精細化工氰化物原料替代技術及污染減排技術與示范

張光晉 閆瑞 王雪松 黃杰 吾滿江

摘 要：該年度課題總體進展達到原任務書中規定的進度。替代有毒有害原料氫氰酸的MMA清潔生產技術方面，應用系統工程的原理與方法，確立催化反應過程的最優工藝技術參數；完成異丁烯選擇氧化制備MMA的分離工藝設計及全流程的模擬，實現全系統能量-物質-環境的多目標優化和集成。提出優化的工藝流程，確定生產工藝與反應設備，并進行催化劑的公斤級生產及噸級放大生產、千噸級中試示范裝置工程設計，提出千噸級工藝基礎數據包，并完成了工程設計與裝置建設。 替代劇毒鉻酐氧化劑的16-DPA綠色工業制備技術方面，完成40噸/年16-DPA綠色生產示范線建設，并在示范線上優化了16-DPA光敏氧化綠色制備技術各項工藝參數，以薯蕷皂苷元計算，16-DPA總收率達到68%，純度大于98%，實現預期年度目標。并在實驗室嘗試利用LED光源替代高壓汞燈開展16-DPA的光敏氧化綠色制備，取得可喜進展。以季鏻鹽類離子液體為催化劑的絕緣油清潔生產技術方面，目前已篩選出具有高催化劑和高穩定性的Lewis酸性季鏻鹽類離子液體，并用于合成PEPE絕緣油。該離子液體催化劑可循環使用30余次而保持催化活性和選擇性不變。同時建成了100噸/年的季鏻鹽類離子液體生產線，為絕緣油PEPE的工業化催化劑來源提供了可靠來源。1 000噸/年的離子液體催化合成絕緣油PEPE生產裝置已開工建設。

關鍵詞：氫氰酸 鉻 硫酸 清潔工藝 甲基丙烯酸甲酯 16-DPA PEPE

Abstract：The project runs well and reaches the main target of assignment book. In the first part， for the clean manufacture technology of MMA， the technology parameter in catalytic process was clarified by using theory of system engineering. The design of the separation technology in selection oxidation of isobutene and simulation of the full process were finished. The optimal technology process was proposed. The reaction facilities were defined. The production of the catalyst in kg scale was finished. The fundamental data pacage for technology in 1 000 t scale was provided. The design of the process and the construction of devices were finished. In the second part， for the green manufacture technology of 16-DPA， the construction of demonstration production line of 16-DPA in 40 T/year scale was finished. The manufacture parameters was optimized in the production line. The total yield of 16-DPA reached 68% and the purity reached 98%. In laboratory， we try to use LED as light sources to replace Hg lamp to produce 16-DPA， and the results are satisfied. In the third part， for the clean technology of insulating oil， the best ionic liquid was selected to synthesis of insulating oil. The ionic liquid can cycle for more than 30 times without changing of its activity. The production line for the ionic liquid in 100 T/year was constructed. And the catalysis synthesis of insulting oil PEPE in 1 000 T/year scale was began to constructed.

Key Words： Hydrocyanic acid； Chromium； Sulfuric acid； Clean process； Methyl methacrylate； 16-dehydropregnenolone acetate； Phenyl ethenyl ethane

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