本文選題：稻稈 + 甲醇解　； 參考：《中國(guó)礦業(yè)大學(xué)》2015年碩士論文

【摘要】：醇解是生物質(zhì)清潔高效利用的一種有效手段,從醇解所得生物油中可以獲取高附加值化學(xué)品。本研究以甲醇為介質(zhì),以三種不同載體的負(fù)載型氟化鉀(KF/Al2O3、KF/Ca O和KF/沸石)為催化劑,分別在微波輔助和超臨界條件下對(duì)稻稈粉末進(jìn)行液化解聚,考察催化與非催化條件下的生物油收率(YL)和生物油組成,并進(jìn)一步解析解聚機(jī)理。首先以YL為指標(biāo)進(jìn)行了催化劑的篩選和醇解條件的優(yōu)化,發(fā)現(xiàn)三種載體KF的較優(yōu)負(fù)載量均為20%,KF/Al2O3和KF/沸石的較優(yōu)焙燒溫度在500 o C,而KF/Ca O為600 o C。超臨界條件下的較優(yōu)反應(yīng)溫度為300 o C,微波條件下為75 o C,而兩種條件下的較優(yōu)反應(yīng)時(shí)間均為30min,較優(yōu)催化劑用量均為5%。微波輻射下,考察了逐級(jí)解聚和催化解聚的規(guī)律。研究表明,第一級(jí)甲醇解生物油的主要成分為甾醇。第二級(jí)和第三級(jí)醇解的主要成分均為鄰苯二甲酸酯,且含量接近50%。催化甲醇解得到的生物油共檢測(cè)到66種化合物,而非催化條件只檢測(cè)到23種。負(fù)載型KF促進(jìn)了酮、醚、酯和脂肪烴的生成。在KF/Al2O3催化下,生物油主要族組分為甾醇;在KF/Ca O催化下主要為酮,達(dá)到了65.7%;KF/沸石催化下則主要為呋喃衍生物。超臨界條件,考察了不同溫度下解聚、逐級(jí)解聚和催化解聚的規(guī)律。實(shí)驗(yàn)表明,生物油的族組分分布隨反應(yīng)溫度顯現(xiàn)出一定的規(guī)律性,一定范圍內(nèi),升高溫度有利于酮、醚和酚的形成。高于一定溫度,部分小分子則會(huì)發(fā)生重聚反應(yīng)。負(fù)載型KF催化下得到的生物油的YL和化合物種類均明顯增加,其中KF/沸石催化下所得YL最高。反應(yīng)溫度在260 o C時(shí),催化所得生物油共檢測(cè)到82種化合物,主要成分為酯,三種載體的KF均促進(jìn)了酮、醚和含硅化合物的生成。另外,KF/Al2O3、KF/Ca O也促進(jìn)了酚的生成,KF/Al2O3、KF/沸石有利于酯的生成。反應(yīng)溫度為300 o C時(shí),催化得到的生物油共檢測(cè)到172種化合物,明顯多于非催化得到的64種。KF/Al2O3和KF/Ca O催化下的主要組分為酮,KF/沸石催化下則為酚。三種載體的KF均促進(jìn)了酮、醚和酚的生成。KF/沸石也促進(jìn)了醇、酯和芳烴的生成。在第二級(jí)甲醇解中,KF/Ca O催化下的YL較非催化條件更高,生物油主要成分為酚,占63.4%。非催化條件下的主要產(chǎn)物為硅酸四甲酯和二硅酸六甲酯,前者相對(duì)含量占65.2%,推測(cè)含硅化合物為稻稈中的植硅體與超臨界甲醇反應(yīng)生成。負(fù)載型KF在微波甲醇解和超臨界甲醇解中均表現(xiàn)出良好的催化性能,推測(cè)其在反應(yīng)中促進(jìn)CH3OH解離出親核試劑CH3O-,從而進(jìn)攻連接纖維素和半纖維素糖環(huán)之間或木質(zhì)素芳環(huán)之間的C-O橋鍵,使其斷裂生成更多的小分子化合物。
[Abstract]:Alcoholysis is an effective method for the clean and efficient utilization of biomass. High value-added chemicals can be obtained from the bio-oil obtained by alcoholysis. In this study, the rice stalk powder was liquefied and depolymerized under microwave assisted and supercritical conditions using three supported KF / Al _ 2O _ 3H _ f / Ca _ 2O and KF/ zeolites as catalysts using methanol as the medium. The yield of bio-oil (YL) and the composition of bio-oil under catalytic and non-catalytic conditions were investigated, and the mechanism of depolymerization was further analyzed. Firstly, the catalyst selection and alcoholysis conditions were optimized by using YL as the index. It was found that the optimum calcination temperature of KF / Al _ 2O _ 3 and KF/ zeolite was KF/Ca OC and 600oC respectively for KF / Al _ 2O _ 3 and KF/ zeolites. The optimum reaction temperature is 300 o C under supercritical condition, 75 o C under microwave condition, and the optimum reaction time is 30 min under both conditions, and the optimal amount of catalyst is 5%. The law of stepwise depolymerization and catalytic depolymerization was investigated under microwave radiation. The results showed that the main component of the first methanololysis bio-oil was sterol. The main components of the