Poly(vinyl pyridine-poly ethylene
glycol methacrylate-ethylene glycol
dimethacrylate) beads for heavy
metal removal
班級:化材延修
學號:49840110
姓名:陳薏如
Introduction
There is noticeable increase in heavy metal contaminant volume to those who make
many serious environmental problems in the recent years.
在最近幾年重金屬污染物的量明顯增加，造成許多嚴重的環境問題。
Heavy metals are metabolic poisons and enzyme inhibitors.
重金屬毒物的代謝和酶抑製劑。
They can cause mental retardation and semipermanent brain damage.
它們能引起智能遲滯和半永久性的腦損傷。
Because of the reason that heavy metals can not be rendered harmless by chemical or
biological remediation processes,they are classified as environmental toxic
substances.
由於重金屬不能由化學或生物修復過程來使其變成無害，所以他們被列為環境有
毒物質。
Toxic metals are released into the environment in a number of different ways.
而有毒的金屬經由許多不同的方式被釋放到環境中
Coal combustion,sewage waste waters, automobile emissions, battery industry,
mining activities, tanneries, alloy industries and the utilization of fossil fuels are just a
few examples.
煤炭燃燒，污水廢水，汽車排放，電池行業，採礦活動，皮革廠，合金產業和化
石燃料的利用率，這只是其中幾個例子。
Many different methods for heavy metal removal from aqueous solution have been
reported in the literature, such as adsorption,extraction , precipitation, neutralization,
dialysis, ion exchange and complexing agent modified polymers, both in microbead
and membrane forms .
在文獻中，用於從水溶液中去除重金屬的方法如，吸附，萃取，沉澱，中和，透
析，離子交換和錯和劑的改良聚合物等，無論是以微珠或薄膜形式[4-9]中已報導
了許多不同的方法
Among these techniques, adsorption is generally preferred for the heavy metal
removal due to availability of different adsorbents, its high efficiency, easy handling
and low cost possibilities.
在這些技術中，由於吸附法由於可以有不同的吸附劑且有著高效率，易於操作，
成本低的優點使其被用於重金屬去除。
So many researches dealing with toxic metal ion removal by using chelating polymers
has a great importance in environmental applications.
因此，許多研究使用螯合高分子來處理去除有毒金屬離子,這對環境應用有著很
大的重要性。
A large number of polymers incorporating a variety of ligands including
polyethyleneimine, amidoxime, acrylamide,
thiazolidine,phosphoricacid,dithiocarbamate and amino acids have been prepared and
their adsorption and analytical properties were investigated.
大量的聚合物組成的配位基，包括各種聚乙烯亞胺，胺肟，丙烯醯胺，噻唑烷，
磷酸，二硫代氨基甲酸鹽類和氨基酸已準備和其吸附和分析性能進行了研究
[18-28]。
An expensive and critical step in this preparation process is coupling of a ligand to the
adsorption matrix.
The major issue is that of slow release of these covalently bonded chelators off the
matrix.
在此製備過程中的一個昂貴的和關鍵的一步的配位體的耦合的吸附基質。
主要的問題是，這些緩慢釋放的共價鍵螯合劑關閉了基質。
Release is a general problem encountered in any ligand chelation technique which
caused a decrease in chelation capacity.
釋放是在配位基螯合技術過程中造成螯合容量減少常會發生的問題。
The time consuming and high cost of chelating procedure has inspired a search for
suitable low cost adsorbents.
螯合過程耗費的時間和成本高的激發了尋找合適低成本吸附劑。
Hence, in the presented study,we have tried to develop chelating beads for the
assembly of a new class of novel heavy metal adsorbents. It is showed that
poly(VP-PEGMA-EGDMA) beads can be used directly for heavy metal removal.
因此，在本研究中，我們試圖發展在螯合珠粒中裝配一類新型的重金屬吸附劑。
而聚（VP-PEGMA-二甲基丙烯酸乙二酯）顆粒可直接用於重金屬的去除。
This approach for the preparation of metal-chelating matrix has so many advantages
over conventional preparation techniques; those needed the activation of the matrix
for metal-chelating ligand immobilization.
