柠檬酸对NiMo/γ-Al_2O_3催化剂中助剂Ni作用的影响
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摘要
向一系列不同金属原子比[r=n(Ni)/n(Ni+Mo)]的NiMo/γ-Al2O3催化剂中引入柠檬酸,考察了柠檬酸对NiMo催化剂加氢脱硫活性的影响,并采用XRD,XPS,HRTEM等表征手段,从活性金属分散性、硫化度、活性相比例以及活性相形貌等方面分析了柠檬酸对助剂Ni作用的影响。结果表明:当r<0.3时,柠檬酸对NiMo催化剂的加氢脱硫活性有促进作用,柠檬酸的引入提高了催化剂的硫化度和NiMoS活性相的比例,有利于形成片晶尺寸较小、堆叠层数较多的活性相,对Ni的助剂效应有小幅促进作用;但是当r≥0.3时,柠檬酸对NiMo催化剂的加氢脱硫活性基本没有促进作用,柠檬酸的引入并未明显改变NiMo催化剂的活性金属硫化度、NiMoS活性相比例以及活性相形貌,对Ni的助剂效应影响较小。
A series of NiMo/γ-Al_2O_3 catalysts with different metal atomic ratio(n(Ni)/n(Ni+Mo))was prepared with or without citric acid(CA)as chelating agent.The effect of CA on the hydrodesulfurization activity of NiMo/γ-Al_2O_3 catalysts was studied.The catalysts were characterized by means of XRD,XPS,HRTEM techniques to inspect active metal dispersion,sulfidation extent,active phase morphology,as well as active phase ratio.The results showed that when the metal atomic ratio was below0.3,CA has a positive effect on the catalytic activity of NiMo/γ-Al_2O_3 catalysts;the sulfidation degree of Mo species and the ratio of NiMoS active phases are increased,which is in favor of forming active phases with smaller slab length and slightly higher stacking number,indicating a moderate positive influence on the role of Ni.However,when the atomic ratio was above 0.3,CA has little effect on the catalytic activity of NiMo/γ-Al_2O_3 catalysts.Due to the fact that CA almost has no influence on the dispersion of active metals,the sulfidation degree of Mo species,the ratio of NiMoS active phases,and the morphology of active phases,the effect of CA on the role of Ni is small.
A series of NiMo/γ-Al_2O_3 catalysts with different metal atomic ratio(n(Ni)/n(Ni+Mo))was prepared with or without citric acid(CA)as chelating agent.The effect of CA on the hydrodesulfurization activity of NiMo/γ-Al_2O_3 catalysts was studied.The catalysts were characterized by means of XRD,XPS,HRTEM techniques to inspect active metal dispersion,sulfidation extent,active phase morphology,as well as active phase ratio.The results showed that when the metal atomic ratio was below0.3,CA has a positive effect on the catalytic activity of NiMo/γ-Al_2O_3 catalysts;the sulfidation degree of Mo species and the ratio of NiMoS active phases are increased,which is in favor of forming active phases with smaller slab length and slightly higher stacking number,indicating a moderate positive influence on the role of Ni.However,when the atomic ratio was above 0.3,CA has little effect on the catalytic activity of NiMo/γ-Al_2O_3 catalysts.Due to the fact that CA almost has no influence on the dispersion of active metals,the sulfidation degree of Mo species,the ratio of NiMoS active phases,and the morphology of active phases,the effect of CA on the role of Ni is small.
