CN113549922A - 一种基于白藜芦醇的碳钢酸洗缓蚀剂 - Google Patents
一种基于白藜芦醇的碳钢酸洗缓蚀剂 Download PDFInfo
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Abstract
本发明涉及了一种化学修饰的白藜芦醇缓蚀剂,结构式如图1所示,其最佳用量为400mg/L,并用电化学法和表面分析法对其抗腐蚀性能进行了测试。所述缓蚀剂的原料简单易得、价格低廉与有机缓蚀剂相比,低毒无害,符合环境友好缓蚀剂的发展趋势。该白藜芦醇衍生物缓蚀剂持续作用能力强,具有良好的缓蚀性能,不仅可以满足1mol/L盐酸溶液中对碳钢缓蚀的要求,还可以避免现有的有机缓蚀剂引起的环境污染问题,具有广阔的市场应用前景。
Description
技术领域
本发明涉及缓蚀剂领域,具体涉及一种基于白藜芦醇的碳钢酸洗缓蚀剂。
背景技术
碳钢作为一种重要的金属材料,广泛应用于建筑、交通、化工、海洋等工业领域。然而,碳钢材料在化学除垢、清洗和酸洗的酸性介质中极易腐蚀(Zhang,W.,etal.Carbohydrate Polymers 2020,238,116216;Obot,I.B.,et al.Journal of MolecularLiquids 2109,277,749)。在各种防腐技术中,化学缓蚀剂的应用被认为是最经济实用的金属防腐方法。尽管如此,传统使用的缓蚀剂大多有毒、昂贵、对环境和生物有害,不能满足工业应用的要求。基于环境保护和可持续发展的战略需要,开发环保型缓蚀剂对钢材的推广应用至关重要。尽管如此,与化学缓蚀剂相比,植物缓蚀剂的研究相对滞后,几乎没有对提取物进行分子修饰以提高其防腐性能和缓蚀机理的研究。基于植物材料的高效环保缓蚀剂的开发仍是一项具有挑战性的工作。
白藜芦醇是虎杖、葡萄等植物中存在的一种天然非黄酮类多酚类物质。广泛应用于医药、食品、保健品、化妆品等领域,是一种具有良好发展潜力的先导化合物(Latruffe,N.,et al.Diseases 2018,6,110;Nawaz,W.,et al.Nutrients 2017,9,1188)。然而,关于白藜芦醇及其衍生物在盐酸溶液中对碳钢的缓蚀作用的研究还很少。白藜芦醇中的O原子和-OH基团具有电负性,为碳钢表面的相互作用提供了必要的活性中心,可作为一种有效的缓蚀剂。为了验证这一假说以便更好地利用植物资源,白藜芦醇被化学修饰为白藜芦醇-3-O-β-D-吡喃葡萄糖苷(R3GP),以提高其溶解性以及与金属离子的络合能力。
本发明将有助于更好地理解结构单元所控制的元素,并为新型酸性碳钢白藜芦醇缓蚀剂的设计提供新的思路。
发明内容
针对现有技术存在的上述不足,本发明的目的在于提供一种基于白藜芦醇的碳钢酸洗缓蚀剂,解决现有缓蚀剂存在毒性大、工艺复杂、易对环境造成二次污染等问题。本发明采用白藜芦醇-3-O-β-D-吡喃葡萄糖苷(R3GP)作为碳钢酸洗缓蚀剂,所述R3GP化合物结构如图1。
为达到上述目的,本发明采用如下技术方案:一种基于白藜芦醇的碳钢酸洗缓蚀剂,所述碳钢酸洗缓蚀剂为白藜芦醇-3-O-β-D-吡喃葡萄糖苷(R3GP)。
优选的,所述碳钢酸洗缓蚀剂中白藜芦醇-3-O-β-D-吡喃葡萄糖苷的浓度为200mg/L-500mg/L,进一步优选为300-400mg/L。
优选的,所述碳钢酸洗缓蚀剂中酸洗溶液为1mol/L HCl水溶液。
优选的,所述碳钢酸洗缓蚀剂用于中温酸性介质中的缓蚀剂,所述中温是指温度为298K-318K,进一步优选为298K-308K。实验结果表明R3GP是一种温度依赖型缓蚀剂,碳钢在非抑制和抑制溶液中的v值均随温度的升高而增大。造成这种情况的可能原因是,当温度较高时,R3GP在腐蚀介质中活动,不易粘附在钢表面。
优选的,所述白藜芦醇-3-O-β-D-吡喃葡萄糖苷由白藜芦醇与α-溴三乙酰葡萄糖的糖基化反应,并用甲醇钠水解除去乙酰基,得到R3GP。
