合成三聚甲醛关键科学问题的实验和理论研究

Trioxane is an important chemical material that has a wide variety of applications, including the preparation of poly(oxymethylene) polymers, polyoxymethylene dimethyl ethers, and dozens of bulk chemicals and fine chemicals. As the market is growing, a rapid expansion of trioxane production has occurred worldwide. This requires optimizing the trioxane-production device and process in order to significantly decrease the production costs on a competitive basis. Such optimization requires developing and then solving a series of reaction kinetic equations and phase equilibrium equations. This program will systematically measure the spectra and concentration data for the solvation and oligomerization reactions, spectral information and quantum chemical calculation results for intermolecular interactions, a series of formation/decomposition kinetic data and the vapor—liquid equilibria data for (CH2O+CH3OH+catalyst+salt+H2O) and its subsystems. On the basis of these results, the mechanism, method, and theoretical equation for shifting the oligomerization equilibria will be developed. All chemical reactions that occur during the synthesis of trioxane will be determined. The theoretical models for prediction of the vapor—liquid equilibria of complex reaction solutions and for prediction of a series of formation/decomposition kinetics will be established and used to yield prediction software. The catalyst and salt effects, including catalytic activity and selectivity, the ability to shift the oligomerization equilibria, and the extraction and distillation agent effect, in the reactive distillation process will be revealed along with the corresponding structure—activity relationship and the underlying mechanism. The above-mentioned results will provide theoretical tools for optimization of device and process and for developing new catalysts and new salt additives. The results will also advance the developments of a series of engineering technologies based on trioxane and formaldehyde solutions in our country.

三聚甲醛是生产聚甲醛工程塑料、聚甲氧基二甲醚和几十种大宗化学品、精细化学品的原料。随着需求快速增长，全球均积极新建装置大幅扩充三聚甲醛产能。为获取竞争优势，需优化生产装置和工艺，显著降低三聚甲醛成本。为此需建立并求解系列反应动力学方程和相平衡理论方程。本项目拟系统测定(CH2O+ CH3OH+催化剂+盐+H2O)及亚系中溶剂化和齐聚反应的光谱信息和浓度数据、分子间相互作用的光谱和量化计算信息、系列生成/分解动力学数据和相平衡数据；建立低聚平衡调控原理、方法、理论方程；确定制备三聚甲醛的化学反应类型，建立系列反应动力学方程和物理化学汽—液相平衡理论模型并形成预测软件；揭示反应精馏工艺独特的催化剂/盐效应(催化活性和选择性、低聚平衡调效应、萃取蒸馏剂效应)的构—效关系及机理。上述成果将为设计生产装置和工艺、研制新型催化剂及助剂提供理论工具，极大推动我国基于三聚甲醛和甲醛溶液的系列工业技术进步。

本项目系统测定了(CH2O+CH3OH+催化剂+盐+H2O)及亚系中溶剂化和齐聚反应的浓度数据、(TOX+催化剂+H2O)的TOX分解反应的K、甲醛转化率和TOX选择性、系列生成/分解动力学数据和相平衡数据；研究了催化剂和盐的结构对溶剂化和低聚平衡的影响，建立了调控溶剂化和低聚平衡的原理和方法；确定了工业生产条件下生产TOX涉及的化学反应类型，建立了物理－化学汽－液相平衡理论模型，并用评价的文献数据和所测数据进行了系统检验和完善；研究了催化剂和盐对馏出液中各组分浓度及釜液中甲酸浓度的影响，揭示了催化剂和盐的结构影响低聚平衡、催化活性和选择性、萃取蒸馏剂性能的构－效关系及机理，为研制新型催化剂及助剂提供理论指导。上述成果将为设计生产装置和工艺、研究催化机理和研制TOX合成的新型催化剂及助剂提供理论工具，极大推动我国以甲醛溶液为基础的工业技术的进步。.在Fuel，Industrial & Engineering Chemistry Research等刊上发表和录用学术论文16篇，发表了1篇学术专著，申请了7项国家发明专利，授权专利有4项，申请中专利有3项。

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