Synthesis and characterization of
dithiocarbamate chelating resin and its
adsorption performance toward Hg(II),
Cd(II) and Pb(II) by batch
and fixed-bed column methods
A.F. Shaaban a,*, D.A. Fadel b, A.A.
Mahmouda, M.A. Elkomy c, S.M. Elbahy a
a
b
Chemistry Department, Faculty of Science, Benha University, Benha, Egypt
Nuclear Research Center, Atomic Energy Authority, P.O. 13759, Inshas, Cairo, Egypt
c
Faculty of Engineering (Shoubra), Benha University, Shoubra, Egypt
Introduction
Environmental pollution with heavy metal gained lately much
concern because of their general and specific toxicities. The most
toxic heavy metals, namely lead, mercury, nickel, zinc, copper and
cadmium can be distinguished from other pollutants, because they
cannot be degraded naturally but accumulates in living organisms.
Therefore they cause different diseases and disorders even in lower
concentrations [1–3]. The major important sources of heavy metal
pollution in water are wastewaters and agricultural sources.
Wastewaters arise from industries like chemical, tanneries, paint
manufacture, plating, mining and petroleum refining. The agricultural
sources arise from fertilizer and fungicidal spray [1]. Different
technological separation
班級：化材延修
學號：49840108
姓名：簡麗淑
Introduction
Environmental pollution with heavy metal gained lately much concern because of
their general and specific toxicities.
重金屬對環境的污染得到，因為他們的一般和特殊毒性近來備受關注。
The most toxic heavy metals, namely lead, mercury, nickel, zinc, copper and
cadmium can be distinguished from other pollutants, because they cannot be degraded
naturally but accumulates in living organisms.
毒性最大的重金屬，包括鉛，汞，鎳，鋅，銅和鎘可以從其他污染物區分開來，
因為它們不能被自然降解，但積聚在活的生物體。
Therefore they cause different diseases and disorders even in lower concentrations
[1–3]. The major important sources of heavy metal pollution in water are wastewaters
and agricultural sources.
因此，它們會導致即使在低濃度[1-3]不同的疾病和障礙。在水中重金屬污染的主
要來源重要是廢水和農業面源。
Wastewaters arise from industries like chemical, tanneries, paint manufacture, plating,
mining and petroleum refining.
廢水產生像化工，制革，油漆製造，電鍍，礦山和石油煉製工業。
The agricultural sources arise from fertilizer and fungicidal spray [1].
農業源產生肥料和殺菌劑噴霧[1]。
Different technological separation methods have been used for toxic heavy metal ions
removal such as precipitation, reverse osmosis, ion exchange, electrodialysis,
membrane filtration and adsorption of metal ions with chelating resins.
不同的技術分離方法已被用於含有毒重金屬。
金屬離子的去除，如沉澱法，反滲透法，離子交換，電滲析，膜過濾和吸附金屬
離子與螯合樹脂。
Amongst all treatment technologies,the adsorption technique using sorbents showed
an effective separation of the toxic metal ions since chelating resins are ease of
handling, reusable and have higher selectivity with high uptake
capacity [4–6].
在所有的處理技術，使用吸附劑的吸附技術顯示的有毒金屬離子的有效分離，因
為螯合樹脂是易於處理，可重複使用的，並有較高的選擇性，高的吸收
容量[ 4-6 ] 。
Numerous chelating resins have been used for removal of heavy metals from
wastewater or aqueous solutions[5–19].
眾多的螯合樹脂已被用於去除重金屬從廢水或水溶液[ 5-19 ] 。
In our previous work, chelating resin containing iminodiacetate group was prepared
for removal of lead, cadmium,manganese and zinc ions from aqueous solution with
high performance [20].
在我們以前的工作中，螯合樹脂含有亞氨基二乙酸組為去除水中的鉛，鎘，錳和
鋅離子的水溶液具有很高的性能[ 20 ]製備了。
Chelating resins containing sulphur as donor atoms have been used extensively as
selective ligands with high bond stability for transition metal [21].
