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  本文關(guān)鍵詞： 新型胺溶劑 吸收 二氧化碳 平衡溶解度 CO_2吸收熱 動力學(xué)　出處：《湖南大學(xué)》2016年博士論文　論文類型：學(xué)位論文

【摘要】：經(jīng)濟發(fā)展使人類對化石燃料的需求不斷增加,導(dǎo)致二氧化碳(CO_2)的排放量逐年提高,造成越來越嚴(yán)重的全球"溫室效應(yīng)"等氣候問題,但與此同時CO_2又是潛在的資源(尤其是在油田注氣驅(qū)油等新領(lǐng)域的應(yīng)用)。因而良好的CO_2捕獲技術(shù)不但能有效緩解氣候問題還能帶來可觀的經(jīng)濟效益。有機胺溶液捕獲CO_2技術(shù)因其良好的吸收和解吸性能成為CO_2捕獲的首選方法,而開發(fā)具有較好吸收性能的吸收溶劑是有機胺溶液捕獲CO_2技術(shù)的關(guān)鍵。4-二乙基-2-丁醇(DEAB)、1-二乙氨基-2-丙醇(1DEA2P)、1-(2-羥乙基)哌啶(1-(2-HE)PP)和1-(2-羥乙基)吡咯烷(1-(2-HE)PRLD)作為新的有機胺溶液,其CO_2吸收性能是其能否作為新型CO_2吸收溶劑的關(guān)鍵因素。因此本文主要探究了 DEAB、1DEA2P、1-(2-HE)PP和1-(2-HE)PRLD溶液在不同溫度條件下的pKa,其與C02反應(yīng)過程中的各個離子隨C02負(fù)載變化的離子形成曲線,其C02平衡溶解度,其吸收CO_2的吸收熱,以及其與C02反應(yīng)的動力學(xué)進(jìn)行研究;同時與MEA及MDEA等工業(yè)應(yīng)用較為成熟的吸收溶劑的CO_2吸收性能進(jìn)行全面的比較,并評估該四種溶劑作為CO_2商業(yè)化溶劑的可能性。本文實驗測得了DEAB、1DEA2P、1-(2-HE)PP 和 1-(2-HE)PRLD 溶液在不同溫度下的 pKa,發(fā)現(xiàn)四種溶液的pKa值隨著溫度的升高而降低,同時建立了四種胺溶液的pKa隨溫度變化的關(guān)系式,結(jié)果發(fā)現(xiàn)這四個關(guān)系式能夠很好的預(yù)測這四種胺溶液在不同溫度下的 pKa 值。為了更好地理解 DEAB、1DEA2P、1-(2-HE)PP 和 1-(2-HE)PRLD 溶液吸收CO_2過程以及建立完整的DEAB、1DEA2P、1-(2-HE)PP和1-(2-HE)PRLD溶液溶液吸收CO_2體系的氣液平衡模型,本文探究了 DEAB、1DEA2P、1-(2-HE)PP和1-(2-HE)PRLD溶液與C02反應(yīng)體系中各個離子濃度隨C02負(fù)載變化的曲線,同時探究了 DEAB、1DEA2P、1-(2-HE)PP 和 1-(2-HE)PRLD 溶液吸收 CO_2 過程中各個離子與pH之間的二維關(guān)系模型;同時還建立其了 DEAB、1DEA2P、1-(2-HE)PP和1-(2-HE)PRLD溶液,pH值與溫度之間的三維體系模型。發(fā)現(xiàn)該二維關(guān)系模型以及三維關(guān)系模型能夠很好的用于該四種胺溶劑的吸收CO_2過程中各個離子的變化曲線的呈現(xiàn)和預(yù)測。本文同時測量2mol/L的DEAB、1DEA2P、1-(2-HE)PP 和 1-(2-HE)PRLD 溶液在溫度為 298-313K,CO_2 分壓為 8-101kPa 的條件下的CO_2平衡溶解度。結(jié)果發(fā)現(xiàn)這四種胺溶液的CO_2平衡溶解度隨著溫度的升高而降低,隨著CO_2分壓的增加而增加。運用吉布斯赫姆霍茲方程估計了 DEAB、1DEA2P、1-(2-HE)PP和1-(2-HE)PRLD溶液吸收CO_2的吸收熱的值分別為-41.4 kJ/mol、-43.6kJ/mol、-34kJ/mol 及-34.2kJ/mol。利用電化學(xué)快速分析儀測得DEAB溶液在濃度為100-900mol/m3,溫度為298-313K的條件下吸收CO_2的一級反應(yīng)速率常數(shù)ko,1DEA2P溶液在濃度為120-751mol/m3,溫度為298-313K的條件下吸收CO_2的一級反應(yīng)速率常數(shù)k0;1-(2-HE)PP溶液在濃度為200-1000mol/m3,溫度為298-313K的條件下吸收CO_2的一級反應(yīng)速率常數(shù)k0。1-(2-HE)PRLD溶液在濃度為200-1000mol/m3,溫度為298-313K的條件下吸收CO_2的一級反應(yīng)速率常數(shù)k0。同時建立了 DEAB、1DEA2P、1-(2-HE)PP和1-(2-HE)PRLD溶液吸收CO_2的動力學(xué)模型。發(fā)現(xiàn)該模型能夠很好地預(yù)測DEAB、1DEA2P、1-(2-HE)PP和1-(2-HE)PRLD溶液吸收CO_2過程中的反應(yīng)速率常數(shù),DEAB、1DEA2P、1-(2-HE)PP與1-(2-HE)PRLD的平均偏差分別為5.8%、8.0%、8.3%與 6.1%。為了全面評估 DEAB、1DEA2P、1-(2-HE)PP 與 1-(2-HE)PRLD 溶液作為 CO_2捕獲領(lǐng)域潛在的溶劑,通過與MEA和MDEA溶液等傳統(tǒng)的商業(yè)化溶劑的比較,對比了四種胺溶液和幾種常用的胺溶劑的CO_2平衡溶解度,反應(yīng)動力學(xué)參數(shù),以及CO_2吸收熱;結(jié)果發(fā)現(xiàn)這四種胺溶液在CO_2平衡溶解度,反應(yīng)動力學(xué)以及CO_2吸收熱都表現(xiàn)出良好的性能。綜上所述,DEAB、1DEA2P、1-(2-HE)PP和1-(2-HE)PRLD這四種胺溶液可以作為新一代潛在的吸收溶劑或者混合溶劑中的一種或幾種溶劑。
[Abstract]:Economic development makes the human demand for fossil fuels is increasing, resulting in carbon dioxide (CO_2) emissions increased year by year, resulting in more serious global greenhouse effect and climate issues, but at the same time, CO_2 is a potential resource (especially the new application field of oil in the oil gas injection) and good. CO_2 capture technology not only can effectively alleviate the problem of climate but also bring considerable economic benefits. The organic amine solution capture CO_2 CO_2 capture technology become the preferred method because of its good absorption and desorption performance, and has good solvent absorption can absorb development is the key to.4- organic amine solution to capture CO_2 technology two -2- ethyl butanol (DEAB). 1- two ethylamino -2- propanol (1DEA2P), 1- (2- hydroxyethyl) piperidine (1- (2-HE) PP) and 1- (2- hydroxyethyl) pyrrolidine (1- (2-HE) PRLD) solution as a new organic amine, the absorption performance of CO_2 is its ability to act as a The key factors of new CO_2 absorption solvents. So this paper mainly discusses the DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) PRLD solution under different temperature conditions pKa, C02 and the various ion ion in the reaction process with C02 load changes of the curve, the equilibrium solubility of C02, the absorption of CO_2 absorption of heat, and the reaction kinetics were studied with C02 and MEA and MDEA; and industrial applications such as the mature absorption solvent of CO_2 absorption performance