臺灣博碩士論文加值系統

研究證實此液-液萃取概念及方法對於自輕油中移除氮化物含量至一極低濃度標準，而生產出更適合作為下游高性能沸石觸媒製程的輕油進料。觸媒上強酸性活性基進行催化反應，但也極易因進料中鹼性氮化物吸附而中毒失活。此方法具非常高萃取效率，萃取來自於液-液萃取或萃取蒸餾製程生產C6 ~ C8芳香烴類中污染的鹼性氮化物，而此芳香烴類萃取生產製程往往使用含氮萃取溶劑。此除氮方法在低溫、低壓狀態下操作，基本上可以回收大部分芳香烴類產品。

萃取方法上使用無毒性、具抗腐蝕性和低成本費用的萃取溶劑。非常特別一點，此極性萃取溶劑為去離子水。該方法及概念能夠完全萃取移除芳香烴類產品中的氮化物以及經由吸附劑吸附能將烯烴類減量到8 ppm以下，使得他們能夠更適合下游觸媒製程。

The present reseacch is related to a liquid-liquid extraction method and conception for removing nitrogen from the light petroleum oils to an ultra-low level and making them suitable as the feedstocks for the down stream catalytic processes, which use high performance zeolitic catalysts. The desirable reactions are catalyzed at the strong acidic sites of these catalysts, which are very vulnerable to poison from the basic nitrogen in the feedstock. This method is highly efficient in extracting contaminate of the basic nitrogen compounds from the C6 to C8 aromatics produced from liquid-liquid extraction process or extractive distillation process, where the nitrogen-containing solvents are used for the aromatics extraction. Nitrogen extraction is conducted at low temperature and pressure with essentially total aromatics product recovery.

The extractive method uses a non-toxic, non-corrosive, and low cost solvent. Specifically, the polar extractive solvent is water. This method can completely to remove the nitrogen compounds from the extracted aromatic products（non-detectable level）and by the way of absorbents can reduce olifens（＜8 ppm）, making them suitable for the down stream catalytic processes.

一、緒論與基本觀念..............................................10
1-1、前言....................................................10
1-1-a、緣起與緣由........................................10
1-1-b、研究背景..........................................11
1-2、除氮方法簡介............................................12
1-2-a、加氫脫氮方法......................................15
1-2-b、非加氫脫氮方法....................................16
1-3、文獻回顧................................................17
1-4、研究動機................................................20
1-5、研究目的與發展..........................................23
二、研究方法....................................................24
2-1、製程生產流程型態了解....................................24
2-2、污然氮化物之生產成因....................................26
2-3、除氮方法與應用原理......................................26
2-3-a、溶劑萃取..........................................27
2-3-b、酸萃取及反應......................................27
2-3-c、吸附劑吸附........................................28
2-3-d、汽提..............................................28
2-4、整體實驗規劃設計與架構..................................29
2-5、實驗分析之儀器..........................................30
2-5-a、氮含量分析儀......................................30
2-5-b、氣相層析儀........................................30
2-5-c、氣相層析質譜儀....................................31
2-5-d、pH Meter..........................................32
2-5-e、烯烴類含量溴值分析儀..............................32
2-5-f、比表面機與孔洞分析儀..............................32
2-5-g、氣體、藥品與設備..................................33
三、研究流程與結果討論..........................................35
3-1、萃取....................................................35
3-1-a、去離子水萃取......................................35
3-1-b、醋酸水溶液萃取....................................36
3-1-c、醋酸反應及水洗....................................38
3-2、水蒸氣汽提..............................................39
3-3、酸性白土吸附劑吸附......................................42
3-3-a、連續式酸性白土吸附條件測試........................44
3-3-b、管柱酸性白土吸附飽和測試..........................46
3-4、除氮製程評估與設備模擬..................................48
3-4-a、液-液萃取塔模擬...................................49
3-4-b、萃取水氮含量飽和濃度測試..........................51
四、結論........................................................53
4-1、除氮方法概念流程........................................53
4-2、除氮方法效能............................................55
五、未來展望....................................................56
六、參考文獻....................................................57
6-1、中文文獻................................................57
6-2、英文文獻................................................58

6-1、中文文獻：
[1]、吴济民、陳聚良、杨炎鋒，『苯部份加氫催化劑失活原因與研究』，化工進展，第22
卷，第3期，295 ~ 297，（2003）
[2]、Dr. Satterfield 著，王奕凱、李秉傑、邱宏明合譯，『非均勻系催化原理與應
用』，國立編譯館主編，民國九十二年
[3]、王安杰、李翔、李轟、魯墨弘，『加氫脫氮反應與加氫脫氮催化劑的研究進展』，
化工進展，第22卷，第6期，583 ~ 588，（2003）
[4]、于道永、徐海、阙囯和，『石油非加氫脫氮技術進展』，技術進展，32 ~ 35，
第10期，，（2001）
[5]、洪正宗、黃文龍，『吸附劑在石化工業之應用』，石油季刊，第40卷，第4期，49
~ 57，（2004）
[6]、D.L.Burdick、W.L.Leffler 原著，胡興中 譯著，『石油化學』，高立圖書有限公
司，民國九十五年
[7]、邱肇堂、洪正宗、鄭福壽、何信杰，『活性白土處理BTX油料之研究』，石油季
刊，第37卷，第3期，43 ~ 55，（2001）
[8]、謝俊雄 著，『石油化學工業；The Petrochemical Industry』，文經圖書有限公
司，民國九十一年
[9]、田松柏、董忠杰，『石油工業苯含氮化合物的類型分析』，化工進展，第24卷，
第2期，193 ~ 195，（2005）
[10]、林雯妤，『環境思維下的煉油程序選擇-邁向工業生態之初探；Refinery
Process Selection with Environmental Concerns: A Step towards
Industrial Ecology』，朝陽科技大學，環境工程與管理系，（2003）
[11]、王少军、吴洪新、凌凤香、钱迈原、『GC-AED法研究催化柴油中硫氮化合物』，
當代化工，第35卷，第1期，（2006）
[12]、吴子明、刘涛、彭紹忠、曾榕辉、潘德满，『FF-14加氫預處理催化劑反應性能
研究』，當代化工，第34卷，第3期，（2005）

