本文關(guān)鍵詞：粉煤灰、硅灰制備有序介孔材料及其有機染料去除性能研究　出處：《中國地質(zhì)大學》2017年博士論文　論文類型：學位論文

  更多相關(guān)文章： 介孔材料 粉煤灰 硅灰 染料廢水吸附 Fenton反應

【摘要】：隨著染料合成及印染工業(yè)的廢水排放量和排放種類不斷增加,由此引發(fā)的環(huán)境污染日益顯著。介孔二氧化硅因其比表面積大、表面官能團豐富等優(yōu)點,成為吸附劑和催化劑載體的不二之選。然而,目前受硅源價格影響,制備成本較高,未能實現(xiàn)大規(guī)模生產(chǎn)。尋找合適硅源制備廉價介孔材料,在環(huán)境治理方向有著廣闊的市場前景。另一方面,粉煤灰和硅灰作為工業(yè)廢棄物,長期得不到合理、有效的利用,造成資源浪費、環(huán)境污染等多重問題。本研究綜合介孔材料以及粉煤灰、硅灰的行業(yè)背景,結(jié)合目前我國染料廢水污染嚴重的現(xiàn)狀,以粉煤灰和硅灰為廉價原料制備高效吸附劑和催化劑載體,去除印染廢水中的有機染料。本論文以燃煤固體廢棄物—粉煤灰為原料,在乙酸乙酯催化作用下,一步水熱法成功合成球形含鋁介孔分子篩Al-MCM-41;以硅鐵冶煉副產(chǎn)物—硅灰為原料,采用新工藝設備快速制備三種不同形貌介孔二氧化硅,并探討其他組成成分,反應溫度,反應時間等條件對介孔材料形貌的影響。以陽離子染料亞甲基藍為吸附對象,研究四種介孔材料吸附性能。除直接用作高效吸附劑,球形硅灰基介孔二氧化硅還可用作催化劑載體,通過負載雙金屬氧化物得到兩種非均相芬頓催化劑,并以亞甲基藍為降解對象,對合成催化劑的催化性能進行了系統(tǒng)評價。具體設計思路與創(chuàng)新點如下:(1)以燃煤固體廢棄物粉煤灰為原料,采用一步水熱法合成球形形貌含鋁介孔分子篩Al-MCM-41,使介孔分子篩的工業(yè)化生產(chǎn)成為可能。所制備介孔分子篩對陽離子染料廢水呈現(xiàn)高效吸附性,在染料廢水治理領(lǐng)域有較大應用前景。(2)以硅金屬或硅鐵合金行業(yè)產(chǎn)生的工業(yè)冶煉副產(chǎn)物硅灰為原料,采用醫(yī)學用高壓滅菌設備為反應器,通過控制催化劑乙酸乙酯添加量,采用水熱法快速合成三種不同形貌介孔二氧化硅,合成介孔二氧化硅粒子在微米級別且尺寸可調(diào)。(3)選擇輕質(zhì)、多孔、吸附能力強、比表面積大的球形硅灰基介孔二氧化硅為載體,通過負載鐵-銅或者錳-銅雙金屬氧化物,開發(fā)了兩種新型雙組分非均相Fenton催化劑,用于染料廢水的處理。對于Fe Cu/SF-S-MCM催化劑,負載的Fe2O3和CuO之間的存在協(xié)同效應可加速催化反應的進行。對于MnCu/SF-S-MCM催化劑,負載的Mn和Cu以尖晶石形式存在于CuMn2O4的特殊結(jié)構(gòu)中,使其具有較好的吸附性能和催化性能。本論文主要得到以下結(jié)論:(1)以粉煤灰為原料,CTAB為表面活性劑,乙酸乙酯為催化劑,采用一步水熱法成功合成具備蜂窩結(jié)構(gòu)特征的球形形貌含鋁介孔Al-MCM-41。單因素制備實驗顯示:乙酸乙酯添加量不僅影響介孔分子篩顆粒尺寸,而且對介孔分子篩結(jié)構(gòu)有一定影響;晶化溫度和晶化時間在一定程度上影響著顆粒的分散性和圓球度。通過單因素實驗得到球形介孔吸附劑的最佳工藝條件:乙酸乙酯添加量為10 mL,晶化溫度為60°C,晶化時間為12 h。(2)以硅灰為原料,CTAB為表面活性劑,采用新的工藝設備,快速合成介孔二氧化硅,將晶化時間由原來的48 h大大縮短至1.5 h。通過控制催化劑乙酸乙酯添加量,得到三種不同形貌介孔二氧化硅,同時研究發(fā)現(xiàn)乙酸乙酯添加量不僅影響產(chǎn)品形貌還影響介孔材料有序性。采用單因素實驗設計方案考察硅灰/CTAB摩爾比、體系水含量、晶化溫度、晶化時間以及外加無機鹽五個因素對介孔二氧化硅形貌的影響,通過以上實驗因素調(diào)節(jié)介孔二氧化硅顆粒形貌和尺寸。(3)靜態(tài)吸附實驗討論了溶液初始pH值,吸附平衡時間,溶液初始濃度以及吸附溫度對四種吸附劑的影響。實驗結(jié)果表明,溶液pH值的升高有利于四種吸附劑對亞甲基藍的吸附,且均在pH為10.0時達到最大吸附量。在相同濃度下,三種硅灰基介孔二氧化硅在30 min達到吸附平衡,快于Al-MCM-41吸附劑(120 min)。四種吸附劑的吸附量隨亞甲基藍初始濃度的升高而增大,直至趨于吸附平衡。數(shù)據(jù)模擬表明,四種吸附劑對亞甲基藍的吸附過程均符合擬二級動力學模型;吸附過程更符合Langmuir模型,為單層吸附;吸附熱力學研究表明,吸附反應為自發(fā)、放熱過程,反應過程中混亂程度減小。(4)以球形硅灰基介孔二氧化硅為載體,負載鐵-銅或者錳-銅雙金屬氧化物,開發(fā)兩種新型雙組分非均相(類)Fenton催化材料。XRD和BET多孔性能測試表明兩種新型催化劑均保留了介孔二氧化硅基體材料的MCM-41介觀結(jié)構(gòu)。XPS結(jié)果顯示,FeCu/SF-S-MCM復合催化材料中Fe和Cu元素分別以+3價和+2價的形式存在于Fe2O3和CuO金屬氧化物中;而MnCu/SF-S-MCM復合催化材料中Mn和Cu分別以+3價和+2價的形式存在于CuMn2O4尖晶石結(jié)構(gòu)中。通過改變Fe/Cu、Mn/Cu摩爾比例,制備多種不同金屬氧化物負載比例的復合催化材料并確定最佳配比。(5)探討體系反應條件對亞甲基藍降解效果的影響。降解實驗結(jié)果表明:同時加入催化劑FeCu/SF-S-MCM和H2O2的體系,在光照反應45 min后,亞甲基藍降解率可達98.38%;而同時加入MnCu/SF-S-MCM催化劑和H2O2,亞甲基藍降解率略低,為96.51%。同時對比了相同實驗條件下,基體材料SF-S-MCM對亞甲基藍的降解率僅為50%左右,說明基體材料固載的雙金屬氧化物可大大提高降解效率。因此,本實驗中亞甲基藍的降解是催化劑、氧化劑(雙氧水)以及紫外光照射共同作用的結(jié)果。(6)經(jīng)單因素實驗得出亞甲基藍染料廢水降解的最佳工藝條件。以FeCu/SFS-MCM為催化劑,當亞甲基藍初始濃度為250.0 mg/L,催化劑投加量為0.50 g/L,H2O2投加量為0.3 mL,光照反應45 min后MB降解率可達99.31%,隨著亞甲基藍初始濃度的升高降解率有所降低,FeCu/SF-S-MCM催化劑在pH值為5.0-9.0的范圍內(nèi)均表現(xiàn)出較好的催化性能。對于MnCu/SF-S-MCM催化劑,當亞甲基藍初始濃度為250.0 mg/L,催化劑投加量為0.50 g/L,H2O2投加量為0.5 m L,反應45min后降解率可達98.22%。隨著亞甲基藍初始濃度的升高,降解率有所降低。MnCu/SF-S-MCM催化劑在pH為3.0-9.0的范圍內(nèi)均表現(xiàn)出較好的催化性能,大大拓寬pH使用范圍。