含有硫作為供體原子的螯合樹脂已被廣泛用作選擇性配體具有高鍵結穩定性為
過渡金屬[21]。
Various sulphur-containing complexingligand used for removal of heavy metal ions
from aqueous medium with a negligible adsorption of alkali and alkaline earth metal
ions [22].
用於除去重金屬離子從水介質中與鹼金屬和鹼土金屬離子[22]的一個可忽略的
吸附各種含硫配位的配體。
Dithiocarbamates were extensively used as sulphur-bearing complexing agents were
anchored onto various polymeric supports to remove metal ions from aqueous
solution[17,23–30].
二硫代氨基甲酸被廣泛用作含硫錯合劑錨定到不同的聚合物載體，從水溶液中
[17,23-30]去除金屬離子。
In the present work, dithiocarbamate chelating resin (DTMAN) was synthesized and
used to remove Hg(II), Cd(II) and Pb(II) metal ions from aqueous medium using
batch and fixed bed column methods.
The effects of the adsorption parameters such as pH value, metal ion concentration,
contact time and the effect of temperature were investigated.
Experimental data was fitted using three models: Langmuir, Freundlich and Temkin.
Kinetic and thermodynamic parameters of metal ions adsorption were also evaluated.
Furthermore, fixed bed column technique was used for heavy metal ions removal
from aqueous solution by synthesized chelating resin.
在本工作中，二硫代氨基甲酸螯合樹脂（DTMAN）的合成和使用（Ⅱ）
，鎘（II）
和 Pb（II）的使用批次和固定床柱方法從含水介質中的金屬離子以除去汞。
吸附參數，例如 pH 值，金屬離子濃度，接觸時間和溫度的作用的影響。
符合 Langmuir，Freundlich 和特姆金：用三種模型的實驗數據進行擬合。
金屬離子的吸附動力學和熱力學參數進行了評價。
此外，固定床柱技術被用於從由合成螯合樹脂水溶液重金屬離子的去除。
Materials and methods
Materials
Acrylonitrile (AN) 丙烯腈 單體
N,N’-methylenebisacrylamide (MBA)亞甲基雙丙烯胺交聯劑單體
2,2-Azobis(isobutyronitrile) (AIBN)起始劑
Ethylenediamine乙二胺
carbon disulphide二硫化碳
sodium ethoxide乙醇鈉
Preparation of dithiocarbamate chelating resin二硫代氨基甲酸螯合樹脂的製備
Synthesis of poly (acrylonitrile-co-N,N’-methylenebisacrylamide)(MAN)
聚（丙烯腈-共-亞甲基雙丙烯胺）（MAN）的合成
MAN beads were synthesized by suspension polymerization method using three neck
round bottom flask equipped with a reflux condenser and a mechanical overhead
stirrer.
使用三頸圓底燒瓶裝有回流冷凝器和機械頂部攪拌器，通過懸浮聚合方法合成
MAN顆粒
Polymerization was carried out at 85C for 3 h.
聚合反應在85℃下保持3小時。
The mixture containing the monomers (9.5 g AN and 0.5 g MBA) and the initiator
(0.2 g AIBN) were suspended into toluene (50 mL).
含有單體（9.5AN克和0.5克MBA）和起始劑（0.2克AIBN）的混合物懸浮於甲苯
（50mL）中。
The employed solution was deaerated by nitrogen gas with flow rate 10 mL min-1 .
所採用的溶液進行脫氣，氮氣以流速10 mL / min的。
After completing the reaction, the mixture was allowed to cool for about 3 h.
反應結束後，將混合物放置冷卻約3小時。
The resin was filtered off, washed with water, methanol, airdried and sieved.
將樹脂濾出，用水洗滌，用甲醇中，空氣乾燥並過篩。
The 150–250 mm fraction was used for the further synthesis with a yield of 73%.