second and third alcoholysis are phthalate, and the content is close to 50%. A total of 66 compounds were detected in bio-oil obtained by catalytic methanol hydrolysis, but only 23 compounds were detected under non-catalytic conditions. Supported KF promotes the formation of ketones, ethers, esters and fatty hydrocarbons. Under the catalysis of KF/Al2O3, the main component of bio-oil is sterol, and the main component is ketone under the catalysis of KF/Ca O, and the furan derivative under the catalysis of 65.7KF / zeolite. Under supercritical conditions, the rules of depolymerization, stepwise depolymerization and catalytic depolymerization at different temperatures were investigated. The experimental results show that the distribution of group components of bio-oil shows certain regularity with reaction temperature, and in a certain range, increasing temperature is favorable to the formation of ketones, ethers and phenols. Above a certain temperature, some small molecules will reunite. The YL and compound types of bio-oil obtained by supported KF catalyst increased obviously, among which the YL obtained by KF/ zeolite was the highest. At the reaction temperature of 260 o C, 82 compounds were detected in the bio-oil. The main components were esters. KF of the three carriers promoted the formation of ketones, ethers and silicon-containing compounds. In addition, KF / Al _ 2O _ 3 / KF / Cao also promoted the formation of phenol. KF / Al _ 2O _ 3 / KF / zeolite was beneficial to the formation of esters. At the reaction temperature of 300o C, 172 compounds were detected in the bio-oil, which was obviously more than 64 kinds of uncatalyzed. KF / Al _ 2O _ 3 and KF/Ca _ O, the main component of which was phenol under the catalysis of ketone KF / zeolite. KF of the three carriers promoted ketone, and the formation of ether and phenol. KF / zeolite also promoted the formation of alcohols, esters and aromatics. In the second stage of methanol hydrolysis, the YL catalyzed by KF / Ca O was higher than that under non-catalytic conditions. The main component of bio-oil was phenol, accounting for 63.443%. The main products under uncatalyzed conditions were tetramethyl silicate and hexyl disilicate, whose relative content was 65.2. It was inferred that the silicon-containing compounds reacted with supercritical methanol in rice stalks. The supported KF exhibited good catalytic performance in microwave methanol hydrolysis and supercritical methanol hydrolysis. It is speculated that it can promote CH3OH dissociation of nucleophilic reagent CH3O-and attack the C-O bridge bond between cellulose and hemicellulose sugar ring or between lignin aromatic ring and make it break down to form more small molecular compounds.
【學(xué)位授予單位】：中國(guó)礦業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TE667