這種方法用於製備金屬螯合基質比起傳統的製備技術具有許多的優點，所需要的
活化的基質金屬螯合配位體固定化。
So, according to this procedure, comonomer VP has a role as the metal-chelating
ligand, and there is no extra need to activate the matrix for the chelating-ligand
immobilization.
因此，根據此過程中，共聚單體VP具有作為金屬螯合配位基的作用，並且也沒
有多餘的需要活化的螯合配位基的固定基質。
I was polymerized with PEGMA and EGDMA without chelating ligand
immobilization step and also there is no leakage of the ligand.
我PEGMA和EGDMA聚合沒有螯合配位基固定步驟，也沒有洩漏的配體。
In the presented work, possible usage of poly(VP-PEGMA-EGDMA) for heavy metal
usage has been discussed.
在所提出的工作，重金屬使用聚（VP-PEGMA-二甲基丙烯酸乙二酯）的可能的
使用進行了討論。
2. Experimental 實驗步驟?
2.1. Materials 材料
1.Poly (ethylene glycol) methacrylate (PEGMA)
2.Vinyl pyridine (VP), selected as the reactive comonomer,
3.Ethylene glycol dimethacrylate (EGDMA) was used as the cross-linking agent as
supplied.
4.An initiator, benzoyl peroxide(BPO)
5.Toluene used as diluent(as a pore former).
6.Poly(vinyl alcohol) (PVA) used as the stabilizer.
7.Distilled deionized water was used in the preparation of the media for
polymerization and all adsorption experiments.
1.聚（乙二醇）甲基丙烯酸酯（PEGMA）
2.乙烯吡啶（VP），作為反應性共聚單體選擇，
3.乙二醇二甲基丙烯酸酯（EGDMA用作交聯劑。
4.一種起始劑，過氧化苯甲酰（BPO）
5.用甲苯作為稀釋劑（作為造孔劑）。
6.聚（乙烯醇）（PVA）作為穩定劑的使用。
7.去離子水，為製備聚合和所有吸附實驗的媒介。
2.2. Preparation of poly(VP-PEGMA-EGDMA) beads
製備poly(VP-PEGMA-EGDMA) 顆粒
Poly(VP-PEGMA-EGDMA) gel beads were prepared by using a suspension
polymerization method developed in previous studies.
使用在以前的研究中研製的懸浮聚合法製備聚（VP-PEGMA-二甲基丙烯酸乙二
酯）凝膠顆粒。
Table 1 gives the recipe and polymerization conditions for preparation of the
poly(VP-PEGMA-EGDMA) beads with a swelling ratio of 65% and in the size range
of 30–100m.
表1給出的配方和聚合反應條件用於製備聚（VP-PEGMA-二甲基丙烯酸乙二酯）
顆粒，溶脹比為65％，粒徑範圍在30-100微米。
2.3. Characterization of poly(VP-PEGMA-EGDMA) beads
poly(VP-PEGMA-EGDMA) 顆粒的
Water uptake ratio of the polymeric beads was determined in distilled water.
在蒸餾水中測定聚合物顆粒的水的吸收率。
The experiment was conducted as follows;initially dry beads were carefully weighed
before being placed in a 50ml vial containing distilled water.
進行實驗如下，一開始將乾燥顆粒稱重後放置於一個50ml且含蒸餾水的小玻璃瓶
中。
The vial was put into an isothermal water bath with a fixed temperature (25 ◦C) for
2 h.
將小瓶放入恆溫水浴中，在固定的溫度（25 ◦C）下放置2小時。
The bead samples were taken out from the water, wiped using a filter paper, and
weighed. The weight ratio of dry and wet samples was recorded.
將樣品從水中取出，用濾紙過濾，並稱重。記錄乾燥和濕樣品的重量比
The surface morphology of the beads was examined using scanning electron
microscopy (SEM).
用掃描式電子顯微鏡（SEM）檢查的顆粒的表面形態。
The samples were initially dried in air at 25 ◦C for 2 days before being analyzed.
A fragment of the dried bead was mounted on a SEM sample mount and was sputter
coated with gold for 2 min.
