NTP再生La改性多级孔HZSM-5及催化提质生物油的试验研究

doi:10.11949/j.issn.0438-1157.20181525

摘要/Abstract

摘要：

以氧气为气源，利用低温等离子体（NTP）喷射系统，在不同温度下对结焦失活的La改性多级孔HZSM-5分子筛进行再生，采用TG、XRD、Py-IR及N₂吸附-脱附等测试技术对再生前后催化剂的理化性质进行表征，并利用再生催化剂进行在线催化提质生物油试验。结果表明，再生温度为250℃时，失活La改性多级孔HZSM-5分子筛再生效果最好，去除了97.4%的积炭，其表面结晶度、酸性、比表面积和孔容恢复程度最高。再生温度上升至300℃时，O₃分解较多，此时O₃分解已经成为积炭氧化分解的限制因素，排气中CO₂和CO浓度峰值减小，失活催化剂再生效果有所下降。再生温度为250℃时，再生催化剂催化性能恢复最好，制得的生物油高位热值最大（36.48 MJ/kg），烃类含量最高（40.51%），其理化性质与新鲜催化剂制得的生物油理化性质最接近。

关键词: NTP, La改性多级孔HZSM-5, 再生温度, 生物油

Abstract:

Regeneration experiments of La modified multistage pore HZSM-5 zeolite were carried out at different regeneration temperatures by non-thermal plasma (NTP) spray system with oxygen as gas source. The physicochemical properties of La modified multistage pore HZSM-5 zeolite before and after regeneration were characterized by TG, XRD, Py-IR and N₂ adsorption-desorption. The experiments of on-line catalytic upgrading of bio-oil were carried out over regenerated catalyst. The results showed that when regeneration temperature was 250℃, the deactivated La modified multistage pore HZSM-5 zeolite had the best regeneration effect, 97.4% of coke was removed, and the surface crystallinity, acidity, specific surface area and pore volume recovery were the best. When regeneration temperature rose to 300℃, the decomposition amount of O₃ was more. At this time, the decomposition of O₃ had become the limiting factor for oxidative decomposition of coke. The peaks of CO₂ and CO concentration decreased, and the regeneration effect of deactivated catalyst declined. When regeneration temperature was 250℃, the catalytic performance recovery of regenerated catalyst was the best. The bio-oil produced by regenerated catalyst had the highest heating value (36.48 MJ/kg) and the highest hydrocarbon content (40.51%), and its physical and chemical properties were closest to that of bio-oil produced by fresh catalyst.

Key words: NTP, La modified multistage pore HZSM-5, regeneration temperature, bio-oil

中图分类号:

TQ 35

朱勇晨, 李小华, 张小雷, 胡超, 董文斌, 程静峰, 邵珊珊. NTP再生La改性多级孔HZSM-5及催化提质生物油的试验研究[J]. 化工学报, 2019, 70(5): 1795-1803.

Yongchen ZHU, Xiaohua LI, Xiaolei ZHANG, Chao HU, Wenbin DONG, Jingfeng CHENG, Shanshan SHAO. Study on regeneration of La modified multistage pore HZSM-5 by NTP and catalytic upgrading of bio-oil[J]. CIESC Journal, 2019, 70(5): 1795-1803.

图/表 11

图1 NTP再生装置示意图

Fig.1 Schematic diagram of NTP regeneration device

图2 再生前后La改性多级孔HZSM-5分子筛的TG和DTG曲线

Fig.2 TG and DTG curves of La modified multistage pore HZSM-5 zeolite before and after regeneration

表1 再生前后La改性多级孔HZSM-5分子筛的积炭分布

Table 1 Coke of La modified multistage pore HZSM-5 zeolite before and after regeneration/%

积炭类型	失活催化剂	H-100	H-150	H-200	H-250	H-300
Ⅰ类	6.88	2.79	2.15	1.38	0.19	1.42
Ⅱ类	1.67	0.62	0.46	0.34	0.03	0.40

图3 再生前后La改性多级孔HZSM-5分子筛的XRD谱图

Fig.3 XRD patterns of La modified multistage pore HZSM-5 zeolite before and after regeneration

图4 再生前后La改性多级孔HZSM-5分子筛的Py-IR谱图和酸量分布图

Fig.4 Py-IR spectra and acid amount distribution of La modified multistage pore HZSM-5 zeolite before and after regeneration

表2 再生前后La改性多级孔HZSM-5分子筛的比表面积和孔容

Table 2 Specific surface area and pore volume of La modified multistage pore HZSM-5 zeolite before and after regeneration

催化剂	比表面积/(m²/g)	孔容/(cm³/g)
新鲜	281.2	0.258
失活	84.6	0.077
H-100	182.8	0.168
H-150	210.9	0.193
H-200	239.2	0.219
H-250	272.8	0.251
H-300	241.8	0.221

图5 排气中CO2和CO浓度变化

Fig.5 Change in CO2 and CO concentration in exhaust gas

表3 再生后La改性多级孔HZSM-5分子筛提质的生物油理化特性

Table 3 Physical and chemical properties of bio-oil upgraded by La modified multistage pore HZSM-5 zeolite after regeneration

生物油	高位热值/(MJ/kg)	pH	含氧率/%	黏度/(mm²/s)
O-100	30.65	4.96	18.08	6.55
O-150	32.88	5.43	16.51	6.02
O-200	35.13	5.82	14.99	5.81
O-250	36.48	5.95	13.83	5.69
O-300	35.21	5.80	14.97	5.79
O-新鲜	37.72	6.01	13.45	5.64

图6 再生后生物油样品中烃类物质含量

Fig.6 Content of hydrocarbons in bio-oil samples after regeneration

图7 再生后生物油样品中含氧化合物分布

Fig.7 Distribution of oxygenates in bio-oil samples after regeneration

图8 再生后生物油样品中化合物的碳链分布

Fig.8 Carbon chain distribution of compounds in bio-oil samples after regeneration

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