序号：
编码：
第十一届“挑战杯”广东大学生课外学术科技作品竞赛
作品申报书
作品名称：以甘蔗渣为原料制备高性能吸附剂及其应用研究
学校全称： 华南农业大学
申报者姓名
（集体名称）： 何连芳 陈翠锦
类别：
■自然科学类学术论文
□哲学社会科学类社会调查报告和学术论文
□科技发明制作A类
□科技发明制作B类
说 明
1．申报者应在认真阅读此说明各项内容后按要求详细填写。
2．申报者在填写申报作品情况时只需根据个人项目或集体项目填写A1或A2表，根据作品类别（自然科学类学术论文、哲学社会科学类社会调查报告和学术论文、科技发明制作）分别填写B1、B2或B3表。所有申报者可根据情况填写C表。
3．表内项目填写时一律用钢笔或打印，字迹要端正、清楚，此申报书可复制。
4．序号、编码由第十一届“挑战杯”广东大学生课外学术科技作品竞赛组委会填写。
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6．作品申报书须按要求由各校竞赛组织协调机构统一寄送。
7．其他参赛事宜请向本校竞赛组织协调机构咨询。
A1．申报者情况（个人项目）
说明：1．必须由申报者本人按要求填写，申报者情况栏内必须填写个人作品的第一作者（承担申报作品60%以上的工作者）；2．本表中的学籍管理部门签章视为对申报者情况的确认。
| 姓 名 | 何连芳 | 性别 | 女 | 出生年月 | １９８７.１１. | ||||||||||
| 申报者情况 | 学校全称 | 华南农业大学 | 专 业 | 制药工程 | |||||||||||
| 现学历 | 本科 | 年级 | ０８级 | 学制 | ４年 | 入学时间 | ２００８.９. | ||||||||
| 作品全称 | 以甘蔗渣为原料制备高性能吸附剂及其应用研究 | ||||||||||||||
| 毕业论文题目 | 无 | ||||||||||||||
| 通讯地址 | 广州市天河区华南农业大学 | 邮政编码 | ５１０６４２ | ||||||||||||
| 单位电话 | |||||||||||||||
| 常住地通讯地址 | 华南农业大学泰山学生公寓１６－２３０ | 邮政编码 | ５１０６４２ | ||||||||||||
| 住宅电话 | １５０１７５０１４５４ | ||||||||||||||
| 合作者情况 | 姓 名 | 性别 | 年龄 | 学历 | 所在单位 | ||||||||||
| 陈翠锦 | 女 | ２１ | 本科 | 华南农业大学资源环境学院制药工程 | |||||||||||
| 资 格 认定 | 学校学籍管理 部门意见 | 是否为2011年7月1日前正式注册在校的全日制非成人教育、非在职的各类高等院校中国学生（含专科生、本科生和研究生）。 □是 □否 若是，其学号为：２００８３０２２０３０５ （部门盖章） 年 月 日 | |||||||||||||
| 院系负责人或导师意见 | 本作品是否为课外学术科技或社会实践活动成果。 □是 □否 负责人签名： 年 月 日 | ||||||||||||||
B1．申报作品情况（自然科学类学术论文）
说明：
1．必须由申报者本人填写；2．本部分中的科研管理部门签章视为对申报者所填内容的确认；3．作品分类请按作品的学术方向或所涉及的主要学科领域填写；4．硕士研究生、博士研究生作品不在此列。
C.当前国内外同类课题研究水平概述
说明：1.申报者可根据作品类别和情况填写；
2.填写此栏有助于评审。
| 国内外对废水治理的研究已取得了较大的进展。目前，工业生产中，印染废水的处理方法主要有活性碳吸附法、絮凝法、膜分离法、生物膜法、氧化和臭氧法等，但以上方法都存在吸附率较低、制备成本较高的缺点，不能推广使用。基于壳聚糖的推广，不少研究人员开展以壳聚糖及其衍生物进行吸附试验的研究。壳聚糖的来源虽广，但制作工艺较麻烦。 为此，人们开始寻找一种廉价易得且具高效吸附力的吸附剂来处理废水。一些农产品废弃物具有吸附剂的作用，近年来，利用农产品废弃物作为原料，制备改性吸附剂用来处理废水的研究文献已陆续被出现。例如：1熊佰炼等人研究的甘蔗渣处理重金属废水的研究进展，其研究结果为蔗渣吸附阳离子的最适pH为5-10，甘蔗渣的吸附反应是一个放热反应等。2.张庆乐等人研究的玉米芯对废水重金属的吸附机制及其影响因素。其结果为不同地点的玉米芯的吸附性能是有一定的差异的。 印染废水和制革废水的处理仍然是个棘手的难题，这些废水里通常含有重金属离子和染料等大量有机污染物，可同时吸附有机染料以及重金属离子吸附剂的研究的相关文献资料尚未见报道。我国是印染大国，特别是在珠三角地区，印染业是重要的传统产业之一，印染工业产生大量含有有机染料以及重金属离子的废水，为了降低染料废水综合治理的成本，研究一种可以同时吸附有机染料以及重金属离子的吸附剂将会是一种有效的手段。 以废弃农作物甘蔗渣作为吸附剂的原料，利用四乙烯五胺对其进行改性后用于废水处理，可以很好地处理印染废水和制革废水。 |
D.推荐者情况及对作品的说明
说明：1．由推荐者本人填写；2．推荐者必须具有高级专业技术职称，并是与申报作品相同或相关领域的专家学者或专业技术人员（教研组 集体推荐亦可）；3．推荐者填写此部分，即视为同意推荐；4．推荐者所在单位签章仅被视为对推荐者身份的确认。
| 推荐者情况 | 姓 名 | 吴启堂 | 性别 | 男 | 年龄 | 49 | 职称 | 教授、博导 | ||
| 工作单位 | 华南农业大学资源环境学院 | |||||||||
| 通讯地址 | 华南农业大学资源环境学院 | 邮政编码 | 510642 | |||||||
| 单位电话 | 020-85288326 | 住宅电话 | ||||||||
| 推荐者所在 单位签章 | （签章） 年 月 日 | |||||||||
| 请对申报者申报情况 的真实性作出阐述 | 申请情况属实。 | |||||||||