to conduct a comprehensive comparison, and evaluation of the four kinds of solvents as potential CO_2 commercial solvent. This experiment measured the DEAB, 1DEA2P, PP and 1- (2-HE) 1- (2-HE) PRLD solution at different temperatures pKa, found that four of the pKa value of the solution decreased with the increase of the temperature, relation and set up four types of amine solution pKa varies with temperature, the results show that the four relations can be a good predictor of the four An amine solution at different temperatures and pKa values. In order to better understand the DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) PRLD CO_2 solution absorption process and the establishment of a complete DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) CO_2 system model of gas-liquid equilibrium absorption of PRLD solution in this paper. To explore the DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) of each ion concentration in the solution with C02 PRLD reaction system with C02 load curve, and explore the DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) two-dimensional model between each ion and pH in the process of CO_2 absorption PRLD at the same time to establish its solution; DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) PRLD solution, pH value and temperature model. The relationship between the two-dimensional model and three-dimensional model can be very good for the curve of each ion of the four kinds of amine solvent absorption in the process of CO_2 presentation and At the same time. The prediction measurement of 2mol/L DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) PRLD solution for 298-313K in temperature, CO_2 partial pressure is CO_2 solubility under the condition of 8-101kPa. The results showed that CO_2 equilibrium solubility of these four kinds of amine solution decreases with the increase of temperature, increased with the increase of CO_2 partial pressure. Using Gibbs Helmholtz equation to estimate DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) value of absorption heat absorption of CO_2 PRLD solution were -41.4 kJ/mol, -43.6kJ/mol, -34kJ/mol and -34.2kJ/mol. by electrochemical analyzer measured DEAB solution at a concentration of 100-900mol/m3, the first-order reaction rate constant temperature Ko under the condition of 298-313K CO_2 absorption, 1DEA2P solution at a concentration of 120-751mol/m3, the first-order reaction rate constant K0 temperature under the condition of 298-313K absorption of CO_2; 1- (2-HE) PP solution at a concentration of 200-1000mol/m3, temperature As a reaction rate constant k0.1- 298-313K absorption under the condition of CO_2 (2-HE) PRLD solution at a concentration of 200-1000mol/m3, the first-order reaction rate constant k0. temperature under the condition of 298-313K CO_2 absorption and the establishment of the DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) CO_2 dynamic model for the absorption of PRLD solution. This model can well predict the DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) absorption rate constant CO_2 in the process of PRLD solution DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) the average deviation of PRLD was 5.8% and 8% respectively, 8.3% and 6.1%. in order to evaluate DEAB 1DEA2P, 1-, PP (2-HE) and 1- (2-HE) PRLD solution as CO_2 capture the potential areas of solvent, by comparing the traditional commercial solvent with MEA and MDEA solution of the comparison of four kinds of amine solution and several amine solvent CO_2 equilibrium solubility, kinetic parameters, and CO_2 absorption Heat; the results show that the four amine solution in CO_2 equilibrium solubility, reaction kinetics and heat absorption CO_2 show good performance. To sum up, DEAB, 1DEA2P, 1- (2-HE) PP and 1- (2-HE) PRLD these four kinds of amine solution can be used as a new generation of potential absorption of one or several solvents or solvent in the mixed solvent.

【學(xué)位授予單位】：湖南大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：X701;TQ028.14

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