腐植酸增值尿素的多谱学分子结构表征

doi:10.3964/j.issn.1000-0593(2022)08-2610-06

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摘要：尿素生产过程中加入腐植酸生产腐植酸增值尿素，可以有效延缓尿素水解，提高作物产量与氮肥利用效率，然而在此过程中腐植酸（HA）与尿素（U）主要发生什么反应还未见报道。利用风化煤源HA生产含腐植酸5%，10%及20%的腐植酸增值尿素（HAU5，HAU10及HAU20），采集并分析了HAU5，HAU10，HAU20及U的红外谱图及其二阶导数谱图，用XPS与O(1s)NEXAFS分别对HAU20，HA及U进行表征；通过无水乙醇溶解HAU20的方式去除了HAU20中的尿素，并利用FTIR与XPS对醇不溶物（UHA）进行表征。结果表明：（1）FTIR原谱图及二阶导数谱图表明，腐植酸增值尿素伯胺C—N振动强度低于普通尿素，且振动强度随着HA添加量的提高而降低，XPS N(1s)与O(1s)NEXAFS检测到HAU20中分别存在较多仲胺氮与非羰基氧，且FTIR发现UHA酰胺特征明显，表明腐植酸增值尿素制备过程中HA与U发生了反应。（2）XPS C(1s)表明，HAU20与UHA羧基碳比例少于HA，FTIR结果表明，UHA中不存在HA中检测到的羧酸C—O—H面内弯曲振动，羧基C═O伸缩振动位置发生偏移且伯胺氮特征明显，表明腐植酸的羧基参与了HA与U的反应，且反应方式为腐植酸羧基C—OH化学键断裂，与尿素胺基结合，脱水形成R—CO—NH—CO—NH₂。因此，采用光谱分析明晰了腐植酸增值尿素制备过程中，腐植酸与尿素的主要反应方式，这将为腐植酸增效尿素机理揭示以及增值尿素研制提供基础资料。

关键词：腐植酸增值尿素；腐植酸；反应方式；傅里叶变换红外光谱；X射线光电子能谱；X射线近边吸收光谱

Abstract：Humic acid-enhanced urea (HAU) can be produced by adding humic acid (HA) into melted urea during urea production. Field studies have proved that HAU showed a better urea hydrolysis rate, crop yield, and nitrogen use efficiency than normal urea (U). However, the main reaction between HA and U during the production of HAU has not been reported yet. In this study, HA, derived from weathered coal, was used to produce HAU, and the added amount of humic acid was 5%, 10%, and 20%, respectively (named HAU5, HAU10, HAU20). The paper collected and analyzed the infrared spectra and their second derivative infrared spectra of HAU5, HAU10, HAU20, and U. HAU20 and U were characterized using X-ray photoelectron spectroscopy (XPS), and oxygen 1s near-edge X-ray absorption fine structure (NEXAFS). The urea in HAU20 was removed by dissolving HAU20 with absolute ethanol, and FTIR and XPS characterized the residue(UHA). The result showed that: (1) FTIR spectra and the second derivative spectra showed that the vibration intensity of primary amine C—N in HAU was lower than that in U, and the vibration intensity decreased with the increase of the addition amount humic acid. There were more secondary amine nitrogen, and non-carbonyl oxygens in HAU20 were separated from the XPS N(1s) spectra and O(1s) NEXAFS spectra, respectively, and prominent amide characteristics were shown from the result of FTIR spectra for UHA, which indicated that HA reacted with urea during the HAU production. (2) the percentage of carboxyl carbon in HAU20 or UHA was lower than in HA. FTIR spectra showed that C—O—H in-plane bending vibration from carboxylic acid detected in HA did not exist in UHA, the C═O stretching vibration position from carboxyl groups in UHA was shifted, and the characteristics of primary amine nitrogen for UHA were obvious. The above indicated that the carboxyl groups of HA participated in the reaction of HA and urea. The structure for R—CO—NH—CO—NH₂ in HAU will be produced after the dehydration reaction between the carboxyl group of HA and the amide group of urea. Therefore, the results from the spectral analysis used in this study clarified the main reaction modes of humic acid and urea during the production of HAU, which will provide basic information for the reveal of the synergistic mechanism of HAU and the development of value-added urea.

