Ni-Ru双金属复合催化剂催化喹啉水热加氢脱氮反应机理与动力学研究

吕恒; 刘旭; 谢丹; 郭洋

doi:10.7652/xjtuxb202111019

您当前的位置：

首页 >

文章列表页 >

Ni-Ru双金属复合催化剂催化喹啉水热加氢脱氮反应机理与动力学研究

更新时间：2025-07-09

- Ni-Ru双金属复合催化剂催化喹啉水热加氢脱氮反应机理与动力学研究
- Mechanism and Kinetics of Quinoline Hydrothermal Denitrogenation Catalyzed by a Ni-Ru Bimetallic Composite Catalyst
- 西安交通大学学报 2021年55卷第11期页码：173-180
- 作者机构：
  
  西安特种设备检验检测院,西安,710065
- 作者简介：
- 基金信息：
  
  : 2021-03-11。作者简介: 吕恒(1983—),男,高级工程师;郭洋(通信作者),男,副教授,博士生导师。基金项目: 国家自然科学基金资助项目(51876174);2020陕西省市场监督管理局科技计划资助项目(2020KY07);陕西省自然科学基金资助项目(2018JM5011)
- DOI：10.7652/xjtuxb202111019
  中图分类号： O622.6
- 网络首发：2021-11-10，
  
  纸质出版：2021
- 稿件说明：
移动端阅览
吕恒, 刘旭, 谢丹, 等. Ni-Ru双金属复合催化剂催化喹啉水热加氢脱氮反应机理与动力学研究[J]. 西安交通大学学报, 2021,55(11):173-180.

Mechanism and Kinetics of Quinoline Hydrothermal Denitrogenation Catalyzed by a Ni-Ru Bimetallic Composite Catalyst[J]. 2021, 55(11): 173-180.
吕恒, 刘旭, 谢丹, 等. Ni-Ru双金属复合催化剂催化喹啉水热加氢脱氮反应机理与动力学研究[J]. 西安交通大学学报, 2021,55(11):173-180. DOI： 10.7652/xjtuxb202111019.

Mechanism and Kinetics of Quinoline Hydrothermal Denitrogenation Catalyzed by a Ni-Ru Bimetallic Composite Catalyst[J]. 2021, 55(11): 173-180. DOI： 10.7652/xjtuxb202111019.

摘要

为探究生物油中难降解的一类重要含氮物质喹啉在水热条件下的催化加氢脱氮反应的机理

研究了Ni-Ru复合金属催化剂作用下喹啉的转化和产物生成规律。实验结果表明:加入甲酸可获得更高喹啉转化率

而加入气态氢则更有利于生成脱氮产物; 苯胺和甲基苯胺是主要的喹啉哌啶环开环物质

2-己烯和甲苯是主要的加氢脱氮产物。通过产物分布规律

获得了喹啉水热加氢脱氮反应网络

并发现喹啉在超临界水条件下的反应符合一级反应规律。通过Weisz-Prater公式计算证明了喹啉在超临界水中的反应不受传质阻力的扩散的影响; 催化剂透射电子显微镜(TEM)的表征表明制备的催化剂中Ni-Ru双金属均匀分布在γ-Al

载体上

但是部分活性金属在水热条件下出现团聚现象。所得结果对生物油水热加氢脱氮提质研究具有一定的借鉴意义。

Abstract

In order to obtain the mechanism of catalytic hydrodenitrogenation reaction of quinoline

an important nitrogen-containing substance difficult to degrade in bio-oil

in hydrothermal conditions

the conversion and product distribution of quinoline under the action of Ni-Ru composite metal catalyst were studied. Experimental results showed that: the addition of formic acid induced higher quinoline conversion rate

while adding gaseous hydrogen was more conducive to the formation of denitrification products; aniline and methylaniline were the main ring opening compounds of quinoline piperidine; and 2-hexene and toluene were the main hydrodenitrogenation products. According to the product distribution

law

the hydrothermal hydrodenitrogenation reaction network of quinoline was obtained

and it was found that the reaction of quinoline under supercritical water conditions conformed to the first-order reaction rule. The Weisz-Prater formula proved that the reaction of quinoline in supercritical water was not affected by the diffusion of mass transfer resistance. TEM characterization of the catalyst showed that the Ni-Ru bimetallic particles in the prepared catalyst were uniformly distributed on the γ-Al

support

but some active metals agglomerated in hydrothermal conditions.

