对四甲基氟化铵(TMAF)、四甲基氯化铵(TMAC)、四甲基溴化铵(TMAB)、四丁基氟化铵(TBAF)和四丁基氯化铵(TBAC)五种季铵盐在低浓度含氧煤层气[30% CH4+65% N2+5% O2 (mol)]中形成水合物的热力学促进作用进行了实验研究，采用恒容压力搜索法得到每种季铵盐在浓度0.17%, 0.29%, 0.62%, 1.38%, 3.5%(mol)、温度282.3~304.5 K、压力0.919~8.435 MPa条件下的水合物相平衡数据. 从季铵盐浓度、季铵盐卤素离子种类及季铵盐烷基种类3个方面综合比较了5种季铵盐的热力学促进效果. 结果表明，5种季铵盐均能改善煤层气水合物形成的热力学条件，最佳促进效果3.5% TBAF>0.62% TMAF>3.5% TBAC>1.38% TMAB>1.38% TMAC，季铵盐卤素离子的促进作用氟离子>氯离子或溴离子，季铵盐烷基的影响丁基>甲基.
The thermodynamic effects were researched in hydrate formation experiments for low-concentration coal mine methane gas (CMM , the mole fraction is 30% CH4, 65% N2, and 5% O2) with five kinds of quaternary ammonium salts (QASs) including tetramethyl ammonium fluoride (TMAF), tetramethyl ammonium chloride (TMAC), tetramethyl ammonium bromide (TMAB) and tetrabutyl ammonium fluoride (TBAF), tetrabutyl ammonium chloride (TBAC). The molar concentration of each quaternary ammonium salt was 0.17%, 0.29%, 0.62%, 1.38%, and 3.5%. Under the conditions of phase equilibrium temperature from 282.3 to 304.5 K. Phase equilibrium pressure changed from 0.919 to 8.435 MPa, an isochoric pressure-search method was used to obtain the phase equilibrium data. Comparing the thermodynamic promoting effects of these five kinds of QASs from three aspects: concentration, species of halogen ion and species of alkyl in quaternary ammonium salts. The results showed that these QASs can improve the thermodynamic condition of CMM hydrate formation, the order of the best promoting effects about the three aspects was 3.5% TBAF>0.62% TMAF>3.5% TBAC>1.38% TMAB>1.38% TMAC, fluorine ion quaternary ammonium salts>chloride quaternary ammonium salts or bromide ion quaternary ammonium salts and tetrabutyl quaternary ammonium salts>tetramethyl quaternary ammonium salts.
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