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吉化油泥熱解燃燒特性及動(dòng)力學(xué)研究
王斌,,馬躍,,岳長(zhǎng)濤,,李術(shù)元,,唐勛,,常少英
1 中國(guó)石油大學(xué)(北京)理學(xué)院,,北京 102249 2 北京國(guó)電龍?jiān)喘h(huán)保工程有限公司,,北京 100039
Thermal and kinetic study into pyrolysis and combustion of Jihua oil sludge
WANG Bin1 , MA Yue1 , YUE Changtao1 , LI Shuyuan1 , TANG Xun2 , CHANG Shaoying
1 College of Science, China University of Petroleum-Beijing, Beijing 102249, China 2 Beijing GuodianLongyuan Environmental Protection Engineering Co., Ltd., Beijing 100039, China

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摘要? 本文對(duì)吉化集團(tuán)煉廠油泥進(jìn)行基本性質(zhì)分析,、熱重實(shí)驗(yàn),、熱解和燃燒特性分析及動(dòng)力學(xué)研究。結(jié)果表明,, 吉化油泥含油率為 14.74%,,含水率為 72.82%。通過(guò)設(shè)置 5,、10,、15、20,、30 ℃/min共 5 組升溫速率,,得到熱 解和燃燒特性及動(dòng)力學(xué)參數(shù)。油泥熱解過(guò)程由揮發(fā)階段及熱解階段組成,,主要分為有機(jī)物的揮發(fā)以及少量易反 應(yīng)雜原子的熱解,、少量有機(jī)物揮發(fā)以及重組分熱解兩個(gè)過(guò)程,。燃燒過(guò)程由揮發(fā)燃燒階段與固定碳燃燒階段構(gòu)成, 第一階段為小分子有機(jī)物揮發(fā)燃燒,,第二階段為大分子有機(jī)物揮發(fā)熱解進(jìn)而燃燒,,以及氧氣擴(kuò)散至坩堝內(nèi)部發(fā) 生固定碳燃燒。燃燒受升溫速率影響較小,,活化能不會(huì)因有機(jī)物消耗而明顯增長(zhǎng),。而且在燃燒過(guò)程中,揮發(fā)燃 燒比熱解揮發(fā)難發(fā)生,,固定碳燃燒比熱解容易發(fā)生,。本文將油泥熱解過(guò)程中存在相互影響的揮發(fā)和熱解階段拆 解,利用Coats-Redfern,、DAEM兩種模型計(jì)算動(dòng)力學(xué)參數(shù),,并與正常處理方法結(jié)果對(duì)比,優(yōu)化動(dòng)力學(xué)計(jì)算過(guò)程,。 DAEM模型揮發(fā)階段活化能為 61.82~81.05 kJ/mol,,熱解階段活化能初始值為 121.60 kJ/mol,隨著轉(zhuǎn)化率增大升 高至 237.07 kJ/mol,。采用DAEM模型對(duì)油泥燃燒過(guò)程進(jìn)行計(jì)算,,燃燒活化能為 73.95~110.93 kJ/mol,并與CoatsRedfern模型及熱解過(guò)程相對(duì)比,。Coats-Redfern模型假設(shè)反應(yīng)單一,,所得為某一區(qū)間的活化能均值,局限性較 大,;DAEM活化能模型的假設(shè)更加貼合油泥復(fù)雜的組成,,方法更優(yōu)。熱解計(jì)算中分峰方法將熱解階段與揮發(fā)段 分離,,所得動(dòng)力學(xué)數(shù)據(jù)更接近真實(shí)數(shù)據(jù),。研究表明DAEM模型準(zhǔn)確性更好,可靠性更高,。最后通過(guò)熱重實(shí)驗(yàn),, 研究吉化油泥熱解及燃燒特性,并計(jì)算動(dòng)力學(xué)參數(shù),,本文研究成果可以為油泥熱解處理技術(shù)提供基出實(shí)驗(yàn)數(shù)據(jù) 支撐,。
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關(guān)鍵詞 : 含油污泥,;熱解特性;熱解動(dòng)力學(xué);燃燒特性,;燃燒動(dòng)力學(xué)
Abstract
The basic properties, thermogravimetry, pyrolysis characteristics and combustion characteristics of Jihua oil sludge were    
determined in this manuscript. The results show that the oil content of Jihua sludge is 14.74   %   and the water content is 72.82   %   . The    
characteristics and kinetic parameters of pyrolysis and combustion were obtained by using thermogravimetric analysis with heating  
rates of 5, 10, 15, 20 and 30 ℃ /min. The pyrolysis process includes volatilization and pyrolysis stages. One is the volatilization of    
organic matter at 150~380℃, and a small proportion of reactive heteroatoms is pyrolyzed. The other is the pyrolysis process of a small    
amount of volatile heavy components at 380~550℃. The combustion process includes the volatilization combustion stage and the fixed    
carbon combustion stage. The combustion of Jihua sludge in the first stage is the volatile combustion of small molecular organics. The    
second stage is the volatile combustion of large molecular organics and pyrolysis combustion, and the diffusion of oxygen into the cru  
cible to produce fixed carbon combustion. The effect of heating rate on combustion is small, and the activation energy will not increase    
significantly due to the consumption of organic matter. In addition, the volatilization combustion stage occurs with more difficulty than    
pyrolysis volatilization, and the fixed carbon combustion stage occurs more easily than pyrolysis.  
Two models, Coats-Redfern and the Distributed Activation Energy Model (DAEM), are used to calculate the kinetic pa  
rameters and the results are compared with those of normal treatment methods to optimize the calculation process. In the DAEM    
model, the activation energy of the volatilization stage is 61.82 to 81.05 kJ/mol, while the activation energy in the pyrolysis    
stage increased from 121.60 kJ/mol to 237.11 kJ/mol with the increase of conversion. When the DAEM model is applied to    
the calculation of the combustion process of oil sludge, the combustion activation energy ranges from 73.95 to 110.93 kJ/mol,    
which is then compared with Coats-Redfern model and pyrolysis process. Coats-Redfern model assumes that the reaction is    
single, and the activation energy obtained is the mean value of a certain range, which has great limitations. The DAEM model is    
more suitable for the complex composition of oil sludge, and the method is better. In the pyrolysis calculation, the peak splitting    
method separates the pyrolysis stage from the volatilization stage, and the kinetics obtained are closer to the real data. According    
to the research, the DAEM model is more accurate and reliable. The research results of this paper can provide experimental data    
foundation support for the sludge pyrolysis treatment technology.  


Key words: sludge; pyrolysis characteristics; pyrolysis kinetics; combustion characteristics; combustion kinetics
收稿日期: 2021-06-30 ????
PACS: ? ?
基金資助:大型燃煤鍋爐處置污泥廢棄物關(guān)鍵技術(shù)研究項(xiàng)目(KH-2018-06) 和大型燃煤鍋爐資源化處置多種污泥固廢關(guān)鍵技術(shù)研究及工程示范
(GJNY2030XDXM-19-10.2) 聯(lián)合資助
通訊作者: [email protected]
引用本文: ??
王斌, 馬躍, 岳長(zhǎng)濤, 李術(shù)元, 唐勛, 常少英. 吉化油泥熱解燃燒特性及動(dòng)力學(xué)研究. 石油科學(xué)通報(bào), 2021, 02: 292-301 WANG Bin, MA Yue, YUE Changtao, LI Shuyuan, TANG Xun, CHANG Shaoying. Thermal and kinetic study into pyrolysis and combustion of Jihua oil sludge. Petroleum Science Bulletin, 2021, 02: 292-301.
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