天然气水合物储运技术中水合物反应器的研究进展

doi:10.16085/j.issn.1000-6613.2017-1969

化工进展 ›› 2018, Vol. 37 ›› Issue (09): 3326-3336.DOI: 10.16085/j.issn.1000-6613.2017-1969

天然气水合物储运技术中水合物反应器的研究进展

施政灼¹, 李玉星¹, 王武昌¹, 宋光春¹, 姜凯¹, 姚淑鹏¹, 张玉乾²

1 山东省油气储运安全省级重点实验室, 中国石油大学(华东), 山东青岛 266580;
2 中国石化销售有限公司华南分公司, 广东广州 510000

收稿日期:2017-09-18 修回日期:2018-01-22 出版日期:2018-09-05 发布日期:2018-09-05
通讯作者: 李玉星,博士,教授,主要从事油气储运工程方面的研究和教学工作。
作者简介:施政灼(1993-),男,硕士研究生,主要从事天然气水合物及管道流动安全保障方向研究。E-mail:shizhengzhuo@sina.com。
基金资助:
山东省自然科学基金（ZR2017MEE057）、中央高校基本科研业务费专项资金（14CX02207A，17CX06017，17CX05006）及中国石油大学（华东）研究生创新工程（YCX2017062）项目。

Review of hydrate reactor in natural gas hydrate storage and transportation

SHI Zhengzhuo¹, LI Yuxing¹, WANG Wuchang¹, SONG Guangchun¹, JIANG Kai¹, YAO Shupeng¹, ZHANG Yuqian²

1 Shandong Key Laboratory of Oil-Gas Storage and Transportation Safety, China University of Petroleum, Qingdao 266580, Shandong, China;
2 Sinopec Chemical Commercial Holding Company Limited South China Branch, Guangzhou 510000, Guangdong, China

Received:2017-09-18 Revised:2018-01-22 Online:2018-09-05 Published:2018-09-05

摘要/Abstract

摘要： 可观的储气率与自保效应的存在使得天然气水合物能作为一种天然气储运的方式，并且在与其他如液化天然气、压缩天然气储运方式比较时有着自己独到的优势。但由于针对水合物储运的研究起步较晚，利用水合物储运天然气的技术尚未成熟。尤其是在水合物反应器的研究上，生成水合物的速率较低，无法达到工业生产所需要的水平。本文通过调研国内外文献与专利等资料，介绍了国内外天然气水合物储运技术发展状况，简述了水合物生成强化的物理化学手段与机械手段，详述了搅拌式等传统天然气水合物反应器与管式、超重力式等新型天然气水合物反应器的结构与工作原理。根据现有水合物反应器的特点与存在的问题，对水合物反应器的研究方向提出建议：未来应当加快对喷淋式、超重力式与流化床式反应器的放大研究，加快针对不同物理强化手段与机械强化手段的协同作用研究，建立起以天然气储运为目的的水合物反应器评价体系。

关键词: 天然气储运, 水合物, 反应器, 快速生成

Abstract: Considerable gas storage rate (about 170 times as much as its volume) and self-preservation effect of natural gas hydrate (NGH) make itself as a favorable ways to storage and transport natural gas. Consequently, NGH has its own unique advantages when compared with LNG, CNG and other ways of natural gas storage and transportation. But, the study of NGH started late in comparison with other ways of natural gas storage and transportation. This way of natural gas storage and transportation has not yet reached maturity. Especially in the study of hydrate reactor. The hydrate formation rate or the gas consumption of reactor cannot attend the achieve requirements of industrial production. This paper investigates domestic and foreign literature and patents of NGH, introduces the development of natural gas hydrate storage and transportation technology, the chemical means and mechanical means of hydrate formation enhancement, the structure and working principle of three type traditional natural gas hydrate reactor, stirred, bubble and spray type reactor, and many new pattern natural gas hydrate like tube reactor, jet reactor and super-gravity reactor. In the existing reactors, the sprayed, super-gravity and fluidized bed reactors have better performance and prospects, and the amplification study of these three kind reactors should be accelerated. The coupling effect between different chemical means and different mechanical means have a significance for natural gas hydrate production. The evaluation system of hydrate reactors for the purpose of natural gas storage and transportation should be established.

Key words: storage and transportation of natural gas, hydrate, reactors, rapid formation

中图分类号:

TE88

施政灼, 李玉星, 王武昌, 宋光春, 姜凯, 姚淑鹏, 张玉乾. 天然气水合物储运技术中水合物反应器的研究进展[J]. 化工进展, 2018, 37(09): 3326-3336.

