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1、湘潭大学 硕士学位论文 粗苯中二硫化碳及噻吩的脱除研究 姓名：王倩 申请学位级别：硕士 专业：化学工程 指导教师：杨运泉 20080501 I 摘 要 本文在查阅大量文献资料的基础之上， 对粗苯中含量较高的两种有机硫化物 二硫化碳和噻吩进行静态吸附和催化氧化的分类脱除研究。 首先针对粗苯中含量为0.3%0.4%(质量分数，下同)的二硫化碳，进行静态 吸附脱除工艺研究，实验结果表明该法具有能耗低、精制深度高、操作方便、不 产生二次废物等优点。具体工作为通过对吸附剂活性炭种类的选择、活性炭投 加量的多少、吸附温度的高低、吸附时间的长短等一系列实验的考查比较，选用 了比表面积较大的不定型颗粒活性炭进
2、行静态吸附实验， 确定了相对于二硫化碳 浓度为0.0252g/L的粗苯溶液，在低温(25)，活性炭投加量为0.15g/mL的条件下 反应7小时，二硫化碳吸附率可达82.6%以上。在随后的活性炭再生问题研究中， 通过对采用了加热再生法再生后的活性炭进行的的静态吸附比对实验， 发现由于 再生无法完全去除活性炭中的全部吸附物， 这些残留物在以后的吸附过程中降低 活性炭的吸附容量，造成再生后的活性炭吸附能力有所降低。 其次对于粗苯中含有的噻吩硫(0.2%1.6%)，则先采用氯甲基化法进行单因 素和正交实验，得出最佳反应条件：反应温度75，反应原料配V粗苯:V甲醛:V盐 酸:=2:1:1，反应时间6小时
3、；之后采用以钛硅分子筛(TS- 1)为催化剂，双氧水为氧 化剂，水为溶剂的反应体系，对粗苯中噻吩的脱除进行了研究。具体为通过单因 素实验考察了时间、温度、氧化剂用量、催化剂用量及溶剂用量对反应的影响， 确定了各因素对反应的影响大小顺序为：TS- 1用量双氧水用量反应时间反应 温度；在以上单因素实验考察的基础上，选取了四个主要影响因素及相应的五个 参数水平进行正交实验，以噻吩的脱除率为考核指标，对整个反应进行了条件优 化，得出最佳的反应条件为：n双氧水/n噻吩=4：1，时间8小时，温度75，TS- 1用量 0.15%（wt） 。在此条件下进行反应，噻吩的脱除率高达99.58%。最后通过对以 上两
4、种方法在脱硫率、反应物分离难易程度、以及环境污染和精制成本等方面的 综合评定确定了钛硅分子筛催化氧化法的可行性及优越性。结果表明：该法具有 操作简单，反应条件温和（低温常压下即可进行） ，低成本费用以及高有机硫脱 除率的特点。确立该法为一条具有较好应用和推广价值的工业有机硫脱除新途 径。 本文最后进行了噻吩氧化反应动力学的初步研究，求得温度为348K、常压 下，噻吩的反应速率方程为： 1.3730.08 224.6*10 vThiophene CatalystH O =；反 应速率随温度的变化方程为： ( 37.21/) 2697 RT ke = 关键词：粗苯；二硫化碳；噻吩；钛硅分子筛；催化
5、氧化；关键词：粗苯；二硫化碳；噻吩；钛硅分子筛；催化氧化； II ABSTRACT On the basis of collecting a great number of references, this thesis report the process for removal of carbon disulfide and thiophene which are comparatively abundant in crude benzene respectively by static- adsorption and over titanium silicalite(TS- 1) by
6、hydrogen peroxide. First of all, static- adsorption was studied to deal with carbon bisulfide, which is about 0.3- 0.4 percent in crude benzene, it is known that this way has many advantages including lowly energy consumption, high removal effeciency, convenient operation, and no waste outgrowth. Ma
7、ny concretely works relating to adsorption have been done includ choice to the type and dose of activiated carbon, adsorption temperature, and adsorption time. Errant granule activiated carbon, which has large surface area has been adopt to adsorption, as to 0.0252g/L carbon disulfide- crude benzene
8、 solution, at 25, the dose of activiated carbon is 0.15g/mL, adsorption ratio can reach 82.6% after 7 hours. In the next, parallel adsorption experiments were carried out by using of activiated carbon regenerated through heating up in the stove, the results showed regeneration can not wiped out all
