DSpace collection: 博碩士論文

3D 列印技術製備活性碳塊材吸附異丙醇及其電化學再生性能之研究;3D-printed activated carbon monolith for adsorption of isopropanol and its electrochemical regeneration

Tue, 20 Oct 2026 09:24:12 GMT

title: 3D 列印技術製備活性碳塊材吸附異丙醇及其電化學再生性能之研究;3D-printed activated carbon monolith for adsorption of isopropanol and its electrochemical regeneration abstract: 隨著半導體產業快速發展，製程排放之揮發性有機化合物（Volatile Organic Compounds， VOCs）已成為重要空氣污染來源，其中異丙醇（IPA）為常見之目標污染物。傳統活性碳吸附雖具有良好去除效果，但仍存在壓降大、流體分布不均及再生能耗高等問題。因此，本研究結合數位光處理（Digital Light Processing， DLP）3D列印技術與電化學再生方法，建立結構化活性碳之製備、固定床吸附及循環再利用技術。本研究利用DLP製備具有直通(NC)及曲折(CC)流道之3D列印活性碳，以固定床系統探討不同流道及活化條件對IPA吸附性能之影響，並建立Thomas、Yoon–Nelson及Adams–Bohart吸附模式。此外比較恆電位與恆電流再生方式，以及不同電解質種類(Na?SO?、NaOH及H?SO?)與濃度對電化學再生效率之影響，並透過循環伏安法(Cyclic Voltammetry ，CV)、線性掃描伏安法(Linear Sweep Voltammetry ，LSV)及電化學阻抗分析(Electrochemical Impedance Spectroscopy ，EIS)探討材料之電化學特性。研究結果顯示，CO?活化可有效提升活性碳孔隙結構與IPA吸附能力，其中曲折流道(CC)因改善質量傳遞而具有較佳固定床吸附效能。吸附模式分析顯示，Thomas及Yoon–Nelson模式可有效描述貫穿曲線行為。電化學再生結果顯示，恆電位模式具有較佳穩定性，而不同電解質皆存在最佳操作條件，透過CV與EIS分析結果顯示，吸附飽和後電荷轉移阻抗增加，再生後雖可部分降低阻抗，但仍未完全恢復至新鮮樣品，顯示電化學再生可有效恢復吸附性能，但材料界面特性仍存在部分不可逆變化。在這其中以Na?SO?於不同濃度下皆展現良好再生效果。於最佳條件下進行五次吸附─再生循環後，再生效率仍維持約90%以上，顯示材料具有良好循環穩定性。根據研究結果，本研究成功建立3D列印結構化活性碳之製備、固定床吸附、電化學再生及循環使用流程，證實藉由流道設計及適當電化學再生條件，可有效提升吸附材料之循環利用效能，對半導體製程VOCs控制及結構化吸附材料之開發具有應用潛力。;With the rapid development of the semiconductor industry， volatile organic compounds (VOCs) emitted from manufacturing processes have become a major source of air pollution. Among them， isopropyl alcohol (IPA) is one of the most common target pollutants. Although conventional activated carbon adsorption exhibits excellent removal performance， it still suffers from several drawbacks， including high pressure drop， non-uniform flow distribution， and high energy consumption during regeneration. Therefore， this study integrates Digital Light Processing (DLP) 3D printing technology with electrochemical regeneration to establish the fabrication， fixed-bed adsorption， and cyclic reuse of structured activated carbon. In this study， DLP 3D printing was employed to fabricate structured activated carbon with straight-channel (NC) and tortuous-channel (CC) flow configurations. A fixed-bed adsorption system was used to investigate the effects of flow-channel design and activation conditions on the adsorption performance of IPA. The adsorption behavior was further analyzed using the Thomas， Yoon–Nelson， and Adams–Bohart models. In addition， potentiostatic and galvanostatic electrochemical regeneration methods were compared， and the effects of different electrolytes (Na?SO?， NaOH， and H?SO?) and their concentrations on regeneration efficiency were evaluated. The electrochemical properties of the materials were characterized by cyclic voltammetry (CV)， linear sweep voltammetry (LSV)， and electrochemical impedance spectroscopy (EIS). The results showed that CO? activation effectively enhanced the pore structure of activated carbon and significantly improved its IPA adsorption capacity. The tortuous-channel (CC) structure exhibited superior fixed-bed adsorption performance owing to enhanced mass transfer. Adsorption model analysis indicated that the Thomas and Yoon–Nelson models accurately described the breakthrough behavior of the adsorption process. Electrochemical regeneration results demonstrated that the potentiostatic mode provided better operational stability than the galvanostatic mode. All investigated electrolytes exhibited optimal operating conditions for regeneration， while Na?SO? achieved consistently high regeneration performance over a wide concentration range. CV and EIS analyses revealed that the charge-transfer resistance increased after adsorption saturation and decreased after electrochemical regeneration; however， it did not fully recover to the level of the fresh sample， indicating that although electrochemical regeneration effectively restored adsorption performance， some irreversible changes remained at the material interface. Under the optimal operating conditions， the regeneration efficiency remained above 90% after five consecutive adsorption–regeneration cycles， demonstrating excellent cyclic stability. Based on these findings， this study successfully established an integrated process for the fabrication， fixed-bed adsorption， electrochemical regeneration， and cyclic reuse of DLP-fabricated structured activated carbon. The results confirm that appropriate flow-channel design combined with optimized electrochemical regeneration conditions can effectively enhance the reusability of adsorption materials， providing promising potential for VOC control in semiconductor manufacturing processes and the development of structured adsorbent materials.

