Preparation of phosphorous-containing W/Al2O3 catalysts via microwave hydrothermal method and their hydrodenitrogen activity

doi:10.16085/j.issn.1000-6613.2015.06.024

Abstract

Abstract: Phosphorous-containing W/Al₂O₃hydrotreating catalysts were prepared via microwave hydrothermal (MWH) method, in which phosphoric acid (PA), triethyl phosphate (TEP) and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) were used as phosphorus sources, respectively. The effects of phosphorus sources, catalyst preparation methods and phosphorus contents on the physicochemical properties and hydrodenitrogenation (HDN) activity of catalysts were studied. The results show that the introduction of HEDP can weaken tungsten-alumina interaction and keep highly dispersed tungsten species by forming H-bonding between the hydroxyl groups of HEDP and H₂WO₄ to prevent tungsten species from aggregation. The MWH method, characterized by rapid and uniform heating, can greatly inhibit the excess growth of H₂WO₄ colloids and help to disperse tungsten oxide on alumina uniformly and quickly. When the HEDP is used as phosphorus resource, catalyst prepared via MWH method shows much higher WO₃ dispersion and HDN activity than that with the same phosphorus and metal contents prepared by impregnation method. The catalyst prepared via MWH method with 3% phosphorus combines high WO₃ dispersion with weak tungsten-alumina interaction, leading to the highest HDN activity.

Key words: catalyst, hydrogenation, microwave, hydrothermal, phosphorous

摘要： 采用微波水热法(MWH)制备含磷W/Al₂O₃加氢精制催化剂, 分别以磷酸(PA)、磷酸三乙酯(TEP)和羟基乙叉二磷酸(HEDP)为磷源, 考察磷源、制备方法和磷含量对催化剂物化性质和加氢脱氮(HDN)性能的影响。结果表明, 使用HEDP为磷源不仅可减弱活性组分-载体间的相互作用, 其结构中的羟基还可与MWH产生的H₂WO₄形成氢键而吸附在H₂WO₄表面, 抑制H₂WO₄团聚, 从而实现WO₃的高分散。MWH快速均匀加热的特点可以有效抑制H₂WO₄的过度生长, 并促进其在Al₂O₃表面的均匀快速分散, 使得以HEDP为磷源制备的W/Al₂O₃中WO₃的分散度和HDN活性远高于浸渍法制备的相同磷源、磷含量和金属含量的催化剂。MWH法制备的磷质量分数为3%的催化剂兼具高的WO₃分散度和弱的WO₃-Al₂O₃相互作用, 有最佳的HDN活性。

关键词: 催化剂, 加氢, 微波, 水热, 磷

CLC Number:

TQ426

WANG Hao, ZHAO Wanying, LIU Zhenwei, YAO Zhenyu, WU Yan. Preparation of phosphorous-containing W/Al₂O₃ catalysts via microwave hydrothermal method and their hydrodenitrogen activity[J]. Chemical Industry and Engineering Progree, 2015, 34(06): 1646-1651.

王豪, 赵婉莹, 刘振伟, 尧振宇, 吴雁. 微波水热法制备含磷W/Al₂O₃催化剂及其加氢脱氮性能[J]. 化工进展, 2015, 34(06): 1646-1651.

