羧甲基硫代丁二酸前后的模拟油田水质进行极化曲线和交流阻抗测试发现,羧甲基硫代丁二酸是一种混合型缓蚀剂,缓蚀机理主要是分子中的S与Fe原子未占据的空d轨道形成配位键,并在金属界面通过界面转化或螯合等作用形成了缓蚀剂吸附膜。
After the advanced stage of development of oilfield, water injection process is commonly adopted. In order to alleviate the problem of scale and corrosion in injection-production system, adding corrosion and scale inhibitor is needed. However, appropriate corrosion and scale inhibitors are rarely used in characters of high temperature, high pressure and high salinity of injection water, and contain phosphorus generally. Caboxyalkylthiosuccinic acids are new kinds of additives developed to meet environmental protection requirements. The synthesis of caboxyalkylthiosuccinic acids were earliest reported by France Elf Atochem S. A. Company in 1999 as a patent. However, Their performances, especially about corrosion and scale inhibitors were rarely researched both at home and abroad.
This paper mainly studied caboxymethylthiosuccinic acid and caboxyethylthiosuccinic acid. Through thermodynamic estimating synthesis of carboxyethylthiosuccinic acid, the appropriate reaction temperature was obtained. Through experiments, the appropriate solution and catalyst were obtained. Eventually, caboxymethylthiosuccinic acid was prepared by mercaptoacetic acid and maleic acid, and carboxyethylthiosuccinic acid was prepared by 3-mercaptopropionic acid and maleic acid. The optimized reaction additions were as follows. Molar ratio of reacant was 1:1, solvent is water, catalyst was resin D301-R, and the reaction was carried at atmospheric pressure and reflux temperature. The yield of product was 84%, and its purity is 90% or so. A purification method was test out, and synthesized products were characterized by 1HNMR, IR, melting point determination and alkali-melting experiment.
Two methods were adopted to evaluate the performances of scale inhibition of synthesized products. One was according to SY/T5673-93, the other was simulating some oilfield conditions. And performances of scale inhibition of some commonly used performances of corrosion and scale inhibition inhibitors and synthesized products were compared. The results showed that under the conditions of high temperature, high pressure and high salinity simulating some oilfield conditions, the scale inhibition rate was reached 90% when using 100mg/L purified caboxymethylthiosuccinic acid, better than commonly used POCA, HPMA and caboxyethylthiosuccinic acid. The influences of concentration, temperature, pressure and flow rate on performances of caboxymethylthiosuccinic acid were investigated. The experiments of caboxymethylthiosuccinic acid dissolving CaCO3 showed caboxymethylthiosuccinic acid had chelating effect of calcium. The scale samples of CaSO4 and CaCO3, prepared by adding different corrosion and scale inhibitors, were analyzed by SEM and XRD. The mechanism of CaSO4 scale inhibition by caboxymethylthiosuccinic acid was to cause distortion of crystal lattice, and the mechanism of CaCO3 scale inhibition by caboxymethylthiosuccinic acid was to cause chelating and solubilization effect.
According to SY/T5273-2000, the corrosion inhibition performance of Caboxymethylthiosuccinic acid to A3 steel in simulated solution was evaluated. The results showed that the corrosion inhibition rate was 49.6% when using 100mg/L purified Caboxymethylthiosuccinic acid. And the influences of concentration and temperature were investigated. Through testing polarization curves and ac impedance of A3 steel in simulated solution before and after adding caboxymethylthiosuccinic acid, it showed that caboxymethylthiosuccinic acid belonged to hybrid type corrosion inhibitor, and its mechanism was mainly the coordination bonds formed by the molecule’s S and the d orbitals of Fe, and forming absorption film on metal surface through interface transform and chelation.
