介孔碳负载Pt催化剂用于抗氧剂7PPD的合成
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摘要
以纳米氧化锌为模板剂,酚醛树脂为碳源,采用硬模板法制备了介孔碳(MC),并以其为载体制备了Pt/MC催化剂,同时,以商品化活性炭(AC)为载体制备了Pt/AC催化剂。对制备的样品进行BET、SEM、ICP和TEM表征。结果表明,氧化锌模板剂可有效调控介孔碳的比表面积和孔结构,Pt/MC催化剂和Pt/AC催化剂的Pt负载量(质量分数,下同)均为2.8%左右,活性金属粒径均为1.8nm左右。将制备的Pt/MC催化剂用于抗氧剂N-(1,4-二甲基戊基)-N'-苯基对苯二胺(7PPD)的合成,与普通Pt/AC催化剂相比,4-氨基二苯胺(p-ADPA)的转化率由97.5%提高至100%,7PPD选择性由94.2%提高至99.5%,催化剂的稳定性明显提高。CO化学吸附、ICP、N_2低温物理吸脱附表征结果表明,催化剂载体的孔结构是影响催化剂稳定性的重要因素。当平均孔径较小时,7PPD等较大尺寸的分子容易堵塞孔道;当平均孔径较大时,孔壁较薄,催化剂使用过程中容易磨损,导致活性组分流失。
Mesoporous carbon(MC) samples were prepared by hard template method using nano-zinc oxide particles with different size as template agents and phenolic resin as carbon source. A series of Pt/MC catalysts were prepared. Meanwhile, Pt/AC catalyst was prepared using commercial activated carbon(AC)as supports. These samples were characterized by N_2 adsorption-desorption, SEM, ICP and TEM. The results showed that nano-zinc oxide particles could effectively control the surface area and pore structure of mesoporous carbon supports. Pt loadings on MC and AC were 2.8%(mass fraction, the same below). The sizes of Pt nanoparticles were about 1.8 nm. These catalysts were used to synthesize antioxidant N-(1,4-dimethylpentyl)-N'-phenylbenzene-1,4-diamine(7 PPD). Compared with those of the conventional Pt/AC catalyst, the conversion of 4-aminodiphenylamine(p-ADPA) increased from 97.5% to 100%, and the selectivity of 7 PPD increased from 94.2% to 99.5%. The stability of the Pt/MC catalysts was obviously higher than that of Pt/AC catalyst. The fresh and used catalysts were characterized by CO chemisorption,ICP and N_2 adsorption-desorption. It was found that the pore structure of the support was an important factor affecting the stability of the catalyst. When the average pore diameter of the catalyst was small,molecules of 7 PPD and other large sizes were easy to block the pore passages. While the average pore diameter was larger, the pore walls were thinner and catalysts were worn easily, and the active component was lost easily.
Mesoporous carbon(MC) samples were prepared by hard template method using nano-zinc oxide particles with different size as template agents and phenolic resin as carbon source. A series of Pt/MC catalysts were prepared. Meanwhile, Pt/AC catalyst was prepared using commercial activated carbon(AC)as supports. These samples were characterized by N_2 adsorption-desorption, SEM, ICP and TEM. The results showed that nano-zinc oxide particles could effectively control the surface area and pore structure of mesoporous carbon supports. Pt loadings on MC and AC were 2.8%(mass fraction, the same below). The sizes of Pt nanoparticles were about 1.8 nm. These catalysts were used to synthesize antioxidant N-(1,4-dimethylpentyl)-N'-phenylbenzene-1,4-diamine(7 PPD). Compared with those of the conventional Pt/AC catalyst, the conversion of 4-aminodiphenylamine(p-ADPA) increased from 97.5% to 100%, and the selectivity of 7 PPD increased from 94.2% to 99.5%. The stability of the Pt/MC catalysts was obviously higher than that of Pt/AC catalyst. The fresh and used catalysts were characterized by CO chemisorption,ICP and N_2 adsorption-desorption. It was found that the pore structure of the support was an important factor affecting the stability of the catalyst. When the average pore diameter of the catalyst was small,molecules of 7 PPD and other large sizes were easy to block the pore passages. While the average pore diameter was larger, the pore walls were thinner and catalysts were worn easily, and the active component was lost easily.
引文
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[11]Xu W,Ni J,Zhang Q,et al.Tailoring supported palladium sulfide catalysts through H2-assisted sulfidation with H2S[J].Journal of Materials Chemistry A,2013,1(41):12811-12817.