关键词

Keywords

references

CHEN Yu, WU Yulong, HUA Derun, et al. Thermochemical conversion of low-lipid microalgae for the production of liquid fuels: challenges and opportunities [J]. RSC Advances, 2015, 5(24): 18673-18701.

XIE Qinglong, ADDY M, LIU Shiyu, et al. Fast microwave-assisted catalytic co-pyrolysis of microalgae and scum for bio-oil production [J]. Fuel, 2015, 160: 577-582.

XU Yufu, HU Yuanhua, PENG Yubin, et al. Catalytic pyrolysis and liquefaction behavior of microalgae for bio-oil production [J]. Bioresource Technology, 2020, 300: 122665.

CHEN Huihui, ZHOU Dong, LUO Gang, et al. Macroalgae for biofuels production: progress and perspectives [J]. Renewable and Sustainable Energy Reviews, 2015, 47: 427-437.

GARGANO I, MAROTTA R, ANDREOZZI R, et al. Alkaline direct transesterification of different species of Stichococcus for bio-oil production [J]. New Biotechnology, 2016, 33(6): 797-806.

WANG Yipeng, NAN Ge, WANG Wenjia, et al. Preparation and application of a new catalyst to produce bio-oil from microalgae liquefaction [J]. International Journal of Agricultural and Biological Engineering, 2017, 10(1): 169-175.

XU Yufu, LIU Kai, HU Yuanhua, et al. Experimental investigation and comparison of bio-oil from hybrid microalgae via super/subcritical liquefaction [J]. Fuel, 2020, 279: 118412.

BASAR I A, LIU Huan, CARRERE H, et al. A review on key design and operational parameters to optimize and develop hydrothermal liquefaction of biomass for biorefinery applications [J]. Green Chemistry, 2021, 23(4): 1404-1446.

MARZBALI M H, KUNDU S, HALDER P, et al. Wet organic waste treatment via hydrothermal processing: a critical review [J]. Chemosphere, 2021, 279: 130557.

DUAN Peigao, SAVAGE P E. Hydrothermal liquefaction of a microalga with heterogeneous catalysts [J]. Industrial Engineering Chemistry Research, 2011, 50(1): 52-61.

HAN Wei, NIE Hong, LONG Xiangyun, et al. A study on the origin of the active sites of HDN catalysts using alumina-supported MoS3 nanoparticles as a precursor [J]. Catalysis Science and Technology, 2016, 6(10): 3497-3509.

DUAN Peigao, WANG Bing, XU Yuping. Catalytic hydrothermal upgrading of crude bio-oils produced from different thermo-chemical conversion routes of microalgae [J]. Bioresource Technology, 2015, 186: 58-66.

BAI Xiujun, DUAN Peigao, XU Yuping, et al. Hydrothermal catalytic processing of pretreated algal oil: a catalyst screening study [J]. Fuel, 2014, 120: 141-149.

GUO Yang, HE Haoran, LIU Xu, et al. Ring-opening and hydrodenitrogenation of indole under hydrothermal conditions over Ni, Pt, Ru, and Ni-Ru bimetallic catalysts [J]. Chemical Engineering Journal, 2021, 406: 126853.

GUO Yang, LIU Xu, DUAN Peigao, et al. Catalytic hydrodenitrogenation of pyridine under hydrothermal conditions: a comprehensive study [J]. ACS Sustainable Chemistry Engineering, 2021, 9(1): 362-374.

GUO Yang, CHEN Zhifeng, RIOUX R M, et al. Hydrothermal reaction of tryptophan over Ni-based bimetallic catalysts [J]. The Journal of Supercritical Fluids, 2019, 143: 336-345.

KABE T, ISHIHARA A, QIAN Weihua. Elucidation of hydrodesulfurization mechanism on molybdenum-based catalysts using 35S radioisotope pulse tracer methods [J]. Catalysis Surveys from Asia, 1999, 3(1): 17-25.

黄澎. SBA-15负载磷化镍催化剂对喹啉加氢脱氮反应网络的影响 [J]. 煤炭学报, 2015, 40(S2): 491-496.

