Ce浸渍方式对CoMo/CeAl_2O_3催化剂反应性能影响
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摘要
针对具有较高脱硫活性的CoMo/CeAl_2O_3催化剂,考察了Ce的不同浸渍方式对催化剂表面金属性质及催化活性的影响。结果表明,Ce采用不同浸渍方式(CoMo共浸渍)制备催化剂的加氢脱硫活性大小顺序为:先浸渍Ce后浸渍CoMo催化剂(CoMoCe/Al_2O_3)>先浸渍CoMo后浸渍Ce催化剂(CeCoMo/Al_2O_3)>Ce与载体混粘后浸渍CoMo催化剂(CoMo/CeAl_2O_3)。对于CoMoCe/Al_2O_3催化剂,先浸渍Ce减弱了二次浸渍CoMo时载体与Mo物种间的相互作用力,有利于Mo物种硫化,提高了硫化度,生成了较多的CoMoS活性相,增加了脱硫率;用实验室自组装固定床微型反应装置对CoMoCe/Al_2O_3催化剂进行了活性评价,以广西石化分公司(广西石化)重馏分油(≥65℃)为原料油时,产物硫含量可以降至8.6μg/g,RON损失1.3个单位。
Series CoMo/CeAl_2O_3 catalysts were prepared by using different impregnation way of cerium and their performance in hydrodesulfurization was investigated. The results showed that the activity of the catalysts is in the following order CoMoCe/Al_2O_3>CeCoMo/Al_2O_3>CoMo/CeAl_2O_3. For the CoMoCe/Al_2O_3 catalyst, cerium was loaded on the Al_2O_3 at the first stage and thus can weaken the interaction between molybdenum and supporter, and are helpful for the sulfurization of molybdenum, which can promote the formation of CoMoS active phase and then enhance the catalytic performance of CoMoCe/Al_2O_3 in hydrodesulfurization. Heavy gas oil from Guangxi Petrochemical Company was processed with the CoMoCe/Al_2O_3 catalyst in a self-made fixed-bed micro reactor and the sulfur content of the product was reduced to 8.6μg/g, and the RON loss was 1.3.
Series CoMo/CeAl_2O_3 catalysts were prepared by using different impregnation way of cerium and their performance in hydrodesulfurization was investigated. The results showed that the activity of the catalysts is in the following order CoMoCe/Al_2O_3>CeCoMo/Al_2O_3>CoMo/CeAl_2O_3. For the CoMoCe/Al_2O_3 catalyst, cerium was loaded on the Al_2O_3 at the first stage and thus can weaken the interaction between molybdenum and supporter, and are helpful for the sulfurization of molybdenum, which can promote the formation of CoMoS active phase and then enhance the catalytic performance of CoMoCe/Al_2O_3 in hydrodesulfurization. Heavy gas oil from Guangxi Petrochemical Company was processed with the CoMoCe/Al_2O_3 catalyst in a self-made fixed-bed micro reactor and the sulfur content of the product was reduced to 8.6μg/g, and the RON loss was 1.3.
引文
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[24]秦鸣霞,俞斌,杨婧,等.金属改性对Co-Mo/γ-Al2O3加氢脱硫催化剂选择性的影响[J].工业催化, 2009, 17(5):45-49.QIN Mingxia, YU Bin, YANG Jing, et al. Effect of metal modification on selectivity of Co-Mo/γ-Al2O3hydrodesulfurization catalysts[J].Industrial Catalysis, 2009, 17(5):45-49.
[25]温广明,王文寿,陈黎行,等. ZnO/θ-Al2O3催化剂上全馏分FCC汽油的选择性加氢脱硫[J].催化学报, 2007, 28(9):823-828.WEN Guangming, WANG Wenshou, CHEN Lixing, et al. Selective hydrodesulfurization of full fraction FCC gasoline over ZnO/θ-Al2O3catalyst[J]. Chinese Journal of Catalysis, 2007, 28(9):823-828.
[26]温广明.全馏分FCC汽油选择性加氢脱硫催化剂的研究[D].大连:大连理工大学, 2007.WEN Guangming. Study on selective hydrodesulfurization catalyst for full fraction FCC gasoline[D]. Dalian:Dalian University of Technology,2007.
[27] HUO Q, DOU T, ZHAO Z, et al. Synthesis and application of a novel mesoporous zeolite L in the catalyst for the HDS of FCC gasoline[J].Applied Catalysis A:General, 2010, 381(1/2):1-8.
[28] EMEIS C A. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. Journal of Catalysis, 1993, 141(2):347-354.
[29] NINH T K T, MASSIN L, LAURENTI D, et al. A new approach in the evaluation of the support effect for NiMo hydrodesulfurization catalysts[J]. Applied Catalysis A:General, 2011, 407(1/2):29-39.
[30] LI H, LI M, NIE H. Tailoring the surface characteristic of alumina for preparation of highly active NiMo/Al2O3hydrodesulfurization catalyst[J]. Microporous and Mesoporous Materials, 2014, 188(4):30-36.