觸媒載體之物化特性對電漿催化系統行甲烷乾重組反應之影響探討;Efficiency of DRM achieved with plasma catalysis: effect of catalyst supports

Tue, 20 Oct 2026 09:20:29 GMT

title: 觸媒載體之物化特性對電漿催化系統行甲烷乾重組反應之影響探討;Efficiency of DRM achieved with plasma catalysis: effect of catalyst supports abstract: 全球二氧化碳與甲烷等溫室氣體(Greenhouse Gases， GHGs)排放量持續增加，過量溫室氣體排放強化溫室效應，造成全球暖化、氣候變遷、極端氣候事件增加、海平面上升及生態系統失衡等環境問題。因此，淨零碳排與溫室氣體利用技術逐漸受到重視。其中，甲烷乾重組(Dry Reforming of Methane， DRM)因可同時轉化甲烷與二氧化碳兩大溫室氣體，並生成具利用價值之合成氣或液態含氧產物而成為近年重要研究方向。本研究以介電質放電進行甲烷乾重組反應，並以銅做為活性相，探討Al2O3、TiO2、La2O3及BaTiO3四種不同載體之物化性質對CH4/CO2轉化、產物分布與能量效率之影響。結果顯示在本研究操作條件下，Cu/TiO2為整體表現最均衡之觸媒，其甲烷與二氧化碳轉化率分別為35.5%及21.2%；一氧化碳與氫氣選擇性分別為31.69%及25.71%；甲醇與甲酸選擇性分別為36.37%及14.35%。Cu/La2O3則因具有較強表面鹼性與二氧化碳吸附能力，展現最高之二氧化碳轉化率與甲酸選擇性，分別為26.87%及26.63%。在能量效率方面，Cu/BaTiO3最具優勢，達0.51 mmol/kJ，顯示高介電特性有助於提升單位能量下之反應物轉化能力。材料特性分析顯示，Al2O3具有最高比表面積，有利於活性相分散；BaTiO3具有最高介電常數，可影響放電行為與能量利用；La2O3具有最強表面鹼性，有助於CO2吸附與活化；TiO2則兼具中高比表面積、較高介電常數及中強表面鹼性，使其在轉化率、液態產物選擇性與能量效率間呈現較佳平衡。綜上所述，本研究選用之四種觸媒載體各具其特性，而實驗結果也顯示其特性對反應具有實質影響，可為後續研究提供參考。此外，本研究成功於低溫條件下生成以甲醇為主之液態產物，可做為能源或化學品原料，顯示電漿催化技術除溫室氣體減量外，亦具有生成液態燃料或化學品原料之發展潛力。;Global emissions of greenhouse gases (GHGs)， such as carbon dioxide and methane， have continued to increase， intensifying the greenhouse effect and causing environmental problems including climate change， frequent extreme weather events， sea level rise， and ecosystem imbalance. Therefore， net-zero carbon emissions and greenhouse gas utilization technologies have received increasing attention. Among them， dry reforming of methane (DRM) has become an important research direction because it can simultaneously convert methane and carbon dioxide into valuable syngas or liquid oxygenated products. In this study， dielectric discharge was applied to the dry reforming of methane， with copper used as the active phase， to investigate the effects of the physicochemical properties of four supports， Al2O3， TiO2， La2O3， and BaTiO3， on CH4/CO2 conversion， product distribution， and energy efficiency. The results showed that， under the operating conditions of this study， Cu/ TiO2 exhibited the most balanced overall performance， with CH4 and CO2 conversions of 35.5% and 21.2%， CO and H2 selectivity of 31.69% and 25.71%， and methanol and formic acid selectivity of 36.37% and 14.35%， respectively. Cu/La2O3， owing to its stronger surface basicity and CO2 adsorption capacity， showed the highest CO2 conversion and formic acid selectivity， reaching 26.87% and 26.63%， respectively. In terms of energy efficiency， Cu/BaTiO3 exhibited the best performance， reaching 0.51 mmol/kJ， indicating that high dielectric properties are beneficial for improving reactant conversion per unit energy. Material characterization showed that Al2O3 had the highest specific surface area， favoring active phase dispersion; BaTiO3 had the highest dielectric constant， affecting discharge behavior and energy utilization; La2O3 had the strongest surface basicity， enhancing CO2 adsorption and activation; and TiO2 possessed a medium-high specific surface area， relatively high dielectric constant， and medium-strong surface basicity， enabling a better balance among conversion， liquid product selectivity， and energy efficiency. Overall， the selected catalyst supports exhibited distinct properties that substantially influenced the reaction performance. In addition， this study successfully generated methanol-dominated liquid products under low-temperature conditions， which can serve as energy sources or chemical feedstocks， demonstrating the potential of plasma catalysis not only for greenhouse gas reduction but also for liquid fuel and chemical production.