樣品在分析前在25度下的空氣中乾燥2天候，將乾燥後的SEM樣品顆粒鍍金，持
續2分鐘。
The sample was then mounted in a scanning electron microscope.
然後，將樣品裝在掃描型電子顯微鏡。
The surface of the sample was then scanned at the desired magnification to study the
morphology of the beads.
然後，對樣品表面的掃描所需的放大倍率，研究的顆粒的形態。
FTIR spectrophotometer,16 scans were taken at 4 cm−1 resolution.
Polymer samples were prepared by dispersing in dry KBr pellets and recorded
between 4600 and 400 cm−1.
用紅外分光光度計，採取了16次掃描4 cm-1的解析度。
製備聚合物樣品分散在無水KBr壓片，並記錄，在4600和400 cm-1處。
2.4. Adsorption studies吸附研究
Chelation of heavy metal ions from aqueous solutions was investigated in batch
experiments.
從水溶液中的重金屬離子螯合批次實驗研究。
Effects of the initial heavy metal ion concentration and pH of the medium on the
chelation rate and capacity were studied.
初始的重金屬離子濃度和pH值的介質上的螯合的速率和容量的影響進行了研
究。
100 ml aliquots of aqueous solutions containing different amounts of heavy metal ions
(in the range of 5–80 mg/l) were treated with the chelating beads.含有不同量的重金
屬離子的水溶液100毫升分裝用的螯合劑有孔玻璃珠
Chelation flasks were stirred magnetically at 250 rpm
磁力攪拌在250轉。
The suspensions were brought to the desired pH by adding sodium hydroxide (NaOH)
and hydrochloric acid (HCl).
The pH was maintained in a range of ±0.1 units until equilibrium was attained.
懸浮液經添加氫氧化鈉（NaOH）和鹽酸（HCl）到其所需的pH值的，pH值保持
在±0.1個單位的範圍內至達到平衡
The concentration of the sample was analyzed by using Flame Atomic Absorption
Spectrophotometer. The instrument response was periodically checked with known
heavy metal solution standards. The experiments were performed in replicates of three
and the samples were analyzed in replicates of three as well. Chelation experiments
were carried out at 25 ◦C. The amount metal ions adsorbed q (mg/g polymer) was
obtained as follows:
使用火焰原子吸收分光光度計分析樣品的濃度。校正儀器的靈敏度與已知的重金
屬溶液標準。重複進行實驗三次，並重複和三個樣品進行分析。
螯合實驗在25度下進行。可得到金屬離子吸附的量q（毫克/克聚合物）：
q = [(Co −C) × V]/m
where, Co and C are the initial and equilibrium concentrations(mg/l), respectively; V
is the volume of the aqueous phase (l);and m is the mass of the beads used (mg).
其中，Co和C是初始和平衡濃度（毫克/升），V是水相的體積（升），m為所使
用的顆粒重量（毫克）。
2.5. Elution and reuse洗脫和再利用
Elution efficiency from the polymer beads was measured for all the metals.
Elution of the metals from the polymer beads was carried out in 100 ml of 0.1M
HNO3 solution for 60 min.
測定所有金屬從聚合物顆粒洗脫的洗脫效率，。
聚合物顆粒在100毫升0.1M硝酸溶液中,60分鐘下洗脫金屬
The chelating beads adsorbed metal ions were placed in the elution medium and
stirred with a magnetic stirrer at 250 rpm at room temperature.
吸附金屬離子的螯合顆粒放置溶出介質中，用磁力攪拌器在室溫下以 250rpm 攪
拌。
The final metal ion concentration in the aqueous phase was determined by using a
flame atomic absorption spectrometer according to the guidelines of the
manufacturers.
根據各廠家的指引，用火焰原子吸收光譜儀測定最終金屬離子在水相中的濃度。
The elution ratio was calculated from the amount of metal ions adsorbed on the beads
and the final metal ions concentration in the desorption medium, by using the
following expression:
金屬離子在顆粒中吸附的量和最終的金屬離子脫附完的量，通過下面的可計算出
洗脫比：
Desorption ratio (%) = (A/B) × 100 (2)
Here, A is the amount of metal ions desorbed to the elution medium (mg) and B is the
amount of metal ions adsorbed on the microbeads (mg).
