玉米棒+四氢呋喃对IGCC合成气水合物生成动力学的影响

doi:10.16085/j.issn.1000-6613.2021-0325

化工进展 ›› 2022, Vol. 41 ›› Issue (1): 174-181.DOI: 10.16085/j.issn.1000-6613.2021-0325

玉米棒+四氢呋喃对IGCC合成气水合物生成动力学的影响

张青宗¹^,²^,³^,⁴^,⁵(), 吕秋楠²^,³^,⁴^,⁵, 李小森²^,³^,⁴^,⁵, 余益松²^,³^,⁴^,⁵(), 周诗岽¹()

^1.常州大学石油工程学院油气储运技术省重点实验室，江苏常州 213016
^2.中国科学院广州能源研究所，广东广州 510640
^3.中国科学院天然气水合物重点实验室，广东广州 510640
^4.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
^5.中国科学院广州天然气水合物研究中心，广东广州 510640

收稿日期:2021-02-10 修回日期:2021-06-05 出版日期:2022-01-05 发布日期:2022-01-24
通讯作者: 余益松,周诗岽
作者简介:张青宗（1994—），男，硕士研究生，研究方向为气体水合物利用技术。E-mail: zhangqz@ms.giec.ac.cn。
基金资助:
国家自然科学基金(22008237);中国科学院前沿科学“从0到1”原始创新项目(ZDBS-LY-SLH041);广东省自然科学基金(2019A1515012086);广州市基础与应用基础研究项目(202102020720)

Kinetics studies of IGCC syngas hydrate formation in the presence of corn cobs and tetrahydrofuran

ZHANG Qingzong¹^,²^,³^,⁴^,⁵(), LYU Qiunan²^,³^,⁴^,⁵, LI Xiaosen²^,³^,⁴^,⁵, YU Yisong²^,³^,⁴^,⁵(), ZHOU Shidong¹()

^1.Jiangsu Key Laboratory of Oil-Gas Storage and Transportation Technology, School of Petroleum Engineering, Changzhou University, Changzhou 213016, Jiangsu, China
^2.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^3.Key Laboratory of Gas Hydrate, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^4.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China
^5.Guangzhou Center for Gas Hydrate Research, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China

Received:2021-02-10 Revised:2021-06-05 Online:2022-01-05 Published:2022-01-24
Contact: YU Yisong,ZHOU Shidong

摘要/Abstract

摘要：

为了明确玉米棒颗粒与四氢呋喃（THF）对整体煤气化联合循环（IGCC）合成气气体水合物生成的协同作用，在温度276.15K、初始压力为6.0MPa的静态反应条件下，通过实验研究了玉米棒颗粒+THF溶液体系中气体水合物的生成动力学过程，并确定了不同THF浓度溶液条件下水合物的生成诱导时间、气体消耗量、CO₂分离效率及水合物的晶体结构。实验结果表明：玉米棒的存在会延长实验的稳定时间，且其压降幅度相较于不含玉米棒颗粒的体系更高；无论是否含玉米棒颗粒，诱导时间均在180s以内，且随着THF浓度上升到摩尔分数4.0%和5.6%，二者的诱导时间变得非常接近；玉米棒颗粒存在时，THF溶液的浓度越大，气体消耗量达到最终气体消耗量90%的时间则越短，且在相同THF浓度下，其所获得的气体消耗量和CO₂分离效率普遍比纯THF溶液体系高，这意味着玉米棒颗粒的存在提高了THF溶液对CO₂的分离效果。同时，微观结构分析表明无论是否含有玉米棒颗粒，THF溶液体系中所生成的IGCC合成气气体水合物的结构均为sⅡ型，纯水体系中生成的IGCC合成气气体水合物结构均为sⅠ型和sⅡ型的混合结构。

关键词: 水合物, 四氢呋喃, IGCC合成气, 动力学, 二氧化碳分离, 水合物结构

Abstract:

A series of experiments was conducted at 276.15K and 6.0MPa to evaluate the kinetics of IGCC synthesis gas hydrate formation in the system containing corn cobs and tetrahydrofuran (THF) by measuring induction time, gas consumption, CO₂ recovery and hydrate structure. The results showed that for all experiment cases with or without corn cobs, the induction time was within 180s. Besides, the induction time of the system containing corn cobs was slightly longer than that without corn cobs and this difference almost disappears as the THF concentration increases to mole fraction 4.0% and 5.6%. Further, relative to the system without corn cobs, the time required to complete hydrate formation was longer in the presence of corn cobs. As the THF concentration increases, less time was required for achieving 90% of final gas consumption in the presence of corn cobs. In addition, at a certain THF concentration, the gas consumptions in the presence of corn cobs were larger than that in the system without corn cobs. These indicate that the addition of corn cobs had a positive effect on the kinetics of IGCC syngas hydrates formation and the CO₂ recovery. Interestingly, structure analysis proves that only s?Ⅱ hydrates were observed in the presence of THF with or without corn cobs, while both s??Ⅰ and s?Ⅱ hydrates were found in pure water.