[Abstract]:With the wastewater emissions and emission type synthesis and dyeing increasing, which caused the environmental pollution becomes more and more significant. Mesoporous silica due to its large surface area, abundant surface functional groups has become the choice of adsorbent and catalyst carrier. However, affected by the current price of silicon source, the manufacturing cost is high, failed to achieve large-scale production. To find suitable silicon source for preparing cheap mesoporous materials, has a broad market prospect in environmental governance. On the other hand, fly ash and silica fume as industrial waste, long-term lack of reasonable and effective use, resulting in a waste of resources, multiple problems of environmental pollution. The study of dielectric porous material and fly ash, silica fume, industry background, combined with present situation of dye wastewater pollution in China is serious, with fly ash and silica fume as cheap raw materials for the preparation of highly efficient adsorbent and catalyst carrier, to In addition to organic dyes in dyeing wastewater. The coal solid waste - fly ash as raw materials in ethyl acetate catalyzed by one step hydrothermal synthesis of spherical aluminum containing Al-MCM-41 mesoporous molecular sieve; in ferrosilicon smelting by-product of wollastonite as raw materials, using new technology and equipment of three different morphologies of mesoporous silica quickly preparing, and discuss other components, reaction temperature, reaction time and other factors to influence the morphology of mesoporous materials. The cationic dye methylene blue adsorption research object, four kinds of mesoporous materials. The adsorption performance is directly used as high efficiency adsorbent, spherical silica based mesoporous silica can be used as a catalyst carrier, two a heterogeneous catalyst by Fenton supported bimetallic oxides, and methylene blue as the degradation object, the catalytic performance of the catalysts for the synthesis of a systematic evaluation of specific design ideas and innovation. Points are as follows: (1) coal solid waste fly ash as raw materials, synthesis of spherical morphology containing mesoporous molecular sieve Al-MCM-41 by one-step hydrothermal method, the mesoporous molecular sieve production possible. The preparation of mesoporous molecular sieve, adsorption of cationic dye wastewater has great application prospect in dye the wastewater treatment field. (2) produced by metal or silicon ferrosilicon alloy industry smelting by-product silica as raw materials, using medical autoclave reactor, by controlling the adding amount of ethyl acetate catalyst, the rapid synthesis of three different morphologies of mesoporous silica hydrothermal synthesis of mesoporous silica particles can be adjusted in micron level and size. (3) choose light, porous, strong adsorption capacity, large surface area of spherical silica based mesoporous silica as the carrier, through the load