Waste Treatment and

Disposal technology

Hazardous Materials and Hazardous Waste Management

(G. Woodside), Chap. 12
常用的廢棄物處理技術及設備分類
 貯存：清除、處理前，將廢棄物置於特定地
點或容器。
 清除：收集、運輸
 處理
– 前置處理：利用物理或機械原理，以減少廢棄物
體積、重量及分離資源或特殊物質，包括壓縮破
碎、選別、脫水、乾燥等。
– 中間處理：利用化學或生化原理，以轉化廢棄物
為熱、燃料或肥料，或變為無害、安定的物質，
以利資源回收利用與最終處置，方法如焚化法、
堆肥法、熱分解法、垃圾衍生燃料法、固化與安
定法等。
– 最終處置：掩埋法與回收再生。
 中間處理：有害廢棄物在最終處置前，經物
理、化學、生物或其它方式，將有害成份分
離 (separation) 、減積 or 減量 (volume redu
ction) 、去毒 or 減毒 (detoxification) 、安定
化 (stabilization) 之行為。

 Purpose: 有害廢棄物被穩定化、解毒 / 去毒
化，成為無害之ㄧ般廢棄物，以利最終處置
。
 Waste treatment can incorporate
several different unit processes
– a wastewater treatment system include
oil-water separation, neutralization,
biological treatment, sedimentation and
sludge dewatering
 Treatment Technology
Based on types of technology or environmental
area
1. Physical/chemical process
2. Biological process
3. Thermal process
4. Soil/groudnwater treatment
5. Land-based treatment

Many facilities use a combination of several types of

treatment.
 Treatment Technology
Based on characteristic of technology
1. Concentration. A physical treatment. Reduce
the volume of hazardous waste; less expensive.
2. Detoxification. Chemical or biological
processes. Destroy toxic components or
reduces these chemicals to less toxic form;
generally more expensive.
3. Fixation/Solidification. Usually a physical
treatment. Reduce the mobility of the toxin.
Concentration: physical treatment
basically

 Purposes: phase change of HW or

concentrate HW for further treatment more
easily
 3 types of technology (purposely)

–a. Gross removal of contaminant:

sedimentation, clarification, precipitation,
flotation
–b. Solid dewatering: centrifugation
–c. Polishing: filtration, evaporation, ion
exchange, peat adsorption, reverse osmosis
(RO)
Concentration: physical treatment

 Processes:
a. Sedimentation (Gravitational settling) and clarification
b. Carbon Adsorption: activated carbon adsorption Flotati
on: opposite of sedimentation Centrifugation
c. Distillation Filtration
d. Evaporation
e. Distillation
f. Solvent Extraction
g. Ion Exchange (Resin Adsorption): cation, anion exchan
ge
h. Membrane technologies: Reverse Osmosis (RO), Dialysi
s, Electrodyalysis
i. Solvent Extraction
j. Stripping
 Physical process
Carbon Adsorption
 Adsorption is the process in which matter
(soluble ) is extracted from one phase and
concentrated at the surface of a second
phase.
 This is a surface phenomenon as opposed to
absorption where matter changes solution
phase, e.g. gas transfer.
Adsorption 吸附 vs. Absorption 吸收

 When a substance is attached to a surf

ace is is called adsorption. For exampl
e, substance is attached to the internal
surface of active carbon.
 When a substance is absorbed in a diff
erent medium it is called absorption. F
or example, a gas is taken in a solutio
n
adsorbent: material doing the adsorbing.
examples are activated carbon (AC)
adsorbate: material being adsorbed
 Activated Carbon

 Activated carbon is produced to achieve a

very big internal surface (between 500 - 1
500 m2/g)
 Granular activated carbon (GAC): parti
cle diamter ~ 1500μm
Powdered activated carbon (PAC): particl
e diamter < 100μm
 Carbon adsorption is effective at removing
organic compounds with low polarity, high MW,
low water solubility and high boiling point.
 Adsorption of organic, non-polar substances such
as:
– Mineral oil
– BTEX 
– Poly aromatic hydrocarbons (PACs)
– (Chloride) phenol
 Adsorption of  halogenated substance:
 Odor
 Taste
 Yeasts
 Various fermentation products
 Physical adsorption: Van der Waals att
raction between adsorbate and adsorb
ent. The attraction is not fixed to a sp
ecific site and the adsorbate is relative
ly free to move on the surface. This is
relatively weak, reversible adsorption.
 Adsorption capacity for particular com
pound or mixed wastes is determined
as an adsorption isotherm 吸附等溫線
and tested in laboratory or a pilot unit.
Point C3 the column starts to breaktrough 破出、貫穿 and
near C4 the column is not purifying anymore. Between poi
nt C3 and C4 regeneration 再生 of the column is needed.
Dissolved Air Flotation （ＤＡＦ）浮除
 Opposite of sedimentation
 Separate suspended solids and oil/grea
se from aqueous streams and to conce
ntrate or thicken sludge
 Oil or SSs float to surface of a tank by
air bubbles. Coagulant chemicals may
needed to improve removal efficiency
 Remove metal hydroxides and oil
 Applicable only for waste having densiti
es close to that of H2O
Distillation 蒸餾 / Fractional distill
ation 分餾
 Separate volatile components by differences
in vapor pressures or boiling points among v
olatile fractions and water
 If a waste contains a mixture of volatile com
ponents with different vapor pressures  Fr
actional distillation