6-2、英文文獻：
[13]、Yao; Keith C. (Sarnia, CA)，『Removal of basic nitrogen compounds from
extracted oils by use of acidic polar adsorbents and the regeneration
of said adsorbents』，（1987），U.S. Patten 4,846,962
[14]、Min; Wha-Sik (Taejon, KR); Choi; Kyung-Il (Taejon, KR); Khang; 　　
　　 Sin-Young (Taejon, KR); Min; Dong-Soon (Taejon, KR); Ryu; 　
　　 Jae-Wook (Taejon, KR); Yoo; Kwan-Sik (Taejon, KR); Kim;
　 　Jyu-Hwan (Taejon, KR)，『Method for manufacturing cleaner fuels』，
（1999），U.S. Patten 6,248,230
[15]、Schmidt; Robert J. (Barrington, IL); Zarchy; Andrew S. (Kildeer,
IL)，『Process and apparatus for the removal of nitrogen compounds
from a fluid stream』，（2003），U.S. Patten 6,894,201
[16]、Miller; Stephen J. (Emeryville, CA)，『Denitrification process for
hydrogenated distillate oils』，（1997），U.S. Patten 4,113,607
[17]、Evans; Wayne E. (Richmond, TX); Blytas; George C. (Houston, TX)，
『Two-step heterocyclic nitrogen extraction from petroleum oils』，
（1989a），U.S. Patten 4,960,507
[18]、Evans; Wayne E. (Richmond, TX)，『Two-step heterocyclic nitrogen
extraction from petroleum oils』，（1989b），U.S. Patten 4,960,508
[19]、Chen; Paul Y. (Huntington Beach, CA); Madgavkar; Ajay M. (Irvine,
CA)，『Process for removing nitrogen from shale oil』，（1982），
U.S.Patten 4,426,280
[20]、Kuk; Myong S. (Monroeville, PA); Albaugh; Edgar W. (Monroeville,
PA); Montagna; John C. (O'Hara Township, Allegheny County, PA)，
『Removal of nitrogen from a synthetic hydrocarbon oil』，（1982）
，U.S. Patten 4,483,763
[21]、Catalystic Clay Treaters，『Operating Instructions for TONSIL
Catalysts』，SüD-CHEMIE INC
[22]、Emmrich Gerhard，Ennenbach Frank，Ranke Uwe，Gehrke Helmut，
『Process And Facility For The Production Of Ultra-Pure
Aromatics』，（2001），U.S. Patten 20020014780
[23]、Irvine; Robert L. (Overland Park, KS)，『Process for desulfurizing
gasoline and hydrocarbon feedstocks』，（1995），U.S. Patten 5,730,860
[24]、Miller; Stephen J. (Emeryville, CA)，『Denitrification by furfural-
ferric chloride extraction of coker oil』，（1978），
U.S. Patten 4,169,781
[25]、Seunghan Shin、Kinya Sakanishi、Isao Mochida，『Indentification
and Reactivity of Nitrogen Molecular Species in Gas Oils』，（2000）
，Energy ＆ Fuels，14，539 ~ 544
[26]、Olobunmi M. Ogunsola、Norbert Berkowitz，『Removal of Heterocyclic
S and N from Oil Precursors By Supercritical Water』，（1995），74，
10，1485 ~ 1490
[27]、C.A. Audeh，『Removal of Nitrogen Compounds from Lubricating Oils』，
（1983），Ind.Eng.Chem.Res.Dev.，22，276 ~ 279
[28]、Peter Wiwel、Kim Knudsen、Per Zeuthen、Duayne Whitehurst，『Assessing
Compositional Changes of Nitrogen Compounds during Hydrotreating of
Typical Deiesel Range Gas Using a Novel Preconcentration Technique
Coupled with Gas Charomatography and Atomic Emisson Detection』，
（2000），39，533 ~ 540
[29]、J.F.Mckay、J.H.Weber、D.R.Latham，『Characterization of Nitrogen Bases
in High-Boling Petroleum Distillates』，（1976），Analytical
Chemistry，48，6，891 ~ 898
[30]、Vito La Vopa、Charles N. Satterfield，『Poisoning of Thiophene
Hydrodesulfurization by Nitrogen Compounds』，（1987），110，375 ~ 387
[31]、Steven A. Holmes、Lila F.Thompson、『Nitrogen Compound Distributions in
Hydrotreated Shale Oil Products from Commerical-Scale Refining』，
（1982），62，709 ~ 717