本论文主要以羧甲基硫代丁二酸和羧乙基硫代丁二酸为研究对象,通过对羧乙基硫代丁二酸合成反应体系进行热力学计算与分析得出适宜的反应温度,通过实验筛选出适宜的溶剂和催化剂,以3-巯基丙酸和马来酸合成了羧乙基硫代丁二酸,以巯基乙酸和马来酸合成了羧甲基硫代丁二酸。适宜的反应条件为:反应物配比为1:1,溶剂为水,催化剂为D301-R,在常压,100℃下进行,产物收率为84%,纯度为90%左右。试验出一种产物提纯的方法,并用1HNMR、IR、熔点测定和碱熔试验等手段对产物进行了表征。
参照行业标准SY/T5673-93和模拟某油田水质两种方法对合成产物的阻垢性能进行了评价,并与几种常用缓蚀阻垢剂的阻垢性能进行了对比。结果表明在模拟油田水质的高温高压高矿化度条件下,100mg/L提纯羧甲基硫代丁二酸的阻垢率达90%,优于POCA、HPMA两种常用缓蚀阻垢剂和羧乙基硫代丁二酸。并考察了浓度、温度、压力和流速等条件对羧甲基硫代丁二酸在模拟某油田水质中的阻垢性能影响。通过羧甲基硫代丁二酸溶解碳酸钙的实验表明,羧甲基硫代丁二酸对钙离子具有螯合作用。对加入不同缓蚀阻垢剂制备的CaSO4垢样和CaCO3垢样进行SEM和XRD分析表明,羧甲基硫代丁二酸的阻CaSO4垢机理主要是使晶格发生畸变作用,阻CaCO3垢机理主要是螯合增溶作用。
参照SY/T5273-2000中常压静态腐蚀速率及缓蚀率测定方法对羧甲基硫代丁二酸的缓蚀性能进行了评价,结果表明100mg/L提纯羧甲基硫代丁二酸对A3钢在模拟某油田水质中的缓蚀率为49.6%。并考察了浓度和温度对羧甲基硫代丁二酸缓蚀性能的影响。通过对A3钢在加入羧甲基硫代丁二酸前后的模拟油田水质进行极化曲线和交流阻抗测试发现,羧甲基硫代丁二酸是一种混合型缓蚀剂,缓蚀机理主要是分子中的S与Fe原子未占据的空d轨道形成配位键,并在金属界面通过界面转化或螯合等作用形成了缓蚀剂吸附膜。
After the advanced stage of development of oilfield, water injection process is commonly adopted. In order to alleviate the problem of scale and corrosion in injection-production system, adding corrosion and scale inhibitor is needed. However, appropriate corrosion and scale inhibitors are rarely used in characters of high temperature, high pressure and high salinity of injection water, and contain phosphorus generally. Caboxyalkylthiosuccinic acids are new kinds of additives developed to meet environmental protection requirements. The synthesis of caboxyalkylthiosuccinic acids were earliest reported by France Elf Atochem S. A. Company in 1999 as a patent. However, Their performances, especially about corrosion and scale inhibitors were rarely researched both at home and abroad.
This paper mainly studied caboxymethylthiosuccinic acid and caboxyethylthiosuccinic acid. Through thermodynamic estimating synthesis of carboxyethylthiosuccinic acid, the appropriate reaction temperature was obtained. Through experiments, the appropriate solution and catalyst were obtained. Eventually, caboxymethylthiosuccinic acid was prepared by mercaptoacetic acid and maleic acid, and carboxyethylthiosuccinic acid was prepared by 3-mercaptopropionic acid and maleic acid. The optimized reaction additions were as follows. Molar ratio of reacant was 1:1, solvent is water, catalyst was resin D301-R, and the reaction was carried at atmospheric pressure and reflux temperature. The yield of product was 84%, and its purity is 90% or so. A purification method was test out, and synthesized products were characterized by 1HNMR, IR, melting point determination and alkali-melting experiment.
Two methods were adopted to evaluate the performances of scale inhibition of synthesized products. One was according to SY/T5673-93, the other was simulating some oilfield conditions. And performances of scale inhibition of some commonly used performances of corrosion and scale inhibition inhibitors and synthesized products were compared. The results showed that under the conditions of high temperature, high pressure and high salinity simulating some oilfield conditions, the scale inhibition rate was reached 90% when using 100mg/L purified caboxymethylthiosuccinic acid, better than commonly used POCA, HPMA and caboxyethylthiosuccinic acid. The influences of concentration, temperature, pressure and flow rate on performances of caboxymethylthiosuccinic acid were investigated. The experiments of caboxymethylthiosuccinic acid dissolving CaCO3 showed caboxymethylthiosuccinic acid had chelating effect of calcium. The scale samples of CaSO4 and CaCO3, prepared by adding different corrosion and scale inhibitors, were analyzed by SEM and XRD. The mechanism of CaSO4 scale inhibition by caboxymethylthiosuccinic acid was to cause distortion of crystal lattice, and the mechanism of CaCO3 scale inhibition by caboxymethylthiosuccinic acid was to cause chelating and solubilization effect.
According to SY/T5273-2000, the corrosion inhibition performance of Caboxymethylthiosuccinic acid to A3 steel in simulated solution was evaluated. The results showed that the corrosion inhibition rate was 49.6% when using 100mg/L purified Caboxymethylthiosuccinic acid. And the influences of concentration and temperature were investigated. Through testing polarization curves and ac impedance of A3 steel in simulated solution before and after adding caboxymethylthiosuccinic acid, it showed that caboxymethylthiosuccinic acid belonged to hybrid type corrosion inhibitor, and its mechanism was mainly the coordination bonds formed by the molecule’s S and the d orbitals of Fe, and forming absorption film on metal surface through interface transform and chelation.
引文
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