【共引文獻(xiàn)】

相關(guān)期刊論文 前10條

1 李衛(wèi)宏;劉學(xué)武;夏遠(yuǎn)景;鄧進(jìn)軍;;木質(zhì)素在超臨界水中氣化制氫反應(yīng)機(jī)理分析[J];中國(guó)農(nóng)機(jī)化;2011年04期

2 李衛(wèi)宏;郭軍;;氣質(zhì)聯(lián)用分析超臨界生物質(zhì)氣化制氫液相產(chǎn)物[J];中國(guó)農(nóng)機(jī)化;2012年03期

3 Wang Yunpu;Liu Yuhuan;Ruan Rongsheng;Wen Pingwei;Wan Yiqin;Zhang Jinsheng;;Microwave-Assisted Decarboxylation of Sodium Oleate and Renewable Hydrocarbon Fuel Production[J];China Petroleum Processing & Petrochemical Technology;2013年03期

4 丁濤;;微波協(xié)同活性炭和H_2O_2處理苯酚廢水的研究[J];廣州化工;2014年19期

5 靳鵬;海國(guó)棟;王旭峰;張靜;王向宇;;微波技術(shù)應(yīng)用于廢棄物處理方面的研究進(jìn)展[J];材料導(dǎo)報(bào);2014年S2期

6 黃玉西;田春蓉;王建華;;液化植物纖維制備聚氨酯泡沫材料研究進(jìn)展[J];化工新型材料;2011年12期

7 陳浩;左薇;張軍;吳曉燕;龔真龍;田禹;;鎳基催化劑對(duì)污泥微波熱解制生物氣效能的影響[J];環(huán)境工程學(xué)報(bào);2014年03期

8 李磊;王文娟;薛森娟;徐炎華;;微波-化學(xué)改性粉煤灰及其處理腐殖酸機(jī)理研究[J];安全與環(huán)境工程;2014年04期

9 朱駿;聶慶秀;朱正林;黃洋;;重有機(jī)污染土壤處理技術(shù)研究進(jìn)展[J];綠色科技;2014年11期

10 張光葳;趙云;沈英;徐新苗;;微波裂解技術(shù)在生物質(zhì)中的應(yīng)用[J];機(jī)電技術(shù);2015年01期

相關(guān)會(huì)議論文 前2條

1 牛文娟;肖衛(wèi)華;韓魯佳;;生物質(zhì)液化及其產(chǎn)物分析方法和應(yīng)用研究進(jìn)展[A];中國(guó)農(nóng)業(yè)工程學(xué)會(huì)2011年學(xué)術(shù)年會(huì)論文集[C];2011年

2 李嫻;解新安;鄭朝陽(yáng);李雁;;玉米秸稈在亞/超臨界環(huán)己烷中的液化過(guò)程與機(jī)理[A];全國(guó)農(nóng)村清潔能源與低碳技術(shù)學(xué)術(shù)研討會(huì)論文集[C];2011年

相關(guān)博士學(xué)位論文 前3條

1 劉華敏;生物質(zhì)輕度預(yù)處理液化技術(shù)與機(jī)理研究[D];華南理工大學(xué);2013年

2 李剛;厭氧發(fā)酵液培養(yǎng)鏈帶藻高生物量累積及熱裂解產(chǎn)物研究[D];中國(guó)農(nóng)業(yè)大學(xué);2014年

3 劉海力;廚余垃圾的燃燒與熱解特性研究[D];華南理工大學(xué);2014年

相關(guān)碩士學(xué)位論文 前2條

1 鄭懷玉;木質(zhì)生物質(zhì)醇解液化的研究[D];福建農(nóng)林大學(xué);2014年

2 李秉碩;源頭調(diào)質(zhì)生物航空燃油制備及改性研究[D];沈陽(yáng)航空航天大學(xué);2014年

，

本文編號(hào)：1979178