本文選題：抗生素菌渣　切入點(diǎn)：改性　出處：《西北農(nóng)林科技大學(xué)》2015年博士論文　論文類(lèi)型：學(xué)位論文

【摘要】：近年來(lái),電鍍、冶金、制革和紡織印染等行業(yè)排出的重金屬污染廢水已成為生態(tài)環(huán)境的重要污染物,并直接或間接地對(duì)人類(lèi)健康造成極大的危害。我國(guó)是抗生素類(lèi)藥物生產(chǎn)與出口大國(guó),菌渣產(chǎn)量很大,因?yàn)榇嬖诳股貧埩舻葐?wèn)題,已經(jīng)被定義為危險(xiǎn)廢物。對(duì)于菌渣的處理國(guó)內(nèi)外尚無(wú)切實(shí)可行的技術(shù)手段,這成為制約制藥行業(yè)可持續(xù)發(fā)展的瓶頸。生物吸附技術(shù)作為新興的重金屬去除技術(shù),愈來(lái)愈受到人們的關(guān)注。與傳統(tǒng)的重金屬離子去除方法相比,生物吸附法的吸附原料來(lái)源廣泛,且在原料的成本及環(huán)境保護(hù)方面顯示出較大的優(yōu)勢(shì),因此具有廣闊的應(yīng)用前景。本論文選用抗生素藥廠廢棄物菌渣(AFD)為原料,通過(guò)對(duì)其進(jìn)行化學(xué)改性和熱解處理,制備了幾種重金屬離子生物吸附劑,并通過(guò)對(duì)水溶液中Cr(VI)、Pb(Ⅱ)和Cd(Ⅱ)吸附行為的研究,考察了改性菌渣和生物炭菌渣吸附劑的吸附性能。采用現(xiàn)代分析檢測(cè)技術(shù),如BET-N2吸附法、紅外光譜分析和掃描電鏡等,對(duì)改性前后菌渣的比表面積、表面電荷、結(jié)構(gòu)、形貌進(jìn)行了表征,探討了菌渣吸附重金屬的機(jī)理,優(yōu)化了改性反應(yīng)的條件。通過(guò)靜態(tài)吸附實(shí)驗(yàn),考察了在不同加入量、p H、溫度、時(shí)間、初始濃度的條件下,改性菌渣吸附劑和生物炭菌渣對(duì)重金屬離子吸附效果的影響,并對(duì)吸附熱力學(xué)及動(dòng)力學(xué)行為進(jìn)行了研究;同時(shí),對(duì)菌渣的再生技術(shù)進(jìn)行了試驗(yàn)。未改性菌渣具備一定的吸附重金屬離子的能力,但是吸附效果較差。因此,對(duì)菌渣進(jìn)行了改性,酸浸泡和鹽浸泡改性法研究發(fā)現(xiàn)HCl改性(AMAFD)和Ca Cl2改性菌渣(CCMAFD)對(duì)Cr(VI)有一定的吸附效果。結(jié)果表明,隨著吸附劑加入量的提高,改性菌渣對(duì)水溶液中陰離子的去除率也隨之提高,增加到一定程度,去除率變化不大,當(dāng)加入量為20 mg·L-1時(shí),改性菌渣對(duì)水溶液中Cr(VI)具有較好的吸附效果。溶液的p H能夠影響改性菌渣的吸附效果,其主要原因是p H值改變了Cr(VI)離子的存在形態(tài)以及吸附劑表面的電荷電性。p H值為1時(shí),改性菌渣對(duì)Cr(VI)去除率達(dá)到90%以上。在不同的初始濃度條件下,改性菌渣對(duì)水中Cr(VI)的吸附動(dòng)力學(xué)曲線有相同的趨勢(shì),AMAFD在3 h、CCMAFD在2 h內(nèi)即可達(dá)到吸附平衡。隨著溫度的提高,改性菌渣吸附陰離子效果稍有下降,說(shuō)明改性菌渣對(duì)陰離子的吸附是放熱反應(yīng),降低溫度可以提高吸附效果,從吸附熱的數(shù)值看,溫度對(duì)吸附效果的影響不大,這就使得改性菌渣能在不同的季節(jié)使用并能取得較好的吸附效果。兩種改性菌渣對(duì)Cr(VI)的理論飽和吸附量分別為9.53 mg·g-1和8.02 mg·g-1。吸附機(jī)理主要涉及:少量的物理吸附作用;以及吸附劑上的一些基團(tuán)與Cr(Ⅵ)的氧化還原作用。另一種化學(xué)處理方法是堿處理。結(jié)果顯示Na OH浸泡改性菌渣(SHMAFD)對(duì)Pb(Ⅱ)和Cd(Ⅱ)有一定的吸附效果。靜態(tài)吸附實(shí)驗(yàn)結(jié)果表明,吸附過(guò)程的最佳p H值為Pb(Ⅱ)是3.5,Cd(Ⅱ)是5;隨著固體吸附劑加入量的提高,改性菌渣對(duì)水溶液中Pb(Ⅱ)和Cd(Ⅱ)的去除率也隨之提高,當(dāng)固液比為16 g·L-1和20 g·L-1時(shí),SHMAFD對(duì)水溶液中Pb(Ⅱ)和Cd(Ⅱ)具有較好的吸附效果;SHMAFD對(duì)重金屬離子的吸附在2 h基本達(dá)到平衡,吸附反應(yīng)速率先快后慢。熱力學(xué)數(shù)據(jù)說(shuō)明堿改性菌渣生物吸附劑對(duì)Pb(Ⅱ)和Cd(Ⅱ)的吸附過(guò)程是自發(fā)進(jìn)行的、熵增大的放熱過(guò)程。吸附機(jī)理主要涉及:少量的物理吸附作用;Na+與Pb(Ⅱ)和Cd(Ⅱ)之間的離子交換,以及吸附劑上的基團(tuán)比如—OH和—COOH與Pb(Ⅱ)和Cd(Ⅱ)的絡(luò)合作用。熱解可能是抗生素菌渣處理的有效方式,因?yàn)橥ㄟ^(guò)熱解有機(jī)物會(huì)分解,無(wú)機(jī)物被濃縮趨于穩(wěn)定。本研究在500℃下熱解1 h得到菌渣生物炭(BAFD),將其用于廢水中重金屬的去除。靜態(tài)吸附實(shí)驗(yàn)結(jié)果表明,隨著菌渣生物炭加入量的增大,對(duì)溶液中Pb(Ⅱ)和Cd(Ⅱ)的去除率也隨之提高,當(dāng)固液比為20 g·L-1時(shí),菌渣生物炭對(duì)溶液中Pb(Ⅱ)和Cd(Ⅱ)的吸附效果較好。菌渣生物炭對(duì)Pb(Ⅱ)和Cd(Ⅱ)的吸附是一個(gè)快速吸附的過(guò)程。溶液的p H能夠影響菌渣生物炭的吸附效果,Pb(Ⅱ)和Cd(Ⅱ)分別在p H 4和5時(shí)取得最大的去除效果。吸附過(guò)程的焓變△H0,表明菌渣生物炭對(duì)Pb(Ⅱ)和Cd(Ⅱ)的吸附是一個(gè)放熱的吸附過(guò)程,吉布斯自由能△G0,說(shuō)明菌渣生物炭對(duì)Pb(Ⅱ)和Cd(Ⅱ)的吸附是自發(fā)進(jìn)行的。使用吸附熱力學(xué)模型研究菌渣的吸附性能,研究表明,菌渣生物吸附劑對(duì)重金屬離子的吸附均符合Langmuir等溫吸附模式。與AFD相比,AMAFD和CCMAFD對(duì)水中Cr(Ⅵ)的吸附容量均得到提高。吸附反應(yīng)的活化能處于8.63~12.56 k J·mol-1范圍內(nèi),說(shuō)明改性菌渣吸附劑吸附重金屬離子是化學(xué)吸附。