| 请对作品的意义、技术水平、适用范围及推广前景作出您的评价 | 该实验以甘蔗渣为原料，通过在表面接枝大量的氨基，制备对印染废水和制革废水具有理想吸附性能的高效吸附剂，可以同时处理含有有机染料和重金属离子的难已处理的工业废水，思路新颖独特。同时，甘蔗渣是农业废弃物，变废为宝，成本低廉，具有生物可降解性，有利于环境经济的可持续发展。 | |||||||||
| 其它说明 | ||||||||||
| 推 荐 者 情 况 | 姓 名 | 廖宗文 | 性别 | 男 | 年龄 | 64 | 职称 | 教授、博导 | ||
| 工作单位 | 华南农业大学资源环境学院 | |||||||||
| 通讯地址 | 华南农业大学资源环境学院 | 邮政编码 | 510642 | |||||||
| 单位电话 | 13802965075 | 住宅电话 | ||||||||
| 推荐者所在 单位签章 | （签章） 年 月 日 | |||||||||
| 请对申报者申报情况 的真实性作出阐述 | 申报情况属实。 | |||||||||
| 请对作品的意义、技术水平、适用范围及推广前景作出您的评价 | 我国纺织印染行业发达，废水对环境造成严重污染，针对目前吸附剂普遍存在价格高，吸附效果有限等问题，本实验探讨了以廉价的废弃甘蔗渣为原料，通过改性，制备对印染废水和制革废水具有优异的的性能的吸附剂。改吸附剂具有高效环保，制备工艺简单价格低廉等特点，具有广阔的市场前景。 | |||||||||
| 其它说明 | ||||||||||
| 学校组织协调机构确认并盖章 | （团委代章） 年 月 日 | |||||||||
| 校主管领导或校主管部门确认盖章 | 年 月 日 | |||||||||
E．大赛组织委员会秘书处资格和形式审查意见
| 组委会秘书处资格审查意见 审查人（签名） 年 月 日 |
| 组委会秘书处形式审查意见 审查人（签名） 年 月 日 |
| 组委会秘书处审查结果 □合格 □不合格 负责人（签名） 年 月 日 |
F．参赛作品打印处
以甘蔗渣为原料制备高性能吸附剂
及其应用研究
何连芳 陈翠锦
（华南农业大学资源环境学院制药工程系）
摘要：多年来印染废水和制革废水的处理一直是个难题。制备廉价易得，吸附性能优异的吸附材料是治理废水的理想手段。本研究通过环氧氯丙烷的开环引入四乙烯五胺对处理过的甘蔗渣（sugarcane bagasse，SB）进行改性，制备成对有机染料伊红和重金属离子
Cu２＋、Cr3+有较强吸附能力的吸附剂，并对甘蔗渣和改性的甘蔗渣（modified sugarcane bagasse，MSB）的结构进行了红外光谱表征。分别探讨了吸附有机染料伊红以及吸附重金属离子Cu２＋、Cr3+的吸附动力学和吸附等温线，研究了样品的初始浓度、pH、温度等因素对吸附的影响。结果表明，当溶液pH为6时，MSB对有机染料伊红的吸附量比SB提高了18倍，对金属Cu2+ 、Cr3+的吸附量也大大强于SB，反映了MSB是一种吸附性能优异的吸附剂，适用于处理印染、电镀等废水的应用。
关键词：改性甘蔗渣 环氧氯丙烷 四乙烯五胺 吸附 有机染料 重金属离子
Study of preparation and applications of an excellent absorbent using sugarcane bagasse
Abstract: Tannery wastewater printing and dyeing wastewater is a powerful pollutant. It can cause severe environmental problems related to its high chemical oxygen demand (COD) together with elevated chrome concentration and deep colour content .In this study, in order to obtain an excellent absorbent with high absorption capability, rich in raw materials and inexpensive, sugarcane bagasse was modified to absorb heavy metal ion and dye.
In this study, we use discarded sugarcane bagasse(SB) as raw material , through the introducing of Epichlorohydrine and Tetraethylenepentamine /TEPA, we has the treated Sugarcane Bagasse modificated. As a result, we obtain an absorbent that is doubling absorbability of organic dye Eosin and heavy metal ion Cu2+、Cr3+. In the meantime, we have both the structure characterizations of the Sugarcane Bagasse (SB) and the Modified Sugarcane Bagasse (MSB) carried on the Infrared Spectrum (IS). We also discuss the influncing factors of absorbability of the SB and the MSB, such as pH, concentration , temperature and so on .
