丁春生,苗世茂,趙世督,肖毛虎,鄒勝男 (浙江工業(yè)大學(xué)建筑工程學(xué)院,浙江 杭州 310014)

O3/GAC降解飲用水中2,6-二氯-1,4-苯醌的研究

丁春生*,苗世茂,趙世督,肖毛虎,鄒勝男 (浙江工業(yè)大學(xué)建筑工程學(xué)院,浙江 杭州 310014)

為了降低飲用水在消毒過(guò)程中產(chǎn)生的消毒副產(chǎn)物(DBPs)2,6-二氯-1,4-苯醌(2,6-DCBQ)對(duì)人體健康帶來(lái)的危害,以 2,6-DCBQ為研究對(duì)象,采用O3/GAC聯(lián)合工藝,系統(tǒng)地研究了2,6-DCBQ的控制技術(shù),并分析和探討了其降解機(jī)理及動(dòng)力學(xué)規(guī)律.結(jié)果表明,單獨(dú)臭氧(O3)和單獨(dú)顆粒活性炭(GAC)對(duì)2,6-DCBQ的去除率分別為29.64%和32.81%,降解效果一般.而O3/GAC聯(lián)合工藝可以有效地降解2,6-DCBQ,其降解效果隨著初始濃度、O3濃度以及GAC的投加量的增大而提高.當(dāng)2,6-DCBQ初始濃度為20μg/L,O3濃度為10.06mg/L,GAC投加量為0.5g/L時(shí),反應(yīng)90min后,2,6-DCBQ降解效率達(dá)到84.93%.O3/GAC聯(lián)合工藝降解 2,6-DCBQ的過(guò)程符合一級(jí)反應(yīng)動(dòng)力學(xué)規(guī)律.

消毒副產(chǎn)物；2,6-DCBQ；O3/GAC聯(lián)合工藝；動(dòng)力學(xué)

飲用水消毒過(guò)程中產(chǎn)生的消毒副產(chǎn)物已引起世界各國(guó)的廣泛關(guān)注[1-3],其中大部分具有嚴(yán)重的致癌、致畸和致突變作用[4-7].鹵代苯醌(HBQs)是一類新發(fā)現(xiàn)的飲用水氯化消毒副產(chǎn)物,有研究稱水體中的苯酚是 HBQs的前體物[8-9]. 2009年,Plewa等[10-11]首次在氯和氯胺消毒飲用水中發(fā)現(xiàn)了二氯苯醌(DCBQ).目前國(guó)內(nèi)外尚無(wú)有關(guān)HBQs的系統(tǒng)研究,國(guó)外對(duì)它的研究尚主要局限于毒理學(xué)方面.

相關(guān)研究表明[12],HBQs的毒性約為常規(guī)的消毒副產(chǎn)物三鹵甲烷和鹵乙酸的 1000倍,且HBQs能與蛋白質(zhì)和DNA基因物質(zhì)等生物活性分子反應(yīng),表明其有潛在基因毒性[13].結(jié)構(gòu)定量毒性關(guān)系分析表明,HBQs是一類可能的膀胱癌致癌物質(zhì)[14-15],能誘導(dǎo)產(chǎn)生一類活性氧化物質(zhì)(ROS)對(duì)T24膀胱細(xì)胞造成DNA氧化損傷蛋白質(zhì)羰基化,脂質(zhì)過(guò)氧化,從而發(fā)生癌變.因此,HBQs已逐漸成為當(dāng)今DBPs研究的熱點(diǎn).

研究發(fā)現(xiàn),O3/GAC工藝與常規(guī)處理工藝相比,可以有效地減少含碳或含氮消毒副產(chǎn)物的生成量[16],表明GAC與O3聯(lián)用時(shí),降解效果比單一工藝更好,在該反應(yīng)體系中 O3具有強(qiáng)氧化性,能有效地將苯環(huán)開環(huán)并轉(zhuǎn)化為易于GAC吸附的中間產(chǎn)物,增強(qiáng)了GAC吸附能力[17-20].

本研究采用 O3/GAC降解2,6-DCBQ,并在不同的條件下分析其降解效果和動(dòng)力學(xué)規(guī)律.

1 材料與方法

1.1 試劑、儀器與試驗(yàn)裝置

試驗(yàn)試劑與材料：2,6-二氯-1,4-苯醌標(biāo)準(zhǔn)品、甲基叔丁基醚(MTBE)、高純氧(純度≥99.999%)、顆?；钚蕴?、鹽酸、無(wú)水硫酸鈉、氫氧化鈉、稀硝酸、碘化鉀、硫代硫酸鈉、淀粉、0.45μm微孔濾膜和純凈水.

