分子筛调变氧化铝载体对Ni-Mo催化剂加氢脱氮活性的影响
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摘要
分别以SAPO-5,Beta,Y分子筛与拟薄水铝石打浆成型制备载体,然后在载体上负载Ni-Mo金属组分制备成加氢催化剂,考察了氧化铝载体中引入不同类型分子筛对催化剂酸性、金属形貌与加氢脱氮性能的影响。NH_3-TPR,Py-IR,H_2-TPR,HR-TEM等表征结果表明:与单纯采用氧化铝载体制备的催化剂相比,载体中引入分子筛提高了催化剂的酸强度与酸量,调变了载体表面性质,减小了MoS_2片晶长度,增加了片晶的堆积层数,分子筛类型不同对催化剂的酸性与金属形貌影响程度亦有所差异。4种催化剂对焦化蜡油加氢脱氮性能的评价结果表明:氧化铝载体中引入分子筛可提高催化剂的加氢脱氮活性,加氢活性高的催化剂对非碱性氮脱除的选择性高,氢解活性高的催化剂对碱性氮脱除的选择性高。
The carriers were prepared by beating and modeling SAPO-5,Beta,Y molecular sieves and pseudo-boehmite,respectively.The hydrodenitrogenation(HDN)catalysts were prepared by loading NiMo metal components on the prepared carriers.The influence of different types of molecular sieves added into alumina carrier on catalyst acidity,metal morphology and HDN performance were investigated.The characterization results of NH_3-TPR,Py-IR,H_2-TPR,HR-TEM indicated that compared with pure alumina carrier catalysts,the introduction of molecular sieve increases catalysts acidity amount and strength,modifies carrier surface property,decreasing MoS_2 lamella length but increasing stacked layers number.Different types of molecular sieves have different impacts on the catalysts acidity and metal morphology.The evaluation results of HDN of coker gasoil illustrated that introducing molecular sieves into alumina carrier improves the HDN activity of catalysts;the catalysts with high hydrogenation activity have a higher selectivity to non-basic nitrogen removal,while the catalysts with high hydrogenolysis activity have a higher selectivity to basic nitrogen removal.
The carriers were prepared by beating and modeling SAPO-5,Beta,Y molecular sieves and pseudo-boehmite,respectively.The hydrodenitrogenation(HDN)catalysts were prepared by loading NiMo metal components on the prepared carriers.The influence of different types of molecular sieves added into alumina carrier on catalyst acidity,metal morphology and HDN performance were investigated.The characterization results of NH_3-TPR,Py-IR,H_2-TPR,HR-TEM indicated that compared with pure alumina carrier catalysts,the introduction of molecular sieve increases catalysts acidity amount and strength,modifies carrier surface property,decreasing MoS_2 lamella length but increasing stacked layers number.Different types of molecular sieves have different impacts on the catalysts acidity and metal morphology.The evaluation results of HDN of coker gasoil illustrated that introducing molecular sieves into alumina carrier improves the HDN activity of catalysts;the catalysts with high hydrogenation activity have a higher selectivity to non-basic nitrogen removal,while the catalysts with high hydrogenolysis activity have a higher selectivity to basic nitrogen removal.
引文
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[19]吕伟超,周亚松,李瑞峰,等.柠檬酸与磷的改性对Ni-Mo?Al2O3焦化蜡油加氢脱氮性能的影响[J].石油学报(石油加工),2014,30(2):218-223
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[2]方向晨,关明华,廖志纲,等.加氢裂化[M].北京:中国石化出版社,2008:90-96
[3]韩崇仁.加氢裂化工艺与工程[M].北京:中国石化出版社,2006:53-60
[4]韩璐,周亚松,魏强,等.NiW?Al2O3催化剂酸性与加氢活性的调变及对重油加氢脱氮性能的影响[J].燃料化学学报,2014,42(10):1233-1239
[5]陈子莲,王继锋,杨占林,等.硼对NiMo?γ-Al2O3加氢处理催化剂性能的影响[J].石油学报(石油加工),2016,32(1):56-63
[6]Ding Lianghui,Zhang Zisheng,Zheng Ying,et al.Effect of fluorine and boron modification on the HDS,HDN and HDAactivity of hydrotreating catalysts[J].Applied Catalysis A:General,2006,301(2):241-250
[7]Lewandowski M,Sarbak Z.The effect of boron addition on hydrodesulfurization and hydrodenitrogenation activity of NiMo?Al2O3catalysts[J].Fuel,2000,79(5):487-495
[8]Nguyen M T,Tayakout-Fayolle M,Chainet F,et al.Use of kinetic modeling for investigating support acidity effects of NiMo sulfide catalysts on quinoline hydrodenitrogenation[J].Applied Catalysis A:General,2017,530:435-445
[9]李伟,戴文新,关乃佳,等.以大孔容TiO2和大孔容Al2O3为混合载体的加氢脱氮(HDN)催化剂的研究[J].燃料化学学报,2000,28(4):352-35
[10]Xiang Chun’e,Chai Yongming,Liu Chenguang,et al.Effect of phosphorus on the hydrodesulfurization and hydrodenitrogenation performance of presulfided NiMo?Al2O3 catalyst[J].Journal of Fuel Chemistry&Technology,2011,39(5):355-360
[11]Fan Yu,Xiao Han,Shi Gang,et al.Citric acid-assisted hydrothermal method for preparing NiW?USY-Al2O3 ultradeep hydrodesulfurization catalysts[J].Journal of Catalysis,2011,279(1):27-35
[12]肖寒,刘红光,杨建国,等.多级孔SAPO-5分子筛的合成及其在柴油加氢精制催化剂中的应用[J].石油炼制与化工,2013,44(1):16-21
[13]Ding Lianghui,Zheng Ying,Zhang Zisheng,et al.Hydrotreating of light cycled oil using WNi?Al2O3catalysts containing zeolite beta and?or chemically treated zeolite Y[J].Journal of Catalysis,2006,241(2):435-445
[14]Fan Yu,Xiao Han,Shi Gang,et al.Alkylphosphonic acid-and small amine-templated synthesis of hierarchical silicoaluminophosphate molecular sieves with high isomerization selectivity to di-branched paraffins[J].Journal of Catalysis,2012,285(1):251-259
[15]肖寒,于海斌,杨建国,等.晶种硅烷化合成小粒径SAPO-11分子筛及其临氢异构化性能[J].石油炼制与化工,2014,45(1):30-36
[16]Coonradt H L,Garwood W E.Hydroisomerization and hydrocracking of long-chain normal paraffins[J].Ind Eng Chem Process Des Dev,1964,3(3):36-38
[17]杨占林,姜虹,唐兆吉,等.FF-56加氢裂化预处理催化剂的制备及其性能[J].石油化工,2014,43(9):1008-1013
[18]肖寒,于海斌,杨建国,等.THDS-I加氢精制催化剂的研发与性能评价[J].石油炼制与化工,2016,47(6):66-71
[19]吕伟超,周亚松,李瑞峰,等.柠檬酸与磷的改性对Ni-Mo?Al2O3焦化蜡油加氢脱氮性能的影响[J].石油学报(石油加工),2014,30(2):218-223
[20]温世昌,周亚松,魏强.焦化蜡油中含氮化合物的加氢反应性能[J].石油学报(石油加工),2008,24(2):151-157