Based on the study results, it is concluded that the absorbability of MSB is far more superior to SB, and MSB is a kind of efficient biosorbent for treating with the organic dye Eosin and heavy metal ion Cu2+、Cr3+.
Key words:
MSB , Epichlorohydrine，Thetetraethylenepentamine, absorbent，organic dye , heavy metal
- 前言
众所周知，印染废水和制革废水非常难处理[1.2]（因其中大量的有机污染物通常需用活性污泥等微生物处理，而里面含有铬等重金属离子，会杀死微生物），其中最常见的金属离子是铬！若能用对染料和金属离子都有很好吸附能力的材料，通过吸附处理，就很有应用前景，若是能利用低成本的材料就更好了[3]。甘蔗渣是大量存在的废弃物，浪费可惜，目前利用效率不高，产生的经济效益不高，若将其做成对付印染废水的吸附剂，就找到了好路子。
目前，工业生产中，染料废水的去除方法主要有活性碳吸附法、絮凝法、膜分离法、生物膜法、氧化和臭氧法等，但这些方法不是吸附率较低，就是制备成本较高，而且容易带来二次污染，这些因素使之不能推广使用。大量文献报道了甘蔗渣及其衍生物[4-13]因具有丰富的毛细管，对金属离子的吸附，效果还是不错的。但对染料吸附不是太好，可能原因是甘蔗渣表面的基团与染料的不能有效的结合，若能通过简单改性，获得对染料和重金属离子有较高吸附率的吸附剂，无疑将给这类废水的处理带来便利。
本实验通过在甘蔗渣中引入四乙烯五胺，制备表面具有大量阳离子氨基的改性甘蔗渣，从而获得一种廉价易得、高效的、可以同时较好地吸附有机污染物（以染料伊红为模拟物）和重金属离子（以Cu2+、Cr3+离子为模拟物）的改性甘蔗渣吸附剂，用来处理废水。并对甘蔗渣和改性甘蔗渣的结构进行了红外光谱表征，且分别探讨了吸附有机染料伊红以及吸附重金属离子Cu２＋、Cr3+的吸附动力学、吸附等温线，研究了溶液的pH等因素对吸附的影响。
- 实验
2.1材料
废弃甘蔗渣 ; 伊红,上海Hebaochem Co.LTD;
无水乙醇 AR,天津市大茂化学试剂厂;
氢氧化钠 AR，天津市大茂化学试剂厂；
四乙烯五胺 AR，天津市福茂化学试剂厂；
环氧氯丙烷 AR，天津市大茂化学试剂厂；
2.2甘蔗渣原料的处理与改性
2.2.1原料处理
把废弃的甘蔗渣置于蒸馏水中浸泡48 h，间歇换水，以去除蔗渣中的糖分。在阳光下晒干后，转至烘箱中105 ℃烘干24 h，粉碎过60目筛备用。
2.2.2改性甘蔗渣的制备
称取5 g甘蔗渣于2%NaOH溶液中，搅拌过夜，得到溶胀后的甘蔗渣。将其转移到三口瓶中，以2%NaOH为溶剂，加入10 mL环氧氯丙烷，40 ℃恒温搅拌反应24 h。继续向反应体系中加入与环氧氯丙烷等量的四乙烯五胺，恒温反应24 h，用无水乙醇洗至中性，抽滤烘干，即得到产品。
2.3结构表征
使用Nicolet 6700傅立叶变换红外光谱仪，以溴化钾压片法，测定甘蔗渣（SB）及改性甘蔗渣（MSB）的红外光谱，扫描波数为4000 cm-1——400 cm-1。
2.4吸附实验
2.4.1对有机染料伊红的吸附实验
量取20 mL伊红溶液于50 mL塑料瓶中，加入一定量的吸附剂后，置于恒温振荡器内，调节温度，转速为200 r/min．震荡吸附一定时间后取出样品，过滤取清液。用ＵＶ2300紫外分光光度计，以蒸馏水为空白，在最大吸收波长λ max=516.5 nm处测待测溶液的吸光度。
2.4.2对Cu2+、Cr 3+的吸附实验
量取25 ml CuSO4溶液于50 ml塑料瓶中，加入0.01 g吸附剂后，置于恒温振荡器内，调节温度，转速为200 r/min,震荡吸附一定时间后取出塑料瓶，过滤取清液，用原子吸收光谱法测定滤液中重金属离子Cu2+的含量。
同法进行对重金属离子Cr3+的吸附实验。
计算吸收率E0。
E0=[(C0-C1)/C0]×100%
上式中：E0为吸附率；C0为吸附前溶液中重金属的浓度；C1为吸附后溶液中重金属的浓度
- 结果与讨论
3.1红外光谱特征分析
图1 为SB和MSB的FT-IR的谱图，红外光谱法是表征一种物质最直接的方法。从以下谱图中可以明显看出，跟SB对比，MSB谱图杂峰较少，在1651.28 cm-1和1425.40 cm-1处有明显的吸收峰，这两处是酰胺键特有的吸收带，还有在666.49 cm-1处有一个较强的吸收峰出现，这些吸收峰都表明在MSB上存在酰胺键[14]。
图1 FT-IR图谱SB和MSB
3.2吸附实验的影响因素
3.2.1 吸附伊红的实验条件的分析
3.2.1.1 pH对吸附的影响
在伊红溶液浓度为200 mg/mL，吸附剂用量为0.02 g，吸附温度为25 ℃，吸附时间为6 h的条件下，紫外分光光度计测定溶液中剩余染料的浓度，初始pH对伊红吸附量的影响如图2所示。
从图2可以看出，SB对伊红的吸附能力受pH值影响不大，总体保持在较低的水平，pH值为7时，吸附效果为最佳。MSB对伊红的吸附能力受pH值影响较大。pH值为6时，伊红的吸附量达到最大，在pH值7~10，MSB对伊红的吸附能力明显降低，但总体水平仍高于SB，MSB对伊红的最大吸附量约是SB的6倍。伊红在水溶液中能电离，呈中等酸性，因此，在实际操作中，以pH值6为最佳吸附pH值，此时MSB对伊红的吸附量约是甘蔗渣原料的19倍。
图2 pH对染料吸附的影响
3.2.1.2温度与染料初始浓度对吸附的影响
在pH值为6，MSB用量为0.02 g，吸附时间为6 h条件下，探讨了温度与染料初始浓度对吸附的影响，实验结果如图3。从图中易看出T=298 K~318 K之间，随着温度的升高，MSB的吸附能力有所下降。当T＝298 K时,伊红的吸附量最大。随着伊红初始浓度的增大，MSB的吸附量也相应的增大，初始浓度为300 mg/L左右时，MSB达到吸附饱和。因此在T=298 K、伊红初始浓度为300 mg/L时，MSB的吸附量能达到最佳值。
图3 温度与染料初始浓度对吸附的影响
3.2.1.3吸附模型比较
图4 和图5分别是在不同温度下以Langmuir 等温吸附模型，Freundlich等温吸附模型考察MSB的吸附性能。
图4 Langmuir 等温吸附模型