這裡，A是經洗脫介質脫附完金屬離子的量（毫克），B是金屬離子在顆粒吸附
的量（毫克）。
In order to determine the reusability of the chelating beads, consecutive chelation and
elution cycles were repeated 10 times by using the same chelating beads.
為了確定的螯合顆粒的可重複使用性，使用相同的螯合劑顆粒進行連續螯合(吸
附?)和洗脫，反覆進行10次。
3. Results and discussion
3.1. Properties of polymer beads 結果與討論
3.1。聚合物顆粒的性能
The suspension polymerization procedure provided
crosslinkedpoly(VP-PEGMA-EGDMA) beads in the spherical form in the size range
of 30–100μm.
由懸浮聚合過程中得到交聯的聚（VP-PEGMA-二甲基丙烯酸乙二酯）顆粒,其尺
寸範圍在30-100微米。
The surface morphology of polymer beads is investigated by the scanning electron
micrographs in Fig.1.
圖1.以SEM照攝的聚合物顆粒的表面形態圖。
Fig. 1. SEM micrograph of poly(VP-PEGMA-EGDMA) beads.
the diffusion of metal ions because of high internal surface area. This also provides
higher metal chelation capacity (Fig. 1).
金屬離子的擴散是由於有較高內表面積而這也提供了更高的金屬螯合能力（圖
1）。
The poly(VP-PEGMA-EGDMA) beads are cross-linked hydrophilic matrices, i.e.,
hydrogels;
therefore they do not dissolve in aqueous media, but do swell, depending on the
degree of crosslinking and on the hydrophilicity of the matrix.
聚（VP-PEGMA-EGDMA）顆粒是交聯了親水基，如:水膠;
因此，它們不溶解在水介質中，但會膨脹，這取決於交聯度和基體的親水性。
The equilibrium swelling ratio of the beads used in this study, which are prepared
with the recipe given in Table 1, is 65%.
在這項研究中，使用表1中給出的配方製備的顆粒，其平衡溶脹率為65％。
Compared with poly(PEGMA-EGDMA) (55%), the water uptake ratio of the
poly(VP-PEGMA-EGDMA) beads increases (65%).
相對於（PEGMA-二甲基丙烯酸乙二酯）（55％），聚（VP-PEGMA-二甲基丙
烯酸乙二酯）顆粒的水分吸收率增加（65％）。
Several possible factors may contribute to this result.
First, incorporating vinyl pyridine actually introduces more hydrophilic functional
groups into the polymer chain, which can attract more water molecules into the
polymer matrices. Second, reacting vinyl pyridine with PEGMA and EGDMA could
effectively decrease the molecular weight.
幾種可能的因素可能會導致這樣的結果。
首先，將乙烯基吡啶實際接上更多的親水性官能團到聚合物鏈中，它可以吸引更
多的水分子進入聚合物基質。其次， PEGMA和二甲基丙烯酸乙二酯跟乙烯基吡
啶反應，可以有效地降低分子量。
Therefore, the water molecules penetrate into the polymer chains more easily,
resulting in an improvement of polymer water uptake in aqueous solutions.
因此，水分子滲透到聚合物鏈更容易，從而改善了聚合物在水溶液中的水分吸收。
It should be also noted that these beads are quite rigid and strong enough due to the
highly cross-linked structure, so they are suitable for packed bed column applications.
還應該注意的是這些顆粒是具有相當的堅硬和足夠強來應付高度交聯的結構，因
此它們適用於填充床柱應用。
Number-average diameter of poly(VP-PEGMA-EGDMA) and
poly(PEGMA-EGDMA) were 57.66 and 54.55 m, respectively. The coefficient of
variation values of poly(VPPEGMA-EGDMA) and poly(PEGMA-EGDMA) were
31.20% and 36.00%, respectively.
