纳米TiO_2光催化颗粒材料的制备及对造纸废水的处理研究
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摘要
随着纳米材料制备与应用基础研究的深入,纳米催化剂的研究近年来受到广泛关注。纳米TiO_2光催化剂作为一种新型环保材料是废水处理中研究的热点。但悬浮态TiO_2极易团聚,存在回收困难等问题,因此,对负载型纳米TiO_2的研发是影响工业化应用的关键。
造纸中段废水水量大、浓度高、颜色深、污染物种类多,且回收价值低,处理难度大。传统的处理方法容易引入某些杂质离子,造成二次污染,难以满足水质排放要求。而不少研究证明光催化氧化法处理造纸废水取得了令人满意的效果。同时,采用低品位的矿物原料制备新型环境材料是矿产资源高效利用的重要途径,有利于节约资源、保护环境和可持续发展。
本文利用纳米TiO_2的光催化作用,通过矿物负载,同时进行造粒研究,使其具备较高的吸附和光催化活性,解决粉状材料回收困难的问题,并进一步研究其回收利用率。结果表明:负载材料累托石与粉煤灰的配比是影响颗粒材料光催化活性的主要因素,造粒过程加入适量膨润土有利于颗粒强度的提高。回收的颗粒经加热处理后,重复使用4次,仍具有很好的去除效果。废水处理过程中,采用絮凝——光催化氧化法联合对造纸废水进行处理,并对其处理造纸废水的动力学模型和反应机理作了简单探讨。研究表明:当硫酸铝投加量为8g/L,pH值6.5～8.5,颗粒材料用量0.12g/mL,流经2个反应柱,光照4.5h后,COD去除率和脱色率均可达80%以上,处理后的水符合国家造纸工业水污染物排放标准(GB3544-2001)的一级标准。处理过程中加入适量H_2O_2有利于COD的降低,缩短光照时间。且颗粒材料对造纸废水的吸附规律较好的符合Freundlich和Langmuir吸附等温模型,光降解反应为准一级反应。最后利用XRD、SEM等表征手段对所制光催化颗粒材料进行结构表征。SEM图谱显示回收的颗粒材料形貌结构清晰可见,没有出现模糊、微孔被堵的现象。说明颗粒在焙烧过程中烧结较好,耐冲击性强,遇水没有发生分散、粉化的现象。
With the further study of nanomaterials, nanocatalysts have attracted wide-range attention for resent several decades. Nano-TiO_2, as a new functional material for environmental protection, was studied in wastewater widely. There were some disadvanteges such as aggregation effect and recycle difficulty for suspended TiO_2. Therefor, the research of TiO_2 with mineral materials is the key for its industrialization..
The treatment is difficult for paper-mill wastewater which has a character of large amount、high concentration、fuscous and little reusable as well as containing lots of contaminants. And traditional treatments are easy to bring some new ions, and induce secondary pollution, so as difficult to conform wastewater discharge standard. By contrary, some researches indicate that photocatalytic degradation of paper-mill wastewater has got satisfied effect. In addition, the production of new type environmental materials using low-grade minerals is an important way to utilize mineral resources efficiently, which helps the saving of resources, the protection of environment and sustainable development.
The preparation method of a novel granulated mineral supported nanometer-TiO_2 material with high adsorption and photocatalysis was studied in this dissertation, as well as the recycle rate. The results showed that the proportion of loaded matirials - rectorite and flyash - was the main factor of photocatalytic process. And adding proper bentonite can enhance the intensity of granulated materials. Furthermore, the granulated material could be regenerated by pyrogenation with quite good removal efficiency after reuse for four times. In the process of wastewater treatment, photocatalysis combined with flocculation was adopted. And reaction kinetics and photocalytic mechanism were also discussed. The results indicated that under the condition of pH 6.5～8.5, the optimal amount of Al_3(SO_4)_2 at 8g/L, and with the addition of granulated nanometer-material of 0.12g/ml, a ultraviolet reaction time of 4 hours, both the rate of removal of chroma and COD achieved more than 80%. And the quality indexes of the wastewater after treatment conformed with paper-mill wastewater discharge standard (GB3544-2001). If add another column with new granulated materials, the quality indexes of the wastewater after only half an hour's reaction conformed with the first discharge standard. In addition, adding proper oxidant was favorable for the removal of COD, and reduced reaction time as well. Furthermore, through imitating the Langmuir and Frundlich adsorption type, the process of photocatalytic degradation could be reasonably represented by first-grade reaction kinetics. In the end, the mineral supported nano-TiO_2 granulated material was characterized by XRD、SEM, and so on. According to the photos of SEM, the recycled granulated materials remained clear configuration without illegible and air-logged phenomenons. Which proved that the granulated nano-materials had high intensity, and could endure the strike of wastewater without dispersion.
