臺灣博碩士論文加值系統

隨著法規需求日益嚴苛，許多煉油廠對於油品脫硫這方面的要求也隨之嚴格，因此研究更有效的替代方法是非常急需的，以氧化脫硫法進行去除油品硫化物是現今熱門的替代方法之一。

本研究使用的離子液體為1-丁基-3-甲基咪唑六氟磷酸鹽(1-Butyl-3-methylimidazolium Hexafluorophosphate，縮寫 : [Bmim][PF6])，模擬油品 : 二苯並噻吩(Dibenzothiophene,縮寫 : DBT)，透過氧化萃取法探討兩種萃取模式，其一 : 雙階段氧化脫硫，當轉速(5400 RPM)、鎢磷酸(0.2 g)、溴化四辛基銨(0.03 g)、雙氧水(10 ml)、高剪斷力乳化時間(30 min)，其氧化效率達99.31 %；當轉速(700 RPM)、[Bmim][PF6](6 ml)、反應時間(5 min)，達到81.82 %脫硫效果。其二 : 單階段氧化脫硫，當轉速(5400 RPM)、鎢磷酸(0.4 g)、溴化四辛基銨(0.06 g)、雙氧水(20 ml)、DBTO (10 ml) : [Bmim][PF6](10 ml)、反應時間(60 min)，其氧化效率為75.86 %，總硫去除率為75.48 %。

研究得知雙階段氧化萃取模式之氧化及萃取之p-values值與F-values值，氧化流程中反應時間、溴化四辛基銨、鎢磷酸和雙氧水較低之p-values值分別為1.97×10-4、4.46×10-4、544.30×10-4和286.29×10-4；較高之F-values值為5077.1、2241.1、16.9和33.4，萃取流程中反應時間、離子液體劑量和轉速較低之p-values值分別為0.3、127.81×10-5和0.2另外，較高之F-values值為1.7、780.7和4.2，並根據其值大小得知氧化流程中四個參數對DBT的硫氧化有顯著影響，其中反應時間具最顯著的影響，萃取流程中三個參數對DBTO的硫萃取有顯著影響，其中離子液體劑量具最顯著的影響。

As the regulatory requirements more stringent, many oil refineries for oil desulfurization requirements are also stricter. Therefore, it is highly desirable to study more efficient alternatives. Removal of oil sulfide by oxidative desulfurization is one of the popular alternatives today.

Which the ionic liquid used in this study was 1-butyl-3-methylimidazole hexafluorophosphate, abbreviated: [Bmim] [PF6]), simulated oil: Dibenzothiophene (abbreviation: DBT) To investigate two extraction modes by oxidative extraction, one of them: bis oxidative desulfurization stage, when the oxidative efficiency of rotational speed (5400 RPM), tungstophosphoric acid (0.2 g), tetraoctylammonium bromide (0.03 g), hydrogen peroxide (10 ml), high shear power emulsification time (30 min), was 99.31%. When the speed (700 RPM), [Bmim] [PF6] (6 ml), reaction time (5 min), with 81.82% desulfurization effect. Second : single stage oxidative desulfurization, when the oxidation efficiency of the Centrifugal speed (5400 RPM), tungstophosphoric acid(0.4 g),tetraoctylammonium bromide(0.06 g), hydrogen peroxide(20 ml),DBTO (10 ml) : [Bmim][PF6](10 ml),Reaction time (60 min) was 75.86% , the total sulfur removal rate was 75.48%.

The study showed that the p-values and F-values of oxidation and extraction in the two-stage oxidation extraction model were lower than those in the oxidation process. The p-values values of the octa-octylammonium bromide, tungstophosphoric acid and hydrogen peroxide were 1.97 × 10-4, 4.46 × 10-4, 543.30 × 10-4 and 286.29 × 10-4. The higher F-values values are 5077.1, 232.1.1, 16.9 and 33.4, and the p-values of the reaction time, ionic liquid dose and rotational speed in the extraction process are 0.3, 127.81 × 10-5 and 0.2 respectively. The higher F-values are 1.7, 780.7 and 4.2. And the four parameters in the oxidation process have a significant effect on the sulfur oxidation of DBT according to their size. There’s the most significant effect in the reaction time, there’s a significant effect on the sulfur extraction of DBTO in the three parameters of the extraction process, in which the ionic liquid dose has the most significant effect.

摘要 i
Abstract iii
誌謝 v
目錄 vii
表目錄 ix
圖目錄 xi

第一章 前言 1
1.1研究動機 1
1.2 研究目的 1

第二章 文獻回顧 3
2.1硫氧化物之來源 3
2.2硫氧化物的影響 4
2.3硫氧化物法規 4
2.4 現行油品脫硫技術探討 6
2.5 新興的油品脫硫技術 14
2.6各項實驗參數之最佳化分析 17

第三章 研究方法 18
3.1研究架構與流程 18
3.3 樣品分析之儀器 33
3.4 實驗藥品 37
3.5 實驗設備 38

第四章 結果與討論 39
4.1 DBT氧化效率之研究 39
4.2 DBT雙階段氧化脫硫效率之研究 58
4.3 單階段氧化脫硫效率之研究 75

第五章 結論與建議 79
5.1 結論 79
5.2 建議 81

1.行政院環境保護署-移動汙染源管制網(https://mobile.epa.gov.tw/oilimprovement_3.aspx ) ，106.06.15

2.高雄市政府環境保護局 (http://www.green99.com.tw/101_air/tech-1.asp)

3.蔣安國，蔣安仁，丁敬哲，鍾健平，2005，以模擬技術和統計方法建構專案排程之可靠度，119-130。

4.羅文亨，國立中正大學化學研究所博士論文，2005，利用室溫離子液體以萃取/氧化法進行油品脫硫及脫氮之研究。

5.Babich, I. V, Moulijn, J. A., 2003. Science and technology of novel processes for deep desulfurization of oil refinery streams: a review. Fuel, 82, 607–631.