電漿觸媒系統去除CF₄ 之效率探討;Effective Removal of CF₄ via Plasma Catalysis

Tue, 20 Oct 2026 09:20:24 GMT

title: 電漿觸媒系統去除CF₄ 之效率探討;Effective Removal of CF₄ via Plasma Catalysis abstract: 四氟化碳（CF₄）為半導體製程中常見之氣體，具有高化學穩定性、全球暖化潛勢及大氣停留時間長等特性，若未妥善處理排放至大氣中，將對全球暖化造成影響，由於CF₄分子中碳氟鍵鍵能高使其難以被分解，傳統處理方法包括燃燒、熱催化及熱電漿，上述方法常伴隨高能耗、設備成本高及觸媒失活等問題，因此本研究以介電質放電（dielectric barrier discharge， DBD）非熱電漿結合觸媒系統處理CF₄，並探討不同觸媒材料與操作條件對CF₄轉化率、能量效率及產物之影響，以評估電漿觸媒系統應用於CF₄去除之可行性。本研究以γ-Al₂O₃為載體，分別搭載Ce與Zn金屬活性相，並以硫酸根進行表面改質，並比較不同鍛燒時間對觸媒性質與CF₄去除效率之影響，其中搭載Ce金屬活性相之觸媒表面具有Ce³⁺/Ce⁴⁺混合價態，有助於形成氧空缺與表面活性氧物種提升去除效率，搭載Zn金屬活性相之觸媒表面形成尖晶石結構，提升觸媒結構穩定性與增強表面Lewis酸性位點，於電漿觸媒系統中ACS觸媒受鍛燒時間影響較明顯，其中鍛燒10小時之ACS觸媒於Ar 90%、總流量50 mL/min及頻率15.5 kHz條件下，在11 kV時可達最高CF₄轉化率為98%，並於9 kV時達到最高能量效率為1.4 g/kWh，為本研究最佳操作條件，相較之下AZS觸媒之CF₄轉化率與能量效率受鍛燒時間影響較小。OES光譜分析結果顯示電漿反應過程中可觀察到N₂ second positive system、N₂⁺ first negative system、N₂ first positive system、OH、Hα、Hβ、CO、F、O I及Ar I等特徵峰，FTIR分析結果則顯示，CF4反應後主要生成CO、HF與H₂O(g)。本研究結果顯示，DBD電漿觸媒系統具有良好之CF₄轉化率與能量效率，其可於常溫操作之特性具有降低能耗之潛力。;Tetrafluoromethane (CF₄) is widely used as an etching gas in semiconductor manufacturing processes. It has high chemical stability， a high global warming potential， and a long atmospheric lifetime. Therefore， emission of CF₄ into the atmosphere may aggravate global warming. The high bond energy of the C–F bonds in CF₄ makes it difficult to decompose. Conventional treatments， such as combustion， thermal catalysis， and thermal plasma treatment， are often associated with high energy consumption， high costs， and catalyst deactivation. In this study， a dielectric barrier discharge (DBD) non-thermal plasma system coupled with catalysts was used for CF₄ decomposition， and the effects of different catalysts and operating conditions on CF₄ conversion， energy efficiency， and product formation were investigated to evaluate the plasma catalysis systems for CF₄ removal. In this study， γ-Al₂O₃ was used as the catalyst support and was loaded with Ce and Zn as metal active phase， followed by surface modification with sulfate. The effects of different catalyst calcination times on CF₄ removal efficiency were compared. The Ce metal active phase catalysts have Ce³⁺/Ce⁴⁺ oxidation states on the catalyst surface， which may form oxygen vacancies and enhance CF₄ removal efficiency. In contrast， the Zn metal active phase catalysts formed a spinel structure， which improved structural stability and enhanced surface Lewis acid sites. In the plasma catalysis system， the ACS catalyst was more effected by calcination time. The ACS catalyst calcined for 10 h had the best performance with 90% Ar， a total flow rate of 50 mL/min， and a frequency of 15.5 kHz. The highest CF₄ conversion of 98% was achieved at 11 kV， and the maximum energy efficiency of 1.4 g/kWh was achieved at 9 kV. In comparison， the CF₄ conversion and energy efficiency of the AZS catalysts were less effected by calcination time. Optical emission spectroscopy (OES) showed that characteristic peaks corresponding to the N₂ second positive system， N₂⁺ first negative system， N₂ first positive system， OH， Hα， Hβ， CO， F， O I， and Ar I were observed in the plasma reaction. These results indicate generated from the excitation of N₂， H₂， CF₄， O₂， CO₂， and Ar in the system. Fourier-transform infrared spectroscopy (FTIR) analysis indicated products were CO， HF， and H₂O. Overall， the results demonstrate that the DBD plasma catalysis system achieved high CF₄ conversion and energy efficiency. Its operation at room temperature has potential for reducing energy consumption.

活性碳噴注量對採行 CF + SCR 為 APCDs 之垃圾焚化廠排放戴奧辛的影響研究;Effects of activated carbon injection rate on dioxin emissions from a MWI plant equipped with CF and SCR

