基于化学亲和力模型的水合物生成动力学

doi:10.16085/j.issn.1000-6613.2019-1070

摘要/Abstract

摘要：

水合物生成促进及动力学模型是水合物利用技术的关键问题。本文回顾了水合物生成促进技术的发展，实验研究了氧化石墨烯（GO）与十二烷基硫酸钠（SDS）复配促进剂体系下CO₂水合物的生成动力学，揭示了不同浓度对水合物生成时间、耗气的影响规律。研究结果表明，在GO与SDS复配体系下，CO₂水合物生成速度加快，诱导时间和生成时间缩短，耗气量增大。得出最佳复配浓度为0.005%GO+0.2%SDS，与纯水和单一0.005%GO体系相比，水合物的生成时间分别缩短69.7%和12.2%，耗气量提高11.24%和3.2%。建立了该体系下CO₂水合物生成化学亲和力模型，并从模型角度研究了GO与SDS复配比例、温度和压力对化学亲和力模型参数的影响。利用Matlab对模型编程计算并与实验结果进行了对比分析，吻合很好。通过研究认为，化学亲和力模型可准确预测复配体系水合物的生成。

关键词: 氧化石墨烯, 十二烷基硫酸钠, 水合物, 化学亲和力模型, 生成动力学

Abstract:

Hydrate generation promotion and kinetic model is key issues in hydrate utilization technology. The formation kinetics of CO₂ hydrate in graphene oxide (GO) and sodium dodecyl sulfate (SDS) compounding accelerator system was studied experimentally, and the influence of different concentrations on hydrate formation time and gas consumption was revealed. The results showed that under the combination of GO and SDS, the formation rate of CO₂ hydrate was accelerated, the induction time and generation time were shortened, and the gas consumption was increased. The optimal compounding concentration was 0.005% GO and 0.2% SDS. Compared with pure water and a single 0.005% GO system, the hydrate formation time was shortened by 69.7% and 12.2%, respectively, and the gas consumption was increased by 11.24% and 3.2%. The chemical affinity model of CO₂ hydrate formation in this system was established. The effects of GO and SDS compound ratio, temperature and pressure on the chemical affinity model parameters were studied from the model point of view. Using Matlab to program the model and comparing it with the experimental results, the agreement was very good. The results showed the chemical affinity model could accurately predict the formation of hydrates in the complex system.

Key words: GO, SDS, hydrate, chemical affinity model, formation kinetics

中图分类号:

TQ 0795

王树立,黄俊尧,闫朔,饶永超,贾茹,刘滨. 基于化学亲和力模型的水合物生成动力学[J]. 化工进展, 2020, 39(3): 966-974.

Shuli WANG,Junyao HUANG,Shuo YAN,Yongchao RAO,Ru JIA,Bin LIU. Hydrate formation kinetics based on chemical affinity model[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 966-974.

图/表 15

图1 水合物生成装置图

表1 实验材料规格表

实验材料	纯度	供应源
二氧化碳	≥99.8%	常州市京华工业气体有限公司
蒸馏水	≥99.9%	实验室自制
十二烷基硫酸钠	≥99%	上海试四赫维化工有限公司
氧化石墨烯	≥99%	江南石墨烯研究院

图2 化学亲和力模型动力学参数计算逻辑框图

图3 0.005%GO和不同浓度SDS复配系统下水合物生成过程中耗气量随时间变化

图4 在纯水、0.2%SDS和不同浓度GO复配系统下水合物生成过程中耗气量随时间变化

图5 0.005% GO和不同浓度SDS复配体系中CO2水合物生成时间

图6 在纯水、0.2%SDS和不同浓度GO复配系统中CO2水合物生成时间

表2 GO与SDS复合促进剂对化学亲和力参数的影响

质量分数/%		模型参数		压力/MPa
SDS	GO	t_k/s	-A_r/RT	P₀	P_f
0	0	33013	0.2126	4	2.1967
0	0.005	11385	0.2227	4	2.1115
0.005	0.005	11337	0.2325	4	2.0789
0.03	0.005	11315	0.2359	4	2.0891
0.05	0.005	11190	0.2249	4	1.9961
0.1	0.005	10088	0.2210	4	1.9563
0.2	0.005	10000	0.2489	4	1.9489
0.3	0.005	10061	0.2375	4	1.9521
0.2	0.003	10291	0.2231	4	1.9563
0.2	0.01	11296	0.2234	4	2.0372
0.2	0.02	11356	0.2221	4	2.0325

表3 不同初始压力时化学亲和力模型参数

温度/K	P₀/MPa	P_f/MPa	模型参数
温度/K	P₀/MPa	P_f/MPa	t_k/s	-A_r/RT
281.15	4	1.9489	10000	0.2489
281.15	5	1.9511	9764	0.2571
281.15	6	1.9589	9218	0.2614

图7 0.005%GO与0.2%SDS体系中281.15K、450r/min和不同初压时亲和力随-ln[(ti/tk)exp(1-ti/tk)]变化曲线

表4 0.005%GO+0.2%SDS体系中不同温度中CO2水合物生成过程中化学亲和力参数

温度/K	P₀/MPa	P_f/MPa	模型参数
温度/K	P₀/MPa	P_f/MPa	t_k/s	-A_r/RT
277.15	4	1.7543	8869	0.2698
279.15	4	1.8714	9632	0.2653
281.15	4	1.9489	10000	0.2489

图8 0.005%GO与0.2%SDS体系中4MPa和450r/min工况时温度对模型参数影响

图9 在纯水、0.005%GO和0.005%GO+0.2%SDS体系中实验和模型所得归一化气体消耗量对比

图10 在纯水、0.005%和0.005%GO+0.2%SDS体系中CO2水合物生成过程中化学亲和力随-ln[(ti/tk)exp(1-ti/tk)]变化曲线

图11 在0.005%GO+0.2%SDS体系中实验和模型计算所得的气体消耗量的对比

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