臺灣博碩士論文加值系統

中文摘要
本研究以微分固定床反應器，在模擬噴霧乾燥法煙道氣除硫系統之袋式集塵器的條件下，探討溫度、濕度和氣體成分對石灰石與二氧化硫反應之影響，並推導石灰石在模擬煙道氣中反應的動力學模式。石灰石來自花蓮和平地區，試樣比表面積為21.4m2/g。
石灰石與二氧化硫的反應速率隨相對濕度和二氧化硫濃度增加而增加。二氧化碳存在與否不會影響反應。氧氣(5-21%)和氮氧化物(200-600ppm)的存在可大幅度提升石灰石的轉化率，但轉化率不受氧氣和氮氧化物濃度的影響。在無氧氣及氮氧化物存在下，反應溫度45oC時之轉化率高於其它溫度，在有這二種氣體存在下，溫度愈低轉化率愈高。
在無氧氣或氮氧化物時，石灰石硫酸化產物為CaSO3，若有氧氣及氮氧化物時，產物為CaSO3．1/2H2O、CaSO4．1/2H2O和CaSO4。
石灰石在模擬煙道氣體中和二氧化硫的反應為化學反應控制，在反應轉化率與時間呈直線階段，可用平板晶粒之反應來描述其反應動力學。轉化率( X,%)與反應時間(t , min)的關係可表示為：
由上式可看出反應速率與石灰石比表面積（Sg , m2/g）的一次方成正比，與二氧化硫濃度(y , ppmv)的0.7次方成正比，隨著相對濕度(RH , %)的增加成指數函數增加，隨著溫度(T , K)的升高而降低。
關鍵詞：石灰石、煙道氣、二氣化硫、反應動力學

Abstract
A differential fixed-bed reactor was employed to study the effects of the components of flue gas on the reaction of limestone with SO2 at low temperatures under the conditions silimiar to those in the bag filters of the spray-drying flue gas desulfurization system. Limestone was from Her-Ping , Hualien , and was ground to a BET surface area of 21.4m2/g.
The rate of the reaction between limestone amd SO2 increased as relative humidity or SO2 concentration increased . The rate , being unaffected by the presence of CO2 , was significantly enhanced by the presence of NOX(200-600ppm) or O2(5-21%) , but concentration of NOX or O2 had no effect .
Without the presence of NOX and O2 , the reaction rate reached the maximum at 45oC ; with the presence of NOX and O2 , the reaction rate increased as temperature decreased；CaSO3 was formed in the former case , and CaSO3．1/2H2O，CaSO4．1/2H2O and CaSO4 were formed in the latter case.
The reaction between limestone and SO2 under simulated flue gas was controlled by chemical reaction , and the constant reaction rate period could be well described by the flat-plate grain model . The equation relating limestone conversion X(%) with time t(min) as a function of limestone specific surface area Sg(m2/g)，SO2 concentration y(ppm) relative humidity (%)，and temperature T( )is
Key words：Flue gas，Sulfur dioxide，Limestone，Reaction kinetics

目錄 Page
中文摘要…………………………………………………………….Ⅰ
Abstract………………………………………………………………Ⅲ
符號說明……………………………………………………………..Ⅴ
圖表索引…………………………………………………………….Ⅶ
第一章緒論……………………………………………………..…1
第二章文獻回顧…………………………………………………..5
2-1 石灰石性質………………………………………………………..……5
2-2 石灰石與二氧化硫在低溫潤濕條件下的反應………………………..6
2-3 氣體成分對吸收劑除硫效率的影響…………………………….……10
第三章實驗與分析方法……………………………………….…14
3-1 試料來源及藥品………………………………………………………14
3-2 反應實驗裝置…………………………………………………………15
3-3 反應實驗步驟…………………………………………………….……21
3- 4 石灰石轉化率之測定………………………………………………....22
3-5 試樣物性與化性分析………………………………………………….27
第四章結果與討論…………………………………………….….29
4-1 微分床操作條件的驗證…………………………………………..……29
4-2 溫度對石灰石反應的影響………………………………………..……29
4-3 添加二氧化碳對石灰石反應的影響……………………………….….31
4-4 添加氮氧化物對石灰石反應的影響…………………………………..34
4-5 添加氧氣對石灰石反應的影響………………………….……………..42
4-6 添加氧氣和氮氧化物對石灰石反應的影響…………………….……..46
4-7 在模擬廢氣中相對濕度、二氧化硫濃度和溫度對石灰石反應的影響……………………………………………………………………..……49
4-8 在模擬廢氣中石灰石的反應動力學分析…………………………...….56
4-9 產物分析…………………………………………………………………68
第五章結論…………………………………………………….….102
參考文獻……………………………………………………………..104

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