根据本发明的另一个方面,本发明提供了一种基于白藜芦醇的碳钢酸洗缓蚀剂缓蚀性能的评价方法,包括如下步骤:
(1)白藜芦醇与α-溴三乙酰葡萄糖的糖基化反应,并用甲醇钠水解除去乙酰基,得到R3GP;
(2)称取10~40mg步骤(1)得到R3GP缓蚀剂充分溶解于2mL的聚乙二醇(0.5mL)和酸洗溶液(1.5mL),然后用酸洗液定容至100mL即可制得测试溶液;
(3)室温下,在步骤(2)制备好的腐蚀溶液中的进行失重挂片实验,评价缓蚀性能;
(4)室温下,用暴露表面积为0.5cm2的碳钢试样作为工作电极,测量加缓蚀剂前后碳钢电极在盐酸溶液中的Tafel极化曲线和交流阻抗数据,评价缓蚀性能;
优选的,所述酸洗溶液为1mol/L HCl水溶液。
进一步,所述温度为室温(~30℃),采用静态法进行失重和电化学实验。
与现有技术相比,本发明具有以下积极有益效果
(1)本发明的R3GP原料简单易得,成本低,易于实现工业化生产。而且对环境低毒无害,为制备绿色环保可持续发展的缓蚀剂提供了新的思路。
(2)本发明用于碳钢及其产品的清洗,可有效抑制金属基体在酸中的有害腐蚀以及酸液的过度消耗,与目前常用的缓蚀剂相比,具用量低、绿色环保、持续作用能力强的突出优点,可反复使用。
附图说明
图1为白藜芦醇-3-O-β-D-吡喃葡萄糖苷的结构。
图2是实施例1中碳钢在1M HCl溶液加入不同浓度白藜芦醇、R3GP缓蚀剂的Tafel极化曲线图谱。
图3是实施例3中碳钢在1M HCl溶液中是否添加R3GP缓蚀剂的Tafel极化曲线对比图谱。
图4是实施例3中碳钢在1M HCl溶液中是否添加R3GP缓蚀剂的Nyquist阻抗对比图谱。
具体实施方式
实施例1
(1)1M HCl水溶液分别配制浓度为200mg/L、400mg/L的白藜芦醇和R3GP测试溶液100mL,配制过程加入0.5mL的聚乙二醇(Mn 400)增加溶解性。
(2)以裸露面积为0.5cm2碳钢棒为工作电极,饱和甘汞电极作为参比电极,铂片电极为对电极,用CHI760E电化学工作站测量动电位极化曲线:扫描速度为1mV/s,扫描区间为-700~-250mV。
图2是实施例1中碳钢在1M HCl溶液加入不同浓度白藜芦醇、R3GP缓蚀剂的Tafel极化曲线图谱。由图2可以看出相同浓度下,R3GP的缓蚀效率明显高于白藜芦醇,在400mg/LR3GP缓蚀效率为90.33%,而白藜芦醇缓蚀效率仅为65.27%。说明白藜芦醇化学修饰接枝糖苷官能团后能大大提高缓蚀能力,取得了意料不到的技术效果。
实施例2
(1)用1M HCl水溶液分别配制浓度为100mg/L、200mg/L、300mg/L、400mg/L的R3GP测试溶液100mL,配制过程加入0.5mL的聚乙二醇(Mn400)增加溶解性。
(2)在室温条件下进行挂片失重实验。根据公式:S=(K0-K1)/K0计算缓蚀效率,其中K0为不加缓蚀剂的腐蚀率,K1为加缓蚀剂的腐蚀率。
实施例2中用失重法获得的R3GP在酸性溶液中对碳钢的缓蚀效率如下表1所示:
表1碳钢在不同浓度R3GP时的缓蚀效率结果
缓蚀剂浓度(mg/L) | 缓蚀效率(%) |
100 | 73.56 |
200 | 84.65 |
300 | 90.02 |
400 | 92.89 |
由表1中数据可知,浓度在400mg/L,缓蚀效率便可达到92.89%,说明R3GP能有效抑制碳钢在酸性溶液中的腐蚀。
实施例3
(1)用1M HCl水溶液分别配制浓度为100mg/L、200mg/L、300mg/L、400mg/L的R3GP测试溶液100mL,配制过程加入0.5mL的聚乙二醇(Mn400)增加溶解性。
(2)以裸露面积为0.5cm2碳钢棒为工作电极,饱和甘汞电极作为参比电极,铂片电极为对电极,利用CHI760e电化学工作站测量碳钢电极在1M HCl中含不同浓度R3GP缓蚀剂的Tafel极化曲线和电化学阻抗谱,评价其缓蚀性能。
