纳米复合光催化剂的制备及其在印染废水中的应用研究
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摘要
印染废水因其毒性大、成分复杂、不易降解等特点，其降解处理已成为废水处理领域中的一大难题。以半导体材料为催化剂的光催化氧化法是近年来兴起的一种水处理技术，与传统方法相比，具有高效、稳定、无二次污染以及对各类有机污染物尤其是难生物降解的有毒污染物进行深度、彻底氧化的突出特点，还具有可直接利用太阳能进行光化学转换的独特优势，因而成为世界各国研究的热点。TiO_2是一种较为理想的光催化剂，但普通TiO_2存在电荷分离效率差、光催化活性低等缺点，致使它的应用受到限制。为了提高TiO_2的光催化活性，通过贵金属Ru对TiO_2进行改性，研究复合光催化剂的制备方法，并以直接耐晒黑G和直接红棕为模型反应物，评价所制催化剂的光催化活性，具体研究工作如下：
1．光催化剂的制备及结构表征
采用Sol-gel-immersion法制备了复合光催化剂RuO_2／TiO_2和RuO_2／La_2O_3／TiO_2，并借助XRD、TEM等测试手段进行了结构表征。结果表明本文所制备的复合催化剂平均粒度为10～20nm，热处理温度升高导致TiO_2由锐钛矿相向金红石相转变。500℃热处
摘要
理所得催化剂中TIOZ主要为锐钦矿相。
2.光催化降解实验
利用自行设计的光催化反应装置，系统地研究了复合光催化剂对偶氮染料直接耐
晒黑G和直接红棕的光催化降解性能，探讨了影响光催化反应的各种因素，确定了有
利一于光催化反应的最佳条件:
尸
(l)RuoZ汀10:光催化体系:RuoZ掺杂量0.16%、锻烧温度500℃、投加量sg/L、
通气量300 mL/min、初始pH值5.05、光源为高压汞幻一时，30min直接耐晒黑G降解
率97.6%;降解过程服从Langmuir一Hinshehwood动力学模型，并求得反应速率常数
胜4 .94x 10一3
·m in)
了，吸附常数K一’4.22 L.mmol一’;催化剂粉体回收实验表明，
其光催化
，乡年一百分点，可重复利用。
(2)RuOZ/LaZo3/Tio:光催化体系:①降解直接耐晒黑G(somg/L):RuO:掺杂址
o一6%、锻烧温度500oC、投加量3g/L、通气量300 mL/min、初始pH值7.32、光源
为高压汞灯时，吸收光谱表明4Omin可见区有色基团己基本降解，6Omin在20Onm一
7O0nm范围吸光度接近零，表明其己完全降解;不论哪种复合光催化剂，其光催化活
性都比纯TIOZ高(约提高1 .2倍以上)，三元复合光催化剂RuOZ/L aZO3汀io:比二元
复合光催化剂RuoZ厅io:催化活性高。②降解直接红棕(80m叭):Ruo:掺杂散0.12
%、锻烧温度500，C、投加量3g/L、通气量100 mL/min、初始pH值8.98、光源为高
压汞灯，30min降解率达100%，测得反应速率常数k=0.206min‘，，半衰期为337而n。
添加HZOZ可明显提高降解速率。
(3)实际印染废水降解:将RuOZ/TIOZ光催化降解体系应用于实际印染废水(初
始值:色度10000、CODer2614 mg/L)，经12omin光催化降解其色度及CoDer分别
降低99.2%和97.6%。
As poisonous and complicated of chemical composition of printing and dyeing wastewater, the degradation and treatment of them is a very difficult problem in the field of wastewater treatment. Photocatalytic oxidation of water contaminants with semiconductors has been reported as one of more promising remediation technologies for complete mineralization of undesirable organic contaminants, particularly toxic and unbiodegradable organic compounds. TiO2 has been shown to be an excellent photocatalyst owing to its stable chemical characteristics and low price, etc. However, due to its low reaction rate and narrow range of available spectrum, photocatalytic oxidation is almost unindustrialized in wastewater treatment. In order to improve the photocatalytic activity and extend energy range of photo-excitation, expensive metal (Ru) was deposit for amend photocatalytic activity of TiO2 in this thesis.
1. Preparation and structural characterization of photocatalyst
RuO2/TiO2 and RuO2/La2O3/TiO2 were prepared by Sol-gel-immersion method. The structure and morphology of catalysts were characterized by means of XRD and TEM. The results indicated that the average particle size of catalysts was below 20nm and anatase TiO2 transformed to rutile TiO2 with increase of calcinations temperature. The percent of anatase TiO2 was about 100% at the calcinations temperature of 500C for 2h.
