Page 124 - 《精细化工》2022年第6期
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第 39 卷第 6 期                             精   细   化   工                                  Vol.39, No.6
             2022 年 6 月                              FINE CHEMICALS                                 June  2022


              催化与分离提纯技术
                                 Ni 改性 Mo C/γ-Al O 催化剂在
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                                      逆水气变换反应中的应用



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                       吴   勇 ,丁   巍 ,戴咏川 ,王宏浩 ,徐   明 ,宋官龙
                 (1.  辽宁石油化工大学  石油化工学院,辽宁  抚顺  113001;2.  辽宁宝来生物能源有限公司,辽宁  盘锦
                 124119)
                 摘要:以掺杂 Y 型分子筛的 γ-Al 2 O 3 为载体,七钼酸铵(AMT)、六次甲基四胺(HMT)为原料,NiCO 3 •2Ni(OH) 2 •
                 4H 2 O 为改性助剂,通过共浸渍和程序升温炭化法制备了 Mo 2 C/γ-Al 2 O 3 (MCAS)和 Ni 改性的 Ni-Mo 2 C/γ-Al 2 O 3
                 (MNCAS)催化剂。采用 XRD、ICP、N 2 吸附-脱附、TEM 和 EDS 对其进行了表征,考察了其在逆水气变换
                 反应中的催化性能。结果表明,MNCAS 催化剂出现了 Ni 3 Mo 3 N 的特征衍射峰,Ni 的加入有效改善了 Mo 2 C 的
                 聚集现象,并且该催化剂具有良好的介孔结构。MCAS 催化剂对逆水气反应有较高的催化活性,300  ℃时 CO
                 选择性为 93.87%,MNCAS-8 催化剂〔n(AMT)∶n(HMT) = 1∶8,Mo 和 Ni 的理论负载量分别为 30%和 5%,实
                 际负载量分别为 28.52%和 4.51%〕倾向于将 CO 2 转化成 CH 4 ,在低温段 CH 4 选择性达到 84.37%,生成的 Ni 3 Mo 3 N
                 有利于提高 CH 4 的选择性。
                 关键词:碳化钼;氮化镍钼;逆水气变换反应;催化剂;催化技术
                 中图分类号:X701;TQ426      文献标识码:A      文章编号:1003-5214 (2022) 06-1190-07



                             Application of Ni modified Mo 2C/γ-Al 2O 3 catalyst in
                                          reverse water-gas shift reaction


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                   WU Yong , DING Wei , DAI Yongchuan , WANG Honghao , XU Ming , SONG Guanlong
                 (1.  College of  Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, Liaoning, China; 2.
                 Bora Bioenergy Co., Ltd., Panjin 124119, Liaoning, China)
                 Abstract: Mo 2C/γ-Al 2O 3 (MCAS) and Ni modified Ni-Mo 2C/γ-Al 2O 3 (MNCAS) catalysts were prepared
                 via co-impregnation and temperature-programmed carbonization using γ-Al 2O 3 doped Y molecular sieve as
                 carrier, ammonium heptadolybdate (AMT) and hexamethylenetetramine (HMT) as  raw materials,  and
                 NiCO 3•2Ni(OH) 2•4H 2O as modifying agent. The synthesized catalysts were characterized by XRD, ICP, N 2
                 adsorption-desorption, TEM and EDS, and their catalytic performances in reverse water-gas shift reaction
                 were further investigated. The analyses revealed  that  MNCAS catalysts displayed the characteristic
                 diffraction peaks of Ni 3Mo 3N with a good mesoporous structure, in which aggregation caused by Mo 2C was
                 effectively improved by the addition of Ni. Moreover, MCAS catalyst exhibited high catalytic activity for the
                 reverse  water-gas shift reaction at 300  ℃  with CO  selectivity of 93.87%. Meanwhile, MNCAS-8 catalyst
                 [n(AMT)∶n(HMT) =  1∶8, the theoretical and actual  loading amount  of Mo  were 30% and  28.52%
                 respectively, and those of Ni were 5%, and 4.51%, respectively] showed a conversion tendency of CO 2 into
                 CH 4, the CH 4 selectivity reached up to  84.37% at low  temperature  range,  which could  be attributed to
                 Ni 3Mo 3N generated after Ni addition.
                 Key words: Mo 2C; Ni 3Mo 3N; reverse water-gas shift reaction; catalyst; catalysis technology

                 收稿日期:2021-11-20;  定用日期:2022-03-10; DOI: 10.13550/j.jxhg.20211184
                 基金项目:国家自然科学基金青年基金(21802061);中央引导地方科技发展专项基金(2021JH6/10500154);辽宁省教育厅重点攻关
                 科研项目(L2020001);抚顺英才计划(FSYC202101001)
                 作者简介:吴   勇(1996—),男,硕士生,E-mail:wuyong1996@126.com。联系人:丁   巍(1978—),女,副教授,E-mail:cicy1125@
                 163.com;戴咏川(1968—),女,副教授,E-mail:ych_dasic@163.com。
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