試驗(yàn)所用主要儀器：Aglent1200型高效液相色譜儀、G1314C VWD-SL型可變波長(zhǎng)檢測(cè)器和G13298自動(dòng)進(jìn)樣器(安捷倫科技有限公司)、臭氧發(fā)生器、BS223S型電子天平(Sartorius公司)、DHG-9146A型電熱恒溫鼓風(fēng)干燥箱(上海精宏試驗(yàn)設(shè)備有限公司)、1000μL移液槍(dragon公司)、IKS KS 130basic型恒溫往復(fù)式搖床(IKS公司)、HYG- II Refrigerator shaker型恒溫振蕩器(華利達(dá)公司).

試驗(yàn)裝置：如圖1所示,主要由干燥器、攪拌器、反應(yīng)器(直徑為18cm,高為25cm)、氧氣瓶、臭氧發(fā)生器、臭氧擴(kuò)散裝置及尾氣處理裝置等組成.

圖1 反應(yīng)裝置及流程示意Fig.1 The reactor and flow chart

1.2 試驗(yàn)配水

用甲醇將2,6-二氯-1,4-苯醌(2,6-DCBQ)稀釋成10μg/mL的母液,儲(chǔ)存于棕色瓶中并在低溫條件下保藏,用去離子水將母液稀釋成要求濃度作為試驗(yàn)水樣.

1.3 水樣的預(yù)處理

準(zhǔn)確量取25mL待測(cè)水樣直接加入到40mL且已經(jīng)裝有 8g無(wú)水硫酸鈉(已在電熱恒溫鼓風(fēng)干燥箱中 118℃下干燥 24h)的樣品瓶中,立即搖動(dòng)使完全溶解.加入2mL甲基叔丁基醚后進(jìn)行密封,放在恒溫往復(fù)式搖床上搖晃 5min,然后靜置5min,目的是讓有機(jī)相和水相明顯分層,取上層液.萃取兩次,合并有機(jī)相,室溫下用溫和氮?dú)獯抵两?加1mL甲醇定容后進(jìn)入HPLC中分析檢測(cè).

1.4 分析條件

以甲醇和純凈水(含 0.1%甲酸)作為流動(dòng)相,甲醇與水的體積比為 50：50,流速為 0.4mL/min,柱溫設(shè)置為30 ,℃色譜柱選用Eclipse XDB-C18 (4.6m×150mm,5μm,USA Agilent Technologies)毛細(xì)管色譜柱,檢測(cè)波長(zhǎng)為 274nm,進(jìn)樣體積為20μL等度洗脫,時(shí)間為7min.

標(biāo)準(zhǔn)曲線的相關(guān)系數(shù)R2=0.9992＞0.999,存在良好的線性關(guān)系,加標(biāo)回收率為93.1%～104.95%,相對(duì)標(biāo)準(zhǔn)偏差為4.19%～8.72%,均符合EPA552.3方法[21]中規(guī)定值的要求,準(zhǔn)確度較高.

2 結(jié)果與討論

2.1 單獨(dú)GAC及O3降解2,6-DCBQ的效果分析

準(zhǔn)確量取定量的2,6-DCBQ母液,分別配制濃度均為20μg/L的溶液,作為試驗(yàn)水樣.2種單一工藝的工況條件為：GAC吸附工藝中GAC投加量為 0.5g/L;O3氧化工藝中 O3投加濃度為10.06mg/L.每隔 15min取樣測(cè)定水樣中剩余的2,6-DCBQ的濃度,結(jié)果如圖2所示.

從圖2可知,單獨(dú)GAC及O3對(duì)2,6-DCBQ的去除率分別為 29.64%和 32.81%,這兩種工藝的去除效果一般.據(jù)文獻(xiàn)報(bào)道[22-23],O3主要是通過(guò)分解產(chǎn)生羥基自由基以及直接與物質(zhì)反應(yīng)兩種方法進(jìn)行有機(jī)物的去除.GAC的比表面積大、孔隙多,主要通過(guò)吸附作用去除2,6-DCBQ.