图5 Freundlich 等温吸附模型
表1 Freundlich’s 和 Langmuir’s 方程参数
| 材料 | 温度 (K) | Langmuir | Freundlich | ||||
| KL(L/mg) | qm(mg/g) | R2 | KF(L/g) | n | R2 | ||
| MSB | 298 | 0.0098 | 399.04 | 0.9898 | 6.296 | 1.888 | 0.9192 |
| 308 | 0.0120 | 328.95 | 0.9991 | 7.881 | 2.194 | 0.9303 | |
| 318 | 0.0182 | 259.61 | 0.9987 | 11.17 | 3.014 | 0.8354 | |
表2 MSB吸附伊红的RL 值
| T(K) | Initial concentration of eosin Y in solution(mg/L) | ||||||||
| 50 | 100 | 150 | 200 | 250 | 300 | 350 | 450 | 500 | |
| 298 | 0.6711 | 0.5050 | 0.4048 | 0.3378 | 0.2898 | 0.2538 | 0.2257 | 0.1848 | 0.1695 |
| 308 | 0.6250 | 0.4545 | 0.3571 | 0.2941 | 0.2500 | 0.2174 | 0.1923 | 0.1562 | 0.1428 |
| 318 | 0.5235 | 0.3546 | 0.2681 | 0.2155 | 0.1802 | 0.1548 | 0.1357 | 0.1088 | 0.0990 |
表1是Langmuir 和 Freundlich 等温吸附方程拟合实验数据，表2为MSB吸附伊红的RL 值。
根据这两个表可以看出，MSB对于伊红的吸附，Langmuir 方程的拟合效果较好，三种温度下的决定系数均在0.98以上，Freundlich 方程的拟合效果较差。根据Langmuir 等温吸附模型的假定，初步推测甘蔗渣对伊红为单层吸附。由Langmuir 方程可得，在25 ℃下伊红的最大吸附量为399.04 mg/g ，可见改性甘蔗渣对伊红有很高的吸附能力，用来处理染料废水可取得较好的效果。
3.2.1.4吸附动力学
在伊红溶液pH=6，常温条件下，探讨了不同时间和不同染料初始浓度对材料吸附性能的影响，结果如图6所示。从图中可以看出，MSB对伊红的吸附量随初始浓度的增加而升高。MSB对伊红的吸附过程主要分为两个阶段，初始吸附速率很快，当吸附时间超过150 min后，随着吸附时间的延长，吸附量变化很小，400 min后认为吸附基本达到平衡。这主要是由于在吸附初期，溶液中MSB表面的吸附空位较多，同时固液界面的伊红浓度梯度提供了较大的驱动力，促使MSB对伊红快速吸附，随着时间的延长，吸附空位逐渐变少，同时固液界面的浓度梯度逐渐降低，MSB的吸附速率降低，达到平衡。
图6 时间与染料初始浓度对材料吸附性能的影响
为了进一步的研究MSB的吸附动力学，本实验还以伪二级吸附动力学和伪一级吸附动力学模型研究MSB的吸附行为。以下图表为研究的结果：
图7 Pseudo-second-order 吸附动力学模型
图8 Pseudo-first-order 吸附动力学模型
表3 伪一级吸附动力学模型和伪二级动力学模型的参数值
| Material | Initial dye concentration (mg/L) | Pseudo-first-order | Pseudo-second-order | ||||
| K1 (min-1) | qe,cal (mg/g) | R2 | K1 (g/(mg·min)) | qe,cal (mg/g) | R2 | ||
| MSB | 100 | 0.01021 | 46.900 | 0.9644 | 8.377×10-4 | 183.80 | 1.000 |
| 200 | 0.00647 | 215.08 | 0.9931 | 7.741×10-5 | 308.64 | 0.9988 | |
| 500 | 0.00952 | 165.93 | 0.9433 | 1.958×10-4 | 349.28 | 0.9999 | |
图7和图8分别是以伪二级吸附动力学和伪一级吸附动力学模型研究MSB的吸附行为，表3为这两个动力学模型的参数值，实验结果表明，MSB对伊红的吸附更符合伪二级吸附动力学西方模型。
3.2.2 吸附重金属Cu2+、Cr3+的实验条件的分析
3.2.2.1 吸附动力学
分别以MSB和SB为吸附剂，常温条件下，研究甘蔗渣改性前后对Cu2+的吸附性能，结果如图9所示。从图中可以看出，MSB对Cu2+的吸附随着时间的延长而增加，在吸附时间为10 h左右达到吸附率最大值，吸附率大约为22%；但12 h时，吸附率降至较低值；在其他相同条件下，其吸附性能几乎都比未改性甘蔗渣的吸附性能高。MSB的吸附率达到最大值后有所下降的原因可能是因为改性甘蔗渣在吸附饱和后发生了解析反应。结果证明：通过改性，甘蔗渣对Cu2+的吸附性能有所提高。
图9 吸附动力学
3.2.2.2 pH值对Cu2+吸附的影响
以MSB为吸附剂，改变溶液的pH值，探讨pH值对吸附效果的影响，结果如图10所示。试验表明，pH值对吸附效果有着显著的影响。从图中明显可以看出MSB对重金属Cu2+的吸附能力随pH值的增大而增强，当pH值为5时，达到最大值。当溶液pH大于5，MSB的吸附率降低，这是由于硫酸铜溶液在pH5.2-5.7之间，重金属Cu2+离子形成沉淀，从而影响了MSB对Cu2+的吸附量。可见弱酸性的环境条件有利于改性甘蔗渣对Cu2+的吸附。但是由实验数据显示，改性甘蔗渣对Cu2+的吸附量对于现今处理重金属的能力还是较低的，没有达到一个比较理想的效果，故还需要做进一步的研究。
图10 pH值对改性甘蔗渣吸附Cu2+的影响
3.2.2.3 pH值对Cr3+吸附的影响
