Fe2O3对甘氨酸热解特性及氮转化的影响

doi:10.11949/j.issn.0438-1157.20181390

摘要/Abstract

摘要：

选用污泥中典型氨基酸-甘氨酸（Gly）为研究对象，利用差式热值分析-质谱联用技术（DSC-MS）和固定床实验研究了Fe₂O₃对甘氨酸热解特性、NO _x 前驱物生成规律以及氮转化特性的影响。结果表明：热解特性实验中，由于Fe₂O₃将Gly的第一热失重阶段一分为二，导致其热解过程由2个阶段增至3个；Fe₂O₃使Gly热解起始温度及气体析出温度降低50℃，并通过促进半焦的二次裂解反应使Gly失重率增加23%。与Fe₂O₃对Gly热解过程的影响一致，Fe₂O₃将含N气体析出过程同样分成3个独立的阶段。固定床实验中，在Fe₂O₃/N=0.5时，Fe₂O₃最大程度地抑制了NO _x 前驱物（NH₃和HCN）析出，使其减少30%。由于Fe₂O₃促进肽脱水缩合、环化和芳香化反应，使得更多P-N、N-5和N-6固定在半焦中，半焦氮残留率增加5%。

关键词: 甘氨酸, 固定床, 热解, 气体, Fe₂O₃, NO _x 前驱物

Abstract:

The influences of Fe₂O₃ on glycine pyrolysis characteristics, generation mechanisms of NO _x precursors and transformation characteristics of nitrogen were investigated by DSC-MS and fixed bed experiment. The results indicated that the first thermal weightlessness stage of glycine (Gly) was divided into two parts by Fe₂O₃, so that the whole pyrolysis process was increased from 2 to 3 stages. Moreover, Fe₂O₃ can not only reduced the pyrolysis initiation temperature and the temperature of gas evolution by 50℃, but also promoted the secondary cracking reaction of char, which increased the weight loss rate of Gly by 23%. Furthermore, the evolution process of N-containing gases was divided into three independent stages by Fe₂O₃, which was corresponded to the Gly pyrolysis process. In the fixed bed experiment, most effective suppression of Fe₂O₃ on NO _x precursors (NH₃ and HCN) was achieved when the molar ratio of Fe₂O₃ to N is 0.5, which was decreased by 30%. Since Fe₂O₃ promotes peptide dehydration condensation, cyclization and aromatization reaction, more P-N, N-5 and N-6 are fixed in the semi-coke, and the semi-coke nitrogen residual rate is increased by 5%.

Key words: glycine, fixed-bed, pyrolysis, gas, Fe₂O₃, NO _x precursors

中图分类号:

TK 16

魏砾宏, 郭良振, 蒋进元, 刘美佳, 杨天华. Fe₂O₃对甘氨酸热解特性及氮转化的影响[J]. 化工学报, 2019, 70(5): 1942-1950.

Lihong WEI, Liangzhen GUO, Jinyuan JIANG, Meijia LIU, Tianhua YANG. Influence of Fe₂O₃ on glycine pyrolysis characteristics and nitrogen conversion[J]. CIESC Journal, 2019, 70(5): 1942-1950.