Key words: hydrate, tetrahydrofuran, IGCC syngas, kinetics, CO₂ separation, hydrate structure

中图分类号:

TQ028

张青宗, 吕秋楠, 李小森, 余益松, 周诗岽. 玉米棒+四氢呋喃对IGCC合成气水合物生成动力学的影响[J]. 化工进展, 2022, 41(1): 174-181.

ZHANG Qingzong, LYU Qiunan, LI Xiaosen, YU Yisong, ZHOU Shidong. Kinetics studies of IGCC syngas hydrate formation in the presence of corn cobs and tetrahydrofuran[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 174-181.

图/表 9

图1 实验装置

图2 温度276.15K、压力6.00MPa条件下玉米棒+4.0%THF溶液体系中典型的水合物生成P-T-t曲线

图3 温度276.15K、压力6.00MPa条件下4.0% THF溶液体系中典型的水合物生成P-T-t曲线

图4 诱导时间随THF摩尔分数的变化曲线

表1 不同实验条件下水合物生成的诱导时间

实验条件	实验体系	THF摩尔分数/%	诱导时间/s
温度276.15K，压力6.00MPa	玉米棒颗粒+THF溶液+IGCC	2.0	78±29
		3.0	149±28
		4.0	18±2
		5.6	13±4
	THF溶液+IGCC	2.0	62±2
		3.0	49±1
		4.0	12±4
		5.6	11±3

图5 THF浓度对IGCC合成气水合物气提量的影响

图6 不同THF浓度的溶液在含玉米棒颗粒和不含玉米棒颗粒系统中水合物生成后的最终气体消耗量

图7 不同THF浓度的溶液在含玉米棒颗粒和不含玉米棒颗粒实验中的CO2回收率

图8 PXRD测试结果*—冰峰

参考文献 18

1	中华人民共和国国家统计局. 中国统计年鉴[M]. 北京: 中国统计出版社, 2019.
	National Bureau of Statistics of People’s Republic of China. National statistical yearbook[M]. Beijing: China Statistics Press, 2019.
2	GAO W L, ZHOU T T, GAO Y S, et al. Molten salts-modified MgO-based adsorbents for intermediate-temperature CO₂ capture: a review[J]. Journal of Energy Chemistry, 2017, 26(5): 830-838.
3	SHAMAIR Z, HABIB N, GILANI M A, et al. Theoretical and experimental investigation of CO₂ separation from CH₄ and N₂ through supported ionic liquid membranes[J]. Applied Energy, 2020, 268: 115016.
4	李水飞, 高利孝. CO₂的化学吸收原理和吸收剂发展研究[J]. 当代化工研究, 2020(17): 146-147.
	LI Shuifei, GAO Lixiao. Research on the principle of CO₂ chemical absorption and the development of absorbent[J]. Modern Chemical Research, 2020(17): 146-147.
5	DESCHAMPS J, DALMAZZONE D. Dissociation enthalpies and phase equilibrium for TBAB semi-clathrate hydrates of N₂, CO₂, N₂+CO₂ and CH₄+CO₂[J]. Journal of Thermal Analysis and Calorimetry, 2009, 98(1): 113-118.
6	RICAURTE M, DICHARRY C, BROSETA D, et al. CO₂ removal from a CO₂-CH₄ gas mixture by clathrate hydrate formation using THF and SDS as water-soluble hydrate promoters[J]. Industrial & Engineering Chemistry Research, 2013, 52(2): 899-910.
7	LIM Y A, BABU P, KUMAR R, et al. Morphology of carbon dioxide-hydrogen-cyclopentane hydrates with or without sodium dodecyl sulfate[J]. Crystal Growth & Design, 2013, 13(5): 2047-2059.
8	LINGA P, ADEYEMO A, ENGLEZOS P. Medium-pressure clathrate hydrate/membrane hybrid process for postcombustion capture of carbon dioxide[J]. Environmental Science & Technology, 2008, 42(1): 315-320.
9	MEKALA P, BUSCH M, MECH D, et al. Effect of silica sand size on the formation kinetics of CO₂ hydrate in porous media in the presence of pure water and seawater relevant for CO₂ sequestration[J]. Journal of Petroleum Science and Engineering, 2014, 122: 1-9.
10	ZHONG D L, LI Z, LU Y Y, et al. Investigation of CO₂ capture from a CO₂ + CH₄ gas mixture by gas hydrate formation in the fixed bed of a molecular sieve[J]. Industrial & Engineering Chemistry Research, 2016, 55(29): 7973-7980.
11	FAKHARIAN H, GANJI H, NADERI FAR A, et al. Potato starch as methane hydrate promoter[J]. Fuel, 2012, 94: 356-360.
12	MAGHSOODLOO BABAKHANI S, ALAMDARI A. Effect of maize starch on methane hydrate formation/dissociation rates and stability[J]. Journal of Natural Gas Science and Engineering, 2015, 26: 1-5.
13	李金平, 姚泽, 李洋, 等. 冰点以下石英砂中二氧化碳水合物的生成特性[J]. 应用基础与工程科学学报, 2020, 28(4): 843-851.
	LI Jinping, YAO Ze, LI Yang, et al. Formation behaviors of carbon dioxide hydrate in quartz sands below freezing point[J]. Journal of Basic Science and Engineering, 2020, 28(4): 843-851.
14	张金华, 张郁, 魏伟. 石英砂介质中CO₂水合物形成影响研究[J]. 天然气化工(C1化学与化工), 2018, 43(2): 34-39.
	ZHANG Jinhua, ZHANG Yu, WEI Wei. Influence factors of carbon dioxide hydrate formation in quartz sand media[J]. Natural Gas Chemical Industry, 2018, 43(2): 34-39.
15	YU Y S, ZHANG Q Z, LI X S, et al. Kinetics, compositions and structures of carbon dioxide/hydrogen hydrate formation in the presence of cyclopentane[J]. Applied Energy, 2020, 265: 114808.
16	PENG D Y, ROBINSON D B. A new two-constant equation of state[J]. Industrial & Engineering Chemistry Fundamentals, 1976, 15(1): 59-64.
17	HO L C, BABU P, KUMAR R, et al. HBGS (hydrate based gas separation) process for carbon dioxide capture employing an unstirred reactor with cyclopentane[J]. Energy, 2013, 63: 252-259.
18	OHNO H, MOUDRAKOVSKI I, GORDIENKO R, et al. Structures of hydrocarbon hydrates during formation with and without inhibitors[J]. The Journal of Physical Chemistry A, 2012, 116(5): 1337-1343.