Tue, 20 Oct 2026 09:20:17 GMT

title: 活性碳噴注量對採行 CF + SCR 為 APCDs 之垃圾焚化廠排放戴奧辛的影響研究;Effects of activated carbon injection rate on dioxin emissions from a MWI plant equipped with CF and SCR abstract: 都市垃圾焚化為國內廢棄物處理主要方式之一，惟焚化過程中可能生成多氯二聯苯戴奧辛與多氯聯苯呋喃（Polychlorinated dibenzo-p-dioxins and dibenzofurans， PCDD/Fs），對環境與人體健康造成潛在危害。活性碳噴注（Activated Carbon Injection， ACI）為焚化廠常用之 PCDD/Fs 控制技術，但其投加量與去除效果並非單純呈線性關係，過量使用亦可能增加操作成本與集塵灰產生量。因此，本研究以國內某採行觸媒濾袋（Catalytic Filter， CF）與選擇性觸媒還原系統（Selective Catalytic Reduction， SCR）之都市垃圾焚化廠為對象，探討不同活性碳噴注量對煙道排氣及灰樣中 PCDD/Fs 濃度、物種分佈與毒性貢獻之影響，並評估活性碳減量操作之可行性。本研究設定活性碳噴注量 8、4 及 0 kg/hr 三種操作條件，並同步分析煙道排氣、底渣、鍋爐灰、觸媒濾袋集塵灰及連續排放監測系統（Continuous Emission Monitoring System， CEMS）參數。結果顯示，煙道排氣 PCDD/Fs 質量濃度與國際毒性當量濃度（International Toxic Equivalent， I-TEQ）未隨活性碳噴注量增加而呈線性下降，而是呈現 8 kg/hr 最低、4 kg/hr 最高、0 kg/hr 居中之趨勢。於 8 kg/hr 條件下，煙道排氣總毒性當量濃度為 0.0202 ng I-TEQ/Nm3；4 kg/hr 條件下升高至 0.0747 ng I-TEQ/Nm3，且 CO 與 HCl 濃度分別達 47.2 ppm 及 18.0 ppm，顯示燃燒完全性較差且氣相氯源較充足，可能提高 PCDD/Fs 生成潛勢。灰樣結果顯示，鍋爐灰之 PCDD/Fs 質量與毒性當量濃度分別為 38.54–79.78 ng/g及 1.22–2.01 ng I-TEQ/g，明顯高於觸媒濾袋集塵灰之 4.40–10.41 ng/g及 0.15–0.39 ng I-TEQ/g，且兩者皆以編號 B之樣品最高，反映燃燒不完全及較高氯源可能促進 PCDD/Fs 於飛灰中生成與累積，而 CF 之觸媒作用則可能降低集塵灰中殘留濃度。未噴注活性碳條件下，煙道排氣總毒性當量濃度為 0.0507 ng I-TEQ/Nm3，雖高於 8 kg/hr，但仍低於 4 kg/hr，顯示 CF 與 SCR 系統正常操作時仍具一定控制能力。整體而言，三種操作條件之煙道排氣 PCDD/Fs 毒性當量濃度皆低於現行排放標準 0.1 ng I-TEQ/Nm3，表示在燃燒條件穩定且後端污染防制設備正常運作之前提下，活性碳噴注量具有減量可行性；惟減量操作仍須同步考量 CO、HCl、燃燒穩定性及污染防制設備效率。;Incineration is a mainstream technology for treating municipal waste in Taiwan; however， polychlorinated dibenzo-p-dioxins and dibenzofurans（PCDD/Fs）may be generated during incineration， posing potential risks to the environment and human health. Activated carbon injection（ACI）is commonly used to control PCDD/Fs emissions， but its dosage and removal efficiency do not follow a simple linear relationship， and excessive use may increase operating costs and CF ash generation. Therefore， this study investigated a municipal