SHI Zhengzhuo, LI Yuxing, WANG Wuchang, SONG Guangchun, JIANG Kai, YAO Shupeng, ZHANG Yuqian. Review of hydrate reactor in natural gas hydrate storage and transportation[J]. Chemical Industry and Engineering Progress, 2018, 37(09): 3326-3336.

参考文献

[1] SLOAN E D. Fundamental principles and applications of natural gas hydrates[J]. Nature, 2003, 426(6964):353-363.
[2] 陈光进, 孙长宇, 马庆兰. 气体水合物科学与技术[M]. 北京:化学工业出版社, 2008:223-225. CHEN G J, SUN C Y, MA Q L. Gas hydrate science and technology[M]. Beijing:Chemical Industry Press, 2008:223-225.
[3] ROGERS R E. Natural gas hydrates storage project[R]. Office of Scientific & Technical Information Technical Reports, 1999.
[4] ROGERS R, ETHERIDGE J. Gas hydrate storage of natural gas[D]. Mississippi State:Mississippi State University, 2011.
[5] SLOAN E D. Clathrate hydrates:The other common solid water phase[J]. Industrial &Engineering Chemistry Research, 2000, 39(9):3123-3129.
[6] KANDA H. Economic study on natural gas transportation with natural gas hydrate (NGH) pellets[C]//23rd World Gas Conference. Amsterdam. 2006.
[7] 樊栓狮. 天然气水合物储存与运输技术[M]. 北京:化学工业出版社, 2005. FAN S S. Naturel gas hydrate storage and transportation technology[M]. Beijing:Chemical Industry Press, 2005.
[8] MAKOGON Y F. Gas hydrate formation conditions during gas transport at t<0℃[J]. Express-Informatsia Min. Gaz. Prom., 1969, 17(243):10-17.
[9] 温永刚, 陈秋雄, 陈运文, 等. 天然气水合物奇异自保护效应研究发展及其应用[J]. 天然气化工(C1化学与化工), 2014(1):82-87. WEN Y G, CHEN Q X, CHEN Y W, et al. Research progress in anomalous self-preservation effect of natural gas hydrate and its application[J]. Natural Gas Chemical Industry, 2014(1):82-87.
[10] GUDMUNDSSON J S. Method and equipment for production of gas hydrates:WO1993001153A1[P]. 1993-01-21.
[11] FITZGERALD A, TAYLOR M. Offshore gas-to-solids technology[C]//Offshore Europe. Society of Petroleum Engineers, 2001.
[12] IWASAKI T. Continuous natural gas hydrate pellet production (NGHP) by process development unit (PDU)[C]//Proceeding of 5th International Conference on Gas Hydrate. Trondheim, Norway, 2005.
[13] NAKAI S. Development of natural gas hydrate (NGH) supply chain[C]//Proceedings of World Gas Conference. 2012.
[14] 刘建辉. 天然气储运关键技术研究及技术经济分析[D]. 广州:华南理工大学, 2012. LIU J H. Key technology research and techno-economic analysis of natural gas storage and transportation[D]. Guangzhou:South China University of Technology, 2012.
[15] SKOVBORG P, RASMUSSEN P. A mass transport limited model for the growth of methane and ethane gas hydrates[J]. Chemical Engineering Science, 1994, 49(8):1131-1143.
[16] SAITO Y. Methane storage in hydrate phase with water soluble guests[C]//Proc. 2nd Int. Conf. on Natural Gas Hydrates. Toulouse, France, 1996, 2:459-465.
[17] DEUGD R M D, JAGER M D, ARONS J D S. Mixed hydrates of methane and water-soluble hydrocarbons modeling of empirical results[J]. AIChE Journal, 2010, 47(3):693-704.
[18] 吕秋楠, 陈朝阳, 李小森.气体水合物快速生成强化技术与方法研究进展[J]. 化工进展, 2011, 30(1):74-79. LIU Q N, CHEN C Y, LI X S. Advances in technology and method for promoting gas hydrate rapid formation[J].Chemical Industry and Engineering Progress, 2011, 30(1):74-79.
[19] 杜建伟, 梁德青, 戴兴学, 等. Span 80促进甲烷水合物生成动力学研究[J]. 工程热物理学报, 2011, 32(s2):197-200. DU J W, LIANG D Q, DAI X X, et al. Investigation on span 80 promoting methane hydrate formation kinetics[J]. Journal of Engineering Thermophysics, 2011, 32(s2):197-200.
[20] ZHONG Y, ROGERS R E. Surfactant effects on gas hydrate formation[J]. Chemical Engineering Science, 2000, 55(19):4175-4187.
[21] SUN Z G, WANG R, MA R, et al. Natural gas storage in hydrates with the presence of promoters[J]. Energy Conversion & Management, 2003, 44(17):2733-2742.
