離子交換樹(shù)脂對(duì)水中高氯酸根的吸附及其機(jī)理研究

曲宏斌，萬(wàn)東錦，肖書(shū)虎，章麗萍，劉瑞霞

1.中國(guó)礦業(yè)大學(xué)(北京)化學(xué)與環(huán)境工程學(xué)院，北京　1000832.中國(guó)環(huán)境科學(xué)研究院城市水環(huán)境科技創(chuàng)新基地，北京　1000123.河南化工大學(xué)化工學(xué)院，河南 鄭州　450001

?

離子交換樹(shù)脂對(duì)水中高氯酸根的吸附及其機(jī)理研究

曲宏斌1,2，萬(wàn)東錦3，肖書(shū)虎2*，章麗萍1，劉瑞霞2

1.中國(guó)礦業(yè)大學(xué)(北京)化學(xué)與環(huán)境工程學(xué)院，北京1000832.中國(guó)環(huán)境科學(xué)研究院城市水環(huán)境科技創(chuàng)新基地，北京1000123.河南化工大學(xué)化工學(xué)院，河南 鄭州450001

摘要通過(guò)對(duì)比幾種常用的離子交換樹(shù)脂，篩選出處理的最佳樹(shù)脂。研究表明：氯型717陰離子交換樹(shù)脂(Cl717)表現(xiàn)出較好的吸附效果，其吸附動(dòng)力學(xué)符合偽二級(jí)動(dòng)力學(xué)模型，吸附等溫線(xiàn)符合Langmuir吸附等溫式，屬于單層吸附；升高溫度和增加投加量有利于Cl717對(duì)的吸附；共存陰離子對(duì)Cl717吸附產(chǎn)生抑制作用，干擾能力依次為

關(guān)鍵詞離子交換樹(shù)脂；；水處理；吸附動(dòng)力學(xué)；吸附機(jī)理

1材料與方法

1.1試驗(yàn)材料

表1　3種樹(shù)脂的技術(shù)參數(shù)

1.2試驗(yàn)方法

1.2.1吸附動(dòng)力學(xué)試驗(yàn)

分別稱(chēng)取0.05 g的3種樹(shù)脂于3個(gè)250 mL的錐形瓶中，各加入200 mL濃度為20 mgL的高氯酸鈉溶液。將錐形瓶于恒溫振蕩箱(298 K、180 rmin)中振蕩，分別于15、30、45、60、90、120、180、360、480和600 min時(shí)取樣，經(jīng)0.45 μm濾膜過(guò)濾，檢測(cè)的濃度。

1.2.2吸附平衡試驗(yàn)

分別稱(chēng)取0.06 g的3種樹(shù)脂于一系列250 mL的錐形瓶中，加入濃度為20～130 mgL的高氯酸鈉溶液200 mL。混合液在恒溫振蕩箱(298 K、180 rmin)中振蕩24 h，用0.45 μm濾膜過(guò)濾，檢測(cè)的濃度，計(jì)算樹(shù)脂對(duì)的吸附容量。

1.2.3樹(shù)脂再生試驗(yàn)

對(duì)吸附效果最好的Cl717進(jìn)行再生，已知其總體積干交換量為3.5～3.6 mmolg，濕交換量為1.38～1.42 mmolmL，以氫氧化鈉溶液為再生劑。依據(jù)美國(guó)ASTM法測(cè)定樹(shù)脂的再生度[10]：用NaCl取代樹(shù)脂上的OH-，用HCl滴定流出液中的OH-，過(guò)量的HCl使樹(shù)脂充分轉(zhuǎn)變?yōu)镃l型，再用Na2SO4取代樹(shù)脂上的Cl-，最后用AgNO3滴定流出液中的Cl-。再生度的計(jì)算公式：

再生度=[(V1-V2)×NA×100(V3×NB)]×100%

式中：V1和V2分別為滴定至pH為9.0和3.9時(shí)所消耗的HCl量，mL；NA和NB分別為所消耗的HCl和AgNO3的濃度，mgL；V3為操作中所消耗的AgNO3量，mL。

1.3分析方法

2分析與討論

2.1吸附動(dòng)力學(xué)

注溶液初始濃度為20 mgL，樹(shù)脂投加量為0.20 gL，初始pH為7.20±0.10。圖1　298 K時(shí)離子交換樹(shù)脂吸附的吸附動(dòng)力學(xué)曲線(xiàn)Fig.1　Adsorption kinetics of perchlorate adsorbedby anion exchange resin at 298 K

一級(jí)反應(yīng)動(dòng)力學(xué)：

(1)

偽二級(jí)反應(yīng)動(dòng)力學(xué)：

(2)