9、the materials adsorbing in activiated carbon, these materials may reduce the volume of activiated carbon and minish adsorption ratio in the following adsoption. Secondly, aimed at thiophene, on one hand, signal parameter and orthogonal design experiments were carried out under the condition of chlor
10、omethylation reaction，the optimum removal parameters were:temperature at 75，V粗苯:V甲醛:V盐酸 :=2:1:1, reacting time 6 hours; on the other hand, the process for removal of thiophene from crude benzene over titanium silicalite (TS- 1) by hydrogen peroxide was studied, the factors affecting the reaction，inc
11、luding reaction time，reaction temperature, the dose of TS- 1 and the dose of H2O2 were investigated. The influence of these factors was in the following order：dose of TS- 1dose of H2O2 reaction timereaction temperature. The removal conditions of thiophene were optimized by orthogonal design with the
12、 goal of maximizing removal efficiency. The optimum removal parameters were:reacting time 8 hours, temperature at 75, nH2O2nC 4H4S=4 1 and TS- 1 0.15%wt. Under the optimal conditions，the removal of thiophene was 99.58%. At last, the two methods were compared on the ground of removal efficiency, III
13、separating operation of reaction products, environment pollution and desulfurization expense, the feasibility and superiority of the removal of thiophene from crude benzene over titanium silicalite (TS- 1) by hydrogen peroxide was firmly assured. A new and highly efficient method for organic- sulfur
14、 removal with the features of easy operation，mild reaction condition (low temperature and normal pressure) and low cost is worth to be commercialized. In the end, the kinetics of thiophene oxidation was also studied. The reaction rate can be expressed as: 1.3730.08 224.6*10 vThiophene CatalystH O =
15、under the condition of 348k, 101kpa. And the obvious reaction constant can be showed as: ( 37.21/) 2697 RT ke = Key word: crude benzene; carbon disulfide; thiophene; silicalite (TS- 1); catalytic oxidation 湘潭大学湘潭大学 学位论文原创性声明学位论文原创性声明 本人郑重声明：所呈交的论文是本人在导师的指导下独立进行研究所 取得的研究成果。除了文中特别加以标注引用的内容外，本论文不包含任 何其
16、他个人或集体已经发表或撰写的成果作品。对本文的研究做出重要贡 献的个人和集体，均已在文中以明确方式标明。本人完全意识到本声明的 法律后果由本人承担。 作者签名： 日期： 年 月 日 学位论文版权使用授权书学位论文版权使用授权书 本学位论文作者完全了解学校有关保留、使用学位论文的规定，同意 学校保留并向国家有关部门或机构送交论文的复印件和电子版，允许论文 被查阅和借阅。本人授权湘潭大学可以将本学位论文的全部或部分内容编 入有关数据库进行检索，可以采用影印、缩印或扫描等复制手段保存和汇 编本学位论文。 涉密论文按学校规定处理。 作者签名： 日期： 年 月 日 导师签名： 日期： 年 月 日 2008 年硕士研究生毕业论文 第 1 章 绪论 1 第1章 绪 论 1.1 粗苯的加工生产概况 粗苯是焦炭生产过程中的副产品,其产率占原料用煤的11.5%，分为加工用 粗苯和溶剂用粗苯两大类，主要成分为苯及其同系物。目前采用吸收法从炼焦过 程中的焦炉煤