在150-250毫米級分用於進一步合成用的73％的收率
Synthesis of crosslinkedpolyacrylonitrile bearing amino group (AMAN)
交聯聚丙烯腈軸承氨基的合成（AMAN）
The AMAN resin was synthesized by aminolysis–hydrolysis reaction of the nitrile
groups with ethylenediamine.
合成由腈基與乙二胺的氨基分解，水解反應的AMAN樹脂。
Thus, 5.0 g of(MAN) was mixed with 100 mL of 80% (v/v in water) ethylenediamine
solution and the mixture was stirred and heated at 118℃
for 10 h.
因此，將5.0克（MAN）和100毫升80％的乙二胺溶液混合攪拌並加熱到118℃進
行混合10小時。
The resin was filtered and washed with NaCl solution (0.2 M) until the filtrate was
free from ethylenediamine, as indicated by the absence of any blue coloration with
ninhydrin reagent.
將樹脂過濾，並用氯化鈉溶液（0.2M）清洗直到濾液無乙二胺(可由茚三酮試劑
檢測藍>無色)
The resin was washed with water (to remove NaCl) and then with methanol, and
finally it was dried at 50C.
將樹脂用水洗滌（以除去NaCl）中，然後用甲醇，最後將其在50℃下乾燥。
The amine value of the resin was determined using the volumetric method [31].
該樹脂的胺值採用容積法[31]測定。
A total amine value of the resin was calculated as 4.6 mmolg-1.
該樹脂的總胺值計算為4.6毫摩爾/克。
Synthesis of chelating resin bearing dithiocarbamate groups (DTMAN)
螯合樹脂軸承二硫代氨基甲酸基團的合成（DTMAN）
Chelating resin (DTMAN) was obtained by stirring and heating a mixture of carbon
disulphide (20 g), sodium ethoxide (22 g) and 3.5 g of (AMAN) at 50℃ for 48 h. The
resin was filtered off, washed with water, acetone and finally air-dried.
螯合樹脂（DTMAN）中通過攪拌和加熱二硫化碳（20克），乙醇鈉（22克）和
3.5克（AMAN）的在50℃下48小時的混合物中得到的。將樹脂濾出，用水洗滌，
用丙酮，最後風乾。
Characterization of the resins樹脂的特性
FT-IR analysis
Water regain吸水量
1 g of swollen resin is placed in a suitable size column and centrifuged at 3000 rpm
for 5 min to remove excess water and then weighed.
The resin was dried at 70–80C until complete dryness then the column is weighed
again with and without the resin.
Surface morphology of the chelating resin and its metal complexes
螯合樹脂的的表面形態及其金屬配合物
Thermal analysis熱分析
Thermal analysis experiments including thermal gravimetric
analysis (TGA) for DTMAN resin were carried out using SDT Q600TA instrument,
USA. The experiment was performed in a dynamic atmosphere of nitrogen from room
temperature to 700 C atheating rate of 10 Cmin-1.
熱分析實驗，包括熱重
重分析（TGA）對DTMAN樹脂進行了利用SDT Q600
TA儀器，美國。在氮氣氣氛中動態進行的實驗是在室溫至700℃於
加熱速率為10℃/ min的
Surface area表面積
Adsorption of metal ions金屬離子的吸附
The optimum pH value for sorption of metal ions was performed by the batch
equilibration technique at 25℃.
The experiments were carried out by shaking 0.1 g of dry resin with 100 mL of metal
ion solution (5 mmolL-1) for 2 h at 200 rpm.
The desired pH was adjusted using 0.1 M HNO3 and 0.1 M NaOH solutions.
The sorption of metal ions in basic medium was avoided due to precipitation of metal
hydroxides.
After equilibration, the residual concentration of the metal ions in the solution was
measured using Hitachi atomic absorption Z-6100 polarized
Zeeman spectrometer before and after treatment to determine the adsorbed amounts of
metal ions.