[31] LIU B, CHAI Y, LI Y, et al. Effect of sulfidation atmosphere on the performance of the CoMo/γ-Al2O3catalysts in hydrodesulfurization of FCC gasoline[J]. Applied Catalysis A:General, 2014, 471:70-79.
[32] GANDUBERT A D, KREBS E, LEGENS C, et al. Optimal promoter edge decoration of CoMoS catalysts:a combined theoretical and experimental study[J]. Catalysis Today, 2008, 130(1):149-159.
[33] BUI V N, LAURENTI D, DELICHèRE P, et al. Hydrodeoxygenation of guaiacol Part II:Support effect for CoMoS catalysts on HDO activity and selectivity[J]. Applied Catalysis B:Environmental, 2011, 1(3/4):246-255.
[34]孙淑玲,石亚华,徐广通,等. Co-Mo加氢脱硫催化剂的TEM表征[J].石油炼制与化工, 2006, 37(11):1-6.SUN Shuling, SHI Yahua, XU Guangtong, et al. TEM characterization of Co-Mo hydrodesulfurization catalysts[J]. Petroleum Processing and Petrochemicals, 2006, 37(11):1-6.
[2] BABICH I V, MOULIJN J. Science and technology of novel processes for deep desulfurization of oil refinery streams:a review[J]. Fuel, 2003,82(6):607-631.
[3] HUANG R J, ZHANG Y, BOZZETTI C, et al. High secondary aerosol contribution to particulate pollution during haze events in China[J].Nature, 2014, 514(7521):218-222.
[4] MCDONALD B C, DE J G, GILMAN J B, et al. Volatile chemical products emerging as largest petrochemical source of urban organic emissions[J]. Science, 2018, 359(6377):760-764.
[5]于沛,柯明,李建鹏,等. La对CoMo/γ-Al2O3催化剂选择性加氢脱硫性能的影响[J].石油炼制与化工, 2016, 47(8):13-19.YU Pei, KE Ming, LI Jianpeng, et al. Effect of La on selective hydrodesulfurization performance of CoMo/γ-Al2O3catalysts[J].Petroleum Processing and Petrochemicals, 2016, 47(8):13-19.
[6]胡乃方,崔海涛,邱泽刚,等.不同P负载量对Co-Mo/γ-Al2O3煤焦油加氢脱硫性能影响的研究[J].燃料化学学报, 2016, 44(6):745-753.HU Naifang, CUI Haitao, QIU Zegang, et al. Effect of different P loads on hydrodesulfurization performance of Co-Mo/γ-Al2O3coal tar catalysts[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6):745-753.
[7] SCHEFFER B, DEKKER N J J, MANGNUS P J, et al. A temperatureprogrammed reduction study of sulfided Co-Mo/Al2O3,hydrodesulfurization catalysts[J]. Journal of Catalysis, 1990, 121(1):31-46.
[8] YU P, KE M, LIU Q, et al. Enhancement of the selective hydrodesulfurization performance by adding cerium to CoMo/γ-Al2O3catalysts[J]. RSC Advances, 2016, 6(99):96662-96668.
[9]申志兵,柯明,张君涛,等.活性金属不同浸渍顺序对Mo-Ni/Al2O3催化剂硫醚化反应性能的影响[J].燃料化学学报, 2017(5):616-623.SHEN Zhibing, KE Ming, ZHANG Juntao, et al. Effect of different impregnation sequences of active metals on the thioetherification performance of Mo-Ni/Al2O3catalysts[J]. Journal of Fuel Chemistry and Technology, 2017(5):616-623.
[10] FAN Y, LU J, SHI G, et al. Effect of synergism between potassium and phosphorus on selective hydrodesulfurization performance of CoMo/Al2O3FCC gasoline hydro-upgrading catalyst[J]. Catalysis Today,2007, 125(3):220-228.
[11]张孔远,刘爱华,燕京,等.不同方法制备的CoMo/Al2O3加氢脱硫催化剂的表征[J].催化学报, 2005, 26(8):639-644.ZHANG Kongyuan, LIU Aihua, YAN Jing, et al. Characterization of CoMo/Al2O3hydrodesulfurization catalysts prepared by different methods[J]. Chinese Journal of Catalysis, 2005, 26(8):639-644.
[12] HENKERM,WENDLANDTKP,VALYONJ,etal.StructureofMoO3/Al2O3-SiO2, catalysts[J]. Applied Catalysis, 2015, 69(1):205-220.
[13] RAJAGOPAL S, MARINI H J, MARZARI J A, et al. Silica-aluminasupportedacidicmolybdenumcatalysts-TPRandXRD characterization[J]. Journal of Catalysis, 1994, 147(2):417-428.
[14] LAURITSEN J V, KIBSGAARD J, OLESEN G H, et al. Location and coordination of promoter atoms in Co-and Ni-promoted MoS2-based hydrotreating catalysts[J]. Journal of Catalysis, 2007, 249(2):220-233.
[15] YOOSUK B, KIM J H, SONG C, et al. Highly active MoS2, CoMoS2and NiMoS2unsupported catalysts prepared by hydrothermal synthesis for hydrodesulfurization of 4, 6-dimethyl-dibenzothiophene[J]. Catalysis Today, 2008, 130(1):14-23.
