三嗪型天然气管道缓蚀型减阻剂合成与应用

doi:10.16085/j.issn.1000-6613.2023-0304

摘要/Abstract

摘要：

天然气管道传统增输方法投资高、施工复杂，在役旧管线无法增输且管道内部存在腐蚀。为达到经济可行的天然气管道低成本不增压增输和缓蚀的双重目的，应用三聚氯氰和有机胺通过亲核取代反应合成了新型添加剂双-2-二丁基胺基-4-N-吗啉-6-N-乙二胺基-1,3,5-三嗪（BDMET），采用氢核磁共振谱图（¹H NMR）和元素分析（EA）对产品进行结构表征。应用BDMET的甲醇溶液作为缓蚀型减阻剂进行现场加注试验，并评价了产品减阻增输效果和缓蚀效果。¹H NMR和EA表征证明了产品的化学结构。现场采用雾化加注5条集输管线，其减阻率在8%~13%，增输率在6%~11%，缓蚀率维持在85%~86%，有效时间大于20天，累计加剂时间大于360天。合成的BDMET兼有优异的缓蚀与减阻效果，避免了普通缓蚀剂需连续加注的问题，且气体质检证明加注BDMET后对天然气气质无影响。

关键词: 天然气, 分子合成, 减阻, 腐蚀, 三嗪

Abstract:

Traditional methods of increasing transportation needed high costs and complicated constructions, and old pipeline in service could not realize. Also, corrosion existed in pipeline. In order to fulfill no-pressurized increasing transportation at low cost and reducing corrosion for nature gas pipeline, bis-2-dibutylamino-4-N-morpholine-6-N-ethylenediamine-1,3,5-triazine (BDMET) was synthesized using cyanuric chloride and organic amine by nucleophilic substitution reaction. The structure of BDMET was characterized with ¹H nuclear magnetic resonance (¹H NMR) spectroscopy and elemental analysis (EA). As corrosion inhibitor and drag reducing agent, BDMET of methanol solution was infused into nature gas pipeline in field, and drag reducing rate and transmission increasing rate were assayed by field experiment. The results of ¹H NMR and EA tests indicated that the product was the target compound. After infusing into five nature gas pipelines by atomization, the drag reducing rate and transmission increasing rate of the product were 8%—13% and 6%—11%, respectively. Meanwhile, the corrosion inhibition of BDMET reached 85%—86% and the valid time was over 20 days. In addition, the field experiment lasted over 360 days. BDMET synthesized possessed excellent corrosion inhibition property and drag reduction property, and avoided continuous infusing for common corrosion inhibitors. Then, gas inspection proved that the quality of the nature gas was unaffected when BDMET was infused into the pipeline.

Key words: natural gas, molecular synthesis, drag reduction, corrosion, triazine

中图分类号:

O622.6

赵巍, 赵德银, 李世瀚, 刘洪达, 孙进, 郭艳秋. 三嗪型天然气管道缓蚀型减阻剂合成与应用[J]. 化工进展, 2023, 42(S1): 391-399.

ZHAO Wei, ZHAO Deyin, LI Shihan, LIU Hongda, SUN Jin, GUO Yanqiu. Synthesis and application of triazine drag reducing agent for nature gas pipeline[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 391-399.