由圖2中的圖線斜率可知,在一定條件下,單獨(dú)GAC及O3具有相似的去除曲線,即在反應(yīng)前期(30min)的去除速率明顯高于反應(yīng)后期,這是因?yàn)樵诜磻?yīng)前期,O3的初始濃度較高,氧化分解2,6-DCBQ的速率較快;2,6-DCBQ初始濃度較高,單位質(zhì)量的活性炭周圍所包含的 2,6-DCBQ也就較多,吸附反應(yīng)也就越快.而在反應(yīng)后期,O3和2,6-DCBQ的濃度都有一定程度的下降,故反應(yīng)后期的去除速率較低.

圖2 單獨(dú)GAC、O3對(duì)2,6-DCBQ降解效果的影響Fig.2 2,6-DCBQ removal with individual GAC or O3

2.2 O3/GAC聯(lián)用降解2,6-DCBQ的效果分析

2.2.1 O3濃度對(duì) O3/GAC 聯(lián)用技術(shù)降解2,6-DCBQ的影響 準(zhǔn)確配制濃度為20μg/L的2,6-DCBQ溶液,GAC投加量控制為0.5g/L, O3濃度分別為 7.88、10.06、10.95、11.72mg/L,間隔15min取樣并檢測(cè)分析剩余2,6-DCBQ的濃度,結(jié)果如圖3所示.

從圖3可看出,O3濃度的變化對(duì)2,6-DCBQ的去除率有一定的影響.通入O3進(jìn)行反應(yīng)90min后,2,6-DCBQ的去除率分別為71.67%、80.51%、86.97%、89.92%.隨著 O3濃度的增大,去除率逐漸提高.

將圖 3中的曲線斜率進(jìn)行對(duì)比,在反應(yīng)開始至45min這段時(shí)間,2,6-DCBQ被降解的速度比較迅速,當(dāng)反應(yīng)接著進(jìn)行至 75min時(shí),2,6-DCBQ濃度下降趨于平緩.這可能因?yàn)?在反應(yīng)前一階段,2,6-DCBQ和O3濃度較高,二者的接觸面積較大,O3對(duì) 2,6-DCBQ氧化的速率較快,降低了GAC吸附的負(fù)荷,更有利于GAC的吸附[24],因此2,6-DCBQ的降解速率較快.而在反應(yīng)階段的后期,O3及2,6-DCBQ的濃度逐步降低,反應(yīng)速率也在降低,雖然2,6-DCBQ總的降解率仍在增加,但是增加的趨勢(shì)逐漸降低,直至降解率趨于穩(wěn)定.

圖3 O3/GAC聯(lián)合工藝中O3濃度對(duì)降解2,6-DCBQ效果的影響Fig.3 Effect of O3concentration on 2,6-DCBQ removal in O3/GAC

根據(jù)2,6-DCBQ的降解趨勢(shì),初步認(rèn)定O3對(duì)2,6-DCBQ的降解過(guò)程符合一級(jí)反應(yīng)動(dòng)力學(xué),則可按照一級(jí)反應(yīng)動(dòng)力學(xué)處理,即

對(duì)式子(1)兩邊進(jìn)行積分得到：

式中：k為反應(yīng)速率常數(shù); C2,6-DCBQ.0, C2,6-DCBQ(C0和C1)為2,6-DCBQ的初始濃度和反應(yīng)t時(shí)間后剩余的濃度.

圖4 不同O3濃度條件下ln(C0/C1)對(duì)時(shí)間的關(guān)系Fig.4 Variation of ln(C0/C1) with time at different O3concentration

將圖3中的數(shù)據(jù)進(jìn)行線性擬合,結(jié)果如圖4、表1所示.

表1 不同O3濃度條件下O3/GAC降解2,6-DCBQ的速率方程Table 1 The rate equations of 2,6-DCBQ degradation at different O3concentration in O3/GAC

由圖 4可知,不同 O3濃度條件下,ln(C.0/C1)與時(shí)間呈線性關(guān)系,相關(guān)系數(shù)均在0.97以上,且隨著 O3濃度的變化,所擬合直線的斜率不同,有關(guān)擬合所得到的速率方程、速率常數(shù)和相關(guān)系數(shù)如表1所示.當(dāng)O3濃度為7.88mg/L時(shí),反應(yīng)速率常數(shù)僅為0.0190,可當(dāng)達(dá)到11.72mg/L時(shí),反應(yīng)速率常數(shù)卻增加到0.0254,可見當(dāng)達(dá)到最佳O3濃度后,繼續(xù)增加O3濃度對(duì)降解2,6-DCBQ的反應(yīng)速度或者說(shuō)去除效果的影響不大[25].