图/表 8

参考文献 30

1	Yang J K , Xu X , Liang S , et al . Enhanced hydrogen production in catalytic pyrolysis of sewage sludge by red mud: thermogravimetric kinetic analysis and pyrolysis characteristics[J]. International Journal of Hydrogen Energy, 2018, 43(16): 7795-7807.
2	Zhu J J , Yang Y , Yang L , et al . High quality syngas produced from the co-pyrolysis of wet sewage sludge with sawdust[J]. International Journal of Hydrogen Energy, 2018, 43(11): 5463-5472.
3	Tang S Q , Zheng C M , Yan F , et al . Product characteristics and kinetics of sewage sludge pyrolysis driven by alkaline earth metals[J]. Energy, 2018, 153: 921-932.
4	Wei F , Cao J P , Zhao X Y , et al . Formation of aromatics and removal of nitrogen in catalytic fast pyrolysis of sewage sludge: a study of sewage sludge and model amino acids[J]. Fuel, 2018, 218: 148-154.
5	Ahlberg G , Gustafsson O , Wedel P . Leaching of metals from sewage sludge during one year and their relationship to particle size[J]. Environmental Pollution, 2006, 144(2): 545-553.
6	Fytili D , Zabaniotou A . Utilization of sewage sludge in EU application of old and new methods—a review[J]. Renewable & Sustainable Energy Reviews, 2008, 12(1): 116-140.
7	Liu T T , Liu Z G , Zheng Q F , et al . Effect of hydrothermal carbonization on migration and environmental risk of heavy metals in sewage sludge during pyrolysis[J]. Bioresource Technology, 2018, 247: 282-290.
8	Wei F , Cao J P , Zhao X Y , et al . Nitrogen evolution during fast pyrolysis of sewage sludge under inert and reductive atmospheres[J]. Energy & Fuel, 2017, 31(7): 7191-7196.
9	Ko J H , Wang J C , Xu Q Y . Characterization of particulate matter formed during sewage sludge pyrolysis[J]. Fuel, 2018, 224: 210-218.
10	侯封校, 金晶, 林郁郁, 等 . Fe₂O₃对污泥热解特性及部分NO _x 前驱物转化规律的影响[J]. 燃烧科学与技术, 2017, 23(1): 90-95.
	Hou F X , Jin J , Lin Y Y , et al . Influence of Fe₂O₃ on sludge pyrolysis characteristics and partial transformation mechanisms of NO _x precursors[J]. Journal of Combustion Science and Technology, 2017, 23(1): 90-95.
11	Wei L H , Wen L N , Yang T H , et al . Nitrogen transformation during sewage sludge pyrolysis[J]. Energy & Fuels, 2015, 29(8): 5088-5094.
12	Wei L H , Wen L N , Liu M J , et al . Interaction characteristics of mineral matter and nitrogen during sewage sludge pyrolysis[J]. Energy & Fuels, 2016, 30(12): 10505-10510.
13	沈洪浩, 金晶, 林郁郁, 等 . CaO对大豆蛋白热解特性及NH₃等含氮化合物释放的影响[J]. 化工进展, 2016, 35(7): 2263-3367.
	Shen H H , Jin J , Lin Y Y , et al . Influence of CaO on soybean protein pyrolysis characteristics and NH₃ and other nitrogenous compounds release[J]. Chemical Industry and Engineering Progress, 2016, 35(7): 2263-2267.
14	Liu H , Zhang Q , Hu H Y , et al . Catalytic role of conditioner CaO in nitrogen transformation during sewage sludge pyrolysis[J]. Proceedings of the Combustion Institute, 2015, 35(3): 2759-2766.
15	Ren Q Q , Zhao C S . NO _x and N₂O precursors (NH₃ and HCN) from biomass pyrolysis: interaction between amino acid and mineral matter[J]. Applied Energy, 2013, 112(4): 170-174.
16	Zhang J , Tian Y , Cui Y N , et al . Key intermediates in nitrogen transformation during microwave pyrolysis of sewage sludge: a protein model compound study[J]. Bioresource Technology, 2013, 132(2): 57-63.
17	Liu G Y , Wright M M , Zhao Q L , et al . Catalytic pyrolysis of amino acids: comparison of aliphatic amino acid and cyclic amino acid[J]. Energy Conversion & Management, 2016, 112: 220-225.
18	Chen H P , Si Y H , Chen Y Q , et al . NO _x precursors from biomass pyrolysis: distribution of amino acids in biomass and tar-N during devolatilization using model compounds[J]. Fuel, 2017, 187: 367-375.
19	Sharma R K , Chan W G , Wang J , et al . On the role of peptides in the pyrolysis of amino acids[J]. Journal of Analytical & Applied Pyrolysis, 2004, 72(1): 153-163.
20	Yi L L , Liu H , Lu G , et al . Effect of mixed Fe/Ca additives on nitrogen transformation during protein and amino acid pyrolysis[J]. Energy & Fuels, 2017, 31(9): 9484-9490.
21	王兴栋, 李春星, 尤甫天, 等 . 污泥水热处理过程中氮元素的迁移转化[J]. 化工学报, 2018, 69(6): 2688-2696.
	Wang X D , Li C X , You F T , et al . Migration and transformation of nitrogen in sewage sludge during hydrothermal treatment[J]. CIESC Journal, 2018, 69(6): 2688-2696.
22	Huang W W , Yuan T , Zhao Z W , et al . Coupling hydrothermal treatment with stripping technology for fast ammonia release and effective nitrogen recovery from chicken manure [J]. ACS Sustainable Chemistry & Engineering, 2016, 4(7): 3704-3711.
23	Tsubouchi N , Hashimoto H , Ohtsuka Y . High catalytic performance of fine particles of metallic iron formed from limonite in the decomposition of a low concentration of ammonia[J]. Catalysis Letters, 2005, 105(3/4): 203-208.
24	Ratcliff M A , Medley E E , Simmonds P G . Pyrolysis of amino acids mechanistic considerations[J]. Journal of Organic Chemistry, 1974, 5(40): 1841.
25	Cao J P , Zhao X Y , Morishita K , et al . Fractionation and identification of organic nitrogen species from bio-oil produced by fast pyrolysis of sewage sludge[J]. Bioresource Technology, 2010, 101(19): 7648-7652.
26	郭明山, 金晶, 刘敦禹, 等 . 添加木质素对污泥热解过程氮转化的影响[J]. 化工学报, 2017, 68(4): 1590-1599.
	Guo M S , Jin J , Liu D Y , et al . Effect of lignin on nitrogen transformation during pyrolysis of sewage sludge[J]. CIESC Journal, 2017, 68(4): 1590-1599.
27	Tian K , Liu W J , Qian T T , et al . Investigation on the evolution of N-containing organic compounds during pyrolysis of sewage sludge[J]. Environmental Science & Technology, 2014, 48(18): 10888-10896.
28	车得福 . 煤氮热变迁与氮氧化物生成[M]. 西安: 西安交通大学出版社, 2013.
	Che D F . Thermal Coal-N Transformation and Nitrogen Oxide Generation[M]. Xi’an: Xi’an Jiaotong University Press, 2013.
29	李尚, 金晶, 林郁郁, 等 . 准东煤与污泥共热解过程中NO _x 前驱物释放规律[J]. 化工学报, 2017, 68(5): 2089-2095.
	Li S , Jin J , Lin Y Y , et al . Release of NO _x precursors in co-pyrolysis process of Zhun Dong coal mixed with sludge[J]. CIESC Journal, 2017, 68(5): 2089-2095.
30	Ohtsuka Y , Xu C B , Kong D P , et al . Decomposition of ammonia with iron and calcium catalysts supported on coal chars[J]. Fuel, 2004, 83(6): 685-692.