图/表 12

参考文献 27

1	中国石油管道公司. 油气管道化学添加剂技术[M]. 北京: 石油工业出版社, 2010: 12-20.
	China National Petroleum Pipeline Corp. Chemical additive technology for oil and gas pipelines[M]. BeiJing: Petroleum Industry Press, 2010:12-20.
2	王琴, 李昂, 谢萍, 等. 天然气减阻剂开发应用现状及研究展望[J]. 油气田地面工程, 2018, 37(10): 6-9.
	WANG Qin, LI Ang, XIE Ping, et al. Development and application status and research prospects of natural gas drag reduction agents[J]. Oil-Gas Field Surface Engineering, 2018, 37(10): 6-9.
3	陈伟锋，尚娟，邢百汇, 等. 关于天然气管网安全掺氢比10%的商榷[J]. 化工进展, 2022, 41(3): 1487-1493.
	CHEN Weifeng, SHANG Juan, XING Baihui, et al. Discussion on 10% as a safe ratio of hydrogen mixing into natural gas grids[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1487-1493.
4	邰军, 姜希彤, 秦伟, 等. 长输天然气管道压气站运行分析[J]. 油气田地面工程, 2020, 39(8): 38-42.
	TAI Jun, JIANG Xitong, QIN Wei, et al. Operation analysis of compressor station for long distance natural gas pipeline[J]. Oil-Gas Field Surface Engineering, 2020, 39(8): 38-42.
5	张双蕾, 明亮, 李巧, 等. 天然气长输管道压气站最大操作压力研究[J]. 天然气与石油, 2021, 39(2): 1-5.
	ZHANG Shuanglei, MING Liang, LI Qiao, et al. Research on MOP for compressor station of long-distance pipeline[J]. Natural Gas and Oil, 2021, 39(2): 1-5.
6	王振声, 董红军, 张世斌, 等. 天然气管道压气站一键启停站控制技术[J]. 油气储运, 2019, 38(9): 1029-1034.
	WANG Zhensheng, DONG Hongjun, ZHANG Shibin, et al. Control technologies for the one-key start and stop of compressor stations of gas pipelines[J]. Oil & Gas Storage and Transportation, 2019, 38(9): 1029-1034.
7	郑安升, 黄留群, 杨学强, 等. 节能环保型无溶剂环氧减阻内涂层技术——以中俄东线天然气管道工程黑河—长岭段为例[J]. 天然气工业, 2020, 40(10): 120-125.
	ZHENG Ansheng, HUANG Liuqun, YANG Xueqiang, et al. Energy-saving and environmental-friendly solvent-free epoxy drag-reduction coating technology: A case study of the Heihe-Changling section of the China-Russian eastern gas pipeline[J]. Natural gas industry, 2020, 40(10): 120-124.
8	周池楼, 何默涵, 肖舒, 等. 不锈钢表面阻氢涂层研究进展[J]. 化工进展, 2020, 39(9): 3458-3468.
	ZHOU Chilou, HE Mohan, XIAO Shu, et al. Review on hydrogen permeation barrier coatings on stainless steels[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3458-3468.
9	LV Xuesen, QIN Yao, LIANG Hang, et al. A facile method for constructing a superhydrophobic zinc coating on a steel surface with anti-corrosion and drag-reduction properties[J]. Applied Surface Science, 2021, 562: 150192.
10	ZHAO Jing, SUN Ruoyu, LIU Chuang, et al. Application of ZnO/epoxy resin superhydrophobic coating for buoyancy enhancement and drag reduction[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 651: 129714.
11	QIN Liguo, LU Shan, LIU Jianbo, et al. Bionic non-smooth epoxy resin coating with corrosion inhibitor for drag-reduction and durability[J]. Progress in Organic Coatings, 2022, 73: 107716.
12	SAADATBAKHSH Mohammad, JAMALI ASL Shahin, KIANI Mohammad Javad, et al. Slip length measurement of pdms/hydrophobic silica superhydrophobic coating for drag reduction application[J]. Surface and Coatings Technology, 2020, 404: 126428.
13	刘畅, 陈旭, 杨江. CO₂腐蚀及其缓蚀剂应用研究进展[J]. 化工进展, 2021, 40(11): 6305-6314.
	LIU Chang, CHEN Xu, YANG Jiang. Corrosion inhibitors and its application in CO₂corrosion[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6305-6314.
14	ESFANDIARI Nadia, ZAREINEZHAD Reza, HABIBI Zahra. The investigation and optimization of drag reduction in turbulent flow of Newtonian fluid passing through horizontal pipelines using functionalized magnetic nanophotocatalysts and lecithin[J]. Chinese Journal of Chemical Engineering, 2020, 28(1): 63-75.