 Separate volatile compounds from nonvolatil

e components  Evaporation 蒸發
 Evaporation is often used to remove residual
moisture or solvents
Evaporation
氰化物之處理 - 蒸發回收法
– 氰化物蒸餾液不具腐蝕性，適合於高濃度的電鍍廠逆
向清洗槽的清洗水
– 蒸發後的冷凝水可以回送到清洗線的前端，而濃縮的
電鍍液則回到電鍍槽中
– 操作費用主要係蒸氣、冷卻水及電費等，使用多重效
益蒸發系統，可以減少蒸汽用量
– 需較大的初設費
E
操作順序 蒸發器

D D D
D E
E E

PR 電鍍槽 1R 2R 3R
 Solvent extraction
溶劑萃取回收法
 Mixing of a waste stream with an
extraction fluid
 When distillation is ineffective (mixtures
of similar vapor pressures or boiling
point)
 Extraction fluid must be immiscible in
the waste stream
 2 steps: 1. solvent waste contact
2. Phase separation of liquids
 酚及氯酚類化合物之處理
 酚及氯酚類化合物污染源
– 酚 ( 為芳香族之羥基 (-OH) 衍生物，羥基直接與
苯環相連者 ) 及氯酚 ( 包括 2- 氯酚、 3- 氯酚、
4- 氯酚及五氯酚等 ) 類化合物在農、工業用途
廣泛。
– 一般含酚類化合物的工業廢水種類，包含製程
中的蒸餾廢液、冷凝廢水、苛性廢液及其他特
殊用途製程廢水
– 最主要的工業產生來源包括：有機化合物製造
業、石油煉製業、鋼鐵及煉焦業、塑膠及合成
工業、炸藥製造業、染整業、木材防腐業、飛
機修護業及橡膠加工業等
 酚及氯酚類化合物之處理
 處理技術 1- 溶劑萃取回收法
– 利用液相溶劑萃取回收法，係基於酚及氯酚化
合物在有機溶劑中之溶解度高於在水中，且有
機溶劑與水不互溶的特性，自高濃度廢液中萃
取回收酚及氯酚化合物
– 當廢水中酚及氯酚化合物濃度大於 2,000 mg/L
且流量高於 200 L/min 時，具有回收價值
– 處理後廢水殘餘濃度仍甚高，且溶劑耗損費用
與酚、氯酚回收價值往往無法達成經濟性平衡
。
 Ion Exchange

 An adsorption process where ionic spe

cies are adsorbed from solution by exc
hanging places on exchange media (ze
olite 沸石 )
 Primarily for metal removal (Ba, Cd, Cr
, Cu, Hg, Ni…), nonmetallic ions (NO3-,
SO42-, CN-, F-…)
 Ion Exchange 離子交換法
原理 樣本分子
將水溶液中不想要
+ + + + Counter