6.Bösmann, A, Datsevich, L, Jess, A, Lauter, A, Schmitz, C,Wasserscheid, P., 2001. Deep desulfurization of diesel fuel by extraction with ionic liquids .Chemistry Communication, 66 (23), 2494-2495.

7.Box, G.E, Draper, N.R., 1997. Empirical Model Building and Response Surface, John Wiley and Sons, New York.

8.Eßer, J, Wasserscheid, P, Jes, A., 2004. Deep desulfurization of oil refinery streams by extraction with ionic liquids. Green Chemistry. 6, 316-322.

9.Fisher, A, Chestnut, L, Violette, D., 1998. The value of reducing risks to death: a note on new evidence. Journal of Policy Analysis and Management, 8(1), 88-100.

10.Gates, B. C, Katzer, J. R, Schuit, G.L.A., 1979. Chemistry of Catalytic Processes, McGrow-Hill, New York.

11.Handy, S. T, Zhang, X., 2001. Worldwide Refining Business Digest, May 2001, P2.

12.Ichinose, H, Wariishi, H, Tanaka, H., 1999. Bioconversion of recalcitrant 4-methyldibenzothiophene to water-extractable products using lignin-degrading basidiomycete. Biotechnology Progress. 15, 706–714.

13.Irvine, R, Benson, B., 2000. Consider Latest Low Cost Breakthrough for Low Sulfur Gasoline, World Refining Sulfur.

14.Kabe, T, Ishihara, A, Tajima, H., 1992. Deep Hydrodesulfurization of Light Gas Oil. 1. Kinetics and Mechanisms of Dibenzothiophene Hydrodesulfurization. Industrial & Engineering Chemistry Research, 31 (6), 1577-1580.

15.Konishi, J, Ishii, Y, Onaka, T, Okumura, K, Suzuki, M., 1997. Thermophilic carbon-sulfur-bond-targeted biodesulfurization. Applied and Environmental Microbiology, 63, 3164–3169.
16.Klein, J, Afferden, M, Van Pfeifer, F, Schacht, S., 1994. Microbial desulfurization of coal and oil. Fuel Process Technology, 40(3), 297-310.

17.Laredo, G. C, Reyes, A. D, Cano, J. L, Castillo, J., 2001. Inhibition effects of nitrogen compounds on the hydrodesulfurization of dibenzothiophene. Applied Catalysis A: General, 207, 103–112.

18.Murali Dhar, G, Srinivas, B. N, Rana, M. S, Manoj Kumar, S. K., 2003. Mixed oxide supported hydrodesulfurization catalysts—a review. Catalysis Today, 86, 45-60.

19.Mei, H, Mei, B. W, Yen, T.F., 2003. A new method for obtaining ultra-low sulfur diesel fuel via ultrasound assisted oxidative desulfurization. Fuel, 82(4), 405-414.

20.Olsson, G, Pott, B. M, Larsson, L, Holst, O, Karlsson, H. T., 1994. Microbial desulfurization of coal by Thiobacillus ferrooxidans and Thermophilic archaea. Fuel Process Technology, 40, 277–282.

21.Otsuki, S, Nonaka, T, Takashima, N, Qian, W, Ishihara, A, Imai, T, Kabe, T., 2000. Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction. Energy & Fuels. 14(6), 1232-1239.

22.Qi, L, Hao, J. M, Lv, M. M.,1995.Water& Air Soil Pollut, 85,1873.

23.Song, C., 2003. An Overview of New Approaches to Deep Desulfurization for Ultra-Clean Gasoline, Diesel Fuel and Jet Fuel. Catalysis Today, 86 (1-4), 211-263.

24.Song, C, Ma, X., 2003. New Design Approaches to Ultra-Clean Diesel Fuels by Deep Desulfurization and Deep Dearomatization. Applied Catalysis B: Environment, 41 (1-2), 207-238.

25.Schmitz, C, Datsevitch , L, Jess, A., 2004. Deep desulfurization of diesel oil:kinetic studies and process-improvement by the use of a two-phase reactor with pre-saturator. Chemical Engineering Science, 59:2821–2829.

26.Setti, L, Lanzarini, G, Pifferi, P. G., 1997. Whole cell biocatalysis for an. oil desulfurization process. Fuel Processing Technology, 52, 145-153.

27.Tippett, H, Knudsen, K.G., 1999. Ultra low sulfur diesel: catalyst and process options, in: NPRA Annual Meeting, AM-99-06, San Antonio, TX.

28.Tailleur ,R. G, Ravigli ,J, Quenza ,S, Valencia ,N., 2005. Catalyst for ultra-low sulfur and aromatic diesel. Applied Catalysis A: General, 282: 227–35.

29.Yang, H, Chen, J. W, Fairbridge, C, Briker, Y, Zhu, Y. J, Ring, Z., 2004. Inhibition of nitrogen compounds on the hydrodesulfurization of substituted dibenzothiophenes in light cycle oil. Fuel Process Technology, 85, 1415–1429.

30.Yang, H, Chen, J. W, Briker, Y, Szynkarczuk, R, Ring, Z., 2005. Effect of nitrogen removal from light cycle oil on the hydrodesulphurization of dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. Catalyst Today, 109, 16–23

31.Zhang, S, Zhang, Z. C., 2001. Hydrocarbon Processing, May 2001, P29.

32.Zhang,S. G, Zhang, Q. L,Zhang, Z. C., 2004. Extractive Desulfurization and Denitrogenation of Fuels Using Ionic Liquids. Industrial & Engineering Chemistry Research, 43(2) ,614-622.