以MSB为吸附剂，改变溶液的pH值，探讨pH值对吸附效果的影响，结果如图11所示。试验表明，pH值对吸附效果有着显著的影响。从图中可以看出MSB对重金属Cr2+的吸附能力随pH值的增大而增强，从实验选择的条件pH值2~6，MSB的吸附量都是与溶液的pH值成正相关的关系，但并不说溶液的pH越大，则MSB对重金属Cr3+离子的吸附效果就越好。因为当含重金属Cr3+离子溶液的pH大于6时，重金属Cr3+离子会随着其溶液的pH的增大而形成沉淀物，从而直接的影响MSB对重金属Cr3+离子的吸附量。因此，当溶液的pH值在5~6，MSB对Cr3+的吸附效果最好。可见弱酸性的环境条件有利于改性甘蔗渣对Cr3+的吸附。但是由实验数据显示，改性甘蔗渣对Cr3+的吸附没有达到一个比较理想的效果，还需要做进一步的研究。
图11 pH值对改性甘蔗渣吸附Cr3+的影响
4. 结论
1.以甘蔗渣为原料，引入四乙烯五胺进行改性，制备了同时具有吸附有机染料伊红和重金属Cu2+、 Cr3+的复合吸附剂材料。
2.对甘蔗渣进行改性后，改性的甘蔗渣对伊红的吸附量显著提高。改性甘蔗渣对有机染料伊红吸附的单因素分析结果显示最佳吸附条件是：温度为298 K，pH值为6，吸附时间为6 h。吸附过程可以用Langmuir 型吸附等温线较好地模拟，由方程可得，在25 ℃下伊红的最大吸附量为399.04 mg/g 。
3.对甘蔗渣进行改性后，改性的甘蔗渣对Cu2+的吸附量有所提高，但仍然没有达到高效吸附的效果，还有待继续研究。改性的甘蔗渣对Cu2+吸附的最佳吸附条件是：pH值为5，吸附时间为10 h。
4.对甘蔗渣进行改性后，改性的甘蔗渣对的吸附量随pH值的增大而增强，从实验选择的条件pH值2~6，MSB的吸附量都是与溶液的pH值成正相关的关系，当溶液的pH值在５～６之间，MSB对Cr3+的吸附效果最好。
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Tetraethylenepentamine modified sugarcane bagasse as a potentially low-cost biosorbent for tannery wastewater treatment
Gang-Biao Jiang, Xiao-Yi Huang, Zuan-Tao Lin, Lian-Fang He, Cui-Jin Chen
1. Intoduction
Tannery wastewater printing and dyeing wastewater is a powerful pollutant. It can cause severe environmental problems related to its high chemical oxygen demand (COD) together with elevated chrome concentration and deep colour content (Song et al., 2000). Although activated sludge has been regarded as an universal biological treating method in tannery wastewater treatment, it comes out be ineffective due to the existing of high concentration of metals (mostly Cr(III)) which could kill the organism. So it is worthwhile to find out efficiency treating methods to deal with this serious environment problem. Among many traditional treatment methods such as coagulation, precipitation, membrane filtration, ion exchange and reverse osmosis etc, adsorption is recognized as one of the most efficient treatment process since it has the advantage of simplicity in operation, low cost and flexibility (Crini, 2006). If we can develop an effective adsorbent with high removal capacity of both dyes and metals, it would have a great deal of application potential in tannery effluent treatment. Recently, a number of low-cost, easily available and effective adsorbents are being studied for wastewater treatments. Many non-convectional low-cost adsorbents including perlite (Dŏgan et al., 2004), bentonite clay (Tahir and Rauf, 2006), sawdust (Khattri and Singh, 2009), chitin (Dolphen et al., 2007), peat (Ho and McKay, 1998), hazelnut shell (Donia et al., 2009), duckweed (Waranusantigula et al., 2003), bagasse (Júnior et al., 2009 and Mall et al., 2006) and activated sludge (Ju et al., 2008) etc, have been reported. However, most of them still lack good adsorption capacity. In order to improve the efficiency of the adsorption processes, it is necessary to develop cheap and easily available adsorbents with high adsorption capacities.
