Study on regeneration of La modified multistage pore HZSM-5 by NTP and catalytic upgrading of bio-oil

ZHU Yongchen; LI Xiaohua; ZHANG Xiaolei; HU Chao; DONG Wenbin; CHENG Jingfeng; SHAO Shanshan

doi:10.11949/j.issn.0438-1157.20181525

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Study on regeneration of La modified multistage pore HZSM-5 by NTP and catalytic upgrading of bio-oil

Catalysis\, kinetics and reactors | 更新时间：2026-07-24

- Study on regeneration of La modified multistage pore HZSM-5 by NTP and catalytic upgrading of bio-oil
- CIESC Journal Vol. 70, Issue 5, Pages: 1795-1803(2019)
- 作者机构：
  
  江苏大学汽车与交通工程学院，江苏镇江 212013
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20181525
  CLC： TQ 35
- Received：28 December 2018，
  
  Revised：2019-02-20，
  
  Online First：24 July 2026，
  
  Published：05 May 2019
- 稿件说明：
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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

ZHU Yongchen, LI Xiaohua, ZHANG Xiaolei, HU Chao, DONG Wenbin, CHENG Jingfeng, SHAO Shanshan. 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
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 DOI： 10.11949/j.issn.0438-1157.20181525.

ZHU Yongchen, LI Xiaohua, ZHANG Xiaolei, HU Chao, DONG Wenbin, CHENG Jingfeng, SHAO Shanshan. 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 DOI： 10.11949/j.issn.0438-1157.20181525.

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N

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，O

分解较多，此时O

分解已经成为积炭氧化分解的限制因素，排气中CO

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。

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 N

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 O

was more. At this time

the decomposition of O

had become the limiting factor for oxidative decomposition of coke. The peaks of CO

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.

关键词

Keywords

references

Dan C , Wang L , Abolghasem S , et al . Characterization of the physical and chemical properties of the distillate fractions of crude bio-oil produced by the glycerol-assisted liquefaction of swine manure [J ] . Fuel , 2014 , 130 : 251 - 256 .

Xu L , Cheng J , Liu P , et al . Production of bio-fuel oil from pyrolysis of plant acidified oil [J ] . Renewable Energy , 2019 , 130 : 910 - 919 .

Yan B , Zhang S , Chen W , et al . Pyrolysis of tobacco wastes for bio-oil with aroma compounds [J ] . Journal of Analytical and Applied Pyrolysis , 2018 , 136 : 248 - 254 .

Hu C S , Zhagn H Y , Xiao R . Catalytic fast pyrolysis of biomass over core-shell HZSM-5@silicalite-1 in a bench-scale two-stage fluidized-bed/fixed-bed reactor [J ] . Journal of Analytical and Applied Pyrolysis , 2018 , 136 : 27 - 34 .

Li X H , Zhang X L , Shao S S , et al . Catalytic upgrading of pyrolysis vapor from rape straw in a vacuum pyrolysis system over La/HZSM-5 with hierarchical structure [J ] . Bioresource Technology , 2018 , 259 : 191 - 197 .

刘亚华 , 李扬 , 王科 , 等 . 二甲醚羰基化催化剂的烧炭再生 [J ] . 化工学报 , 2017 , 68 ( 10 ): 3816 - 3822 .

Liu Y H , Li Y , Wang K , et al . Charcoal regeneration of dimethyl ether carbonylation catalyst [J ] . CIESC Journal , 2017 , 68 ( 10 ): 3816 - 3822 .

刘守新 , 张世润 , 孙承林 . 木质活性炭的光催化再生 [J ] . 林产化学与工业 , 2003 , ( 2 ): 12 - 16 .

Liu S X , Zhang S R , Sun C L . Photocatalytic regeneration of woody activated carbon [J ] . Chemistry and Industry of Forest Products , 2003 , ( 2 ): 12 - 16 .

于丽丽 , 易红宏 , 宁平 , 等 . 改性活性炭水解COS催化剂的再生方法 [J ] . 中南大学学报(自然科学版) , 2011 , 42 ( 3 ): 841 - 847 .

Yu L L , Yi H H , Ning P , et al . Regeneration method of modified activated carbon hydrolyzed COS catalyst [J ] . Journal of Central South University(Natural Science) , 2011 , 42 ( 3 ): 841 - 847 .

