13X分子筛耦合四丁基溴化铵促进剂作用下CO2/H2水合物形成动力学

doi:10.16085/j.issn.1000-6613.2019-0018

化工进展 ›› 2019, Vol. 38 ›› Issue (9): 4036-4043.DOI: 10.16085/j.issn.1000-6613.2019-0018

13X分子筛耦合四丁基溴化铵促进剂作用下CO₂/H₂水合物形成动力学

燕然^1,²(),陈朝阳²,夏志明²(),李小森²(),徐纯刚²,颜克凤²,蔡晶²

1. 中国科学技术大学热科学和能源工程系，安徽合肥230027
2. 中国科学院广州能源研究所，中国科学院天然气水合物重点实验室，广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640

收稿日期:2019-01-03 出版日期:2019-09-05 发布日期:2019-09-05
通讯作者: 夏志明,李小森
作者简介:燕然（1994—），男，硕士研究生，研究方向为水合物分离技术。E-mail：yanran@mail.ustc.edu.cn。
基金资助:
国家自然科学基金(51736009);国家重点研发计划(2016YFC0304002);中科院前沿科学重点研究计划(QYZDJ-SSW-JSC033);广东省海洋经济发展专项(GDME-2018D002);广州市科技计划（珠江科技新星专题）(201710010098)

Kinetic study on CO₂/H₂ hydrate formation with 13X molecular sieve coupled TBAB

Ran YAN^1,²(),Zhaoyang CHEN²,Zhiming XIA²(),Xiaosen LI²(),Chungang XU²,Kefeng YAN²,Jing CAI²

1. Department of Thermal Science and Energy Engineering, University of Science and Technology of China, Hefei 230027, Anhui, China
2. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Key Laboratory of Gas Hydrate CAS, Guangzhou Institute of Energy Conversion CAS, Guangzhou 510640, Guangdong, China

Received:2019-01-03 Online:2019-09-05 Published:2019-09-05
Contact: Zhiming XIA,Xiaosen LI

摘要/Abstract

摘要：

水合物法捕集CO₂技术因其清洁环保、工艺简单等优点成为研究热点。但气液传热传质速度慢导致的形成速率慢、储气能力低等关键问题亟待解决。利用13X分子筛耦合四丁基溴化铵（TBAB）促进剂在279.15～280.65K、3.0～6.0MPa研究了CO₂/H₂（39.8% CO₂/60.2% H₂）水合物的形成过程的压降曲线和气体消耗量，并对比分析了TBAB浓度、压力对其促进效果的影响。实验结果表明，与采用搅拌方式的TBAB/CO₂/H₂水合物形成过程相比，13X分子筛可显著提高TBAB/CO₂/H₂水合物的压降速率和气体消耗量。在279.15K、3.0MPa，随着TBAB溶液浓度增大，CO₂/H₂水合物形成过程的气体消耗量先增大后减小；而当温压条件为280.65K、3.0MPa时，气体消耗量随耦合促进剂中TBAB浓度变化仍遵循类似规律。此外，13X分子筛耦合TBAB促进剂对CO₂/H₂水合物压降速率和气体消耗量的影响随着实验压力升高而升高。

关键词: 四丁基溴化铵, 水合物, 合成气, 动力学, 13X 分子筛

Abstract:

As an emerging CO₂ capture technology, hydrate method has been widely accepted as a research focus owing to the environmental protective characteristic and simplified approach. However, a group of key issues involving slow formation rate and low gas storage caused by the relatively low speed of gas-liquid transfer remain to be solved. Based on the characteristics of 13X molecular sieve coupling TBAB promoter at 279.15—280.65K and 3.0—6.0MPa, the study explored the pressure drop curve and gas uptake in the formation process of CO₂/H₂ hydrate (39.8% CO₂/60.2% H₂). Furthermore, this study analyzed the impact of TBAB concentration and experimental pressure on its promotion effect and compare with the other research respectively. The outcome of this study indicated that compared with the hydrate formation process in TBAB solution by agitation, 13X molecular sieve coupled TBAB can significantly enhance the rate of pressure drop and the gas uptake of CO₂/H₂ hydrate. Nevertheless, with the increase of TBAB solution concentration, gas uptake climb to the peak first and then decreased at 279.15K and 3.0MPa. And the gas uptake follow the similar regular pattern with the increase of TBAB solution concentration at 280.65K and 3.0MPa. Additionally, the impact of 13X molecular sieve coupling TBAB promoter on the rate of pressure drop and the consumption of gas of CO₂/H₂ hydrate increased with the increase of experimental pressure.