由振盪平衡法在25度C、適當pH值進行對金屬離子的吸附作用的。
該實驗進行了搖動0.1克幹樹脂用100mL的金屬離子的溶液（5毫摩爾L'1），用於
在200rpm2小時。
用0.1M HNO 3和0.1M NaOH溶液所需的pH值的調整。
在鹼性介質中的金屬離子的吸附被避免由於金屬氫氧化物的沉澱。
平衡後，在溶液中的金屬離子的殘留濃度是使用日立原子吸收的Z-6100偏光塞曼
光譜處理前後，以確定金屬離子的吸附量的測定。
Experiments of adsorption isotherms were conducted at 25℃.
The experiments were performed by shaking 0.1 g of dry chelating resin with 100 mL
of solution containing metal ions in a concentration range of 1–25 mmolL-1 at the
optimum pH value for 2 h.
After equilibration the resin was filtered and the residual metal ion concentration in
the aqueous phase was determined.
吸附等溫線的實驗均在25℃進行。
本實驗是通過振盪0.1克乾燥螯合樹脂與含有在1-25mmol L-1的濃度範圍內的金
屬離子100毫升溶液中進行2小時的最佳pH值。
平衡後，將樹脂過濾，並在水相中的殘留金屬離子濃度進行測定。
The effect of shaking time on the adsorption process was examined at 25℃.
A quantity of 0.1 g of dry chelating resin was shaken with 100 mL of a solution
containing metal ion at optimum pH and optimum concentration of aqueous metal ion
solutions.
The bottles containing the mixtures were withdrawn at suitable time intervals to
determine the metal ion concentration and the time of equilibrium.
在吸附過程中振盪時間的影響進行了檢查，在 25℃。
將 0.1g 乾燥的螯合樹脂的量振盪用在最適 pH 和水性金屬離子溶液的最佳濃度為
100 毫升含有溶液中的金屬離子。
含有該混合物的瓶子被撤回在合適的時間間隔，以確定金屬離子的濃度和平衡的
時間。
The adsorption of metal ion by the chelating resin as a function of temperature was
studied in the temperature range of 25–45℃.
A sample of 0.1 g of chelating resin was shaken with 100 mL of aqueous solutions
(1.0 mmol L1) containing metal ion under the optimum pH and shaking time. After
adsorption, the solution was filtered and the residual concentration of the metal ions
was determined.
金屬離子的螯合樹脂作為溫度的函數的吸附研究了在 25-45℃的溫度範圍內。
將 0.1g 的螯合樹脂的樣品振搖用 100mL 水溶液（1.0 毫摩爾 L'1）含有金屬離子
下的最佳 pH 值和振盪時間。吸附後，將溶液過濾，將金屬離子的殘留濃度。
Elution and regeneration of the chelating resin was performed using 0.2 M HNO3
after that, the resin was washed with water, 0.2 NaOHsolution, finally, the resin
washed with water until neutral pH to become ready for reuse.
The sorption–desorption cycle of metal ions was repeated 5 times.
Elution and regeneration of the chelating resin was performed using 0.2 M HNO3
after that, the resin was washed with water, 0.2 NaOHsolution, finally, the resin
washed with water until neutral pH to become ready for reuse.
先將樹脂置於用0.2M的硝酸後，將樹脂用水洗滌，再用0.2 NaOH溶液，最後，
用水洗滌，直到中性pH後便可得到經脫附和可在再使用的螯合樹脂。
接著在吸附-脫附重複循環5次。
Results and discussion
In this study, dithiocarbamate chelating resin (DTMAN) was
synthesized from the grain size of 150–250 mm (MAN) through the
steps presented in Scheme 1.
在這項研究中，二硫代氨基甲酸螯合樹脂（DTMAN）為
從150-250毫米（MAN）通過粒徑合成的
在方案1中給出的步驟。
Characterization of the synthesized resins合成樹脂的特性
FT-IR spectra of the synthesized resins are shown in Fig. 1.
