本文關(guān)鍵詞： 油頁巖干餾殘渣 鋸末 熱重紅外聯(lián)用 氣體產(chǎn)物釋放特性 表面結(jié)構(gòu) 反應(yīng)動力學(xué)　出處：《東北電力大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：油頁巖干餾殘渣因其自身含有大量對環(huán)境造成危害的苯酚類、硫化物和多環(huán)芳香烴等污染物，已經(jīng)成為制約油頁巖工業(yè)發(fā)展的關(guān)鍵問題。針對其處理問題，本文提出以鋸末與干餾殘渣混燒的方案，基于熱重紅外聯(lián)用技術(shù)和比表面積分析技術(shù)，對其混燒特性進(jìn)行了深入研究，，主要研究內(nèi)容包括：混燒基礎(chǔ)燃燒特性、混燒氣體產(chǎn)物釋放規(guī)律分析、混燒表面形態(tài)特性分析和混燒反應(yīng)動力學(xué)解析。 在對燃料基礎(chǔ)特性分析的基礎(chǔ)上，研究了油頁巖干餾殘渣與鋸末的燃燒特性和氣體釋放規(guī)律,深入探討了燃料混合比及升溫速率等因素對其混燒特性的影響。通過對燃燒TG-DTG曲線的分析，研究結(jié)果表明隨著生物質(zhì)的摻入，混合樣品著火、燃盡溫度降低，燃燒速率增加，明顯改善其燃燒特性。隨著升溫速率的提高，混合樣品的燃燒曲線向高溫段遷移，著火和燃盡溫度升高，但單位時間內(nèi)的反應(yīng)特性有所提高。Glam-Schmidt曲線與DTG曲線中峰的位置相對應(yīng)，表征氣體的析出規(guī)律。有機化合物多產(chǎn)生于鋸末熱解過程中；而無機物則產(chǎn)生于燃燒的各個階段，以CO2和CO為主要產(chǎn)物，同時還有少量SO2和NOx。 利用氮等溫吸附脫附法研究了燃燒過程對油頁巖干餾殘渣和鋸末混合物表面孔隙結(jié)構(gòu)特性的影響，并應(yīng)用分形維數(shù)來定量描述混合物表面形態(tài)的復(fù)雜程度。結(jié)果顯示混合物各個孔徑范圍內(nèi)的孔體積較干餾殘渣明顯減少，在水分析出段尤為明顯，燃燒前期表面孔隙以中微孔為主，后期以中大孔和大孔為主；混合物的中微孔結(jié)構(gòu)在揮發(fā)分燃燒階段得到充分發(fā)展，比表面積在顯著增大，對反應(yīng)進(jìn)程具有促進(jìn)作用。通過FHH方程線性回歸得到的分形維數(shù)反映出混合物內(nèi)部孔隙的立體化程度比干餾殘渣更高，燃燒階段化學(xué)反應(yīng)及力學(xué)作用的交替影響，引起分形維數(shù)隨溫度的變化。 結(jié)合經(jīng)典熱力學(xué)理論和過渡態(tài)理論，應(yīng)用熱分析動力學(xué)方法對FWO方程和KAS方程進(jìn)行了推導(dǎo)。應(yīng)用同步解析的思想同時求取了反應(yīng)機理函數(shù)和活化焓，并深入研究了油頁巖干餾殘渣與鋸末混燒過程中活化熵和活化自由能的變化規(guī)律。研究結(jié)果表明兩種計算方法所求解的結(jié)果呈現(xiàn)一致規(guī)律，更好地描述了各樣品的燃燒反應(yīng)動力學(xué)機理。為提高計算結(jié)果精度，應(yīng)用改進(jìn)的等轉(zhuǎn)化率法對樣品的活化能進(jìn)行計算，其數(shù)值傳統(tǒng)等轉(zhuǎn)化率法計算結(jié)果相符，從而驗證了等轉(zhuǎn)化率法對于所選樣品燃燒的可行性。
[Abstract]:Oil shale retort residue has become a key problem restricting the development of oil shale industry because of its large amount of pollutants such as phenol sulfide and polycyclic aromatic hydrocarbons which are harmful to the environment. Based on thermogravimetric infrared (TIR) and specific surface area analysis technology, the mixing characteristics of sawdust and dry distillation residue are studied in depth. The main research contents are as follows: the basic combustion characteristics of mixed combustion. The law of gas product release, the surface morphology and kinetics of mixed burning were analyzed. Based on the analysis of fuel basic characteristics, the combustion characteristics and gas release laws of oil shale retort residue and sawdust were studied. The effects of fuel mixing ratio and heating rate on the combustion characteristics were discussed in depth. Through the analysis of combustion TG-DTG curves, the results showed that the mixed samples were on fire with the addition of biomass. With the increase of the heating rate, the combustion curve of the mixed sample moved to the high temperature section, and the ignition and burnout temperature increased. But the reaction characteristics in unit time are improved. Glam-Schmidt curve corresponds to the position of peak in DTG curve. The organic compounds are produced in the pyrolysis process of sawdust. The inorganic compounds are produced in various stages of combustion, with CO2 and CO as the main products, and a small amount of SO2 and no _ x at the same time. The effect of combustion process on pore structure of oil shale mixture of dry distillation residue and sawdust was studied by isothermal adsorption and desorption of nitrogen. The fractal dimension is used to quantitatively describe the complex degree of the surface morphology of the mixture. The results show that the pore volume in each pore size range of the mixture is obviously reduced than that in the dry distillation residue, especially in the water analysis section. The surface pores are mainly mesoporous in the early stage of combustion, and mainly in the mesoporous and macropore in the later stage. The mesoporous structure of the mixture was fully developed during the combustion of volatile matter, and the specific surface area increased significantly. The fractal dimension obtained by linear regression of FHH equation shows that the three-dimensional degree of pores in the mixture is higher than that of dry distillation residue. The alternation of chemical reaction and mechanical action in combustion stage results in the change of fractal dimension with temperature. Based on the classical thermodynamic theory and transition state theory, the FWO equation and KAS equation are derived by using the kinetic method of thermal analysis. The reaction mechanism function and activation enthalpy are obtained simultaneously by using the idea of simultaneous analysis. The changes of activation entropy and activation free energy in the process of oil shale dry distillation residue and sawdust were studied. The results show that the results obtained by the two methods are consistent. The kinetic mechanism of combustion reaction of each sample is better described. In order to improve the accuracy of the calculation, the activation energy of the sample is calculated by using the improved equal-conversion method, and the calculated results are consistent with those calculated by the traditional numerical equal-conversion method. The feasibility of the iso-conversion method for the combustion of the selected sample is verified.
【學(xué)位授予單位】：東北電力大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：X742;TQ038

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