Sugarcane bagasse is an important by-product of agro-industry in China and there has been rising interest in the country in finding new uses for this material. Sugarcane bagasse has around 50% cellulose, 27% polyoses, and 23% lignin (Jr. et al., 1996). These three biological polymers have many hydroxyl and/or phenolic functions that can be chemically modified to produce materials with new properties. Sugarcane bagasse and its derivatives have been reported to have substantial adsorption capacity for metal ions (Júnior et al., 2009, Homagai et al., 2010, Gurgel and Gil, 2009), however, fewer research has been carried out to investigate their removal efficiency of dyes. This may due to the fact that the bearing on carboxylic and hydroxyl groups facilitate their excellent chelating properties toward metal ions while not so effective for dye removal.
In this study, SB was chemical modified with tetraethylenepentamine (TEPA) to introduce large amount of amino or imino groups to obtain a new material. The removal efficiency toward an anionic dye eosin Y was extensively investigated and the effect of pH on adsorption capacity of Cr(III) was studied as well.
- Materials and methods
2.1. Materials
Sugarcane bagasse was obtained from , Eosin Y was an acid dye purchased from Hebaochem Co., LTD (Shanghai, China). Tetraethylenepentamine (TEPA), epichlorohydrin (ECH), and other reagents used in this experiment were of analytical grade and used directly.
2.2. Sugarcane bagasse (SB) preparation
The raw sugarcane bagasse was dipped in distilled water for 48 h, during which period water was changed constantly in order to eliminate residual sugars. After filtration, they were dried under sunlight and subsequently dried at 105 oC in an oven for 24 h. Afterwards, sugarcane bagasse was powdered and sieved size to 60 mesh.
2.3 Sugarcane bagasse mercerization
Sugarcane bagasse (SB) (5 g) was treated with 100 ml of aqueous NaOH solution (10 wt%) at 60 oC for 8 h under constant stirring in order to obtain mercerized sugarcane bagasse (MSB). In the end of the treatment, the alkali was separated of bagasse by filtration and washed with distilled water up to pH 7.
2.4 Synthesis of TEPA modified SB (TEPA-MSB)
The mercerized sugarcane bagasse (MSB) obtained in the above step was reacted with 10 ml epichlorohydrine (ECH) under ethanol reflux for 24 h. Afterwards, 10 mL of TEPA was added to the system and stirred at room temperature for another 24 h. The product obtained was washed with ethanol up to pH 7 and air dried.
2.5Charaterization of TEPA-MSB
FT-IR spectra of SB and MSB were recorded with an FTIR spectrometer (Thermo FTIR-6700, Nicolet Instrument Co., USA) in the range of 4000~400 cm−1 using KBr pellets containing the prepared materials.
2.6Adsorption experiments
2.6.1 The adsorption experiments of an anionic dye eosin Y from aqueous solution
Stock solution of eosin Y (1 g/L) was prepared in deionized water. The experimental solutions with desired eosin Y concentration were obtained by successive dilution of this stock solution with deionized water. Calibration curve of eosin Y was prepared by measuring absorbance of samples with predetermined concentrations at 516 nm (corresponding to a maximum absorbency of eosin Y) using UV–vis spectrophotometer (UV-2300, Tian Mei CO. LTD. China).
For the adsorption experiment, a known amount of sorbent and a measured volume of eosin Y solution were placed in 50 mL closed plastic bottles resistant to acid or base. The system remained under agitation in a thermostatic bath. Parameters like pH, temperature, agitation rate, adsorbent dosage and particle size, contact time and initial dye concentration were set according to the relevant adsorption studies. Triplicate measurements were carried out for each study, and the mean values are presented, the error obtained was ±2%. The adsorbent was finally separated from the solution by filtration and small amount of dye remaining in the filter is omitted. Concentration of dye in supernatant was analyzed from the linear regression equation of the calibration curve. The removal efficiency (R, %) and the amount of eosin Y adsorbed (q, mg/g) were calculated by using the following equations, respectively.
(1)
(2)
Where Ci and Cf are the initial and final concentration (mg/L) of dye after adsorption. V is the volume (ml) of experimental solution and W is the weight (g) of the adsorbent.