2.2.2 GAC投加量對(duì) O3/GAC聯(lián)用技術(shù)降解2,6-DCBQ的影響 準(zhǔn)確配制濃度為20μg/L的2,6-DCBQ溶液, O3濃度控制為10.06mg/L,GAC投加量分別為 0.1、0.3、0.5、0.7、0.9g/L,間隔15min取樣并檢測(cè)分析剩余2,6-DCBQ的濃度,結(jié)果如圖5所示.

圖5 O3/GAC聯(lián)合工藝中GAC投加量對(duì)降解2,6-DCBQ效果的影響Fig.5 Effect of GAC dose on 2,6-DCBQ removal in O3/GAC

從圖 5可看出,改變 GAC的投加量對(duì) 2,6-DCBQ的去除率有著較大的影響.O3濃度控制為10.06mg/L,當(dāng)GAC投加量為0.1g/L時(shí),經(jīng)歷90min反應(yīng)時(shí)間后,去除率為64.56%;當(dāng)GAC投加量逐漸增大到0.9g/L時(shí),2,6-DCBQ的去除率達(dá)到93.72%,明顯提高了去除率.由此可知,當(dāng)GAC的投加量較少且達(dá)到吸附飽和后,可以采用增加GAC投加量的方式,使GAC繼續(xù)吸附2,6-DCBQ和其被O3氧化開環(huán)所形成的氧化副產(chǎn)物[16,26].因此,O3/GAC對(duì)2,6-DCBQ的去除率越來(lái)越高.

將圖5中的數(shù)據(jù)進(jìn)行線性擬合,結(jié)果如圖6、表2所示.

圖6 不同GAC投加量條件下ln(C0/C1)對(duì)時(shí)間的關(guān)系Fig.6 Variation of ln(C0/C1) with time at different GAC doses

表2 不同GAC投加量條件下O3/GAC降解2,6-DCBQ的速率方程Table 2 The rate equations of 2,6-DCBQ degradation at different GAC dosage in O3/GAC

由圖6知,不同GAC投加量下,ln(C0/C1)與時(shí)間呈線性關(guān)系,相關(guān)系數(shù)均在0.95以上,且隨著初始濃度的變化,所擬合直線的斜率不同,有關(guān)擬合所得到的速率方程、速率常數(shù)和相關(guān)系數(shù)如表2所示.當(dāng) GAC投加量為 0.1g/L時(shí),速率常數(shù)為0.0127,當(dāng)GAC投加量增加到0.9g/L時(shí),速率常數(shù)為0.0300,可見 GAC投加量的變化對(duì)去除 2,6-DCBQ的反應(yīng)速率或者去除效果影響很大.

由表1、表2可知,相關(guān)系數(shù)R2均大于0.917,即證明O3/GAC降解2,6-DCBQ符合一級(jí)反應(yīng)動(dòng)力學(xué).

2.2.3 初始濃度對(duì) O3/GAC聯(lián)用技術(shù)降解2,6-DCBQ的影響 分別配制濃度為10、20、50、80μg/L的2,6-DCBQ溶液, O3投加濃度控制為10.06mg/L,GAC 投加量控制為 0.5g/L,間隔15min取樣并檢測(cè)分析剩余2,6-DCBQ的濃度,結(jié)果如圖7所示.

圖7 O3/GAC聯(lián)合工藝中初始濃度對(duì)O3/GAC降解2,6-DCBQ去除率的影響Fig.7 Effects of initial concentration on 2,6-DCBQ removal in O3/GAC

由圖 7可知,2,6-DCBQ的去除率隨著初始濃度的增大而提高,同時(shí)隨著2,6-DCBQ初始濃度的遞增,反應(yīng)速率也逐漸加快.當(dāng)2,6-DCBQ初始濃度為10μg/L,反應(yīng)進(jìn)行90min后,2,6-DCBQ的去除率為80.04%.當(dāng)初始濃度逐漸增加至20、50、80μg/L時(shí),2,6-DCBQ 的去除率依次為84.93%、86.98%、87.96%.這表明GAC對(duì)2,6-DCBQ的吸附還未達(dá)到飽和狀態(tài),2,6-DCBQ的初始濃度越大,與 O3的接觸面積也越大,就越容易被 GAC吸附.除此之外,O3氧化分解一部分GAC上的2,6-DCBQ或?qū)⑵溟_環(huán)[20,26],更容易被GAC吸附,因此2,6-DCBQ的去除率得到了提高. 2.3 不同工藝降解2,6-DCBQ效果的比較

將單獨(dú)工藝與聯(lián)用技術(shù)對(duì)2,6-DCBQ的去除效果進(jìn)行對(duì)比,將初始濃度為20μg/L的2,6-DCBQ去除效果數(shù)據(jù)并進(jìn)行分析,結(jié)果如圖8所示.