的陽離子或陰離子 + ion
與離子交換樹脂上 + +
較不具毒性的離子
+ 擔 体 + ＋
交換，所交換的離
+ + 陰離子
子並未被摧毀，而
+ + 流動相
是濃 縮在樹脂上， + ++
以利後續處理。 陽離子基團
 離子與固相擔体帶 +
電基團間的爭奪戰
陽離子交換 Cationic exchang
(Ion wars) e
 氟化物之處理
 處理技術 1- 離子交換法
– 僅適合用來處理低濃度含氟
硼酸離子 (BF4-) 清洗廢水
– 處理流程 ( 如右 )
 廢水抽至陽離子交換柱，
先行去除 Pb2+ 、 Sn2+ 等陽
離子
 流入陰離子交換柱，以去
除廢水中 BF4- 及 F- 等陰離
子
 經陰、陽離子交換樹脂吸
附後之處理水可回收作為
製程清洗水循環再利用
 氟化物
 氟化物之污染源
– 印刷電路板製造業 ( 簡稱 PC 板業 )
 雙面板及多層板工廠在外層板線路鍍錫鉛製
程中，使用氟硼酸系列的電鍍液
廢液含 – 電鍍錫鉛的製作清洗過程，會產生連續性
氟、鉛
排放之低濃度清洗廢水
及錫
 電鍍程序之高濃度槽液 ( 如氟硼酸預浸液及
氟硼酸錫、鉛電鍍液等 )
– 若老化或受污染不堪使用時亦必須加以排
棄並重新配製
 氟化物
 氟化物之污染源
–半導體工業
 常使用氫氟酸來蝕刻晶圓表面與清洗用具
 在蝕刻與清洗的過程中，部分氫氟酸會與晶
圓中的矽產生反應而生成氟矽酸，蝕刻後再
用大量的水清洗晶圓，而造成大量的氫氟酸
廢水
 因廢水中氫氟酸濃度低處理不易
 根據統計，台灣半導體工業每年平均約有三十位
工程師氫氟酸中毒，在人人稱羡的光環背後，也
暗藏致命危機 。
 氫氟酸 (HF) 毒性
 對人體的傷害主要經由氫離子及氟離子兩
個機轉所產生：
–立即的傷害 ~ 氫離子
 對人體組織產生脫水及腐蝕作用，產
生嚴重的灼傷。
–次發性的傷害 ~ 氟離子
 和鈣、鎂離子形成不解離的氟化鈣或
氟化鎂等鹽類，產生嚴重的低血鈣及
低血鎂，甚至可快速致人於死。
 藉由結合鎂的作用而抑制 Na+/K+ATPas
e
 中毒初期沒有明顯症狀，以致容易被忽視
而延誤就醫；病患甚至可能在沒有明顯前
兆的狀況下，突然心臟停止。
 氟化物之處理
 處理技術 1- 離子交換法
– 處理過程中陰離子交換柱中樹脂顏色會由灰色
變成白色，當出流水 pH 值降至 3-3.5 時，氟濃
度接近 10 mg/L 時，應停止處理，進行樹脂再
生 (regeneratioin)
– 再生陽離子交換柱： 1-2 N HCl 溶液；
陰離子交換柱： 4-5 ％ NaOH 溶液
– 再生後之酸、鹼廢液合併收集處理，廢液中含
BF4- 、 Pb2+ 、 Sn2+ 與製程中廢棄之高濃度電鍍
槽液共同收集，採用鋁鹽 - 石灰處理法處理
 Membrane Filtration

 Several processes: Reverse Osmosis

(RO), Dialysis, Electrodyalysis based o
n the driving force (electricity or press
ure) to filter particles, ions, or organic
molecules through a membrane
 薄膜分離法比較
薄膜法 薄膜之功能 主要推動力

逆滲透 (Reverse o 讓水分子通過 壓力

smosis)
超過濾 (Ultrafiltrati 依據分子大小形狀 壓力
on) 選擇性讓分子通過

透析 (Dialysis) 對溶質具有選擇性 濃度差

讓其通過
電透析 (Electrodial 對離子具有選擇性 電位差
ysis) 讓其通過
 Membrane Filtration
 Individual membrane filtration processes ca
n be defined by pore size:
– Microfiltration 微過濾 : 0.1~1.0 μm ，液體澄清
，無菌過濾
– Ultrafiltration 超過濾： 0.002~0.1 μm ，大分子
溶液分離
– Nanofiltration 奈米過濾： 0.001~0.01 μm ，將微
小有機物及多價離子自溶液中分離
– Reverse osmosis 逆滲透 : 0.0005~0.002 μm ，將
微溶質及鹽類自溶液中分離
 Membrane technology
 在重金屬廢水處理的主要功能為替代傳統
沉降或浮除單元，提昇固液分離效率，可
濃縮水中固體物含量至 2-5 % ；或作為排放
水去除懸浮固體與有機物
– 設置與操作成本都較傳統方式為高，因此多用
於含高量金屬螯合劑廢水
– 需注意廢水中不可含有油脂，造成薄膜阻塞 (f
ouling 結垢 )
– 通常薄膜單元每週需進行 1 次化學清洗 (acids, a
lkalines, oxidizer, detergents or organic solvent) ；
且需特別注意避免薄膜破裂
 Neutralization

 pH adjustment of acidic or caustic

waste to more neutral range; simply
mix acidic wastes with alkali waste to
neutralize each other
 common for wastewater and gases
treatment, but less use with solid
wastes
 inexpensive treatment
 Neutralization

Most common neutralizing agents are lime [ 石灰 , Ca (OH)2]fo

r acidic wastewater and H2SO4 for basic wastewater.
 Neutralization

 Neutralization of acid gases with liquid

caustic solution  wet scrubbing 濕式
洗滌
 Flue gas from incineration is scrubbed
with soda ash solution (Na2CO3 ) or lim
e to remove acid gases
Flue gas
 gas that exits to the atmosphere via a flue, which
is a pipe or channel for conveying exhaust gases
from a fireplace, oven, boiler or steam generator
 Often refers to the combustion exhaust gas
produced at power plants
 Contain nitrogen (typically more than two-thi
rds) derived from the combustion air, carbon
dioxide (CO2), water vapor, as well as polluta
nts such as particulate matter, CO, NOx and
SOx
 Precipitation 沉澱
 Most commonly used for metal removal fro
m aqueous wastewater.
 Accomplished by pH adjustment or addition
of a chemical reagent to forms a precipitant
with metal
 Hydroxide precipitation, sulfide precipitation
and carbonate precipitation are the common
metal forms.
 Flouride (F-)can be also removed by precipit
ation
 氟化物之處理
 處理技術 2- 化學混凝沉澱法
1) 鈣鹽沉澱法
 最常用方法。常使用之鈣鹽包括 Ca(OH)2
、 CaSO4 、 CaCl2 等，產生非溶解性的氟
化鈣沉澱
 處理機制： Ca2++2F-→CaF2(s) ↓

