中国科学院新疆理化技术研究所机构知识库
Advanced  
XJIPC OpenIR  > 资源化学研究室  > 学位论文
题名: 甘油甲酸介入法合成丙烯醇的研究
作者: 李严红
答辩日期: 2014-05-30
导师: 文彬
专业: 材料物理与化学
授予单位: 中国科学院大学
授予地点: 北京
学位: 硕士
关键词: 甘油 ; 丙烯醇 ; 甲酸烯丙酯 ; 甲酸介入脱氧 ; 酯化
摘要: 随着石油、煤等化石能源的日益耗竭,以可再生的生物质资源代替不可再生资源作为原料和燃料来源已经成为国际上的研究热点。生物质是一类丰富的可再生的原料,甘油是生物柴油生产过程中的主要副产物。以生物柴油的副产物——甘油为原料与甲酸反应合成大宗化学品丙烯醇,改变了传统丙烯醇的以不可再生的石油为原料的生产路线。由于甘油甲酸介入法合成丙烯醇是一个两步反应,第一步反应为甘油与甲酸发生酯化反应;第二步反应为甲酸甘油酯在甲酸介入作用下发生脱氧反应。本文对甘油甲酸介入法合成丙烯醇的工艺和过程机理进行了系统的研究,对影响反应产物的各因素进行了系统的分步骤研究,得到了该反应过程工艺参数。
(1) 设计了一条实验室工艺路线,丙烯醇的总产率达到86%。1mol甘油与4mol甲酸在氮气保护下,先在140 °C反应3h,然后迅速升温,温度达到200 °C后,切换接液瓶,温度达到235 °C后,开始滴加甲酸,滴加量为0.6mol,滴加时间约0.5h,控制反应温度在230 ~ 240 °C间,反应至无气泡产生。反应完全后的底物加入0.4 mol甲酸继续进行甲酸介入脱氧实验。反应粗产物经除酸、除水处理后得0.86 mol丙烯醇。
(2) 考查了温度和加料比(MR=甲酸(mol):甘油(mol))对甘油甲酸酯化反应酯化率的影响。在相同加料比条件下,随温度升高甘油酯化率升高,当大于140 °C,酯化率下降;在相同温度条件下,加料比越大酯化率越大。在MR=4,温度为140 °C时,最大酯化率为78%。
(3) 丙烯醇的产率随加料比和酯化率的提高而提高,但甲酸烯丙酯生成量都也会随着增加。
(4) 在脱氧反应过程滴加甲酸,滴加甲酸有利于丙烯醇的生成。在酯化率为75%,滴加甲酸量为0.6mol时,丙烯醇的最大单程产率可达到79%。
(5) 甘油甲酸介入脱氧反应生成甲酸烯丙酯与酯化率有直接关系,酯化率越高,甲酸甘油酯中二甲酸甘油酯的含量越大,生成的甲酸烯丙酯的量就越多。在MR=5时,脱氧反应生成的甲酸烯丙酯与丙烯醇的质量比为67.8:31.7。经过碳酸钾处理的产物中,甲酸烯丙酯的量减小。甲酸烯丙酯与丙烯醇的混合液与过量的碱反应,经过蒸馏可得纯度达99.2%的丙烯醇产品。(6) 催化剂在甲酸介入脱氧反应中效果不理想,不能起到提高丙烯醇的产率的作用,除氧化铝作催化剂时丙烯醇产率无影响外,其他催化剂降低了丙烯醇的产率。
英文摘要: Developing sustainable pathway and solution for material and energy from resources has become an international research hotspot. Biomass is a renewable abundant material. In bio-diesel production process, glycerol is a major by-product. The synthesis of allyl alcohol from glycerol, reacted with formic acid, has changed the traditional production routes that used non-renewable petroleum as feedstock. Formic acid mediated deoxygenation is a two seep reaction, the first reaction was esterification of glycerol with formic acid; the second reaction was that glycerol formate undergo deoxygenation reaction. In this paper, the process and mechanism of the synthesis of allyl alcohol with formic acid-deoxygenation was studied. Various factors affecting the efficiency of the reaction were studied systematically; the reaction process parameters were obtained. (1) A process route in the laboratory was designed; the total allyl alcohol yield was up to 86%. 1 mol glycerol reacted with 4mol formic acid under nitrogen protec-tion at 140 °C, 3h. then quickly heated, when the temperature reached 200 °C, replace the bottle ,while the temperature reached 235 °C, 0.6mol formic acid was added, drop-wise in 0.5h, the reaction temperature was controlled between 230-240 °C, The reaction was stopped until no bubbles formed. Subsequently, the reaction substrate was added 0.4 mol formic acid to proceed with formic acid-mediated deoxygenation reaction. 0.86mol of allyl alcohol was obtained as crude product after the treatment with anhydrous potassium carbonate and anhydrous sodium sulfate. (2) The effect of temperature and mole ratio (=n(formic acid): n(glycerol), MR) on the esterification of glycerol was examined. Under the same conditions of the feed ratio, esterification rate of glycerol increase with the temperature, when the temperature is higher than 140 °C,the esterification rate decrease. The result showed that, at the same temperature, the greater of the feed ratio the greater of the esterification. While MR = 4, at 140 °C, the maximum rate of esterification was up to 78%. (3) The yield of allyl alcohol increased with feed ratio and the esterification rate, the amount of allyl formate also increased. (4) The addition of formic acid in the deoxygenation reaction, addition of formic acid promotes generating allyl alcohol. The esterification rate was 0.75; an addition of 0.6mol formic acid, the maximum yield of allyl alcohol was up to 79%. (5) The formic acid-mediated deoxygenation process to synthesis allyl formate is directly related to the rate of the esterification , the higher the rate of esterifica-tion ,the more the amount of glycerol di-formate, the higher yield of allyl formate. In MR=5, the mass ratio of allyl formate and allyl alcohol was 67.8: 31.7. After treatment with potassium carbonate, the amount of allyl formate was reduced. The mixture of allyl formate and allyl alcohol react with excess base, allyl alcohol purity of 99.2% can be obtained through the distillation. (6) Catalyst to promote the synthesis of allyl alcohol was studied; the results showed that the alumina oxide catalyst increased the yield slightly. Keyword:Glycerol; Allyl alcohol; Allyl formate; formic acid-mediated deoxygenation; esterification
内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/3419
Appears in Collections:资源化学研究室_学位论文

Files in This Item:
File Name/ File Size Content Type Version Access License
李严红.pdf(2971KB)学位论文--暂不开放View 联系获取全文

作者单位: 中国科学院新疆理化技术研究所

Recommended Citation:
李严红. 甘油甲酸介入法合成丙烯醇的研究[D]. 北京. 中国科学院大学. 2014.
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[李严红]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[李严红]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
文件名: 李严红.pdf
格式: Adobe PDF
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace