水热碳化温度对污泥有机氮固液相迁移转化路径影响研究

doi:10.11949/0438-1157.20220832

化工学报 ›› 2022, Vol. 73 ›› Issue (11): 5220-5229.DOI: 10.11949/0438-1157.20220832

• 生物质与有机固废热化学转化专栏 • 上一篇下一篇

水热碳化温度对污泥有机氮固液相迁移转化路径影响研究

成珊¹(), 罗睿², 田红¹, 王振琦³, 黄经春³, 乔瑜³()

^1.长沙理工大学能源与动力工程学院，湖南长沙 410076
^2.湖南中冶长天节能环保技术有限公司，湖南长沙 410205
^3.华中科技大学煤燃烧国家重点实验室，湖北武汉 430074

收稿日期:2022-06-15 修回日期:2022-09-01 出版日期:2022-11-05 发布日期:2022-12-06
通讯作者: 乔瑜
作者简介:成珊（1987—），女，博士，讲师，shancheng@csust.edu.cn
基金资助:
国家自然科学基金项目(52006016);湖南省自然科学基金项目(2021JJ40573);湖南省教育厅科学研究项目(18C0023);长沙市自然科学基金项目(kq2014104);煤燃烧国家重点实验室（华中科技大学）开放基金项目(FSKLCCA2114);“可再生能源电力技术”湖南省重点实验室开放基金项目(2019ZNDL005);华中科技大学自主创新研究基金学科交叉专项(2172019kfyXKJC002)

Effect of hydrothermal carbonization temperature on transformation path of organic nitrogen in sludge

Shan CHENG¹(), Rui LUO², Hong TIAN¹, Zhenqi WANG³, Jingchun HUANG³, Yu QIAO³()

^1.School of Energy and Power Engineering, Changsha University of Science and Technology, Changsha 410076, Hunan, China
^2.Hunan Zhongye Changtian Energy Conservation and Environmental Protection Company Limited, Changsha 410205, Hunan, China
^3.State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2022-06-15 Revised:2022-09-01 Online:2022-11-05 Published:2022-12-06
Contact: Yu QIAO

摘要/Abstract

摘要：

利用污泥与大豆蛋白研究了不同温度下水热碳化过程中有机氮迁移转化路径和规律，氮元素全过程平衡分析结果表明随着水热碳化温度由150℃升高至240℃，焦炭中残留的氮占污泥总氮比例由68.9%下降至29.8%，焦油中由4.2%升高至35.0%，水溶液中则由18.8%提升至30.4%，含氮气体释放量低于0.02%。原污泥中蛋白质主要转化路径为通过分解转化和水解反应依次产生焦油态胺类、水溶性有机氮、NH₃和NH $4 +$ ，反应程度随温度上升而加深。胺类在高温下通过美拉德、曼尼希等反应形成较稳定的吡咯、吡啶等杂环氮。焦炭中残留的含氮物质包括未分解的蛋白质、杂环氮以及季氮和少量腈类；焦油中的含氮物质为胺类氮和杂环氮，无腈类氮出现；水溶液中以有机氮为主，其次有大量NH $4 +$ ；释放的含氮气体主要为HCN。

关键词: 污泥, 再生能源, 蛋白质, 水热, 转化

Abstract:

The migration and transformation path and characteristics of organic nitrogen during hydrothermal carbonization at different temperature were studied by using sludge and soybean protein. The nitrogen balance of the whole process showed that with the hydrothermal carbonization temperature increase from 150℃ to 240℃, the ratio of residual nitrogen in hydrochar to total nitrogen in sludge decreased from 68.9% to 29.8%. Proportion of nitrogen transferred to tar and aqueous solution increased from 4.2% to 35.0% and 18.8% to 30.4%, respectively, while the nitrogen in gas only counted for less than 0.02%. The main transformation path of proteins in sludge was to produce amines in tar, then water-soluble organic nitrogen, NH₃ and NH $4 +$ successively through decompose and hydrolysis. The reaction degree increased with the increase of temperature. More stable heterocyclic nitrogen compounds such as pyrrole and pyridine were formed through Maillard, Mannich and other reactions at high temperature. The residual nitrogen-containing substances in hydrochar include undecomposed protein, heterocyclic nitrogen, quaternary nitrogen and a small amount of nitrile. Nitrogen species in tar were amine and heterocyclic nitrogen compounds, while nitrile is not presented. The aqueous solution is dominated by organic nitrogen, followed by a large amount of NH $4 +$ . The nitrogen-containing gas released is mainly HCN.

Key words: sludge, renewable energy, protein, hydrothermal, transformation

中图分类号:

TK 6

成珊, 罗睿, 田红, 王振琦, 黄经春, 乔瑜. 水热碳化温度对污泥有机氮固液相迁移转化路径影响研究[J]. 化工学报, 2022, 73(11): 5220-5229.

Shan CHENG, Rui LUO, Hong TIAN, Zhenqi WANG, Jingchun HUANG, Yu QIAO. Effect of hydrothermal carbonization temperature on transformation path of organic nitrogen in sludge[J]. CIESC Journal, 2022, 73(11): 5220-5229.

图/表 15

表1 污泥样品基础特性

Table 1 Basic characteristics of sewage sludge sample

工业分析/%

(质量,干燥基)

图1 水热碳化实验系统

Fig.1 Hydrothermal carbonation experimental apparatus

图2 水热碳化产物收集方法（污泥-N、焦炭-N、焦油-N、水溶-N及气态-N分别表示污泥、焦炭、焦油、水溶液及气体中含氮物质）

Fig.2 Hydrothermal carbonation products collection procedure (sludge-N, hydrochar-N, oil-N, aqueous-N and gas-N represent nitrogen-containing species in sludge, hydrochar, oil, aqueous solution and gas, respectively)

图3 固体产物中有机物与氮残留率

Fig.3 Organic matter and nitrogen residue rate in solid products

图4 产物中的氮分布

Fig.4 Nitrogen distribution in products

图5 污泥中含氮物质形态

Fig.5 Nitrogen species in sewage sludge

图6 焦炭中含氮物质形态

Fig.6 Nitrogen species in hydrothermal carbonization char

图7 焦炭中含氮物质含量

Fig.7 Nitrogen species content in hydrochar

图8 水解蛋白焦炭中含氮物质

Fig.8 Nitrogen species in hydrochar of hydrolyzed protein

表2 焦油产物中主要含氮组分

Table 2 Main nitrogen species in tar

分类	种类	化学结构
胺类	胺	R-NH₂
	酰胺	R-CO-NH₂
		R-CO-NHR′
		R-CO-NR′R″
腈类	腈	R-CN
杂环类	吡咯
	吡啶
	吡唑
	嘧啶
	吲哚
	喹啉
	嘌呤

图9 焦油中含氮物质含量

Fig.9 Nitrogen species content in hydrothermal carbonization tar

图10 水解大豆蛋白焦油中含氮物质

Fig.10 Nitrogen species in hydrothermal carbonization tar of hydrolyzed soybean protein

图11 水热碳化水溶液中含氮物质含量

Fig.11 Nitrogen species content in hydrothermal carbonization solution

图12 水热碳化过程释放含氮气体

Fig.12 Nitrogen-containing gasesreleased during hydrothermal carbonization

图13 水热碳化过程中有机氮转化路径

Fig.13 Transformation path of organic nitrogen during hydrothermal carbonization

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水热碳化温度对污泥有机氮固液相迁移转化路径影响研究

Effect of hydrothermal carbonization temperature on transformation path of organic nitrogen in sludge

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