2) 混凝法
 常使用混凝劑為多元氯化鋁 [PAC ，﹝ Al2
（ OH ） n Cl 6-n﹞m ] 及硫酸鋁 [Al2(SO4)3]
，混凝劑在水中形成膠羽，其去除氟主要
是使氟離子吸附在 Al(OH)3 膠羽粒子上，
故膠凝速率會影響氟化物的去除效率。
氟化物之處理
3) 高溫鋁鹽 - 石灰處理法 ( 處理 BF4-)
 原理：必須先破壞安定的 BF4- 螯合物，再
使之形成 CaF2 沉澱。安定之 BF4- 可於高溫
下以鋁鹽為觸媒進行水解，使形成 HF ，再
加入 Ca2+ 以生成 CaF2 沉澱
 本法必須設置加溫設備且處理時必須投加
大量鋁鹽、鈣鹽等藥劑，一般來說，此法
僅適合用來處理少量的高濃度電鍍製程廢
液及離子交換樹脂再生廢液
 氟化物之處理 ( 續 )
3) 高溫鋁鹽 - 石灰處理法 ( 處理流程及技術 )
– 流入收集槽中收集，俟收集槽達滿水位時，由泵
將槽內廢液抽送至批反應槽處理
– 先調整廢液 pH 值，使混合廢液 pH 維持在 6-7 之間
，加入適量的 Al2(SO4)3 ，並於 70-95 oC 溫度下經
2 小時左右的時間反應後，使 BF4- 完全水解生成硼
酸及三氫六氟化鋁（ H3AlF6 ），然後再加 Ca(OH)2
，使 F- 與 Ca2+ 結合，形成不溶性的 CaF2 沉澱
– 反應槽之最終 pH 值宜調整至 8-10 之間，使混合廢
液中的 Pb2+ 、 Sn2+ 等重金屬離子形成不溶性的氫氧
化物沉澱
– 待反應完成後靜置冷卻，然後進行固液分離 。污
泥餅含高量 F- 、 Pb2+ 等，需做最終處置。
 氟化物之處理
4) 常溫鋁鹽 - 石灰處理法 ( 原理 )
– 無需加溫反應，需要較長的反應時間（ >24 h
r ），反應時需投加較多量的鋁鹽始能獲得較
佳的處理效果
– 與高溫法相同，僅適用於處理含 BF4- 濃度較高
的電鍍製程廢液及離子交換樹脂再生廢液
 常溫鋁鹽 - 石灰處理法 ( 處理流程及技術 )
– 與高溫鋁鹽 - 石灰處理法之處理流程極為相近
，唯一的差別是本法無需加溫處理
– 需投加之鋁鹽劑量較高，反應時亦較長 ( 約需
24 小時以上 )
 六價鉻
 六價鉻之污染源 0
-1 [H+] [OH-]
– 電鍍廠使用三氧化鉻 (CrO3 -2
[CrO42-]
) 或重鉻酸鹽 (Cr2O72- ) 六價 -3
-4
鉻，在水中解離關係如右圖 -5

– 當 pH = 1.5-6.0 時，以 HCr -6

[HCrO4-]

-pC
-7
O4- 為主 -8

– pH = 6.5 時， HCrO4- 約等於 -9

-10
CrO42- -11 [H2CrO4]
-12
– 在高 pH 值時，則以 CrO42- -13

為主 -14
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

– 電鍍廢液中以酸性居多，故 pH

廢水中亦以 HCrO4- 為主
 六價鉻
 六價鉻之污染源
– 電鍍工廠廢水來自鍍件清洗及鍍液廢棄或意外洩漏
– 顏料、染料及媒染劑製造鋅鉻黃或鉻黃，廢水來自
產品過濾、脫水或洗滌設備水
– 皮革工廠廢水來自鉻鞣排水及水洗過程
– 大理石及玉石加工廠，使用 Cr2O3 為磨光劑，水洗
帶出
– 金屬表面加工業，六價鉻化合物配方用來作為清潔
劑、氧化劑、表面保護劑、表面裝飾用電鍍化學劑
– 一般工廠冷卻水使用鉻酸鹽為腐蝕抑制劑，以致冷
卻水排放水含有鉻酸根離子的污染
 六價鉻之處理
 處理技術 1- 還原沉澱法（最常用六價鉻處理法）
– 鉻酸根離子溶液中加入鹼性物質提高 pH 後，並
不生成氫氧化物沈澱，而須將其先還原成三價
鉻離子，始可將其轉變成氫氧化物型態之沈澱
– 還原劑 ( 二氧化硫 ) 將六價鉻還原，其基本反應
均在水中先生成亞硫酸：
 SO2+H2O↔H2SO3

