臺灣博碩士論文加值系統

本研究是以回收廢輪胎製備成吸附劑，以磷酸活化法再以硝酸改質燃油脫硫吸附劑，研究其對於二苯並塞吩(dibenzothiophene -DBT)的去除效果。在材料性質上使用BET、XRD、SEM、EDX和Boehm分析其性質。
以濃硫酸處理廢輪胎回收橡膠，並經裂解後獲得之碳黑，不僅可提高碳黑比表面積和降低平均孔徑之優點，也可去除輪胎橡膠中的雜質如Si、S和Zn等元素，達到純化碳材的效果。
磷酸活化法中，分別探討了磷酸活化溫度及磷酸/碳黑比例對材料性質與吸附性能影響。在活化溫度650°C和磷酸/原料質量比為2:1下製備之吸附劑，有最佳的DBT吸附去除率為49.4%。
硝酸表面改質中，使用硝酸濃度15 M在改質溫度70°C下反應3 h，有最佳的DBT吸附去除率為72% 。吸附性能的提升主要受到吸附劑表面官能基的影響，其官能基包括內脂0.27 mmol g-1、羥基0.48 mmol g-1和苯酚1.61mmol g-1，表面官能基的增加有利於活性碳對模擬油中DBT的吸附。
在吸附條件的優化中：活性碳對DBT的最佳吸附時間是1小時；吸附劑用量為0.2 g時吸附脫硫率最大，脫硫率為95 %。且活性碳對模擬油中DBT吸附脫硫率，隨著吸附溫度提高而降低。
採用Langmuir等溫線方程式和Freundlich等溫線方程式對所得實驗結果進行擬合。結果表明Langmuir吸附等溫線模型更適合於活性碳對二苯并噻吩吸附行為的描述(R2=0.9933)，所得參數qm及b分别為254.45 mg g-1和0.106 mL mg-1。
吸附動力學研究中採用擬一階動力學模型與擬二階動力學模型對所得實驗結果進行擬合。結果表明擬二階動力學模更適合於活性碳對二苯并噻吩吸附行為的描述(R2=0.9998)，所得參數Cal.qe及K2分别為166.3893 mg g-1和0.0188 min-1。

The adsorbent used for recycling waste tires, were prepared by phosphoric acid-activation and nitric acid modification. We investigate the removal effects of the dibenzothiophene. The characteristics of preparing materials are analyzed by BET, XRD, SEM, EDX and Boehm.
The waste rubber is treated with concentrated sulfuric acid to recover the rubber, and the carbon black obtained by the cracking not only can improve the specific surface area and lower the average pore diameter, but also remove impurities such as Si, S and Zn in the tire rubber.To achieve the effect of purified carbon material.
In the phosphoric acid activation method, the effects of phosphoric acid activation temperature and phosphoric acid/carbon black ratio on material properties and adsorption properties were investigated. The adsorbent prepared at an activation temperature of 650 ° C and a phosphoric acid / raw material mass ratio of 2:1 has an optimum DBT adsorption removal rate of 49.4%.


In the surface modification of nitric acid, the optimum DBT adsorption removal rate was 72% when the concentration of nitric acid was 15 M, modification temperature 70 °C and modification time 3 hours. The adsorption performance is mainly affected by the functional groups on the surface of the adsorbent. The functional groups include lactone 0.27 mmol g-1, hydroxyl group 0.48 mmol g-1 and phenol 1.61 mmol g-1. The increase of surface functional groups is beneficial to the activated carbon pair.
In the optimization of adsorption conditions: the optimal adsorption time of activated carbon for DBT is 1 hour; when the amount of adsorbent is 0.2 g, the adsorption desulfurization rate is the highest, and the desulfurization rate is 95%. Moreover, the desulfurization rate of activated carbon to DBT adsorption in simulated oil decreases with increasing adsorption temperature.
The experimental results were fitted the Langmuir isotherm equation and the Freundlich isotherm equation. The results show that the Langmuir adsorption isotherm model is more suitable for the adsorption behavior of dibenzothiophene on activated carbon (R2=0.9933), and the obtained constant qm and b are 254.45 mg g-1 and 0.106 mL mg-1, respectively.
In the adsorption kinetics study, the pseudo-first-order kinetic model and the pseudo-second-order kinetic model were used to fit the experimental results. The results show that the pseudo-second-order kinetic model is more suitable for the adsorption behavior of dibenzothiophene on activated carbon (R2=0.9998). The obtained parameters Cal.qe and K2 are 166.3893 mg g-1 and 0.0188 min-1.

