负载型改性纳米TiO_2光催化降解染料废水的试验研究
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摘要
纳米TiO_2具有高比表面积、高密度、表面晶格缺陷以及高比表面能等特点，具有化学性质稳定、无毒、催化活性高、反应速度快、对有机物的降解选择性低且能使之彻底矿化、无二次污染等优点，在废水处理、空气净化中掺杂一定量的金属离子或对其进行表面改性，能有效地阻止电荷在转移过程中的复合，使其光催化活性提高。为了充分利用太阳光，必须对半导体光催化剂进行改性，希望在提高光催化活性的同时能扩展光谱响应范围，提高太阳能的利用率。利用太阳能进行污染物的处理研究，对于保护环境，维持生态平衡，实现可持续发展具有重要的意义。
本文着眼于我国染料废水的污染现状，研究了用负载型纳米TiO_2光催化剂和改性负载型纳米TiO_2光催化剂处理常见染料废水的实验条件和作用机理。
本实验采用焦炭为载体，Na_2SiO_3为粘结剂，研究了负载型纳米TiO_2光催化剂和分别掺Fe、Cu的改性负载型纳米TiO_2光催化剂的降解能力。在相同的试验条件下，分别考察了以紫外灯为光源和以太阳光为光源时光催化剂对染料废水的降解率。通过实验考察了影响降解效果的主要因素及其影响规律，并对不同光催化剂的降解机理进行了探讨。
本文研究了粘结剂浓度、改性金属掺杂量、煅烧温度、煅烧时间等因素对降解效率的影响，分别设计进行了L_9(3~3)、L_9(3~4)的正交实验，考察这几个因素的影响程度；同时考察了涂覆量、涂覆次数、太阳光强度等因素对染料废水的降解效果的影响。
本文得到的实验结果是：
(1)负载型TiO_2光催化剂：浸涂液最佳的TiO_2质量百分含量为18％；正交实验优化出来的实验条件是：400℃的煅烧温度，粘结剂取质量百分比为20％的Na_2SiO_3溶液，煅烧时间为3h，对亚甲基蓝染料废水的最高降解率为80.88％，各因素对降解效果影响由大到小的排列顺序是：煅烧温度＞Na_2SiO_3浓度＞煅烧时间。但负载的TiO_2粉末剥落严重，出水浑浊，重复利用性差。同时发现，染料废水的降解效率与光强度Ⅰ成正比，本实验在最高光强时4.585×100μw/cm~2时的降
广东工业大学工学硕士学位论文
解率为89名6%。
(2)改性负载型Ti仇光催化剂:以紫外灯为光源时负载型掺Fe改性光催
化剂正交实验得出各因素对降解效果的影响由大到小的排列顺序是:锻烧时间>
锻烧温度>N匆S心浓度>Fe掺杂量:以太阳光为光源时负载型掺Fe改性光催化
剂正交实验得出各实验因素对降解效果的影响由大到小的排列顺序是:锻烧时间
>Fe掺杂量>N匆S心百分比习毅烧温度。分别以紫外灯和太阳光为光源时Fe改性
实验优化出来的实验条件都是:粼刃℃的锻烧温度，粘结剂质量百分比浓度为200/0
的NaZsi几溶液，锻烧时间为3h。对于负载型掺Fe改性光催化剂，F勿仇改性光
催化剂的降解率明显高于F《。田3改性光催化剂的降解率。掺Fe量为2%时F之岛
和Fe(0卿3改性光催化剂的降解率最高，且出水澄清，光催化剂几乎不剥落。掺
Cu的改性光催化剂中市售C侧0改性光催化剂对染料废水的降解效果高于
C试OI场改性光催化剂的降解效果，且在掺杂量为2%时降解率最高。Fe改性光
催化剂的降解效果要明显高于掺Cu改性光催化剂。
Nanosized T1O2 has the properties of high superficial area, high density, superficial crystal lattice lacuna and high superficial area energy, and it has excellent chemical stability, innocuity, high catalyzed activity, high reaction speed, low option to organics degradation and fully mineraling organics to CO2 & H2O. Doped some metallic ion or alter its property on surface when treating wastewater and purifying air can effectively hinder charge recovery in the course of transferring and improve its catalyst activity. In order to make full use of sunlight, it is necessary to dope some semiconductor photocatalyst to improve catalyst activity and expand its responding spectrum area. The study on using sunlight to deal with pollutants is very important for protecting environment, maintaining zoology balance and achieving sustained development.
Basing on the present situation of dye water pollution, the paper studies experiments conditions on immobilized nanosized T1Q2 photocatalyst and doped immobilized nanosized TiO2 photocatalyst degrading common dye wastewater and working mechanism.