References

[1] 于道永, 徐海, 阙国和. 石油非加氢脱氮技术进展[J]. 化工进展, 2001, 20(10):32-35.
[2] 李矗, 王安杰, 鲁墨弘, 等. 加氢脱氮反应与加氢脱氮催化剂的研究进展[J]. 化工进展, 2003, 22(6):583-588.
[3] 刘志红, 王豪, 鲍晓军. 提高柴油加氢精制催化剂活性的方法[J]. 化工进展, 2008, 27(2):173-179.
[4] Yu G, Zhou Y, Wei Q, et al. A novel method for preparing well dispersed and highly sulfided NiW hydrodenitrogenation catalyst[J]. Catalysis Communications, 2012, 23:48-53.
[5] 周同娜, 尹海亮, 韩姝娜, 等. 磷对Ni(Co)Mo(W)/Al₂O₃加氢处理催化剂的影响研究进展[J]. 化工进展, 2008, 27(10):1581-1587.
[6] 孙艳茹, 李凤艳, 李庆杰, 等. 磷含量对负载型磷化钼催化剂性能的影响[J]. 石油炼制与化工, 2008(8):46-49.
[7] Fan Y, Bao X J, Wang H, et al. A surfactant-assisted hydrothermal deposition method for preparing highly dispersed W/γ-Al₂O₃ hydrodenitrogenation catalyst[J]. Journal of Catalysis, 2007, 245(2):477-481.
[8] Wang H, Fan Y, Shi G, et al. Preparation of hydrotreating catalysts via an oxalic acid-assisted hydrothermal deposition method[J]. Journal of Catalysis, 2008, 260(1):119-127.
[9] Wang H, Fan Y, Shi G, et al. Highly dispersed NiW/γ-Al₂O₃ catalyst prepared by hydrothermal deposition method[J]. Catalysis Today, 2007, 125(3-4):149-154.
[10] Wang H, Wu Y, Liu Z W, et al. Deposition of WO₃ on Al₂O₃ via a microwave hydrothermal method to prepare highly dispersed W/Al₂O₃ hydrodesulfurization catalyst[J]. Fuel, 2014, 136:185-193.
[11] Raghuveer C S, Thybaut J W, De Bruycker R, et al. Pyridine hydrodenitrogenation over industrial NiMo/γ-Al₂O₃ catalyst:Application of gas phase kinetic models to liquid phase reactions[J]. Fuel, 2014, 125:206-218.
[12] Anabtawi J A, Mann R S, Khulbe K C. Hydrogenation of pyridine over Ni-W/Al₂O₃ catalyst[J]. Journal of Catalysis, 1980, 63(2):456-462.
[13] 姜传海. X射线衍射技术及其应用[M]. 上海:华东理工大学出版社, 2010:210-213.
[14] 吴雁, 王豪, 钟婷, 等. 水滑石负载碳酸钾的微波法制备及其催化酯化原油脱酸性能[J]. 燃料化学学报, 2011(11):831-837.
[15] Cremonesi A, Bersani D, Lottici P, et al. WO₃thin films by sol-gel for electrochromic applications[J]. Journal of Non-Crystalline Solids, 2004, 345/346:500-504.
[16] Fan Y, Xiao H, Shi G, et al. Citric acid-assisted hydrothermal method for preparing NiW/USY-Al₂O₃ ultradeep hydrodesulfurization catalysts[J]. Journal of Catalysis, 2011, 279(1):27-35.
[17] Sun M, Nicosia D, Prins R. The effects of fluorine, phosphate and chelating agents on hydrotreating catalysts and catalysis[J]. Catalysis Today, 2003, 86(1-4):173-189.
[18] 唐清华. 微波辐射下PET水解过程中分子量的变化与解聚机理研究[D]. 温州:温州大学, 2012.
[19] Atanasova P, Tabakova T, Vladov C, et al. Effect of phosphorus concentration and method of preparation on the structure of the oxide form of phosphorus-nickel-tungsten/alumina hydrotreating catalysts[J]. Applied Catalysis A:General, 1997, 161(1-2):105-119.
[20] 靳明程, 段爱军, 兰玲, 等. 磷改性的含USL沸石催化剂在柴油加氢精制中的应用[J]. 工业催化, 2010(10):42-49.
[21] Yang X, Gao R, Dai W, et al. Influence of tungsten precursors on the structure and catalytic properties of WO₃/SBA-15 in the selective oxidation of cyclopentene to glutaraldehyde[J]. The Journal of Physical Chemistry C, 2008, 112(10):3819-3826.
[22] Cruz J, Avalos Borja M, López Cordero R, et al. Influence of pH of the impregnation solution on the phosphorus promotion in W/Al₂O₃ hydrotreating catalysts[J]. Applied Catalysis A:General, 2002, 224(1):97-110.
[23] Duan A, Li R, Jiang G, et al. Hydrodesulphurization performance of NiW/TiO₂-Al₂O₃ catalyst for ultra clean diesel[J]. Catalysis Today, 2009, 140(3-4):187-191.
[24] Yao S, Zheng Y, Ng S, et al. The role of nanobeta zeolite in NiMo hydrotreating catalysts[J]. Applied Catalysis A:General, 2012, 435-436:61-67.
[25] Xiang C, Chai Y, Fan J, et al. Effect of phosphorus on the hydrodesulfurization and hydrodenitrogenation performance of presulfided NiMo/Al₂O₃ catalyst[J]. Journal of Fuel Chemistry and Technology, 2011, 39(5):355-360.

Preparation of phosphorous-containing W/Al₂O₃ catalysts via microwave hydrothermal method and their hydrodenitrogen activity

微波水热法制备含磷W/Al₂O₃催化剂及其加氢脱氮性能

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHANG Mingyan, LIU Yan, ZHANG Xueting, LIU Yake, LI Congju, ZHANG Xiuling. Research progress of non-noble metal bifunctional catalysts in zinc-air batteries [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 276-286.
[2]	SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[3]	XIE Luyao, CHEN Songzhe, WANG Laijun, ZHANG Ping. Platinum-based catalysts for SO₂ depolarized electrolysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 299-309.
[4]	YANG Xiazhen, PENG Yifan, LIU Huazhang, HUO Chao. Regulation of active phase of fused iron catalyst and its catalytic performance of Fischer-Tropsch synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 310-318.
[5]	WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.
[6]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[7]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[8]	WANG Jingang, ZHANG Jianbo, TANG Xuejiao, LIU Jinpeng, JU Meiting. Research progress on modification of Cu-SSZ-13 catalyst for denitration of automobile exhaust gas [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4636-4648.
[9]	WANG Peng, SHI Huibing, ZHAO Deming, FENG Baolin, CHEN Qian, YANG Da. Recent advances on transition metal catalyzed carbonylation of chlorinated compounds [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4649-4666.
[10]	ZHANG Qi, ZHAO Hong, RONG Junfeng. Research progress of anti-toxicity electrocatalysts for oxygen reduction reaction in PEMFC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4677-4691.
[11]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[12]	WANG Weitao, BAO Tingyu, JIANG Xulu, HE Zhenhong, WANG Kuan, YANG Yang, LIU Zhaotie. Oxidation of benzene to phenol over aldehyde-ketone resin based metal-free catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4706-4715.
[13]	GE Yafen, SUN Yu, XIAO Peng, LIU Qi, LIU Bo, SUN Chengying, GONG Yanjun. Research progress of zeolite for VOCs removal [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4716-4730.
[14]	WANG Xueting, GU Xia, XU Xianbao, ZHAO Lei, XUE Gang, LI Xiang. Effectiveness of hydrothermal pretreatment on valeric acid production during food waste fermentation [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4994-5002.
[15]	MAO Shanjun, WANG Zhe, WANG Yong. Group recognition hydrogenation: From concept to application [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3917-3922.