图3是实施例3中碳钢在1M HCl溶液中不加和加入缓蚀剂的Tafel极化曲线图谱。图4是实施例3中碳钢在1M HCl溶液中不加和加入缓蚀剂的Nyquist阻抗图谱。
由图3和图4中的电化学腐蚀特性研究可以看出,随着R3GP缓蚀剂浓度的增加,缓蚀效率增大,且浓度超过300mg/L后,缓蚀效率增加不明显,此时不宜再增大浓度。此外,极化曲线结果与电化学阻抗结果相一致,均证明了R3GP缓蚀剂的良好缓蚀能力。
实施例4
(1)用1M HCl水溶液配制浓度为400mg/L的R3GP测试溶液100mL,配制过程加入0.5mL的聚乙二醇(Mn 400)增加溶解性。
(2)在在298K至328K的不同温度下进行挂片失重实验。根据公式:S=(K0-K1)/K0计算缓蚀效率,其中K0为不加缓蚀剂的腐蚀率,K1为加缓蚀剂的腐蚀率。
实施例4中用失重法获得的R3GP在不同温度下对碳钢的缓蚀效率如下表2所示:
表2 R3GP在400mg/L时在不同温度下对碳钢的缓蚀效率结果
T(K) | v<sub>HC1</sub>(mg cm<sup>-2</sup>h<sup>-1</sup>) | v<sub>R3GP</sub>(mg cm<sup>-2</sup>h<sup>-1</sup>) | η<sub>w</sub> |
298 | 10.41 | 0.74 | 92.89 |
308 | 12.54 | 1.17 | 90.67 |
318 | 16.88 | 2.21 | 86.91 |
328 | 27.12 | 4.72 | 82.60 |
在表2中,碳钢在非抑制和抑制溶液中的v值均随温度的升高而增大。造成这种情况的可能原因是,当温度较高时,R3GP在腐蚀介质中活动,不易粘附在钢表面。也就是说,R3GP是一种温度依赖型缓蚀剂,R3GP可以作为中温酸性介质中的缓蚀剂。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种基于白藜芦醇的碳钢酸洗缓蚀剂,其特征在于:所述碳钢酸洗缓蚀剂包含白藜芦醇-3-O-β-D-吡喃葡萄糖苷。
2.根据权利要求1所述的碳钢酸洗缓蚀剂,其特征在于:所述碳钢酸洗缓蚀剂中白藜芦醇-3-O-β-D-吡喃葡萄糖苷的浓度为200mg/L-500mg/L。
3.根据权利要求2所述的碳钢酸洗缓蚀剂,其特征在于:所述碳钢酸洗缓蚀剂中白藜芦醇-3-O-β-D-吡喃葡萄糖苷的浓度为300-400mg/L。
4.根据权利要求1所述的碳钢酸洗缓蚀剂,其特征在于:所述碳钢酸洗缓蚀剂用于中温酸性介质中的缓蚀剂,所述中温是指温度为298K-318K。
5.根据权利要求4所述的碳钢酸洗缓蚀剂,其特征在于:所述碳钢酸洗缓蚀剂用于中温酸性介质中的缓蚀剂,所述中温是指温度为298K-308K。
6.根据权利要求4所述的碳钢酸洗缓蚀剂,其特征在于:所述碳钢酸洗缓蚀剂中酸洗溶液为1mol/L HCl水溶液。
7.一种权利要求1所述的基于白藜芦醇的碳钢酸洗缓蚀剂缓蚀性能的评价方法,包括如下步骤:
(1)白藜芦醇与α-溴三乙酰葡萄糖的糖基化反应,并用甲醇钠水解除去乙酰基,得到R3GP;
(2)称取10~40mg步骤(1)得到R3GP充分溶解于0.5mL聚乙二醇和1.5mL酸洗溶液中,然后用酸洗液定容至100mL即可制得测试溶液;
(3)室温下,在步骤(2)制备好的腐蚀溶液中的进行失重挂片实验,评价缓蚀性能;
(4)室温下,用暴露表面积为0.5cm2的碳钢试样作为工作电极,测量加缓蚀剂前后碳钢电极在盐酸溶液中的Tafel极化曲线和交流阻抗数据,评价缓蚀性能。
8.根据权利要求7所述的方法,其特征在于:所述酸洗溶液为1mol/L HCl水溶液。
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