waste incinerator equipped with a catalytic filter（CF）and selective catalytic reduction （SCR） system to evaluate the effects of ACI rate on PCDD/Fs concentration， congener distributions， toxicity contributions， and the feasibility of reducing activated carbon usage. Three ACI dosages of 8， 4， and 0 kg/hr were tested. Stack gas， bottom ash， boiler ash， CF ash， and continuous emission monitoring system（CEMS）parameters were analyzed. The mass and international toxic equivalent（I-TEQ）concentrations of PCDD/Fs in stack gas did not decrease linearly with increasing ACI rate. The lowest concentration occurred at 8 kg/hr， the highest at 4 kg/hr， and an intermediate level at 0 kg/hr. The total toxic equivalent concentration was 0.0202 ng I-TEQ/Nm3 at 8 kg/hr and 0.0747 ng I-TEQ/Nm3 at 4 kg/hr. At 4 kg/hr， carbon monoxide（CO）and hydrogen chloride（HCl）concentrations reached 47.2 and 18.0 ppm， respectively， indicating poorer combustion completeness and a more abundant gaseous chlorine source， which may have enhanced PCDD/Fs formation. The PCDD/Fs mass and toxic equivalent concentrations in boiler ash were 38.54–79.78 ng/g and 1.22–2.01 ng I-TEQ/g， higher than those in CF ash at 4.40–10.41 ng/g and 0.15–0.39 ng I-TEQ/g. Both ash types had the highest concentrations in Sample B， suggesting that incomplete combustion and higher chlorine availability may promote PCDD/Fs formation and accumulation， while CF catalysis may reduce residual PCDD/Fs. Without ACI， the total toxic equivalent concentration was 0.0507 ng I-TEQ/Nm3， suggesting that the CF and SCR systems still provided PCDD/Fs control. Overall， all three conditions were below the current emission standard of 0.1 ng I-TEQ/Nm3， indicating that reducing ACI is feasible under stable combustion and proper operation of downstream air pollution control devices. However， CO， HCl， combustion stability， and control efficiency should also be considered.