本文選題：水合物 + 煤層氣　； 參考：《太原理工大學(xué)》2017年碩士論文

【摘要】：隨著工業(yè)的迅猛發(fā)展,我國對能源的需求日益增加,經(jīng)濟增長與能源供需、環(huán)境的矛盾日益突出。為響應(yīng)“節(jié)能減排,低碳經(jīng)濟”的號召,天然氣利用比重逐年增加。煤層氣屬于非常規(guī)天然氣,在我國儲量豐富,但由于利用不合理和技術(shù)的限制,煤層氣排放量逐年遞增,資源浪費嚴(yán)重,同時加重了溫室效應(yīng)。合理、高效、安全利用煤層氣迫在眉睫。水合物法利用煤層氣中各組分相平衡條件不同分離提純低濃度煤層氣,相比傳統(tǒng)的分離技術(shù)有其獨有的優(yōu)勢。目前水合物法工業(yè)應(yīng)用存在相平衡壓力高、誘導(dǎo)時間長、儲氣率低下等問題,為克服這些障礙,國內(nèi)外學(xué)者對水合物生成的熱力學(xué)以及動力學(xué)促進劑進行了廣泛的研究,發(fā)現(xiàn)了如十二烷基硫酸鈉(SDS)、四氫呋喃(THF)等性能優(yōu)良的促進劑。季銨鹽是常見的表面活性劑,大量研究表明四丁基溴化銨(TBAB)、四丁基氯化銨(TBAC)和四丁基氟化銨(TBAF)對氣體水合物同樣具有優(yōu)良的熱力學(xué)和動力學(xué)促進效果。鑒于此,本文選用TBAC、TBAF、四甲基溴化銨(TMAB)、四甲基氯化銨(TMAC)和四甲基氟化銨(TMAF)五種季銨鹽,實驗研究了各季銨鹽對低濃度煤層氣(CBM,摩爾分?jǐn)?shù)為30%CH_4+65%N2+5%O2)熱力學(xué)和動力學(xué)的影響,研究因素包括水合物的相平衡條件、相變潛熱、誘導(dǎo)時間以及儲氣率;并使用修正的水的逸度模型對TBAB、TBAC和TBAF與純甲烷及煤層氣水合物相平衡進行了模擬。具體工作內(nèi)容如下:(1)實驗研究了TBAC、TBAF以及TMAB、TMAC、TMAF在內(nèi)的5種季銨鹽對低濃度煤層氣水合物形成的熱力學(xué)和動力學(xué)影響,濃度均涉及0.17、0.29、0.62、1.38以及3.5 mol%五種,采用恒容壓力搜索法獲得水合物相平衡數(shù)據(jù),相平衡溫度282.3~304.5 K,相平衡壓力0.919~8.435 MPa,季銨鹽濃度對水合物促進作用呈現(xiàn)非線性,存在最佳濃度,本實驗最佳促進濃度排序為:3.5 mol%TBAF0.62 mol%TMAF3.5 mol%TBAC1.38mol%TMAB1.38 mol%TMAC;使用Clausius-Clapeyron獲取季銨鹽氣體水合物的相變潛熱,排序為:3.5mol%TBAF0.62mol%TMAF3.5mol%TBAC1.38 mol%TMAB1.38 mol%TMAC;獲得誘導(dǎo)時間數(shù)據(jù),排序為:3.5 mol%TBAF3.5 mol%TBAC1.38 mol%TMAC≈1.38 mol%TMAB0.62 mol%TMAF;計算得季銨鹽水合物儲氣率,總體上TBAC儲氣率高于TBAF。(2)采用修正的水的逸度模型描述水合物相行為,PRSV2狀態(tài)方程計算氣體組分逸度,e-NRTL電解質(zhì)活度系數(shù)模型計算季銨鹽溶液各組分活度系數(shù)。修正的水的逸度模型對季銨鹽與單組份氣體水合物相平衡模擬效果欠佳,平均相對誤差在15%以下;對TBAX與煤層氣水合物相平衡模擬效果較好,平均相對誤差在9%以下,為季銨鹽應(yīng)用于水合物法分離煤層氣提供了理論依據(jù)。
[Abstract]:With the rapid development of industry, the demand for energy in China is increasing day by day, and the contradiction between economic growth and energy supply and demand and environment is becoming more and more prominent. In response to the call of "energy saving and emission reduction, low-carbon economy", the proportion of natural gas utilization is increasing year by year. Coal bed methane (CBM) is a kind of unconventional natural gas, which is rich in reserves in our country. However, due to unreasonable utilization and technical limitation, CBM emissions are increasing year by year, resources are wasted seriously, and Greenhouse Effect is aggravated at the same time. Rational, efficient and safe use of coalbed methane is imminent. The method of hydrate is used to separate and purify low concentration CBM by using different equilibrium conditions of each component in CBM, which has its unique advantages compared with the traditional separation technology. At present, there are some problems in the application of hydrate method, such as high phase equilibrium pressure, long induction time, low gas storage rate and so on. In order to overcome these obstacles, domestic and foreign scholars have carried out extensive research on thermodynamics and kinetic accelerators for hydrate formation. Excellent accelerators, such as sodium dodecyl sulfate (SDS), tetrahydrofuran (THF), were found. Quaternary ammonium salts are common surfactants. A large number of studies have shown that tetra ammonium bromide (TBABN), tetra- ammonium chloride (TBACN) and tetra ammonium fluoride (TBAFs) also have excellent thermodynamic and kinetic effects on gas hydrates. In view of this, five quaternary ammonium salts, TBAC, TMAB, TMAC and TMAF) were selected. The effects of quaternary ammonium salts on the thermodynamics and kinetics of low concentration CBM in 30%CH_4 65%N2 5O2 were studied experimentally. The research factors include the phase equilibrium condition of hydrate, latent heat of phase transition, induction time and gas storage rate, and the modified fugacity model of water is used to simulate the phase equilibrium of TBABN TBAC and TBAF with pure methane and coal-bed methane hydrate. The thermodynamic and kinetic effects of five quaternary ammonium salts, including TBACU TBAF and TMABX TMACU TMAF, on the formation of low concentration coal-bed methane hydrates were studied. The concentrations of these quaternary ammonium salts were 0.170.290.290.62% 1.38 and 3.5 mol%, respectively. The phase equilibrium data of hydrate were obtained by constant volume pressure search method. The phase equilibrium temperature was 282.3n 304.5 K, the phase equilibrium pressure was 0.919 ~ 8.435 MPa, and the concentration of quaternary ammonium salt was nonlinear and the best concentration existed. 鏈疄楠屾渶浣充績榪涙祿搴︽帓搴忎負:3.5 mol%TBAF0.62 mol%TMAF3.5 mol%TBAC1.38mol%TMAB1.38 mol%TMAC;浣跨敤Clausius-Clapeyron鑾峰彇瀛ｉ摰鐩愭皵浣撴按鍚堢墿鐨勭浉鍙樻綔鐑，

本文編號：1793328