– 亞硫酸再與六價鉻作用，還原成三價鉻：
 2H2CrO4+3H2SO3→Cr2(SO4)3+5H2O
 六價鉻之處理
 處理技術 1- 還原沉澱法
– 還原作用與 pH 有關，因為 pH 100 0
影響亞硫酸的解離 ( 如右圖 )
 H2SO3↔H++HSO3-(Ka=1.72× 80 20
10-2)
60

% HSO3
40

% H2SO3
 HSO3-↔H++SO32-

(Ka=1.0×10-7) 40 60
– 低 pH 時，六價鉻的還原反應
速率進行很快 (H2SO3 的濃度最 20 80
大)
0 100
– 六價鉻還原均在酸性 (pH ＜ 3. 0 1 2 3 4 5
0) 進行，通常加入硫酸降低 p pH

H
 六價鉻之處理
 處理技術 1- 還原沉澱法
– 六價鉻還原為三價鉻後，即可用 3.50

NaOH 或 Ca(OH)2 中和沈澱，同 3.00

時與殘餘之 Na2SO4 、 H2SO3 、 N

可溶性三價鉻[mg/L Cr(Ⅲ)]
2.50

aHSO3 等一併反應
2.00
 Cr2(SO4)3+ 3Ca(OH)2→
1.50

2Cr(OH)3+3CaSO4
1.00
 H2SO3+Ca(OH)2→CaSO3 +2H2
0.50
O
0
– 氫氧化鉻為兩性化合物， pH = 7. 5.5 6.5 7.5 8.5 9.5 10.5 11.5
pH
5-10.0 之間有最低的溶解度 ( 如
右圖 )
 Treatment Technology
Based on characteristic of technology
1. Concentration. A physical treatment. Reduce
the volume of hazardous waste; less expensive.
2. Detoxification. Chemical or biological
processes. Destroy toxic components or
reduces these chemicals to less toxic form;
generally more expensive.
3. Fixation/Solidification. Usually a physical
treatment. Reduce the mobility of the toxin.
 Detoxification Technologies

 concentration processes end up with small

volume but concentrated toxic product
 Purpose: reduce toxicity of end products
from concentration processes
 Chemical or biological processes
(concentration usually physical processes):
chemical oxidation/reduction, neutralization,
incineration, and biodegradation
 Most of these processes will not reduce the
toxicity all the way to zero, but down to
certain level only
 Oxidation/Reduction
 Partial or complete degradation of many org
anic and inorganic compounds
 Oxidation :  the valence of an ion with a lo
ss of e-
reduction :  the valence with a gain of e-
 render hazardous wastes less hazardous or
harmless via addition of strong oxidants (Cl2,
O3, H2O2) or reductants (sulfur dioxide SO2,
sodium bisulfite NaHSO3, FeSO4, sodium bor
ohydride NaBH4)
Chemical oxidation
 treat many inorganic and organic liquid and soli
d wastes such as cyanide, alcohol, phenols, biph
enyls, organic sulfide, and some pesticides
 can be a pretreatment for biological treatment;
oxidize COD to BOD
 limit: usually not complete reaction, may produc
e more toxic product
 Factors affect oxidation: pH, type and quantity o
f oxidizable compounds, metals (can react with
oxidants)
 Example: cyanide-bearing wastewater from met
al-finishing industry is typically oxidized with alk
aline chlorine or hypochlorite solutions
 氰化物
 氰化物之污染源
– 氰化物例如氰化鈉 (NaCN) 或氰酸 (HCN)
– 最主要來源為 電鍍工業，電鍍業者使用氰化物
槽使金屬離子如鋅及鎘等存在溶液中
– 電鍍溶液經鍍件帶出，含氧化物離子及金屬氰
化物等複合物，污染了清洗槽。氰化鈉水解為
氰酸 (1) ， HCN 的離子化，視 pH 值而定 (2)
：
(1)NaCN+H2O↔HCN+NaOH
(2)HCN↔H++CN-(Ka = 4.8 × 10-10 ， 25℃)
 氰化物之處理
 處理技術 - 氧化法
– 鹼性加氯法 （最常用技術）
 反應分二個階段：
氰化物 氰酸鹽 (cyanat
Fast 第一階段： C12+2OH-+CN-e)
→CNO-+2C1- + H2
O
Slow
第二階段： 3C12+6OH-+2CNO-→2HCO3-
+N2+6Cl-+2H2O
 氰化物之處理 ( 續 )
 鹼性加氯法實際上中間反應產物氯化氰 (cy
anogen chloride, CNCl) 可能形成，其反應如
下：
半反應 1 ： CN-+OCl-+H2O→CNCl+2OH-
半反應 2 ： CNCl+2OH-→CNO-+Cl-+H2O
總反應： CN¯+OCl¯→CNO¯+Cl¯
– 處理系統的加氯量可用氧化還原電位 (ORP) 器
控制
 氰化物之處理 ( 續 )
 鹼性加氯法– 改良式分批處理技術
– 氰化物之廢水加入含有 NaOCl 的濃溶液清洗液
中，洗出氰化物在 pH=10-12.5 時很快氧化成氰
酸鹽，而在此清洗槽中自由氯含量在 0.3-1.0 g/
L ，氰酸鹽則慢慢分解為 CO2 及 N2 ( 改良式分
批式處理 )
– 在氰化物廢水中除非將其他金屬分離，否則氧
化金屬，則需額外的氯需要量， ( 例如： Ni+
→ Ni2+ ， Fe2+ → Fe3+ ， Cr(Ⅲ) → Cr(Ⅵ) 等 ) ，
將顯著增加氰化物的處理費用
Other oxidants :

