间硝基甲苯液相催化加氢制备间甲苯胺论文.pdf

南京理工大学硕士学位论文间硝基甲苯液相催化加氢制备间甲苯胺姓名:陈晓冬申请学位级别:硕士专业:化学工艺指导教师:叶志文 20070701 硕士论文闻硝基甲苯液相催化加氯制各问甲苯胺摘要本论文主要研究了间硝基甲苯液相催化加氢制备间甲苯胺并由问甲苯胺合成问甲酚和N一乙基间甲苯胺的反应工艺条件。催化加氢步骤中分别采用了Raney Ni、。研究发现,采用Raney Ni为催化剂,NaOH与AI- 时制得的催化剂活性较高,:‘10,甲醇作溶剂,反应时间为1h,反应压力1MPa,反应温度为80。C条件下间硝基甲苯转化率达100 %;,当B酬i2+----2左右制得的催化剂活性较高,在催化剂与原料质量比为3:10,无水乙醇作溶剂,反应时间为lh,反应压力1MPa, 反应温度为100℃条件下问硝基甲苯转化率达100%,同时通过XRD、TEM对 Ni-B非晶态合金进行表征;采用漆原镍为催化剂,展开剂为醋酸,锌粉与 NiCl2·6H20质量比为3:2时制得的催化剂活性较高,在催化剂与原料质量比为5: 3,甲醇作溶剂,,氢气流速15mL/min条件下间硝基甲苯转化率达100%,新鲜催化剂放置一周后活性才开始下降,催化剂可以循环使用lO 次,活性基本不变。三种催化剂是催化加氢的优良的催化剂,且各有特点。Raney Ni优点在于一次反应所需的用量较少,易自燃是它的不足;Ni-B非晶态合金不自燃,但反应条件的要求比Raney Ni高:温度低,常压反应是漆原镍最大优点,反应时间也适中,缺点是一次性需要加入的催化剂的量较大。合成间甲酚步骤中采用了重氮化、边水解边水蒸气蒸馏的反应工艺。通过单因素分析和正交实验得出较佳工艺条件,当tt2S04质量分数为25%,NaN02 质量分数为30%,反应时间为35rain,重氮化时NaN02滴加速度2mL/min,水解时重氮盐滴加速度9mL/min,水解时硫酸的浓度为4moFL时,%,%以上。合成N--乙基问甲苯胺步骤中,采用溴乙烷为烷化剂,在常压下进行反应。考察了反应物比例、时间和温度对N一乙基问甲苯胺选择性和间甲苯胺转化率的影响。可以得出最佳反应条件:间甲苯胺与溴乙烷物质的量的比为3:l,反应时间为8h,反应温度为50℃。在此条件下,%,N %,%以上。关键词:间硝基甲苯,催化加氢,间甲苯胺,重氮化,问甲酚,溴乙烷,N一乙基间甲苯胺硕士论文问硝基甲苯液相催化加氢制各间甲苯胺 ABSTRACT The m-toluidine was synthesized by catalytic hydrogenation from m-e and thenm-cresol andN-ethyl-m-toluidineⅥ憾prepared from m-tolnidine. T岫different catalysts were used intheprocess ofcatalytic has been found that theRaney Nicatalyst which wasprepared on the condition that m科aOa):m(AbNi)= has the best pcrfb“瞰In∞.Under the condition that re(catalyst):m(m-nitrotoluene)=:10,methanol硒solvent,reaction time was 1 reaction pressure was IMPa,reaction temperature WaS 80℃.the conversion of m-nitrolotuene reached 100%.Ni-Bamorphous alloycatalyst whichwasprepared on the condition thatBpl4-/Ni2+=2 hasthe thecondition that m(catalyst):m(m-nitrotoluene)=3:10,anhydrous ethanol器solvent,reaction time was lh,reaction pressure was 1MPa,reaction temperature was 100"(2,the conversion ofm-nitrolomene reached 100%.And t