聚（VP-PEGMA-二甲基丙烯酸乙二酯）和聚（PEGMA-二甲基丙烯酸乙二酯）
的數均直徑分別為57.66和54.55米。聚（VPPEGMA-二甲基丙烯酸乙二酯）和聚
（PEGMA-二甲基丙烯酸乙二酯）的係數的變化值分別為31.20％和36.00％
Although, the suspension polymerizations were performed identical conditions, VP
containing beads with slightly higher average size.
雖然，在條件相同的進行懸浮聚合，平均粒徑略高的含VP顆粒。
This result probably originated from the higher viscosity of VP based beads with
respect to the other.
這個結果可能由於從較高的粘度，VP為基礎的顆粒的其他方面。
The determined coefficient of variation values indicated that
poly(VP-PEGMA-EGDMA) beads had a narrower size distribution relative to the
poly(PEGMA-EGDMA) beads.
確定的係數的變化值表明，比起聚（PEGMA-二甲基丙烯酸乙二酯）顆粒，聚
（VP-PEGMA-二甲基丙烯酸乙二酯）顆粒的粒度分佈較窄，。
Note that the average size values and size distribution were determined in the aqueous
medium since the swollen bead size was significant for the intended application.
需要注意的是在水性介質中確定的平均粒徑值和粒度分佈，自膨脹的的顆粒大小
於其應用是顯著的。
In order to identify the polymeric structure, FTIR spectra of the
poly(VP-PEGMA-EGDMA) and poly(PEGMA-EGDMA) were taken (Fig. 2).
為了確定聚合物的結構，用紅外光譜來分析聚（VP-PEGMA-二甲基丙烯酸乙二
酯）和聚（PEGMA-二甲基丙烯酸乙二酯）（圖2）
Fig. 2. (a) FTIR spectra of poly(VP-PEGMA-EGDMA) beads and (b) FTIR
spectra of poly(PEGMA-EGDMA) beads.
FTIR spectra of poly(VP-PEGMAEGDMA) have the characteristic C=O stretching
bands belongs to ester functional group in the structure of EGDMA, appear at 1745
cm−1.
在poly(VP-PEGMAEGDMA)地IR圖中有代表是EGDMA特徵的C=O伸縮振動峰
(帶屬於酯官能團的結構)，出現在1745 cm-1處。
The C–O stretching bands appear between 1290 and 1100 cm−1 with wide and
medium effected peaks.
C-O伸縮振動峰出現在1290和1100 cm-1間
Also, between 3525 and 3200 cm−1 O–H stretching bands and between 3000 and
2800 cm−1 aliphatic C–H stretching bands appear for all spectra.
此外，在3525和3200 cm-1的O-H伸縮振動峰和在3000和2800 cm-1處的代表
脂肪族的C-H伸縮振動峰。
The most important point in these spectra is that it can be exactly seen the C–C and
C–N bands in the structure of pyridine between 1600 and 1430 cm−1.
在這些光譜中最重要的就是它可以準確地看到吡啶在1600和1430 cm-1處的結構
的C-C和C-N的吸收峰。
These peaks also can be seen in both surface and bulk structures. These data
confirmed that the poly(VP-PEGMA-EGDMA) beads were formed with functional
groups vinyl pyridine (Fig. 2).
這些峰也中可以看到表面和整體結構。這些數據證實，聚（VP-PEGMA-二甲基
丙烯酸乙二酯）顆粒，形成有乙烯基吡啶的官能團（圖2）。
To evaluate the amount of vinyl pyridine incorporation within the polymeric structure,
elemental analysis of the synthesized poly(VP-PEGMA-EGDMA) beads was
performed. C (%), H (%) and N (%) were found 59.92, 8.47 and 2.40, respectively.
The incorporation percentage of vinyl pyridine was found to be 2.40%, from nitrogen
stoichiometry.
評估在聚合物結構中乙烯基吡啶量的摻入，以合成聚（VP-PEGMA-二甲基丙烯
酸乙二酯）顆粒進行元素分析。C（％），H（％）和N（％）分別是9.92，8.47
和2.40。
The nitrogen amount that was found in elemental analysis only comes from the
incorporation of vinyl pyridine within the polymeric structure.