[16] JACOBSEN C J H, TORNQVIST E, TOPS?E H. HDS, HDN and HYD activities and temperature-programmed reduction of unsupported transition metal sulfides[J]. Catalysis Letters, 1999, 63(3):179-183.
[17] EMEIS C A. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. Journal of Catalysis, 1993, 141(2):347-354.
[18]朱玉霞,林伟,田辉平,等.固体酸催化剂酸性分析方法的研究进展[J].石油化工, 2006, 35(7):607-614.ZHU Yuxia, LIN Wei, TIAN Huiping, et al. Research progress on acid analysis methods of solid acid catalysts[J]. Petrochemical Technology,2006, 35(7):607-614.
[19] MASSOTH F E, MURALIDHAR G, SHABTAI J. Catalytic functionalities of supported sulfides:Ⅱ. Effect of support on Mo dispersion[J]. Journal of Catalysis, 1984, 85(1):53-62.
[20] RAYBAUD P, HAFNER J, KRESSE G, et al. Structural and electronic properties of the MoS2edge-surface[J]. Surface Science, 1998, 407(1/2/3):237-250.
[21] TOPS?E N, TOPS?E H, MASSOTH F E. Evidence of Br?nsted acidity on sulfided promoted and unpromoted Mo/Al2O3catalysts[J]. Journal of Catalysis, 1989, 119(1):252-255.
[22] PAUL J, CRISTOL S, PAYEN E. Computational studies of(mixed)sulfide hydrotreating catalysts[J]. Catalysis Today, 2008, 130(1):139-148.
[23] DEL ANGEL G, GUZMáN C, BONILLA A, et al. Lanthanum effect on the textural and structural properties ofγ-Al2O3obtained from boehmite[J]. Materials Letters, 2005, 59(4):499-502.
[24]秦鸣霞,俞斌,杨婧,等.金属改性对Co-Mo/γ-Al2O3加氢脱硫催化剂选择性的影响[J].工业催化, 2009, 17(5):45-49.QIN Mingxia, YU Bin, YANG Jing, et al. Effect of metal modification on selectivity of Co-Mo/γ-Al2O3hydrodesulfurization catalysts[J].Industrial Catalysis, 2009, 17(5):45-49.
[25]温广明,王文寿,陈黎行,等. ZnO/θ-Al2O3催化剂上全馏分FCC汽油的选择性加氢脱硫[J].催化学报, 2007, 28(9):823-828.WEN Guangming, WANG Wenshou, CHEN Lixing, et al. Selective hydrodesulfurization of full fraction FCC gasoline over ZnO/θ-Al2O3catalyst[J]. Chinese Journal of Catalysis, 2007, 28(9):823-828.
[26]温广明.全馏分FCC汽油选择性加氢脱硫催化剂的研究[D].大连:大连理工大学, 2007.WEN Guangming. Study on selective hydrodesulfurization catalyst for full fraction FCC gasoline[D]. Dalian:Dalian University of Technology,2007.
[27] HUO Q, DOU T, ZHAO Z, et al. Synthesis and application of a novel mesoporous zeolite L in the catalyst for the HDS of FCC gasoline[J].Applied Catalysis A:General, 2010, 381(1/2):1-8.
[28] EMEIS C A. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. Journal of Catalysis, 1993, 141(2):347-354.
[29] NINH T K T, MASSIN L, LAURENTI D, et al. A new approach in the evaluation of the support effect for NiMo hydrodesulfurization catalysts[J]. Applied Catalysis A:General, 2011, 407(1/2):29-39.
[30] LI H, LI M, NIE H. Tailoring the surface characteristic of alumina for preparation of highly active NiMo/Al2O3hydrodesulfurization catalyst[J]. Microporous and Mesoporous Materials, 2014, 188(4):30-36.
[31] LIU B, CHAI Y, LI Y, et al. Effect of sulfidation atmosphere on the performance of the CoMo/γ-Al2O3catalysts in hydrodesulfurization of FCC gasoline[J]. Applied Catalysis A:General, 2014, 471:70-79.
[32] GANDUBERT A D, KREBS E, LEGENS C, et al. Optimal promoter edge decoration of CoMoS catalysts:a combined theoretical and experimental study[J]. Catalysis Today, 2008, 130(1):149-159.
[33] BUI V N, LAURENTI D, DELICHèRE P, et al. Hydrodeoxygenation of guaiacol Part II:Support effect for CoMoS catalysts on HDO activity and selectivity[J]. Applied Catalysis B:Environmental, 2011, 1(3/4):246-255.
[34]孙淑玲,石亚华,徐广通,等. Co-Mo加氢脱硫催化剂的TEM表征[J].石油炼制与化工, 2006, 37(11):1-6.SUN Shuling, SHI Yahua, XU Guangtong, et al. TEM characterization of Co-Mo hydrodesulfurization catalysts[J]. Petroleum Processing and Petrochemicals, 2006, 37(11):1-6.