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新型复合促进剂作用下气体-水体系中甲烷水合物生成的研究

Study on methane hydrate formation in gas-water systems with a new compound promoter.

作者信息

Lv Xiaofang, Lu Dayong, Liu Yang, Zhou Shidong, Zuo Jiangwei, Jin Hao, Shi Bohui, Li Entian

机构信息

Jiangsu Key Laboratory of Oil and Gas Storage and Transportation Technology, Changzhou University Changzhou 213016 China

The 714 Research Institute of CSIC (China Shipbuilding Industry Corporation) Building 1, 55 Kehui Road Beijing 100101 China.

出版信息

RSC Adv. 2019 Oct 18;9(57):33506-33518. doi: 10.1039/c9ra06467b. eCollection 2019 Oct 15.

Abstract

The effects of a new promoter on the growth kinetics of methane hydrates were investigated using a visualized constant-pressure autoclave. The experimental results show that when the 1#, 2# and 3# unit promoter was compounded at a ratio of 2 : 1 : 1, the induction time was shortened greatly from 30 h to 0.64 h compared to the no promoter situation. Meanwhile, there was a larger amount of hydrate formation, and final hydrate volume fraction was 83.652%. Then, the hydrate formation characteristics under different additive dosages (500 ppm, 1000 ppm, 2000 ppm, 5000 ppm) and different subcooling degrees (2.5 °C, 3.5 °C, 4.5 °C, 5.5 °C, 6.5 °C) were investigated. The new promoter at these 4 concentrations could effectively shorten the induction time. And the higher the concentration, the smaller the induction time (0.22 h at 5000 ppm). It was also found that gas consumption and hydrate production rate increased first and then decreased with increasing promoter dosage. Finally, the optimal dosage was determined to be 2000 ppm, at which the induction time was shortened to 0.52 h, and the final hydrate volume fraction was 85.74%. Under the dosage of 2000 ppm and the subcooling degree of 6.5 °C, the shortest induction time (0.29 h) and the maximum formation rate (20.950 ml h) were obtained among all the experimental conditions in this work. Moreover, the greater the subcooling degree, the faster the hydrate nucleation, and the shorter the induction time. However, if the subcooling degree was too high, a hydrate layer formed rapidly at the gas-liquid interface in the autoclave, which would hinder hydrate formation and lead to the reduction of hydrate volume fraction to 60.153%. Therefore, a reasonable selection of the proportioning of promoters, dosage of the promoter and formation temperature could significantly promote the formation of hydrates. The findings in this work are meaningful to hydrate associated applications and can provide useful references for the selection of hydrate promoters.

摘要

使用可视化恒压高压釜研究了一种新型促进剂对甲烷水合物生长动力学的影响。实验结果表明,当1#、2#和3#单元促进剂按2∶1∶1的比例复配时,与无促进剂的情况相比,诱导时间从30小时大幅缩短至0.64小时。同时,水合物生成量更大,最终水合物体积分数为83.652%。然后,研究了不同添加剂用量(500 ppm、1000 ppm、2000 ppm、5000 ppm)和不同过冷度(2.5℃、3.5℃、4.5℃、5.5℃、6.5℃)下的水合物生成特性。这4种浓度的新型促进剂均能有效缩短诱导时间。且浓度越高,诱导时间越短(5000 ppm时为0.22小时)。还发现随着促进剂用量的增加,气体消耗和水合物生成速率先增加后降低。最终确定最佳用量为2000 ppm,此时诱导时间缩短至0.52小时,最终水合物体积分数为85.74%。在2000 ppm的用量和6.5℃的过冷度下,在本工作的所有实验条件中获得了最短的诱导时间(0.29小时)和最大生成速率(20.950 ml/h)。此外,过冷度越大,水合物成核越快,诱导时间越短。然而,如果过冷度过高,高压釜中气液界面会迅速形成水合物层,这会阻碍水合物生成并导致水合物体积分数降至60.153%。因此,合理选择促进剂配比、促进剂用量和生成温度可显著促进水合物的生成。本工作的研究结果对水合物相关应用具有重要意义,并可为水合物促进剂的选择提供有用参考。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d84d/9073376/82d6bcf2a3bd/c9ra06467b-f1.jpg

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