本文關(guān)鍵詞：赤泥基類Fenton催化劑的制備及其性能研究　出處：《廣西大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 赤泥 Fenton α-Fe_2O_3 ZnO 橙黃 Ⅱ

【摘要】：隨著我國工業(yè)化進(jìn)程的加快,工業(yè)廢水大量排放,對自然環(huán)境及人類健康造成了嚴(yán)重的危害,其中有機(jī)廢水由于具有水質(zhì)復(fù)雜、COD高、毒性大、難降解等特點,其處理一直是環(huán)保領(lǐng)域的熱點話題,高級氧化法被認(rèn)為是處理有機(jī)廢水比較可行的方法之一。其中,Fenton氧化法因具有高效、穩(wěn)定、污染物降解相對徹底等優(yōu)勢而被廣泛應(yīng)用。但是均相Fenton法存在鐵離子難回收,容易造成二次污染等缺點,限制了其工業(yè)化應(yīng)用。為此,國內(nèi)外學(xué)者利用天然鐵礦或?qū)⒋呋钚澡F組分固定在載體上,制備出不溶于水的非均相催化劑,以解決催化劑難回收等問題。赤泥是制鋁工業(yè)提取氧化鋁時排出的污染性廢渣,根據(jù)氧化鋁不同生產(chǎn)方法可分為拜耳法赤泥、燒結(jié)法赤泥和聯(lián)合法赤泥。赤泥呈強(qiáng)堿性(pH 10.0-12.5),主要的化學(xué)成分包括Fe203、Si02、A1203、Ti02、Na2O、CaO等,其中拜耳法赤泥通常鐵含量高,鐵氧化物含量高達(dá)30%以上,這一特性為拜耳法赤泥制備非均相類Fenton催化劑提供了可能。本研究工作,從循環(huán)經(jīng)濟(jì)的角度出發(fā),同時立足于廣西區(qū)域發(fā)展,以廣西制鋁行業(yè)大量排放的拜耳法赤泥為基礎(chǔ)材料,通過無機(jī)酸酸化對赤泥進(jìn)行預(yù)處理,再經(jīng)高溫焙燒過程制備出酸化/焙燒赤泥;通過引入糖蜜酒精廢液協(xié)同無機(jī)酸酸化對赤泥進(jìn)行預(yù)處理,再經(jīng)高溫焙燒過程制備出糖蜜酒精廢液-硫酸酸化/焙燒赤泥;通過對赤泥進(jìn)行焙燒預(yù)處理,充分釋放赤泥的堿性物質(zhì),然后將預(yù)處理后的赤泥制成漿液,并向漿液中投加鋅鹽,利用赤泥自身堿源,沉淀水相中的鋅離子,得到前驅(qū)體,再經(jīng)焙燒處理,將具有光催化活性的半導(dǎo)體材料ZnO固載于赤泥基體上,制備出赤泥基ZnO/α-Fe2O3復(fù)合材料。并以黃藥和橙黃Ⅱ模擬有機(jī)廢水,研究酸化/焙燒赤泥、糖蜜酒精廢液-硫酸酸化/焙燒赤泥、赤泥基ZnO/α-Fe2O3復(fù)合材料的類Fenton催化性能,確定其最佳制備工藝及部分應(yīng)用工藝條件。借助XRD、SEM、EDS以及N2吸附與脫附等技術(shù)對催化劑進(jìn)行表征分析,研究所制備催化劑的結(jié)構(gòu)特點。研究成果可為赤泥的資源化利用提供參考,主要研究結(jié)果如下:(1)酸化/焙燒赤泥制備過程中關(guān)鍵控制步驟的最佳工藝條件包括:硫酸酸化至泥漿的pH=3、焙燒溫度673K、焙燒時間1 h。催化劑的表征顯示,酸化/焙燒赤泥中的鐵相主要是α-Fe203,并且該催化劑是一種多孔的材料,具有粗糙的表面。在上述條件下所制備出的酸化/焙燒赤泥具有優(yōu)良的類Fenton催化性能,在催化劑投加量0.2g.L-1 H202初始濃度5mmol·L-1的條件下,對于50 mg.L-1的丁基黃藥溶液在反應(yīng)進(jìn)行到40 min時,黃藥去除率達(dá)到90.2%,并且所制備的催化劑在Fenton過程中性能穩(wěn)定。另外酸化/焙燒赤泥催化類Fenton過程中羥基自由基的產(chǎn)生以及丁基黃藥的降解機(jī)理被探究。(2)糖蜜酒精廢液-硫酸酸化/焙燒赤泥制備過程中關(guān)鍵控制步驟的最佳工藝條件包括:對于3 g赤泥,9 mL濃度為0.7 mol·L-1 H2S04配以2 g糖蜜酒精廢液作為酸化試劑,焙燒溫度573K,焙燒時間1h。催化劑的表征顯示,糖蜜酒精廢液-硫酸酸化/焙燒赤泥中的鐵相主要是α-Fe203,有微量的炭生成,并且該催化劑是一種多孔的材料,表面粗糙。另外,糖蜜酒精廢液的加入,節(jié)省了H2SO4的用量,同時也顯著增強(qiáng)了所制備催化劑的物化性能。催化劑近中性的微環(huán)境、優(yōu)良的孔結(jié)構(gòu)、炭的生成都促使糖蜜酒精廢液-硫酸酸化/焙燒赤泥的催化性能顯著提高。其中,炭的生成以及優(yōu)良的孔結(jié)構(gòu)完全歸因于催化劑制備過程中糖蜜酒精廢液的加入。在上述條件下所制備出的催化材料具有優(yōu)良的類Fenton催化性能,在初始溶液pH 3、H202投加量50mmol·L-1、橙黃Ⅱ質(zhì)量濃度40mg.L-L、反應(yīng)時間6h的條件下,橙黃Ⅱ去除率達(dá)到86.79%;該催化降解過程符合一級動力學(xué)模型。并且,所制備的催化劑在Fenton過程中具有優(yōu)良的沉降性能以及較好的穩(wěn)定性,反應(yīng)溶液中總鐵離子質(zhì)量濃度在5次重復(fù)使用過程中均遠(yuǎn)低于10 mg.L-1的國家標(biāo)準(zhǔn)。(3)赤泥基ZnO/α-Fe2O3復(fù)合材料制備過程中關(guān)鍵控制步驟的最佳工藝條件包括:預(yù)處理溫度973K、預(yù)處理時間1 h、赤泥與Zn(N03)2質(zhì)量比2:1、焙燒溫度623K、焙燒時間2 h。催化劑的表征顯示,赤泥基ZnO/α-Fe2O3復(fù)合材料中的鐵相主要是α-Fe2O3,ZnO成功固載于赤泥基體上,并且該催化劑是一種多孔的材料,具有粗糙的表面和良好的孔隙結(jié)構(gòu),而且對紫外光和可見光具有較好的吸收能力。在上述條件下所制備出的赤泥基ZnO/α-Fe2O3復(fù)合材料具有優(yōu)良的光助Fenton催化性能,在催化劑投加量0.1g·L-1、反應(yīng)溫度303K、H2O2初始濃度20mmol·L-1條件下,40 mg·L-1的橙黃Ⅱ溶液在熒光高壓汞燈持續(xù)照射4 h時,去除率達(dá)到74.75%。