The experiments use cokes as the carriers, Na2SiO3 as adhensive. The degradation ability of immobilized nanosized TiO2 photocatalyst, Fe or Cu doped immobilized nanosized TiQ2 photocatalysts are studied. Using ultra-light and sunlight as lamp-house respectively, degradation results of different immobilized nanosized T1Q2 photocatalyst are studied under the same experimental conditions. Meanwhile, kinds of photocatalysts degradation mechanisms are discussed.
At the same time, in order to studied the factor, such as adhensive concentration, doped metal quality, calcining temperature, calcining time, orthogonal tests of L9(33) L9(34) have been done. The other factors, such as coated quality, coated times and sunlight density are studied as well.
The experimental results of the study are as follows:
(1) Immobilized nanosized TiO2 photocatalyst: the optimal TiO2 weight percent of coated liquid is 18%; the optimal conditions by orthogonal test are: calcining temperature is 400癈, adhensive aqueous weight percent is 20%, calcining time is 3h, and the highest degradation rate to dye wastewater is 80.88%. The factor importance order is: calcining temperature> Na2SiO3 weight percent > calcining time. However, Immobilized nanosized TiO2 photocatalyst powder flaked away heavily, and its reuse is poor. The degradation rate of Methylene blue wastewater is in proportion to light intensity I, the degradation rate is 89.86% at the highest sunlight intensity 4.585x100uw/cm2.
(2) Doped immobilized nanosized TiO2 photocatalyst: when using ultra-light as lamp-house, The factor importance order by the doped Fe orthogonal test is: calcining time > calcining temperature> Na2SiO3 weight percent > doped Fe quantity; when using sunlight as lamp-house, The factor importance order by the doped Fe orthogonal test is: calcining time > doped Fe quantity > Na2SiO3 weight percent > calcining temperature; the optimal conditions by doped Fe orthogonal tests are: calcining temperature is 400癈, adhensive aqueous weight percent is 20 %, calcining time is 3h. The degradation rates of Fe2O3 doped immobilized photocatalyst are obviously higher than that of Fe(OH)3 doped immobilized photocatalyst When Fe doped weight percent is 2%, the highest degradation rate is obtained. Moreover, TiO2 flaked away little, and its reuse was good. As for the Cu doped immobilized nanosized TiO2 photocatalyst, the degradation rates of CuO doped immobilized photocatalyst are higher than that of Cu(OH)2 doped immobilized
photocatalyst. When Cu doped weight percent was 2%, the highest degradation rate is obtained. The degradation rates of Fe doped immobilized photocatalyst are obviously higher than that of Cu doped immobilized photocatalyst.
本文着眼于我国染料废水的污染现状，研究了用负载型纳米TiO_2光催化剂和改性负载型纳米TiO_2光催化剂处理常见染料废水的实验条件和作用机理。
本实验采用焦炭为载体，Na_2SiO_3为粘结剂，研究了负载型纳米TiO_2光催化剂和分别掺Fe、Cu的改性负载型纳米TiO_2光催化剂的降解能力。在相同的试验条件下，分别考察了以紫外灯为光源和以太阳光为光源时光催化剂对染料废水的降解率。通过实验考察了影响降解效果的主要因素及其影响规律，并对不同光催化剂的降解机理进行了探讨。
本文研究了粘结剂浓度、改性金属掺杂量、煅烧温度、煅烧时间等因素对降解效率的影响，分别设计进行了L_9(3~3)、L_9(3~4)的正交实验，考察这几个因素的影响程度；同时考察了涂覆量、涂覆次数、太阳光强度等因素对染料废水的降解效果的影响。
本文得到的实验结果是：
(1)负载型TiO_2光催化剂：浸涂液最佳的TiO_2质量百分含量为18％；正交实验优化出来的实验条件是：400℃的煅烧温度，粘结剂取质量百分比为20％的Na_2SiO_3溶液，煅烧时间为3h，对亚甲基蓝染料废水的最高降解率为80.88％，各因素对降解效果影响由大到小的排列顺序是：煅烧温度＞Na_2SiO_3浓度＞煅烧时间。但负载的TiO_2粉末剥落严重，出水浑浊，重复利用性差。同时发现，染料废水的降解效率与光强度Ⅰ成正比，本实验在最高光强时4.585×100μw/cm~2时的降
广东工业大学工学硕士学位论文
解率为89名6%。
(2)改性负载型Ti仇光催化剂:以紫外灯为光源时负载型掺Fe改性光催
化剂正交实验得出各因素对降解效果的影响由大到小的排列顺序是:锻烧时间>
锻烧温度>N匆S心浓度>Fe掺杂量:以太阳光为光源时负载型掺Fe改性光催化
剂正交实验得出各实验因素对降解效果的影响由大到小的排列顺序是:锻烧时间
>Fe掺杂量>N匆S心百分比习毅烧温度。分别以紫外灯和太阳光为光源时Fe改性
实验优化出来的实验条件都是:粼刃℃的锻烧温度，粘结剂质量百分比浓度为200/0
的NaZsi几溶液，锻烧时间为3h。对于负载型掺Fe改性光催化剂，F勿仇改性光
催化剂的降解率明显高于F《。田3改性光催化剂的降解率。掺Fe量为2%时F之岛
和Fe(0卿3改性光催化剂的降解率最高，且出水澄清，光催化剂几乎不剥落。掺
Cu的改性光催化剂中市售C侧0改性光催化剂对染料废水的降解效果高于
C试OI场改性光催化剂的降解效果，且在掺杂量为2%时降解率最高。Fe改性光
催化剂的降解效果要明显高于掺Cu改性光催化剂。