2.6.2 The adsorption experiment of Cr(III) from aqueous solution
The effect of pH on the adsorption of Cr(III) by TEPA-MSB was studied. The experiment was carried out as follows: An amount of 10.0 mg of TEPA-MSB was placed in a 50 mL plastic bottle with 20.00 mL of Cr(III) solution at fixed concentrations of 0.50 mg/L. The pH of the Cr(III) solution was adjusted to the range of 2~6, using either hydrochloride acid or sodium hydroxide. The bottles were shaken vigorously in a thermostated shaker at 298 K at 150 rpm for 12 h to ensure the equilibrium to be attained. The initial and equilibrium concentrations of the metal ions were measured by using Z-2300 atomic absorption spectrophotometer. All experiments were performed in triplicate at least and mean values were presented in all the cases studied. The removal efficiency (R, %) and the amount of Cr (III) adsorbed (q, mg/g) were calculated by using equation (1) and (2), respectively.
3. Results and discussion
3.1 Characterizations of MSB
FT-IR spectra of SB and TEPA-MSB are presented in Fig.1.
Fig.1FT--IR SB and MSB
3.2 Adsorption experiments of eosin Y from aqueous solution
3.2.1 Effect of pH on the removal of eosin Y
The pH of the dye solution is an important controlling parameter that strongly affects the adsorption process. The experiment was carried out by measuring the dye uptake of 0.0200 g adsorbent after 6 h immersion at 25 oC. The pH of the dye solution (20 mL of 200 mg/L initial concentration) was adjusted to the range of 5~10, using either hydrochloride acid or sodium hydroxide. The result shown in Fig.2.indicated that TEPA-MSB and SB exhibited extremely different adsorption behavior toward eosin Y. It was found that the adsorption capacity of SB was much lower at all pH values and was not affected substaintially by pH variation. While for TEPA modified SB (TEPA-MSB), the dyes adsorption capacity was significantly changed over the pH value 5 to 10. It reached maximum at pH 6 where it's 18 times higher than that of SB, and then decreased drastically when pH increased from 7 to 10. As the pH of the solution decreased (more acidic), the adsorption process of the anionic dye eosin Y by TEPA-MSB is an electrostatic interaction, where the protonated amine groups of TEPA-MSB interact with the anionic groups of the dye. While at high pH from 7 to 10, more OH- ions present and compete with the anionic bromide groups of eosin Y for the adsorption sites of TEPA-MSB, thus the available adsorption sites for anionic eosin Y decrease. This, however, didn't apply to SB, as it remained almost constant when pH range from 5 to 6 or from 7 to 10. There might be another mode of adsorption, such as ion exchange (Saad etc, 2010).
Fig.2Effect of pH on eosin Y adsorption
3.2.2 Effect of temperature and initial concentration on the adsorption of TEPA-MSB
This experiment was carried out as following: 20 mg adsorbent and 20 mL aqueous solution of eosin Y (pH=6) with predetermined initial concentration (50~500 mg/L) was taken in 50 mL plastic bottle. The bottles were agitated (200 rpm) at 25 oC for 6 min. At the end of incubation, the beads were separated by filtration and the concentration of the dye in the solution was estimated spectrophotometrically. The same series experiments were carried out at other two temperatures (viz., 35 oC and 45 oC) to investigate the effect of temperature on eosin Y removal.
In Fig.3, the equilibrium uptake of eosin Y by TEPA-MSB at three temperatures (25 oC, 35 oC and 45 oC) is plotted as a function of equilibrium dye concentration in the solution.
The results show that adsorption of eosin Y depends on the concentration of the dye. The adsorption capacity increased with the increase of eosin Y concentration from 50 mg/L to 500 mg/L. The initial gradient of dye provides the necessary driving force to overcome the resistances to the mass transfer of eosin Y between the aqueous and solid phases (Luo et al., 2010). Temperature also plays a key role in dye adsorption process, that is, when the temperature increases, the equilibrium adsorption falls, indicating the exothermic nature of the adsorption process.
Fig.3Effect of temperatures on MSB
3.2.3. Adsorption isotherm
The adsorption equilibrium isotherm is important for describing the distribution of adsorbate molecules between the liquid and the solid phases at equilibrium. Adsorption equilibrium is established when the amount of dye being adsorbed onto the adsorbent is equal to the amount being desorbed. In the present investigation, the equilibrium data were fitted to the linear form of Freundlich (Eq. (6)) and Langmuir (Eq. (7)) model of adsorption isotherm.
Freundlich:
(6)
Langmuir:
(7)
Where Ce is the remaining dye concentration (mg/L) in solution, qe the dye concentration (mg/g) in the adsorbent, KF the Freundlich constant and 1/n is the heterogeneity factor. While qm is the maximum adsorption amount of eosin Y per gram of adsorbent (mg/g) and KL is the Langmuir adsorption equilibrium constant (L/mg).