[Abstract]:With the acceleration of China's industrialization, industrial wastewater emissions caused serious damage to the natural environment and human health, including organic wastewater with a complex quality, high COD, high toxicity, refractory and other characteristics, it has been a hot topic in the field of environmental protection, advanced oxidation method is considered to be one of the methods for treatment of organic the waste water is feasible. The oxidation of Fenton method is efficient, stable, relatively complete degradation of pollutants advantages and is widely used. But all phase Fenton iron ions difficult to recycle, easy to cause two pollution and other shortcomings, limiting its industrial application. Therefore, the scholars at home and abroad by natural or catalytic activity of iron ore component fixed on the carrier, the preparation of a water insoluble heterogeneous catalyst, to solve the problem of catalyst. The red mud is difficult to recycle aluminum industry pollution discharged waste when extracting alumina According to different production methods of alumina slag can be divided into the Bayer process, sintering red mud and combined method of red mud is strongly alkaline (pH 10.0-12.5), the main chemical composition including Fe203, Si02, A1203, Ti02, Na2O, CaO and so on, which is usually the Bayer red mud high iron content, iron oxide content is as high as 30% above, this characteristic for Bayer red mud preparation of heterogeneous Fenton catalyst may be provided. In this paper, from the perspective of circular economy, and based on regional development in Guangxi, Bayer red mud emissions in Guangxi aluminum industry as the basic materials, the inorganic acid of red mud pretreatment after the calcination process was prepared by acidification / roasting red mud; molasses alcohol wastewater by introducing inorganic acid coordination of red mud was pretreated by high temperature roasting process of preparation of molasses alcohol wastewater - sulfur acid / red mud through roasting; After roasting pretreatment of red mud, alkaline substances released in full of red mud, and red mud after pretreatment into slurry into the slurry, and adding zinc salt and its utilization of red mud alkali source, precipitation of zinc ion in aqueous phase. The obtained precursor, followed by calcination, ZnO semiconductor materials with photocatalytic activity immobilized on red mud substrate prepared by red mud ZnO/ alpha -Fe2O3 composites. With xanthate and orange simulated organic wastewater, acidification / roasting red mud, molasses alcohol waste sulfuric acid roasting / red mud, the catalytic properties of red mud based ZnO/ alpha -Fe2O3 composite Fenton, determine the process and part of the application process the best preparation conditions. With the help of XRD, SEM, EDS and N2 adsorption and desorption technique to characterize the catalyst, study its structure characteristics of the catalyst. The research results can provide reference for the resource utilization of red mud, the main The results are as follows: (1) acidification / roasting red mud preparation including optimum conditions of key steps in the process: sulfuric acid to mud pH=3, 673K calcination temperature, calcination time characterization of 1 h. catalyst showed that the acidification / roasting in the red mud iron phase is mainly alpha -Fe203, and this is a kind of porous catalyst the material has a rough surface. Under these conditions, the acidification / prepared roasting Fenton red mud has