摘要.……………………………………………………………………ii
Abstract………………………………………………………………...iv
圖目錄……………………………………………………….………...ix
表目錄…………………………………………………..……………..xv
第一章論………………………………………………..………………1
1.1 引言…………………………………………………..…………….1
1.2 油品中的硫化物…………………………………………..……….2
1.3 常見脫硫方式………………………………………………..…….3
1.3.1加氫脫硫………………………………………………..……3
1.3.2生物脫硫………………………………………………..……5
1.3.3萃取脫硫………………………………………………..……6
1.3.4吸附脫硫………………………………………………..……7
1.3.4.1分子篩……………………………………………..…..7
1.3.4.2金屬氧化物…………………………………………....8
1.3.4.3活性碳…………………………………………………9
1.4 活性碳改質…………………………………………………….....10
1.4.1表面物理結構改質…………………………………………10
1.4.2表面化學性質改質…………………………………………12
1.4.3金屬離子改質…………………………………………..…..13
1.5吸附原理………………………………………………………..…16
1.5.1吸附概論…………………………………………………....16
1.5.2影響吸附能力之因素………………………………………19
1.5.3等溫吸附模式………………………………………………22
1.5.3.1等溫吸附曲線類型…………………………………..26
1.5.3.2等溫吸附曲線之遲滯現象…………………………..29
1.5.4吸附動力學………………………………………………....31
1.6研究動機…………………………………………………………..32
第二章 實驗設備與程序……………………………………………..35
2.1本實驗所使用之藥品與儀器…………………………………......35
2.1.1實驗儀器……………………………………………………35
2.1.2實驗藥品……………………………………………………37
2.2實驗程序…………………………………………………………..39
2.2.1輪胎橡膠清洗………………………………………………39
2.2.2輪胎硫化與熱裂解…………………………………………39
2.2.3磷酸活化法………………………………………………....40
2.2.4硝酸表面化學改質………………………………………....41
2.3吸附性能分析……………………………………………………..42
2.3.1模擬油配製…………………………………………………42
2.3.2吸光度檢量線…………..…………………………………..42
2.3.3批式吸附實驗………………………………………………43
2.3.4吸附動力學實驗……………………………………………44
2.3.5等溫吸附曲線實驗…………………………………………44
2.4材料性質分析……………………………………………………..45
2.4.1 BET測量比表面積…….…………………………………...45
2.4.2 FE-SEM觀察表面形態…………………………………….48
2.4.3 XRD分析結晶性質………………………………………..51
2.4.4 Boehm法分析表面官能基……………………………...….53
第三章 結果與討論…………………………………………………..58
3.1硫化橡膠對材料性質之影響………………………………...58
3.1.1硫化橡膠衍生碳對孔結構之影響…………………………58
3.1.2硫化橡膠衍生碳之SEM和EDX圖………………………..62
3.1.3 XRD分析硫化橡膠衍生碳………….…………………......65
3.2磷酸活化溫度對材料性質之影響………………………………..67
3.2.1磷酸活化溫度對孔結構之影響……………………….…...67
3.2.2磷酸活化溫度下製備吸附劑之表面官能基分析…………70
3.2.3磷酸活化溫度下製備吸附劑之SEM圖…………………...71
3.2.4磷酸活化溫度對DBT吸附性能之影響…………………..74
3.3磷酸/碳黑比例對材料性質之影響…………………………….....76
3.3.1磷酸/碳黑比例對孔結構之影響…………………………...76
3.3.2磷酸/碳黑比例下製備吸附劑之SEM圖…..........................79
3.3.3磷酸/碳黑比例下製備吸附劑之表面官能基分析………...82
3.3.4磷酸/碳黑比例對DBT吸附性能之影響……………….....83
3.4硝酸改質溫度對材料性質之影響………………………………..86
3.4.1硝酸改質溫度對活性碳孔結構之影響………………..…..86
3.4.2 硝酸改質溫度下製備吸附劑之表面官能基分析……...…89
3.4.3硝酸改質溫度下製備吸附劑之SEM和EDS圖…………..90
3.4.4 XRD分析硝酸改質溫度下製備吸附劑…………………...93
3.4.5硝酸改質溫度對DBT吸附性能之影響……………..……95
3.5硝酸改質濃度對材料性質之影響…………………………..……98
3.5.1硝酸濃度對活性碳孔結構之影響…………………..……..98
3.5.2硝酸濃度下製備吸附劑之表面官能基分析………..……101
3.5.3硝酸濃度下製備吸附劑之SEM和EDS圖………………102
3.5.4硝酸濃度對DBT吸附性能之影響……………………....105
3.6 硝酸改質時間對材料性質之影響………………………..…….107
3.6.1硝酸改質時間對活性碳孔結構之影響……………..……107
3.6.2硝酸改質時間下製備吸附劑之表面官能基分析……..…110
3.6.3硝酸改質時間下製備吸附劑之SEM和EDS圖…………111
3.6.4硝酸改質時間對DBT吸附性能之影響………………....114
3.7吸附條件優化……………………………………………………116
3.7.1吸附溫度的影響…………………………………………..116
3.7.2吸附劑用量影響…………………………………………..117
3.7.3吸附劑時間確定…………………………………………..119
3.8活性碳對DBT吸附模式研究…………………………………..121
3.9吸附動力學………………………………………………………126
3.9.1擬一階吸附動力學………………………………………..126
3.9.1擬二階吸附動力學………………………………………..126
3.10吸附機制.…………………………………………………….....129
3.11 製備所得吸附劑吸附性能比較…………………………….....133
第四章 結論與建議……………………………………………..…..135
第五章 參考文獻……………………………………………..……..138
個人簡介………………………………………………………..……145

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