of iron - copper or copper - manganese double metal oxide, development Two novel two-component heterogeneous Fenton catalyst for dye wastewater treatment. The Fe Cu/SF-S-MCM catalyst, the synergetic effect between Fe2O3 and CuO load can accelerate the reaction. For the MnCu/SF-S-MCM catalyst, the special structure of Mn and Cu load with spinel form in CuMn2O4, which has adsorption performance and good catalytic performance. This paper obtained the following conclusions: (1) using fly ash as raw materials, CTAB as surfactant, ethyl acetate as catalyst by one-step hydrothermal method successfully synthesized with cellular morphology of aluminum spherical mesoporous Al-MCM-41. structure characteristics of the single factor experiment showed that the preparation of ethyl acetate amount not only affects the mesoporous molecular sieve particle size, but also has a certain influence on the structure of mesoporous molecular sieve; crystallization temperature and time have some influence on the particle dispersion and ball Degrees. Through the single factor experiment, the optimum process conditions of spherical mesoporous adsorbent obtained: ethyl acetate was added to 10 mL, the crystallization temperature of 60 C, the crystallization time was 12 h. (2) with wollastonite as raw material, CTAB as surfactant, using new technology equipment, rapid synthesis of mesoporous oxide two silicon, the time of crystallization from the original 48 h greatly shortened to 1.5 h. by controlling the added amount of ethyl acetate catalyst, obtained three different morphologies of mesoporous silica, the study also found that ethyl acetate addition products not only affect the morphology also affected the ordered mesoporous material. The influences of /CTAB molar ratio of silica fume by single factor experimental design, crystallization temperature the water content of the system, and influence the crystallization time and adding inorganic salts of five factors on the morphology of mesoporous silica particles, adjusting the size and morphology of mesoporous silica through the above experimental factors. (3) the static adsorption experiment is discussed. The initial pH value of solution, adsorption time, initial concentration of solution and the effect of temperature on the adsorption of four kinds of adsorbent. The experimental results show that the pH value of the solution increased to four kinds of adsorbents on the adsorption of Ya Jiaji blue, and when the pH is 10 the maximum absorption capacity. At the same concentration, three kinds of silica fume based on mesoporous silica reached adsorption equilibrium in 30 min, faster than the Al-MCM-41 adsorbent (120 min). Four increase of adsorption amount increased with the initial concentration of Ya Jiaji blue, to reach adsorption equilibrium data. Simulation results show that four kinds of adsorbents on the adsorption process of Ya Jiaji blue are in line with the quasi two level dynamic model; the adsorption process