不同降温模式对天然气水合物合成的影响
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摘要
水合物实验室合成过程中,降温模式对诱导、结晶阶段都具有明显的影响。反应温度过低时,表现为反应速率慢、诱导期长,同时温度过高时,随着反应的进行压力降低,生成水合物会分解。基于升温提高合成反应速率的同时,为了形成稳定、均一分布的高质量水合物样品,在一次降温的基础上,进行了4～2℃和3～1℃两种阶梯降温和4轮次温度震荡的不同降温模式实验研究。结果表明:阶梯降温为3～1℃时比4～2℃诱导期略有增加,但最终形成时间相差不大,同时压降明显增大,气体转化率提高;增加温度震荡次数,压降逐渐增大,但具有次效性。可见阶梯降温和温度震荡均有利于水合物的增量合成,形成多孔介质中分布均一的水合物。
In the process of hydrate synthesis in laboratory,the cooling mode has obvious influence on the induction and crystallization stages. When the reaction temperature is too low,the reaction rate is slow and the induction period is long. At the same time,when the reaction temperature is too high,the formation of hydrate will decompose as the reaction pressure decreases. In order to form high quality hydrate samples with stable and uniform distribution,two different cooling modes,4 ～ 2 ℃ and 3 ～ 1 ℃,have been experimentally studied in order to increase the reaction rate and form stable and homogeneous hydrate samples. The results show that the induction period of step cooling of 3 ～ 1 ℃ is slightly higher than that of 4 ～ 2 ℃,but there is not different in the final formation time. At the same time,the pressure drop increases obviously,and the gas conversion rate increases. With the increase of temperature oscillation times,the pressure drop increases gradually,but with secondary effect. It can be seen that both step cooling and temperature oscillation are beneficial to the incremental synthesis of hydrates and the formation of homogeneous hydrates in porous media.
In the process of hydrate synthesis in laboratory,the cooling mode has obvious influence on the induction and crystallization stages. When the reaction temperature is too low,the reaction rate is slow and the induction period is long. At the same time,when the reaction temperature is too high,the formation of hydrate will decompose as the reaction pressure decreases. In order to form high quality hydrate samples with stable and uniform distribution,two different cooling modes,4 ～ 2 ℃ and 3 ～ 1 ℃,have been experimentally studied in order to increase the reaction rate and form stable and homogeneous hydrate samples. The results show that the induction period of step cooling of 3 ～ 1 ℃ is slightly higher than that of 4 ～ 2 ℃,but there is not different in the final formation time. At the same time,the pressure drop increases obviously,and the gas conversion rate increases. With the increase of temperature oscillation times,the pressure drop increases gradually,but with secondary effect. It can be seen that both step cooling and temperature oscillation are beneficial to the incremental synthesis of hydrates and the formation of homogeneous hydrates in porous media.
引文
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12 李刚,李小森.过冷度对气体水合物合成影响的实验研究[J].现代地质,2010,24(3):627-631,637Li Gang,Li Xiaosen. Experimental investigation of the supercooling effect on methane hydrate formation[J]. Geoscience,2010,24(3):627-631,637
13 李明川,樊栓狮.天然气水合物形成过程3阶段分析[J].可再生能源,2010,28(5):80-83Li Mingchuan,Fan Shuanshi. Analysis on the three stages in the formation of natural gas hydrates[J]. Renewable Energy,2010,28(5):80-83
14 李燕,诸林,朱天阁.促进天然气水合物生成的研究进展[J].西南石油大学学报,2007,8(增刊1):46-49Li Yan,Zhu Lin,Zhu Tiange. Research progress in promoting gas hydrate formation[J]. Journal of Southwest Petroleum University,2007,8(S1):46-49