2. Photocatalytic degradation experiments
The photocatalytic activity of multi-photocatalyst was evaluated by the photodegradation of Direct Fast Blank G and Direct Fast Brown, and the effects of various conditions on the photocatalytic characteristics were investigated. The experimental results were as follows:
(1) Photodegradation system of RuO2/TiO2: when addition of RuO2 0.16%, calcinations temperature 500C , amount of photocatalyst 5g/L, air flow rate 300 mL/min, initial pH 5.05, mercury lamp as light source, Direct Fast Blank G was degraded 97.6% in 30min.The results showed that the degradation reaction of the Direct Fast Blank G almost followed Langmuir-Hinshehwood model, and the reaction was the apparent first order. The reaction rate constant k and the absorption constant K were determined to be 4.94x10-3 mmol (L min)-1 and 14.22L mmol-1 respectively. The photocatalytic activity of used photocatalyst declined less than 3 percentage when compared with unused,'so it could be used repeatedly.
(2) Photodegradation system of RuO2/La2O3/TiO2: (1) Degradation of Direct Fast Blank G: addition of RuO2 0.16% , calcinations temperature 500C , amount of photocatalyst 3g/L, air flow rate 300 mL/min> initial pH 7.32, mercury lamp as light source, the groups of visible spectrum were degraded in 40min, and the absorption spectrum from 200nm to 700nm were almost zore in 60min, this result indicates that the dye has been degraded completely. Compared with single nanosized TiO2, activity of multi-photocatalyst promoted 1.2 times. The half-degradation period by RuO2 /La2O3 /TiO2 been cut down 5min than RuO2/TiO2. (2) Degradation of Direct Fast Brown: addition of RuO2 0.12%, calcinations temperature 500C,amount of photocatalyst 3g/L, air flow rate 100 mL/min, initial pH 8.98, mercury lamp as light source, the degraded efficiency was 97.6% in 30min, and absorption constant k=0,206min-1,t1/2=3.37 min. The degraded rate improved obviously when addition of H2O2 to the system of RuO2/La2O3/TiO2 photocatalyt
ic degradation.
(3) Degradation of real printing and dyeing wastewater: By using of RuO2/TiO2 photocatalytic degradation system, the photocatalytic degradation of the real printing and dyeing wastewater (the value of initiation Chromaticity: 10000, CODCr value: 2614mg/L) was carried out for 120min, the results showed that the Chromaticity and CODCr value were reduced to be 99.2% and 97.6%, respectively.
1．光催化剂的制备及结构表征
采用Sol-gel-immersion法制备了复合光催化剂RuO_2／TiO_2和RuO_2／La_2O_3／TiO_2，并借助XRD、TEM等测试手段进行了结构表征。结果表明本文所制备的复合催化剂平均粒度为10～20nm，热处理温度升高导致TiO_2由锐钛矿相向金红石相转变。500℃热处
摘要
理所得催化剂中TIOZ主要为锐钦矿相。
2.光催化降解实验
利用自行设计的光催化反应装置，系统地研究了复合光催化剂对偶氮染料直接耐
晒黑G和直接红棕的光催化降解性能，探讨了影响光催化反应的各种因素，确定了有
利一于光催化反应的最佳条件:
尸
(l)RuoZ汀10:光催化体系:RuoZ掺杂量0.16%、锻烧温度500℃、投加量sg/L、
通气量300 mL/min、初始pH值5.05、光源为高压汞幻一时，30min直接耐晒黑G降解
率97.6%;降解过程服从Langmuir一Hinshehwood动力学模型，并求得反应速率常数
胜4 .94x 10一3
·m in)
了，吸附常数K一’4.22 L.mmol一’;催化剂粉体回收实验表明，
其光催化
，乡年一百分点，可重复利用。
(2)RuOZ/LaZo3/Tio:光催化体系:①降解直接耐晒黑G(somg/L):RuO:掺杂址
o一6%、锻烧温度500oC、投加量3g/L、通气量300 mL/min、初始pH值7.32、光源
为高压汞灯时，吸收光谱表明4Omin可见区有色基团己基本降解，6Omin在20Onm一
7O0nm范围吸光度接近零，表明其己完全降解;不论哪种复合光催化剂，其光催化活
性都比纯TIOZ高(约提高1 .2倍以上)，三元复合光催化剂RuOZ/L aZO3汀io:比二元
复合光催化剂RuoZ厅io:催化活性高。②降解直接红棕(80m叭):Ruo:掺杂散0.12
%、锻烧温度500，C、投加量3g/L、通气量100 mL/min、初始pH值8.98、光源为高
压汞灯，30min降解率达100%，测得反应速率常数k=0.206min‘，，半衰期为337而n。
添加HZOZ可明显提高降解速率。
(3)实际印染废水降解:将RuOZ/TIOZ光催化降解体系应用于实际印染废水(初
始值:色度10000、CODer2614 mg/L)，经12omin光催化降解其色度及CoDer分别
降低99.2%和97.6%。
