臺灣博碩士論文加值系統

本研究主要是針對現有己內醯胺製程中環己烷進行空氣氧化生產環己醇和環己酮，其低產率之缺失以及存在反應器中的潛在爆燃危害，加以改善來提昇產率並尋求一本質較安全的操作方法。本文研究在瞭解環己烷之爆炸上限及飽和蒸氣壓對溫度之變化情形後，進行操作變數(富氧濃度、溫度以及氣體分壓等)對於產物之分佈、反應速率之影響以及在質傳上的限制，並提出一本質安全化之純氧氧化方式。
純環己烷在溫度165℃時之飽和蒸氣壓為7.43bara，在進行環己烷與純水共沸時添加重量百分比5%及25%水時其飽和蒸氣壓分別可升至12.1及13.1bara；另依據先前的研究在165℃、氧氣/氮氣混合至12barg點火的測試結果，可以觀察到環己烷之爆炸上限(Upper flammability)為進氣氧濃度17%的情況下，亦即等於氣相空間氧氣濃度之上限範圍為7.5%。另外，環己烷與水共沸並加入純氧，在相同條件下點火後並未有任何升溫升壓之狀況發生，證明水蒸氣可以彌補氮氣之惰性化功能，降低爆炸之危害，亦即可使用純氧作氧化而不會有爆然的危害。
在160℃添加5%水時，通入純氧氧化，酮醇比(K/A ratio)最高可高達4，這是所有文獻中的最高值，可大幅降低環己醇脫氫之負載，並且利用水蒸氣彌補氮氣惰性化功能亦是本質較安全之操作，對於整個製程效率實為一大突破。

This work aims directly at improving the low yield and potential deflagration hazards of cyclohexane oxidation to produce cyclohexanol and cyclohexanone in the caprolactam process.
With the undenstanding of the upper flame limit of cyclohexane in oxidation process condition and vapor pressure to temperature relationship, this work performed various tests on the effects of operation parameters on product profile, reaction rates and mass transfer limitation. An inherently safer method of oxidation with pure oxygen is also proposed.
The saturated vapor pressure of pure cyclohexane at 165℃ is 7.43bara. Upon adding 5% and 25% weight percent of water, the vapor pressure of cyclohexane rises to 12.1 and 13.1 bara, respectively. According to previous research results, the upper flammability of cyclohexane at 165℃ and 12 barg is around feed oxygen concentration of 17%. That is equivalent to upper oxygen concentration of 7.5%. When azeotropic mixture of cyclohexane and water is fed with pure oxygen to the same condition and ignited , there is no ignition, indicating that water vapor can replace nitrogen and act as an inert gas to prevent gas phase deflagration. Thus pure oxygen can be used safely to oxidize cyclohexane.
Oxidation at 160℃ with pure oxygen for cyclohexane with 5% water give K/A ratio around 4. This is the highest K/A ratio in all known literatures. The load for dehydrogenation of cyclohexanol can thus be reduced significantly. This is also an inherently safer process and a significant improvement upon traditional air oxidation process.

目錄
中文提要i
英文提要ii
致謝iv
圖目錄vii
表目錄ix
第一章 前言1
第二章 文獻回顧5
2-1反應機構5
2-2反應製程10
2-2-1均相觸媒10
2-2-2非均相觸媒12
2-2-3特殊反應方式13
第三章 研究方法與設備15
3-1實驗裝置15
3-2實驗方法15
3-2-1藥品：15
3-2-2反應操作步驟：17
3-3 樣品分析方法18
3-3-1 環己基過氧化物 - 碘滴定量法18
3-3-2環己醇和環己酮 - 氣相層析儀分析19
第四章 實驗結果25
4-1高溫無觸媒氧化與分解之測試25
4-2環己烷富氧條件氧化之爆炸界限測試28
4-3環己烷富氧氧化之測試30
4-4環己烷與水共沸34
4-4-1 環己烷與水共沸物之飽和蒸氣壓測試34
4-4-2環己烷與水共沸物之純氧氧化爆炸界限測試36
4-5環己烷與水共沸物之純氧氧化測試37
4-5-1不同溫度下反應氣體採一進一出連續進氣方式對於轉化率及產物分佈之影響37
4-5-2不同溫度下反應氣體採不足即補給之進氣方式對於轉化率及產物分佈之影響43
4-5-3相同溫度不同氧氣分壓下對於轉化率及產物分佈之影響50
第五章 討論55
5-1 反應機構與動力學55
5-2 富氧氧化57
5-3環己烷與水共沸純氧氧化58
5-3-1 不同反應溫度之影響58
5-3-2不同氧氣分壓對之影響64
第六章 結論與建議66
參考文獻68

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