[22] 李玉星, 朱超, 王武昌. 表面活性剂促进CO₂ 水合物生成的实验及动力学模型[J]. 石油化工, 2012, 41(6):699-703. LI Y X, ZHU C, WANG W C. Promoting effects of surfactants on carbon dioxide hydrate formation and the kinetics[J]. Petrochemical Technology, 2012, 41(6):699-703.
[23] PERRIN A, CELZARD A, MARECHE J F, et al. Methane Storage within dry and wet active carbons:a comparative study[J]. Energy & Fuels, 2003, 17(5):1283-1291.
[24] ZANG X Y, FAN S S, LIANG D Q, et al. Influence of 3A molecular sieve on tetrahydrofuran (THF) hydrate formation[J]. Science in China Senries B:Chemistry, 2008, 51(9):893-900.
[25] PARK Sung-seek, SEO Hyang-min, KIM Nam-jin, et al. Methane hydrate formation using carbon nano tubes[J]. The Korean Society for New and Renewable Energy, 2009, 11:549-552.
[26] 陈玉龙. 氨基酸促进甲烷水合物形成的机理研究[D]. 广州:华南理工大学, 2016. CHEN Y L. Mechanism of amino acids in promoting methane hydrates formation[D]. Guangzhou:South China University of Technology, 2016.
[27] VELUSWAMY H P, KUMAR A, KUMARR S, et al. Natural gas storage via SNG (solidified natural gas) technology -Pathway to commercialization[C]//Proceedings of the 9th International Conference on Gas Hydrates, Denver, Colorado, USA, 2017.
[28] 刘春阳, 毕研军, 李玉星, 等. 天然气水合物生成的影响因素[J]. 油气储运, 2009, 28(12):37-40. LIU C Y, BI Y J, LI Y X, et al. Factors influencing on formation of natural gas hydrate[J]. Oil & Gas Storage and Transportation, 2009, 28(12):37-40.
[29] TAJIMA H, NAGATA T, ABE Y, et al. HFC-134a hydrate formation kinetics during continuous gas hydrate formation with a kinetics static mixer for gas separation[J]. Industrial & Engineering Chemistry Research, 2010, 49(5):2525-2532.
[30] MORK M. Formation rate of natural gas hydrate-reactor experiments and models[J]. Industryal & Engineering Chemistry Research, 2010, 49(5):2525-2532.
[31] 郝文峰, 孟广波, 刘文林, 等. 半连续搅拌槽式反应器甲烷水合物生成实验[J]. 科技信息:科学·教研, 2007(18):275-276. HAO W F, MENG G B, LIU W L, et al. Formation experiment of methane hydrate in semi-continuous stirred tank reactor[J]. Science & Technology Information, 2007(18):275-276.
[32] 刘芙蓉, 王胜杰, 张文玲, 等. 冰-水-气生成天然气水合物的实验研究[J]. 西安交通大学学报, 2000, 34(12):66-69. LIU F R, WANG S J, ZHANG W L, et al. Experimental study of natural gas hydrate formed from ice-water-gas[J]. Journal of Xi'an Jiaotong University, 2000, 34(12):66-69.
[33] TAKAHASHI M, OONARI H, YAMAMOTO Y. A novel manufacturing method of gas hydrate using the micro-bubble technology[C]//Proceedings of the 4th International Conference on Natural Gas Hydrates, Yokohama, Japan. 2002, 825:828.
[34] 周春艳, 郝文峰, 冯自平. 孔板气泡法缩短天然气水合物形成诱导期[J]. 天然气工业, 2005, 25(7):27-29. ZHOU Y C, HAO W F, FENG Z P. Shortening the induction period of forming gas hydrate by orifice bubbling method[J]. Natural Gas Industry, 2005, 25(7):27-29.
[35] LUO Y T, ZHU J H, FAN S S, et al. Study on the kinetics of hydrate formation in a bubble column[J]. Chemical Engineering Science, 2007, 62(4):1000-1009.
[36] 张建文, 杨林. 一种制造天然气水合物的方法:CN103571557A[P]. 2014-02-12. ZHANG J W, YANG L. A method of producing natural gas hydrate:CN103571557A[P]. 2014-02-12.
[37] ROGERS R, YEVI G Y, SWALM M. Hydrate for storage of natural gas[C]//Proceedings of the 2nd NGH. Toulouse, Elf Aquitaine, 1996:423-429.
[38] OHMURA R, KASHIWAZAKI S, MORI Y H. Structure-Ⅰ and structure-hydrate formation using water spraying[J]. Energy & Fuels, 2002, 16:1141-1147.
[39] 赵建忠, 赵阳升, 石定贤. 喷雾法合成气体水合物的实验研究[J]. 辽宁工程技术大学学报, 2006, 25(2):286-289. ZHAO J Z, ZHAO S Y, SHI D X. Experimental study on forming hydrate by spray reactor[J]. Journal of Liaoning Technical University, 2006, 25(2):286-289.
[40] 郝文峰, 盛伟, 樊栓狮, 等. 喷淋式反应器中甲烷水合反应实验研究[J]. 武汉理工大学学报, 2007, 29(12):39-43. HAO W F, SHENG W, FAN S S, et al. Experimental investigation of methane hydrate formation in a spraying reactor[J]. Journal of Wuhan University of Technology, 2007, 29(12):39-43.
[41] TAKASHI A, TOSHIO Y. Apparatus for producing hydrate:JP2002356685A[P]. 2006-12-23.