HUANG Peng. Effect of SBA-15-supported nickle phosphate catalyst on hydrodenitrogenation network of quinolone [J]. Journal of China Coal Society, 2015, 40(S2): 491-496.

YANG Changyan, LI Rui, CUI Chang, et al. Catalytic hydroprocessing of microalgae-derived biofuels: a review [J]. Green Chemistry, 2016, 18(13): 3684-3699.

GONG Yanmeng, GUO Yang, WANG Shuzhong, et al. Supercritical water oxidation of quinazoline: effects of conversion parameters and reaction mechanism [J]. Water Research, 2016, 100: 116-125.

GONG Yanmeng, GUO Yang, WANG Shuzhong, et al. Supercritical water oxidation of quinazoline: reaction kinetics and modeling [J]. Water Research, 2017, 110: 56-65.

YU Jianli, SAVAGE P E. Decomposition of formic acid under hydrothermal conditions [J]. Industrial Engineering Chemistry Research, 1998, 37(1): 2-10.

LIU Xu, YANG Mei, DENG Zihao, et al. Hydrothermal hydrodeoxygenation of palmitic acid over Pt/C catalyst: mechanism and kinetic modeling [J]. Chemical Engineering Journal, 2021, 407: 126332.

BOUKIS N, DIEM V, HABICHT W, et al. Methanol reforming in supercritical water [J]. Industrial Engineering Chemistry Research, 2003, 42(4): 728-735.

MIAO Chao, MARIN-FLORES O, DAVIDSON S D, et al. Hydrothermal catalytic deoxygenation of palmitic acid over nickel catalyst [J]. Fuel, 2016, 166: 302-308.

WANG Xiaoguang, YANG Yang, ZHONG Heng, et al. Molecular H2O promoted catalytic bicarbonate re-duction with methanol into formate over Pd0.5Cu0.5/C under mild hydrothermal conditions [J]. Green Chemistry, 2021, 23(1): 430-439.

GUO Yang, WANG Shuzhong, HUELSMAN C M, et al. Products, pathways, and kinetics for reactions of indole under supercritical water gasification conditions [J]. The Journal of Supercritical Fluids, 2013, 73: 161-170.

GUO Yang, WANG Shuzhong, HUELSMAN C M, et al. Kinetic model for reactions of indole under supercritical water gasification conditions [J]. Chemical Engineering Journal, 2014, 241: 327-335.

PATIL T A, RAGHUNATHAN T S, SHANKAR H S. Thermal hydrolysis of vegetable oils and fats. 2. Hydrolysis in continuous stirred tank reactor [J]. Industrial Engineering Chemistry Research, 1988, 27(5): 735-739.

DICKINSON J G, POBEREZNY J T, SAVAGE P E. Deoxygenation of benzofuran in supercritical water over a platinum catalyst [J]. Applied Catalysis: B Environmental, 2012, 123/124: 357-366.

LIU Fang, OKOLIE C, RAVENELLE R M, et al. Silica deposition as an approach for improving the hydrothermal stability of an alumina support during glycerol aqueous phase reforming [J]. Applied Catalysis: A General, 2018, 551: 13-22.

LI Haitao, ZHAO Yongxiang, GAO Chunguang, et al. Study on deactivation of Ni/Al2O3 catalyst for liquid phase hydrogenation of crude 1, 4-butanediol aqueous solution [J]. Chemical Engineering Journal, 2012, 181-182: 501-507.

卢伟光, 龙军, 田辉平. 镧和铈改性对氧化铝性质的影响 [J]. 催化学报, 2003, 24(8): 574-578.

LU Weiguang, LONG Jun, TIAN Huiping. Effect of lanthanum and cerium modifiers on properties of alumina [J]. Chinese Journal of Catalysis, 2003, 24(8): 574-578.

LABALME V, BEGUIN B, GAILLARD F, et al. Characterisation and acid properties of some modified combustion catalysts: Pt/alumina with barium and Pt/zirconia with yttrium [J]. Applied Catalysis: A General, 2000, 192(2): 307-316.

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

La1-xYxNi 4.8Mn 0.2合金的贮氢性能研究

含油废水的超临界水氧化反应机理及动力学特性

烟煤与生物质秸秆共气化反应动力学研究

机械合金化Mg2Ni储氢材料的吸氢动力学实验研究

张角凹坑气膜孔对双层壁气膜冷却特性的影响