生物炭/地聚物复合膜的制备及其对四环素的去除

doi:10.16085/j.issn.1000-6613.2021-0127

摘要/Abstract

摘要：

以碱木质素、偏高岭土、矿渣为原料，通过原位炭化同步自活化的方法制备了一种低成本、易回收、绿色无污染的生物炭/地聚物复合膜（BC/GM）用于催化H₂O₂产生?OH以降解水中的四环素。通过SEM、XRD、FTIR、XPS等一系列的表征手段分析了BC/GM的形貌结构和理化性质，并且探究了水玻璃模数、碱木质素溶液添加量、煅烧温度对BC/GM催化H₂O₂降解盐酸四环素效率的影响。结果表明，地聚物无机膜（GM）不仅充当了一种便于生物炭回收利用的多孔载体，防止生物质前体直接炭化结焦，而且有助于碱木质素前体在原位炭化过程中实现同步自活化；在水玻璃模数为1.2、碱木质素溶液添加量为0.2 mL、煅烧温度为600℃时，BC/GM催化H₂O₂降解盐酸四环素的去除率达到了92.55%，比纯生物炭作为催化剂时提升了近40%。BC/GM具有更高的比表面积和更丰富的含氧官能团，有助于催化H₂O₂产生?OH，从而实现盐酸四环素的高效降解。

关键词: 生物炭, 地质聚合物, 盐酸四环素, 催化降解, 失活

Abstract:

A low-cost, easy-to-recycle, green and pollution-free biochar/geopolymer composite film (BC/GM) was prepared by in-situ synchronous carbonization and self-activation with alkali lignin, metakaolin and slag for the catalytic degradation of tetracycline antibiotics in water. The morphology and physical and chemical properties of BC/GM were analyzed by SEM, XRD, FTIR and XPS. The effects of water glass modulus, alkali lignin content and calcination temperature on the degradation efficiency of tetracycline hydrochloride by H₂O₂ were investigated. The results showed that the geopolymer inorganic film (GM) not only acted as a porous carrier to facilitate the recycling of biochar and prevent the biomass precursors from direct carbonization and coking , but also helped to realize synchronous self-activation of alkali lignin precursor in the process of in-situ carbonization. When the water glass modulus was 1.2, the removal rate of alkali lignin was 0.2mL and the calcination temperature was 600℃, the removal rate of H₂O₂ catalyzed degradation of tetracycline hydrochloride by BC/GM reaches 92.55%, which was 40% higher than that of biochar. The graphitized carbon in BC/GM had a porous structure, which contributes to the generation of ?OH, and eventually realized the efficient degradation of tetracycline hydrochloride.

Key words: biochar, geopolymer, tetracycline hydrochloride, catalytic degradation, deactivation

中图分类号:

TQ129

黄嘉绮, 葛圆圆, 李志礼, 王艺频, 崔学民. 生物炭/地聚物复合膜的制备及其对四环素的去除[J]. 化工进展, 2022, 41(1): 427-434.

HUANG Jiaqi, GE Yuanyuan, LI Zhili, WANG Yipin, CUI Xuemin. Preparation of biochar/geopolymer composite film and its removal of tetracycline[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 427-434.

图/表 10

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水玻璃模数	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
1.1	28.34±1.7	0.061	10.59
1.2	38.13±2.2	0.137	17.49
1.3	29.10±0.9	0.091	12.75
1.4	22.93±2.5	0.066	11.65
1.5	26.38±2.1	0.080	12.38

水玻璃模数	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
1.1	28.34±1.7	0.061	10.59
1.2	38.13±2.2	0.137	17.49
1.3	29.10±0.9	0.091	12.75
1.4	22.93±2.5	0.066	11.65
1.5	26.38±2.1	0.080	12.38

煅烧温度/℃	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
400	16.41±0.9	0.080	19.80
500	20.62±2.0	0.066	13.19
600	38.13±2.2	0.137	17.49
700	23.98±1.4	0.054	9.36
800	8.54±2.5	0.013	6.72

煅烧温度/℃	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
400	16.41±0.9	0.080	19.80
500	20.62±2.0	0.066	13.19
600	38.13±2.2	0.137	17.49
700	23.98±1.4	0.054	9.36
800	8.54±2.5	0.013	6.72

样品	结合能/eV	C 1s键合状态	含量/%
BC	284.6	C sp²	78.1
	286.1	C=O	7.69
	288.5	O—C=O	14.21
BC/GM	284.6	C sp²	68.02
	286.1	C=O	23.89
	288.6	O—C=O	8.09