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Student Number 953206011
Author Kuo-Yuen Kao(高國源)
Author's Email Address No Public.
Statistics This thesis had been viewed 1716 times. Download 10 times.
Department Graduate Institute of Environmental Engineering
Year 2008
Semester 1
Degree Master
Type of Document Master's Thesis
Language zh-TW.Big5 Chinese
Title Waste derived thermite melting preparation to dispose of chromium sludge
Date of Defense 2008-12-18
Page Count 130
Keyword
  • chromium recycling
  • lead recycling
  • multing
  • resources
  • thermite reaction
  • Abstract It is beneficial to recover Cr and Pb from chromium plating sludge (referred to as CrPS) since it is primarily composed of PbCrO4 and PbO. This study investigated a novel technology for recovering chromium and lead from CrPS, by using thermite reaction between chromium oxide and aluminum (i.e., waste, parings and scrap). Sludge from Chromium wastewater treatment process (referred to as CrWS) , mainly composing of chromium oxide (Cr2O3) and silicon dioxide (SiO2), was also added in the recovering process to function as a glass-former that facilitate the separation of metal and slag and improves the quality of slag. In this study, the recovery process was divided into 3 stages: refinement of the CrPS, recovery of lead form the CrPS, and again, recovery of chromium as Cr-Fe alloy from the resultant slag. 
      During the refinement of the starting CrPS, the sludge was heated at a temperature ranging from 100℃ to 600℃. It was found that the major species identified as PbCrO4, PbO, Cr3O4, and CrO were not changed; the total concentration of crystal phases, however, increased at 500℃. This suggests that the loss on ignition (i.e., 8.53 w/w% for CrPS) and the oxidized degree of thermit oxides might affect. The thermite reaction between chromium oxide and aluminum may proceed in a one-step path: CrO3+2Al→Al2O3+Cr, or in a two-step path: 2CrO3+2Al→Cr2O3+Al2O3 and CrO3+2Al→2Cr+Al2O3. The PbCrO4 in the starting CrPS might decompose into PbO and CrO3 when heated, which led to the activation of thermite reactions between PbO and Al, as well as between CrO3 and Al. However, the species, the oxidized degree, the reaction path, and the stoichiometry of Al were not clear. Therefore, the actual stoichiometry between CrPS and Al has to be determined experimentally by properly assuming what the thermit oxides are in the starting material. Several mixes of CrPS and Al, with Al in excess of its stoichiometry were tested.  
      Thus, the highest reaction temperature developed would then determine the optimum mix of CrPS and Al, reflecting a mix under the balanced effects of factors such as species, oxidized degree, reaction path, impurities, non- reactive oxides, Al stoichiometry, and heat loss from the reactor wall. In this study, a mix ratio of CrPS:Al=4.53:1 showed the optimum mix for the CrPs and Al thermite. However, in this case, the recovered alloy and slag were not separated.
      In the recovering of Pb by thermite reactions, it was found that one kg of the above optimum mix, when added with 0.72 kg of CrWS, would result in a maximum recovery of lead alloy (18 w/w%), with 95.61% of Pb purity. The Pb recovery rate reached 76.79% as compared to initial Pb in the inputs. The 69 % of slag by weight of inputs was also recovered that retained most of the chromium oxides.
      In the subsequent recovery of chromium as Cr-Fe alloy, the above slag was further pulverized and mixed with Fe2O3-Al thermite with proper amount of Al stoichiometry. Optimum recovery of Cr-Fe alloy was achieved with Cr:Fe ranging from 4.61:1 to 1.55:1. Chromium recovery rate reached 80.78% as compared to the Cr input at second phase. This process also recovered 62.3 w/w% of slag compared to the inputs at second phase. The recovered slag was vitrified and stable.
      The results of this work suggest that to recover Pb and Cr from CrPS and CrWS using thermite reactions is a promising technology not only energy conservative but also recycling-beneficial.