[1]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[2]	汪鹏, 张洋, 范兵强, 何登波, 申长帅, 张贺东, 郑诗礼, 邹兴. 高碳铬铁盐酸浸出过程工艺及动力学[J]. 化工进展, 2023, 42(S1): 510-517.
[3]	刘阳, 王云刚, 修浩然, 邹立, 白彦渊. 基于动力学分析的核桃壳最佳炭化工艺[J]. 化工进展, 2023, 42(S1): 94-103.
[4]	黄益平, 李婷, 郑龙云, 戚傲, 陈政霖, 史天昊, 张新宇, 郭凯, 胡猛, 倪泽雨, 刘辉, 夏苗, 主凯, 刘春江. 三级环流反应器中气液流动与传质规律[J]. 化工进展, 2023, 42(S1): 175-188.
[5]	董佳宇, 王斯民. 超声强化对二甲苯结晶特性及调控机理实验[J]. 化工进展, 2023, 42(9): 4504-4513.
[6]	王谨航, 何勇, 史伶俐, 龙臻, 梁德青. 气体水合物阻聚剂研究进展[J]. 化工进展, 2023, 42(9): 4587-4602.
[7]	李由, 吴越, 钟禹, 林琦璇, 任俊莉. 酸性熔盐水合物预处理麦秆高效制备木糖及其对酶解效率的影响[J]. 化工进展, 2023, 42(9): 4974-4983.
[8]	尹新宇, 皮丕辉, 文秀芳, 钱宇. 特殊浸润性材料在防治油气管道中水合物成核与聚集的应用[J]. 化工进展, 2023, 42(8): 4076-4092.
[9]	王俊杰, 潘艳秋, 牛亚宾, 俞路. 分子水平催化重整装置模型构建及应用[J]. 化工进展, 2023, 42(7): 3404-3412.
[10]	张凯, 吕秋楠, 李刚, 李小森, 莫家媚. 南海海泥中甲烷水合物的形貌及赋存特性[J]. 化工进展, 2023, 42(7): 3865-3874.
[11]	李瑞东, 黄辉, 同国虎, 王跃社. 原油精馏塔中铵盐吸湿特性及其腐蚀行为[J]. 化工进展, 2023, 42(6): 2809-2818.
[12]	杨扬, 孙志高, 李翠敏, 李娟, 黄海峰. 静态条件下表面活性剂OP-13促进HCFC-141b水合物生成[J]. 化工进展, 2023, 42(6): 2854-2859.
[13]	赵毅, 杨臻, 张新为, 王刚, 杨旋. 不同裂缝损伤和愈合温度条件下沥青自愈合行为的分子模拟[J]. 化工进展, 2023, 42(6): 3147-3156.
[14]	曾天续, 张永显, 严渊, 刘宏, 马娇, 党鸿钟, 吴新波, 李维维, 陈永志. 羟胺对硝化菌活性及其动力学参数的影响[J]. 化工进展, 2023, 42(6): 3272-3280.
[15]	张成松, 张静, 龚斌, 李明洋, 袁佳新, 李宏业. 自吸射流柔性搅拌桨振动特性[J]. 化工进展, 2023, 42(4): 1728-1738.

玉米棒+四氢呋喃对IGCC合成气水合物生成动力学的影响

Kinetics studies of IGCC syngas hydrate formation in the presence of corn cobs and tetrahydrofuran

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 18

相关文章 15

编辑推荐

Metrics

本文评价