15 Holder G,Manganiello D J. Hydrate dissociation pressure minima multicomponent systems[J]. Chemical Engineering Science,1982,37(1):9-16
2 李淑霞,刘佳丽,武迪迪,等.神狐海域水合物藏降压开采的数值模拟[J].科学技术与工程,2018,18(24):38-43Li Shuxia,Liu Jiali,Wu Didi,et al. Numerical study of hydrate depressurization dissociation in Shenhu area[J]. Science Technology and Engineering,2018,18(24):38-43
3 郭平,冉文博,刘煌.天然气水合物生成条件预测研究进展[J].科学技术与工程,2018,18(29):133-139Guo Ping,Ran Wenbo,Liu Huang. Research advance of the prediction of nature gas hydrate formation conditions[J]. Science Technology and Engineering,2018,18(29):133-139
4 郝玉超,孙始财,刘昌岭,等.四氢呋喃水合物热物性非原位测量方法[J].科学技术与工程,2018,18(32):179-183Hao Yuchao,Sun Shicai,Liu Changling,et al. Ex-situ measurement of thermophysical property of tetrahydrofuran hydrate[J]. Science Technology and Engineering,2018,18(32):179-183
5 张郁,李小森,陈朝阳,等.冰点下多孔介质中甲烷水合物的生成特性[J].现代地质,2016,30(4):922-928Zhang Yu,Li Xiaosen,Chen Zhaoyang,et al. Formation behaviors of methane hydrate in porous media below freezing point[J]. Geoscience,2016,30(4):922-928
6 陈敏,曹志敏,业渝光,等.海洋天然气水合物合成的模拟实验研究[J].海洋学报,2006,28(6):39-43Chen Min,Cao Zhimin,Ye Yuguang,et al. Experimental technology on elemental geochemical study during the formation of marine gas hydrates[J]. Acta Oceanologica Sinica,2006,28(6):39-43
7 唐良广,肖睿,李刚,等.热力法开采天然气水合物的模拟实验研究[J].过程工程学报,2006,6(4):548-553Tang Liangguang,Xiao Rui,Li Gang,et al. Experimental investigation of production behavior of gas hydrate under thermal stimulation[J]. The Chinese Journal of Process Engineering,2006,6(4):548-533
8 李刚,李小森,唐良广,等.降温模式对甲烷水合物形成的影响[J].过程工程学报,2007,7(4):723-727Li Gang,Li Xiaosen,Tang Liangguang,et al. Experimental study on the effect of temperature cooling profile on methane hydrate formation[J]. The Chinese Journal of Process Engineering,2007,7(4):723-727
9 蒋观利,吴青柏,蒲毅彬.降温过程对粗砂土中甲烷水合物形成的影响[J].地球物理学报,2009,52(9):2387-2393Jiang GuanLi,Wu Qingbai,Pu Yibin. The effect of cooling process on the formation of methane hydrate within the coarse sand[J]. Chinese Journal of Geophysics,2009,52(9):2387-2393
10 张鹏,吴青柏,蒋观利.降温速率对零度以上介质内甲烷水合物形成的影响[J].天然气地球科学,2009,20(6):1000-1004Zhang Peng,Wu Qingbai,Jiang Guanli. Effects of temperature reducing ratios on methane hydrate formation inside media above zero celsius degree[J]. Journal of Natural Gas Geoscience,2009,20(6):1000-1004
11 蒋观利,吴青柏,展静.降温速率和粒径对砂土中甲烷水合物形成过程影响研究[J].天然气地球科学,2011,22(5):920-925Jiang Guanli,Wu Qingbai,Zhan Jing. The effects of cooling rate and particle size of medium to the formation of methane hydrate in sands[J]. Natural Gas Geoscience,2011,22(5):920-925
12 李刚,李小森.过冷度对气体水合物合成影响的实验研究[J].现代地质,2010,24(3):627-631,637Li Gang,Li Xiaosen. Experimental investigation of the supercooling effect on methane hydrate formation[J]. Geoscience,2010,24(3):627-631,637
13 李明川,樊栓狮.天然气水合物形成过程3阶段分析[J].可再生能源,2010,28(5):80-83Li Mingchuan,Fan Shuanshi. Analysis on the three stages in the formation of natural gas hydrates[J]. Renewable Energy,2010,28(5):80-83
14 李燕,诸林,朱天阁.促进天然气水合物生成的研究进展[J].西南石油大学学报,2007,8(增刊1):46-49Li Yan,Zhu Lin,Zhu Tiange. Research progress in promoting gas hydrate formation[J]. Journal of Southwest Petroleum University,2007,8(S1):46-49
15 Holder G,Manganiello D J. Hydrate dissociation pressure minima multicomponent systems[J]. Chemical Engineering Science,1982,37(1):9-16