Nanosized T1O2 has the properties of high superficial area, high density, superficial crystal lattice lacuna and high superficial area energy, and it has excellent chemical stability, innocuity, high catalyzed activity, high reaction speed, low option to organics degradation and fully mineraling organics to CO2 & H2O. Doped some metallic ion or alter its property on surface when treating wastewater and purifying air can effectively hinder charge recovery in the course of transferring and improve its catalyst activity. In order to make full use of sunlight, it is necessary to dope some semiconductor photocatalyst to improve catalyst activity and expand its responding spectrum area. The study on using sunlight to deal with pollutants is very important for protecting environment, maintaining zoology balance and achieving sustained development.
Basing on the present situation of dye water pollution, the paper studies experiments conditions on immobilized nanosized T1Q2 photocatalyst and doped immobilized nanosized TiO2 photocatalyst degrading common dye wastewater and working mechanism.
The experiments use cokes as the carriers, Na2SiO3 as adhensive. The degradation ability of immobilized nanosized TiO2 photocatalyst, Fe or Cu doped immobilized nanosized TiQ2 photocatalysts are studied. Using ultra-light and sunlight as lamp-house respectively, degradation results of different immobilized nanosized T1Q2 photocatalyst are studied under the same experimental conditions. Meanwhile, kinds of photocatalysts degradation mechanisms are discussed.
At the same time, in order to studied the factor, such as adhensive concentration, doped metal quality, calcining temperature, calcining time, orthogonal tests of L9(33) L9(34) have been done. The other factors, such as coated quality, coated times and sunlight density are studied as well.
The experimental results of the study are as follows:
(1) Immobilized nanosized TiO2 photocatalyst: the optimal TiO2 weight percent of coated liquid is 18%; the optimal conditions by orthogonal test are: calcining temperature is 400癈, adhensive aqueous weight percent is 20%, calcining time is 3h, and the highest degradation rate to dye wastewater is 80.88%. The factor importance order is: calcining temperature> Na2SiO3 weight percent > calcining time. However, Immobilized nanosized TiO2 photocatalyst powder flaked away heavily, and its reuse is poor. The degradation rate of Methylene blue wastewater is in proportion to light intensity I, the degradation rate is 89.86% at the highest sunlight intensity 4.585x100uw/cm2.
(2) Doped immobilized nanosized TiO2 photocatalyst: when using ultra-light as lamp-house, The factor importance order by the doped Fe orthogonal test is: calcining time > calcining temperature> Na2SiO3 weight percent > doped Fe quantity; when using sunlight as lamp-house, The factor importance order by the doped Fe orthogonal test is: calcining time > doped Fe quantity > Na2SiO3 weight percent > calcining temperature; the optimal conditions by doped Fe orthogonal tests are: calcining temperature is 400癈, adhensive aqueous weight percent is 20 %, calcining time is 3h. The degradation rates of Fe2O3 doped immobilized photocatalyst are obviously higher than that of Fe(OH)3 doped immobilized photocatalyst When Fe doped weight percent is 2%, the highest degradation rate is obtained. Moreover, TiO2 flaked away little, and its reuse was good. As for the Cu doped immobilized nanosized TiO2 photocatalyst, the degradation rates of CuO doped immobilized photocatalyst are higher than that of Cu(OH)2 doped immobilized
photocatalyst. When Cu doped weight percent was 2%, the highest degradation rate is obtained. The degradation rates of Fe doped immobilized photocatalyst are obviously higher than that of Cu doped immobilized photocatalyst.
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