圖8 不同工藝降解2,6-DCBQ的效果對(duì)比Fig.8 Comparison of 2,6-DCBQ removal by different processes

從圖 8可以看出,對(duì)于單獨(dú) O3降解2,6-DCBQ,當(dāng)O3濃度為10.06mg/L,2,6-DCBQ的去除率為32.81%;單獨(dú)GAC降解2,6-DCBQ,當(dāng)GAC投加量為 0.5g/L,2,6-DCBQ的去除率為29.64%;采用 O3/GAC聯(lián)用技術(shù),當(dāng) O3濃度為10.06mg/L,GAC投加量為 0.5g/L時(shí),2,6-DCBQ的去除率為84.93%,與單獨(dú)O3及單獨(dú)GAC相比, O3/GAC聯(lián)用明顯提高了對(duì)2,6-DCBQ的去除率,而且這不是單一工藝效果的簡(jiǎn)單疊加.這主要是因?yàn)?O3具有強(qiáng)氧化性,能夠?qū)⒊跗谝盐皆贕AC上的2,6-DCBQ的結(jié)構(gòu)打開變成小分子物質(zhì),釋放了GAC的吸附空隙,從而增強(qiáng)了GAC吸附能力,提高了去除效率[20,26,27].

3 結(jié)論

3.1 對(duì)于初始濃度為20μg/L的2,6-DCBQ溶液,在 GAC投加量為 0.5g/L、O3投加濃度為10.06mg/L的條件下,反應(yīng)時(shí)間為 90min,單獨(dú)采用GAC、O3和O3/GAC聯(lián)合工藝對(duì)2,6-DCBQ的去除率分別為29.64%、32.81%和84.93%.

3.2 O3/GAC聯(lián)用技術(shù),比單獨(dú)O3及單獨(dú)GAC對(duì)2,6-DCBQ的去除率明顯提高.這是因?yàn)镺3能夠?qū)⒊跗谝盐皆贕AC上的2,6-DCBQ的結(jié)構(gòu)打開變成小分子物質(zhì),釋放了 GAC的吸附空隙,從而增強(qiáng)了GAC吸附能力.O3/GAC聯(lián)合工藝降解2,6-DCBQ符合一級(jí)反應(yīng)動(dòng)力學(xué).

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Removal of halogenated carbon disinfection by-product 2,6-dichloro-1,4-benzoquinone by ozone and granular

activated carbon. DING Chun-sheng*

MIAO Shi-mao, ZHAO Shi-du, XIAO Mao-hu, ZOU Sheng-nan (College of CivilEngineering and Architecture, Zhejiang University of Technology, Hangzhou 310014, China). China Environmental Science, 2017,37(6)：2173～2178

2,6-dichloro-1,4-benzoquinone (abbreviated as 2,6-DCBQ), one kind of disinfection by-products (DBPs) in drinking water has a vital impact on human health. Therefore, the study on the control of 2,6-DCBQ by an integrated ozone-granular activated carbon (O3/GAC) process was made. In addition, the degradation mechanism and its dynamics were analyzed and discussed. The results indicated that the 2,6-DCBQ removal with individual O3or GAC process reached 29.64% and 32.81% respectively. The 2,6-DCBQ could be removed more effectively by O3/GAC compared to the individual O3or GAC process, and the efficiency was increased with the raise of initial concentration of 2,6-DCBQ, O3levels and GAC dosage. It was also found that the 2,6-DCBQ removal reached 85.37% after the reaction time of 90minutes with the initial 2,6-DCBQ concentration, O3concentration and GAC addition of 20μg/L, 10.06mg/L and 0.5g/L, respectively. The degradation process of 2,6-DCBQ by O3/GAC fit the first-order reaction kinetic model.

disinfection by-products；2,6-dichloro-1,4-benzoquinone；O3/GAC combined process；dynamics

X703.5

A

1000-6923(2017)06-2173-06

丁春生(1965-),男,安徽懷寧人,教授,博士,主要從水污染控制理論與技術(shù)研究.發(fā)表論文50余篇.

2016-10-24

浙江省自然科學(xué)基金資助項(xiàng)目(Y5110339);浙江省公益性技術(shù)應(yīng)用研究計(jì)劃項(xiàng)目(2012C23055)

* 責(zé)任作者, 教授, dingcs99@163.com