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

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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

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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

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