摘 要

氯酚因其具有强毒性、“三致”效应被列入水中污染物黑名单，处理水中的氯酚意义重大。目前利用载体负载金属催化剂处理氯酚是一种有效的方法。活性炭具有物理、化学吸附性质，常用于负载催化剂，而废旧橡胶颗粒含有大量碳元素，可制成活性炭。以废旧橡胶制成活性炭负载金属催化剂处理废水中的污染物，将实现废物资源利用。

本文采用废旧橡胶颗粒自制活性炭载体负载铁镍金属，制备负载型双金属催化剂，考察了铁/镍比例、初始浓度、温度、pH值等因素对2,4-二氯酚处理效果的影响，综合比较处理效果确定了2,4-二氯酚的优化处理条件。

实验结果表明，自制的橡胶基活性炭本身对2,4-二氯酚有一定的吸附效果，平衡吸附量为6.74mg/g，制备的最优负载金属活性炭为1Ni-30Fe/NAC，其平衡吸附量为16.80mg/g，相对于活性炭提高了10.06mg/g。1Ni-30Fe/NAC的平衡吸附量随着废水初始浓度和温度的，且用和拟合吸附等温线的结果表明吸附符合，吸附过程为吸热过程。1Ni-30Fe/NAC受，pH更低时更有利于其对2,4-二氯酚的去除，在pH=5时平衡吸附量达到21.45mg/g。

本论文初步确定了制备废旧橡胶基活性炭负载铁镍双金属催化剂的工艺条件，探讨了处理2,4-二氯酚的影响因素，可为废旧橡胶的资源化利用以及活性炭负载双金属处理实际工业废水提供实验依据。

关键词：废旧橡胶 活性炭 铁镍双金属 2,4-二氯苯酚

Study on treatment of 2,4-dichlorophenol wastewater using rubber base activated carbon supported iron-nickel bimetallic catalyst

Abstract

Chlorophenol is listed in the blacklist of water contaminants because of its strong toxicity and “triad” effect, so the treatment of chlorophenol in water is of great significance. At present, treatment of chlorophenol with a supported metal catalyst is an effective method. Activated carbon has physical and chemical , and is often used as a carrier for catalysts. Waste rubber particles contain a large amount of carbon and can be made into activated carbon. Using waste rubber to prepare activated carbon supported metal catalyst to treat pollutants in wastewater can realize waste the utilization of waste resources.

In this paper, the activated carbon carrier-loaded iron-nickel bimetallic metal catalyst was prepared, and the effects of iron/nickel ratio, initial concentration, temperature and pH on the treatment of 2,4-dichlorophenol were investigated. The comparative treatment determined the optimal treatment conditions of 2,4-dichlorophenol treatmen .

The experimental show that the self-made rubber-based has a certain effect on 2,4-dichlorophenol. The equilibrium adsorption capacity is 6.74mg/g. The optimal catalyst is 1Ni-30Fe /NAC, and the equilibrium adsorption capacity is 16.80 mg / g, an increase of 10.06 mg / g relative to activated carbon. The adsorption of 1Ni-30Fe/NAC increased with the initial concentration and temperature of wastewater, and the of fitting th adsorption isotherms with and indicate that the adsorption is in accordance with the and the adsorption process is an . 1Ni-30Fe /NAC is greatly affected by pH. Under low pH conditions, it is more favorable for the removal of 2,4-dichlorophenol. At pH=5, the equilibrium adsorption amount reaches 21.45mg/g.

In this paper, the process conditions for preparing waste rubber-based activated carbon-supported iron-nickel bimetallic catalysts were preliminarily determined, and the influencing factors of 2,4-dichlorophenol treatment were discussed. It can provide experimental basis for the resource utilization of waste rubber and the actual industrial wastewater of activated carbon loaded bimetals.

Keywords: waste rubber;activated carbon;iron-nickel bimetal;2,4-dichlorophenol

目 录

摘要 ……………………………………………………………………………………………I

ABSTRACT………………………………………………………………………………………II

第一章 绪论……………………………………………………………………………………1

1.1 背景……………………………………………………………………………………1

1.1.1 橡胶的成分分析…………………………………………………………………1

1.2 氯酚废水简介及其主要处理方法……………………………………………………1

1.2.1 氯酚废水简介……………………………………………………………………1

1.2.2 主要处理方法……………………………………………………………………2

1.3 负载型金属催化剂的研究进展………………………………………………………2

1.3.1 金属组分…………………………………………………………………………2

1.3.2 活性炭及其改性…………………………………………………………………3

1.3.3 负载方法…………………………………………………………………………3

1.4 项目研究意义和研究内容……………………………………………………………4

1.4.1 研究意义…………………………………………………………………………4

1.4.2 研究内容…………………………………………………………………………5

第二章 实验部分………………………………………………………………………………6

2.1 实验试剂和仪器………………………………………………………………………6

2.1.1 试剂………………………………………………………………………………6

2.1.2 仪器………………………………………………………………………………6

2.2 实验步骤………………………………………………………………………………7

2.2.1 橡胶基活性炭的制备……………………………………………………………7

2.2.2 双金属催化剂的负载……………………………………………………………7

2.2.3 2,4-二氯酚标准曲线的绘制……………………………………………………7

2.2.4 吸附实验…………………………………………………………………………7

第三章 实验结果与分析………………………………………………………………………9

3.1 2,4-二氯酚标准曲线…………………………………………………………………9

3.2 吸附实验………………………………………………………………………………9

3.2.1 确定最优铁/镍金属负载比例 …………………………………………………9

3.2.2 不同温度对1Ni-30Fe/NAC吸附效果的影响…………………………………10

3.2.3 不同pH对1Ni-30Fe/NAC吸附效果的影响 …………………………………14

3.2.4 未负载金属活性炭与1Ni-30Fe/NAC的对照实验……………………………15

第四章 总结与展望 …………………………………………………………………………17

4.1 总结 …………………………………………………………………………………17

4.2 展望 …………………………………………………………………………………17

参考文献………………………………………………………………………………………19

致谢……………………………………………………………………………………………21

第一章 绪论

1.1 背景

汽车工业的迅速发展产生了大量废旧橡胶轮胎。据统计，2009年我国轮胎产量已经达到3.8亿条^[1]，居全球第一。大量废弃轮胎的产生，不仅造成资源的严重浪费，而且带来严重的环境污染，影响人体健康。废轮胎处理过程可能产生二恶英、呋喃等持久性有机污染物以及锌、镉、镍、铅等重金属污染物^[2]，污染土壤、大气和地下水。

因此废旧轮胎的综合利用意义重大，不仅可以节约和补充大量的橡胶、钢丝、石油能源等资源，而且可以实现废旧轮胎的减量化、再利用和资源化^[1]。已有研究表明，含有大量的碳元素，是潜在的制备活性炭的大宗材料，且废旧橡胶轮胎可以通过、活化的方法制得中孔结构发达的活性炭。活性炭是很好的载体，可以负载金属催化剂吸附降解水中的污染物。以橡胶基活性炭为催化剂载体，负载不同的金属体系(铁、镍、铜、锌、锰、钴、铈等)，强化去除废水中的污染物，将会使废旧橡胶得到有效利用，也拓宽了橡胶基活性炭的应用范围。

1.1.1 橡胶的成分分析