 Ozone (O3)
– light blue gas, a powerful oxidizing agent
advantage :
 avoidance of chlorinated by-products of
using Cl.
 Excess O3 decomposes to O2 (half-life in
H2O @20oC: 20 minutes, @ 20oC: 15
minutes)
– Disadvantage:
 Short half-life in H2O
 Low water solubility
 Can be generated only on-site, high electrical cost
How is ozone produced?

 principally O3 is produced by irradiation of

dry air wit Ultra-violet light
 just like that occurs naturally from the sun
in the upper atmosphere producing O3 layer
Other oxidants :

 Hydrogen Peroxide H2O2

– one of the most powerful oxidizers

– Oxidize many organic compounds via hydroxy

radical (·OH)
Advanced Oxidation Processes
(AOPs) 高級氧化程序
 active intermediates (·OH free radicals
….) were produced during redox reacti
on to destroy target hazardous compo
unds
 usually for treatment of recalcitrant or
ganics (benzene, phenol, chlorophenol
, toluene, xylene…)
 example: Fenton
Fe2+ + H2O2  Fe(OH)2+ + OH  Fe3+ +
OH + OH-
Fe2+ : catalyst
H2O2: oxidant
- pH controlled at acidic condition (pH 2 ~ 3)

 others: UV/O3, O3/H2O2, UV/H2O2, O3/TiO2

Chemical Reduction

 hexavalent chromium (Cr+6), Hg, Pb

 Cr+6: highly toxic, generated from metal finishing in
dustry
 “Hex chromium” is reduced to comparatively innocu
ous trivalent chromium, Cr+3 by SO2
SO2 + H2O  H2SO3
2 CrO3 + 3 H2SO3  Cr2(SO4)3 +3 H2O
Cr2(SO4)3 + 3 Ca(OH)2  2 Cr(OH)3(s)  + 3 CaSO4
Chromic hydroxide

 not applicable for organic waste reduction

 Photolysis ( 光解 )

 light energy (UV) to break up chemical

bonds of hazardous material
 treatment of pesticides and dioxin (in t
he presence of hydrogen): Dehalogen
ation reaction ( 脫鹵反應 )
h
 Aryl-H + RCl Aryl-Cl + RH
 酚及氯酚類化合物之處理
 處理技術 2- 光催化處理法
– 光化學反應一般分為直接光解 (direct photolysis)
與間接光解 (indirect photolysis) ，其特色在於
可處理多種污染物、能源取自於天然日光及可
處理生物系統難去除物質以促進生物處理系統
效能
– 直接光解通常利用紫外光線照射污染物質，物
質吸收光線能量後到達激發態而進行化學反應
，然而由於直接光解應用於有機物氧化破壞效
率不佳與實際應用上限制，故近年來利用催化
劑來增加其適用性，即所謂間接光解（又稱光
催化反應）
 Electrolysis 電解 \

 recovery of metals in wastewater

metal ions  metal molecules on cathode

 treat high concentration of cyanide, heavy

metal-containing wastewaters
 Wet Air Oxidation 濕式氧化法
 Oxidation of soluble or suspended components in wa
ter using oxygen as the oxidizing agent. When air is
used as the source of oxygen the process is referred t
o as wet air oxidation (WAO)
 oxidation reactions occur at temperatures of 150º C t
o 320º C and pressures from 10 to 220 bar (150 to 32
00 psig) to oxidize organics and some inorganics (cy
anide or ammonia ) in aqueous wastes in presence of
catalyst
 At these elevated temperature and pressure, the solub
ility of oxygen in water is dramatically increased, thu
s providing a strong driving force for the oxidation.
 system must be maintained under pressure to avoid e
xcessive evaporation of water
 Wet Air Oxidation

