由甲缩醛合成甲氧基乙酸甲酯及高浓度甲醛的研究
沈鑫权
Subtype硕士
Thesis Advisor高志贤 ; 吾满江·艾力
2013-06-01
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline材料工程
Keyword甲缩醛 甲酸 甲氧基乙酸甲酯 甲醛 程序升温表面反应
Other Abstract

甲缩醛以其无毒,低含水量且有与甲醛相似的化学性质,越来越引起人们的重视,可合成一系列的高附加值化学品,具有重要意义。本文在综述了甲氧基乙酸甲酯及高浓度甲醛的合成研究进展及现实意义的基础上,确定了以甲缩醛为原料合成甲氧基乙酸甲酯及高浓度甲醛的工作,具体研究内容如下:

甲氧基乙酸甲酯的合成

①通过一系列实验建立了一套通过气相色谱分析原料、产物的方法,以甲缩醛为基准物,测定了其它组分(甲醛、水、甲醇、甲酸、甲氧基乙酸甲酯)的相对校正因子,使用校正归一法计算各种组分的含量,从而得到各种反应物的转化率及产物的收率。

②研究了甲缩醛与甲酸的偶联反应,产物用气相色谱-质谱联用进行鉴定。

③通过间歇反应釜探索了几种酸催化剂的效果。实验结果表明无催化剂时,反应几乎不进行。分别以阳离子交换树脂、分子筛、对甲苯磺酸、氯化铝、氯化亚锡为催化剂,研究了甲缩醛与甲酸的偶联反应,其中,对甲苯磺酸取得较好的结果。

④在以上工作基础上,考察了催化剂用量、原料配比、反应温度和反应时间对甲氧基乙酸甲酯收率的影响。得出以对甲苯磺酸为催化剂时,最佳反应条件为:原料配比n(甲缩醛)/n(甲酸)=0.36(摩尔比),催化剂用量为甲缩醛投料量质量比1.8%,反应温度140℃,反应时间4h。在此条件下,甲氧基乙酸甲酯的收率为87.1%

甲缩醛空气氧化制高浓度甲醛的表面反应研究

①采用浸渍法制备了氧化铝担载的Fe-Mo的催化剂,以及单组分的FeMo参比催化剂。

②采用程序升温技术和在线质谱仪分析,对甲缩醛催化氧化制甲醛的影响因素进行了程序升温表面反应(TPSR)的研究。研究表明:除了甲缩醛氧化生成甲醛的主反应之外,还有生成甲醇、氢气、水、二氧化碳、一氧化碳、二甲醚的副反应。

③氧化铝担载的Fe-Mo的催化剂比单组分的FeMo催化剂效果要好。

④当反应温度为50oC时甲醛的生成量最大。

;

Methylal has drawn more and more attention due to its non-toxic, low water content and similar chemical properties to formaldehyde. A series of value-added fine chemicals such as methyl methoxy acetate and formaldehyde could be synthesized with methylal as the main feed. In this thesis, the practical significance and the recent developments of the synthesis of methyl methoxy acetate and formaldehyde are reviewed briefly, from which the research ideas of the present work, e.g. synthesis of methyl methoxy acetate and formaldehyde, are derived. And the main contents and conclusions are listed as follows:① Synthesis of methyl methoxy acetate① A method for detecting different reactants and products was developed through a series of experiments. Relative correction factors to methylal of different constituents were ascertained. The contents of different reactants and products were calculated by means of area normalization method, which enabled the calculation of conversion and selectivity. ② The coupling reaction of methylal and formic acid was studied. The products were characterized by GC-MS to be methyl methoxy acetate. ③ The effects of several acid catalysts such as cationic resin, molecular sieves and P-toluene sulphonic acid were explored in the batch autoclave. No methyl methoxy acetate was detected when the reaction was performed without a catalyst. P-toluene sulphonic acid showed the best result among those acid catalysts.④ The effect of reaction conditions such as reaction temperatures, reaction time, mole ratio of reactant and catalyst/methylal mass ratio on the methyl methoxy acetate synthesis has been investigated. And the optimized reaction conditions are 0.36 mole ratio of methylal to formic acid, 0.018 catalyst/methylal mass ratio, 140℃ reaction temperature and 4 h reaction time. Under the optimized reaction conditions, 87.5% methyl methoxy acetate could be achieved.⑵ Study on the preparation of formaldehyde by means of the surface reaction of methylal oxidation.① A series of catalysts of Al2O3 supported Fe, Mo and Fe-Mo were prepared by an impregnation technique.② The surface reaction of formaldehyde synthesis was carried out with varied catalysts under different reaction conditions by the temperature program surface reaction (TPSR) techniques and the on-line mass spectrometer. The results showed that there were many side reactions besides the main reaction.③ The results of TPSR showed that the catalyst of Al2O3 supported Fe-Mo was better than the catalysts of Al2O3 supported Fe or Mo respectively. ④ The quality of formaldehyde came to the maximum when the reaction temperature was 50 oC.

Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/2489
Collection新疆维吾尔自治区精细化工工程技术研究中心
Affiliation中国科学院新疆理化技术研究所
Recommended Citation
GB/T 7714
沈鑫权. 由甲缩醛合成甲氧基乙酸甲酯及高浓度甲醛的研究[D]. 北京. 中国科学院大学,2013.
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