FT-IR spectrum of MAN resin (Fig. 1a) exhibited the characteristic bands of C≡N (2245
cm-1), C=O (1666 cm-1) and NH– (3371 cm-1)[5,20].
FT-IR spectrum of AMAN resin (Fig. 1b) showed that the intensity of C≡N peak (2245
cm-1) decreased by the conversion of C≡N group to –NH2 (3431 cm-1).
For DTMAN chelating resin(Fig. 1c) the peaks at (1155 cm-1) and (1430 cm-1) are
attributed to C=S and N–C=S of dithiocarbamate group [27].
合成樹脂的FT-IR光譜示於圖1。
MAN樹脂（圖1a）的FT-IR光譜顯示出C≡N的特徵峰（2245厘米？-1）
，C = O（1666
厘米？-1）和NH-（3371厘米-？1）[5，20]。
AMAN樹脂（圖1b）的FT-IR光譜表明，C≡N峰的強度（2245厘米？-1）減少C
≡N基團轉化為-NH 2（3431厘米？-1）。
對於DTMAN螯合樹脂（圖1c）在峰（1155厘米？-1）和（1430厘米？-1）
，是由
於二硫代氨基甲酸酯基[27] C = S和N-C = S。
The water regain for (DTMAN) chelating resin was estimated to be 26.11
mmol/g(W% = 47).
This high value indicates the hydrophilic character of the resin which increases the
adsorption of heavy metal ions.
吸水量（DTMAN）螯合樹脂估計為26.11毫摩爾/克？（W％=47）。
此高值表示這增加了重金屬離子的吸附樹脂的親水特性。
The SEM images were taken to study the surface morphology of DTMAN chelating
resin and its metal complex (DTMAN-Pb as example).
As shown in Fig.2 chelating resin before adsorption has least packed structure with
many pores or cavities in the surface, which facilitates mass transfer of metal ions to
chelating resin.
After metal ion adsorption, the resin surface became completely packed and the pores
or cavities disappeared which may be due to adsorption of the metal ions.
拍攝的SEM圖像，研究DTMAN螯合樹脂的表面形態和其金屬配合物（DTMAN 鉛作為例子）。
如圖2所示的螯合樹脂的吸附已經至少堆積結構具有許多孔或腔的表面，這有利
於金屬離子的傳質，以螯合樹脂之前。
後金屬離子的吸附，在樹脂表面變得完全填充，孔或腔消失可能是由於吸附的金
屬離子。
The BET surface area, BJH pore volume and average pore diameter for DTMAN
chelating resin were estimated from the nitrogen adsorption data and listed in Table 1.
These results indicate that the resin possess mesoporous structure (pore diameter 2–50
nm) [43].
的BET比表面積，BJH孔體積和平均孔徑DTMAN螯合樹脂是從氮氣吸附數據估
計，並在表1中列出。
這些結果表明，該樹脂具有介孔結構（孔徑2-50納米）[43]。
The thermal analysis (TGA) was performed to evaluate thermal stability of the
DTMAN chelating resin.
The thermogram of the chelating resin is shown in Fig.3.
The TGA curve shows that DTMAN resin undergoes degradation in three stages.
The first stage ranges from 27 to 174℃ with partial weight loss of 13.84% due to loss
of water molecules which is present in external surface and internal pores or cavities
of the resin.
The higher water content confirms the hydrophilic nature of the resin.
The second stage ranges from 174 to 324 with partial weight loss 30.5% which
assigned to degradation of grafted functional groups.
The third stage ranges from 324 to 700 with partial weight loss 84.5% which
could belong to decomposition of the residual MAN resin.