Operating parameters: temperature, pressure, oxygen

concentration, residence time
 Wet Air Oxidation

 Suitable for high strength of industrial waste

water (COD of 10,000 to over 100,000 mg/
L)
 Waste must be in the liquid phase.
 Limited to wastewaters containing oxidizable
organic and inorganic compounds. For exam
ple, WAO cannot destroy PCBs, some haloge
nated aromatics and some pesticides.
 High energy input, expensive
 Biological processes
 Detoxification process
 Utilize degradation 降解 capability of natural decom
poser – microorganism (bacteria, actinomycetes, fun
gi) under engineering controls to break down hazard
ous wastes to innocuous metabolites
 apply only to water-containing, biodegradable organi
c wastes. Generally for removal of organic pollutants
from wastewater having low-to-moderate concentrat
ions of simple organic compounds (aliphatic, oil) or l
ower concentration of complex compounds (aromati
c, phenolic, cyanide)
 Biological processes
 Most are aerobic processes (in presenc
e of oxygen), some are anaerobic (with
out oxygen)
 Biodegradation products:
– Aerobic: CO2, NH3, NO3-, SO42- ,H
, 2O and bio
mass
– Anaerobic: CO2, CH4, NH3, H2S ,H, 2O and bi
omass
 Biological removal of hazardous wastes

Organic or Inorganic

Special selected and maintained microorganisms

Mechanisms

Biodegradation by microorganisms Sorption onto microorganisms

Harvesting cells

Aerobic Anaerobic
Subsequent Disposal of
biodegradation residue
 Biodegradability 生物可降解性

 Aliphatic hydrocarbons  easily degrade

– Substituted group → increase refractory
(persistent)
 Aromatic  not so difficult
– Halogenated aromatic → increase refractory
 Polymer  hard to degrade
Refractory, persistent, recalcitrant com
pounds 頑抗物、難分解物
 biodegradation-resistant compound; includes ma
ny xenobiotic compounds & some natural produ
cts such as humus, lignin.
 usually toxic to cells (including microbes), so
compound may kill microbes that could
potentially degrade them if it is too concentrated
 Including:
– Halides
– high-branched molecules
– low solubility compounds
 General guidelines for biodegradability
 Aliphatic with carboxyl (-COOH), ester (-COO-R)
(-
or hydroxyl (-OH) groups → readily biodegradable
 Compounds with carbonyl (-C=O-) group or double
bond → moderately biodegradable (slow for acclim
ation 馴化 )
 Compounds with amino (NH2-R) or hydroxyl group
decrease biodegradability relative to degree saturati
on (1o >2o >3o)
 Biodegradability decreases with increasing degree o
f halogenation
Biodegradability:
aliphatic > aromatic > halogenated aliphatic > halogenated aromatic
 Biological processes
 Liquid/slurry-phase treatment: activated sludg
e 活性污泥 , aerated lagoon 氧化塘 , contact s
tabilization pond 接觸穩定塘 , Extended aerati
on 延長曝氣法 , trickling filter 滴濾池 , rotatin
g biological contactor 生物旋轉盤 (RBC), slud
ge digestionj 污泥消化
 Solid-phase treatment: composting 堆肥法 , la
nd farming 土耕法
 On-site (In-situ) vs. Off-site (Ex-situ) treatme
nt
 Require more sophisticated operational contro
ls: microbes sensitive to rapid change of wast
es concentration or feeding rate.
Process control parameters:
1. Hydraulic Retention Time (HRT)
 the average length of time the wastewater remains in a re
actor
 HRT = Volume of aeration tank(V)/influent flowrate (Q in)
2. MLSS/MLVSS: microbes concentration in the reactor
3. Food/Microorganism ration (F/M ratio 食微比 ) 或 Sludg
e loading ratio (SLR, 污泥負荷比 )
 BOD (or COD) in the influent divided by MLVSS in the react
or
 Measurement of organic loading on the system
 A high F/M leads to high oxygen consumption, insufficient t
reatment; low F/M encourage filamentous organisms to pre
dominate, leading to poor settleability
 Other parameters: Mean cell residence time [MCRT 平均污泥停
留時間 or Sludge residence time (SRT), Sludge age], pH, DO
 Thermal processes
 destroy, break down or aid in desorption of
contaminants in gases, vapors, liquids, slud
ges and solids.
 Most are incineration 焚化 processes: comb
ust HW in the presence of oxygen @ T= 80
0~1650oC
 Materials become ash
 Process: catalytic oxidation (typically use m
etal oxides as catalyst, Pd or Pt), Fluidized B
ed 流體化床 , Liquid injection 液體噴注式焚
化爐 , Rotary kiln 旋轉窯式焚化爐 , Multiple
Hearth 多床式焚化爐
 Fluidized Be
d incinerator

Liquid injection
incinerator
Rotary kiln incinerator 旋轉窯式焚化爐
Incineration offers:
 the destruction of waste,
 the production of energy from waste
 the disposal of hazardous waste

Products of incineration:
gaseous: CO2, H2O, SOx, POx, HF, HCl, HBr, I2,
also present are metal oxides and
traces of unburnt waste
solids: Fly Ash 飛灰 (metals, oxides and non-com
bustibles
Incineration control parameters:
 Temperature 溫度 : 900 – 1100oC will destruct
hydrocarbon, 1100 to 1300°C are needed for chl
orinated solvents and other wastes which are diff
icult to incinerate; below 900°C hazardous by- pr
oducts (dioxins and furans 夫喃類 ) will formed.
 Residence Time 停留時間 : hold the waste at hig
h temperatures for sufficient time to ensure dest
ruction (gas, 2 sec; solid, min~hrs)
 Turbulence or mixing 攪拌 : enables waste and a
ir to be well mixed, should be maximized so that
contact between the waste and the oxygen in air
is as high as possible