使用吸附動(dòng)力學(xué)模型研究菌渣生物炭的吸附性能,研究表明,菌渣生物炭對(duì)水溶液中Pb(Ⅱ)和Cd(Ⅱ)的吸附過(guò)程符合準(zhǔn)二級(jí)動(dòng)力學(xué)方程和顆粒內(nèi)擴(kuò)散方程。吸附速率主要受顆粒內(nèi)擴(kuò)散控制。改性菌渣在使用一段時(shí)間后,由于吸附雜質(zhì)的增多,吸附孔徑的改變,致使吸附容量下降,吸附效率降低。因此,需要對(duì)吸附效率降低的菌渣吸附劑進(jìn)行再生處理。使用0.1 mol·L-1 HCI溶液、0.1 mol·L-1EDTA溶液和0.2 mol·L-1Na OH溶液對(duì)吸附飽和的生物吸附劑上的Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅵ)進(jìn)行解吸,解吸率可達(dá)到90%以上。通過(guò)至少4次吸附-解吸循環(huán)試驗(yàn)表明,菌渣的吸附容量未發(fā)生明顯的變化,可以循環(huán)利用。綜上所述,本文制備的改性菌渣在Cr(VI)、Pb(Ⅱ)和Cd(Ⅱ)廢水凈化處理中的有著良好的應(yīng)用前景。同時(shí)將為抗生素菌渣的資源化及深度利用提供一種新的思路。
[Abstract]:In recent years, electroplating, metallurgy, heavy metal pollution in tannery wastewater and textile printing and dyeing industry has become an important pollutant discharge of the ecological environment, and directly or indirectly caused great harm to human health. China is the antibiotic production and export country, mushroom production is very big, because of the problem of antibiotic residues, has been defined as hazardous waste. For handling domestic mushroom residue and there is no feasible technical means, which have become the bottleneck restricting the sustainable development of the pharmaceutical industry. Biosorption technology as a novel technique to remove heavy metals, has received more and more attention. Compared with the traditional method of removing heavy metal ions, adsorption material source biological adsorption method widely. Showed great advantages and cost and environmental protection material, so it has broad application prospect. This paper selected antibiotics plant waste Mushroom residue (AFD) as raw materials, through the chemical modification and pyrolysis process, the preparation of some heavy metal ions biosorption, and through the solution Cr (VI), Pb (II) and Cd (II) study on the adsorption behavior, adsorption properties of modified bacteria and bacteria biological carbon residue slag adsorbent was studied. By using modern analytical techniques, such as BET-N2 adsorption, infrared spectroscopy and scanning electron microscopy, the modified residue specific surface area, surface charge, structure and morphology were characterized and discussed the mechanism of adsorption of heavy metal residue, modified reaction conditions were optimized. Through static adsorption experiments under different amount of P, H, temperature and time were investigated, the initial concentration under the condition of modified bacteria residue adsorbent and biological carbon residue effect on the adsorption of heavy metal ions. And the adsorption thermodynamics and kinetics were studied; at the same time, the regeneration technology of mushroom residue in 琛屼簡(jiǎn)璇曢獙.鏈敼鎬ц弻娓ｅ叿澶囦竴瀹氱殑鍚擱檮閲嶉噾灞炵瀛愮殑鑳藉姏,浣嗘槸鍚擱檮鏁堟灉杈冨樊.鍥犳,瀵硅弻娓ｈ繘琛屼簡(jiǎn)鏀規(guī)，

本文編號(hào)：1595770