粒內(nèi)擴(kuò)散模型：

qt=k3t0.5

(3)

式中：qe為平衡時(shí)吸附量，mgg；qt為t時(shí)刻吸附量，mgg；k1為一級(jí)吸附速率常數(shù)，min-1；k2為偽二級(jí)吸附速率常數(shù)，mg(g·min)[17]；k3為粒內(nèi)擴(kuò)散速率常數(shù)，mg(g·min0.5)。

表2　3種反應(yīng)動(dòng)力學(xué)模型在298 K時(shí)的擬合參數(shù)

注：qe exp為平衡時(shí)吸附量的試驗(yàn)值，mgg；qe cal為平衡時(shí)吸附量的擬合值，mgg。

2.23種樹(shù)脂的吸附等溫線(xiàn)

采用Langmuir 和Freundlich等溫吸附模型對(duì)298 K時(shí)3種樹(shù)脂的吸附能力進(jìn)行擬合，擬合后的參數(shù)如表3所示。

表3　298 K時(shí)等溫吸附參數(shù)

1)qe為平衡時(shí)吸附量，mgg；Ce為平衡時(shí)溶液中濃度，mgL；Q0為最大吸附量，mgg；K為吸附能量相關(guān)的常數(shù)，Lmg。2)KF為Freundlich吸附常數(shù)，(mgg)(Lmg)n；n為吸附常數(shù)。

注：吸附劑投加量為0.24 gL，吸附時(shí)間24 h，初始pH為7.20 ± 0.10。圖2　298 K時(shí)離子交換樹(shù)脂吸附的吸附等溫線(xiàn)Fig.2　Adsorption isotherms of perchlorate adsorbedby anion exchange resin at 298 K

2.3影響因素

2.3.1溫度的影響

表4　Cl717不同溫度下的吸附參數(shù)

注：同表3。

標(biāo)準(zhǔn)吉布斯函數(shù)由下述公式確定：

ΔGΘ=-RT·lnKL

(6)

式中：R為理想氣體常數(shù)，8.314 J(mol·K)；T為開(kāi)氏溫度，K；KL為L(zhǎng)angmiur常數(shù)，Lmol。標(biāo)準(zhǔn)摩爾焓變(ΔHΘ)和標(biāo)準(zhǔn)摩爾熵變(ΔSΘ)可以由范特霍夫回歸方程的斜率和截距確定。方程如下：

(7)

注：吸附劑投加量為0.08 gL，吸附時(shí)間為24 h，初始pH為7.20 ± 0.10。圖3　不同溫度下Cl717吸附的吸附等溫線(xiàn)Fig.3　Adsorption isotherms of perchlorate adsorbedby Cl717 at different temperature

溫度∕KlnKLΔGΘ∕(kJ∕mol)ΔHΘ∕(kJ∕mol)ΔSΘ∕〔J∕(mol·K)〕28810.27-24.5811.53125.3529810.40-25.8430810.61-27.1731810.71-28.30

2.3.2共存離子的影響

注：溫度為298 K，吸附時(shí)間為24 h，初始pH為7.20±0.10，平衡時(shí)pH為11.20±0.10。圖4　共存離子存在時(shí)對(duì)Cl717吸附的影響Fig.4　Effects of perchlorate adsorbed by Cl717when competitive anion exists

2.3.3投加量的影響

圖5　Cl717投加量對(duì)去除率和吸附容量的影響Fig.5　Effect of Cl717 resin dosage on removal rate

2.3.4再生試驗(yàn)

分別用0.54、1.08、1.62、2.16、3.25 molL的NaOH溶液，對(duì)失效的Cl717進(jìn)行再生，結(jié)果見(jiàn)圖6。由圖6可見(jiàn)，隨著NaOH溶液濃度和用量的增加，樹(shù)脂再生度逐漸增大。NaOH溶液濃度為3.25 molL，用量為樹(shù)脂體積的7倍時(shí)，再生度達(dá)89%以上，樹(shù)脂再生效果基本令人滿(mǎn)意。但由于再生液濃度過(guò)高會(huì)導(dǎo)致樹(shù)脂破碎率增加，故試驗(yàn)得出最佳再生液濃度為2.16 molL，再生液用量為樹(shù)脂體積的5倍。

圖6　再生液濃度、用量與再生度的關(guān)系Fig.6　The relationship between the concentration ofregenerate liquid, the dosage and the degree of regeneration

2.4紅外光譜分析

圖7　Cl717吸附前后紅外光譜Fig.7　Infrared spectrum diagram beforeand after adsorption by Cl717

3結(jié)論

(4)再生試驗(yàn)表明：堿法再生方法可行，最佳再生液濃度為2.16 molL，再生液用量為樹(shù)脂體積的5倍。

參考文獻(xiàn)

[1]邱華.高氯酸鹽污染地下水生物修復(fù)研究[D].長(zhǎng)春:吉林大學(xué),2015.

