臺灣博碩士論文加值系統

本研究為針對國內煤焦油蒸餾工業僅歷經不到十年的運轉，即在製程中發生嚴重腐蝕並造成管線與設備嚴重損壞。從86年至91年短短數年中的紀錄，更因上述原因使製程遭受到十餘次的緊急停車與腐蝕生成物自燃所引發的火警工安事故；而統計因腐蝕問題所造成的檢修費用、緊急停車時數與次數、設備的損壞頻率等，均有偏高的情形。
過去該蒸餾工廠並未深入探討腐蝕發生原因與形成的機制，僅採取全面更換遭受腐蝕管線與添加藥劑的方式處理此一問題，但從製程操作狀況與非破壞性檢測分析證實上述改善方式成效十分有限。
該產業所遭遇的腐蝕問題在國外相同的產業領域中均未被深入的探討，因此本研究即對化工與煉油業中所有可能的腐蝕機制逐一比對篩選、並分析受腐蝕的設備，最後確認該製程的腐蝕機制為該流體中所含少量硫化物所造成的高溫硫化腐蝕，並排除較早所懷疑的硫化氫腐蝕或環烷酸腐蝕。而此項研究結果對一般普遍認定硫含量低於0.6%即不具腐蝕性而言為一新的發現。
在確認腐蝕原因之後從各種方式探討抑制該腐蝕的策略，並提出更換設備管線材質或者變更製程設計為較可行的改善方式，也屬於本質較安全的作法；本研究並深入探討業界所使用的材料並提出適合該製程於不同操作條件下的金屬材料建議，期望在經過此改善措施能使該工廠除了能降低因此問題所造成的損失之外，也能對人員與設備在環境保護、安全與衛生的議題上有所助益。

This study is based the observation of corrosion on a circulation loop system at the coal tar distillation plant over a period of several years. Leakage of the pipeline and major facility was damaged as well. Seventeen emergency shut off had been occurred for this reason from 1997 to 2002. Fire alerts were also occurred due to autoignition of FeS, product in the corrosion reaction, which has drew the attention of the safety concerns. Corrosions of the equipment, frequencies of emergency shut down, and the cost of the inspection is relatively higher than the expected. This potential industrial hazardous of the distillation plant was not well studied in the past. Changing the corroded pipeline and adding corrosion inhibitor might be beneficial of preventing corrosion of the system. However, the improvements of using these methods are limited.
Based on the literature search regarding the corrosion mechanism, corrosion in this case was believed to be triggered under the presence of trace amount of sulfide in the fluid at a high operation temperature. Either H2S or naphthenic acid is not able to initiate the reaction as we originally expected. It was generally believed that there will be no corrosion reactions over the equipment if the sulfide content in the mixture stream is lower than 0.6%. Nevertheless, it is not true upon completion of this study.
Corrosion protection strategies have been studied by knowing the various reasons triggering the corrosion reaction over the equipment. Changing the equipment pipeline will be the best remedy under the economical and safety concerns. Suggestions of using different plumbing materials under different operation condition were made in this study, which may reduce the potential industrial hazard under the operation condition. The suggestions may also be beneficial of enhancing the public safety concerns.

摘要………............i
英文提要iii
誌 謝v
目 錄vi
表 目 錄ix
圖 目 錄x
第一章 前言1
1.1 過去經歷問題概述1
1.2 國內外文獻資料缺乏2
1.2.1 原料成份的差異對腐蝕影響至鉅3
1.2.2 製程設計未考慮腐蝕問題3
1.3 主要議題說明4
1.4 煤焦油工廠所遭遇到的問題6
1.4.1 煤焦油蒸餾的製程說明6
1.4.2 循環油系統與煤焦油蒸餾的關係8
1.4.3 循環油系統所造成的損失12
1.4.4 循環油的問題對操作生產的影響14
1.4.5 循環油問題對安全、衛生與環保的影響18
1.5 研究目的說明20
1.5.1 資料收集與腐蝕機制研判20
1.5.2 研究目的與方向21
第二章 文獻回顧23
2.1.環烷酸的腐蝕機制23
2.2 硫化氫腐蝕24
2.3 硫腐蝕25
2.4 腐蝕與使用材質26
2.5 腐蝕控制策略28
2.6 腐蝕所發生之事故30
第三章 研究設計32
3.1 高溫硫腐蝕與可能部位之比對33
3.1.1 高溫硫腐蝕的特性33
3.1.2 潛在硫腐蝕之區域之篩選33
3.1.3 設備與管線腐蝕部位與潛在硫腐蝕區域之比對34
3.2 高溫硫腐蝕現象與機制之比對37
3.2.1 硫腐蝕之形態與機制簡介37
3.3 過去腐蝕位置與硫腐蝕機制比對39
3.3.1 設備部份與硫腐蝕機制比對40
3.3.2 管線部份與硫腐蝕機制比對47
第四章 煤焦油蒸餾製程與腐蝕分析51
4.1 煤焦油蒸餾工廠所有可能腐蝕原因探討51
4.1.1 循環油系統腐蝕的特徵51
4.2 可能的腐蝕原因探討57
4.2.1 低溫腐蝕種類與製程關連性說明57
4.2.2 高溫腐蝕形態與製程關連性說明61
4.3 循環油腐蝕原因進一步探討66
4.3.1 硫化氫與循環油系統腐蝕的關係66
4.3.2 環烷酸與循環油系統腐蝕的關係69
4.3.3 硫腐蝕可能性之探討71
4.3.4 循環油系統腐蝕原因初步確認73
4.4 硫腐蝕的抑制對策73
4.4.1 使用低硫或無硫之原料可能性評估74
4.4.2 製程改善降低硫腐蝕評估74
4.4.3 變更操作條件降低硫腐蝕評估75
4.4.4 改善材質降低硫腐蝕評估75
4.5 材料之性質與選用76
4.5.1 材料的種類77
4.5.3 碳鋼材料成分與化工業的應用78
4.5.3 低合金鋼材料成分與化工業的應用80
4.5.4 不鏽鋼材料成分與化工業的應用81
第五章 討論84
5.1 建議使用材質84
5.2 煤焦油工廠實例探討85
5.2.1 腐蝕問題發現86
5.2.2 初期所採取對策87
5.2.3 初步改善成效確認88
5.2.4 腐蝕原因的初期研判90
5.3 高溫硫腐蝕的改善方向91
5.3.1 更換循環油抑制腐蝕評估91
5.3.2 添加抗硫腐蝕之藥劑評估92
5.3.3 更換材質93
第六章 結論與建議95
參考文獻98
附錄一 歷年來循環油管線破孔造成生產中斷記錄102
附錄二 煤焦油蒸餾設備廢氣管線檢測含有硫化氫之報告104
附錄三 循環油成份與其化學式114
附錄四 各種油品酸度值委外分析報告118
附錄五 蒸餾塔腐蝕板層分析報告124
附錄六 循環油泵浦葉輪腐蝕分析報告132
附錄七 加熱爐爐管非破壞性檢驗報告139
附錄八 循環油系統內沉積物委託顧問公司分析報告144
附錄九 煤焦油工廠自行委託分析沉積物計畫報告149

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