López A , de Marco I , Caballero B M , et al . Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes [J ] . Waste Management , 2011 , 31 ( 8 ): 1852 - 1858 .

Serrano D P , Aguado J , Rodríguez J M , et al . Catalytic cracking of polyethylene over nanocrystalline HZSM-5: catalyst deactivation and regeneration study [J ] . Journal of Analytical and Applied Pyrolysis , 2007 , 79 ( 1 ): 456 - 464 .

Li X Y , Li P , PAN X L , et al . Deactivation mechanism and regeneration of carbon nanocomposite catalyst for acetylene hydrochlorination [J ] . Applied Catalysis B: Environmental , 2017 , 210 : 116 - 120 .

Wang W Z , Wang H L , Zhu T L , et al . Removal of gas phase low-concentration toluene over Mn, Ag and Ce modified HZSM-5 catalysts by periodical operation of adsorption and non-thermal plasma regeneration [J ] . Journal of Hazardous Materials , 2015 , 292 : 70 - 78 .

Okubo M , Arita N , Kuroki T , et al . Carbon particulate matter incineration in diesel engine emissions using indirect nonthermal plasma processing [J ] . Thin Solid Films , 2007 , 515 ( 9 ): 4289 - 4295 .

Li X H , Li W J , Cai Y X , et al . Deposit removal in EGR cooler and effectiveness improvement by non-thermal plasma reactor with different gas sources [J ] . Applied Thermal Engineering , 2017 , 111 : 694 - 702 .

施蕴曦 , 蔡忆昔 , 王静 , 等 . 空气流量对低温等离子体再生DPF的影响 [J ] . 江苏大学学报(自然科学版) , 2017 , 38 ( 5 ): 509 - 515 .

Shi Y X , Cai Y X , Wang J , et al . Effect of air flow on low temperature plasma regeneration DPF [J ] . Journal of Jiangsu University(Natural Science Edition) , 2017 , 38 ( 5 ): 509 - 515 .

郑益 , 蔡忆昔 , 陈亚运 , 等 . 再生温度对NTP再生EGR冷却器的影响 [J ] . 内燃机工程 , 2016 , 37 ( 6 ): 210 - 215 .

Zheng Y , Cai Y X , Chen Y Y , et al . Effect of regeneration temperature on NTP regenerative EGR cooler [J ] . Internal Combustion Engine Engineering , 2016 , 37 ( 6 ): 210 - 215 .

邵珊珊 . 生物质催化热解中催化剂积炭与再生特性研究 [D ] . 南京 : 东南大学 , 2016 .

Shao S S . Study on catalyst carbon deposition and regeneration characteristics in biomass catalytic pyrolysis [D ] . Nanjing : Southeast University , 2016 .

张瑾 , 李小华 , 董良秀 , 等 . 碱处理HZSM-5分子筛在线催化提质生物油 [J ] . 燃料化学学报 , 2017 , 45 ( 7 ): 828 - 836 .

Zhang J , Li X H , Dong L X , et al . On-line catalytic catalyzed upgrading of bio-oil by alkali-treated HZSM-5 molecular sieve [J ] . Journal of Fuel Chemistry , 2017 , 45 ( 7 ): 828 - 836 .

Chu L B , Wang J L . Regeneration of sulfamethoxazole-saturated activated carbon using gamma irradiation [J ] . Radiation Physics and Chemistry , 2017 , 130 : 391 - 396 .

Calafta A , Sanchez N . Production of carbon nanotubes through combination of catalyst reduction and methane decomposition over Fe–Ni/ZrO 2 catalysts prepared by the citrate method [J ] . Applied Catalysis A: General , 2016 , 528 : 14 - 23 .

Jia L Y , Farouha A , Pinard L , et al . New routes for complete regeneration of coked zeolite [J ] . Applied Catalysis B: Environmental , 2017 , 219 : 82 - 91 .

唐松山 , 泮泽优 , 张长森 , 等 . 碱改性HZSM-5催化热解木质素催化剂失活分析 [J ] . 化工学报 , 2017 , 68 ( 12 ): 4739 - 4749 .

Tang S S , Pan Z Y , Zhang C S , et al . Deactivation analysis of catalyzed pyrolysis lignin catalyst by alkali-modified HZSM-5 [J ] . CIESC Journal , 2017 , 68 ( 12 ): 4739 - 4749 .