[2]盧寧,高乃云,楚文海.離子色譜法測(cè)定飲用水中痕量高氯酸根的數(shù)學(xué)分析[J].同濟(jì)大學(xué)學(xué)報(bào)(自然科學(xué)版),2009,37(9):1203-1206.

LU N,GAO N Y,CHU W H.Mathematical analysis of an ion chromatography determination for trace level perchlorate in drinking water[J].Journal of Tongji University(Natural Science),2009,37(9):1203-1206.

[3]胡洪營(yíng),吳乾元,楊揚(yáng),等.面向毒性控制的工業(yè)廢水水質(zhì)安全評(píng)價(jià)與管理方法[J].環(huán)境工程技術(shù)學(xué)報(bào),2011,1(1):46-51.

HU H Y,WU Q Y,YANG Y,et al.Evaluationand management methods for toxicity control of industrial wastewater[J].Journal of Environmental Engineering Technology,2011,1(1):46-51.

[4]GULLICK R W,LECHEVALLIER M W,BARHORST T S.Occurrence of perchlorate in drinking water sources[J].Journal American Water Works Association,2001,93:66-77.

[5]THEODORAKIS C,RINCHARD J,ANDERSON T,et al.Perchlorate in fish from a contaminated site in east-central Texas[J].Environmental Pollution,2006,139:59-69.

[6]SHI Y,ZHANG P,WANG Y,et al.Perchlorate in sewage sludge,rice,bottled water and milk collected from different areas in China[J].Environment International,2007,33:955-962.

[7]劉勇建,牟世芬,林愛(ài)武,等.北京市飲用水中溴酸鹽、鹵代乙酸及高氯酸鹽研究二維離子色譜法同時(shí)測(cè)定環(huán)境水樣中的碘離子、硫氰酸根和高氯酸根[J].環(huán)境科學(xué),2004,25(2):51-55.

LIU Y J,MU S F,LIN A W,et al.Investigation of bromate,haloacetic acids and perchlorate in Beijing′s drinking water[J].Environmental Science,2004,25(2):51-55.

[8]林立,王海波,史亞利.二維離子色譜法同時(shí)測(cè)定環(huán)境水樣中的碘離子、硫氰酸根和高氯酸根[J].色譜,2013,31(3):281-285.

LIN L,WANG H B,SHI Y L.Determination of iodide,thiocyanate and perchlorate ions inenvironmental water by two-dimensional ion chromatography[J].Chinese Journal of Chromatography,2013,31(3):281-285.

[9]高乃云,李富生,湯淺晶,等.去除飲用水中高氯酸鹽的研究進(jìn)展[J].中國(guó)給水排水,2003,19(7):47-49.

[10]朱躍,宋玉棟,劉儀生,等.循環(huán)流一體式生物反應(yīng)器處理ABS樹(shù)脂生產(chǎn)廢水[J].環(huán)境工程技術(shù)學(xué)報(bào),2014,4(5):367-372.

ZHU Y, SONG Y D, LIU Y S, et al. Treatment of ABS resin wastewater with integrated cycling bioreactor[J]. Journal of Environmental Engineering Technology, 2014,4(5):367-372.

[11]陳家俊.顆粒活性炭氮官能化制備低濃度高氯酸鹽去除材料的應(yīng)用研究[D].長(zhǎng)沙:湖南大學(xué),2013.

[12]柴麗敏.大孔弱堿性陰離子交換樹(shù)脂D301R處理DSD酸還原廢水的研究[D].天津:天津大學(xué),2005.

[13]單永平,曾萍,宋永會(huì),等.樹(shù)脂吸附法處理黃連素模擬廢水[J].環(huán)境工程技術(shù)學(xué)報(bào),2011,1(4):300-304.

SHAN Y P,ZENG P,SONG Y H,et al.Treatment of simulated berberine wastewater using resin adsorption[J].Journal of Environmental Engineering Technology,2011,1(4):300-304.

[14]賴(lài)波,周岳溪.ABS廢水中芳香類(lèi)污染物在微電解處理前后的熒光特征變化[J].環(huán)境工程技術(shù)學(xué)報(bào),2012,2(2):90-95.

LAI B,ZHOU Y X.Fluorescence characteristics variation of the aromatic pollutants in ABS wastewater before and after degradation by micro-electrolysis[J].Journal of Environmental Engineering Technology,2012,2(2):90-95.

