臺灣博碩士論文加值系統

在印刷業製程中會使用到酚醛樹酯，這些樹酯的原料含有甲醛
(formaldehyde)的成分，若印刷廠的甲醛暴露濃度超過時量平均容許濃度 1ppm
時，會刺激勞工的眼睛鼻腔與咽喉，導致水腫、發炎等。
印刷廠業者常使用的活性碳吸附甲醛，但是單獨使用活性碳吸附設備無
法滿足排放標準要求，常要搭配其他技術處理，因此，本研究應用鉛筆為石
墨來源，以製備氧化石墨烯(graphene oxide)，添加不同比例的橘子皮與咖啡渣
以合成複合物(composite materials)，作為吸附甲醛的材料，代替印刷廠業者常
用的活性碳。
本實驗使用 GilAir Plus 高/低流量採樣幫浦選擇模擬人類呼吸頻率之流
速，以線香為甲醛的來源，將直讀式空氣測定儀器放入自行組裝設備進行實
驗，偵測並記錄甲醛濃度的變化，進一步探討甲醛吸附效能的最佳吸附之比
例與重量。
結果發現使用氧化石墨烯與咖啡渣比例為 1：3 時，1.5 克所製成之複合
材料的吸附效果最佳，其去除率達到 88.3%，而吸附效能最差為氧化石墨烯
與咖啡渣比例為 1：1 時，1.5 克製成之複合材料的去除率為 75.7%；此外，本
研究製備之氧化石墨烯複合材料在甲醛濃度為 1.40 mg/m3 時，1：3 比例的氧
化石墨烯與咖啡渣製備之複合材料對於空氣甲醛去除率可達 92.5%。
iii
本研究以 Freundlich 以及 Langmuir 等溫吸附模式以及動力學吸附模式進
行探討，發現本研究製備之複合材料吸附甲醛的模式不適用 Freundlich 與
Langmuir 兩者等溫吸附模式，甲醛的吸附較符合動力學吸附模式之擬二階吸
附動力學模式。

Phenolic resins contain formaldehyde are used in the printing process.
If the exposure concentration of formaldehyde in the printing factory exceeds
the average allowable concentration of 1ppm, it will irritate the eyes, nose
and throat of workers, resulting in edema, Inflammation etc.
Activated carbon is often used to adsorb formaldehyde in printing
factories, but activated carbon adsorption equipment alone cannot meet the
emission standards and often needs to be treated with other technologies.
Therefore, this study utilizes pencils as a graphite source to prepare graphene
oxide, and then add different proportions of orange peel or coffee grounds to
synthesize composite materials, which are used as materials for adsorbing
formaldehyde, instead of activated carbon commonly used by printing
manufacturers.
In this experiment, the GilAir Plus high/low flow sampling pump is used
to select the flow rate that simulates the human respiratory rate, and the
incense sticks are used as the source of formaldehyde. The direct-reading air
measuring instrument is put into the self-assembled equipment, and the
formaldehyde concentration is detected and recorded changes, and further
explore the ratio and weight of the optimal adsorption for formaldehyde
adsorption performance.
It was found that when the ratio of graphene oxide and coffee grounds
was 1:3, the adsorption effect of 1.5 grams of the composite material was the
best, and the removal rate reached 88.3%, while the adsorption performance
of graphene oxide and coffee grounds was the worst. When the ratio is 1:1,
the removal rate of 1.5 grams of the composite material is 75.7%; in addition,
when the formaldehyde concentration of the graphene oxide composite
material prepared in this study is 1.40 mg/m3, the ratio of 1:3 graphite The
v
composite material prepared by graphene oxide and coffee grounds can
remove 92.5% of air formaldehyde.
In this study, Freundlich and Langmuir isothermal adsorption models
and kinetic adsorption models were investigated. It was found that the
composite materials prepared in this study did not apply to the isothermal
adsorption models of Freundlich and Langmuir. The formaldehyde
adsorption kinetics followed the pseudo-second order kinetic model.