编辑推荐 0

Metrics

阅读次数

全文

165

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	3	0	0	162

来源	本网站	其他网站

次数	118	47
比例	72%	28%

摘要

474

最新录用	在线预览	正式出版

0	0	474

来源	本网站	其他网站

次数	315	159
比例	66%	34%

样品编号	T _s/°C	T _max/°C	T _1/2/°C	DTG_max/(%/min)	R _v×10⁸/(%/(min·℃³))
Gly	240	273	257.5	1.43	8.47
GF0.75	190	568.3	554.8	0.63	1.05

样品编号	T _s/°C	T _max/°C	T _1/2/°C	DTG_max/(%/min)	R _v×10⁸/(%/(min·℃³))
Gly	240	273	257.5	1.43	8.47
GF0.75	190	568.3	554.8	0.63	1.05

气体	Gly		GF0.75
气体	温度区间/℃	峰面积×10⁹	温度区间/°C	峰面积×10⁹
合计		0.10		0.57
NH₃[border:border-top:solid;]	250～402	69.5	191～309	61.6
	—	—	309～367	17.0
	—	—	367～601	41.0
合计		69.5		119.6
HCN[border:border-top:solid;]	251～543	4.7	200～357	1.4
	543～800	7.6	357～515	1.8
	—	—	515～718	1.9
合计		12.3		5.1
NO[border:border-top:solid;]	250～359	0.9	192～359	3.6
	359～575	1.1	359～533	3.0
	—	—	533～635	1.0
合计		2		7.6
HNCO[border:border-top:solid;]	256～333	0.3	191～331	0.4
	333～572	1.6	331～521	0.5
	572～794	0.8	521～631	0.3
合计		2.7		1.2
NO₂[border:border-top:solid;]	247～375	0.10	190～327	0.19
	—	—	327～520	0.25
	—	—	520～618	0.13