15	Abdelsalam AL-SARKHI, NAKLA Meamer EL, AHMED Wael H. Friction factor correlations for gas-liquid/liquid-liquid flows with drag-reducing polymers in horizontal pipes[J]. International Journal of Multiphase Flow, 2011, 37(5): 501-506.
16	袁颖, 敬加强, 尹然, 等. 阳离子型表面活性剂与聚合物复配体系协同减阻作用[J]. 化工进展, 2022, 41(5): 2593-2603.
	YUAN Ying, JING Jiaqiang, YIN Ran, et al. Synergistic drag reduction effect of cationic surfactant and polymer compound system[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2593-2603.
17	王帅, 赵金柱, 王荣元, 等. 乳化/润湿耦合作用稠油流动减阻新思路[J]. 化工进展, 2021, 40(S2): 126-139.
	WANG Shuai, ZHAO Jinzhu, WANG Rongyuan, et al. New ideas of heavy oil flow drag reduction by emulsification and wetting coupling action[J]. Chemical Industry and Engineering Progress, 2021, 40(S2): 126-139.
18	CHEN Yang, LI Changjun, NECHVAL Andrey M, et al. Mechanical degradation of polyalphaolefin in turbulent drag reduction flow in rheometer and pipeline[J]. Chemical Engineering Research and Design, 2023, 189: 333-346.
19	MOAYEDI Hossein, AGHEL Babak, VAFERI Behzad, et al. The feasibility of Levenberg-Marquardt algorithm combined with imperialist competitive computational method predicting drag reduction in crude oil pipelines[J]. Journal of Petroleum Science and Engineering, 2020, 185: 106634.
20	赵巍, 王晓司, 王晓霖, 等. 双(N,N'-二正己基-乙烯基胺)-1,4-二乙烯基-哌嗪-二丁二酸盐的合成与减阻性能[J]. 化工进展, 2018, 37(7): 2814-2819.
	ZHAO Wei, WANG Xiaosi, WANG Xiaolin, et al. Synthesis and drag reduction of bis(N,N'-di-n-hexyl-vinylamine)-1,4-divinyl-piperazine disuccinate[J]. Chemical Industry and Engineering Progress, 2018, 37(7): 2814-2819.
21	赵巍, 王晓霖, 李遵照, 等. 一种磷酸胺盐天然气减阻剂及其制备方法和应用: CN108017666A[P]. 2021-03-05.
	ZHAO Wei, WANG Xiaolin, LI Zunzhao, et al. Phosphoric acid amine salt natural gas drag reducer, preparation method and application thereof: CN108017666A[P]. 2021-03-05.
22	王晓霖, 赵巍, 李遵照, 等. 磷酸胺盐天然气减阻剂及其制备方法和用途: CN108017667A[P]. 2021-04-06.
	WANG Xiaolin, ZHAO Wei, LI Zhunzhao, et al. Ammonium phosphate natural gas drag reducer, and preparation method and use thereof: CN108017667A[P]. 2018-05-11.
23	赵巍, 王晓霖, 李遵照, 等. 一种三嗪系天然气减阻剂及其合成方法和用途: CN108017587A[P]. 2018-05-11.
	ZHAO Wei, WANG Xiaolin, LI Zhunzhao, et al. Triazine natural gas drag reducer, and synthesis method and use thereof: CN108017587A[P]. 2018-05-11.
24	王晓司, 王晓霖, 赵巍, 等. 一种天然气减阻剂雾化喷涂效果测试系统及方法: CN110763265B[P]. 2021-08-31.
	WANG Xiaosi, WANG Xiaolin, ZHAO Wei, et al. Natural gas drag reducer atomization spraying effect test system and method: CN110763265B[P]. 2021-08-31.
25	赵巍, 王晓霖, 李遵照, 等. 一种三嗪类天然气减阻剂及其合成方法和用途: CN108003107A[P]. 2021-01-05.
	ZHAO Wei, WANG Xiaolin, LI Zhunzhao, et al. Triazine natural gas drag reducer and synthesis method and use thereof: CN108003107A[P]. 2021-01-05.
26	马丽, 葛维娟, 张金凯, 等. 均三嗪系列膨胀型阻燃剂的合成及应用[J]. 功能材料, 2015, 46(12): 12001-12008, 12013.
	MA Li, GE Weijuan, ZHANG Jinkai, et al. Synthesis and application of 1,3,5-triazine-based intumescent flame retardants[J]. Journal of Functional Materials, 2015, 46(12): 12001-12008, 12013.
27	DAI Jinfeng, LI Bin. Synthesis, thermal degradation, and flame retardance of novel triazine ring-containing macromolecules for intumescent flame retardant polypropylene[J]. Journal of Applied Polymer Science, 2010, 116(4):2157-2165.