引文
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[19]Shimizu T,Hiroshima K,Honma T,et al.Highly active hydrotreatment catalysts prepared with chelating agents[J].Catalysis Today,1998,45(1):271-276
[20]Qiu Limei,Xu Guangtong.Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts[J].Applied Surface Science,2010,256(11):3413-3417
[21]邱丽美,刘清河,徐广通.X射线光电子能谱法研究加氢脱硫催化剂中活性元素的化学态[J].石油学报(石油加工),2011,27(4):638-642
[22]张乐,李明丰,丁石,等.原料性质对柴油超深度加氢脱硫NiMoW/Al2O3催化剂活性稳定性的影响[J].石油学报(石油加工),2017,33(5):834-841
[2]郑丽君,朱庆云,李雪静.我国汽柴油质量升级步伐加快[J].中国石化,2017(3):39-42
[3]任正时,姜晓辉,丁扬,等.我国车用汽柴油质量升级进程及其积极意义分析[J].中国石油和化工标准与质量,2017(11):39-41
[4] Absi H M,Stanislaus A,Al Dalama K.Performance comparison of alumina-supported NiMo,NiW and Ni-Mo-W catalysis in hydrotreating vacuum residue[J].Fuel,1998,77(7):787-790
[5] Pratt K C,Sanders J V,Tamp N.The role of nickel in the activity of unsupported NiMo hydrodesulfurization catalysts[J].Journal of Catalysis,1980,66(1):82-92
[6] Egorova M,Prins R.Hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene over sulfided NiMo/γ-Al2O3,CoMo/γ-Al2O3,and Mo/γ-Al2O3catalysts[J].Journal of Catalysis,2004,225(2):417-427
[7]聂红,李会峰,龙湘云,等.络合制备技术在加氢催化剂中的应用[J].石油学报(石油加工),2015,31(2):250-258
[8] Yoshimura Y,Sato T,Shimada H,et al.Preparation of nickel-tungstate catalysts by a novel impregnation method[J].Catalysis Today,1996,29(1/2/3/4):221-228
[9] Calderón-Magdaleno M,Mendoza-Nieto J A,Klimova T E.Effect of the amount of citric acid used in the preparation of NiMo/SBA-15catalysts on their performance in HDS of dibenzothiophene-type compounds[J].Catalysis Today,2014,220:78-88
[10]Rinaldi N,Kubota T,Okamoto Y.Effect of citric acid addition on the hydrodesulfurization activity of MoO3/Al2O3catalysts[J].Applied Catalysis A:General,2010,374(1):228-236
[11]Li Huifeng,Li Mingfeng,Chu Yang,et al.Essential role of citric acid in preparation of efficient NiW/Al2O3 HDS catalysts[J].Applied Catalysis A:General,2011,403(1):75-82
[12]Kubota T,Rinaldi N,Okumura K,et al.In situ XAFS study of the sulfidation of Co-Mo/B2O3/Al2O3hydrodesulfurization catalysts prepared by using citric acid as a chelating agent[J].Applied Catalysis A:General,2010,373(1):214-221
[13]聂红,龙湘云,刘清河,等.柠檬酸对NiW/Al2O3加氢脱硫催化剂硫化行为的影响[J].石油学报(石油加工),2010,26(3):329-335
[14]倪雪华,龙湘云,聂红,等.硫化温度对NiW/Al2O3催化剂加氢脱硫性能的影响[J].石油学报(石油加工),2014,30(1):7-14
[15]Lélias M A,Kooyman P J,Mariey L,et al.Effect of NTA addition on the structure and activity of the active phase of cobalt-molybdenum sulfide hydrotreating catalysts[J].Journal of Catalysis,2009,267(1):14-23
[16]Lélias M A,Le Guludec E,Mariey L,et al.Effect of EDTA addition on the structure and activity of the active phase of cobalt-molybdenum sulfide hydrotreatment catalysts[J].Catalysis Today,2010,150(3/4):179-185
[17]户安鹏,聂红,陈文斌,等.柠檬酸对CoMo/Al2O3催化剂中助剂作用的影响[J].石油炼制与化工,2015,46(9):1-6
[18]Klimova T E,Valencia D,Mendoza-Nieto J A,et al.Behavior of NiMo/SBA-15catalysts prepared with citric acid in simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene[J].Journal of Catalysis,2013,304:29-46
[19]Shimizu T,Hiroshima K,Honma T,et al.Highly active hydrotreatment catalysts prepared with chelating agents[J].Catalysis Today,1998,45(1):271-276
[20]Qiu Limei,Xu Guangtong.Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts[J].Applied Surface Science,2010,256(11):3413-3417
[21]邱丽美,刘清河,徐广通.X射线光电子能谱法研究加氢脱硫催化剂中活性元素的化学态[J].石油学报(石油加工),2011,27(4):638-642
[22]张乐,李明丰,丁石,等.原料性质对柴油超深度加氢脱硫NiMoW/Al2O3催化剂活性稳定性的影响[J].石油学报(石油加工),2017,33(5):834-841