is more accord with the Langmuir model for monolayer adsorption; adsorption thermodynamics research showed that the adsorption reaction is exothermic, spontaneous process, the degree of confusion in the reaction process decreases. (4) with spherical silica based mesoporous silica as the carrier two, loaded with iron Copper or copper - manganese - double metal oxides, the development of two novel two-component heterogeneous (class) Fenton catalyst.XRD and BET porous performance test showed that two new catalysts were retained.XPS MCM-41 mesoscopic structure of mesoporous silica matrix material. The results show that Fe and Cu elements in FeCu/SF-S-MCM composite catalytic materials respectively. In Fe2O3 and CuO metal oxides to the +3 price and +2 price form; while Mn and Cu MnCu/SF-S-MCM composite catalytic materials were performed with a +3 price and +2 price exists in the form of CuMn2O4 spinel structure. By changing the molar ratio of Fe/Cu, Mn/Cu, catalytic composite material preparation of different metal oxides and to determine the proportion of the load the best proportion (5). To investigate the effects of reaction conditions on the system of methylene blue degradation. The degradation experiment results show that the addition of catalyst FeCu/SF-S-MCM and H2O2 system, in the light of the reaction after 45 min sub The degradation rate of methyl blue was 98.38%; while adding MnCu/SF-S-MCM and H2O2 catalyst, the degradation rate of Ya Jiaji blue is slightly lower, as compared to those of 96.51%. under the same experimental conditions, SF-S-MCM matrix materials on the degradation rate of Ya Jiaji blue is only about 50%, indicating that the dual metal oxide matrix materials supported can greatly improve the degradation efficiency. Therefore, degradation Ya Jiaji blue in this experiment is the catalyst, oxidant (hydrogen peroxide) as well as the result of joint action of UV irradiation. (6) the optimum conditions of single factor experiments of Ya Jiaji blue dye wastewater degradation. With FeCu/SFS-MCM as catalyst, when Ya Jiaji blue initial concentration was 250 mg/L, adding 0.50 g/L catalyst, H2O2 the quantity is 0.3 mL, MB light degradation rate is up to 99.31% after 45 min reaction, with Ya Jiaji blue initial concentration increased the degradation rate decreased, FeCu/SF-S-MCM catalyst in the pH value of 5.0-9. 0 the range showed good catalytic performance for MnCu/SF-S-MCM catalyst, when the initial concentration of methylene blue was 250 mg/L, adding 0.50 g/L catalyst, the dosage of H2O2 is 0.5 m L, after reaction of 45min degradation rate was up to 98.22%. with increasing the initial concentration of methylene blue, the degradation rate decreased in.MnCu/SF-S-MCM catalyst pH is in the range of 3.0-9.0 showed good catalytic performance, greatly broaden the application range of pH.

【學位授予單位】：中國地質(zhì)大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：X703;O643.36;TB383.4

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