工艺参数	1号集输管线	2号集输管线	3号集输管线	4号集输管线	5号集输管线
管长/km	125.3	22.6	15	8.8	9.1
管径/mm	457×6.4	273×6.4	200×6.4	168.3×5.6	168.3×5.6
材质	20^#	20^#	20^#	20^#	20^#
输量/10⁴m³·d^-1	50	60	65	1.5	1.0
输送压力/MPa	3.6~4.0	3.6~4.0	1.3	0.72	0.76
初始压降/MPa	1.41	1.43	0.61	0.196	0.198
加注方式	雾化式	雾化式	雾化式	雾化式	雾化式
每次加剂总量/L	401.9	484.0	520.3	9.0	32
加剂流量/L·h^-1	4.17	5.05	5.42	0.09	0.33
每次加剂天数/d	5~6	4~5	4~5	4~5	4~5

工艺参数	1号集输管线	2号集输管线	3号集输管线	4号集输管线	5号集输管线
管长/km	125.3	22.6	15	8.8	9.1
管径/mm	457×6.4	273×6.4	200×6.4	168.3×5.6	168.3×5.6
材质	20^#	20^#	20^#	20^#	20^#
输量/10⁴m³·d^-1	50	60	65	1.5	1.0
输送压力/MPa	3.6~4.0	3.6~4.0	1.3	0.72	0.76
初始压降/MPa	1.41	1.43	0.61	0.196	0.198
加注方式	雾化式	雾化式	雾化式	雾化式	雾化式
每次加剂总量/L	401.9	484.0	520.3	9.0	32
加剂流量/L·h^-1	4.17	5.05	5.42	0.09	0.33
每次加剂天数/d	5~6	4~5	4~5	4~5	4~5

项目	C	H	N	O
计算值/%	59.79	9.05	26.18	4.98
测试值/%	59.13	8.72	26.85	4.63

项目	C	H	N	O
计算值/%	59.79	9.05	26.18	4.98
测试值/%	59.13	8.72	26.85	4.63

项目	检测依据	结果
甲烷摩尔分数/%	GB/T13610—2020	91.16
乙烷摩尔分数/%		1.6
丙烷摩尔分数/%		0.65
异丁烷摩尔分数/%		0.16
正丁烷摩尔分数/%		0.28
新戊烷摩尔分数/%		0.00
异戊烷摩尔分数/%		0.08
正戊烷摩尔分数/%		0.09
己烷及己烷以上摩尔分数/%		0.00
氧气摩尔分数/%		0.24
氮气摩尔分数/%		5.62
二氧化碳摩尔分数/%		0.12
氦气摩尔分数/%		0.00
氢气摩尔分数/%		0.00
高位发热量（在101.325KPa，20^oC下）/MJ·m^-3	GB/T11062—2020	36.25
低位发热量（在101.325KPa，20^oC下）/MJ·m^-3		32.69
相对密度/g·cm^-3		0.6032
沃泊指数/ MJ·Sm^-3		46.67