高分散Ru-PEG_x/NaY催化对硝基甲苯加氢制对甲基环己胺
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摘要
以聚乙二醇[PEG(400)]为分散剂、(NH_4)_2CO_3水溶液为沉淀剂,采用浸渍沉淀法,制备了高分散的Ru-PEG_x/NaY催化剂,利用XRD、TEM、H_2-TPR、ICP-AES及XPS等手段对样品进行了表征。结果表明:适量的(7.5 mL)PEG可以包裹住Ru~(3+),增大Ru~(3+)之间的排斥力,从而有效地阻止Ru~(3+)的团聚。以对硝基甲苯液相(PNT)加氢制对甲基环己胺(PMC)为探针反应,以PNT转化率和PMC选择性为指标考察了不同Ru催化剂的催化性能。结果表明:Ru-PEG7.5/NaY的催化性能最优,在催化剂0.50 g、反应时间35 min、H_2压力3.5 MPa、反应温度160℃、对硝基甲苯5.00 g、搅拌速率900 r/min、异丙醇300 mL的条件下,PNT的转化率为100%,PMC的选择性高达95.0%。此外,发现Ru-PEG7.5/NaY催化剂重复使用5次后,活性未明显降低,说明其稳定性良好。
A high dispersion Ru-PEG_x/Na Y catalyst was prepared by impregnation-precipitation method using PEG(400) as dispersant and(NH_4)_2 CO_3 as precipitant. The samples were characterized by XRD, TEM, H_2-TPR, ICP-AES and XPS. The results showed that the suitable PEG(7.5 mL) could trap the Ru~(3+)ions and increas the repulsion among Ru~(3+) ions, consequently, which could effectively prevent agglomeration of the Ru~(3+) particles. The catalytic performances of different samples were evaluated vialiquid-phase hydrogenation of p-nitrotoluene(PNT) to p-methyl-cyclohexylamine(PMC) reaction, with the PNT conversion and PMC selectivity as indicator. The results indicated that Ru-PEG7.5/Na Y exhibited the best catalytic performance. The PNT conversion and the selectivity of PMC were found to be as high as 100% and 95.0% under the optimum conditions of Ru-PEG_x/NaY dosage 0.50 g, reaction time 35 min, pressure of H_2 3.5 MPa, reaction temperature 160 ℃, amount of PNT 5.00 g, stirring rate 900 r/min, and isopropyl alcohol 300 m L. In addition, it was found that the activity of Ru-PEG7.5/Na Y was not significantly decreased after five repeated recycling runs, indicating Ru-PEG7.5/NaY catalyst had good stability.
A high dispersion Ru-PEG_x/Na Y catalyst was prepared by impregnation-precipitation method using PEG(400) as dispersant and(NH_4)_2 CO_3 as precipitant. The samples were characterized by XRD, TEM, H_2-TPR, ICP-AES and XPS. The results showed that the suitable PEG(7.5 mL) could trap the Ru~(3+)ions and increas the repulsion among Ru~(3+) ions, consequently, which could effectively prevent agglomeration of the Ru~(3+) particles. The catalytic performances of different samples were evaluated vialiquid-phase hydrogenation of p-nitrotoluene(PNT) to p-methyl-cyclohexylamine(PMC) reaction, with the PNT conversion and PMC selectivity as indicator. The results indicated that Ru-PEG7.5/Na Y exhibited the best catalytic performance. The PNT conversion and the selectivity of PMC were found to be as high as 100% and 95.0% under the optimum conditions of Ru-PEG_x/NaY dosage 0.50 g, reaction time 35 min, pressure of H_2 3.5 MPa, reaction temperature 160 ℃, amount of PNT 5.00 g, stirring rate 900 r/min, and isopropyl alcohol 300 m L. In addition, it was found that the activity of Ru-PEG7.5/Na Y was not significantly decreased after five repeated recycling runs, indicating Ru-PEG7.5/NaY catalyst had good stability.
引文
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[4]HouJie(侯洁),GuoFang(郭方),WangYue(王越).Selective hydrogenation of m-D initrobenzene to m-Nitroaniline over modified skeletal Ru[J]. Fine Chemicals(精细化工), 2006, 23(11):1064-1067.
[5]LuX,JieH,Jing R,etal.Microwave-activatedNi/carboncatalysts for highly selective hydrogenation of nitrobenzene to cyclohexylamine[J].Scientific Reports, 2017, 7(1):2676-2677.
[6]JiaL,ZhangQ,LiQ,etal.Thebiosynthesisofpalladium nanoparticlesbyantioxidantsinGardeniajasminoidesEllis:long lifetime nanocatalysts for p-nitrotoluene hydrogenation[J]. Nanotechnology,2009, 20(38):385601-385611.
[7]WangZhi(王植),LiuBiwu(刘必武).Developmentofcatalystfor makingcyclohexylamineanddicyclohexylaminebyhydrogenation ofaniline[J].JiangsuChemicalIndustry(江苏化工),2002,30(4):31-34.
[8]Lu Jianghuan(鲁新环), Jiang Hezhan(江和展), Wei Xianlong(危先龙).Highlyselectivecatalytichydrogenationsteppreparationof cyclohexylaminemethodofnitrobenzene:CN103772207B[P].2014-5-7.
[9]Li G, Dong P, Ji D, et al. Effect of support materials on liquid-phase hydrogenationofhydroquinoneoverrutheniumcatalysts[J].Solid State Sciences, 2013, 23(9):13-16.
[10]LiH,JiD,LiY,etal.Effectofalkalineearthmetalsonthe liquid-phasehydrogenationofhydroquinoneoverRu-based catalysts[J]. Solid State Sciences, 2015, 50:85-90.
[11]SongL,LiX,WangH,etal.RuNanoparticlesentrappedin mesopolymersforefficientliquid-phasehydrogenationof unsaturated compounds[J]. Catalysis Letters, 2009, 133(2):63-69.
[12]DongRulin(董如林),MaLi(马丽),ZhangFeng(张锋).Effectof polyethyleneglycolonthedispersionofAl2O3particlesinan aqueous suspension[J]. Journal of Jiangsu Polytechnic University(江苏工业学院学报), 2009, 21(1):28-33.
[13]Bai G, Li F, Fan X, et al. Continuous hydrogenation of hydroquinone to1,4-cyclohexanedioloveralkalineearthmetalmodifiednickelbased catalysts[J]. Catalysis Communications, 2012, 17(1):126-130.
[14]Yang Xiaolong(杨晓龙), Xia Chungu(夏春谷), Tang Liping(唐立平).EffectofMgOsupportandBaOpromoteronstructureand catalyticactivityofRutheniumcatalystsforammoniasynthesis[J].ChineseJournalofInorganicChemistry(物理化学学报),2010,26(12):3263-3272.
[15]WangZiqing(王自庆),ChenGeng(陈赓),LinJianxin(林建新).Preparation of Ru/Ba-ZrO2 catalyst and its performance for ammonia synthesis[J]. Acta Chimica Sinica(化学学报), 2013, 71(2):205-212.
[16]DingY,LiX,PanH,etal.Runanoparticlesentrappedinordered mesoporouscarbons:anefficientandreusablecatalystforliquidphase hydrogenation[J]. Catalysis Letters, 2014, 144(2):268-277.
[17]EgorovKV,LebedinskiiYY,SolovievAA,etal.Initialand steady-state Ru growth by atomic layer deposition studied by in situ,angle resolved X-ray photoelectron Spectroscopy[J]. Applied Surface Science, 2017, 419:107-113.