熱重分析（TGA）進行了評估DTMAN螯合樹脂的熱穩定性。
螯合樹脂的溫譜圖如圖3所示。
在TGA曲線顯示DTMAN樹脂發生降解三個階段。
第一級範圍從27到174℃，局部減肥，由於水分子，其存在於外部表面和內部的
孔或樹脂的孔洞的損失13.84％。
較高的含水量證實了樹脂的親水性。
第二階段範圍從174到324與局部減肥的分配接枝官能團的降解30.5％。
第三階段範圍從324到700與局部減肥84.5％，其中
可能屬於剩餘MAN樹脂的分解。
Uptake of metal ions by batch technique
Optimum pH of metal ions uptake金屬離子吸收的最適pH
The influence of the pH of the medium on the adsorption of metal ion was examined
by batch technique at 25℃ in the pH range of 2.0–6.0 and the results were presented
in Fig.4.
介質的pH對金屬離子的吸附的影響進行了檢查批次技術在2.0-6.0的pH範圍25℃，
其結果表示在圖4中給出。
At lower pH value, H+ ions compete with M(II) to occupy adsorption sites and
therefore the chelating resin will have low adsorption capacity.
在較低pH值時，H +離子與M（II）競爭佔據的吸附位點，因此該螯合樹脂將具
有較低的吸附能力。
By increasing pH value, the concentration of H+ ions decreased and active adsorption
sites exist converted into dissociated forms which lead to high attraction of metal ions
toward adsorption active sites.
通過提高pH值，H +離子濃度降低，活性吸附位點存在轉化成游離形式而導致的
金屬離子向吸附活性部位的高亮點。
As indicated in Fig.4, by increasing pH value adsorption capacity increases until it
reaches to maximum value.
正如在圖4中，通過提高pH值的吸附容量增加，直到它達到最大值。
The optimum pH value (natural pH) at which the maximum adsorption capacity for
metal ion were obtained as 5, 6 and 5.6 for Hg(II), Cd(II) and Pb(II), respectively.
金屬離子在最大吸附量，可得到為5,6和5.6分別為汞（Ⅱ）
，鎘（II）和鉛的最適
pH值
All the following experiments were carried out at these optimum pH values. Above
natural pH for all metal ions, metal(II) hydroxide precipitate is formed
(M2++ 2OH-→ M(OH)2↓) and adsorption data cannot be measured.
以下所有實驗均在這些最佳pH值。上述自然pH值對所有的金屬離子，金屬（Ⅱ）
氫氧化物沉澱形成（M 2 ++2 OH-→M（OH）2↓）和吸附數據不能被測量。
Effect of initial concentration and equilibrium isotherm models
初始濃度和平衡等溫線模型的影響
The influence of the initial concentrations on equilibrium adsorption is presented in
Fig.5.
圖5為初始濃度對吸附平衡的影響
The adsorption curves indicate that the amount of metal ion adsorbed on chelating
resin increases with increasing initial concentration of metal ion until reaching the a
plateau shape.
吸附曲線表明，螯合樹脂的吸附量隨金屬離子的初始濃度增加而增加，直到達平
衡。
The loading capacity ( mmolg-1 ) was determined at optimum pH of each metal ion
and at 25℃, Table 2.
The optimum concentration of metal ions for Hg(II), Cd(II) andPb(II) are 20, 17 and
15 (mmolL-1), respectively.
裝載容量在各金屬離子的最佳pH值並在25℃，表2中確定。
金屬離子對Hg（Ⅱ），鎘（II），Pb的最佳濃度（II）是20，17和15，分別為。
It is displayed in Fig.5 that,the maximum level of sorption of metal ions was in the
order of Hg(II) > Cd(II) >Pb(II).
A comparison of the present (DTMAN) chelating resin with those of different types of
chelating resins in recent references is shown in Table 2.
The data presented in Table 2 reveals that, generally, the prepared chelating resin in
this work has a good advantage in metal ion adsorption more than the previously
reported resins.
它被顯示在圖5中的是，金屬離子的吸附的最高水平是在汞（Ⅱ）>鎘（Ⅱ）>鉛
（II）的順序。
目前（DTMAN）螯合樹脂與不同類型的近引用螯合樹脂的比較見表2。
在表2中給出的數據表明，通常，在本工作所製備的螯合樹脂具有良好的優勢，
在金屬離子吸附比以前報導的樹脂。
The Langmuir, Freundlich and Temkin isotherm parameters for adsorption of metal
ions onto chelating resin are calculated by using isotherms and their correlation
coefficients are listed in Table 3.