[42] HIROYOKI IDA, KAZUO KODA. Manufacturing method and apparatus of gas hydrate:JP2002356685A[P]. 2000-12-13.
[43] 周诗岽, 武玉宪, 王树立, 等.一种气体水合物生产方法及装置:CN101513600 A[P].2009-08-26. ZHO S D, WU Y X, WANG S L, et al. A method and apparatus for producing natural gas hydrate:CN101513600 A[P].2009-08-26.
[44] MORIYA H, TAKAHASHI M. Gas-hydrate producing device:JP2016030254A[P]. 2016-03-07.
[45] MITSUI ENG & SHIPBUILD CO LTD. Method for producing gas hydrate and gas hydrate production:JP2016111786A[P]. 2006-04-27.
[46] SZYMCEK P, MCCALLUM S D, TABOADA-SERRANO P, et al. A pilot-scale continuous-jet hydrate reactor[J]. Chemical Engineering Journal, 2008, 135(1/2):71-77.
[47] 杜燕, 何世辉, 黄冲, 等. 喷射反应器中天然气水合物生成实验[J]. 天然气工业, 2008, 28(8):126-128. DU Y, HE S H, HUANG C, et al. Laboratory tests on NGH generation in jet reactor[J]. Natural Gas Industry, 2008, 28(8):126-128.
[48] BUDHIJANTO B. Reaction engineering study of natural gas hydrate formation in special packed-bed reactors by controlling the boundary layer surfaces of the gas-liquid-solid phases[D]. Morgantown, West Virginia:West Virginia University, 2003.
[49] BAI J, LIANG D, LI D, et al. Continuous formation process of CO₂ gas hydrate via a vortex and impinging stream reactor[J]. Energy & Fuels, 2010, 24(2):1207-1212.
[50] 白净, 梁德青, 李栋梁, 等. 采用静态超重力快速制备天然气水合物的方法及装置:CN101225338 B[P].2011-03-23. BAI J, LIANG D Q, LI D L, et al. Method and apparatus for rapid preparation of natural gas hydrate by static supergravity:CN 101225338 B[P]. 2011-03-23.
[51] 刘有智, 邢银全, 崔磊军. 超重力旋转填料床中天然气水合物含气量研究[J]. 化工进展, 2007, 26(6):853-856. LIU Y Z, XING Y Q, CUI L J. Experimental study on capacity of gas hydrate in a rotating packed bed[J]. Chemical Industry and Engineering Progress, 2007, 26(6):853-856.
[52] 宋勇, 卢泽华, 王登飞, 等. 一种天然气水合物制备装置:CN 205313484U[P].2016-06-15. SONG Y, LU Z H, WANG D F, et al. A natural gas hydrate preparation device:CN205313484 U[P].2016-06-15.
[53] MOBIL OIL CORPORATION. Method for producing gas hydrates utilizing a fluidized bed:US6180843B1[P]. 2001-01-30.
[54] MARATHON OIL COMPANY. Production of a gas hydrate slurry using a fluidized bed heat exchanger:US6350928[P]. 2002.
[55] OAK RIDGE NATIONAL LABORATORY, US. Gas hydrate cool storage system:US4540501A[P].1985-09-10.
[56] DRINKER BIDDLE & REATH, ATTN:INTELLECTUAL PROPERTY GROUP. Process and device for the thermal stimulation of gas hydrate formation:US20060070732A1[P]. 2006-04-06.
[57] LIANG D Q, HE S, LI D L. Effect of microwave on formation/decomposition of natural gas hydrate[J]. Chinese Science Bulletin, 2009, 54(6):965-971.
[58] 孙始财, 樊栓狮. 超声波作用下天然气水合物的形成[J]. 化学通报, 2005, 68(11):867-870. SUN S C, FAN S S. The formation of natural gas hydrates with ultrasonic[J]. Chemistry, 2005, 68(11):867-870.
[59] 刘勇, 郭开华, 梁德青, 等. 在磁场作用下HCFC——141b制冷剂气体水合物的生成过程[J]. 中国科学:B辑, 2003, 33(1):89-96. LIU Y, GUO K H, LIANG D Q, et al. The formation process of HCFC-141b gas hydrate under the action of magnetic field[J]. Science in China(Series B), 2003, 33(1):89-96.
[60] MITSUI ENG & SHIPBUILD CO LTD. Apparatus for forming gas hydrate:JP2006160828A[P]. 2006-06-22.
[61] 黄林, 张建文.一种制备固体天然气的方法和装置:CN1621502 A[P]. 2005-06-10. HUANG L, ZHANG J W. A method and apparatus for preparing solid natural gas:CN1621502 A[P]. 2005-06-10.
[62] 于达, 宫敬.天然气水合物(NGH)的储存和输送[C]//全国油气储运技术交流研讨会论文集. 东营:中国石油大学出版社, 2002:145-149. YU D, GONG J. Natural gas hydrate (NGH) storage and transportation[C]//Proceedings of the National Symposium on Oil and Gas Storage and Transportation. Dongying:Petroleum University Press, 2002:145-149.
[63] 张萌, 任远, 陈炜, 等.车载天然气水合物储运装置[J].当代化工, 2016, 45(1):179-181. ZHANG M, REN Y, CHEN W, et al. Vehicle natural gas hydrate storage and transportation device[J].Contemporary Chemical Industry, 2016, 45(1):179-181.