excellent catalytic performance, the catalyst dosage and the initial concentration of H202 0.2g.L-1 5mmol L-1, the Ding Ji xanthate solution of 50 mg.L-1 to 40 min in the reaction, the removal rate of xanthate 90.2%, and the catalyst stability in the process of Fenton. In addition, acidification / hydroxyl radical activated red mud generated in the process of catalytic Fenton and Ding Ji xanthate degradation mechanism was explored. (2) - molasses alcohol wastewater Roasting sulfuric acid / red mud preparation including the optimum conditions of key steps in the process: for 3 G red mud, 9 mL concentration of 0.7 mol L-1 H2S04 with 2 g of molasses alcohol wastewater as acidifying reagent, 573K calcination temperature, calcination time characterization of 1h. catalyst showed that the molasses alcohol waste sulfuric acid / roasting in the red mud iron phase is mainly alpha -Fe203, a carbon trace, and the catalyst is a porous material, surface roughness. In addition, addition of molasses alcohol waste, saving the amount of H2SO4, but also significantly enhance the physicochemical properties of the catalyst for preparing the catalyst. The micro environment of nearly neutral the pore structure, excellent carbon, Chengdu to molasses alcohol waste sulfuric acid roasting / catalytic performance of red mud increased significantly. The carbon formation and fine pores completely due to the catalyst preparation process of honey alcohol wastewater Join. Under these conditions, the catalytic material prepared with Fenton excellent catalytic performance in the initial solution, pH 3, H202 dosage of 50mmol, L-1, orange 40mg.L-L concentration, reaction time 6h, orange removal rate reached 86.79%; the degradation process meets the first grade dynamic model. And the catalyst in the Fenton process has good stability and excellent settleability, total iron ion concentration in the reaction solution after 5 times of repeated use process are far lower than the national standard of 10 mg.L-1. (3) the optimum conditions including key control steps of red mud ZnO/ alpha -Fe2O3 composite material preparation process: pretreatment temperature 973K, pretreatment time of 1 h, red mud and Zn (N03) 2 623K mass ratio 2:1, calcination temperature, calcination time characterization of 2 h. catalyst showed that the red mud ZnO/ alpha -Fe2O3 composite iron phase in the main If a -Fe2O3 ZnO was successfully immobilized on red mud substrate, and the catalyst is a porous material with rough surface and good pore structure, but also has better absorption ability of UV and visible light. Under these conditions the asorbent ZnO/ alpha -Fe2O3 composites prepared with photo Fenton excellent catalytic performance, the dosage of the catalyst is 0.1g L-1 303K H2O2, reaction temperature, initial concentration of 20mmol and L-1 under the condition of orange solution 40 mg - L-1 in high-pressure mercury lamp continuous irradiation of 4 h, the removal rate reached 74.75%.

【學(xué)位授予單位】：廣西大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：X703;O643.36

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