Comparison of the correlation coefficients values shows that adsorption of Hg(II),
Cd(II) and Pb(II) onto dithiocarbamate chelating resin is fitted better by the Langmuir
model (R2 = 0.990–0.998) than the Freundlich and Temkin models (R2 = 0.977–0.989)
and (R2 = 0.946–0.966), respectively.
Langmuir吸附，Freundlich和的Temkin等溫線參數，吸附金屬離子到螯合樹脂是
通過使用等溫線計算出兩者的相關係數列於表3中。
相關性的比較系數值表明，吸附汞（II），鎘（II）和鉛（II）的上二硫代氨基甲
酸螯合樹脂被裝配好由Langmuir模型（R 2 =0.990-0.998）
，比Freundlich和Temkin
動力學模型（R2 =0.977-0.989）和（R2 =0.946-0.966），分別為。
Plotting RL versus C0 is shown in Fig.6.
The obtained values of RL were found to be between zero and one for all metal ions
which shows that the adsorption of metal ions on chelating resin is favorable.
As shown in Fig.6 increasing of metal ion concentration result in decreasing of RL
values which implies that the adsorption process is more favorable at higher
concentration of metal ions.
Similarly, the values of Freundlich parameter (N) for all metal ions were found to be
between zero and one indicating the facile adsorption process of metal ions onto
chelating resin.
繪製RL與C0如圖6所示。
發現RL的得到的值是0和1之間的所有的金屬離子這表明金屬離子對螯合樹脂的
吸附是有利的。
如圖6中所示的金屬離子濃度結果在減小RL值的增加，這意味著，該吸附過程是
在金屬離子濃度較高時更為有利。
同樣地，被發現Freundlich等參數（N）的所有金屬離子的值是0和1之間，表示金
屬離子的輕便吸附過程到螯合樹脂。
Adsorption kinetics吸附動力學
Kinetic studies were performed using the optimum pH and optimum initial
concentration of metal ion adsorption at 25℃ and the results are indicated in Fig.7.
As shown in Fig.7, equilibrium was reached in 20, 30 and 25 min for Hg(II),Cd(II)
and Pb(II), respectively. Half-load time (t1/2) was below 5 min for Hg(II) and Pb(II)
and below 10 min for Cd(II).
The high initial rate suggests that the adsorption occurs mainly on the surface of
chelating resin[44].
動力學研究用的最適pH和金屬離子的吸附最佳初始濃度在25℃下進行，並且結
果示於圖7。
如圖7所示，平衡在20，30和25分鐘對Hg達到（Ⅱ）
，鎘（II）和Pb（Ⅱ）中，分
別。半負載時間（t1/ 2）為下5分鐘，使汞（II）和鉛（II）和低於10分鐘，鎘（II）。
高初始速率表明吸附主要發生螯合樹脂[44]的表面上。
Pseudo-first order and pseudo-second order parameters are given in Table 4.
Obviously, as it can be seen from the result represented in Table 4, correlation
coefficients of the second order kinetic are higher than the results obtained from the
first-order kinetics.
Therefore, the sorption behavior of Hg(II), Cd(II) and Pb(II) onto chelating resin
obeys the second-order kinetics.
假一級和假二級參數列於表4。
很明顯，因為它可以從表4中所示的結果可以看出，在二級動力學的相關係數均
大於從一級動力學所得到的結果高。
因此，汞的吸附行為（Ⅱ），鎘（Ⅱ）和鉛（Ⅱ）到螯合樹脂服從二級動力學。
As can be seen from Fig.8, the adsorption process was controlled by three stages: (1)
rapid transportation of metal ions from aqueous solution to chelating resin surface; (2)
gradual adsorption stage where intraparticle diffusion is rate-limiting step and (3)
final equilibrium step due to lower concentration of metal ions in aqueous phase, as
well as fewer number of adsorption sites are accessible.