天然气水合物储运技术中水合物反应器的研究进展

Review of hydrate reactor in natural gas hydrate storage and transportation

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	盛维武, 程永攀, 陈强, 李小婷, 魏嘉, 李琳鸽, 陈险峰. 微气泡和微液滴双强化脱硫反应器操作分析[J]. 化工进展, 2023, 42(S1): 142-147.
[2]	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.
[3]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[4]	刘炫麟, 王驿凯, 戴苏洲, 殷勇高. 热泵中氨基甲酸铵分解反应特性及反应器结构优化[J]. 化工进展, 2023, 42(9): 4522-4530.
[5]	罗成, 范晓勇, 朱永红, 田丰, 崔楼伟, 杜崇鹏, 王飞利, 李冬, 郑化安. 中低温煤焦油加氢反应器不同分配器中液体分布的CFD模拟[J]. 化工进展, 2023, 42(9): 4538-4549.
[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]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[8]	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.
[9]	邓建, 王凯, 骆广生. 面向硝基化学品安全生产的绝热连续微反应技术发展及思考[J]. 化工进展, 2023, 42(8): 3923-3925.
[10]	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.
[11]	李洞, 王倩倩, 张亮, 李俊, 付乾, 朱恂, 廖强. 非水系纳米流体热再生液流电池串联堆性能特性[J]. 化工进展, 2023, 42(8): 4238-4246.
[12]	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.
[13]	鲁少杰, 刘佳, 冀芊竹, 李萍, 韩月阳, 陶敏, 梁文俊. 硅藻土基复合填料制备及滴滤塔去除二甲苯的性能[J]. 化工进展, 2023, 42(7): 3884-3892.
[14]	王松松, 刘培乔, 陶长元, 王运东, 陈恩之, 苗迎彬, 赵风轩, 刘作华. 工业物联网技术在搅拌反应器领域的应用[J]. 化工进展, 2023, 42(7): 3331-3339.
[15]	刘卫孝, 刘洋, 高福磊, 汪伟, 汪营磊. 微反应器在含能材料合成与品质提升中的应用[J]. 化工进展, 2023, 42(7): 3349-3364.