Key words: tetra-n-butylammonium bromide, hydrate, syngas, kinetics, 13X molecular sieve

中图分类号:

TQ028

燕然,陈朝阳,夏志明,李小森,徐纯刚,颜克凤,蔡晶. 13X分子筛耦合四丁基溴化铵促进剂作用下CO₂/H₂水合物形成动力学[J]. 化工进展, 2019, 38(9): 4036-4043.

Ran YAN,Zhaoyang CHEN,Zhiming XIA,Xiaosen LI,Chungang XU,Kefeng YAN,Jing CAI. Kinetic study on CO₂/H₂ hydrate formation with 13X molecular sieve coupled TBAB[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4036-4043.

图/表 12

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物理参数	数值
粒径/mm	3.0～5.0
颗粒密度/g·cm^-3	0.914
比表面积/m²·g^-1	303.945
微孔体积（＜1.7nm）/cm³·g^-1	0.027
介孔体积(1.7~300nm)/cm³·g^-1	0.072
实际孔容/cm³·g^-1	0.099
平均孔径/nm	3.281
含水饱和度/cm³·g^-1	0.998

物理参数	数值
粒径/mm	3.0～5.0
颗粒密度/g·cm^-3	0.914
比表面积/m²·g^-1	303.945
微孔体积（＜1.7nm）/cm³·g^-1	0.027
介孔体积(1.7~300nm)/cm³·g^-1	0.072
实际孔容/cm³·g^-1	0.099
平均孔径/nm	3.281
含水饱和度/cm³·g^-1	0.998

实验	分子筛型号	TBAB摩尔分数/%	P/MPa	T/K	120min单位气体消耗量/mmol·(mol H₂O)^-1	单位气体消耗量/mmol·(mol H₂O)^-1
1	13X	0	4	279.15	—	—
2	13X	0.29	4	279.15	14.70	21.97
3		0.29	3	279.15	3.06	4.47
4	13X	0.29	3	279.15	9.50	12.76
5	13X	0.60	3	279.15	9.26	13.20
6	13X	1.00	3	279.15	9.39	13.76
7	13X	1.38	3	279.15	8.64	11.18
8	13X	2.34	3	279.15	3.45	7.55
9	13X	0.29	6	279.15	18.75	27.71
10	13X	0.29	3	280.65	9.62	12.43
11	13X	0.6	3	280.65	8.56	12.75
12	13X	1.00	3	280.65	8.43	12.56
13	13X	1.38	3	280.65	7.89	10.81
14	13X	2.34	3	280.65	7.16	8.66

实验	分子筛型号	TBAB摩尔分数/%	P/MPa	T/K	120min单位气体消耗量/mmol·(mol H₂O)^-1	单位气体消耗量/mmol·(mol H₂O)^-1
1	13X	0	4	279.15	—	—
2	13X	0.29	4	279.15	14.70	21.97
3		0.29	3	279.15	3.06	4.47
4	13X	0.29	3	279.15	9.50	12.76
5	13X	0.60	3	279.15	9.26	13.20
6	13X	1.00	3	279.15	9.39	13.76
7	13X	1.38	3	279.15	8.64	11.18
8	13X	2.34	3	279.15	3.45	7.55
9	13X	0.29	6	279.15	18.75	27.71
10	13X	0.29	3	280.65	9.62	12.43
11	13X	0.6	3	280.65	8.56	12.75
12	13X	1.00	3	280.65	8.43	12.56
13	13X	1.38	3	280.65	7.89	10.81
14	13X	2.34	3	280.65	7.16	8.66

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13X分子筛耦合四丁基溴化铵促进剂作用下CO₂/H₂水合物形成动力学

Kinetic study on CO₂/H₂ hydrate formation with 13X molecular sieve coupled TBAB

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