[12]Zhang Q,Feng F,Su C,et al.Preparation of supported core-shell structured Pd@PdxSy/C catalysts for use in selective reductive alkylation reaction[J].Rsc Advances,2015,5(81):66278-66285.
[13]Zhang Q F,Wu J C,Su C,et al.Preparation,structural characterization of a novel egg-shell palladium sulfide catalyst and its application in selective reductive alkylation reaction[J].Chinese Chemical Letters,2012,23(10):1111-1114.
[14]Ding Junwei(丁军委),Ren Kun(任鲲).Preparation of antioxidant4030 by reductive alkylation of Pt/C catalyst[J].Modern Chemical Industry(现代化工),2015,35(2):69-72.
[15]Li Penggang(李鹏刚),Wang Jingxuan(王靖轩),Guo Feifei(郭飞飞),et al.Research progress and application of mesoporous carbon[J].Chemical Industry and Engineering Progress(化工进展),2018,37(1):149-158.
[16]Zhou Y,Lan G,Zhou B,et al.Effect of pore structure of mesoporous carbon on its supported Ru catalysts for ammonia synthesis[J].Chinese Journal of Catalysis,2013,34(7):1395-1401.
[2]Merten H L,Baclawski L M.Process for producing N,N'-disubstituted paraphenylene diamine mixtures by sequential reductive alkylation:US 4900868 A[P].1990-02-13.
[3]D'Sidocky R M,Parker D K.Process for the reductive alkylation of aromatic nitro-containing compounds with ketones or aldehydes:EP,US 4463191 A[P].1984-07-31.
[4]Yu W,Ding J,Yu S,et al.Effects of water on a catalytic system for preparation of N-(1,4-dimethylamyl)-N′-phenyl-p-phenylenediamine by reductive alkylation[J].Rsc Advances,2018,8.DOI:10.1039/C8RA03397H
[5]Wu Jiehua(吴结华).A new catalyst for synthesis of rubber antioxidant6PPD[J].Industrial Catalysis(工业催化),2012,20(7):43-45.
[6]Wu Jiehua(吴结华),Yuan Haoran(袁浩然),Zhou Lianfeng(周莲凤).Laboratory research of catalyst for synthesis of rubber antioxidant4010NA[J].Journal of chemical Industry&Engineering(化学工业与工程技术),2009,30(1):13-16.
[7]Lv Yongmei(吕咏梅).Technical progress and market demand analysis of p-phenylenediamine rubber anti-aging agent[J].Rubber Technology Market(橡胶科技市场),2010,8(21):1-5.
[8]Gomez S,Peters J A,Waal J C V D,et al.Preparation of benzylamine by highly selective reductive amination of benzaldehyde over ru on an acidic activated carbon support as the catalyst[J].Catalysis Letters,2002,84(1/2):1-5.
[9]Wei J,Sun W,Pan W,et al.Comparing the effects of different oxygen-containing functional groups on sulfonamides adsorption by carbon nanotubes:Experiments and theoretical calculation[J].Chemical Engineering Journal,2017,312:167-179.
[10]Wang X,Li N,Webb J A,et al.Effect of surface oxygen containing groups on the catalytic activity of multi-walled carbon nanotube supported Pt catalyst[J].Applied Catalysis B Environmental,2010,101(1):21-30.
[11]Xu W,Ni J,Zhang Q,et al.Tailoring supported palladium sulfide catalysts through H2-assisted sulfidation with H2S[J].Journal of Materials Chemistry A,2013,1(41):12811-12817.
[12]Zhang Q,Feng F,Su C,et al.Preparation of supported core-shell structured Pd@PdxSy/C catalysts for use in selective reductive alkylation reaction[J].Rsc Advances,2015,5(81):66278-66285.
[13]Zhang Q F,Wu J C,Su C,et al.Preparation,structural characterization of a novel egg-shell palladium sulfide catalyst and its application in selective reductive alkylation reaction[J].Chinese Chemical Letters,2012,23(10):1111-1114.
[14]Ding Junwei(丁军委),Ren Kun(任鲲).Preparation of antioxidant4030 by reductive alkylation of Pt/C catalyst[J].Modern Chemical Industry(现代化工),2015,35(2):69-72.
[15]Li Penggang(李鹏刚),Wang Jingxuan(王靖轩),Guo Feifei(郭飞飞),et al.Research progress and application of mesoporous carbon[J].Chemical Industry and Engineering Progress(化工进展),2018,37(1):149-158.
[16]Zhou Y,Lan G,Zhou B,et al.Effect of pore structure of mesoporous carbon on its supported Ru catalysts for ammonia synthesis[J].Chinese Journal of Catalysis,2013,34(7):1395-1401.