乙烯基吡啶的摻入百分比發現，從氮的化學計量比為2.40％。
元素分析中發現的氮的量，只加入來自乙烯基吡啶聚合物結構內。
Because,there is no nitrogen in the other monomers and chemicals used in the
polymerization. This result also showed that the copolymerization reaction was
exactly completed, as some vinyl pyridine monomers did not form part of the polymer
andwould have been removed during extensive washing.
因為，在聚合反應中使用的化學品和其它單體中沒有氮在。這一結果也表明，共
聚反應完全完成，而一部分沒有形成的聚合物的乙烯基吡啶單體在廣泛的洗滌過
程後被去除。
3.2. Adsorption of heavy metal ions吸附重金屬離子
Figs. 3–6 show the initial concentration of metal ions dependence f the adsorbed
amount of the Pb(II), Cd(II), Cr(III)nd Cu(II), relatively onto the both
poly(VP-PEGMA-EGDMA) and poly(PEGMA-EGDMA) beads.
圖3-6顯示比較聚（VP-PEGMA-二甲基丙烯酸乙二酯）和聚（PEGMA EGDMA）
顆粒對Pb（Ⅱ），鎘（II），鉻（III）和銅（II）金屬離子初始濃度的吸附量的
的依賴性
Adsorption of metal ions onto the poly(PEGMA-EGDMA) beads was very low, around
0.7 mg/g. Because there is no any reactive functional groups in the poly(PEGMA-EGDMA)
structure for complexation of metal.
聚（PEGMA-二甲基丙烯酸乙二酯）顆粒對金屬離子的吸附是非常低的，大約
0.7毫克/克。因為在聚（PEGMA-二甲基丙烯酸乙二酯）的結構上沒有任何可使金
屬離子配位的活性官能團
But this low adsorption value of metal ions may be due to diffusion of metal ions into the
pores of the swollen matrix of the beads and weak interactions between metal ions and
hydroxyl groups on the surface of the poly(PEGMA-EGDMA) beads.
但是，這樣低的金屬離子吸附值可能是由於金屬離子擴散進入顆粒孔隙的溶脹基
或在聚（PEGMA-二甲基丙烯酸乙二酯）顆粒表面上羥基基團和金屬離子之間微
弱的相互作用。
However, VP incorporation into the polymeric structure significantly increased the
adsorption capacity up to 18.23 mg/g for Pb(II), 16.50 mg/g for Cd(II), 15.81 mg/g for
Cr(III) and 18.25 mg/g for Cu(II).
然而，含VP的聚合物其吸附能力增加為鉛（II）：18.23毫克/克，鎘（Ⅱ）：16.50
毫克/克，Cr（III）：15.81毫克/克和銅（II）：18.25毫克/克。
The adsorption values increased with increasing initial concentration of metal ions, and a
saturation value is achieved around ion concentration of 20 mg/l, which represents
saturation of the active binding sites on the poly(VPPEGMA-EGDMA)beads.
隨著初始濃度的增加，金屬離子的吸附值增加，在離子濃度為20毫克/升時吸附
值達到飽和
The order of these four kinds of metalion chelation on mass basis for the single component metals
isCu(II) >Pb(II) > Cd(II) > Cr(III). This affinity trend is presentedon the mass basis (mg) metal
chelation per gram beads and theseunits are important in quantifying respective metal capacities inreal
terms.
吸附量在不同金屬離子中Cu(II) >Pb(II) > Cd(II) > Cr(III)
Fig. 3. Adsorption of Pb(II) ions on the poly(VP-PEGMA-EGDMA) and
poly(PEGMA-EGDMA) beads; pH 6.0; temperature: 25 ◦C.
Fig. 4. Adsorption of Cd(II) ions on the poly(VP-PEGMA-EGDMA) and
poly(PEGMA-EGDMA) beads; pH 6.0; temperature: 25 ◦C.
Fig. 5. Adsorption of Cr(III) ions on the poly(VP-PEGMA-EGDMA) and
poly(PEGMA-EGDMA) beads; pH 6.0; temperature: 25 ◦C.