如可以從圖8中可以看出，在吸附過程中被控制的三個階段：（1）快速輸送從水
溶液中螯合樹脂表面的金屬離子，
（2）逐步的吸附階段，內擴散是速率控制步驟
和（3）最終平衡步驟，由於較低的濃度在水相中的金屬離子，以及更少的吸附
位點的數量都可以訪問。
Adsorption thermodynamics吸附熱力學
Thermodynamic parameters (DH8ads and DS8ads) of the adsorption of metal ions
onto DTMAN resin is calculated from the slope and intercept of lnKd versus 1/T plots
respectively, Fig. 9.
Thermodynamic parameters including DG8ads, DH8ads and DS8ads were given in
Table 5. Positive values of DH8ads represent that the metal ion adsorption is an
endothermic process [45,46].
Also, the positive values of DS8ads may be related to the increased
randomness due to the liberation of water of hydration drying the adsorption of metal
ions [45,46].
Finally, the thermodynamic parameters reflect the spontaneity of metal ion adsorption
which is indicated by negative values of DG8ads.
Uptake of metal ions using column techniques使用列方法的金屬離子的吸收
Chelating resin (DTMAN) was also found efficient in column adsorption method for
the removal of Hg(II), Cd(II) and Pb(II).
The break-through curves for adsorption of metal ions are shown in Fig.10.
The solution containing metal ions was continuously passed through the column at 25
C with a flow rate of 1.0 mL min1.
The experimental break-through curves indicate that using 1.0 mL min1 flow rate of
metal ions solutions start to break-through at 160, 140 and 80 mL of effluent for
Hg(II), Cd(II) and Pb(II), respectively.
The breakthrough capacities of the metal ions were estimated and listed in Table 6.
螯合樹脂（DTMAN）也被發現有效的在柱吸附法對汞的去除（Ⅱ）
，鎘（II）和
鉛（II）。
用於吸附金屬離子的突破曲線示於圖10。
含有溶液中的金屬離子被連續地通過在25℃下的柱，用1.0毫升的流速通過1。
實驗突破曲線表明，用1.0毫升分？金屬離子的1流速溶液開始損壞，通過在160，
140和80毫升流出物的汞（Ⅱ），鎘（II）和Pb（Ⅱ）中，分別。
金屬離子的穿透能力估計和列於表6中。
Elution and regeneration cycles洗脫和再生循環
Elution of metal ions from the resin packed in the column was performed using 0.2 M
HNO3 solution at 25℃ followed by neutralization with 0.2 M NaOH.
使用 0.2M 的硝酸溶液中，在 25℃進行中和用 0.2M 的 NaOH 進行從裝在柱中的
樹脂溶出的金屬離子。
In order to examine the reusability of dithiocarbamate chelating resin, successive
adsorption–desorption cycles were repeated 5 times. From the adsorption–desorption
process, it is clear that the break-through capacities showed a little decrease after five
cycles of repeated use.
為了檢查二硫代氨基甲酸螯合樹脂的可重用性，連續吸附 - 脫附循環，重複 5
次。
The break-through capacity decreased to 92%, 91%, and 92% for Hg(II), Cd(II) and
Pb(II), respectively after 5 regeneration cycles.
從吸附 - 脫附過程，很顯然，該突破的能力表明後重複使用 5 次循環稍微下降。
的突破容量下降至 92％，91％，和 92％的汞（Ⅱ）
，鎘（II）和 Pb（Ⅱ）中，分
別經過 5 再生循環。
Therefore it is concluded that dithiocarbamate chelating resin is a durable sorbent in
removal of the metal ions under study from their single-metal ion solutions.
因此可以得出結論，二硫代氨基甲酸螯合樹脂是一種耐用的吸附劑中除去下從它
們的單金屬離子溶液研究了金屬離子。
作業