 燃燒過程的 3T
Stabilization Technology (Solidifi
cation, Fixation ) 穩定化、固化
 Desinged to limit or reduce the ultimate release of
hazardous material from a waste; usually for liquid
or semi-solid wastes (sludge)
 Accomplished by reducing the solubility of the haza
rdous materials  reduce the mobility of the toxin
 Done by mixing (or fixing) hazardous wastes with a
nonleachable matrix, then ship the matrix to TSDF
or hazardous waste landfill
 Required for hazardous wastes containing heavy m
etals
Process Classification

 Cement-based process: 氧化鈣、二氧化矽、氧化鋁

及三氧化鐵
 Lime-based process: 石灰 , CaCO3 碳酸鈣
 Thermoplastic process: paraffin 石蠟
, polyethylene, bitumen, asphalt as solidifying agen
t
 Organic polymer process: urea-formaldehyde, polye
ster, polyethylene
 Self-cementing process: pozzolanic material
 Encapsulation: microencapsulation & macroencapsu
lation
 各種固化法之比較
固化法 優點 缺點
• 固化劑成分價錢適中 1. 低強度水泥與廢棄物混合，易受酸性
• 水泥之混合和操作技術已有優異發展 滲出液破壞，可能導致固著之廢棄物
• 固化處理所需之工具容易取得 成分之分解和加速滲出污染因子
• 對污泥所含之化學成份變化有適當之忍 2. 如廢棄物含有影響水泥定形和凝固
水泥固化法 受性 的成分，需先處理或採用較貴之水泥
• 終產物之滲水性和強度可由水泥含量加 或其他填劑
以控制 3. 水泥和其加填劑大大增加廢棄物的
重量和體積

1. 固化劑和加填劑容易買到價格便宜 1. 石灰和其加填劑增加廢棄物的重量
2. 所需之工具容易取得且操作簡單 和體積
石灰固化法
3. 火山灰反應之化學變化已有明確 2. 固化後之污泥易受酸性溶液破壞
4. 之建立
1. 污染因子移動率一般較其他固化法低 1. 所需之工具貴且須熟練工人操作
2. 終產物水溶液抵抗力強 2. 如污泥含有能在低溫度蒸發之成分
熱塑物固化法 3. 熱塑物對其所固化之廢棄物黏性強 操作需小心
3. 熱塑物是可然性物質
4. 濕污泥需先乾燥才能和固化劑混合
1. 僅需少量固化劑即可使混合物定形 尿素甲醛固化法所用之催化劑為強酸，如
有機聚合物固化 2. 適用於乾或濕污泥 在聚合過程中有水份沒有被截留在
法 3. 終產物之密度低 塊內，將使部分金屬溶於低 pH 值的
水中而易洩出
1. 終產物穩定，無著火性及生物分解性 1. 只適用於固化含硫酸鈣或亞硫酸鈣
自行膠結固化法 2. 不需完全乾燥廢棄物 高之廢棄物
2. 所需之工具貴且須熟練工人操作
1. 能將溶解性很高之污染物自環境中隔離 1. 材料很貴
2. 經微表面包封後再經巨表面包封處理無 2. 污泥需先預乾
包封法
須再置於桶內 3. 巨表面包封往往須要特殊工具和加
熱處理
Final Disposal of Hazardous Waste
 Landfill
– developed previously for the disposal of municip
al refuse  Sanitary landfill as an alternative t
o the open dump
– Hazardous Waste Landfills (secure landfill): b
ury pretreated hazardous wastes in a landfill con
structed with low-permeable soil material (clay)
or synthetic non-leachable liners (butyl rubber, c
hlorinated polyethylene…), along with a leachate
collection system and a final cover
 3 classes of disposal site (for hazardous and
non-hazardous)
 Classes of Disposal Sites
Class I – 封閉掩埋塲 Waste Management Unit
s for hazardous Waste
 accept only hazardous waste treatment resid
ues
 sites must be designed and constructed very
carefully, includes groundwater monitoring
wells, leak detection system, liners (double-l
ayered), leachate collection systems and cov
ers
 U.S.: Utah, Idaho, Nevada, Washington
Classes of Disposal Sites
Class II – 安定掩埋場 Waste Manageme
nt Units for Designated wastes
 allow only certain solid hazardous was
tes (asbestos, construction debris, lo
w-level contaminated soil)
 have least control system
Classes of Disposal Sites
Class III – 衛生掩埋場 Landfill for Nonh
azardous Waste
 accept common household trash and o
ther nonstable wastes municipal lan
dfill
 simply bury with only a few control sy
stem (leachate collection, groundwate
r monitoring)
 hazardous waste disposal in a Class II
I site is against the law
 Class II

Class III

Class I