造纸中段废水水量大、浓度高、颜色深、污染物种类多,且回收价值低,处理难度大。传统的处理方法容易引入某些杂质离子,造成二次污染,难以满足水质排放要求。而不少研究证明光催化氧化法处理造纸废水取得了令人满意的效果。同时,采用低品位的矿物原料制备新型环境材料是矿产资源高效利用的重要途径,有利于节约资源、保护环境和可持续发展。
本文利用纳米TiO_2的光催化作用,通过矿物负载,同时进行造粒研究,使其具备较高的吸附和光催化活性,解决粉状材料回收困难的问题,并进一步研究其回收利用率。结果表明:负载材料累托石与粉煤灰的配比是影响颗粒材料光催化活性的主要因素,造粒过程加入适量膨润土有利于颗粒强度的提高。回收的颗粒经加热处理后,重复使用4次,仍具有很好的去除效果。废水处理过程中,采用絮凝——光催化氧化法联合对造纸废水进行处理,并对其处理造纸废水的动力学模型和反应机理作了简单探讨。研究表明:当硫酸铝投加量为8g/L,pH值6.5～8.5,颗粒材料用量0.12g/mL,流经2个反应柱,光照4.5h后,COD去除率和脱色率均可达80%以上,处理后的水符合国家造纸工业水污染物排放标准(GB3544-2001)的一级标准。处理过程中加入适量H_2O_2有利于COD的降低,缩短光照时间。且颗粒材料对造纸废水的吸附规律较好的符合Freundlich和Langmuir吸附等温模型,光降解反应为准一级反应。最后利用XRD、SEM等表征手段对所制光催化颗粒材料进行结构表征。SEM图谱显示回收的颗粒材料形貌结构清晰可见,没有出现模糊、微孔被堵的现象。说明颗粒在焙烧过程中烧结较好,耐冲击性强,遇水没有发生分散、粉化的现象。
With the further study of nanomaterials, nanocatalysts have attracted wide-range attention for resent several decades. Nano-TiO_2, as a new functional material for environmental protection, was studied in wastewater widely. There were some disadvanteges such as aggregation effect and recycle difficulty for suspended TiO_2. Therefor, the research of TiO_2 with mineral materials is the key for its industrialization..
The treatment is difficult for paper-mill wastewater which has a character of large amount、high concentration、fuscous and little reusable as well as containing lots of contaminants. And traditional treatments are easy to bring some new ions, and induce secondary pollution, so as difficult to conform wastewater discharge standard. By contrary, some researches indicate that photocatalytic degradation of paper-mill wastewater has got satisfied effect. In addition, the production of new type environmental materials using low-grade minerals is an important way to utilize mineral resources efficiently, which helps the saving of resources, the protection of environment and sustainable development.
The preparation method of a novel granulated mineral supported nanometer-TiO_2 material with high adsorption and photocatalysis was studied in this dissertation, as well as the recycle rate. The results showed that the proportion of loaded matirials - rectorite and flyash - was the main factor of photocatalytic process. And adding proper bentonite can enhance the intensity of granulated materials. Furthermore, the granulated material could be regenerated by pyrogenation with quite good removal efficiency after reuse for four times. In the process of wastewater treatment, photocatalysis combined with flocculation was adopted. And reaction kinetics and photocalytic mechanism were also discussed. The results indicated that under the condition of pH 6.5～8.5, the optimal amount of Al_3(SO_4)_2 at 8g/L, and with the addition of granulated nanometer-material of 0.12g/ml, a ultraviolet reaction time of 4 hours, both the rate of removal of chroma and COD achieved more than 80%. And the quality indexes of the wastewater after treatment conformed with paper-mill wastewater discharge standard (GB3544-2001). If add another column with new granulated materials, the quality indexes of the wastewater after only half an hour's reaction conformed with the first discharge standard. In addition, adding proper oxidant was favorable for the removal of COD, and reduced reaction time as well. Furthermore, through imitating the Langmuir and Frundlich adsorption type, the process of photocatalytic degradation could be reasonably represented by first-grade reaction kinetics. In the end, the mineral supported nano-TiO_2 granulated material was characterized by XRD、SEM, and so on. According to the photos of SEM, the recycled granulated materials remained clear configuration without illegible and air-logged phenomenons. Which proved that the granulated nano-materials had high intensity, and could endure the strike of wastewater without dispersion.
引文
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