高大毛壳对硝化纤维素的降氮机理

doi:10.12382/bgxb.2022.0832

摘要/Abstract

摘要：

针对废旧火药存在严重的安全隐患问题,通过对硝化纤维素(Nitrocellulose,NC)生产的废液处理池及其周边进行采样、富集、驯化和分离纯化,获得5株能够降低NC含氮量的微生物,并对其中降氮效果最佳的高大毛壳进行时间优化实验,发现随着时间的延长,NC含氮量可从13.06% 降至10.83%,X射线光电子能谱结果显示NC表面氮元素含量逐渐降低;利用傅里叶变换红外光谱、显微共聚焦拉曼仪和凝胶渗透色谱仪对NC分子结构和分子量进行表征,红外光谱表明高大毛壳与O—NO₂发生水解反应,导致NC在3400cm^-1左右的—OH峰强逐渐增大,拉曼光谱图显示NC含能基团(O—NO₂)的强度发生了显著降低,同时通过凝胶色谱发现,高大毛壳可使NC的数均分子质量和重均分子质量分别降低2.34%和6.40%。为进一步确定作用于NC的生物酶,利用胞外酶、胞内酶的分离以及硫酸铵梯度沉淀实验,证明0~30%硫酸铵沉淀的胞外酶能够有效降低NC的含氮量;高大毛壳对降低NC含氮量的显著作用,使其在废旧火药的再利用、高渐增发射药的生物脱硝等方面具有广阔的应用前景。

关键词: 硝化纤维素, 高大毛壳, 含氮量, 分子结构, 生物脱硝

Abstract:

In view of the serious potential safety problems of waste propellants, five microorganisms that can reduce the nitrogen content of nitrocellulose (NC) are obtained by sampling, enriching, domesticating, separating and purificating near and around the wastewater treatment tank of nitrocellulose production. The time optimization experiment was carried out on the chaetomium elatum which has the best denitrification effect among them. It is found that the nitrogen content of NC could be reduced from 13.06% to 10.83% over time, and the X-ray photoelectron spectroscopy(XPS) results show that the content of N element on the surface of NC gradually decreases. Fourier Transform infrared spectroscopy (FT-IR), inVia Raman microscope (Raman) and gel permeation chromatography (GPC) are used to characterize the structure and molecular weight of NC. The infrared spectrum shows that the —OH peak intensity of NC at about 3400cm^-1 is gradually increased because the hydrolysis of chaetomium elatum and O—NO₂ occurs and the Raman spectrum shows that the intensity of NC energetic groups (O—NO₂) decreases significantly. At the same time, it is found by GPC that the number-average molecular weight and weight-average molecular weight of NC could be reduced by 2.34% and 6.40%, respectively, due to chaetomium elatum. In order to further determine the biological enzymes acting on NC, the separation of extracellular enzymes and intracellular enzymes, and ammonium sulfate gradient precipitation experiments proved that the extracellular enzymes precipitated by 0-30% (NH₄)₂SO₄ could effectively reduce the nitrogen content of NC. The significant effect of chaetomium elatum on reducing the nitrogen content of NC makes it have broad application prospects in the reuse of waste military NC and the biological denitrification of propellants.

Key words: nitrocellulose, chaetomium elatum, nitrogen content, molecular structure, biological denitrification

中图分类号:

TQ562

黄娟, 薛会会, 张阿磊, 陈可泉, 周杰, 丁亚军, 肖忠良. 高大毛壳对硝化纤维素的降氮机理[J]. 兵工学报, 2024, 45(3): 875-884.

HUANG Juan, XUE Huihui, ZHANG Alei, CHEN Kequan, ZHOU Jie, DING Yajun, XIAO Zhongliang. Denitrification Mechanism of Investigation Chaetomium Elatum on Nitrocellulose[J]. Acta Armamentarii, 2024, 45(3): 875-884.

图/表 11

图1 NC与微生物的共培养反应和重提过程

Fig.1 Co-culture reaction and reextraction process of NC and microorganism

图2 NC脱硝微生物

Fig.2 Denitrification microorganisms for NC

图3 微生物处理NC的含氮量变化

Fig.3 Changes of nitrogen content in NC treated by microorganisms

图4 高大毛壳脱硝NC的全谱图

Fig.4 The full-scale XPS survey spectra of NC

图5 高大毛壳不同反硝化程度下NC的N 1s区域高分辨率XPS曲线

Fig.5 The high resolution XPS analysis curves of NC obtained in the areas of N 1s at different degrees of denitrification by chaetomium elatum

图6 高大毛壳脱硝前后NC的红外光谱图

Fig.6 Infrared spectra of NC before and after denitrification by chaetomium elatum

图7 高大毛壳脱硝前后NC的Raman光谱图

Fig.7 Raman spectra of NC before and after denitrification by chaetomium elatum

图8 高大毛壳对NC不同程度反硝化的Raman光谱线扫图

Fig.8 Raman line sweep spectra of NC with different denitrification degrees of chaetomium elatum

图9 高大毛壳脱硝前后NC相对分子质量分布的变化

Fig.9 Changes of relative molecular mass distribution of nitrocellulose before and after denitrification by chaetomium elatum

图10 胞内酶与胞外酶对NC的脱硝

Fig.10 Denitrification of NC by intracellular and extracellular enzymes

图11 硫酸铵分级沉淀蛋白质对NC的降氮

Fig.11 Denitrification degree of NC by protein precipitated by ammonium sulfate

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