目錄
致謝 ...........................................................................................................................i
摘要..........................................................................................................................ii
Abstract...................................................................................................................iv
目錄.........................................................................................................................vi
表目錄 ..................................................................................................................... x
圖目錄 ...................................................................................................................xii
第一章 緒論 ........................................................................................................ 1
1-1 研究動機............................................................................................. 1
1-2 研究目的............................................................................................. 3
第二章 文獻回顧................................................................................................ 4
2-1 室內空氣品質 ..................................................................................... 4
2-2 甲醛 .................................................................................................... 7
2-3 氧化石墨烯與其製備.......................................................................... 9
2-3-1 Brodie 法 .....................................................................................12
2-3-2 Staudenmaier 法 ..........................................................................12
2-3-3 Hummers 法 ................................................................................13
vii
2-3-4 Tour 法 ........................................................................................14
2-3-5 修飾型的 Hummers 法及 Iron-based Approach 法......................15
2-3-6 Tang-Lau’s 法 ............................................................................17
2-3-7 電化學法....................................................................................18
2-4 植物纖維複合材料.............................................................................20
2-5 印刷業甲醛的空氣汙染 .....................................................................22
2-6 吸附理論............................................................................................24
2-6-1 吸附作用 .....................................................................................24
2-6-2 吸附作用之種類..........................................................................24
2-6-3 等溫吸附模式 .............................................................................26
2-6-4 動力學吸附模式..........................................................................29
2-7 去除效率............................................................................................31
第三章 研究方法.............................................................................................. 32
3-1 研究流程............................................................................................32
3-2 實驗材料與方法 ................................................................................34
3-2-1 實驗藥品 .....................................................................................34
3-2-2 實驗設備 .....................................................................................34
viii
3-3 研究方法............................................................................................35
3-3-1 氧化石墨烯製備..........................................................................35
3-3-2 氧化石墨烯複合材料製備 ..........................................................36
3-3-3 氧化石墨烯複合材料之實驗流程 ...............................................38
3-4 實驗儀器分析與方法.........................................................................39
3-4-1 拉曼光譜儀(Raman)....................................................................39
3-4-2 ESCA 化學分析電子能譜儀(ESCA/XPS) ...................................40
3-4-3 高解析熱場發射掃描式電子顯微鏡(FE-SEM) ...........................41
3-4-4 X-ray 繞射分析(X-ray Diffraction，XRD)..................................42
3-4-5 傅立葉紅外光譜(FTIR)...............................................................43
第四章 結果與討論.......................................................................................... 44
4-1 氧化石墨烯及氧化石墨烯複合材料定性分析 ...................................44
4-1-1 紅外線光譜分析(FT-IR) .............................................................44
4-1-2 電子能質譜儀之表面分析(XPS).................................................46
4-1-3 拉曼光譜分析(Raman) ................................................................48
4-1-4 X-ray 繞射分析(XRD).................................................................50
4-1-5 掃描電子顯微鏡(SEM) ..............................................................52
ix
4-2 廢棄物與氧化石墨烯之不同比例與不同重量吸附甲醛的效能探討56
4-2-1 不同重量氧化石墨烯與不同比例橘子皮吸附甲醛之效能探討..57
4-2-2 不同重量氧化石墨烯與不同比咖啡渣例吸附甲醛之效能探討..61
4-3 應用最佳比例之複合材料探討甲醛之吸附效能 ...............................65
4-4 使用不同起始濃度甲醛之吸附效能 ..................................................67
4-5 等溫吸附模式探討.............................................................................68
4-6 動力學吸附模式探討.........................................................................72
第五章 結論與建議.......................................................................................... 76
5-1 結論 ...................................................................................................76
5-2 本研究的限制與建議.........................................................................77
參考文獻 ............................................................................................................... 78

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