Fig. 6. Adsorption of Cu(II) ions on the poly(VP-PEGMA-EGDMA) and
poly(PEGMA-EGDMA) beads; pH 6.0; temperature: 25 ◦C.
3.3. Effect of pH on metal binding
The metal ion complexation of polymeric ligands is highlydependent on
theequilibrium pH of the medium.
聚合物配位基與金屬離子的錯合很大程度取決於介質的pH值的平衡。
In the absenceof metal chelating groups, the precipitation of the metal ionsis affected
by the concentration and form of solublemetalspecies.
在金屬螯合基的情況下，金屬離子的沉澱是受的可溶性金屬物種的形式和濃度。
The solubility of metal ions is governed by hydroxide or carbonate concentration.
Precipitation of metal ions becomes significant at high pHs for all metal ions.
金屬離子的溶解度是由氫氧化物或碳酸鹽濃度。
所有的金屬離子在高pH值下沉澱變成明顯。
The theoretical and experimental precipitation curves indicate that precipitation begins
above these pHs, which also depends on the concentration of metal ions in the medium.
Therefore, in our study, in order to establish the effect of pH on the chelation of metal ions
onto the chelating beads, we repeated the batch equilibrium studies at different pH in the
range of 2.0–10.0.
In this group of experiments, the initial concentration of metal ions was 20 mg/l for all
metal ions at 100 ml volume.
Fig.7 shows the pH effect. The chelation capacities of the chelating beads are 18.23 mg/g
for Pb(II), 16.50 mg/g for Cd(II), 17.38 mg/g for Cr(III) and 18.25 mg/g for Cu(II),
respectively. It appears that the newly synthesized chelating beads had the strongest
affinity for Cu(II). The affinity order of metal ions at initial concentration of 20 mg/l is
Cu(II) >Pb(II) > Cr(III) > Cd(II).
沉澱曲線的理論和實驗表明，以上這些pH值，這也取決於在介質中的金屬離子
的濃度開始沉澱。
因此，在我們的研究中，為了建立pH值對金屬離子的螯合到螯合顆粒的效果，
我們重複的批量平衡的研究，在不同的pH值在2.0-10.0的範圍內。
在這組實驗中，金屬離子的初始濃度為20毫克/升，在100毫升體積的所有金屬離
子。
圖7顯示pH值的影響。的螯合能力的螯合劑有孔玻璃珠為18.23毫克/克的鉛（II），
16.50毫克/克，鎘（Ⅱ），17.38毫克/克的Cr（III）和18.25毫克/克的銅（II），分
別。似乎新合成的螯合劑顆粒，對銅（II）的親和力最強。金屬離子的初始濃度
為20毫克/升的親和力順序是銅（II）>鉛（II）鉻（III）>鎘（Ⅱ）。
Poly(VP-PEGMA-EGDMA) chelating beads exhibited a low affinity for heavy metal ions
in acidic conditions (pH < 4.0), a somewhat higher affinity between pH 6.0 and 8.0.
具（VP-PEGMA-EGDMA）螯合珠具有較低的親和力，對重金屬離子在酸性條件
下（pH值<4.0），pH為6.0和8.0之間的親和力稍高。
The difference in chelation behaviour of heavy metal ions can be explained by the different
affinity of heavy metal ions for the donor atoms (i.e., nitrogen) in the VP.
重金屬離子螯合行為的差異可以被解釋，在VP的供電子原子對重金屬離子的親
和力的不同。
In the case of poly(PEGMA-EGDMA) beads,adsorption is pH independent.
吸附在聚（PEGMA-二甲基丙烯酸乙二酯）顆粒的情況下，pH值是獨立的。
But it is indicated that the adsorption of metal ions onto the poly(VP-PEGMA-EGDMA)
beads was pH dependent.
但它表明金屬離子的吸附在poly（VP-PEGMA-二甲基丙烯酸乙二酯）
顆粒的pH依賴性。
3.4. Elution and repeated use 洗脫和反覆使用
The repeated use of the polymer beads is a key factor in improving process
economics.
聚合物珠粒的重複使用是提高經濟方法的關鍵因素。
Elution of the adsorbed metal ions from the poly(VP-PEGMA-EGDMA) beads was also
studied in batch experiments.
