【作者】 陈鹏；

【导师】 丁维平； 彭路明；

【作者基本信息】 南京大学 ， 化学工程（专业学位）， 2019， 硕士

【摘要】 化工生产中,酸催化反应为数众多,传统上使用液体酸催化效果良好,但伴随着设备腐蚀、分离困难、产生难处理的废液等问题,不符合绿色化学生产理念。固体酸具有腐蚀性小、废液少、催化剂可再生、易于分离等优点,其取代液体酸催化剂是必然的发展趋势。本文在课题组前期工作基础上,在整体式不锈钢丝网碳纳米管磺酸催化剂的批量制备以及新型金属-固体酸双功能催化剂制备与性能研究上进行了一些有所创新的研究工作,主要内容及结果概括如下:1、采用旋转管式炉制备碳纳米管@不锈钢丝网拉西环,应用浮动催化化学气相沉积方法,成功地将一次制备量扩大至40 mL。对不锈钢丝网前处理条件、有机碳源种类、进样速率、温度程序等制备条件进行了逐一考察,获得了最佳制备条件:(1)不锈钢丝网用9 mol/L的硫酸溶液处理5 min;(2)苯作为碳源,进样速率为0.08 mL/min;(3)700℃生长60 min。如此得到的不锈钢丝网拉西环样品上的碳纳米管阵列整齐、纯净。对该碳纳米管@不锈钢丝网拉西环样品,通过多硫化钠硫化与过氧化氢氧化结合的方法进行磺化处理,可获得高达2.17 mmol/g的磺酸密度,且稳定性较好。2、针对硝基苯在酸介质中进行催化加氢反应一次合成对氨基苯酚的新技术路线,本文研究了一种新型固体双功能催化剂,用聚苯乙烯包裹负载于活性炭上的镍硅合金纳米粒子,进而将聚苯乙烯磺化,从而得到一种耐酸的镍硅合金纳米粒子与聚苯乙烯磺酸密切配合的硝基苯经加氢异构反应一次合成对氨基苯酚的双功能固体催化剂,优化了催化剂制备条件,较详细地表征了催化剂的结构,并测试了该新型双功能固体催化剂在中性介质下催化硝基苯转化成对氨基苯酚的催化性能,结果显示这种催化剂活性高,生成对氨基苯酚的选择性好,且循环性能较稳定,具有较好的应用前景。更多还原

【Abstract】 In chemical industry,there are many acid-catalyzed reactions and,traditionally,liquid acids have been used as catalysts and shown good performances,but accompanied with problems such as corrosion of equipment,difficulty in separation,and emission of intractable waste water.Compared with liquid acids,solid acids have the advantages of less corrosivity,less waste liquid,good recyclability,easy separation,and etc.The replacement of liquid acids by solid acids as catalysts is inevitable in the future.Based on the previous work of out lab,this paper has carried out futher research work on the preparation in a large quantity of the sulfonated carbon nanotubes grown on monolithic stainless steel mesh catalyst(HSO3-CNs@SSM)and the preparation and catalytic performance of a novel metal-solid acid bifunctional catalyst(NiSi nanoparticles supported on activated carbon and encapsulated by sulfonated polystyrene,NiSi-NPs@HSO3-PS).And the results are summarized as follows:1、The CNs@SSM Raschig rings were prepared in a rotary tube furnace using the method of chemical vapor deposition with gasesous suspended catalyst.In a batch of preparation,～40 mL high-quality CNs@SSM Raschig rings can be obtained.The parameters for the preparation,such as the pretreatment of the stainless steel mesh,the source type organic carbon,the injection rate and the program of temperature control were optimized.The optimized condidtions for the preparation were obtained:(1)the stainless steel wire mesh was etched in 9 mol/L sulfuric acid solution for 5 min as pretreatment;(2)the benzene was the best carbon source and the injection rate was 0.08 mL/min;(3)the growth continued for 60 min at 700℃.Thus obtained CNs@SSM Raschig rings possessed neat and pure carbon nanotubes on the stainless steel wire mesh.The CNs@SSM Raschig rings were then sulfonated by a combinated treatment of sulfuration with sodium sulfide and oxidation by hydrogen peroxide to give HSO3-CNs@SSM Raschig rings,of which the sulfonic acid density was up to 2.17 mmol/g.The acidity of the HSO3-CNs@SSM Raschig rings was fairly stable during uses.2、For a new technical route of the synthesis of p-aminophenol in a one-pot process with the catalytic hydrogenation of nitrobenzene in an acid medium,a novel solid bifunctional catalyst was developed.The nickel-silicon alloy nanoparticles supported on an activated carbon were firstly encapsulated with a posous polystyrene,and then the polystyrene is sulfonated to form a solid bifunctional catalyst with the cooperation of the acid-resistant nickel-silicon alloy nanoparticles as reactive centers of hydrogenation and the sulfonated porous polystyrene closely surrounded for rearrangement of the intermediate of phenyl hydroxylamine to p-aminophenol.The catalyst preparation conditions were optimized and the structure and properties the catalyst was characterized in detail.The catalytic performance of the novel bifunctional solid catalyst for the one-pot conversion of nitrobenzene to p-aminophenol under conditions of acid-base neutrality was tested.The results showed that the catalyst was fairly active and highly selective for the one-pot production of p-aminophenol.The performance of the catalyst appeared stable in reuse of several times.更多还原