Key words：Humic acid-enhanced urea;Humic acid;Reactive mode;Fourier Transform Infrared Spectroscopy;X-ray Photoemission Spectroscopy; X-ray Near-edge Absorption Spectroscopy

收稿日期: 2021-07-30 修订日期: 2021-09-02

中图分类号:

TQ441.4

基金资助: 国家现代农业产业技术体系建设专项（CARS-03），国家“十三五”重点研发计划项目（2016YFD0200402）资助

通讯作者: 赵秉强 E-mail: zhaobingqiang@caas.cn

作者简介: 景建元，1990年生，中国农业科学院农业资源与农业区划研究所博士研究生 e-mail: jyjing90@163.com

引用本文:

景建元，袁亮，张水勤，李燕婷，赵秉强. 腐植酸增值尿素的多谱学分子结构表征[J]. 光谱学与光谱分析, 2022, 42(08): 2610-2615.
JING Jian-yuan, YUAN Liang, ZHANG Shui-qin, LI Yan-ting, ZHAO Bing-qiang. Multispectral Structural Characterization of Humic Acid-Enhanced Urea. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(08): 2610-2615.

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[1] Li Y Y, Huang L H, Zhang H, et al. Sustainability, 2017, 9(1): 132.
[2] Van Vuuren J A J, Claassens A S. Communications in Soil Science and Plant Analysis, 2009, 40(1-6): 576.
[3] LI Jun, YUAN Liang, ZHAO Bing-qiang, et al(李军, 袁亮, 赵秉强, 等). Plant Nutrition and Fertilizer Science(植物营养与肥料学报), 2017, 23(2): 524.
[4] Zhang S Q, Yuan L, Li W, et al. Journal of Integrative Agriculture, 2019, 18(3): 178.
[5] LIU Yan-li, DING Fang-jun, GU Duan-yin, et al(刘艳丽, 丁方军, 谷端银, 等). Soil(土壤), 2015, 47(1): 42.
[6] LIU Hong-en, ZHANG Sheng-nan, LIU Shi-liang, et al(刘红恩, 张胜男, 刘世亮, 等). Acta Agriculturae Boreali-Occidentalis Sinica(西北农业学报), 2018, 27(7): 944.
[7] YUAN Liang, ZHAO Bing-qiang, LIN Zhi-an, et al(袁亮, 赵秉强, 林治安, 等). Plant Nutrition and Fertilizer Science(植物营养与肥料学报), 2014, 20(3): 620.
[8] ZHANG Shui-qin, YUAN Liang, LI Wei, et al(张水勤, 袁亮, 李伟, 等). Plant Nutrition and Fertilizer Science(植物营养与肥料学报), 2017, 23(5): 1207.
[9] LIU Zeng-bing, ZHAO Bing-qiang, LIN Zhi-an(刘增兵, 赵秉强, 林治安). Plant Nutrition and Fertilizer Science(植物营养与肥料学报), 2010, 16(1): 208.
[10] LIANG Zong-cun, CHENG Shao-xin(梁宗存, 成绍鑫). Humic Acid(腐植酸), 1997, 2(2): 1.
[11] Saha B K, Rose M T, Wong V, et al. Science of the Total Environment, 2017, 601-602: 1496.
[12] LIANG Zong-cun, CHENG Shao-xin, WU Li-ping(梁宗存, 成绍鑫, 武丽萍). Journal of Fuel Chemistry and Technology(燃料化学学报), 1999, 27(2): 81.
[13] Zhang S Q, Yuan L, Li W, et al. Chemosphere, 2017, 166: 334.
[14] WENG Shi-fu(翁诗甫). Fourier Transform Infrared Spectroscopy(傅里叶变换红外光谱分析). 3rd ed.(第3版). Beijing: Chemical Industry Press(北京: 化学工业出版社), 2016. 490.
[15] Ritchie J D, Perdue E M. Organic Geochemistry, 2008, 39(6): 783.
[16] Wang C, Chen W, Yang L, et al. Science of the Total Environment, 2019, 693: 133455.
[17] Doskočil L, Burdíková-Szewieczková J, Enev V, et al. Fuel, 2018, 213: 123.
[18] Kim K S, Zhu P Y, Li N, et al. Carbon, 2011, 49(5): 1745.