在批次實驗中，還研究了吸附了金屬離子的聚（VP-PEGMA-二甲基丙烯酸乙二
酯）顆粒的洗脫。
The poly(VP-PEGMA-EGDMA) beads loading the maximum amounts of the respective
metal ions were placed within the elution medium containing 0.1M HNO3 and the amount
of metal ions desorbed in 1 h was measured.
將吸附了金屬離子最大值的 聚（VP-PEGMA-二甲基丙烯酸乙二酯）顆粒，放置
在含有0.1M HNO溶出介質中脫附1小時。
The elution efficiency was then calculated.
計算洗脫效率.
Elution efficiencies were very high (up to 92%) with the elution agent and conditions used
for all metal ions.
At the other conditions such as 30 min and 50 ml, the recoveries are not quantitative.
洗脫效率非常高（高達92％）的洗脫劑和用於所有的金屬離子的條件下。
上面的其他條件，如30分鐘和50毫升，回收率不定量。
It must be pointed out that in metal chelating systems;chelation (i.e., binding of heavy
metal ions with vinyl pyridine) is completely reversible.
In order to obtain the reusability of the poly(VP-PEGMA-EGDMA) beads,
chelation–elution cycle was repeated 10 times by using the same adsorbent. As shown in
Fig. 8, the adsorbents were reused for subsequent chelation–elution cycles with
comparable chelation efficiencies over 10 cycles.
必須指出的是，在金屬螯合劑系統;螯合（即，結合重金屬離子與乙烯基吡啶）
是完全可逆的。
為了獲得可重用性的聚（VP-PEGMA-二甲基丙烯酸乙二酯）顆粒，通過使用相
同的吸附劑，螯合洗脫循環重複10次，。
在圖8，比較超過10次吸附-脫附的螯合效率。
Fig. 8. Heavy metal ions adsorption capacity of poly(VP-PEGMA-EGDMA)
beads after repeated adsorption–desorption cycle; initial concentration of metal
ions: 20 mg/l; pH 6.0; temperature: 25 ◦C.
4. Conclusion
Adsorption technology enables the use of polymeric chelating beads for rapid,
cost-effective and selective heavy metal removal.
In this study, chelating beads were prepared and, was applied to the removal of lead,
cadmium, chromium and copper ions from aqueous solutions.
吸附技術可以使用的聚合物螯合顆粒為快速的，成本效益的和有選擇性的去除重
金屬。
在本研究中製備了螯合顆粒應用於從水溶液中去除鉛，鎘，鉻和銅離子。
In this study, we focused our attention on the development of metal-chelating beads
for the assembly of new adsorbents. This approach for the preparation of
metal-chelating matrix has many advantages over conventional preparation techniques;
those needed the activation of the matrix for metal-chelating ligand immobilization.
In this procedure, comonomer VP acted as the metal-chelating ligand, and there is no
need to activate the matrix for the chelating ligand immobilization. Metal-chelating
ligand immobilization step was also eliminated.
VP was polymerized with EGDMA and PEGMA.
There is no leakage of the ligand also.
These results suggest that poly(VP-PEGMA-EGDMA) beads may be good heavy
metal adsorbers and have great potential applications in environmental protection.
The new adsorbent has higher adsorption properties than other adsorbents used in
previous works in literature [34–38].
在這項研究中，我們集中注意力的發展金屬螯合微珠的裝配新的吸附劑。這種方
法用於製備金屬螯合矩陣的常規製備技術相比有許多優點，所需要的活化的基質
金屬螯合配位體的固定化。
共聚單體VP在此過程中，作為金屬螯合配位體，沒有必要激活的螯合配位體的
固定基質。金屬螯合配體固定步驟也被淘汰。
VP與EGDMA和PEGMA一起聚合，。
有沒有洩漏的配位體也。
這些結果表明，聚（VP-PEGMA-EGDMA）微珠可能是良好的重金屬吸附，並
在環保中的應用有很大的潛力。
新型吸附劑具有較高的吸附性能比過去的作品在文獻[34-38]中使用的其他吸附
劑。