    Table of Content 第一章 前言......................................................................................................................... 1
    1-1 研究緣起................................................................................................................ 1
    1-2 研究目的與內容..................................................................................................... 2
    第二章 文獻回顧................................................................................................................. 3
    2-1 鉻污泥產出現況及資源化技術.............................................................................. 3
    2-1-1 鉻污泥來源................................................................................................. 3
    2-1-2 資源化技術................................................................................................. 5
    2-2 鋁熱反應................................................................................................................ 8
    2-2-1 鋁熱反應熱力學.......................................................................................... 8
    2-2-2 鋁熱反應影響因素.................................................................................... 13
    2-2-3 鋁熱反應於環工領域之運用.................................................................... 18
    2-3 鉻污泥鋁熱熔融技術........................................................................................... 22
    2-3-1 鉻污泥鋁熱熔融技術原理........................................................................ 22
    2-3-2 鋁熱熔融處理鉻污泥操作因素................................................................. 24
    2-3-3 鋁熱熔融處理的效應................................................................................ 28
    2-4 鉻污泥鋁熱熔融處理之問題............................................................................... 31
    2-4-1 鋁熱熔融劑成份........................................................................................ 31
    2-4-2 金屬分離效果............................................................................................ 32
    2-4-3 回收產物品質............................................................................................ 32
    第三章 實驗材料與方法.................................................................................................... 34
    3-1 研究架構.............................................................................................................. 34
    3-2 實驗材料與設備................................................................................................... 36
    3-2-1 實驗材料................................................................................................... 36
    3-2-2 實驗設備................................................................................................... 37
    3-3 實驗條件配置...................................................................................................... 39
    3-3-1 原物料基本特性分析................................................................................ 39
    3-3-2 純化處理實驗條件配置............................................................................ 39
    3-3-3 鉻電鍍污泥鋁熱處理最佳配比實驗之實驗配置...................................... 40
    3-3-4 鉻污泥鋁熱處理-鉛、鉻回收之實驗配置................................................ 43
    3-4 實驗分析.............................................................................................................. 45
    3-4-1 分析儀器................................................................................................... 45
    3-4-2 分析方法................................................................................................... 45
    第四章 結果與討論............................................................................................................ 49
    4-1 原物料基本性質................................................................................................... 49
    4-1-1 原物料基本物化性質................................................................................ 49
    4-1-2 原物料粒徑分佈........................................................................................ 50
    4-1-3 原物料化學組成........................................................................................ 53
    4-1-4 原物料熱重熱差分析-熱行為................................................................... 55
    4-1-5 原物料重金屬毒性特性溶出試驗............................................................. 59
    4-1-6 原物料掃瞄式電子顯微鏡與X 光繞射分析............................................. 60
    4-2 純化處理實驗...................................................................................................... 62
    4-2-1 純化處理鉻電鍍污泥之成分變化............................................................. 62
    4-2-2 純化處理鉻電鍍污泥之結晶物種探討..................................................... 64
    4-2-3 純化處理鉻電鍍污泥之鋁熱反應變化..................................................... 66
    4-2-4 小結........................................................................................................... 68
    4-3 鉻電鍍污泥鋁熱處理最佳配比實驗.................................................................... 69
    4-3-1 配比實驗之反應特性變化........................................................................ 69
    4-3-2 配比實驗之熱重熱差分析........................................................................ 72
    4-3-3 配比實驗之熔渣(含金屬)物化特性.......................................................... 74
    4-3-4 配比實驗之熔融飛灰之化學特性............................................................. 83
    4-3-5 配比實驗之主要元素分佈........................................................................ 84
    4-3-6 小結........................................................................................................... 88
    4-4 鉻污泥鋁熱處理-鉛、鉻回收實驗...................................................................... 89
    4-4-1 鉻廢水污泥添加量與反應特性之變化-鉛回收........................................ 89
    4-4-2 鉻污泥鉛回收實驗之熱重熱差分析......................................................... 92
    4-4-3 鉻污泥鉛回收實驗之熔渣特性................................................................. 95
    4-4-4 鉻污泥鉛回收實驗之熔融飛灰特性....................................................... 104
    4-4-5 鉻污泥鉛回收實驗之金屬錠特性........................................................... 105
    4-4-6 鉻污泥鉛回收實驗之主要元素分佈....................................................... 106
    4-4-7 鉻污泥熔渣鐵鉻合金回收實驗............................................................... 109
    4-4-8 小結......................................................................................................... 118
    第五章 結論與建議.......................................................................................................... 120
    5-1 結論.................................................................................................................. 120
    5-2 建議.................................................................................................................. 122
    第六章 參考文獻........................................................................................................ 123
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    68.詹炯淵,「垃圾焚化飛灰管理對策之研究」,國立台灣大學環境
      工程學研所,碩士論文 (2001)。
    69.楊敏鑫,「廢棄物衍生Thermite熔融劑處理焚化飛灰-反應機制
      及重金屬移行之研究」,國立中央大學環境工程研究所,碩士論
      文,2006。
    70.廖錦聰、馬文松,「鉻污泥無害化處理」,中華民國專利,專利
      證號:044928 ,民國80 年2 月1 日公告。
    71.鍾宇翔,「廢棄物鋁熱反應熔融處理焚化飛灰-熔渣基本特性研
      究」,國立中央大學環境工程研究所,碩士論文,2006。
    Advisor
  • none(王鯤生)
  • Files
  • 953206011.pdf
  • disapprove authorization
    Date of Submission 2009-01-07

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