Freundlich isotherm supposes that adsorbent surface sites have a spectrum of different binding energies. It describes the adsorption as reversible and not restricted to the monolayer formation. This isotherm does not predict any saturation of the sorbent surface, so dye concentration in the adsorbent will increase with increase of dye concentration in the solution. On the contrary, Langmuir model is valid for monolayer adsorption onto a surface with a finite number of identical sites which are homogeneously distributed over the adsorbent surface. It represents chemisorption on a set of well defined localized sorption sites, supposing that once a particular site of the adsorbent is occupied by an adsorbate molecule, no further adsorption takes place at that site (Kyzas and Lazaridis, 2009). The parameters of Langmuir equation (see Table.1 in Supplementary data) show that the maximum adsorption capacity (qm) of TEPA-MSB is 399.04 mg/g at 25oC. The correlation coefficients of the isotherms are all higher than 0.98 at the three temperatures, thereby indicating that the Langmuir isotherm fits the equilibrium data very well. On the contrary, the low R2 values at the test temperatures (0.83< R2 <0.94) indicated the poorer agreement with Freundlich isotherm. These results suggest that the surface of TEPA-MSB is homogeneous and a monolayer of eosin Y covers the surface after adsorption.
It has been reported that the effect of isotherm shape with a view to predict if an adsorption system is “favourable” or “unfavourable”. The essential features of a Langmuir isotherm can be expressed in terms of a dimensionless constant separation factor or equilibrium parameter, RL, which is expressed by the following equation:
(8)
where KL is the Langmuir constant as described above and Co is the initial dye concentration. Value of RL less than one but greater than zero indicates favourable adsorption.
Table.2 lists the RL values calculated at different initial dye concentrations. All the RL values are very close to lower acceptable range indicating high degree of irreversibility of the process.
Table.1 Freundlich’s and Langmuir’s model of adsorption isotherm
| material | Temperature (K) | Langmuir | Freundlich | ||||
| KL(L/mg) | qm(mg/g) | R2 | KF(L/g) | n | R2 | ||
| MSB | 298 | 0.0098 | 399.04 | 0.9898 | 6.296 | 1.888 | 0.9192 |
| 308 | 0.0120 | 328.95 | 0.9991 | 7.881 | 2.194 | 0.9303 | |
| 318 | 0.0182 | 259.61 | 0.9987 | 11.17 | 3.014 | 0.8354 | |
Table.2 RL values of MSB on eosin Y
| T(K) | Initial concentration of eosin Y in solution(mg/L) | ||||||||
| 50 | 100 | 150 | 200 | 250 | 300 | 350 | 450 | 500 | |
| 298 | 0.6711 | 0.5050 | 0.4048 | 0.3378 | 0.2898 | 0.2538 | 0.2257 | 0.1848 | 0.1695 |
| 308 | 0.6250 | 0.4545 | 0.3571 | 0.2941 | 0.2500 | 0.2174 | 0.1923 | 0.1562 | 0.1428 |
| 318 | 0.5235 | 0.3546 | 0.2681 | 0.2155 | 0.1802 | 0.1548 | 0.1357 | 0.1088 | 0.0990 |
3.2.4 Kinectic models
Kinetics of adsorption gives important information for designing and modeling the full-batch adsorption process and helpful in examining the efficiency of the adsorption process. In order to examine the controlling mechanism of adsorption processes such as mass transfer and chemical reaction, the pseudo-first-order adsorption, and the pseudo-second-order adsorption model were used to test the adsorption of eosin Y onto TEPA-MSB. The best-fit model was selected based on the linear regression correlation coefficient (R2).
The two kinetic models equations are given as follow:
pseudo-first-order equation:
(3)
pseudo-second-order equation:
(4)
where qe and qt are the amounts of eosin Y adsorbed on adsorbent (mg/g) at equilibrium time and at time t (min), respectively ; K1 is the rate constant of pseudo-first-order adsorption (min−1), K2 is the rate constant of second-order adsorption (g/(mg·min)) .
The straight line plots of each model equation (seen from Fig. 4(a) and Fig. 4(b)) were used to determine the applicability of the models and relative parameters could be obtained.
The results of the kinetic parameters for different initial dye concentrations are listed in Table 1. Based on the correlation coefficients, the adsorption of eosin Y is best described by the pseudo-second-order equation, suggesting that the rate-limiting step may be the adsorption mechanism but not the mass transport (Kamari et al., 2009).
Fig.4(a) Adsorption kinetic model of Pseudo-second-order
Fig.4(b) Adsorption kinetic model of Pseudo-first-order
3.3 Adsorption experiment of Cr (III) from aqueous solution
The pH of a solution played an important role for adsorption of metal ions, since it stongly affects both the degree of ionization and the surface characteristics of the adsorbent (Gurgel etc, 2008). At low pH, there is high concentration of H+ that has high mobility as compared to metal ions and competition between H+ with metal ions decreases their adsorption (Homagai et al, 2010). Therefore, a study to optimize the pH was performed. The results are presented in Fig. 5, the adsorption of Cr (III) ion increased as the pH value of the solution increases from 2 to 6 due to lesser number of H+ to compete with Cr (III). On the other hand, the solubility of metal in solution decreases with increasing pH (pH > 6). The optimum pH for Cr (III) adsorption was decided to be 6. At pH 6, the amine groups of TEPA-MSB were partly protonated which can lead to cationic ion exchange between the adsorbent and Cr (III). On the other hand, the carboxyl groups existing would ionize to complex Cr (III) as well thus increasing the adsorption capacity of the adsorbent. The adsorption capacity of SB and TEPA-MSB were compared and results showed that no distinct enhancement of adsorption was perceived. This may contribute to the fact the carboxyl groups but not the amine groups may play a key role in the participation of the adsorption process.
Fig.5 Effect of pH on Cr (III)
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