As poisonous and complicated of chemical composition of printing and dyeing wastewater, the degradation and treatment of them is a very difficult problem in the field of wastewater treatment. Photocatalytic oxidation of water contaminants with semiconductors has been reported as one of more promising remediation technologies for complete mineralization of undesirable organic contaminants, particularly toxic and unbiodegradable organic compounds. TiO2 has been shown to be an excellent photocatalyst owing to its stable chemical characteristics and low price, etc. However, due to its low reaction rate and narrow range of available spectrum, photocatalytic oxidation is almost unindustrialized in wastewater treatment. In order to improve the photocatalytic activity and extend energy range of photo-excitation, expensive metal (Ru) was deposit for amend photocatalytic activity of TiO2 in this thesis.
1. Preparation and structural characterization of photocatalyst
RuO2/TiO2 and RuO2/La2O3/TiO2 were prepared by Sol-gel-immersion method. The structure and morphology of catalysts were characterized by means of XRD and TEM. The results indicated that the average particle size of catalysts was below 20nm and anatase TiO2 transformed to rutile TiO2 with increase of calcinations temperature. The percent of anatase TiO2 was about 100% at the calcinations temperature of 500C for 2h.
2. Photocatalytic degradation experiments
The photocatalytic activity of multi-photocatalyst was evaluated by the photodegradation of Direct Fast Blank G and Direct Fast Brown, and the effects of various conditions on the photocatalytic characteristics were investigated. The experimental results were as follows:
(1) Photodegradation system of RuO2/TiO2: when addition of RuO2 0.16%, calcinations temperature 500C , amount of photocatalyst 5g/L, air flow rate 300 mL/min, initial pH 5.05, mercury lamp as light source, Direct Fast Blank G was degraded 97.6% in 30min.The results showed that the degradation reaction of the Direct Fast Blank G almost followed Langmuir-Hinshehwood model, and the reaction was the apparent first order. The reaction rate constant k and the absorption constant K were determined to be 4.94x10-3 mmol (L min)-1 and 14.22L mmol-1 respectively. The photocatalytic activity of used photocatalyst declined less than 3 percentage when compared with unused,'so it could be used repeatedly.
(2) Photodegradation system of RuO2/La2O3/TiO2: (1) Degradation of Direct Fast Blank G: addition of RuO2 0.16% , calcinations temperature 500C , amount of photocatalyst 3g/L, air flow rate 300 mL/min> initial pH 7.32, mercury lamp as light source, the groups of visible spectrum were degraded in 40min, and the absorption spectrum from 200nm to 700nm were almost zore in 60min, this result indicates that the dye has been degraded completely. Compared with single nanosized TiO2, activity of multi-photocatalyst promoted 1.2 times. The half-degradation period by RuO2 /La2O3 /TiO2 been cut down 5min than RuO2/TiO2. (2) Degradation of Direct Fast Brown: addition of RuO2 0.12%, calcinations temperature 500C,amount of photocatalyst 3g/L, air flow rate 100 mL/min, initial pH 8.98, mercury lamp as light source, the degraded efficiency was 97.6% in 30min, and absorption constant k=0,206min-1,t1/2=3.37 min. The degraded rate improved obviously when addition of H2O2 to the system of RuO2/La2O3/TiO2 photocatalyt
ic degradation.
(3) Degradation of real printing and dyeing wastewater: By using of RuO2/TiO2 photocatalytic degradation system, the photocatalytic degradation of the real printing and dyeing wastewater (the value of initiation Chromaticity: 10000, CODCr value: 2614mg/L) was carried out for 120min, the results showed that the Chromaticity and CODCr value were reduced to be 99.2% and 97.6%, respectively.
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