[15]王春麗,吳俊奇,宋永會(huì),等.活化赤泥顆粒吸附除磷的效能與機(jī)制研究[J].環(huán)境工程技術(shù)學(xué)報(bào),2015,5(2):143-148.

WANG C L,WU J Q,SONG Y H,et al.Research on performance and mechanisms of activated red mud particleson adsorbing and removing phosphorus[J].Journal of Environmental Engineering Technology,2015,5(2):143-148.

[17]HO Y S,MCKAY G.The kinetics of sorption of divalent metal ions onto sphagnum moss peat[J].Water Research,2000,34:735-742.

[18]WAN D,LIU Y,XIAO S,et al.Uptake fluoride from water by caclined Mg-Al-CO3hydrotalcite:MgAl ratio effect on its structure,electrical affinity and adsorptive property[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2015,469:307-314.

[19]熊利芝,李佳焱,王家堅(jiān),等.D-101大孔吸附樹(shù)脂對(duì)黃花蒿黃酮的吸附熱力學(xué)和動(dòng)力學(xué)研究[J].離子交換與吸附,2014,30(4):334-342.

XIONG L Z,LI J Y,WANG J J,et al.Adsorption thermodynamics and kinetics of artemisia annua flavonoids adsorbed on macroporous adsorbent resins D-101[J].Ion Exchange and Adsorption,2014,30(4):334-342.

[21]張莉祥,楊志泉,李婷,等.改性橘子皮對(duì)水中高氯酸鹽及共存陰離子的競(jìng)爭(zhēng)吸附研究[J].環(huán)境科學(xué)學(xué)報(bào),2015,35(10):3137-3143.

ZHANG L X,YANG Z Q,LI T,et al.Competitive adsorption of perchlorate and coexisting anions from water by modified orange peels[J].Acta Scientiae Circumstantiae,2015,35(10):3137-3143.

[22]朱蕾,蘇艷.傅里葉紅外光譜分析在環(huán)境試驗(yàn)中的應(yīng)用[J].環(huán)境技術(shù),2002(3):5-9.

ZHU L,SU Y.Application of fourier transform infrared spectroscopy(FTIR)analysis in environmental testing[J].Environmental Technology,2002(3):5-9.

[23]馬楠楠,趙娟,陳福花.紅外與化學(xué)法聯(lián)用表征環(huán)氧樹(shù)脂環(huán)氧值[J].玻璃鋼復(fù)合材料,2013(5):3-6. ○

Study on Adsorption of Perchlorate by Anion Exchange Resins and Its Mechanisms

QU Hongbin1,2, WAN Dongjin3, XIAO Shuhu2, ZHANG Liping1, LIU Ruixia2

1.School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing 100083, China2.Department of Urban Environmental Research, Chinese Research Academy Environmental Sciences, Beijing 100012, China3.School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China

AbstractSeveral commonly used ion exchange resins were compared and the optimal resins to absorb perchlorate were screened out. It showed that Cl717 anion exchange resin acquired the best adsorption efficiency. The adsorption process attributed to the pseudo second order kinetics model, and the equilibrium isotherm for perchlorate uptake corresponded closely to the Langmuir model, belonging to the adsorption type of single layer. The increase of temperature and dosage was beneficial to the adsorption. Co-existed anions could affect the adsorption process with the interference order of

Key wordsexchange resin; perchlorate; water treatment; adsorption kinetics; adsorption mechanism

收稿日期：2016-01-11

基金項(xiàng)目:國(guó)家自然科學(xué)基金項(xiàng)目(21277134，21107103)；環(huán)境基準(zhǔn)與風(fēng)險(xiǎn)評(píng)估國(guó)家重點(diǎn)實(shí)驗(yàn)室自由探索基金

作者簡(jiǎn)介：曲宏斌(1990—)，男，碩士研究生，主要從事水污染控制技術(shù)研究，1151337802@qq.com *責(zé)任作者：肖書(shū)虎(1979—)，男，副研究員，博士，主要從事水質(zhì)凈化技術(shù)與原理研究，xiaoshuhu@126.com

中圖分類(lèi)號(hào):X703

文章編號(hào):1674-991X(2016)04-0343-07

doi:10.3969?j.issn.1674-991X.2016.04.051

曲宏斌，萬(wàn)東錦，肖書(shū)虎,等.離子交換樹(shù)脂對(duì)水中高氯酸根的吸附及其機(jī)理研究[J].環(huán)境工程技術(shù)學(xué)報(bào),2016,6(4):343-349.

QU H B, WAN D J, XIAO S H, et al.Study on adsorption of perchlorate by anion exchange resins and its mechanisms[J].Journal of Environmental Engineering Technology,2016,6(4):343-349.