气体	Gly		GF0.75
气体	温度区间/℃	峰面积×10⁹	温度区间/°C	峰面积×10⁹
合计		0.10		0.57
NH₃[border:border-top:solid;]	250～402	69.5	191～309	61.6
	—	—	309～367	17.0
	—	—	367～601	41.0
合计		69.5		119.6
HCN[border:border-top:solid;]	251～543	4.7	200～357	1.4
	543～800	7.6	357～515	1.8
	—	—	515～718	1.9
合计		12.3		5.1
NO[border:border-top:solid;]	250～359	0.9	192～359	3.6
	359～575	1.1	359～533	3.0
	—	—	533～635	1.0
合计		2		7.6
HNCO[border:border-top:solid;]	256～333	0.3	191～331	0.4
	333～572	1.6	331～521	0.5
	572～794	0.8	521～631	0.3
合计		2.7		1.2
NO₂[border:border-top:solid;]	247～375	0.10	190～327	0.19
	—	—	327～520	0.25
	—	—	520～618	0.13

[1]	金伟其, 吴月荣, 王霞, 李力, 裘溯, 袁盼, 王铭赫. 化工园区工业气体泄漏气云红外成像检测技术与国产化装备进展[J]. 化工学报, 2023, 74(S1): 32-44.
[2]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[3]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[4]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.
[5]	盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.
[6]	张瑞航, 曹潘, 杨锋, 李昆, 肖朋, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8纳米流体天然气乙烷回收工艺的产品纯度关键影响因素分析[J]. 化工学报, 2023, 74(8): 3386-3393.
[7]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[8]	杨峥豪, 何臻, 常玉龙, 靳紫恒, 江霞. 生物质快速热解下行式流化床反应器研究进展[J]. 化工学报, 2023, 74(6): 2249-2263.
[9]	朱风, 陈凯琳, 黄小凤, 鲍银珠, 李文斌, 刘嘉鑫, 吴玮强, 高王伟. KOH改性电石渣脱除羰基硫的性能研究[J]. 化工学报, 2023, 74(6): 2668-2679.
[10]	葛泽峰, 吴雨青, 曾名迅, 查振婷, 马宇娜, 侯增辉, 张会岩. 灰化学成分对生物质气化特性的影响规律[J]. 化工学报, 2023, 74(5): 2136-2146.
[11]	王荣, 王永洪, 张新儒, 李晋平. 6FDA型聚酰亚胺炭分子筛气体分离膜的构筑及其应用[J]. 化工学报, 2023, 74(4): 1433-1445.
[12]	王倩倩, 刘明言, 马永丽. 水中超声波脱气的效应研究[J]. 化工学报, 2023, 74(4): 1693-1702.
[13]	衣思敏, 马亚丽, 刘伟强, 张金帅, 岳岩, 郑强, 贾松岩, 李雪. 微晶菱镁矿蒸氨及水化动力学研究[J]. 化工学报, 2023, 74(4): 1578-1586.
[14]	吴选军, 王超, 曹子健, 蔡卫权. 数据与物理信息混合驱动的固定床吸附穿透深度学习模型[J]. 化工学报, 2023, 74(3): 1145-1160.
[15]	陈瑞哲, 程磊磊, 顾菁, 袁浩然, 陈勇. 纤维增强树脂复合材料化学回收技术研究进展[J]. 化工学报, 2023, 74(3): 981-994.

Fe₂O₃对甘氨酸热解特性及氮转化的影响

Influence of Fe₂O₃ on glycine pyrolysis characteristics and nitrogen conversion

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 30

相关文章 15

编辑推荐 0

Metrics

本文评价