本文選題：催化劑 + 二氧化鋯��； 參考：《浙江大學(xué)》2015年碩士論文

【摘要】：苯選擇加氫制備環(huán)已烯路線具有良好的原子經(jīng)濟(jì)性,有著重要的工業(yè)應(yīng)用價(jià)值。近年來大量的研究成果表明,以釕為活性中心的催化劑具有高的選擇性和轉(zhuǎn)化率,可用于工業(yè)化生產(chǎn)。由于資源的稀缺性,研究失效催化劑中有價(jià)金屬釕和鋯的回收利用具有重要的應(yīng)用價(jià)值和一定的學(xué)術(shù)意義。針對(duì)目前工業(yè)上失效催化劑存在的只回收貴金屬釕,并且回收方法采用的是存在危險(xiǎn)性的氧化蒸餾法等問題,提出對(duì)失效催化劑中的有價(jià)金屬釕和鋯的分離提取進(jìn)行研究,達(dá)到安全高效地綜合回收利用釕和鋯的目標(biāo)。通過對(duì)苯選擇加氫制環(huán)己烯失效催化劑回收的系統(tǒng)研究,得到了以下結(jié)論。利用現(xiàn)有熱力學(xué)數(shù)據(jù),借助HSC(熱力學(xué)數(shù)據(jù)庫軟件)分析了硫酸氫鈉與二氧化鋯的平衡產(chǎn)物組成。結(jié)果表明在100℃～650℃的溫度范圍內(nèi),提高溫度有利于硫酸氫鈉與二氧化鋯反應(yīng)的進(jìn)行,平衡固相產(chǎn)物為硫酸鋯和含硫的鈉鹽等,其存在形式與原料中二氧化鋯和硫酸氫鈉的比例和反應(yīng)溫度有關(guān)。系統(tǒng)考察了反應(yīng)溫度、硫酸氫鈉和二氧化鋯的比例、反應(yīng)時(shí)間對(duì)二氧化鋯分解率的影響,確定了硫酸氫鈉熔融分解鋯的優(yōu)化工藝條件。結(jié)果表明：在反應(yīng)溫度為300℃～600℃范圍內(nèi),原料中硫酸氫鈉和二氧化鋯的摩爾配比為5-7,反應(yīng)時(shí)間40 min的優(yōu)化工藝條件下,二氧化鋯的分解反應(yīng)可以完全進(jìn)行。并詳細(xì)考察了鋯的硫酸氫鈉熔融料的浸出過程中,攪拌速率、液固比、反應(yīng)溫度、浸出時(shí)間等因素對(duì)鋯浸出率的影響,得到鋯浸出的優(yōu)化工藝條件為：攪拌速度為100 r/min,液固比為4：1,浸出溫度為40℃,浸出時(shí)間6 min。最后制備得到的氯氧化鋯符合工業(yè)八水合氯氧化鋯的行業(yè)標(biāo)準(zhǔn)(HG/T 2772-2012),在貴金屬釕回收的研究過程中,分別對(duì)釕堿性熔融和釕的還原沉淀兩個(gè)工序進(jìn)行了研究。對(duì)于堿熔融釕過程中的堿熔熔劑的選擇、堿熔反應(yīng)的溫度和堿熔反應(yīng)的時(shí)間進(jìn)行了研究,得到了堿熔釕的最優(yōu)工藝參數(shù)為：采用Na202為堿熔劑,堿熔反應(yīng)溫度為650℃,堿熔反應(yīng)時(shí)間為3 h。在此工藝條件下,釕的一次堿熔出量可達(dá)到83.5%。利用在堿性條件下,溶液中的高價(jià)釕離子容易被還原生成沉淀的性質(zhì),對(duì)堿性溶液中釕離子的還原沉淀過程進(jìn)行了研究,結(jié)果表明：在還原沉淀劑選擇無水乙醇,無水乙醇的用量為水溶液中釕離子的8倍摩爾量,還原沉淀反應(yīng)的溫度為30℃,反應(yīng)時(shí)間為90min的條件下,釕離子基本沉淀完全。最后制備得到的水合氯化釕符合工業(yè)氯化釕的行業(yè)標(biāo)準(zhǔn)(HG/T 3679-2011)。
[Abstract]:Selective hydrogenation of benzene to cyclohexene has good atomic economy and important industrial application value. In recent years, a large number of research results show that the catalyst with ruthenium as the active center has high selectivity and conversion, and can be used in industrial production. Due to the scarcity of resources, it is of great value and academic significance to study the recovery and utilization of valuable ruthenium and zirconium in the catalyst. Aiming at the problem that only precious metal ruthenium is recovered from the defunct catalyst in industry and the dangerous oxidation distillation method is used in the recovery method, the separation and extraction of valuable ruthenium and zirconium from the failed catalyst are studied. To achieve the goal of safely and efficiently recycling ruthenium and zirconium. Based on the systematic study on the recovery of failed catalysts for selective hydrogenation of benzene to cyclohexene, the following conclusions are obtained. The equilibrium product composition of sodium bisulfate and zirconia was analyzed by means of the available thermodynamic data and the thermodynamic database software HSC. The results show that the reaction of sodium bisulfate with zirconia can be facilitated by increasing the temperature in the temperature range of 100 鈩，

本文編號(hào)：1911872