陆强 , 李文志 , 张栋 , 等 . 锯末快速热解气的在线催化裂解 [J ] . 化工学报 , 2009 , 60 ( 2 ): 351 - 357 .

Lu Q , Li W Z , Zhang D , et al . On-line catalytic cracking of rapid pyrolysis gas from sawdust [J ] . CIESC Journal , 2009 , 60 ( 2 ): 351 - 357 .

施梅勤 , 郑慧新 , 魏爱平 , 等 . Zn助剂对WC/HZSM-5催化正己烷芳构化性能影响 [J ] . 化工学报 , 2015 , 66 ( 2 ): 553 - 560 .

Shi M Q , Zheng H X , Wei A P , et al . Effect of Zn promoter on the aromatization performance of n -hexane catalyzed by WC/HZSM-5 [J ] . CIESC Journal , 2015 , 66 ( 2 ): 553 - 560 .

张向京 , 马仁娟 , 孙瑞钰 , 等 . HZSM-5催化剂在MTG反应中的积炭失活 [J ] . 化工学报 , 2015 , 66 ( 9 ): 3483 - 3489 .

Zhang X J , Ma R J , Sun R Y , et al . Carbon deposition inactivation of HZSM-5 catalyst in MTG reaction [J ] . CIESC Journal , 2015 , 66 ( 9 ): 3483 - 3489 .

Fan Y S , Cai Y X , Li X H , et al . Regeneration of the HZSM-5 zeolite deactivated in the upgrading of bio-oil via non-thermal plasma injection (NTPI) technology [J ] . Journal of Analytical and Applied Pyrolysis , 2015 , 111 : 209 - 215 .

Yang Y J , Jia J B , Liu Y , et al . The effect of tungsten doping on the catalytic activity of α-MnO 2 nanomaterial for ozone decomposition under humid condition [J ] . Applied Catalysis A: General , 2018 , 562 : 132 - 141 .

Jiang N , Guo L J , Qiu C , et al . Reactive species distribution characteristics and toluene destruction in the three-electrode DBD reactor energized by different pulsed modes [J ] . Chemical Engineering Journal , 2018 , 350 : 12 - 19 .

Guan B , Lin H , Zhan R , et al . Catalytic combustion of soot over Cu, Mn substitution CeZrO 2- δ nanocomposites catalysts prepared by self-propagating high-temperature synthesis method [J ] . Chemical Engineering Science , 2018 , 189 : 320 - 339 .

Lydia K E , Liu J , Sotira Y , et al . Contribution of acidic components to the total acid number (TAN) of bio-oil [J ] . Fuel , 2017 , 200 : 171 - 181 .

Leng L , Li H , Yuan X , et al . Bio-oil upgrading by emulsification/microemulsification: a review [J ] . Energy , 2018 , 161 : 214 - 232 .

赵岩 , 刘银 . HZSM-5分子筛催化热裂解生物质制备芳烃化合物 [J ] . 化工新型材料 , 2017 , 45 ( 2 ): 145 - 147 .

Zhao Y , Liu Y . Preparation of aromatic compounds by catalytic pyrolysis of biomass by HZSM-5 molecular sieve [J ] . New Chemical Materials , 2017 , 45 ( 2 ): 145 - 147 .

Melchor J J , Fortes I C P . Bio-oil production by pyrolysis of metal soaps derived from macauba pulp oil [J ] . Journal of Analytical and Applied Pyrolysis , 2018 , 135 : 101 - 110 .

Rahman M M , Liu R H , Cai J M . Catalytic fast pyrolysis of biomass over zeolites for high quality bio-oil — a review [J ] . Fuel Processing Technology , 2018 , 180 : 32 - 46 .

刘莎 , 蔡忆昔 , 樊永胜 , 等 . MCM-41分子筛在线提质生物油工艺优化及耐久性分析 [J ] . 林产化学与工业 , 2016 , 36 ( 4 ): 55 - 63 .

Liu S , Cai Y X , Fan Y S , et al . Process optimization and durability analysis of MCM-41 molecular sieve on-line bio-oil improvement [J ] . Chemistry and Industry of Forest Products , 2016 , 36 ( 4 ): 55 - 63 .

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