【作者】 谢广群；

【导师】 曹端林；

【作者基本信息】 中北大学 ， 应用化学， 2006， 硕士

【摘要】 均苯三酚是一种十分重要的有机中间体,主要用于医药、染料等方面。本论文以 2,4,6-三硝基甲苯（TNT）为原料,经氧化得到中间产物 2,4,6-三硝基苯甲酸（TNBA）,再经还原、水解得到均苯三酚。选择 TNT 为原料合成均苯三酚具有特殊的目的。由于环保因素,TNT 在军工方面的应用被禁止,而我国 TNT 生产工艺成熟,年产量达十几万吨。本文把 TNT转化为均苯三酚能有效的利用 TNT 的整个生产线,避免该生产流程资源的浪费,同时为 TNT 的应用开拓新的领域。实验中采用了三种氧化剂对 TNT 进行氧化,分别为 Na₂Cr₂O₇/H₂SO₄（98%）、KClO₃/HNO₃（68%）、KClO₄/ H₂SO₄（98%）/ H₃PO₄（98%）,并着重考查了后两种氧化剂作用下的工艺条件。以 KClO3/HNO3（68%）为氧化剂,成功的把 TNT 氧化为 TNBA。采用正交实验对该氧化工艺进行优化,得到最佳工艺条件为:TNT:KClO3:HNO3=1:3:13（物质的量之比）,反应温度 75⁸0℃,反应时间 1.5h。在最佳工艺条件下,TNBA 的得率可达 90%。以 KClO₄/ H₂SO₄（98%）/ H3PO4（98%）为氧化剂,氧化 TNT 为 TNBA,得到了最佳工艺条件:TNT:KClO-4:H₂SO₄:H₃PO₄=1:4:12:3（物质的量之比）,反应温度 70℃,反应时间为 1h。在最佳工艺条件下 TNBA 的得率为 94%。分别采用铁粉还原法和催化加氢还原法对 TNBA 进行还原。讨论了铁粉还原TNBA 的工艺条件,对催化加氢还原 TNBA 进行了初步探索。以 36%的盐酸为反应介质,将 TNBA 和铁粉混合逐次加料,利用正交实验对铁粉还原、水解工艺进行优化,得到的最优条件是:TNBA:Fe=1:15（物质的量之比）,还原反应温度 75℃,水解 pH 值 1.0¹.5,N2保护下水解 24h。其中反应温度对均苯三酚得率的影响最大,其次是水解液的 pH 值、还原物料比,水解时间对反应的影响最小。在最佳工艺条件下均苯三酚的得率可达到 70%。在催化加氢方法中,以丙酮-水为溶剂,骨架镍为催化剂,压力恒定为0.5×10⁶Pa,更多还原

【Abstract】 As an important organic intermedium, 1,3,5-benzenetriol is widely used inpharmaceutics, dying and the related fields. In this paper, 1,3,5-benzenetriol wasprepared through three steps using 2,4,6-trinitrotoluene as raw material.2,4,6-trinitrotoluene was first oxidized to 2,4,6-trinitrobenzoic acid, then2,4,6-trinitrobenzoic acid was reduced to 1,3,5-triaminobenzene, at last1,3,5-triaminobenzene was hydrolyzed to 1,3,5-benzenetriol.It has special significance to choose 2,4,6-trinitrotoluene as raw material.2,4,6-trinitrotoluene has been forbidden to use in the field of military project because ofthe environment factors. But in our country, the preparation technology of2,4,6-trinitrotoluene is very mature and its annual output reaches ten thousandstons .Transforming 2,4,6-trinitrotoluene to 1,3,5-benzenetriol can make good use of theproduce route of 2,4,6-trinitrotoluene and find a new outlet for 2,4,6-trinitrotoluene.2,4,6-trinitrotoluene was oxidized separately by Na2Cr2O7/H2SO4, KClO3/HNO3 andKClO4/H2SO4/H3PO4. The processes of oxidation using the latter two oxidizers weremainly argued.2,4,6-trinitrotoluene was successfully oxidized to 2,4,6-trinitrobenzoic acid byKClO₃/HNO₃（68%）. The process was optimized by orthogonal experiment .When thereaction proceeded at 75⁸0℃ for 1.5h, molar ratio of 2,4,6-trinitrotoluene to KClO₃ toHNO3 was 1:3:13, the yield of 2,4,6-trinitrobenzoic acid reached 90%.2,4,6-trinitrobenzoic acid was also obtained by oxidizing 2,4,6-trinitrotoluene usingthe oxidizer of KClO₄/H₂SO₄（98%）/H₃PO₄（98%）. The effects of several factors on thereaction were discussed and an optimized synthetic condition was obtained. When themolar ratio of 2,4,6-trinitrotoluene to KClO₄ to H₂SO₄ to H₃PO₄ was 1:4:12:3, the yieldof 2,4,6-trinitrobenzoic acid reached 94% after acting at 70℃ for 1 hour.2,4,6-trinitrobenzoic acid was reduced separately by iron-powder and catalytichydrogenation.The process for making 1,3,5-triaminobenzene was studied by reducing2,4,6-trinitrobenzoic acid with iron-powder as reduced agent in the presence ofhydrochloric acid （36%）, which consisted in adding successive small quantities of themixture of 2,4,6-trinitrobenzoic acid and iron-powder to hydrochloric acid containing asmall quantity of iron chloride. The process and the followed hydrolyzed condition wereoptimized by orthogonal experiment. When the reaction at 75℃ , molar ratio of2,4,6-trinitrobenzoic acid to iron-powder was 1:15, the pH of hydrolyzed solvent was1.0¹.5, the yield of 1,3,5-benzenetriol reached 70% after hydrolyzing the reducedproduction（1,3,5-triaminobenzene） for 24 hours in the N2 atmosphere. The order ofeffects of these factors on the yield was as follows: reduced temperature>the pH of thehydrolyzed solvent>molar ratio> hydrolyzed time.When using acetone-water as solvent, Raney Ni as catalyst, 2,4,6-trinitrobenzoic acidwas reduced by catalytic hydrogenation after reacting 2.5h at 60⁶5℃ under thepressure of 0.5×106Pa. Although 1,3,5-benzenetriol was obtained by hydrolyzing thereduced production（1,3,5-triaminobenzene ）in the N2 atmosphere with pH1¹.5 for20²4h, the yield of 1,3,5-benzenetriol was low. The process of catalytic hydrogenationneeds to be further studied.更多还原